1988 Techniques in Sedimentology

f
Techniques in Sedimentology
Edited by
MAURICE
TUCKER
BSc, P h D
D e p a r t m e n t of Geological Sciences
University of D u r h a m
Durham D H 1 3LE
UK
Blackwell Scientific Publications

OXFORD LONDON E D I N B U R G H BOSTON
MELBOURNE
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Contents
1988 by
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List of contributors vii

Preface ix
1
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Techniques in sedimentology.
1. Sedimentology Technique
I. Tucker, Maurice E.
551.3'04'028
QE471
MILLER
X-ray powder diffraction of sediments 191

R O N H A R D Y and M A U R I C E
TREWIN
Chemical analysis of sedimentary rocks 2 7 4

IAN FAIRCHILD, G R A H A M
MAURICE TUCKER
Library of Congress
Cataloging-in-Publication Data
References 3 5 5
Techniques in sedimentology.
Bibliography: p.
Includes index.
1. Sedimentology I. Tucker, Maurice E.
471 .T37 1988
552'.5
87-34120
ISBN 0-632-01361-3
ISBN 0-632-01372-9 (pbk.)
Index 3 8 7
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Mllll mm
TUCKER
Use of the scanning electron microscope in sedimentology 2 2 9

NIGEL
ISBN 0-632-01361-3
ISBN 0-632-01372-9 Pbk
lllllllllll
HARWOOD
Cathodoluminescence microscopy 1 7 4
JOHN
British Library
Cataloguing in Publication Data
MILLER
Microscopical techniques: II. Principles of sedimentary petrography 108

GILL
MCMANUS
Microscopical techniques: I. Slices, slides, stains and peels 8 6

JOHN
Australia
(Australia) Pty Ltd
107 Barry Street
Carlton, Victoria 3053
(Orders: Tel. (03) 347 0300)
GRAHAM
Grain size determination and interpretation 6 3

JOHN
TUCKER
Collection and analysis of field data 5

JOHN
Canada
Oxford University Press
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Don Mills
Ontario M3C 1J9
(Orders: Tel: (416) 441-2941)
mm
Introduction 1
MAURICE
HENDRY,
MARTIN
Q U E S T and
List of contributors
IAN
FAIRCHILD
D e p a r t m e n t of Geological Sciences, T h e University, Birmingham B15 2 T T .
JOHN
GRAHAM
D e p a r t m e n t of Geology, Trinity College, D u b l i n , E i r e .
RON
HARDY
D e p a r t m e n t of Geologial Sciences, T h e University, D u r h a m D H 1 3 L E .
GILL
HARWOOD
D e p a r t m e n t of Geology, T h e University, Newcastle upon T y n e N E 1 7 R U .
GRAHAM
HENDRY
JOHN
MCMANUS
D e p a r t m e n t of Geology, T h e University, D u n d e e D D I 4 H N .
JOHN
MILLER
G r a n t Institute of Geology, T h e University, E d i n b u r g h E H 9 3JW.
MARTIN
QUEST

Present address: C o r e L a b o r a t o r i e s , Isleworth, Middlesex T W 7 5 A B .
N IAGUERLI CTER E T
WUI C
NK E R
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D ee pp aa rr tt m
m ee nn tt of
of Geological
Geology and
Mineralogy,
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B .9 I A S .
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Sciences,
T h e University,
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LE
http://jurassic.ru/
iHiiiiM
Preface
Sedimentologists a r e keen t o discover t h e processes, conditio

position a n d diagenesis of their rocks. T h e y currently use
cated instruments a n d machines, in addition t o routine
e n v i r
whoi "^
n m e n t s of de
n g e of
. "
'
^ W o r W
Quite s o D h i s t i A l t h o u g h geologists have b e e n making field observations f
" d microsco '
two decades t h e r e have been many new approaches to the c o l i e ^ ^ ^00 years in"the last
d a t a . N e w sedimentary structures a n d relationships are stil) b e T '
Processi'n oilfield
studied rocks. T h e microscopic examination of sediments i
' ^ Ûnd i 'classic' well
tion a n d interpretation of sediments, but there are ways to r n ^
tool in t h e ' d ' ^
slice of rock will yield. Chemical analyses a r e being increa*;., ?
e infr,r
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o u t of sedimentary minerals a n d rocks a n d many of the analytj
P ' s e the stories
from o t h e r branches of the earth sciences or a r e m o r e f r e a u , ' P r o c e d u r e u
. ,
i
. u
^ n t l y . . . ^ u r e s have come
This b o o k aims to cover all t h e various techniques used '
^y other
rocks. It aims t o provide instructions a n d advice on the vari" ^
d y of sed' ^ t
examples of t h e information obtained a n d interpretations p o ^ ? ' P a c h e s a n d to ive
O n e chapter is concerned with t h e collection of field d a t ' .
these d a t a can b e analysed a n d presented. T h e follow; ' ,

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,
,
.
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,
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8 chanty , P " a s i s o n how
analyses, a n d grain size p a r a m e t e r s a n d their i n t e r p r e t
P r looks
microscopic studies: o n e being concerned with t h e p r o d u c t j
chapters deal with
slices, a n d t h e o t h e r with t h e description a n d interpretation
n ser..
, ' j
...
. ,
t,,
,
of s e d i ^ ^ " o n s , peels and
depositional and diagenetic textures. T h e now popular t e c h r , ;
enta.-v
,
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i l j j
.
.
t ii
t u v
q u e of ,
n e r a l s and
which can reveal hidden structures, follows. T h e X ^
t h o d o l u m i n i s c e n c e
bonates a n d cherts, providing information o n mineralogy .
n f
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u d r o c k s , cars o m e d e p t h . A c h a p t e r o n Scanning E l e c t r o n Microscopy , . ""Position .
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.
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A
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> treated i n
and h o w samples a r e best p r e p a r e d a n d viewed, and then g j
w the machine works
soft-rock geology. A final c h a p t e r reviews t h e principles behi H
of S E M uses in
m e n t a r y rocks a n d discusses t h e collection a n d p r e p a r a t i ^
chernistr of sedi
techniques of electron b e a m microanalysis, X R F , A A S , T Q p
p l e s , followed b t6h e
M S . Sections a r e included o n analytical quality and the r e p o ' Â.A
y is
concludes with examples of t h e application of chemcial anal,, ^ ^ &ults
,
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This b o o k is a multi-authored volume a n d so naturally t h e
d i r n e n t o ,
u .u
u . .u . .
are ri;
a r y problems,
m e n t a n d emphasis t h r o u g h o u t t h e text.
e r e n t levels of treat
is written for final year under
to give t h e m information and ideas o n how t o deal with their ' ^
s a n d post
in t h e laboratory during dissertation and thesis research. Much
^
' d a n d s a " T'
is also provided which will b e relevant t o lecture courses Tu ,
ul backor^
,
c
i
A| . . . ' A * .
A
.
b o o t . , , 8 n n d material
to professional sedimentologists, in industry and c a d e m j
^ also b e invaluable
scientists, as a source book for t h e various techniques c o v e r s ' ' k e ,
.
'
.
.
,
.
,
,
e d and t
other earth
extracting information from sedimentary rocks.
" tor t i p
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U a t e
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U s e r
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Maurice Tucker
rhani,
March 1988
IX
http://jurassic.ru/
1
1.1
Introduction
MAURICE TUCKER
INTRODUCTION AND
RATIONALE
T h e study of sediments and sedimentary rocks has

c o m e a long way from t h e early days Of field obser
vations followed by a cursory examination of samples
in t h e laboratory. N o w m a n y sophisticated techni
ques are applied to d a t a collected in t h e field and to
specimens back in t h e laboratory. S o m e of these
techniques have b e e n brought in from o t h e r branches
of the earth sciences, while s o m e have been speci
fically developed by sedimentologists.
R e s e a r c h on sediments and sedimentary rocks is
usually a progressive gathering of information. First,
t h e r e is t h e fieldwork, an essential part of any
sedimentological project, from which data relating
t o t h e conditions and e n v i r o n m e n t s Of deposition
a r e o b t a i n e d . With m o d e r n sediments, measure
m e n t s can be m a d e of t h e various environmental
p a r a m e t e r s such as salinity, current velocity and
suspended sediment c o n t e n t , and t h e sediments
themselves can be subject to close scrutiny and
sampling. W i t h ancient sediments, t h e identification
of facies types a n d facies associations follows from
detailed examination of sedimentary structures,
lithologies, fossil c o n t e n t e t c . , and subsequent
laboratory w o r k o n representative rocks. After con
sideration of depositional e n v i r o n m e n t , t h e larger
scale context of t h e sequence in its sedimentary
basin may b e sought, necessitating information on
t h e b r o a d palaeogeographical setting, t h e tectonics
of t h e region, both in t e r m s of synsedimentary and
post-sedimentary m o v e m e n t s , and t h e subsurface
structure, p e r h a p s with input from seismic sections.
W i t h an u n d e r s t a n d i n g of a sedimentary rock's de
position and tectonic history, leading to an a p p r e
ciation of the rock's burial history, t h e diagenetic
changes can b e studied t o throw light o n t h e patterns
of c e m e n t a t i o n and alteration of t h e original sedi
m e n t , and on t h e n a t u r e of p o r e fluids which have
m o v e d through the sedimentary sequence. A l t h o u g h
m u c h information on t h e diagenesis can be obtained
from petrograpic microscopic examination of thin
sections of t h e rock, sophisticated instruments are
increasingly used to analyse t h e rocks and their

c o m p o n e n t s for mineralogical composition, major,
m i n o r and trace e l e m e n t s , isotopic signatures and
organic content. T h e d a t a obtained provide much
useful information on t h e diagenesis, and also on t h e
original depositional conditions.
Which techniques t o use in sedimentological re
search d e p e n d of course o n t h e questions being
asked. T h e aims of a project should be reasonably
clear before work is c o m m e n c e d ; knowing what
answers a r e being sought m a k e s it much easier to
select t h e a p p r o p r i a t e t e c h n i q u e . T h e r e is usually
n o t m u c h point in hitting a rock with all t h e sophisti
cated techniques going, in t h e h o p e that something
meaningful will c o m e out of all t h e data. It may be
t h a t t h e p r o b l e m would b e solved with a few simple
field m e a s u r e m e n t s or five minutes with the micro
scope o n a thin section, rather than a detailed
geochemical analysis giving h u n d r e d s of impressive
n u m b e r s which add little to o n e ' s understanding of
t h e rock.
T h e techniques available to sedimentologists, and
those covered in this b o o k , often cannot be used for
all sedimentary rock types. It is necessary to be
aware of what all the various instruments available
in a well-found earth sciences d e p a r t m e n t can d o
and how they can be used with sedimentary rocks.
M a n y such instruments are m o r e frequently used
and o p e r a t e d by h a r d rocks petrologists and g e o - '
chemists, b u t they can be used with great success on
sedimentary rocks, as long as one is still seeking an
answer to a particular question rather than just
another analysis. Certain techniques are best suited
to specific sedimentary rock types and cannot be
used generally to analyse any rock. In the next
sections of this introduction (1.2 to 1.9), t h e tech
niques covered in this b o o k , in Chapters 2 to 9 are
briefly reviewed. N o t all the possible techniques
available are included in this b o o k and Section 1.10
notes what is omitted and where to find details. It
also indicates w h e r e new techniques in soft-rock
geology are frequently published, so that the keen
student can k e e p up to date with developments in
this field.
http://jurassic.ru/
Ill
M.E.TUCKER
1.2
COLLECTION AND ANALYSIS

OF FIELD DATA: C H A P T E R 2
In C h a p t e r 2, John G r a h a m examines t h e rationale

behind fieldwork, and the various ways in which
field d a t a can be collected and presented in graphic
form are shown. T h e various sedimentary structures
and t h e identification of lithologies and fossils are
not described in detail since t h e r e are t e x t b o o k s on
these topics (e.g. Collinson & T h o m p s o n , 1982;
T u c k e r , 1982), but t h e p r o b l e m s of recognizing cer
tain structures are aired. T h e collection and analysis
of palaeocurrent d a t a (described in Section 2.3) are
important in facies analysis and palaeogeographical
reconstruction and statistical t r e a t m e n t s are avail
able t o m a k e t h e d a t a m o r e meaningful. T h e r e are
many ways in which to examine a sedimentary se
q u e n c e for rhythms and cycles (Section 2.4) and
again t h e field d a t a can b e manipulated by statistical
analysis to reveal trends. This chapter also shows the
many ways in which information from t h e field can
be presented for publication.
1.3 G R A I N S I Z E D E T E R M I N A T I O N
AND INTERPRETATION:
CHAPTER 3
It is very i m p o r t a n t t o k n o w quite precisely what t h e
grain size distribution is in a sediment sample and
the procedures here are described by John McManus.
Sample preparation varies from t h e unnecessary to
having to break u p the rock into its constituent
grains, dissolve out t h e c e m e n t in acid, or m a k e a
thin section of the sample. Sieving, sedimentation
m e t h o d s and Coulter c o u n t e r analysis can be used
for unconsolidated or disaggregated samples, but
microscopic m e a s u r e m e n t s are required for fully
lithified sandstones and most limestones. With a
grain size analysis at h a n d , various statistical para
m e t e r s are calculated. F r o m these, with c a r e , it is
possible to m a k e deductions on t h e sediment's con
ditions and e n v i r o n m e n t of deposition.
1.4
M I C R O S C O P I C T E C H N I Q U E S I:
SLICES, SLIDES, STAINS AND
PEELS: CHAPTER 4
T h e rock thin section is t h e basis of much routine

description and interpretation but all too often the
INTRODUCTION
production of the slide is not given t h o u g h t . J o h n
Miller explains how the best can be achieved by
double-polished thin sections and describes the vari
ous techniques of impregnating, staining and etching
to encourage the slide to give up more of its hidden
secrets. A c e t a t e peels are frequently m a d e of lime
stones and the manufacture of these is also discussed.
1.5
1.6
CATHODOLUMINESCENCE:
CHAPTER 6
This chapter is presented by John Miller and de

scribes a technique which has been very popular
amongst carbonate sedimentologists for t h e last few
years. Very pretty colour p h o t o g r a p h s can be ob
tained with C L and these have e n h a n c e d many a
lecture and published p a p e r . T h e specimen in a
vacuum c h a m b e r is b o m b a r d e d with electrons and
light is emitted if activator elements are present. A n
explanation of the luminescence is given, with a
consideration of excitation factors and luminescence
centres, and then a discussion of e q u i p m e n t needs
and operation. Sample preparation is relatively easy;
polished thin sections (or slabs) are used. G e n e r a l
principles of the description and interpretation of
C L results are given, along with applications to
sedimentology. It is with c a r b o n a t e rocks that C L is
most used and h e r e it is particularly useful for recog
nizing different c e m e n t generations and for distin
guishing replacements from cements. In sandstones
it can differentiate between different types of quartz
grain, help to spot small feldspar crystals, and reveal
overgrowths on detrital grains. G o o d p h o t o g r a p h y is
important in C L studies and hints are provided on
how the quality of photomicrographs can be im
proved. T h e s e days, a study of carbonate diagenesis
is not complete without consideration of c a t h o d o luminescence and t h e textures it reveals.
MICROSCOPIC TECHNIQUES II:

P R I N C I P L E S OF S E D I M E N T A R Y
PETROGRAPHY: CHAPTER 5
This chapter is by Gill H a r w o o d and follows on from

t h e previous o n e by explaining how the various
minerals and textures in sedimentary rocks can be
recognized and interpreted. T h e chapter is written in
such a way so that it is applicable to all sedimentary
rock types, rather than discussing each separately,
as is frequently t h e case in sedimentary p e t r o g r a p h y
texts. T h e r e is a huge t e x t b o o k literature on 'sed.
p e t . ' and many of t h e books will be readily available
in a university or institute library (see, e.g. Folk,
1966; Scholle, 1978, 1979; T u c k e r , 1981; Blatt,
1982). T h u s , in depositional fabrics (Section 5.2),
grain identification, modal composition, point count
ing techniques, grain morphology, size and orient
ation, and p r o v e n a n c e studies are briefly treated
with pertinent literature references and many dia
g r a m s , p h o t o m i c r o g r a p h s and tables. In diagenetic
fabrics (Section 5.3), again a topic with a volumin
ous literature, t h e various diagenetic e n v i r o n m e n t s
and porosity types are n o t e d , and t h e n compactionrelated fabrics are described and illustrated. H e r e ,
compaction is divided into that resulting from
mechanical processes, from chemical (solution) pro
cesses b e t w e e n grains, and from chemical processes
in lithified sediments. C e m e n t a t i o n is a major factor
in a rock's diagenesis and Section 5.3.3 d e m o n s t r a t e s
t h e variety of cements in sandstones and limestones,
their precipitational environments and how the
timing of c e m e n t a t i o n can be d e d u c e d . Typical
fabrics of dissolution, alteration and replacement
are described and illustrated, with emphasis on how
these can be distinguished from o t h e r diagenetic
fabrics. This overview of microscopic fabrics shows
what can b e seen, how they can be described, and
their significance in terms of depositional and dia
genetic processes. Sound microscope work is a fun
d a m e n t a l prerequisite for geochemical analyses, and
of course it provides much basic information on t h e
n a t u r e , origin and history of a sedimentary rock.
1.7 X - R A Y D I F F R A C T I O N O F
SEDIMENTARY ROCKS:
CHAPTER 7
X-ray diffraction is a routine technique in the study
of m u d r o c k s and is frequently used with c a r b o n a t e
rocks t o o , and cherts. R o n H a r d y and Maurice
T u c k e r provide a brief general introduction to X R D ,
the theory and the instrument. X R D is t h e standard
technique for determining clay mineralogy and vari
ous procedures are a d o p t e d to separate t h e different
clay minerals. E x a m p l e s are given of how X R D data
from m u d s can be used to infer palaeoclimate, trans
port direction, conditions of deposition, and the
p a t t e r n of diagenesis. With carbonates, X R D is
mostly used to study the composition of m o d e r n
sediments, the Mg content of calcite, and t h e stoichiometry and ordering of dolomites. T h e proce
d u r e is relatively straightforward and the precision is
good, and much useful information is provided.
http://jurassic.ru/
Fine-grained siliceous rocks are often difficult to

describe petrographically, but X R D enables the
minerals present, opal A , opal C-T or quartz, to be
d e t e r m i n e d readily. It has been especially useful in
documenting the diagenesis of d e e p sea siliceous
oozes through to radiolarian and diatom cherts.
1.8 S C A N N I N G E L E C T R O N
M I C R O S C O P Y IN
SEDIMENTOLOGY: CHAPTER 8
T h e S E M has b e c o m e p o p u l a r for studying fine
grained sedimentary rocks and for examining the
ultrastructure of grains, fossils and cements. Nigel
Trewin briefly describes the microscope and p r o
vides an account of how sedimentary materials are
p r e p a r e d for t h e machine. T h e S E M is a delicate
machine and often t h e picture on t h e screen or the
p h o t o g r a p h s may not be as good as expected. C o m
m e n t s are given on how such difficulties can be
o v e r c o m e or minimized. T h e S E M also has t h e
facility for attachments providing analysis, E D S and
E D A X , and these can be most useful when the
elemental composition of t h e specimen is n o t k n o w n .
A n S E M can also be adjusted to give a back-scattered
electron image and with m u d r o c k s this can reveal
t h e n a t u r e of t h e clay minerals themselves. T h e
S E M has b e e n applied to m a n y branches of sedi
mentology, particularly t h e study of the surface
textures of grains, both c a r b o n a t e and clastic. In
diagenetic studies, t h e S E M is extensively used with
sandstones, to look at t h e n a t u r e of clay cements,
evidence of grain dissolution and quartz over
growths. In c a r b o n a t e s t o o , the fine structure of ooids
and cements is only seen with S E M examination.
1.9
C H E M I C A L A N A L Y S I S OF
SEDIMENTARY ROCKS:
CHAPTER 9
In many branches of sedimentology, chemical ana

lyses are m a d e to d e t e r m i n e major, minor and trace
element concentrations and stable isotope signa
tures, to give information on t h e conditions of de
position and diagenesis, and on long- and short-term
variations in seawater chemistry and elemental
cycling. In this chapter, largely written by Ian Fairchild, with contributions from his colleagues G r a h a m
H e n d r y and Martin Q u e s t , and Maurice T u c k e r , a
quite detailed background is given on some of the
M.E.TUCKER
important principles of sedimentary geochemistry:

concentrations and activities, equilibrium, adsorp
tion, incorporation of trace elements and partition
coefficients, and stable isotope fractionation This
chapter should help t h e r e a d e r appreciate s o m e of
t h e p r o b l e m s in interpreting gepchemical d a t a from
rocks w h e r e , commonly, inferences a r e being m a d e
about t h e n a t u r e of fluids from which precipitation
t o o k place. In sedimentary geochemistry much em
phasis is now placed on the sample itself since there
is a great awareness of t h e chemical inhomogeneities
in a coarse-grained, well-cemented rock. Individual
grains or growth zones in a cement are now analysed
w h e r e possible, rather t h a n the bulk analyses of
whole rocks.
T h e techniques covered in this c h a p t e r are X-ray
fluorescence, atomic absortion spectrometry, in
ductively-coupled plasma optical emission and mass
spectrometry, electron microbeam analysis, n e u t r o n
activation analysis and stable isotope ( C . O . S ) ana
lysis. With t h e t r e a t m e n t of most of these techni
ques, t h e accent is not on t h e instrument o p e r a t i o n ,
or theory since t h e r e are many textbooks cover
ing these aspects (e.g. Potts, 1987) but on how
sedimentary rocks can be analysed by these m e t h o d s
and t h e sorts of d a t a that are obtained. A further
section discusses precision and accuracy, t h e use of
standards and how d a t a can be p r e s e n t e d .
T o illustrate t h e use of geochemical d a t a from
sedimentary rocks, applications are described to the
study of provenance and weathering, the deduction
of environmental p a r a m e t e r s , diagenesis and p o r e
fluid chemistry, and elemental cycling.
1.10
TECHNIQUES NOT INCLUDED
facies and diagenesis. It does not cover techniques

m o r e in the field of basin analysis, such as seismic
stratigraphic interpretation, and d e c o m p a c t i o n ,
backstripping and geohistory analysis. A recent
b o o k on this which includes wire-line log interpreta
tion and t h e tectonic analysis of basins is published
by t h e O p e n University (1987). T h e m e a s u r e m e n t
of porosity-permeability is also not covered.
T h i s . b o o k does not discuss t h e techniques for
collecting m o d e r n sediments through shallow cor
ing, including vibracoring. T h e latter is described
by Lanesky et al. (1979). Smith (1984) and others.
T h e r e are many papers describing very simple in
expensive coring devices for marsh, tidal flat and
shallow subtidal sediments (see, e.g. Perillo et al.,
1984). Also with m o d e r n deposits (and s o m e older
unconsolidated sands), large peels can be taken to
d e m o n s t r a t e the sedimentary structures. Cloth is put
against a s m o o t h e d , usually vertical surface of d a m p
sand and a low viscosity epoxy resin sprayed or
painted on to and through the cloth to t h e sand. O n
drying and removal, t h e sedimentary structures are
neatly and conveniently preserved on t h e cloth.
This technique is fully described by B o u m a (1969).
T h e techniques used by sedimentologists are con
stantly being improved and new ones developed.
Many sedimentological journals publish t h e occa
sional accounts of a new techique or m e t h o d , and in
many research p a p e r s t h e r e is often a m e t h o d s
section, which may reveal a slightly different, per
haps better, way of doing something. T h e Journal of
Sedimentary
Petrology publishes many 'researchm e t h o d s p a p e r s ' , all collected together into o n e
particular issue of t h e year. It is useful to k e e p an
eye out for this section for the latest d e v e l o p m e n t s
in techniques in sedimentology.
This b o o k describes most of the techniques currently

employed by sedimentologists in their research into
2
2.1
Collection and analysis of field data
JOHN GRAHAM
INTRODUCTION
M u c h of t h e information preserved in sedimentary

rocks can b e observed and recorded in t h e field. T h e
a m o u n t of detail which is r e c o r d e d will vary with t h e
p u r p o s e of the study and t h e a m o u n t of time and
m o n e y available. This c h a p t e r is primarily concern
ed with those studies involving sedimentological
aspects of sedimentary rocks r a t h e r than structural
or other aspects. C o m m o n aims of such studies are
t h e interpretation of depositional environments and
stratigraphic correlation. Direction is towards an
cient sedimentary rocks rather t h a n m o d e r n sedi
m e n t s , since techniques for studying t h e latter are
often different and specialized, and are admirably
covered in o t h e r texts such as B o u m a (1969). In
fieldwork the tools and aids c o m m o n l y used a r e
relatively simple, and include m a p s and aerial p h o t o
graphs, h a m m e r and chisels, dilute acid, h a n d lens,
penknife, t a p e , c a m e r a , binoculars and compassclinometer.
D u r i n g fieldwork, information is recorded at
selected locations within sedimentary formations.
This selection is often d e t e r m i n e d naturally such
that all available exposures are examined. In o t h e r
cases, e.g. in glaciated terrains, exposure may be
sufficiently a b u n d a n t t h a t deliberate sampling is
possible. T h e generation of natural exposures may
well include a bias t o w a r d s particular lithologies,
e.g. sandstones t e n d t o b e exposed preferentially to
m u d r o c k s . T h e s e limitations must be considered if
statements regarding bulk properties of rock units
a r e to b e m a d e . F o r m a n y p u r p o s e s , vertical profiles
of sedimentary strata a r e most useful. In o r d e r to
construct t h e s e , continuous exposures perpendicular
to dip a n d strike a r e preferred. W i t h such continu
ous exposures, often chosen w h e r e access is easy,
o n e must always be cautious of a possible bias
because of an underlying lithological control.
T h e main aspects of sedimentary rocks which are
likely to b e r e c o r d e d in t h e field are:
Lithology:
Texture:
Beds:
Sedimentary
structures:
Fossil content:
Palaeocurrent
data:
mineralogy/composition and colour of

the rock.
grain size, grain shape, sorting and fabric,
designation of beds and bedding planes,
bed thickness, bed geometry, contacts
between beds.
internal structures of beds, structures on
bedding surfaces and larger scale
structures involving several beds,
type, mode of occurrence and
preservation of both body fossils and
trace fossils.
orientation of palaeocurrent indicators
and other essential structural
information.
In s o m e successions t h e r e will be an a b u n d a n c e of
information which must be recorded concisely and
objectively. R e c o r d s are normally p r o d u c e d in t h r e e
c o m p l e m e n t a r y forms and may be a u g m e n t e d by
data from samples collected for further laboratory
work. T h e s e are:
(i)
Field notes: T h e s e a r e written descriptions of

observed features which will also include pre
cise details of location. G u i d a n c e on t h e produc
tion of an accurate, concise and neat n o t e b o o k
is given in B a r n e s (1981), Moseley (1981) and
T u c k e r (1982).
(ii) Drawings and p h o t o g r a p h s : M a n y features are
best described by m e a n s of carefully labelled
field sketches, s u p p l e m e n t e d where possible by
p h o t o g r a p h s . All p h o t o g r a p h s must be cross
referenced to field notes or logs and it is impor
tant to include a scale on each photograph and
sketch.
(iii) G r a p h i c logs: T h e s e are diagrams of m e a s u r e d
vertical sections through sedimentary rock
units. T h e r e a r e a variety of formats which are
discussed below (Section 2.2.9). A l t h o u g h
m a n y logs a r e constructed on pre-printed forms,
additional field notes accompany t h e m in most
cases.
http://jurassic.ru/
mm*.
mmm
M.E.TUCKER
important principles of sedimentary geochemistry:

concentrations and activities, equilibrium, adsorp
tion, incorporation of trace elements and partition
coefficients, and stable isotope fractionation This
chapter should help t h e r e a d e r appreciate s o m e of
t h e p r o b l e m s in interpreting gepchemical d a t a from
rocks w h e r e , commonly, inferences a r e being m a d e
about the n a t u r e of fluids from which precipitation
t o o k place. In sedimentary geochemistry much em
phasis is now placed on t h e sample itself since there
is a great awareness of t h e chemical inhomogeneities
in a coarse-grained, well-cemented rock. Individual
grains or growth zones in a cement are now analysed
where possible, rather than t h e bulk analyses of
whole rocks.
T h e techniques covered in this chapter a r e X-ray
fluorescence, atomic absortion spectrometry, in
ductively-coupled plasma optical emission and mass
spectrometry, electron microbeam analysis, n e u t r o n
activation analysis and stable isotope ( C . O . S ) ana
lysis. With t h e t r e a t m e n t of most of these techni
ques, the accent is not on the instrument o p e r a t i o n ,
or theory since there are many textbooks cover
ing these aspects (e.g. P o t t s , 1987) but on how
sedimentary rocks can be analysed by these m e t h o d s
and the sorts of data that are obtained. A further
section discusses precision and accuracy, t h e use of
standards and how d a t a can be p r e s e n t e d .
T o illustrate the use of geochemical data from
sedimentary rocks, applications are described to t h e
study of p r o v e n a n c e and weathering, t h e deduction
of environmental p a r a m e t e r s , diagenesis and p o r e
fluid chemistry, and elemental cycling.
1.10
TECHNIQUES NOT INCLUDED
facies and diagenesis. It does not cover techniques

m o r e in t h e field of basin analysis, such as seismic
stratigraphic interpretation, and d e c o m p a c t i o n ,
backstripping and geohistory analysis. A recent
b o o k o n this which includes wire-line log interpreta
tion and t h e tectonic analysis of basins is published
by t h e O p e n University (1987). T h e m e a s u r e m e n t
of porosity-permeability is also not covered.
T h i s . b o o k does not discuss t h e techniques for
collecting m o d e r n sediments t h r o u g h shallow cor
ing, including vibracoring. T h e latter is described
by Lanesky et al. (1979). Smith (1984) and others.
T h e r e are many p a p e r s describing very simple in
expensive coring devices for marsh, tidal flat and
shallow subtidal sediments (see, e.g. Perillo et al.,
1984). Also with m o d e r n deposits (and s o m e older
unconsolidated sands), large peels can be t a k e n to
d e m o n s t r a t e t h e sedimentary structures. Cloth is put
against a s m o o t h e d , usually vertical surface of d a m p
sand and a low viscosity epoxy resin sprayed or
painted on to and through the cloth t o t h e sand. O n
drying and r e m o v a l , t h e sedimentary structures are
neatly and conveniently preserved on t h e cloth.
This technique is fully described by B o u m a (1969).
T h e techniques used by sedimentologists are con
stantly being improved and new ones developed.
M a n y sedimentological journals publish t h e occa
sional accounts of a new techique or m e t h o d , and in
many research papers t h e r e is often a m e t h o d s
section, which may reveal a slightly different, per
haps b e t t e r , way of doing something. T h e Journal of
Sedimentary
Petrology publishes many 'researchm e t h o d s p a p e r s ' , all collected together into o n e
particular issue of t h e year. It is useful to k e e p an
eye out for this section for the latest d e v e l o p m e n t s
in techniques in sedimentology.
This b o o k describes most of the techniques currently

employed by sedimentologists in their research into
Collection and analysis of field data

JOHN GRAHAM
2.1
INTRODUCTION
Much of t h e information preserved in sedimentary

rocks can b e observed and r e c o r d e d in the field. T h e
a m o u n t of detail which is r e c o r d e d will vary with the
p u r p o s e of t h e study and t h e a m o u n t of time and
m o n e y available. This c h a p t e r is primarily concern
ed with those studies involving sedimentological
aspects of sedimentary rocks rather t h a n structural
or o t h e r aspects. C o m m o n aims of such studies are
t h e interpretation of depositional e n v i r o n m e n t s and
stratigraphic correlation. Direction is t o w a r d s an
cient sedimentary rocks rather t h a n m o d e r n sedi
m e n t s , since techniques for studying t h e latter are
often different and specialized, and a r e admirably
covered in o t h e r texts such as B o u m a (1969). In
fieldwork t h e tools and aids commonly used are
relatively simple, and include m a p s and aerial p h o t o
graphs, h a m m e r and chisels, dilute acid, hand lens,
penknife, t a p e , c a m e r a , binoculars and compassclinometer.
D u r i n g fieldwork, information is recorded at
selected locations within sedimentary formations.
This selection is often d e t e r m i n e d naturally such
that all available exposures are examined. In o t h e r
cases, e.g. in glaciated terrains, exposure may be
sufficiently a b u n d a n t that deliberate sampling is
possible. T h e generation of natural exposures may
well include a bias t o w a r d s particular lithologies,
e.g. sandstones t e n d t o b e exposed preferentially to
m u d r o c k s . T h e s e limitations must be considered if
statements regarding bulk properties of rock units
are to b e m a d e . F o r m a n y p u r p o s e s , vertical profiles
of sedimentary strata a r e most useful. In o r d e r to
construct these, continuous exposures perpendicular
to dip and strike a r e preferred. With such continu
ous exposures, often chosen w h e r e access is easy,
o n e must always b e cautious of a possible bias
because of an underlying lithological control.
T h e m a i n aspects of sedimentary rocks which a r e
likely to be r e c o r d e d in t h e field a r e :
Lithology:
Texture:
Beds:
Sedimentary
structures:
Fossil content:
Palaeocurrent
data:
mineralogy/composition and colour of

the rock.
grain size, grain shape, sorting and fabric.
designation of beds and bedding planes,
bed thickness, bed geometry, contacts
between beds.
internal structures of beds, structures on
bedding surfaces and larger scale
structures involving several beds.
type, mode of occurrence and
preservation of both body fossils and
trace fossils.
orientation of palaeocurrent indicators
and other essential structural
information.
In s o m e successions t h e r e will be an a b u n d a n c e of
information which must b e recorded concisely and
objectively. R e c o r d s are normally produced in t h r e e
c o m p l e m e n t a r y forms and may be a u g m e n t e d by
d a t a from samples collected for further laboratory
w o r k . T h e s e are:
(i)
Field notes: T h e s e are written descriptions of

observed features which will also include pre
cise details of location. G u i d a n c e on the produc
tion of an accurate, concise and neat n o t e b o o k
is given in B a r n e s (1981), Moseley (1981) and
T u c k e r (1982).
(ii) Drawings and p h o t o g r a p h s : Many features a r e '
best described by m e a n s of carefully labelled
field sketches, s u p p l e m e n t e d where possible by
p h o t o g r a p h s . All p h o t o g r a p h s must be cross
referenced to field notes or logs and it is impor
tant to include a scale on each p h o t o g r a p h and
sketch.
(iii) G r a p h i c logs: T h e s e a r e diagrams of measured
vertical sections through sedimentary rock
units. T h e r e are a variety of formats which are
discussed below (Section 2.2.9). Although
m a n y logs are constructed on pre-printed forms,
additional field notes accompany t h e m in most
cases.
http://jurassic.ru/
COLLECTION AND ANALYSIS OF FIELD DATA
J.GRAHAM
2 . 2 R E C O R D I N G IN T H E F I E L D
2.2.1 Lithology identification and
description
T h e ability to recognize different sedimentary rock
types is e m b o d i e d in most geology courses and is
amply covered in texts such as T u c k e r (1981) and
Blatt (1982). Such identification is generally quicker
and m o r e reliable with increased experience in t h e
field, acquired initially u n d e r controlled conditions,
i.e. with supervision and laboratory back u p . Al
though t h e r e is a huge range of sedimentary rock
types, by far t h e majority of successions contain only
m u d r o c k s , sandstones, conglomerates, limestones
a n d dolomites, evaporites, and their admixtures.
T h u s s o m e c o m m e n t s are m a d e h e r e on t h e record
ing of these major rock types.
MUDROCKS
M u d r o c k s can b e subdivided in t h e field according to
a simple objective scheme such as t h e widely accep
ted o n e shown in T a b l e 2.1 ( I n g r a m , 1953). It in
volves only t h e a p p r o x i m a t e d e t e r m i n a t i o n of grain
size a n d fissility. Colour, which is also particularly
useful in m u d r o c k s , is generally e m p l o y e d as a
prefix. Application of m o r e sophisticated laboratory
techniques is necessary to obtain compositional in
formation ( C h a p t e r s 7, 8 and 9).
SANDSTONES
T h e lithology of sandstones, in terms of t h e grains/
matrix ratio, the main detrital constituents, and the
type of c e m e n t , can c o m m o n l y be identified in t h e
field, although detailed description and classification
require thin section analysis (Chapters 4 and 5). T h e
p r o b l e m of matrix p e r c e n t a g e and origin is difficult,
Table 2.1. Scheme for nomenclature of fine-grained clastic

sedimentary rocks
Breaking characteristic
Grain size
General terms
Non-fissile
Fissile
Silt + clay
S i l t clay
Clay silt
Mudrock
Siltrock
Clayrock
Mudstone
Siltstone
Claystone
Shale
Silt shale
Clay shale
1 Sorting size distribution
even in thin section (Blatt, 1982), but it is often

possible in a crude way to distinguish matrix-rich
(wackes) from matrix-poor (arenites) sandstones in
the field. This is most difficult when lithic grains are
d o m i n a n t and the sandstones are dark coloured and
slightly m e t a m o r p h o s e d and/or deformed.
CONGLOMERATES
C o n g l o m e r a t e s contrast with o t h e r rock types in that
most of t h e m e a s u r e m e n t , description and classifica
tion is u n d e r t a k e n in t h e field, and laboratory study
often takes a secondary role. A full description will
involve m e a s u r e m e n t of size, determination of clast
or matrix support, description of internal fabric and
structures and d a t a on composition (Fig. 2.1). S o m e
commonly used descriptive terms for these coarse
grained sedimentary rocks are:
Clast supported
bimodal
matrix well sorted
Clast supported
polymodal
matrix poorly sorted
Matrix supported
polymodal
Flow
Flow
2 Fabric
Diamictite: a non-genetic term referring to any

poorly sorted, terrigenous, generally non-calcare
o u s , clast-sand-mud admixture regardless of deposi
tional e n v i r o n m e n t .
Breccia: a term used w h e n t h e majority of t h e clasts
are angular (in t h e sense of Section 2.2.2).
Extraformational: a t e r m to describe clasts from
source rocks outside t h e basin of deposition.
a (p) a (i)
Intraformational: a t e r m to describe clasts from

fragmentation processes that take place within t h e
basin of deposition and that are c o n t e m p o r a n e o u s
with sedimentation.
a (t) b (i)
3 Stratification
O O O O O C O ) O
<0 o o
o o
.
.o
...
Inclined
. o
Q. O
\ .
o .
e>
CD
Unstratified
4 Grading
C ? 0
<=> o
O O O o
o CD
o
o
o
o o
. :.0'.0'o o
Ooooo
CD
Normal
O
o
O
Inverse
o'oo
o
oo
Ungraded
Fig. 2.1. Features used in a textural and structural classification of conglomerate (from Harms, Southard & Walker, 1982).
Under fabric, codes a and b refer to long and intermediate axes respectively; p = parallel to flow, t = transverse to flow,
i = imbricate. (Reproduced by permission of SEPM.)
http://jurassic.ru/
IIIHIHIIHHHW
o o
Horizontal
Polymict (petromict): a t e r m to describe conglomer
ates w h e r e several clast types are present.
Or
OCxZ>&
Oligomict: a term to describe conglomerates w h e r e

o n e clast type, usually of stable, resistant material, is
dominant.
Description can be e n h a n c e d by using the d o m i n

ant clast size and clast type as prefixes, e.g. granite
b o u l d e r c o n g l o m e r a t e . A special series of t e r m s is
used where volcanic processes are involved in con
g l o m e r a t e formation (Lajoie, 1984).
F u r t h e r information o n t h e sedimentary struc
tures present in conglomerates can be conveyed by
use of t h e concise lithofacies codes as developed by
Miall (1977, 1978), Rust (1978) and Eyles, Eyles &
Miall (1983) (Table 2.2). A l t h o u g h these have been
developed specifically for alluvial fan, fluvial and
glacial lithofacies, t h e r e is every likelihood that they
will and can be used for all conglomerates. T h e s e
Unordered fabric
J . GRAHAM
(a) Criteria used for low sinuosity and glaciofluvial stream deposits (modified
from Miall, 1977)
Code
Lithofacies
Gms
Massive, matrixsupported gravel

Gm
Massive or crudely
bedded gravel
Gt
Gravel, stratified
Gp
Gravel, stratified
St
Sand, medium to
coarse, may be
pebbly
Sp
Sand, medium to
coarse, may be
pebbly
Sand, very fine to
Sr
coarse
Sand, very fine to very
Sh
coarse, may be
pebbly
SI
Sand,fine
Se
Erosional scours with
intraclasts
Ss
Sand, fine to coarse,
may be pebbly
Sse, She, Spe Sand
Fl
Sand, silt, mud
Fsc
Silt, mud
Mud
Fcf
Fm
Mud, silt
Silt, mud
Fr
Coal, Carbonaceous
C
mud
P
Carbonate
Table 2.2. Use of concise lithofacies

codes in field description
Code
Sedimentary structures
Lithofacies
Dmm(c)
Dmm with evidence of

current reworking
Dmm(s)
Matrix-rupported,
massive, sheared
Dms
Matrix-supported,
stratified diamict
Dms(r)
Dms with evidence of

resedimentation
Initially appears structureless but

careful cleaning, macro-sectioning,
or textural analysis reveals fine
structures and textural variability
produced traction current activity
(e.g. isolated ripples or ripple trains).
Stratification less than 10% of unit
thickness
Dense, matrix supported diamict with
locally high clast concentrations.
Presence of distinctively shaped flatiron clasts oriented parallel to flow
direction, sheared
Obvious textural differentiation or
structure within diamict.
Stratification more than 10% of unit
thickness
Flow noses frequently present; diamict
may contain rafts of deformed
silt/clay laminae and abundant
silt/stringers and rip-up clasts. May
show slight grading. Dms(r) units
often have higher clast content than
massive units; clast clusters common.
Clast fabric random or parallel to
bedding. Erosion and incorporation
of underlying material may be
evident
Dms(c)
Dms with evidence of

current reworking
Dmg
Matrix-supported,
None
Horizontal bedding, imbrication
Trough crossbeds
Planar crossbeds
Solitary (theta) or grouped (pi) trough
crossbeds
Solitary (alpha) or grouped (omicron)
planar crossbeds
Ripple marks of all types
Horizontal lamination, parting or
streaming lineation
Low angle (10) crossbeds
Crude crossbedding
Broad, shallow scours including eta
cross-stratification
Analogous to Ss, Sh, Sp
Fine lamination, very small ripples
Laminated to massive
Massive with freshwater molluscs
Massive, dessication cracks
Rootlet traces
Plants, mud films
Pedogenic features
(b) Diagnostic criteria for recognition of common matrix-supported diamict

lithofacies (from Eyles et al., 1983)
Code
Lithofacies
Description
Dmm
Matrix-supported,
massive
Dmm with evidence of
resedimentation
Structureless mud/sandVpebble
admixture
Initially appears structureless but
careful cleaning, macro-sectioning, or
X-ray photography reveals subtle
textural variability ahd fine structure
(e.g. silt or clay stringers with small
flow noses). Stratification less than
10% of unit thickness
graded
Dmm(r)
Dmg(r)
Dmg with evidence

of resedimentation
schemes are still being refined and modified (cf.

Eyles et al., 1983 with M c C a b e , Dardis & H a n v e y ,
1984 and Shultz, 1984) and t h e overlap b e t w e e n t h e
http://jurassic.ru/
Diamict often coarse (winnowed)

interbedded with sandy, silty and
gravelly beds showing evidence of
traction current activity (e.g. ripples,
trough or planar cross-bedding). May
be recorded as Dmm, St, Dms, Sr
etc. according to scale of logging.
Abundant sandy stringers in diamict.
Units may have channelized bases
Diamict exhibits variable vertical
grading in either matrix or clast
content; may grade into Dcg
Clast imbrication common
D (diamictite) and G (gravel) codes needs further

clarification. T h e codes should not be regarded as all
that is n e e d e d for environmental interpretation
10
J . GRAHAM
(Dreimanis, 1984; K e m m i s & Hallberg, 1984) but

simply a concise and convenient shorthand descrip
tion of s o m e of t h e main observable features.
In addition to information on depositional pro
cesses and e n v i r o n m e n t s , polymict conglomerates
can yield s o m e information on t h e relative contribu
tion of various source lithologies. H o w e v e r , there
are many factors which affect the presence and size
of clasts in conglomerates. T h e initial size of frag
ments released from the source area varies with
lithology, being related to features such as bed thick
ness, joint spacing and resistance to weathering. In
addition clasts have varying resistances to size re
duction during transport. T o avoid spurious sizerelated effects, compositional data can be c o m p a r e d
at constant size. This can be achieved either by
counting t h e clast assemblage for a given size class
or by a m o r e detailed analysis in which the propor
tion of clast types is examined over a spectrum of
size classes at a single site.
T o d e t e r m i n e the distribution of clast types by
size, an area of several square metres should be
chosen on a clean exposure surface on which all
clasts can be identified easily. A r e a s of strong shape
selection, c o m m o n in s o m e proximal fluvial and
beach e n v i r o n m e n t s , should be avoided since this
can introduce a bias towards anisotropic clast litho
logies. Preliminary observations and the n a t u r e of
t h e study will d e t e r m i n e t h e n u m b e r of lithological
types to which clasts are assigned. Often crude dis
criminants, e.g. granite porphyry, e t c . , will suffice.
M o r e detailed studies require m o r e subtle subdivi
sion and may involve thin section checks on field
identification.
Clast counting should proceed from the finest
clast size interval. It is i m p o r t a n t that all clasts are
counted to eliminate bias; repetition may be avoided
by using chalk to m a r k counted clasts. A s coarser
size clasts are c o u n t e d , t h e a r e a over which clasts are
counted may be increased as a representative clast
population ( > 1 0 0 ) is sampled. T h e s e d a t a can be
summarized by constructing a plot of percentage
clast types against grain size. T h e proportion of any
clast type at a given grain size can easily be read
from the plot, allowing direct comparison from
locality to locality (Fig. 2.2). T o present d a t a from
many localities, stratigraphic columns can be used to
show changes in clast composition, or a m a p can be
devised to show the regional distribution of clast
types (Figs 2.3 and 2.4).
M a n y published studies of clast composition are
11
Composition
of limited value, either d u e to lack of specification of

clast size or to problems of how the clasts to be
m e a s u r e d were selected. Techniques of r a n d o m
selection of clasts involve the placing of a sampling
grid, for example chalked squares or a piece of fish
net, over the exposure and measuring either at grid
intersections or within small grid squares. T h e former
may be difficult to apply if only certain sizes are
accepted; the latter may introduce bias if only a
limited n u m b e r of clasts per square are to be mea
sured. It is important that the m e t h o d of data collec
tion is clearly stated so that its limitations can be
assessed by later w o r k e r s .
Clasts in
conglomerate
Carboniferous Lavas;
\ / Lava
/V/>l|
Sandstone
petrography
Lithic-arenites
derived from
local lavas
Sub-arkosic
^ Q u a r t z
f xarenite
Lutites and carbonates
Dalradian
clasts
LIMESTONES AND DOLOMITES

Field distinction of c a r b o n a t e rocks is possible, but
detailed description is best performed in t h e labora
tory using thin sections and acetate peels ( C h a p t e r
4) although u n d e r favourable conditions the latter
may be m a d e in the field. Dilute 1 0 % HC1 is a
standard field aid. Whilst limestones will react vigor
ously, most dolomites will show little or n o reaction
unless they are p o w d e r e d . T h e addition of Alizarin
red S in HC1 will stain limestones but not dolomite
( C h a p t e r 4) and this can be used in the field. In
addition many dolomites are yellow or brown
weathering, h a r d e r than limestones and may show
p o o r fossil preservation. In sequences of alternating
Sub-lithic
.arenite
o
c
CO
"co
Q
c
CD
>
Lava s
\'\
\ ^ i V
OVX/^
i '
100
200
300
400
500
O
i
Q_
O
Lithic
arenite
si
100
0
w
GO
100
Fig. 2.3. Diagram to show changes in clast composition with time for the Midland Valley of Scotland (from Bluck, 1984).
GS = greenschist, G = granite, O = other. (Reproduced by permission of the Royal Society, Edinburgh.)
Clast size (mm)
Fig. 2.2. Plot of percentage clast types versus grain size for
one locality for a Lower Devonian fluvial conglomerate
(diagram kindly supplied by Peter Haughton, University of
Glasgow). Key to clast types: GS = greenschist, LA =
lithic arenite, VQ = vein quartz, G = granite, Vv =
vesicular volcanics, V = other volcanics, O = other.
limestones and dolomites, t h e beds of dolomite are

commonly m o r e intensely jointed and fractured than
the beds of limestone.
Limestones are classified according to two well
tried and tested schemes which, although designed
for microscope w o r k , can often be applied in the
http://jurassic.ru/
field. It is m o r e likely t h a t a field identification can

be m a d e using the classification of D u n h a m (1962),
while later laboratory work can identify t h e con
stituent c o m p o n e n t s through which the Folk (1962)
classification may be applied. E v e n if a full identifi
cation is not possible, any recognizable allochem
12
J . GRAHAM
2.2.2 Texture
2.3. Differing techniques for measuring maximum

clast size in conglomerates
Table
GRAIN SIZE
B e c a u s e t h e determination of grain size is basic to
sedimentological fieldwork, it is fortunate that the
grade scale proposed by W e n t w o r t h (1922) is now
internationally accepted as a standard (see C h a p t e r
3 and T a b l e 3.4). H o w e v e r , the choice of what to
m e a s u r e can be somewhat different for different
parts of the grade scale. For conglomerates it is
commonly m a x i m u m clast size that is m e a s u r e d ,
although it is advisable" to estimate modal size(s) as
well. Techniques for measuring m a x i m u m clast size
have varied considerably a m o n g different w o r k e r s ,
as shown in T a b l e 2.3. In t h e absence of an accepted
standard it is thus necessary to state how the mea
s u r e m e n t was m a d e . T h e maximum size of clasts is
used as a p a r a m e t e r partly because the measure
m e n t is easily m a d e but also because of its known
relationship to flow c o m p e t e n c e .
5 km
Contour interval = 4%
Based on 110 pebble counts,
100 pebbles per count
Author
Measurement of maximum clast size
Bluck (1967)
Steel et al.
(1977)
Heward (1978)
Surlyk (1978)
Allen (1981)
Average of 10 largest clasts in 0.5 x 0.5 m

square
Average of 10 largest clasts (after
omission of 'outsized' clasts) from an
area over several metres on either side
of the point of bed thickness
measurement
Average of longest axes of 25 largest
clasts 15 m each side of section line at
intervals 1 m
Measure 12 largest clasts from each bed;
omit two largest then average
Average of 10 largest clasts in rectangular
sampling area, height 0.5 m, width
determined by size of largest clast such
that / = 0.69 r where / = lateral
sampling distance (cm), r = long axis/2
of largest clast (cm)
2
F o r sandstone it is usually modal size which is

estimated by m e a n s of visual comparison t o a refer
ence card or block. T h e s e reference sets are con
structed either by glueing sieved sand of each size
Transparent tape
3 mm
2 mm
Fig. 2.4. Regional distribution of gabbro pebbles in the Solund Conglomerate, Devonian, Norway (from Nilsen, 1968).
(Reproduced by permission of Norges Geologiske Undersokelse.)
-80 mmtype or fossil c o m p o n e n t should be recorded. If the

degree of weathering is suitable, these can usually
be determined with a hand lens.
calcite, quartz or dolomite. Collapse features are

also c o m m o n w h e r e dissolution has occurred and a
careful check should be m a d e w h e r e disrupted or
brecciated horizons are found.
0-1 <b
1.0-0.50 mm
1-2 cb
0.50-0.25 mm
Coarse
sand
Medium
sand
EVAPORITES
Evaporites are chemical sediments that have been
precipitated from water following t h e evaporative
concentration of dissolved salts. W h e r e these rocks
are preserved at o u t c r o p there is little difficulty in
field description and preliminary identification (see
Kendall, 1984 for a recent review). H o w e v e r , be
cause of their soluble n a t u r e , evaporites are fre
quently dissolved or replaced in the subsurface. It is
thus important to be aware of t h e typical pseudom o r p h s of evaporites which can be recognized, e.g.
cubic halite crystals. R e p l a c e m e n t is commonly by
2-3 <b
0.250.125 mm
3-4 cb
0.1250.063 mm
4-5 <b
0.0630.031 mm
Very fine
sand
Coarse
silt
MIXED LITHOLOGIES
Lithologies which are essentially mixtures of o t h e r
rock types a r e frequent in s o m e successions. A t
present there seems to be little a g r e e m e n t on the
n o m e n c l a t u r e of admixtures. A n objective and con
sistent p r o c e d u r e of labelling these rocks whilst
identifying t h e main and admixing lithologies is
necessary. T h e c o m m o n e s t admixtures are of siliciclastic and c a r b o n a t e sediments and a textural and
compositional classification for these has recently
been proposed by M o u n t (1985).
30 mm
Fig. 2.5. Construction of simple grain size comparator for field use in (a) sectional and (b) plan views (after Blatt, 1982).
(Reproduced by permission of Freeman.)
http://jurassic.ru/
13
14
J.GRAHAM
(Rosenfield & Griffiths, 1953; Folk, 1955) but never

theless their use may serve to highlight problems
requiring m o r e rigorous laboratory investigation.
Similarly form (overall shape) is normally de
scribed by assigning grains to o n e of the four major
classes erected by Zingg (1935) (Fig. 2.7). T h e
p a r a m e t e r of form includes, but is not completely
defined by, sphericity, t h e m e a s u r e of approach of a
particle to a s p h e r e . It is also possible to use a visual
comparison chart which combines t h e measures of
roundness and sphericity (Powers, 1982; Fig. 2.8).
Such information may help to indicate features such
as lithological control of particle shape, shape sort
ing and depositional fabric.
Oblate (disc, tabular)
Equant
(spherical)
Bladed
Prolate
(roller,
rod-like)
0.2
Fig. 2.6. Graph for determining the size of sedimentary grains (from Chilingar, 1982). Sand grains (or rock particles) are
placed in the central part of the circle light particles in the left chart and dark particles in the right chart and compared
with those on the graph using a hand lens. The numbers are used for notebook reading. (Reproduced by permission of the
American Geological Institute.)
fraction on to an a n n o t a t e d card (e.g. Friend et al.,

1976) or by placing sieved sand within a series of
depressions in a plastic ruler (e.g. Blatt, 1982 and
Fig. 2.5). T h e s e reference sets must be small and
d u r a b l e . A similar a p p r o a c h for most sand sizes and
finer gravels has long been used by Soviet geologists
(Chilingar, 1982; Fig. 2.6). T h e s e charts can be
easily fixed into the field n o t e b o o k .
Grain size of m u d r o c k s is much m o r e difficult to
estimate in the field and it is probably unrealistic to
a t t e m p t m o r e than t h e determination of w h e t h e r silt
exceeds clay or vice versa. This can be accomplished
by using a combination of hand lens and 'feel'.
Nibbling a small piece of m u d r o c k with t h e teeth can
be a useful test. Lack of abrasion plus a generally
greasy or soapy feel will suggest d o m i n a n c e of clay;
a gritty abrasive feel indicates the presence of silt
grade q u a r t z , of which s o m e estimate may be possi

ble with a powerful h a n d lens. In m u d r o c k s w h e r e
t h e r e is a regionally developed cleavage, t h e spacing
of cleavage planes may locally be a useful guide.
GRAIN SHAPE
S h a p e of sedimentary particles is a complex pro
perty such that t h e r e are even differences of opinion
as to what constitutes s h a p e . It is t a k e n h e r e in t h e
sense of Barrett (1980) as comprising form, r o u n d
ness and surface texture. Only aspects of t h e first
two are normally observable in the field.
R o u n d n e s s is generally described by m e a n s of
comparison to standard images which can be readily
taped into t h e field n o t e b o o k . It has been shown that
there is considerable o p e r a t o r variation with these
FABRIC
Fabric refers to t h e mutual a r r a n g e m e n t of grains
within a rock, i.e. their orientation and packing.
Fabrics may be produced during sedimentation or
by later tectonic processes. Careful m e a s u r e m e n t
will generally allow this distinction. T h e commonest
fabrics are those p r o d u c e d by the orientation of
elongate particles such as fossils in limestones, discs,
blades and rods in conglomerates. This alignment
may define bedding or may provide evidence of
palaeocurrent direction as in imbrication (Section
2.3.2; P o t t e r & Pettijohn, 1977). Fabrics also occur
in finer-grained sedimentary rocks but are n o t always
observable in t h e field.
POROSITY AND PERMEABILITY

It may b e possible to m a k e rough estimates of t h e
a m o u n t and origin of porosity and permeability in
t h e field even t h o u g h accurate m e a s u r e m e n t is not
possible. F o r e x a m p l e , o n e may n o t e partially filled
openings in fossils, or irregular channels formed by
fracturing, leaching or alteration. H o w e v e r , t h e r e
http://jurassic.ru/
fff* +
I
_l
SORTING
In the field degrees of sorting are most commonly
d e t e r m i n e d for sandstones, usually by visual com
parison with a n u m b e r of standard images which can
b e taped into t h e field n o t e b o o k (Fig. 2.9). Field
estimation of sorting in mudrocks is generally not
possible. W h e n studying limestones and conglomer
ates t h e presence of clast or matrix support is impor
tant in description and classification, e.g. in the
application of t h e D u n h a m n o m e n c l a t u r e .
15
0.2
0.4
~Ii l_l i
0.6 %
i
L_
0.8
Cfs
di
Fig. 2.7. Major shape classes of sedimentary particles _
(after Zingg, 1935). d , a\, d = shortest, intermediate and
longest diameters respectively.
s
a r e many p r o b l e m s such as lateral variability of

porosity over small distances and the fact that sur
face samples may not be representative of the rock's
average porosity.
2.2.3 Colour
This can an i m p o r t a n t attribute in t h e description of
many sedimentary rocks. T h e r e are basically two
m e t h o d s of description. By far t h e most rapid and
simple is t h e subjective impression of t h e geologist
in t h e field. Whilst this may be a d e q u a t e for s o m e
general surveys it does lack objectivity, for colour
perception is known t o vary considerably a m o n g
w o r k e r s . M o r e objective is t h e use of a standard
colour chart such as that published by t h e Geological
Society of A m e r i c a ( G o d d a r d et al., 1975) based on
t h e Munsell Colour System. T h e form and arrange
m e n t of t h e colour system a r e shown in Fig. 2.10.
T h e first step is to d e t e r m i n e t h e h u e of the rock.
T h e r e a r e 10 major hues (Fig. 2.10), each o n e
divided into 10 divisions. T h u s 5P would refer t o t h e
mid-point of t h e purple h u e , 10P to a hue mid-way
b e t w e e n purple and purple-blue and 7.5P to a hue
mid-way b e t w e e n these two. N u m b e r i n g is clock
wise as shown in Fig. 2.10. After this a value is selec
t e d from 1 to 9 with 1 being t h e darkest and 9 the
16
J . GRAHAM
17
Fig. 2.10. The form and arrangement of the Munsell Colour System (from Goddard et al., 1975). See text for explanation.
(Reproduced by permission of the Geological Society of America.)
lightest (black to white when there is n o h u e ) . Also
selected is a chroma which is a degree of colour
saturation. T h e s e are given values from O (no colour
saturation) t o 6 for t h e most vivid colours. T h u s a
colour can be represented by a code such as 5P4/2 as
well as a n a m e greyish-purple. Several standard
colours are arranged o n sheets in a small booklet
which is taken into the field and then visually com
p a r e d with the rocks. Intermediates are estimated.
Extremely hard:
Sharp hard hammer blow required.

Sample breaks across most grains.
T h e degree of weathering will be a complex func

tion of lithology, t o p o g r a p h y , climate and vegeta
tion. In particular in humid tropical regions there
may be an extremely thick regolith and little avail
able 'fresh' bedrock. Some general c o m m e n t s on the
n a t u r e and degree of weathering are a p p r o p r i a t e ,
especially w h e r e these may influence or restrict
interpretation.
2.2.4 Induration and degree of weathering

Although induration (hardness) cannot be readily
quantified, it may be useful to record the variation in
this property using the qualitative scheme below:
Unconsolidated:
Very friable:
Friable:
Well
sorted
Very well
sorted
1
Moderately
sorted
Very poorly
sorted
Poorly
sorted
Hard:
Fig. 2.9. Sorting images and standard terms (from Compton, 1962). The numbers indicate the number of size classes
included by c. 80% of the material. The drawings represent sandstones seen with a hand lens. (Reproduced by permission
ofWiley.)
Very hard:
http://jurassic.ru/
Loose.
Crumbles easily between fingers.
Rubbing with fingers frees numerous
grains. Gentle blow with hammer
disintegrates sample.
Grains can be separated from sample
with a steel probe. Breaks easily when hit
with hammer.
Grains are difficult to separate with a
steel probe. Difficult to break with a
hammer.
2.2.5 Bedding
In descriptive t e r m s , a b e d is a layer that is suffi
ciently distinct from adjoining layers. In genetic
terms, a bed represents a depositional episode during
which conditions were relatively uniform. T h e main
problem is that these two definitions d o not always
coincide, leading to s o m e contention over exactly
what constitutes a bed.
Campbell (1967) stated that distinction of beds
d e p e n d s o n recognition of bedding surfaces pro
duced during periods of non-deposition or by an
a b r u p t change of conditions. This is t h e concept of
the 'sedimentation unit' ( O t t o , 1938) which has been
J . GRAHAM
T h e definition of a bed as a sedimentation unit,

after Campbell (1967) and Reineck & Singh (1975)
should be retained, despite its p r o b l e m s . Assign
m e n t of a particular thickness limitation is not
necessary; thicknesses may range from a few milli

m e t r e s to several metres and can be described using
t h e terms in Fig. 2.13. T h e main use of bed thickness
m e a s u r e m e n t s has been in helping to estimate com
petence and capacity of the transporting m e d i u m ,
particularly in terrestrial a q u e o u s systems. For ex
a m p l e , Bluck (1967), Steel (1974) and N e m e c &
Steel (1984) presented many plots of maximum par
ticle size versus bed thickness and show that t h e
relationship varies for different depositional pro
cesses (Fig. 2.14). Potter & Scheidegger (1965) sug
gested a correlation between maximum particle size
and bed thickness in turbidites and between median
clast diameter and bed thickness in ash falls. In all
these cases interpretation is clearly d e p e n d e n t upon
t h e sedimentation unit concept for bed thickness.
T h u s if t h e r e is any uncertainty in the definition of
High quality exposure
L_
adopted by many later w o r k e r s (e.g. Reineck &

Singh, 1975; Collinson & T h o m p s o n , 1982). O t h e r
workers follow the convention that beds are recog
nizably distinct strata that have some lithologic or
structural unity (Pettijohn, 1975, p . 102). Campbell
acknowledged that bedding surfaces (using his de
finition) might not be readily recognized or may
a p p e a r to be discontinuous. T h u s there can be dif
ferent j u d g e m e n t s of the positions, thicknesses and
features of beds d e p e n d i n g on which concept is
followed. T h e p r o b l e m can be d e m o n s t r a t e d by
exposures of turbidites in the Carboniferous of
M o r o c c o (Figs 2.11 and 2.12). Following O t t o (1938)
or Campbell (1967), a ' b e d ' in Fig. 2.11 would be (1)
+ (2), a turbidite, or (3), a hemipelagite; the bed
ding surfaces would be between (3) and (1) and
between (2) and (3). H o w e v e r , in many examples
t h e b o u n d a r y between units (2) and (3) is not recog
nizable d u e either to low quality exposure or simply
to a lack of lithological contrast between units (2)
and (3). H e r e the ' b e d s ' recognized may well be (1)
and (2) + (3). Such ambiguity of description is
clearly undesirable but at times difficult t o avoid. In
general the problems will be least w h e r e exposure is
best and these are t h e areas in which detailed mea
s u r e m e n t is most likely to be m a d e . H o w e v e r , t h e
problem illustrates that t h e r e should be a consistent
single definition of a b e d .
Ico
18
3
2
Low quality exposure
Beds
Very thick bed
1000
Thick bed
Laminae
300
Medium bed
Very thick
lamina
30
100
Thin bed
10
Very thin bed
IEf 10
Thick lamina
Medium lamina
v> 3
Thin lamina
m
CO
1 Very thin
lamina
Fig. 2.13. Terminology for thickness of beds and laminae

(modified after Ingram, 1954, Campbell, 1967 and
Reineck & Singh, 1975). (Reproduced by permission of
Springer.)
bedding surfaces, this must be m a d e very clear in the

field notes. This p r o b l e m may be particularly acute
in many limestone successions w h e r e the bedding
surfaces may show e x t r e m e diagenetic modification,
usually accompanied by pressure solution and the
formation of stylolites. Recognition is complicated
because bedding parallel stylolitic seams may form
at levels unrelated t o true bedding surfaces (Simpson,
1985). A summary of the complexity observed in a
series of tabular limestone beds from t h e Lower
Carboniferous of South W a l e s is shown in Fig. 2.15
(after Simpson, 1985).
A single b e d may b e internally h o m o g e n e o u s ,
show continuous gradational variation, or be inter
nally layered, these smaller layers being t e r m e d
laminae. L a m i n a e are generally a few millimetres
thick but may exceptionally reach a few centimetres
(Fig. 2.13). Beds may also show a variety of internal
structures, such as types of cross stratification. It is
c o m m o n to find two superimposed beds that are
3, h e m i p e l a g i c m u d
I
2,turbidite m u d
\ .
1, turbidite s a n d
Fig. 2.11. Recognition of beds with varying quality of

exposure, an example from interbedded turbidites and
hemipelagites.
0-5
3. West Mull
0-15
0-1 h
Fig. 2.12. Interbedded turbidites and

hemipelagites from the Lower
Carboniferous of Morocco showing
rapid variation in exposure quality
over short distances. Only the
bedding surfaces at the base of
turbidite sands (1) can be followed
with any certainty.
0-05
Fig. 2.14. Plots of maximum particle size (vertical axis)
against bed thickness (horizontal axis) showing differences
between different processes (from Steel, 1974) in the New .
Red Sandstone of western Scotland. Locality: 1 mudflow
units, 2stream flood conglomerates, 3 braided
stream conglomerates. All measurements in metres.
(Reproduced by permission of SEPM.)
http://jurassic.ru/
19
0
0-5
20
J. GRAHAM

Layers defined by weathering surfaces
Coincident with
lithological changes
and/or sedimentary
structures
Not coincident with

lithological changes
and/or sedimentary
structures
BED GEOMETRY
Lithological changes
and/or sedimentary
structures absent
Most description of bedding concentrates on the

vertical changes in layered successions. Sedimentary
layers usually d o have a large lateral extent relative
to their thickness, but it is, of course, finite. T h e
three-dimensional geometry of beds and bedsets can
yield very valuable information w h e r e it can be
observed. B e d s terminate laterally by: (i) conver
gence and intersection of bedding surfaces; (ii)
lateral gradation of material comprising the bed into
a n o t h e r in which bedding surfaces b e c o m e indistin
guishable; (iii) abutting against a fault, unconfor
mity or cross cutting feature such as a channel.
T h e way in which beds thicken and thin is impor
tant. F o r example channelling is manifested by
change in t h e position of t h e lower bedding surface
whereas preserved bedforms such as ripples, d u n e s
and h u m m o c k s are characterized by changing posi
tion of the u p p e r bedding surface. It is important to
m e a s u r e the spacing between such thickness changes
to see if t h e r e is any p a t t e r n such as rhythmic spacing.
T h e relationship of internal structures to the external
geometry is also i m p o r t a n t in interpretation.
Some beds can be delineated within a single expo
sure whereas others may extend for tens or even
h u n d r e d s of kilometres. T h e lateral extent can be
useful in environmental distinction of superficially
similar deposits, e.g. thin outer fan turbidites versus
thin interchannel turbidites of the u p p e r fan, sheetflood versus fluvial channel deposits.
2.2.6 Sedimentary structures
Different lithologies
Fig. 2.15. Complexity of depositional units (beds) and bedding parallel weathering surfaces in limestones from the Lower
Carboniferous of South Wales (from Simpson, 1985).
related genetically and these are t e r m e d bedsets.

T h e y are called simple w h e r e the superimposed beds
are similar and composite where they are different
in a p p e a r a n c e .
T h e primary n a t u r e of contacts between beds and
bedsets may be most important in environmental
analysis. A n y information which can be observed

relating to the time span of non-deposition, e.g.
burrowed surfaces, h a r d g r o u n d s , soil formation,
palaeokarsts, or evidence of erosional contacts
should be carefully recorded.
T h e accurate recognition and recording of sedimen

tary structures is vital to most attempts at environ
mental reconstruction. Description and interpretation
of such structures are the subject of several texts at
various levels, e.g. Allen (1982), Collinson &
T h o m p s o n (1982), C o n y b e a r e & C r o o k (1968),
Pettijohn & Potter (1964), T u c k e r (1982, chapter 5).
T h e s e are not duplicated here but s o m e c o m m e n t s
on m e t h o d s of recording and recognition are a p p r o
priate. A list of t h e c o m m o n structures and groups
of structures classified predominantly by position
(after Pettijohn & Potter, 1964) is given in Table
2.4.
A l m o s t all sedimentary structures are threedimensional, although recognition of many is based
on observation of two-dimensional sections. T h e
value of c o m m e n t i n g on the three-dimensional geo-
21
Table 2.4. Sedimentary structures

Observed primarily as internal structures of beds in section
Cross stratification
Lamination
Grading
Soft sediment deformation
Bioturbation and trace fossils, stromatolites
Pedogenic horizons, hardgrounds
Cavities (mainly in limestones)
Concretions
Stylolites
Observed primarily on bedding surfaces
(i) Bottom surfaces:
Flute marks
Tool marks
Load casts
Geometry due to scour or topographic fill
(ii) Top surfaces:
Surface topography
Bedforms, e.g. ripples, dunes, hummocks
Primary current lineation
Shrinkage cracks
Trace fossils
Sand volcanoes
Raindrop impressions
metry of any available structures cannot be over

stated. It is always important t o examine any exposed
bedding surfaces as well as vertical sections. In
recording sedimentary structures reliance is placed
b o t h on objective observation and m e a s u r e m e n t and
also on existing theoretical framework. Every field
record of sedimentary structures will be a com
promise between measuring all basic and indisput
able p a r a m e t e r s o n t h e o n e hand and using available
classes of structures o n t h e o t h e r h a n d .
For e x a m p l e , m a n y schemes for recording crossstratification are so constricted that they imply that
t h e r e are two basic types of cross-bedding tabular
and trough. If such a scheme was used to record
cross stratification in a section containing h u m mocky cross stratification ( H C S ) (Fig. 2.16) then
these would probably be recorded as trough cross
strata, possibly with t h e lower angle of cross stratal
dip n o t e d . In this case t h e use of a limited theoreti
cal framework leads to the amalgamation of H C S
with cross strata of rather different origins and to the
loss of valuable information. If d a t a on angle of
cross stratal dip and three-dimensional geometry of
http://jurassic.ru/
"HIIII!
22
J . GRAHAM
0.5 m
Fig. 2.16. Block diagram showing the main features of hummocky cross stratification (HCS) (from Harms et al., 1982).
Current directions unknown.
t h e structures had been r e c o r d e d , later interpreta

tion of t h e structures as H C S would remain possible.
H o w many examples of H C S can be confidently
identified from pre-1965 publications? In spite of
this t h e recording of all p a r a m e t e r s of cross strata in
every case would be t o o time consuming.
In most cases t h e available theoretical framework
is used much m o r e than is realized. T h u s s o m e
general guidelines are available for field recording.
(a) B e as familiar as possible with useful distinc
tions between the various sedimentary struc
tures. If differences from a typical example of a
particular structure are suggested it is better to
over-divide t h a n the reverse.
(b) R e m e m b e r that o u r knowledge is never com
plete. If t h e observed structures d o n o t neatly fit
any of our present theoretical pigeonholes,
t h e r e is a need for objective and descriptive
measurement.
(c) H a v e a clear k n o w l e d g e , preferably as a written
r e c o r d , of t h e r a n g e of variation accepted within
any particular category of structure that is used.
(d) If a suite of structures is relatively unfamiliar t o
you, although well known in general, carry sum
mary diagrams or p h o t o g r a p h s in t h e field until
familiarity is achieved.
2.2.7 Fossil and trace fossil content

Fossils are important c o m p o n e n t s of many sedimen
tary rocks a n d , even w h e r e present in small n u m b e r s ,
they can provide useful, often critical, information.
Extracting t h e m a x i m u m information from fossils
will usually require the services of a specialist

palaeontologist. Nevertheless, important observa
tions, particularly those useful for environmental
rather than stratigraphic use, can and should be
m a d e by any investigator of sedimentary rocks. A
useful checklist is given by T u c k e r (1982) (see also
T a b l e 2.5).
Similarly, trace fossils and o t h e r biogenic struc
tures provide valuable information. Biogenic struc
tures vary from trace fossils possessing a definite
form that can be described and n a m e d , to rather
vague disruptions or even complete homogenization
of stratification. T h e latter can often only be d e
scribed as bioturbation. T r a c e fossils can provide
information on both palaeoecology and environ
m e n t and may be especially valuable w h e r e body
fossils a r e limited or absent. Description and classi
fication of trace fossils utilize t h r e e main approaches:
(a) T a x o n o m i c : traces can be assigned to m o r p h o

logical ichnogenera. Details of this a p p r o a c h
can b e found in Crimes & H a r p e r (1970), Frey
(1975), Hantzschel (1975), Basan (1978) and
E k d a l e , B r o m l e y & P e m b e r t o n (1984). A con
cise s u m m a r y of a p r o c e d u r e to follow is given
in Collinson & T h o m p s o n (1982, chapter 9) (see
also T a b l e 2.6).
(b) T o p h o n o m i c : description is based on m o d e of
preservation of t h e trace fossils (Fig. 2.17).
(c) Behavioural (ethological): subdivision is m a d e
on t h e interpretation of behavioural p a t t e r n re
p r e s e n t e d by t h e trace fossil, i.e. crawling,
grazing, resting, dwelling, feeding o r escaping.
23
Table 2.5. Checklist for the examination of fossils in the

field
Table 2.6. Trace fossils: how to describe them and what to

look for
Distribution of fossils in sediment

(i) Fossils largely in growth position
(a) Do they constitute a reef? characterized by
colonial organisms; interaction between organisms, e.g.
encrusting growth; presence of original cavities (infilled
with sediment and/or cement); unbedded appearance:
Describe growth forms of colonial organisms; do these
change up through reef? Are some skeletons
providing a framework?
(b) If non-reef, are fossils epifaunal or infaunal?; if
infaunal, how have fossils been preserved?
(c) Do epifaunal fossils have a preferred orientation, if
so, measure
(d) Are fossils encrusting substrate, i.e. is it a
hardground surface?
(e) Are the plant remains rootlets?
(ii) Fossils not in growth position
(a) Are they concentrated into pockets, lenses or
laterally persistent beds or are they evenly distributed
throughout the sediment?
(b) Do fossils occur in a particular lithofacies; are there
differences in the faunal content of different lithofacies?
(c) If fossil concentrations occur, what proportion of
fossils are broken and disarticulated? Are delicate
skeletal structures preserved? Check for sorting, degree
of rounding; look for sedimentary structures
(d) Do fossils show a preferred orientation?, if so,
measure
(e) Have fossils been bored or encrusted?
(f) Note the degree of bioturbation and any trace fossils
present
(1) Sketch (and/or photograph) the structures; measure

length, width, diameter etc.
(2) For trails and tracks: (seen on bedding surfaces)
(a) Note whether regular or irregular pattern, whether
trial is straight, sinuous, curved, coiled, meandering or
radial
(b) Has the trail a continuous ridge or furrow?; is
there any central division or ornamentation?; if there
are appendage marks or footprints measure the size
and spacing of the impressions; look for tail marks
(3) For burrows (best seen within beds but also on bedding
surfaces):
(a) Describe shape and orientation to bedding, i.e.
horizontal, oblique, vertical; simple straight tube,
simple curved or irregularly disposed tube. If
branching note if regular or irregular branching
pattern and any changes in burrow diameter
(b) Examine burrow wall; is the burrow lined with
mud or pellets?; are there scratch marks?; are laminae
in adjacent sediment deflected by the burrow?
(c) Examine the burrow fill; is it different from
adjacent sediment?; e.g. coarser or finer, richer or
poorer in skeletal debris?; is the fill pelleted?; are
there curved backfill laminae within the burrow fill
sediments?
Fossil assemblagesand diversity

(i) Determine the composition of the fossil assemblages by
estimating the relative abundance of the different fossil
groups.
(ii) Are fossil assemblages different for different
lithofacies?.
(iii) Consider the composition of the fossil assemblage. Is
it dominated by only a few species, are they euryhaline or
stenohaline? Are certain groups notably absent? Do all
fossil groups present have a similar mode of life? Do
pelagic forms dominate? Are infaunal organisms absent?
Diagnesis of fossil skeletons
(i) Is the original mineralogy preserved or have the
skeletons been replaced, if so, by what?
(ii) Have the fossils been dissolved out to leave moulds?
(iii) Do the fossils preferentially occur in nodules?
T h e last two a p p r o a c h e s can usually be performed

in t h e field without specialist knowledge. T a x o n o m i c
identification of c o m m o n trace fossils is often possi
ble but is best aided by accurate drawings and p h o t o
graphs and by consultation with specialists.
2.2.8 Measurement of stratigraphic

sections
T h e m e t h o d s employed in measuring sections in
sedimentary rocks will b e d e t e r m i n e d by the degree
of detail required, by t h e physical nature of the
terrain and t h e exposures, and by t h e time, funds,
e q u i p m e n t and personnel available. Details of the
various procedures available are given in C o m p t o n
(1962), K r u m b e i n & Sloss (1963) and Kottlowski
(1965). In cases of suitable exposure m e a s u r e m e n t
can be m a d e simply by direct contact of a tape or
ruler held n o r m a l to b o t h dip a n d strike directions.
W h e r e this is feasible t h e most c o m m o n m e t h o d
for measuring vertical sections is probably t h e use of
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"'lllll
24
J. GRAHAM
Seilacher
Bed
Martinsson
1-5m
Full relief
Exichnia
Semirelief (epirelief)
Epichnia
(top of bed B)
Full relief
g .
(a)
Endichnia
(interior of bed B)
Semirelief (hyporelief)
Hypichnia
Fig. 2.17. A toponomic classification
(bottom of bed B)
Full relief
Exichnia
(outside bed B)
rftrac
a compass and tape m e a s u r e . This is relatively quick

and with care is sufficiently precise for most pur
poses. It is most difficult to be accurate w h e r e the
dip of the strata is at a low angle to the section to b e
m e a s u r e d . T h e p r o c e d u r e is easier with t w o persons
but can b e performed by individuals. I m p o r t a n t
points to note where the line of section is not at 90
to the d i p of the beds a r e : (a) measure carefully the
slope of the surface along with the strike a n d dip of
t h e b e d s ; (b) r e a d the a p p a r e n t thickness of b e d s ,
bedsets or facies units from t h e stretched tape (Fig.
2.18); (c) correct for both slope angles and oblique
sections (Fig. 2.19); (d) k e e p readings s e p a r a t e be
tween changes of slope.
In many cases where the beds are very steeply
inclined relative to t h e surface of m e a s u r e m e n t , the
t a p e can b e used as a small J a c o b staff (see below)
with reasonable accuracy, rendering t h e laborious
corrections for slope unnecessary.
A n alternative to t h e use of a t a p e , w h e r e terrain
permits, is to u s e a g r a d u a t e d pole t e r m e d a J a c o b
staff (Fig. 2.20). T h e p o l e provides a steady s u p p o r t
for a level or clinometer, an A b n e y hand level being
the most accurate. T h e dip of t h e units to b e mea
sured is d e t e r m i n e d and then this value is set on the
Strike of
beds
fossils
for
u s e j n t h e
field
(afterEkdaleefa/., 1984). (Reproduced

by permission of SEPM.)
Upper part of Jacob staff
Line of
measurement
AC=AB cos a
Horizontal
ilane^
a. Slope and dip are opposed

and angle of slope (y) plus
angle of dip (x) is < 90
BC=AB sin (x+y)
b. Slope and dip are opposed

and angle of slope plus angle
of dip is > 90
Fig. 2.20. Use of the Jacob staff for measuring sections (from Kottlowski, 1965).
(a) Setting dip on clinometer of Abney hand level used with a Jacob staff.
(b) Measuring stratigraphic thickness AB.
(c) Measuring a unit with thickness less than the length of a Jacob staff.
(Reproduced by permission of CBS.)
BC=AB cos (x+y-90)

or BC=AB sin [180-(x+y)]
c. Slope and dip are in the
same direction, with dip
> slope
AC=ABsin (x-y)
d. Slope and dip are in the
same direction, with dip
< slope
BC=AB sin (y-x)
Thickness
(b)
Fig. 2.18. Measurement of strata on a slope by reference

to a stretched tape. Note the projection of contact between
units (2) and (3) to the tape (from Compton, 1962).
(Reproduced by permission of Wiley.)
25
Fig. 2.19. Corrections for slope angles and oblique

sections (from Compton, 1962).
(a) Correction of slope distance that was measured
oblique to the dip of the beds.
(b) Formulae used for various combinations of direction
and amount of ground slope and dip of beds. (Reproduced
by permission of Wiley.)
clinometer (Fig. 2.20). T h e base of the staff is placed

at the base of t h e unit to b e m e a s u r e d and the staff
tilted forward until the level bubble of the clinometer
is centred. T h e line of sight is then in a direction
parallel to the dip of the beds and the Abney level can
be slid u p and down t h e staff as required ( H a n s e n ,
1960) until the t o p surface of the unit is in t h e line of
sight (Fig. 2.20). If t h e staff is oriented within 10 of
normal to t h e d i p , then the error is likely to be n o
m o r e than 2 % ( C o m p t o n , 1962). O u t c r o p s are rare
ly exposed in a straight upslope line but a stepwise
course of m o v e m e n t s can easily be m a d e .
2.2.9 Graphic logs

T h e prime moving force behind the use of graphic
logs in t h e field is the need to record very large
http://jurassic.ru/
n u m b e r s of observations, often in a routine repeti

tive m a n n e r . T h e first major formulation of such a
scheme was presented by B o u m a (1962) w h o de
monstrated a successful application to a succession
of turbidites. H e used in the field a series of pre
printed recording sheets of the format shown in Fig.
2.21. T h e s e were later supplemented by an accom
panying sheet based on laboratory investigations.
H o w e v e r , t h e field record r e m a i n e d as t h e final dis
play, with t h e addgd laboratory data shown along
side. B o u m a ' s recording format was accompanied
by a complex series of codes and notation symbols
which permitted an u n a m b i g u o u s and detailed
record.
Broadly similar techniques have since been e m
ployed by many o t h e r workers investigating a var
iety of sedimentary successions. S o m e examples of
26
J.GRAHAM

different recording sheets are shown in Fig. 2.22.
W h a t are the reasons for this multiplicity of record
ing sheets?
Thickness (cm)
Rock type
Type
O "O CD
III
Structures
CD (Q
0)
Current direction
"O
CD -<
CD
Coarse
Fine
Coarse
Medium
Fine
Silt
Very sandy
Sandy
Silty
Clayey
Gravel
Sand
Pelite
c
CD
Pelite
O
O
CO
Carbonates
Supplementary data
Fossils
Induration
Colour
Number of layer
Units
Remarks
Fig. 2.21. Format for fieldTecording sheets designed by
Bouma (Bouma, 1962). Field records are drawn to scale

(chosen according to the nature of the succession) and the
sheets are accompanied by a complex set of notation
symbols. (Reproduced by permission of Elsevier.)
(1) T h e features commonly recorded vary consider

ably with t h e type of succession, i.e. turbidites,
fluvials, c a r b o n a t e s etc. If the b r o a d n a t u r e of
t h e succession is k n o w n in a d v a n c e , t h e r e is an
advantage in adapting the recording form to t h e
particular d a t a t o be r e c o r d e d . This is usually
t h e case for a d v a n c e d , detailed studies t h a t fol
low a reconnaissance examination. A n e x a m p l e
of a complex b u t informative scheme is t h a t of
t h e U t r e c h t school used in their studies of an
cient marginal-marine sediments in southwest
Ireland (Kuijpers, 1972; V a n G e l d e r , 1974; D e
Raaf, B o e r s m a & V a n G e l d e r , 1977; Fig. 2.22a).
H a r l a n d & Cutbill, 1970; Friend et al., 1976). T h e

main advantages over and above the use of graphic
logs were speed, rapid d a t a retrieval and processing,
and easier data presentation, e.g. the data for com
puter-drawn stratigraphic sections are already stored
in a retrievable form. T h e main disadvantage is the
difficulty of building flexibility into the form whilst
maintaining a m a n a g e a b l e size and simplicity. Friend
et al. (1976) d e m o n s t r a t e d the value of this approach
for recording thick, relatively m o n o t o n o u s succes
sions u n d e r difficult and expensive field conditions
(Fig. 2.23).
PRESENTATION OF G R A P H I C LOGS
G r a p h i c logs are used in a large proportion of
publications dealing with sedimentary rock succes
sions b u t for a p p r o p r i a t e reasons t h e r e is n o stan
dardization. Information must be presented on a
variety of scales, and for a wide variety of facies
associations. E v e n the basic unit of the logs may
vary from being the bed or bedset to 'facies' which
are defined either on the basis of a detailed field log
or during a pilot study. A n a t t e m p t to provide a
comprehensive scheme of notation and symbols to
cover all eventualities may be either too limiting for
very detailed studies or t o o complex. Nevertheless
t h e r e are m a n y conventions which m a k e comparison
of different logs easier.
(2) O n e can maintain at a higher level and for a

longer period a discipline in t h e routine listing of
features than o n e can in a free-format note
b o o k . Conversely, t h e r e may be s o m e loss of
flexibility, leading to a tendency for t h e field
geologist to neglect features o t h e r t h a n those on
t h e check list.
(3) Subsequent d a t a retrieval is generally easier and
m o r e rapid than from written n o t e b o o k records.
(4) T h e use of a s t a n d a r d format can give greater
consistency of recording/observation w h e r e
different o p e r a t o r s are employed.
(5) If t h e logs are d r a w n to scale in the field, the
investigator has a useful visual display which
may assist t h o u g h t processes and t h e formula
tion of hypotheses.
(6) T h e r e is often a tendency to think that t h e
construction of a graphic log provides a com
plete description of a succession. In fact, vertical
changes in t h e succession b e c o m e o v e r - e m p h a
sized at the expense of lateral relations.
(7) T h e r e is a strong similarity between most field
logs and t h e final published logs used in forma
tion description and interpretation.
(8) S o m e sort of r e m a r k s column is invariably
necessary to a c c o m m o d a t e features which a r e
rare or were neglected during design of the
form. E v e n with this, a field n o t e b o o k remains a
necessary aid for sketches etc. which cannot be
a c c o m m o d a t e d on t h e recording forms.
2.2.10 Recording lateral relations
A natural extension of graphic logs as t h e main

recording technique was t h e a t t e m p t to design and
use machine r e a d a b l e forms for field records
( A l e x a n d e r - M a r r a c k , Friend & Y e a t s , 1970; Piper,
Lateral variability of rock units is often obvious

w h e r e t h e r e a r e large natural or m a n - m a d e ex
posures. In h u m i d , t e m p e r a t e regions these are
mainly cliff faces, road cuts and quarry sections in
Thickness is almost always the vertical scale and

t h e horizontal scale is most frequently grain size.
O t h e r features which can be readily presented are
lithology, sedimentary structures and n a t u r e of con
tacts between units. Palaeocurrent d a t a (Section
2.3) and s o m e o t h e r d a t a on vertical sequences
(Section 2.4) can be conveniently located at the side
of these logs. Figure 2.24 shows a variety of typical
examples.
A n overall aim in the presentation of logs should
be that the r e a d e r has a good basis for comparison
with the literature and the data on which to build
preliminary interpretations of depositional environ
m e n t s and t i m e - d e p e n d e n t changes.
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27
shallowly dipping strata. Extensive strike sections

also occur in steeply dipping strata on many fore
shore sections and in recently glaciated areas. In
arid areas with shallowly dipping strata, large lateral
exposures are c o m m o n . Description of lateral
changes generally relies on the use of photo-mosaics
supplemented by field sketches, use of binoculars,
examination of accessible portions and, where possi
ble, measuring spaced vertical logs. If t h e exposure
is accessible, plane table m a p p i n g can also be useful,
e.g. Bluck (1981) (Fig. 2.25).
For reports and publications it is m o r e c o m m o n to
d e m o n s t r a t e lateral relations with line diagrams than
with p h o t o g r a p h s although in some cases both ap
p r o a c h e s can b e useful (e.g. Allen & M a t t e r , 1982,
fig. 7). This is often due to t h e difficulty of present
ing p h o t o g r a p h s at a scale w h e r e they are clear but
can still be a c c o m m o d a t e d within t h e r e p o r t format.
This p r o b l e m can also apply to line drawings and in
many journals pull outs are only rarely tolerated due
to the e x p e n s e of production. S o m e examples of the
presentation of lateral variability are shown in Figs
2.25 t o 2.28.
2.3 P A L A E O C U R R E N T
DATA
2.3.1 Introduction
Palaeocurrent d a t a are those which provide infor
m a t i o n o n t h e direction(s) of sediment transport in
the past. A s such they are an important part of
sedimentological analysis on a variety of scales from
individual bedforms to the whole sedimentary basin.
T h e main categories of interpretation which may
result from analysis of palaeocurrent data are direc
tion of palaeoslope, patterns of sediment dispersal,
relationship of palaeocurrent direction to lithosome
( K r u m b e i n & Sloss, 1963, p . 300) geometry and
location of source area. Such interpretations may
have economic as well as academic applications when
dealing with p h e n o m e n a such as washouts in coal
fields or placer deposits.
T h e subject of palaeocurrents and basin analysis
has been exhaustively treated by Potter & Pettijohn
(1977). T h e y emphasized that a variety of observa
tions can contribute palaeocurrent data and these
may be grouped into two classes:
(a) Properties which acquire directional significance
only when m a p p e d regionally. T h e s e consist of:
28
J.GRAHAM
Basic rock types
[W
Sa
Sandstone
facies
Large-scale cross-stratified
sandstone (bulk sand content
95-100%)
Guide to
reading of the logs
to
C
O <
c
<ll Herringbone
Low angle
cross-stratification
Structures not
detectable
Evenly laminated sandstone

(bulk sand content 95-100%)
I\-"-
\ Sc
i i To
oiAenJ)m
i-
Small-scale cross-laminated
sandstone
gradual upward decrease in sand content

along several rock types
240 f
The horizontal lines

correspond to
boundaries of
intervals consisting 230
either of a 'uniform'
rock type or a
complex alternation
of rock types, which
could not be drawn
as separate units
because of the 11
scale used
210
Additional sedimentary structures

| Ha
Sandy flaser bedding

Flaser bedding
(bulk sandstone content 50-75%)
Heterolithic
facies
Hc1
Sand-lensed mud
Hc2
Sand-streaked mud
current-ripples "] symbols without

> directional
climbing ripples J significance
wave-ripples
shale-flakes
^,
Mudstone
gradual increase in sand content within one

rock-type (here mudrock with intercalated
sandstone sheets)
sharp junction
gradual increase in sand content
downcutting surface
flaser bedding, wave-ripples observed
cross-laminated sandstone, structure at base
not determinable
-scouring surface
scouring surface with
=-parallel infill
Mudstone _
facies
gradual replacement of even lamination by

cross-lamination from base to top
scouring surface
2001- ^-""
- downcutting surface
scouring surface with shale flakes

scouring surface with parallel infill
Composite rock types

Mudstreaks in cross-laminated sand (Sc) also occurring
in Sa, Sb, Ha, and Hb. Bulk sand content 75-100%
gradual increase in sand content

along several rock types
180
sand content estimated (binocular)
Mud flasers in cross-laminated sand (Sc) also occurring

in Ha. Bulk sand content 75-100%
. Weakly
\ bioturbated
U Moderately
bioturbated
\\\ Strongly
bioturbated
Mudcracks
Lenticular and flaser bedding in random alternations.

Both components up to a few metres thick. Bulk
sandstone content 10-75%
Slumping
Loadcasting
Mudstone (up to a few metres thick) with intercalations

of evenly laminated sandstone sheets (up to 2 m thick)
Bulk sandstone content 10-95%
Sandballs
Concretions
Channel of small size (width up
to a few metres) filled with sand
or mud-flakes
Channel of small size with
fine grained infill
Local unconformities
within heterolithic unit
Cross-laminated sand (up to 10 cm thick) and mudbands

(up to 4 cm thick) in regular alternation.
Bulk sandstone content 5 0 - 7 5 %
Sandy mudstone homogenized by bioturbation.
Bulk sand content 10-50%
Rock types in
Plant remains
(a)
regular alternation
Fossiliferous
Reddish colours
Strongly tectonized
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| Currents flowing to the south (small-scale

current ripples)
JJ, Id. Large-scale current ripples
,
Oppositely directed currents of equal
* importance
Id. One current predominant
\
Id. One current strongly predominant
*> Wave-ripples, direction of oscillation

east-west (crestline orientation at right
angles
^
Wave ripples, interference pattern
30
J . GRAHAM
(0
Locality
Section log
Location
from
Sheet no.
to
Geologist
from
= X-bedded
Flat bedding
= X-laminated
Laminated bedding
= Trough
v_/
Parting lineation
= Tabular
/ / / /
Cumthick
Lithology
W\J
= Mud cracks
= Convoluted bedding
= Channel
= Imbrication
Continues f r o m .
Erosive
| to
AA/\
Gradational
Abrupt (not known -
M a p sheet no.
Sharp, non-erosive
Aerial photo no.

Date(s)
v v
J
Sheets
Grid co-ordinates
Altitude
Massive bedding
31
Fossils,
trace
fossils
Deformed (load casts etc.) "\J^
B = black Gr = green Lt = light

G = grey P = purple Dk = dark
Sample
Cum
thick
Unit
thick
Pom, grain size

F M C
S SlGIC
Rock
type
Structures
L.B.S.
Sorting/ Colour Uncorrected Local

round
palaeobedding
if erosional)
Undulating
Not seen
G = good M = moderate P = poor
Locality no.
D = dull
Remarks ( + comp. of
coarse clasts)
PSL
number
clsls
Fig. 2.22. Examples of different recording sheets.

(a) A detailed and complex scheme devised specifically for marginal marine sediments by De Raaf, Boersma, Leflef &
Kuijpers (from Kuijpers, 1972).
(b) A more general scheme for recording vertical sequences in sedimentary successions designed for the Greenland
Geological Survey by L.B. Clemmensen and F. Surlyk.
(c) A scheme with a limited number of symbols and columns designed specifically for recording large thicknesses of fluvial
sediments (from Russell, 1984).
(i) attributes presence/absence of s o m e dis

tinctive feature such as boulder type or mineral
assemblage; (ii) scalars magnitude of s o m e
p r o p e r t y such as grain size, r o u n d n e s s or unit
thickness.
In these cases t h e r e is little extra recording of
field d a t a but merely a selection of specific pro
perties from available records. Accordingly this
class is given little t r e a t m e n t h e r e apart from
s o m e examples.
(b) Properties which provide some directional in
formation at t h e point of observation, although
m o r e information will b e conveyed by present

ing many observations in m a p form. T h e s e
directional properties can indicate either: (i) a
line of flow, e.g. primary current lineation,
groove m a r k s , symmetrical ripple crests or (ii) a
u n i q u e direction of flow, e.g. imbrication, cross
stratification, flute m a r k s .
Directional properties form the basis of most
palaeocurrent analysis because of t h e greater
a m o u n t of information they contain.
2.3.2 Measurement of directional

structures
F o r each m e a s u r e m e n t it is important to record the
exact location, type and scale of structure, as well as
the lithofacies in which it occurs. F o r e x a m p l e , it
may b e useful to investigate t h e relationship of cross
bedding direction to set thickness, foreset dip angle
or foreset s h a p e , as environmental interpretation
becomes m o r e refined.
http://jurassic.ru/
LINEAR STRUCTURES
In this category are structures in which it is n o t
possible to distinguish between o n e ' e n d ' of a struc
ture and t h e o t h e r , e.g. primary current lineation,
striae, groove m a r k s , gutter casts, channels, s o m e
oriented elongate fossils and symmetrical ripple
crests. T h e orientation of t h e lineation is recorded as
a pitch on inclined strata or in horizontal beds as a
direction. Techniques for u n a m b i g u o u s recording of
32
J.GRAHAM
COLLECTION AND ANALYSIS OF FIELD DATA 3 3
Station number
B
100
200
00
300
400
__30
2_
500
600
700
800
900
70
SO
90
_ 8 _
7 _
40
4
10
20
_ 30
_ 40 ^
4
50
60
'
70
80
8 _
Legend
MUOROCK
coarse SANDY siltrock
sandstone
Sheet number
-.90
Tabular cross-bedding
Trough cross-bedding
-. .
El
Write station and sheet numbers on stub
intraclasts
Horizontal lamination
=:!:=
0
00
i
|
.:?-.
EXPOSED
M.SL
C.SL
GRAD
SHP
SMTH
.9.
.A
-0
00
VF.SS
F.SS_
SCR
TOOL
EXPOSED
M.SL
C.SL
VF.SS
GRAD
SHP
SMTH
SCR
-3
9..
0
:~=
00
EXPOSED
VF.SS
F.SS
SCR
TOOL
3 _
-3
?. .
PEBBLY
00
NO
(M)
LIN
_RED
P.RD
^GN_
OTHER
NO DIR
M.SS
C.SS
VC.SS
TR.FOS
1
MKS.
-9.X.
CON
MD.CR
TR.FOS.
PEBBLY
RIPPLES
00
NO
-5
LIN
RED
P.RD
GN
GY
M.SS
C.SS^
VC.SS
CON
MD.CR
TR.FOS
Thick
(M)
PEBBLY
RIPPLES
DOL
FLAT
10
20
30
FOSSILS
40
CaCO.1
ROCK
10
20
30
CEM
cco3
?S5
CONCR- C 0
2 DIR
1 DIR
00
10
20
K
:
30
STUBSPEC
NO
-6
-7
LIN
CEM
CaC0 ,
3
ROCK
-zzz:
TR.X
VERT
OTHR
TR
100
200
300
50
60
70
80
90
SPARE
CANC'L
FLAT
SY.P
AS.R
PL.X
TR.X
NO
VERT
OTHR
TR
000
100
200
300
70
80
FOSSILS
40
50
RESTART
f?i
OR STUB
FLAT
FOSSILS
60
SPARE
SY.P
AS.R
=!,
PL.X
ripple cross lamination
fc-r-Ij
fine lamination
AND / OR BIOTURBATION
T h e most commonly used sedimentary structure for

palaeocurrent analysis is cross stratification. T h e foresets represent t h e former slip faces of bedforms that
migrated in t h e direction of foreset dip. T h e average
direction of foreset dip is a m e a s u r e of t h e average
local flow direction. T h e geometrical variability of
cross stratification mirrors t h e natural variability of
bedforms. A l t h o u g h most workers categorize cross
stratification in the two very broad subdivisions of
planar a n d trough varieties ( M c K e e & W e i r , 1953;
Section 2.2.4) there is, in n a t u r e , much m o r e of a
form continuum between these two (Meckel, 1967;
NO
VERT
OTHR
TR
000
100
200
300
60
70
80
SPARE
FLAT
SY.P
AS.R
PL.X
TR.X
NO
VERT
OTHR
TR
10H
90
CANC'L
25-
20-
0
(b)
Allen, 1982). T h e dimensions of the foresets will

clearly be related to the size of the bedform, but this
relationship is n o t simple. C o m m o n l y each foreset is
truncated by an erosion surface, and thus the set
thickness can only give a minimum estimate of
bedform height. Nevertheless set thickness is valu
able information, i m p o r t a n t in t h e interpretation of
p a l a e o e n v i r o n m e n t a l conditions and must always be
recorded. Similarly the angle of inclination of t h e
foresets is the result of a complex balance of factors
such as grain size, current velocity, sediment load
etc., but it can still yield useful information on both
t h e bedforms and transport processes. T h u s the dip
and shape of the foresets should also be recorded.
111111 1
ffl ' i n c n) at to
sand
10-+
Fig. 2.24. Examples of presentation styles of graphic logs.
(a) Representative logs of the coarse grained fluvial facies
of the Upper Devonian Munster Basin, Ireland showing
variation between proximal (A) and more distal (B) types.
Lithology and structures are shown separately (from
Graham, 1983).
(b) Log of marginal marine sediments from the Tertiary of
South England displaying inferred sequential organization
as well as data on structures and trace fossils (from Plint,
1983).
T h e m e a s u r e m e n t of cross stratification is most

simply accomplished where there is a reasonable
degree of three-dimensional exposure. In these cases
(a)
http://jurassic.ru/
Mill!
m.
35-
20-
CROSS-STRATIFICATION
f Bedding
15
Fig. 2.23. Example of a machine readable field recording form (from Alexander-Marrack etal., 1970). This form was used
for recording thick, relatively monotonous fluvial successions in East Greenland (Friend et al., 1976) where fieldwork was
expensive, time very limited and compatability among records from different investigators was important.
Marks are made on the form with soft pencil and each form has an accompanying stub on which additional notes can be
made. (Reproduced by permission of Academic Press.)
lines and planes are given in texts such as R a g a n

(1973) and C o m p t o n (1962).
Flaser
TR.X
50
FOSSILS
j2^|
90
40
DOL
^1] Ripple lamination

j s Lenticular "|
cross beoding
CANC'L
RESTART
CONCR-C0 OR STUf3
3
PL.X
NO
DIR
NO DIR
DOL
:::::
CONCR- COj OR STUB

2 DIR
AS.R
"00
RESTART
CEM
SY.P
CONCR - C 0 O R S T U B
STUB- -SPEC
OTHER
DEF
CaC0
ROCK
STUB-SPEC
(M)
C.SL
0N
RIPPLES
Thick
SMTH
VC.SS
SHP
==-.:=
C.SS
LIN
CEM
NO DIR | 2 DIR 1 DIR
MD CR
:::::
M.SL
__1.
M_SS
OTHER
_6_
TOOL | MKS
COVERED
9
_GY_
MKS
F.SS
F.SL
F\RD
Thick
GRAD
_RED
COVERED
F.SL
. A .
(M)
COVERED
F.SL
.. .-
Thick
NO
n i t e
Low-angle lamination
[ =| flat beoding
4
Convolute bedding
Mud clasts
i'sms Flint pebbles
''
k'9
' * Roots
6
Plant debris
J
Ophiomorpha
~JT Burrows
mm
m
55-
Intraclast
36 cm x 31 cm
Intraclast
24 cm
50-
45-
S6
40-
. 'Above
BedZ
"77-22
Green Foresets
35-
t h e orientation of a foreset plane is m e a s u r e d direct

ly with a compass/clinometer (along with any addi
tional structural information as noted in Section
2.3.3). W h e r e such suitable exposure is lacking, the
true (maximum) foreset dip can be calculated by
measuring two a p p a r e n t dips and solving by m e a n s
of a stereographic projection.
M e a s u r e m e n t p r o b l e m s generally centre a r o u n d
the ability to distinguish the three-dimensional geo
metry of the bedforms at o u t c r o p . T h e s e p r o b l e m s
may be c o m p o u n d e d when the filling of troughs is
asymmetrical. T h u s it has been noted by several
workers that trough axis orientations are much less
variable than cross strata orientations (Meckel, 1967;
D o t t , 1973; Michelson & D o t t , 1973; Slingerland &
Williams, 1979) and are to be preferred for m e a s u r e
m e n t . Unfortunately suitable exposures are only
u n c o m m o n l y available and less accurate approxima
tions must generally be m a d e . Careful recording of
the geometry of t h e structures on the m e a s u r e d
faces is most important for subsequent interpretation.
Techniques for deriving palaeocurrent d a t a from

c o m m o n exposure types have been suggested by
Slingerland & Williams (1979) and D e Celles, Long
ford & Schwartz (1983). O n e m e t h o d suggested by
the latter is to a t t e m p t to m e a s u r e both opposing
trough limbs in relatively equal n u m b e r s on n o r m a l
n-10
oblique exposures. Plotting these d a t a on a stereoGravel passes
graphic net should yield two clusters of opposing
laterally to sand
limb sets from which t h e trough axis orientation can
?H Interclasts 15 m x 0-3 m I >" be estimated (Fig. 2.29). This t e c h n i q u e may be
. 0>
useful for relatively flat lying strata but would be
m
particularly susceptible to tectonic modification since
the plunge of undisturbed trough axes is c o m m o n l y
Green Foresets
less than 10.
\356 Below
D e Celles et al. (1983) also suggested a semi
BedZ
quantitative t e c h n i q u e which relies on assessing t h e
overall geometry of t h e troughs by inspection of t h e
foreset geometry relative to that of t h e basal scour
surface, claiming accuracy to within 25 of t h e true
palaeocurrent direction. T h e closer that a section
approximates a true longitudinal section, t h e greater
the a p p a r e n t widening of the trough and t h e n u m b e r
of foresets that are t r u n c a t e d .
Green Foresets
^
Euestheria minuta Von Zeiten
Vj|B ppssiblyhere
Many Green,,,,.
Foresets \
B
Fig. 2.25. A plane table map of an Upper Old Red Sandstone sand body from central Scotland and accompanying section.
Both lateral and vertical relations of bedforms are well demonstrated. CI, C2 etc. refer to lithofacies described in text, a, b,
c refer to zones of facies interfingering and d to an area of soft sediment deformation (from Bluck, 1981). (Reproduced
by permission of IAS.)
fc
30-
25-
20-
15-
10-
fiSi*
(c)
(c) Log of Triassic fluvial sediments from central England

which shows palaeocurrent data and comments on specific
features of interest. Assignment of particular beds and
bedsets to defined lithofacies is shown to the left of the log
(from Steel & Thompson, 1983).
Fig. 2.26. Field sketches of extensive motorway cuttings in shallowly dipping strata which demonstrate lateral relationships
within multistorey conglomerate channel bodies. Numbers refer to storeys: dense stipple - overbank sandstones and
mudstones; blank channel sandstone and wings; diffuse stipple conglomerate; SB 1 to 5 sidebar units (from Allen
et al., 1983). (Reproduced by permission of the Geological Society of London.)
http://jurassic.ru/
HIHIHIimiHimiHIHIHIWffllHIl
o
E
00
a
o
D.
o
a E
8
Q "a 3
- 3 3
U
a c "
a- S
3 a
S = 2
E
u
3
13
O O
O S gO <
T3
c -
S- <^>
E "
E o 1
Fig. 2.29. A method of estimating trough axes from

measurements on trough limbs using a stereo net. Trough
limb data show clusters of right hand (open circles) and left
hand (closed circles) poles; average poles are indicated by
stars. The intersection of the two corresponding great
circles (biplanar method) and the pole to the best fit great
circle both give the trough axis (from De Celles etal.,
1873). (Reproduced by permission of SEPM.)
1I
s
S E
O -5
^ 2 "S
9cd oo
CL Ov
a
5
5
.2
>
o a
-c o
a
M
j2 5
IMBRICATION AND CLAST ORIENTATION

Ellipsoidal clasts frequently show a preferred align
m e n t , particularly in coarse grained sedimentary
rocks. This alignment is visible in both plan view,
h e r e t e r m e d orientation, and in vertical sections,
h e r e t e r m e d imbrication. In some cases this align
ment is d u e t o t h e position of t h e clasts within
structures such as foresets of cross strata. H e r e they
show a similar d o w n s t r e a m dip direction to t h e
foresets but commonly a shallower inclination
(Johansson, 1965). In contrast t h e dip of t h e clasts
not contained in large foresets is preferentially u p
stream . Clearly the presence or absence of foresets
in these coarse grained rocks must be determined at
the outset. Several factors a p p e a r to control the
range of inclination including clast size, clast spheri
city, degree of clast contact, and palaeohydraulic
conditions (Johansson, 1965; Rust, 1975; Koster,
Rust & Gendzwill, 1980). It has also been shown
that t h e orientation of the longest a-axis (where
a>b>c) tends to be either normal to or parallel to
o
oo
D. _T
2 U
M 2
00
s -3
o
a
- _ o
a
~ O ^ .
e5 h
3 oo
_ -o
o
^ -a 3 2
. S |
b i S S
en , J2
http://jurassic.ru/
37
t h e flow direction, the difference d e p e n d i n g in part

on the n a t u r e of the flow. T h e former is the charac
teristic result of clasts rolling o n the bed (Johansson,
1965; Rust, 1972) whereas t h e latter appears to be
c o m m o n only in conglomerates associated with
sediment gravity flows (Walker, 1975), although t h e
precise mechanism of formation is less clear.
In sedimentary rocks the best m e a s u r e of palaeo
current direction is to obtain the m e a n vector of t h e
ab pla'ne. T h e need to m e a s u r e rod- or disc-shaped
clasts involves some selection, usually by m e a n s of
ignoring clasts m o r e e q u a n t than say 2:2:1 (Rust,
1975). T h e dip and strike of the ab plane is estimated
by eye and m e a s u r e d from a n o t e b o o k held in that
plane. If the rocks are poorly indurated t h e clasts
may be extracted after m e a s u r e m e n t and the orient
ation of the a-axis d e t e r m i n e d . Application of this
technique clearly requires good quality exposures.
R a n d o m selection of clasts can be achieved by placing
a sampling grid, e.g. a piece of fish net or chalk
lines, over t h e bedding surface. T h e stronger align
m e n t of larger clasts which has commonly been
observed (Johansson, 1965; Rust, 1972, 1975) may
suggest that s o m e selection in terms of size as well as
shape is useful. T h e n u m b e r of clasts to be m e a s u r e d
should be such that a clear n o n - r a n d o m distribution
is achieved (Koster et al., 1980). Experience sug
gests that a b o u t 40 clasts is generally sufficient.
In m a n y cases t h e quality of exposure does not
permit this technique of m e a s u r e m e n t . W h e r e t h e r e
is extensive bedding plane exposure but estimation
of the dip of ab plane is difficult, a technique for
m e a s u r e m e n t 'described by Nilsen (1968) can be
e m p l o y e d . T h e elongation directions of 50 randomly
selected clasts with axial ratios 1.5:1 are measured.
This technique can also be used with a p h o t o g r a p h
and overlay if preferred. Such orientation readings
may not provide an u n a m b i g u o u s palaeocurrent
direction as long axis orientation m o d e s tend to be
either current normal or current parallel. T h u s t h e
same technique must also b e applied to m e a s u r e
imbrication o n vertical sections. W h e r e possible ver
tical sections either parallel to the long axis orient
ation or perpendicular to it or both have commonly
been chosen (Nilsen, 1968; Davies & W a l k e r , 1974;
Fig. 2.30). Davies & W a l k e r (1974), in a study of the
d e e p water C a p E n r a g e F o r m a t i o n of Q u e b e c , noted
that most of the available sections were fortuitously
oriented parallel to modal clast orientation and that
orthogonal faces had an incliniation not significantly
different from horizontal c o m p a r e d to a m e a n of 12
38
J . GRAHAM
Sample size
50
30
10
-iii^
PERCENT
Distribution of
clasts in one
typical example
obtained. It is clearly necessary as a first stage to

distinguish slump folds from (a) those produced by
vertical soft sediment m o v e m e n t ; these generally
p r o d u c e little or n o preferred orientation of axes,
and (b) tectonic folds. T h e latter distinction is fre
quently m o r e difficult. Criteria are summarized by
W o o d c o c k (1976a) w h o suggested that t h e m o r e
objective and reliable ones are: (i) angular dis
cordance at s o m e u p p e r slump sheet contacts; (ii)
miscellaneous but important features such as bur
rowed folds, dewatering structures, sand volcanoes,
undeformed clasts and fossils; (iii) absence of tension
cracks and veins in folds; (iv) absence of geometri
cally related macroscopic folds; (v) a r r a n g e m e n t of
slump sheets in a sequence in which unit thicknesses
have strongly skewed distributions.
Plan view
orientation
W
Distribution of
vector means of
Vector mean individual examples
Clasts parallel
to bedding
In m a n y o t h e r respects slump folds and tectonic

folds may be geometrically indistinguishable, e.g.
similar range of layer and surface s h a p e , similar
lineation and cleavage p a t t e r n s and similar spatial
attitudes.
If slump folds can be confidently recognized, then
a m e t h o d of determining mean downslope direction
is n e e d e d . Variability occurs mainly because slump
sheets are three-dimensional structures and com
monly lobate in plan view. Detailed p r o c e d u r e s are
given by W o o d c o c k (1979) and only a brief summary
is given below. T h e two m e t h o d s used are known as
the mean axis method which estimates downslope
direction as perpendicular to the m e a n s slump fold
axis, and the separation arc method which uses the
bisector of a planar separation angle between groups
of folds with opposite downplunge asymmetry (Fig.
2.31).
Fig. 2.30. Block diagram showing clast orientation in plan view (face A), imbrication (face B) and clasts parallel to bedding
(face C). Solid rose diagrams show the distribution of vector means of individual examples and stippled rose diagrams show
distribution of individual clast orientations in a typical example. Data are from the Cap Enrage Formation (deep water
Cambro-Ordovician) of Quebec (from Davies & Walker, 1974). (Reproduced by permission of SEPM.)
for t h e current parallel in this case long axis

parallel sections. T h u s they were able to obtain a
statistical three-dimensional alignment.
H o w e v e r , in m a n y cases the available exposures
may n o t be parallel to the palaeocurrent, and bed
ding plane exposures from which orientation can be
estimated may also not be available. In these cases
m e a s u r e m e n t is m o r e difficult and less precise. It is
necessary t o m e a s u r e imbrication on two faces, pre
ferably < 9 0 apart. T h a t showing t h e greater dip
would be closer t o t h e t r u e p a l a e o c u r r e n t direction,
but t h e r e is n o quantitative way of solving this
a p p a r e n t dip problem as t h e r e is for foresets of cross
strata. T h u s accuracy in m a n y cases will be limited
to an octant of the compass for each reading and this
should be clearly stated.
FLUTE MARKS
Flute m a r k s are found predominantly but not exclu
sively in turbidite successions. T h e origin of these
39
structures and their relationship to fluid flow has

b e e n considered at length by Allen (1971), 1982).
T h e y are usually seen on t h e bases of sandstone
beds, commonly in association with o t h e r sole m a r k s
such as groove casts. W h e r e a s most sole m a r k s are
linear structures, flute m a r k s uniquely specify a
direction with t h e d e e p e r , bulbous end indicating
u p c u r r e n t . Flutes generally occur in large n u m b e r s
on a particular bedding plane and a m e a n direction
should be specified, although variation is typically
very small. M e a s u r e m e n t is as f o T linear structures
although t h e end of the structure which is bulbous
must also be recorded.
T h e simpler m e a n axis m e t h o d is preferred as it is

a m e n a b l e to t h e derivation of confidence limits, it is
applicable where asymmetry data are unavailable,
and it relies on average properties of t h e data. T h e
average trend is taken either as t h e m o d e or, in most
quantitative studies, as t h e m e a n of t h e axes. H o w
ever, the separation arc m e t h o d , which relies m o r e
on t h e e x t r e m e properties of t h e d a t a , has advan
tages with strongly skewed distributions. Most
studies have used data specified in two dimensions
only but the technique is equally applicable to threedimensional data. T h e m e t h o d specifies a strike of
palaeoslope and leaves two alternatives for dip.
Solution generally comes from considering either
t h e vergence or facing of the slump folds, or from
regional considerations (Fig. 2.32).
SLUMP FOLDS
Slump folds are p r o d u c e d when unconsolidated
sediments resting on a slope b e c o m e unstable and
move downslope u n d e r t h e influence of gravity.
T h u s if t h e direction of that m o v e m e n t could be
estimated a m e a n s of determining palaeoslope is
http://jurassic.ru/
iHimimiHiiHummiinHiifm
i
o
o
Fold axis (clockwise down

plunge asymmetry)
Fold axis (anticlockwise down
plunge asymmetry)
Mean fold axis
Separation line
Separation arc
Downslope direction estimate
(mean axis method)
Downslope direction estimate
(separation arc method)
Fig. 2.31. An equal area stereo plot of hypothetical fold

axis distribution to illustrate the mean axis and separation
arc methods (see text). The palaeoslope dips due south
(from Woodcock, 1979).
SAMPLING HOW MANY

MEASUREMENTS?
In palaeocurrent analysis, population p a r a m e t e r s
can almost never be evaluated and it is only possible
to m a k e estimates based on samples. A close iden
tity between the orientation of directional structures
at o u t c r o p and those not available for m e a s u r e m e n t
is assumed. In cases of p o o r exposure or restricted
d e v e l o p m e n t of particular units there may be an
40
J.GRAHAM
Cwm-y-bont
C w m Blithus
pled as e n c o u n t e r e d and some effort is m a d e to

distribute sample points evenly within a given area.
T h e n u m b e r of m e a s u r e m e n t s will d e p e n d largely on
the objectives of the study which must be defined
before any specifications can be given. T h e r e has
perhaps been a tendency to concentrate on estima
tion of mean values at the expense of investigating
variability. Both are very important p a r a m e t e r s in
environmental interpretation. Despite the obvious
advantages t h e r e have been few attempts at 'nested'
or hierarchical sampling where an a t t e m p t is m a d e
to analyse different c o m p o n e n t s of the total vari
ance. A n interesting exception is the work of Kelling
(1969) which is discussed in Section 2.3.5.
2.3.3 Removal of tectonic effects
(b) W E S T E R N M A R G I N
Ring Hole
Fold axes
s
Fold facing direction
</
Fold vergence direction
X
n
Dip and strike of

predicted palaeoslope
RQ ""*"--*-AaL-
"axes
Fig. 2.32. Use of vergence and facing to determine palaeoslope direction in slump folds from Silurian strata in Wales. The
facing direction is a line within the axial surface, locally perpendicular to the fold hinge. The tick indicates the facing sense.
A similar convention is used to indicate fold vergence (from Woodcock, 1976b). (Reproduced by permission of the
Geologists' Association.)
enforced sample such t h a t every available m e a s u r e
m e n t must be taken. Designed sampling can only
occur w h e r e there is a surfeit of d a t a and may be
d e t e r m i n e d by cost (time + access) or for purely
analytical reasons.
Over larger areas sampling usually aims at equal

izing a r e a coverage and uses s o m e sort of pre-devised
grid system. Selection of sample points within grid
squares should be r a n d o m but this is only rarely
possible. In practice, outcrops are commonly sam-
A s it is t h e original current direction at t h e time of

deposition that is required for interpretation, any
subsequent reorientation or deformation of the
primary structures being used should be estimated
and r e m o v e d . T h e former of these operations is
relatively simple but t h e latter may be difficult and
in s o m e cases impossible.
Neglect of tectonic modification will clearly intro
duce e r r o r into t h e resultant observation. For exam
ple, the error that is introduced by failing to untilt
beds has b e e n compiled graphically by R a m s a y
(1961, fig. 2). T h e e r r o r will d e p e n d on the angle of
dip and the angle b e t w e e n the sedimentary structure
(expressed as a lineation) and t h e fold axis. F o r tilts
less than 30 t h e r e is little introduction of error, and
t h e original orientation of directional structures as
m e a s u r e d in t h e field could be employed. For tilts in
excess of this it is necessary to m a k e a correction.
R e m o v a l of tilt can be accomplished by rotating the
bedding about an axis parallel to its strike until it
comes to lie in a horizontal position. T h e m e t h o d is
applicable for simple flexural folds having horizontal
axes and is most conveniently accomplished using a
stereographic net.
If the fold axis is inclined (i.e. a plunging fold),
the strike of a bed at any position on the fold can
never be parallel t o it. This fact invalidates the
m e t h o d of unfolding about the strike which would
introduce an a m o u n t of error varying with b o t h the
dip of t h e beds and the plunge of the fold. This error
was presented graphically by R a m s a y (1961, fig. 5)
w h o showed that for steeply dipping or overturned
beds it can be very large. T o prevent this e r r o r the
structure must first be unfolded by rotation about
t h e fold axis to a position of lowest dip (equal to t h e
http://jurassic.ru/
41
plunge of the fold axis) and then the final tilt re

moved by rotation about the strike. T w o worked
examples for the c o m m o n cases of cross bedding and
sole m a r k s are shown in Figs 2.33 and 2.34.
Correct for tectonic effects is much m o r e prob
lematical when flexural folding has been accom
panied by significant compression (flattening) and
when similar folding is involved. In these cases lines
and planes suffer significant distortion which must
be r e m o v e d in the following order: (i) removal of
compression effects, (ii) removal of shear folding,
(iii) removal of plunge and tilt.
For the removal of compression it is necessary to
know both the orientation of the tectonic axes and
the a m o u n t of compression. A l t h o u g h techniques
for this exist ( R a m s a y , 1961, 1967), they require a
considerable a m o u n t of detailed structural informa
tion which in some cases may be u n o b t a i n a b l e . T h e
errors which may be introduced by neglecting these
effects may be large (see graphs in R a m s a y , 1961).
G2=137
Fig. 2.33. A worked example of re-orientation of groove

marks.
Field record: Bedding (S) 055/60SE. Intersection lineation
(L) pitches 30NE on bedding. Groove marks (G) ptich
85SW on bedding.
(1) Rotate bedding (S) about the fold axis (L) to position
where dip = plunge (P). G moves to Gl such that L Z. G =
65 I . / . G 1 .
(2) Rotate the bedding (S') to horizontal. Gl moves along
a small circle to give the original direction of the lineation,
G2 = 137.
42
J.GRAHAM

N
Fig. 2.34. A worked example of reorientation of cross

beds.
Field record: Bedding (S) 040/40SE. Foreset (F) 010/48SE.
Intersection lineation pitches 30NE on bedding. Plot the
poles to the bedding (PS) and foreset (PF) as well as the
bedding (S) and foreset (F) planes. Plot the intersection
lineation (L).
(1) Unfold by rotation about the fold axis (L) to position
where dip = plunge (p). PS and PF move along great
circles to PS' and PF' as S rotates about L. Position PS'
determined by L. PF Z. PF' = PS L PS'.
(2) Rotate the bedding to the horizontal. Return PS' to
the centre along small circle and move PF' the same angle
along a small circle to PF". This is the pole of the original
foreset orientation (F ). Read off the direction and amount
of dip (25 to 040).
expected if the mechanisms of folding are consider

ed ( R a m s a y , 1961, 1967). In flexural folding there is
generally a systematic increase in angle b e t w e e n t h e
cross bedding and the regional bedding on o n e fold
limb and a decrease in angle on the other limb.
W h e r e flexural folding is accompanied by compres
sion normal to the axial plane the angle of inclination
of the cross bedding is further modifed. A b n o r m a l l y
high and low cross bedding inclinations are pro
duced on both folded limbs (Fig. 2.35). T h e magni
t u d e of the modifications is d e p e n d e n t on the radius
of curvature of the base of the b e d , t h e thickness of
t h e cross b e d d e d unit, the a m o u n t of dip of the
bedding and t h e position of the foreset/regional
bedding intersection before folding. Most complex
modifications result from the combination of shear
folding and compression. This can result in abnor
mally high or low inclinations on both fold limbs and,
in t h e e x t r e m e case of the limbs of isoclinal folds, the
structure may be completely unrecognizable.
It is clear that the removal of tectonic effects from
palaeocurrent readings can be laborious and timeconsuming. Such a repetitive process is a m e n a b l e to
t h e application of c o m p u t e r techniques and some
authors have advocated doing this in the field with
pocket calculators ( F r e e m a n & Pierce, 1979). A
p r o g r a m that adequately considers both plunge and
tilt removal is presented by C o o p e r & Marshall
E v e n for those sedimentologists who are clearly

aware of structural limitations (e.g. D o t t , 1974;
M c D o n a l d & T a n n e r , 1983), there is seldom evi
dence that regional compression and fold style have
been adequately considered. Unless considerable
effort is spent in collecting the necessary structural
d a t a , palaeocurrent analysis in rocks which have
u n d e r g o n e significant shear and compression can at
best be considered as approximate and at worst may
be misleading.
Several published palaeocurrent studies showed
that reoriented foresets commonly showed inclina
tions much higher than t h e stable angle of repose of
sand (Pelletier, 1958; Cassyhap, 1968). This is to be
Fig. 2.35. Demonstration of the distortion of angles with

flexural folding and compression.
(a) Original orientation of bedding with foresets inclined
at 30.
(b) The same bed subjected to flexural folding.
(c) The same bed subjected to flexural folding and 50%
compression.
Note how abnormally high and low foreset dips can be
generated depending on position within the fold structure.
(Reproduced by permission of McGraw-Hill.)
(1981), who reviewed most earlier a t t e m p t s . Such

programs also frequently present the data in s o m e of
the standard formats outlined in the next section.
T h e s e packages are now widely available and will
probably be used increasingly in the future. Despite
this s o m e w o r k e r s in structurally complex areas pre
fer to perform these operations by hand so that a
careful check can be kept on the precision of each
recording ( M c D o n a l d & T a n n e r , 1983). It is impor
tant to state clearly any manipulations that were
performed and to note any likely limitations, such as
not taking account of tectonic deformation.
43
4
North-east
region
North region
n = 120
n = 258
2.3.4 Presentation of data

In a few cases w h e r e data are scarce but geologically
significant, e.g. major channel orientations or giant
cross beds (Collinson, 1968), each palaeocurrent
m e a s u r e m e n t may be shown individually. M o r e
normally, m e a s u r e m e n t s are grouped into classes of
10, 15, 20 or 30, the choice of interval d e p e n d i n g
on both the n u m b e r of readings and directional
variability. In general, the lower the variability the
smaller the class interval although t o o small an
interval can lead to irregular class frequencies. T h e s e
are presented in the form of a histogram converted
to a circular distribution and t e r m e d a current rose
(see Fig. 2.36). T h e s e histograms (roses) can plot
either total n u m b e r of observations per class or
p e r c e n t a g e s , t h e latter often being useful for com
parative purposes. In the geological literature the
current rose conventionally indicates the direction
toward which the current moved.
Although many structures used to infer palaeocurrents are vectors, i.e. possessing magnitude as
well as direction, they are all usually considered as
having unit m a g n i t u d e . This relates to the geological
uncertainty of objectively assigning a magnitude
c o m p o n e n t . H o w e v e r , t h e r e are many cases w h e r e
presentation of only standard current roses may lead
to loss of valuable data. T h u s amongst workers in
aeolian sediments it is c o m m o n practice to present
data on a polar stereographic projection (Reiche,
1938; Kiersch, 1950; M c K e e , 1966; C a r r u t h e r s , 1985;
Fig. 2.37). Not only does this allow all readings to be
shown individually but it also places visual emphasis
on the larger dip angles as indicators of palaeowind
directions. In addition Glennie (1970) has suggested
the possibility that the type of d u n e structure can be
recognized from the distribution of poles of dip
planes.
http://jurassic.ru/
Fig. 2.36. Rose diagrams based on semi-octant classes of

cross-stratal azimuths. Dotted lines represent the
partitioning into two distributions for statistical analysis ,
(from Kelling, 1969). (Reproduced by permission of
SEPM.)
Most palaeocurrent studies are concerned with
t h e preferred orientation direction, if one exists, and
the degree of spread about that orientation. These
are measures which are analogous to the m e a n s and
variance of linear distributions but must be calcu
lated differently t o account for the circular nature of
the data. T h e simplest form of calculation is:
V = " cos 6,
W = E',' sin 9,
x = arctan WIV,
2
R = (v +
L
0
n
x
R
L
R
=
=
=
=
=
=
=
/2
wy ,
(R/n). 100,
individual azimuth,
n u m b e r of readings,
vector m e a n ,
magnitude of resultant vector,
magnitude of resultant vector ( % ) .
R/n
T h e values of L and n can be used for the Rayleigh

test of significance outlined below.
For two-dimensional orientation data such as
primary current lineation or goove casts, all orient
ations can be expressed within a 180 range. In these
cases t h e calculations b e c o m e :
V = Li cos 2 0,
W = " sin 2 9,
44
J . GRAHAM
x = 1/2 arctan WIV,
R = (w V)',
L = (Rlri). 100.
45
T h e vector m e a n (x) is an expression of preferred

orientation whilst t h e vector magnitude (%) (L) is a
sensitive m e a s u r e of dispersion.
It is necessary to test w h e t h e r a set of p a l a e o
current d a t a possesses a distribution of orientation
which is significantly different from r a n d o m . Several
ways of performing this test a r e reviewed by P o t t e r
& Pettijohn (1977, p p . 3 7 7 - 3 8 0 ) . T h e simplest is
probably t h e Rayleigh test as outlined by C u r r a y
(1956), for which a graph can be used (Fig. 2.38) to
r e a d t h e probability t h a t t h e m e a s u r e m e n t s a r e uni
formly distributed in t h e interval 0360. A desired
level of significance, usually p < 0.05, is chosen at
which the null hypothesis of a uniform distribution is
rejected.
t h e concentration of t h e mass and 8 is the angle w h e r e

t h e function takes its m a x i m u m value. I (K) is a
Bessel function whose values are tabulated. Such
distributions a r e not always p r e s e n t as is often as
s u m e d , e.g. Sengupta & R a o (1966), although this
can b e readily checked by t h e m e t h o d outlined by
H a r v e y & Ferguson (1976).
It is generally vector m e a n s which a r e presented
in published data either on m a p s or accompanying
stratigraphic columns. "The n u m b e r of readings a n d
value of L (or R) should also be readily accessible. It
is often useful to present s o m e visual impression of
t h e a m o u n t of confidence attached t o a vector m e a n
by showing a confidence interval (of, say, 90 or
9 5 % ) , e.g. Kelling (1969). This can be most readily
p r o d u c e d b y using a Batschelet chart as shown in
Fig. 2.39. T h e techniques for calculating these con
fidence intervals numerically from t h e raw d a t a are
given by M a r d i a (1972, p p . 144145).
T h e use of vector statistics in a c o m p a r a b l e man

n e r to t h e use of m o m e n t s of a n o r m a l distribution
implies t h e presence of a von Mises (circular n o r m a l )
distribution of d a t a . T h e density function of t h e v o n
Mises distribution m a y be written as f(x) =
jnI (K)
(e
) w h e r e K is a p a r a m e t e r t h a t expresses
It is also necessary to quantify t h e spread of values

a r o u n d t h e vector m e a n . F o r t h e von Mises distri
bution, R is an estimate of t h e spread of the angular
values a r o u n d a unit circle. T h e m e a n angular devia
tion, s, can b e calculated by s = V(2(l R)) w h e r e s
is m e a s u r e d in radians. A l t h o u g h s behaves mostly
1 2
c o s
( x _ e )
1 0
20
50
100
200
400
600 800 1000
2000
4000
6000
10,000
20,000
40,000 60,000 100,000
Number of observations, n
Fig. 2.38. Rayleigh test of significance. The graph plots the probability of a given vector magnitude (L) occurring by
chance for varying numbers of observations. A significance level is chosen, commonly p < 0.05, at which the hypothesis of a
random distribution of orientations is rejected (from Curray, 1956). (Reproduced by permission of University of Chicago
Press.)
http://jurassic.ru/
46
J . GRAHAM
0.1 0.2 0.3 0.4 6.5 0.6 0.7 0.8 0.9 1.0
Length of mean vector R
Fig. 2.39. Batschelet chart for obtaining a 95% confidence

ipterval for the mean direction (from Batschelet, 1981).
(Reproduced by permission of Academic Press.)
in the same way as the standard deviation of a
n o r m a l distribution, it is not its circular analogue
which is K. Tables are available for converting R to
K and indeed K is used in many further tests
( M a r d i a , 1972).
Having obtained reliable estimates for preferred
orientation and concentration of values s o m e fur
ther tests may be desirable or possible d e p e n d i n g on
t h e n a t u r e of the p r o b l e m . Perhaps the c o m m o n e s t
p r o b l e m is that of comparing preferred current
orientations for significant differences. Before ad
vancing to testing equality of m e a n directions it is
necessary to test that the samples are drawn from
populations with equal concentration ( M a r d i a , 1972,
p p . 1 5 8 - 6 2 ; C h e e n y , 1983, p p . 1 0 2 - 1 0 3 ) . T h e test
for equality of preferred direction is s o m e w h a t com
plex as it d e p e n d s in part on t h e ratio of t h e two
sample sizes and also on t h e strength of t h e concen
tration p a r a m e t e r , K, of the samples c o m b i n e d .
Details and worked examples are given by R e y m e n t
(1971, p p . 4 8 - 5 0 ) , M a r d i a (1972, p p . 1 5 2 - 1 5 5 ) and
C h e e n e y (1983, p p . 1 0 1 - 1 0 6 ) .
A l t h o u g h vector statistics are both precise and
powerful, it is clear that the underlying populations
of directional d a t a must be thoroughly u n d e r s t o o d
and defined. For e x a m p l e , sole marks and ripple
marks from t h e bases and tops of beds could, in the
case of storm-modified turbidites, represent differ
ent current systems operating at different times.
G r o u p i n g of data and assumption of one population

may be statistically possible but would not be geo
logically reasonable. M o r e o v e r the application of
vector statistics implies a unimodal distribution and
they are not directly applicable when the d a t a are
bimodal or polymodal. For this reason in particular
current roses should always be drawn and the d a t a
inspected qualitatively.
S o m e m e t h o d s have been proposed for further
t r e a t m e n t of bimodal and polymodal distributions.
For example the problem of bimodality may be
resolved by calculating separate vector m e a n s for
two circular frequency distributions, the overlap
being separated by partition about the midpoint of
the two shared classes containing the lowest fre
quencies (Fig. 2.36). This is possible w h e r e the two
m o d e s are almost opposite in direction but difficult
to apply w h e r e they are closer together.
For polymodal distributions w h e r e vector statistics
are i n a p p r o p r i a t e , simpler, semi-quantitative tech
niques can be used to express preferred direction
( T a n n e r , 1959; Picard & H i g h , 1968; Fig. 2.40). A
compass is divided into 12 x 30 intervals and the
m e a n n u m b e r of occurrences per interval and the
standard deviation are calculated. T h o s e intervals
that contain palaeocurrent directions in excess of
o n e standard deviation above or below the m e a n
represent p r o m i n e n t m o d e s or nodes respectively.
Intervals within o n e standard deviation a r e con
sidered to be qualitatively indistinguishable from
r a n d o m distributions.
10 15
Fig. 2.40. Recognition of modes and nodes in polymodal

distributions (see text for explanation) (from Picard &
High, 1968). (Reproduced by permission of SEPM.)
1971; Bluck, 1974; Miall, 1974) but also applies in

varying degrees to o t h e r environments (Field et al.,
1981; Link, Squires & C o l b u r n , 1984). T h u s o n e
would be likely to regard the orientation of a single
channel form as being in s o m e way m o r e significant
than the orientation of a single set of trough cross
integrated system
47
beds. T h e r e have been only a few attempts to quan

tify this difference in scale by introducing a 'weight
ing factor'. In many ways this is d u e to the difficulty
of defining an objective a n d operational m e t h o d o
logy. Miall (1974) suggested using the cube of set
thickness as it may crudely reflect the volume of
sediment displaced by t h e current. Erosional loss of
varying p r o p o r t i o n s of the sets clearly presents p r o b
lems as d o assumptions of geometrical similarity.
A l t h o u g h this m e t h o d has b e e n little used it does
qualitatively emphasize t h e differing significance t h a t
might be attached to different bedforms.
It is sometimes possible to analyse or even sample
palaeocurrent data with this concept of hierarchical
organization in mind (Olson & Potter, 1954; Potter
& Olson, 1954; Kelling, 1969). H o w e v e r , an as
sumption that chosen sampling levels (e.g. outcrops)
will match any natural hierarchical level n e e d s t o b e
justified. A n example of this is given by Kelling
(1969) w h o carefully sampled and analysed the
palaeocurrents of some U p p e r Carboniferous fluvial
order one
order two
Channel-form
Point bar
Large-scale ripples
Small-scale ripples
Channel-form
2.3.5 Interpretation of results

BEDFORM HIERARCHIES
order three
It has long been realized that sedimentary structures
show an hierarchical a r r a n g e m e n t such that n o o n e
sedimentary structure fully specifies a complex flow
system. Such a specification can only be m a d e after
sampling all types of structure g e n e r a t e d within the
limits of preservation. T h e concept of bedform hier
archies was formalized by Allen (1966), Bluck (1974)
and Miall (1974) by w h o m parts of a fluvial system
were given orders or r a n k s (Figs 2.41 and 2.42). In a
general sense, t h e smaller structures in the hierarchy
tend to be m o r e variable because t h e currents form
ing t h e m are controlled both by t h e overall transport
direction and also by local deviations caused by
larger bedforms. This p h e n o m e n o n is particularly
well known from fluvial systems (Collinson, 1968,
order four
Legend
Small-scale
ripples
Channel-form
Point bar
Large-scale
ripples
rrfc
rrr
1
Large-scale ripple
crestlines
Small-scale ripple
crestlines
Flow direction within
flow-vector field
Fig. 2.41. Hierarchical organizational of flow-vector fields in a fluvial system illustrating the dependence of currentdirectional data on rank of bedform (from Allen, 1966). (Reproduced by permission of Elsevier.)
http://jurassic.ru/
1UJIM1
lit
48
J . GRAHAM
49
Variability of orientation
Fig. 2.42. Illustration of the possible relationships between flow stage, variability in orientation of structures and the kind
of sedimentary structures in a fluvial system. Ripples are often an exception because they tend to be caught in major
channel troughs and orientated along them (from Bluck, 1974).
sediments in South W a l e s . Sampling design followed

a pilot study in a well-exposed area which gave s o m e
indication of variability and minimum n u m b e r of
m e a s u r e m e n t s . T h e resultant data, summarized in
Fig. 2.43, show clearly t h e m e a n direction with con
fidence limits for each sample sector. A n hierarchi
cal analysis of variance at four different levels
was also a t t e m p t e d and related to natural levels of
variation in a river system, i.e.
(i)
different parts of drainage net or different

sources;
(ii) different streams or portions of s t r e a m s ;
(iii) deviations of laterally or vertically adjacent
sand bodies within major stream courses;
(iv) divergence of superposed bedforms.
M o r e importantly, c o m p l e m e n t a r y d a t a on t h e
n a t u r e of the sedimentary structures (e.g. cross
stratification t y p e , set thickness, foreset dip angle)
allow an objective assessment of the data by the
reader.
U S E O F V A R I A B I L I T Y IN
ENVIRONMENTAL INTERPRETATION
It can be seen from t h e above section that the
a m o u n t of variability, even in a predominantly uni
directional transport system, will d e p e n d in part on
t h e level of bedform hierarchy which is sampled.
Much of our knowledge of palaeocurrent variability
comes from specific m o d e r n e n v i r o n m e n t s (Allen,
1967; Miall, 1974). A t t e m p t s to distinguish environ
m e n t s by m e a n s of the variance of their palaeocur
rent p a t t e r n have been m a d e by Potter & Pettijohn
(1977) and Long & Y o u n g (1978) w h o tabulated
large a m o u n t s of d a t a from case histories. H o w e v e r ,
it should be r e m e m b e r e d that m o d e r n e n v i r o n m e n t s
record variability over a very short time period
w h e r e a s most geological studies have data bases that
are fundamentally different because the strata ac
cumulated with an appreciable time dimension such
that the grouping of data over a longer time interval
might be expected to increase variance. M o r e im-
Fig. 2.43. An example of hierarchical sampling of palaeocurrent data from the Upper Carboniferous of South Wales. The
map shows vector mean cross-stratal azimuths and 95% confidence limits for sectors and regions within the study area
(from Kelling, 1969). (Reproduced by permission of SEPM.)
portantly, t h e inequalities and uncertainties of timed e p e n d e n t changes and t h e difficulty of separating

t h e m from spatial variation m a k e overall variance at
best a very crude criterion.
In specific studies it is possible and often desirable
to examine variability of palaeocurrents in both time
and space (e.g. Chisholm & D e a n , 1974; Miall,
1976; Pickering, 1981; G r a y & B e n t o n , 1982),
Variation in time generally involves splitting vertical
sections into meaningful subdivisions which can t h e n
be c o m p a r e d , e.g. by testing whether their vector
m e a n s are significantly different. Clearly this tech
nique will be limited by t h e accuracy with which
such subdivisions can be correlated.
ficance usually requires i n d e p e n d e n t interpretation

of lithofacies and structures. It is particularly impor
tant in this respect that t h e structures that are mea
sured in palaeocurrent analysis are described as
thoroughly as possible. F o r example Bourgeois
(1980) (Fig. 2.44) c o m p a r e d t h e dip a m o u n t s , as
well as direction of, from H C S and trough cross beds
and showed m a r k e d differences. In many earlier
studies, written before the c o m m o n recognition of
H C S , such m e a s u r e m e n t s would probably have been
grouped as trough cross stratification. H o w e v e r if
sufficient d a t a w e r e given on foreset inclination t h e
possible presence of H C S might be suggested and
re-investigation stimulated.
RELATIONSHIP OF SEDIMENTARY
STRUCTURES TO ENVIRONMENT
PALAEOCURRENT PATTERNS
A l t h o u g h palaeocurrent data themselves can be im

p o r t a n t environmental discriminants, their full signi-
http://jurassic.ru/
ll!!ll!!ll!!ll!!l!HIHIl!lllHlllltl
It has been noted on a m o r e general scale that

palaeocurrent d a t a tend to form a set pattern when
seen over appreciable areas. Potter & Pettijohn
50
J.GRAHAM
51
Mean
ripple-crest
orientation
o
OJ
Trough X-beds
Fluvial p a l a e o c u r r e n t s , because of their basic con

trol by gravity, tend to be unidirectional although
with considerable spread over small areas (e.g.
L e e d e r , 1973). O v e r larger areas it has b e e n shown
that major drainage often occurs parallel t o tectonic
strike (Van H o u t e n , 1974; Steel e r a / . , 1977; Bluck,
1978). Similar p a t t e r n s have b e e n shown to exist for
d e e p e r water m a r i n e sediments, particularly w h e r e
t h e r e are submarine fan systems present (Jipa, 1966;
Convergent
Divergent
Curvelinear
Random
Rotary
(D
Hummocky beds
Fig. 2.44. Comparison of dip direction (arrows) and dip angle of trough cross-beds and hummocky beds in the Cape
Sebastian Sandstone, Cretaceous, Oregon. Dots are poles to cross bedding; dots within the small circle represent dips less
than 15 (from Bourgeois, 1980). (Reproduced by permission of SEPM.)
(1977) suggested that, based purely o n g e o m e t r y ,

t h e r e are seven basic patterns (Fig. 2.45). At
t e m p t s have also been m a d e t o p r o d u c e environ
mental classifications of palaeocurrent p a t t e r n s ,
(e.g. by Selley, 1968) and also to relate these to
geotectonic setting (e.g. by Potter & Pettijohn
1977). A t a smaller scale palaeocurrent d a t a can
s u p p o r t environmental discrimination suggested by
o t h e r criteria. T h u s Laming (1966) showed that
palaeocurrents derived from strata i n t e r p r e t e d as
aeolian have a totally different p a t t e r n from those
inferred to be fluvial. Chisholm & D e a n (1974) used
palaeocurrent data as the main evidence that parts
of a largely fluvial Carboniferous formation in Scot
land were deposited u n d e r the influence of tidal
currents.
Parallel
Ricci Lucchi, 1975b, 1981; M c D o n a l d & T a n n e r ,

1983).
A e o l i a n current directions are typically indepen
d e n t of o t h e r terrestrial transport directions (e.g.
H u b e r t & M e r t z , 1984) and in favourable cases it
may be possible to relate patterns to t r a d e wind
circulation (e.g. Fryberger & D e a n , 1979; K o c u r e k ,
1981). Shallow m a r i n e p a t t e r n s a r e typically t h e
most complex (Klein, 1967) and difficult to inter
pret. In t h e cases w h e r e the currents are of different
types and with different controls it is particularly
i m p o r t a n t to a t t e m p t to relate palaeocurrent d a t a to
the p a l a e o e n v i r o n m e n t a l interpretation of t h e sedi
m e n t a r y structures from which they are derived.
2.4 S E D I M E N T A R Y F A C I E S A N D
SEQUENCE ANALYSIS
2.4.1 Erection and use of facies
Much of t h e field recording of sedimentary rocks is
aimed at classifying t h e strata being investigated into
recurrent units and attempting to detect an o r d e r in
t h e vertical and lateral a r r a n g e m e n t of those units.
Reversing
Fig. 2.45. Seven basic palaeocurrent patterns based on geometry (from Potter & Pettijohn, 1977). (Reproduced by
permission of Springer.)
T h e term applied to these units is facies which are

defined o n a combination of lithological, structural
and organic aspects in the field. T h e facies may be
given informal designations, e^g. 'facies A ' or brief
descriptive designations, e.g. 'pebbly sandstone
facies'. T h e main criteria used in delimiting facies
will vary with the strata being investigated. A facies
unit may in s o m e cases be an individual bed or
bedset but may also comprise several beds or bedsets. T h e origin and m o d e r n usage of the term facies
has been reviewed by R e a d i n g (1978b) and W a l k e r
(1984).
T h e scale of facies subdivision is in part d e p e n d e n t
http://jurassic.ru/
on the variety of physical and biological structures in

t h e rocks but also partly on the time and m o n e y
available for t h e study and t h e scale and p u r p o s e of
t h e investigation. Standardization becomes impor
tant particularly w h e n several different investigators
a r e describing the same succession, e.g. in many
industrial studies, but must not be allowed to
'straightjacket' new observations. Objectivity of de
finition is most i m p o r t a n t . Unless t h e general n a t u r e
of a succession is relatively well known at t h e outset,
a reconnaissance study will generally precede facies
subdivision. It is difficult to give general rules on
how finely to subdivide in t h e field but it is better to
52
J.GRAHAM
over-subdivide than t h e reverse. Subdivisions can

always be combined during later analysis but split
ting without a field check is much m o r e h a z a r d o u s .
Classic examples of the objective definition of facies
are given by D e Raaf, Reading & W a l k e r (1965),
J o h n s o n (1975) and D e Raaf et al. (1977).
2.4.2 Facies relationships

Individual facies vary in interpretative value but
only a very few facies in isolation allow unambigu
ous interpretations. T h e key to interpretation is to
study facies in association, in particular their relative
vertical and lateral positions. T h e n a t u r e of t h e
contact between two facies is fundamental in assess
ing their original depositional proximity.
LATERAL RELATIONSHIPS
Lateral relationships are in s o m e cases directly o b
servable and d o not rely on an inferential step from
the application of Walther's Law (Middleton, 1973)
to a vertical sequence. H o w e v e r , t h e limited physical
size of most exposures m e a n s that such situations
are u n c o m m o n and require favourable circum
stances. Such exposures are valuable in the descrip
tion of t h e larger scale geometry of facies which is
also seldom possible with limited vertical sections.
For example H o m e et al. (1978) gave s o m e excellent
examples of interpretative block diagrams con
structed from laterally extensive road cuts through
deltaic successions w h e r e exposure levels are be
tween 60 and 9 5 % over 1 0 2 - 1 0 3 m .
Spectacular examples of lateral facies changes on
a large scale are given by Bosellini (1984) for Triassic
c a r b o n a t e platform margins in the A l p s , by H u r s t &
Surlyk (1984) for Silurian carbonate platform mar
gins in N o r t h G r e e n l a n d , by Newell et al. (1953) for
t h e Permian reef complex of Texas and N e w Mexico,
by Playford (1980) for the D e v o n i a n reef complex of
t h e Canning Basin, W e s t e r n Australia, and by Ricci
Lucchi (1975b) for t h e Miocene turbidites of the
A p e n n i n e s . In these and o t h e r cases unusually large
natural exposures allow lateral relationships of
mega-units such as c a r b o n a t e platforms and slope
complexes t o be observed. O n a smaller scale lateral
tracing can, for e x a m p l e , illustrate the position of
levee deposits in both submarine fan valleys (Ricci
Lucchi, 1981) and in river systems ( H o m e et al.,
1978, fig. 7; Stewart, 1981), t h e geometry of fluvial
channel sandstones (Friend, Slater & Williams,

1979), and the lateral pinch out of delta front sands
(Ryer, 1981).
53
. Burrowed horizon
- L Major sandstonez
VERTICAL RELATIONSHIPS
V e r y extensive studies have been m a d e of vertical
sequences of facies from almost every e n v i r o n m e n t .
This is largely because sections with appreciable
vertical thickness but limited lateral extent are the
most c o m m o n d a t a sources. T h e r e is probably also
s o m e element of tradition in this emphasis in that
t h e simplest pictorial representation of such d a t a
resembles a stratigraphic c o l u m n . It is often possible
from such diagrams to see r e p e a t e d patterns of
facies or changes with time by simple inspection.
H o w e v e r , not all observers will have the same in>
pression of a succession, and thus it is necessary to
present and analyse t h e d a t a as objectively as poss
ible. T h e recognition of r e p e a t e d patterns of facies
(facies sequences, cycles) has proven to be a most
powerful tool in environmental interpretation
( R e a d i n g , 1978a).
For any given succession t h e r e are two simple
techniques which will normally form the first stage
of any analysis. T h e first is to present a graphic log
of t h e succession (see Section 2.2.7), and the second
is to p r o d u c e a facies relationship diagram ( F R D ) to
s u m m a r i z e t h e observed vertical sequence of facies
(Fig. 2.46a). In Fig. 2.46(a) the basic d a t a are still
accessible but have been arranged in an o r d e r sug
gested by visual inspection of the graphic logs; the
accompanying pictorial representation (Fig. 2.46b)
helps to summarize the information.
2.4.3 Markov Chains

Few successions have as clear a vertical o r d e r as t h e
U p p e r Carboniferous deltaic sediments studied by
D e R a a f etal. (1965) (Fig. 2.46). S o m e simple statis
tical techniques have been employed to investigate
t h e possible presence of vertical o r d e r in sedimen
tary successions. A l m o s t all use probability matrices
and employ t h e idea of M a r k o v Chains. T h e under
lying questions can be generalized as: (i) is the
observed vertical sequence of lithologies r a n d o m or
o r d e r e d ? ; (ii) in which way is it o r d e r e d ?
Early work in this field was presented by Potter &
Blakey (1968) and Gingerich (1969) with similar
techniques proposed and used by R e a d (1969),
Schwarzacher (1969), Selley (1969), L u m s d e n
(1971), D o v e t o n (1971), Miall (1973), T u r n e r (1974),
A. Black mudstone
\
/ '
* K
* V
\\
/ L . Majorsandstones\\
,1
J. Cross-stratified K. Fining upwards units i

sandstones and mudstones
E. Sandy streak
q o,o.oio
!^\\f
_9b^8
Tl~ T D . S i l t y streak
1 i
a.o-o
it,
Q. Oscillatory 2
'
e"o: e
Q.'s
So
-.D"0: tOa
;
6 ' - e . P o ee.B'.e.
F. Oscillatory 1:
B. Silty
mudstone
F. Oscillatory 1
C. Turbidite
A. Black mudstone
- A . Black mudstone-
- 2 Sharp boundary between facies; occurs twice

- 1 G r a d a t i o n a l passage between facies; occurs once
(b)
(a)
Fig. 2.46. (a) A facies relationship diagram for the Upper Carboniferous Abbotsham Formation of SW England showing
both number and type of facies boundaries.
(b) Pictorial representation of (a) and suggested sedimentary 'cycle'. (From Reading, 1978b after De Raaf etal., 1965.)
E t h i e r (1975), H a t t o r i (1976) and C a n t & W a l k e r

(1976).
A first o r d e r M a r k o v process is a stochastic pro
cess in which the^state of t h e system at time t is
influenced by or d e p e n d e n t on t h e state of t h e
system at time f_ but not t h e previous history that
led to the state at time t-. . T h e presence of a
Markov process implies a degree of o r d e r in a sys
t e m but this must b e extended to a n u m b e r of states
to imply cyclicity. In most studies the raw data
consist of an observed n u m b e r of upward transitions
which are plotted in matrix form. T h e often quoted
data of Gingerich (1969) are used h e r e for illustra
tion (Table 2.7a, b ) . This transition probability
matrix is then c o m p a r e d to one generated by ran
d o m m e t h o d s ( i n d e p e n d e n t trials matrix T a b l e
2.7c, d ) . T h e comparison is by m e a n s of a % test
{
http://jurassic.ru/
which a t t e m p t s to answer question (i) above, i.e. is

t h e observed sequence r a n d o m or o r d e r e d ?
H o w e v e r , subsequently it has been shown that
this technique is not entirely justifiable statistically
and must be modified (Carr, 1982; Powers & Easterling, 1982). T h e matrices employed in T a b l e 2.6 are
t e r m e d embedded
matrices because they contain
structural zeros, i.e. zeros implicit in t h e technique
and not due to sampling. T h e s e occur because transi
tions from a bed of o n e iithology or facies to a n o t h e r
case of the same are held t o be objectively nonrecordable and thus the diagonal frequencies are
forced to be z e r o . It was pointed out by Schwarzacher
(1975) that t h e presence of previously defined zeros
was a major obstacle to rigorous analysis. It be
comes impossible t o g e n e r a t e an ' i n d e p e n d e n t trials
matrix' by a simple i n d e p e n d e n t r a n d o m process.
54
J . GRAHAM

Table 2.8. Calculation of expected
frequencies under a model of
quasi-independence after Goodman
(1968) and Powers & Easterling (1982)
Table 2.7. Matrices for Markov analysis (data from

Gingerich, 1969)
(a) Transition count matrix
MS
SS
SS
MS
LIG
LS
Total
21
20
1
42
37
25
14
76
LIG
LS
Total
3
41
2
14
0
16
42
76
45
16
179
1
45
(b) Transition probability matrix

LIG
MS
SS
SS
MS
LIG
LS
0.28
0.44
0.06
0.88
0.56
0.88
0.07
0.54
0.06
(c) Independent trials probability matrix

LIG
MS
SS
SS
MS
LIG
LS
0.41
0.31
0.26
0.55
0.57 .
0.47
0.33
0.43
0.27
LS
0.05
0.18
0.00
SS
MS
LIG
LS
Total
23.3
31.0
14.1
4.1
49.2
25.5
7.5
56.3
13.8
33.2
4.4
51.4
+0.33
-0.13
+0.13
-0.20
-0.01
+0.41
-0.07
+0.02
-0.12
-0.21
-0.26
+0.11
31.38
34.06
10.06
76.00
8.17
34.05
2.78
45.00
E(n ) = a b ,
u
ii= j
= 0,
i=j
The iterative procedure for calculating a, and b, under the model is as follows:
First iteration
a,' = n /(m
- 1)
i+
bj = n+j/'Zai'
1
(f) Independent trials matrix (after Carr, 1982 and Powers

& Easterling, 1982)
Total
LS
LIG
MS
SS
31.28
8.17
2.56
42.01
The model termed quasi-independence is
LS
2.56
10.66
2.78
16.00
i = 1, 2,
y = 1,2,
/th iteration
a? = n j'2bf'- )
i = l,2,
b,' =
a'
7=1,2,
42.01
75.99
45.01
16.00
f)
1
Beginning with a, as the average of the rth row entries provides a useful
starting point. Iteration is continued until:
| a / - a , < ) | < 0.01 a / for / = 1,
m
/-1
(g) Difference matrix (after Carr, 1982 and Powers &

Easterling, 1982)
LIG
LS
MS
SS
0.12
0.16
0.12
4.9
11.8
5.4
22.0
SS
MS
LIG
LS
SS
MS
LIG
LS
1 S
(d) Independent trials matrix (data calculated by

Gingerich method)
LIG
LS
MS
SS
(e) Difference matrix (after Gingerich)

LIG
MS
SS
and
/ _ 1
|b/-i/
)|<0.01b/
for
y=l,
When a, and b are the final values of a/ and b / then the estimated expected
frequencies are given by = a,b, for i i= j . For example consider the data from
Table 2.7(a). On the first iteration:
y
/;
SS
MS
LIG
LS
-0.13
+0.26
-0.10
+0.14
-0.20
+0.21
-0.13
+0.09
-0.11
-0.01
+0.04
-0.06
ai = n l(m
a ' = n / ( m - 1) = 45/3 = 15.0

3
3+
ft, =
Total
Both C a r r (1982) and Powers & Easterling (1982)

independently suggested a m e t h o d (effectively t h e
same one) of overcoming this p r o b l e m using a tech
n i q u e initially developed by G o o d m a n (1968). T h e
model proposed by G o o d m a n (1968) is termed quasii n d e p e n d e n c e which is similar to i n d e p e n d e n c e but
is applied t o a subset of a contingency table. This
m o d e l can be applied t o e m b e d d e d matrices and
allows preservation of b o t h row and column totals
which was not possible in earlier m e t h o d s (cf. T a b l e
2.7d,f).
T h e expected transition frequencies u n d e r a m o d e l
of quasi-independence are generated by an iterative
b
m e t h o d illustrated in T a b l e 2.8 using Gingerich's
d a t a as calculated by Powers & Easterling (1982).
This model of quasi-independence can b e tested
using a chi-square statistic which has (m l ) m
degrees of freedom. A comparison of the expected
transition frequencies derived by quasi-independence
and by the Gingerich m e t h o d is given by T a b l e
2.7(d, f ) . Testing for goodness of fit of t h e quasii n d e p e n d e n c e model yields % = 35.7 (cf. 42.3 for
t h e Gingerich m e t h o d ) , which rejects t h e assump
tion of quasi-independence. In this case, t h e earlier
m e t h o d of Gingerich would have given a similar
conclusion but t h e strata w e r e deliberately chosen to
d e m o n s t r a t e o r d e r and in o t h e r cases t h e conclu
sions would be different.
n /al
1+
a = n l(m
2
2+
- 1) = 76/3 = 25.33
a ' = n / ( m - 1) = 16/3 = 5.33

4
4+
= 42/(25.33 + 15.0 + 5.33) = 0.92
= 76/(14.0 + 15.0 + 5.33) = 2.21
& 3 = 45/(14.0 + 25.33 + 5.33) = 1.01

1
&4 = 16/(14.0 + 25.33 + 15.0) = 0.29
On the second iteration:

a? = 42/(2.21 + 1.01 + 0.29) = 11.97
a
Further
2
2
= 34.23
2
3
= 13.16
a/ = 3.86
b , = 42/(34.23 + 13.16 + 3.86) = 0.82

b
2
2
= 2.62
2
3
= 0.90
2
4
= 0.27
Convergence to achieve 1% change requires 13 iterations at which point the

estimates are:
A n alternative m e t h o d h a s b e e n p r o p o s e d , al
though not widely used, to avoid p r o b l e m s caused
by e m b e d d e d matrices. This is to sample at regular
intervals such that t h e r e a r e n o structural zeros (e.g.
E t h i e r , 1975). H o w e v e r , this also creates m a n y
d, = 10.22
d = 42.61
a = 11.12
a = 3.48
bi = 0.73
b = 3.06
b = 0.80
b = 0.25
Thus a value of = a b = 11.12 x 0.25 = 2.78

These values are tabulated in Table 2.7(f)
3 4
http://jurassic.ru/
mam
- 1) = 42/3 = 14.0
l+
42.0
76.0
45.0
16.0
55
56
J. GRAHAM
problems as t h e choice of sample interval is very

important. T h e sample interval must be sufficiently
small to catch important transitions and this usually
leads to large diagonal frequencies with which test
ing the full matrix for i n d e p e n d e n c e can b e mislead
ing. This can be o v e r c o m e by testing off-diagonal
frequencies against the model of quasi-independence.
In general, there seems to be little advantage in
following this m o r e complex m e t h o d .
Having established that a succession contains s o m e
o r d e r , the next question concerns the n a t u r e of that
o r d e r and an identification of preferred transitions
(question (ii) a b o v e ) . Gingerich (1969) a t t e m p t e d to
express that order by constructing a difference matrix
(Table 2.7e) p r o d u c e d by subtracting t h e indepen
dent trials matrix (the 'expected' results) from t h e
transition probability matrix (the 'observed' results).
A n assumption is m a d e t h a t the positive elements in
this matrix have a higher t h a n r a n d o m chance of
occurring. All positive differences are used to indi
cate t h e path of the sedimentary 'cycle'. With m i n o r
alterations most later workers have employed a
similar t e c h n i q u e . H o w e v e r , small positive differ
ences can arise from a r a n d o m process and failure to
evaluate t h e significance of positive differences can
lead to the identification of t o o many preferred
transitions ( H a r p e r , 1984). Similarly, negative d e
partures are ignored by this technique even t h o u g h
they contribute to the test statistic and to t h e rejec
tion of t h e model of i n d e p e n d e n c e .
T h e currently used techniques for identifying

sources of n o n - r a n d o m n e s s are relatively crude and
d e m o n s t r a t e the need for further research. Such
techniques involve t h e identification of ' e x t r e m e '
cells, i.e. those which show t h e largest differences
between observed and expected transition frequen
cies. A simple m e t h o d (Turk, 1979; Powers &
Easterling, 1982) is to tabulate
A n alternative m e t h o d is described by Brown

(1974) and C a r r (1982). T h e x , is calculated for each
cell and that whose elimination produces the smallest
X is deleted, i.e. treated as a structural zero. T h e
remaining cells are then refitted by a quasi-indepen
d e n t m o d e l a n d the % test for quasi-independence is
recalculated. This stepwise p r o c e d u r e is continued
until a chosen level of significance. Correct identifi
cation of a single cell when it is the only cell that
d o e s not fit a quasi-independent model is a far
simpler problem than identifying a subset of cells, all
of which deviate from a model fitted to t h e other
cells. A n optimal solution to this latter problem has
yet to be found but all e x t r e m e cells are likely to be
identified. In t h e case of the Gingerich d a t a , a
chosen level of significance of a = 0.1 was exceeded
after selection of t h e first cell (sandstone over lig
nite). This shows good a g r e e m e n t with the normal
ized differences a p p r o a c h above.
2
E )IEJ .
n
T h e Z,y's are squared and s u m m e d to yield % and

they have approximately the standard normal distri
bution. A s 9 5 % of t h e standard normal distribution
falls b e t w e e n 2 . 0 , so a Z value outside this is
fairly unusual. Analysis of the Gingerich data (Table
2.9) shows that t h e primary contributor t o t h e large
X is the large n u m b e r of transitions from lignite to
sandstone.
V]
Table 2.9. Normalized differences (0, - , )/, "

y
^Mudstone
* Lignite
LIG
LS
+ 1.02
-1.84
+4.14
-0.98
-1.81
+ 1.19
-0.35
+ 1.02
-1.67
-1.07
-1.55
+ 1.02
Sandstone
MS
SS
SS
MS
LIG
LS
grams. Their aim is t o present either the raw d a t a or

statistics based o n those d a t a in a format which aids
interpretation. Figure 2.46(a) above was derived
from the raw data and retained information on the
n a t u r e of facies b o u n d a r i e s as well as n u m b e r of
transitions. O t h e r workers have a t t e m p t e d to select
from t h e raw data the more commonly occurring
transitions (e.g. Allen, 1970 and Fig. 2.47), in s o m e
cases implying preferred sequence.
Preferred sequence has been suggested mainly
following statistical analysis of d a t a , usually by plot
ting the positive elements of the difference matrix
(Gingerich, 1969; Miall, 1973; H u b e r t & H y d e , 1982)
(Figs 2.48, 2.49 and 2.50). T h e data of Gingerich
Z,j = {Oij -
57
DATA PRESENTATION AND

INTERPRETATION
Limestone
Fig. 2.48. Tree diagram constructed from the positive
elements of the differences matrix (Table 2.8d) (after
Gingerich, 1969). (Reproduced by permission of SEPM.)
Vertical a r r a n g e m e n t of different facies can be re

presented by a variety of facies relationship dia-
Where 0 is shown in Table 2.7(a), , is shown in Table

2.7(f).
/ y
D*~ A *
Bo
B -*- D
3
Difference matrix, Lower Peel Sound Formation
D A B
Fig. 2.47. Tree diagrams for Devonian fluvial sediments which show upward facies transition probabilities >0.15.
Arbitrary selection of this value is used to imply order of sequence (from Allen, 1970). (Reproduced by permission
ofSEPM.)
Fig. 2.49. Difference matrix

constructed for Devonian fluvial
sediments, Arctic Canada, following
the methodology of Gingerich (1969).
The accompanying tree diagram
distinguishes between 'major'
transition paths (solid lines) and
'minor' transition paths (dashed lines).
on the basis of values in the difference
matrix (from Miall, 1973).
http://jurassic.ru/
Conglomerate
Red sandstone
Red siltstone
Red limestone
Grey sandstone
Grey siltstone
Grey limestone
1
2
3
4
5
6
7
0.00
0.33
0.19
0.20
0.03
-0.20
-0.21
0.25
0.00
-0.23
-0.23
-0.15
-0.12
-0.17
0.02
-0.03
0.00
-0.02
0.00
-0.02
-0.02
0.02 - 0 . 0 6 -0.09 -0.14

-0.01 -0.20 - 0 . 0 6 -0.02
-0.01 0.01 0.16 - 0 . 1 3
0.00 -0.23 0.41 -0.13
-0.01 0.00 0.07 0.07
-0.01 0.25 0.00 0.11
- 0 . 0 1 0.39 0.03 0.00
=d,j
Fan cycle C
58
J . GRAHAM
Observed facies relationships
Battery point
model s e q u e n c e
Sharp
Gradational
Facies
SS
G
Palaeoflow
V
\
F
D
Preferred facies relationships
Channel
floor
Vertical
accretion
Bar
top
i
C
D
C
C
O
Vertical
accretion
fssj
o
c
In-channel
A
(b)
SS
Channel
floor
(c)
Fig. 2.50. Summary of vertical facies relationships for the Battery Point Formation, Devonian, Canada (after Cant &
Walker, 1976).
(a) Facies relationship diagram which displays the basic field data (cf. Fig. 2.46a)
(b) Preferred facies relationships based on data from a difference matrix. Higher values in the difference matrix are given
greater emphasis; thus, heavy solid arrows >0.30, light solid arrows 0.100.30, dotted arrows 0.05-0.10. A
generalized environmental interpretation has been added.
(c) A representation of (b) in the form of a vertical log with average facies thicknesses and palaeocurrents taken from the
field data. (Reproduced by permission of Canadian Journal of Earth Sciences.)
(1969) can again be used to d e m o n s t r a t e how differ

ences in interpretation might result. Gingerich in
ferred a fully developed cycle (represented by Fig.
2.48) about which r a n d o m 'deviations' might occur.
T h u s m u d s t o n e would be expected t o follow sand
stone and lignite to follow m u d s t o n e . In contrast, reanalysis of these data by C a r r (1982) showed that
most of t h e n o n - r a n d o m n e s s can be explained by t h e
upward transition from lignite to sandstone. T h u s
lignite would be t h e terminal state of r a n d o m suc
cession of fluvial facies after which the system dis
played a preferred transition to sandstone (?rapid
channel migration). Knowledge of t h e n a t u r e of t h e
facies transitions might increase confidence in the
correctness of this interpretation. T h e original inter
pretation of Gingerich clearly suggests m o r e organ
ization than is justifiable from t h e data.
O t h e r attempts to construct inferred facies rela

tionship diagrams have also used difference matrices
b u t have m a d e subjective j u d g e m e n t s on t h e statis
tical data (e.g. Figs 2.49 and 2.50). T h e assignment
of environmental interpretations to t h e different
facies in such diagrams is clearly useful b u t t h e r e is
little statistical justification for the separation of
values from t h e difference matrix into groups of
differing significance. F o r example Fig. 2.50 was
used to generate expected sequences of facies t o
which further data such as thickness of facies w e r e
a d d e d . Such an a p p r o a c h is potentially useful and
care must be t a k e n that t h e u p w a r d transitions used
a r e statistically meaningful. It is particularly valu
able to accompany presentation of t h e raw d a t a with
t h e n u m b e r of transitions and t h e n a t u r e of bound
aries (see C a n t & W a l k e r , 1976 and Fig. 2.50a).
Conglomerates
Fig. 2.51. Plot of maximum particle size accompanying a

vertical log for Devonian alluvial fan conglomerates,
Hornelen Basin, Norway. Sequential organization is
inferred from visual inspection of the data (from Steel et
http://jurassic.ru/ al., 1977). (Reproduced by permission of the Geological
Society of America.)
Fig. 2.52. Plot of maximum particle size accompanying

graphic logs for some Upper Carboniferous alluvial fan
conglomerates, northern Spain. Sequences and
megasequences are inferred from visual inspection of the
data (from Heward, 1978).
illllM
60
J. GRAHAM
Fig. 2.54. Vertical variations of

sandstone bed thickness from deep
sea fan sediments in the upper
Carboniferous of Cantabrian
Mountains, Spain. Vertical scale is
sandstone bed number and not
stratigraphic thickness. Moving
means are used to show some general
trends but 'third-order sequences' are
schematic (from Rupke, 1977).
(Reproduced by permission of the
University of Chicago Press.)
200
Sandstone
300
Bed
400
Thickness ( n
200
Sandstone
Bed
300
400
500
T h Ick ness t m m )
Sandstone bed thickness (cm)
E n v i r o n m e n t a l interpretation commonly includes

statements on the lateral a r r a n g e m e n t of facies as
d e d u c e d from vertical sequences. This involves ap
plication of W a l t h e r ' s Law of Facies, as succinctly
summarized by R e a d i n g (1978a). Inferring lateral
juxtaposition often necessitates the presence of
'gradational' contacts in vertical sequence. T h e
techniques for analysing vertical sequences d o not
normally consider t h e n a t u r e of contacts between
Fig. 2.53. Vertical profile of

sandstone bed thickness for possible
outer fan turbidites in the Lower
Carboniferous of Morocco. Thickness
values are drawn outwards from the
mid-point of each sandstone bed. The
bars indicate generalized trends from
visual inspection (after Graham,
1982). (Reproduced by permission
of Elsevier.)
http://jurassic.ru/
moving average
61
sequences
facies. This must be b o r n e in mind during interpre

tation and preferably presented on facies relation
ship diagrams such as that in Fig. 2.46.
T h u s M a r k o v analysis provides a powerful tool to
test for o r d e r in vertical sequences. Techniques for
investigating the n a t u r e of that o r d e r , where it exists,
are less well developed b u t are available and allow
for statistically definitive statements on vertical
sequence.
62
J . GRAHAM
2.4.4 Non-Markov t e c h n i q u e s f o r
sequence analysis
Presentation and analysis of vertical sequences of
rock is not limited to M a r k o v analysis. Several
o t h e r , often simpler, techniques have been employ
ed with considerable success. P e r h a p s t h e most com
m o n are those that consider vertical changes in grain
size or bed thickness. T h e former have c o m m o n l y
been employed in t h e study of conglomerates (Figs
2.24c, 2.51 and 2.52) (Bluck, 1967; Steel etal., 1977;
H e w a r d , 1978; Surlyk, 1978; Allen, 1981). T h e aim
has largely been the detection of sequences showing
a unidirectional variation of m a x i m u m clast size, i.e.
coarsening up ( C U ) or fining up ( F U ) sequences.
T h e detection of such sequences has often been by
simple visual inspection of t h e d a t a but they are also
susceptible to techniques such as moving m e a n s .
Vertical changes in layer thickness have also b e e n
useful, particularly in turbidite successions (Ricci

Lucchi, 1975b; R u p k e , 1977; S h a n m u g a m , 1980;
G r a h a m , 1982). T e c h n i q u e s of presentation show
considerable variation, e.g. the vertical scale may be
stratigraphic thickness as in Fig. 2.53 or sandstone
n u m b e r as in Fig. 2.54. A criticism of many of these
presentations is that ' t r e n d s ' a r e designated from
visual inspection of the data (Fig. 2.53, Fig. 2.54
third o r d e r sequences) without any statistical justifi
cation. Techniques such as moving m e a n s (Fig. 2.54)
can be useful h e r e although these should always be
presented along with t h e original d a t a as averaging
will lead to displacement of the peak values that are
commonly used to delimit packets of sediment
(rhythms or cycles). O n e must t a k e care that com
p a r e d units of thickness have similar definition and
that their significance is u n d e r s t o o d (see Section
2.2.3).
Grain size determination and

interpretation
JOHN MCMANUS
3.1
INTRODUCTION
T h e size of the c o m p o n e n t particles is one of the

fundamental textural characteristics of all fragmen
tary deposits and their lithified equivalents. F r o m
t h e earliest days of observation and recording of
geological features, terms such as 'coarse', ' m e d i u m '
or 'fine' grained have b e e n applied to unconsoli
dated deposits. A l t h o u g h considered a useful litho
logical discriminator for tracing individual horizons
during geological m a p p i n g , little systematic study of
grain size characterization and m e a s u r e m e n t oc
curred before t h e end of t h e nineteenth century. By
that time there was already an appreciation that very
substantial currents of water were necessary to trans
port coarse sediments but, without systematic m e a n s
of establishing precisely t h e sizes of particles and the
range of particle sizes within a deposit, little scienti
fic advance was m a d e .
In general t e r m s , 'size' of particles is not readily
defined as it is a m e a s u r e of t h e dimensions which
best describe a specific g r o u p of particles. A t one
e x t r e m e the particle dimensions may exceed one
m e t r e , b u t at t h e o t h e r are t h e very fine particles less
t h a n o n e m i c r o m e t r e in diameter. A cube may be
best described by its edge length, a sphere by its
d i a m e t e r , a rod p e r h a p s by its intermediate axis and
a flake by its projection area. T h u s 'size' is partly
d e p e n d e n t on s h a p e , a fact which was gradually
recognized during t h e early years of t h e present
century.
T h e m e t h o d s used in determination of size vary
widely from calipers on t h e coarsest fragments,
through sieving and techniques d e p e n d e n t u p o n set
tling velocity, t o those detecting changes in electrical
resistance as particles are passed through small elec
trolyte-filled orifices. N o single technique of assess
ing particle size is applicable t h r o u g h o u t t h e entire
size spectrum, and each is suited to specific size
ranges.
A l t h o u g h when measuring pebbles to d e t e r m i n e
axial lengths individually, relatively small n u m b e r s
of grains are considered, in most m e t h o d s large
n u m b e r s of grains are examined so that a statistically

meaningful set of n u m b e r s is obtained to character
ize t h e sample.
T h e techniques of processing t h e d a t a on grain
size were largely explored during t h e 1920s and
1930s when a series textural classifications was in
troduced. In their simplest forms these classifica
tions indicate average grain size, and the degree and
form of the spread a r o u n d that average. Statistical
analysis is aided by m e a n s of a simple transforma
tion of size from a metric scale to a logarithmic o n e
which enables application of b o t h graphic and m o
m e n t statistical techniques. Explored initially for
sand-dominated assemblages, the m e t h o d s were re
fined during t h e 1950s and applied to thin section
analysis of lithified sediments during the early 1960s.
Fresh techniques of exploring t h e information on
grain populations with a view to interpreting deposi
tional e n v i r o n m e n t or transportation experienced by
t h e deposits continue to be introduced with varying
degrees of success. M a n y have a p p e a r e d , b e e n ex
plored and found applicable only u n d e r certain re
stricted conditions.
E v e n t h e most sanguine grain size enthusiast would
agree that n o universal solution exists as yet to
enable the sedimentologist unequivocally to distin
guish depositional e n v i r o n m e n t s in ancient deposits
on grain size criteria alone. Nevertheless, an enor
m o u s a m o u n t of information about a sedimentary
deposit may be o b t a i n e d from systematic examina
tion of t h e multiple sub-populations of which most
are formed. Specific sub-populations may be sourceor process-diagnostic, a factor which frequently
emerges from regional surveys.
F r o m t h e outset it is most important that t h e
investigator should decide precisely what informa
tion is required from t h e sediments to be analysed
( M c C a v e , 1979a). Analysis solely to obtain numeri
cal assessment of the texture of a deposit is unlikely
to satisfy t h e sedimentologist but this information
may be all that is required t o d e m o n s t r a t e to a
fisheries expert t h e potential value of a site for the
introduction of an economically important species
63
http://jurassic.ru/
64
J. MCMANUS
GRAIN SIZE DETERMINATION
such as Nephrops (Scampi). In assessment of the

suitability of a deposit for supplying specific coarse
concrete aggregates or finer m o r t a r sands, very pre
cise r e q u i r e m e n t s are laid down by the construction
industry. T h e s e often d e m a n d restricted ranges of
particle sizes in fixed p r o p o r t i o n s within the gravel.
In tracing characteristic source-specific sub-popula
tions of sediment passing through a river system t h e
closest possible spacing of sieves may b e r e q u i r e d .
In estimating t h e potential 'activity' of a soil it may
be necessary to d e t e r m i n e the m a x i m u m projection
area of t h e particle surfaces of various sizes t o assist
in the assessment of potential cationic exchanges;
scanning electron microscopy may be necessary.
In this chapter attention is devoted to t h e techni
ques used commonly by sedimentologists to deter
mine sizes of particles, i.e. sieving, pipetting, settling
and Coulter counting, coupled with optical micro
scopy. W h e r e o t h e r a p p r o p r i a t e m e t h o d s exist refer
ence will be m a d e t o useful sources of information.
3.2 S A M P L E P R E P A R A T I O N
T h e selection of materials to be processed is m a d e in
t h e field and usually collections comprising many
samples arrive in the laboratory at any o n e time.
T h e initial p r o c e d u r e in preparing for analysis is t h e
systematic checking of t h e materials to e n s u r e that
identification n u m b e r s and labels are all p r e s e n t and
legible. This is most readily achieved by laying out
cores, sample bags, bottles or blocks of material
sequentially. A n y internal n u m b e r i n g , unless en
graved o n indestructible material, may rapidly be
c o m e obliterated, and relabelling with external labels
is essential. G a p s in numerical sequences may b e
identified and samples lacking clear labels may at
this stage be r e t u r n e d to their correct sequential
position. If identification of misplaced samples can
not be completed with certainty at this stage t h e
samples have little value for subsequent analysis
and should be discarded. B e t t e r to have n o d a t a
t h a n unreliable data.
F u r t h e r p r e p a r a t i o n of all sediments relates t o t h e
form of size d e t e r m i n a t i o n to be carried out. Lithi
fied materials may require little m o r e than decision
o n t h e orientations of thin sections n e e d e d for later
examination u n d e r the optical microscope, but
special slide p r e p a r a t i o n and cementing media may
be required, particularly if soluble minerals are
thought t o be present (see C h a p t e r 4 ) .
Prior to examination of large particles s o m e

cleaning may be necessary. In unconsolidated
materials washing in running t a p water may be suffi
cient to r e m o v e u n w a n t e d m u d d y coatings (assum
ing d a t a from t h e m u d s are not r e q u i r e d ) . Lithified
coarse sediments frequently release large fragments
once cements a r e w e a k e n e d in w a r m dilute hydro
chloric acid, but care must be t a k e n that t h e clasts
themselves are not susceptible to attack.
Sands derived from b e a c h e s , estuaries or t h e sea
bed may contain quantities of salt within their inter
stitial waters. Unless r e m o v e d by washing the salts
b e c o m e deposited during drying before sieving,
cementing adjacent particles together, to p r o d u c e
misleading analyses. If n o very fine grains a r e pre
sent in t h e sediment t h e sands may b e freely washed
in well-agitated water to r e m o v e the salts. Normally
t h r e e washings, each in o n e litre of distilled or
deionized water, a r e n e e d e d to r e m o v e the salt from
about 200 g of sediment with t h o r o u g h stirring
(Buller & M c M a n u s , 1979). It is, of c o u r s e , impor
tant that n o particles are lost during each process of
decanting t h e water after washing.
achieved since. Interpretations of settling character

istics based on t h e most m i n u t e elemental particles,
of which many thousands may combine naturally to
p r o d u c e floes or aggregates, may give a very mis
leading guide to t h e energy levels in the depositional
e n v i r o n m e n t , for floes settle at much greater rates
t h a n their individual c o m p o n e n t particles.
Size analysis of fine particles therefore presents
p r o b l e m s , for the pre-analytical preparations may
largely d e t e r m i n e t h e ultimate results obtained.
Nevertheless, most investigators r e m o v e t h e salts
before subjecting t h e samples to pipette, hydro
m e t e r or C o u l t e r analysis, in all of which s o m e
dispersing agent is introduced to ensure separation
of individual particles.
R e m o v a l of water salts from fine sediments is best
achieved using dialysis. T h e sample, placed in a
dialyser bag, is suspended in distilled or deionized
water, circulation of which encourages osmotic ex
change of t h e salts over a period of several days.
Ideally m a n y samples are dialysed simultaneously.
O n c e sample p r e p a r a t i o n has been completed t h e
simplest analyses may be performed on the largest
particles.
W h e n fine materials are present it is necessary to

s e p a r a t e t h e m by wet sieving so that sands and the
silt/clay fraction may be examined separately using
different size d e t e r m i n a t i o n techniques. It is most
i m p o r t a n t that separation of t h e fines be carried out
before drying of the sediment for, o n h e a t i n g , silts
and clays p r o d u c e crusts or durable pellets. A l t h o u g h
these may be later b r o k e n down physically t o release
individual particles there is n o g u a r a n t e e that indivi
dual flakes of clay would b e c o m e separated by p u r e
ly physical m e a n s . Division of t h e sediment into two
fractions at an early stage is therefore r e c o m m e n d
e d . E a c h fraction must be labelled to p e r m i t later
recombination of partial analytical results.
Silt and clay sized particles d o m i n a t e m a n y m a r i n e ,
estuarine and lacustrine deposits. F r e q u e n t l y the
behaviour of t h e finest size fractions is d e t e r m i n e d
by t h e concentrations, identities and valencies of
salts in t h e interstitial w a t e r s . W h e t h e r t h e clays
remain as discrete particles or cluster together to
form floes or aggregates with diameters much larger
t h a n t h e individual c o m p o n e n t particles is often a
function of these waters. Modification of t h e fluids
t h r o u g h washing thus n o t only changes the salt con
centrations, but may also induce separation or ag
gregation of t h e particles, so that s u b s e q u e n t size
analysis may not indicate t h e natural interrelation
ship between t h e particles during deposition or
3.3 D I R E C T M E A S U R E M E N T O F
GRAIN SIZE
T h e analysis of particle sizes of coarse unconsolid
ated sediments may be achieved through direct
m e a s u r e m e n t of individual pebbles. T h e lengths of
representative diameters or axes are d e t e r m i n e d
with t h e aid of vernier calipers (Briggs, 1977). F o r
every p e b b l e several possible diameters may be
recognized along t h e t h r e e principal axes of the
p e b b l e . A nominal d i a m e t e r may also be derived
from the volume of t h e p e b b l e .
T h e particle is placed o n a flat surface and t h e
length of t h e intermediate axis, / , is d e t e r m i n e d as
t h e shortest visible diameter. T h e length of the
largest axis, L , at right angles to / is next m e a s u r e d ,
and rotation of t h e particle by 90 about that axis
reveals the shortest axis, S which may then be
directly m e a s u r e d . It should be noted that L is not
t h e greatest possible dimension of the pebble but is
quite strictly defined in geometric terms. T h u s t h r e e
mutually perpendicular axes may be used to charac
terize t h e pebble (Fig. 3.1). Addition of the three
lengths, / , L and 5 , and division by three yields a
m e a n d i a m e t e r D for t h e particle. A second mean
M
http://jurassic.ru/
F
11111
65
d i a m e t e r is derived by immersing t h e pebble in

water to d e t e r m i n e t h e volume of water displaced,
from which t h e volumetric d i a m e t e r , D is c a l c 'ated
using t h e expression
v
volume = ^ r D .
6
v
Such m e a s u r e m e n t s should be r e p e a t e d for 1 0 0 - 4 0 0

pebbles at a site. Thereafter some workers analyse
t h e results according to t h e n u m b e r s of pebbles
falling into specific categories. H o w e v e r , because it
is t h e weight distribution rather than t h e frequency
distribution which d e t e r m i n e s sediment behaviour
during transport and deposition t h e weight of the
pebbles falling into each size class should b e used for
t h e purposes of comparison. In most cases the length
of / provides a useful assessment of t h e m e a n dia
m e t e r , and if determinations a r e to be m a d e in the
field this d i a m e t e r provides a useful m e a s u r e of
average size.
3.4
SIEVING
A l t h o u g h it may be advantageous for specific pur

poses to examine individual pebbles, u n d e r most
circumstances t h e sedimentologist seeks to establish
the character of an entire deposit, not simply the
coarser fractions. F o r such purposes a m o r e general
form of mechanical analysis to d e t e r m i n e grain size,
t h e sieving m e t h o d , is used ( K r u m b e i n & Pettijohn,
I
Fig. 3.1. The principal axes measured in characterizing
pebble size.
Table 3.1. Typical sieve analysis record sheet
2000
10
-0.75
12
-0.49
14
-0.27
16
-0.00
18
0.23
22
0.52
25
0.74
30
1.00
36
1.24
44
1.50
52
1.76
60
1.99
72
2.24
85
2.49
100
2.72
120
3.01
150
3.26
170
3.49
200
3.71
240
3.91
BS sie\ie. analysis
PG
VCS
3
oo
1
1000
CS
CS
E
3
00
i
2
500
Ta> Estuary sec iments programrr e
MS
MS
E
3
on
1
4
250
FS
FS
3.4.1 Dry sieving

Perhaps t h e most commonly used m e t h o d of deter
mining particle sizes, dry sieving, is subject to p o t e n
tial errors from m a n y sources.
(a) D u r i n g t h e drying process particle
aggregation
m a y occur and it is most i m p o r t a n t that sieve resi
dues should be checked, using a h a n d lens w h e r e
necessary, to detect t h e presence of aggregates which
form clusters considerably larger t h a n t h e original
single c o m p o n e n t grains.
(b) Thorough
cleaning of t h e sieve m e s h e s is
i m p o r t a n t as retained particles severely restrict t h e
a p e r t u r e spaces available for grains t o pass t h r o u g h .
(c) Overloading of t h e sieves restricts t h e oppor
tunity for particles t o progress down t h e nest t o an
a p p r o p r i a t e m e s h . T h e greatest load on a sieve
should n o t exceed 46 grain d i a m e t e r s ( M c M a n u s ,
Pan
(loss)
E
3
on
1
8
125
VFS
http://jurassic.ru/
||^
| y ^ ^^^^^^^^^^^^^^^^^
Original weight
Sieving loss . . .
VFS
E
3
on
1
16
62
St/Cl
Total
(I
VCS
Fig. 3.2. Sieve nest and shaker (photograph Fritsch).
be calculated. A n example of such a record sheet is

provided in T a b l e 3 . 1 .
PG
" Recombine fractions to full cp units and store
St/Cl
Cumulative
(%)
.2?
Weight %/
Wentworth
classification
-1.04
Weight/
Wehtworth
classification
Weight
retained (g)
Approx.
value (urn)
T h e material retained in each successive sieve is

emptied in turn on to a sheet of glazed p a p e r , the
sieve t a p p e d gently in a direction diagonal t o t h e
meshes and swept with a p p r o p r i a t e sieve brushes
(camel hair for fine a p e r t u r e s , brass for coarse
screens) to dislodge particles which have b e c o m e
firmly held. E a c h fraction of sediment o b t a i n e d is
weighed to 0.01 g. T h e material retained on each
sieve screen is weighed in turn and the weight of any
residue in the final pan is also d e t e r m i n e d .
Most w o r k e r s find it convenient to r e c o r d their
sieving analysis d a t a systematically on forms de
signed for t h e p u r p o s e . T h e sieve m e s h sizes, raw
weights, weight percentages and cumulative percen
tages, finer or coarser than t h e specific sieve, may be
displayed. Likewise, further groupings such as per
centage of coarse sand o r of very fine sand may also
Approx.
value (mm)
1961, Folk, 1974b, Buller & M c M a n u s , 1979). With

a p p r o p r i a t e sieves, particles varying b e t w e e n 0.002
and 250 m m may be separated into regular size class
intervals. Most c o m m o n l y sieving is used for size
determination in t h e p e b b l e and sand ranges, i.e.
particles coarser t h a n 0.063 m m .
F o r t h e coarser particles sieve screens a r e formed
of plates or strong wire of stainless steel or brass,
and finer wire meshes are used for smaller particles.
B e t w e e n t h e wires are square openings, the n u m
bers of which per unit length give t h e m e s h n u m b e r
and t h e diagonal t h e nominal size.
T h e coarsest sieve required is placed at t h e t o p of
a nest of sieves in which t h e screen openings b e c o m e
progressively smaller d o w n w a r d s . A p a n is placed
b e n e a t h t h e lowest sieve to retain t h e 'fines' which
pass through t h e entire column. F o r the most detail
ed analysis the meshes a r e arranged at t h e closest
possible intervals, b u t greater spacings by size may
b e used if less detail is required.
T h e sample for testing is placed on t h e u p p e r m o s t
sieve after weighing, t h e retaining lid closed and the
nest of sieves arranged in a mechanical shaker (Fig.
3.2). T h e nest is agitated by t h e shaker for a pre
d e t e r m i n e d time interval? usually 1520 m i n u t e s . It
is most important that t h e base of t h e sieve nest is
arranged exactly parallel to t h e shaker base and is
firmly held in position during agitation ( M e t z , 1985).
N o t u n c o m m o n l y only half of the sieves required
may b e m o u n t e d o n t h e shaker at a t i m e , so t h e p a n
residue from t h e coarser fraction is released into t h e
u p p e r sieve of t h e finer part of the nest in o r d e r to
complete the analysis. This nest also requires a
terminal p a n .
<t>
values
J . MCMANUS
Sieve
number
66
68
J . MCMANUS
1965). Overloading may also cause mesh distortion,

a factor which is most evident on coarse screens.
Distortion may be avoided by following the maxi
m u m sieve loadings r e c o m m e n d e d in B S 1377:1975
(Table 3.2). E x a m i n a t i o n of t h e condition of t h e
meshes in t h e sieve nest should always be carried out
before undertaking a major sieving p r o g r a m m e . F o r
most sands about 100 g of material is a d e q u a t e for
sieving analysis but larger weights are required for
coarse gravelly deposits.
(d) T h e ideal duration of agitation by mechanical
shaker ( R o - t a p or Frisch) is still a m a t t e r of discus
sion. In most laboratories standardization is to 15 or
20 minutes but s o m e researchers r e c o m m e n d only
1015 minutes (Friedman & J o h n s o n , 1982, Lewis,
1984) and still others suggest t h a t significant changes
in t h e final analytical figures obtained may be de
tected after 35 minutes of shaking (Mizutani, 1963).
For most purposes acceptable reproducibility of
analyses is obtained after 20 minutes.
(e) T h e sieving t e c h n i q u e is strongly d e p e n d e n t
u p o n sieve mesh s h a p e . Platey particles such as mica
flakes may readily pass diagonally through meshes
which m o r e nearly spherical grains of identical inter
m e d i a t e diameters cannot pass as a result of the
length of their short d i a m e t e r s . T h u s size d e t e r m i n a
tion using sieves is partly controlled by t h e particle
s h a p e ( R i t t e n h o u s e , 1943). Substantial deviation of
Table 3.2. List of maximum permissible sieve loadings,
after BS 1377:1975
BS sieve
mesh
(mm)
Maximum
weight
(kg)
Sieve
diameter
(mm)
20
14
10
6.3
5
3.35
2.0
1.18
0.600
0.425
0.300
0.212
0.150
0.063
2.0
1.5
1.0
0.75
0.5
0.3
0.200
0.100
0.075
0.075
0.050
0.050
0.040
0.025
300
300
300
300
300
200
200
200
200
200
200
200
200
200
particle shapes from spheres may lead to under

estimation of t h e characteristic intermediate dia
m e t e r according to Ludwick & H e n d e r s o n (1968).
H o w e v e r , it takes longer for irregularly s h a p e d par
ticles to pass down a sieve column than grains which
a r e smooth surfaced or e q u a n t ( K e n n e d y , Meloy &
D u r n e y , 1985). Visual inspection of sieve residues
should b e u n d e r t a k e n t o confirm the presence or
absence of substantial proportions of strongly nonspherical particles in the sediment.
In a better a t t e m p t to define t h e intermediate
d i a m e t e r (I) of particles retained on sieves of speci
fic nominal diameters (> ) K o m a r & Cui (1984)
d e m o n s t r a t e d that the relationship
m e t h o d is not r e c o m m e n d e d . T h e satisfactory dis

persion of initially oven dried sediments as recom
m e n d e d in BS 1 3 7 7 is not guaranteed by this m e t h o d .
If further size analysis is to be u n d e r t a k e n the best
p r o c e d u r e is to use two identical sub-samples. O n e
is wet sieved as a b o v e , and both the mud and sand
fractions dried and weighed to establish their relative
p r o p o r t i o n s . T h e second sub-sample is wet sieved
with sand retention for drying and weighing while
the m u d fraction, whose proportional contribution
to t h e whole sediment is now k n o w n , remains in a
receptacle for further analysis.
sv
/ = 1.32
sv
provided a m e a n s of obtaining a m o r e closely r e p r e

sentative grain d i a m e t e r t h a n currently given by the
sieve mesh itself. This correction factor may be
applied to metric measures of diameter.
3.4.2 Wet sieving

Since many sediments contain mixtures of gravels,
sands and finer particles t h e dry sieving t e c h n i q u e
may be a p p r o p r i a t e for examination of only part of
t h e whole assemblage of particles. T h e finer particles
require o t h e r m e t h o d s of analysis. Separation of the
coarse from the fine fractions is customarily m a d e at
63 urn, which is t h e most commonly used lower limit
of dry sieving. H o w e v e r , it is not possible to analyse
satisfactorily both the coarse and t h e fine fractions
fully once t h e split has b e e n achieved.
S o m e workers suggest that the entire sediment
sample should be oven dried at 110C and weighed
to 0 . 1 % before being immersed in water containing
a dispersant such as sodium h e x a m e t a p h o s p h a t e .
T h e sample is periodically agitated in t h e water for
over an h o u r before being washed through 2 m m
and 0.063 m m stainless steel meshes using wash
bottles containing dispersant solution. T h e fines
continue to be washed through t h e sieve until t h e
water runs clear. T h e residue (not m o r e than 105 g)
on t h e 0.063 m m sieve is dried at 110C and sieved as
a b o v e . T h e total fines content is d e t e r m i n e d as t h e
difference between t h e initial and the retained
material weights. H o w e v e r , many clay sized par
ticles, whether organic or inorganic, b e c o m e struc
turally altered at t e m p e r a t u r e s approaching 100C
so if any further study is to be u n d e r t a k e n this
69
U s e of t h e equation is based on t h e precept that

particles are dominantly spheres and are of identical
densities. T h e assumption that most are of quartz
permits c o m p u t a t i o n of equivalent grain diameters.
In practice natural sediments are rarely composed of
spherical grains, and most contain assemblages of
many shapes. Particles of identical composition and
d i a m e t e r settle at greatly differing velocities if their
shapes or surface textures differ, for the drag coeffi
cients resisting passage through the water vary with
both of these properties.
3.5.1 Pipette m e t h o d
3.5 S I Z E A N A L Y S I S B Y
SEDIMENTATION METHODS
Grain size analysis of fine sediments d e p e n d s not on
direct m e a s u r e m e n t of the particles themselves but
rather upon indirect c o m p u t a t i o n s of diameters
based on observation of t h e grain behaviour in fluids
or t h e response of t h e fluids to displacement by the
grains. T h e principal m e t h o d s based on the speed
with which particles settle through fluids yield set
tling velocities from which equivalent grain dia
m e t e r s are c o m p u t e d . Characterization of particles
in t e r m s of their dynamic behaviour is thought by
many to be m o r e environmentally significant than
direct m e a s u r e m e n t of particles with calipers or
sieves. In consequence t h e use of sedimentation
columns o r tubes to d e t e r m i n e the fall velocities of
sediment particles has b e c o m e very popular. T h e
t e c h n i q u e is relatively quick for coarse sediments
and may also be relevant for silt sized particles,
although time for completion of analyses increases
greatly within the silt size range.
C o m p u t a t i o n of t h e diameters of grains from a
knowledge of their settling velocities is d e p e n d e n t
u p o n the exploitation of Stokes' Law of settling.
W h e n a particle in static water settles at a constant
velocity t h e gravitational force exerted on t h e par
ticle is balanced by fluid resistances r e p r e s e n t e d by
viscosity and particle drag coefficient. T h e balance is
normally r e p r e s e n t e d within t h e equation
2
d (p
p)g
1 8 M-
w h e r e V is t h e settling velocity, d t h e particle dia

m e t e r , p and p the densities of the grain and water
respectively, g is the gravitational acceleration and u,
is the dynamic viscosity of the fluid.
Inexpensive size analysis of naturally occurring fine

sediments or of material obtained from wet sieving
of a sediment containing significant fines is most
satisfactorily achieved by the use of the pipette
m e t h o d ( K r u m b e i n & Pettijohn, 1961; G a l e h o u s e ,
1971b; Folk, 1974b). In essence this technique re
lies o n t h e fact that in a dilute suspension, parti
cles settle through a column of water at velocities
which are d e p e n d e n t u p o n their size. If a material
behaves according to Stokes' Law t h e n , by repeat
edly sampling at a fixed depth below the surface
progressively finer and finer sediments are present at
t h e sampling d e p t h . T e m p o r a l variations of solid
concentrations at that level indicate the relative
a b u n d a n c e of particles whose diameters may be
calculated.
A s particles decrease in diameter through the silt
and clay sizes they b e c o m e increasingly cohesive as
surface ionic charges grow in relative significance. In
natural environments such as rivers and estuaries,
these materials form aggregates or floes within which
interparticulate cohesion may be strong. T h e size
characteristics of t h e floes may be examined by
permitting settling in natural waters in which sedi
m e n t and ionic concentrations may be high (Peirce
& Williams, 1966). Likewise where organic particles
play potentially important roles in sedimentation,
settling in low sediment and ionic concentrations
may be useful ( D u c k , 1983). H o w e v e r , if t h e size of
t h e smallest c o m p o n e n t particles in a
flocculated
sediment is to be d e t e r m i n e d , it is necessary to
introduce a dispersing or peptising agent. U n d e r
most circumstances this is o n e of the first stages in
the preparation of material for pipette analysis.
http://jurassic.ru/
Sodium h e x a m e t a p h o s p h a t e solution is perhaps

t h e c o m m o n e s t dispersing agent used sedimentologically. It is p r e p a r e d by dissolving 33 g of sodium
70
J . MCMANUS
h e x a m e t a p h o s p h a t e and 7 g of sodium c a r b o n a t e in
distilled water to give one litre of solution. Although
many variations of concentration have been tried
that found most useful is 50 ml of the solution to
1000 ml of distilled water. Alternative dispersants
used in some laboratories are Calgon (2 g per 1000
ml water) and Teepol (4 drops per 1000 ml of
water).
A sample of 20 g of fine sediment is suspended in
a 1000 ml measuring cylinder charged with water
containing dispersant, and thoroughly mixed through
end over end rotation or by m e a n s of a manual stirer
which travels from t h e base to the t o p of the fluid
column. A s t h e suspension begins standing a timing
device is started.
A pipette is inserted gradually into the fluid so
that its inlet is 20 cm below the surface and a volume
of 20 ml is withdrawn 58 s from the start of settling.
T h e fluid is released into a n u m b e r e d 50 ml b e a k e r
and any particles retained within the pipette washed
into the b e a k e r using distilled water.
Successive 20 ml aliquots are extracted from the
column at time intervals which calculations have
shown reveal particles of known d i a m e t e r (Table 3.3
after K r u m b e i n & Pettijohn, 1961). T h e aliquots are
withdrawn from specified depths at the time inter
vals shown for a full analysis of the fine particle
content.
If n o more than the contents of m e d i u m silt, fine

silt or clay are required, aliquots may be withdrawn
after the a p p r o p r i a t e time intervals and t h e relative
a b u n d a n c e calculated from differences in weights of
suspension in each. In establishing s a n d : s i l t : c l a y
ratios of sediments it may be necessary to withdraw
samples no m o r e often than after 58 s at 20 cm
(0.063 m m ) and 123 min at 10 cm (0.004 m m ) .
In each case the pipette should be gently inserted
and withdrawn from t h e fluid in o r d e r to minimize
disturbance. T h e lowering and extraction phases
should each take about 10 s. Fluid withdrawal is
most readily achieved with the aid of a manually
o p e r a t e d vacuum device (Fig. 3.3). B e a k e r s con
taining the fluids are placed in a ventilated oven and
dried at 100C for at least 24 hr, cooled in a desic
cator, and weighed to 0.001 g.
In calculating t h e weight of sediment retained in
each withdrawn aliquot, allowance must be m a d e
for the dispersant. T h e simplest computation is
achieved by comparing the weights of successive
Table 3 . 3 . Table of settling times, after Krumbein &

Pettijohn (1961)
Phi
mm
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
10.5
11.0
0.063
0.0312
0.0156
0.0078
0.0039
0.00195
0.00098
0.00049
urn
63
31.2
silt
15.6
7.8
3.9
1.95
clay
0.98
0.49
Depth (cm)
20
20
10
10
10
10
10
10
10
10
10
10
10
5
5
min
1
2
4
8
16
32
32
65
1
1
3
7
15
31
1
3
5
10
21
42
42
25
s
58
56
56
52
42
71
withdrawals. As both contain the same quantity of

dispersant the difference represents the weight within
the size interval concerned. Since each aliquot forms
2 % of the original sample the full size distribution
may be calculated through continued withdrawals to
the finest required size. T h e total weight of fine
sediment undergoing analysis is fifty times the sedi
ment extracted in t h e initial (58 s) sample.
Because the m e t h o d d e p e n d s on Stokes' Law the
dynamic viscosity of t h e water is i m p o r t a n t . Visco
sity varies greatly with t e m p e r a t u r e and t h e table of
timings provided is calculated for analysis at the
standardized t e m p e r a t u r e of 20C. A s full analysis
may t a k e several days to complete it is very impor
tant that it b e carried out in a thermally regulated
laboratory. In many countries stabilization may be
possible but not to t h e relatively warm 20C. Modi
fied tables may be established for lower t e m p e r a
t u r e s , t h e greater viscosities requiring extension of
t h e sampling times as settling velocities decrease as
t h e t e m p e r a t u r e falls.
T h e earliest sedimentation tube widely used is the

E m e r y tube ( E m e r y , 1938). Particles released simul
taneously at t h e t o p settle through a broad t u b e
which narrows into a smaller d i a m e t e r tube at the
base. T h e heights of accumulation at known time
intervals are m e a s u r e d by optical micrometer and
the particle sizes calculated from these figures.
T h e introduction of a pressure transducer to de
t e r m i n e the t e m p o r a l variations of weight in the
water column above a specific level permitted elec
trical recorders t o be used. Initially, this modification
involved simultaneous comparison of the weights of
identical columns of water with and without sedi
m e n t ( W o o d s H o l e Rapid Sediment Analyser:
Zeigler, Whitney & H a y e s , 1960), but improve
ments in transducer technology have since enabled
t h e devices to be used in single tubes. T h e gradual
decrease of weight of material in t h e column through
time as sediment passes the transducer levels during
settling enables estimation of t h e particle size ranges
involved.
T h e quantities of initial sample used in different

centres varies from 4 to 35 g per 1000 ml b u t in
practice t h e most satisfactory concentrations from
the viewpoint of reproducibility have been found to
be between 10 and 20 g p e r 1000 ml. T h e higher the
concentrations the greater t h e possibility of entering
into t h e realms of h i n d e r e d settling and settling
convection in which upward motion of escaping
waters impedes settling ( K u e n e n , 1968).
This time consuming analytical p r o c e d u r e has t h e
advantage of simplicity and requires little specialist
e q u i p m e n t . It also provides sufficient time to permit
several analyses to be carried out simultaneously.
Most workers find that four to six sets of analyses
can be dealt with even if a very detailed withdrawal
p a t t e r n is r e q u i r e d . If for any reason a withdrawal
time is missed t h e entire p a t t e r n of settling may be
restarted by restirring and allowing t h e material to
r e c o m m e n c e settling until t h e required time interval
has elapsed. Resuspension may also permit t h e
analyst to leave the laboratory for sleep if the timings
are carefully pre-arranged.
A further variation introduced a balance pan

within and near t h e base of the t u b e . T h e varying
weights of particles retained through time are re
corded in t h e sedimentation balance m e t h o d
(Sengupta & V e e n s t r a , 1968; T h e i d e et al., 1976).
In t h e sedimentation tube technique t h e particles
a r e released simultaneously from the water surface,
a process achieved by holding a 25 g sample on a
platten by m e a n s of a wetting agent and lowering it
into t h e water surface. T h e sample is kept small to
minimize bunching of the cloud of settling particles.
If the concentration exceeds 1% hindered settling
occurs and this may decrease settling velocities by
5 % below those of individual identical particles
(Richardson & Z a k i , 1954). T h e diameter of the
t u b e is i m p o r t a n t h e r e , b r o a d tubes being required
for analysis of coarse sediments ( C h a n n o n , 1971).
3.5.2 Sedimentation tube

T h e second widely used technique based on settling
velocity is that of t h e sedimentation t u b e . H o w e v e r ,
unlike t h e pipette t e c h n i q u e , this m e t h o d is not
confined to analysis of silts and clays, but is com
monly applied to the sand fraction of the sediments.
Fig. 3 . 3 . Settling column, pipettes and beakers for

estimation of particle size by withdrawal.
http://jurassic.ru/
Since most sedimentation tubes a r e at least 2 m in

height problems arise of ensuring static water, for
such columns develop internal convection currents
unless maintained in thermally stable conditions.
T h e reliability of the sedimentation t u b e m e t h o d s ,
as d e t e r m i n e d by good reproducibility of results
from r e p e a t e d analysis of the same samples and by
analysis of multiple sub-samples from individual
sediments, has been recorded by many workers.
H o w e v e r , interpretation of t h e m e a s u r e m e n t s ob
tained is less clear. A l t h o u g h fall velocities of indivi
dual particles may permit confident calculation of
particle d i a m e t e r s , the behaviour of clusters of par-
J . MCMANUS
t i d e s of a range of sizes is less easy to calculate. In

most cases individual tubes require to be calibrated
against well characterized particles such as single
spheres (Zeigler & Gill, 1959) or clusters of spheres
of single sizes and combinations of sizes (Schlee,
1966) before their performance may be k n o w n . Total
calibration against the full range of particle size
combinations and particle shapes is impracticable.
In practice t h e particle sizes in the sediment are
c o m p u t e d from the weights settled at specific time
intervals. T h e m e a s u r e d settling velocities are con
verted into 'equivalent sedimentation d i a m e t e r s ' , or
the diameters of spheres settling at the same rate as
t h e natural particles being tested ( G i b b s , M a t t h e w s
& Link, 1971).
O n e of the most relevant particle characteristics
derived from sieve analysis is the size of t h e inter
mediate diameter. Investigation of settling of natural
quartz sands enabled B a b a & K o m a r (1981) to o b
tain a relationship:
V
= 0.977
13
deviations related to the presence of heavy minerals

with densities considerably greater t h a n quartz and
also to mica flakes whose shapes differ from t h e
spherical.
3.6 C O U L T E R C O U N T E R
A second technique which provides t h e possibility of
analysing sand, silt and clay sized particles in t h e size
range 0.00050.85 m m d e p e n d s on the detection of
variation in electrical current as fluids containing t h e
particles are passed through a p e r t u r e s of various
d i a m e t e r s . T h e principle on which t h e Coulter
c o u n t e r o p e r a t e s is that t h e particles are s u s p e n d e d
in an electrolyte which is drawn t h r o u g h t h e aper
t u r e . In t h e absence of particles an electrical current
across t h e a p e r t u r e r e m a i n s constant, but w h e n
particles of low electrical conductivity, such as
q u a r t z , pass the a p e r t u r e they cause current fluctua
tions, d e p e n d i n g upon their volume. T h e stream of
particles generates a series of pulses of c u r r e n t , u p
to 5,000 s ~ , which may be automatically recorded
as n u m b e r s and particle volumes.
1
in which V is t h e settling rate of t h e equivalent

sphere of d i a m e t e r , / , and V is the m e a s u r e d
settling velocity. Combining this relationship with
that of Gibbs et al. (1971) enabled K o m a r & Cui
(1984) to c o m p u t e intermediate grain d i a m e t e r s
rather than equivalent sedimentation d i a m e t e r s
using the expression:
s
2V0.003114 V p + fe(ps 4
in which p and p are the densities of water and the

grains, and p, the dynamic viscosity of water.
In early comparisons of sizes d e t e r m i n e d by siev
ing and settling techniques Sengupta & V e e n s t r a
(1968) and Sanford & Swift (1971) concluded that in
general t h e results were very similar but that settling
over-estimated fine particle sizes and under-esti
m a t e d coarse particles. T h u s settling a p p e a r e d to
decrease t h e spread of sizes as estimated from
sieving.
Following the application of correction factors to
permit comparison of intermediate diameters from
both sieving and settling techniques K o m a r & Cui
(1984) d e m o n s t r a t e d extremely close similarity be
tween the results from the two forms of analysis
applied to sediments from a wide range of deposi
tional e n v i r o n m e n t s . H o w e v e r , they noted s o m e
s
P)(4.5 u V + 0.0087 V p)]}/g(ps s
p)
Nevertheless, sedimentologists dealing in the lithi

fied materials frequently wish to m a k e statements
about the textural characteristics of their rocks. In
the only systematic study of this topic, Friedman
(1958) c o m p a r e d thin section analysis of artificially
c e m e n t e d and sectioned sands with sieving analyses
of t h e same materials. T h e correction factors derived
empirically were expressed in graphical form (Fig.
3.4).
Because t h e r e is a preferred grain orientation in
most sediments, t h e particles lying with long and
intermediate axes parallel to the depositional sur
face, thin sections for size analysis of such sediments
should be cut parallel to bedding o r cross-bedding
surfaces. T h e size of the smaller axes e n c o u n t e r e d ,
i.e. intermediate axes of the grains e n c o u n t e r e d at
grid intersections as in point-counting, should be
d e t e r m i n e d . T h e use of gridded photomicrographs
( M c C a v e , 1979b) by what is a very rapid and highly

reproducible t e c h n i q u e . M a n y samples may be pro
cessed in o n e day. T h e m e t h o d is simple, but d e
pends u p o n a relatively expensive a p p a r a t u s which is
n o t , but should b e , available in all sedimentological
laboratories, particularly w h e r e fine sediments are
to be analysed. T h e Coulter counter is widely used
in industrial laboratories and in medical situations
but relatively rarely by academic sedimentologists.
71
E
i
125
Ba)
C
>D
CD
500
>
CD
3.7 G R A I N S I Z E A N A L Y S I S O F
LITHIFIED SEDIMENTS
Ancient sedimentary deposits which cannot be read
ily disaggregated present major difficulties to the
potential size-analyst. Any grain size estimation
GO
1000
500
250
125
63
Thin section derived diameters (|xm)
Fig. 3.4. Correlogram between thin section and sieve

derived size data (Friedman, 1961).
73
printed to a convenient size permits analysis at the

desk rather than down the microscope.
3.8 G R A I N S I Z E A N A L Y S I S
3.8.1 Scales of size
Since sediment particles range in size from several
m e t r e s to less t h a n o n e m i c r o m e t e r , a scale using
uniform divisions by size places too much emphasis
on coarse sediment and too little on fine particles. In
c o n s e q u e n c e , a geometric scaling was introduced to
place equal emphasis on small differences in fine
particles and larger differences in coarse particles.
A l t h o u g h there is fairly general a g r e e m e n t on the
terms to be applied to sediment particles of various
sizes the definitions used for the bounding sizes is
not uniform. Most w o r k e r s take values based o n t h e
U d d e n - W e n t w o r t h scale (Table 3.4), which is a ratio
scale in which the grade boundaries differ by a factor
of 2. O n e grade coarser is twice the size of its
predecessor a n d o n e grade finer is half t h e size. T h e
g r a d e boundaries are established at 4, 2, 1, 0.5 and
0.25 m m etc. E v e n with a g r e e m e n t on the form of
t h e scale and g r a d e b o u n d a r i e s in t h e coarser ranges
different a u t h o r s still place t h e siltclay b o u n d a r y
variously at 2 urn (Briggs, 1977; Friedman & Sanders,
1978), which is a size commonly used by soil scien
tists, o r at 4 |xra, as in t h e original U d d e n - W e n t w o r t h
system ( T a n n e r , 1969; Pettijohn, 1975) as is m o r e
n o r m a l amongst geological sedimentologists.
In o r d e r to plot the results of grain size analysis
using the ratio scale it is necessary to use logarithmic
scale graph paper for size so that visual equality is
given t o the scale divisions. This led Krumbein
(1934) to introduce the phi transformation, which
recognized t h e logarithmic equality of scale divi
sions. H e expressed grain size such that
<h = - i
E
CO
r> 250
ed
/ = {0.111608 V p
T h e system was originally introduced for size

determination of fine particles (Sheldon & Parsons,
1967) but has been extended into t h e sand r a n g e
(McCave & Jarvis, 1973). Using suitable techniques
very fine increments of size may be detected
must be u n d e r t a k e n from t h e rock itself or from

polished or thin sections of the rock.
A thin section cut through a randomly p a c k e d set
of spheres reveals circular outlines of a range of
sizes. Knowing t h a t all w e r e of uniform original size
permits calculation of that size from t h e density
distribution observed. W i t h o u t the knowledge that
the grains were initially uniform it would have been
impossible to reconstruct t h e original population
( K r u m b e i n , 1934). In natural sediments t h e grains
are rarely uniform in size and few are spherical, so
that t h e u n k n o w n elements in the analysis r e n d e r
t h e mathematical p r o b l e m of interpreting the ori
ginal grain size populations from thin section in
soluble (Blatt, M i d d l e t o n & M u r r a y , 1980).
rs
72
o g 2
w h e r e d is t h e grain d i a m e t e r in millimetres. This

permitted t h e use of arithmetic graph papers for
plotting. According to t h e phi transformation a
coarse particle 4 m m in d i a m e t e r has an equivalent
d i a m e t e r of 2<h, w h e r e a s a finer grain 0.125 mm in
d i a m e t e r equates with a +3cJ> diameter. T h e larger
t h e particle phi n u m b e r t h e finer t h e particle. T h e
relationship between metric and phi scales present
ed in tables by Page (1955) is illustrated in Fig. 3.5.
T h e arithmetic form of t h e phi scaling also poten
tially simplifies statistical analysis of grain size d a t a ,
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lillll
74
J . MCMANUS
GRAIN SIZE DETERMINATION 7 5
Table 3.4. Size scales of Udden & Wentworth

UddenWentworth
(1922)
Friedman & S a n d e r s
(1978)
phi
mm
-11
2048
-10
1024
-9
512
-8
256
-7
128
-6
64
-5
32
-4
16
Histogram
-3
Cobbles
Pebbles
Granules
V. coarse
Coarse
Medium
Fine
V. fine
Clay
-3
-2
-1
30
Frequency
percentage 2 0 h
by weight
20
10h
10
Unique
frequency
curve
phi 0
V. large
Large
Medium
30 h
100
Boulder
2001300 500
1000
2000
5000
3000
1000
Small
Large
Small
Cobbles
V. c o a r s e
9
10
Coarse
Medium
phi
- 4 - 3 - 2 - 1
1
10
20 30
50
100
Pebbles
Fine
- 4 - 3 - 2 - 1
Grain diameter (phi)
Fig. 3.6. Histogram and unique frequency plots.

Fig. 3.5. Interrelationship between metric and phi scales
of size.
V.fine
V. coarse
m i c r o n s Coarse
TJ 1
500
c
Medium
C
D
250
C
O Z
Fine
125
3
V.fine
62
4
V. coarse
31
5
Coarse
16
6
Medium
7
8
Fine
8
4
V.fine
9
2
Clay
Sand
Silt
but confusion concerning the properties of the phi

scale dimensions led to an accepted redefinition in
which
<t> = ~log2 4w h e r e d is the d i a m e t e r of a 1 m m grain. This
stresses that t h e phi system is o n e of dimensionless
n u m b e r s and so may. be correctly used for statistical
analysis to derive factors such as the standard devia
tion, skewness and kurtosis of grain size distribu
tions ( M c M a n u s , 1963; K r u m b e i n , 1964).
a
3.8.2 Graphic presentation

T h e simplest m e t h o d of presenting grain size d a t a
graphically is by m e a n s of the histogram. In this the
grain size is t h e i n d e p e n d e n t variable, which is

therefore plotted on t h e horizontal axis and the
vertical axis is used for t h e d e p e n d e n t variable, i.e.
t h e d e t e r m i n e d weight p e r c e n t a g e . T h e weight per
centage of sediment retained on each sieve is plotted
as a column rising to that value and extending from
t h e relevant sieve mesh to the next coarser mesh
used. T h e o u t p u t from most Coulter c o u n t e r s is also
given in this format. T h e resulting graphical con
struction is simplified if the size scale is r e p r e s e n t e d
by equal i n c r e m e n t s , usually r e p r e s e n t e d by phi,
half-phi or quarter-phi divisions. A line g r a p h , which
is t h e u n i q u e frequency curve of the s e d i m e n t , may
be formed by linking t h e mid-points of t h e histo
gram columns (Fig. 3.6). Ideally the frequency curve
should be formed from t h e most detailed possible
size analysis of t h e sediment. W h e n sieving is used
t h e sieves are arranged at ^ phi scale intervals. T h e
frequency curve a p p r o x i m a t e s to a c o n t i n u o u s func
tional relationship b e t w e e n grain size and weight
percentage variation. T h e resultant curve closely
resembles t h e Gaussian or ' n o r m a l ' probability curve
of statisticians, with high values n e a r t h e centre of
t h e size range and low value tails in t h e coarse and
fine ends of the scale. Traditionally sedimentologists
have r e g a r d e d grain size populations as approxima
ting to this form of distribution and have based their
m e t h o d s of d a t a plotting and statistical analysis on
this assumed relationship. In that t h e size scale is
logarithmic in reality the distribution a p p r o x i m a t e s
to log n o r m a l . Because a limited a m o u n t of statistical
http://jurassic.ru/
rfffiifffffii
information may be extracted from the frequency

curve the same facts are most commonly used to
construct the cumulative frequency curve.
In constructing t h e curve of cumulative
frequency
by weight the abscissa retains its size scaling. T h e
weight p e r c e n t a g e r e t a i n e d on t h e coarsest sieve is
plotted at t h e a p p r o p r i a t e grain d i a m e t e r , t h e sum
of weight percentages retained in t h e two coarsest
sieves is plotted at the next finer mesh, t h e cumula
tive contents of the first t h r e e sieves at t h e next finer
mesh and so on until t h e entire sediment has b e e n
accounted for at 1 0 0 % . A l t h o u g h t h e ordinate scale
of such curves may be arithmetic a second scaling is
m o r e c o m m o n l y used which assumes the normal
probability distribution. Plotting is therefore carried
out on arithmetic probability graph p a p e r . T h e or
dinate scaling is derived by dividing the a r e a be
n e a t h a n o r m a l distribution curve into columnar
segments of equal area. T h o s e n e a r t h e centre of the
distribution are long and relatively n a r r o w w h e r e a s
those towards t h e tails a r e low and proportionately
b r o a d e r (Fig. 3.7). Since the spacing patterns are the
same for all n o r m a l distributions t h e divisions are
carried forward to provide the probability ordinate
scaling for the arithmetic probability graph which is
used for plotting cumulative size distributions.
W h e r e a s plotting o n t h e arithmetic ordinate scale
generally yields ' S ' s h a p e d grain size distribution
p a t t e r n s , using t h e probability ordinate scale
straightens t h e curve (Fig. 3.8). Perfect log-normal
grain size distributions plot as straight lines on t h e
probability p a p e r . H o w e v e r , natural sediments
99
Probability
scale of
percentage
finer than
a given size
70
50
30
10
1
-2-1 0 1 2
3
Grain size (phi)
Curve of
normal
distribution
Fig. 3.7. Derivation of the graphical scale used in

probability plots.
rarely conform to this p a t t e r n and t h e deviations

from log-normality have provided much scope for
discussion, interpretation and speculation.
By convention t h e geologist plots coarse grains to
t h e left of t h e abscissa and fine to t h e right. In
c o m p u t i n g values for cumulative distributions it is
n o r m a l to consider values in terms of t h e percentage
coarser t h a n a given grain size. T h u s the higher
values on t h e cumulative percentage by weight plot
occur in t h e range characterized by the finer par
ticles. This is the exact opposite of and neither m o r e
n o r Jess correct t h a n t h e practise a d o p t e d in civil
engineering analysis of soils and aggregates.
76
J . MCMANUS
Cum
%
by
100
90
weight 80
70
CD
< in
60
50
40
30
20
10
0
/
J
-4-3-2-1
I
0
I
1
I I
2 3
L
4
Cum %
by
weight
99
98
95
90
80
S
70
j o 60
S 8 50
- co 40
30
20
10
5
2
1
weight ( F r i e d m a n & J o h n s o n , 1982) but others ad

vocate its derivation by recalculation from t h e gra
dient of t h e cumulative curve (Griffiths, 1967; Folk,
1974b).
Median (Md). Half of the grains are coarser and

half finer t h a n t h e m e d i a n d i a m e t e r , whose size is
most readily d e t e r m i n e d from the 5 0 % line of the
cumulative distribution curve. A l t h o u g h useful for
many unimodal s e d i m e n t s , in polymodal distribu
tions the median may fall in the tails of two subpopulations of grains, in a size fraction which is
scarce.
/
/
/
/
Mean (M). T h e best m e a s u r e of average grain size,

t h e m e a n is c o m p u t e d from sizes of particles spread
through a range of percentile values. In its simplest
form the G r a p h i c M e a n , M , , is calculated from
(tp + c|>5o + <j> ) which assumes that t h r e e values
alone are sufficient to give a useful m e a n . W h e r e
m o r e confidence in t h e average value is required
m o r e p e r c e n t a g e values m a y b e used, e.g. M9 is
c o m p u t e d by ((b , + 4> + 4> , + <t> + ( b + <l>60
+ <|>7o + (j>8o + 4>9o) provided the percentile values
used a r e evenly spread t h r o u g h the distribution. In
practise this a p p r o x i m a t e s to t h e m e a n of m o m e n t
statistics.
J
I I L
J
I I I
-4-3-2-1
0 1 2
3 4
16
Fig. 3.8. Cumulative frequency distribution curves plotted or arithmetic and probability scales.
Whilst data p r e s e n t e d in graphical form have pic

torial value, permitting crude general s t a t e m e n t s to
b e m a d e about a s e d i m e n t , they are of little value
for detailed comparisons with o t h e r samples. In
c o n s e q u e n c e , simple statistical techniques are used
to characterize t h e grain size distribution d a t a . A n
i m p o r t a n t difference b e t w e e n conventional statistics
and statistics of grain size distributions is that in the
former frequency is expressed as n u m b e r s w h e r e a s
in t h e latter it is as weight p e r c e n t a g e .
T w o principal forms of analysis are normally used,
graphical m e t h o d s , in which values derived directly
from plotted cumulative curves are e n t e r e d into
established formulae, and moment m e t h o d s in which
t h e characteristics of every grain in t h e sample
analysed from t h e sedimentary deposit are used in
the c o m p u t a t i o n . In all cases t h e n u m b e r s o b t a i n e d
serve to define t h e position of the distribution plot,
its slope, and the n a t u r e of any irregularities. T h e
values of these p a r a m e t e r s permit characterization
of the curves, and e n a b l e numerical c o m p a r i s o n s to
be m a d e b e t w e e n samples.
T h e p a r a m e t e r s used fall into four principal
groups: those measuring (a)-average size, (b) spread
of t h e sizes a b o u t t h e a v e r a g e , (c) symmetry or
preferential spread to o n e size of the a v e r a g e , a n d

(d) kurtosis or d e g r e e of concentration of t h e grains
to t h e central size.
In discussion of particle sizes a s t a n d a r d form of
notation is used. T h e size of particle for which 25 or
3 2 % of the grains are coarser, F s
P32 respective
ly in metric units, or <j) and fa in t h e phi system
may b e read directly from the cumulative frequency
curve. G r a i n sizes in corresponding t o specified
percentile values are e n t e r e d into simple formulae
to permit calculation of the various graphic para
meters.
o
3(
40
(b) S P R E A D A B O U T T H E A V E R A G E
S O R T I N G (a)
In m a n y forms of analysis the full range of sizes

p r e s e n t is of relevance. H o w e v e r , it is rarely possi
ble to define t h e size of t h e largest or smallest
particles precisely in a size distribution. Of m o r e
i m p o r t a n c e is an assessment of the spread of par
ticles a b o u t the a v e r a g e , to define the dispersion or
sorting of the sediment, as represented by the breadth
of the frequency curve or the shape of the cumula
tive frequency distribution.
(a) M E A S U R E S O F C O M M O N S I Z E A N D
A V E R A G E SIZE
Mode. O n a size frequency histogram t h e size class
in which the greatest percentage of grains is r e p r e
sented provides t h e m o d a l class. O n the size fre
quency distribution plot the highest point on the
curve provides t h e m o d a l value. T h e m o d a l size is,
t h e r e f o r e , the c o m m o n e s t grain size in a distribution.
T h e frequency curves of many sediments exhibit
several p e a k s , the polymodal distributions indica
ting the presence of m o r e than o n e p o p u l a t i o n of
grains. S o m e w o r k e r s use modal values abstracted
directly from the size frequency distribution by
In all metric m e a s u r e s a n d their direct phi-based

equivalents only t h e 25th, 50th and 75th percentiles
are used, so that attention is only given t o t h e
central half of t h e grain p o p u l a t i o n present. A s a
m e a s u r e of t h e characteristics of the sediment they
are of limited v a l u e , but as a m e t h o d of character
izing the central s e g m e n t of a curve t h e Trask Sort
ing coefficient ( / W ^ s ) i equivalent, t h e phi
Quartile Deviation y((j>75 (fes) may have s o m e
value.
o
http://jurassic.ru/
84
16
_ 1 /<l>84 ~ <|>16 , 4>95 ~ <t>s\
01
~A
3.3
or
<t>84 ~ <t>16 , <j>95 ~ <t>5
6.6
'
t s
T h e best sorted sediments a p p r o x i m a t e to, a single

size a n d have low O) values (Table 3.5).
50
25
Ideally a m e a s u r e of sorting should e m b r a c e a

b r o a d e r spectrum of t h e grains p r e s e n t , and t h e
graphic s t a n d a r d deviation o^ of I n m a n (1952),
c o m p u t e d from ^(<t> - (j> ), provides a m e a s u r e of
t h e spread of size of 6 8 % of the population (one
s t a n d a r d deviation on either side of the m e a n ) .
F u r t h e r extension to include 9 0 % of the curve yields
t h e inclusive graphic s t a n d a r d deviation Oi (Folk &
W a r d , 1957), which uses the 5th and 95th percentiles
to define a spread corresponding to 1.65 s t a n d a r d
deviations on either side of the m e a n . Taking the
m e a n of t h e contributions from t h e 68 and 9 0 %
population fractions p r o d u c e d the expression:
84
1(
3.8.3 Curve characterization by statistical

methods
77
(c) P R E F E R E N T I A L S P R E A D
S K E W N E S S (a)
In a n o r m a l distribution with a bell-shaped fre
quency curve the median and m e a n values coincide.
A n y tendency for a distribution to lean to o n e side,
i.e. to deviate from normality, leads to differences
b e t w e e n t h e m e d i a n and m e a n values. T h e s e differ
ences are used t o characterize t h e asymmetry or
skewness of t h e curve. T h e skewness has a positive
or negative value w h e n m o r e fine or m o r e coarse
materials are p r e s e n t than in a normal distribution,
seen as tails to t h e right or left respectively on
frequency distribution plots. A g a i n , although skew
ness may be c o m p u t e d for t h e central s e g m e n t of the
distribution, for most p u r p o s e s b r o a d e r spreads are
used. Effectively skewness is d e t e r m i n e d from t h e
value of t h e m e a n less t h e m e d i a n , all divided by t h e
range used in defining t h e m e a n . M a n y possible
combinations of c o m p u t a t i o n are available. E x
pressed simply:
a<j> = ^ ( M 16 + <t>S4 ~ 2c()so

2(<j)g4 - + (j) 5 - 2(j>50

2((j> - cb )
5
95
78
GRAIN SIZE DETERMINATION 79
J . MCMANUS
T h e principles of m o m e n t statistics a r e lucidly
reviewed in F r i e d m a n & J o h n s o n (1982). Effectively
each grain in t h e population is t a k e n into account in
computing t h e characteristic p a r a m e t e r s of t h e sedi
m e n t . W h e r e a s in mechanics t h e m o m e n t is calcu
lated as t h e product of a force and t h e distance of its
application from a fulcrum, in statistics t h e m o m e n t
is c o m p u t e d from t h e p r o d u c t of t h e weight percen
tage in a given size class a n d t h e n u m b e r of class
grades from t h e origin of t h e curve. T h e first m o
m e n t , t h e m o m e n t p e r unit frequency, is t h e m e a n ,
x, of t h e distribution:
Table 3 . 5 . Statistical formulae used in calculating grain size parameters

(a) Statistical measures in the metric and phi systems
Median
Metric
Phi
Dispersion
Mean
Md = P, M
Md = <j)
50
P75 + ^25
Azcj) =
PlS
QDa =
.
Ska ;
So = (Pis/Pis)*
Sk
Otj)
Mz =
Skewness
P25
<l>84 - <t>16
a, =
+ P -
2Md
Kqa
P75 ~ P25
2(Pc)o P10)
Md
M(() - Md$
a<t> o<()
SK,
995
P s
Kurtosis
V5
ocj)
x =
100
<t>16 + <1>84 2<t>5l

2(<t>4 - >1&)
2.44(<t> -ij> )
75
25
<t>5 + <t>9:- 2<t
50
6.6
2(4>95 - <t>s)
(b) Descriptive terms applied to parameter values

Skewness (SKj)
Sorting (o )
t
Very well sorted

Well sorted
Moderately well sorted
Moderately sorted
Poorly sorted
Very poorly sorted
Extremely poorly sorted
<0.35
035-0.50
0.50-0.70
0.70-1.00
1.00-2.00
2.00-4.00
>4.00
Very positively skewed

Positively skewed
Symmetrical
Negatively skewed
Very negatively skewed
+0.3 to +1.0
+0.1 to +0.3
+0.1 to - 0 . 1
-0.1 to-0.3
-0.3 to-1.0
Kurtosis ( K )
G
Very platykurtic
Platykurtic
Mesokurtic
Leptokurtic
Very leptokurtic
Extremely leptokurtic
<0.67
0.67-0.90
0.90-1.11
1.11-1.50
1.50-3.00
>3.00
w h e r e x is t h e m e a n , / t h e frequency in weight p e r
cent a n d
is t h e mid-point of each class interval.
O n c e t h e position of t h e m e a n is defined t h e
spread of t h e distribution about it is calculated by
summing t h e m o m e n t s of each class interval about
the m e a n . In each of t h e subsequent m o m e n t calcu
lations t h e difference (m^ - x) is raised t o higher
powers.
T h e second m o m e n t has a value which is t h e
square of t h e standard deviation of t h e distribution:
,
Lf(m^
=
xf
Too
T h e third m o m e n t m e a s u r e s t h e symmetry of t h e
distribution about t h e m e a n a n d yields a value which
is t h e cube of t h e skewness:
,
Lf(m^
xf
100
Skewness is a positively or negatively signed
dimensionless n u m b e r ; it h a s neither metric n o r phi
value and lies within t h e range 1 to + 1 (Table 3.5).
(d) C O N C E N T R A T I O N O R P E A K E D N E S S O F
THE DISTRIBUTION KURTOSIS
N o t widely used, although frequently calculated, t h e
kurtosis is related b o t h t o t h e dispersion a n d t h e
normality of t h e distribution. Very flat curves of
poorly sorted sediments or those with bimodal fre
quency curves a r e platykurtic, whereas very strongly
p e a k e d curves, in which t h e r e is exceptionally good
sorting of t h e central part of t h e distribution, a r e
leptokurtic. T h e m e a s u r e of kurtosis, which is a
ratio of t h e spreads of t h e tails a n d centre of t h e
distribution (and is therefore also dimensionless) is
given by t h e expression:
4>95 ~ 4>5
2.44(<J, " 4>2 )'
75
T h e fourth m o m e n t yields a value for kurtosis

raised t o t h e fourth power:
A listing of commonly used formulae a n d verbal

descriptions of t h e values obtained is p r e s e n t e d in
T a b l e 3.5.
3.8.4 Moment m e t h o d s
T h e second major a p p r o a c h t o analysing grain size
distributions, m o m e n t statistics, differs in concept
b u t yields measures analogous t o those of graphical
m e t h o d s . Neither technique is 'better' t h a n t h e
other. G r a p h i c techniques a r e especially appropri
ate for analysis of o p e n e n d e d distributions w h e r e a s
the m o m e n t m e t h o d s should n o t b e applied unless
all grain sizes present lie within t h e defined grain
size limits.
_ E/(m,|, 100
xf
A l t h o u g h t h e p a r a m e t e r s obtained a r e analogous to
those of graphical statistics their derivation e m
ploys t h e entire grain population a n d so they a r e
m o r e representative t h a n t h e graphically derived
values. O n c e again it should b e stressed that, b e
cause all grains a r e used, this form of analysis should
n o t be used unless t h e size distribution is fully known.
Distribution of t h e ' p a n residue' fraction from siev
ing a m o n g a specified n u m b e r of p h i classes 'to
permit application of m o m e n t m e t h o d s ' is n o t good
practise a n d m a y lead t o misleading, if n o t meaning. less, results being obtained. If a total of less than 1%
http://jurassic.ru/
of t h e population is undefined then t h e errors a r e

unlikely t o b e great, b u t t h e reliability of t h e m o
m e n t s decreases sharply as t h e proportions of u n d e
fined materials increases, a n d t h e technique should
not b e used with a higher p r o p o r t i o n of u n k n o w n s
notwithstanding t h e convenience a n d availability of
pocket calculators suitable t o perform the arithmetic.
3.8.5 Alternative grain size d i s t r i b u t i o n s

T h e grain size distributions of some sediments yield
linear log-normal cumulative plots, b u t others d e
viate from t h e linear p a t t e r n s t o a greater or lesser
d e g r e e , especially in t h e tails of t h e distributions. I n
consequence some authors suggest that t h e conven
tionally applied log-normal probability law is n o t
suitable for universal applications in grain size
analysis.
Early work by Rosin & R a m m l e r (1934) revealed
that -crushed coal exhibited regular grain size char
acteristics controlled by natural fracture patterns of
t h e material. They established expressions from
which Rosin p a p e r was introduced for plotting grain
sizes of crushed particulate m a t t e r (Kittleman, 1964).
S o m e natural sediments such as pyroclastic debris,
glacial tills and w e a t h e r e d crystalline rock products
exhibit linear plots on Rosin p a p e r , suggesting that
they behave very much as crushed products, b u t t h e
similarity vanishes swiftly with transport after which
they rapidly c o m e t o resemble m o r e commonly en
c o u n t e r e d materials t r a n s p o r t e d a n d deposited from
natural fluids.
A l t h o u g h Bagnold (1941) suggested that wind
blown s a n d s , which deviated from log-normality,
might have some o t h e r probability function, it was
not until recently that his suggested log-hyperbolic
distribution has b e e n closely examined as an alter
native (Barndorff-Nielsen,
1977; Bagnold &
Barndorff-Nielsen, 1980; Wyrwoll & Smyth, 1985).
T h e log-hyperbolic distribution offers t h e possibility
of a range of curve fittings, o n e limiting case of
which is t h e log-normal distribution. In practise t h e
natural logarithm of t h e frequency curve is plotted
against grain size (Bagnold, 1968), and t h e four
p a r a m e t e r s of t h e best fitting log-hyperbolic curve
are c o m p u t e d . T w o of these relate t o t h e curve
position (grain size and peakedness) a n d t h e o t h e r
two t o inclination of t h e limbs of t h e curve. T h e
distribution has b e e n examined principally within
the context of wind blown d u n e sands (Bagnold &
Barndorff-Nielsen, 1980; Christiansen, 1984) for
80
J . MCMANUS
which it was claimed t h e hyperbolic function en

compassed the e x t r e m e values of the size distribu
tion tails better than the log-normal plot. H o w e v e r ,
comparative studies of Wyrwoll & Smyth (1985),
who suggested that the 'improved' performance may
be partly a function of shape-influenced deficiencies
in the sieving t e c h n i q u e , led to the conclusion that
only a marginal i m p r o v e m e n t in fitting over the lognormal curve was achieved. T h e y also pointed out
that substantial computational skills were required
to obtain the best-fit log-hyperbolic curves from
which the p a r a m e t e r s could be derived.
3.9
ENVIRONMENTAL
INTERPRETATION FROM
GRAIN SIZE DATA
T h e m e t h o d s of analysis and presenting d a t a are

standard descriptive techniques, but it is always t h e
aim of scientists to derive m o r e than simple descrip
tions of their materials. T h e sedimentologist is no
exception. T h e prospect of a universally applicable
technique of abstracting, from sediment grain size
distributions measures diagnostic of depositional
environment has encouraged generations of sedi
mentologists. T h e uncomfortable fact remains that
though many have tried only modest success has
been achieved and n o overall m e t h o d has yet been
discovered. I n d e e d , s o m e consider the quest, though
h o n o u r a b l e , most unlikely to succeed (Erlich, 1983)
and potentially wasteful of effort through diverting
attention away from attainable research targets.
With this warning the r e a d e r is introduced to t h e
final section of this chapter in which s o m e of the
approaches to t h e analysis of the distribution curves
and t h e abstracted measures are outlined.
T h e simplest tool employed by the sedimentologist
is t h e geographical m a p on which variations of in
dividual p a r a m e t e r s may be plotted, so that patterns
of regional variation may be recognized. Systematic
variation of m e a n grain size with environmental
dynamics is normally detectable, and systematic
changes in standard deviation and skewness may
also be detected in suitable areas. Within a local or
regional context recognizable patterns related to
dynamics or supplied materials are not unexpected
(Folk & W a r d , 1957; Allen, 1971; R y a n & G o o d e l l ,
1972; C o o k & M a y o , 1977).
C o m m o n l y , there are covariations of two or m o r e

measures, such as mean size and sorting, which
Griffiths (1967) illustrated as being hydraulically
controlled, so that in all e n v i r o n m e n t s t h e best sor
ted sediments had their m e a n sizes in the fine sand
category. This energy related universal relationship
has been confirmed by many subsequent studies.
O n e of the earliest attempts to characterize de
positional environments by m e a n s of bivariate scattergrams was that of Stewart (1958) w h o plotted
median against skewness and standard deviation for
sediments from rivers, wave d o m i n a n t zones and
quiet water e n v i r o n m e n t s , and defined envelopes
within which his analyses occurred (Fig. 3.9): A l s o ,
using graphic techniques, Schlee, Uchupi & T r u m
bull (1965) were unable to distinguish beach and
d u n e sands from grain size data alone.
Following early studies by F r i e d m a n (1961, 1967)
the use of scattergrams of sorting and skewness to
provide discrimination between river, beach and
d u n e sands has been repeatedly explored (Moiola &
Weiser, 1968). T h e relatively fine grained unimbdal
sand deposits from many parts of t h e world yielded
similar characteristics: beach sands were well sorted
and negatively skewed, w h e r e a s river sands w e r e
less well sorted and usually positively skewed. D u n e
sands also had positive skewness but were finer than
beach sands. H o w e v e r , the best separations report
ed were achieved using a combination of m o m e n t
standard deviation and an unusual graphic skewness
(Friedman & S a n d e r s , 1978). A l t h o u g h general
separation of points by e n v i r o n m e n t was achieved
t h e r e was always s o m e overlap between adjacent
fields. N o clear cut distinction has been found in
most forms of bivariate plot. Leaving t h e b e a c h ,
dune and river sediments, which were mainly medium
or fine sands, the greater spread of grain size en
abled L a n d i m & F r a k e s (1968) successfully to dis
tinguish till from alluvial fan and outwash deposits
using m o m e n t m e t h o d s .
In few studies have t h e higher m o m e n t s b e e n used
to a d v a n t a g e , the principal exception being that of
Sly (1977, 1978) who used t h e skewness kurtosis
interrelationships to recognize differing environ
mental energy levels in deposits of t h e G r e a t Lakes
(Fig. 3.10). Deposits without pebbles, essentially of
m u d d y materials from low energy e n v i r o n m e n t s , fall
in fields A , B , C and D w h e r e a s those with p e b b l e s ,
either lag deposits or high energy b e a c h e s , lie in
fields E , F , G and H .
In some of the simplest forms of analysis ratios of
the sand, silt and clay contents may have value. T h e
3-5
3-0
/ Quiet water i
I/ slow deposition ]
\
2-5
c
o
to 2-0
>
+0-8
+0-6
+0-4
+ 0-2
0 4
-0-2-
CD
o
Z 1-5
Q1-0 -\Rivers
\
0-5
0
I
^
v Waves
\
j
1-0 2-0 3-0 4-0 5-0

Median diameter (phi)
Skewness
R i
6-0
Quiet water
slow deposition
I
I
^<s
--'
' Waves
v e r S l
N
J_J
I L
0-4h iVy
01
2 3 4 5 6 7 8
Median diameter (phi)
Fig. 3 . 9 . Bivariate plots which Stewart (1958) believed were of environmental significance.
10 000
Bedload.
Graded
\.
suspension
\
_
Fluvial
1000
Uniform
\
suspension
J
Pelagic / C \
suspension VL_y
i
1
-4!
-81
- 8 4 0
-4
-8 1-2 1-6 2 0 2-4
Beach
/W ^ Turbidity
currents
/
i
10
100
M median (u,m)
I
1000 10 000
Fig. 3.11. The CM plot of Passega (1964) with envelopes

with which he believed sediments should plot according to
dynamics of the transport experienced.
Skewness
Fig. 3.10. Skewness - kurtosis plots of sediments from the
Lake Ontario low energy ABCD and active environments
EFGH.
silt-clay relationship has been explored in an en

vironmental energy context for lake and m a r i n e
systems. Pelletier (1973) d e m o n s t r a t e d that the ex
pected decrease of size with increasing d e p t h of
water was much stronger in lakes than in oceans.
Using information abstracted from t h e cumulative
distribution curve, Passega (1957, 1964) suggested
that t h e ratio of t h e coarsest o n e percentile, C, to
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illllllllllllllilllll
81
t h e median d i a m e t e r , M, could be used as an indi

cator of t h e dynamics of t h e depositional environ
m e n t . T h e strongest currents should define the
largest stable particle size. Counter-plotting gave
the CM diagram within which he defined en
velopes typifying deposits from traction currents,
from beaches or from various forms of suspension
(Fig. 3.11). In separate plots, LM diagrams, he
also examined the role of L , the proportion of
particles finer t h a n 31 um. With deposits of limited
size variations t h e technique has s o m e success but
better discrimination is achieved w h e r e t h e r e are
large size differences.
82
J. MCMANUS
M a n y sediments are c o m p o s e d not of o n e single

grain size p o p u l a t i o n , but r a t h e r of a combination of
sub-populations. E a c h sub-population may be d e
fined by dynamic considerations or by supply char
acteristics. In t h e natural e n v i r o n m e n t individual
sub-populations may be p r e s e n t in varying p r o p o r
tions from site to site. T h u s in allied localities it may
be possible to trace material from o n e specific source
using its m o d a l size a n d s p r e a d , noting the increases
and decreases in its contribution to local materials
( C u r r a y , 1960; M c M a n u s , Buller & G r e e n , 1980).
E l s e w h e r e the effect of wave activity may b e par
ticularly intensely experienced by o n e size fraction
which is either totally r e m o v e d or greatly increased
in p r o p o r t i o n . T h e combination of the sub-popula
tions in different p r o p o r t i o n s d e t e r m i n e s t h e grain
size characteristics of the overall sediment.
Following the work of Moss (1962, 1963) who
CD
99-9
99
d e m o n s t r a t e d t h r e e sub-populations of pebbles form

most gravel deposits, Visher (1969) suggested that
cumulative frequency curves could often be sub
divided into t w o , t h r e e or four linear segments (Fig.
3.12). Because log-normal distributions follow linear
trends on t h e cumulative probability plot he con
sidered each segment to represent a separate subpopulation whose character was d e t e r m i n e d by the
dynamics of transport: traction, saltation and sus
pension. Many plots required a two-fold saltation
Suspension-,
>>
D -
90
50
Saltation-
10 Saltation'
E
o
0-1
0
-Rolling + sliding
J
I
I
1 2
3
4
Fig. 3.12. The linear segments of cumulative size

frequency curves as suggested by Visher (1969).
load to b e considered. This apparently simplistic and

attractive technique which has b e e n readily espoused
by many w o r k e r s merits further a t t e n t i o n . Replotting data from the cumulative curve to the frequency
curve shows that linear segments d o sometimes coin
cide with recognizable sub-populations but in o t h e r
cases inflexions w h e r e linear segments join also
coincide with population p e a k s . Experimentally
combining two unimodal sediments produces not a
two-fold linear p a t t e r n , but a three-fold o n e , the
central segment forming in the size overlap z o n e .
Nevertheless, this form of analysis may still merit
further exploration.
In a further n o n - s t a n d a r d bivariate plot, Buller &
M c M a n u s (1972) suggested using the central subp o p u l a t i o n , which frequently spans over half of the
distribution, t o provide a metric quartile deviation
m e a s u r e y ( P 5 P75) to plot against t h e m e d i a n
d i a m e t e r . Using m a n y h u n d r e d s of analyses they
defined field envelopes each embracing 6 8 % of all
relevant d a t a points from t h e river, b e a c h , a eolian
a n d quiet w a t e r deposits. M a n y of t h e envelopes
partly o v e r l a p p e d , particularly in the m e d i u m to fine
sand r a n g e , but good separations w e r e achieved
outside those sizes. L a t e r envelopes for turbidites
83
T h e sedimentologist assesses materials with r e

spect to their conformity to an ideal of sorting in
which perfection is realized in a deposit in which all
particles are identical. In an extremely well sorted
sediment all particles a p p r o x i m a t e to the same size.
F o r t h e civil engineer dealing with concrete design,
sorting in the geological sense is undesirable. T h e
graded aggregate, in which a defined spread of
particle sizes is r e p r e s e n t e d , is considered ideal. In a
g r a d e d aggregate small particles occupy intergranular spaces, partly filling voids between larger par
ticles. This p e r m i t s reduction in quantities of c e m e n t
and water required to give desirable properties such
as workability, strength a n d durability potential.
T h e poorly sorted sample of the sedimentologist
may b e the well graded material of the engineer. In
practice t h e engineer achieves design optimization
by blending t o g e t h e r ' c o a r s e ' and 'fine' aggregates
of suitable strictly defined grading characteristics.
A s m a n y of these are readily obtained by simple
screening techniques applied to natural sedimentary
deposits it is of interest t o record the prescribed
0-1
1
Median diameter (mm)
^
'.'
glacial
eolian
0
0
quiet water
flowing water
wave dominant
Fig. 3.13. Metric quartile-deviation

- median diameter plots of Buller &
McManus (1972) and their
environmental envelopes together
with the 'sorting' levels indicated by
Folk & Ward (1957).
'
(Buller & M c M a n u s , 1973a), tills (Buller &

M c M a n u s , 1973b), screes a n d pyroclastic (Buller &
M c M a n u s , 1973c) deposits w e r e a d d e d . Plotting t h e
graphic sorting characteristics of the same sediment
gradients enables recognition of the sorting charac
teristics which m a y be expected to occur with sedi
m e n t s from each depositional e n v i r o n m e n t (Fig.
3.13). This m e t h o d of analysis met with s o m e suc

cess (Sedimentation S e m i n a r , 1981) but has not
b e e n widely applied.
While t h e geological sedimentologist has devel
o p e d o n e set of criteria by which sedimentary de
posits are assessed, an entirely different a p p r o a c h to
sands and gravels is taken by the construction in
dustry which uses such materials for c o n c r e t e , road
metal aggregates, m o r t a r s and plastering.
I
i
2-36
4-8
9-6
19-1
Test sieve aperture (mm)
38-1
j /i6"-1 V2" graded aggregate

3
.] /i6"- A" graded aggregate

3
|\\\\\^ /i6"- /2" graded aggregate

Fig. 3.14. Nominal diameter limits of size specifications
for graded concrete aggregates, after BS 882:1973.
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ill
84
J . MCMANUS
'
1 0 0 %
C L A Y
Fig. 3.16. Ternary diagrams interrelating sand, silt and

clay components and their controls over porosity and
permeability. WS, well sorted; P, S, poorly sorted; MSW,
moderately well sorted.
20
30
40
Porosity (%)
limitations of the aggregate gradings. T h e gradings

r e c o m m e n d e d for coarse aggregates arranged ac
cording to specified nominal diameters in BS 882:
1973 are indicated in Fig. 3.14 and those for the four
zones of fine aggregates of BS 812: 1975 in Fig. 3.15.
Materials whose grain size distributions fall within
t h e limits specified for zone 3 fine aggregates are
well suited for certain tasks.
According to C o n n o r (1953), only restricted
gradings of sand produce good mortars. Later,
Swallow (1964) d e m o n s t r a t e d that the best m o r t a r
sands had median diameters in the range 440570
urn and graphic standard deviations of 2 0 0 - 2 7 5 pm.
Nevertheless, a b r o a d e r range of potentially useful
m o r t a r sands is indicated in BS 1199:1976.
A second p r o p e r t y of sediments which is of economic importance is the porosity, t h e spaces be
tween the solids, which may b e c o m e filled with
water or o t h e r fluids such as oil and gas. T h e poros
ity of a deposit is expressed as the percentage of
voids in a given volume of rock. T w o forms of pores
are recognized, t h e primary pores, which develop
during deposition of the sediment, and secondary
pores, which develop after deposition, principally
through solution of the rock particles themselves.
T h e former a r e important in unconsolidated or
c e m e n t e d siliciclastic rocks whereas the latter is
m o r e commonly considered in the context of carb o n a t e sands and limestones.
T h e intercrystalline or interparticle voids are pre
sent in all rocks. T h e y are m o r e open and better
interconnected in most coarse clastic deposits than
in fine sediments. T h e efficiency with which fluids
pass through the rocks d e p e n d s heavily on t h e interconnections, the spaces available in the p o r e throats
and t h e sorting of the sediment. In very well sorted
coarse u n c e m e n t e d sediments p o r e spaces are large
and may have free interconnections whereas in
poorly sorted sediments fine particles occupy void
85
spaces, reducing t h e porosity and blocking many

interconnections. Early c e m e n t a t i o n serves a similar
purpose and may lead to closure of the throat pass
ages. Compaction may cause fine particles to move
into direct contact with their neighbours so a high
initial porosity may b e c o m e drastically r e d u c e d with
burial.
M e a s u r e m e n t of porosity is achieved by deter
mining t h e volume of gas displaced from t h e p o r e
spaces of a k n o w n bulk v o l u m e of rock. T h e latter is
d e t e r m i n e d by displacement using total immersion
in mercury, t h e former using a sealed pressure vessel
and measuring the increased volume of gas present
w h e n pressure is decreased by a known a m o u n t .
T h e associated property of permeability is impor
tant for this is the factor which determines the ability
of a fluid to pass through a porous m e d i u m . Mea
sured as t h e r a t e at which fluids pass through cores
of t h e rock or a bed of sand, t h e permeability is
calculated according to Darcy's Law and t h e unit
relevant in most natural sediments in the millidarcy.
Again t h e permeability is largely d e p e n d e n t u p o n
sediment sorting and t h e presence of cements,or
authigenic growths in the p o r e throats. Particle shape
may also be important. A s grain size decreases so
d o e s t h e permeability in most cases, d u e t o an
increase in the associated capillary pressure resisting
passage of t h e fluids.
T h e general interrelationships between grain size,
permeability and porosity a r e s u m m a r i z e d in a ter
nary diagram of sand, silt and clay contents in Fig.
3.16. T h e detailed impacts of sorting and grain size
on porosity and permeability of unsorted sands is
given in Fig. 3.17 (after Selley, 1985).
T h e analysis of sediment size distributions is thus
not only of considerable academic interest but has
highly practical significance to the construction in
dustry, for extraction of water supplies and t h e p r o
duction of hydrocarbons.
50
Fig. 3.17. Relationship between grain size, sorting,

porosity and permeability in uncemented sands (after
Selley, 1985).
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SLICES, SLIDES, STAINS AND PEELS
Microscopical techniques: I.
Slices, slides, stains and peels
ROCK SAMPLE
Sawing
JOHN MILLER
Recording
(photograph or Xerox)
4.1
INTRODUCTION
Since the pioneering work of H e n r y Clifton Sorby

(1851), slices of rock ground thin enough to transmit
light have been t h e staple material of sedimentary
p e t r o g r a p h y . Sorby's work simply involved ex
amination of thin sections in polarized light on a
petrographic microscope. T o d a y ' s sedimentologists
are able to extract a great deal m o r e information
from thin sections by using special techniques to
study fabrics, t e x t u r e s , mineralogy and geochemis
try. In o r d e r to recover so much extra information,
thin section preparations must be of consistent high
quality.
T o achieve the required precision in thin section
making, a considerable degree of mechanization is
required, and this is expensive. H o w e v e r , most
laboratories which p r o d u c e m o r e than a m o d e s t
n u m b e r of thin sections are now e q u i p p e d with
a p p r o p r i a t e a u t o m a t i c and semi-automatic systems.
This does n o t , however, m e a n that high quality
results can be achieved only by such m e t h o d s : w h e r e
a small volume of sections is involved, many of t h e
techniques described in this chapter can easily be
a d a p t e d for m a n u a l p r e p a r a t i o n of thin sections. A
simple, m a n u a l slide-making process is outlined by
A d a m s , M a c K e n z i e & Guildford (1984, p . 97). Sec
tions required for teaching purposes d o not n e e d to
m e e t t h e stringent r e q u i r e m e n t s of those used for
research, but they should be of good s t a n d a r d ; they
a r e , after all, the primary material on which all
geologists are trained.
M a n y workers proceed directly to examination of
thin sections, but t h e r e is a great deal of information
to be obtained from examining rock slices and cut
faces, particularly in t h e case of limestones and
sandstones. First, t h e three-dimensional arrange
ment of grains can be better studied in slices, whereas
thin sections are essentially two-dimensional. Second,
fabrics are studied m o r e effectively at low magni
fications and on faces larger than those possible on
thin sections, w h e r e t h e microscope concentrates on
detail by restricting t h e field of view. P e r h a p s m o r e
87
importantly, examination of cut faces enables ap

praisal of which areas should be m a d e into thin
sections. Careful selection of critical a r e a s for sec
tioning saves time and e x p e n s e , and allows sub
sequent petrographic study to be based on knowledge
of the section's context. Suggestions are given below
for p r e p a r a t i o n and study of rock faces, slices and
slabs, and the way in which these p r e p a r a t i o n s sup
port examination of thin sections in a broad-based
a p p r o a c h to sedimentary p e t r o g r a p h y .
X-ray
CUT FACE OR SLICE | Select area
6 0 0 F
* J
Oiling
Smoothing
(
carborundum)
\
Etch
Thin section process
J }
Polish
Stain
Peel
-J
Low-medium power
binocular microscopy
Direct photographic print
Projected
microscopy
Covered
Normal thickness
30 vm
Ultra-thin
10 ixm
Uncovered
/ \
Etch^Stain
CL
Direct photographic print
Low-medium power
binocular microscopy
4.2 P R O C E S S I N G S A M P L E S
Detailed petrographic microscopy

A t t h e outset of any petrographic analysis, it is wise
to begin by planning the kinds of sample p r e p a r a t i o n
which will be r e q u i r e d , and what information is t o
be sought from t h e m . Samples can be collected
which not only adequately represent t h e facies or
lithosomes u n d e r study, but are a p p r o p r i a t e in
orientation, size, s h a p e and freshness to t h e selected
preparation techniques. Processing is t h e n designed
to minimize wastage and maximize d a t a collection.
A general scheme for processing samples for micro
scopical study is shown in Fig. 4 . 1 . This flow chart is
fairly c o m p l e t e ; not every petrographic study will
need to be so t h o r o u g h , but particular paths are
easily selected.
4.3
SLICES
In this section, I use t h e following terms: faced

sample a smooth cut across a rock sample, with
the rest of the specimen left rough. Slice a section
through t h e sample with two parallel cut faces.
Slices may be up to several centimetres thick. T h o s e
less than about 6 m m thick are sometimes called
plaquettes.
Usually, plaquettes are approximately
the same area as thin sections: they may often be
p r e p a r e d as a first step in section-making.
J
Reflected-light
microscopy
Ultra-violet
Fluorescence
Cathodoluminescence Electron microprobe SEM

microscopy
^
>
Secondary Backscatter
Fig. 4.1. Flow diagram showing various methods of sample preparation and possible techniques for microscopical study.
4.3.1 Slice preparation

L a r g e samples (above t h e size of two clenched fists)
m u s t first b e t r i m m e d o n a saw with a large radius
blade (steel i m p r e g n a t e d with diamond or a com
pressed c a r b o r u n d u m disc), lubricated with water.
Slabs or successive slabs with faces suitable for serial
reconstruction of large-scale fabrics can be m a d e at
this stage. F u r t h e r trimming can be carried out o n
smaller d i a m o n d saws, which are capable of pro
ducing thin slices. T h e s e saws normally use an oil/
water emulsion as lubricant.
O n e o r m o r e faces a r e t h e n lapped s m o o t h either
by h a n d or by an automatic lapping machine, using
fine c a r b o r u n d u m (silicon carbide) p o w d e r (e.g.
600F g r a d e ) . Very coarse grits, e.g. 120F, should be
avoided, because of their plucking and shattering
effects, and their tendency t o e r o d e specimen edges
preferentially, m a k i n g it difficult t o obtain t r u e , flat

faces.
A t this stage, faces are suitable for general study
by low power microscopy or for peel p r e p a r a t i o n
(see Section 4.6), but better results will be obtained
by washing and taking through 800F and even 1000F
abrasives. F o r even better finishes, lapping is con
tinued with silica gel suspensions, Aloxite or fine
diamond pastes to a good surface polish. T h e secret
of g o o d , s m o o t h surface finishes, particularly with
polishing by h a n d , is careful washing and complete
removal of abrasive from both specimen and lap
before moving o n to finer grades. It is also vital to
k e e p alLabrasives dust-free, and if possible to work
in a dust-free e n v i r o n m e n t .
It is best-to avoid cutting soft or friable rocks such
as shales, evaporites, coals and chalks o n a lubri-
86
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111
88
J . MILLER
cated saw. With evaporites and coals, cutting usually

produces bad fracturing, and for all t h r e e rock-types
t h e effect of a q u e o u s lubricants may be disastrous.
Slices are produced dry as in the early stages of thin
section m a k i n g (Section 4.4.2), with a glass backing.
T h e y are left a few millimetres thick and lapped flat
or polished, using a lapping c o m p o u n d with paraffin
oil lubricant.
Poorly consolidated sediments, or those for which
porosity information is required, must first be
v a c u u m - i m b e d d e d in resin (see Section 4.5). T h e
resin may be stained to show the void s p a c e .
their features well with low power biocular micro

scopy. Light coating of mineral oil (or glycerol if the
faces are to be etched or stained later) can be used
to e n h a n c e detail and contrast (Fig. 4.2a). H o w e v e r ,
highly polished surfaces are easier to p h o t o g r a p h
t h a n oiled o n e s , as reflections are m o r e easily con
trolled. Slices with two p r e p a r e d faces give a threedimensional context which aids identification of bioclasts and study of depositional and diagenetic
fabrics. T h e partial transparency of t h e rock allows
focussing up and down to assess grain packing. T h e
determination of w h e t h e r a fabric is grain- or m u d s u p p o r t e d otherwise takes considerable experience
to d e t e r m i n e from thin sections, which are essential
ly two-dimensional.
4.3.2 Examination of cut faces
Chalk fabrics are usually cryptic or apparently

h o m o g e n e o u s when sliced normal to bedding.
Bromley (1981) has shown how a b u n d a n t biogenic
and inorganic sedimentary textures can be revealed
by lightly brushing thin mineral oil o n a dry chalk
surface and allowing it to ' d e v e l o p ' over about 30
minutes. F u r t h e r e n h a n c e m e n t of detail can be o b
tained from these surfaces by p h o t o g r a p h i n g t h e m
with Kodalith o r equivalent high-contrast o r t h o chromatic line film.
Argillaceous, d a r k , fine-grained c a r b o n a t e s may
also have cryptic fabrics. A technique used for re
vealing flaws in metal casings is often helpful in such
cases. It relies on t h e preferential absorption on to
clay minerals of an ultra-violet sensitive dye. T h e r e
are t h r e e reagents, conveniently supplied in aerosol
cans. A p r e - s m o o t h e d face is gently etched with 5 %
hydrochloric acid. Zyglo P e n e t r a n t is sprayed on
t h e surface until completely w e t , and allowed to soak
in for at least 10 m i n u t e s . T h e surface is t h e n flushed
with Solvent spray, allowed to dry and then sprayed
with D e v e l o p e r . All these operations should be
carried out in a fume cupboard as t h e vapours are
harmful, and surgical gloves should be used to pro
tect t h e hands from t h e dye. V i e w e d u n d e r a low
energy ultra-violet l a m p , structures such as crosslamination and bioturbation fluoresce bright blue
and yellow.
Most of the techniques used to develop detail on cut

faces of slices or plaquettes are non-destructive, so
t h a t a different technique can be used o n t h e same
face after washing or re-polishing.
SANDSTONES AND SILTSTONES

A light coating of clear mineral oil, even o n polished
surfaces, e n h a n c e s contrast and increases resolution
by filling surface irregularities. If t h e surface is t o be
stained or etched (see Section 4.5), glycerol may be
used, as even traces of oil will inhibit b o t h these
processes, but glycerol can be washed away with
water. With the aid of a z o o m binocular microscope,
small-scale s e d i m e n t a r y structures, such as graded
bedding, can be viewed. T h e d e p t h of field at low
power ( x l . 5 to X20 magnification) allows study of
three-dimensional grain relationships so that packing
and p o r e n e t w o r k s can b e visualized, although frac
ture surfaces need to be examined for comparison.
Slices are also suitable for X-radiography. Slices
from 3 to 10 m m thick give good results because
'soft' (550 k V ) X-rays can be used for high con
trast. This technique is particularly valuable for fine
grained clastic rocks such as siltstones, revealing
otherwise unseen small-scale sedimentary struc
tures. V e r y thin slices can be used to m a k e radiomicrographs for examination on a grain-to-grain
basis. A discussion of these X-radiographic tech
niques is given by H a m b l i n (1971).
CARBONATE ROCKS
B e c a u s e of t h e inherent translucency of their ce
menting mineral crystals, many carbonates display
Bockelie (1973), also working with cryptic argil

laceous limestones, d e m o n s t r a t e d how effectively a
simpler t e c h n i q u e combining light acid etching with
p h o t o g r a p h y using o r t h o c h r o m a t i c film could en
hance fabric contrast and reveal burrow p a t t e r n s .
Micritic carbonates such as those from m u d build
ups and s o m e calcretes may also have cryptic tex
tures which can b e revealed by gentle etching with a
http://jurassic.ru/
89
Fig. 4.2. Cut and smoothed face of Waulsortian facies limestone, Dinantian, Ireland, showing 'sheet spars' with fibrous
ca cite and i n t e r f e r e d carbonate mud. Approximately x2. (a) Smoothed face photographed after coating with mineral
oil (b) Face after etching in dilute hydrochloric acid. Note the fine detail now revealed in the carbonate mud and the
differentiation of coarser geopetal floors in the spar-filled cavities. Photographs courtesy of A Lees
dilute acid (e.g. 5 % hydrochloric acid). G e o p e t a l

sediments in stromatactoid cavities, for e x a m p l e ,
may be difficult or impossible to see on unetched,
polished surfaces (Fig. 4.2a), but are clearly seen
after etching (Fig. 4.2b), although other features
a r e b e t t e r revealed o n t h e polished surface. T h e
techniques of polishing and etching are thus
complimentary.
S m o o t h e d or polished slices can also be observed
directly u n d e r cathodoluminescence (see C h a p t e r
6); they may be etched o r stained for this p u r p o s e .
cherts, and orientation of fluid and crystal inclusions

in evaporites. Various combinations of diffused
transmitted light and bright incident light (delivered
via fibre-optic tubes) can be tried. Contrast can be
optimized and specific features emphasized by ex
perimenting with coloured filters on t h e light sources.
4.4 T H I N S E C T I O N P R E P A R A T I O N
4.4.1 Requirements f o r t h i n s e c t i o n s
OTHER ROCKS
With translucent or transparent rocks, the depth of
field of low power z o o m binocular microscopes can
be used advantageously for three-dimensional study
of included bioclasts and replacement fabrics in
A n acceptable rock thin section is of 30 u m nominal

thickness, b o n d e d to a glass slide. Such standard
thin sections (STs) can b e p r o d u c e d by h a n d o r with
machine aid: they will usually be used for rapid bulk
s a m p l e examination or in teaching collections w h e r e
robustness outweighs their limited resolution. H o w
ever, much m o r e information can b e o b t a i n e d from
88
J . MILLER
cated saw. With evaporites and coals, cutting usually

produces bad fracturing, and for all t h r e e rock-types
t h e effect of a q u e o u s lubricants may be disastrous.
Slices are produced dry as in t h e early stages of thin
section making (Section 4.4.2), with a glass backing.
T h e y are left a few millimetres thick and lapped flat
or polished, using a lapping c o m p o u n d with paraffin
oil lubricant.
Poorly consolidated sediments, o r those for which
porosity information is r e q u i r e d , must first be
v a c u u m - i m b e d d e d in resin (see Section 4.5). T h e
resin may be stained to show the void space.
4.3.2 Examination of c u t faces

Most of t h e techniques used to develop detail on cut
faces of slices or plaquettes are non-destructive, so
that a different technique can be used on t h e same
face after washing or fe-polishing.
SANDSTONES AND SILTSTONES

A light coating of clear mineral oil, even on polished
surfaces, e n h a n c e s contrast and increases resolution
by filling surface irregularities. If t h e surface is to b e
stained or etched (see Section 4.5), glycerol may be
used, as even traces of oil will inhibit both these
processes, but glycerol can be washed away with
water. With the aid of a zoom binocular microscope,
small-scale sedimentary structures, such as graded
bedding, can be viewed. T h e depth of field at low
power ( x l . 5 to x 2 0 magnification) allows study of
three-dimensional grain relationships so that packing
and p o r e networks can be visualized, although frac
ture surfaces need to be examined for comparison.
Slices are also suitable for X-radiography. Slices
from 3 to 10 m m thick give good results because
'soft' (550 kV) X-rays can be used for high con
trast. This technique is particularly valuable for fine
grained clastic rocks such as siltstones, revealing
otherwise unseen small-scale sedimentary struc
tures. Very thin slices can be used to m a k e radiomicrographs for examination on a grain-to-grain
basis. A discussion of these X-radiographic tech
niques is given by H a m b l i n (1971).
CARBONATE ROCKS
Because of the inherent translucency of their ce
menting mineral crystals, many carbonates display
89
their features well with low power biocular micro

scopy. Light coating of mineral oil (or glycerol if t h e
faces are to be etched or stained later) can be used
to e n h a n c e detail and contrast (Fig. 4.2a). H o w e v e r ,
highly polished surfaces are easier to p h o t o g r a p h
t h a n oiled o n e s , as reflections are m o r e easily con
trolled. Slices with two p r e p a r e d faces give a threedimensional context which aids identification of bioclasts and study of depositional and diagenetic
fabrics. T h e partial transparency of the rock allows
focussing u p and down to assess grain packing. T h e
determination of w h e t h e r a fabric is grain- or muds u p p o r t e d otherwise takes considerable experience
to d e t e r m i n e from thin sections, which are essential
ly two-dimensional.
Chalk fabrics are usually cryptic or apparently
h o m o g e n e o u s w h e n sliced normal to bedding.
Bromley (1981) has shown how a b u n d a n t biogenic
and inorganic sedimentary textures can be revealed
by lightly brushing thin mineral oil on a dry chalk
surface and allowing it to ' d e v e l o p ' over a b o u t 30
minutes. F u r t h e r e n h a n c e m e n t of detail can be ob
tained from these surfaces by p h o t o g r a p h i n g t h e m
with Kodalith or equivalent high-contrast o r t h o chromatic line film.
Argillaceous, d a r k , fine-grained c a r b o n a t e s may
also have cryptic fabrics. A technique used for re
vealing flaws in metal casings is often helpful in such
cases. It relies o n t h e preferential absorption on to
clay minerals of an ultra-violet sensitive dye. T h e r e
are t h r e e r e a g e n t s , conveniently supplied in aerosol
cans. A p r e - s m o o t h e d face is gently etched with 5 %
hydrochloric acid. Zyglo P e n e t r a n t is sprayed on
t h e surface until completely wet, and allowed to soak
in for at least 10 m i n u t e s . T h e surface is t h e n flushed
with Solvent spray, allowed to dry and then sprayed
with D e v e l o p e r . All these o p e r a t i o n s should be
carried o u t in a fume c u p b o a r d as t h e vapours are
harmful, and surgical gloves should be used to p r o
tect t h e hands from t h e dye. Viewed u n d e r a low
energy ultra-violet l a m p , structures such as crosslamination and bioturbation fluoresce bright blue
and yellow.
Fig. 4.2. Cut and smoothed face of Waulsortian facies limestone, Dinantian, Ireland, showing 'sheet spars' with fibrous
calcite and interlayered carbonate mud. Approximately x2. (a) Smoothed face photographed after coating with mineral
oil. (b) Face after etching in dilute hydrochloric acid. Note the fine detail now revealed in the carbonate mud, and the
differentiation of coarser geopetal floors in the spar-filled cavities. Photographs courtesy of A. Lees.
dilute acid (e.g. 5 % hydrochloric acid). G e o p e t a l

sediments in stromatactoid cavities, for example,
may b e difficult or impossible to see on u n e t c h e d ,
polished surfaces (Fig. 4.2a), but are clearly seen
after etching (Fig. 4.2b), although other features
a r e b e t t e r revealed on t h e polished surface. T h e
techniques of polishing and etching are thus
complimentary.
S m o o t h e d or polished slices can also be observed
directly u n d e r cathodoluminescence (see C h a p t e r
6); they may be etched or stained for this p u r p o s e .
Bockelie (1973), also working with cryptic argil

laceous limestones, d e m o n s t r a t e d how effectively a
simpler t e c h n i q u e combining light acid etching with
p h o t o g r a p h y using o r t h o c h r o m a t i c film could en
h a n c e fabric contrast and reveal b u r r o w p a t t e r n s .
Micritic carbonates such as those from m u d build
ups and some calcretes may also have cryptic tex
tures which can be revealed by gentle etching with a
OTHER ROCKS
With translucent or transparent rocks, the depth of
field of low p o w e r zoom binocular microscopes can
be used advantageously for three-dimensional study
of included bioclasts and replacement fabrics in
http://jurassic.ru/
iiiiiiiimmiHiiiiiiiimi
cherts, and orientation of fluid and crystal inclusions

in evaporites. Various combinations of diffused
transmitted light and bright incident light (delivered
via fibre-optic tubes) can be tried. Contrast can be
optimized and specific features emphasized by ex
perimenting with coloured filters on the light sources.
4.4 T H I N S E C T I O N P R E P A R A T I O N
4.4.1 Requirements f o r thin sections
A n acceptable rock thin section is of 30 pm nominal
thickness, b o n d e d t o a glass slide. Such s t a n d a r d
thin sections (STs) can be produced by hand or with
machine aid: they will usually be used for rapid bulk
sample examination or in teaching collections where
robustness outweighs their limited resolution. H o w
ever, much m o r e information can be obtained from
90
J . MILLER
matic and semi-automatic m e a n s . T h e extra e x p e n s e
of making these sections is offset by their versatility:
an uncovered D P T can be used for several different
analytical p u r p o s e s , and offers much m o r e p e t r o
graphic information. Machine-based systems give a
considerable increase in t h r o u g h p u t c o m p a r e d with
hand p r e p a r a t i o n . A flow-chart for t h e process (Fig.
4.3) shows stages at which section-making can be
simplified for less exacting r e q u i r e m e n t s , or where
special techniques can be followed for difficult rock
types.
sections m a d e t o a higher specification, with (1) both

rock surfaces ground optically flat and polished, and
(2) special care t a k e n to p r o d u c e an extremely thin
and uniform b o n d i n g film b e t w e e n glass and slice.
T h e s e double-polished thin sections ( D P T s ) can only
b e satisfactorily p r o d u c e d by m a c h i n e ; they a r e t h e
best sections for research work and critical p e t r o
graphic studies.
R e c e n t advances in t h e technology of sectionmaking show clearly t h a t t h e c o m m o n practice of
using coarse abrasives results in unacceptable d a m
age to samples. D i a m o n d - i m p r e g n a t e d buffing
wheels, commonly used for rapid p r e p a r a t i o n of
surfaces after cutting, cause just as much d a m a g e ,
shattering minerals and distorting grain/cement re
lationships. This stricture about severe abrasion
applies both to ST and D P T p r e p a r a t i o n .
In the following account, details are given for
p r e p a r a t i o n of high quality thin sections by a u t o
MOST ROCKS
4.4.2 High quality section-making p r o c e s s

PREPARATION
Unconsolidated sediments, highly porous and fri
able rocks, as well as chips and cuttings, must be at
least partially e m b e d d e d in resin before slicing (also
EVAPORITES, MUDROCKS
AND COALS
POORLY-CONSOLIDATED
AND FRIABLE ROCKS
Slice or grind
flat face IN DRY
Vacuum embed in resin

stain if needed
1
Cut first face
on diamond saw
I
I
\
Lap first face with
abrasive and water
Mount face on glass

slide with epoxy
600 F
carborundum
Lap first face with

abrasive and paraffin
1 (i.m
diamond
Mounting zero bond with epoxy
DPT
600F
1 u.m
diamond
- Cure
Add coverslip
-22 cmRubber O ring
t
ST
Rotating rods
with handles
Uncovered
Sealed by
O rings
Pre-section cut (wet)
PTFE pots for resin
DPT
Finishing lap
polish 1 u.m or
0.25 ixm diamond
GLASS SLIDE
8 mm thick Perspex base
Finishing lap
600-800F
ST
Lap with 600F carbororundum
(a)
ST
/ V Vacuum gauge
Vacuum
Trim
DPT
8 mm thick Perspex lid
-Handle
Trim
I
I
see Section 8.5.5). If the sediments are wet, a watermiscible acrylic or polyester resin can be used.
Otherwise, the specimen can be dehydrated by
passage through successively m o r e concentrated
ethanol/water mixtures, through absolute alcohol
into a c e t o n e , before placing in resin. If oil is pre
sent, r e m o v e as described in Section 8.5.1. Organic
matter can be removed with chlorox or hydrogen
peroxide. Poorly consolidated sediments and p o r o u s
sandstones may require impregnation with resin
u n d e r vacuum. Impregnation u n d e r pressure has
been advocated, but comparative tests have shown
that it may d a m a g e pores in sandstones, particularly
those lined with delicate clay minerals. V a c u u m
(strictly, low pressure: 1015 m m Hg) impregnation
has been found consistent and satisfactory for most
sediment types. Cold setting resins such as ' E p o - t e k '
are convenient for impregnation as they have a low
initial viscosity and thus p e n e t r a t e very well. It is
also possible to dilute s o m e Araldite resins with
t o l u e n e for pre-casting soak. D e p e n d i n g o n the
n a t u r e of t h e s a m p l e , a degree of experimentation
with resins of different types may be necessary before
Fig. 4.3. Flow chart showing sequence of operations in production of standard thin sections (ST) and double- polished thin
sections (DPT) for different types of rock samples.
Fig. 4.4. A chamber for resin impregnation of porous or

friable rock samples prior to slicing and thin section
preparation, (a) Side elevation, (b) Plan view. Depending
on the diameter of the chamber, one or more sets of
rotating spindles can be used, according to the required
throughout of samples. For procedure, see text.
91
satisfactory results a r e achieved. A simple m e t h o d

is described in Section 8.5.5, using a desiccator and
mains water v a c u u m p u m p . T h e m o r e elaborate
c h a m b e r illustrated in Fig. 4.4, which can be con
structed quite cheaply, is designed to overcome some
problems in simpler c h a m b e r s , w h e r e either t h e resin
is drawn into t h e c h a m b e r after the sample is outgassed, or t h e sample is placed in the resin and both
are evacuated together (as in Section 8.5.5). In the
first case, the resin itself does not outgas thoroughly
before coming into contact with the specimen, so gas
and resin are both drawn into the p o r e s ; resin also
solidifies in t h e inlet line. In t h e second case, frothing
may be produced as both t h e sample and the resin
outgas together. T h e a p p a r a t u s shown in Fig. 4.4 is
loaded with P T F E plastic p o t s , previously sprayed
with a silicone release agent (e.g. silicone household
polish) and containing the resin mixture. Samples,
t r i m m e d to suitable size, are suspended above t h e
pots on the blades of t h e cross-rails. Evacuation is
continued until t h e resin ceases to froth, when the
samples will also have b e e n outgassed. T h e crossrails a r e t h e n rotated so as to tip t h e samples into t h e
resin pots. Samples can be left in t h e impregnation
c h a m b e r overnight before curing u n d e r gentle heat.
A t t h e end of the impregnation period, care should
b e t a k e n to release t h e vacuum slowly so as not to
cause boiling.
Following impregnation, small samples may have
to be cast into blocks which a r e m o r e convenient for
t h e sawing or for hand-holding while grinding a face
on abrasive p a p e r . Small moulds for casting blocks
can be m a d e from aluminium foil.
Estimation of porosity in rocks is aided by im
pregnation with stained resin. Special resin-miscible
dyes are r e q u i r e d , such as E p o - t e k Blue Keystone or
Waxoline B l u e , mixed in a 1 0 % dye:epoxy ratio.
Blue resin areas in t h e final thin section depict the
porosity clearly.
Generally speaking, the machine system of
section-making is so gentle that only very difficult
lithologies and loose sediments will need impregna
tion. T h e following account details the sectionmaking process for s t a n d a r d rocks, with special
p r o c e d u r e s for friable or soluble lithologies de
scribed in Section 4.4.3.
CUTTING AND TRIMMING

Several sizes of thin sections can be m a d e , d e p e n d
ing on e q u i p m e n t available and the area required for
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Iii
fffffffffffffffffff|f
92
J . MILLER
examination. Useful and fairly standard sizes are 25

x 76 m m , 28 x 48 m m (best for electron m i c r o p r o b e
and cathodoluminescence work) and 110 x 75 m m
(good for fabric studies and coarse sediments). T h e
selected area of a faced sample or hand specimen
must be m a r k e d with water insoluble felt tip pen
before cutting. Slices from 4 to 6 m m thickness are
cut on a saw with a diamond impregnated wheel
(Fig. 4.5a), usually with water or an oil/water mix as
a lubricant.
by saw d a m a g e . T h e slices are trimmed to avoid

rock overhanging the slide. This discourages mount
ing adhesive from oozing on to the lower surface of
the p r e p a r a t i o n , w h e r e it would affect attachment
on the lapping machine's vacuum chucks.
E a c h slice is m a r k e d in waterproof felt-tip pen
with the corresponding sample n u m b e r and any 'way
up' information.
Cutting should be d o n e gently (slowly) to mini

mize shattering, especially with crystalline or welljointed rocks. Several slices or plaquettes may be
cut, which can be examined separately (see Section
4.2) or used as a b a c k - u p , should there be a failure
at some subsequent stage in t h e section-making pro
cess. T h e s e relatively thick slices give good mechani
cal rigidity and wide zones of waste for first face
lapping and final finishing, so that t h e completed
section is m a d e from that part of t h e slice unaffected
100 m m . D e p e n d i n g on slide size, up to about 24

slices can b e flattened in o n e timed half h o u r r u n .
In all cases, the lap is run at a slow speed, 2530
r p m , as o p p o s e d to the greater speeds r e c o m m e n d
ed by t h e lapping m a c h i n e manufacturers. T h i s gives
m o r e control over the process, with the advantage of
keeping t h e sections cool, further reducing d a m a g e
and enabling the preparations to be used for fluid
inclusion work.
FIRST FACE LAP

T h e key to success of the whole process lies in the
production of a first face which is as smooth and flat
as possible. This is accomplished on a precision free
abrasive flat lapping machine (Fig. 4.5b). T h e slices
are m o u n t e d on chucks with a sponge backing to
a c c o m m o d a t e different thicknesses and irregular
specimens (Fig. 4.6). Completely omitting coarse
abrasives, a face of t h e slice is ground with 600F
C a r b o r u n d u m p o w d e r with water as a lubricant, for
a minimum of 30 minutes (regardless of rock t y p e ) ,
until the face approaches optical flatness.
A t this stage, slices destined to b e c o m e Standard
Thin sections (STs) can be r e m o v e d h e r e for resin
bonding to glass. O t h e r w i s e , they are lapped for a
further period using 8 um diamond paste if required
for D o u b l e Polished T h i n sections ( D P T s ) (Fig. 4.3).
This extra lapping stage produces a polished lower
surface, giving increased resolution in microscopy
by reducing dispersion at the first face/resin junc
tion. T h e face has enough 'key' to ensure bonding
with resin. H i g h e r degrees of polish produced by
lapping with finer d i a m o n d pastes give n o noticeable
i m p r o v e m e n t in optical properties and can lead to
adhesion p r o b l e m s , notably to lifting of the thin slice
at later p r e p a r a t i o n stages. With a properly main
tained precision lapping m a c h i n e , it should easily be
possible to maintain a flatness of at least 2 um over
Lead weight
Pressure block
with handle
Sponge rubber
Fig. 4.5. Equipment used in semi-automatic preparation of thin sections, (a) Bench-mounted diamond-impregnated saw
with diamond-impregnated buffing wheel (to right) for rapid sample trimming. Note safety guards, (b) Precision flat
lapping machine (Logitech Ltd), showing vacuum chuck positioned on lap. (c) Close up view of sole face of vacuum chuck
for precision flat lapping machine. Note the slots for slide mounting, and the diamond impregnated rim which helps to
condition the lap. (d) Zero-bonding jig for applying controlled pressure to rock slice and section glass while resin cures
under gentle heat from hot-plate below.
Sliced rock samples

Cross-section of lap
Fig. 4.6. Cross-section of chuck for holding sample on

precision flat grinder when making the first face.
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iiiiimiiiimiiiiiiiwiiii
93
GLASS SLIDE P R E P A R A T I O N
F o r t h e precision machine finishing process, the
glass slides must be of a precise and standard thick
ness. Commercial microscope slides rarely m e e t this
r e q u i r e m e n t and so are first ground on t h e flat
lapping machine as described above for rock slices.
F o r STs, polishing with 1 um d i a m o n d paste is usual.
With D P T p r e p a r a t i o n s , the 600F ground glass sur
face is used without final polish, as a slightly rough
zone is required as a 'key' to ensure adhesion at the
glass/resin interface.
BONDING SLICE TO GLASS SLIDE

Glass and rock surfaces must be cleaned of all
abrasives, freed of grease by rinsing in acetone or
p e t r o l e u m e t h e r , and dried. T h e prime requirement
t h e n is to p r o d u c e an extremely thin but uniform
glass/rock b o n d ('zero b o n d ' ) with an adhesive whose
refractive index is close t o that of glass. It is vital to
p r o d u c e consistent and minimum cement thickness,
otherwise there will be unpredictable variations in
the thickness of t h e finished section.
C a n a d a Balsam and Lakeside 70C have long been
used as slide m o u n t a n t s , but they cannot produce a
reliable bond for machine finishing, particularly with
polished first faces. M o r e o v e r , they have poor stab
ility, becoming brittle or discoloured with age. Being
thermolabile, these resins a r e also unsuitable for
sections to be studied in cathodoluminescence or
electron microprobe e q u i p m e n t . Resins with all t h e
required characteristics can be found in the E p o x y
family. Allman & L a w r e n c e (1972) give a useful dis
cussion of t h e properties of E p o x y resins for geo
logical use. Araldite MY750 mixed with Versamid
polyamide h a r d e n e r ( 1 : 1 ) is an excellent all-round
bonding resin with good high t e m p e r a t u r e stability
and t h e correct refractive index. If sections have
been pre-impregnated in a cold-setting resin such as
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J . MILLER
E p o - t e k , then they should be b o n d e d with the same

material.
Glass sides are first m a r k e d with the specimen
n u m b e r of t h e sample and any 'way u p ' indications
which have been preserved, using a d i a m o n d scribe
near o n e edge of t h e obverse glass face.
A small a m o u n t of mixed low-viscosity resin/
h a r d e n e r is applied to the first face, which is m o u n t
ed on the lapped surface of the slide. T h e assembly
is then placed in a spring-loaded jig (Fig. 4.5d)
u n d e r a pressure of about 1 k G c m . A t first, t h e
section 'floats', but as t h e adhesive rapidly squeezes
out, t h e rock locks on to t h e glass and n o longer
slips. B o n d s m a d e in this way are extremely trans
p a r e n t , bubble-free and introduce n o dimensional
errors into final lapping.
D P T polishing can be d o n e on the same m a c h i n e ,

using graduated d i a m o n d pastes, but in t h e Edin
burgh w o r k s h o p we have found that better results
are obtained on a separate polishing machine. This
also has the advantage of freeing the precision lap
ping machine for preparing successive batches of
slides, as the polishing stage can be protracted. T h e
polishing machine consists of a simple rotary polish
ing lap running at up to 30 r p m , on which is placed a
precision lapping chuck (Fig. 4.7a) with several
slides held by vacuum suction (Fig. 4.7b). Polishing
is carried out on adhesive-backed paper discs (Engis
papers) attached to t h e lap. It begins with a charge
of 8 um diamond slurry such as H y p r e z c o m p o u n d .
This does not need replenishing unless t h e surface is
very h a r d (quartzite or chert).
M o u n t s must be left to cure u n d e r pressure. With

t h e resin combination used a b o v e , the jig is placed
on a hotplate and curing carried out at 80C for
a b o u t 15 minutes. F o r h a n d - p r e p a r e d specimens,
spring-loaded clothes pegs can be used to provide
even pressure, and these are also .very useful for
large sections, w h e r e four or m o r e pegs can p r o d u c e
a m o r e even b o n d than the standard jig.
A n y faults in previous p r e p a r a t i o n stages will

show up h e r e : if t h e section is not flat, because of a
p o o r first face or incorrect bonding, polishing will
follow t h e irregularity and a wedged slice with e r o d e d
edges will result.
Lapping is continued until t h e section reaches
3035 um (about 10 minutes for soft rocks, up to 30
minutes for h a r d e r o n e s ) . A s this is t h e stage at
which material is actively r e m o v e d , t h e sections
should be watched carefully during this process.
After washing and change of lap p a p e r , polishing is
continued with 1 um d i a m o n d . Little or n o material
is r e m o v e d during t h e final stages; the surface is
being improved and so time is not critical. For
critical w o r k , final lapping is d o n e with 0.25 um
diamond paste. This is n e e d e d for electron micro
p r o b e or back-scattered Scanning Electron Micro
scope work where a perfect surface is r e q u i r e d .
E x p e r i m e n t s h a v e shown that t h e most flawless sur
faces are produced by carrying out t h e final lapping
stages on a lead lap. This consists of a very flat sheet
of metallic lead, about 8 m m thickness, b o n d e d to a
s t a n d a r d steel lap disc. T h e lead is p r e p a r e d by
engraving a spiral groove several millimetres d e e p ,
pitched so that t h e lead strip is n a r r o w e r than t h e
groove. Sections are lapped using paraffin oil as a
lubricant. N o material is r e m o v e d , but t h e surface is
perfected, so lapping time is not critical. This m e t h o d
can only b e used for n o n - p o r o u s and crystalline rocks
(particularly limestones), as t h e lead tends t o be
forced into any p o r e s and, unlike p o w d e r e d abras
ives, it cannot b e washed away. B e c a u s e of its very
soft surface, trueing and conditioning of t h e lead lap
must be d o n e frequently, and care t a k e n to exploit
the whole surface to avoid worn spots and dishing.
- 2
PRE-SECTION GUTTING
B o n d e d sections are next cut with a d i a m o n d blade
to form a parallel second face, leaving a slice 300
400 um thick on t h e slide. This initial thickness
allows the final 30 um section to be entirely in the
u n d a m a g e d layer. Cutting can be d o n e automati
cally on a d i a m o n d - i m p r e g n a t e d saw with a vacuum
chuck, holding u p to six slides simultaneously. Pre
cision is not i m p o r t a n t h e r e , as there is a machine
finishing stage to follow.
FINISHING
A t this stage, ST preparations are r e t u r n e d t o t h e
precision lapping machine for lapping to a final 30
um thickness with 600F or 800F C a r b o r u n d u m .
Thickness is automatically d e t e r m i n e d by pre-setting
t h e vacuum slide-holding chuck (Fig. 4.5c); slides
have reached t h e set thickness when they begin to
'float' on t h e lap, a process aided by t h e d i a m o n d i m p r e g n a t e d surround o n t h e lower face of t h e
chuck. Slide thickness can b e checked with a microm
eter or, less reliably, o n a microscope, looking for
the required interference colours, e.g. quartz greys.
This optical m e t h o d is of little use for limestones.
95
Fig. 4.7. (a) Polishing lap for final finishing of thin sections, showing a vacuum chuck and a weighted chuck in position,
(b) Sole face of vacuum chucks showing how various sizes and types of thin sections can be polished simultaneously.
Ultra-thin sections are valuable for some pur

poses, particularly for very fine grained rocks, if it is
necessary to m e a s u r e grain size accurately (Halley,
1978) or to study fine structures such as algal fila
m e n t s . Such sections are produced by extending t h e
1 um diamond finishing stage, at which material is
slowly r e m o v e d and t h u s m o r e easily controlled.
M i c r o m e t e r m e a s u r e m e n t s must be m a d e frequent
ly, as it is very easy to polish the section away
completely if the rock is soft. Optical m e t h o d s of
checking thickness by examining the interference
colours will not work for these very thin slices,
which produce very bright, high order colours.
COVERING
For research purposes it is best to leave thin sections
uncovered, as they may then be subjected to a
variety of t r e a t m e n t s including staining, etching,
cathodoluminescence and microprobe work. Coverslips a r e , of course, required for thin sections des
tined for teaching collections. D P T preparations
need n o oil for microscopic examination, but un
covered S T surfaces, being finished only t o 600F or
800F C a r b o r u n d u m , require oil or glycerine before
microscopic study.
All sections should be cleaned of abrasive residue
before examination. This may be d o n e by wiping
D P T s with a soft, d a m p tissue, or by brief immer
sion in an ultrasonic b a t h . ST preparations may be
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left uncovered b u t sprayed with a p o l y u r e t h a n e resin

to give a protected surface for general microscopy
(Moussa, 1976, 1978). T h e best medium for attach
ing standard glass coverslips is C a n a d a Balsam. This
has t h e required refractive index and the advantage
that the slip can be r e m o v e d if n e e d e d , after gentle
heating on a h o t p l a t e . C o v e r e d slides should be
cured in a warm place for at least 24 hours before
use.
LABELLING
Standard thin sections required for teaching collec
tions o r archive purposes can now be given selfadhesive labels on which can be written all the
details of the sample. H o w e v e r , p a p e r labels should
not be used for those sections destined for use in
cathodoluminescence a n d scanning electron micro
scopes or m i c r o p r o b e , as they tend to char in the
b e a m and may interfere with conductive coatings.
4.4.3 Variations in p r o c e s s f o r
'difficult' rock t y p e s
Certain rocks, such as shales, evaporites, coals, soft
chalks and poorly-consolidated sediments require
special t r e a t m e n t at various stages of t h e sectionmaking p r o c e d u r e . Initial impregnation and em
bedding, if required, will have been completed as
96
J . MILLER
detailed above. With such difficult material, cutting

on t h e usual d i a m o n d trimming saw is inadvisable,
and water-based lubricants cannot be used.
Flat faces are produced by hand grinding on car
b o r u n d u m - i m p r e g n a t e d papers ('wet and dry' p a p e r )
in the dry. With h a r d e r samples, a hacksaw will
p r o d u c e a face ready for lapping. T h e surface need
not b e perfectly flat or s m o o t h . Evaporites can then
be t a k e n directly o n to the precision grinder for first
face lapping using paraffin oil as lubricant, but o t h e r
rocks need a further stage. This involves m o u n t i n g
t h e g r o u n d face o n to a glass slide of a p p r o p r i a t e
size, using epoxy resin: again this can be d o n e quite
crudely. Using a dry trimming saw (with t h e oper
ator wearing a m a s k ) , excess rock is r e m o v e d . This
sawn surface will b e c o m e t h e first face of t h e section,
and it is lapped with paraffin oil and 600F C a r b o
r u n d u m on the precision lapping machine. After t h e
best flat surface is o b t a i n e d , the paraffin oil is re
moved by placing t h e preparation o n a warm plate
for some hours. T h e sections are then zero b o n d e d
with epoxy as described in Section 4 . 4 . 2 , t o form a
double glass m o u n t with a few millimetres of rock
sandwiched b e t w e e n .
If the first face is not satisfactory at this stage
(wedged or with air bubbles), then o n e of the glass
slides can b e cut off and the section re-lapped and
r e - m o u n t e d . O t h e r w i s e , the sandwich is placed on
the saw and t h e first glass slide cut off. T h e section is
t h e n returned to the Precision Lapping Machine
with paraffin oil and 600F grit and taken down to 100
urn thickness, or 30 um if it is to be covered. For best
results it is transferred, after rinsing in paraffin o r
k e r o s e n e (inflammable!), to the polishing lap for
final surfacing as for D P T s (see Section 4.4.2). Shale
sections benefit from a long period with 0.25 um
p o w d e r , as this gives very slow removal of material
without plucking of quartz grains. Sections of
evaporites are either glass covered or stored in a
desiccator.
ed with various weak acids. In all cases surfaces to

be etched must be grease-free (no
fingerprints!).
ETCHING LIMESTONES
Hydrofluoric acid treatment
Etching vessels should be shallow, tightly-closing

and m a d e of p o l y t h e n e or similar soft plastic. Small
plastic food containers are suitable, with an impro
vised plastic sling-like support for plaquettes or thin
sections suspended from t h e lid (Fig. 4.8). E x p o s e d
surfaces of glass slides, especially t h e u n d e r s i d e s ,
should be painted with paraffin wax before placing
in t h e container. This prevents H F from frosting the
slide and reducing its transmissivity. T h e H F needs
to be a strong solution (5255%), with the vessel
filled to a depth of a b o u t 56 m m . Etching times in
H F vapour d e p e n d on t h e n a t u r e of t h e rock: feld
spars, for e x a m p l e , require about 30 minutes etch be
fore they are to be stained. Stubborn cases can be
etched directly in t h e H F solution. Samples should be
inserted and r e m o v e d from t h e a p p a r a t u s using
plastic o r r u b b e r gloves, a n d care t a k e n n o t to b r e a t h
t h e v a p o u r . Copious washing u n d e r clean t a p water is
required before t h e samples can be t r e a t e d further,
and wax scraped from slides. T h e latter process is
II
4.5.2 Staining
While the mineralogical composition of rocks can be
d e t e r m i n e d by optical study of thin sections, this can
be a tedious, time consuming and error p r o n e pro
cess. F o r e x a m p l e , distinction between calcite and
dolomite is difficult because they have similar optical
properties. For similar reasons, small untwinned
feldspar grains and q u a r t z grains cannot easily be
distinguished. Chemical staining involves a reaction
which produces a coloured precipitate on a specific
mineral surface and therefore m a k e s that mineral
m o r e easily recognized. Usually the surface requires
s o m e p r e p a r a t i o n , often etching, t o receive and
retain t h e precipitate.
Sling support
FELDSPARS
Fig. 4.8. Simple apparatus for etching thin sectons or small

slices with HF vapour to be used in a fume cupboard
only.
Thin sections for etching should be left a little

thicker than usual, after being taken down to at least
the 600F C a r b o r u n d u m stage. In some instances, t h e
complete removal of c a r b o n a t e from a thin section
can provide additional information (Lees, 1958).
This leaves the insoluble c o m p o n e n t s available for
H o u g h t o n (1980) gave a m e t h o d for staining plagioclase and alkali feldspars which is much m o r e reli
able than previous recipes.
R e a g e n t s : (a) Potassium rhodizonate (0.01 g
K-rhodizonate in 30 ml distilled water, filtered b e
fore use). M a x i m u m useful life o n e hour.
Thin section glass
1 V
Wax coating
T h e success of staining slices and thin sections

d e p e n d s , as does etching, on various factors: strength
a n d 'age' of r e a g e n t s , t e m p e r a t u r e , p r e - t r e a t m e n t ,
grain size, orientation, fabric, grain interactions,
cleavage and surface finish. T o achieve consistently
good results with any staining p r o c e d u r e requires a
considerable degree of skill. Much patient experi
m e n t a t i o n may b e required. Staining times in par
ticular are highly variable, and those given herein
should only b e used as a starting point.
Detailed guides for staining are given by Allman
& L a w r e n c e (1972) and F r i e d m a n (1971). In this
section only the most successful techniques for com
mon sedimentary minerals are given, with an em
phasis on those which have been recently refined.
Thin section face being etched

HF solution
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observation in a dry state by reflected light or

transmitted light with crossed nicols. F o r this tech
n i q u e , t h e lower sample face is etched with 3 0 %
acetic acid for 5 min before rinsing, drying and
bonding to t h e glass slide. This preliminary etch
ensures that a replica is formed in resin of the
c a r b o n a t e phases, and t h a t t h e n o n - c a r b o n a t e com
p o n e n t s a d h e r e to t h e p r e p a r a t i o n . T h e 30 um sec
tion is then immersed in 3 0 % acetic until all the
c a r b o n a t e is dissolved. T h e replica shows details to
at least 5 um resolution.
Etching is simply carried out by placing the slice

or thin section face u p in t h e chosen etching solu
tion. If the specimen is immersed face-down, bub
bles cannot be released and remain attracted by
surface tension to t h e surface, locally impeding fur
ther reaction and giving a very uneven etch.
T h e rate of etching varies according to the n a t u r e
and strength of the solution, its t e m p e r a t u r e , and
t h e grain size, crystallinity and mineral composition
of the substrate. Etching times may vary from less
than a m i n u t e to over half an hour. T h e o p t i m u m
time must be d e t e r m i n e d by trial and error. G e n t l e
agitation of t h e acid, and slight tilting of the face
prevents t h e formation of b u b b l e trains which trench
the surface. F o r critical applications, t h e progress of
etching can be observed with a binocular microscope
(with a clear plastic bag tied over t h e optics to
prevent corrosion from acid spray). This works best
with t h e slower and m o r e easily-controlled action of
d i N a E D T A , and is ideal for studying t h e location of
delicate organic m a t t e r , such as shell m e m b r a n e s or
algal and fungal filaments. Etching a thin section in a
10% solution of N H C 1 for 2 minutes is also good
for revealing filaments, which a r e t h e n best seen in
a combination of reflected and transmitted light.
Plastic box -
Etching involves selective partial dissolution of a cut

face. It may be d o n e to emphasize certain textural
characteristics or to p r e p a r e a surface for staining
(see Section 4.52). Hydrofluoric acid is t h e etching
agent for silicate-rich rocks; carbonates can be etch-
Several reagents are available for etching carbonate

minerals. Hydrochloric acid (15% by volume)
gives a vigorous reaction with a tendency t o give a
rather unselective etch. It affects minerals other
than calcite and aragonite, especially if the solution
is w a r m . Acetic acid ( a b o u t 2 0 % by volume) gives a
m o r e selective etch, bringing out details of grain
textures and fabrics m o r e subtly t h a n HC1. Disodium ethyl diaminotetracetic acid ( d i N a E D T A ) is
an even m o r e subtle etching agent: it has a chelating
(complexing) action with comparatively little effer
vescence, thus reducing gas bubble d a m a g e of de
licate structures. Miller & Clarkson (1980) used
saturated E D T A solutions to reveal ultra-structure
in calcitic trilobite cuticles.
HF is a dangerous chemical with a poisonous and

corrosive vapour. It attacks glass, metal and some
plastics. Severe burns result after skin contact even
with dilute solutions; the burns may not appear until
hours after exposure. Splashes on skin should be
neutralized immediately
with a sodium
bicarbonate
solution, washed with copious amounts of water and
treated with special HF Burn jelly, which should be
available in all laboratories where HF is used. All
operations involving HF should be carried out in a
fume cupboard,
and the operator protected
with
gloves and goggles. Surplus and discarded acid should
be neutralized with alkali before
disposal.
4.5 E T C H I N G A N D S T A I N I N G
4.5.1 Etching
m a d e easier by placing the slide in a refrigerator for

a few minutes.
97
98
J . MILLER
(b) Sodium cobaltinitrate (saturated solution; a b o u t

50 g p e r 100 ml distilled w a t e r ) . Six m o n t h s shelf life
in d a r k bottle.
(c) Barium chloride ( 5 % solution in distilled w a t e r ) .
Stable.
P r o c e d u r e : (a) E t c h over H F vapour ( 5 5 % H F solu
tion, see Section 4.5.1) for 2 5 - 3 5 s: increase time if
H F is loosing potency.
(b) R e m o v e slide from etching box with polythene
forceps and d r o p into b e a k e r with Na-cobaltinitrate
solution. L e a v e for 45 s.
(c) Rinse slide twice in distilled or de-ionized water.
Gently shake off excess water and blot end of slide
by touching to a p a p e r towel.
(d) D i p slide quickly into b e a k e r with B a C l solution
for n o m o r e than 2 s.
(e) D i p slide immediately in distilled water and
agitate for about 10 s.
(f) Place several drops of t h e rhodizonate solution
on the wet surface of t h e section, tilting back and
forth to spread t h e stain; leave until plagioclase
grains b e c o m e pink, t h e n rinse in water.
(g) D r y with compressed air and e x a m i n e with a
microscope. If plagioclase is light grey or pale pink,
dip in distilled water and* r e p e a t rhodizonate stage.
T h e intensity of t h e pink plagioclase stain is p r o p o r
tional t o t h e a m o u n t of calcium in t h e molecule:
albite/oligoclase will stain lighter than a m o r e calcic
plagioclase. P u r e Na-albite will not t a k e u p any of
the rhodizonate stain. Alkali feldspars a r e stained
yellow. T h e accuracy of t h e m e t h o d decreases ac
cording to grain size: with finer grained specimens,
t h e pink stain tends to p e r v a d e t h e surface and
obscure t h e quartz grains.
Cathodoluminescence is a much b e t t e r way of
detecting feldspars in fine sands and siltstones (see
C h a p t e r 6).
2
nitrate with constant stirring until the milky p r e

cipitate just dissolves or is just about to approxi
mately 8 drops of acid is usually sufficient.
(d) Test t h e reagent by adding a few d r o p s to small
crystals of N a S 0 or K S 0 in a watch glass. A
yellow precipitate should form immediately. If n o t ,
t h e reagent is t o o acid and a further gram of mer
curic nitrate a d d e d to produce a slight cloudiness
should produce t h e yellow precipitate.
(e) Filter t h e solution when the test is successful and
store in a dark bottle.
P r o c e d u r e : (a) I m m e r s e the section, slab or plaq u e t t e in the reagent contained in a suitable dish or
tray for a few seconds or until the yellow precipitate
forms.
(b) Gently rinse t h e stained face in de-ionized or
distilled water and allow to dry before microscopic
examination.
Both minerals are stained yellow; other minerals are
unstained.
2
specific stains for dolomite, but have the disadvan

tage for thin sections of needing to boil.
Titan yellow reagent: (a) 0.2 g Titan yellow
is dissolved in 25 ml m e t h a n o l in a small b e a k e r
over a hot water bath. R e p l a c e any alcohol lost by
evaporation.
(b) 30 g sodium hydroxide pellets dissolved cauti
ously in 70 ml distilled water.
Titan yellow p r o c e d u r e : (a) A d d 15 ml of t h e
3 0 % N a O H solution to the Titan yellow solution
and bring to t h e boil.
(b) I m m e r s e t h e thin section or p l a q u e t t e in boiling
Titan yellow reagent for at least 5 min until a d e e p
orange-red colouration is formed. A d d a few drops
of m e t h a n o l to c o m p e n s a t e for evaporation.
Alkaline Alizarin red S reagent: (a) Dissolve
0.2 g Alizarin red S in 25 ml m e t h a n o l in a small
b e a k e r over a hot water b a t h ,
(b) Carefully dissolve 30 g sodium hydroxide pellets
in 70 ml water.
Alkaline Alizarin red p r o c e d u r e : (a) A d d 15 ml
of t h e 3 0 % N a O H solution t o t h e Alizarin red
solution and bring to the boil.
(b) I m m e r s e t h e section or p l a q u e t t e in boiling
r e a g e n t for at least five m i n u t e s . A d d a few drops of
m e t h a n o l to c o m p e n s a t e for evaporation.
(c) Rinse t h e section in distilled water.
D o l o m i t e is stained p u r p l e , calcite is unstained in
the alkaline solution.
ARAGONITE
T h e most sensitive stain for aragonite was developed
by Fiegl (1937). Despite its sensitivity, it is not
always reliable.
R e a g e n t s : (a) 1 g commercial grade A g S 0 is a d d e d
to a boiling solution of 11.8 g M n S O . 7 H 0 in 100
ml distilled water.
(b) Cool and filter t h e suspension; add 2 d r o p s 1 0 %
sodium hydroxide solution.
(c) Stand for 2 h o u r s and then filter into a dark
storage bottle.
P r o c e d u r e : I m m e r s e t h e p l a q u e t t e or thin section in
t h e Fiegl's solution for a b o u t 10 min at 20C. Some
times a hot solution works better.
A r a g o n i t e is stained black while calcite remains
unstained.
2
MG-CALCITE
C h o q u e t t e & Trusell (1978) devised a m e t h o d of
making an alkaline Titan yellow stain p e r m a n e n t ,
enhancing the value of this technique. T h e stain can
detect t h e presence of Mg-calcite containing more
than about 3 % M g C 0 .
R e a g e n t s : (a) Stain: 1.0 g Titan yellow p o w d e r , 8.0 g
N a O H and 4.0 g d i N a E D T A dissolved in 1 litre
distilled water at r o o m t e m p e r a t u r e . Store in d a r k
bottle; shelf life at least two years,
(b) Fixer: 200 g N a O H pellets dissolved slowly in 1.0
litre distilled water. Caution! heat and fumes and
evolved, so best carried o u t in fume c u p b o a r d . Solu
tion is corrosive t o flesh. Store in polythene bottles
as 5 M caustic soda etches glass. Shelf life indefinite.
P r o c e d u r e (Caution! use surgical gloves as solutions
are corrosive): (a) Thin sections must be epoxy
m o u n t e d : Lakeside and C a n a d a Balsam are soluble
in t h e stain solution.
3
GYPSUM AND ANHYDRITE

H o u n s l o w (1979) gave a m e t h o d for staining these
minerals, useful in t h e field as well as o n drill cores,
soil samples, slabs and sections.
R e a g e n t s : (a) 1:1 nitric acid solution (10 ml con
centrated nitric acid slowly added to 10 ml water in a
50 ml b e a k e r ) .
(b) 10 g mercuric nitrate in 100 ml de-ionized water.
Stir until dissolved. A fine, milky precipitate will
form. Caution! Mercuric nitrate is extremely poi
sonous and may be absorbed through the skin.
(c) Slowly add the 1:1 nitric acid t o t h e mercuric
DOLOMITE
D o l o m i t e is often distinguished from calcite by its
failure to stain with solutions which react with cal
cite (see below). It can also be recognized after
etching, especially on a universal stage: dolomite
remains at 30 u m , giving fourth- and
fifth-order
pinks and greens, while calcite is reduced to 10 um
or s o , giving second- and third-order r e d s , blues and
yellows (Dickson, 1966, p . 491). Titan yellow in
alcohol and alkaline Alizarin r e d S a r e two reliable
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(b) E t c h u n c o v e r e d , grease-free thin section or faced

s a m p l e for a b o u t 30 s in 5 % acetic acid solution.
(c) D r y surface in stream of warm air.
(d) I m m e r s e specimen in stain solution for about 20
min.
(e) D r y stained surface in stream of warm air; d o not
touch surface in any way.
(f) I m m e r s e stained surface in fixer solution for
about 30 s.
(g) Air dry again and cover. A s t h e residual caustic
would attack Lakeside or C a n a d a Balsam, epoxy
c e m e n t is required for cover slips.
C h o q u e t t e & Trusell (1978) found that the intensity
of t h e stain was proportional to the M g content of
calcite. Calcite with 58% M g C 0 takes o n a pink
to pale red colour, and 'high-Mg' calcite takes on a
d e e p red colour, c-axis normal sections of crystals
stain m o r e vividly t h a n parallel sections, as d o very
fine-grained substrates. This stain is very valuable
for its m i n u t e selectivity o n a scale discernible with a
petrographic microscope.
3
CALCITE
F r i e d m a n (1959) gave a n u m b e r of stains for calcite.
O n e of t h e simplest and most reliable is Alizarin red
S. Many c a r b o n a t e workers routinely acid etch o n e half of a thin section and stain it in acidified Alizarin
red S solution before covering. While this helps to
distinguish between red-stained calcite and unstain
ed dolomite and q u a r t z , it gives very little o t h e r
information about diagenesis and mineralogy. It
also m a k e s microphotography of that slide difficult.
A far m o r e valuable s c h e m e was given by Dickson
(1965, 1966) which in o n e operation differentiates
b e t w e e n ferroan phases in calcites and dolomites,
and is capable of revealing subtle growth zones in
c e m e n t crystals.
Dickson's m e t h o d reagents: (a) Etching sol
ution 15 ml of 3 6 % HC1 dissolved in 500 ml dis
tilled water, then topped up to 1000 ml with distilled
water.
(b) Staining solution part 1:0.2 g Alizarin red S
dissolved in 100 ml 1.5% HC1 solution.
(c) Staining solution part 2 : 2 g potassium ferricyanide crystals dissolved in 100 ml 1.5% HC1 solu
tion. This solution must be freshly m a d e for each
staining session.
(d) Mix staining solutions parts 1 and 2 in the ratio 3
of d y e t o 2 ferricyanide. T h e c o m b i n e d solution lasts
for only o n e staining session.
100
J . MILLER
Dickson's m e t h o d p r o c e d u r e (Caution!
use
r u b b e r gloves): (a) I m m e r s e thin section (grease
free surface) or faced sample in etching solution,
face u p p e r m o s t , for 1015 s at 20C (times are only
a p p r o x i m a t e , and may vary widely with grain size,
etc.). Cold solutions give very p o o r results. Experi
m e n t a t i o n is necessary to achieve the o p t i m u m etch.
W e a k etching gives a thin, patchy stain. Overetching, particularly with Alizarin red S, produces a
very dense stain which tends to spread a precipitate
even over dolomite and quartz if they are present.
(b) I m m e r s e specimen in t h e combined solution for
3045 s (again experimentation is r e q u i r e d ) . F o r
thin sections, best results are obtained if the stain is
w a r m e d . A s H C N fumes can be evolved from t h e
mixed stain, the safest way of doing this is t o im
m e r s e t h e slide in a dish of hot water before placing
in t h e bath of stain which is at r o o m t e m p e r a t u r e .
Avoid skin contact with the stain: ferricyanide
is
poisonous. Dickson suggested a further stage, briefly
dipping t h e stained slide or surface into Alizarin red
solution alone, but this is not often n e e d e d and
indeed may detract from t h e first stain.
(c) Wash the specimens gently in two changes of
distilled water (not tap water, which contains F e and
C a ) for only a few seconds at a time the stains a r e
relatively soluble.
(d) D r y t h e specimen surface quickly in a stream of
w a r m air (from a hair drier or equivalent). H a n d l e
carefully; the stain is a thin surface film and is easily
damaged.
This m e t h o d produces the following colour differ
entiation in c a r b o n a t e minerals:
Calcite
Varying through very pale pink
to red.
F e r r o a n calcite
Varying through m a u v e , purple
to royal blue with increasing F e
content.
Dolomite
N o colour.
Ferroan dolomite Pale t o d e e p turquoise with in
creasing Fe content.
Dickson (1966) pointed out s o m e useful features of
this stain coupling. Alizarin red S can differentiate
slightly different types of calcite: for e x a m p l e , dif
ferent kinds of bioclasts stain with differing intensi
ties depending on their crystallite size and structure.
T h e optic orientation of sparry c e m e n t crystals can
be discerned, as sections n o r m a l to t h e c-axis a r e
stained very pale pink, whereas sections parallel to
that axis stain d e e p pink. This is due to different
rates of etching. T h e potassium ferricyanide com
ponent is very sensitive, and will detect iron in

calcite with 1% ferrous c a r b o n a t e in solid solution.
A l t h o u g h it is convenient to stain sections by
Dickson's m e t h o d before microprobe analysis so
that the mineral phases can easily be distinguished,
S o m m e r (1975) showed that m i c r o p r o b e d e t e r m i n a
tions of iron in carbonates stained with potassium
ferricyanide showed depletion by an o r d e r of mag
nitude c o m p a r e d with unstained crystals.
material is best in o r d e r to avoid carbohydrate

contamination.
(b) Polish with 600F or 800F C a r b o r u n d u m , again
using water only.
(c) W a s h the slab thoroughly with tap water.
(d) Place the face d o w n w a r d s in 1% periodic acid
(by weight) in distilled water. Support the slab in a
dish with glass rods at t h e edges. Gently swirl the
liquid. Leave for 30 min. For very large blocks, the
solution can be painted on.
(e) Rinse thoroughly for 30 s in running water.
(f) Place face down in Schiff's reagent (commer
cially available) for 30 min, in the dark.
(g) Wash for several minutes in running water.
(h) E x a m i n e with binocular microscope. Store
specimens in t h e dark, w h e r e they will remain unfaded for at least several years.
T h e P A S reaction is not porosity-controlled. Speci
m e n s which are bioturbated will have a light purple
background with dark stains marking the burrows.
A r t h r o p o d burrows d o not stain as they d o not
normally have mucoid linings.
CLAY MINERALS
Stains for particular clay minerals usually require
p o w d e r e d and acid-extracted samples (Allman &
L a w r e n c e , 1972, p p . 1 0 9 - 1 1 1 ) and a r e therefore
beyond t h e scope of this chapter. It is often useful,
however, to be able to visualize the distribution of
clays in a sandstone or argillaceous c a r b o n a t e , since
clays are often related to otherwise obscure fabric in
these rocks. T h e Zyglo ultra-violet sensitive dye
described in Section 4.3.2 is useful h e r e . A simpler,
but not always predictable, technique is to soak
grease-free surfaces in a q u e o u s solutions of 0.5 g
malachite green, congo red or methylene blue in 250
ml water. T h e surface is lifted out of the solution
occasionally and gently washed until the stain is
found to be satisfactorily d e v e l o p e d : T h e dye colour
chosen should be c o m p l e m e n t a r y to the rock colour
so as to provide t h e greatest degree of contrast. A n
alcoholic solution of dye (equal parts ethanol or
m e t h a n o l and water) of methylene blue works well
on limestones, including chalks, with t h e alcohol
acting as a wetting agent and aiding p e n e t r a t i o n .
4.6
PEELS
Making a replica of an etched surface on transparent

plastic film is a very rapid and c h e a p way of pre
paring a sample for microscopic examination. A
solvent is flooded o n to t h e p r e p a r e d face. T h e lower
side of t h e film is softened a n d , as the solvent
e v a p o r a t e s , the film settles down into the irregulari
ties of the etched face and produces t h e replica.
T h e r e is very little sample wastage. Serial peels can
easily be p r o d u c e d by re-grinding surfaces after each
peel, to a fixed distance if required. This is much
quicker than m a k i n g serial thin sections for threedimensional visualization of fabrics like void spaces
or for reconstructing fossils in full relief.
P O L Y S A C C H A R I D E STAIN FOR
BIOTURBATION
Burrowing in sandstones and siltstones may often be
cryptic, and sometimes difficult to distinguish from
water escape structures. Risk & Szczuczko (1977)
developed a reliable m e t h o d for enhancing t h e mor
phology of burrowing in siliciclastics. It is based on
t h e tendency of many burrowing organisms to secrete
polysaccharide mucus as a burrow lining. T h e pre
sence of this c a r b o h y d r a t e can be detected by a
periodic acid Schiff ( P A S ) reaction. T h e m e t h o d
is not suitable for use with carbonates because of the
HC1 in t h e Schiff reagent.
P r o c e d u r e : (a) Cut a face or slice using water only as
a lubricant; avoid all grease and oil; d o not touch the
cut face with uncovered hands. Massive, unjointed
Peels are mostly used for limestones and calcitec e m e n t e d clastic rocks, although cherts and siliceous
elastics can be successfully treated. Best results are
obtained with n o n - p o r o u s samples; surface cavities
cause the film to bulge into t h e void, causing blisters
and a risk of tearing the completed peel. Porosity
can be reduced by v a c u u m impregnation with resin
before facing t h e samples (the resin used must not
b e soluble in acetone w h e n c u r e d ) . Larger holes
should be filled with d e c o r a t o r ' s filler paste (such as
Polyfilla), which is allowed to h a r d e n before t h e face
is rubbed down.
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111111l i l l l l l i l l
101
Replicas can be m a d e of quite large surfaces, even

up to h u n d r e d s of s q u a r e centimetres in area, but
t h e difficulty of producing good surfaces (and satis
factory solvent distribution cross t h e m ) increases
rapidly with samples larger than about 0.5 m x 0.5 m.
A l t h o u g h simple in principle, manufacture of
good peels is a craft learned only through consider
able experience. Beginners should not be satisfied
with their earliest efforts, but should p e r s e v e r e ,
using a single rock sample and experimenting with
etching times, pre-polishing, staining e t c . , until high
quality peels can be consistently obtained.
4.6.1 Peel material and solvents

Davies & Till (1968) advocated making peel sheets
by pouring solutions of ethyl cellulose in trichloroethylene on to glass plates. While very thin sheets
can be p r e p a r e d in this way, they are fragile, non
uniform in thickness, and tedious and time-consum
ing to p r e p a r e . Commercially p r o d u c e d cellulose
acetate is now available in sheets and rolls in a wide
range of thicknesses. It is uniform in thickness and
free from blemishes and density variation. 0.1 m m
thick film (polished o n both sides) is suitable for
making peels from a wide range of rocks and p r o
duces excellent resolution. Thicker films, while less
liable to crinkle and curl on p o r o u s or high relief
specimens, are much m o r e difficult to m o u n t flat,
and give lower contrast and microscopic resolution.
T h e film is vulnerable to t h e collection of static
charges and therefore to contamination. It should be
stored in the roll or interleaved with tissue p a p e r in a
dust-free (and preferably slightly d a m p ) drawer.
Film left lying a r o u n d t h e laboratory becomes dusty
and scratched, and m a k e s p o o r quality replicas.
A c e t a t e sheets are soluble in methyl a c e t a t e , ethyl
acetate, ethyl lactate, diacetone alcohol and tetrac h l o r o e t h a n e . H o w e v e r , the cheapest and most use
ful solvent for laboratory use is commercial grade
acetone. Acetone has a damaging effect on cell mem
brane lipids, and inhalation of the vapour should be
minimized.
It also dissolves fat from the skin with
extreme rapidity, leading to dermatitis, so hands
should always be protected by surgical gloves.
4.6.2 Stained peels

Katz & F r i e d m a n (1965) d e m o n s t r a t e d how effec
tive stained peels were in c a r b o n a t e petrography.
N o special p r e p a r a t i o n is required: dry, stained
102
J . MILLER
surfaces are t a k e n immediately to the acetone flood

ing stage (see below). Different stains can b e used
on t h e same specimen since earlier stains a r e re
m o v e d by re-polishing. This provides a very quick
way to obtain a set of peels representing many of t h e
nineralogical and fabric properties of a specimen.
4.6.3 Procedure
PREPARING THE CUT FACE
Sawn faces should be lapped to at least 600F Car
b o r u n d u m stage. F o r greater detail, further smooth
ing by polishing with 1 um Aloxite or d i a m o n d
abrasives is r e c o m m e n d e d . Etching such a polished
surface gives a relief which is m o r e subtly fabricselective t h a n etches controlled by an imperfect
surface.
ETCHING THE SMOOTHED FACE

Limestones can b e etched with hydrochloric acid,
acetic acid or d i N a E D T A d e p e n d i n g o n t h e degree
of detail required (see Section 4.5.1). L a r g e slabs
are conveniently etched (and stained, if required) in
plastic photographic developing trays; t h e cut face
preferably being u p p e r m o s t in t h e solution unless
t h e sample is t o o large, in which case t h e face is held
d o w n w a r d s and gently swirled to r e m o v e bubble
trains.
Price (1975) showed that good peels could be
m a d e from cherts and o t h e r siliceous rocks after
etching with H F . T h e rock slice is placed face down
in a polythene tray into 3 0 % H F solution for 3 or 4
min. T h e vapour alone does not give a d e e p e n o u g h
etch for replicas, but is sufficient for stain p r e p a r a
tion. All t h e usual safety precautions for using H F
must be observed (Section 4.5.1)
WASHING THE PREPARED SAMPLE

H o l d samples in a b a t h with slowly running water for
several minutes. I n h a r d water areas, use distilled or
de-ionized water only, to avoid residues after dry
ing. If H F was used, the specimen must be totally
immersed. Avoid touching t h e etched face, or agita
ting violently, as t h e delicate relief may be d a m a g e d .
D r a i n t h e sample and dry in a stream of w a r m air.
Drying may b e accelerated by flooding t h e surface
with a c e t o n e several times; this carries off s o m e
T h e specimen should be supported so that the etch

ed face is almost horizontal, tilting by only a few
degrees. Some workers use a sand tray to hold
specimens, but this should be avoided because of t h e
likelihood of contaminating t h e surface. Plasticene
is a good m e d i u m for supporting all sizes of speci
m e n as it is easily m o u l d e d and re-used.
across the specimen, pushing t h e solvent in front of

it. E x t r a liquid exuding from the far edge can be
evaporated away quickly by blowing across the
specimen; this avoids wrinkling at t h e edge of the
film, which would m a k e it difficult to flatten the peel
for subsequent study.
For a few m o m e n t s , the film should just float on
t h e liquid, then it will draw down as evaporation
starts. If t h e r e are wrinkles or silvery air bubbles at
this stage, d o n o t try to r e m o v e the film, as a very
messy, sticky surface will b e left. Discard the bad
peel after it has dried, t h e n repolish and etch the
face.
P R E P A R A T I O N OF FILM
DRYING THE PREPARATION
Cut a fresh piece of acetate film, free of scratches, t o

a s h a p e which allows about 1 cm overlap b e y o n d t h e
specimen edge. If t h e sheet is heavily charged with
static, this can be r e m o v e d by discharging with a
piezo-electric antistatic pistol available from audio
e q u i p m e n t shops. T h e discharged sheet is m u c h
easier to m a n a g e and does not attract dust and lint.
T h e specimen should be left for at least half an h o u r

for t h e a c e t o n e to e v a p o r a t e . This time can be
shortened by blowing w a r m (not hot) air evenly
across t h e surface: uneven drying causes p r e m a t u r e
lifting. A 250 W infra-red reflector bulb placed
a b o u t 0.3 m above t h e specimen dries t h e film in
about 10 min.
APPLYING THE A C E T A T E FILM
TAKING THE PEEL
T h e specimen should be cold and in a cool r o o m ,

otherwise the acetone will e v a p o r a t e t o o quickly
from its surface. Gently flood t h e etched face with
acetone from a washbottle. T o o m u c h a c e t o n e will
cause wrinkling, t o o little will cause air bells. Place
t h e acetate film gently across t h e lower margin of the
specimen w h e r e a pool of acetone will h a v e collec
ted. Holding t h e sheet in a curve (Fig. 4.9), unroll it
Gently lift back t h e film from o n e edge of t h e

specimen ahd steadily pull it off the surface in one
continuous m o t i o n . If a tear develops, peel from the
opposite corner and work towards t h e d a m a g e . Films
which have b e e n left to dry t o o long (e.g. a day or
m o r e ) may be very difficult to r e m o v e without tear
ing. It is a m a t t e r of experience to j u d g e the best
time to r e m o v e a peel, but flicking t h e edge upwards
immediately releases the peel slightly when ready,
producing a diagnostic 'dry' sound.
water w h e n it evaporates. D r i e d and etched surfaces

should be peeled immediately, as they collect dust
rapidly.
O R I E N T A T I O N OF THE SPECIMEN
Direction of application
Acetone pool
103
D o not leave peels lying about in the laboratory

before mounting or filing t h e m : they attract dust and
lint and a r e easily scratched.
While it may be difficult to k e e p t h e m flat, ex
amining peels u n m o u n t e d has t h e advantage of being
able to use oblique incident and transmitted light
combinations t o increase contrast, a n d for viewing
t h e relief m o r e effectively to gain a three-dimen
sional effect. U n m o u n t e d peels can also be examined
with high power objectives which have smaller
working distances t h a n glass m o u n t i n g plates. H o w
ever, small peels, or cut-out sections of large o n e s ,
can be m o u n t e d between two standard microscope
slides for examination with a low power binocular or
stereomicroscope. Larger glass mounting plates can
be obtained from photographic dealers. Very large
peels may have to be m o u n t e d between specially cut
pieces of thin window glass. In all cases, t h e glass
should be thoroughly clean and grease free before
sandwiching the peel and binding the edges with
adhesive plastic t a p e . T h e best tape to use is m a t t
'invisible' m e n d i n g t a p e , as standard Sellotape
rapidly becomes brittle and splits. H a n d l e t h e peels
only by their edges to avoid grease m a r k s , and lay
t h e m on clean, lint-free p a p e r or cloth while they
wait for m o u n t i n g , to avoid dust and scratch collec
tion. M o u n t e d peels should be stored in a dust-free
box or drawer, a n d stained peels are best k e p t in the
dark.
Peels and thin sections should be regarded as
c o m p l e m e n t a r y . Some peels show n o signs of the
' p h a n t o m t e x t u r e s ' , e.g. in recrystallized limestones,
which a r e otherwise visible in thin sections. O n t h e
o t h e r h a n d , t h e etched surfaces of peels frequently
reveal details not seen in thin sections. Stained
peels, w h e n m a d e with great c a r e , h a v e very high
resolution and can be as good as a D P T for point
counting and studies of diagenesis.
TRIMMING AND MOUNTING OF PEELS

With a sharp pair of scissors, trim t h e excess film
from the peel (but leave a small area as a finger
h o l d ) , and immediately either m o u n t it between two
sheets of glass, or mark it with specimen n u m b e r
and store it b e t w e e n t h e leaves of a thick b o o k . T h e
slightly d a m p , hygroscopic pages of a book provide
excellent storage for peels which are either awaiting
p e r m a n e n t mounting or are only n e e d e d for tem
porary examination. With s o m e materials, coal balls
for e x a m p l e , part of t h e rock surface is actually
incorporated in the peel. Dipping t h e peel briefly in
2 % HC1 'clears' the film before mounting.
Curved acetate sheet
Etched surface
Plasticine or
modelling clay
Fig. 4 . 9 . Side view of sample prepared for acetate replica
process, showing how the curved acetate film is applied at
the edge of the slightly tilted sample before being unrolled
across its face, pushing the acetone before it.
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imiHimimiHiimiiHMtHHiim
4.7 E X A M I N A T I O N O F M I C R O S C O P
ICAL PREPARATIONS
Having gone to s o m e trouble to obtain high quality
sample p r e p a r a t i o n s , it is i m p o r t a n t to realize their
potential by using a p p r o p r i a t e techniques when
studying t h e m . Many workers begin immediately
with detailed study u n d e r m e d i u m to high power on
a petrographic microscope which has a very small
field of view. T h e r e is much to be gained from
104
J.MILLER
preliminary survey of t h e whole preparation at low

p o w e r , to provide a context for later detailed work.
4.7.1 Photographic m a p
A suggested first step in t h e use of any p r e p a r a t i o n ,
be it peel or thin section, is to m a k e o n e or m o r e
p h o t o g r a p h s of t h e entire preparation (Fig. 4.10).
This ' m a p ' has m a n y advantages: it preserves a
record of the sample in its initial state before treat
m e n t ; it gives an overall view of the section o r peel
which can be used as a guide for s u b s e q u e n t d e

tailed w o r k , and it offers a convenient and rapid
way of comparing samples.
T h e simplest and cheapest way of p h o t o g r a p h i n g
a slide or peel is t o use it as a photographic negative.
Place the slide or peel m o u n t into t h e negative
carrier of a p h o t o g r a p h i c enlarger and project t h e
image on t o an international A 4 size sheet of print
ing p a p e r of a p p r o p r i a t e g r a d e , d e t e r m i n e t h e expo
sure and print two copies. O n e of these can form
part of a reference archive, t h e other is a working
copy, upon which notes and details can be written,

or over which can be placed transparent overlays to
mark grains, microprobe analysis sites etc.
Small thin sections will fit into t h e carrier of a
35 m m enlarger: larger preparations and peels re
quire a plate enlarger. T h e negative print obtained
has t h e advantage of increased contrast, enhancing
many details in t h e p r e p a r a t i o n . If a positive image
is required, a whole plate negative film sheet can be
substituted for photographic paper at the first stage:
this intermediate negative is developed and then
contact printed. Alternatively, the thin section or
peel can be placed on t h e stage of a 35 m m trans
parency copying m a c h i n e , and a black and white or
colour p h o t o g r a p h t a k e n by flash for later printing
or projection.
With very large slices or bulky faced samples, a
very simple m e t h o d of producing a ' m a p ' image is to
place t h e face carefully on to the glass of a xero
graphic machine (Ireland, 1973). T h e image can be
produced o n a t r a n s p a r e n t sheet or on p a p e r as
required. Contrast can be adjusted by varying the
t o n e r applied.
105
m e a s u r e m e n t s of grains can be m a d e if t h e stage is

fitted with a vernier mechanical stage.
This instrument has m a n y advantages. Several
people can examine a preparation at t h e same time.
Very large peels or sections can be scanned at low
magnifications. Tracings of fabrics and grains can be
quickly and accurately m a d e at a r a n g e of magni
fications. Point counting can be d o n e by preparing
transparent overlay coordinate grids at various sizes;
eye strain is found to be less than with a petrographic
microscope. Grids can also be prepared for deter
mination of roundness and sphericity. Polarizing
filters can easily be interposed. Photographs may be
p r e p a r e d by placing negative sheets or printing
papers face down on t h e glass viewing plate. O n e
disadvantage is that t h e viewing r o o m must be dar
k e n e d while the instrument is in use.
4.7.2 L o w power examination and drawing
Fig. 4.10. Negative print of thin section, showing good contrast and detail obtained by projecting a thin section directly on
to bromide paper. Waulsortian facies, Dinantian, Crow Hill, near Clitheroe, Lancashire, England. Lime muds are pale
grey, fibrous calcite spars mid-grey and clear blocky calcite late cavity fill cements are black. Cavities are partially or
completely filled with peloidal geopetal sediment. Bioclasts include abundant sponge spicules, fenestellid bryozoan
fragments, gastropods and echinoderms. Scale is 5 mm.
Lees (1962) drew attention t o a noticeable gap

which existed in t h e instrumentation for examina
tion of t r a n s p a r e n t thin sections or surface replicas
such as peels, particularly with sizes larger t h a n a
standard thin section. H e advocated t h e use of an
industrial measuring projector for this p u r p o s e . T h e
Watson Manasty 'Shadomaster' Model V M P (no
longer in production) was chosen as being the best
(Fig. 4.11). Viewers for microfilm are a good sub
stitute, but lack t h e dimensional stability for accurate
m e a s u r e m e n t which is a feature of the ' S h a d o m a s t e r '
projectors.
In t h e ' S h a d o m a s t e r ' , samples are placed o n a
viewing stage and illuminated from above with a
quartz-halogen projection lamp and a condenser.
Below t h e stage, o n e of several interchangeable
magnifying lens systems focusses t h e image on to an
inclined plane mirror at t h e base of t h e instrument.
T h e final image is formed on a large frosted glass
plate held at a convenient viewing angle. T h e re
solution is g o o d , a n d grains less t h a n 10 u m can b e
seen at xlOO. F o r work at these magnifications, the
frosted glass plate can be replaced by clear glass with
a m a t t drafting plastic film taped over. Accurate
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.1iiimiiiiiiiimimiiHHMiHii
Fig. 4.11. 'Shadomaster' industrial measuring projector

used for examining thin sections and acetate peels. The
quartz-iodide lamp at the top projects a beam through the
specimen and sub-stage lens system, which is reflected by a
mirror in the base of the instrument on to a large groundglass screen. A grid overlay is shown, used for pointcounting.
106
J . MILLER
A n alternative for viewing and drawing small

peels or segments of larger peels is to m o u n t t h e m in
35 m m transparency m o u n t s (preferably with glass
both sides) and to project t h e m on to white p a p e r or
card, on which tracings can b e m a d e . L a r g e r peels
can be sandwiched between two glass plates and
placed in an episcope for projection.
4.7.3 Petrological m i c r o s c o p e
In o r d e r to optimize viewing conditions, t h e micro
scope should be correctly adjusted and all optical
surfaces clean. In particular, care should be t a k e n to
set t h e condenser correctly this is probably t h e
single greatest cause of p o o r results in microscopy.
C u r r y , Grayson & H o s e y (1982) gave details of how
to adjust substage condensers for s t a n d a r d and
K o h l e r illumination.
T h e next important factor is adjusting t h e contrast
to suit each specimen. Thin sections of c a r b o n a t e
rocks in particular require a high contrast, and this
may be obtained by stopping down t h e substage iris
s o m e w h a t . C o m p l e t e stopping-down, h o w e v e r , p r o
duces spurious interference effects at grain edges
and reduces resolution. N e u t r a l density filters should
then b e interposed to r e d u c e light intensity. R e
ducing t h e illuminator lamp intensity m a y n o t be
desirable as this alters t h e colour t e m p e r a t u r e of t h e
incident light.
Highly recrystallized and dolomitized c a r b o n a t e s
present particular difficulties. D e l g a d o (1977) n o t e d
that details such such as bioclasts and voids visible in
hand specimens or peels of such rocks vanished
u n d e r t h e petrological microscope. H e discovered
that diffusing the transmitted light resulted in a
dramatic increase in t h e resolution of such cryptic
features. T h e best diffuser was p r o d u c e d by coating
t h e undersurface of a thin section by b u r n i n g mag
nesium ribbon s o m e 0.20.25 m below t h e slide. A t
this distance, a 0.07 m length of Mg ribbon p r o d u c e s
a coating of about 20 urn thickness. T h e coated glass
surface is protected by a n o t h e r glass slide before
mounting on t h e microscope stage. (Caution!
use
goggles the bright flame of burning magnesium
can
cause retinal damage!) E x p e r i m e n t s n e e d to b e d o n e
with and without t h e condenser in place, d e p e n d i n g
on t h e specimen. Best results are o b t a i n e d with
magnifications of x l O or less.
In all cases, it is advantageous to take time to
4.8 M A N U F A C T U R E R S A N D
SUPPLIERS
experiment with lighting, filters, iris and c o n d e n s e r

setting e t c . , so as to optimize t h e results from each
rock type and m e t h o d of p r e p a r a t i o n .
4.7.4 P h o t o m i c r o g r a p h y
Most research petrological microscopes have p h o t o micrographic a t t a c h m e n t s , while simpler micro
scopes can be used with 35 m m S L R cameras fitted
with a p p r o p r i a t e a d a p t o r rings. Curry et al. (1982)
give useful hints a b o u t using these systems. In
genera], t h e most a p p r o p r i a t e films a r e fine grained,
high contrast types. This usually m e a n s they have
slow speed and concomitantly long exposure times,
so it is necessary to ensure that t h e microscope is
free from vibration, best d o n e by working on a stone
or concrete optical bench. T h e p h o t o m i c r o s c o p e
should be rigidly s u p p o r t e d .
A c e t a t e film for peels: Charles T e n n a n t & C o m p a n y

Limited, 214 Bath Street, Glasgow G 2 4 H R ,
Scotland.
A u t o m a t e d and semi-automated thin-sectioning
e q u i p m e n t : Logitech Limited, Erskine Ferry
R o a d , Old Kilpatrick, D u n b a r t o n s h i r e , Scotland.
A r a l d i t e , E p o - t e k and Versamid: Ciba-Geigy
Plastics and Additives C o m p a n y ,
Duxford,
Cambridge CB2 4 Q A , England.
Blue keystone resin stain: E p o x y Technology I n c . ,
P O Box 567, 14 F o r t u n e Drive, Billerica, Mass
01821, U S A .
Since t h e optics of t h e microscope are arranged

for white light, w h e r e each wavelength is brought to
a slightly different focus, o p t i m u m resolution in
m o n o c h r o m e p h o t o g r a p h s is obtained by employing
a m e d i u m density green filter (selecting a wave
length in the middle of t h e r a n g e ) . This also has t h e
effect of producing s o m e differential contrast within
t h e specimen. Stained peels or thin sections may b e
e n h a n c e d by using a c o m p l e m e n t a r y filter on t h e
illuminator.
Correct colour photographs are difficult to achieve.
O n e of t h e main p r o b l e m s is to match t h e colour
t e m p e r a t u r e of t h e film with that of t h e incident
light, assuming correct exposure. T h e p r o b l e m is
particularly acute with pictures t a k e n with crossed
polars, w h e r e often t h e identification of t h e minerals
d e p e n d s on t h e subtle rendition of characteristic
interference colours. Daylight colour film ( a r o u n d
5500 K colour t e m p e r a t u r e ) can only be used direct
ly with daylight and a substage mirror. If a substage
illuminator is fitted, t h e n a colour compensation
filter is required ( K o d a k W r a t t e n n o . 8 0 A ) . With
tungsten light film (3200 K ) , n o filter is n e e d e d if t h e
substage illuminator has a tungsten l a m p . T h a t does
not, however, g u a r a n t e e that exact colour rendition
will b e o b t a i n e d , as t h e colour t e m p e r a t u r e of tung
sten lamps d e p e n d s on the voltage at which they are
run and on the age of t h e l a m p . For critical applica
tions, a colour t e m p e r a t u r e m e t e r should be used, or
t h e manufacturer's graphs consulted.
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llilii
107
C a r b o r u n d u m abrasives: Sohio E l e c t r o Minerals

C o m p a n y ( U K ) Limited, Mosley R o a d , Trafford
P a r k , M a n c h e s t e r M17 1 N R , England.
D i a m o n d powders, engis p a p e r s , silicon carbide
discs, lapping machines, lead lap faces: Engis
Limited, Park W o o d Trading E s t a t e , Sutton R o a d ,
Maidstone, Kent ME15 9NJ, England.
Stains and reagents: B D H Chemicals Limited,
F o u r w a y s , Carlyon Industrial E s t a t e , A t h e r s t o n e ,
Warwickshire C V 9 1 J Q , E n g l a n d .
Zyglo p e n e t r a n t 2 L . 2 2 A , Solvent Z C 7 and devel
o p e r aerosols: Magnaflux Limited, South D o r c a n
Industrial E s t a t e , Swindon, Wiltshire SN3 5 H E ,
England. ( U s e d for detecting cracks in industrial
castings.)
PRINCIPLES OF SEDIMENTARY PETROGRAPHY
Microscopic techniques: II.

Principles of sedimentary petrography
provenance
FIELD/SUBSURFACE
TECHNIQUES
mineralogy
DEPOSITIONAL
FABRICS
109
modal composition
grain m o r p h o l o g y
grain size
GILL HARWOOD
grain orientation
SEDIMENTARY
PETROGRAPHY
-mechanical compaction
5.1
INTRODUCTION
Sedimentary p e t r o g r a p h y is the analysis of b o t h

depositional and diagenetic fabrics from thin sec
tions, and includes mineralogic composition, grain
and sediment p r o v e n a n c e , fabric studies and deter
mination of t h e sequence of diagenetic events.
Petrographical studies of thin sections form t h e basis
of m u c h m o d e r n research o n sedimentary rocks,
w h e t h e r siliciclastic, volcanic, c a r b o n a t e or evaporitic, and the information gained can greatly supple
m e n t d a t a from field- or core-based studies.
P e r h a p s t h e first question t o b e answered is why
d o so m a n y sedimentologists c o n c e n t r a t e o n sedi
m e n t a r y p e t r o g r a p h y ? A brief literature review of
t h e p o p u l a r sedimentological journals indicates an
increasing emphasis o n p e t r o g r a p h y within E u r o p e ,
w h e r e a s within t h e U n i t e d States and C a n a d a sedi
m e n t a r y petrology has for long b e e n a necessary
c o m p o n e n t of integrated sedimentological research
projects. M a n y such studies a r e related to hydro
carbon evaluation b o t h for source rocks and for
reservoir potential. A s u m m a r y of the interrelation
ships together with s o m e of t h e applications of
aspects of sedimentary p e t r o g r a p h y is given in Fig.
5 . 1 . It should be emphasized that much information
gained from petrofabric research can be used to
back up field studies and forms an aid to p r o v e n a n c e
studies, including facies analysis and construction of
depositional m o d e l s ; these applications are com
monly lost amongst an ever-growing n u m b e r of
p a p e r s solely o n aspects of diagenesis.
5.1.1 Techniques and t o o l s

A l t h o u g h s o m e techniques used in sedimentary
p e t r o g r a p h y are quantitative, many are solely quali
tative and are principally descriptive. M a n y research
projects concentrate on either siliciclastic or car
b o n a t e sediments; few investigate combined carbonate-siliciclastic systems and fewer yet reference
volcanogenic sediments, m u d r o c k s or evaporites.
This chapter a t t e m p t s to portray fabrics which may
develop within any sediment, i n d e p e n d e n t of

mineralogy. A l t h o u g h s o m e specific fabrics are in
cluded, t h e aim is to p r o d u c e a general 'guide' for all
sedimentary p e t r o g r a p h e r s , with references leading
to m o r e detailed texts. E x a m p l e s used in p h o t o m i
crographs a r e predominantly from
'grain-supported''
rocks (sandstones, grainstones/packstones) as many
petrofabrics are m o r e readily a p p a r e n t within these
sediments. This is not to say that these features are
n o t present within m o r e clay-rich or c a r b o n a t e m u d rich sediments. T h e y a r e , however, commonly m o r e
difficult t o discern, and to p h o t o g r a p h , in clay-rich
and mud-rich sediments. Their examination profits
from t h e use of ultra-thin sections ( C h a p t e r 4 ) ,
employed initially in studies of c a r b o n a t e diagenesis
(Lindholm & D e a n , 1973), so that initial research
into m u d r o c k diagenesis can now be carried out
with a good petrological microscope.
-solution compaction
DIAGENETIC
FABRICS
-cementation
-dissolution
-replacement
S O U R C E ROCK P O T E N T I A L
MIGRATION CONDUIT POTENTIAL
RESERVOIR P O T E N T I A L
Fig. 5 . 1 . Relationship of sedimentary petrography and petrographic fabrics to other branches of sedimentology.
care must be t a k e n to ensure that these are not

obscured by local variations.
A good petrological microscope is t h e essential

tool for sedimentary p e t r o g r a p h y , with refinement
by t h e addition of subsidiary c o m p o n e n t s w h e r e
necessary. O n e tool commonly ignored by many
sedimentary p e t r o g r a p h e r s is a Shadowmaster, or
similar e q u i p m e n t , w h e r e a thin section is projected
on to a ground glass screen to p r o d u c e an image (a
s h a d o w g r a p h ) . This can b e extremely useful for
overviews of a thin section, grain shape and size
determinations and for fabric analysis.
5.1.2 C o m p o n e n t s and petrofabrics

T h e general fabric of a sedimentary rock will d e p e n d
on t h r e e major c o m p o n e n t s : (1) the original detrital
grains,
(2) authigenic minerals, both cements and replacive minerals, which have formed since deposi
tion, and
(3) p o r e spaces.
Detrital grains may be of any size (from clays to
pebbles or larger) and of varying shape. Sand or
larger sized grains commonly form a framework
within t h e sediment (Fig. 5.2a, b) between which the
finer matrix (silt and clay sized particles) may have
accumulated (Fig. 5.2a). In well-winnowed sedi
ments there is generally little or n o matrix, leaving
resultant p o r e spaces which may be partially or
totally occluded (or filled) by cement during dia
genesis (Fig. 5.2b). W h e r e t h e r e are higher propor
tions of matrix the grains d o not form a framework,
but float within t h e finer grained matrix, forming a
matrix-supported sediment (Fig. 5.2c). W h e r e a s
these may a p p e a r to be easy to recognize in theory,
A t this point a word of warning should be in

cluded: it is little use spending days/weeks describing
and analysing o n e thin section if you a r e not sure
w h e t h e r this section is representative of the sedi
m e n t a r y sequence you are evaluating. It is always
tempting t o sample t h e m o r e 'interesting' sections of
a sedimentary sequence and to find, on r e t u r n to t h e
laboratory, that you have few or n o samples of t h e
m o r e m u n d a n e lithologies which comprise t h e
greater portion of t h e sequence. In practice it is very
difficult to decide what is representative; p e r h a p s
t h e best m e t h o d is to m a k e a general study of several
sections from t h e same sequence before proceeding
t o detailed description and analysis. In most cases it
is m o r e important to n o t e the regional t r e n d s ; thus
108
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in practice it can be difficult to d e t e r m i n e w h e t h e r a

sediment is grain s u p p o r t e d or matrix supported in a
hand specimen, but particularly when seen in two
dimensions within a thin section (e.g. Fig. 5.2d).
Authigenic minerals grow after sediment deposi
tion, during diagenesis; they include both cements
and replacive minerals. Cements are t h e crystals
which grow into existing pore spaces. T h e y may, or
may n o t , totally occlude t h e available p o r e space
(e.g. Fig. 5.2b). T h e form of many c e m e n t crystals
can be indicative of the environment in which they
grew (see Section 5.3.3). Replacive minerals grow,
as their n a m e suggests, in the place of pre-existing
minerals and not into p o r e spaces. They are com
monly alteration products of t h e primary detrital
grains, b u t may also form from the introduction of
additional ions by circulating p o r e fluids, as in many
instances of dolomitization of a precursor carbonate.
Pore spaces are t h e voids not filled by grains or
matrix within a sediment. Impregnation of the sam
ple with a coloured epoxy resin (commonly blue)
m a k e s the p o r e spaces m o r e easily visible in thin
section ( C h a p t e r 4) and allows distinction between a
t r u e p o r e space and a void w h e r e a grain or crystal
has been plucked out during t h e process of making a
thin section.
110
G. HARWOOD

A minor, but i m p o r t a n t constituent of many sand
stones are t h e heavy minerals, with a specific gravity
in excess of 2.9. T h e s e a r e usually studied by separ
ating t h e m from a crushed rock with heavy liquids,
notably t e t r a b r o m o e t h a n e , which is extremely toxic.
T h e p r o c e d u r e is well described in K r u m b e i n &
Pettijohn (1961), H u b e r t (1971) a n d F r i e d m a n &
J o h n s o n (1982). It is also possible to use a magnetic
separator. Identification of t h e heavy minerals is by
microscopic examination of t h e m o u n t e d grains (see
references cited above for properties of the mine
rals). T h e value of t h e heavy minerals is in t h e
information they give on a sediment's p r o v e n a n c e ,
although their dissolution during diagenesis may
result in modification to t h e original assemblage
( M o r t o n , 1985b).
fine matrix (clays or

carbonate muds)
cement
5.2.2 Modal c o m p o s i t i o n
grains
porosity
T h e modal composition of a sediment is a m e a s u r e

of t h e proportions of t h e different major deposi
tional c o m p o n e n t s . T h e s e h a v e t h r e e e n d m e m b e r s ;
(i) detrital, dominantly siliciclastic (or terrigenous)
c o m p o n e n t s derived from outside the depositional
a r e a , (ii) allochemical c o m p o n e n t s p r o d u c e d within,
or adjacent t o , the depositional a r e a , and (iii) o r t h o chemical c o m p o n e n t s resulting from chemical p r e
cipitation within the area. Five major classes of
sedimentary rock are defined using a triangular plot
of these c o m p o n e n t s (Fig. 5.3; Table 5.2) (Folk,
1974b). This classification is based solely on com
position immediately after deposition; cements and
authigenic minerals a r e n o t included. Difficulties are
e n c o u n t e r e d w h e r e considerable dissolution has
t a k e n place during diagenesis of t h e sediment
(Section 5.3.5).
Fig. 5.2. Fabrics of sedimentary rocks: (a) Grain-supported sediment; finer matrix has accumulated between a framework
of grains.
(b) Grain-supported sediment; pore spaces between grains are partially occluded by cement, although there is some
remaining porosity.
(c) Matrix-supported sediment; grains appear to 'float' in finer-grained matrix.
(d) In three-dimensional samples, this specimen can be seen to be grain-supported, with matrix between skeletal fragments.
In the two dimensions of a thin section, however, it appears to be matrix-supported.
T h e combination of these t h r e e c o m p o n e n t s forms

the fabric of any sedimentary rock. Using a m o r e
genetic a p p r o a c h , h o w e v e r , petrofabrics are divided
into two major types, each t h e result of different
processes:
(1) Depositional fabrics fabrics which result
from processes which were active during deposition
of t h e sediment. T h e s e include grain mineralogy,
grain morphology, grain orientation and p r o v e n a n c e
studies.
(2) Diagenetic fabrics fabrics which result from
processes which occurred after deposition of t h e
sediment. T h e s e include compaction, c e m e n t a t i o n ,
mineral replacement and dissolution of pre-existing
phases, and their study can lead to t h e construction
of a diagenetic history of t h e sediment.
5.2 D E P O S I T I O N A L F A B R I C S
5.2.1 Grain identification
Mineral identification in thin sections can be back
ed u p by X R D analysis of p o w d e r e d rock samples
( C h a p t e r 7 ) . T h e r e are many excellent texts on
mineral identification, all with much m o r e detail
than can be included h e r e . T h e properties of s o m e
c o m m o n e r minerals in sedimentary rocks are given
in Table 5 . 1 ; examples of these minerals in thin
sections are shown in m o d e r n coloured guides to
sedimentary constituents (Scholle, 1978, 1979;
A d a m s et al., 1984) plus the older s t a n d a r d descrip
tive texts (Carozzi, 1960; K r u m b e i n & Pettijohn,
1961; Milner, 1962a, b ; Pettijohn, 1975).
T o obtain the m o d a l composition of any sediment

o n e n e e d s t o know (i) t h e n a t u r e of t h e contained
grains and (ii) the p r o p o r t i o n s of these grains pre
sent within the sediment. T h e n a t u r e of the contain
e d grains can b e o b t a i n e d from grain mineralogy
(Section 5.2.1) plus the origin of lithic clasts (Table
5.3). T h e p r o p o r t i o n of the different grains present
is m o r e difficult to ascertain and is d o n e using two
main techniques, point counting and visual esti
mates. Several systems of c o m p u t e r e n h a n c e m e n t
and image analysis which can be used with a petro
graphic microscope are beginning to c o m e on the
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111
m a r k e t a n d promise relative ease of m o d a l composi

tion evaluation.
POINT COUNTING
TECHNIQUES
Point counting is the most accurate m e t h o d of estab

lishing t h e m o d a l composition of a sediment, albeit a
time-consuming m e t h o d (Chayes, 1956; G a t e h o u s e ,
1971a). Point counting of many thin sections is tedi
ous; however, its uses generally outweigh the time
spent in d a t a accumulation. T h e r e are various
m e t h o d s of point counting, t h e most obvious being
t h e spot identification of each grain as it appears
u n d e r the cross wires of the microscope (e.g. Van
der Plas & Tobi, 1965; Soloman & G r e e n , 1966).
H o w e v e r , in a sediment with a large proportion of
lithic clasts this may involve changing many times t o
a different magnification (generally larger, to iden
tify the whole clast). O n e m e t h o d (Ingersoll et al.,
1984) obviates this by identifying minerals within the
clast, rather than t h e complete clast, although this
produces a m o d a l composition based on total
mineralogy rather than based on detrital grain
mineralogy.
D u r i n g point counting, t h e thin section is placed
on a mechanical stage screwed to t h e rotating stage
of the microscope, which is then clamped. T h e
mechnical stage is connected to a counting unit,
which, w h e n a master key is pressed, moves the
section a given distance along a traverse. This dis
tance can b e varied, d e p e n d e n t on the grain size of
t h e sediment. Six (or m o r e ) additional keys can be
m a r k e d for different c o m p o n e n t s within the section.
O n e of t h e s e ' k e y s is pressed each time that com
p o n e n t is visible u n d e r t h e cross hairs of t h e micro
scope. T h e master key both advances the stage and
records the total n u m b e r of points counted. G r a i n s
p r e s e n t , b u t not e n c o u n t e r e d u n d e r the cross hairs,
are noted as additional minerals (Table 5.4). Several
traverses a r e m a d e for each thin section, and a total
of s o m e 250300 points p e r section need to b e
counted to obtain sufficiently accurate percentages
of t h e c o m p o n e n t s present. All d a t a are rigorously
tabulated (Table 5.4). T h e position of t h e traverses
should be noted as this enables the counting of
additional points, should this be necessary; it also
enables checking of the original data. A l t h o u g h
point counting is t i m e consuming, any p e t r o g r a p h e r
should practice this m e t h o d o n several thin sections
before proceeding to much m o r e rapid m e t h o d s ,
such as the use of visual estimates.
Table 5 . 1 .
S U M M A R Y
AND TUCKER
OF C O M M O N
MINERALS IN SEDIMENTARY
ROCKS A N D THEIR OPTICAL PROPERTIES.
COMPILED
FROM KERR
(1959)
Table 5 . 1 .
(Continued)
( 1 9 8 1 )
GROUP/
CRYSTAL
MINERAL
SYSTEM
Quartz
TRIGONAL
COLOUR
RELIEF
CLEAVAGE
BIREFRINGENCE
OTHER
C E M E N T
N O N E
COLOURLESS
L O W
+ V E
N O N E
COLOURLESS
L O W
GREY
+ V E
AND
OCCURRENCE
OVERGROWTH
CEMENT
C O M M O N
Cherts
F O R M
FEATURES
GREY
A S
DETRITAL G R A I N S , C E M E N T S A N D AS D I A G E N E T I C
(REPLACIVE)
CHALCEDONY
AND
QUARTZ
A C I C U L A R CHERT ( C H A L C E D O N Y ) , M E G A Q U A R T Z
AND
MEGAQUARTZ
M I C R O Q U A R T Z ; ALL F O R M S D I A G E N E T I C U N L E S S A S
OCCLUDE
DETRITAL
VOIDS
GRAIN
FELDSPARS
MICROCLINE
TRICLINIC
COLOURLESS
PRESENT
L O W
VE
GREY
CROSSHATCH
ORTHOCLASE
MONOCLINIC
COLOURLESS
PRESENT
L O W
VE
GREY
SIMPLE
PLAGIOCLASE
TRICLINIC
COLOURLESS
PRESENT
L O W
VE
GREY
MULTIPLE
MONOCLINIC
COLOURLESS
PROMINENT
MODERATE
TWINS
M A Y
TWINS
TWINS
FORM
P R E S E N T AS DETRITAL M I N E R A L S B U T
COMMONLY
OVERGROWTH
H A V E C L O U D Y A P P E A R A N C E A S ALTER TO C L A Y
CEMENTS
MINERALS
MICAS
MUSCOVITE
+ V E
BRIGHT
COLOURS
PARALLEL
PLANAR
BIOTITE
MONOCLINIC
PROMINENT
BROWN-GREEN
MODERATE
+ V E
BRIGHT
PLANAR
CLAY
C O M M O N
DETRITAL
MINERAL
C O M M O N
DETRITAL
MINERAL
EXTINCTION
COLOURS,
PARALLEL
M A S K E D B Y COLOUR
EXTINCTION,
MINERALS
PLEOCHROIC
CHLORITE
MONOCLINIC
GREEN/BLUE
KAOLINITE
TRICLINIC
GREEN
PLANAR
MODERATE
COLOURLESS
PLANAR
L O W
+ V E
L O W
+ V E
VE
+ V E
GREY
P R E S E N T AS DETRITAL M I N E R A L S ,
GREY
C O M M O N
FINE
ILLITE
MONOCLINIC
COLOURLESS
PLANAR
SMECTITE
MONOCLINIC
COLOURLESS
PLANAR
L O W
GLAUCONITE
MONOCLINIC
GREEN
PLANAR
MODERATE,
AS
AS
ALTERATION P R O D U C T S OF SILICATES A N D
GRAINED
GREY
BURIAL
CEMENTS
AS C E M E N T S
GREY^
GREY, MASKED
MASKED BY
ZEOLITES
MOST
L O W ,
COLOURLESS
MOST
COLOUR
VE
BY
C O M M O N L Y
COLOUR
C O M M O N L Y
REPLACES
CHARACTERISTIC OF LOW S E D I M E N T A T I O N
RATES,
M A Y INFILL F O R A M TESTS, E T C .
PELLETS
GREY
C O M M O N
WHERE
AS C E M E N T S
ASSOCIATED WITH VOLCANOGENIC
SEDIMENTS
VOLCANICS
CARBONATES
ARAGONITE
ORTHORHOMBIC
COLOURLESS
RECTILINEAR
MODERATEHIGH
H I G H
COLOURS
CALCITE
TRIGONAL
COLOURLESS
R H O M B I C
L O W H I G H
VERY
H I G H COLOURS
DOLOMITE
TRIGONAL
COLOURLESS
R H O M B I C
L O W H I G H
V E R Y H I G H COLOURS
SIDERITE/
TRIGONAL
COLOURLESS/
R H O M B I C
L O W - H I G H
VERY
ANKERITE
PALE
C O M M O N L Y
|
DISTINGUISHED
>
BY
M A N Y
ACICULAR.
CEMENT
MORPHOLOGIES
STAINING
H I G H COLOURS J
P R E S E N T AS DETRITAL G R A I N S , C E M E N T S
AND
R E P L A C E M E N T FABRICS I N CARBONATES.
C O M M O N
REPLACEMENT MINERAL IN
IRONSTONES
BROWN
EVAPORITES
G Y P S U M
MONOCLINIC
COLOURLESS
PLANAR
L O W
GREY
ANHYDRITE
ORTHORHOMBIC
COLOURLESS
RECTILINEAR
MODERATE
BRIGHT
C O M M O N
COLOURS
BURIAL
CELESTITE
ORTHORHOMBIC
COLOURLESS
PLANAR
LOWMODERATE
GREY
BURIAL
HALITE
CUBIC
COLOURLESS
RECTILINEAR
L O W
ISOTROPIC
O N L Y PRESENT IF SECTION
C O M M O N
P R E P A R E D I N OIL
BARYTE
ORTHORHOMBIC
PLANAR
COLOURLESS
LOWMODERATE
C O M M O N L Y
EVAPORITE
CEMENT
CEMENT
C O M M O N L Y
C R Y S T A L L I N E D U E TO R E P L A C E M E N T
PARTIALLY REPLACIVE
BURIAL
CEMENT
M A Y
GREY
B E ASSOCIATED WITH
SULPHIDE
M I N E R A L I Z A T I O N ; DIFFICULT TO
F R O M CELESTITE U N D E R
IRON
OF
SEQUENCES
DISTINGUISH
MICROSCOPE
MINERALS
PYRITE
CUBIC
O P A Q U E
MAGNETITE
CUBIC
O P A Q U E
HAEMATITE
CUBIC
O P A Q U E ,
CHAMOSITE/
MONOCLINIC
GREEN
DISTINGUISHED
BROWN
TINGE
MODERATE
GREY,
BY
NON-CRYSTALLINE
BROWNS
BITUMENS
NON-CRYSTALLINE
O P A Q U E
("YELLOW
-{
[
BERTHIERINE
COLLOPHANE
IN
REFLECTED LIGHT
MODERATE
GREY-BLACK
C O M M O N
AUTHIGENIC
MINERALS
RED-GREY
O C C U R S I N O O I D S I N I R O N S T O N E S A N D AS
MASKED
P A R T I A L P O R E FILLS
COLOUR
R E P L A C I V E TEXTURES, C O M M O N L Y
ISOTROPIC
OCCURS I N PORE SPACES A N D I N

DISTINGUISHED
http://jurassic.ru/
FLUORESCENCE
IN
I N CARBONATES
FLUID
INCLUSIONS
114
G. HARWOOD

1955), or be c o m p u t e r - g e n e r a t e d r a n d o m percen
tages (Folk, A n d r e w s & Lewis, 1970) (Fig. 5.4).
Care must be t a k e n in making visual estimates, and
results are usually much less accurate than with
point counting techniques. T h e m e t h o d is both sim
ple and quick, but should only be used for estima
tions and not w h e r e accurate results are required.
C o m p u t e r - a i d e d techniques will help by providing
higher accuracy results, but will not bypass t h e need
for previous detailed petrographic study.
Terrigenous
ABUSES AND USES
10%
Allochemical
Orthochemical
Fig. 5.3. The five basic classes of sedimentary rock types

(after Folk, 1974b). Descriptions of the classes are in Table
5.2.
VISUAL ESTIMATION TECHNIQUES

M a n y petrographic texts include visual c o m p a r a t o r s
to be used in estimations of modal composition/
mineral percentages, etc. T h e s e may include grains
of different shapes and sizes (Terry & Chilingar,
Symbol from
Fig. 5.3
T
Terrigenous rocks
IA Impure allochemical
rocks
IO Impure orthochemical
rocks
A Allochemical rocks
O
Orthochemical rocks
Examples and comments
With both visual estimation and point counting tech

niques it must be r e m e m b e r e d that values are being
c o m p u t e d from t h e two dimensions of the thin sec
tion into t h e t h r e e dimensions of a sediment for
modal composition. F o r i n h o m o g e n e o u s sediments,
particularly those with a distinct fabric, total measure
m e n t of modal composition should b e a combination
of the m e a s u r e m e n t s from t h r e e perpendicular thin
sections. It is also important that t h e thin sections
counted are representative of the sequence studied,
thus necessitating preliminary overviews of the thin
sections.
E a c h of the major c o m p o n e n t s of a sedimentary
rock (Fig. 5.3) can be further subdivided during
detailed modal analysis (Table 5.3). Expression of
m o d a l composition is commonly shown o n a tri
angular diagram, using three a p p r o p r i a t e major
Approx, % of
strat. record
Most mudrocks, sandstones and

conglomerates
Most terrigenous rocks fall into the
shaded area of Fig. 5.3
Very skeletal shales, sandy skeletal
or ooid-rich carbonates
Clayey carbonate mudstones
6 5 - 75
Skeletal, ooid-rich, pellet or

intraclastic carbonates
Carbonate mudstones, anhydrite,
chert
Collectively IA and IO are classed
as impure chemical rocks and A
and O as pure chemical rocks
8 - 15
Table 5.2. Explanation of symbols

used in the classification of
sedimentary rocks of Fig. 5.3 (from
Folk, 1974b)
10- 15
2- 5
2- 8
115
Table 5.3. Summary of the components of sedimentary rocks and their symbols, for use with triangular compositional
diagrams similar to those of Fig. 5.5 (modified from Folk, 1974b)
Symbol
Origin
Components
Igneous quartz
Qi
Q
Quartz (Q)
Metamorphic quartz
Plagioclase
P
K
R
Rv
Rmet
Rpu
it
Pel
s
O
G
M
M
F
r n s
d e p
ic
^
ap
Cvh
ert
J
]
Orthoclase/microcline
J
Sedimentary rock fragment
Volcanic rock fragment
Metamorphic rock fragment
Plutonic rock fragment
Feldspar (F)
Terrigenous
components
Rock fragments
(or lithic clasts)
(LorRF)
Detrital
Skeletal fragments
Pellets/peloids
Ooids
Unidentifiable grains
Some carbonate muds
Carbonates
Allochemical
Some carbonate muds

Evaporites
Cherts
Chemical/diagenetic
Orthochemical
c o m p o n e n t s (Fig. 5.5a, b ) . C a r e should be t a k e n

that t h e same classification m e t h o d is used for all
samples plotted, particularly if data are obtained
from o t h e r w o r k e r s , as different classifications can
result in variation of t h e position of plotted points
(and h e n c e composition) (Zuffa, 1985). Modal com
positions have commonly b e e n used by sandstone or
c a r b o n a t e p e t r o g r a p h e r s but Zuffa (1986) has de
m o n s t r a t e d t h e i m p o r t a n c e of consideration of silici
clastic plus detailed carbonate c o m p o n e n t s . It is also
i m p o r t a n t to n o t e the presence of later dissolution
( M c B r i d e , 1985) as this can greatly affect the re
sultant m o d a l composition (Section 5.3.4). T h e use
of multivariate analysis ( c o m m o n in igneous geo
chemistry) has b e e n little applied to m o d a l composi
tions of sediments, although it offers considerable
potential. This lapse may be d u e to t h e lack of point
counting in recent years, concomitant with lack of
communication b e t w e e n various branches of t h e
geological sciences. In addition to m o d a l composi
tion, point counting can be used to assess t h e rela
tive proportions of grains and matrix, grains and
c e m e n t and cement or grains and porosity.
in situ
5,2.3 Grain m o r p h o l o g y , size, s o r t i n g

measurements a n d orientation
Several authors have considered t h e difficulties of
evaluating these p a r a m e t e r s from thin sections of
lithified sediments as opposed to those of uncon
solidated or disaggregated sediments (Rosenfeld,
Jacobsen & F e r m , 1953; F r i e d m a n , 1962; Klovan,
1966; Folk, 1966, 1974b). A l t h o u g h these para
m e t e r s a r e commonly m e a s u r e d for unconsolidated
or disaggregated sediments, t h e geological signi
ficance of t h e difference in grain size within sedi
m e n t s is not fully u n d e r s t o o d (Folk, 1974b). In
addition, disaggregation of sediments may lead to
inaccurate results if overgrowth cements are present
(Section 5.3.3). T h e size of detrital grains within a
sediment is proportional to t h e available materials
and to t h e a m o u n t of energy imparted t o the sedi
m e n t . T h e degree of sorting of a sediment is d e p e n
d e n t on t h e size r a n g e of t h e supplied grains, t h e
m o d e of deposition (for example, whether wave
reworking or current deposition), t h e current char
acteristics (predominantly strength) and t h e time
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llllllllillillililiilllllll
1111
r
i
)
116
G. HARWOOD
117
Table 5 . 4 . Data sheet for use when point counting thin sections (or grain mounts). Modified from Galehouse (1971a)
Thin section/sample number
Rock name
Stage type
Counter type
Initial slide position
Horizontal interval
Vertical interval
Mineral
Number
Date
Operator initials
Percentage
:
.
Counter reading
Start
Name
Finish
Number
of
Points
Comments
1
2
3
4
5 '
6
7
8
9
10
11
Opaque
Total
Accessory minerals:
(present but not at point count sites)
involved in deposition. Field or core studies can give

information on s o m e of these features and thin
section petrography can aid further evaluation, b u t
care must be t a k e n to avoid diagenetic fabrics in any
such analysis. Shadowgraphs are particularly useful
in grain morphology and orientation studies, as they
enable overviews of a large a r e a of t h e thin section.
GRAIN MORPHOLOGY
Fig. 5 . 4 . Percentage estimation comparison charts (from Folk et al., 1970). This chart combines the visual comparator of
Terry & Chilingar (1955) with computer-generated visual comparators.
Recognition of detrital grain morphology (form,

sphericity, roundness a n d , in s o m e cases, surface
textures) in thin section is only possible w h e r e grain
surfaces have not b e e n modified during diagenesis.
P a r a m e t e r s such as roundness and sphericity are
readily m e a s u r a b l e from thin section. F o r m (or

s h a p e ) , however, is d e p e n d e n t on t h e orientation of
the thin section; d e t e r m i n a t i o n of grain form therefore involves m e a s u r e m e n t of shape of many grains
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in different orientations within one thin section,

a n d , preferably, the use of t h r e e perpendicular thin
sections,
118
G. HARWOOD
119
Quartz
Q
F
Feldspar
RF
Rock (or lithic)
fragments
Terrigenous sediments
Fig. 5.6. A random section through a solid comprising a

framework of spherical grains of equal size (from Harrell,
1984).
(b)
Brachiopods and
bryozoans
Carbonate mud
GRAIN SIZE AND SORTING

MEASUREMENTS
Crinoids
Carbonate sediments
Fig. 5 . 5 . Component diagrams for demonstrating modal

composition of (a) siliciclastic/terrigenous sediments and
(b) carbonate sediments. Components can be modified to
suit the individual study.
A thin section is a r a n d o m two-dimensional slice

through a three-dimensional solid. A n y slice through
a solid comprising spherical grains of equal size will
show spheres of m a n y , apparently, different sizes
(Fig. 5.6). Both grain size and sorting c a n n o t , t h e r e
fore, b e m e a s u r e d directly from a thin section and
can only be estimated. This can be d o n e by direct
m e a s u r e m e n t s of t h e m a x i m u m dimension of a
h u n d r e d grains through a calibrated eye piece grati
cule, or o n a screen, followed by calculation of t h e
standard deviation of these dimensions and applica
tion of a conversion equation which adjusts this
value for t h e effects of r a n d o m sectioning (e.g.
Harrell & Eriksson, 1979). Alternatively, visual
estimation using a c o m p a r a t o r can be used, a proce
d u r e which is considerably less time consuming and
much easier, although such estimates may lack ac
curacy. Harrell (1984) c o m p a r e d actual and a p p a r e n t
sorting images for sets of spheres with log n o r m a l
distribution, and d e m o n s t r a t e d that t h e a p p a r e n t
sorting is less accurate for well sorted sediments,
b u t , that using his visual c o m p a r a t o r s (Fig. 5.7), t h e
a p p a r e n t sorting is very nearly t h e same as for actual
sorting within t h e sand and gravel size ranges. It
(0
(d)
Fig. 5.7. Visual comparators for random sections through log normally distributed sets of spherical grains. Actual sorting
in (a) is 0.35 <t>, in (b), 0.50 <t>, in (c), 1.00 (j> and in (d) is 2.00 <t>. Apparent sorting is 0.69,0.77,1.16 and 2.08 (j) respectively
(from Harrell, 1984).
should be emphasized t h a t use of sorting and grain

size c o m p a r a t o r s is only valid for sediments which
have not u n d e r g o n e compaction (see Section 5.3.2).
A b n o r m a l sorting or textural inversion (e.g. Fig.
5.8) a r e c o m m o n in sediments and indicate unusual
http://jurassic.ru/
environmental conditions, possibly mixing of sedim e n t from two different e n v i r o n m e n t s , storm mixing
of material in a high energy environment or multiple
sources of sediment supply. T h e s e conditions a r e
n o t always a p p a r e n t from field/core studies and
120
G. HARWOOD
121
Fig. 5.8. Bimodal distribution in modern ooid sands. Radial ooids from Great Salt Lake are mostly 600 urn in diameter, but
larger grains average over 1,000 urn. Recent, Utah, USA.
Fig. 5.9. Grain orientation in a carbonate turbidite. Elongate grains have preferential near-horizontal orientation with
some imbrication. Miocene, Site 626, ODP Leg 101, Straits of Florida. Sample courtesy of ODP.
illustrate the uses of t h e additional information o b
tainable from thin section petrography. In inter
p r e t a t i o n , it should b e r e m e m b e r e d t h a t t h e r e is
very little size reduction of quartz sand grains during
t r a n s p o r t , b u t that selective sorting may m e a n that
t h e small grains are carried farther, or are w i n n o w e d
and deposited by w e a k e r currents (Folk, 1974b).
GRAIN ORIENTATION
M e a s u r e m e n t of grain orientation (e.g. Fig. 5.9)
necessitates t h e use of oriented field samples plus
m e a s u r e m e n t s from t h r e e perpendicular thin sec
tions. T h e orientation of t h e long axis of t h e grains
can be m e a s u r e d directly from the microscope or
s h a d o w g r a p h , or it can be m e a s u r e d by a p h o t o
metric m e t h o d which integrates t h e extinction be
haviour of all the grains in t h e field of view (Sippel,
1971). Orientations d e t e r m i n e d can be plotted on
rose diagrams, balloon diagrams or, b e t t e r , stereonets as for field palaeocurrent analysis ( C h a p t e r 2).
Compaction after sedimentation may have consider
ably reduced any a n g l e o f cross lamination m e a s u r e d
from grain orientation;'the significance of this can be
estimated from compaction features visible in t h e
s a m e thin sections (Section 5.3.2). M o r e detailed

accounts of grain orientation m e t h o d s from thin
sections are given in B o n h a m & Spotts (1971) and
G i b b o n s (1972).
QUARTZ PROVENANCE STUDIES
5.2.4 Provenance studies

P r o v e n a n c e studies of s a n d s t o n e sequences are pos
sible using t h e m o d a l composition plus maturity
indicators (Fig. 5.10; T a b l e 5.5) (Valloni & M a y n a r d ,
1981; Dickinson, 1985; Valloni, 1985). Sandstone
sequences a r e t h e result of both p r o v e n a n c e and
tectonic e n v i r o n m e n t , modified by climate, deposi
tional e n v i r o n m e n t and later diagenetic events. Such
broad groupings a r e only possible when many separ
ate thin section analyses are grouped t o g e t h e r ; they
a r e n o t applicable w h e r e t h e study is of o n e sand
stone sequence from o n e particular area of a sedi
mentary basin.
In addition to studies using t h e m o d a l composi
tion of a sediment, o t h e r p r o v e n a n c e determinations
can be m a d e from individual q u a r t z grains. This
technique was initiated by Krynine (1940, 1946) and
can detail sources not recognized in m o r e regional
composition-based provenance studies.
Q u a r t z grains may b e single crystals (monocrystalline) and show straight extinction or undulose
extinction (best m e a s u r e d on a universal stage).
T h e y may also be composite (or polycrystalline)
with straight o r u n d u l o s e extinction within individ
ual subcrystals and m a y , or may n o t , show elonga
tion within t h e subcrystals. Q u a r t z grains may also
contain trails of inclusions, commonly fluid or gas
filled. Subparallel trails of very small inclusions, or
B o e h m lamellae, are t h e products of intense strain,
and indicate strain to have occurred within the
quartz lattice, either in situ or before incorporation
in t h e present sediment. T h e two. may be distin
guished by measuring t h e strain directions in several
quartz grains; a r a n d o m strain direction indicates
strain prior to deposition, whereas a constant strain
direction indicates stress was applied to the sedi
m e n t . Q u a r t z grains may also contain solid inclu
sions, t h e mineralogy of which may give evidence of
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p r o v e n a n c e (e.g. sillimanite inclusions a r e excellent

evidence for a m e t a m o r p h i c source a r e a ) . A sum
m a r y of quartz grain features is given in Fig. 5.11
and p h o t o m i c r o g r a p h s in Fig. 5.12. A m o r e detailed
discussion of quartz grains as indicators of proven
ance is given by Folk (1974b) who includes further
references.
5.2.5 Depositional fabrics a c o n c l u s i o n

In conclusion t o this section o n depositional fabrics
it can b e seen that a considerable a m o u n t of infor
mation can b e gained from petrographic studies
which can be used to supplement field studies and
gain insight into t h e origins of t h e s e d i m e n t . In
particular p r o v e n a n c e studies, both from modal
compositions and from quartz grain variations, a r e
n o t possible without petrographic analysis; these
form an important aid in t h e interpretation of an
cient sediments and their depositional environ
m e n t s . G r a i n size, form, roundness and sphericity
122
G. HARWOOD

data a r e s u p p l e m e n t e d from grain orientations mea
sured and mineralogical composition established.
5.3 D I A G E N E T I C F A B R I C S
Sedimentary rocks exhibit a vast r a n g e of diagenetic
fabrics from compaction to c e m e n t a t i o n , dissolution
to complete replacement. T h e s e diagenetic fabrics
can be important indicators both of the depositional
environment of t h e sediment and of t h e chemistry of
a variety of fluids which have been flushed through
t h e sediment during burial. Mineralogical changes
can also b e u s e d t o indicate t e m p e r a t u r e and d e p t h
of burial; this is of particular importance when
correlated with organic t e m p e r a t u r e / d e p t h indi
cators in studies of petroleum generation and migra
tion. T h e sequence of diagenetic events within a
sediment governs its potential as a hydrocarbon
reservoir, as a host for mineralization, as a conduit
for mineralizing fluids/hydrocarbons, or as a source
for hydrocarbons. Research o n diagenetic fabrics
supplements information from field/core based work
and from studies of depositional fabrics.
Fig. 5.10. Average modal compositions of groups of sandstones from different tectonic environments. This technique is
only valid where many different sandstone modal compositions are available and cannot be used for single sandstone
samples (modified from Folk, 1974b). Component details are documented in Table 5.5.
Symbol and mineral

Q
Quartz
Explanation
Association
All detrital quartz grains

Mature sediments with
plus metaquartzite clasts
little tectonic or igneous
(but not chert)
activity
F Feldspar
All detrital feldspars
Post-tectonic granitic
(whether orthoclase,
intrusions plus uplift of
microcline or plagioclase)
basement metamorphics
plus granite and gneiss
clasts
Rapid uplift and erosion
RF Rock fragments All other rock fragments
rate; more detailed
(chert, slate, schist,
associations possible on
volcanics, carbonates,
prevalence of rock
sandstone, mudrock, etc.)
fragment types
Table 5 . 5 . Explanation of original

quartz, feldspar and rock fragment
end members used for the triangular
plots of Fig. 5.10. Compiled from
Folk (1974b)
Diagenetic fabrics can be subdivided into two

major types those d u e to compaction and those
d u e t o chemical alteration, w h e t h e r cementation,
dissolution o r replacement (Fig. 5.13). A sediment
may exhibit o n e or m o r e phases of a n y , or all, of
these processes; t h e task of t h e sedimentary petrogr a p h e r is to unravel the different events, place
these in a paragenetic sequence and then build on
these in interpreting t h e burial history of the sedi
m e n t . Sound p e t r o g r a p h i c interpretations are essen
tial before geochemical o r isotopic analysis of t h e
different diagenetic c o m p o n e n t s is a t t e m p t e d .
Increased research into diagenesis has resulted in
the introduction of m a n y n e w terms; to aid the
r e a d e r a brief review of general n o m e n c l a t u r e re
lating to diagenetic e n v i r o n m e n t and to porosity
fabrics is included h e r e before description of t h e
various diagenetic fabrics.
5.3.1 General nomenclature used in

diagenetic s t u d i e s
DIAGENETIC ENVIRONMENTS
T h r e e major diagenetic regimes w e r e defined by
C h o q u e t t e & Pray (1970) (Fig. 5.14) a n d a r e sum
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123
marized, with slight refinements, in T a b l e 5.6. In

most texts, simplification has led to t h e t e r m s
'eogenetic', 'mesogenetic' and 'telogenetic' being
replaced by 'near-surface', 'burial' and 'uplift' (or
'unconformity-related'). Near-surface
diagenetic
e n v i r o n m e n t s a r e further subdivided d e p e n d i n g o n
w h e t h e r t h e p o r e spaces are saturated with fluids,
within t h e phreatic zone, or w h e t h e r they lie a b o v e
t h e water t a b l e so a r e partially fluid filled and par
tially gas filled, within the vadose zone (Fig. 5.15).
T h e origin of the p o r e fluids, whether m a r i n e o r
m e t e o r i c (or fresh), also controls t h e diagenetic
reactions which take place within these zones (Sec
tions 5.3.3, 5.3.4 and 5.3.5).
POROSITY NOMENCLATURE
Porosity n o m e n c l a t u r e is based on two classic
p a p e r s : C h o q u e t t e & Pray (1970) a n d Schmidt,
M c D o n a l d & Piatt (1977). Porosity within a sedi
m e n t may be primary, a result of depositional voids
between or within grains, or secondary, the result of
dissolution, shrinkage or fracturing within the sub
surface ( C h o q u e t t e & Pray, 1970). Primary porosity
is commonly intergranular (or interparticle) (Fig.
5.16a), although r a r e intragranular porosity may be
p r e s e n t within rock fragments, skeletal material and
o t h e r detrital grains (Fig. 5.16b); intracrystalline
primary porosity can be significant within clays and
clay coatings and s o m e dolostones. Secondary p o r o
sities can be d u e to t h e dissolution of detrital grains
(Fig. 5.16c, d ) , of cements a n d authigenic minerals
(Fig. 5.16e) plus shrinkage of certain sediments
(particularly glauconitic sediments), a n d fracturing
after c e m e n t a t i o n . B o t h primary and secondary
porosity types may be mutually interconnected (Fig.
5.16a), therefore resulting in high permeabilities, or
isolated (Fig. 5.16b), with consequent low p e r m e
abilities. T h e effective porosity of a sediment is
d e p e n d e n t on t h e degree of interconnection of t h e
p o r e spaces, which a r e t h u s utilized during fluid
migration t h r o u g h t h e sediment.
Submicroscopic porosity (in places mistakenly term
ed 'chalky' porosity) is present in chalks, mudrocks
and some altered detrital grains. Efficient impregna
tion with coloured resin within these sediments will
d e m o n s t r a t e t h e presence of submicroscopic poro
sity u n d e r a good p e t r o g r a p h i c microscope; further
124
G. HARWOOD
totally
recrystallized
metamorphic
stressed
igneous
volcanic
reworked
sedimentary
recrystallized
metamorphic
(gneiss)
igneous
hydrothermal
125
stressed
metamorphic
(schist)
stressed
metamorphic
(gneiss)
increasing recrystallization
authigenic
increasing d e f o r m a t i o n
straight extinction
slightly undulose extinction

undulose extinction
*~
single quartz crystal
composite
Fig. 5.12. Provenance of quartz grains: (a) Single, subrounded, monocrystalline quartz grain, showing straight extinction,
from an igneous or vein quartz source. Crossed polars. Permian, Yellow Sands, Co. Durham, UK.
(b) Single, rounded, monocrystalline quartz grain, with undulose extinction, from an igneous, or stressed igneous, source.
Crossed polars. Permian, Yellow Sands, Co. Durham, UK.
(c) Single, rounded, composite quartz grain, showing numerous subcrystals from a metamorphic source. Crossed polars.
Permian, Yellow Sands, Co. Durham, UK.
(d) Authigenic, euhedral quartz grain in carbonate grainstone. Inclusions of carbonate are present in the outermost
portions of the quartz crystal. Jurassic, Gilmer Formation, east Texas, USA.
* * solid inclusions
"
:
f l u i d inclusions
quartz o v e r g r o w t h
Boehm lamellae
Fig. 5.11. Summary diagram of quartz grain fabrics for use as provenance indicators (modified from Folk, 1974b).
research on its fabrics and genesis requires electron

microscopy.
contacts a n d compaction starts t o proceed by chemi

cal processes.
5.3.2 Compaction fa b r i c s
C O M P A C T I O N BY M E C H A N I C A L
PROCESSES
In thin section grainy sediments c o m m o n l y show

evidence of compaction, t h e result of progressive
increase in o v e r b u r d e n during burial. Before ce
m e n t a t i o n , compaction takes place dominantly by
mechanical processes, with slippage between indivi
dual grains, grain reorientation and subsequent frac
ture of s o m e grains. With increase in o v e r b u r d e n
p r e s s u r e , m o r e stress is placed on the grain to grain
COMPACTION
FABRICS
DIAGENETIC
FABRICS
C o m p a c t i o n by mechanical processes involves move

ment by slippage between grains and t h e b r e a k a g e ,
or fracture, of individual grains; as such it is some
times t e r m e d brittle compaction.
A n y increase in
o v e r b u r d e n pressure in an unconsolidated s e d i m e n t
tends to result in a denser configuration of that
sediment by m o v e m e n t between the individual
mechanical
(or brittle)
solution (or c h e m i c a l )
compaction
compaction
. cementation
CHEMICAL .
ALTERATIONFABRICS
dissolution
mineral r e p l a c e m e n t
(authigenic mineral formation)
Fig. 5.13. Major classes of diagenetic fabrics.
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126
G. HARWOOD
sediment
Table 5.6. Summary of the different

diagenetic environments of
sedimentary rocks. Modified from
Choquette & Pray (1970)
deposition
I
penecontemporaneous _
processes
\ ^
near-surface
burial
(eogenetic)
depth
processes
uplift o r
unconformity-related
(telogenetic) p r o c e s s e s
Diagenetic environment
Penecontemporaneous
(syndepositional)
Eogenetic
(near-surface)
Mesogenetic
(burial)
burial
(mesogenetic)
processes
Telogenetic
(uplift or unconformity
related)
time
127
Description
Diagenetic processes which occur within the
depositional environment
Diagenetic processes which occur within the zone
of action of surface-related processes and
surface-promoted fluid migration
Diagenetic processes that take place during burial,
away from the zone of major influences of
surface-related processes
Diagenetic processes which are related to uplift
and commonly result from surface-related fluid
migration
Fig. 5.14. Major diagenetic regimes (see also Table 5.6).

result of secondary porosity creation during burial
diagenesis in both carbonate and siliciclastic host sedi
m e n t s (Fig. 5.18d, e ) . Mechanical compaction is re
latively easy to envisage in near-surface regimes and
can be readily demonstrated experimentally (Vinopal
& C o o g a n , 1978; Shinn & R o b b i n , 1983). It is, how
ever, m o r e difficult to envisage t h e formation of a
substantial a m o u n t of secondary porosity followed
by fracturing during d e e p burial; this may necessitate
a reduction in hydrostatic pressure (perhaps a re
laxation of overpressuring), a change in p o r e fluid
chemistry (cessation of secondary porosity forma
tion) allowing subsequent fracture, or slight tectonic
m o v e m e n t . Little research has yet been carried out
o n controls of brittle fracture within t h e subsurface,
although Bjorlykke (1983) attributed cement dis
solution (and c o n s e q u e n t secondary porosity genera
tion) to overpressuring, with subsequent cementation
in the overlying strata a consequence of pressure
release.
mixing of
meteoric and m a r i n e
phreatic z o n e s
Fig. 5.15. Theoretical cross-section showing near-surface diagenetic environments.
grains and the c o n s e q u e n t grain reorientation. Most

spherical, cylindrical, disc-shaped or ellipsoidal
grains (the regular grains of Vinopal & C o o g a n ,
1978) simply slip against each other. H o w e v e r , any
larger grains within t h e sediment c o m m o n l y form
bridges b e t w e e n t h e smaller grains creating a shelter
porosity (Fig. 5.17a). If these larger grains are platey
o r concavo-convex (the radical grains of Vinopal &
C o o g a n , 1978), brittle fracture may take place with
continued increase of o v e r b u r d e n pressure, resulting
in destruction of the shelter porosity and tighter
packing of the grains (Fig. 5.17b). T h e combination
of grain size plus grain morphology therefore dic

tates which grains are susceptible t o brittle fracture;
these grains are c o m m o n l y thin walled skeletal frag
m e n t s (Fig. 5.18a), including bryozoans ( M e y e r s ,
1980), mica flakes (Fig. 5.18b) and plant material
(Fig. 5.18c) (Ting, 1977). Such mechanical compac
tion is c o m m o n during early diagenesis, prior to
cementation.
Mechanical compaction a n d brittle failure may
also t a k e place after c e m e n t a t i o n , both as a result of
shrinkage, expansion, and s u b s e q u e n t fracturing b e
n e a t h a soil zone (Fig. 5.16e), a n d , c o m m o n l y , as a
C O M P A C T I O N BY C H E M I C A L P R O C E S S E S
I: S O L U T I O N C O M P A C T I O N B E T W E E N
INDIVIDUAL GRAINS
Compaction by chemical processes, or pressure
solution, takes place in two ways: (i) in an unce
m e n t e d sediment, by dissolution at isolated stressed
grain to grain contacts and (ii) within a cemented
sediment, by dissolution being concentrated along a
particular surface, usually irregular, t e r m e d a stylolite. Pressure solution has been defined as t h e pre
ferential dissolution of mineral material at points of
stress (Wanless, 1979).
O n c e the grains within an u n c e m e n t e d sediment

h a v e assumed their densest configuration by slippage
on grain surfaces, grain reorientation and fracture of
radical grains, o v e r b u r d e n pressure is transferred
through grain to grain contacts, commonly point
contacts (Fig. 5.19a). Progressive increase in over
b u r d e n pressure increases t h e stress at grain to grain
contacts, with resultant deformation of the crystal
lattice at these contact points plus changes in the
chemical potential within t h e immediate area of the
contact (Fig. 5.19b). Continuation of stress causes
dissolution of the contact area. Pressure solution is
controlled not only by t h e degree of crystal strain,
but also by t h e solubility of the specific crystal, its
orientation, t h e saturation state of t h e surrounding
fluid, t h e thermodynamics and kinetics of dissolu
tion and ion concentration gradients in addition to
t h e mechanism of solute transport (whether by dif
fusion or fluid flow) (Wanless, 1983). Progressive
solution compaction leads to alteration of t h e grain
to grain contacts, from t h e original point contacts,
through planar (or tangential) contacts to inter
penetrating (concavo-convex) and sutural grain to
grain contacts (Fig. 5.19ce). In sediments with
monomineralic, or monocompositional, grains, the
grain to grain contacts in, or near t o , t h e principle
stress direction commonly show similar degrees of
solution compaction, with, for example, planar o r
interpenetrating contacts (Fig. 5.20a). H o w e v e r ,
sections transverse to the principle stress direction
may exhibit a much lesser degree of solution com
paction (Fig. 5.20b). T h e a m o u n t of solution is
partially d e p e n d e n t on t h e orientation of t h e grains,
as many anisotropic minerals dissolve m o r e readily
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llllllllll
Fig. 5.16. Porosity types: (a) Intergranular porosity in aeolian sandstone; sandstone has been impregnated with coloured
epoxy to demonstrate porosity. Cretaceous, Loch Aline Sandstone, Argyll, UK.
(b) Intragranular porosity within foraminifer test in poorly cemented carbonate sands; sample has been impregnated with
coloured epoxy to demonstrate porosity. Holocene, Shark Bay, western Australia.
(c) Secondary porosity (arrowed) resulting from feldspar dissolution; clays indicate original shape of grain. If the clays were
removed by flushing, an oversized pore would result. Sandstone was cemented prior to feldspar dissolution or pore space
would not have been preserved. Cretaceous, Woodbine Formation, subsurface Arkansas, USA. Photomicrograph courtesy
o f D r W . Ward, UNO.
(d) Secondary, intragranular, porosity (arrowed), resulting from partial dissolution of aragonitic ooid coatings.
Surrounding cement, which maintains sediment fabric, is low Mg calcite. Pleistocene, Shark Bay, western Australia.
(e) 'Expansion' porosity, later occluded by calcite, in fitted-texture grainstone. Fractures surrounded individual grains after
fitted-texture had been developed. Jurassic, Smackover Formation, east Texas, USA.
Fig. 5.17. Shelter porosity and brittle fracture: (a) Shelter porosity created by large platey benthic foraminifer bridging pore
space. Grains (ooids, superficial ooids and peloids) are packed on top of foraminifer, whereas shelter porosity (here later
occluded by calcite cement) is maintained below. Eocene carbonates, east India.
(b) Brittle fracture of foraminifer, a result of increase in overburden pressure before cementation. Brittle fracture has
destroyed shelter porosity. Fractures have since been healed by calcite cement. Eocene carbonates, east India.
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aiiiiiiiiiiiiiiiiiiiiiiiiii
Fig. 5.18. Brittle fracture: (a) Brittle fracture of large foraminifer and thin-walled brachiopod (arrowed) in carbonate
wackestone. Permian, Cadeby Formation, Yorkshire, UK.
(b) Brittle fracture and deformation of detrital mica flake in sandstone; acicular carbonate cement has later grown around
mica. Lower Carboniferous, Lower Crag Point Sandstone, Northumberland, UK.
(c) Brittle fracture in plant material; section through conifer wood from peat showing collapse of earlier, central cells.
Reflected light, oil immersion. Palaeocene, North Dakota, USA (from Ting, 1977).
(d) Brittle fracture after formation of secondary porosity. Flushing by fluids during diagenesis has caused ooids to dissolve,
leaving framework of dolomitized circumgranular cements which have since fractured (arrowed). Jurassic, subsurface
Smackover Formation, east Texas, USA.
(e) Brittle fracture of clay coatings. Clay coatings originally formed around altering feldspar grain, which has since
completely dissolved (cf. Fig. 5.16c) leading to collapse of clay coatings. Surrounding pore space maintained by earlier
cementation of quartz sand grains. Cretaceous, Tuscaloosa Formation, subsurface Arkansas, USA. Photomicrograph
courtesy of Dr W. Ward, UNO.
131
Fig. 5.19. Solution compaction between individual grains

(porosity is stippled throughout): (a) Point grain to grain
contacts (arrowed).
(b) Stressed grain to grain contacts (large arrows), leading
to formation of dislocations in crystal lattice and
subsequent dissolution, with lateral fluid transport of
solutes (small arrows).
(c) Planar grain to grain contacts.
(d) Interpenetrating grain to grain contacts.
(e) Sutural grain to grain contacts.
along a certain crystallographic axis (Fig. 5.20c).

Solution a m o u n t s are also d e p e n d e n t on the relative
stability of different grains; stabilities may differ
between mineral grains (Fig. 5.20d), or between
grains and m u d r o c k clasts w h e r e the clasts u n d e r g o
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illilll
ductile deformation so that, in places, they simulate

a dispersed clay matrix (Scholle, 1979, p . 162).
Solution compaction b e t w e e n grains reduces the
effective intergranular porosity within a grainy sedi
m e n t (Fig. 5.19b) and is therefore important in
132
G. HARWOOD
800 /j,m
Fig. 5.20. Grain to grain solution compaction: (a)

Vertical section through ooid grainstone, showing
intense compaction solution between grains with
sutural and interpenetrating grain to grain
contacts. Jurassic, subsurface Gilmer Formation,
east Texas, USA.
(b) Horizontal section through the same grainstone
as (a), showing that much less solution compaction
has occurred in this plane, with planar and some
point grain to grain contacts; any sutural contacts
are less well developed than in vertical section.
(c) Effects of crystallographic orientation; the same
quartz grain (Q) has a variety of grain to grain
contacts with adjacent quartz grains, primarily due
to the different orientations of the crystallographic
axes. Cretaceous, Loch Aline Sandstone, Argyll,
UK.
(d) Effects of different mineralogies; feldspar
grains (F) show preferential dissolution with
respect to surrounding quartz grains. Precambrian,
Torridonian Group, Sutherland, UK.

reservoir evaluation; in s o m e cases solution com
paction may account for most of the overall porosity
reduction. Considerable solution compaction be
tween grains indicates that c e m e n t a t i o n did not t a k e
place until relatively late in the diagenetic history of
t h e sediment. This may be a factor of e n v i r o n m e n t
of deposition, or a consequence of rapid sedimenta
tion rates, particularly in c a r b o n a t e environments.
T h e relative timing of solution compaction and
c e m e n t a t i o n is i m p o r t a n t in reservoir evaluation
(Fig. 5.21).
D u r i n g solution compaction, t h e a r e a i m m e d i a t e
ly adjacent to t h e stressed grain to grain contact is
t a k e n into solution and may be flushed away from
t h e i m m e d i a t e area by p o r e fluid migration. T h e s e
solutes are thought to be t h e origin of c e m e n t s
within t h e subsurface, either as q u a r t z overgrowth
cements (e.g. Sibley & Blatt, 1976) or as calcite
c e m e n t s . T h e y may be precipitated locally ( T h o m p
son, 1959) or carried for s o m e distance in solution
(Bathurst, 1975; Wanless, 1979). F o r example,
M o o r e (1985) attributed t h e formation of zoned
burial cements to be t h e result of former grain to
grain solution compaction within the surrounding
Jurassic grainstones, w h e r e a s J a m e s , Wilmar &
Davidson (1986) concluded that the Nugget Sand
stone is an overall exporter of silica, despite t h e
d e v e l o p m e n t of s o m e q u a r t z overgrowth c e m e n t s .
A s c e m e n t a t i o n proceeds in clean sandstones o r
grainstones, or t h e matrix in clayey-sandstones and
Table 5.7. Common diagenetic

processes which affect detrital grain
types, after McBride (1985). For each
mineral, processes are listed with the
most common first
133
packstones becomes lithified, pressure is transmitted

through t h e whole rock and t h e r e is n o excess of
stress at t h e grain to grain contacts. Solution com
paction between individual grains therefore ceases,
but continues over a much wider area along stylolites,
seams and sutures within t h e sediment. Stylolites
are commonly formed within c a r b o n a t e sediments
w h e r e cementation takes place early in t h e sedi
m e n t ' s diagenetic history.
C O M P A C T I O N BY C H E M I C A L P R O C E S S E S
I I : S O L U T I O N C O M P A C T I O N IN
CEMENTED SEDIMENTS
Stylolites and solution seams are present within
many sediment types ( H e a l d , 1955,1959; T h o m p s o n ,
1959; Weller, 1959; T r u r n i t , 1968; B r o w n , 1969;
B a t h u r s t , 1975; L o g a n & S e m e n i u k , 1976; M i m r a n ,
1977; Wanless, 1979; Gillett, 1983 and o t h e r s ) . Both
stylolites and solution seams transect t h e c e m e n t e d
sediment and develop perpendicular to the axis of
m a x i m u m stress, which may b e either o v e r b u r d e n
pressure or tectonic stress. Because stylolites and
solution seams are zones of preferential solution
within a sediment, small fragments of less soluble
minerals tend to accumulate along the solution seam.
T h u s , in i m m a t u r e sandstones and carbonates, clay
minerals may b e c o m e concentrated along a seam.
B o t h Weyl (1959) and Oldershaw & Scoffin (1967)
K-feldspar
calcitized
zeolitized
dissolved
kaolinized
albitized
Plagioclase
calcitized
dissolved
albitized
zeolitized
Carbonate rock
fragments
dissolved
dolomitized
recrystallized
Volcanic rock
fragments
calcitized
dissolved
chloritized
zeolitized
Micaceous metamorphic
rock fragments
mashed
dissolved
Chert rock
fragments
dissolved
calcitized
Claystone/shale/
siltstone rock
fragments
mashed
Muscovite
kaolinized
dissolved
Biotite
dissolved
argillized
Unstable heavy
minerals
dissolved
calcitized
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ill
134
G. HARWOOD
135
Fig. 5.21. Relative timing of

compaction and cementation:
(a) Floating grains (arrowed) and
point grain to grain contacts in calcitecemented sandstone. Cement
contains oxidized pyrite crystals
(opaque). Cementation occluded
porosity before little compaction had
taken place. Permian, Yellow Sands,
Co. Durham, UK.
(b) Point and planar (arrowed) grain
to grain contacts in poorly cemented
sandstone. Grains have been slightly
compacted before cementation with a
thin coating of iron-rich calcite;
considerable intergranular porosity
remains. Recent, Lafourche Delta,
Louisiana, USA.
(c) A combination of early,
echinoderm overgrowth (E) and later,
intergranular (I) cements.
Echinoderm overgrowth cement grew
before much compaction as
echinoderm fragment has few
contacts with other grains. Away from
areas of overgrowth cement,
considerable grain to grain
compaction has taken place, resulting
in sutural grain contacts (arrowed).
Intergranular cement occluded
remaining porosity. Jurassic,
subsurface Gilmer Formation, east
Texas, USA.
(d) Interpenetrating grain to grain
contacts in ooid grainstone. The
presence of only thin early cements
(arrowed) resulted in interpenetration
between adjacent grains with loss of
intergranular porosity. Remaining
porosity was occluded by calcite
cement. Jurassic, subsurface
Smackover Formation, Louisiana,
USA.
d o c u m e n t e d how stylolites and solution seams p r e

ferentially develop in clay-rich layers in c a r b o n a t e
sediments, with t h e solution residue accumulating in
stylocumulates (Logan & S e m e n i u k , 1976) (Fig.
5.22a).
Wanless (1979) proposed that t h e r e were t h r e e
basic styles of solution compaction, d e p e n d e n t o n
t h e maturity of the sediments and the responsiveness
of t h e various units (Fig. 5.23). H e d e m o n s t r a t e d
that pervasive (or n o n - s e a m ) solution compaction
may result in considerable reductions in thickness

(commonly u p t o 5 0 % and m o r e , rarely as much as
8 0 % ) of finely crystalline c a r b o n a t e units. T h e m o r e
visible solution seams (whether high-amplitude sty
lolites, microstylolite swarms, or fine clay seams)
m a y also r e p r e s e n t considerable a m o u n t s of dissolu
tion in t h e subsurface. With high-amplitude stylo
lites, t h e m i n i m u m dissolution is equivalent to t h e
m a x i m u m amplitude of the stylolite (Fig. 5.22b, c).
Until t h e last ten years most authors thought that
solution seam and stylolite formation took place

during d e e p burial diagenesis. Recently, however,
Shinn & R o b b i n (1983) have d e m o n s t r a t e d the for
mation of stringers, superficially very similar to solu
tion s e a m s , forming in R e c e n t B a h a m i a n m u d s
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llllll
u n d e r relatively low pressures (6,784 psi, equivalent

to burial depths of approximately 2,000 m ) over
short periods of time. T h e s e stringers were com
posed of organic m a t t e r , principally sea grasses. In
Mississippian carbonates of t h e United States,
Fig. 5.22. Solution compaction in

cemented sediments:
(a) Thin, low-amplitude,
stylocumulate in silty carbonate
mudstone. Quartz silt and clay
minerals are concentrated along the
stylocumulate. Jurassic, subsurface
Gilmer Formation, east Texas, USA.
(b) High-amplitude stylolite in
carbonate mudstone. Fine residue
(probably clay minerals) emphasizes
the line of the stylolite. Permian,
Yates Formation, New Mexico, USA.
(c) Tracing of stylolite from (b).
Minimum dissolution that has taken
place is distance D , (here 2,400 urn
[2.4 mm]), the greatest amplitude
between adjacent peaks of the
stylolite.
(d) Low magnification
photomicrograph of the ooid
grainstone of Fig. 5.21(c), showing
high-amplitude stylolite (arrowed)
cutting both echinoderm overgrowth
cements and post-compaction,
intergranular cements. Jurassic,
subsurface Gilmer Formation, east
Texas, USA.
(e) Medium- to low-amplitude
microstylolites in silty carbonate
mudstone. Jurassic, subsurface
Gilmer Formation, east Texas, USA.
Meyers (1980) and Meyers & Hill (1983) have de

m o n s t r a t e d mechanical a n d chemical compaction at
less than 2,000 m burial d e p t h with initiation of
chemical compaction at d e p t h s of 'tens to h u n d r e d s
of m e t r e s ' . Earlier, Beall & Fischer (1969) had o b
served that t h e transition from mechanical compac
tion to solution compaction occurs at a r o u n d 250 m
sediment d e p t h in s o m e N o r t h Atlantic D S D P sites.
H a r r i s ( M e y e r s , 1984 personal communication) has
found that high amplitude stylolites formed at burial
137
depths of less t h a n 1,000 m in t h e Burlington F o r m a

tion (Mississippian). This combined evidence indi
cates that some stylolite and solution seam formation
can take place during shallow burial; these solution
features should n o t , therefore, be used as evidence
for d e e p burial.
T h e timing and m o d e of formation of stylolites
remains a n a r e a of contention in sedimentary p e t r o
graphy, although m a n y stylolites show evidence of
at least s o m e c o m p o n e n t of their formation relative-
http://jurassic.ru/
fMWtiHHHHIItHlimttlllllttlimHHWMtlHttHtiiHHIl
It,
''Wllllllllllilll
138
G. HARWOOD
tation, connecting the two processes in most instances

requires a 'leap of faith'.
Unconformable
Conformable
Internal
Interweaving
ESTIMATION OF AMOUNTS OF
COMPACTION
SUTURED SEAM SOLUTION

Stylolites, grain contact solution sutures
A l t h o u g h t h e r e a r e m a n y qualitative studies d e m o n
strating t h e wide distribution of mechanical and
chemical compaction fabrics, published quantitative
results are considerably rarer. M e a s u r e m e n t of sty
lolite amplitudes (Fig. 5.22b, c) or of solution seam
thickness provides only a m i n i m u m estimate of t h e
a m o u n t of sediment r e m o v e d (Stockdale, 1926;
M o s s o p , 1972) and becomes m o r e difficult with low
amplitude stylolites and solution seams (Fig. 5.22f).
V o l u m e reductions in c a r b o n a t e s of approximately
4 0 % were detailed by D u n n i n g t o n (1967) and Park
& Schot (1968, p . 72); similar calculations a r e lack
ing for o t h e r sediments. P e r h a p s a future valid
contribution to this field could be m a d e by a com
bination of experimental simulation of mechanical
and chemical compaction in conjunction with the
use of c o m p u t e r imagery in volume reconstruction;
at present we only k n o w compaction is extremely
effective at reducing b o t h absolute volume and
porosity in m a n y sediments.
Clean limestone with stucturally resistant elements
-III boundary
NON-SUTURED SEAM SOLUTION
NON-SEAM SOLUTION
Microstylolites, swarms, seams
Pervasive solution-dolomitization
Clayey limestones
Clean limestone without resistant elements
5.3.3 Cementation
Scattered
micro stylolites
Uniform
stress and
responsiveness
S w a r m s or
seams in
responsive
zone
Limestone ^ C l a y e y &o/r
HSdolomitc
g C l a y &o/r
dolomite
Non-uniform
responsiveness
g j S e a m rjTJResistant unit
^ R e s i s t a n t grains
Fig. 5.23. Basic styles of solution compaction in carbonates (from Wanless, 1979). These styles can also be used to describe
solution compaction in siliciclastic sediments.
ly late, if not necessarily d e e p , in t h e diagenetic

history of their containing sediment (Fig. 5.22d).
H o w e v e r and w h e n e v e r they form, stylolites and
solution seams a r e i m p o r t a n t in reservoir evalua
tion. Koepnick (1985) has d e m o n s t r a t e d how stylo
lites act as migration barriers; d e n s e stylocumulates
in particular a r e barriers to fluid migration. Stylo
lites with little insoluble residue a n d high amplitudes
m a y , h o w e v e r , be pathways of preferential fluid
migration, a n d m a y remain o p e n , o r b e later filled
by c e m e n t s . Solution compaction along seams may
involve dissolution of considerable volumes of min

erals, commonly q u a r t z and calcite; these solutes
m a y locally source c e m e n t a t i o n , lessening t h e per
meability of t h e z o n e s u r r o u n d i n g t h e solution seams
( W o n g & O l d e r s h a w , 1981). H o w e v e r , s o m e a u t h o r s
(notably Scholle, 1971 and W a c h s & H e i n , 1974) a r e
of t h e opinion that pressure solution is t o o late to
account for t h e origin of most burial c e m e n t s . M o r e
recently, Scholle & Halley (1985) concluded t h a t ,
although solution compaction features are wide
spread in m a n y rocks, as is evidence of late cemen-
Many different minerals form c e m e n t s . Q u a r t z and

calcite a r e p e r h a p s t h e most c o m m o n but chlorite,
clay minerals, h e m a t i t e , d o l o m i t e , siderite, ara
gonite, p h o s p h a t e s and evaporite minerals (partic
ularly halite) also occur as c e m e n t s , as d o zeolites,
particularly in volcanogenic sediments (Table 5.1).
M o r e rarely, hydrocarbons may also form a c e m e n t .
A l t h o u g h t h e mineralogy m a y differ, the relation
ships b e t w e e n t h e various generations of c e m e n t s
and their adjacent grains enable t h e timing of
c e m e n t a t i o n relative to o t h e r diagenetic events to be
evaluated (Fig. 5.21). M a n y c e m e n t s can be clearly
recognized using a combined transmitted-reflected
light petrological microscope. H o w e v e r , c a t h o d o
luminescence ( C h a p t e r 6) can give additional infor
mation on crystal growth directions and can aid
elucidation of many c e m e n t relationships; it is an
i m p o r t a n t adjunct for t h e study of many c a r b o n a t e ,
q u a r t z and feldspar c e m e n t s . Staining ( C h a p t e r 4)
and blue light emission spectroscopy (Dravis &
Yurewicz, 1985) may also aid evaluation of some
diagenetic s e q u e n c e s , particularly in carbonates. In
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139
addition, scanning electron microscopy, both of solid

specimens and of etched thin sections (e.g. Sandb e r g , 1985), can be used to confirm further de
ductions based o n thin section p e t r o g r a p h y (see
C h a p t e r 8).
Conformable c e m e n t s may form as an overgrowth
o n existing grains within a sediment, in many places
growing in optical continuity with a substrate of t h e
same mineralogy (e.g. Fig. 5.21c). Alternatively,
cements may nucleate on grains as s e p a r a t e , or
disconformable,
crystals (Fig. 5.24a), or they may
grow from a few nucleation points so that they
enclose t h e grains as poikilotopic cements (Fig.
5.24b); they m a y b e t h e same mineralogy as the
grains they enclose. T h e m o r p h o l o g y of these sep
a r a t e , disconformable crystal c e m e n t s is, in many
cases, d e p e n d e n t o n t h e diagenetic e n v i r o n m e n t
a n d contained fluids in which they form (e.g. Folk,
1974a; L o n g m a n , 1980), although growth kinetics
(Given & Wilkinson, 1985) are also an important
factor. A s u m m a r y of t h e m a n y descriptive terms
used in petrologic identification of c e m e n t m o r p h o
logy is given in Fig. 5.25.
C E M E N T T Y P E S I: G R A I N O V E R G R O W T H
CEMENTS
G r a i n overgrowth c e m e n t s (or conformable ce
ments) commonly develop o n q u a r t z and feldspar
detrital grains and o n s o m e skeletal c a r b o n a t e frag
m e n t s (Fig. 5.26). Q u a r t z overgrowth cements can
b e clearly recognized using a petrological micro
scope if clay- o r hematite-rich coatings (commonly
inaccurately t e r m e d 'dust' rims) a r e t r a p p e d be
tween overgrowth c e m e n t and grain (Fig. 5.26a, b ) .
M o r e rarely, two coatings may b e c o m e t r a p p e d ,
indicating two stages of d e v e l o p m e n t of t h e over
growth c e m e n t . W h e r e n o such coatings are present,
quartz overgrowth cements are much m o r e difficult
to recognize. Such c e m e n t s a r e , however, typically
inclusion-free (or, at least, inclusion-poor) and t h u s ,
with c a r e , may b e distinguished from t h e p a r e n t
grain. F u r t h e r , if sufficient intergranular p o r e space
is present within t h e sediment, t h e overgrowth ce
m e n t s will develop planar euhedral crystallographic
faces (Fig. 5.26c, d ) , although it should b e r e m e m
bered that continued e n l a r g e m e n t of the overgrowth
cements will lead to c o m p r o m i s e b o u n d a r i e s b e
tween the cements. Such compromise boundaries
may be difficult to distinguish from compacted
fabrics: cathodoluminescence can, in some cases,
140
G. HARWOOD
Cement
terminology
Less correct
terminology
needle
(or fine acicular)
whisker
needle fibre
pendant or
microstalactitic
cement forms on 'droplets'

beneath grains within vadose
zone
fibrous
dark, microcrystalline irregular

coating to grains and pores; marine
phreatic organ
'micritic' or
microcrystalline
microcrystalline cement coats

grains and may form 'bridges'
between grains; marine
phreatic environment
broad cements (~ 20 /xm +),
commonly longer than broad.
Common in mixed meteoric/
marine phreatic environments
circumgranular
isopachous
acicular
equal thickness acicular cements

surround grains; characterize marine
phreatic environments
equant
blocky
circumgranular
equant
cement
cement forms at or near

grain-to-grain contacts;
meniscus characterizes vadose
zone
thin straight long form
(~ 10 / u m x 300 x i m +), typical of
marine phreatic zone
pelodial
columnar
Fig. 5.24. Disconformable crystal cements: (a) Multiple nucleation sites, resulting in circumgranular, acicular, aragonite
cements growing on skeletal fragments in modern, shallow-water, carbonate sands. Crossed polars. Recent, US Virgin
Islands.
(b) Few nucleation sites, resulting in poikilotopic calcite cement enclosing quartz grains; two calcite cement crystals only
are present, their boundary is arrowed. Crossed polars. Permian, Yellow Sands, Co. Durham, UK.
Description
thin (do /xm) cements of single
or en echelon crystals; form in
or near soil zone
equidimensional cement crystals,

(commonly ~ 100 / x m +); form in
meteoric phreatic or burial
phreatic environments
equidimensional cements surround
grains; typify meteoric phreatic
regime
overg rowth
cement is in optical continuity

with grain substrate; form
during burial diagenesis
sparry
coarse cement crystals (~ 300 /xm),

commonly equidimensional;
typify burial environments
poikilotopic
coarse cement crystals enclose

grains; form in phreatic,
commonly burial, regime
baroque
(or saddle)
coarse cement crystals with

undulose extinction;
characterize deep burial
environments
grain
porosity
Fig. 5.25. Summary diagram of descriptive terms used for cement morphologies. For scale, grains shown have an average
diameter of 500 urn.
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Fig. 5.27. Grain overgrowth cements II: (a) Echinoderm overgrowth cements in crinoidal grainstone. Original grains (G)
appear greyer than overgrowth cements as they include traces of the original internal pores plus some microdolomite
crystals. Overgrowth cements occlude intergranular porosity and form compromise boundaries. Mississippian, Burlington
Formation, Illinois, USA. Sample courtesy of W.B. Meyers, SUNY.
(b) Crossed polars photomicrograph of (a), demonstrating optical continuity of overgrowth cements and occlusion of
intergranular porosity.
(c) Echinoid overgrowth cement on echinoderm spine from winnowed carbonate tubidite. Overgrowth cement grew in
deep water (>1000 m) sediment. Miocene, Site 626, ODP Leg 101, Straits of Florida. Sample courtesy of ODP.
(d) Radiating overgrowth cements (arrowed) on planktonic foraminifer. Cements grow in optical continuity with radial
calcite of foraminifer test in deep water (>1000 m) sediment. Miocene, Site 626, ODP Leg 101, Straits of Florida. Sample
courtesy of ODP.
Fig. 5.26. Grain overgrowth cements I: (a) Thin quartz overgrowth cements (arrowed) adjacent to open pore (P).
Overgrowth cements grew on rounded and subrounded grains, Permian, Penrith Sandstone, Cumbria, UK.
(b) Crossed polars photomicrograph of (a), showing composite nature of detrital quartz grain plus optical continuity of
overgrowth cements with their substrate. Haematite-rich coatings (arrowed) define detrital grain surfaces.
(c) Planar, euhedral faces of quartz overgrowth cements, which have grown into pore.spaces (P). Cement thickness varies
around pore space and is partially a function of crystal orientation and subsequent growth direction. Haematite-rich
coatings on detrital grain surfaces are clearly visible. Permian, Penrith Sandstone, Cumbria, UK.
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(d) Crossed polars photomicrograph of (c). Note optical continuity of overgrowth cement on strained, detrital quartz grain
(Q). Altered feldspar grain (F) has no overgrowth cement.
itiiimmmmmi
144
G. HARWOOD

4 km burial
2 km burial
Secondary
porosity
K Al S i 0 + AI Si 0 (OH)
Feldspar
Kaolinite
3
K AI Si O (OH) + S i 0 + H 0
lllite
Quartz Water
3
10
Fig. 5.28. Chemical reactions between feldspar and kaolinite are triggered by continued burial to produce illite, quartz
overgrowth cements plus secondary porosity (from Bj0rlykke, 1983).
be used for this p u r p o s e (Sippel, 1968). Scholle

(1979, p p . 1123) used p h o t o m i c r o g r a p h s and S E M
p h o t o g r a p h s to d e m o n s t r a t e t h e progressive devel
o p m e n t of q u a r t z overgrowth cements with con
comittant reduction of porosity. Q u a r t z grains with
overgrowth cements may be r e w o r k e d into younger
sediments (see Fig. 5.11) where their i m p o r t a n c e is
commonly u n d e r e s t i m a t e d (Sanderson, 1984). R e
worked grains with overgrowth cements are recog
nized by t h e lack of interlocking overgrowths, t h e
presence of q u a r t z overgrowth c e m e n t s o n isolated
grains a n d , less c o m m o n l y , t h e presence of r o u n d e d
or b r o k e n terminations (Scholle, 1979). C a u t i o n
also has to b e expressed w h e r e thin sections contain
possible volcanic q u a r t z grains; these can exhibit
zonation and r o u n d i n g which closely mimic q u a r t z
overgrowth c e m e n t s . H o w e v e r , t h e presence of
microlites and vacuoles in the o u t e r rim distinguishes
these volcanic fabrics from those of overgrowth
cements.
O v e r g r o w t h c e m e n t s on feldspars and c a r b o n a t e
e c h i n o d e r m fragments a r e similar to q u a r t z over
growth cements in that they contain few or n o
inclusions or a r e commonly in optical continuity
with t h e p a r e n t grain (Fig. 5.27a, b ) . Chemically,
feldspar overgrowth c e m e n t s are commonly t h e
p u r e sodium or potassium feldspar end m e m b e r s
and a r e rarely calcic; clear overgrowth cements may
s u r r o u n d partially altered feldspar grains (e.g.
H e a l d , 1956). E c h i n o d e r m grains contain a regular
p a t t e r n of internal p o r e s which contrast with t h e
surrounding, inclusion-free overgrowth cements
warn
(e.g. Figs 5.21 and 5.27a, b ) . T h e e c h i n o d e r m grains

may also contain small solid inclusions of d o l o m i t e ,
euhedral or subhedral, t h e microdolomites of
Meyers & L o h m a n n (1978), which result from t h e
alteration of t h e original high M g calcite skeleton to
low M g calcite and dolomite.
Overgrowth c e m e n t s on e c h i n o d e r m fragments
are commonly a relatively early p h a s e in t h e dia
genetic history of a sediment, b o t h in shallow water
carbonates (Fig. 5.27a, b) ( M e y e r s , 1980) and in
d e e p water c a r b o n a t e turbidites (Fig. 5.27c)
(Schlager & J a m e s , 1978; R e i d & Mazzullo, 1985,
personal c o m m u n i c a t i o n ) . In both shallow and d e e p
water examples t h e origin of the overgrowth c e m e n t
calcite is generally thought to b e from aragonite
dissolution during early diagenesis, although modi
fications of sea water chemistry with ocean d e p t h
and with shallow burial m a y be in part responsible.
O v e r g r o w t h c e m e n t s also form o n s o m e m o r e com
plex c a r b o n a t e grains, including planktonic foraminifers (Fig. 5.27d). It is noticeable that overgrowth
cements only develop o n biogenic c a r b o n a t e grains,
and d o n o t form w h e r e t h e skeletal wall has been
heavily b o r e d by fungi or algae (thus forming a
'micrite' e n v e l o p e ) .
T h e timing of t h e d e v e l o p m e n t of q u a r t z over
growth c e m e n t s is m o r e variable. M a n y sandstones
with overgrowth cements exhibit little solution com
paction at grain-to-grain contacts (Fig. 5.26c, d ) ; the
source of silica in such sediments can only partially
be derived from t h e solution compaction and may
largely result from the dissolution of opaline silica.
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145
Fig. 5.30. Carbonate cements I: (a)

Low Mg calcite meniscus cements
(arrowed) forming in ooid grainstone
subaerial dune. Holocene, Joulters
Cay, Bahamas. Sample courtesy of
C.H. Moore, LSU.
(b) Low Mg calcite needle cements in
aeolian dune. Pleistocene, Yucatan,
Mexico. Sample courtesy of W.B.
Ward.
(c) Microcodium (M), a low Mg
calcite growth form associated with
root zones. Pleistocene, Yucatan,
Mexico.
(d) Acicular, isopachous,
circumgranular cements in shallow
marine grainstone; acicular cements
may have been aragonite, since
converted to low Mg calcite with a
high degree of textural preservation,
or originally low or high Mg calcite.
Mississippian, Moyvoughly Beds, Co.
Meath, Ireland. Modern acicular,
circumgranular, aragonite cements
are shown.in Fig. 5.24(a).
(e) High Mg calcite, peloidal,
circumgranular cements (opaque)
coating grains, with later acicular
aragonite cements growing into
intergranular porosity. Holocene, San
Salvador, Bahamas.
(f) Microcrystalline, aragonite,
circumgranular cements on aragonite
grains. Cements are not isopachous
and form distinct bridges between
grains; textures are very different
from 'micrite envelopes'. Crossed
polars. Recent, US Virgin Islands.
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148
G. HARWOOD
Fig. 5.31. Carbonate cements II: (a) Columnar, isopachous, circumgranular cements on ooids and ooid-coated echinoderm
fragments. Remaining porosity is occluded by equant low Mg calcite cements. Lower Carboniferous, Brofiscin Oolite
Formation, Glamorgan, UK. Photomicrograph courtesy of K. Hird and M.E. Tucker, University of Durham, UK.
(b) Acicular, aragonite, 'ray' cements which grew within a reef cavity, later filled by internal sediment (IS). 'Ray' fans
exhibit sweeping extinction. Crossed polars. Recent, Jamaica. Photomicrograph taken courtesy of C.H. Moore, LSU.
(c) Radiaxial acicular calcite cements, showing characteristic curved cleavages of crystals; crystals are now low Mg calcite but
149
analysis (M.C. Akhurst, personal communication) indicates they were originally high Mg calcite. Growth direction was from
right to left; Mississippian, Carbonate mound core, Co. Galway, Ireland.
(d) Compromise boundaries (arrowed) formed by columnar cements competing for growth in intergranular pore spaces in
ooid grainstone (see also Harwood & Moore, 1984). Jurassic, subsurface Smackover Formation, east Texas, USA.
(e) Equant low Mg calcite cements in exposed ooid grainstone. Holocene, Joulters Cay, Bahamas.
(f) Baroque (or saddle) dolomite cement (D) in ooid grainstone. Dolomite is inclusion-rich and shows undulose extinction.
Calcite spar cement (C) occludes remaining pore space. Crossed polars. Jurassic, subsurface Gilmer Formation, east Texas,
USA.
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151
Fig. 5.32. Carbonate cements in

sandstones: (a) 'Needle' cements in
supratidal sandstone nodule. Crossed
polars. Recent, Lafourche Delta,
Louisiana, USA.
(b) Low Mg calcite cements growing
preferentially on carbonate grain (C)
in sandstone. Crossed polars. Recent,
Lafourche Delta, Louisiana, USA.
In o t h e r sandstones, q u a r t z overgrowth c e m e n t s d o
n o t form until after considerable solution c o m p a c
tion; h e r e t h e solution compaction can b e t h e major
source of silica, although reactions b e t w e e n clay
minerals in i m m a t u r e sandstones may also contri
b u t e silica (Fig. 5.28) (Bj0rlykke, 1983).
C E M E N T TYPES II: D I S C O N F O R M A B L E
CRYSTAL CEMENTS
Disconformable crystal c e m e n t s nucleate as separ
ate crystals o n sediment grains and, as such, are
distinct from overgrowth c e m e n t s . T h e size and
n u m b e r of these crystals a r e largely d e p e n d e n t o n
Fig. 5.33. Cements in carbonate sediments: (a) Anhydrite cement (A) occluding porosity in dolomitized ooid grainstone.
Dolomitized circumgranular cements (arrowed) coat ooids which have been partially dolomitized before dissolution of
remaining calcite. Opaque coating in ooid centres is bitumen, from hydrocarbon migration after anhydrite cementation
(see also Harwood & Moore, 1984). Jurassic, subsurface Smackover Formation, east Texas, USA.
(b) Multiphase carbonate cements. Dolomitized algal laminae (D) adjacent to void. Void fill was in several stages; first,
zoned dolomite cement (Z), second, rare marcasite (M), third, complexly zoned large calcite spar (C|) and last, voidoccluding calcite spar (C ). Photomicrograph taken under cathodoluminescence. Permian, subsurface Cadeby Formation,
Selby Coalfield, Yorkshire, UK.
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152
G. H A R W O O D
the composition of the enclosing p o r e fluids and on

t h e availability of t h e substrate to provide nuclea
tion sites. T h u s circumgranular (or rim) c e m e n t s
(Fig. 5.24a) form w h e r e t h e r e are many nucleation
sites o n a sediment grain, w h e r e a s poikilotopic ce
m e n t s (Fig. 5.24b) a r e t h e result of few nucleation
sites and, in general, slower crystal growth. Char
acterization of t h e diverse morphologies of c e m e n t s
formed in m o d e r n diagenetic e n v i r o n m e n t s of rapid
c e m e n t a t i o n has aided recognition of ancient ana
logues, particularly for near-surface c a r b o n a t e dia
genetic e n v i r o n m e n t s (for s u m m a r i e s see L o n g m a n ,
1980; J a m e s & C h o q u e t t e , 1983, 1984; H a r r i s ,
Kendall & L e r c h e , 1985). T h e s e , plus the c a r b o n a t e
c e m e n t s formed during burial diagenesis are sum
marized in Fig. 5.29 with examples in Figs 5.30, 5.31
and 5.32; relevant additional c o m m e n t s o n t h e s e
diagenetic e n v i r o n m e n t s a r e included below.
VADOSE AND SHALLOW MARINE

CARBONATE CEMENTS
A l t h o u g h t h e c e m e n t morphologies s u m m a r i z e d in
Fig. 5.29 occur principally in c a r b o n a t e sediments,
quartz meniscus c e m e n t s have b e e n described from
sandstones (e.g. Scholle, 1979, p . 114) a n d may
comprise partial overgrowth c e m e n t s . Near-surface
c a r b o n a t e c e m e n t s also occur in quartzose sand
stones b u t d o n o t , h o w e v e r , form so readily on
quartz grains (Fig. 5.30b, c). This may be partly a
factor of reduced possible nucleation sites and partly
a result of the decreased supply of calcium carbon
a t e . Siliciclastic sediments in general r e m a i n almost
u n c e m e n t e d until buried to d e p t h s of 1000 m or
m o r e , w h e r e a s c a r b o n a t e sediments a r e c o m m o n l y
c e m e n t e d at or n e a r t h e sedimentwater interface,
or in subaerial e n v i r o n m e n t s . Indirect evidence of
vadose diagenesis in c a r b o n a t e s comes from 'fittedtextures' (Fig. 5.16e), w h e r e expansion and or dis
solution a r o u n d grain margins has occurred b e n e a t h
a soil z o n e .
A n o t e of caution n e e d s to be a d d e d concerning
c e m e n t a t i o n in t h e m e t e o r i c vadose z o n e . A l t h o u g h
t h e r e is an ever-increasing literature on c e m e n t
morphologies and diagenesis within this z o n e , espe
cially within soils, it is i m p o r t a n t to r e m e m b e r that
m a n y such c e m e n t s are t h e exception r a t h e r than t h e
rule. In m a n y m o d e r n examples, diagenetic r e
actions in t h e m e t e o r i c zones are minimal. B o t h
m o d e r n and ancient zones show intense reaction
within a few centimetres of t h e soil surface, p e r h a p s
PRINCIPLES OF S E D I M E N T A R Y P E T R O G R A P H Y
the a r e a with least preservation potential, b u t very

little alteration of t h e original sediment below that
d e p t h . T h u s t h e presence of m a n y ancient m e t e o r i c
vadose zones may be difficult to d e t e r m i n e from
p e t r o g r a p h i c evidence and from field/core o r geochemical t e c h n i q u e s .
A further complication arises as m a n y ancient
shallow m a r i n e c a r b o n a t e c e m e n t s w e r e of different
mineralogies to those occurring in modern carbonates
(e.g. Figs 5.24a, 5.30d, 5.31b, c). H o w e v e r , although
t h e mineralogies may differ, t h e c e m e n t m o r p h o
logies are commonly similar, t h u s enabling inter
pretation of ancient early diagenetic e n v i r o n m e n t s .
153
c
HI
BURIAL CEMENTS
C a r b o n a t e burial c e m e n t s are commonly coarsely
crystalline, and include b a r o q u e d o l o m i t e and cal
cite spar (Fig. 5.31f), in places z o n e d . Burial c e m e n t s
in o t h e r sediments are c o m p o s e d of a complex range
of mineralogies, n o t all of which are readily distin
guishable with a petrological microscope ( T a b l e 5.1).
S o m e are finely crystalline (clay minerals, h e m a t i t e ,
limonite), o t h e r s are coarsely crystalline (similar to
c a r b o n a t e burial cements) and c o m m o n l y poikilo
topic, w h e r e a s yet o t h e r s are both coarsely crystal
line a n d , to s o m e extent, a p p e a r to replace t h e host
sediment ( a n h y d r i t e , halite, p h o s p h a t e s , glauconite)
(Fig. 5.33a). Q u a r t z overgrowth c e m e n t s a r e a fur
ther c o m m o n burial c e m e n t , although their p r e s e n c e
alone is not an indication of d e e p burial. In silici
clastic sediments careful attention to p e t r o g r a p h i c
detail, particularly t h e compaction history, is neces
sary t o d e t e r m i n e w h e t h e r a c e m e n t formed during
d e e p burial ( > 2 , 0 0 0 m ) or at an earlier stage in t h e
diagenetic history.
A t w h a t e v e r stage in the diagenetic history of t h e
sediment they form, c e m e n t s are a record of t h e
fluctuating
p o r e w a t e r history of a s e d i m e n t .
N u m e r o u s , clearly identifiable stages of c e m e n t a t i o n
in a sediment are evidence of changes in p o r e w a t e r
chemistry and saturation states, even if all the p r e
cipitated phases are of a single mineralogy (e.g. Fig.
5.33b). M o r e i m p o r t a n t , p e r h a p s , is t h e evidence
given by the termination of precipitation of a c e m e n t
p h a s e , indicating a decrease in saturation, or supersaturation, of that phase within the p o r e fluid and, in
places, dissolution of pre-existing c e m e n t phases
w h e n u n d e r s a t u r a t e d p o r e fluids are introduced into
a sediment. Analysis of t h e chemistry and isotopic
compositions of t h e various c e m e n t phases can give
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G. HARWOOD
Fig. 5.35. Corrosion and dissolution of grains: (a) Corrosion of detrital quartz grain margins (arrowed) by migrating pore
fluids prior to precipitation of poikilotopic calcite cement (C). Adjacent grain margins (G) show no corrosion but planar
margins from euhedral overgrowth cements. Permian, Penrith Sandstone, Cumbria, UK.
(b) Corrosion of precursor dolomite. Dolomitization of former carbonate grains with micrite envelopes has resulted in
coarsely crystalline dolostone with remnants of micrite envelopes preserved. Subsequent corrosion of dolomite crystals has
led to truncation of micrite relics (arrowed) with later porosity occlusion by calcite. This apparent replacement of dolomite
by calcite is termed calcitization or, less correctly, dedolomitization. Section stained with Alizarin red S. Permian, Cadeby
Formation, Yorkshire, UK.
(c) Corrosion along cleavages in dolomite, probably an effect of recent weathering. Dolomite within 5 mm of pore
space has been corroded along cleavage planes with subsequent precipitation of iron oxides, defining amount of
dissolution. Further away from pore space (bottom right corner of photomicrograph) dolomite remains uncorroded.
Permian, Cadeby Formation, Yorkshire, UK.
(d) Corrosion and secondary porosity formation along cleavage planes in feldspar. Impregnation has shown intragranular
porosity (arrowed) within feldspar grains Carboniferous, Upper Crag Point Sandstone, Northumberland, UK.
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156
G. HARWOOD
157
Fig. 5.36. Dissolution of grains and

cements: (a) Dissolution of zones
(arrowed) within carbonate cement
crystals in former dolomite. Permian,
Cadeby Formation, Yorkshire, UK.
(b) Dissolution along cleavages in
detrital feldspar grain (F) has resulted
in isolated grain remnants which have
collapsed within pore spaces.
Surrounding quartz grains were
cemented, largely by overgrowth
cements, before feldspar dissolution.
Complete dissolution of other detrital
grains has led to formation of pore
spaces (P), slightly oversized.
Carboniferous, Upper Crag Point
Sandstone, Northumberland, UK.
(c) Isolated pore spaces (arrowed)
formed from dissolution of replacive
anhydrite in peloid grainstone. Lack
of interconnection between pore
spaces means they are ineffective as
migration conduits for pore fluids.
Porosity has subsequently been
occluded by calcite. Permian, Cadeby
Formation, Yorkshire, UK.
(d) Interconnected secondary
porosity formed by collapse after
selective dissolution of some ooids.
Fracture between oomolds produced
linked 'chains' which were later used
for hydrocarbon migration; black
bitumen relics remain in pore spaces.
Jurassic, subsurface Smackover
Formation, east Texas, USA.
clear indications of concomittant variations in t h e

n a t u r e of t h e p o r e fluids ( C h a p t e r 9) (e.g. in a
c a r b o n a t e system, Dickson & C o l e m a n , 1980).
5.3.4 Dissolution fa b r i c s
Dissolution in t h e subsurface generates secondary
porosity ( C h o q u e t t e & Pray, 1970) (Section 5.3.1).
This m a y n o t necessarily b e large-scale dissolution
(e.g. Fig. 5.16d), b u t may result only in slight corro
sion of t h e detrital grains or pre-existing cements in
t h e sediment. Dissolution may b e very subtle, with

dissolution of calcic plagioclase whereas albite and
potassium feldspar a r e n o t affected (Boles, 1984). In
carbonates preferential solution of s o m e grain types
(e.g. Harris & Kendall, 1986) occurs in what would
otherwise a p p e a r t o b e a chemically h o m o g e n e o u s
sediment. T h e delicate textural changes commonly
e n c o u n t e r e d in studies of dissolution fabrics em
phasize t h e i m p o r t a n c e of effective impregnation of
t h e sediment prior t o thin section m a k i n g ; this is n o t
only essential to identify plucked grains, or grains
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partially plucked from their matrix as opposed to

secondary porosity, but is also necessary for reflec
t e d light p e t r o g r a p h y of grain and c e m e n t margins
w h e n investigating corrosion fabrics. C o m m o n dis
solution fabrics (based o n t h e work of several
a u t h o r s , e.g. Schmidt et al., 1977; H a y e s , 1979;
M c B r i d e , 1980; S h a n m u g a n , 1985) are shown diagramatically in Fig. 5.34.
CORROSION FABRICS
Initial dissolution leads to t h e corrosion of grain
margins and c e m e n t t e r m i n a t i o n s . This is c o m m o n
in many sediments and takes place adjacent to p o r e

spaces as t h e result of flushing by u n d e r s a t u r a t e d
p o r e fluids and n o t , as is sometimes mistakenly
stated, as the result of 'corrosive' growth of a later
mineral phase (Section 5.3.5). Such corrosion may
be selective, only effecting certain mineralogies, or
non-selective, so that all existing minerals adjacent
t o p o r e spaces are c o r r o d e d . Corrosion fabrics show
grain margins and c e m e n t terminations to have a
pitted or corrugated character (Fig. 5.35a) which in
o r e mineralogy is t e r m e d a 'caries' texture. If t h e r e
is n o later c e m e n t a t i o n , corrosion produces a m o r e
effective connection b e t w e e n p o r e spaces and thus
158
G. HARWOOD
e n h a n c e s existing porosity, whether this be primary

or secondary. M o r e c o m m o n l y , however, t h e ad
jacent p o r e space is later occluded by c e m e n t (Fig.
5.35b) which may r e n d e r t h e corrosion, if m i n o r ,
m o r e difficult to distinguish. Corrosion may also
t a k e place during t h e precipitation of what, super
ficially, a p p e a r s to be a single c e m e n t p h a s e ; in
carbonates this can b e detailed using c a t h o d o
luminescence p e t r o g r a p h y ( C h a p t e r 6). Corrosion
fabrics a r e very c o m m o n in evaporite sediments, or
sediments w h e r e t h e r e is a phase of evaporite
mineral c e m e n t a t i o n , as these minerals are very
soluble and h e n c e susceptible to slight changes in
fluid salinity (e.g. Schreiber, 1978).
PENETRATIVE DISSOLUTION FABRICS

M o r e progressive selective dissolution of cements
and grains within a sediment leads to attack of t h e
whole mineral, commonly commencing by corrosion
along cleavage planes (Fig. 5.35c, d ) . A s dissolution
p r o c e e d s , a h o n e y c o m b texture may result, parti
cularly w h e r e a mineral has near rectilinear clea
vages. Slight changes in mineral chemistry are also
p r o n e to selective dissolution (Fig. 5.36a), as are
zones of less stable mineralogies (e.g. W a r d &
Halley, 1985). C o n t i n u e d dissolution will result in
collapse of remaining grain fragments (Fig. 5.36b)
a n d , in t i m e , may r e m o v e t h e entire detrital grain
(Fig. 5.16c), forming oversized pores. In addition,
subsequent collapse of grain coatings, w h e t h e r ori
ginal or p r o d u c e d by earlier diagenetic alteration,
may occur (Fig. 5.18d). Selective dissolution is re
stricted to less stable mineralogies and, in places, to
strain b o u n d a r i e s within grains ( M c B r i d e , 1985); it
results in intragranular, or partial intragranular,
secondary porosity (Schmidt et al., 1977). This en
h a n c e d porosity will only be effective if t h e r e is
either a considerable p r o p o r t i o n of t h e m i n e r a l , or
minerals, susceptible to dissolution, so forming a
connection b e t w e e n isolated intragranular p o r e
spaces, or if t h e r e is an existing intergranular p o r o
sity. F o r e x a m p l e , t h e c o m m o n dissolution of iso
lated evaporite minerals forms isolated, secondary
p o r e spaces (Fig. 5.36c) which rarely e n h a n c e t h e
effective porosity of a sediment. This contrasts with
Fig. 5.36(d), w h e r e selective dissolution of s o m e
ooids, together with s u b s e q u e n t brittle collapse of
t h e supporting framework, has formed an inter
connecting fracture porosity.
It is very i m p o r t a n t to detail t h e a m o u n t of mineral
dissolution that has t a k e n place in t h e subsurface,

especially w h e r e m e a s u r e m e n t s of m o d a l composi
tion (Section 5.2.2) or p r o v e n a n c e estimates (Section
5.2.4) a r e being m a d e . McBride (1985, 1986) detail
ed dissolution and grain modification from t h e z o n e
of weathering to the d e e p subsurface of heavy
mineral grains, rock fragments and feldspars, result
ing in an a p p a r e n t composition very different from
t h e original (Fig. 5.37). Dissolution of diagnostic
minerals, together with alteration of o t h e r s , can
significantly modify original grain composition, par
ticularly as t h e original grain can rarely b e confident
ly identified (e.g. Fig. 5.36b). Modal composition
and p r o v e n a n c e studies can therefore only be par
tially accurate in many siliciclastic formations.
F u r t h e r m o r e , t h e a m o u n t of dissolution/alteration
must b e assessed separately for each formation
studied.
5.3.5 Alteration and replacement f a b r i c s

Dissolution in t h e subsurface is commonly associ
ated with mineral alteration and replacement. Within
t h e subsurface, m a n y minerals are altered to form
either new minerals, or a new suite of minerals
(commonly clay minerals) which grow o n , or ad
jacent t o , t h e site of the precursor grain or c e m e n t
(e.g. Fig. 5.28). In contrast, replacive fabrics result

b o t h from the growth, during diagenesis, of indivi
dual, isolated crystals, or clusters of these minerals,
and from large-scale or complete replacement of a
pre-existing fabric. R e p l a c e m e n t fabrics also result
from t h e recrystallization of t h e alteration products
of metastable minerals. T h e s e fabrics result from
t e m p e r a t u r e and pressure increases and from inter
action with migrating p o r e fluids, although altera
tion does not necessarily require the introduction of
additional ions within these fluids.
ALTERATION FABRICS
D u r i n g t h e t e m p e r a t u r e a n d pressure increases
through burial and during migration of p o r e waters,
m a n y previously-stable minerals, or minerals which
w e r e deposited a n d b u r i e d t o o rapidly t o b e c o m e in
equilibrium with surface t e m p e r a t u r e s and pres
sures, are "brought into a regime w h e r e they are
unstable in the prevailing conditions. T h e s e minerals
break down to form m o r e stable products, generally
in t h e site of t h e original mineral (e.g. Fig. 5.16c);
c o m m o n examples are heavy minerals w h e r e , in U S
Gulf Coast sandstones, t h e degree of alteration has
b e e n related t o burial depths (Fig. 5.38) (data of
159
Milliken in M c B r i d e , 1985). Alteration of feldspars

to clay minerals (Fig. 5.16c) a n d of aragonite t o low
Mg calcite (Fig. 5.39a) also occurs. Unless later
modified (e.g. Fig. 5.18d), alteration fabrics are
recognizable as they mimic the form of t h e precursor
mineral, even although t h e original texture is com
m o n l y destroyed t o s o m e extent.
INDIVIDUAL MINERAL REPLACEMENT

FABRICS
Replacive minerals grow in t h e place of earlier
mineral phases. T h e y commonly cut across p r e
existing grain and c e m e n t boundaries (Fig. 5.39b)
a n d t h u s can b e seen t o post-date all phases they
traverse. Most individual replacive minerals have
e u h e d r a l , planar crystallographic faces although
they may contain inclusions, r e m n a n t s of their p r e
cursor phases (e.g. Figs 5.12d and 5.39c, d ) . M a n y
have crystal forms m u c h larger than their precursors;
they therefore destroy t h e original fabric (Fig. 5.39b)
(e.g. A s s e r e t o & Folk, 1980). H o w e v e r , s o m e fabric
r e t e n t i o n may b e achieved t h r o u g h a b u n d a n t inclu
sions, although this is n o t always immediately a p
p a r e n t (Fig. 5.40a, b ) . T r u e fabric retention is rare
with individual r e p l a c e m e n t minerals, although it
Heavy mineral species
4H
c
6-
C
O.
i
CD
CD
D.
F
Fig. 5.37. Triangular diagram showing the present
composition of five sandstones, after dissolution and
alteration, and their reconstructed composition, assuming
15% of the grains which occupied oversized pores were
rock fragments and 85% were feldspar (from McBride,
1985).
Fig. 5.38. Depth plot of the

distribution of seven heavy mineral
species in Plio-Pleistocene
sandstones from the northern Gulf of
Mexico basin, USA. Solid line =
abundant; dashed line = rare (data
from Milliken in McBride, 1985).
E .
>.
Q.
CD
Q
12 H
1.4 H
16 H
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1111
160
G. HARWOOD
does occur w h e r e the replacive phase mimics t h e

precursor mineral.
LARGE-SCALE REPLACEMENT FABRICS
Large-scale replacement can be either fabric-reten
tive (Fig. 5.40c) or fabric-destructive (Fig. 5.40d).
Large-scale replacement occurs w h e r e sediments are
reactive; it is c o m m o n in evaporites (where fabrics
are similar to m a n y m e t a m o r p h i c textures), car
b o n a t e s , volcaniclastics a n d , to a lesser d e g r e e ,
greywackes. Volcaniclastic sediments a r e extremely
susceptible t o alteration and dissolution. Mathisen
(1984) d o c u m e n t e d secondary porosity e n h a n c e
m e n t of 4 0 % in P l i o - P l e i s t o c e n e volcaniclastic
sandstones from Indonesia in addition t o alteration
of many of t h e original grains and c e m e n t s (e.g.
feldspars, volcanic fragments, zeolites); this has oc
curred in burial depths of only 4 0 0 - 9 0 0 m . In grey
wackes there is commonly little secondary porosity
generation, but considerable mineral alteration and
recrystallization takes place within both rock frag
ments and matrix (Brenchley, 1969).
W h e r e t h e r e is a monominerallic, or n e a r - m o n o minerallic, precursor fabric, as in c a r b o n a t e s and

evaporites, replacement is commonly by a single
mineral. R e p l a c e m e n t within evaporite sequences is
c o m m o n , especially w h e r e potassium-rich minerals
are present. Evaporites also replace large a m o u n t s
of adjacent carbonate sediment (Fig. 5.40e), although
t h e volume of c a r b o n a t e replaced is difficult to as
certain. H a r w o o d (1986) estimated that s o m e 23 m
of t h e u p p e r m o s t P e r m i a n C a d e b y F o r m a t i o n has
b e e n replaced by (former) anhydrite within t h e sub
surface of Y o r k s h i r e , but in o t h e r c a r b o n a t e forma
tions within t h e Zechstein Basin m o r e considerable
a m o u n t s of replacement have probably t a k e n place.
O n e c o m m o n form of large-scale replacement in car
b o n a t e sediments is dolomitization (Fig. 5.40c, d ) .
TIMING OF DISSOLUTION, A L T E R A T I O N
AND REPLACEMENT
T h e timing of dissolution, alteration and replace
m e n t can be established relative to o t h e r diagenetic
events. For e x a m p l e , L o u c k s , D o d g e & Galloway
Fig, 5.39. Mineral replacement

fabrics: (a) Coarsely crystalline calcite
which has replaced aragonite of
scleractinian coral structure in clast
from debris flow deposit. Relics of
aragonite skeleton walls are visible
(arrowed) within calcite crystals.
Calcite partially fills intraskeletal pore
spaces apart from where internal
sediment (S) is present. Miocene, Site
626, ODP Leg 10i. Sample courtesy
of ODP.
(b) Laths of anhydrite replacing
dolomitized silty mudstone.
Anhydrite laths cross-cut sedimentary
laminae, indicating replacive nature.
The morphology of the cluster of laths
is a common form of anhydrite
replacement of carbonates in
sedimentary basins. Permian, Z2
carbonate, UK sector of North Sea.
(c) Calcite replacing anhydrite.
Rectilinear outline of crystal with
castellated margins (arrowed) is
typical of anhydrite, but crystal has
since been replaced by single calcite
crystal (see also Harwood, 1980).
Permian, Cadeby Formation,
Yorkshire, UK.
(d) Corroded relic of anhydrite
(arrowed) within calcite of (c);
rectilinear cleavages of anhydrite
visible. Section stained with alizarin
red S. Calcite stains pink but anhydrite
remains clear.
(e) Contrasting fabric where replacive
anhydrite, identifiable by rectilinear
outlines (arrowed), has been
subsequently dissolved with the pore
space later filled by calcite spar.
Fabric of calcite, from small crystals
near the void margins to larger
crystals in the void centre
(competitive growth, Bathurst, 1975)
indicates dissolution preceded calcite
cement precipitation, and that this is a
'dissolution-precipitation' texture,
rather than a replacement texture.
Jurassic, subsurface Smackover
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161
Fig. 5.40. Mineral replacement and large-scale replacement fabrics:

(a) Large lath of anhydrite (A) replacing ooid grainstone. Ooids had little or no early circumgranular cements and grain to
grain compaction occurred with formation of interpenetrating grain to grain contacts before precipitation of intergranular
calcite cements. Anhydrite replacement took place after compaction and cementation. Anhydrite lath has minor rectilinear
outlines (arrowed). Jurassic, subsurface Smackover Formation, Arkansas, USA.
(b) Crossed polars view of (a), with anhydrite lath in extinction position. Trails of small calcite inclusions, not apparent in
normal transmitted light, define original fabric of ooid grainstone. The timing of anhydrite replacement, after compaction,
is confirmed as ooid outlines are continuous from grainstone into anhydrite lath.
Bitlillill
(c) Partial fabric retention during doldmitization; dolomitized ooid grainstone retains fabric of original isopachous
circumgranular cements and form of ooids. although textures within the ooids are obliterated with formation of partial
oomoldic porosity. Intergranular porosity has been partially occluded by bitumen. Jurassic, subsurface Smackover
(d) Fabric destruction during dolomitization; dolomitization has produced coarse sub- to euhedral dolomite crystals with
vestige of original fabric and considerable variation in dolomite crystal size. Crystal size also varies according to position
within sediment (Harwood, 1986). Permian, Cadeby Formation, Nottinghamshire, UK.
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165
Fig. 5.41. Timing of replacement: (a) Dolomite rhombs in crinoid grainstone; dolomite has grown replacively after
formation of crinoid overgrowth cements in crinoid grainstone of low porosity and permeability. Voids (arrowed) are the
result of plucking during section-making and thus show false porosity. Section stained with alizarin red S. Mississippian,
Burlington Formation, Illinois, USA. Sample courtesy of W.B. Meyers, SUNY.
(b) Dolomite rhombs in ooid grainstone; dolomite has formed after cementation of ooid grainstone and after partial
dissolution and compaction of ooid (arrowed) (from Harwood & Moore, 1984). Jurassic, subsurface Smackover
(c) Dolomite and euhedral authigenic quartz growth after compaction and cementation. Ooid grainstone with
interpenetrating grain to grain contacts and later intergranular calcite cements (see also Fig. 5.40a, b) with later replacive
dolomite rhombs (D) and authigenic quartz crystals (Q). The relative timing of dolomite and quartz growth is not
determinable as the two are not found intergrown. Jurassic, subsurface Smackover Formation, Arkansas, USA.
(c) Replacement of certain parts of detrital sedimentary grains; calcite of intergranular cement has replaced components of
the derived sediment grains, leaving quartzose portions unreplaced. Permian, Yellow Sands, Co. Durham, UK.
(e) Crossed polars view of Fig. 5.40(d), showing that calcite within detrital grains is in optical continuity with poikilotopic
intergranular calcite. Former mineralogy of replaced components cannot be determined.
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Quartz

(1984) d e m o n s t r a t e d feldspar dissolution to have
t a k e n place after t h e formation of quartz over
growth cements in s o m e U S Gulf Coast Lower Ter
tiary sandstones, w h e r e a s , in similar sandstones,
Siebert, M o u c u r e & L a h a n n (1984) showed feldspar
dissolution occurred after calcite cementation but
before hydrocarbon m a t u r a t i o n and migration.
M o o r e & D r u c k m a n (1981) detailed late, non-selec
tive dissolution of c a r b o n a t e sediments, in advance
of hydrocarbon migration. A l t h o u g h existing car
b o n a t e phases may be dissolved by non-organic acids
within t h e p o r e fluids, feldspar dissolution necessi
tates aluminium complexing, only possible with
s o m e organic constituent of t h e p o r e fluids (Surdam,
B o e s e & Crossey, 1984; E d n a m & S u r d a m , 1986;
M e s h r i , 1986).
Such dissolution related to hydrocarbon migration
has b e e n d o c u m e n t e d t o t a k e place within t h e d e e p
subsurface, but other selective and non-selective
dissolution can take place at various d e p t h s , d e p e n
ding m o r e o n t h e efficiency of p o r e fluid migration
and p o r e fluid chemistry. Considerable dissolution is
unconformity-related, w h e r e active meteoric circu
lation can r e m o v e less stable mineralogies, parti
cularly evaporites, s o m e c a r b o n a t e phases and
w e a t h e r e d silicates.
If a grain or c e m e n t retains its form during altera
tion it is sometimes very difficult to d e t e r m i n e when
that alteration t o o k place, unless it can be linked to
o t h e r dissolution/replacement phases. Only if t h e
alteration product is otherwise modified is it possible
to fit the alteration precisely into t h e diagenetic
history of t h e sediment. Similar problems occur
when a sediment has been completely replaced,
particularly when replacement has destroyed the
original texture. Dravis & Yurewicz (1985) found
that blue light emission spectroscopy aided identi
fication of predolomitization fabrics; Goodall &
H u g h e s (1985, personal communication) success
fully used this technique in evaporite petrography.
C a t h o d o l u m i n e s c e n c e p e t r o g r a p h y ( C h a p t e r 6) may
also help to 'see t h r o u g h ' complete replacement
fabrics. Individual mineral replacement fabrics a r e ,
o n t h e whole, easier to place in a diagenetic sequence
(e.g. Fig. 5.41a, b , c) as relationships with pre
existing diagenetic events a r e visible.
Fig. 5.42. Diagenetic potential of sedimentary rocks: (a) Triangular diagram of siliciclastic end members, demonstrating
mechanical and chemical resistance to diagenetic alteration (modified form Bj0rlykke, 1983). Width of arrow increases
with increased diagenetic potential.
(b) Similar diagram for carbonate mineralogical end members, showing high diagenetic potential of aragonite and high Mg
calcite dominated sediments. Carbonate minerals have similar rigidities, but the aragonite-low Mg calcite transformation is
by dissolution-reprecipitation (albeit on a fine scale in some cases) whereas that of high Mg calcite to low Mg calcite appears
to involve no structural recrystallization, but simply magnesium 'stripping'. It should be remembered that many Palaeozoic
carbonates were dominated by high Mg calcite or low Mg calcite, with little or no aragonite. Width of arrow increases with
increased diagenetic potential.
5.3.6 Diagenetic potential

Many sediments are m o r e susceptible than others to
change during diagenesis. T h e diagenetic changes
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which take place within a s u p e r m a t u r e quartz sand

stone a r e limited; quartz overgrowth cements may
form, but, unless pore fluids are extremely aggres
sive, neither dissolution, alteration nor replacement
of detrital quartz grains are likely to occur. T h e
presence of feldspar grains within a sandstone
r e n d e r s it m o r e susceptible to change during dia
genesis as alteration, replacement or dissolution of
these grains may take place. Feldspar grains there
fore have a higher diagenetic potential than quartz
grains, particularly to chemical change; mechanical
ly, they are almost as rigid as quartz grains when
fresh. O t h e r minerals (e.g. pyroxenes, amphiboles,
micas and m a n y rock fragments) have a consider
ably higher potential for alteration and dissolution
and a r e also less rigid. O n a quartzfeldsparrock
fragments triangular diagram these m o r e susceptible
minerals plot together in o n e corner. Sandstones
with compositions which plot in this a r e a a r e there
fore m u c h m o r e susceptible to diagenetic change
t h a n those with compositions n e a r e r a quartzose
sandstone (Fig. 5.42); they thus have a m u c h higher
diagenetic
potential.
C a r b o n a t e and evaporite sediments also have a
high diagenetic potential. Many m o d e r n carbonate
sediments a r e a mixture of aragonite and high Mg
calcite, minerals which a r e theoretically .unstable at
surface t e m p e r a t u r e s and pressures. D u r i n g early
diagenesis these minerals rapidly change to low Mg
calcite, either by dissolution/reprecipitation or by
alteration. H o w e v e r , many ancient carbonates, par
ticularly those in t h e Palaeozoic, have a somewhat
lower diagenetic potential, being initially dominantly high and/or low Mg calcite. E v a p o r i t e sediments
have a yet higher diagenetic potential than m o d e r n
c a r b o n a t e sediments, producing a n e a r - m e t a m o r phic fabric. T h e diagenetic fabric of a sedimentary
rock is therefore largely d e p e n d e n t on the original
sediment composition, although fluctuating p o r e
fluid compositions may govern t h e r a t e , t h e extent
and t h e relative timing of diagenetic reactions.
5.4
CONCLUSIONS
Petrographic examination of thin sections can t h e r e

fore reveal much information about the depositional
and diagenetic history of t h e sediment. Recording of
these data in a systematic m a n n e r is vital to its
interpretation. This is best d o n e by systematically
working through a given series of points on a data
168
G. HARWOOD
Components on triangular diagrams

Sedimentary Petrography
Petrographer
Date
Description Form
Specimen
Terrigenous s e d i m e n t s
Hand s p e c i m e n
Colour: Fresh
Weathered
Structures:
Grain size:
Max
Min
Models)
mm
Roundness
Sphericity
Allochemical
Orthochemical
Sorting:
Other features:
Framework
Cement
Diagenetic events
Thin s e c t i o n
Apparent grain size:
Detrital composition
Quartz
K feldspar
Plagioclase
Rock fragments
Muscovite
Biotite
Heavy minerals
Opaque minerals
Carbonates
Matrix
Others
Diagenetic components
Cement
Other authigenic
minerals
Max
Min
Models)
Roundness.
Sphericity .
Sorting
Sketch of key fabric(s)

Quartz varieties:
Comments and interpretations
monocrystalline < ^ ,
polycrystalline < ^
Matrix components:
Porosity:
Type
Primary
Secondary
Compaction (type and degree)

(a)
Fig. 5.43. Data sheets for systematically recording petrographic observations; sheet A is for terrigenous sediments and
sheet B for carbonates. Sheets can be combined if all observational criteria are not itemized.
http://jurassic.ru/
170
PRINCIPLES OF SEDIMENTARY PETROGRAP
G. HARWOOD
Sedimentary Petrography
Diagenetic components
Petrographer ...
Date ...
Description Form
Cement type
Porosity
%
Specimen ...
Primary
Secondary
Carbonate/evaporite sediments
Hand s p e c i m e n
Colour: Fresh
Weathered ..
Induration:
Grain size:
Type
Other authigenic
minerals
Structures:
x
Compaction (type and degree)
Max.
Min.
Mode(s)
Rock type (Durham class.)

Skeletal clasts
Sorting:
Other features
Components on triangular diagrams
1. Origin of components
Thin s e c t i o n
2. Fabric of components.
Detrital
Detrital grains
Skeletal types
Size
((im)
Roundness
Fragmentation
Allochemical
Orthochemical
Framework
grains
Cement
(I = impure)
Intraclasts
Ooids
Pellets
Peloids
Quartz grains
Feldspar grains
Other detrital
minerals
Matrix
Evaporites
Gypsum
Anhydrite
Halite
Others
A Matrix
3. Three
appropriate
components
Diagenetic events
...
Size
Comments
,
Sketch of key fabric(s)

Comments and interpretation
(b)
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T
172
G. HARWOOD

Fig. 5 . 4 5 . Things are not always as
they seem! Dolomite rhombs
replacing ooid grainstone have hollow
centres with irregular outlines. These
centres were originally interpreted as
being the result of calcitization of the
dolomite, thus accounting for the
corrosive nature of the secondary
calcite/dolomite margins. Closer
investigation, however, demonstrates
that the textures of the ooids and
intergranular cements are continuous
through the centres of the dolomite
crystals and, when viewed in colour,
the differences in stain colour persist
from outside of to within the dolomite
rhombs (arrowed). The dolomite
therefore has only partially replaced
the original carbonate and the hollow
centres are a primary feature of the
dolomite rhombs, representing
unreplaced grains and cements.
Interpenetrating and sutural grain to
grain contacts between the ooids
demonstrate that the diagenetic
history of this sediment can be
itemized as: (i) mechanical followed
by dissolution compaction, (ii)
precipitation of late intergranular
ferroan calcite spar cements, and (iii)
partial dolomitization. Jurassic,
Smackover Formation, subsurface
Arkansas, USA.
Location/well
Elevation/depth
Grain supported
Matrix supported
Carbonate minerals
Calcite
Fe-calcite
Dolomite
Fe-dolomite
Diagram/photomicrograph
Terrigenous minerals
Quartz
K feldspar
Plagioclase
Mica
Rock name
Others (biotite, a m p h . etc.)

Other minerals
Anhydrite
Gypsum
Halite
'
Skeletal components
Chert
Others
Matrix
Cement
fabrics therefore creates a complex texture within a

sediment, representing b o t h sedimentation events
and events which have t a k e n place during diagenesis.
T h e s e events are closely linked to the setting and
evolution of t h e containing sedimentary basin with
burial diagenetic events representing different stages
of basin history. Petrofabric evaluation should
therefore form an integral part of any study of basin
evolution. A s m o d e r n weathering masks many of
these textures, petrographic studies are best carried
out o n subsurface samples wherever possible, parti
cularly if samples a r e to be chemically analysed
Porosity
Comments
(c)
Fig. 5.44. Abridged data sheet of a type used by many petroleum company research laboratories.
sheet (Figs 5.43a, b and 44), particularly at t h e start

of a project. D a t a compiled in this way can t h e n b e
used by co-workers to c o m b i n e results into a m o r e
regional synthesis t h a n otherwise possible. Familiar
ity with a certain sediment type, however, can lead
to abbreviated d a t a sheets, containing only those
nill
173
aspects p r e s e n t in those sediments, which, in t u r n ,

may lead to unusual or less c o m m o n fabrics being
overlooked. U n f o r t u n a t e l y , experience is t h e best
guide to fabric interpretation, and this can only b e
obtained by study of many different sediment types.
T h e combination of depositional and diagenetic
http://jurassic.ru/
later. T h e study of petrographic fabrics forms t h e

basis for later analytical research, both chemically
and isotopically. Diagenetic fabrics are also linked
to subsurface porosity evolution and hydrocarbon
migration and closer future links with organic geochemists will evaluate potential interrelationships
b e t w e e n these events. P e r h a p s t h e o n e point that
should be emphasized is that e x t r e m e care should be
t a k e n in d o c u m e n t a t i o n and interpretation of p e t r o
fabrics, as o n e can b e easily misled by what appears
to be a straightforward thin section (Fig. 5.45)!
CATHODOLUMINESCENCE MICROSCOPY
Cathodoluminescence microscopy
(1985). T h e energy of a beta-ray (electron) is suffi

cient to excite an a t o m or molecule and cause a
q u a n t u m j u m p , with t h e input energy being totally
absorbed. After a short delay time ( 1 0 s) the
excited a t o m or molecule returns to its former energy
state and may emit radiation in the form of light,
alpha-, beta- or gamma-rays. T h e wavelength of the
emitted radiation is always longer than that of the
exciting radiation. F o r geological purposes, we are
usually only interested in emission in t h e visible
spectrum, although it should be noted that a propor
tion of emission in s o m e minerals may be in t h e
infra-red or ultra-violet (e.g. in feldspars).
T h e intensity of C L is a function of current density
at t h e specimen and t h e voltage (accelerating poten
tial) of t h e applied electron b e a m . T h e relationship
of luminescence intensity to electron b e a m intensity
is n o t a simple linear o n e , however, and m o r e o v e r
varies within the mineral families (Coy-yll, 1970).
Coy-yll (1970) also showed that, for a given crys
talline solid, there is a point at which increasing the
electron b e a m current ceased to p r o d u c e greater
luminescence intensity; h e t e r m e d this t h e saturation
level. Increasing b e a m energy beyond this level
actually produces a decrease in luminescence inten
sity; this is the inhibition phase. F o r a given current,
saturation occurs with b e a m s of a b o u t 8 k V poten
tial in feldspars but at m o r e than 16 k V with quartz.
In practical terms this m e a n s that attempting to
elicit m o r e luminescence from a mineral by simply
increasing b e a m power can have the reverse effect if
t h e saturation level is exceeded. Overly powerful
b e a m s are also likely to have a local heating effect,
causing t h e r m o l u m i n e s c e n c e . T h e r m o l u m i n e s c e n c e
and C L spectra may then c o m b i n e , giving a false
impression of t h e luminescence colour. Intense,
narrowly-focussed b e a m s may also cause local heat
ing to t h e point of incandescence, particularly with
micas, which flare and collapse. F u r t h e r d a m a g e to
preparations caused by local heating includes blis
tering of thin section bonding resins and even crack
ing of t h e glass slide.
JOHN MILLER
- 8
6.1
INTRODUCTION
Luminescence is t h e emission of light from a solid

which is 'excited' by s o m e form of energy. T h e term
broadly includes the commonly-used categories of
fluorescence and p h o s p h o r e s c e n c e . Fluorescence is
said to occur w h e r e emission ceases almost i m m e
diately after withdrawal of t h e exciting source and
w h e r e there is no t h e r m a l cause, w h e r e a s in p h o s
phorescence the emission decays for s o m e time after
removal of excitation. T h e distinction b e t w e e n these
so-called types of luminescence is s o m e w h a t arbi
trary and confusing; for e x a m p l e , many minerals
have very long post-excitation decay times. Confu
sion is avoided by using the term luminescence, and
specifying the activating energy as a descriptive
prefix. T h u s roentgenoluminescence is p r o d u c e d by
X-rays, photoluminescence by light (e.g. ultra
violet) and cathodoluminescence (CL) results from
excitation by electrons. T h e r m o l u m i n e s c e n c e results
from heating.
Luminescence has b e e n known in geological
materials since 1604, w h e n t h e alchemist Cascierolo
described light emission from barite. N o w a d a y s t h e
p h e n o m e n o n is very familiar: C L provides our televi
sion pictures from excitation of chemical p h o s p h o r s
by t h e cathode-ray t u b e ' s electron b e a m . C L of
minerals was first investigated systematically by
C r o o k s (1880), w h o sealed d i a m o n d s , rubies and
o t h e r gems into a discharge t u b e and observed their
brilliant emission colours. This work was not follow
ed u p thoroughly by geologists until t h e advent of
t h e analytical electron m i c r o p r o b e (Smith & Stenstrom, 1965). T h e small b e a m size and p o o r optics of
t h e m i c r o p r o b e w e r e restrictive, h o w e v e r , and it was
quickly realized t h a t a simple device specifically
designed for C L p e t r o g r a p h y was required. L o n g &
Agrell (1965) and Sippel & Glover (1965) both
published descriptions of such a device, which could
be attached to a petrographic microscope for ex
amination of thin sections. T h e r e a r e now several
commercial luminescence machines available, most
ly d e v e l o p m e n t s of these early designs.
Ultra-violet fluorescence microscopy is often used

in examination of h y d r o c a r b o n residues in sediments
(e.g. B u r r u s s , C e r c o n e & H a r r i s , 1985). Polished
thin section surfaces are required, and a special
microscope with U V source and quartz lenses is
n e e d e d , such as used for immunological w o r k in
many biological laboratories. V a r i o u s wavelengths
of U V can be selected by m e a n s of filters, and filters
can be interposed w h e n viewing t h e emission. Hy
d r o c a r b o n inclusions show strong luminescence, t h e
colour varying with t h e gravity of t h e oil. Recrystal
lized organic-rich fossils, such as renalcid micro
organisms in reefs, may show u p very well u n d e r
U V , whereas they may b e invisible in transmitted
light and C L . Dravis & Yurewicz (1985) have shown
that in s o m e limestones, c e m e n t generations and
fine crystal growth zoning can b e revealed by U V .
Certainly U V microscopy is attractive because it
does not require e l a b o r a t e vacuum a r r a n g e m e n t s ,
but inorganic materials such as calcite often show
only very weak U V luminescence, so U V micros
copy is not a general substitute for C L w o r k .
Sedimentologists have now found a wide variety

of applications for C L , and it has b e c o m e a very
i m p o r t a n t tool for petrographic analysis. N e v e r t h e
less, despite t h e growing volume of publications
reporting C L results, t h e r e is still much fundamental
work to b e d o n e on understanding t h e precise causes
and significance of luminescence p h e n o m e n a in geo
logical situations. It is therefore-essential to have at
least a general knowledge of t h e physical background
of C L to avoid serious misinterpretation.
Within that part of a sample b o m b a r d e d by elec

trons (the 'reaction v o l u m e ' ) , t h e r e are many effects
o t h e r than cathodoluminescence. Secondary, backscattered and auger electrons are p r o d u c e d , as well
as X-rays. With suitable detectors, in scanning electron microscopes or microprobes, s o m e of these
effects can be used for analytical or imaging pur
poses. H o w e v e r , in cold c a t h o d e luminescence
machines (see below), many ions a r e produced in
6.2 P H Y S I C A L E X P L A N A T I O N O F
LUMINESCENCE
6.2.1 Excitation f a c t o r s
A n explanation of luminescence was not forth
coming until the d e v e l o p m e n t of q u a n t u m theory.
Q u a n t u m approaches to luminescence a r e outlined
by Nickel (1978), Marfunin (1979) and W a l k e r
1
i
174
http://jurassic.ru/
. A
^ l, . I.
y u
u ,
175
addition to the electrons. T h e s e also e n t e r the re

action volume and can induce d a m a g e in the upper
most layers of a thin section by remobilizing elements
and homogenizing luminescence activators (see
Section 6.2.2). T h e r e f o r e , a thin section remaining
in the b e a m for a long time may show a decrease in
luminescence intensity as ionic b o m b a r d m e n t and
t h e r m a l diffusion take place. According to R e m o n d ,
L e Gressus & O k u z u m i (1979), this change in C L is
irreversible and t h e affected section must be repolished, removing the d a m a g e d layer. Certain
minerals are very susceptible to irradiation d a m a g e ,
and may b e c o m e p e r m a n e n t l y coloured after re
moval from t h e electron b e a m . For example, halite
is 'electron-stained' blue in a few minutes, and
Dickson (1980) reported a stable purple colouration
in e l e c t r o n - o m b a r d e d
fluorospar.
6.2.2 Luminescence centres

A n excellent s u m m a r y of the present knowledge
of C L generation in minerals is given by W a l k e r
(1985), and only a simplified outline follows h e r e .
A t any t e m p e r a t u r e , a real crystalline solid is in a
state of dynamic unrest, with t h e various electrons
and a t o m s in its lattice vibrating a b o u t their m e a n
positions. This state* of energy is called 'ground
state'. Few crystals are perfect. D u r i n g n o r m a l
growth, they may acquire defects from distorted
internal structure b e t w e e n mosaic crystals, suffer
omission defects w h e r e g r o u n d s of atoms or mole
cules a r e missing from lattice sites, h a v e charge
displacements (for example w h e r e t h e r e are abnor
mally ionized atoms), or undergo mechanical damage
such as formation of distorted surfaces a n d cracks.
U p o n excitation by an electron b e a m , such local
sites of crystal imperfection are m o r e liable to ab
sorb energy from t h e b e a m t h a n a r e neighbouring
lattice sites. T h e domains of imperfection b e c o m e
luminescence centres; they preferentially trap energy
from the c a t h o d e b e a m which induces ' j u m p s ' in
their lattice electron orbitals. O n subsequent decay
to the resting state, p h o t o n s are emitted and lumine
scence occurs.
1
T h e excitationemission process is often t e m

p e r a t u r e d e p e n d e n t . Cooling samples with liquid
nitrogen, for e x a m p l e , increases C L efficiency in
s o m e minerals such as quartz, producing much
greater luminescence intensity for a given b e a m
energy. O t h e r minerals, such as calcite, tend to emit
less on cooling. A l s o , cooling can produce spectral
176
J . MILLER
shifts in emission wavelength, so although it may

have potential uses for geological applications w h e r e
C L emission at r o o m t e m p e r a t u r e is m e a g r e , t h e full
effects of cooling are at present poorly k n o w n and
t h e technique cannot be r e c o m m e n d e d as a regular
practice for petrographic purposes.
Luminescence centres may occur in two general
forms: intrinsic and extrinsic. Intrinsic centres are
d u e to lattice imperfections such as growth distor
tions and other electronic lattice defects, acquired
independently of the composition of the precipita
ting m e d i u m . Extrinsic centres are those acquired
from t h e p a r e n t m e d i u m during crystallization, such
as impurities in surface, regular lattice and intersti
tial sites, or compositional inhomogeneities b e t w e e n
different parts of a crystal. In practice, it may be
very difficult to d e t e r m i n e t h e principal cause of C L
in a mineral, as often t h e r e are complex interactions
between extrinsic and intrinsic centres.
Extrinsic luminescence centres may b e h a v e dif
ferently d e p e n d i n g on their response to electron
b e a m excitation, and t h e following types can be
distinguished:
(1) Activator centres: those where radiactive tran
sitions (luminescence) are highly p r o b a b l e as
t h e energized centre returns to its g r o u n d state.
(2) T r a p centres: those w h e r e additional energy is
required to raise t h e energy state sufficiently to
p r o d u c e luminescence on transition to the
ground state.
(3) Q u e n c h e r centres: w h e r e even t h e excited state
of t h e centre is close to a radiationless transition
level, so little or n o luminescence is emitted.
Extrinsic luminescence centres are t h e best k n o w n ,
and p e r h a p s the easiest to detect by geochemical
analysis, whereas t h e causes of intrinsic C L require
detailed crystallographic and solid state physical
investigation. Transition metal ions are t h e com
m o n e s t activator impurities causing extrinsic C L ,
substituting in crystal lattices for n o r m a l ions with
a p p r o p r i a t e ionic radii. R a r e earth e l e m e n t s , such as
Eu , Sm
and D y , are also implicated as in
ducing activator centres ( M a r i a n o & R i n g , 1975).
In geological materials, luminescence is commonly
controlled by t h e balance of activator and q u e n c h e r
centres. F o r e x a m p l e , M n
is the main activator
causing luminescence in calcite, whereas F e
is a
q u e n c h e r in the same mineral. H o w e v e r , t h e r e is no
g u a r a n t e e that activator or q u e n c h e r elements will
always have t h e same effect in different minerals;
3 +
3 +
3 +
2 +
2 +
177
3 +
for e x a m p l e , F e is an activator in s o m e feldspars,

despite the quenching activity of Fe in calcite.
T h e colour (wavelength) and intensity of C L may
also vary according to t h e sites in t h e crystal lattice
where activator ion substitutions occur. Because of
interactions between activators and q u e n c h e r s , and
b e t w e e n intrinsic and extrinsic luminescence cen
tres, it is often difficult to be certain of t h e cause of
luminescence in a given mineral. Nickel (1978) and
A m i e u x (1982) summarized known emission colours
and activators for many minerals b u t , in o u r present
state of knowledge, these d a t a should only b e used
as a guide.
D e p e n d i n g on t h e activator, a single excited
mineral may radiate at several different wavelengths;
for e x a m p l e , apatite C L may be green, yellow, pink,
violet or white, with a variety of rare earths acting as
activators. Activator and q u e n c h e r ions may p r o
duce their effects at extremely low concentrations,
below t h e detection limits of t h e electron micro
p r o b e . Analytical techniques such as atomic absorp
tion s p e c t r o p h o t o m e t r y and n e u t r o n activation
analysis may be required for quantitative d e t e r m i n a
tion at such low levels. T h e surest m e t h o d of identi
fication of CL-activating ions is by analysing lumine
scence excitation spectra (Walker, 1983, 1985) and
combining this with studies of emission spectra
( M a r i a n o & R i n g , 1975).
6.3
EQUIPMENT
T h e r e several ways of generating electron b e a m s

u n d e r vacuum: by stripping electrons from a hot
filament; utilizing field effect or c o r o n a discharge
from metal points; or by generating a plasma across
a low pressure gas using a cold metal c a t h o d e disc.
Zinkernagel (1978) and R a m s e y e r (1983) described
a hot filament luminescence a p p a r a t u s especially
suitable for observation of very dull emission from
quartz. While this e q u i p m e n t gives good results with
such difficult cases, it is bulky and expensive, difficult
to construct and maintain, and requires a high vacuum
from diffusion p u m p s . Cold c a t h o d e machines a r e
m u c h less complex, easily m o u n t e d on a standard
petrographic microscope and perfectly suited to
most sedimentological r e q u i r e m e n t s . T h e y offer t h e
advantages of cheapness, ease of operation and sim
ple m a i n t e n a n c e , and a r e ideal for routine p e t r o
graphic purposes. Commercial C L machines (Figs
6.1 and 6.2) use the cold c a t h o d e m e t h o d at present.
Pump valve
High
voltage
cable
Deflection
magnet
assembly
25 mm
1"
Stage motion
knobs
Microscope p - ,
objective | i |
Specimen
Optic axis
-J
- Focus
coil
Cathode
Fig. 6 . 1 . Schematic drawings of the Nuclide ELM-2A Luminoscope specimen chamber in top view and cross-section.
Courtesy of D. Marshall, Nuclide Corporation.
With the cold c a t h o d e system (Fig. 6.1), there are

always sufficient positive ions in t h e vicinity of the
specimen t o p r e v e n t it acquiring a space charge,
eliminating t h e need for p r e - t r e a t m e n t of samples by
evaporating a conductive coating on to t h e m . Since
a steady leak of gas must be maintained for plasma
g e n e r a t i o n , a small r o t a r y v a c u u m p u m p is a d e q u a t e .
In contrast to h o t filament c a t h o d e systems, a sud
den loss of vacuum causes n o d a m a g e to the equip
m e n t . B e a m s can also be established at low acceler
ating voltages, thus reducing t h e risk of specimen
damage.
T h e r e a r e , h o w e v e r , a n u m b e r of disadvantages to
cold c a t h o d e systems. Delicate a r r a n g e m e n t s are
required to maintain t h e controlled gas leak and
these are p r o n e to wear and m a i n t e n a n c e p r o b l e m s .
T h e discharge plasma produces a blue glow which
m a y interfere with luminescence observation, par
ticularly with m e a g r e emitters such as quartz: this
p r o b l e m may b e o v e r c o m e by using helium r a t h e r
t h a n air as t h e leak gas. Because of t h e presence of
gas (usually air) in t h e system, a stream of positive
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and negative ions is also g e n e r a t e d and this may

induce sample d a m a g e . All of these effects m e a n
that cold cathode e q u i p m e n t , while eminently con
venient for qualitative w o r k , is unsuitable for malring
reliable and precise observations on C L intensity
and emission wavelengths (see Section 6.5). For this
p u r p o s e a new generation of hot c a t h o d e machines
must b e developed.
6.3.1 Operation
Figure 6.1 shows a schematic cross-section of a
typical C L a p p a r a t u s . T h e electron b e a m is gener
ated by applying a potential u p to 30 k V between a
small tungsten steel c a t h o d e disc and an annular
a n o d e which lie within an evacuated glass t u b e . A t
low pressures, a plasma is established with a dis
charge of positive ions travelling towards the cathode.
A n electron b e a m (together with s o m e negative
ions) is emitted in the opposite direction, attracted
towards t h e collimating a n o d e and passing t h r o u g h
its central hole. In t h e Nuclide Luminoscope (Fig.
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J . MILLER
Fig. 6.2. Technosyn luminescence chamber on a Nikon

binocular microscope with photomicrographic attachment.
Note the oblique electron gun and the projecting XY
specimen traverse controls to the right of the chamber. The
HT and vacuum control box is behind the microscope and
the photographic exposure meter lies to the left.
6.1), the b e a m then passes through a focussing coil,

which carries a variable D C voltage to give control
over t h e b e a m size impinging on t h e specimen.
N a r r o w b e a m s with high current density can be used
for observation with high magnification lenses or on
samples with poor C L ; t h e b e a m can be also ex
p a n d e d to cover an area of several square centi
m e t r e s for macro-photography of small slabs or large
thin sections. T h e electrons are deflected down on to
t h e specimen by a pair of adjustable magnets attach
ed to a movable carriage on the top of the specimen
c h a m b e r . In t h e Technosyn e q u i p m e n t , t h e gun is
arranged so that t h e b e a m fires obliquely down on to
t h e specimen (Fig. 6.2) and these magnets are not
n e e d e d . A focussing coil is not required, and as t h e
b e a m cross-section is relatively constant, t h e current
density at t h e specimen surface is also relatively
constant. T h e r e are s o m e advantages to a lateral gun
position and focussing device; larger viewing win
dows can be a c c o m m o d a t e d so that greater sample
areas may be excited by de-focussing t h e b e a m , and
t h e occurrence of sample d a m a g e by direct b o m
b a r d m e n t is lessened.
Samples are placed o n a glass tray s u p p o r t e d on
an XY bearing carriage. T h e y can thus b e m o v e d
6.3.2 Microscopes f o r
cathodoluminescence
scopes meeting t h e criteria outlined above should be

tried, using a fairly dull C L subject such as a sand
stone sample, before deciding on o n e which will be
dedicated to t h e C L e q u i p m e n t .
F o r those setting u p a C L unit for the first t i m e ,
and considering purchasing a new microscope, the
inexpensive O l y m p u s P O S Student Microscope has
o n e of t h e best transmissivities. H o w e v e r , it is a
simple monocular design and suffers slightly from
pin-cushion distortion, but m a k e s a good generalp u r p o s e C L microscope w h e r e low cost is i m p o r t a n t .
If long-term viewing comfort and high quality flatfield optics a r e r e q u i r e d , a stripped-down version of
t h e Nikon binocular petrological microscope is re
c o m m e n d e d (Fig. 6.2), w h e r e t h e r e is a 'straightt h r o u g h ' p a t h for photomicrography.
T h e objective lenses required for cathodolumine
scence must have long working distances, so choice
is often limited and prices high. Measuring or Uni
versal Stage objectives are usually suitable. H o w
ever, these a r e complex multi-element systems, and
their transmissivity decreases rapidly with increased
magnification. S o m e of these lenses a p p e a r t o have
selective absorption at certain wavelengths, and
t h e r e can be distinct changes in perceived C L colour
w h e n such lenses are interchanged during viewing of
a single sample. It is important to carry out s o m e
experimentation with various objectives and objec
tive-eyepiece combinations so as to be familiar with
the optical properties of the microscope system in
use.
It is of capital i m p o r t a n c e that t h e microscope u p o n

which C L e q u i p m e n t is m o u n t e d should be of the
highest possible transmissivity. Because most p e t r o
logical microscopes are designed for use with trans
mitted light which can be provided at any required
intensity, manufacturers mostly pay little attention
to this p a r a m e t e r . Luminescence is rarely m o r e t h a n
1% efficient and thus of comparatively low intensity.
Marshall (1980) investigated the behaviour of several
microscopes with C L samples. H e found that the
controlling factors were t h e magnifications and
numerical a p e r t u r e s of eyepieces and objectives,
transmission of individual optical e l e m e n t s , a n d
o t h e r details of t h e optical p a t h , including prisms,
splitters and polarizers. T h e o p t i m u m system for C L
should have as few optical elements and lens/air
surfaces as possible, with good coatings on lens
surfaces. T h e r e f o r e , monocular microscopes with
'straight through' ray paths have t h e greatest trans
missivity. It is r e c o m m e n d e d that several micro-
T o maintain o p t i m u m transmissivity, it is also

vital to k e e p viewing windows clean. Lower window
surfaces rapidly b e c o m e coated with a brown layer
of pyrolized h y d r o c a r b o n s , derived partly from
h e a t e d resin on thin sections and from vacuum p u m p
oil mist. T h e window coating problem is consider
ably reduced by using a foreline trap on t h e vacuum
system, but t h e trap filter material must be regularly
replaced, otherwise p u m p - d o w n times are increased.
W i n d o w coatings not only impair transmissivity but,
as they build u p , selectively absorb certain wave
lengths. Acting as a coloured filter, such coats give a
misleading impression of C L colours.
Viewing windows a r e best cleaned with a pinch of
non-abrasive laboratory glass detergent and a d a m p
wad of soft tissue or cloth, taking care to avoid t h e
sealing gasket a r o u n d the window. Stubborn de
posits may require application Of organic solvents
such as acetone or p e t r o l e u m e t h e r , but as these
have harmful effects on skin and may. also dissolve
in any direction across t h e microscope stage. Viewing

may be by transmitted light, C L , or a combination
of t h e t w o , observed through a lead glass window
which absorbs X-radiation. T h e e q u i p m e n t should
be used in a well-darkened r o o m , and a red p h o t o
graphic safelight usefully provides illumination for
operating and note-taking without disturbing t h e
w o r k e r ' s 'night-vision', which is essential for obser
vation of low intensity C L .
D u r i n g excitation, samples are heated and begin
to outgas, producing m o r e ions and concomitantly
increasingly the electron b e a m current, which if
unchecked will reach a preset level within t h e power
unit and cause t h e high tension to be switched off to
protect the gun. T h e art of achieving a steady-state
b e a m d e p e n d s o n balancing t h e controlled gas leak
and the sample outgassing with the continuous p u m p
evacuation at a given b e a m voltage.
Sample changing is rapid. T h e b e a m is turned off,
t h e vacuum valve closed and t h e c h a m b e r vented to
air. Several samples can often be placed in t h e
c h a m b e r at o n c e , d e p e n d i n g on their size. F o r view
ing with higher magnification lenses, which are
necessarily of shorter working distance, a recessed
window is usually required to a c c o m m o d a t e the
smaller working distance of the lens.
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179
or h a r d e n t h e window sealing gaskets, they should

only be used as a last resort.
6.3.3 Radiation precautions

A t the voltages used for C L , electron b e a m s are
capable of generating appreciable a m o u n t s of Xrays. Luminescence c h a m b e r s are designed to cope
with this and are tested up to specified voltages with
metal targets as samples. H o w e v e r , it is important to
check radiation levels regularly with a geiger counter
at worst-case operating levels, paying particular at
tention to joints and gaskets, particularly a r o u n d the
viewing window and a n o d e . In E u r o p e a n countries
t h e mains supply voltage may fluctuate consider
ably, often being above any r a t e d working voltage
of the C L power pack, so that actual b e a m voltages
may be appreciably higher than those set on the
instrument panel. A potential X-ray hazard could
then exist. If t h e r e is any suspicion of fluctuating
voltages, instruments should be fitted with stabilized
power supplies.
With t h e Nuclide Luminoscope, a standard glass
coverslip may be used in t h e recessed viewing win
dow when the thicker lead glass window does not
allow t h e shorter working distance objectives t o
focus. This u n p r o t e c t e d window provides an X-ray
hazard. It may be covered with a lead f o i l a n n u l u s
a r o u n d t h e lens barrel, but a much better arrange
m e n t is to manufacture brass collars for the high
magnification lenses. These should fit into the well
of the recessed window and have a flange which
overlaps the edge of the well. Focussing m o v e m e n t s
of the objective can then be a c c o m m o d a t e d without
risking radiation scatter.
6.4 S A M P L E P R E P A R A T I O N
C L observations are usually m a d e on uncovered thin
sections. T h e y must be b o n d e d with thermo-stable
epoxy resin (see C h a p t e r 4). Bonding agents such as
Lakeside 70 a n d C a n a d a Balsam "are unsuitable
m o u n t a n t s for C L work as they a r e volatile, causing
blistering and rapid charring under the electron beam.
S o m e epoxy resins also show luminescence (usually
yellow) which can interfere with observations.
Polished surfaces give t h e best optical resolution,
and t h e double polished thin sections described in
C h a p t e r 4 are ideal. If great detail is not required,
surfaces can be quite crudely p r e p a r e d . Etching of
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J . MILLER
limestones with dilute acid gives an a p p a r e n t in

crease in luminescence intensity, but this is d u e to
points of high relief catching t h e oblique b e a m , with
shadowing giving an increase in contrast but at t h e
expense of resolution. Nevertheless, both etched
and stained surfaces (see C h a p t e r 4) can be used.
Stained surfaces, however, rapidly fade and acquire
a brown discolouration in t h e b e a m , so transmittedlight examination and p h o t o g r a p h y of stained sam
ples should be carried out before irradiation.
Mechanically strained or d a m a g e d crystals t e n d to
b e c o m e strong C L emitters, and their luminescent
patterns can be mistaken for geologically significant
features. Such artefacts can easily be g e n e r a t e d by
rapid or crude p r e p a r a t i o n of thin sections, using
coarse abrasives and forcing rocks through d i a m o n d impregnated saw blades. T h e gentle and conserva
tive m e t h o d of high quality thin section preparation
described in C h a p t e r 4 is particularly r e c o m m e n d e d
for samples to be investigated with C L . Scratches,
cleavage shattering and o t h e r features of mechanical
d a m a g e in crystals luminesce brightly and can be
recognized by experienced observers.
All sample surfaces to be placed in t h e C L cham
ber should be dry, clean-and free of c o n t a m i n a t i o n ,
including fingerprints as well as dust and lint. Fibres
t e n d to cast shadows in t h e b e a m , wave about or
b e c o m e incandescent, blemishing time exposure
p h o t o g r a p h s . A blast from a compressed air canister
or a jet of petroleum e t h e r across t h e surface helps
to give a contamination-free surface before samples
are irradiated. It is also important t o r e m o v e all
traces of abrasive p o w d e r s u s e d in sample p r e p a r a
tion, because they usually have a bright lumine
scence themselves and can be mistaken for heavy
mineral grains in t h e sample. Even t h e smallest
particles of d i a m o n d are revealed by their brilliant
green emission.
C L is essentially a surface p h e n o m e n o n . B e a m
p e n e t r a t i o n is proportional to accelerating voltage,
and is only a few tens of microns at 18 k V , so 30 um
thin sections are a d e q u a t e . Thicker sections may
give better heat dissipation for prolonged C L ex
a m i n a t i o n . Ultra-thin sections are n o t r e c o m m e n
d e d , as t h e b e a m may b e able to p e n e t r a t e to t h e
resin or glass and p r o d u c e a n o m a l o u s luminescence.
E v a p o r a t e d conductive coatings are n e e d e d only for
use with high voltage h o t cathode cathodolumin
escence instruments. Slides which have been carboncoated for p r o b e work, however, can be examined
directly in cold c a t h o d e e q u i p m e n t ; t h e thin coating
offers n o i m p e d i m e n t to t h e electron b e a m .
D e p e n d i n g on the size of t h e specimen c h a m b e r ,
rock slices can also be examined u n d e r C L . T h e
standard Nuclide Luminoscope c h a m b e r in parti
cular is large enough to take slices over 5 m m in
thickness, and t h e r e is a special d e e p version which
can take sawn core samples for rapid examination,
possibly on site. Best results are obtained from
s m o o t h e d surfaces, but even b r o k e n faces can give
useful information. P u m p - d o w n times a r e corres
pondingly increased for these larger and m o r e por
ous samples, which should be well dried before
evacuation.
Single crystals and loose sediment can also be
viewed with little p r e p a r a t i o n . A rapid a n d simple
technique for checking t h e mineralogy of placer
sands is simply to sprinkle s o m e sand on t o t h e speci
m e n tray glass or on a standard slide and evacuate
it in t h e c h a m b e r ( R y a n & Szabo, 1981). If t h e r e is
a tendency for grains to b e c o m e charged and leap
about disconcertingly in t h e b e a m , a dried a q u e o u s
grain suspension usually has sufficient adhesion.
6.5 I N T E R P R E T A T I O N A N D
DESCRIPTION OF CL RESULTS
C L colour and brightness are d e p e n d e n t o n several
factors, including b e a m voltage, current, surface
current density (a function of beam focus), n a t u r e of
sample surface, time for which sample has previous
ly b e e n irradiated, degree of heating (thermal quen
ching or emission of thermoluminescence) and t h e
geochemical composition of t h e sample itself. Mar
shall (1978) has suggested a standard for reporting
C L results so that comparisons b e t w e e n t h e results
of different w o r k e r s m a y be m o r e valid. With t h e
cold c a t h o d e e q u i p m e n t , so many variable factors
are involved that t h e r e is s o m e d o u b t w h e t h e r a true
standard can be established (Fairchild, 1983). H o w
ever, it certainly facilitates communication and com
parison if t h e observation conditions are r e p o r t e d as
Marshall suggested. Experience has also shown that
t h e same samples can have different a p p e a r a n c e s
u n d e r C L in machines from different manufacturers.
Details such as fine zonation in calcite c e m e n t s may
be visible in o n e case but not in a n o t h e r . T h e
reasons for this are not fully u n d e r s t o o d ; t h e metal
used for the c a t h o d e disc may be a factor, and t h e
angle at which the beam impinges on the specimen
surface may b e a n o t h e r . Cold c a t h o d e systems may
g e n e r a t e s o m e C L as a result of ion b o m b a r d m e n t ,
and t h e n a t u r e of t h e ion content of t h e plasma is
likely to be m a c h i n e - d e p e n d e n t . T h e r e f o r e , t h e type
of e q u i p m e n t should be specified as well as t h e
observation conditions.
P r o b l e m s in communication of results arise from
t h e difficulty of describing C L colours and intensi
ties. A u t h o r s refer t o 'bright' o r 'dull' luminescence,
but such t e r m s are relative to their sample suites and
a r e also highly subjective. T h e descriptions d e p e n d
o n t h e sensitivity of t h e observer's eye to specific
wavelengths, instrumental variation (such as cham
b e r p r e s s u r e , voltage, b e a m focus and b e a m current)
and t h e wavelength-dependent transmission proper
ties of t h e optical system, including t h e gradual build
u p of b r o w n pyrlysis deposits o n t h e viewing window.
F u r t h e r m o r e , h u m a n eyes a r e u n e v e n in their per
ception of t h e visible spectrum, with p e a k s and
troughs in sensitivity across t h e frequency r a n g e .
A significant p r o p o r t i o n of t h e population (mainly
males) is also affected with 'colour-blindness' of o n e
kind or a n o t h e r , often to a subtle d e g r e e which may
n o t b e a p p a r e n t in n o r m a l life. R e p o r t i n g of colour
perception is also subject to variations in linguistic
understanding of words for describing colours. T h e s e
a r e learned at an early age and reflect t h e bias and
b a c k g r o u n d of o u r p a r e n t s . U p o n asking a n u m b e r
of p e o p l e to describe t h e C L colour of a given
sample, I have received responses including 'bright
r e d ' , 'dull o r a n g e ' , 'purple-brown' and 'crimson'; a
red-green colour-blind person perceived 'grey'. T o
help overcome this potentially serious p r o b l e m , o b
servations should b e m a d e u n d e r internally consis
tent operating conditions and descriptions of C L
characteristics chosen to b e as u n a m b i g u o u s as pos
sible. Careful p h o t o g r a p h i c recording is most impor
tant t o support subjective descriptions, but this has
p r o b l e m s in itself (see below).
W h a t steps can be t a k e n to minimize subjectivity
in recording and reporting C L results? Several
petrographic uses of C L involve comparisons of C L
intensities and colours between samples or within
different areas of a single sample. Pierson (1981)
suggested t h a t a s a m p l e with t h e brightest observed
luminescence be k e p t in t h e c h a m b e r and used as a
reference against which t h e intensity of o t h e r sample
areas could be less arbitrarily j u d g e d . H e also advo
cated t h e use of a colour chart (fig, 21-1 in Pauling,
1970) for determining C L colour. This colour chart
is quite i n a d e q u a t e for registering t h e subtle range
of C L colours, and s t a n d a r d rock colour charts d o
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mmmm
181
not contain an a p p r o p r i a t e range or scale for com

parison either. Until special colour charts or refer
ence sample scales b e c o m e available, C L o p e r a t o r s
can d o little m o r e t h a n ensure internal consistency,
or a t t e m p t to construct a system for quantification of
C L intensity and wavelength.
6.5.1 Quantification of CL results

T h e r e a r e m a n y difficulties in designing ways of
obtaining meaningful and consistent m e a s u r e m e n t s
of C L intensity from extant cold cathode C L equip
m e n t . T h e current density at the specimen must
r e m a i n fixed during t h e observation period, and
t h e r e is n o direct way of measuring this in present
C L devices. Variables such as window and micro
scope transmissivity must be calibrated. Since o n e
usually needs t o m e a s u r e emission from only a
small a r e a of t h e viewing field rather than t h e whole
field, a fibre-optic p r o b e inserted in t h e light p a t h
would probably b e t h e best m e t h o d , with t h e lightp i p e o u t p u t directed o n t o a highly sensitive p h o t o
electric cell or photomultiplier, whose o u t p u t would
also have to be calibrated against s o m e standard
p h o s p h o r . N o commercial e q u i p m e n t for this ap
plication exists at present.
Production of a C L emission spectrum is t h e only
way t o record and c o m p a r e C L 'colours' objectively.
M a r i a n o & Ring (1975) t o o k spectra from feldspars
on a Nuclide Luminoscope. T h e y used a fibre optic
p r o b e of 1250, 700 or 450 um d i a m e t e r m e a s u r e m e n t
a r e a , transmitting t h e C L through an external light
pipe t o t h e e n t r a n c e of a grating m o n o c h r o m a t o r .
T h e o u t p u t of the m o n o c h r o m a t o r was detected by a
photomultiplier, amplified and t h e n plotted o n a
wavelength-synchronized xy recorder. Spectra
were p r o d u c e d by a scanning spectroradiometer
which was calibrated against a U S B u r e a u of Stand
ards incandescent standard. Plots of luminescence
intensity against wavelength thus o b t a i n e d must be
corrected for any variations in spectral response of
optical fibre, m o n o c h r o m a t o r and photomultiplier.
A l t h o u g h b e a m conditions should be kept steady
while spectral m e a s u r e m e n t s are m a d e , this is less
critical t h a n with C L intensity m e a s u r e m e n t s , as C L
frequency is not d e p e n d e n t on b e a m current or
voltage.
So far, quantitative m e a s u r e m e n t s have mainly
been d o n e in o r d e r to discover t h e n a t u r e of the
emitting centres, but t h e r e is considerable scope for
using emission spectra from different growth zones
182
J . MILLER
in crystals as 'fingerprints' in establishing c a r b o n a t e

c e m e n t stratigraphies (see below) on a m o r e certain
and detailed basis.
Clearly, at the present state of t h e art, both
communication and interpretation of C L results in
petrography are dominantly subjective. T h e r e is an
urgent need to develop quantitative and thus m o r e
objective m e t h o d s for assessing C L intensity and
wavelength. This poses a formidable p r o b l e m for
instrumentation, because of the very low light levels
for most C L emission, and t h e difficulty of keeping
b e a m p a r a m e t e r s constant while making t h e optical
m e a s u r e m e n t s . H o t c a t h o d e devices a p p e a r to pro
vide much better capabilities for quantification of
C L results, and the next generation of instruments
may well be built o n this principle. E l e c t r o n microp r o b e s and scanning electron microscopes are now
appearing with custom-designed C L a t t a c h m e n t s ,
allowing spectra to b e t a k e n and computer-assisted
image e n h a n c e m e n t processes to be used. E l e m e n t
analysis and C L can thus be m o r e closely and con
veniently linked.
Because of t h e subjectivity referred to a b o v e ,
interpretations of C L results should therefore be
framed critically and cautiously. M a n y assumptions
are involved: apart from variables inherent in instru
m e n t a t i o n , our understanding of activating factors
in many minerals is incomplete. It would be most
unwise at present to rely solely o n luminescence
interpretations of geological p h e n o m e n a . T h e tech
nique should only be used in conjunction with other
standard petrographic a p p r o a c h e s . Its greatest
strength lies in revealing fabrics and ' m a p p i n g ' com
positional variation, rather t h a n in providing direct
geochemical information, wherein t h e greatest un
certainties exist.
6.6 A P P L I C A T I O N S
Cathodoluminescence has several general applica
tions in sedimentology:
(1) Rapid visualization of mineral distribution,
w h e r e minerals have closely similar optical p r o p e r
ties or are very fine-grained. F o r e x a m p l e , yelloworange C L of calcite generally distinguishes it from
t h e d a r k e r red-crimson of d o l o m i t e , and feldspars
are very bright blues, reds or greens c o m p a r e d with
subdued violets and browns for q u a r t z grains. C o m
plex intergrowths of minerals such as halite and
sylvite (blue-grey and silver-grey C L respectively)
can be easily visualized. It is essential to be very
cautious and check mineral identifications with other
techniques, as C L has complex origins and emission
colours are rarely diagnostic.
(2) Fabric and textural characteristics are often
m o r e easily visible, especially in recrystallized car
b o n a t e rocks (Fig. 6.3). Fossils in n e o m o r p h o s e d
limestones or c a r b o n a t e - c e m e n t e d sandstones re
a p p e a r and can give otherwise unavailable strati
graphic and environmental information (Figs 6.4c, d,
6.5a, b ) . Point counts carried o u t o n such rocks
u n d e r C L may differ significantly from those per
formed u n d e r transmitted light, particularly in t h e
greater proportion of bioclasts detected. C L m a k e s
it much easier to d e t e r m i n e if sparry fabrics are of
n e o m o r p h i c or cement origin by displaying growth
zones in crystal aggregates (Dickson, 1983). Sparry
crystal aggregates might display t h e outline of pri
mary void systems u n d e r C L (Fig. 6.3a, b ) , p r o
viding m o r e information on porosity evolution than
available with transmitted light alone.
(3) Small-scale features, which a r e difficult or
impossible to see in transmitted light microscopy,
may be well-displayed with C L . Fine veins, grain
fractures (caused by extension or c o m p a c t i o n ) , and
authigenic mineral overgrowths readily b e c o m e ap
p a r e n t (Fig. 6.5c, d ) .
(4) P r o v e n a n c e studies a r e m o r e exact, since
m a n y grain suites carry characteristic luminescence
'fingerprints' which can be related to their source
rocks (Fig: 6.5f). T h e origin of quartz grains can be
d e t e r m i n e d to s o m e d e g r e e , and mixing of quartz
grains, feldspars and heavy minerals from different
sources m o r e easily detected, e.g. Stow & Miller
(1984), Richter & Zinkernagel (1975). This aspect
of C L p e t r o g r a p h y has received little a t t e n t i o n , but
it could be extremely valuable in p e t r o l e u m explora
tion, giving an extra feature for use in correlation of
borehole core sequences and interpretation of their
depositional e n v i r o n m e n t s .
(5) Diagenetic and geochemical studies a r e en
hanced by t h e very fine C L resolution of growth
histories in crystals (Fig. 6.4). T a k e n t o g e t h e r with
o t h e r evidence, these geochemical variations may
indicate variations in g r o u n d w a t e r chemistry and
burial d e p t h s , greatly increasing t h e resolution of
diagenetic histories (e.g. G r o v e r & R e a d , 1983).
(6) Mechanically
induced
post-depositional
changes in sediments such as compaction, stylolitization and structural deformation can m o r e easily b e
detected and evaluated with the aid of C L .
Fig. 6.3. Drawings made from photographs of CL in limestones from the Dinantian (Lower Carboniferous) of Ireland.
(a) Coarse sparry calcite mass seen in transmitted light, (b) Same view but with cathodoluminescence, showing a void
developed in micrite (coarse stipple), with a cement sequence of radial fibrous spar (light stipple), non-luminescent ferroan
calcite (black) and brightly luminescent outer zone (white). The void fill is completed by dolomite (hashures). (c) Mediumgrained blocky spar mosaic seen under transmitted light is revealed under cathodoluminescence (d) as a neomorphosed,
brightly luminescent biomicrite with gastropods, bivalves and foraminifera which are weakly luminescent.
6.7 E X A M P L E S O F C L U S E IN
SEDIMENTOLOGY
Exhaustive discussions of t h e C L properties of
minerals are beyond the scope of this chapter, and
t h e r e a d e r is referred t o t h e reviews of Nickel (1978),
A m i e u x (1982) and W a l k e r (1985). S o m e of t h e
most i m p o r t a n t petrographic uses of C L a r e outlined
below for t h e m o r e c o m m o n sedimentary rock types.
6.7.1 Carbonate r o c k s
PRINCIPLES
C a r b o n a t e minerals give bright and stable lumine
scence at low accelerating voltages, so limestones
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ill
183
and dolomites h a v e attracted m u c h attention from

sedimentologists working with C L ( A m i e u x , 1982).
Chemically p u r e calcite m a y show a blue C L
which is probably d u e to an intrinsic lattice defect.
Mn
is t h e p r i m a r y activator and produces yellow
to red emission, dominating any low intensity blue
p e a k . F e is t h e c o m m o n e s t quencher ion, but N i
has a similar effect. C o m p l e t e quenching by F e
produces a black luminescence distinct from nonluminescence ( A m i e u x , 1982); Pierson (1981) found
this to occur in dolomites at 1.5 w t . % F e . Mostly,
h o w e v e r , M n a n d F e t e n d to co-precipitate in t h e
lattice of c a r b o n a t e minerals a n d varying degrees of
quenching, occur, reducing the intensity of M n
emission and inducing a brownish colouration ac
cording t o t h e quenching. A m i e u x (1982, fig. 5) has
2 +
2 +
2 +
2 +
184
J . MILLER
Fig. 6.4. Paired photomicrographs of limestone thin sections, with transmitted light view to the left and
cathodoluminescence view to the right. All from the Dinantian (Lower Carboniferous) of South Wales, (a), (b) Pwll-yCwm Oolite. Calcite cement fill of bivalve mould, showing details of crystal growth by fine luminescent and nonluminescent growth bands, (c), (d) Blaen Onneu Oolite. Syntaxial calcite overgrowth on an echinoid spine, showing
preferential nucleation on the crystallographically suitable substrate. CL reveals detail of the internal structure of the
recrystallized spine. Changes in CL intensity in the overgrowth cement are due to varying concentrations of F e quencher,
(e), (f) Gilwern Oolite. Details of the internal structure of ooids is better revealed by CL. Thin, non-luminescent calcite
cement fringes occur on the ooids, followed by brightly-luminescent microspar associated with calcrete formed during
subaerial exposure. Photographs by courtesy of Dr M. Raven.
185
Fig. 6.5. Paired photomicrographs of sandstones from North Sea cores, transmitted light view to the left and CL view to
the right, (a), (b) Medium-grained sandstone with a carbonate cement is seen under CL to have a fairly high fossil content,
mainly echinoderms: crinoid fragments and an echinoid spine (top left) provide substrates for large, zoned overgrowths
which have occluded the primary porosity, (c), (d) Coarse sandstone with non-luminescent authigenic quartz overgrowths
on violet-luminescing quartz grains. A subsequent zoned calcite cement is being dissolved by kaolinite (white on picture,
royal blue CL). (e), (f) Violet luminescing (V) and brown (B) quartz grains showing a mixture of metamorphic and igneous
sources. A sparry calcite cement (S) is suffering dissolution by brightly-luminescing kaolinite (K).
2 +
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J . MILLER
186
related M n / F e ratios and their emission colours t o

geochemical e n v i r o n m e n t s , particularly t o r e d o x
potential changes during crystallization.
T r a c e elements such as Sm, D y , E u , E r , C e and
P b act as sensitizers or 'co-activators', facilitating
M n activation ( M u k h e r j e e , 1948; Schulman etal.,
1947; M a c h e l , 1985). Empirical studies, comparing
M n and F e contents of calcite and dolomite with
their luminescence, have indicated that the M n / F e
ratio is the main controlling factor influencing C L
intensity in these minerals, at F e
concentrations
below 1% (Fairchild, 1983). Cross-plots of F e / M n
a r e given by Fairchild (1983) and G r o v e r & R e a d
(1983). T h e s e observations a r e s u p p o r t e d by the
correspondence of dull C L with blue ferricyanide
stained areas in calcites, w h e r e the Prussian Blue
precipitate is specific for t h e F e
ion.
2 +
2 +
2 +
T h e C L colours p r o d u c e d in calcite and dolomite

by M n
range from yellow to dark reds and pinks.
S o m m e r (1972a) d e t e r m i n e d that with increasing
substitution of M n
into M g
rather than C a
sites, the colour tends t o w a r d s red (see also A m i e u x ,
1982). Broadly, therefore, low Mg calcites give yel
low C L and high Mg calcites are o r a n g e t o red.
D o l o m i t e is characteristically a 'brick-red' colour.
H e a v y quenching by Fe was considered by A m i e u x
to p r o d u c e a dull b r o w n - m a r o o n C L quite distinct
from black non-luminescence.
& H e y n e n suggested that differential M n u p t a k e

d u r i n g crystal growth may b e caused by two p r o
cesses: (1) Changes in the bulk chemical composition
of t h e precipitating solution, such as an increase in
its M n c o n t e n t during crystal growth. (2) C h a n g e s in
the rate of crystal growth related to variations in t h e
supersaturation level of t h e solution. While t h e
crystals w e r e growing slowly, t h e lattice was able t o
'sweep o u t ' impurities such as t h e M n activator ions
and thus exhibit less luminescence. M o r e M n was
incorporated during rapid crystal growth.
Both processes resulted in similar C L zonation
p a t t e r n s . This implies that variations in C L intensity
n e e d not necessarily reflect changes in bulk p o r e
fluid composition. However, the experimental growth
rates are probably much higher than those encoun
t e r e d u n d e r geological conditions, b u t this effect
should be born in mind.
sub-stages and zones, divided on the basis of uncon

formities, crystal habit and composition. F u r t h e r ,
they noted a tendency to concentrate on c e m e n t
stratigraphies to the exclusion of many o t h e r dia
genetic events, such as dissolution, compaction,
stylolitization, n e o m o r p h i s m and mineralization. In
stead, they emphasized that the detailed c e m e n t
sequences revealed by C L could be used as a time
framework u p o n which to locate other diagenetic
events, providing a complete 'diagenetic stratig
raphy'. This provides a powerful tool for analysis of
post-depositional changes in sedimentary rocks.
Uncertainties exist in o u r present interpretation
of C L and its relation to t h e geochemistry of car
b o n a t e precipitation from p o r e fluids. C a r b o n a t e
minerals are also inherently unstable and liable to
both obvious and subtle alteration during diagenesis.
T h e r e f o r e , additional criteria, such as evidence of
dissolution or fracturing, changes in crystal habit,
inclusions, carbon/oxygen isotope ratos and accur
ate geochemical analyses of individual
luminescent
zones using m i c r o p r o b e , A A S and n e u t r o n activa
tion techniques must be integrated with C L results.
This involves very precise, t e d i o u s w o r k , often using
very small samples of cements for analysis. A t t h e
very least, t h e precaution of staining thin sections
with Alizarin R e d S and potassium ferricyanide
( C h a p t e r 4) is r e q u i r e d as a rapid a n d sensitive
m e t h o d of determining w h e t h e r variation in C L
intensity is likely to be d u e t o fluctuations in M n
activator or to t h e presence of F e as a q u e n c h e r .
G e n e r a l l y , C L work is d o n e in conjunction with
m i c r o p r o b e analysis performed on t h e same thin
sections. C L cannot b e used alone for other t h a n
general interpretations of c e m e n t histories.
2 +
2 +
2 +
2 +
T e n H a v e & H e y n e n (1985) investigated t h e in

corporation of M n
into calcite crystals in over 50
crystal synthesis experiments from gels a n d solu
tions. Normal temperatures and pressures were used.
T h e y r e p o r t e d that 1 5 - 3 0 p p m M n w e r e sufficient
to induce luminescence in t h e synthetic calcites (Fe
less than 200 p p m ) . Dolomites from t h e Jurassic of
t h e Middle E a s t and M i o c e n e of the B a h a m a s were
also analysed. T h e s e w e r e found to luminesce w h e n
M n was higher than 3 0 - 3 5 p p m and F e less t h a n 300
p p m . A higher level of activator was thus required in
dolomite c o m p a r e d t o calcite, d u e to t h e m o r e
efficient luminescence of M n
when present in t h e
C a lattice sites t h a n w h e n substituting M g sites.
In d o l o m i t e , M n
largely occupies t h e M g
sites
( S o m m e r , 1972b). T h e minimum a m o u n t of M n
activator for C L is thus lower in calcite than in
dolomite.
2 +
2 +
2 +
2 +
2 +
2 +
2 +
M a n y of the synthetic calcites produced in t h e

experimental work displayed zonation in C L com
parable t o that found in many natural c a r b o n a t e
crystals. Variations in C L intensity in the zones w e r e
related to variations in their M n content. T e n H a v e
CEMENT STRATIGRAPHY
O n e of the c o m m o n e s t applications of C L in car
b o n a t e rocks is in revealing successive stages o r
zones of void-filling cements with far greater pre
cision than that possible with optical microscopy.
C e m e n t stratigraphy (Fig. 6.4) involves t h e applica
tion of stratigraphic principles at an inter-granular
and void level, correlating stages of cementation
within a given basin of s e d i m e n t a t i o n .
Meyers (1974, 1978) p i o n e e r e d c e m e n t strati
graphy, demonstrating that 'zones' of c a r b o n a t e
c e m e n t s , as revealed by their C L and o t h e r p e t r o
graphic characteristics, could b e correlated both
vertically and regionally in the Mississippian of the
S a c r a m e n t o M o u n t a i n s , New Mexico. G r o v e r &
R e a d (1983) performed a similar study in t h e O r d o vician of Virginia, and related the sequence to dia
genetic changes resulting from changes in formation
water composition during shallow a n d d e e p burial.
W a l k d e n & Berry (1984) correlated C L zones in
overgrowth cements from the U p p e r Dinantian of
n o r t h e r n Britain, and ascribed t h e m to cyclic re
plenishment of vadose and shallow meteoric water
tables in calcretized m a r i n e limestones.
Studies of c e m e n t sequences must pay particular

attention t o veining p h a s e s . M a n y post-burial cement
generations can be linked to specific sets of veins,
s o m e of which are extremely fine and are only
visible with C L . C o m m o n l y , later stages of cements
precipitated during veining episodes may induce
n e o m o r p h i s m of earlier cements, replacing t h e m
partially or completely, or may merely precipitate
films of new material along crystal interfaces be
tween existing c e m e n t s . In all cases this leads to a
p r o n o u n c e d change in t h e C L o f the affected cements
which is an important e l e m e n t in the diagenetic
event stratigraphy. Large thin sections (see C h a p t e r
4) are important for this work, as veins and their
conjunction with voids are often missed in small
samples. It is also necessary specifically to select
Miller & Gillies (in press) discussed the principles

and practise of c e m e n t stratigraphy, especially t h e
confused and varied terminology existing in t h e
literature. In order t o i m p r o v e communication and
comparison of C L results, they suggested standard
terms for cement sequences, using n u m b e r e d stages,
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187
veined material for study, hitherto not a regular

practise in traditional c a r b o n a t e petrography.
Studies of stable isotopes in c a r b o n a t e minerals
and skeletal materials can provide valuable environ
mental and diagenetic information. Prior examina
tion of material to be sampled for stable isotope
analysis with C L enables selection of areas uncont a m i n a t e d by n e o m o r p h i s m or inter-crystal infil
tration as described a b o v e .
6.7.2 Sandstones
QUARTZ
T h e causes of C L in quartz a r e not yet fully deter
mined (Walker, 1985). A l p h a quartz shows visible
C L with t w o b r o a d emission b a n d s in t h e blue and
r e d ( Z i n k e r n a g e l , 1978). Various authors have attri
buted these emissions to Ti and M n respectively b u t ,
as W a l k e r (1985) pointed out, t h e spectral b a n d s are
present in highly p u r e synthetic silica, and it seems
certain that emission is intrinsic rather t h a n d u e to
impurities. C L from natural q u a r t z is characteristi
cally thermally unstable. H e a t i n g collapses the blue
spectral p e a k , causing t h e violet luminescence t o
shift t o w a r d s red. T h i s p r e s e n t s a major p r o b l e m for
observation of quartz grains u n d e r an electron b e a m :
its heating effect can quickly cause t h e fed coloura
tion to b e assumed. H i g h accelerating voltages and
current densities speed t h e change, which is per
m a n e n t . It may b e very difficult t o obtain accurate
colour p h o t o g r a p h s of q u a r t z luminescence because
t h e shift to red may occur during t h e time of
exposure.
Z i n k e r n a g e l showed t h a t natural q u a r t z grains
have a luminescence which apparently reflects their
source (or, m o r e correctly, their thermal history).
Broadly, violet C L is typical of igneous sources, but
brown grains originate in certain types of m e t a m o r
phic rocks (Fig. 6.5f). This scheme of provenance
using C L was further elaborated by M a t t e r & R a m seyer (1985). Q u a r t z overgrowths and other forms
of authigenic quartz a r e commonly non-luminescent
u n d e r n o r m a l C L conditions (Fig. 6.5d), while zoned
C L is typical of grains derived from hydrothermal veinquartz. C L is thus a very sensitive m e t h o d of deter
mining presence and timing of p o r e occlusion by
quartz authigenesis, particularly where t h e r e are n o
obvious dust-rims on grain cores.
Owing to the t h e r m a l instability described above,
with violet grains easily becoming brown while in
188
J . MILLER
HODOLUMINESCENCE MICROSCOPY
t h e electron b e a m , much care and s o m e skill is

n e e d e d t o distinguish q u a r t z C L colours successful
ly. Given this, C L affords a rapid m e a n s of detecting
different quartz grain populations in sandstones and
in ascertaining their p r o v e n a n c e . T h e different
shades of violet and b r o w n in a grain population
probably represent various grain sources, since
t h e r e is n o evidence that crystal orientation exerts
significant control over C L wavelength and intensity
in quartz. Of course, it is wise to check t h e o t h e r
properties of the grains, such as inclusions and type
of extinction, to gain confirmation of C L deter
minations.
Sippel (1968) and Sibley & Blatt (1976) have
applied C L in investigations of silica authigenesis in
sandstones. Burley, Kantorowicz & W a u g h (1985)
suggested how C L may profitably b e c o m b i n e d with
o t h e r techniques in elucidating diagenesis of clastic
rocks.
FELDSPARS
T h e causes of C L in this mineral g r o u p are relatively
well-known from investigations on lunar rocks
( G e a k e et al., 1977) and-carbonatites ( M a r i a n o , Ito
& Ring, 1973). Feldspars have low C L thresholds
and are thus obvious even at low accelerating volt
ages. Typical C L colours are brilliant blue (possibly
Ti
activation), red to infra-red ( F e
substitution
for A l ) and green ( M n substitution probably for
C a ) . Feldspar C L is polarized and s o m e intensity
variation is seen u p o n rotation of a polaroid sheet
interposed b e t w e e n t h e viewing window and t h e
microscope eyepiece. This property often helps to
distinguish feldspars from o t h e r minerals of similar
C L colour. In general, authigenic feldspars a r e nonluminescent or very dully luminescent (Kastner,
1971), serving to differentiate detrital cores from
their overgrowths.
2 +
3 +
3 +
2 +
2 +
In t e r m s of p r o v e n a n c e , t h e r e is n o evidence to
suggest that feldspar C L is related to specific igneous
or m e t a m o r p h i c origins. H o w e v e r , t h e presence of
feldspar 'suites' containing consistent p r o p o r t i o n s of
t h e rarer red and/or green emitter grains amongst
t h e c o m m o n blue emitters can be used t o trace
particular sources of clastic feldspar supply (e.g.
Stow & Miller, 1984).
Because even the smallest feldspar grains
luminesce brightly, a far m o r e accurate estimate of
t h e percentage of feldspar in a clastic sediment is
6.8 P H O T O G R A P H I C
OF CL
obtained by point-counting u n d e r C L . This is par

ticularly true for fine sandstones and siltstones.
E v e n grains which a r e badly w e a t h e r e d or altered
still register t h e typical emission.
RECORDING
Prior to t h e realization that high transmissivity

microscopes were m a n d a t o r y for successful C L
w o r k , p h o t o g r a p h y of C L was extremely difficult
and the results highly variable. Minerals giving very
low intensity emission, such as quartz grains, re
quired many minutes or even hours of exposure with
fast films. Generally, these films w e r e working at
luminance ranges beyond their zones of reciprocity
failure, resulting in p o o r resolution, low contrast
and indifferent colour rendition. G o o d microscope
transmissivity, aided by straight-through light paths
between objective and film, m e a n s that slower (and
thus finer-grained) films can now be used, working
well within their o p t i m u m exposure ranges.
HEAVY MINERALS
M a n y accessory minerals of clastic rocks contain at
least traces of r a r e earth or transition metal impuri
ties and are therefore liable to luminesce. Nickel
(1978) listed the k n o w n C L characteristics of such
minerals. A p a t i t e s give particularly bright C L , with
e u r o p i u m a c o m m o n activator ( M a r i a n o & Ring,
1975). A p a t i t e emissions r a n g e from bluish-violet,
lilac, pink and o r a n g e to yellow. P o r t n o v & G o r o b e t s
(1969) have p r o p o s e d that certain of these colours
a r e related to particular igneous or m e t a m o r p h i c
origins. If this can b e confirmed, it would b e an
invaluable adjunct to p r o v e n a n c e studies. A g a i n ,
t h e small size of many heavy mineral grains m e a n s
that they are often overlooked and easily u n d e r
estimated in transmitted light p e t r o g r a p h y of clastic
rocks. Invariably, use of C L produces an often sur
prising re-evaluation of the i m p o r t a n c e of accessory
grains.
Most petrological microscopes can be fitted with

photomicrography accessories which allow auto
matic exposure d e t e r m i n a t i o n (Fig. 6.3). T h e large
viewing window of the Nuclide Luminoscope also
allows t h e use of a 55 m m / 7 3 . 5 macro lens directly
m o u n t e d on a c a m e r a body to t a k e pictures of whole
thin sections or slabs u n d e r C L . Such pictures are
invaluable for m a p p i n g C L zones in carbonate ce
m e n t s whch are t o be sampled for A A S and stable
isotope analysis by drilling or scraping from indivi
dual c e m e n t stages. T h e y also show up fabrics and
small-scale sedimentary structures in sandstones and
siltstones.
CEMENTS AND DIAGENESIS

C a r b o n a t e cements are commonly involved in occlu
sion of sandstone porosity (Fig. 6.5b, f ) . Their
mineralogy and sequence of d e v e l o p m e n t are m o r e
accurately followed by using C L than by transmitted
light alone (see a b o v e ) . O t h e r diagenetic features
such as corrosion of q u a r t z grains by c a r b o n a t e ,
relative timing of q u a r t z overgrowth formation and
c e m e n t a t i o n and t h e onset of dolomitization can
also be rapidly d o c u m e n t e d with C L . Authigenic
kaolinite or dickite commonly form late stage ce
m e n t s in sandstones (Fig. 6.5f, Burley et al., 1985,
fig. 7 f ) , and they usually have a brilliant royal blue
C L , whose origin is u n k n o w n . T h e extent and timing
of these c e m e n t s and their relationship to c o m p a c
tion and tectonic e v e n t s , such as extension veining,
is much m o r e easily appreciated u n d e r C L t h a n with
transmitted light microscopy.
R e c e n t advances in film technology have increased

t h e r a n g e of films suitable for C L recording. F o r
routine w o r k , particularly with limestones, w h e r e
t h e colour range is restricted and can b e adequately
r e p r e s e n t e d in grey t o n e s , black and white films are
satisfactory. Invariably, good quality prints will show
up m o r e detail than was a p p a r e n t to t h e observer
viewing the C L , because of fatigue and insensitivity
of t h e eye at low light levels. Suitable films a r e
m e d i u m - s p e e d types ( I S O 125400) which possess
fine grain, good contrast range and s o m e exposure
latitude, such as Ilford F P 4 or X P 1 . Normally, pair
ed exposures a r e m a d e , o n e showing t h e transmitted
light view and o n e t h e C L view. C L negatives often
have a somewhat restricted contrast r a n g e , and these
'flat' negatives may b e enhanced by printing on
h a r d e r p a p e r t h a n t h e transmitted light frames.
A good example of t h e combined use of C L , S E M

and transmitted light petrography in d o c u m e n t i n g
t h e p r o v e n a n c e and diagenetic history of a Jurassic
reservoir sandstone is given by Olaussen et al.
(1984).
Sandstones are difficult subjects; quartz C L is

very s u b d u e d but feldspars are very bright, often
with a high U V c o m p o n e n t . It is almost impossible
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189
to get brilliant and d a r k grains properly exposed o n

t h e same frame. Correct exposure for dull q u a r t z
usually results in serious over-exposure of feldspars,
with d e v e l o p m e n t of halation areas a r o u n d t h e
grains, while correct exposure of feldspars produces
m a r k e d under-exposure of q u a r t z grains. A series of
half-stop u n d e r - and over-exposure gradations will
usually p r o d u c e o n e frame which is satisfactory for
each. Correction can also be d o n e by changing t h e
film speed b e t w e e n exposures on an automatic
centre-weighted averaging m e t e r setting a slower
film speed will trick the m e t e r into underexposing a
bright grain. A light m e t e r with a movable spot, as
in the Nikon system (Fig. 6.3) can provide direct
exposure readings for particular grains.
It is also important, with p o r o u s rocks, to r e m o v e
carefully all traces of t h e d i a m o n d polishing abra
sives from t h e slide: industrial d i a m o n d grains have
a brilliant green C L which produces halation spots,
giving t h e impression of a larger grain, which is apt
to be mistaken for an apatite or other heavy mineral
grain.
Colour pictures are s o m e w h a t m o r e p r o b l e m a t i c ,
in that t h e precise colours of C L are very difficult to
r e p r o d u c e exactly. Daylight films give t h e best colour
balance, with a blue compensating filter for t h e
transmitted light (tungsten lamp) frames. T h e choice
lies b e t w e e n print films with a n a r r o w e r contrast
range and variable colour balance depending on
printing filtration, and reversal films with a higher
contrast and resolution range b u t w h e r e s u b s e q u e n t
correction is not possible. Agfa, K o d a k and Fuji
p r o d u c e ranges of colour slide and print films rang
ing from I S O 25 to 1000, with an H R suffix indica
ting the films' high resolution capability by virtue of
t h e very thin emulsions used in t h e colour separation
layers. T h e slower t h e s p e e d , t h e finer t h e grain and
t h e greater the resolving p o w e r of these films. I S O
1000 films may be n e e d e d t o collect C L images of
thermally unstable q u a r t z grains which rapidly red
d e n u n d e r excitation. E a c h w o r k e r is advised t o
e x p e r i m e n t with a range of films, both colour and
m o n o c h r o m e , a n d t h e n t o b e c o m e thoroughly fami
liar with those which a r e best suited.
C L d e p e n d s so often o n rendition of a r a n g e of
colours, s o m e soft and subtle, s o m e brilliant, that
o p t i m u m reporting of C L studies in publications
may d e m a n d expensive colour plates. While m o n o
c h r o m e C L images a r e a d e q u a t e for limestones, as
noted a b o v e , sandstone C L recorded in m o n o -
190
J . MILLER
c h r o m e is unsatisfactory (Fig. 6.5). Several publica

tions have colour plates, e.g. Zinkernagel (1978),
Richter & Zinkernagel (1981), A m i e u x (1982),
Olaussen et al. (1984), Dickson (1985), Burley et al.
(1985) and M a t t e r & R a m s e y e r (1985). T h e y are
very few c o m p a r e d with t h e many t h o u s a n d s of
m o n o c h r o m e illustrations which a p p e a r each year.
T h e cost of providing a d e q u a t e colour reproduction
in publication could dissuade s o m e p e t r o g r a p h e r s
from using C L , particularly with sandstones.
6.8
H o w e v e r , a great deal of d e v e l o p m e n t work re

mains to be d o n e in determining t h e causes of C L in
minerals and in understanding the geochemical signi
ficance of changes in activator concentration in
minerals precipitated during diagenesis. It is clear
even at this early stage that C L is not a substitute for
existing petrological techniques b u t , when c o m b i n e d
with these a p p r o a c h e s , it provides a rapid and
powerful way of eliciting m o r e data from geological
samples. T h e r e are now overwhelming a r g u m e n t s
for considering C L to be a standard technique and
n o t an esoteric diversion.
CONCLUSIONS
T h e r e is little d o u b t that t h e availability of relative

ly c h e a p and convenient machines for viewing C L is
o n e bf t h e most i m p o r t a n t d e v e l o p m e n t s in sedi
m e n t a r y p e t r o g r a p h y in t h e last twenty years. T h e
t e c h n i q u e significantly e n h a n c e s b o t h t h e quality
and quantity of information to b e derived from thin
sections and rock surfaces, and provides a powerful
tool for the construction of extremely detailed dia
genetic event stratigraphies.
6.9 M A N U F A C T U R E R S OF
CL EQUIPMENT
Nuclide C o r p o r a t i o n , A G U Division, 916 M a i n
Street, P O B o x 315, A c t o n , M A 01720, U S A .
T E C H N O S Y N Ltd, Coldhams Road, Cambridge
CB1 3EW, England.
7
7.1
X-ray powder diffraction of sediments

RON HARDYand MAURICE TUCKER
INTRODUCTION
X-ray diffraction ( X R D ) is a basic tool in t h e minera

logical analysis of sediments, and in t h e case of fine
grained sediments an essential o n e . It has the advan
tage, with m o d e r n i n s t r u m e n t a t i o n , that almost
complete a u t o m a t i o n can be achieved to give fast,
precise results. This chapter discusses the basic
theory of t h e t e c h n i q u e , in so far as it is n e e d e d to
set u p systems of analysis, and goes o n to describe
several specific applications to sediments with ap
p r o p r i a t e preparative techniques and guides to
interpretation.
(ii) A n u m b e r of discrete lines of varying intensity

called t h e characteristic radiation which represents
t h e energy released by r e a r r a n g e m e n t s of the orbital
electrons of a t o m s of t h e a n o d e target following
ejection of o n e or m o r e electrons during the excita
tion process. T h e s e lines a r e k n o w n as K, L, M lines
e t c . ; the type of line p r o d u c e d is d e t e r m i n e d by t h e
orbital electrons taking part in t h e r e a r r a n g e m e n t
(Fig. 7.3).
Various a n o d e materials are commonly used as
Water cooled
7.2 T H E O R Y O F X - R A Y
DIFFRACTION
F o r a comprehensive t r e a t m e n t of theory, the r e a d e r
is referred to t h e classic text of Klug & A l e x a n d e r
(1974). Only a simplified t r e a t m e n t for the under
standing and evaluation of basic analytical proce
d u r e s is given h e r e . A very useful introduction can
be obtained from t h e Philips organization in the U K
called ' A n introduction to X-ray p o w d e r diffractom e t r y ' by R. Jenkins and J . L . de Vries. T h e address
is Pye U n i c a m L t d , Y o r k Street, C a m b r i d g e C B 1
2 P X , tel. C a m b r i d g e (0223) 358866.
7.2.1 Production of X-rays

In a n o r m a l commercially available laboratory diffractometer (assumed t h r o u g h o u t this c h a p t e r ) ,
X-rays are p r o d u c e d by b o m b a r d m e n t of a metal
a n o d e (the t a r g e t ) , by high energy electrons from a
heated filament in a R o n t g e n X-ray tube (Fig. 7.1).
T h e resulting radiation e m e r g e s from a thin, usually
beryllium, window and consists of (Fig. 7.2):
(i) A b r o a d b a n d of continuous radiation (white
radiation) p r o d u c e d by the electrons from the fila
m e n t converting their kinetic energy to X-rays on
collision with t h e atoms of t h e a n o d e target.
:
5-35 mA
12 V
Fig. 7 . 1 . A section of a Rontgen X-ray tube (based on
Phillips & Phillips, 1980).
191
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192
R.G. HARDY and M.E. TUCKER
X-RAY POWDER DIFFRACTION
a
Koci
5000
K a ,
Continuous
spectrum
Characteristic line
spectrum from
copper
-2500
0.5
1.0
1.5
2.0
Wavelength \(A)
2.5
Fig. 7.2. The spectrum from a copper anode X-ray tube.

targets in X-ray t u b e s , they include: C u , C r , F e , C o ,
M o and A g . E a c h has advantages and disadvantages
and these will b e discussed later in connection with
t h e analysis of sediments.
Considerable advantages are to be gained by the

use of purely m o n o c h r o m a t i c radiation, i.e. radia
tion of a single wavelength a n d this is achieved by
t h e use of a p filter, or alternatively by using a crystal
monochromator.
T h e (3 filter consists of a thin metal foil which is
positioned in the X-ray b e a m generally close to t h e
beryllium window of the X-ray t u b e . T h e type of
metal foil selected is such that t h e intensity of t h e K$
radiation of a particular X-ray tube is effectively
r e m o v e d from t h e spectrum (Fig. 7.4). This is
achieved by using the variation of mass absorption
of metals with wavelength (Fig. 7.5) in such a way
that the high absorption of the K A b s o r p t i o n E d g e
of t h e metal falls b e t w e e n the K$ and Ka. radiations
of t h e X-ray t u b e .
T a b l e 7.1 lists t h e usual combinations of target
element and filters. It should be r e m e m b e r e d that as
well as greatly reducing the K$ radiation intensity,
t h e P filter also reduces t h e overall intensity of t h e
continuous
and t h e intensity of t h e Kcc
radiation.
F u r t h e r i m p r o v e m e n t s can be achieved in the
production of m o n o c h r o m a t i c radiation with t h e use
Tadiation
193
Table 7.1. X-ray tube targets and suitable filters

Target
element
K<x(k) ATf3(A) Filter K Absorption Thickness

Edge (A)
(urn)*
Cr
Fe
Co
Cu
Mo
2.291
1.937
1.791
1.542
0.710
2.085
1.757
1.621
1.392
0.632
V
Mn
Fe
Ni
Zr
2.269
1.897
1.744
1.488
0.688
16
16
18
21
108
This thickness reduces Kfi/Ka to 1/600.
0.5
5000
1.0
1.5
2.0
Wavelength \(A)
Fig. 7.4. The copper X-ray spectrum after passing through

a nickel filter.
Ka2
o 2500
K a b s o r p t i o n e d g e (1.49A)
Ka-]
Q. C
Transmission
Transmission
M shell
X-ray
-A,
0.5
Absorption
1.0
2.0
1.0
1.5 _ 2.0
Wavelength (A)
2.5
Fig. 7.6. The copper X-ray spectrum after passing through

a nickel filter and subjected to pulse height analysis.
W a v e l e n g t h (A)
Fig. 7.5. The variation of mass absorption coefficient of

nickel at different X-ray wavelengths.
Electrons
Fig. 7.3. The generation of X-rays of the line spectrum of copper due to the transfer of electrons into the K shell and the
generation of the continuous spectrum due to complete or partial electron collisions (from Phillips & Phillips, 1980).
of electronic filters (pulse height analysis) associated

with t h e detection and recording devices of the
diffractometer (Fig. 7.6).
In t h e case of a graphite curved crystal m o n o
c h r o m a t o r (Fig. 7.7), adjustments of the graphite
crystal can be m a d e such that only t h e desired
wavelengths, i.e. Ka, pass to the detection device,
thus filtering out the u n w a n t e d K and continuous
radiation without t h e use of p filters and pulse height
analysis.
http://jurassic.ru/
7.2.2 Diffraction of X-rays by a sample

Figure 7.8 shows a schematic representation of a
typical diffractometer. T h e X-rays are first collim a t e d to p r o d u c e a subparallel b e a m , t h e a m o u n t of
divergence being controlled by the size of the diver
gent slit, i.e. a 4 large divergence slit for high angle
work t o a 1/12 small divergence slit for low angle
work.
T h e divergent b e a m is then directed at the sample,
which is m o t o r driven to rotate at a regular speed in
degrees p e r m i n u t e . W h e n mineral planes in t h e
sample attain an a p p r o p r i a t e angle, they will diffract
the X-rays according to Bragg's Law,
i.e. rik = 2d sin 0
194
X-ray source
Monochromator
crystal
Specimen
w h e r e n is an interger, X is the wavelength of the Xrays, d is the lattice spacing in angstroms and 0 is the
angle of diffraction (Fig. 7.9). T h e diffracted b e a m
is passed through a receiving slit and collimator a n d ,
then a scatter slit is introduced to reduce any scat
tered X-rays o t h e r than the diffracted b e a m s from
finally entering t h e detector. In the case of a m o n o
c h r o m a t o r being used (Fig. 7.7), the b e a m passes
straight from t h e receiving slit to the crystal m o n o
c h r o m a t o r and then t o the detector. T h e signal
produced by the X-ray p h o t o n s on the detector is
first amplified, and then passed on to the electronic
recording e q u i p m e n t .
Fig. 7 . 7 . Schematic representation of

the geometry of a curved crystal
monochromator (from Philips UK
information sheet).
Fig. 7.9. An illustration of Bragg's Law: a, a and a are

lattice arrays of atoms that can be regarded as an infinite
stack of parallel, equally spaced planes. If a wavefront
XY is incident on aa the reflection path from the lower
plane ( i ) is longer, i.e. AB+BC = A = difference in paths
of wavefronts
l
Scatter slit
7.2.3 Output devices

O u t p u t from a diffractometer can be in either analo
gue or digital form. T h e conventional analogue re
cording is a strip chart whose speed in millimetres
per minute is synchronized with that of the detector
in degrees of 20 per minute so that the x-axis is
calibrated in 20 (Fig. 7.10). Deflections recorded
can be easily converted into lattice (d) spacings of
the minerals present by applying Bragg's Law. Most
diffractometers possess a digital counter which can
record actual X-ray intensities in counts per second.
Early X R D was carried out using p o w d e r cameras
which used a film recording technique. This is now
largely restricted t o specialized applications such as
structural determinations and to instances w h e r e the
a m o u n t of sample available is very small, the o r d e r
of a few micrograms. It is a very time-consuming
m e t h o d and not easily susceptible to a u t o m a t i o n .
U s e of the diffractometer has b e e n transformed
by the advent of microprocessor control, microcom
puters and automatic sample loaders. T h e s e have
led to completely a u t o m a t e d instrument operation
and data processing.
Receiving parallel
slit assembly
Counter tube
Scatter slit
Receiving parallel Uf.
slit assembly
1
I
Divergence
slit
Specimen
Receiving slit
Focusing circle-
7.3 X R D A N A L Y S I S O F S E D I M E N T S
X R D is particularly useful in the analysis of fine
grained material which is difficult to study by other
m e a n s , but t h e r e are a whole range of applications
to the various c o m p o n e n t s of sediments, as defined
by either size and/or mineralogy.
Fig. 7 . 8 . Schematic representation of
the geometry of a typical
diffractometer (from Philips UK
Goniometer Manual).
7.3.1 Whole rock analysis

T h e most basic application of X R D to sediments is
in the analysis of whole rock samples. T o obtain
http://jurassic.ru/
Mllilll
195
2d
d sin 8 + d sin 6 =
sin 9 = A.
For diffraction to occur A must equal a whole number of
wavelengths: 2d sin 9 = rik (Bragg's Law).
satisfactory results the original grain size must be

reduced to a m e a n particle diameter of 510 pm
with, preferably, a limited size range. C a r e must be
t a k e n in particle size reduction not to damage the
crystallite by strain as this can lead to diffraction line
broadening, which is in any case related to particle
size (see Klug & A l e x a n d e r , 1974, chapter 9). Care
ful grinding by h a n d can give satisfactory results but
mechanical devices such as the M c C r o n e Micronizing Mill (Walter M c C r o n e Associates, Chicago)
have b e e n shown t o p r o d u c e very reproducible par
ticle size distributions without damaging the crystal
lattice, both very i m p o r t a n t criteria in quantitative
work. C a r e must also b e taken to obtain a repre
sentative sample this can b e achieved by applying
appropriate sampling techniques, e.g. riffle boxes,
quartering, etc.
Having ground a representative sample to the
appropriate grain size, t h e next stage is to present
the sample to the X-ray b e a m . T h e r e are basically
two m e t h o d s to do this; o n e method is to p r o d u c e a
cavity m o u n t , and the o t h e r is to produce a smear
mount.
T h e cavity m o u n t holder (Fig. 7.11) is usually
m a d e of aiuminium and the sample is packed in
from the rear of the cavity in the m a n n e r described
by Klug & A l e x a n d e r (1974, p . 373). This type of
196
<O
C
O
Ci\
C
M
oO
<D
05
ro
iii i.. .
40
i
oo
7.3.2 Qualitative analysis
C
O
<
Assuming that a simple qualitative analysis is re

quired t h e only task is t h e interpretation of the chart
record (see Fig. 7.10). First the p e a k s must be
00
c\i
C
D
IS)
identified, then m e a s u r e d in terms of 26 and con

verted to lattice spacings. A p e a k (Fig. 7.13a) is
c o m m o n l y defined as being any reflection reaching a
height 2 o above the adjacent average background
(JV). T h e laws of X-ray production m e a n t h a t o =
V'/V to a close approximation.
F o r most experimental purposes t h e position of
t h e diffraction p e a k is t a k e n as t h e position of t h e
point of greatest intensity; problems arise in the case
JL
Background X-rays
45
o
oo
^r oo
50
<
C
D
<>
t C
N
J
wavelengths are effectively filtered o u t , thus allow

ing the use of a copper a n o d e in t h e determination
of iron-rich sediments (Fig. 7.12).
35
30
25
20
26
Fig. 7.10. A strip chart of diffractometer trace of the X-ray diffraction pattern of the mineral calcite. The 29 angle increases
from right to left on the horizontal scale and the intensity of the diffracted peak above background is given by the vertical
scale. The X-ray tube target was copper.
taped to the back

Fig. 7.11. Aluminium cavity mount.
m o u n t p r o d u c e s an almost r a n d o m sample especial

ly if care is t a k e n n o t to put any form of pressure on
the crystallites w h e n filling in t h e cavity.
T h e s m e a r m o u n t is p r e p a r e d by s m e a r i n g t h e
sample with a volatile organic solvent, such as ace
t o n e , o n to a glass slide. This type of m o u n t pro
duces a partially oriented sample which can p r o d u c e
p r o b l e m s during interpretation, e.g. estimating cor
rect relative intensities.
T h e cavity m o u n t or s m e a r m o u n t is t h e n inserted
into t h e diffractometer and t h e a p p r o p r i a t e condi
tions set and r e c o r d e d : (1) X-ray radiation u s e d ; (2)
g e n e r a t o r voltage a n d current; (3) t h e slit combina
tion used; (4) scanning speed; (5) recording device
p a r a m e t e r s (if a chart recorder u s e d ) ; time constant,
Wth
i monochromator
rate m e t e r and chart speed should be recorded; (6)

t h e start a n d t h e finish positions.
If a graphite crystal m o n o c h r o m a t o r is not avail
able, the choice and target of t h e X-ray t u b e used
d e p e n d s t o a large e x t e n t o n t h e predicted n a t u r e of
t h e s a m p l e . F o r clay mineral analysis and for most
sediment samples with low a m o u n t s of iron minerals
p r e s e n t , a c o p p e r a n o d e is preferred. If t h e sedi
m e n t s contain high levels of iron minerals, t h e use of
a c o p p e r a n o d e will cause iron fluorescence radia
tion from t h e sample as well as t h e diffraction p e a k s
from t h e lattice planes. This results in very high
backgrounds and h e n c e a p o o r p e a k to b a c k g r o u n d
ratio (Fig. 7.12). T h e iron fluorescent radiation (Fe
Ka) is caused by t h e incoming copper Ka radiation
from t h e X-ray t u b e being t h e correct energy to
displace K orbital electrons from t h e iron atoms in
t h e sample. In this case, an iron or a cobalt a n o d e Xray t u b e is used. Similarly, in t h e analysis of m a n
ganese sediments, an iron or a c h r o m i u m a n o d e is
u s e d as b o t h c o p p e r a n d cobalt a n o d e s c a u s e m a n
ganese fluorescence radiation to occur.
Cu radiation 40 kV/25 mA
1 divergence slit
0.2 mm receiving slit
4 scatter slit
j
Scanning speed 126 m i n
Full scale 2.000 cps
Pulse height analyser
Proportional counter
- 1
U
High background due to FeKa fluorescence
Wtihout monochromator
Cu radiation 40 kV/25 mA
1 divergence slit
0.2 mm receiving slit
1 scatter slit
If a graphite curved crystal m o n o c h r o m a t o r is

available, then as only t h e desired C u Ka wave
lengths are adjusted t o enter the detector, t h e F e Ka
Scanning speed 1 200 min

Full scale 4.000 cps
Pulse height analyser
Proportional counter
Fig. 7.12. A comparison of diffractometers with and without a curved crystal monochromator on the mineral haematite
using copper radiation (from Philips UK Information Sheet).
http://jurassic.ru/
197
198
R.G. HARDY and M.E. T U C K E R
X-RAY POWDER D I F F R A C T I O N
Table 7.2. (a) Conversion charts of 29 to angstroms (D-spacing) for copper Ka radiation (Computed by M.J. Smith,
University of Durham)
CuKaIpha
0
2
3
4
5
6
7
8
9
18
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
I ambda = 1 .5418A
4 4 . 172 4 2 . 0 6 8 4 0 . 156
2 9 . 450 2 8 . 500 2 7 . 609
2 2 . 089 21 . 551 21 . 038
17. 673 17. 327 16. 994
1 4 . 730 1 4 . 489 14. 255
12. 628 1 2 . 450 12. 277
11 . 051 1 0 . 915 10. 782
9. 826 9 . 718 9 . 612
8 . 845 8 . 758 8 . 672
8 . 0 4 3 7 . 971 7. 900
7 375 7 314 7 255
6 8 1 0 6 758 6 707
6 326 6 281 6 237
5 906 5 867 5 829
5 539 5 505 5 471
5 216 5 185 5 155
4 928 4 901 4 874
4 647 4 623
4 671
4 439 4 418 4 396
4 230 4 210 4 191
4 040 4 022 4 004
3 867 3 850 3 834
3 708 3 6 9 3 3 678
3 562 3 548 3 534
3 427 3 414 3 401
3 302 3 290 3 278
3 187 3 175 3 164
3 079 3 069 3 058
2 979 2 969 2 959
2 885 2 876 2 867
2 .797 2 . 7 8 8 2 780
2 . 7 1 4 2 . 7 0 6 2 698
2 .637 2 . 6 2 9 2 622
2 .564 2 .557 2 .550
2 . 4 9 5 2 . 4 8 8 2 .481
2 . 4 3 0 2 . 4 2 3 2 .417
2 . 3 6 8 2 . 3 6 2 2 .356
2 . 3 0 9 2 . 3 0 4 2 .298
2 . 2 5 4 2 . 2 4 9 2 .243
2 .201
2 . 1 9 6 2 .191
2 . 151 2 . 1 4 6 2 . 141
2 . 1 0 3 2 .099 2 . 0 9 4
2 . 0 5 8 2 . 0 5 3 2 .049
2 .014 2 .010 2 .006
1 .965
1 .973
1 .969
1 .926
1 .929
1 .933
1 .888
1 .892
1 .895
1 .852
1 .859
1 .855
1 .817
1 .824
1 .821
1 .791
1 .787 1 .784
2. 0
3 8 . 411
26. 773
20 549
16 674
14 029
12 109
10 6 5 3
9 509
8 588
7 830
7 196
6 657
6 194
5 791
5 438
5 126
4 848
4 599
4 375
4 171
3 986
3 818
3 663
3 520
3 389
3 267
3 153
3 048
2 950
2 858
2 771
2 691
2 614
2 .543
2 .475
2 .411
2 .350
2 .292
2 .238
2 . 186
2 .137
2 .090
2 .045
2 .002
1 .961
1 .922
1 .884
1 .848
1 .814
1 .781
3 6 . 810
2 5 . 986
20 082
16. 3 6 5
13 8 1 0
11 946
10 526
9 408
8 506
7 762
7 138
6 607
6 151
5 754
5 405
5 096
4 822
4 575
4 353
4 152
3 969
3 802
3 648
3 507
3 376
3 255
3 143
3 038
2 940
2 849
2 763
2 683
2 607
2 536
2 468
2 404
2 344
2 287
2 .233
2 .181
2 .132
2 .085
2 .040
1 .998
1 .957
1 .918
1 .881
1 .845
1 .811
1 .778
35 338
2 5 . 244
19 636
16 068
13 598
11 787
10 402
9 309
8 425
7 695
7 081
6 559
6 109
5 717
5 372
5 068
4 796
4 552
4 332
4 133
3 952
3 786
3 633
3 493
3 363
3 243
3 132
3 028
2 931
2 840
2 755
2 675
2 600
2 529
2 462
2 398
2 338
2 281
2 .227
2 176
2 . 127
2 .080
2 .036
1 .993
1 .953
1 .914
1 .877
1 .841
1 .807
1 .774
of
2THETA
979
543
209
781
392
632
282
213
346
628
025
511
067
680
340
039
770
529
311
114
3 934
3 770
3 619
3 480
3 351
3 232
3 121
3 018
2 921
2 831
2 747
2 667
2 592
2 522
2 455
2 392
2 332
2 276
2 222
2 171
2 .122
2 .076
2 032
1 .989
1 .949
1 910
1 .873
1 .838
1 .804
1 .771
32 721
23 879
18 801
15 504
13 192
11 481
10 164
9 118
8 268
7 563
6 970
6 463
6 026
5 644
5 309
5 011
4 745
4 506
4 291
4 095
3 917
3 754
3 604
3 466
3 339
3 220
3 110
3 008
2 912
2 823
2 739
2 659
2 585
2 515
2 449
2 386
2 327
2 270
2 217
2 166
2 117
2 071
2 027
1 985
1 945
1 907
1 870
1 834
1 .801
1 .768
33
24
19
15
13
11
10
9
8
7
7
6
6
5
5
5
4
4
4
4
to
8
31
23
18
15
12
11
10
9
8
7
6
6
5
5
5
4
4
4
4
4
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1
1
1
1
553
251
409
237
999
334
048
025
192
500
916
417
985
609
277
983
720
484
270
077
900
739
590
453
326
209
100
998
903
814
730
652
578
508
442
380
321
265
212
161
113
067
023
981
941
903
866
831
797
765
CuKaIpha
51 . 9
, lambda = 1.5418A
.1
9
30
22
18
14
12
11
9
8
8
7
6
6
5
5
5
4
4
4
4
4
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1
1
1
1
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
465
655
034
979
810
191
936
934
117
437
862
371
946
574
246
955
695
462
250
058
883
723
576
440
314
198
089
988
894
805
722
644
571
501
436
374
315
259
206
156
108
062
019
977
937
899
863
828
794
762
1 .759
1.728
1 .698
1 .670
1.642
1 .616
1 .590
1 .566
1 .542
1 .519
1 .497
1 .475
1 .455
1 .435
1 .415
1 .397
1 .379
1 .361
1 .344
1 .328
1 .312
1 .296
1 .281
1 .266
1 .252
1 .238
1 .225
1 .212
1 .199
1 . 187
1 .175
1 . 163
1 . 152
1 .141
1 .130
1 .120
1.110
1 . 100
1 . 090
1 .081
1 .072
1 .063
1 .054
1 .046
1 .037
1 .029
1 .021
1 .014
1 .006
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
.755
.725
.695
.667
.639
.613
.588
.563
.539
.517
.495
.473
.453
.433
.414
.395
.377
.359
.342
.326
.310
.294
.279
.265
.251
.237
.224
.211
.198
.186
.174
1 . 162
151
140
129
1.119
1 .109
1 .099
1 .089
1 .080
1 .071
1 .062
1 .053
1 .045
1 .037
1 .029
1 .021
1 .013
http://jurassic.ru/
i l l l
52.0
.2
1 .752
1 .722
1 .692
1 .664
1 .637
1 .610
1.585
1 .561
1.537
1 .514
1 .492
1 .471
1 .451
1 .431
1 .412
1 .393
1 .375
1 .358
1 .341
1 .324
1 .308
1 .293
1 .278
1 .263
1 .249
1 .236
1 .222
1 .209
1 .197
1 . 185
1 .173
1.161
1 . 150
1 . 139
1 . 128
1 .118
1 . 108
1 .098
1 .088
1 .079
1 .070
1 .061
1 .052
1 .044
1.036
1 .028
1.020
1-.012
of
2THETA
to
.6
1 .749
1 .719
1 .689
1 .661
1 .634
1 .608
1 .583
1 .558
1 .535
1 .512
1 .490
1 .469
1 .449
1 .429
1 .410
1 .391
1 .373
1 .356
1 .339
1 .323
1 .307
1 .291
1 .277
1 .262
1 .248
1 .234
1 .221
1 .208
1 .196
1 .183
1 .172
1 . 160
1 . 149
1 . 138
1 . 127
1.117
1 . 107
1 .097
1 .087
1 .078
1 .069
1 .060
1 .052
1 .043
1 .035
1 .027
1 .019
1 .012
1 .746
1 .716
1 .687
1 .658
1 .631
1 .605
1 .580
1 .556
1 .533
1 .510
1 .488
1 .467
1 .447
1 .427
1 .408
1 .389
1 .372
1 .354
1 .337
1 .321
1 .305
1 .290
1 .275
1 .261
1 .247
1 .233
1 .220
1 .207
1 .194
1 . 182
1 .170
1 .159
1 .148
137
126
116
106
1 .096
1 .086
1 .077
1 .068
1 .059
1 .051
1 .042
1 .034
1 .026
1 .018
1 .011
1 .743
1 .713
1 .684
1 .656
1 .629
1 .603
1 .578
1 .554
1 .530
1 .508
1 .486
1 .465
1 .445
1 .425
1 .406
1 .388
1 .370
1 .352
1 .336
1 .319
1 .304
1 .288
1 .274
1 .259
1 .245
1 .232
1 .218
1 .206
1 . 193
1 .181
1 .169
1 .158
1 . 147
1 . 136
1 .125
1.115
1 . 105
1 .095
1 .085
1 .076
1 .067
1 .058
1 .050
1 .041
1 .033
1 .025
1.018.
1 .010
1 .740
1 .710
1 .681
1 .653
1 .626
1 .600
1 .575
1 .551
1 .528
1 .506
1 .484
1 .463
1 .443
1 .423
1 .404
1 .386
1 .368
1 .351
1 .334
1 .318
1 .302
1 .287
1 .272
1 .258
1 .244
1 .230
1 .217
1 .284
1 .192
1 .180
1 .168
1 .157
145
135
124
114
1 .104
1 .094
1 .085
1 .075
1 .066
1 .058
1 .049
1 .041
1 .032
1 .025
1 .017
1 .009
100.0
.9
1 .737
1 .707
1 .678
1 .650
1 .623
1 .598
1 .573
1 .549
1 .526
1 .503
1 .482
1 .461
1 .441
1 .421
1 .402
1 .384
1 .366
1 .349
1 .332
1 .316
1 .301
1 .285
1 .271
1 .256
1 .242
1 .229
1.216
1 .203
1 . 191
1 .179
1 .167
1 . 155
1 .144
1 . 134
1 .123
1.113
1 .103
1 .093
1 .084
1 .074
1 .065
1 .057
1 .048
1 .040
1 .032
1 .024
1 .016
1 .009
1 .734
1 .704
1 .675
1 .647
1 .621
1 .595
1 .570
1 .546
1 .523
1 .501
1 .480
1 .459
1 .439
1 .419
1 .400
1 .382
1 .365
1 .347
1 .331
1 .315
1 .299
1 .284
1 .269
1 .255
1 .241
1 .228
1 .215
1 .202
1 . 189
1 .177
1 .166
1 .154
1 .143
1 . 132
1 . 122
1.112
1 . 102
1 .092
1 .083
1 .073
1 .065
1 . 056
1 .047
1 .039
1 .031
1 .023
1 .015
1 .008
1 .731
1 .701
1 .672
1 .645
1 .618
1 .593
1 .568
1 .544
1 .521
1 .499
1 .478
1 .457
1 .437
1 .417
1 .399
1 .380
1 .363
1 .346
1 .329
1 .313
1 .298
1 .282
1 .268
1 .254
1 .240
1 .226
1 .213
1 .201
1 . 188
1 . 176
1 .165
1 .153
1 .142
1 . 131
1 .121
1.111
1 . 101
1 .091
1 .082
1 .073
1 .064
1 .055
1 .046
1 .038
1 .030
1 .022
1 .015
1 .007
199
200
(b) Conversion charts of 20 to angstroms (D-spacing) for cobalt Ka radiation

CoKalpha
0
51 . 288
3 4 . 194
2 5 . 648
2 0 . 521
17. 103
14. 662
1 2 . 832
11 . 409
10. 270
9 . 339
8. 563
7. 907
7 345
6 858
6 432
6 056
5 722
5 423
5 155
4 912
4 691
4 490
4 305
4 136
3 979
3 834
3 700
3 575
3 458
3 349
3 247
3 152
3 062
2 977
2 897
2 821
2 749
2 681
2 617
2 .556
2 .498
2 .442
2 .389
2 .339
2 .291
2 .245
2 .201
2 .158
2 .118
2 .079
4 8 . 846 4 6 . 626 44 599

3 3 . 091 3 2 . 058 31 086
2 5 . 0 2 3 2 4 . 427 23 859
2 0 . 119 1 9 . 732 19 360
1 6 . 8 2 3 1 6 . 552 16 289
14. 456 14. 255 14 060
12 674 12 519 12 369
11 283 11 161 11 041
10 169 10 069 9 972
9 255 9 173 9 092
8 493 8 423 8 355
7 847 7 788 7 729
7 293 7 242 7 191
6 812 6 768 6 724
6 392 6 353 6 314
6 021 5 986 5 952
5 691 5 660 5 629
5 395 5 367 5 340
5 129 5 104 5 079
4 889 4 866 4 843
4 670 4 649 4 629
4 471 4 452 4 433
4 288 4 270 4 253
4 119 4 103 4 087
3 964 3 949 3 934
3 820 3 807 3 793
3 687 3 674 3 662
3 5 6 3 3 551 3 539
3 447 3 436 3 425
3 339 3 329 3 318
3 238 3 2 2 8 3 218
3 142 3 133 3 124
3 0 5 3 3 044 3 036
2 968 2 960 2 952
2 889 2 881 2 873
2 814 2 806 2 799
2 742 2 735 2 729
2 675 2 668 - 2 662
2 611 2 605 2 598
2 .550 2 .544 2 .538
2 . 4 9 2 2 .486 2 .481
2 .437 2 .432 2 . 4 2 6
2 . 3 8 4 2 .379 2 .374
2 . 3 3 4 2 .329 2 .324
2 . 2 8 6 2 .281 2 .277
2 . 2 4 0 2 . 2 3 6 2 .231
2 . 1 9 6 2 .192 2 . 188
2 . 1 5 4 2 . 1 5 0 2 . 146
2 . 114 2 . 1 1 0 2 . 106
2 . 0 7 5 2 .072 2 .068
2.0
5
4
42 741
30 172
23 317
19 002
16 035
13 871
12 222
10 924
9 876
9 012
8 288
7 672
7 142
6 681
6 276
5 918
5 599
5 313
5 055
4 821
4 608
4 414
4 236
4 071
3 920
3 779
3 649
3 527
3 414
3 308
3 208
3 115
3 027
2 944
2 866
2 792
2 722
2 655
2 592
2 532
2 475
2 421
2 369
2 319
2 272
2 227
2 .184
2 .142
2 .102
2 064
41
29
22
18
15
13
12
10
9
8
8
7
7
6
6
5
5
5
5
4
4
4
4
4
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
032
311
799
656
789
686
078
809
782
934
222
615
093
638
238
884
569
286
030
799
588
395
219
056
905
766
636
516
403
298
199
106
018
936
858
785
715
649
586
526
470
416
364
315
268
222
179
138
098
060
of
6
39
28
22
18
15
13
11
10
9
8
8
7
7
6
6
5
5
5
5
4
4
4
4
4
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
454
497
304
324
550
506
938
697
690
857
157
560
044
595
201
851
539
259
006
777
568
377
202
040
891
753
624
504
392
287
189
097
010
928
851
778
708
642
580
521
464
410
359
310
263
218
175
134
094
057
2THETA
7
37
27
21
18
15
13
11
10
9
8
8
7
6
6
6
5
5
5
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
993
727
830
002
318
331
801
587
600
782
093
505
997
554
164
818
509
232
982
755
548
359
185
025
877
739
612
493
381
277
180
088
002
920
843
770
701
636
574
515
459
405
354
305
258
214
171
130
091
053
to
8
36
26
21
17
15
13
11
10
9
8
8
7
6
6
6
5
5
5
4
4
4
4
4
4
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
636
997
375
692
093
160
667
479
511
708
030
451
950
512
127
786
480
206
958
734
529
341
168
009
862
726
599
481
371
267
170
079
993
912
836
763
695
630
568
509
453
400
349
300
254
209
167
126
087
049
CoKalpha
51.9
35
26
20
17
14
12
11
10
9
8
7
7
6
6
6
5
5
5
4
4
4
4
4
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
373
305
939
393
874
994
536
374
424
635
968
397
903
472
091
754
452
180
935
712
509
323
152
994
848
713
587
470
360
257
161
070
985
904
828
756
688
623
562
503
448
395
344
296
249
205
163
122
083
046
http://jurassic.ru/
i
, Iambda = 1.7902A
2 042
2 006
1 972
1 939
1 907
1 876
1 846
1 818
1 790
1 764
1 738
1 713
1 689
1 666
1 643
1 622
1 601
1 580
1 561
1 541
1 523
1 505
1 487
1 470
1 454
1 438
1 422
1 407
1 393
1 378
1 364
1 351
1 338
1 325
1 312
1 300
1 289
1 277
1 266
1 255
1 244
1 234
1 224
1 214
1 204
1 .195
1 .186
1 177
1.168
2 038
003
1 968
1 935
1 903
1 873
1 843
1 815
1 788
1 761
1 735
1 711
1 687
1 664
1 641
1 620
1 599
1 578
1 559
1 540
1 521
1 503
1 486
1 469
1 452
1 436
1 421
1 406
1 391
1 377
1 363
1 350
1 336
1 324
1 311
1 299
1 287
1 276
1 265
1 254
1 243
1. 233
1 223
1 213
1 204
.1 . 1 9 4
t .185
1 .'176
CM
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
, lambda = 1.7902A
.2
2.035
1 .999
1 .965
1 .932
1 .900
1 .870
1 .840
1 .812
1 .785
1 .758
1 .733
1 .708
1 .684
1 .661
1 .639
1 .617
1 .597
1 .576
1 .557
1 .538
1 .519
1 .501
1 .484
1 .467
1 .451
1 .435
1 .419
1 .404
1 .390
1 .375
1 .362
1 .348
1 .335
1 .322
1 .310
1 .298
1 .286
1 .275
1 .264
1 .253
1 .242
1 .232
1 .222
1.212
1 .203
1 . 193
1,184
1 .175
52.0
of
2THETA
.4
.5
.6
.7
2 031
1 .996
1 962
1 929
1 897
1 867
1 838
1 809
1 782
1 756
1 730
1 706
1 682
1 659
1 637
1 615
1 595
1 574
1 555
1 536
1 517
1 500
1 482
1 465
1 449
1 433
1 418
1 403
1 388
1 374
1 360
1 347
1 334
1 321
1 309
1 297
1 285
1 274
1 263
1 252
1 241
1 231
1 221
1 211
1 202
1 192
1 183
1 175
2 027
1 .992
1 .958
1 .926
1 894
1 864
1 835
1 .807
1 .779
1 753
1 728
1 703
1 680
1 657
1 635
1 613
1 592
1 572
1 553
1 534
1 516
1 498
1 480
1 464
1 447
1 432
1 416
1 401
1 387
1 373
1 359
1 346
1 333
1 320
1 308
1 296
1 284
1 273
1 261
1 251
1 240
1 230
1 220
1 210
1 201
1 191
1 182
1 174
2 .024
1 .989
1 .955
1 .922
1 .891
1 .861
1 .832
1 .804
1 .777
1 .751
1 .725
1 .701
1 .677
1 .655
1 .633
1 611
1 590
1 570
1 551
1 532
1 514
1 496
1 479
1 462
1 446
1 430
1 415
1 400
1 385
1 371
1 358
1 344
1 331
1 319
1 306
1 294
1 283
1 271
1 260
1 250
1 239
1 229
1 219
1 209
1 200
1 191
1 182
1 173
2 .020
1 .985
1 .952
1 .919
1 .888
1 .858
1 .829
1 .801
1 .774
1 .748
1 .723
1 699
1 675
1 .652
1 630
1 609
1 588
1 568
1 549
1 530
1 512
1 494
1 477
1 460
1 444
1 428
1 413
1 398
1 384
1 370
1 356
1 343
1 330
1 317
1 305
1 293
1 282
1 270
1 259
1 249
1 238
1 228
1 218
1 208
1 199
1 190
1 181
1 172
2 .017
1 .982
1 .948
1 .916
1 .885
1 .855
1 .826
1 .798
1 .771
1 .746
1 .720
1 .696
1 .673
1 .650
1 .628
1 .607
1 .586
1 .566
1 .547
1 528
1 510
1 493
1 475
1 459
1 443
1 427
1 412
1 397
1 382
1 368
1 355
1 342
1 329
1 316
1 304
1 292
1 280
1 269
1 258
1 247
1 237
1 227
1 217
1 207
1 198
1 189
1 180
1 171
to
.8
100.
.9
2 .013 2 .010
1 .978 1 .975
1 .945 1 .942
1 .913 1 .910
1 .882 1 .879
1 .852 1 .849
1 . 8 2 3 1 .821
1 .796 1 .793
1 .769 1 .766
1 .743 1 .740
1 .718 1 .716
1 . 6 9 4 1 .691
1 .671
1 .668
1 .648 1 .646
1 .626 1 .624
1 .605 1 .603
1 .584 1 .582
1 .564 1 .563
1 .545 1 .543
1 .527 1 .525
1 508 1 507
1 491
1 489
1 474 1 472
1 457 1 456
1 441
1 439
1 425 1 424
1 410
1 409
1 395 1 394
1
381 1 380
1 367 1 366
1 354
1 352
1 340 1 339
1 327 1 326
1 315 1 314
1 303 1 302
1 291
1 290
1 279 1 278
1 268
1 267
1 257 1 256
1 246
1 245
1 236 1 235
1
226 1 225
1 216 1 215
1 206
1 .205
1 . 197 1 .196
1 188 1 .187
1 .179 1 .178
1 .170 1 .169
201
202
R.G. HARDY and M.E. T U C K E R
203
(c) Conversion charts of 28 to angstroms (D-spacing) for chromium Ka radiation

CrKalpho)
0
57. 073
3 9 . 781
3 0 . 533
24. 775
20 845
17 9 9 3
15 828
14 129
12 761
11 635
10 692
9 891
9 203
8 605
8 088
7 616
7 283
6 833
6 500
6 198
5 923
5 672
5 442
5 230
5 035
4 854
4 686
4 529
4 383
4 246
4 118
3 998
3 885
3 778
3 677
3 582
3 492
3 406
3 .325
3 .248
3 .175
3 .105
3 .038
2 .974
2 .914
2 .855
2 .800
2 .746
2 .695
2 .646
5 4 . 695
3 8 . 611
2 9 . 839
2 4 . 316
20 520
17 750
15 640
13 979
12 638
11 5 3 3
10 606
9 818
9 139
8 549
8 031
7 573
7 164
6 798
6 468
6 169
5 897
5 649
5 420
5 210
5 016
4 836
4 669
4 514
4 369
4 233
4 106
3 986
3 874
3 768
3 667
3 573
3 483
3 398
3 317
3 241
3 168
3 098
3 .032
2 .968
2 .908
2 .850
2 .794
2 .741
2 .690
2 .641
5 2 . 508
3 7 . 508
2 9 . 176
23 874
20 205
17 514
1 5 . 456
13 8 3 3
12 518
11 433
10 522
9 745
9 077
8 494
7 983
7 530
7 126
6 764
6 437
6 141
5 871
5 625
5 399
5 190
4 998
4 819
4 653
4 499
4 355
4 220
4 093
3 975
3 863
3 757
3 658
3 564
3 474
3 390
3 309
3 233
3 160
3 091
3 025
2 962
2 902
2 .844
2 .789
2 .736
2 .685
2 .637
5 0 489
36 467
28 542
23 448
19 899
17 284
15 277
13 689
12 401
11 335
10 438
9 674
9 015
8 440
7 935
7 487
7 088
6 730
6 406
6 113
5 846
5 601
5 377
5 170
4 979
4 802
4 637
4 484
4 341
4 207
4 081
3 963
3 852
3 747
3 648
3 554
3 466
3 382
3 302
3 226
3 153
3 084
3 019
2 956
2 896
2 .838
2 .784
2 .731
2 .680
2 .632
2THETA
7
48
35
27
23
19
17
15
13
12
11
10
9
8
8
7
7
7
6
6
6
5
5
5
5
4
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
619
482
935
037
602
059
102
548
285
238
357
604
954
387
888
445
050
696
376
085
820
578
356
150
961
785
622
469
327
194
069
952
841
737
638
545
457
373
294
218
146
078
012
958
890
833
778
726
675
627
51 . 9
to
883
548
354
641
314
841
930
418
172
143
276
535
894
334
841
484
813
662
345
058
795
555
334
131
943
768
606
455
313
181
057
940
830
727
629
536
448
365
286
211
139
071
086
944
884
827
773
721
670
622
45
33
26
22
19
16
14
13
12
11
10
9
8
8
7
7
6
6
6
6
5
5
5
5
4
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
, lambda = 2.2909A
8
46
34
27
22
19
16
14
13
12
11
10
9
8
8
7
7
7
6
6
6
5
5
5
5
4
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
CrKalpha
52
53
54
55
56
57
58
59
68
61
62
63
64
65
66
67
68
69
78
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
98
91
92
93
94
95
96
97
98
99
100
267
663
796
257
035
628
763
275
860
050
197
466
834
282
795
363
977
629
315
030
770
532
313
111
925
751
590
440
300
168
045
929
820
717
619
527
440
357
278
204
132
064
000
938
878
822
767
715
666
618
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1
613
567
523
481
440
401
363
326
291
257
224
192
162
132
103
075
048
022
997
973
949
926
903
882
1 861
1 840
820
1 801
1 782
1 764
1 746
1 729
712
1 695
1 680
664
1 649
1 634
1 620
1 606
1 592
579
1 566
1 554
541
1 529
1 518
1 506
1.494
11
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
608
563
519
477
436
397
359
323
287
254
221
189
159
129
108
073
046
020
995
970
1 946
923
1 901
1 879
1 858
838
1 818
1 799
1 780
1 762
1 744
1 727
710
694
1 678
1 663
1 647
633
1 618
1 605
1 591
1 578
1 565
1 552
548
528
51 /
505 .
1
1
1
52.0
2THETA
.3
.4
.5
.6
.7
604
558
514
472
432
393
355
319
284
250
218
186
156
126
098
070
043
017
992
968
944
921
1 899
1 877
1 856
1 836
1 816
1 797
1 778
1 760
1 742
725
1 709
1 692
676
1 661
646
1 631
1 617
603
1 598
1 577
564
1 551
1 539
527
1. 515
584 .
2 .599
2 .554
2 518
2 .468
2 428
2 389
2 352
2 315
2 281
2 247
2 214
2 183
2 153
2 123
2 895
2 067
2 840
2 015
1 990
1 965
1 942
1 919
1 897
1 875
1 854
1 834
1 814
1 795
1 776
1 758
1 741
1 724
1 707
1 691
1 675
1 659
1 644
1 630
1 616
1 602
1 588
1 575
1 562
1 550
1 538
1 526
1 514
1 503
2 .594
2 .549
2 .506
2 .464
2 .424
2 .385
2 348
2 .312
2 277
2 244
2 .211
2 180
2 150
2 120
2 092
2 064
2 038
2 012
1 987
1 963
1 939
1 917
1 895
1 873
1 852
1 832
1 812
1 793
1 775
1 757
1 739
1 722
1 705
1 689
1 673
1 658
1 643
1 628
1 614
1 608
1 587
1 574
1 561
1 .549
1 .537
1 .525
1 .513
1 .582
2 .598
2 .545
2 .502
.460
2 .420
.381
2 .344
2 .308
2 .274
2 .240
2 .208
2 .177
2 .147
2 .117
2 .089
2 062
2 835
2 010
1 985
961
1 937
1 914
1 892
1 871
1 850
830
810
791
773
1 755
1 737
720
1 704
687
1 672
656
642
627
613
599
586
573
560
1 547
.
1 .535
1 524
.
1 .512
501
2.585
2.540
2.497
2.456
2.416
2.378
2.341
2.305
2.270
2.237
2.205
2 . 174
2 . 144
2.115
2.086
2.059
2.033
2.007
1 .982
1 .958
1 .935
1 .912
1 .890
1 .869
1 .848
1 .828
1 .808
1 .789
1 .771
1 .753
1 .736
1 .719
1 .702
1 .686
1 .670
1 .655
1 .640
1 .626
1 .611
1 .598
1 .584
1 .571
1 .559
1 .546
1 .534
1 .522
1 .511
1 .500
2.581
2.536
2.493
2.452
2.412
2.374
2.337
2.301
2.267
2.234
2.202
2 . 171
2.141
2.112
2.084
2.056
2.030
2.005
1 .980
1 .956
1 .933
1 .910
1 .888
1 .867
1 .846
1 .826
1 .807
1 .788
1 .769
1 .751
1 .734
1 .717
1 .700
1 .684
1 .669
1 .653
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1 1 1
1 1
1
1 1
1
1
1
1 11 1
1
1 1
CM
6 5 . 6 3 3 6 2 . 508 5 9 . 667
4 3 . 7 5 8 4 2 . 347 41 . 0 2 4
3 2 . 821 3 2 . 021 31 . 259
2 6 . 2 6 0 2 5 . 746 2 5 . 251
21 . 887 21 . 528 21 . 181
1 8 . 7 6 3 18. 499 18. 242
1 6 . 421 16. 218 16. 021
1 4 . 599 14. 439 14. 2 8 3
1 3 . 143 1 3 . 0 1 3 12. 8 8 6
11 . 951 11 . 844 11 . 738
1 0 . 9 5 8 18. 868 10 7 7 9
1 0 . 119 10. 042 9 966
9 . 399 9 . 333 9 267
8 . 776 8 . 718 8 661
8 230 8 180 8 129
7 750 7 705 7 660
7 322 7 282 7 242
6 9 4 0 6 904 6 868
6 596 6 564 6 532
6 286 6 256 6 227
6 8 8 3 5 976 5 950
5 7.45 5 721 5 697
5 589 5 487 5 464
5 292 5 271 5 251
5 892 5 073 5 054
4 987 4 889 4 871
4 735 4 718 4 702
4 575 4 559 4 544
4 426 4 411 4 397
4 286 4 273 4 259
4 156 4 143 4 131
4 8 3 3 4 021 4 009
3 918 3 907 3 896
3 809 3 799 3 788
3 .707 3 .697 3 687
3 . 6 1 0 3 .601 3 591
3 . 5 1 8 3 .509 3 501
3 . 4 2 3 3 415
3 .431
3 . 3 4 9 3 .341 3 . 3 3 3
3 .263 3 .256
3 .271
3 . 1 9 6 3 . 189 3 . 1 8 2
3 . 1 2 5 3 .118 3 . 1 1 2
3 . 0 5 8 3 .051 3 . 0 4 5
2 . 9 9 3 2 .987 2 .981
2 .932 2 .926 2 .928
2 . 8 7 3 2 .867 2 .861
2 . 8 1 6 2 .811 2 . 8 0 5
2 . 7 6 2 2 .757 2 . 7 5 2
2 . 7 1 0 2 .705 2 . 7 0 0
2 .656 2 .651
2 .661
of
CM
2
3
4
5
6
7
8
9
18
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
2 0
I ambda = 2 .2909A
111
1
1
1
111
111 .
11 .
1.
1
1
1
1
1
1
.8
2.576
2.532
2.489
2.448
2.408
2.370
2.333
2.298
2.264
2.230
2.199
2.168
2.138
2.109
2.081
2.054
2.027
2.002
1 .977
1 .953
1 .930
1 .908
1 .886
1 .865
1 .844
1 .824
1 .805
1 .786
1 .767
1 .749
1 .732
1 .715
1 .699
1 .683
1 .667
1 .652
1 .637
. 6.2643 91 . 6 2 3
1 .609
. 5.9661 01 . 5 9 5
. 5 8 3 1 .582
1 .569
. 5.5577 01 . 5 5 6
1 .544
. 5.3534 51 .532
.521 1 . 5 2 0
1 .509
. 4 9 9 1 .497
1
1
1
1
.510
1
to
1
.9
2.572
2.527
2.485
2.444
2.404
2.366
2.330
2.294
2.260
2.227
2.195
2 . 165
2 . 135
2.106
2.078
2.051
2.025
2.000
1 .975
1 .951
1 .928
1 .906
1 .884
1 .863
1 .842
1 .822
1 .803
1 .784
1 .766
1 .748
1 .730
1 .714
1 .697
1 .681
1 .666
1 .650
1 .636
1 .621
1 .607
1 .594
1 .580
1 .567
1 .555
1 .543
1 .531
1 .519
1.507
1 .496
http://jurassic.ru/
.III
lUUUliUlllllllliI.
illllll
204
(a)
X-RAY POWDER DIFFRACTION 2 0 5
Peak position = maximum intensity = 2 0
Measure mid-point
at i height
.26
(b)
of ragged p e a k s (Fig. 7.13b) and overlapping p e a k s

(Fig. 7.13c). A reasonably successful m e t h o d of
estimating t h e position of a ragged p e a k is to t a k e
t h e mid-point position at 2/3 of t h e height a b o v e
background. O n e should bear in mind, however, that
t h e reason that t h e p e a k is ragged in the first place
is likely to be related to a poorly defined crystal
structure. Overlapping p e a k s can b e d e c o n v o l u t e d
by graphical or c o m p u t a t i o n a l m e a n s , but in practice
a visual estimate of t h e position of the m a x i m a is
a d e q u a t e for qualitative analysis if o n e bears in mind
t h e t e n d e n c y of t h e p e a k s t o m o v e towards a com
m o n 'centre of gravity'.
I n s t r u m e n t a l conditions also play a n i m p o r t a n t
role in t h e correct m e a s u r e m e n t of p e a k position.
A s t h e time constant is a pulse averaging circuit, if a
large value of t h e time constant is used t o g e t h e r with
a fast scanning s p e e d , errors will result d u e t o t h e
formation of asymmetric p e a k s , in which t h e p o i n t
of greatest intensity is shifted t o a higher value of 2 0 .
Generally the p r o d u c t of t h e time constant and t h e
scanning speed is k e p t as low as possible, b u t is
never greater t h a n 4.
T h e diffraction angles (20) of t h e p e a k s a r e con
verted to lattice spacings (d) by m e a n s of conversion
tables (Fang & Bloss, 1966), by conversion charts
(Parrish & M a c k , 1963) or by c o m p u t i n g into a
X
calculator/computer t h e e q u a t i o n d = - . T a b l e
2 sin 0
7.2 shows 20 t o lattice spacing conversion tables for
c o p p e r Koc, cobalt Ka and c h r o m i u m Ka radiations.
T h e lattice spacings (d) a r e in angstroms (A), still
c o m m o n l y u s e d by X-ray mineralogists, t h o u g h t h e
n a n o m e t e r ( n m ) is t h e technically correct SI unit.
O n c e all p e a k s h a v e b e e n m e a s u r e d t o g e t h e r with a n
estimate of their relative intensities, it only remains
to assign t h e m t o mineral p h a s e s .
n
Apparent maxima can be

shifted towards each other
due to overlap
26
20,
(c)
Fig. 7.13. (a) Definition of a peak on an X-ray chart

record, (b) Ragged X-ray diffraction peak,
(c) Overlapping X-ray diffraction peaks.
A s all minerals and i n d e e d all crystalline materials

possess a u n i q u e X-ray diffraction p a t t e r n , a com
parison of diffraction p a t t e r n s of u n k n o w n mineral
phases with a set of standard p a t t e r n s will lead to
their identification. This m e t h o d is very similar to
h u m a n fingerprint identification. T h e s e standard
p a t t e r n s have b e e n compiled by a n international
organization called t h e Joint C o m m i t t e e on P o w d e r
Diffraction S t a n d a r d s ( J C P D S ) , which collects and
u p d a t e s p o w d e r diffraction d a t a . In principle, by a
systematic searching of t h e J C P D S P o w d e r Diffrac
tion Index for Minerals, it is possible to identify
almost any mineral that may be p r e s e n t , provided
that sufficient p e a k s a r e present for that mineral
(usually a m i n i m u m of t h r e e ) . This o p e r a t i o n can of

course, b e carried out by c o m p u t e r s and the J C P D S
provide just such a commercially available c o m p u t e r
system. F o r further information contact J C P D S
I n t e r n a t i o n a l C e n t r e for Diffraction D a t a , 1601 P a r k
L a n e , S w a r t h m o r e , Pennsylvania, P A 19081, U S A .
F o r sediments, h o w e v e r , the total n u m b e r of
possibilities is fairly limited, and can be limited
further if o n e has s o m e idea of its p r o v e n a n c e . With
this knowledge a reverse search of t h e Index, begin
ning with t h e most likely minerals and eliminating
the p e a k s as they are identified, is a useful short-cut.
Alternatively o n e can m a k e u p a t e m p l a t e on chart
r e c o r d e r p a p e r , of t h e diffraction patterns of com
m o n l y - e n c o u n t e r e d minerals, and t h e n use this as an
overlay for t h e u n k n o w n chart records. B r o w n &
Brindley (1980, table 5.18, p p . 3 4 8 - 3 5 5 ) c o m p u t e d
a c o m p r e h e n s i v e table of consecutive lattice spacings
for t h e c o m m o n clay and sedimentary minerals.
T a b l e 7.3 lists the main diffraction spacings of s o m e
selected minerals likely to occur in sediments to
gether with their relative intensities ( / / / , ) , hkl values
and 20 conversion angles for Cu and C o Ka
radiations.
7.3.3 Quantitative analysis

A s t h e intensity of t h e diffraction p a t t e r n (generally
estimated either as p e a k height or preferably p e a k
a r e a ) of a mineral in a mixture is proportional t o its
c o n c e n t r a t i o n , it is possible to m a k e r o u g h estimates
of t h e relative p r o p o r t i o n s of t h e minerals in a
sample by m e a s u r i n g their relative p e a k heights or
areas. This m e t h o d , h o w e v e r , is unreliable d u e to
t h e different 'diffracting abilities' of minerals from
different crystal systems. A n e x a m p l e of this would
b e to c o m p a r e the intensities of halite (cubic system)
with illite (monoclinic system) which would be seen
to b e completely u n r e l a t e d .
Most ' q u a n t i t a t i v e ' systems of sediment analysis
d e p e n d u p o n t h e p r e p a r a t i o n of calibration curves.
This entails t h e m e a s u r e m e n t of t h e intensity of
selected diffraction lines plotted against t h e quanti
ties of the respective minerals in k n o w n mixtures.
Generally an internal s t a n d a r d is a d d e d in constant
a m o u n t to the k n o w n mixtures and u n k n o w n sam
ples t o c o m p e n s a t e for any errors introduced during
the sample p r e p a r a t i o n or caused by m a c h i n e drift,
etc. T h e internal s t a n d a r d m e t h o d has been used
widely since being described by A l e x a n d e r & Klug
(1948). V a r i o u s substances have b e e n p r o p o s e d as
http://jurassic.ru/
llliil
internal s t a n d a r d s . Generally it is a completely new

substance to t h e system, such as potassium perman
g a n a t e K M n 0 , halite N a C l , or cerium oxide C e 0 ,
but it is an a d v a n t a g e to have a substance which has
a similar r e s p o n s e to that of t h e analysed minerals.
Griffin (1954) used the mineral boehmite (y-AlOOH)
in his study of clay minerals because they both have
a similar response to X-rays.
T h e principal alternative to t h e addition of an
internal standard is to use a mineral already present
in t h e sample (e.g. q u a r t z ) as t h e internal standard.
A relatively simple version of this latter m e t h o d
(after H o o t o n & G i o r g e t t a , 1977) is r e c o m m e n d e d
here.
T h e e q u a t i o n used is derived from t h e Klug &
A l e x a n d e r basic e q u a t i o n :
4
W,
T),7,p
K;
(1)
where
= intensity of diffraction p a t t e r n of com

p o n e n t i,
Kj = a constant d e p e n d i n g on t h e n a t u r e of
the c o m p o n e n t and t h e geometry of the
apparatus,
W; = weight fraction of c o m p o n e n t i in the
sample,
r), = density of c o m p o n e n t ,
Pn, = mass absorption of the total sample.
A s T), and K a r e b o t h constant for any mineral (in a
given instrument) they can b e r e p r e s e n t e d in t h e
e q u a t i o n by t h e symbol H giving
t
(2)
If all c o m p o n e n t s are t a k e n into account, e q u a t i o n
(2) b e c o m e s 1LW = u ^ E F L I i = 1 the sum of all
t h e weight fractions.
t
Rearranging: ^
= " E r r y and substituting into

in
e q u a t i o n (2)
w. =
HiIi
(3)
T h e m e t h o d can b e simplified by determining rela

tive H values instead of absolute values, i.e. to select
o n e mineral as a reference s t a n d a r d , in this case,
quartz. If e q u a t i o n (2) is n o w rewritten as
W M I N
^ M I N ^ M I N M T H
(unknown component)
^QUARTZ
^QUARTZ ^QUARTZ Mm
(reference c o m p o n e n t ) .
206
Table 7.3. Dominant X-ray diffraction peaks of selected minerals likely to occur in sediments in order of decreasing
intensities (I/h) including 26 angles for Cu and Co Ka radiations. Minerals are listed in order of decreasing d (A) value of
the most intense line (from JCPDS, 1974).
RECTORITE
Regular interstratified
mica - montmorillonite
d(k)
Ilh
hkl
24.7
100
001
12.4
50
002
3.10
18
008
4.94
8
005
1.902
4
0013
Table 7.3.
(Continued)
CHLORITE
d(k)
Penninite
Hh
hkl
7.19
100
002
4.80
100
003
3.60
100
004
14.3
60
001
2.88
60
005
2.56
40
132
20
26 o
12.31
14.30
18.48
21.49
24.73
28.79
6.18
7.18
31.05
36.21
35.05
40.93
3.54
2
007
C u
26
C u
26
c
SMECTITE
d(k)
Saponite
Vh
hkl
3.58
4.15
15.7
100
001
7.13
8.28
4.58
100
020
28.79
33.56
2.56
100
200
17.95
20.88
1.53
100
060
47.82
56.15
3.63
60
004
25.16
29.30
KAOLINITE
d(k)
2.95
60
005
Hh
hkl
7.17
100
001
26
26
12.34
14.34
62.36
73.90
7.07
100
002
14.1
90
001
12.52
14.55
6.27
7.28
25.15
29.28
Hh
hkl
6.26
100
020
3.29
90
120
2.47
80
031
26
26
14.15
16.44
27.10
31.57
36.37
42.49
46.90
55.05
52.86
62.24
4.53
100
020
15.0
90
002
4.97
75
006
30.0
60
001
2.54
50
19.60
22.79
5.89
6.84
17.85
20.75
2.94
3.42
34.34
41.27
Hh
hkl
4.18
100
110
2.69
30
130
26
26
21.25
24.73
33.31
38.87
C o
20
26
SMECTITE
Montmorillonite
C u
C o
d(k)
Hh
hkl
26
26
VERMICULITE
C u
C o
d(A)
I'h
hkl
5.63
6.54
15.0
100
001
5.89
6.84
14.2
100
002
19.38
22.54
4.50
80
020
19.73
22.95
1.528
70
060
35.05
40.93
5.01
60
003
17.70
20.58
4.57
60
020
60.51
71.61
3.02
60
005
29.58
34.48
2.615
50
200
24.52
28.55
1.50
50
060
61.85
73.27
2.570
50
132
30.30
35.33
CHLORITE
d(k)
Thuringite
Hh
hkl
1.493
50
62.17
73.67
LEPIDOCROCITE
2e
Cu
26
C o
d(k)
2.525
45
202
CORRENSITE
chloritemontmorillonite
26
C u
26
C u
d(k)
Hh
hkl
26
26
ILLITE
Cu
Co
d (A)
Hh
hkl
6.22
7.23
14.0
100
002
6.31
7.33
10.0
100
002
60.60
71.72
7.08
60
004
12.50
14.53
4.48
90
020
19.42
22.59
3.53
60
008
25.23
29.38
3.33
90
006
34.29
40.03
29.0
30
001
3.05
3.54
2.61
60
200
34.91
40.76
4.72
30
006
18.80
21.86
1.53
60
060
35.55
41.53
montmorillonite - chlorite
d(k)
Hh
hkl
4.62
30
020
19.21
22.34
26
26
GOETHITE
C u
C o
d(k)
2.42
40
133
C o
29cu
26 o
8.84
10.27
d(A)
9.97
100
003
MUSCOVITE
Hh
hkl
26
C u
2e
GYPSUM
Co
d (A)
8.87
10.30
7.56
100
020
26
26
11.70
13.60
C u
3.331
100
009
26.76
31.18
26.77
31.18
4.99
55
006
17.77
20.67
34.36
40.11
1.999
45
0015
45.37
53.20
60.51
71.61
2.564
25
112
35.00
40.86
37.15
43.42
ARAGONITE
d(k)
Hh
hkl
4.49
20
100
19.77
23.00
26
26
QUARTZ
3.059
55
141
29.19
34.03
4.27
50
121
20.80
24.20
2.679
28
022
33.44
39.04
2.867
25
002
31.20
36.38
3.79
20
031
C u
C o
d(k)
:
Hh
hkl
19.82
23.05
207
Hh
hkl
20 -
20<
c
23.47
27.32
http://jurassic.ru/
111
3.396
100
111
26.24
30.56
3.343
100
101
; 26.67
31.06
1.489
90
060
1.977
65
221
45.90
53.84
4.26
35
100
20.85
24.26
3.579
80
002
24.88
28.97
3.541
60
004
2.452
25
111
36.65
42.82
3.273
52
021
27.25
31.74
1.817
17
112
50.21
. 59.03
1.620
70
133
56.83
67.08
4.726
30
003
18.78
21.84
1.937
70
200
2.192
20
140
41.18
48.20
2.700
46
012
33.18
38.72
1.541
15
211
60.03
71.02
4.366
60
110
20.34
23.66
2.845
30
005
31.44
36.68
1.732
40
151
1.721
20
221
53.22
62.68
2.372
38
112
37.93
44.34
2.458
12
110
36.56
42.71
1.589
60
134
58.04
68.57
2.576
30
131
34.83
40.67
1.524
40
231
60.77
71.94
1.509
50
060
61.44
72.77
2.490
16
040
36.07
42.14
2.481
33
200
36.21
42.30
2.282
12
102
39.49
46.19
208
Table 7.3.
(Continued)
A = area
d(A)
ALKALI FELDSPAR
Orthoclase
ilh
hkl
26
C u
26
C o
3.31
100
220
3.77
80
130
4.22
70
201
3.24
65
002
3.29
60
202
26.94
31.38
23.60
27.47
21.05
24.49
27.53
32.07
27.10
31.57
2.992
50
131
counts not only d u e to t h e p e a k intensity, but also

t h e b a c k g r o u n d . T h e b a c k g r o u n d counts a r e esti
m a t e d by fixed counting at each of the positions 2 0 !
and 2 0 , for exactly half t h e total time of t h e inte
grated scan. T h e sum of these two readings equals
t h e background N which is substracted from JV t o
give t h e n u m b e r of counts of the integrated p e a k ,
i.e. N 7V = A R E A .
H o w e v e r , if a digital counter is n o t available
either a simple polar planimeter can be u s e d or a
simple geometrical calculation can be m a d e , i.e.
p e a k height above background multiplied by t h e
width at half p e a k height b o t h p r o d u c e reason
able estimates of area. In certain cases the use of
p e a k heights is u n a v o i d a b l e , especially w h e r e par
tially overlapping p e a k s m a k e area m e a s u r e m e n t s
difficult (Fig. 7.14b). T h e r e a r e mathematical tech
niques available using c o m p u t e r p r o g r a m s which can
separate overlapping p e a k s ; an example of this
m e t h o d using L o r e n z i a n profile calculations is given
in M a r t i n e z & Plana (1987).
2
29.86
34.82
d(A)
PLAGIOCLASE FELDSPAR
Albite
Hh
hkl
20
26co
C u
d(A)
CALCITE
C u
C o
d(A)
DOLOMITE
Cu
C o
30.99
36.14
d(A)
Ilh
hkl
2.79
100
104
26
26
32.08
37.43
d(k)
llh
hkl
2.69
100
104
29cu
26
33.31
38.87
C o
3.780
25
111
23.54
27.40
2.285
18
113
39.43
46.12
2.192
30
CO
hkl
SIDERITE
29.43
34.31
2.886
100
104
///,
2G
26
27.92
32.53
3.035
100
104
Illi
hkl
26
26
3.196
100
002
41.18
48.20
1.734
80
018
52.79
62.16
6.39
20
001
13.86
16.10
2.095
18
202
43.18
50.59
1.786
30
009
51.14
60.16
3.684
20
130
24.16
28.12
1.913
17
108
47.53
55.80
1.804
20
018
50.60
59.50
4.03
16
201
22.06
25.67
3.663
16
130
201
24.30
28.29
2.495
14
110
48.55
57.03
36.00
42.05
2.015
15
202
1.389
15
030
44.99
52.75
3.59
60
012
0.931
70
3012
2.13
60
113
24.80
28.88
111.80
148.07
42.44
49.70
2.51
50
110
1.838
40
024
~J~
20 peak
207
(a)
1.875
17
116
C o
1.633
100
311
d(A)
PYRITE
Ilh
hkl
26
28
Dividing:
MIN
QUARTZ
C u
C o
56.34
66.48
'MIN
Hi
QUARTZ
QUARTZ
(4)
A series of binary calibration mixtures of q u a r t z

and o t h e r major sedimentary minerals can t h e n be
1.690
60
116
54.28
63.96
2.709
85
200
33.07
38.59
35.77
41.78
2.423
65
210
37.10
43.36
49.60
58.29
2.212
50
211
40.79
47.74
1.484
35
214
67.42
80.24
1.963
60
202
46.25
54.26
62.59
74.19
1.916
40 ,..
220
47.45
55.70
1.452
35
300
(b)
Fig. 7.14. Measurement of intensity of a diffraction peak
by integration of area, (a) Single peak, (b) Overlapping
peaks.
64.14
76.12
3.128
35
111
28.54
33.26
p r e p a r e d by accurate weighing and t h e intensities of

t h e chosen analytical p e a k s m e a s u r e d . C u r v e s can
t h e n be plotted, t h e slope of which gives / /
/
^ Q U A R T Z if we assume / / Q U A R T Z = 1; a series of H
values can t h e n be obtained for all t h e major sedi

m e n t a r y minerals which can t h e n be substituted
together with t h e intensities of t h e minerals into
equation (3).
T h e m e a s u r e m e n t of intensity in all quantitative
m e t h o d s is best d o n e using a digital counter and
integrating a whole a r e a of p e a k (Fig.-7.14a). This is
achieved by starting t h e counter and t h e X-ray scan
from position 2 0 s i m u l t a n e o u s ^ and allowing both
to run until position 2 0 is attained and then stop
ping t h e m simultaneously; the total integrated counts
(N{) and t h e time are t h e n recorded. N includes
t
M I N
http://jurassic.ru/
11
T h e r e a r e m a n y m o r e published m e t h o d s of quan
titative analysis b u t all suffer from similar p r o b l e m s
which affect t h e m e a s u r e m e n t of intensities, in par
ticular: (i) t h e crystallinity of s o m e species can vary
widely, e.g. micas, kaolinites (Fig. 7.15); (ii) chemi
cal variations, e.g. solid solution series, which can
cause p e a k shifts as well as varying intensities; (iii)
t h e ordering of t h e c o m p o n e n t chemical elements
within t h e structure, e.g. d o l o m i t e ; (iv) large mass
absorption differences b e t w e e n standards and u n
k n o w n samplers.
peak
HEMATITE
209
m m i i f mill
7.4 C L A Y M I N E R A L A N A L Y S I S
X R D provides t h e most efficient m e t h o d for t h e
d e t e r m i n a t i o n of clay minerals in m u d r o c k s , sand
stones and limestones. A knowledge of t h e clay
mineralogy can b e most useful for p r o v e n a n c e
studies and it can also give information o n t h e burial
history for t h e formation. A l t h o u g h s o m e clay
minerals are evident in whole rock diffractograms,
the most satisfactory m e t h o d is to extract and separ
ately analyse t h e clay fraction (usually defined as
less than 2 microns, < 2 urn). It is particularly impor
tant t o d o this in t h e case of very fine grained and
poorly crystalline clays, which are unlikely to give
recognizable diffraction patterns in a whole rock
scan. Also chemical p r e - t r e a t m e n t s are sometimes
210
211
Distilled water
Rock samples
^Jransdûcer^,
(a)
Power supply
Distilled water
Sample
Fig. 7.16. Ultrasonic disaggregation,

(a) Ultrasonic bath, (b) Ultrasonic
probe.
12
Degrees 2G
(b)
12
Degrees 26
(a)
(b)
Fig. 7.15. X-ray diffraction scans of the (001) lattice spacing of: (a) a well crystalline kaolinite from Cornwall; (b) a poorly
crystalline kaolinite from a fireclay from N England, using Cu Ka radiation and similar analytical conditions.
necessary to r e m o v e large a m o u n t s of certain nonclay and cementing materials and in so doing con
centrate t h e clay mineral fraction in t h e samples.
If high levels of c a r b o n a t e material are expected
this can be r e m o v e d by acid attack. H o w e v e r , cer
tain clay minerals, in particular chlorites and s o m e
smectites, are susceptible t o attack from dilute
mineral acids, e.g. dilute hydrochloric acid. Instead,
weak organic acids a r e r e c o m m e n d e d , in particular
t h e m e t h o d described by H e i n , Scholl & G u t m a c h e r
(1976) in which t h e samples are heated in a buffered
solution of sodium acetate and glacial acetic acid
( M o r g a n ' s solution).
Similarly, if large quantities of organic m a t t e r a r e
expected, this may be r e m o v e d by p r e - t r e a t m e n t
with 3 5 % hydrogen peroxide ( H 0 ) after Jackson
(1958, 1979). L a r g e amounts, of iron c o m p o u n d s
2
After t h e sample is disaggregated, the resulting

suspension should be transferred to a settling column
(e.g. a measuring cylinder) and allowed to stand for
an a p p r o p r i a t e time until t h e required size fraction
can b e r e m o v e d . Stokes' Law is used to calculate t h e
settling velocity (i>) of t h e clay particles:
may b e r e m o v e d using sodium dithionite ( N a S 0 )

together with a citrate-chelating agent after t h e
m e t h o d of M e h r a & Jackson (1960).
2
2ga\d
7.4.1 Separation
C o m p l e t e disaggregation is desirable before size
separation is a t t e m p t e d , and this is best effected by
ultrasonic m e a n s ( G i p s o n , 1963), although, for
poorly lithified samples, vigorous shaking with dis
tilled water will sometimes suffice. T h e sediments
should be b r o k e n (e.g. by percussion) to particles of
approximately 10 m m d i a m e t e r or less, placed in a
b e a k e r , covered with distilled water and immersed
in an ultrasonic bath (Fig. 7.16a). Alternatively, an
ultrasonic p r o b e can b e inserted into t h e b e a k e r
(Fig. 7.16b).
d)
2
w h e r e g is t h e acceleration d u e to gravity, a is t h e
sphere radius, d is t h e density of the particles, d
that of t h e settling m e d i u m (usually water) and u, its
viscosity. This law is empirical only, and applies t o
spherical particles in a non-turbulent m e d i u m at a
constant t e m p e r a t u r e , w h e r e t h e suspension is suffi
ciently dilute to avoid particleparticle interaction.
Because of the platey n a t u r e of clay particles, they
must b e regarded as having an equivalent spherical
d i a m e t e r (esd) w h e n applying Stokes' Law. A cen
trifuge may be used as an alternative to a settling
column, the effect being to increase t h e value of g in
the e q u a t i o n . T h e usual size fraction separated for
routine clay analysis is < 2 u m , and T a b l e 7.4 gives
1
http://jurassic.ru/
11J11111I11111111
settling times for this and o t h e r fractions using both

a settling column and a centrifuge. T h e m e t h o d as
described by G a l e h o u s e (1971) is r e c o m m e n d e d
here.
A major p r o b l e m in t h e separation of clays is
flocculation; this may be avoided in a n u m b e r of
ways: (i) by r e p e a t e d washing in distilled water t o
r e m o v e any electrolyte present; (ii) by t h e addition
of a deflocculant, commonly sodium h e x a m e t a p h o s
p h a t e solution (calgon); (iii) by t h e addition of
a m m o n i u m hydroxide N H O H .
In principle, any chemical additive, either as a
p r e - t r e a t m e n t or a deflocculant, is to be avoided,
however, since this may have an undesirable effect
on the clay minerals themselves.
4
7.4.2 Preparation
After extraction by p i p e t t e , at t h e required depth
from t h e measuring cylinder, the less than 2 um
fraction is p r e p a r e d for X R D analysis as an oriented
and also as an u n o r i e n t e d m o u n t . T h e r e are various
schools of thought on making oriented samples;
212
Table 7.4. (a) Pippette withdrawal times calculated from Stokes' Law for spherical particles (SG = 2.65) in a settling
column of water at different temperatures (after Galehouse, 1971)
Oriented clay
Pippetted
suspension
Temperature
Diameter in
micrometres
finer than
Withdrawal
depth
(cm)
62.5
44.2
20
20
31.2
22.1
15.6
7.8
3.9
1.95
0.98
0.49
10
10
10
10
5
5
5
5
20 s
1 m 54 s
Restir
1 m 54 s
3 m 48 s
7 m 36s
30 m 26 s
60 m 51s
4h3m
16 h 14 m
64h 54 m
20 s
1 m49s
Restir
1 m 49 s
3 m 37 s
7 m 15 s
28 m 59 s
57 m 58 s
3h52m
15 h 28 m
61 h 50 m
20 s
lm51s
Restir
1 m 51 s
3 m 42 s
7 m 25 s
29 m 41 s
59 m 23 s
3h58m
15 h 50 m
63 h 20 m
20 s
1 m46s
Restir
1 m46s
3 m 32 s
7m5s
28 m 18 s
56 m 36 s
3h46m
15h6m
60 h 23 m
20 s
1 m44s
Restir
1 m44s
3 m 27 s
6 m 55 s
27 m 39 s
55 m 18 s
3h41 m
14 h 45 m
48 h 59 m
20 s
1 m41 s
Restir
1 m41 s
3 m 22 s
6 m 45 s
27m I s
54 m 2s
3h36m
14 h 25 m
57 h 38 m
(b) Time required at various centrifuge speeds and temperatures for sedimentation of particles using a standard 100 ml
tube, 100 mm suspension depth, 90 mm of fall and 1000 mm (1 cm ) of sediment (from Jackson, Whitting & Pennington,
1950)
3
Limiting particle
diameter
(um)
5
2
0.2
Ceramic tile
Elapsed time for withdrawal of sample in hours (h), minutes (m), and seconds (s)
22
23
24
20
21
25
Density of
particles
gem"
3
2.65
2.65
2.50
t h r e e principal m e t h o d s are: (i) smearing t h e clay

slurry on to a solid substrate, e.g. a glass slide; (ii)
pipetting t h e clay suspension into a glass b e a k e r
containing a glass slide, then placing t h e b e a k e r in
an oven at 60C and allowing t h e distilled water to
e v a p o r a t e and t h e clays t o settle on to t h e slide; (iii)
sedimenting a suspension u n d e r a vacuum on to a
p o r o u s substrate, e.g. a ceramic tile (Fig. 7.17).
T h e objectives in t h e various m e t h o d s are to
achieve an orientation of the clay plates parallel to
the surface of t h e substrate, and to avoid differential
settling of t h e clay mineral species (average dia
m e t e r s of kaolinite particles, for example, tend to b e
larger than those of smectite).
Centrifuge
speed
(rpm)
300
750
2400
Centrifuge time in minutes

at two temperatures
20C
25C
3.3
3.3
35.4
2.9
2.9
31.4
This problem of differential settling of t h e less

than 2 urn fraction in t h e initial extraction stage can
cause serious p r o b l e m s , especially w h e r e quantita
tive results are being used to interpret or substan
tiate geological theories, and t h e p r o b l e m s a r e
discussed by T o we (1974).
U n o r i e n t e d samples a r e m o r e difficult to achieve.
In most cases, cavity m o u n t s are employed for bulk
analysis, and unfortunately pressure is usually applied
at s o m e point in o r d e r to fill t h e cavity. B e c a u s e of t h e
predominantly platey n a t u r e of clay particles, they
tend to reorient u n d e r pressure, and s o m e way must
be found to avoid this. T h e m e t h o d s r e c o m m e n d e d
are: (i) adding a material whose s h a p e will prevent
Vacuum p u m p
Fig. 7.17. Vacuum settling of pippetted suspension on to a

ceramic tile.
orientation but will not complicate the diffraction
p a t t e r n , e.g. non-crystalline; (ii) e m b e d d i n g t h e
sample in a resin (e.g. Araldite) and regrinding to
give approximately equal particles which will not
orient.
7.4.3 Qualitative analysis

F o r a comprehensive description of clay mineral
analysis by X R D t h e r e a d e r is referred to Carroll
(1970), T h o r e z (1974) and Brindley (1980). A large
p r o p o r t i o n of sediments, however, can be treated in
a fairly simple fashion by a combination of examin
ing t h e basal spacings on t h e oriented samples, and
t h e o t h e r lattice spacings on t h e unoriented samples.
T h e s e are summarized comprehensively in flowchart
form by Starkey, Blackmon & Hauff (1984), see
T a b l e 7.5, but t h e principal features are described
here.
After t h e sample has been air-dried, a p a t t e r n is
obtained from approximately 23420 with copper
radiation (Fig. 7.18). T h e four principal clay mineral
groups give t h e basal spacings: kaolinite: 7 A , illite:
10 A , smectite: 1215 A , chlorite: 14 A , and mixedlayer minerals at intermediate or higher values.
In o r d e r to distinguish smectite minerals from
chlorite, w h e r e a possible overlap occurs, the sam
ple is treated with an organic c o m p o u n d which
systematically intercalates itself into t h e lattice.
E t h a n e d i o l (ethylene glycol) is generally used for
this p u r p o s e , although glycerol may also be employ
ed. E t h y l e n e glycol has the effect of expanding
smectite t o a basal spacing of a b o u t - 1 7 A . T h e
213
m e t h o d described by B r u n t o n (1955) in which the

oriented slides a r e introduced into a desiccator con
taining half a pint (0.25 litre) of ethylene glycol,
instead of the usual drying agent, and then placing
t h e desiccator in an oven at 60C for about 4 hours is
recommended here.
F u r t h e r t r e a t m e n t involving heating t h e sample in
a furnace also helps to distinguish the individual
clays. H e a t i n g to 375C collapses smectite (and illitesmectites) to 10 A while leaving the other clays
unaffected. H e a t i n g to 550C destroys kaolinite and
certain chlorites. T h e effects of these tests on the
various clay minerals are summarized in T a b l e 7.6.
T h e distinction b e t w e e n t h e basal spacing of kao
linite at (7 A ) and the second-order chlorite reflec
tion also at 7 A is not satisfactorily d e t e r m i n e d by
heating to 550C. T h e p r o b l e m can be resolved by a
convenient m e t h o d suggested by Schultz (1964) w h o
dissolved the chlorite by HC1 t r e a t m e n t ( 6 N at 60C
for 16 h) before obtaining a n o t h e r diffractogram.
A n y remaining 7 A peak is therefore attributable to
kaolinite although, as certain chlorites are known to
offer variable resistance to acid attack ( K o d a m a &
O i n u m a , 1963), care must b e t a k e n .
T o d e t e r m i n e if a clay is a dioctahedral or trioctahedral-type, the d spacing of t h e (060) reflection is
recorded. If a dioctahedral clay is present the spacing
falls b e t w e e n the values 1.481.50 A , if the clay is
trioctahedral t h e spacing is 1 . 5 3 - 1 . 5 5 A . H o w e v e r ,
if several clays are p r e s e n t in a sample this becomes
a very difficult exercise.
Mixed-layer clays have spacings generally inter
m e d i a t e between those of their c o m p o n e n t s (Fig.
7.19) and an excellent t r e a t m e n t of this topic is
presented by Reynolds & H o w e r (1970) and Rey
nolds (1980). Of particular i m p o r t a n c e is the posi
tion of t h e basal spacing after glycolation of the
oriented m o u n t which, in t h e case of illite-montomorillonite mixed layer clays, occurs between 10
and 17 A , the exact position depending on the
composition of the mixed layering (Fig. 7.20). It
should b e n o t e d that regular interstratified mixed
layer clays give a rational sequence of higher orders
(see T a b l e 7.3) and randomly interstratified clays
give an irrational sequence (Fig. 7.19c, d ) .
For identification of m o r e complex phases, T a b l e
7.5 gives most of t h e necessary information. T o
obtain data on non-basal spacings, the unoriented
samples are used.
http://jurassic.ru/
214
R.G. HARDY a n d M.E. TUCKER
a.
< y
K Q
<
l l
-C
060 near 1.
<I
001's
<
060 near 1.'

hk bands pi
moderately
060 near 1.
in
060 near 1.
hk bands p
<
060 near 1 .
Check hkls
against sta
pu
Check hkls
against sta nd;
LLI
tttt r r T T r ^ s v
26
CuKa
Fig. 7.18. Diffractometer traces of a typical clay sample and component clay minerals (after Gibbs, 1967).
7.4.4 Quantitative analysis

T h e quantitative analysis of clays is subject t o simi
lar, b u t m o r e severe, p r o b l e m s as for whole-rock
analysis. T h e X-ray response for a particular clay
mineral is strongly d e p e n d e n t o n , a m o n g o t h e r
things, grain size, crystallinity, structure and chemi
cal composition. T h e p r o b l e m s have b e e n discussed
at length in t h e literature: J o h n s , G r i m & Bradley
(1954), Schultz (1960), Bradley & G r i m (1961),
Hinckley (1963), Gibbs (1967) a n d Carroll (1970),
etc., and calculations o r assumption of 'diffracting
ability' factors a n d crystallinity indexes t o correct
t h e m e a s u r e d intensities have been p r o p o s e d with

varying degrees of success.
F o r rapid, reproducible semi-quantitative results,
expecially w h e r e large n u m b e r s of samples a r e in
volved, m e t h o d s proposed by Schultz (1964), Biscaye
(1965) and Weir, O r m e r o d & El-Mansey (1975) a r e
particularly useful for comparative p u r p o s e s . In
these m e t h o d s t h e intensitites of t h e individual clay
c o m p o n e n t s a r e m e a s u r e d o n an oriented m o u n t ,
after various t r e a t m e n t s (air dried, glycol solvated,
and heating t o 375 a n d 550C in o r d e r t o isolate t h e
clay c o m p o n e n t s ) a n d t h e sum normalized t o 1 0 0 % .
http://jurassic.ru/
<s
o 3O
If
I f
ft.
E
~
5
<
,
J3
Ii! iii
I i 1
E
o
is
c
E
LI
O
2 S
-
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to
J3
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CU
http://jurassic.ru/
XX
 O
S "c 2
215
2i
Table 7.6. X-ray identification of the principal clay minerals (<2 um) in an oriented mount of a separated clay fraction
from sedimentary material (from Carroll, 1970)
Basal d spacings (00/)
Mineral
Glycolation effect;
1 hr, 60C
Kaolinite
7.15 A (001); 3.75 A (002)
No change
Kaolinite, disordered
7.15 A (001) broad; 3.75 A

broad
10 A (001) broad
7.2 A (001) broad
No change
Halloysite, 4 H 0
Halloysite, 2 H 0
2
No change
No change
Mica, 2M
10 A (002); 5 A (004) generally

referred to as (001) and (002)
No change
Mite, lMd
10 A (002), broad, other basal

spacings present but small
No change
Montmorillonite Group
15 A (001) and integral series of

basal spacings
Vermiculite

basal spacings
basal spacings
(001) expands to 17 A
with rational sequence
of higher orders
No change
Chlorite, Mg-form
Chlorite, Fe-form
Mixed-layer minerals
Attapulgite
(palygorskite)
Sepiolite
Amorphous clay,
allophane
http://jurassic.ru/
14 A (001) less intense than in

Mg-form; integral series of
basal spacings
Regular, one (001) and integral
series of basal spacings
Random, (001) is addition of
individual minerals and
depends on amount of those
present
High intensity d reflections at
10,5,4.5,3.28,2.62 A
High intensity reflections at
12.6, 4.31,2.61 A
No d reflections
No change
No change
No change unless an
expandable
component is present
Expands if
montmorillonite is a
Heating effect,
1 hr
Becomes amorphous at
550-600C
Becomes amorphous at lower
temperatures than kaolinite
Dehydrates to 2 H O at 110C
Dehydrates at 125-150C;
becomes amorphous at
560-590C
(001) becomes more intense on
heating but structure is
maintained to 700C
(001) noticeably more intense on
heating as water layers are
removed; at higher
temperatures like mica
At 300C (001) becomes 9 A
z
Dehydrates in steps
(001) increases in intensity;
<800C shows weight loss but
no structural change
(001) scarcely increases;
structure collapses below
800C
Various, see descriptions of
individual minerals
Depends on minerals present in
inter-layered mineral
constituent
Dehydrates stepwise
No change
No change
Dehydrates and loses weight
No change
216
217
001
004
(a)
003
004
003
I/004
Mineral A
002
1.0 16.9A M
002
(Mixture of
'Iminerals
001
Q01
B+ C
(b)
005
004
003
, , 002
Regularly
|interstratified(
mineral
(B-C)
(c)
Fig. 7.19. Diagram showing the XRD
peaks of: (a) single clay mineral; (b)
mixture of clay minerals; (c) tegular
interstratified clay minerals (rational
sequence); and (d) randomly
interstratified clay minerals (irrational
sequences) (fromThorez, 1976).
"004"
"003"
"002
Randomly
interstratified
structure
B-C
001"
(d)
2eCuKa
T h e m e t h o d proposed by Weir et al. (1975) uses
t h e equation:
^KAOLINITE
25
,
'iLLiTE
.
1
,
'sMEcrrTE
,
'
^CHLORITE
20
= 100%.
T h e divisors have the function of correcting for t h e
relatively greater X-ray responses of kaolinite and
chlorite.
This m e t h o d has t h e serious disadvantage com
m o n to all normalizing techniques in that an e r r o r in
o n e c o m p o n e n t affects all t h e others, and also n o
account is t a k e n of t h e presence of X-ray a m o r p h o u s
material.
If o n e wants a truly quantitative t e c h n i q u e a m o r e
rigorous a p p r o a c h must be a d o p t e d . T h e introduc
tion of an internal s t a n d a r d is certainly necessary
and a material such as b o e h m i t e ( y - A I O O H ) which
has a similar mass absorption coefficient and X-ray

response to clays, b u t a separate diffraction p a t t e r n ,
can be used. Just such a m e t h o d is described by
Griffin (1954) in which a known a m o u n t of b o e h m i t e
(generally 10% by weight) is added to mixtures of
standard clay minerals to produce calibration charts
of percentage mineral against t h e relative intensity
of t h e m e a s u r e d diffraction line to that of t h e 1 0 %
b o e h m i t e diffraction line.
T w o difficulties a r e : (i) the mixing of platey par
ticles satisfactorily, a n d (ii) variability of composi
tion and degrees of crystallinity within clay groups.
T h e first p r o b l e m can be alleviated by using a
commercial mixing/grinding device (e.g. M c C r o n e
mill); t h e second p r o b l e m can only really b e over
c o m e by preparing calibration curves from t h e actual
clays u n d e r investigation. This technique was used
by Gibbs (1967) in which he extracted, using a
variety of techniques, the individual clay mineral
Fig. 7.20. Calculated diffraction profiles assuming random interstratification of 10 and 16.9 A layers (illite and
montmorillonite, glycolated). Fraction of montmorillonite layers are 1.0,0.8,0.6,0.4,0.2 0 1 and 0 (from Reynolds &
Hower, 1970).
c o m p o n e n t s from selected samples, which w e r e t h e n

used in t h e preparation of calibration curves. It is
particularly useful in t h e analysis of large num
bers of similar samples.
F o r m o r e general purposes, 'typical' p u r e clays
a r e used and these can be obtained from various
commercial sources, an example being the Source
Clays Repository. This organization was established
by t h e Clay Mineral Society of t h e U S A to provide
workers with reference clay materials ('Source
Clays'). F o r further information contact the curator
of t h e s a m p l e collection, Professor William D . J o h n s ,
http://jurassic.ru/
Source Clays, D e p a r t m e n t of Geology, University

of Missouri, C o l u m b i a , Missouri 65211, USA.. A n
o t h e r example is O E C D , the Organization for
E c o n o m i c C o - o p e r a t i o n a n d D e v e l o p m e n t which
also provides reference clays. F u r t h e r details from
Mile S. Caillere, L a b o r a t o i r e d e Mineralogie du
M u s e u m National d'Histoire Naturelle, 61 rue de
Buffon, Paris 5e, F r a n c e . D a t a for t h e clay samples
of t h e two organizations, together with useful in
formation, a r e s u m m a r i z e d in V a n O l p h e n & Fripiat
(1979).
218
7.4.5 Mite crystallinity

T h e X-ray diffraction response of illite is often used
to give an indication of t h e diagenetic and low-grade
m e t a m o r p h i c history of a sedimentary rock (e.g.
W e a v e r , 1960; Kubler, 1968; D u n o y e r d e Segonzac,
1970; Frey, 1970; Gill, Khalaf & M a s s o u d , 1977;
Stalder, 1979). In essence, there is an increase in t h e
degree of crystallinity and a change in t h e chemical
composition of illite in the late d i a g e n e t i c - e a r l y
m e t a m o r p h i c realm. T h e degree of illite crystal
linity, t h e sharpness ratio of W e a v e r (1960), is m e a
sured from t h e ratio of t h e height of t h e illite 001
p e a k at 10 A to t h e height above the base line at 10.5
A . In a study of clay minerals as an indicator of
degree of m e t a m o r p h i s m in Carboniferous sedi
ments of t h e South Wales Coalfield, Gill et al. (1977)
o b t a i n e d a sharpness ratio of 2.0 in areas of n o
m e t a m o r p h i s m , rising to 6.0 in a region of low grade
m e t a m o r p h i s m , w h e r e coals were u p t o anthracite
rank.
In s o m e studies (e.g. D u n o y e r de Segonzac, 1970),
it appears that t h e r e is also a change in t h e chemistry
of t h e illite, with an increase in t h e A l / F e + M g ratio
with increasing m e t a m o r p h i c g r a d e . This has b e e n
quantified by calculating "an intensity ratio ( I R ) of
t h e illite 5 A and 10 A p e a k s , i.e. 7(oo2)/7(ooi)-
7.4.6 Use of XRD data o n m u d r o c k s

F o r the study of m u d r o c k s , X-ray diffraction analysis
is t h e basic tool to d e t e r m i n e t h e n a t u r e and p r o p o r
tions of t h e clay minerals present and from t h e r e to
m a k e deductions o n , for e x a m p l e , t h e likely p r o
venance of t h e s e d i m e n t , t h e conditions of deposi
tion and palaeoclimate, and t h e diagenesis and burial
history. Clays in sandstone and limestones are also
best identified by X R D . A brief n o t e of these aspects
of clay mineralogy is presented h e r e , but a full
review is not i n t e n d e d or w a r r a n t e d ; t h e r e are m a n y
textbooks and papers reviewing these topics (e.g.
Millot, 1970; V e l d e , 1977; E b e r l , 1984) and t h e
interested student should p e r u s e the current issues
of Clay Minerals, Clays and Clay Minerals,
Journal
of Sedimentary
Petrology, Sedimentology
and t h e
Proceedings of the International Clay Conference,
held every 3 years or so, and generally published as
a book (e.g. V a n O l p h e n & Veniale, 1982).
Clay minerals in a sediment or sedimentary rock
have t h r e e origins: (1) inheritance, (2) neoformation
and (3) transformation. In the first, t h e clays are

detrital and have been formed in a n o t h e r a r e a ,
p e r h a p s at a much earlier t i m e , and they a r e stable
in their present location. In t h e second, t h e clays
have formed in situ, and they have either b e e n
precipitated from solution or formed from amor
p h o u s silicate material. With transformation, in
herited clays are modified by ion exchange or cation
r e a r r a n g e m e n t . In t h e study of m u d r o c k s , it is clear
ly important to be certain of t h e origin of t h e clays if
meaningful interpretations a r e to be m a d e . Inherited
clays will give information on t h e provenance of the
deposit and probably the climate t h e r e , whereas
neoformed clays reflects t h e p o r e fluid chemistry, de
gree of leaching and t e m p e r a t u r e that existed within
t h e sample at s o m e stage. Transformed clays will
carry a m e m o r y of inherited characteristics from t h e
source a r e a , together with information on the
chemical e n v i r o n m e n t to which t h e sample was later
subjected.
T h e r e are t h r e e major locations w h e r e these t h r e e
processes of clay mineral formation t a k e place: (1)
in t h e weathering and soil e n v i r o n m e n t , (2) in the
depositional e n v i r o n m e n t and (3) during diagenesis
and into low grade m e t a m o r p h i s m . In t h e weather
ing e n v i r o n m e n t , t h e types of clays p r o d u c e d , main
ly by neoformation if fresh rock is being w e a t h e r e d ,
d e p e n d o n t h e climate, drainage, rock t y p e , vegeta
tion and time involved. In very b r o a d t e r m s , illite is
typical of soils w h e r e the degree of leaching is mini
mal, as in t e m p e r a t e and higher latitudes. Chlorite
also forms u n d e r these conditions but, since it is
m o r e easily oxidized, it occurs preferentially in acid
soils. Illite and chlorite are also in soils of arid
regions where- chemical processes are limited.
Smectites are p r o d u c e d w h e r e t h e degree of leaching
is intermediate or w h e r e soils are poorly drained.
T h e y also form in alkaline arid-zone soils. Mixedlayer clays mostly form through the leaching of p r e
existing illite and mica. Kaolinite and halloysite are
characteristic of acid tropical soils w h e r e leaching is
intensive. F u r t h e r leaching leads t o vermiculite and
t h e n gibbsite through removal of silica. S o m e less
c o m m o n clay minerals are developed in particular
soil e n v i r o n m e n t s , such as palygorskite and sepiolite
in calcretes, Mg-rich soils and silcretes (e.g. M e y e r
& P e n a dos Rois, 1985).
Clay minerals are generally little altered during
transportation, by wind or water. In t h e m a r i n e
e n v i r o n m e n t , w h e r e most clays are eventually de
posited, pelagic m u d s of t h e ocean basins have a clay
mineralogy which is largely a reflection of t h e climate
and weathering p a t t e r n of t h e source areas on ad

jacent land masses (e.g. Griffin, W i n d o m & Gold
berg, 1968). T h u s kaolinite is most c o m m o n in low
latitudes, particularly off major rivers draining re
gions of tropical weathering, and illite and chlorite
are m o r e c o m m o n in higher latitude marine muds.
Smectites a r e a c o m m o n alteration p r o d u c t of vol
canic ash so that their distribution on t h e seafloor
does reflect oceanic volcanicity as well as the com
position of river-derived and wind-borne m u d . O n
continental shelves, t h e r e are local variations in the
clay mineralogy of m u d s , reflecting the proximity to
rivers and deltas. T h u s clays can be used to d e m o n
strate sediment dispersal p a t t e r n s in estuaries, bays
and on shelves (e.g. Knebel et al., 1977, studying t h e
m u d s of San Francisco Bay, and B a k e r , 1973, fol
lowing the path of suspended sediment from the
River Columbia, off t h e N W United States coast).
T h e r e a r e differences in t h e grain sizes of t h e clay
minerals which affect t h e distribution. Kaolinite is
the coarsest (up to 5 u m ) , illite intermediater (0.1
0.3 um) and smectite finer still, although the last
commonly occurs as floccules several micrometres
in diameter. As a result of these size differences a
kaolinite-rich zone may occur inshore of smectite
illite m u d . T h e r e is t h e potential h e r e for using t h e
regional distribution of clays within a sedimentary
basin t o infer t h e direction of sediment transport
and distance from source a r e a . Studies of the clays
o n the Atlantic O c e a n floor off t h e A m a z o n River
revealed decreases in kaolinite and 10 A mica (illite
+ muscovite), and increases in montmorillonite with
increasing distance from t h e river m o u t h ( G i b b s ,
1977). T h e s e trends are explained as the result of
physical sorting of t h e clays by size.
Transformation of terrestrial clays and neoforma
tion a p p e a r s to b e minor on the seafloor, although
chamosite and glauconite d o form in sedimentstarved locations. Glauconite may form from altera
tion of degraded micaceous clays by absorption of
K
and F e
or from neoformation within p r e
existing particles such as c a r b o n a t e grains, clay
minerals or faecal pellets (Odin & M a t t e r , 1981).
T h e r e is, however, much evidence for chemical
alteration of clays; N a , M g
and K may all be
a d s o r b e d , commonly exchanged for C a
(e.g.
Sayles & Mangelsdorf, 1979).
+
2 +
2 +
2 +
N o n - m a r i n e m u d r o c k s of lacustrine, fluvial and

glacial environments will also be largely of the in
herited, detrital t y p e , with little transformation and
neoformation taking place. In some lakes, however,
219
with quite e x t r e m e salinities and chemistries, clay

minerals may be transformed or neoformed. Sepio
lite, palygorskite, attapulgite and corrensite (mixed
layer chlorite-montmorillonite) occur in Mg-rich,
alkaline lake sediments for e x a m p l e . W h e r e t h e r e is
volcanic ash in a lake sediment or soil, then clay
minerals are commonly formed by alteration of t h e
ash, along with o t h e r minerals such as zeolites.
In t h e burial diagenetic e n v i r o n m e n t , t h e r e is a
progressive alteration of t h e clay minerals with rising
t e m p e r a t u r e . O n e of the first transformations is
smectite t o mixed-layer smectiteillite and t h e n this
goes to illite. Chlorite also develops at d e p t h , and
into the zone of incipient m e t a m o r p h i s m kaolinite is
converted to illite and chlorite. T h e s e changes are
discussed by Perry & H o w e r (1970), H o w e r et al.
(1976), I m a n & Shaw (1985), Jennings & T h o m p s o n
(1986) and others and frequently they are related to
vitrinite reflectance and timing of hydrocarbon
g e n e r a t i o n . In addition, t h e r e is an increase in t h e
crystallinity of illite, as explained in Section 7.4.5.
Clearly, in interpreting t h e clay mineralogy of t h e
m u d r o c k the burial history of t h e formation has to
be taken into account. Burial diagenetic changes in
clays may largely account for t h e uneven distribu
tion of clays t h r o u g h t i m e , with smectites and t o a
lesser extent kaolinite being less a b u n d a n t in older,
especially Palaeozoic and Precambrian m u d r o c k s ,
which are composed largely of illite and chlorite
( D u n o y e r de Segonzac, 1970).
F r o m this brief discussion, it can be seen that the
clay mineralogy of a s e d i m e n t o r sedimentary rock
may reveal information on t h e palaeoclimate in t h e
source a r e a and on t h e n a t u r e of the source area
itself. Samples t a k e n vertically through a sequence
of m u d r o c k s may show variations in t h e clay mineral
assemblage which reflect changing climate or chan
ging source area. Jacobs (1974), for example, dis
cussed variations in t h e clay minerals of Cainozoic
seafloor m u d s of t h e Southern O c e a n in terms of t h e
impending Pleistocene glaciation of the Antarctic
continent and its effect on weathering and erosion
rates. In a detailed study of just 2 m of rock, Spears
& Sezgin (1985) recorded a decrease in kaolinite and
increases in illite, chlorite, vermiculite and illite to
illite/smectite ratio across a Coal Measures m a r i n e
b a n d . T h e y attributed this to a decrease in t h e
contribution of m a t u r e clay from within the basin
and to an increase in the proportion of less weather
ed clay from outside the basin, through time and
during t h e marine transgression. With the Triassic
http://jurassic.ru/
iitmwmiittiiiiiiimiiiiiini
220
R.G. H A R D Y and M.E.
X-RAY POWDER
TUCKER
2 +
K e u p e r Marl (Mercia M u d s t o n e s ) , Jeans (1978) was

able to distinguish a detrital (inherited) illite and
chlorite assemblage occurring t h r o u g h o u t t h e
s e q u e n c e , from an assemblage of neoformed Mgrich clays (sepiolite, palygorskite, chlorite, smectite
and corrensite) which occurs at particular horizons.
T h e neoformed clays a r e t h e result of changes in
water chemistry within t h e K e u p e r Basin, probably
arising from t h e influx of marine waters. Retallack
(1986) d e m o n s t r a t e d that t h e r e was a change in t h e
clay mineralogy of C r e t a c e o u s to Tertiary paleosols
of t h e N W United States, with decreasing kaolinite
and increasing illite and chlorite u p through t h e
sequence resulting from a change in climate from
m o r e humid to m o r e arid.
Clays can be neoformed within sandstones during
diagenesis, a n d t h e r e a r e m a n y case studies docu
menting this (see, e.g. H a n c o c k & Taylor, 1978,
discussing the Jurassic B r e n t Sand of the N o r t h Sea,
which shows a change from kaolinite to illite with
increasing d e p t h , and an i m p r o v e m e n t in the illite
crystallinity Fig. 7.21). Authigenic clays in sand
stones may show much better-defined diffraction
than the C a
ion, this results in a decrease in t h e
rf
lattice spacing (Goldsmith & Graf, 1958a).
Several authors have p r o d u c e d a graph showing t h e
mole % M g C 0 against d
in angstrom units and
20 for C u Ka radiation and Fig. 7.22 from Gold
smith, Graf & H e a r d (1961) is the o n e most com
monly used. T h e precise position of the rf 4 p e a k is
obtained by using an internal standard such as halite,
quartz or fluorite which has a major peak close to
t h e main calcite p e a k (Table 7.3).
O n t h e basis of magnesium content, calcite occurs
in two forms: low Mg calcite ( L M C ) with 0 to 4 mole
% M g C 0 and high M g calcite ( H M C ) with m o r e
than 4 mole % , but with a range of 1 1 - 1 9 mole %
being most c o m m o n . In m o d e r n tropical c a r b o n a t e
sediments, H M C is mainly of biogenic origin, coming
from calcareous red algae, echinoderms, bryozoans
and some benthic foraminifera. H M C micritic and
bladed c e m e n t s are c o m m o n in reefs. L M C is also
mostly of biogenic origin, coming from planktonic
foraminifera, coccoliths and some molluscs. In addi
tion t o t h e 'vital' effect, t h e M g
content of bio
genic calcite is d e t e r m i n e d by water t e m p e r a t u r e :
lower M g occurs in skeletons precipitated in cooler
waters. With marine calcite c e m e n t s , t o o , those
precipitated in colder, commonly d e e p e r waters,
have lower M g . A l t h o u g h H M C grains and ce
m e n t s generally lose their M g
during diagenesis,
so that most ancient calcite is low in magnesium, a
m e m o r y of t h e original high M g is commonly retain
ed. In limestones, original L M C will typically have
01 m o l e % M g C 0 , w h e r e a s original H M C may
have a little m o r e (23 mole % ) .
p e a k s than those in adjacent shales (e.g. Wilson &

P i t t m a n , 1977).
104
7.5 XRD of carbonates

X-ray diffraction is commonly used in t h e study of
m o d e r n c a r b o n a t e sediments, limestones and d o l
omites. X R D data can give information on t h e
chemical composition of c a r b o n a t e minerals, n a m e
ly t h e M g content of calcite and t h e C a or M g excess
of dolomite. T h e y can also b e used t o d e t e r m i n e t h e
ordering of dolomite crystals. T h e percentages of
t h e various C a C 0 minerals in a mixture can be
calculated from X-ray p e a k s , but estimates of t h e
dolomite content of dolomitic limestones are less
precise. T h e main peaks of the c o m m o n c a r b o n a t e
minerals, calcite, aragonite a n d dolomite a r e given
in T a b l e 7.3.
10
7.5.1 Magnesium in calcite
2 +
T h e magnesium ion can substitute for calcium in t h e

calcite lattice, a n d , since the Mg " " ion is smaller
2
Percentage of rock
Kaolinite
Illite
2 +
XRD traces
2 +
(untreated clay fraction: < 2/u,m)
2 +
Upper
Brent
Sand
Middle
Brent
Sand
7.5.2 Mixtures of C a C 0
feet
Lower
Brent
Sand
Kaolinite
peak
7.16A
0 10 20
10 20
http://jurassic.ru/
minerals
M a n y m o d e r n c a r b o n a t e sediments consists of a
mixture of t h r e e C a C 0 minerals, aragonite, low
M g calcite and high M g calcite. A r a g o n i t e is a major
constituent, coming from t h e shells and skeletons of
green algae, corals and molluscs, and forming ooids
and m a n y marine c e m e n t s . X-ray diffraction is t h e
quickest m e t h o d for determining the mineralogical
composition of m o d e r n c a r b o n a t e s , although there
has been discussion over w h e t h e r peak height or
p e a k area analysis should b e used.
Careful grinding of the sample is important since
this process determines t h e particle size of the
p o w d e r and t h e structural d a m a g e to the minerals,
which respond differently to the grinding. T h e s e
differences can affect t h e X R D p e a k intensities
3
Fig. 7.21. Clay mineralogy of the

Middle Jurassic Brent Sand from the
North Sea. Petrographic data show
that kaolinite is replaced downwards
by increasingly abundant illite.
Representative X-ray diffraction
traces (right) show changing emphasis
from kaolinite to illite downhole,
together with downward
improvement in illite crystallinity
(sharper peak). Note some detrital
mixed-layer illite/montmorillonite in
sample 2 (second peak on flank of
10 A peak) (from Hancock & Taylor,
1978).
MlllllllllltlllttMllllllllf
CaC0
.0
3.04
3.02
3.00
2.98
2.96
2.94
2.90 2.88
10
DIFFRACTION
mole % M g C 0
20
30
221
40
50
29.4
29.6
29.8
30.0 *
30.2
s
\
\
\
\
\
\
\
CD
30.4 m
\
\
30.6
\
N 30.8
31.0
Fig. 7.22. Displacement of the d peak of calcite with
increasing M g C 0 to dolomite (based on Goldsmith et al.
1961).
i(H
(Gavish & F r i e d m a n , 1973). A n original very fine

crystal size or overgrinding producing too fine a
p o w d e r results in a decrease of p e a k intensity. This
effect is shown m o r e by calcite than aragonite (e.g.
Fig. 7.23 and Milliman, 1974), but even then it
varies with t h e particular calcite skeleton being
analysed. Excessive and hard grinding is to be
avoided as this may lead to mineralogical changes in
t h e sample through the heat generated and pressure
applied. In general, marine biogenic calcites have
similar p e a k intensities, largely because t h e crystal
lite size is similar. T h e exception is echinoid material,
which shows a greater p e a k intensity because of its
larger crystal size. R e a g e n t grade calcite also shows
a greater p e a k intensity, and so should b e avoided as
a standard. A particle size of less than 63 um is
generally acceptable, obtained by grinding t h e sam
ple for several minutes until all t h e p o w d e r will pass
through a 200-mesh sieve. If aragonite is present this
can be used as an internal standard to d e t e r m i n e
precisely t h e displacement of the high M g calcite
p e a k . If b o t h L M C and H M C a r e present, t h e n t h e
two p e a k s will overlap; o n e will be a shoulder to t h e
other. T o d e t e r m i n e t h e a m o u n t s of each mineral
present, the ratio of the aragonite p e a k intensity to
all p e a k intensities is calculated: I A / I A + I L M C +
I H M C (Fig. 7.24). Peak intensity can b e measured
by either p e a k height or p e a k area and in both cases
a base-line is taken just above the background level.
Gavish & F r i e d m a n (1973) considered that peak
height analysis was m o r e reliable for separating
L M C and H M C . T h e y showed that t h e particle size
and a m o u n t of structural d a m a g e through excessive
grinding affected the p e a k areas more than the peak
heights. Milliman & Bornhold (1973), on t h e other
222

was devised by G u n a t i l a k a & Till (1971). T h e y
p r e p a r e d a spike mixture by h a n d picking grains
from t h e s e d i m e n t , identifying their mineralogy by
X R D , and then mixing t h e m t o g e t h e r in a deter
mined p r o p o r t i o n . T h e spike mixture was a d d e d to
the u n k n o w n in 1:1 ratio and from a c o m p a r i s o n of
t h e diffraction traces of t h e spike a n d spike +
u n k n o w n , calculation of peak areas a n d use of an
e q u a t i o n , the percentages of the various minerals
p r e s e n t can b e d e d u c e d quite accurately. T h e ad
vantage of this p r o c e d u r e is that t h e s t a n d a r d (the
spike) is m a d e from c o m p o n e n t s which a r e p r e s e n t
in the s e d i m e n t , so that the diffraction b e h a v i o u r
will b e similar.
r~
30
28
26
Fig. 7.23. X-ray diffractograms (A, and A aragonite; C,
calcite) showing the effect of extended grinding on the
peak intensity of a 5050 mixture of mollusc aragonite
and oyster calcite. Grinding times (circled numbers) are in
cumulative minutes (from Milliman, 1974).
2
h a n d , w e r e able to d e m o n s t r a t e that t h e p e a k heights

and asymmetries of H M C grains varied b e t w e e n
different algal genera b u t that total p e a k intensity
was relatively constant and t h a t , for aragonite a n d
calcite mixtures, p e a k a r e a was m o r e reliable. In
p e a k a r e a analysis, t h e areas can b e d e t e r m i n e d by
(a) tracing off t h e p e a k s , cutting o u t their shapes
a n d weighing t h e s e , (b) using a planimeter or (c)
accurate measuring of t h e height a n d width of each
p e a k . T h e accuracy of this m e t h o d is probably
around 5 % .
F r o m t h e ratio for aragonite peak intensity, a
calibration curve is n e e d e d to convert this to a
p e r c e n t a g e , since t h e X R D response of similar
a m o u n t s of calcite a n d aragonite is not the s a m e .
A r a g o n i t e gives lower intensity p e a k s for a given
p e r c e n t a g e c o m p a r e d to calcite. Milliman (1974)
p r e s e n t e d a s t a n d a r d curve for aragonite d e t e r m i n a
tion from p e a k a r e a analysis (Fig. 7.25). F r o m this,
t h e p e r c e n t a g e of aragonite which c o r r e s p o n d s to
t h e ratio can b e read off, a n d the a m o u n t of calcite
p r e s e n t can b e found by subtraction. If both calcite
minerals a r e in t h e s a m p l e , then a small calculation
is n e e d e d to find t h e p e r c e n t a g e of each (Fig. 7.24).
A m e t h o d for determining weight p e r c e n t a g e s of
c a r b o n a t e minerals in a m o d e r n sediment by spiking
hA-,
hA-, + hC-,
7.5.3 XRD and d o l o m i t e s

T h e mineral d o l o m i t e , C a M g ( C 0 ) , is c o m m o n l y
not stoichiometric, but has an excess of C a , u p to
C a : M g 58:42, or less commonly an excess of M g , u p
to C a
T h e effect of C a
substitution for
Mg
is t o increase t h e cation lattice spacing (Fig.
7.22) a n d X R D is often used to d e t e r m i n e this a n d
give t h e C a / M g r a t i o , by m e a s u r e m e n t of t h e posi
tion of t h e d
p e a k relative to a s t a n d a r d . A p a r t
from reference t o Fig. 7.22, t h e Ca excess can b e
calculated from t h e e q u a t i o n of L u m s d e n (1979)
relating m o l e % C a C 0
spacing
CaC 3 to t h e d
m e a s u r e d in angstrom units (d):
Md + B,
CaC
w h e r e M is 333.33 and B is - 9 1 1 . 9 9 . T h e
d
spacing for 5 0 . 0 % C a C 0 is t a k e n as 2.886 A a n d
for 5 5 . 0 % C a C 0 as 2.901 A , based o n Goldsmith
& Graf (1958a).
3
2 +
4 8
Mg52-
2 +
(b)
U wAi
(hA-wA) V
aA-, + aCi
V* {hA wA) + V (hC wC)
_
hA wA
hA wA + hC wC
2
2 +
W4
(Af o )
Af o, =
W4
lM
Iron can substitute for t h e cations in d o l o m i t e to

give ferroan dolomite ( > 2 m o l e % F e C 0 ) a n d
a n k e r i t e with m u c h higher values reaching 25 m o l e
% F e C 0 . In view of t h e slightly larger size of t h e
Fe
ion relative to M g , with m o r e t h a n a few
m o l e % F e C 0 t h e r e is a noticeable increase- in t h e
lattice spacing of d
(Goldsmith & Graf, 1958b;
R u n n e l l s , 1970; A l - H a s h i m i & H e m i n g w a y , 1974).
In addition, the intensities of t h e X R D reflections
a r e commonly w e a k e r in ferroan dolomites. A l Hashimi & H e m i n g w a y (1974) p r e s e n t e d a calibra
tion curve for ferroan dolomites (Fig. 7.26), by first
analysing t h e iron c o n t e n t with atomic absorption
( C h a p t e r 6). Clearly, care has to b e exercised in
interpreting dolomite X R D d a t a , a n d n o t e t a k e n of
t h e iron c o n t e n t .
(c)
aA-,
aA-, + S a d
2 +
% m g calcite =
% t
~ where
X R D of dolomites also gives information o n t h e
laC-, = aC-, + a mg
aC, = 2 x ( a d / 2 )
W4
o r d e r i n g of t h e crystals. A s a result of t h e segrega

tion of t h e cations into s e p a r a t e sheets in the do
lomite crystals, a set of superstructure reflections
corresponding t o d 2i> ôis and d
is revealed with
X R D (Fig. 7.27), which is n o t present in the struc
turally similar calcite. T h e sharpness a n d relative
intensities of these ordering p e a k s c a n b e used to
give a m e a s u r e of t h e d e g r e e of ordering of t h e
0
http://jurassic.ru/
n n
C l
{*?' x *
calcite
SaCi
2 +
Fig. 7.24. Calculation of carbonate

mineralogy by X-ray diffraction. In
peak height analysis (a), the simple
ratio h /(h
+ h ) is calculated. A
geometric calculation can be used (b)
with simple calcitearagonite
mixtures, in which both peaks are
assumed to be triangles, and the area
of each is calculated. Where the
calcite curve is composed of two or
more types of calcite, a more complex
analysis is required (c). The intensity
of the free half of the major peak (the
right side of the low Mg calcite curve)
is calculated and multiplied by 2. This
intensity is then compared to the total
intensity in order to differentiate
between it and the other calcites
present. The integrated peak intensity
is calculated either by planimeter
analysis or by weighting (from
Milliman, 1974).
A
d o l o m i t e crystal. T h e g r e a t e r t h e ratio of t h e heights

of t h e o r d e r i n g p e a k 015 t o diffraction p e a k 110, t h e
higher t h e d e g r e e of o r d e r .
D o l o m i t e s which a r e non-stoichiometric are
generally less well o r d e r e d t h a n 'ideal' d o l o m i t e ,
t h r o u g h t h e o c c u r r e n c e of s o m e C a ions in t h e M g
s h e e t (or vice v e r s a ) . It is theoretically possible for a
50:50 C a : M g c a r b o n a t e t o h a v e n o ordering reflec-
224
100
1.4
1.3
80
2.9
1.2
<
60
1.1 h
o 2.89
to40
1.0
0.9
Order
ratio 0.8
l[221]
0.7
l[101]
A'
20
2.88
6
10
F e C 0 wt%
14
18
0.6
20
40
60
80
100
Fig. 7.26. Calibration curve relating d spacing of

dolomite to the F e C 0 content (from Al-Hashimi &
Hemingway, 1974).
0.5
104
Percentage aragonite
Fig. 7.25. Standard curve for aragonite determination

using peak area analysis. Each data point represents eight
to ten analyses of various calcite and aragonite standards.
In most instances the standard deviation (represented by
vertical bars) is considerably less than 5% (from Milliman,
1974).
0.4
0.3
tions if t h e cation sheets in t h e lattice are equal

mixtures of Ca a n d M g . In practice, all naturally
occurring dolomites are o r d e r e d to an extent (other
wise, strictly, the mineral is not dolomite) with most
m o d e r n dolomites showing p o o r ordering reflec
tions, c o m p a r e d with m a n y ancient dolomites. T h e
term p r o t o d o l o m i t e was introduced by Goldsmith &
Graf (1958a) for dolomite manufactured in t h e lab
with n o or only p o o r ordering reflections. H o w e v e r ,
it has occasionally b e e n used for m o d e r n naturallyoccurring dolomites with weak ordering p e a k s ,
although t h e concensus n o w ( L a n d , 1980) is that t h e

word should b e restricted to synthetic dolomites,
and if a naturally occurring CaMg c a r b o n a t e has
t h e ordering reflections, n o m a t t e r h o w w e a k , t h e n
it is a dolomite. D o l o m i t e with an excess of C a can
simply b e referred t o as calcian d o l o m i t e .
X R D d a t a from dolomites can be useful in pro
viding a m o r e detailed knowledge of t h e crystal
structure and chemistry, a n d they can b e used t o
distinguish b e t w e e n different types of dolomite
within o n e c a r b o n a t e formation. F o r e x a m p l e , Fig.
7.28 presents data from the L o w e r Carboniferous of
South Wales w h e r e peritidal dolomicrites h a v e dif
ferent degrees of o r d e r and C a / M g ratios from
mixing-zone dolomites and from burial 'vein' bar
o q u e dolomites. L u m s d e n & Chimahusky (1980) and
0.2
0.1
50
51
52
Mole% C a C 0 in dolomite
3
M o r r o w (1978, 1982) identified t h r e e b r o a d groups

of dolomite, based o n stoichiometry, texture and
w h e t h e r associated with evaporites o r n o t (Fig. 7.29):
I coarsely-crystalline, sucrosic dolomites whch
a r e generally nearly stoichiometric ( m o d e 50.0
5 1 . 0 % C a C Q ) , I I fine-grained dolomites
associated with evaporites which are also nearly
stoichiometric ( m o d e 5 1 . 0 - 5 2 . 0 % C a C 0 ) a n d I I I
finely crystalline dolomites n o t associated with
evaporites which a r e generally Ca-rich ( 5 4 - 5 6 %
C a C 0 ) . G r o u p s I I a n d I I I are usually early dia
genetic, near-surface in origin. T h e underlying cause
of these associations is t h o u g h t to b e t h e salinity a n d
M g / C a ratio of dolomitizing solutions, with a climatic
control i m p o r t a n t for groups I I and I I I . W h e r e t h e r e
is an evaporite association (group I I ) , indicating an
arid climate, t h e n p o r e fluids a r e likely to have h a d a
high M g / C a ratio from precipitation of gypsum
anhydrite a n d aragonite. It is c o n t e n d e d that t h e
a b u n d a n c e of M g ions in t h e fluids would result in
n e a r stoichiometric d o l o m i t e . T h e calcian dolomites
3
Degree of ordering
Intensity 015 peak

Intensity 110 peak
2 +
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.llM i l l
53
Key
vein dolomites
pervasive dolomites
dolomicrites
Fig. 7.27. The diffraction peaks of

dolomite, showing the ordering
reflections (*). Peaks identified in
hexagonal indices, e.g. 104, and
rhombohedral indices, e.g. (211).
Degrees 29, Cu Koc radiation (after
Goldsmith & Graf, 1958b).
Fig. 7.28. XRD data from some

Lower Carboniferous dolomites from
South Wales showing stoichiometry
(as mole % C a C 0 ) plotted against
ordering. The three types of
dolomite, peritidal dolomicrites,
pervasive mixing-zone dolomites and
burial dolomites developed along
joints, plot in different areas, with
some overlap (from Hird, 1986).
of g r o u p I I I are thought t o have formed from solu

tions with lower M g / C a ratios, such as occur in
mixing-zones, which a r e m o r e active during humid
climatic times. G r o u p I dolomites are generally of
late diagenetic burial origin and t h e near stoichio
m e t r y could reflect slow growth from dilute solu
tions, possibly aided by elevated t e m p e r a t u r e s .
Using n e w a n d published X R D d a t a , Sperber,
Wilkinson & Peacor (1984) obtained two pronounced
m o d e s at 51 a n d 55 mole % C a C 0 in Phanerozoic
dolomites which ranged from 48 to 57 mole %
C a C 0 . T h e y also found a bimodal distribution in
t h e percentage of dolomite in carbonate rocks: a
m o d e at 9 7 % dolomite (dolostones) and at 2 0 %
(dolomitic limestones), indicating that carbonate
rocks a r e either partially or completely dolomitized.
S p e r b e r et al. (1984) suggested that t h e dolomitic
limestones, which generally contain r h o m b s of cal
cian dolomite, originated in diagenetically closed
systems during high M g calcite dissolution low M g
calcite a n d dolomite precipitation, so that in these
3
226
227
Trends in dolomite
stoichiometry
Precipitational
conditions
Mg:Ca Salinity (%>)
Mole % C a C 0
48
50
52
54
Fig. 7.31. Calibration curves: curve 1 for calcite-ankerite

( F e C 0 = 22%); curve 2 for calcite + highly ferroan
dolomite ( F e C 0 = 15%); curve 3 for calcite + medium
ferroan dolomite ( F e C 0 = 10%); curve 4 for calcite +
low ferroan dolomite ( F e C 0 = 5%); curve 5 for calcite +
dolomite ( F e C 0 = 0) (from Al-Hashimi & Hemingway,
1974).
3
Fig. 7.29. Diagram of dolomite stoichiometry data and inferred precipitational conditions. Group 1 is composed of ancient
sucrosic and sparry dolomites. Group 2 is composed of finely crystalline modern and ancient dolomites not associated with
evaporites and Group 3 are finely crystalline modern and ancient dolomites associated with evaporites (from Morrow,
1982).
rocks there was an internal supply of M g . T h e

dolostones, on t h e o t h e r h a n d , consist of m o r e stoich
iometric dolomite, and are thus considered to
have originated in m o r e o p e n diagenetic systems. A
trend towards m o r e stoichiometric dolomite in older
dolostones is evident from t h e d a t a of L u m s d e n &
Chimahusky (1980) and S p e r b e r et al. (1984) and
t h e r e is also a broad correlation of increasing stoich
iometry with increasing crystal size. B o t h these
features are consistent with dolomites u n d e r g o i n g
solution-reprecipitation through diagenesis and t h e
formation of m o r e stoichiometric, b e t t e r o r d e r e d
dolomite from a less stoichiometric, poorly o r d e r e d
original precipitate.
7.5.4 Calcite-dolomite mixtures

X R D charts have long b e e n used to calculate t h e
proportions of calcite and dolomite in a s a m p l e . A s
with C a C 0 minerals, t h e ratio of t h e p e a k area of
dolomite to calcite plus dolomite is converted t o a
percentage using a calibration curve. Several of these
have been published (e.g. T e n n a n t & B e r g e r , 1957;
W e b e r & Smith, 1961; B r o m b e r g e r & H a y e s , 1965;
R o y s e , Waddell & P e t e r s e n , 1971; L u m s d e n , 1979;
3
Fig. 7.30) and they have generally been constructed

from a set of s t a n d a r d mixtures. H o w e v e r , t h e r e a r e
several potential e r r o r s in t h e m e t h o d which n e e d to
be considered and have been identified by com
paring X R D d a t a with dolomitecalcite ratios m e a
sured from stained thin sections ( L u m s d e n , 1979;
G e n s m e r & Weiss, 1980). O n e major p r o b l e m is t h e
stoichiometry of the dolomite. T h e position of t h e
d 4 peak d e p e n d s o n t h e Ca excess and at higher
C a C 0 contents ( > 5 5 % ) ; this p e a k overestimates
t h e dolomite content by s o m e 1012% ( L u m s d e n ,
1979). F o r this r e a s o n , it is best t o use t h e d
peak
of dolomite which is not affected by non-stoichiometry. T h e d
p e a k position is also affected by iron
c o n t e n t (Fig. 7.26) and Al-Hashimi & H e m i n g w a y
(1974) d e t e r m i n e d calibration curves for c a l c i t e dolomite, calciteferroan dolomite and calcite
ankerite mixtures (Fig. 7.31). A difference in particle
size of p o w d e r e d samples relative to the crystallite
size of t h e standard mixtures can introduce a n o t h e r
e r r o r , since particle size influences p e a k a r e a ratios.
In preparing a calibration curve o n e should clearly
try and have crystallites of similar size to those in t h e
u n k n o w n samples. In addition, calcite and dolomite
crystals may break up at a different rate during
10
U3
..
i ....i
i . i
i . i
.i
5 10 20 30
70 80 90 95 98
% Dolomite (probability scale)
Fig. 7.30. Calibration curve for determination of dolomite
in calcite, using dolomite/calcite ratio of area of [113]
peaks. Main line connects points obtained with standards
prepared using calcite ground for 30 minutes. Vertical bars
give range of one standard deviation. Dashed line
connecting squares is for standards prepared with calcite
ground for 15 minutes, i.e. relatively coarse crystalites.
Dashed line connecting triangles is for standards prepared
with chemical calcite, i.e. relatively fine crystallites (from
Lumsden, 1979);
W4
HHnmmTiHmtMitiMMifmHfl
grinding or b e of different grain size. G e n s m e r &

Weiss (1980) found that grinding samples for be
tween 10 and 20 minutes t o give a particle size of
a r o u n d 5 urn o v e r c a m e this p r o b l e m . A further error
arises if t h e r e is much q u a r t z in t h e sample. T h e
quartz d
p e a k (d = 2.285 A ) interferes with t h e
calcite d
p e a k (d = 2.285 A ) and if there is m o r e
t h a n a r o u n d 2 0 % q u a r t z t h e n the intensity of t h e
calcite p e a k is increased, so that t h e r e appears to b e
m o r e present t h a n t h e r e actually is.
W2
1 1 3
http://jurassic.ru/
Recently, several m e t h o d s have been described

for quantitative X-ray analysis of mixtures of min
erals. F a n g & Zevin (1985) p r e s e n t e d a standardless
m e t h o d whereby sample absorption is m e a s u r e d , as
well as p e a k intensity. M a r t i n e z & Plana (1987) have
devised a m e t h o d for a mixture of carbonate minerals
using t h e technique of fitting Lorentzian profiles.
7.6 X R D O F S I L I C A
MINERALS
T h e metastable silica minerals which occur in young

cherts, that is opaline silica a n d o p a l - C T , are best
identified by X-ray diffraction. Opaline silica, some
times referred to as O p a l - A (Jones & Segnit, 1971)
is a highly disordered, nearly a m o r p h o u s hydrous
silica, with a very fine crystallite size of 11 15 A .
T h e X R D p a t t e r n of opal is a diffuse band between
6 and 2.8 A , with a m a x i m u m at a b o u t 4.0 A (see
Fig. 7.32). T h e tests of radiolarians, diatoms and
sponge spicules, which a r e t h e main constituents of
d e e p sea siliceous oozes, are composed of opaline
silica. Precious opal is also o p a l - A . D i s o r d e r e d cristobalite, sometimes called lussatite and t e r m e d opalC T by J o n e s & Segnit (1971), is m o r e obviously
crystalline, although still h y d r o u s , and consists of
irregularly stacked layers of low-(a-) cristobalite and
228
opal
Use of the Scanning Electron Microscope

in sedimentology
NIGELTREWIN
8.1
This chapter is i n t e n d e d t o introduce t h e r e a d e r to

t h e use of the S E M in sedimentology. In the space
available it is n o t possible to go into details and
theory of machine o p e r a t i o n , and neither is it in
t e n d e d t o evaluate t h e great range of S E M machines
and ancilliary instrumentation now on t h e m a r k e t .
W h e n purchasing an S E M it is essential to consider
carefully t h e features required and to ensure that t h e
machine is capable of taking any additions such as
analytical e q u i p m e n t and a backscattered electron
detector at a later d a t e . In general it is advisable to
buy t h e best S E M o n e can afford as small models
have limited versatility.
Fig. 7.32. Typical X-ray diffraction

patterns of silica minerals arranged in
order of increasing maturity: (a)
opaline silica, such as precious opal,
(b) immature chert or porcelanite of
Middle Eocene age from the
Equatorial Pacific, (c) Monterey chert
from California, (d) granular chert
and (e) vitreous chert from the Lower
Tertiary of Cyprus. C = cristobalite,
T = tridymite, Q = quartz.
low-tridymite. T h e X R D p a t t e r n consists of broad

e n e d , but well-defined p e a k s of low cristobalite,
especially d
at 4.1 A and d no at 2.5 A , and
tridymite peaks, notably rfion at 4.254.3 A . Dis
o r d e r e d cristobalite is an intermediate mineral in t h e
diagenesis of opaline silica t o quartz chert. It occurs
in porcelanites, most c o m m o n opals, bentonitic clays
and silica glass. In fact, with increasing d e p t h of
burial, t h e r e is a decrease in t h e d
spacing of opalC T , from a m a x i m u m of 4.11 A to a m i n i m u m of
4.04 A . T h e cristobalite also becomes m o r e o r d e r e d
(sharper p e a k ) relative to tridymite (Mizutani, 1977).
10l
INTRODUCTION
Chalcedony is a fibrous variety of q u a r t z , dis

o r d e r e d , with crystals much larger t h a n a micro
m e t r e . It has t h e same p e a k s as t h e o t h e r varieties of
T h e techniques and examples described here are

those most commonly in use in general sedimento
logical studies involving t h e S E M and will be found
sufficient for most studies u n d e r t a k e n in under
g r a d u a t e and p o s t g r a d u a t e courses in sedimentology.
If m o r e detail is required o n either theory or prac
tice t h e r e a d e r is referred to Smart & Tovey (1982),
M c H a r d y & Birnie (1987) and to the volumes edited
by H a y a t (197478). Types of backscattered elec
tron detectors are described by Pye & Krinsley
(1984). T h e s e publications illustrate the great
advances that have been m a d e in S E M techniques
from t h e early days of S E M development in
Cambridge. With the advent of the first commercially
available S E M in 1965 (Cambridge Scientific In
struments) t h e r e has b e e n a rapid expansion of
techniques and applications to suit a great variety
of scientific disciplines, and within the b r o a d area of
sedimentology the S E M is used for a wide variety of
investigations as described by many authors in
Whalley (1978).
q u a r t z , cryptocrystalline ( < 1 u m ) , microquartz (1

10 um) and m e g a q u a r t z ( > 1 0 u m ) , i.e. a major p e a k
at 3.343 A and a secondary p e a k at 4.26 A , which
coincides with t h e m a i n tridymite peak. T h e s e var
ieties of q u a r t z comprise t h e older, diagenetically
' m a t u r e ' cherts, such as occur in Mesozoic and older
successions. In fact, t h e r e is also a progressive in
crease in t h e crystallinity of t h e q u a r t z , until it has
p e a k s as strong a n d sharp as q u a r t z of m e t a m o r p h i c
and igneous origin. P a p e r s noting t h e X-ray diffrac
tion patterns of siliceous sediments and rocks can b e
found in H s u & J e n k y n s (1974), notably v o n R a d &
Rosch (1974) and in Garrison etal. (1981). Williams
et al. (1985) have recently reviewed t h e changes in
silica minerals during diagenesis.
T h e S E M is of great value in any situation re

quiring examination of rough surfaces at a magnifi
cation range from X20 u p to x 100.000. It is t h e
great d e p t h of focus which enables excellent p h o t o
graphs to be t a k e n of features t o o small and rough to
be within t h e focus range of a binocular microscope,
and features so small and delicate t h a t t h e y would be
destroyed in t h e making of thin sections. T h e major

contribution of the S E M to sedimentology has been
in t h e general field of diagenesis w h e r e rock texture,
p o r e s and delicate p o r e fillings can be examined on
fresh b r o k e n surfaces (Wi)son & Pittman, 1977;
Blanche & W h i t a k e r , 1978; W a u g h , 1978a, b ; H u r s t
& Irwin, 1982; W e l t o n , 1984). With an analytical
facility (essential for most diagenesis work) indivi
dual grains can be analysed and identified in situ and
information gained on diagenetic sequences.
E x a m i n a t i o n of b r o k e n surfaces is frequently ap
p r o p r i a t e for p o r o u s rocks; n o n - p o r o u s rocks can be
examined o n polished and etched surfaces, t h e
m e t h o d of etching being d e t e r m i n e d by t h e desired
feature to be observed. Backscattered electron
( B S E ) images of polished surfaces provide atomic
n u m b e r contrast so enabling recognition of different
mineral phases and permitting the use of automatic
image analysis systems (Dilks & G r a h a m , 1985).
Applications of B S E imagery are illustrated by Pye
& Krinsley (1984, 1986b) and White, Shaw &
Huggett (1984). Individual grains can be examined
for details of surface texture with a view to eluci
dating their t r a n s p o r t
history
(Krinsley
&
D o o r n k a m p , 1973; Bull, 1981); grains from heavy
mineral separations can be rapidly examined,
analysed and p h o t o g r a p h e d . Individual grains or
loose sediments can be e m b e d d e d in resin, polished
and etched to reveal internal structures and origins;
this is particularly useful with carbonates ( H a y ,
Wise & Stieglitz, 1970).
In sediments and rocks with an organic com
p o n e n t , detailed information can be gained on the
physical and chemical b r e a k d o w n of bioclasts
(Alexandersson,
1979). Biological
destruction
by boring algae ( L u k a s , 1979) and fungi and also
by organisms grazing grain surfaces can be d e d u c e d
(Farrow & Clokie, 1979). T h e extensive use of
t h e S E M in t h e study of microfossils is outside
t h e scope of this b o o k . T h e S E M can also be ex
tremely useful as an auxiliary tool for checking sizes
of objects, such as the crystal size of clay separations
i n t e n d e d for X R D w o r k .
229
http://jurassic.ru/
JiliJiiJMiMiim
230
THE SEM IN SEDIMENTOLOGY
N.H. TREWIN
8.2 B A S I C F U N C T I O N A N D M O D E S
OF OPERATION OF THE SEM
T h e S E M (Fig. 8.1) comprises an electron gun which
produces a stream of electrons to which an acceler
ating voltage of 2 - 3 0 k V is applied. T h e b e a m
passes through a series of two o r m o r e electromag
netic lenses t o p r o d u c e a small (10 n m or less)
demagnified image of t h e electron source o n the
specimen. F o r most geological work a tungsten hair
pin filament is used as t h e electron source with a
vacuum of about 1 0
torr. Brighter images and
better definition can b e obtained with a L a B gun at
1 0 ~ torr and for ultrafine definition a field emission
source operating at I O t o r r can b e used, b u t this
requires special seals and p u m p i n g a r r a n g e m e n t s to
achieve t h e required v a c u u m .
- 5
- 9
Before passing through t h e final electromagnetic

lens a scanning raster deflects t h e electron b e a m so
that it scans t h e surface of t h e specimen. T h e scan is
synchronized with that of t h e c a t h o d e ray t u b e a n d a
picture built u p of t h e scanned area of t h e specimen.
C o n t r a s t in t h e c a t h o d e ray picture is d u e to varia
tion in reflectivity across t h e surface of specimen.
W h e n t h e electron b e a m strikes the surface of t h e

specimen (Fig. 8.2) s o m e electrons a r e reflected as
backscattered electrons ( B S E ) and s o m e liberate
low energy secondary electrons ( S E ) . Emission of
electromagnetic radiation from the specimen occurs
at various wavelengths but those of principle interest
are visible light (cathodoluminescence) and X-rays.
T h e backscattered ( B S E ) and secondary (SE)
electrons reflected and emitted from t h e specimen
are collected by a scintillator which emits a pulse of
light at t h e arrival of an electron. T h e light emitted
is t h e n converted to an electrical signal and ampli
fied by t h e photomultiplier. After further amplifica
tion t h e signal passes t o t h e c a t h o d e ray t u b e grid.
T h e scintillator is usually held at a positive p o t e n
tial of 510 kV to accelerate low energy emitted
electrons sufficiently for t h e m to emit light when
they hit t h e scintillator. T h e scintillator has t o be
shielded to p r e v e n t t h e high potential of t h e scintil
lator deflecting t h e primary electron b e a m . T h e
metal shield includes an o p e n metal gauze which
faces t h e specimen and allows passage of most elec
trons to the scintillator surface.
Filament (negative HT)

Electron gun
Electron beam
b
a
=
Anode (earthed)
8.2.1 Emission (SE) and reflection (BSE)

m o d e s of o p s r a t i o n s
D u r i n g n o r m a l operation both reflected and emitted
electrons a r e collected (Fig. 8.3), and t h e scintillator
shield and gauze are kept at a positive potential.
W h e n o p e r a t e d in t h e reflective ( B S E ) m o d e the low
energy secondary electrons (SE) a r e prevented from
reaching t h e collector by appljpation of a negative
potential (100 to 300 V ) t o t h e shield and gauze
and only t h e high energy reflected electrons are
collected. T h e standard type of collector used is a
highly directional scintillator-photomultiplier which
can be placed well away from t h e specimen since t h e
low energy secondary electrons are attracted to t h e
scintillator by the applied voltage. This type of d e
tector is not very efficient at collecting high energy
reflected electrons and a purpose-built B S E detector
is required. T h r e e types of B S E detectors are in
c o m m o n use.
T h e s e are: (1) Solid State C o n d u c t o r Devices; (2)
Wide-angle Scintillator-Photomultiplier D e t e c t o r s
such as t h e R o b i n s o n D e t e c t o r (Fig. 8.4); (3) Multi
ple Scintillator-Photomultiplier Detectofs.
T h e basic function of these B S E detectors is d e
scribed by V . N . E . R o b i n s o n (1980) and Pye &
Krinsley (1984); all designs of B S E detectors sub
t e n d a large solid angle with respect to the specimen
to collect as many high-energy electrons as possible
(see also Section 8.3.4).
Contrast in t h e image p r o d u c e d is d u e to a n u m
ber of factors:
Spray aperture
Condenser lens 1
Condenser aperture
Condenser lens 2
Scan coils
Collector Photomultiplier
Scan
generator
Video
amplifier
Screen
Fig. 8.1. Schematic diagram to illustrate basic functional

features of a Scanning Electron Microscope.
231
(a) General topography

and orientation
of the
specimen surface. Reflected electrons (BSEs) gen
erally have high e n o u g h energy t o travel in straight
lines and thus a suitable angular relation must exist
between b e a m , surface and collector, hence the
advantage of wide angle detectors. L o w energy
secondary electrons (SEs) have paths which a r e
easily bent by t h e field created by the potential o n
t h e collector shield. T h u s information can b e col
lected from areas which d o not have a direct line of
sight to the collector.
Tilting t h e specimen towards the collector in
creases t h e efficiency of collection, and h e n c e bright
ness, particularly in t h e reflective m o d e . T h u s bright
ness of image d e p e n d s o n orientation of surfaces o n
t h e specimen.
(b) Chemistry of the specimen surface. T h e effi
ciency of reflection of electrons from a flat surface
inclined towards t h e detector is d e p e n d e n t on t h e
chemistry of t h e surface. T h e reflection coefficient
increases as t h e atomic n u m b e r increases ( T h o r n t o n ,
1968) and hence particles with higher atomic num
bers a p p e a r brighter. O p e r a t e d in t h e normal re
flection-emission
m o d e (SEs + BSEs) this effect is
usually m a s k e d by topographic effects, but can b e
most effectively utilized with a B S E detector to
p r o d u c e images of polished surfaces which, u n d e r
favourable conditions, can reveal differences in
atomic n u m b e r d o w n t o 0.12 (Hall & Lloyd, 1981).
Electron beam
Electron beam
Specimen
/
Fig. 8.2. Types of emission generated by an electron beam

striking the surface of a specimen in the SEM.
(a) High energy electron produced by single reflection.
(b) Low energy secondary electrons generated close to
surface.
(c) Secondary electrons generated at such a depth within
specimen that all are absorbed.
(d) Generation of X-rays or cathodoluminescence.
Fig. 8.3. Collection of low energy emitted electrons (a

paths) by scintillator in positively chargedcdlleetor shield.
Reflected electrons (b path) are also collected.
http://jurassic.ru/
Fig. 8.4. Collection of high energy reflected electrons by a

wide-angle scintillator-photomultiplier type of
backscattered electron collector such as the Robinson
detector.
232
N.H. TREWIN
(c) Differences
in electrical potential
on the
specimen surface. T h e trajectories of low energy
secondary electrons a r e affected by small variations
in surface charge on the specimen. A r e a s of t h e
specimen which are relatively negative a p p e a r bright
on the image and this results in t h e effect k n o w n as
charging which occurs if t h e point of b e a m impact is
not effectively e a r t h e d by either the natural conduc
tivity of t h e specimen o r its applied coating. C h a r g e
accumulations of only a few volts give rise to charging
features with low energy electrons, but with high
energy reflected electrons a charge build-up of
several kilovolts is required; thus B S E images are
charge free.
F o r t h e examination of most geological materials
t h e S E M is o p e r a t e d in the combined S E - B S E
m o d e . Increasing use is being m a d e of B S E imaging
of polished surfaces with t h e advent of efficient
back-scattered detectors. A l t h o u g h on many instru
m e n t s it is possible t o obtain a back-scattered image,
with t h e n o r m a l d e t e c t o r t h e quality is usually p o o r
since t h e detector is not designed for t h e collection
of reflected electrons.
8.2.2 X-ray m o d e of operation

T h e X-rays given off when the electron b e a m strikes
t h e specimen can b e used for X-ray micro-analysis of
t h e target a r e a , by comparing either the wavelengths
or energies of t h e X-rays with emissions from stan
d a r d s . W h e n incident electrons-collide with a t o m s in
t h e specimen, electrons may be displaced from inner
to outer electron shells. X-rays are emitted w h e n an
electron falls back t o t h e inner shell. X-rays are
emitted relevant t o K, L a n d M electron shells
within t h e constraints of electron b e a m energy.
In analysis by wavelength discrimination t h e X rays are passed t o a spectrometer to b e diffracted by
a crystal from which those that satisfy t h e Bragg
equation of X = 2d sin 6 pass on to the d e t e c t o r to b e
c o u n t e d . T h e lightest e l e m e n t detected by wave
length discrimination is b o r o n , Z = 5.
Energy discriminating systems ( E D S ) are in m o r e
general u s e and have a solid state lithium drifted
silicon single crystal detector, which must b e k e p t
cool with liquid nitrogen. T h e entire X-ray b e a m is
passed t o t h e d e t e c t o r a n d t h e resulting signal is
divided by a multichannel pulse height analyser.
With a conventional beryllium detector w i n d o w , t h e
lightest element readily detected is sodium ( Z = 11),
but with ultra-thin windows and windowless detec

tors lighter elements such as C , O and N can b e
detected.
Most samples to be analysed require a conduc
tive coating (Section 8.6.4). C a r b o n is most suitable,
but t h e coating must not contain any elements for
which an analysis is required. Ultra-thin gold coat
ing is frequently used but has t h e disadvantage that
gold produces many spectral lines. F u r t h e r details of
X-ray analysis of sediment and relevant references
a r e given in C h a p t e r 9 of this volume.
8.2.3 C a t h o d o l u m i n e s c e n t m o d e o f
operation
T h e C L operation m o d e utilizes t h e visible light
emitted when electrons strike t h e specimen. M a t e r
ials vary greatly in their luminescent p r o p e r t i e s a n d
minor traces of impurities can affect t h e luminescent
properties. Emission is also altered by lattice strain
resulting from crystal defects a n d residual strain.
Collection of t h e emitted light is achieved by
focussing it with a lens into a light guide a n d o n t o a
photomultiplier. Picture contrast is d u e t o a variety
of factors. T o p o g r a p h y of t h e specimen is i m p o r t a n t
but t h e resulting features of greater interest are d u e
to chemical variations, crystal defects a n d crystal
orientation. F u r t h e r details on this t e c h n i q u e using
t h e S E M can b e found in Muir & G r a n t (1974),
G r a n t (1978), Krinsley & Tovey (1978) a n d Smart &
Tovey (1982). T h e multiple scintillator-photomultiplier type of B S E detector can b e a d a p t e d for catho
doluminescence work. In the Philips Multi-Function
D e t e c t o r , cathodoluminescence detector elements
can b e substituted for B S E detector elements (Pye
& W i n d s o r - M a r t i n , 1983). R u p p e r t et al. (1985)
illustrated contrasting B S E and C L images of a
s a n d s t o n e , and further examples are shown in Fig.
8.8. T h e r e a d e r is also referred to C h a p t e r 6 on
cathodoluminescence in this volume.
8.3 S E M A N C I L L A R Y E Q U I P M E N T
AND TECHNIQUES
8.3.1 Photographic equipment a n d
techniques
are e q u i p p e d with a good quality 35-mm single lens

reflex c a m e r a for r o u t i n e w o r k . This is t h e cheapest
m o d e of o p e r a t i o n , using a high speed film such as
Uford H P 5 or K o d a k Tri-X. F o r many purposes a
slower film such as Ilford F P 4 is satisfactory and may
be preferable if long scan times of 5 minutes or
m o r e are used. It m a y b e preferred to have a larger
negative size to reduce t h e photographic enlarge
m e n t phase a n d to use a '120' or a 70-mm c a m e r a .
S o m e machines are designed to take a Polaroid
camera a n d this system has t h e great advantage that
an instant picture is obtained and the o p e r a t o r can
ensure that a picture of t h e desired quality has been
obtained before moving o n t o examine o t h e r areas
of the specimen. T h e great disadvantages are that
picture quality is lost if t h e print has to b e r e p h o t o graphed to p r o d u c e copies and it is an expensive
process.
A n ideal system is a Polaroid positive/negative
film which produces b o t h a print and a large size
negative. T h e necessary photographic solutions have
t o be k e p t fresh a n d at h a n d , but w h e r e both rapid
results and a quality negative are required t h e system
is excellent.
TECHNIQUES
T h e excellent resolution a n d great d e p t h of field of
t h e S E M have m a d e it very p o p u l a r for providing
illustrations for a wide variety of geological studies.
T h e quality of S E M p h o t o g r a p h s in geological jour
nals is highly variable, ranging from excellent to
examples displaying m a n y of t h e faults illustrated
and discussed in Section 8.6.2. In s o m e cases the
p a p e r quality of t h e journal is responsible for p o o r
reproduction.
F o r most sedimentological work simple views of
surfaces a r e all that is required a n d with most
machines a zoom facility enables t h e o p e r a t o r to
c o m p o s e t h e p h o t o g r a p h satisfactorily. If it is pro
p o s e d t o m a k e a multiple plate of p h o t o g r a p h s it is
helpful to t a k e t h e shots at t h e same magnification
or at multiples of a basic magnification. T h e incor
p o r a t i o n of a micron m a r k e r in the p h o t o g r a p h is
essential and easier to ' r e a d ' t h a n a p h o t o g r a p h
captioned as x 4350! E n s u r e that t h e micron m a r k e r
contrasts with its b a c k g r o u n d , o r e n h a n c e and label
t h e m a r k e r for publication p u r p o s e s .
EQUIPMENT
T h e choice of a c a m e r a for use with an S E M is
largely a m a t t e r of user preference. Many machines
233
MONTAGES
P h o t o g r a p h i c m o n t a g e s m a y h a v e t o b e constructed
to cover large areas at high magnification. T h e
construction of both controlled a n d uncontrolled
montages is discussed by Smart & Tovey (1982).
U n c o n t r o l l e d m o n t a g e s a r e m a d e merely by match
ing features in the overlap area of the p h o t o g r a p h s
(Fig. 8.5), b u t because the area scanned is generally
trapezoidal severe distortions in orientation develop
if large n u m b e r s of micrographs a r e joined. It is
preferable that p h o t o g r a p h s are t a k e n at magnifica
tions > 2 0 0 0 a n d that less t h a n c. 10 p h o t o g r a p h s a r e
joined together.
Controlled m o n t a g e s (Fig. 8.5) a r e p r e p a r e d by
photographing on a regular grid p a t t e r n and noting x
a n d y shift co-ordinates of t h e centre of each p h o t o
graph a n d then mounting t h e p h o t o g r a p h s on a
regular grid. Matching will n o t b e perfect but dis
tances and orientations will be better preserved. All
p h o t o g r a p h s must b e t a k e n with ample overlap (c.
2 5 % ) , without altering the magnification, and must
be enlarged by the same factor in processing.
Distortion effects in m o n t a g e construction are
greatest at low magnifications and high tilt angles of
t h e specimen. T h e m o u n t i n g a n d printing of p h o t o
graphs for m o n t a g e s requires skill. Contrast of ad
jacent p h o t o g r a p h s must b e reasonably close to
General scan area of

tilted specimen
(a)
(b)
Uncontrolled montage with

distortion buildup
Controlled montage with

orientation preserved
Fig. 8.5. Production of (a) uncontrolled and (b) controlled

photographic montages.
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N.H.
TREWIN
provide a pleasing match. W h e n mounting t h e photo

graphs, joins can be m a d e less obvious by matching
along p r o m i n e n t features such as sharp grain mar
gins to avoid contrast differences.
It may b e possible to t a k e m o n t a g e p h o t o g r a p h s
in the emission m o d e without tilting t h e specimen,
thus avoiding t h e worst features of distortion, and
s o m e machines have a tilt compensation device
which helps reduce distortion. Generally a balance
has to b e struck b e t w e e n distortion a n d picture
quality. T h e value of m o n t a g e s is that fine detail and
its distribution can b e evaluated over large areas:
t h e ultimate e x a m p l e must be the 3 x 3 m m o n t a g e
by Wellendorf & Krinsley (1980) consisting of over
1100 S E M p h o t o g r a p h s t a k e n at x 4300 to cover a
single q u a r t z grain! Unfortunately the m o n t a g e loses
a little detail in t h e required reduction to 135 m m
d i a m e t e r for publication!
STEREOSCOPIC MICROGRAPHS
A n y specimen stage which enables t h e specimen to
be tilted permits t h e taking of stereoscopic pairs.
M e t h o d s that can b e employed are discussed by
T o v e y (1978) and Smart & Tovey (1982). T h e most
c o m m o n m e t h o d used is t h e 'tilted convergent'
m e t h o d whereby t h e specimen is tilted by a small
angle (25) about a m e a n tilt angle. This m e t h o d
ensures that t h e specimen is facing t h e detector in
both positions. T h e illumination is effectively from
t h e side in this m e t h o d and t h e p h o t o g r a p h s must b e
rotated by 90 for stereoscopic viewing.
Techniques vary d e p e n d i n g o n t h e t y p e of speci
m e n stage, but in general o n e must ensure that t h e
same a r e a is p h o t o g r a p h e d on each occasion. This
can b e achieved by sketching t h e first view o n a
t r a n s p a r e n t overlay on t h e screen. T h e magnifica
tion is t h e n reduced t o less t h a n x 200 while keeping
track of a convenient reference feature n e a r t h e
centre of t h e screen. T h e stage can t h e n be tilted by
t h e desired a m o u n t and t h e reference feature
brought back t o its previous position using t h e X , Y
controls. T h e magnification can t h e n be increased t o
t h e correct figure and t h e desired feature checked
with its outline previously d r a w n o n t h e screen over
lay. A n y refocussing should be d o n e with t h e Z
control to avoid image rotation and magnification
changes d u e t o alteration of working distance. T h e
second p h o t o g r a p h can t h e n be t a k e n .
D e t a i l e d discussion of stereographic techniques
can b e found in Clarke (1975) including m e t h o d s for
T H E S E M IN S E D I M E N T O L O G Y
accurate calculation of dimensions of surface relief

features. Surprisingly little use has b e e n m a d e of
stereographic techniques in sedimentology, but ex
amples can b e seen in Smart & Tovey (1982), and
W h i t a k e r (1978) used stereo pairs to illustrate dia
genetic textures in t h e B r e n t Sandstone (Middle
Jurassic, N o r t h Sea). Much m o r e use could be
m a d e of this t e c h n i q u e for illustrating diagenetic
textures on rough surfaces.
8.3.2 Alpha-numeric displays

S o m e machines have built in alpha-numeric displays
on which a variety of information can be r e c o r d e d
directly o n to t h e p h o t o g r a p h i c negative, for o t h e r
machines such a display can be a d d e d as an optional
extra. Most simple displays permit t h e o p e r a t o r to
identify t h e p h o t o g r a p h with o n e or m o r e serial
n u m b e r s , so saving lengthy cross-checking with
notes o n long negative sequences, and also provide
information on o p e r a t i n g k V , scale b a r length and
laboratory or user's n a m e or n u m b e r .
T h e information display may only a p p e a r o n t h e
recording screen, t h u s t h e o p e r a t o r must e n s u r e t h a t
vital areas of t h e object to be p h o t o g r a p h e d will not
be covered by t h e display.
8.3.3 Analytical equipment

F o r most sedimentological work it is essential to
have s o m e form of analytical facility on t h e S E M for
rapid checking of grain compositions. A n E n e r g y
Dispersive X-ray analysis system ( E D S ) is c o m m o n
ly used which generally permits analysis at a specific
spot of a b o u t 1 um d i a m e t e r (Fig. 8.7) or to collect
emissions from a specific line on the screen or the
whole screen area. M a n y systems also have t h e
facility whereby m a p s of t h e distribution of parti
cular elements in t h e screen a r e a can be built up and
these can be c o m p a r e d with both S E arid B S E
images as illustrated by L o u g h m a n (1984), W h i t e et
al. (1984), G a w t h o r p e (1987) and Fig. 8.9.
D e p e n d i n g o n a suitable system being available,
quantitative analysis can be p e r f o r m e d on t h e S E M
b u t for most sedimentological work a good qualita
tive system is satisfactory. T h e majority of sedimen
tological S E M work involves the study of rough
surfaces, and surface topography affects factors such
as t h e intensity and d e p t h of X-ray p r o d u c t i o n , as
well as t h e absorption effect. R o u g h surfaces can
also obstruct t h e path of X-rays to t h e collector and
backscattered electrons and X-rays can p r o d u c e

radiation from areas outside t h e primary target area
of t h e b e a m (Fig. 8.6).
T o eliminate this situation, t h e specimen should
be reasonably flat and tilted to face t h e detector.
E v e n in this situation t h e r e will b e areas (e.g. within
d e e p pores) from which low count rates result in
small p e a k s with m u c h background noise. Back
ground noise may mask relatively low intensity peaks.
A n o t h e r p r o b l e m is that of e x t r a n e o u s X-rays
arriving at t h e d e t e c t o r . T h e s e u n w a n t e d X-rays are
p r o d u c e d by backscattered electrons and X-rays
from t h e target a r e a of t h e b e a m which strike o t h e r
surfaces which have a line of sight to t h e detector.
T h e result can b e that in an a t t e m p t e d analysis of a
grain in a quartzose s a n d s t o n e , Si may b e detected
from e x t r a n e o u s X-rays from q u a r t z rather t h a n
from the grain being analysed. Some of the effects of
analysis of rough surfaces are illustrated by Fig. 8.7.
W h e r e a s s o m e of these factors can be compensated
for as described by B o m b a c k (1973), it is essential to
d o quantitative analysis using polished surfaces
which can be c o m p a r e d with similarly p r e p a r e d
standards ( C h a p t e r 9).
8.3.4 Back scattered electron detectors

T h e p u r p o s e of these detectors has b e e n explained
(Section 8.2.1) and such a detector is an excellent
addition to an S E M for t h e production of chargefree images of rough surface material and for images
of polished surfaces t o show atomic n u m b e r contrast
(Fig. 8.9).
T h e solid state c o n d u c t o r type of B S E detector
consists of an annular silicon diode m o u n t e d b e
tween the specimen and t h e final lens. U n l i k e early
versions, t h e m o d e r n o n e s can o p e r a t e at T V scan
rates. This form of detector a p p e a r s to be t h e cheap
est, b u t p r o d u c e s good results as shown by Pye &
Krinsley (1984) and Dilks & G r a h a m (1985).
T h e wide-angle scintillator-photomultiplier type
of detector is typified by t h e R o b i n s o n detector
235
Enlarged rough
specimen surface
Fig. 8 . 6 . Analysis of rough surfaces in the SEM; examples

of angles to the detector. Beam position 1 grain B to be
analysed. Count rate reduced by partial obstruction A, and
extraneous X-rays reach detector from C.
Beam position 2 surface of C at virtually ideal 45
position with respect to detector.
Beam position 3 grain D has no line of sight to detector.
No counts from grain.
( R o b i n s o n , 1975) which performs well b u t has a
rather bulky detector h e a d . T h e r e can be space
p r o b l e m s with relatively small S E M c h a m b e r s if an
E D S detector is also required t o be in position.
Multiple scintillator-photomultiplier
detectors
have u p to four detection elements m o u n t e d be
t w e e n t h e specimen a n d final lens. This is a highly
efficient (but m o r e expensive) system and in t h e case
of t h e Philips Multi-Function D e t e c t o r can be modi
fied t o perform cathodoluminescence w o r k .
F o r further details of t h e operation and uses of
these types of detector refer t o V . N . E . R o b i n s o n
(1980) and t h e well-illustrated account by Pye &
Krinsley (1984).
8.3.5 Charge-Free A n t i c o n t a m i n a t i o n
System (CFAS)
T h e C F A S system can b e used in conjunction with a
back-scattered electron detector such as the Robin
son detector and o p e r a t e s by maintaining a small
residual gas pressure of b e t w e e n 0.01 and 0.5 torr in
Fig. 8 . 7 . General view of sandstone to illustrate the use of EDS analysis at five points. The sample was gold coated, hence
the gold peaks on the EDS traces. Analysis identifies at point (1) quartz overgrowths; (2) K-feldspar with overgrowth;
(3) ferroan calcite of diagenetic origin growing into pore space and overgrowing quartz; (4) kaolinite in pore space either
growing around the ferroan calcite or being forced apart by growth of the carbonate; (5) siderite rhomb on quartz grain
surface. Minor Si peaks associated with siderite and calcite analyses are probably due to secondary reflection.
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T H E S E M IN S E D I M E N T O L O G Y
N.H. T R E W I N
t h e specimen c h a m b e r . It is o p e r a t e d by having
s e p a r a t e diffusion p u m p s o n t h e c h a m b e r a n d
column, gas leakage through the 200 um final aper
ture is not significant. In fitting t h e C F A S system t h e
secondary electron detector H V supply is discon
nected, thus it is not possible to switch directly from
n o r m a l operation to C F A S o p e r a t i o n .
T h e advantage of t h e system is that specimens can
b e p u t in as received without t h e n e e d for any
special preparations and coatings. G a s ionization in
t h e c h a m b e r is always equal to charge accumulation
and t h u s charging is automatically eliminated.
Specimens which a r e d a m p or oily and which would
normally c o n t a m i n a t e t h e column can be e x a m i n e d .
This system is excellent for geological use on any
samples requiring rapid examination for mineralogi
cal composition, especially rapid search for small
heavy-element grains ( B . W . R o b i n s o n , 1980; Robin
son & Nickel, 1979). A n a d d e d advantage is t h a t
filament life is r e p o r t e d t o b e increased as c o m p a r e d
with conventional o p e r a t i o n , b u t m o r e frequent
cleaning of t h e column may b e found necessary.
8.3.6 Image analysis

T h e use of image analysis of B S E images p r o d u c e d
from flat surfaces promises to be an extremely useful
t e c h n i q u e . Dilks & G r a h a m (1985) h a v e described
the application of a K o n t r o n S E M - I P S image
analyser coupled to a S E M and d e m o n s t r a t e how
powerful and fast t h e technique can b e to machinediscriminate minerals and porosity on t h e basis of
levels of grey of a calibrated B S E image. Using t h e
system, rocks can be screened for particular minerals
and point c o u n t e d for a r a n g e of defined minerals.
G r a i n size distributions of c o m p o n e n t s of the rock
239
can b e p r o d u c e d , and p o r e size and two-dimensional

p o r e throat size analysed. T h e limitation of t h e
technique is t h e inability to discriminate b e t w e e n
two minerals which have t h e same image intensity.
8.4 S A M P L E C O L L E C T I O N
8.4.1 Surface material and o u t c r o p s
Field sampling of material for S E M studies r e q u i r e s
that s o m e elementary precautions are t a k e n and
sufficient observations m a d e at the sample site. Since
S E M studies will probably only constitute part of
any laboratory study, sufficient material m u s t b e
g a t h e r e d for all possible aspects, such as grain-size
analysis and thin section p r e p a r a t i o n .
Unconsolidated material in which t h e fabric is not
required t o b e preserved can b e collected as a bag
sample (dry) or bottle sample (wet). Samples con
taining live or d e a d organic material may n e e d to be
preserved in alcohol if t h e samples cannot be i m m e
diately t r e a t e d . A l u m i n i u m foil is useful for w r a p
ping small samples t o prevent contamination and t h e
w r a p p e d samples can b e safely t r a n s p o r t e d in plastic
bottles. Cloth or p a p e r is to b e avoided since fibres
are likely to be shed into t h e sample.
I m p r e g n a t i o n of unconsolidated sediments in t h e
field provides a later opportunity to e x a m i n e fabric
details using thin sections or t h e S E M . F o r suggest
ed sample p r e p a r a t i o n see Section 8.5.2.
Consolidated rock material is generally collected
in t h e traditional geological m a n n e r by use of a
h a m m e r . H o w e v e r , such violence can have t h e effect
of producing cracks, fracturing grains and crushing
p o r o u s material. Samples must b e sufficiently large
to avoid such effects and (unless it is t h e object of
Fig. 8.8. Comparison of cathodoluminescence and backscattered electron imagery.

(a, b, c) The rock is a Precambrian dolostone from the Dalradian of Scotland in which phlogopite mica crystals grew during
metamorphism. Subsequently veins developed, tending to propagate parallel to the phlogopite crystals, and were filled by
chemically-zoned calcite crystals, (a) (cathodoluminescence image) shows the fine-grained dolomite host-rock luminescing
dully, the phlogopite crystals not luminescing, whilst the calcite shows an intricate zonal pattern invisible in plane polarized
light, (b) This backscattered electron image is of a similar area to (a). Faint zonation is visible in the calcite which is overall
brighter than the phlogopite and the dolomite because of its higher average atomic number. Bright flecks in the dolomite
and calcite are artefacts, (c) shows a magnified backscattered image in which the atomic number contrast has been
electronically amplified to show the zonation more distinctly. Microprobe analysis shows Fe, Mn and Mg zonation in the
calcite.
(d,e,f) Rock is a porous sandstone from the Jurassic Brent Group, N North Sea. (d) BSE image with quartz (grey) and
porosity (black). Cathodoluminescence image (e) negative and interpretation (f) showing detrital quartz grain shapes
(q) and zoned quartz overgrowths (o) representing different stages of quartz cementation. Minor kaolinite (k) is also
present within pore space (p).
(c)
Fig. 8.9. Backscattered electron images and element distributions, (ac) Growth of carbonate cements within a specimen
of Dactylioceras cf. commune from the Toarcian of NE Yorkshire, (a) Backscattered electron image of polished, carboncoated thin section. Cement stages are interpreted in (b) in which S is a section of an ammonite septum defined by apatite
rims and with associated pyrite framboids. Cement growth stages: (1) high Mg calcite (filling fracture in septum); (2) low
Mg calcite; FeS ; (3) high Mg, Fe calcite; (4) high Fe calcite; (5) high Mn, Fe calcite (replaces septum) fills void, (c)
Histogram and X-ray intensity ( a element abundance) map showing the different concentration of Mg across part of the
area of (a). Cement growth stages are clearly picked out in the elemental map (black and white print derived from a colour
image, hence both high and low Mg concentrations appear pale in this image).
(dh) Chemical variations in a dolomite crystal from the Pendleside Limestone, Lower Carboniferous, Bowland Basin,
northern England, (d) Subhedral dolomite crystal in silicified limestone. The light zones rimming the crystal suggest the
presence of elements with higher atomic: numbers compared with the dull core. Note the irregular contact between the dull
and light zones. Scale bar = 50 \ t m . Back-scattered electron photomicrograph (BSEM). (e) DIGIMAP of view in (d) for
Ca. Note relatively uniform distribution. Scale bar = 25 \ i m (same for f - h ) . (f) DIGIMAP of view in (d) for Mg. Depletion
in Mg in the crystal rim relative to the corgis-indicated by the darker nature of the rim. (g) DIGIMAP of view in (d) for Fe.
Note the very low Fe content in the black core compared with the grey rim. (h) DIGIMAP for Mn showing similar
distribution to Fe (g).
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N.H. TREWIN

study) to b e unaffected by weathering. Since t h e
final sample to be used in any S E M study must be
clean it is not practicable merely to collect small
rock chips in the field. M a n y pitfalls exist in p r e p a r a
tion and ample material should be collected. It is
advisable to collect oriented specimens so that both
way-up and geographical orientation a r e k n o w n .
Field collection of p o r o u s rocks should be d o n e
with regard to possible fluids in the p o r e space. For
e x a m p l e , on a shore section the pores may be filled
with fresh or salt water and may also be regularly
air-filled as tides fall or cliffs dry. Such possibilities
of long continued interchange of gas and fluid and of
flow through t h e p o r e system should be considered
in any study of surface collected material.
Collection of material by use of a p o r t a b l e drill
producing a short, small d i a m e t e r core is also likely
t o be unsatisfactory if it is h o p e d to observe delicate
growths within p o r e space. T h e forces of fluid pres
sure and vibration are likely t o affect t h e fabric
within p o r e space. Joslin (1977) described a tool for
collecting samples of poorly consolidated soft sedi
m e n t s (e.g. chalk). A n 80-mm core barrel with
t o o t h e d e n d is gently drilled into t h e rock with a
h a n d o p e r a t e d drill (brace). T h e core obtained can
b e m o u n t e d direct o n t o a stub in t h e field after
trimming if n o further t r e a t m e n t is required prior to
mounting.
8.4.2 Subsurface material

Material from subsurface cores must be examined
and sampled with as much knowledge as possible of
t h e conditions u n d e r which t h e core was t a k e n and
any subsequent laboratory t r e a t m e n t that may have
t a k e n place.
Preserved samples (pore fluids sealed immediate
ly t h e core is b r o u g h t t o t h e surface) a r e obviously
t h e best to work with and will preserve most in the
way of original t e x t u r e . Such samples are suitable
for advanced techniques such as critical-point drying
(Section 8.5). If t h e core is fresh and still wet w h e n
sampled it can be advantageous t o prevent further
drying by sealing samples or keeping t h e m in simu
lated formation fluid.
If the core has already been air dried there is little
point in using advanced techniques of p r e p a r a t i o n ;
t h e d a m a g e to delicate structures such as illite has
probably already t a k e n place. Should t h e core have
been slabbed it m a y already have Been dried and
rewetted.
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W h a t e v e r t h e state of a core any sample for S E M

examination should be taken from as n e a r the centre
of t h e core as possible w h e n t h e core is still in 'the
r o u n d ' . This will hopefully avoid drilling m u d which
may have invaded p o r e space at t h e margin of the
core. A z o n e of invasion or else of flushing can
frequently be seen in freshly cut cores. If t h e core to
b e sampled has been slabbed t h e sawcut and adjacent
areas should also be avoided for similar reasons.
P e n e t r a t i o n of organic material such as coccolith
plates into p o r e s during injection of sea water into
reservoir rocks has b e e n described by Hancock
(1978a); it is thus advisable to consider t h e possibi
lity that any rock with l a r g e pores and high per
meability may have had material introduced to t h e
p o r e space by t h e passage of fluids through the
sample.
Sidewall cores a r e less satisfactory as they are
usually t a k e n by shooting a short tube into t h e wall
of t h e b o r e h o l e with an explosive charge. This pro
cess frequently results in visible crushing of fabric
and fracturing of grains. C a r e should b e taken to
avoid any m u d c a k e that may be present on the walls
of t h e b o r e h o l e .
Cuttings from boreholes a r e t h e least satisfactory,
but can be cleaned and may provide useful informa
tion. H o w e v e r they are normally only obtained from
relatively well lithified, low porosity material and
not from t h e m o s t p o r o u s and p e r m e a b l e rocks in
t h e b o r e h o l e . In all cases w h e r e borehole material is
used electric logs should b e consulted for information
on o t h e r sedimentological and petrological aspects.
8.5 S A M P L E T R E A T M E N T
8.5.1 Porous r o c k s t o be viewed o n
fractured surfaces
T h e following p r e p a r a t i o n techniques a r e generally
used for viewing b r o k e n surfaces of porous rocks
which fracture a r o u n d grains rather t h a n through
grains. T h e m e t h o d of p r e p a r a t i o n of material can
have a m a r k e d effect o n t h e fabric of delicate clays
such as filamentous illite present within p o r e space.
M c H a r d y , Wilson & Tait (1982) have shown how
critical-point drying can preserve features which
would be destroyed by air-drying and freeze-drying
techniques. T h e value of using critical-point drying
is that the technique prevents the passage through
t h e p o r e s of an airliquid interface or an interface
242
N.H. TREWIN
between immiscible liquids. It is t h e passage of such

an interface which can cause collapse and reorienta
tion of clays within p o r e space. If it is known that t h e
specimen has already been air dried, advanced tech
niques of p r e p a r a t i o n cannot restore t h e situation.
F u r t h e r useful details of preparation techniques for
clays are given by M c H a r d y & Birnie (1987).
AIR-DRIED SAMPLES
Samples previously air dried and which contained
water as the p o r e fluid can be examined without
further t r e a t m e n t , but it is frequently advisable t o
wash the specimen with distilled water t o r e m o v e
any chlorides or other soluble salts which may have
crystallized in p o r e space d u e to the evaporation of
saline p o r e water. This is best achieved by soaking a
sample, not m o r e than 1 cm thick, in distilled water
until it is chloride free. ( T h e time t a k e n will d e p e n d
on permeability and salinity of the e v a p o r a t e d p o r e
water.) This technique is also useful for m o d e r n
m a r i n e sediments and rock material collected from
shore sections.
A i r drying, combined with removal of water solu
ble material, is also a technique which can b e used to
study t h e soluble salts and t h e effects of their re
moval. This has applications in the study of weather
ing of rocks and t h e formation of evaporites.
If delicate material such as fibrous illite is suspect
ed to exist in p o r e space and either time or lack of
a p p a r a t u s precludes use of critical-point drying, bet
ter results may b e o b t a i n e d by air drying samples
from amyl acetate. T h e advantage of this m e t h o d is
that amyl acetate has a much lower surface tension
than water and so the forces exerted at t h e liquid
gas interface as the specimen dries a r e r e d u c e d .
OIL-SATURATED SAMPLES
Rocks that are oil-saturated, or which contain oil
residues after evaporation of lighter h y d r o c a r b o n s ,
must have t h e hydrocarbon r e m o v e d prior to S E M
examination. If oil is n o t r e m o v e d it is vaporized by
t h e electron b e a m and will m a k e t h e S E M column
dirty and reduce picture quality. Oil also prevents
t h e efficient coating of t h e sample with gold, result
ing in charging of t h e specimen and p o o r resolution
pictures.
Oil can be r e m o v e d by use of solvents such as
a c e t o n e , xylene, t o l u e n e , chloroform and trichlor o e t h a n e . Chloroform and trichloroethane are the
most efficient at removing oil. It is possibly safer to

use trichloroethane t h a n chloroform, b u t full safety
precautions (gloves and fume c u p b o a r d ) should b e
t a k e n in handling all these solvents.
Method. A sample measuring about 10 x 10 x 5
m m is immersed in the solvent and sealed in an air
tight jar (to prevent fumes). T h e solvent is changed
every 12 h o u r s . T h e process is r e p e a t e d until all t h e
oil has been r e m o v e d ; this can be judged by lack of a
residual oil film on evaporation of a few d r o p s of t h e
used solvent on a glass slide. With reasonably per
m e a b l e rocks two changes of trichloroethane are
normally sufficient to r e m o v e the oil. T h e sample is
then allowed to air dry at r o o m t e m p e r a t u r e for 24
h o u r s . If residual oil a p p e a r s on t h e specimen sur
face after drying, a final washing in solvent will
usually r e m o v e t h e last traces. A fresh fracture
surface can then be produced for observation in t h e
S E M . C o m p a r i s o n s of oil saturated and oil-free
samples treated by t h e above m e t h o d show n o ap
p a r e n t difference in clay morphology or orientation.
R e m o v a l of oil from rocks with p o o r permeability
can be exceedingly difficult and t h e samples may
have t o be flushed of oil by application of a pressure
difference across the sample. Oil can be t r a p p e d in
p o r e s which a r e n o longer connected, and in cases
such as this only the surface of t h e sample can be
effectively cleaned and only small specimens should
be used to minimize t h e a m o u n t of oil that may be
released from the rock w h e n u n d e r vacuum in t h e
SEM chamber:
In commercial core analysis laboratories oil is
frequently r e m o v e d using a Soxhlet extractor. T h e
sample is first flushed with methanol to r e m o v e
water, a process which may t a k e from 8 hours to 3
days depending o n permeability. T h e sample is then
dried in air until t h e bulk of t h e m e t h a n o l has
evaporated and then put back in a n o t h e r extractor
with xylene or t o l u e n e and flushed until clean. Clean
liness is generally judged by a lack of
fluorescence
u n d e r U V light. T h e sample can then b e air dried as
required. T h e r e is t h e possibility that t h e m o r e
active flushing in this m e t h o d and t h e i n t e r m e d i a t e
drying stage could affect clay fabrics.
Drying of wet specimens can be accomplished at
r o o m t e m p e r a t u r e , by use of an oven or by applica
tion of a vacuum. All these m e t h o d s involve a
volume decrease of clay or m u d specimens with the
result that depositional textures of clays are p r o b
ably not retained. If specimens are oven dried, a low
t e m p e r a t u r e (50C) should be used to avoid loss of
structural water in clays. If washed cuttings from oil

wells are being examined it is essential to ensure that
the cuttings were not dried at a high t e m p e r a t u r e
after the washing process.
FREEZE DRYING
Freeze-drying techniques a r e used extensively on
biological material and have been applied success
fully to claywater systems in soils. This m e t h o d is
favoured by E r o l , L o h n e s & D e m i r e l (1976) for
preparation of swelling clays such as Na-montmorillonites. It does not involve replacement of water
with an organic liquid which could cause swelling
and ion exchange in the clays.
Method. T h e m e t h o d described by M c H a r d y et
al. (1982) used 10-mm pieces of rock (Jurassic,
Magnus Field reservoir from t h e N o r t h Sea) which
were either directly frozen with the contained p o r e
water or frozen after the samples were washed free
of chloride. Samples w e r e plunged into liquid nitro
gen or freon for at least 30 m i n u t e s , they were t h e n
vacuum-dried from the frozen state in an E d w a r d s
M o d u l y o freeze-drier. T h e drying p h a s e takes sev
eral days.
F o r the m e t h o d to b e a success t h e specimen must
be cooled very rapidly so that the water is frozen in
place and ice crystals d o not form. T h e rate of
cooling required is several h u n d r e d degrees p e r
second and this will only be accomplished on t h e
o u t e r surface of t h e rock, and possibly to a d e p t h of
only 0.1 m m (Greene-Kelly, 1973). A n o t h e r prob
lem is e n c o u n t e r e d in t h e drying p h a s e w h e n it is
necessary t o w a r m t h e specimen t o a t e m p e r a t u r e
greater than 40C t o achieve sublimation of t h e ice
in a reasonable time, but at this t e m p e r a t u r e rapid
growth of ice crystals will occur which will displace
matrix clays.
T h e main applications of freeze-drying of samples
a r e in t h e study of soils and swelling clays. M c H a r d y
et al. (1982) found this m e t h o d inferior to criticalpoint drying for preservation of delicate illite in p o r e
space.
CRITICAL-POINT DRYING
T h e advantage of t h e critical-point drying technique
is that it eliminates t h e surface-tension forces ap
plied to delicate crystals during t h e drying stage by
avoiding t h e passage of an airwater interface
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243
through t h e p o r e space. This results in better pre

servation of delicate structures, such as fibrous illite
( M c H a r d y et al., 1982). T o v e y & W o n g (1978)
favoured this m e t h o d for t h e preparation of wet
sediment samples. T h e disadvantage of the m e t h o d
is that it is time-consuming, requires special appar
atus, and has disadvantages if swelling clays are
present (see a b o v e ) .
T h e m e t h o d of preparation used by M c H a r d y
et al. (1982) is as follows. Pieces of rock of 10-mm
size which contained simulated formation water had
t h e water replaced by m e t h a n o l by the successive
passage through t h e specimens of 1:3, 1:1 and 3:1
methanolwater mixtures and finally 100% m e t h a
nol. T h e m e t h a n o l was then replaced daily until free
from chloride which was t a k e n to indicate t h a t all
p o r e fluid h a d b e e n replaced by m e t h a n o l . T h e
samples were then transferred to t h e critical-point
drying a p p a r a t u s (Polaron model E3000 with a liquid
transfer boat with integral drain valve). T h e boat
with six to eight samples in m e t h a n o l was loaded
into t h e pressure c h a m b e r which was pre-cooled by
cold mains water. T h e c h a m b e r was flushed with
liquid CO2 for a b o u t 10 min and allowed to stand for
several h o u r s with t h e C 0 level above t h e samples
at all times. T o ensure replacement of m e t h a n o l by
liquid C 0 t h e c h a m b e r was flushed with C 0 for
510 min twice a day for a week. Finally t h e pres
sure a p p a r a t u s was h e a t e d to 37C by water circula
tion from a 40 t h e r m o s t a t to bring it above t h e
critical point of C 0 (32C) and the t e m p e r a t u r e
held for 30 min to e n s u r e equilibrium was reached in
t h e samples. T h e C 0 was t h e n slowly vented from
t h e c h a m b e r at 2 ml s
which was slow enough to
p r e v e n t condensation of C 0 in the c h a m b e r . T h e
dried samples w e r e then ready for production of a
clean fracture face and m o u n t i n g as described below
in Section 8.6.
2
- 1
Critical-point drying has b e e n found useful for t h e

t r e a t m e n t of illite-bearing sandstones ( M c H a r d y et
al., 1982; M c H a r d y & Birnie, 1987) and has also
been used in studies on pore-size distribution in soils
( L a w r e n c e , 1977; M u r r a y & Q u i r k , 1980) and
should be considered as a preparation method well
worth trying with p o r o u s samples that have their
original p o r e fluids preserved. Farrow & Clokie
(1979) used critical-point drying in a study of boring
algae to reveal algal filaments within the borings.
T h e samples were first fixed with glutaraldehyde,
d e h y d r a t e d through a series of alcohols and brought
to acetone and t h e n critically point dried.
244
N.H. TREWIN
8.5.2 Non-porous r o c k s
Rocks which have low porosity or in which grains
and cement give similar resistance to fracturing, as is
t h e case in many quartz-cemented sandstones and
well-cemented limestones or dolomites, may not
reveal much information when rough b r o k e n sur
faces are examined. In such cases it is frequently
necessary to view a polished and etched surface to
obtain useful information.
This technique is particularly useful in t h e ex
amination of c a r b o n a t e c e m e n t e d sandstones, lime
stones and dolomites, since by suitable choice of
etching agent different minerals can be attacked and
their role as grains or c e m e n t elucidated. T h e tech
nique can also b e used on unconsolidated sediments
which have been resin-impregnated in t h e field or
laboratory.
GENERAL METHODS
A slice of t h e rock t o be examined is cut to a suitable
thickness (say 35 m m ) . T h e specimen can thus be
oriented in any required m a n n e r and part of t h e
rock slice used to m a k e a thin section or polished
section for examination by other techniques.
T h e rock slice or chip should be polished t o a
reasonable standard with respect to t h e features
required to t h e viewed (polishing details in Lister,
1978). T h e specimen slice should be cut or b r o k e n to
t h e required size for insertion in the S E M c h a m b e r
and mounted on the stub prior to etching to minimize
t h e possibility of d a m a g e to the delicate etched
surface. S o m e S E M c h a m b e r s will a c c o m m o d a t e a
polished thin-section; this enables t h e same area t o
be examined using a variety of techniques and is an
obvious advantage.
T h e etching process can be varied to suit the
particular situation. F o r limestones, dilute hydro
chloric, acetic or formic acid can be used for lowrelief etching. It is best to use as dilute a solution as
possible to avoid vigorous gas generation which
could damage delicate features. Sandberg & Hudson
(1983) used 0 . 2 5 % formic acid and an etch time of
6090 s to reveal aragonite relics in calcite-replaced
shells. H a y et al. (1970) used 1% HC1 and found 30 s
of etching sufficient to reveal the ultrastructure of
fine c a r b o n a t e grains of biogenic origin. Despite
t h e above examples of gentle etching, Wilkinson,
J a n e c k e & Brett (1982) used 5 0 % glacial acetic acid
and an etch time of 60 s with success on Ordovician

limestones.
D e e p etching can be employed profitably in rocks
with a soluble cement. A calcite-cemented sandstone
can be etched down from a flat broken surface to re
veal t h e pre-cement morphology and to observe re
lics of carbonate replaced grains. T h u s it is possible
by use of suitable acids to manufacture examples
of secondary porosity in c a r b o n a t e c e m e n t e d rocks.
Particularly interesting results can be achieved with
dolomite/calcife rocks and partially silicified lime
stones. It is useful t o p r e p a r e a n u m b e r of stubs of
each rock to be examined so that ample material is
available for experimentation with different acids
and etch times. In this way p h o t o g r a p h s can be t a k e n
of examples 'before' and 'after' t r e a t m e n t . Polished
surfaces of quartzitic sandstones can be etched with
hydrofluoric acid to reveal rock texture and internal
structures of grains such as heavy minerals.
With all etching techniques t h e specimen must be
well washed with distilled water following etching to
r e m o v e any traces of t h e acid or its reaction pro
ducts, which otherwise may crystallize on t h e speci
m e n surface during drying.
8.5.3 M u d r o c k s and fine grained sediment

Freshly fractured surfaces of m u d r o c k s can b e ex
amined for features such as mineral orientation,
shape and size, and organic content. C a r e m u s t be
t a k e n to ensure that specimens are properly dried,
and only small samples should b e used since t h e high
porosity of mudrocks combined with their low per
meability results in large specimens degassing for
long periods when placed in a vacuum for coating o r
observation.
Well-lithified m u d r o c k s can be p r e p a r e d as un
covered polished thin sections or as polished chips
m o u n t e d in plastic; these can be examined with
advantage in B S E images as shown by Krinsley, Pye
& Kearsley (1983), White et al. (1984) and Huggett
(1986). Preparation of t h e polished surface for high
resolution S E M work has been discussed by Pye &
Krinsley (1984). Conventional polishing m e t h o d s
can cause smearing of the surface which is a p p a r e n t
at magnifications greater than X 2500. V e r y gentle
etching with H F may improve the surface but etch
ing must not proceed to the point w h e r e unaccept
able topographic differences are produced b e t w e e n
grains. Ion-beam etching is a m e t h o d which can be
employed to r e m o v e a surface layer of even thick

ness to leave a 'cleaner' and flat surface (Smart &
T o v e y , 1982).
O ' B r i e n , N a k a z a w a & T o k u h a s h i (1980) recorded
a m a r k e d difference in texture in turbidite and
hemipelagic m u d s w h e n viewed on b r o k e n surfaces
parallel to bedding. Hemipelagic m u d s show a pre
ferred grain orentation d u e to dispersed settling of
clays and turbidites exhibit a r a n d o m texture caused
by deposition of flocculated clays.
R e c e n t sediments, both natural and artificial, have
been p r e p a r e d by freeze-drying techniques (Osipov
& Sokolov, 1978) to examine t h e microtexture of
high porosity (to 9 9 % ) samples of various clays.
L o o s e sediments of fine grain size can be ex
amined by mounting grains directly on a stub using
double-sided sticky t a p e , or a thin layer of glue on
the stub. Sediment can be e m b e d d e d in resin as
described below (Section 8.5.5) and observed o n
polished and etched surfaces; this technique is par
ticularly useful for c a r b o n a t e s ( H a y et al., 1970).
a r e t h e n boiled in stannous choride solution for 20

min and rewashed in distilled water. Organic debris
can be removed by a strong oxidizing solution.
Krinsley & D o o r n k a m p (1973) used 1.5 g each of
potassium dichromate and potassium p e r m a n g a n a t e
dissolved in 15 ml of c o n c e n t r a t e d H S 0 . W a n g
et al. (1982) boiled their samples in 3 0 % hydrogen
peroxide for 10 min. T h e grains a r e given a final
wash in distilled water and dried before mounting on
a stub.
2
This p r e p a r a t i o n technique might be considered

r a t h e r violent, but t h e fact that populations of quartz
grains d o exhibit features characteristic of their en
vironments (Section 8.9) after such t r e a t m e n t sug
gests that relevant features a r e not destroyed in t h e
process. It is usually stressed that ultrasonic cleaning
should n o t be used as it m a y d a m a g e the grain
surfaces, but L e Ribault (1978) processed samples
through H C 1 , washing with distilled water then dry
ing, sieving and selecting grains before subjecting
t h e m to ultrasonic cleaning and an alcohol wash
prior to drying and mounting.
8.5.4 Sedimentary grains

T h e S E M is extensively used for examination of
individual sedimentary particles. T h e t r e a t m e n t
given to the particles prior to mounting on a stub is
d e p e n d e n t on the type of material being examined
and t h e object of the study. It is essential to ensure
that t h e p r e p a r a t i o n m e t h o d does not destroy or
modify t h e features to be observed and does not
create features which are artefacts of t h e p r e p a r a
tion t e c h n i q u e . If t h e grains to be examined have to
b e released from a partly-consolidated rock t h e
m i n i m u m of force should be used and grinding of
t h e sample must be avoided. T h e m e t h o d employed
will d e p e n d on t h e study to be u n d e r t a k e n , but
ultrasonic and freeze-thaw techniques can be used as
well as gentle mechanical and chemical m e t h o d s .
SURFACE T E X T U R E S OF GRAINS
It is generally considered that only small n u m b e r s of
detrital quartz grains n e e d be examined from a
sample to obtain representative surface textures
(Krinsley & M c C o y , 1977). T h e m e t h o d described
by Krinsley & D o o r n k a m p (1973) and used by
W a n g , Piper & Vilks (1982) is as follows.
Five grams of the sample are boiled for 10 min in
c o n c e n t r a t e d HC1 and then washed .With distilled
water. If iron oxide coatings are present t h e grains
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245
GENERAL PURPOSE GRAIN MOUNTS

G r a i n assemblages to b e m o u n t e d for general pur
pose examination or analysis will include minerals
that would be d a m a g e d or destroyed by t h e above
t e c h n i q u e . Careful washing of the grains in distilled
water with gentle agitation can b e sufficient to re
m o v e loose surface particles, but still leave a d h e r e n t
particles and coatings (which may themselves be of
interest) on t h e grain surfaces.
T h e t r e a t m e n t employed will largely d e p e n d o n
t h e object of t h e study, but t r e a t m e n t s can readily
be devised t o r e m o v e organic m a t t e r (hydrogen
peroxide) or calcite (formic or acetic acid). It is
frequently instructive to examine samples to which
various t r e a t m e n t s have been applied. Which treat
m e n t is employed should b e clearly stated in any
publication, a factor often ignored in many S E M
studies of sedimentary grains.
8.5.5 Impregnation of pores and b o r i n g s

(see also Section 4.4.2)
It is frequently useful to impregnate p o r o u s media to
reveal details of p o r e geometry or details of borings
within grains. T h e impregnation allows t h e frame
work of t h e grains or rock t o be dissolved to leave
246
N.H. TREWIN
t h e p o r e network or boring preserved as a cast which

can be examined with the S E M . Various materials
have been used for impregnation of rock pores
including coloured lakeside c e m e n t , W o o d ' s metal
and wax, but plastics a r e now used which are h a r d ,
strong and stable. Various epoxy resins a r e available
which will dissolve a suitable dye (required for thin
section w o r k ) , have low viscosity and high wetting
characteristics together with high final h a r d n e s s a n d
negligible shrinkage or expansion o n setting.
S o m e techniques involve alternate use of vacuum
and pressure (Pittman & Duschatko, 1970) to achieve
impregnation. Impregnation can be achieved with
no m o r e vacuum than that provided by a water vac
u u m p u m p connected to a mains water supply and
has been found satisfactory for impregnation of por
ous rocks with permeabilities above 30 md and for
impregnation of fungal borings less t h a n 1 urn m
diameter.
PROCEDURES PRIOR TO IMPREGNATION

Prior to impregnation the sample may have to be
treated in t h e m a n n e r described in Section 8.5.1 to
r e m o v e oil, since t h e presence of oil m a k e s impreg
nation difficult as it h i n d e r s t h e ability of t h e resin t o
wet t h e grain surfaces and may restrict impregnation
d e p t h to 1 or 2 m m . If organic m a t t e r is present, as
may b e t h e case in recent borings, it should be
r e m o v e d by use of chlorox o r hydrogen peroxide. If
it is desired to retain organic m a t t e r t h e m e t h o d s of
Golubic, B r e n t & Lecampion (1974) (summarized
by L u k a s , 1979) can be used.
If sediment grains a r e to b e e m b e d d e d and/or im
pregnated it is a d v a n t a g e o u s to clean t h e m by wash
ing in distilled water and by brief use of an ultrasonic
cleaner to r e m o v e loose surface material which may
b e partly blocking the cavities to be i m p r e g n a t e d .
Samples should b e dry before impregnation.
In the following simple m e t h o d , developed by
I.S.C. Spark at A b e r d e e n , t h e epoxy resin 'Epofix'
is used. T h e t e m p e r a t u r e of the resin is critical for
good impregnation t o t a k e place. Below 40C im
pregnation is difficult t o achieve as t h e resin has t o o
high a viscosity (550 cP at 25C as against 150 cP at
60C). A b o v e 70C the resin sets very rapidly when
t h e h a r d e n e r is added since the reaction is exother
mic. A t e m p e r a t u r e of between 55 and 65C is
usually satisfactory. A t 60C t h e dye ('Waxoline
blue') dissolves m o r e easily in the resin t h a n at lower
t e m p e r a t u r e s b u t it still has a pot life of about 45

min. This limits the impregnation time but it is
generally found t o b e a d e q u a t e . T h e d e g r e e of
vacuum applied is important t o achieve good im
pregnation. T o o high a vacuum (less t h a n 2 m m H g )
results in the resin boiling, but t o o low a vacuum
results in lack of impregnation. A v a c u u m p u m p
connected to t h e mains water supply provides a
sufficient v a c u u m . T o avoid waste of resin it is
usually convenient t o i m p r e g n a t e material in b a t c h e s
of 10 or m o r e samples at a t i m e .
EQUIPMENT AND MATERIALS

Glass vacuum desiccator connection t o mains water
vacuum p u m p . Cylindrical p o l y t h e n e moulds 40-mm
d i a m e t e r (suspplied by Struers).
O v e n (60C).
V a c u u m grease.
' P r e p o ' release p o w d e r .
'Waxoline B l u e ' dye p o w d e r .
'Epofix' resin and h a r d e n e r .
First ensure that the samples to b e impregnated
will fit into t h e moulds and are clean and dry and
have had any oil r e m o v e d . Seal t h e contact b e t w e e n
t h e mould body and base with vacuum grease to
p r e v e n t leakage, and s m e a r t h e w h o l e internal m o u l d
surface with ' P r e p o ' release p o w d e r t o prevent ad
hesion of t h e h a r d e n e d resin to the m o u l d . Clean off
any loose p o w d e r .
T w o h u n d r e d ml of resin (for 10 samples) are
mixed with a level teaspoon of 'Waxoline b l u e ' dye
and placed in an oven at 60C and gently stirred at
5 m i n intervals until t h e dye h a s dissolved (30 min'
a p p r o x . ) . Twenty-five ml of h a r d e n e r is a d d e d and
well mixed in for 1 min. T h e resin is t h e n immedi
ately p o u r e d into t h e 10 labelled moulds a n d t h e
samples d r o p p e d in. ( D o n o t p u t t h e samples in first
as a flat based sample may n o t b e w e t t e d or may
a d h e r e to grease.) Put the moulds plus samples in the
desiccator and apply t h e vacuum. Every 4 min re
lease air into t h e c h a m b e r for 1 min and r e p e a t this
process for 30 min. T h e n r e m o v e t h e moulds and
allow t o set a n d h a r d e n for 24 h o u r s a t r o o m t e m
p e r a t u r e ; d o not allow the resin t o set u n d e r vacuum
as small remaining air bubbles will n o t dissolve in
t h e resin. Finally release the i m p r e g n a t e d samples
from t h e m o u l d s and cut suitable sections for treat
ment and examination by S E M . (It is n o t essential to
use a dye for t h e S E M work but it is useful if a thin
section is also r e q u i r e d . )
A similar m e t h o d of impregnation is described by
http://jurassic.ru/
W a l k e r (1978) which he utilized for preparation

of casts of chalk porosity (Fig. 8.10). W a l k e r ' s
m e t h o d uses t h e epoxy resin Araldite A Y - 1 8 which
has t h e advantage of low viscosity which is retained
for up to a week after mixing. Curing is started by
heating the resin to 80C. Using the m e t h o d , spectac
ular detailed impregnation of pores only 0.10.2
um across was o b t a i n e d and even pores in foramini
fera walls w e r e i m p r e g n a t e d . Patsoules & Cripps
(1983) h a v e described an impregnation m e t h o d also
used on chalk in which Trylon C L 223 P A resin is
used. A m o r e e l a b o r a t e impregnation c h a m b e r is
described in Section 4.42 and Fig. 4.4.
T h e ' A b e r d e e n ' m e t h o d described previously has
t h e great a d v a n t a g e of cheapness, simplicity and
speed of o p e r a t i o n , but W a l k e r ' s (1978) m e t h o d
probably achieves a greater penetration of p o r e s .
Commercially available impregnation units are now
o n t h e m a r k e t which provide better vacuum condi
tions and permit a greater n u m b e r of samples t o b e
i m p r e g n a t e d at o n e time u n d e r m o r e easily con
trolled conditions. H o w e v e r , there is still consider
able scope for e x p e r i m e n t a t i o n with impregnation
techniques. E x a m p l e s of impregnated rocks and
grains are illustrated in Fig. 8.21 ( p o r e casts) and
Fig. 8.24 (microborings).
8.6 S A M P L E M O U N T I N G , C O A T I N G
AND STORAGE
8.6.1 General considerations
W h e n t h e required p r e p a r a t i o n techniques have
b e e n performed on t h e sample it may be of suitable
size and s h a p e for m o u n t i n g directly on t o a stub for
examination o r it may r e q u i r e s o m e final shaping.
Prior to m o u n t i n g t h e sample t h e stubs to b e used
must b e labelled; this is simply d o n e by scratching or
engraving a n u m b e r o n t h e side or u n d e r s i d e of t h e
stub.
Specimens a r e usually individually m o u n t e d on
10-mm d i a m e t e r stubs designed t o fit t h e particular
m a k e of machine being o p e r a t e d but larger 25-mm
stubs can be used to t a k e several specimens. It is
generally possible to design an a d a p t o r to m a k e
different stubs transferable b e t w e e n machines if this
becomes desirable.
It is useful to have a k n o w n reference point o n t h e
stub surface so that the sample can be placed in a
k n o w n orientation in t h e sample holder within the
247
c h a m b e r . This can greatly facilitate t h e finding of a

particular field of view when a sample is re-examined
at a later d a t e , provided X and Y co-ordinates of t h e
a r e a a r e also n o t e d .
Using 10-mm stubs o n e can examine o n e stub at a
time, but if changing t h e sample in t h e S E M cham
ber involves bringing t h e column t o air it is advisable
to have a m o u n t which allows t h r e e stubs to be
inserted and examined without t h e n e e d for a speci
m e n change. A p a r t from t h e obvious advantage of
time saving, t h e reduction in n u m b e r of specimen
changes gives longer filament life and aids mainten
ance of cleanliness. H o w e v e r , it is essential to en
sure that any modifications m a d e to sample holders
d o n o t interfere with take-off angles to detectors a n d
that the modified sample holder cannot touch t h e
detector w h e n t h e stage is tilted.
8.6.2 Mounting rock c h i p s and slices

It is essential t o ensure that t h e r e is a good contact
between t h e specimen a n d t h e stub. F o r this reason
samples should be as flat-based as possible. Samples
should n o t seriously overlap t h e edges of the stub
since t h e underside of the sample will not be coated
in t h e sputter-coating process. T h e s a m p l e should
also h a v e as flat a surface as possible, particularly if
analytical work is to be carried out. It is also an
advantage to try and m a k e t h e samples of approxi
mately the s a m e thickness. Figure 8.11 illustrates
correct and incorrect sample configuration.
P o r o u s samples can be t r i m m e d using small pliers
or whittled to size using a variety of p r o b e s ; dental
picks a r e very useful for this operation. O n c e t h e
freshly-fractured surface to b e observed has been
exposed it is essential to prevent transference of dust
t o this surface a n d t o p r o t e c t it from d a m a g e . S o m e
samples can be m o u n t e d prior t o producing the fresh
fracture; this is ideal, but frequently difficult to
achieve. If t h e chosen rock chip has an irregular
base this can b e gently filed down or r u b b e d on glass
until flat, t h e m e t h o d e m p l o y e d d e p e n d i n g on t h e
friability of t h e specimen. C u t slices of relatively
n o n - p o r o u s material are best cut to size and m o u n t
ed o n t h e stub prior to any etching techniques which
p r o d u c e a delicate surface.
T h e glue u s e d t o stick t h e sample o n t h e stub
should be stable u n d e r high t e m p e r a t u r e and vacuum
conditions and have good adhesion to gold and
carbon coatings. T h e silicone r u b b e r glue 'Loctite'
has these properties and has the added advantage of
248
N.H. TREWIN
T H I N S A M P L E (5 c m x 5 c m x 1 c m ) C U T F R O M O R I E N T A T E D B L O C K
15
1
CRITICAL POINT
O R F R E E Z E D R Y I N G IF D E S I R E D
SAMPLE WASHED SEVERAL TIMES

IN D I S T I L L E D W A T E R A N D D R I E D
S A M P L E P L A C E D IN M O U L D A N D C O V E R E D W I T H E P O X Y
USING A R A L D I T E A Y 18
A Y 18
5 0 % by vol
HY18 HARDENER
4 8 % by vol
N-DIBUTYL PHTHALATE
RESIN
(a)
Incorrect
2 % by vol ( P L A S T I C I S E R )
ZEZ
S A M P L E P L A C E D U N D E R V A C U U M O F 60 - 70 c m Hg
FOR 3 - 6 H O U R S TILL FULLY I M P R E G N A T E D
Fig. 8.11. Correct and incorrect configuration for

specimen mounting on a stub. Note lack of overhangs, flat
surface and complete bond in (b).
~ z z
R E S I N C U R E D IN O V E N A T 80"C F O R B E T W E E N O N E A N D T W O D A Y S
z z z
j ^ ^ ^ ^ z
C U B E (1 C M X 1 C M x 1 C M ) C U T F R O M I M P R E G N A T E D S A M P L E A N D
E T C H E D IN D I L U T E H Y D R O C H L O R I C A C I D O R O T H E R D E S I R E D A C I D
FOR T W O TO THREE DAYS
(b)
Correct
Z Z
C U B E W A S H E D A N D D R I E D T H E N I T IS B R O K E N T O E N A B L E A
FRACTURE SURFACE FREE FROM SURFACE ARTEFACTS
TO BE VIEWED
~ T ~
SPECIMEN MOUNTED A N D COATED FROM SEM STUDY
Fig. 8.10. Impregnation technique for the production of

epoxy resin pore casts. Modified from Walker's (1978)
technique for the production of casts of chalk porosity.
being initially very viscous and fast setting s o that

fracture surfaces can b e easily m o u n t e d in a suitable
orientation even w h e n t h e s a m p l e b a s e is unavoid
ably u n e v e n . A n advantage can sometimes b e o b
tained by using a conducting glue t o h e l p carry away
any charge from t h e specimen surface. If for u n
avoidable reasons an irregular specimen has t o b e
m o u n t e d which is poorly coated at t h e sides it can b e
partly coated with conducting glue o r carbon-dag t o
help p r e v e n t charging of t h e specimen. G l u e s of t h e
Polyvinylacetate type must b e allowed t o h a r d e n
fully for a day before coating is a t t e m p t e d as they
continue t o de-gas for s o m e time after initial drying.
E p o x y resin glues such as ' A r a l d i t e ' can b e u s e d b u t
must also b e allowed t o cure properly.
8.6.3 M o u n t i n g of grains and loose

sediments
Individual grains can b e m o u n t e d using d o u b l e sided sticky t a p e o r alternatively t h e stub can b e
coated with a thin layer of glue o r conducting silver

paint and t h e grains d r o p p e d or pressed o n t o t h e
surface. T h e glue layer must be thin e n o u g h t o
p r e v e n t t h e grains sinking into t h e glue. L o o s e
sediments from which a r a n d o m sample of grains is
to b e m o u n t e d can b e placed o n a flat surface and
t h e glued stub gently pressed on t o t h e grains. G l u e
types a r e discussed in t h e section a b o v e .
G r a i n s m o u n t e d on double-sided t a p e have a
smaller a r e a in contact with t h e stub than d o those
m o u n t e d with a spot o r thin layer of glue a n d thus
have a greater tendency t o charge u p in t h e electron
b e a m d u e to p o o r conductivity t o t h e s t u b . This is
e n h a n c e d by t h e shadow area b e n e a t h t h e grain
which is poorly covered in t h e coating process.
W h e n individual grains a r e being m o u n t e d it is
advisable t o have s o m e sort of reference point o r
grid o n t h e stub surface so that a simple m a p of t h e
stub surface can b e m a d e t o aid t h e location of
individual grains (Fig. 8.12a).
Roughly spherical grains, of which as m u c h of t h e
surface as possible is required t o b e viewed, can be
m o u n t e d on modified stubs of r o d s h a p e o r stubs
with a vertical semicircular rim as in Fig. 8.12(b).
M a n y studies require surface textures and/or grain
size t o b e d e t e r m i n e d with t h e S E M and frequently
very small n u m b e r s (1020) of grains have b e e n
used. Most w o r k e r s dealing with sand grain surface
textures u s e 1520 grains. Culver et al. (1983) con
cluded t h a t 30 is a n a d e q u a t e n u m b e r a n d it a p p e a r s
that o p e r a t o r bias in recognition of features would
outweigh anything gained by examination of m o r e
samples. T o v e y & W o n g (1978) gave evidence t h a t a
sample of 50 grains chosen at r a n d o m is reasonably
representative of t h e grain size distribution of a
sample d e t e r m i n e d by sieve analysis. T h u s a r a n d o m
m e t h o d of selection of grains for m o u n t i n g must b e
o
o
O o
II
(a) Vl
Fig. 8.12. (a) Stub with simple orientation marks and grid
engraved on surface to facilitate location of specific grains,
(b) Modifications of specimen stubs to permit viewing of
greater proportions of the surfaces of spherical grains
(modified from fig. 6.2.1 of Smart & Tovey, 1982).
used to ensure an a d e q u a t e sample of grains for t h e
intended project.
8.6.4 Coating t h e specimen

W h e n t h e specimen h a s b e e n m o u n t e d and after t h e
glue is fully dried t h e sample must b e coated with a
conductive layer to take away t h e electrical charge
which builds u p o n t h e specimen surface d u e t o
b o m b a r d m e n t by t h e electron b e a m . T h e two most
commonly used types of coating a r e gold a n d car
b o n , b u t various metal alloys such as platinumpalladium and gold-palladium can be used.
Samples a r e normally gold coated using o n e of
the m a n y models of sputter coater now on t h e mar
ket. Coating units with a carbon evaporation power
supply a r e also readily available. T h e quality of t h e
coating achieved d e p e n d s on t h e quality of vacuum
obtained; thus it is worth spending time obtaining
a good vacuum rather than o n e which is only mar
ginally satisfactory before commencing coating.
T h e thickness of gold coating t o be applied should
b e considered in relation t o t h e type of work t o b e
u n d e r t a k e n and t h e type of specimen. Porous speci
mens with grains which a r e only in p o o r contact with
each o t h e r generally require a longer coating t i m e in
o r d e r to eliminate charging effects on t h e specimen
at any particular operational voltage ( a n d con
sequently may give better results if examined in
backscattered m o d e ) . T h e merits of different thicks
nesses a n d types of coating a r e summarized below:
(1) Gold coating. 100 A o r m o r e . (2) Gold coating.
25 A o r m o r e . (3) C a r b o n coating. (4) U n c o a t e d
samples.
(1) T h e thicker gold coating is advantageous in
http://jurassic.ru/
249
eliminating a n y charge effects a n d is useful for o b

taining good resolution pictures. T h e disadvantage
of a thick gold coating is found if energy dispersive
analysis is t o b e performed on t h e sample, since
large gold peaks a r e obtained which can obscure
p e a k s d u e t o o t h e r elements (e.g. sulphur). R e d u c
tion of p e a k heights for elements such as N a , K and
Mg also occur. In addition has been found that if t h e
coating is increased t o 200 A t h e N a o r K in feldspar
may not give p e a k s so leaving only Si, Al a n d t h e
gold p e a k s . T h u s thick gold coatings should b e used
only for obtaining better pictures w h e n analysis is
not required. Figure 8.7 illustrates analytical results
from a gold coated specimen.
(2) T h e thin gold coating of 25 A h a s t h e dis
advantage that charging effects may b e a p r o b l e m ,
particularly at high magnifications, a n d it is usually
necessary t o apply a conductive m e d i u m (carbond a g o r conducting glue) to t h e sides of t h e specimen
m o u n t e d o n t h e stub. T h i n coating has t h e advan
tage that gold p e a k s on E D S analysis traces a r e very
small o r absent a n d elements such as sulphur can b e
easily detected a n d t h e absorption effects o n o t h e r
elements a r e greatly r e d u c e d .
(3) C a r b o n coating is of great advantage in that
carbon is outside t h e detection r a n g e of t h e analyser
and does n o t affect p e a k intensities on E D S traces.
C a r b o n coating is achieved by vaporizing carbon
r o d s o r c a r b o n fibre; it is m o r e difficult t o achieve an
even coating with carbon than with gold a n d charging
effects may b e experienced. H o w e v e r , if good car
b o n coating a p p a r a t u s is available it is a preferable
m e t h o d if analysis is envisaged,
(4) U n c o a t e d samples. Sometimes it is desired
not t o coat a sample, possibly for a rapid evaluation
or if t h e specimen is a eurated mineral o r fossil
specimen, I n this ease t h e s a m p l e can b e viewed a n d
analysed b u t charging will build u p rapidly on t h e
specimen. If, however, a back scattered electron
detector ( e , g . R o b i n s o n d e t e c t o r ) together with a
C F A S (Charge-Free Anti-Contamination System)
working at a low vacuum is available t h e sample can
b e o b s e r v e d , analysed a n d p h o t o g r a p h e d without
specimen charging, a n d with t h e a d d e d advantage
that atomic n u m b e r contrast images a r e p r o d u c e d
(Robinson & Nickel, 1979).
8.6.5 Storage and handling of s t u b s

Storage of S E M stubs can b e t h e responsibility of
individual w o r k e r s ( m o s t academic establishments)
r
250
N.H. TREWIN
o r can be a technical responsibility of t h e S E M

laboratory. In either case t h e r e q u i r e m e n t is for dust
tight boxes, lidded trays or a cabinet in which stubs
are firmly held and can be labelled in such a way that
file n u m b e r s can be read without having to pick u p
t h e stub. It is a d v a n t a g e o u s to have small storage
units taking tens of samples rather t h a n large units
with h u n d r e d s of specimens in a single container
this results in minimal disturbance for each stub.
Stubs can also be stored individually in glass o r
plastic tubes by having a hole in a cork t o take the
stem of t h e stub. It is commonly found that a coated
specimen stored for a period of m a y b e only a few
days, but m o r e normally m o n t h s , will charge badly
when re-examined. This applies particularly to rock
samples containing e x p a n d a b l e clays. B o h o r &
H u g h e s (1971) r e c o m m e n d e d keeping clay samples
individually in glass tubes as above with the addition
of a small a m o u n t of desiccant in t h e t u b e to k e e p
the sample in stable, dry conditions, and to prevent
swelling of clays causing r u p t u r e of t h e conductive
coating. Samples with hygroscopic salt content are
also p r o n e t o charging following storage.
8.7.2 Possible reasons f o r poor image o n

screen
Storage units can b e m a d e sturdy e n o u g h for

transmittal by post if ttie stubs are firmly secured in
their cavities. W h e n handling stubs it is advisable to
use a pair of suitably shaped tweezers which will
hold t h e stub firmly. It is easy to d a m a g e a coated
stub with careless handling.
(c) Filament not correctly centred. If the filament is

n o t correctly centred a low intensity picture with
p o o r focus will result. Occasionally a filament
will go off centre during operation a n d it is
advisable to check t h e centering of t h e filament
following specimen changes.
(d) Specimen faults. A specimen that is charging
badly will give a p o o r picture with bright spots
and p h o t o g r a p h s will have bright horizontal
lines e m a n a t i n g from charged areas (Fig. 8.14).
Charging of t h e specimen could b e t h e result of
p o o r specimen coating, p o o r connection of t h e
sample t o t h e stub, or p o o r earthing of stub or
stage. Samples which were wet or contained
volatiles such as oil w h e n coated, give p o o r
pictures d u e t o p o o r coating. Samples m o u n t e d
with volatile glue may also give noisy'pictures,
as d o specimens with a large quantity of organic
m a t t e r . Microporous samples can t a k e a signifi
cant time to de-gas in t h e vacuum and perform
ance may improve if t h e specimen is left in t h e
vacuum for an h o u r before observation.
8.7 P R O B L E M S O F S E M O P E R A T I O N
8.7.1 General
It is not possible or desirable t o a t t e m p t to provide a
trouble-shooting m a n u a l for t h e S E M o p e r a t o r in a
short chapter such as this. Details differ b e t w e e n
machines of different m a k e s , and technology is ad
vancing so rapidly that any technical specifications
will soon b e o u t of d a t e . It is therefore assumed that
all machine functions are operating correctly, and
only those features most commonly found to affect
image quality a r e listed h e r e . In all cases t h e o p e r a
tion m a n u a l supplied by t h e m a k e r s of t h e S E M
should b e followed in t h e setting u p and running of
t h e m a c h i n e . It much be stressed at t h e outset that
many of t h e problems e n c o u n t e r e d in day t o day
running of an S E M a r e a direct result of lack of
cleanliness and p o o r specimen quality.
(a) Dirty column, apertures or filament housing.

S E M models w h e r e specimens can b e changed
without bringing t h e column to air have a distinct
advantage in this respect. In other models dust
can m o r e easily e n t e r t h e c h a m b e r during speci
m e n changes and so contaminate t h e column. A
spare clean column should be k e p t available. If
t h e final a p e r t u r e in t h e column becomes dirty
and starts charging t h e n distortion of t h e image
and sudden shifts of image can occur.
(b) Unstable filament.
T h e tungsten filament is
heated close to its melting point to provide t h e
electron b e a m , and can behave in an unstable
m a n n e r , resulting in rapid changes in filament
current and hence rapid fluctuations in picture
brightness. Unless t h e filament current is stable
there is n o point in attempting t o t a k e p h o t o
graphs. A n e w filament frequently takes an h o u r
to settle down and may b e c o m e unstable to
wards the end of its life.
(e) Image not sharp. If t h e image cannot be sharp

e n e d by use of t h e focus control, and charging is
n o t a p r o b l e m , it is possible that the spot size is
t o o large, b u t if spot size if reduced t o o much
t h e image will b e c o m e excessively noisy. R e d u c
tion in b e a m current or photo-multiplier gain
may also help sharpen the image.
(f) Astigmatism
effects. If at high magnifications
( x 10,000) t h e r e is distortion giving oblique
elongation of features when the focus is adjust
ed the astigmatism controls are probably in
n e e d of adjustment. Serious astigmatism may be
d u e t o p o o r alignment of the column or dirt in
o n e of t h e column a p e r t u r e s .
(g) Extraneous 'noise' problems.
Many buildings
are n o t particularly stable and vibration due to
traffic, o t h e r machinery, high wind and the S E M
p u m p itself can be a p r o b l e m . T h e S E M should
be set u p in t h e most stable and quiet environ
m e n t possible. If vibration is suspected com
p a r e operation at different times of day and
place t h e p u m p as far from t h e machine as
possible. Vibration results in straight edges
having a saw-tooth a p p e a r a n c e at high
magnifications.
8.7.3 Possible reasons f o r poor

p h o t o g r a p h i c results
P h o t o g r a p h y of images on t h e S E M should result in
a slightly i m p r o v e d image t o t h a t s e e n in t h e slow
scan m o d e on t h e screen, and a greatly improved
image over that seen o n T V m o d e . Photographic
instructions should be followed for t h e individual
machine and m i n o r adjustments to practice are
generally m a d e to suit t h e individual machine and
provide acceptable negatives for t h e t y p e of inves
tigation u n d e r t a k e n .
Brightness and contrast a r e usually judged from
t h e amplitude and position of t h e waveform of the
image o n the viewing screen. T h e o p t i m u m position
a n d amplitude will d e p e n d o n film speed and aper
t u r e used o n the c a m e r a ; thus it is worthwhile
experimenting with both brightness and contrast to
achieve t h e best negatives or Polaroid prints. It is a
simple m a t t e r t o fix a reference scale at the side of
t h e viewing screen o n which can be m a r k e d t h e
o p t i m u m positions of t h e waveform for different
film speeds and apertures as shown in Fig. 8.13.
T h e following factors can be responsible for p o o r
photographic results:
(a) Incorrect exposure resulting in either a pale
or d a r k negative or one with too much or too little
contrast. This can b e easily corrected by experiment
as described above.
(b) Camera not focussed o n photo-screen- If all
p h o t o g r a p h s appear out of focus, despite t h e Viewed
image having been good, this is a probable reason.
http://jurassic.ru/
251
Increase brightness
100 A S A
ff11
V
Increase contrast
Fig. 8.13. Appearance of waveform on viewing screen

adjusted to lie within marks determined by experiment to
be suitable for 100 ASA film speed and aperture / / l 1. To
increase contrast the waveform should be expanded, and
to increase overall brightness the waveform should be
moved up the screen.
(c) Unsuitable views. It is not possible to take

excellent p h o t o g r a p h s of all views! T h e d e p t h of
focus required can be t o o great and t h e contrast may
n o t b e adjustable t o a suitable level; however, t h e
provision of a g a m m a control o n s o m e instruments
Fig. 8.14. Faults commonly observed on photographs.

A. Bands due to fluctuation of filament current.
B. Picture dislocation due to vibration.
C. Bright, washed-out area, due to over-exposure, or poor
specimen coating.
D. Specimen charging.
EXAMPLES AND
8.8.1
REVIEWS
introduction
T h e relative ease with which publish&ble quality

p h o t o g r a p h s can be o b t a i n e d Using t h e S E M b o t h in
S E and B S E mode's gives great scope for illustration
of reports and p a p e r s . T h e r e is a strong tendency
when viewing Material to p h o t o g r a p h t h e unusual
and t h e beautiful at t h e expense of the general
features. Sedimentologists are attracted by wellfounded aeolian quartz grains, vermicular kaolinite
Q u a r t z grain surface textures Section 8.9.

Diagenesis of sandstones Section 8.10.
Limestones and dolomites Section 8.11.
Endolithic microborings Section 8.12.
O t h e r topics for which t h e S E M is a useful tool
b u t which a r e n o t covered by specific sections a r e
t h e examination of fine grained n o n - c a r b o n a t e m u d s
and m u d r o c k s as illustrated by O'Brien (1987) in a
study o n the effects of bioturbation on t h e fabric of
shales. T h e examination of heavy mineral assem
blages is greatly aided by use of t h e S E M with E D S
system for analysis. Surface textures of grains o t h e r
than quartz are also providing useful information as
in t h e study by Hansley (1987) c o m p a r i n g natural
etch features on garnets with those p r o d u c e d ex
perimentally using organic acids. T h e S E M has also
proved valuable in the investigation of detailed fea
tures of framboidal pyrite as illustrated by L o v e
et al. (1984). E x a m p l e s of o t h e r applications can
b e found in Whalley (1978) and in the volumes of
the proceedings of the A n n u a l Scanning E l e c t r o n
Microscopy Symposium.
SURFACE
% GRAINS SHOWN
IG
FEATURE
QUARTZ GRAIN
SURFACE
TEXTURES
8.9.1 Introduction
T h e main impetus in the study of surface textures of
quartz grains is t h e belief that e n v i r o n m e n t a l inter
pretations can b e m a d e o n t h e basis of characteristic
ABUNDANT
[]
COMMON
25 - 75
[o]
SPARSE
25 - 75
RARE
ex.
8.9
[]
>75
<5
FEATURE
T h e S E M is now r e g a r d e d as a standard instrument

for use in sedimentological studies t o provide in
formation and illustrations of small-scale t h r e e dimensional surfaces. In recent years t h e r e h a s b e e n
a m a r k e d increase in t h e n u m b e r of sedimentological
p a p e r s utilizing t h e S E M a n d it is not t h e intention
to review all the current applications, but to concen
t r a t e on s o m e aspects w h e r e S E M use is essential t o
t h e study. It should b e stressed that t h e S E M is
seldom used in isolation from o t h e r t e c h n i q u e s ; thus
in the examples discussed it must be appreciated
that t h e contribution f r o m X R D , thin sections,
cathodoluminescence, isotopes and biologieal studies
may also be essential.
T h e four topics below h a v e b e e n selected to pro

vide a wide range of examples and also because they
account for m u c h of t h e sedimentological use of t h e
S E M in t h e c u r r e n t literature. T h e y a r e topics in
which S E M w o r k is essential to achieve t h e best
understanding.
Margolis & Krinsley (1974) discussed the physical and

chemical conditions responsible for the production
of surface t e x t u r e s , a n d related textures to the crys
tallography of quartz. S o m e 22 surface textures were
recognized a n d their relative a b u n d a n c e in different
e n v i r o n m e n t s discussed. Higgs (1979) recognized 30
main textures and Culver et al. (1983) utilized 32
features in a useful c o m p a r a t i v e study w h e r e five
different o p e r a t o r s e x a m i n e d the same c o d e d sam
ples. This study revealed considerable variance be
tween o p e r a t o r s in recognition a n d scoring of t h e
t e x t u r e s , but nevertheless t h e o p e r a t o r s correctly
classified t h e samples in t e r m s of e n v i r o n m e n t in 49
o u t of 50 cases. C a t e r (1984) used 22 surface tex
t u r e s and usually estimated t h e p e r c e n t a g e of t h e
grain surface covered by each feature.
A s can b e seen from t h e list of features (Fig. 8.15,
| 30 CRYSTALLINE OVERGROWTH
| 29 SILICA PELLICLE
I 28 SILICA FLOWERS
| 27 SILICA GLOBULES
| 26 SCALING
| 25 SOLUTION CREVASSES
| 24 SOLUTION PITS
| 23 ANASTOMOSING ETCH PATTERN
| 22 ORIENTED ETCH PITS
| 21 HIGH RELIEF (>10p)
| 20 MEDIUM RELIEF
| 19 LOW RELIEF (<0.5jj)
| 18 ROUNDED OUTLINE
| 17 ANGULAR OUTLINE
| 16 V ' s
| 15 CURVED SCRATCHES
| 14 STRAIGHT SCRATCHES
| 13 MEANDERING RIDGES
| 12 ADHERING PARTICLES
| 11 IMBRICATED GRINDING FEATURES
| 10 PARALLEL STRIATIONS
| 9 FRACTURE PLATES/PLANES
I 8 ARCUATE STEPS
| 7 STRAIGHT STEPS
'.J
| 6 LARGE CONCHO I DAL FRACTURE (>1 OOf.)
| 5 MEDIUM C0NCH0IDAL FRACTURE
| 4 SMALL C0NCH0IDAL FRACTURE (<10fi)
| 3 LARGE IRREGULAR PITS (>100p)
| 2 MEDIUM IRREGULAR PITS
I 1 SMALL IRREGULAR PITS (<10 )
8.14);
(f) Vibration.
Vibration at high magnifications
results in a wavy image on t h e screen; sharp knocks
t o t h e i n s t r u m e n t while a p h o t o g r a p h is being t a k e n
can result in fault-like dislocations in pictures as in
Fig. 8.14.
(g) Dirty photo-screen. In some instruments t h e r e
is a strong tendency for t h e photo-screen t o b e c o m e
electrically charged and attract dust particles which
a d h e r e to the surface. T h e patches w h e r e dust
a d h e r e s a p p e a r as diffuse d a r k e r areas o n p h o t o
graphic prints since t h e dust h a s cut o u t s o m e light
from t h e c a m e r a . T h e photo-screen should b e in
spected and cleaned regularly to prevent t h e accum
ulation of dust.
8.9.2 Processes, textures a n d procedures
surface textures. T h e main p r o b l e m facing a n e w

recruit to this field of study is t h e proliferation of
n a m e s of surface features and t h e subjective m a n n e r
in which m a n y h a v e b e e n described. T h e atlas of
Krinsley & D o o r n k a m p (1973) remains a useful
source of illustration of textures but m a n y have been
described since and illustrations a r e scattered in t h e
literature. G o o d illustrations are provided by C a t e r
(1984) a n d by Higgs (1979) w h o also gave definitions
and sources of original descriptions and summarized
t h e relationships of surface textures t o depositional
e n v i r o n m e n t . Bull (1981) provides a valuable review
of t h e use of surface textures in e n v i r o n m e n t a l
interpretation in m o r e detail than can b e given h e r e
a n d provides an excellent reference list. It is essen
tial to stress from t h e outset that surface textures are
p r o d u c e d by processes of erosion, t r a n s p o r t a n d
deposition, many of which a r e duplicated in different
environments.
a n d aragonite n e e d l e s , a n d these a r e frequently

illustrated, whilst less attractive and less easily inter
p r e t e d features t e n d to b e ignored. S E M use is n o w
entering a quantitative phase and every effort should
be m a d e t o quantify observations. T h e recent devel
o p m e n t s in quantitative analysis of B S E images of
polished surfaces (Dilks & G r a h a m , 1985) are most
i m p o r t a n t and should contribute to many branches
of geology. Studies combining several of t h e avail
able S E M techniques are most valuable, and t h e
current trend is away from repetitive illustration
and towards integrated studies using S E , B S E ,
cathodoluminescence and e l e m e n t m a p p i n g .
aids in producing aeeeptabie contrast for p h o t o

g r a p h y in otherwise poof a r e a s .
(d) Charging effects. if t h e specimen is affected
by charging* light or d a r k fines will be p r o d u c e d
e m a n a t i n g Itom t h e charged areas (Fig. 8.14).
(g) Unstable jilaWent current. Fluctuations in
filament current wili result in abrupt changes in
brightness; forming b a n d s on t h e p h o t o g r a p h (Fig.
8.8
253
N.H. T R E W I N
S U B A Q U E O U S
252
SOURCE ROCK
r LOW ENERGY
.,
1 MEDIUM ENERGY
FLUVIAT1LE
HIGH ENERGY
I TORRENTIAL
r
SUBAERIAL
MARSH
DELTAIC
( LANDWARD
CHANNEL < MEDIAL
I SEAWARD
MARINE
/ INTERTIDAL
"
\ SUBTIDAL
' COASTAL
AEOLIAN
<y HOT DESERT '
GLACIAL
f SILICA
. / TEMPERATE :
J DISSOLVED '.\ TROPICAL
PED0L0GIC
| SILICA
'/'TEMPERATE.';'
I PRECIPITATED \ IRC'ICAI
SUBSURFACE D I A G E N ;T .J-.C :
CRYSTALINE
r
l r
A K 1 N t
o
O
o
O
Fig. 8.15. Quartz grain surface textures characteristic of various sedimentary environments. Redrawn from Higgs (1979).
http://jurassic.ru/
N.H. TREWIN
Tendency
T3
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textures
during Ion
transport
O
~
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of acquire
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Production of
large overgrowths,
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and grain con tact
points
THE SEM IN SEDIMENTOLOGY 2 5 5

beach e n v i r o n m e n t s , thus confirming t h e n e e d t o
observe a n assemblage of features. F e a t u r e s can also
be inherited from a previous e n v i r o n m e n t as in t h e
case of 'glacial' features such as conchoidal fractures
and angular edges being still recognizable in grains
transported by turbidites for 120 k m from t h e shelf
edge over t h e L a u r e n t i a n F a n ( W a n g et al., 1982).
Before proceeding with any study of surface tex
t u r e s , b e they o n q u a r t z o r any o t h e r m i n e r a l , it is
pertinent t o consider t h e likely history of t h e grains
in question. T h e m a j o r features a r e summarized in
T a b l e 8.1. M a n y studies either omit to consider these
basic geological principles o r m a k e t h e assumption
that the transport regime p r o d u c e d all t h e observed
features a n d that t h e depositional regime reflected
t h e transport r e g i m e .
Grains with i
different sur
features botl
inherited am
acquired
a d a p t e d from Higgs, 1979) many of t h e n a m e s a r e

subjective a n d rely o n visual interpretation by t h e
o p e r a t o r . Contrasting surface textures of q u a r t z
grains from beach e n v i r o n m e n t s a r e illustrated in
Fig. 8.16.
T h e statistical analysis employed by Culver et al.
(1983) showed that a combination of features should
be used t o distinguish b e t w e e n samples and t h a t t h e
use of a single microtexture t o distinguish t h e en
v i r o n m e n t is invalid. This feature w a s stressed by
Krinsley & D o n a h u e (1968) b u t much work in t h e
1970s failed t o live u p t o their standards.
T h e same surface features c a n develop in very
different e n v i r o n m e n t s . M a n k e r & P o n d e r (1978)
showed that grains from fluvial e n v i r o n m e n t s d e
velop s o m e features also found in aeolian d u n e and
resulting
254
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.91
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3 CO
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3 CO
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E w
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W CL
i f f
.
I
i
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,9 O >5 .Ci XS
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60
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S
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hem
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to
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edd
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itior
Fig. 8.16. Examples of contrasting

quartz grain surface textures from
recent beach environments.
(a) Aberdeen beach, North Scotland.
Grain with conchoidal fractures partly
smoothed by abrasion. Probably a
grain of glacial origin reworked into
beach sediment. Split screen
enlargement area x 5 marked scale
(first scale bar 100 u m ) .
(b) Rottnest Island, West Australia.
Rounded grain, probably reworked
from older sediments but typical of
this sub-tropical beach environment.
Surface etched along percussion
cracks and crystal imperfections. Split
screen enlargement area x 10 marked
scale (first scale bar 100 urn).
hysi cal
? An
ika
ro ~o
8 Q.
5
f i l l !
>
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'5b
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cog*
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256
N.H. TREWIN
It is clear that in many cases it will be impossible

to answer all t h e questions posed in T a b l e 8.1 and
t h e fact that ' e n v i r o n m e n t s ' can be recognized from
surface textures implies that in many cases t h e final
transport regime does impart a new surface texture
to t h e grain and that t h e texture remains for a
significant time after deposition. T h e cases which d o
not ' w o r k ' are seldom r e p o r t e d so a bias t o w a r d s
successful interpretations builds up in published
work.
T h e only way to arrive at a satisfactory conclusion
in studies of surface textures is to examine sufficient
n u m b e r s of grains ( 3 0 - 4 0 ) to record all features
seen and employ a suitable statistical technique in
processing the data. Bull (1978) used cluster analysis
in cave sediments with effect and Culver etal. (1983)
used canonical variate analysis. By t h e very n a t u r e
of the study, statistical t r e a t m e n t s must be e m p l o y e d
to test for significant combinations of features.
Clearly, as r e m a r k e d by Bull (1978), one conchoidal
fracture d o e s not indicate glacial modification.
In the description of surface features it is now
essential to refer to an identifiable surface texture
without prejudice as to its origin, thus, for e x a m p l e ,
conchoidal fractures should not be referred to as
being of glacial origin prior t o consideration of all
t h e evidence. Conchoidal fractures are c o m m o n on
glacial grains due to the frequency of crushing, but
crushing also occurs in o t h e r e n v i r o n m e n t s , for ex
ample during bed load transport by high energy
s t r e a m s , and conchoidal fractures are also recorded
as a mechanical weathering feature of a C a r b o n i
ferous sandstone by Wilson (1978) and of granite
and gneisses by Krinsley & D o o r n k a m p (1973). Pye
& Sperling (1983), in weathering experiments on the
production of silt using a climatic cabinet, discover
ed that salt weathering is effective in producing
angular quartz silt with conchoidal and blocky
textures.
O n e factor which n e e d s standardization in studies
on surface textures is that of grain size. S o m e
w o r k e r s pick grains 'at r a n d o m ' while o t h e r s specify
'sand size'. W a n g et al. (1982) used 1 5 - 1 8 grains of
2 . 0 - 0 . 4 m m d i a m e t e r , Mazzullo & Ehrlich (1983)
fine sand of 0.1800.125 m m and M a n k e r & P o n d e r
(1978) used grains of 'approximately t h e same size
(1.0 m m ) and s h a p e ' .
Tovey & W o n g (1978) discussed selection of grains
advocating either a r a n d o m selection or o n e based
on size fractions of t h e sample. It would a p p e a r that
m o r e studies need to be d o n e on grain size effects

on surface t e x t u r e , particularly with regard to water
transport. T r a n s p o r t by rolling, saltation or by sus
pension should result in different surface textures in
t h e same way that rounding is affected. H e n c e grains
of the different t r a n s p o r t populations (Visher, 1969)
should be examined. Krinsley & D o o r n k a m p (1973)
noted that features changed with grain size and
considered 200 um a suitable divide b e t w e e n small
and large grains; this may in many cases reflect a
generalized break b e t w e e n suspension and traction
populations of grains. Larger grains > 4 0 0 um tend
to show records of abrasion and grains < 2 0 0 urn are
biased towards showing chemical effects (Margolis
& Krinsley, 1974). Middleton & Kassera (1987)
have shown that t h e r e is a considerable variation in
the density of V-shaped impact pits with grain size
in intertidal sands, a n d stress t h e n e e d t o a d o p t
standardized techniques for such studies. T h e pitdensity recorded varied with the magnification Used
for the photographs from which the pits were counted;
thus t h e scale at which observations are m a d e is
most i m p o r t a n t . M a n i c k a m & B a r b a r o u x (1987)
have described seasonal variations in surface tex
tures of suspended sand grains from t h e River Loire;
mechanical features are d o m i n a n t o n samples col
lected in winter floods and chemically produced
features during low s u m m e r flows.
- 1
s p e e d ' of 20 km - h r . F e a t u r e s such as small Vshaped pits produced in a beach environment were

virtually destroyed and replaced by the new 'aeolian'
texture. In the e x p e r i m e n t s , 'before and after'
p h o t o g r a p h s of the same area of each grain could be
studied. Wellendorf & Krinsley (1980) related artifi
cially produced u p t u r n e d cleavage plates to quartz
crystallography.
Krinsley & Wellendorf (1980) took this experi
mentation further in recognizing that both the size
and spacing of platelets p r o d u c e d by aeolian bom
b a r d m e n t are influenced by the impact velocity.
Such studies lead the way t o possibilities of inter
preting energy levels of t h e e n v i r o n m e n t .
8.9.4 Ancient d e p o s i t s
T h e vast majority of p a p e r s on surface textures
utilize material from c o n t e m p o r a r y e n v i r o n m e n t s .
Extension of t h e technique to the interpretation of
ancient sedimentary environments requires that t h e
surface texture survives diagenesis, probably in
cluding s o m e d e g T e e of lithification. In most cases
quartz solution, overgrowths and cementation will
have destroyed surface textures produced during
transport but m a n y examples d o exist, such as aeolian
textures preserved on Triassic sand grains (Krinsley,
Friend & Klimentidis, 1976), and R e h m e r &
H e p b u r n (1974) recovered grains with typical glacial
textures from t h e Palaeozoic S q u a n t u m 'Tillite' of
Massachusetts.
T h e correlation of e n v i r o n m e n t with surface tex

tures as summarized by Higgs (1979) is a useful
approach b u t , as stressed a b o v e , the mechanism of
transport is most i m p o r t a n t in surface texture pro
duction and the mechanism need not be environ
mentally confined.
Mazzullo & Ehrlich (1983) identified two grain

populations in the Ordovician St Peter Sandstone in
M i n n e s o t a which retained surface textures of aeolian
and fluvial origin. T h e s a n d s t o n e w a s deposited in a
m a r i n e e n v i r o n m e n t , thus little reworking took
place, and they postulated that the sand grains by
passed t h e active beach e n v i r o n m e n t from their
fluvial and aeolian source areas.
Higgs (1979) examined textures on Lower C r e
t a c e o u s t o P a l a e o c e n e grains from t h e western N o r t h
Atlantic continental margin. H e concluded that
m a n y inherited features were present due to deriva
tion of the sands from crystalline rocks undergoing
acid weathering and that deposition was in both
m a r i n e and non-marine e n v i r o n m e n t s . Such general
conclusions could probably b e reached m o r e easily
than by the study of surface t e x t u r e s , but on occa
sion surface texture studies may: provide valuable
information.
T h e study by C a t e r (1984) on quartz grains in 10
8.9.3 Experimental w o r k
S o m e experimental work has been d o n e to repro
duce surface textures in the laboratory. Krinsley &
D o o r n k a m p (1973) report the reproduction of tex
tures similar to those on glacially transported grains
by freeze and thaw e x p e r i m e n t s , and the production
of V-shaped pits and grooves by water transport.
Most experimental work has been performed on the
production of aeolian surface textures. Kaldi,
Krinsley & Lawson (1978) m o u n t e d individual grains
from different e n v i r o n m e n t s on a stub together with
crushed quartz and p r o d u c e d the characteristic ' u p
turned p l a t e ' textures on the grains in only 24 h o u r s
of abrasion by q u a r t z in a 'wind bottle' with a 'wind
http://jurassic.ru/
257
samples from a 145 m thick N e o g e n e carbonate

sequence in the Finestrat Basin of Spain provides an
example of surface texture analysis applied to a
sequence lacking indigenous fauna, and in which
characteristic first cycle grains could be recognized.
Hill & N a d e a u (1984) used surface features of
Wisconsin sands from t h e C a n a d i a n Beaufort Shelf
to reconstruct depositional environments in a situ
ation where it was not possible to produce sedimen
tological logs of boreholes. In these cases surface
texture analysis provides Useful additional environ
mental evidence to that available from field sedi
mentology, but diagenetic features and grain
reworking are recognized as problems in interpre
tation. O n e limitation of such studies is that the
time-consuming n a t u r e of the practical work does
n o t enable great n u m b e r s of samples to be analysed,
and grain surface texture studies inevitably have to
be regarded as an addition to basic field sedimen
tology rather t h a n an i n d e p e n d e n t topic.
It appears difficult to distinguish many surface
textures of diagenetic origin from those gained
during transport and deposition. T h e r e a d e r might
c o m p a r e illustrations of diagenetic surface tex
tures, as in Burley & Kantorowicz (1986), with t h e
fluvially transported grains figured by M a n i c k a m &
B a r b a r o u x (1987).
8.9.5 C o n c l u s i o n
T h e study of surface textures has certainly been
shown to be of practical value, but a great deal m o r e
controlled experimentation with source rock dis
integration, weathering and transport media still
needs to be d o n e . M o r e comparative studies of
experimental and natural systems using the same
starting material would also be most useful. Perhaps
t h e greatest need is for a new 'atlas of surface
textures' to provide a fresh impetus to the studies. It
is a p p a r e n t that many workers have evolved their
own t e r m s which are not adequately defined. A t
t e m p t s have b e e n m a d e to redefine features, such as
t h e proposed terminology for cracks and hollows of
Baynes & D e a r m a n (1978), but unless a generally
accepted and m a n a g e a b l e list is adopted the tech
nique will possibly die or remain in the hands of a
few faithful a d h e r e n t s .
For the practical sedimentologist the grain surface
texture technique is a useful adjunct to other studies
leading to environmental discrimination. It should
be used in conjunction with detailed grain size and
258
N.H. TREWIN
s h a p e analysis, field sedimentology a n d p a l a e o n t o

logy. Surface textures a r e seldom e m p l o y e d as a
primary discriminator between fossil e n v i r o n m e n t s
d u e to the complexity of textures, lack of generally
accepted s t a n d a r d s , a n d t h e n u m e r o u s possibilities
for textural destruction a n d modification outlined in
Table 8.1.
Hansley (1987) on experimental etching of garnets

by organic acids. Chemical a p p r o a c h e s to diagenesis
are also discussed in the volume edited by McDonald
& S u r d a m (1984).
8.10.2 Practical c o n s i d e r a t i o n s
IDENTIFICATION OF MINERALS
8.10 S A N D S T O N E D I A G E N E S I S
8.10.1 General
T h e S E M with E D S is an essential tool for t h e
examination of p o r o u s sandstones. I m p r e g n a t e d and
stained thin sections, and X R D analysis of clays,
feldspars a n d c a r b o n a t e s can provide much infor
mation, but to investigate the morphologies and
detailed textures of grain overgrowths and diagenetic
minerals t h e S E M is essential. Details of fine-grained
clays a n d o t h e r grain coatings a n d pore-fillings can
not generally b e obtained from thin sections. W i t h
t h e S E M , mineralogy, textures a n d diagenetic
sequences can b e b e t t e r elucidated a n d porosity a n d
permeability can b e related to diagenetic a n d d e
positional textural features. It is the study of oil and
gas reservoir rocks which has provided t h e greatest
boost for S E M studies in t h e past ten years a n d t h e
S E M studies have now sparked off considerable
experimental diagenesis w o r k .
Burley et al. (1985) h a v e provided a useful review
of clastic diagenesis which clearly shows t h e impor
tant role of S E M studies a n d their relation to other
essential experimental m e t h o d s . T h e contribution of
t h e S E M in studies of sandstone diagenesis a n d t h e
essential use of o t h e r techniques t o provide a bal
anced study is well illustrated by H u g g e t t (1984b,
1986) on t h e controls a n d diagenetic sequence of
Coal M e a s u r e s sandstones, Kantorowicz (1985) on
t h e M i d d l e Jurassic of Y o r k s h i r e a n d Burley (1986)
o n Jurassic sandstones of t h e Piper a n d T a r t a n fields
of t h e N o r t h Sea. Increasing use is being m a d e of
c o m b i n e d S E a n d B S E studies of sandstones as illus
t r a t e d by Pye & Krinsley (1986a) on Rotliegend
sandstones, and of combined B S E a n d c a t h o d o
luminescence ( R u p p e r t et al., 1985 a n d Fig. 8.8).
F u t u r e progress will involve m o r e e x p e r i m e n t a l
work and comparison of natural and laboratoryproduced features in a t t e m p t s to simulate diagenetic
conditions. H u a n g et al. (1986) d o c u m e n t e d experi
m e n t s o n the conversion of feldspar to illite, a n d
T h e identification of minerals, particularly t h e clay

minerals, is frequently a p r o b l e m ; even with t h e
help of E D S analysis positive identification is not
always possible with t h e S E M . Reliance on mor
phology alone is most d a n g e r o u s , particularly with
illites, chlorites a n d smectites which commonly exist
as mixed-layer structures. T h e SEM Petrology
Atlas
( W e l t o n , 1984) provides a useful combination of
pictures a n d spectra for most c o m m o n minerals.
W i t h o u t analytical b a c k u p t h e S E M is of limited
use, frequently leaving t h e o p e r a t o r with severe
p r o b l e m s in the identification of fine-grained phases.
With t h e use of an analytical facility it is possible
to build u p a file of spectra of k n o w n c o m m o n
minerals to c o m p a r e against u n k n o w n s . S o m e phases
may require separation for quantitative or X R D
analysis (if not available with t h e S E M ) , b u t for
m a n y studies qualitative analysis is sufficient to con
firm identification.
R e f e r e n c e to t h e literature provides m a n y excel
lent examples of typical morphologies. Clays are
illustrated by M c H a r d y & Birnie (1987), a n d Wilson
& Pittman (1977) illustrated t h e c o m m o n m o r p h o l o
gies of clays in p o r o u s sandstones. Clays a n d m a n y
o t h e r minerals a r e well covered by Scholle (1979)
and W e l t o n (1984). A u t h i g e n i c feldspar is illustrated
by Stablein & D a p p l e s (1977), W a u g h (1978a, b )
and Ali & T u r n e r (1982). Authigenic quartz over
growths are commonly illustrated ( W a u g h , 1970;
P i t t m a n , 1972) a n d s o m e forms of iron a n d titanium
oxides are shown by Ixer, T u r n e r & W a u g h (1979)
and by W a l k e r , W a u g h & C r o n e (1978).
Fig. 8.17. (a) Filamentous illite growing into pore space.

Rotliegend aeolian sandstone, Lower Permian, Southern
North Sea.
(b) Quartz overgrowth which partly post-dates growth of
siderite rhombs and fine-grained illitic clay. Biggada
Sandstone Member, Hermite No. 1, NW Australian Shelf.
(c) Books of coarse kaolinite in pore space. Well
developed quartz overgrowths partly post-date kaolinite
formation as shown by 'impressions' of kaolinite in quartz.
Mungaroo Formation, Flinders Shoal No. 1, NW
Australian Shelf.
(d) Diagenetic kaolinite with vermicular habit, typical of
'freshwater' diagenesis, probably resulting from alteration
of a feldspar grain. Upper Jurassic paralic facies, Piper
Formation, Claymore Field area, North Sea (enlarged area
x 5 indicated scale). (Photograph by I.S.C. Spark.)
(e) K-feldspar grain with diagenetic overgrowth. Needle
like projections in a grain contact area may represent
incomplete development of overgrowth or dissolution at
the grain contact. Lower Cretaceous; Claymore Field area,
North Sea. (Photograph by I.S.C, Spark.)
(f) Microquartz crystals covering part of a single grain
surface, such coatings can inhibit the development of
quartz overgrowths and help preserve porosity. Lower
Cretaceous, Claymore Field area, North Sea.
Illustrations h e r e (Fig. 8.17) show s o m e of t h e

most frequently observed morphologies of a few
c o m m o n minerals.
DETRITAL AND AUTHIGENIC PHASES
T h e distinction b e t w e e n authigenic a n d detrital
material is normally based on t h e general rule that
authigenic minerals display characteristic crystal
forms with evidence of in situ growth within p o r e
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260
N.H. TREWIN
space or on grain surfaces. S o m e authigenic material

such as iron hydroxide grain coatings and amor
p h o u s silica d o not have a characteristic shape but
tend to plaster detrital grains (Fig. 8.18).
Detrital grains may be clearly recognizable or may
be so enclosed in clays of diagenetic origin that their
surfaces are obscured (Fig. 8.18). Detrital clays pose
t h e greatest p r o b l e m for identification. T h e distinc
tion between detrital and authigenic matrix clays is
usually based on t h e assumption that detrital clays
have p o o r crystal form, and may show distortion d u e
greywackes from Sweden. Detrital clays can also

infiltrate p o r e space as shown by experiment and in
n a t u r e by W a l k e r et al. (1978).
A p a r t from completely new-formed authigenic
minerals in sandstones t h e r e are several minerals
which are commonly overgrown during diagenesis.
Q u a r t z most commonly exhibits overgrowths ranging
from micron-sized features scattered on grain sur
faces, to cases w h e r e the sand grain is converted to a
perfect bi-pyramidal quartz crystal ( W a u g h , 1970).
Feldspars also commonly have overgrowths ( W a u g h ,
1978a, b ; Ali & T u r n e r , 1982). T h e s e overgrowths
may b e in t h e form of smooth faced terminations or
may grow in a 'skeletal' o p e n form when they bear a
strong resemblence to etch features (Fig. 8.17e).
Stablein & D a p p l e s (1977) illustrated well the dif
ferent forms overgrowths may take on different
crystal faces of the same grain.
to compaction and a tendency to wrap a r o u n d larger

grains. H o w e v e r , m a n y ' m u d d y ' o r 'dirty' sand
stones have a matrix comprising a mixture of detrital
and authigenic c o m p o n e n t s which may include d e
trital clays which have b e c o m e overgrown or re
crystallized during burial (Wilson & P i t t m a n , 1977).
T h u s , as recognized by C u m m i n s (1962) it has not
been possible to distinguish between 'detrital matrix'
and authigenic clays in greywackes, but M o r o d
(1984) uses t h e S E M to d e m o n s t r a t e a diagenetic
origin for t h e matrix of some U p p e r Proterozoic
DISSOLUTION AND R E P L A C E M E N T OF
GRAINS
Dissolution and replacement features are c o m m o n
in sandstones and most frequently involve feldspar,
carbonates and clays.
Dissolution of feldspar grains resulting in creation
of secondary porosity (Schmidt & M c D o n a l d , 1979a,
b) may leave small etched relics of feldspar or a
skeletal relic of clays. A l t e r a t i o n of feldspar to
aggregates of kaolinite is frequently responsible for
t h e patchy distribution of kaolinite seen in thin
section and with the S E M . Dissolution of ferromagnesian minerals such as amphibole (hornblende)
and pyroxene (augite) is well d o c u m e n t e d by W a l k e r
et al. (1978) and W a u g h (1978a) w h o illustrated
spectacularly etched crystals.
C a r b o n a t e s frequently c e m e n t sandstones and
also replace detrital grains. T h e replacement is fre
quently highly selective resulting in replacement of
particular minerals. Feldspar and quartz are most
frequently affected, but many examples exist w h e r e
o n e or t h e o t h e r is attacked preferentially. Replace
m e n t features of c a r b o n a t e - c e m e n t e d sandstones
can be revealed by etching the carbonate to reveal
surfaces of replaced grains and relics of part re
placed grains (Fig. 8.18c). Burley & Kantorowicz
(1986) illustrated features of quartz grain surfaces
resulting from replacement textures caused by car
b o n a t e c e m e n t s , so allowing recognition of some
sandstone from which c a r b o n a t e cement had been
Fig. 8.18. (a) Detrital grain (right) with amorphous coating containing Si, Al, K, Mg and Fe. Mg-chlorite rosettes grow on
the grain coating and pre-date development of isolated euhedral authigenic quartz. Permian aeolian sandstone, Corrie
Shore, Arran, Scotland.
(b) Sandstone with amorphous Fe-rich coatings on detrital grains from which illite has grown into pore space. Quartz grain
contact solution surface at top left. Rotliegend aeolian sandstone. Lower Permian, southern North Sea.
(c) Cut and acid-etched surface of calcite cemented sandstone. Cut grains stand out from the (darker) etched calcite
cement. Detail shows two grains extensively replaced by calcite but with preserved illitic clay rims. Carboniferous
sandstone, Canning Basin, West Australia.
(d) Solution contact between detrital mica and quartz grains; the platy mica is broken away to reveal the smooth flat
contact-solution surface of the quartz grains beneath. Upper Jurassic sandstone, Claymore Field area, North Sea.
(Photograph by I.S.C. Spark.)
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261
r e m o v e d . H o w e v e r , it must be stressed that car

b o n a t e c e m e n t s of a passive nature may leave n o
clear evidence of their previous presence.
Clays also replace detrital grains, particulalry volcanigenic grains, feldspars and other chemically un
stable grains. Clay transformations during burial
diagenesis such as the smectite-illite transformation
result in modification of clay morphologies and
chemistry. Kaolinite is frequently replaced by illite
at d e p t h resulting in distinctive modification of
kaolinite morphology ( H a n c o c k & Taylor, 1978;
J o u r d a n etal., 1987).
MECHANICAL
DEFORMATION
D u r i n g early burial mechanical compaction results

in reorientation of grains to produce closer grain
packing, mechanically weak grains (e.g. shale frag
m e n t s , glauconite) may be deformed and squeezed
into p o r e space and micas are frequently bent a r o u n d
framework grains. Evidence of a mechanical defor
mation phase is not always obvious in S E M studies
of 'clean' sandstones, but it is frequently evident in
fine grained m u d d y and micaceous sandstones, and
is well shown in studies of m u d r o c k s using backscattered electron images.
DISSOLUTION AT GRAIN CONTACT

Chemical compaction, resulting in dissolution at
grain contacts, is seen in most sandstones, usually
only being absent w h e r e early introduction of cement
p r o d u c e d a rigid frame. T h e surfaces of grain to
grain contacts of q u a r t z display pitted and grooved
solution surfaces (Fig. 8.18b) which contrast with
surfaces of overgrowths on detrital grains.
Solution surfaces are found at many different
mineralogical contacts, but are often impressively
developed at quartz/mica contacts where quartz is
preferentially dissolved (Fig. 8.18d) and similarly at
quartz/organic carbon contacts.
A s pointed o u t by Sellwood & P a r k e r (1978), and
others in the same discussion, this p h e n o m e n o n of
'pressure solution' does n o t bear a simple relation to
d e p t h of burial for any particular facies, there being
a d e p e n d e n c e on evolution of p o r e fluids and the
presence of grain coatings to catalyse reactions. Or
ganic acids are extremely important in diagenetic
reactions by increasing aluminium mobility and aid
ing feldspar dissolution (e.g. S u r d a m et al., 1984).
262
N.H. TREWIN
T h e early cementation of a sandstone will also pro

tect grain contact points by reducing stress at grain
contacts. P o r e fluid pressure may largely support t h e
o v e r b u r d e n weight and inhibit chemical compaction
in over-pressured formations.
E V I D E N C E OF O R D E R OF D I A G E N E T I C
EVENTS
T h e o r d e r of d e v e l o p m e n t of authigenic minerals is
usually stratigraphically based on the assumption
that the younger phases grow on the older. C o m
plications arise in t h e case of grain r e p l a c e m e n t s
w h e n it is not always possible to tell w h e n replace
m e n t took place relative to o t h e r diagenetic events.
D e s p i t e t h e simplicity of the basic premise t h e r e are
several factors which can combine to produce ambig
uous evidence of t h e o r d e r of diagenetic events.
T w o mineral phases may grow at the same time and
a later mineral p h a s e may grow to enclose previous
ly formed material. S o m e minerals have favoured
substrates for growth and diagenetic minerals will
not be evenly distributed on grain surfaces; thus
grains both with and without a particular overgrowth
or coating may occur in close proximity.
In rocks with low permeability diagenetic phases
a r e not evenly distributed, possibly d u e t o differing
local flow rates and chemistry of p o r e water, ion
availability from altered grains, or substrate avail
ability. Such variations can occur on a large scale as
with the obviously different diagenetic histories be
t w e e n c a r b o n a t e c e m e n t e d concretions in sand
stones and the adjacent u n c e m e n t e d rock. T h u s a
wide study of m a n y specimens is required t o establish
a full diagenetic sequence for a particular formation.
8.10.3 A p p l i c a t i o n s of SEM studies of

sandstones
A p a r t from the identification of fine grained mine
rals, matrix, c e m e n t s , grain coatings a n d p o r e fillings
t h e most important S E M applications are the eluci
dation of diagenetic sequences with progressive
burial, the relation of diagenesis to depositional
facies and t h e explanation of factors relating to
porosity and permeability of reservoir sandstones.
W o r k on reservoir sandstones has now advanced to
t h e stage w h e r e t h e S E M is used in studies of
'artificial diagenesis' during reservoir t r e a t m e n t , such
as t h e effects of steam injection on C r e t a c e o u s tar
sands of Alberta described by H u t c h e o n (1984).
d e p t h and/or facies-related p h e n o m e n a but in all

cases a wide range of c o m p a r a b l e material (grain
size, sorting, composition etc.) is n e e d e d , and the
clay mineralogy of any enclosing shales should also
be examined to d e t e r m i n e likely detrital and dia
genetic clays present. T h e following notes on specific
facies types can provide only a basic idea of the
diagenetic variation in sandstones.
DIAGENETIC SEQUENCE
T h e S E M is an essential tool in the elucidation of
diagenetic sequences involving the d e v e l o p m e n t of
authigenic minerals. H u r s t & Irwin (1982) have
summarized s o m e of t h e sequences recorded in re
cent years and their s u m m a r y illustrates well t h e
variation to be found in the o r d e r in which authigenic
minerals develop u n d e r different circumstances.
H u r s t & Irwin listed important factors influencing
diagenesis; their list can be modified as follows:
RED BEDS
1
2
3
Temperature
Pressure
Detrital mineralogy, roles of stable and unstable
grains
4 O r g a n i c geochemistry
5 Availability of c a r b o n a t e , both biogenic and
non-biogenic
6 P o r e water composition, migration of p o r e fluids
and gases, and evolution
7 S e d i m e n t t e x t u r e , porosity and permeability
8 Sedimentary facies, including enclosing forma
tions
9 Tectonics
10 T i m e
In view of the n u m e r o u s variable influences, pro
jects involving interpretation of diagenetic sequence
require a great deal of background information.
Evidence should certainly be sought o n t h e follow
ing p o i n t s :
Depositional e n v i r o n m e n t . M a r i n e or fresh water
and if fresh water, vadose or phreatic? Likely initial
p o r e water type, and later p o r e water modifications?
Mineralogy. Is t h e original detrital mineralogy
preserved or recognizable; what major changes have
t a k e n place?
T e x t u r e . W h a t was t h e original texture (grain
size, sorting) and how has it been modified? H o w
has porosity and permeability b e e n altered?
Burial history. W h a t is t h e burial history.ln terms
of maximum burial d e p t h , when did this occur, and
h a s m o r e than o n e cycle of burial t a k e n place?
P o r e fluid and gas. H a s the rock been flushed by
different pore fluids at any t i m e , what was the final
p o r e filling prior to collection (e.g. air, gas, oil, fresh
water, saline water?
F r o m these considerations it may be possible in
well-explored areas to estimate likely pressures and
t e m p e r a t u r e s and reconstruct with s o m e accuracy
t h e geological history of t h e formation.
Diagenetic studies can be organized to examine
W a l k e r (1967) and W a l k e r et al. (1978) have d e m o n

strated how the red pigmentation in first-cycle desert
sandstones forms in response to the alteration of Febearing minerals such as h o r n b l e n d e and augite by
solution. T h e iron released is probably deposited as
ferric hydrate which gradually converts to h a e m a t i t e
with burial and ageing. T h e iron oxide or hydroxide
rims to grains are frequently associated with clays
which m a y initially b e mixed-layer illite/smectites
but are converted to illite during burial as in the
extensively studied Rotliegend (Lower P e r m i a n )
sandstones of the southern N o r t h Sea.
N u m e r o u s studies on the Rotliegend sandstone
(Rossel, 1982; G l e n n i e , M u d d & Nagtegaal, 1978;
H a n c o c k , 1978b; N a g t e g a a l , 1979; Pye & Krinsley,
1986) illustrate the general diagenetic features and
some of t h e variable factors. G e n e r a l features are
iron oxide grain coatings of early diagenetic origin
which include illite probably representing original
illite/smectite (Rossel, 1982). Second stage dia
genesis results in feldspar overgrowths, dolomite
cement and r e p l a c e m e n t , and also q u a r t z over
growths. Feldspar is frequently converted to kao
linite prior to the final stage when the characteristic
'hairy' or ribbon illite (Fig. 8.17a) is p r o d u c e d along
with s o m e chlorite. Many variations on this t h e m e
are recorded such as early calcite, halite and gypsum
facies controlled c e m e n t s (Glennie et al., 1978).
L a t e anhydrite cements are found n e a r faults
(Glennie et al., 1978) or close to overlying Zechstein
evaporites ( H a n c o c k , 1978b).
Burley (1984) p r o d u c e d a detailed diagenetic his
tory of the Triassic Sherwood Sandstone G r o u p and
recognized distinct stages of diagenesis related to de
positional environment, burial and subsequent uplift.
T h e value of S E M work is greatly e n h a n c e d by the
use of o t h e r techniques (isotopes, X R D , microprobe
analysis a n d p e t r o g r a p h y ) b o t h in this p a p e r a n d in
Burley (1986) on reservoir sandstones of t h e Piper
and T a r t a n fields in t h e N o r t h Sea. .""
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263
'MARINE' SANDSTONES
Sandstones with original m a r i n e p o r e waters have
varied diagenetic histories (Hurst & Irwin, 1982)
which may c o m m e n c e with illite/smectite (Hawkins,
1978) or chlorite (Tillman & A l m o n , 1979) or con
cretionary c a r b o n a t e , but frequently are c e m e n t e d
by quartz overgrowths. T h e earliest phase of quartz
c e m e n t , particularly in sandstones adjacent to shales,
may be of randomly oriented microquartz crystals
on grain surfaces (Fig. 8.17f), which subsequently
inhibit the formation of quartz overgrowths (Spark
& Trewin, 1986).
Following establishment of a rigid frame, dissolu
tion of unstable grains may result in secondary
porosity or production of kaolinite by feldspar alter
ation. T h e kaolinite in m a r i n e sandstones frequently
forms p o r e filling c e m e n t s of well formed euhedral
crystals of 4 - 1 0 um size ( H u r s t & Irwin, 1982).
C a r b o n a t e is frequently introduced after the initial
quartz overgrowth phase both as cement and as
grain replacement, particularly of feldspars, and this
p h a s e of diagenesis may eliminate most porosity.
D e e p e r burial may, however, result in carbonate
dissolution producing secondary porosity (Schmidt
& M c D o n a l d , 1979a, b) which can be available for
occupation by migrating hydrocarbons. Production
of organic acids during the maturation of organic
matter is frequently thought responsible for second
ary porosity d e v e l o p m e n t by silicate (frequently
feldspar) dissolution.
E n t r y of h y d r o c a r b o n s effectively stops diagenetic
reactions (Hawkins, 1978) but reactions can con
tinue in adjacent water-saturated sandstones to pro
duce further q u a r t z , kaolinite or illite cements,
resulting in diagenetic contrasts at oilwater
contacts.
'FRESHWATER'
SANDSTONES
T h e r e is a full range in p o r e water compositions

b e t w e e n highly saline and fresh water giving a great
variety of environmental controls to diagenesis, but
sandstones such as fluvial sandstones with fresh pore
waters display s o m e apparently distinctive features
(Hurst & Irwin, 1982). T h e major feature is"a ten
dency for kaolinite d e v e l o p m e n t (at the expense of
feldspar) to precede quartz overgrowth formation
and for the kaolinite to form coarse vermicular
crystals with ragged or skeletal edges (Fig. 8.17d)
264
N.H. TREWIN
which may have grown more rapidly than the char

acteristic ' m a r i n e ' form of kaolinite. H o w e v e r , it is
important to recognize that a great many sandstones
deposited u n d e r shallow marine conditions are sub
sequently flushed by fresh water from adjacent land
areas during early burial or later uplift.
C a r b o n a t e s may be developed at m o r e than o n e
stage in the diagenetic history, ranging from p e d o genic carbonate of caliche soils, or early pre-compaction carbonate nodules through to late diagenetic
calcite, dolomite or siderite precipitation post-dating
quartz cementation and occuring at depths of 23
k m . Flushing of. originally marine sandstones by
fresh water will frequently superimpose new diagene
tic features, thus formations involved in uplift and
reburial can possess complex diagenetic histories.
P O R O S I T Y A N D ^ P E R M E A B I LITY
T h e permeability of a sandstone is related to the size
and shape of p o r e throats which connect larger p o r e
volumes in a s a n d s t o n e , the tortuosity of pores, and
t h e specific surface area within p o r e space. T h e
S E M is ideal for examination of pore geometry by
m e a n s of p o r e casts and also ideal for viewing t h e
factors which serve to reduce porosity and p e r m e
ability in sandstone. O n e of the most obvious exam
ples of permeability reduction by t h e formation of
authigenic minerals within p o r e space is that pro
vided by the illite diagenesis of the Rotliegend sand
stone of the southern N o r t h Sea where delicate illite
crystals bridge and block p o r e throats (Fig. 8.18b),
so reducing permeability. T h e Brent Sandstone
(Middle Jurassic, North Sea) displays similar fea
tures with illite also responsible for permeability
reduction (Hancock & Taylor, 1978; Blanche &
W h i t a k e r , 1978), and t h e M a g n u s reservoir ( U p p e r
Jurassic, N o r t h Sea) is similarly affected ( M c H a r d y
et al., 1982). Kaolinite is not usually so detrimental
to permeability as illite since it has a larger grain
size, and smaller surface area (Fig. 8.17c) so that
p o r e tortuosity and water absorption o n t h e clay
surface are not so great. Kaolinite also tends to be
m o r e patchy in its distribution in the rock. S E M
studies can be valuable in the assessment of microporosity in reservoirs as in t h e case of p o r c e l a n e o u s
c e m e n t of opal, microquartz and montmorillonite
described from M i o c e n e turbidite sandstones of t h e
Los Angeles Basin by Sears (1984).
As oil migrates into a reservoir diagenesis is arrest
ed as in the case of the B r e n t Sandstone ( H a n c o c k &

Taylor, 1978; S o m m e r , 1978) w h e r e it can be shown
that oil migrated into place synchronously with illite
formation, there being a d o w n w a r d increase in illite
within t h e reservoir. T h u s the relative timing of
generation and migration of h y d r o c a r b o n s during
diagenesis can be d e t e r m i n e d and predictions can be
m a d e on reservoir quality with respect to facies,
geographical a r e a and d e p t h of burial.
Porosity can be observed with t h e S E M a n d , by
use of image analysis e q u i p m e n t on polished sec
tions, particularly in the backscattered m o d e , can be
d e t e r m i n e d quantitatively. P o r e surfaces are best
examined on rough broken rock surfaces. Pore throat
size and pore connection is most easily studied using
p o r e casts (Fig. 8.21).
B a t h u r s t (1975) provides an excellent account and

Scholle (1978) illustrates the use of the S E M in
c a r b o n a t e studies and provides a useful bibliography
t o selected topics a n d techniques. A variety of tech
niques such as thin section, X R D and c a t h o d o
luminescence and isotope analysis are all of great
value in c a r b o n a t e studies a n d the S E M can m a k e a
useful contribution in many cases and provides ex
cellent illustrative material.
Only a few examples can be quoted in the space
available and these are chosen to illustrate the wide
r a n g e of use of t h e S E M in c a r b o n a t e studies,
without attempting to review theories on t h e various
examples p r e s e n t e d .
CONCLUSION
8.11.2 Examples
F r o m these few examples it is a p p a r e n t that t h e

diagenesis of any sandstone formation must be
studied with reference to all available information
on facies; p o r e fluids, burial history and composi
tion. Utilization of S E M techniques can greatly aid
explanation of porosity and permeability para
m e t e r s , relating t h e m to depositional and diagenetic
factors by examination of p o r e morphologies and
fillings.
CARBONATE GRAINS
8.11 L I M E S T O N E S A N D D O L O M I T E S
8.11.1 General
Utilization of t h e S E M for t h e study of limestones is
most valuable in the examination of fine-grained
p o r o u s limestones such as chalk (Scholle, 1977) and
for tracing t h e evolution of cement and r e p l a c e m e n t
fabrics in Recent to sub-Recent carbonates (Bathurst,
1975; F o l k , 1974a; J a m e s et al., 1976; Wilkinson
et al., 1982). In studies of m o d e r n fine-grained car
b o n a t e sediments the morphologies and origins of
grains can be d e t e r m i n e d ( H a y et al., 1970) and
detail of biogenic particles m o r e easily recognized.
Textures and p o r e geometry of dolomitized and
dedolomitized sediments a r e also suitable for ex
amination as in examples of Silurian dolomite dia
genesis in the L o c k p o r t F o r m a t i o n , U S A (Shukla &
F r e i d m a n , 1983), dolomitized C r e t a c e o u s chalk of
E u r o p e ( J o r g e n s e n , 1983) and recent Australian
C o o r o n g dolomites (Von D e r Borch & Lock, 1979).
F o r a general discussion of c a r b o n a t e petrology,
Unconsolidated c a r b o n a t e sediments can be ex

amined as scattered grain m o u n t s for t h e identifica
tion of fine c a r b o n a t e grains. T h i s t e c h n i q u e is useful
for the identification of biogenic particles as shown
experimentally by H a y et al. (1970) w h o crushed
examples of known invertebrate material and were
able to recognize distinctive skeletal morphologies
in fine sands and even in s o m e grains as small as
4 p m . M o u n t i n g the grains in resin and examining
polished and etched surfaces enabled t h e m to recog
nize distinctive skeletal internal structures.
T h e contributions which t h e fragmentation p r o
ducts of organisms m a k e to c a r b o n a t e m u d s , such as
aragonite needles derived from t h e b r e a k d o w n of
the calcified algae Halimeda and Penicillus, and the
contribution of coccoliths, discoasters and o t h e r
planktonic organisms to d e e p sea oozes can be
ascertained (illustrations in Scholle, 1978). Alexandersson (1979) illustrates t h e contribution that t h e
b r e a k d o w n products of mussel (Mytilus) shells m a k e
t o sediments of t h e S k a g e r r a k , N o r t h Sea. A similar
process o p e r a t e s in m u d s of the Y t h a n Estuary,
N o r t h Scotland, w h e r e characteristic calcite needles
and plates are released by t h e b r e a k d o w n within the
sediment of mussel shell fragments originally contri
buted t o t h e sediment by t h e p r e d a t o r y activities of
eider ducks feeding on the local mussel beds (Trewin
& Welsh, 1976; Fig. 8.19). Calcite needles origina
ting from the b r e a k d o w n of m u s s e l shells also occur
in suspended sediment on the north-eastern U S A
Continental shelf (Fitzgerald, Parmenter & M i l l i m a n ,
1979).
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265
Sediments may also be e x a m i n e d for grains of

non-biogenic origin such as the 220 |xm high-Mg
calcite grains precipitated in L a k e M a n i t o b a
( C a n a d a ) illustrated by Last (1982) and the numer
ous studies of ooids and their structure such as that
of L a n d , B e h r e n s & Frishman (1979) on the ooids
of Baffin Bay, T e x a s , and Sandberg (1975) and
Halley (1977) on t h e ooids of t h e G r e a t Salt L a k e .
S a n d b e r g ' s study utilizes S E M examination of etched
surfaces to show that coarse radial aragonite is of
depositional rather than recrystallization origin. T h e
S E M provides evidence not available from micro
scope petrography.
Evidence of aragonite replacement by calcite can
also be revealed by S E M preparations such as t h e
relic aragonite structures in calcitized Jurassic bi
valves illustrated by S a n d b e r g & H u d s o n (1983).
T h e s e and m a n y o t h e r studies illustrate the
general use of t h e S E M in studies involving car
b o n a t e grains.
CEMENTATION OF C A R B O N A T E S
T h e r e are many cases in which early cementation of
c a r b o n a t e s occurs in m a r i n e subtidal and intertidal
conditions and in freshwater phreatic and vadose
situations. T h e morphology of the cements pro
duced can ideally b e examined using the S E M and
much m o r e detail obtained than is possible in thin
section. In freshwater solutions with low M g
con
centrations there is a tendency for simple r h o m b s to
grow, but in solutions with a high M g
concentra
tion sideways growth of t h e crystals may b e poi+ +
+ +
Fig. 8.19. Bivalve (Mytilus) shell fragment breaking up to

release individual calcite laths into the sediment. From
recent intertidal mudflat, Ythan Estuary, North Scotland.
266
N.H. TREWIN
soned by M g and fibrous crystals of Mg-calcite or

aragonite form (Folk, 1974a); however, s o m e uncer
tainties exist concerning this mechanism. B a t h u r s t
(1975), Folk (1974a), F r i e d m a n (1975) a n d M o o r e
(1979) provided s u m m a r i e s of early c e m e n t a t i o n in
m a r i n e and freshwater e n v i r o n m e n t s , and only a
few examples can be m e n t i o n e d h e r e .
Oolite cementation by calcite in freshwater con
ditions o n Joulters Cay, B a h a m a s described by
Halley & Harris (1979) results in cementation a r o u n d
grain contacts with blocky calcite in t h e vadose zone
producing a form of meniscus c e m e n t . A similar
c e m e n t is found in s u b - R e c e n t oolite d u n e sands
a r o u n d H a m e l i n P o o l , Shark B a y , West Australia
(Logan etal., 1974) as illustrated h e r e in Fig. 8.20(a).
Below t h e water table at Joulters Cay t h e calcite
c e m e n t is n o t c o n c e n t r a t e d at grain contacts, but
consists of small dog-tooth crystals of 2040 um in
isopachous grain coats and in d e e p e r samples scat
t e r e d r h o m b o h e d r a of 2030 um which decrease in
size to 510 um s o m e 4 m below t h e w a t e r table.
Using t h e S E M evidence Halley & H a r r i s w e r e able
to calculate aragonite dissolution rates and calcite
cementation rates and show that local rainfall is
sufficient to account for t h e observed c e m e n t a t i o n .
T h e result of continued aragonite solution a n d cal
cite deposition is well displayed by c e m e n t e d Pleis
tocene oolite d u n e sands a r o u n d Shark Bay w h e r e
comoldic porosity is developed (Fig. 8.20b).
T h e value of S E M work is well illustrated by t h e
work of Steinen (1978) on t h e diagenesis of lime
m u d using subsurface material from B a r b a d o s . H e
recognized microspar deposition in voids created or
enlarged by dissolution and showed that m u d s
c e m e n t early and in m a n y stages. In thin section t h e
textures resembled aggrading n e o m o r p h i s m , but t h e
S E M allowed t r u e crystal shapes and relations t o b e
recognized.
S u b m a r i n e c e m e n t a t i o n by aragonite a n d calcite
has b e e n widely r e p o r t e d from different environ
ments [James et al. (1976) from tropical reefs in
Belize; A d a m s & Schofield (1983) from gravel at
Islay, Scotland]. Alexandersson (1974) illustrated a
variety of aragonite and Mg-calcite c e m e n t s related
to biochemical activity of living red algae in calcium
c a r b o n a t e u n d e r s a t u r a t e d waters of t h e Skagerrak
( N o r t h Sea) a n d showed that the c e m e n t and coral
line algae u n d e r g o dissolution following t h e d e a t h of
the algae.
Characteristic aragonite cements comprise deli
cate needles coating grains as shown in an example
267
of an oolitic h a r d g r o u n d from Shark Bay (Fig. 8.20c,

d ) . S u b m a r i n e calcite c e m e n t s frequently consist of
high-Mg calcite occurring as micrite in fine p o r e s
a n d o n grain surfaces and followed by bladed s p a r as
r e p o r t e d by J a m e s et al. (1976) from Belize reefs.
L o n g m a n (1980) provided an SEM-illustrated ac
count of c a r b o n a t e cementation features in m a r i n e
and freshwater environments a n d related processes
t o t h e n u m e r o u s cementation p r o d u c t s b o t h aragonitic and calcitic.
'Beach rock' formed by cementation in the inter
tidal to supratidai z o n e is c o m m o n in t h e tropics but
also occurs in m o r e t e m p e r a t e climates. C e m e n t is
frequently acicular aragonite but m a y also be of
high-Mg calcite.
C e m e n t a t i o n and structures in calcretes such as
t h e variety of calcified filaments of soil fungi, algae,
actinomycetes and root hairs described and illu
strated by K l a p p a (1979, 1980) from M e d i t e r r a n e a n
Q u a t e r n a r y calcretes can b e ideally studied with t h e
S E M , as also d e m o n s t r a t e d by W a t t s (1980) in a
study of calcretes from t h e Kalahari, southern Africa,
w h e r e both high- and low-Mg calcite a r e deposited
in passive, displacive and replacive m o d e s and are
associated with authigenic palygorskite, sepiolite and
minor dolomite.
DIAGENESIS OF LIMESTONE CHALK

Whilst m a n y limestones can be e x a m i n e d advan
tageously using S E M techniques t h e examination of
chalks has been particularly instructive. Scholle,
(1977) summarized t h e diagenetic modifications of
t r u e nannofossil chalks from t h e N o r t h Sea a n d
surrounding E u r o p e a n o u t c r o p s as well as N o r t h
A m e r i c a n Gulf Coast and Scotia Shelf examples.
In early diagenesis compactional dewatering of
t h e highly p o r o u s m u d s leads to a grain s u p p o r t e d
frame; s o m e selective dissolution m a y t a k e place at
this stage, particularly in d e e p water' examples.
D e p t h of burial is t h e single most i m p o r t a n t factor in
chalk diagenesis and t h e progressive d e v e l o p m e n t of
an interlocking calcite c e m e n t which overgrows coccoliths is admirably displayed by fig. 8 of Scholle
(1977).
T h e mechanism of cementation in low-perme
ability chalks is by solution transfer. C e m e n t is
introduced into a load bearing frame a n d p r e v e n t s
mechanical compaction as burial loading increases.
T h e source of t h e c e m e n t is internal to t h e formation
and results partly from selective dissolution of cal-
Fig. 8.20. Examples of cementation and dissolution in RecentPleistocene oolitic rocks and sediments from Shark Bay,
West Australia.
(a) Blocky clacite cement concentrated at grain contacts as a meniscus cement in a oolite cemented in the vadose zone.
Lithified sub-Recent oolitic aeolian dune deposit. Carbla Point, Hamelin Pool.
(b) Oolite with aragonitic ooids largely dissolved to leave secondary oomoldic porosity, some primary intergranular
porosity remains within blocky calcite cement. Pleistocene oolitic aeolian dune sand below calcrete crust. Hutchison
Embayment.
(c) Bladed aragonite cement. Recent submarine cementation of oolitic hardround in Hamelin Pool.
(d) Aragonite cement evenly coating grains in a recent oolitic hardground. Enlargement (marked scale x 5) shows etched
quartz grain surface beneath an ooid rim. Some borings present in ooid surfaces. Hamelin Pool.
citic or aragonitic organisms but originates mainly

from solution seams and stylolites. Over-pressured
chalks retain high porosities since stress is reduced
at grain contacts, and chalk in oil reservoirs may re
tain high porosity d u e to t h e influx of oil preventing
further c e m e n t a t i o n . In fine-grained chalk reservoirs
t h e S E M is t h e only practical m e a n s of examining
details of p o r e g e o m e t r y and rock framework.
DIAGENESIS CARBONATE POROSITY

A useful example of S E M use on ancient reefs
( U p p e r Miocene of southern Spain) is that of A r m
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strong, Snavely & A d d i c o t t (1980) in which thin

section and S E M information is neatly combined to
illustrate t h e modifications of primary porosity d u e
to aragonite solution and dolomitization of lime
mud.
P o r e geometry in c a r b o n a t e s has been investi
gated by producing resin p o r e casts of chalk (Walker,
1978) to reveal intersecting laminar pores 12 um x
0.10.2 pm resulting in non-laminar pores which
connect larger p o r e spaces such as those within
foraminifera. T h e small size of p o r e throats results
in t h e low (less than 10 md) permeabilities of most
chalks. Patsoules & Cripps (1983) have illustrated a
268
N.H. TREWIN
variety of p o r e types in chalk by use of resin casts.

Wardlaw & Cassan (1978) illustrated a wide var
iety of limestone and dolomite porosity by use of
p o r e casts and related porosity type to recovery
efficiency in reservoir rocks; their illustrations of
p o r e casts c o m p a r e d with thin section a r e most
instructive. Bimodal porosity in oolites described by
Keith & Pittman (1983) is d u e to micropores within
ooids which a r e w a t e r filled w h e r e a s gas is confined
to the larger primary p o r e s between ooids, thus t h e
S E M can aid in the assessment reservoir p r o d u c
tivity. Contrasting p o r e casts of both primary and
secondary limestone porosity are illustrated in Fig.
8.21.
DOLOMITIZATION
Dolomitization of limestones frequently results in
t h e creation of useful interconnected porosity as
discussed and illustrated by W a r d l a w (1976),
W a r d l a w & Cassan (1978) a n d Davies (1979). D o l o
mite formation has been attributed to a variety of
processes in early diagenesis (summaries in Bathurst,
1975 and Z e n g e r , D u n h a m & E t h i n g t o n , 1980).
Dolomitization frequently affects only specific
c o m p o n e n t s of a limestone, as for e x a m p l e w h e n
bioclasts a r e dissolved and cementing calcite dolo
mitized. Figure 8.22 shows an example from t h e
subsurface Devonian of West Australia (geology of
area summarized by Playford, 1980) w h e r e ooids
have b e e n dissolved and t h e c e m e n t dolomitized,
and also an e x a m p l e with diagenetic illite a n d k a o
linite developed in p o r e space of t h e d o l o m i t e during
freshwater invasion of a marine limestone following
its dolomitization. In these examples dolomitization
probably took place by mixing of fresh and marine
water.
Dolomitization of chalk from t h e N o r t h Sea
(Jorgensen, 1983) results in t h e production of dolo
mite r h o m b s of 1030 urn size which clearly over
grow original texture and fossils. D o l o m i t e forms
only 28% of t h e rock and appears to have formed
early in diagenesis. M o r e extensive dolomitization
of limestones is described by Shukla & F r i e d m a n
(1983) from the Lockport Formation (Middle Silurian)
of N e w Y o r k State w h e r e early incipient dolomitiza
tion of micrite took place in a supratidal environ
m e n t . Successive stages of dolomitization resulted in
dolomitization of all the g r o u n d m a s s , dolomitization
of g r o u n d m a s s and allochems a n d finally totally
obliterative dolomitization. S E M examination of
269
dolomites clearly reveals the p r o b l e m s of low per

meability dolomite reservoirs which are usually
caused by n a r r o w , poorly connected p o r e t h r o a t s in
intercrystalline porosity, and t h e presence of non
effective porosity in small vugs.
8.12 E N O O L O T H I C M I C R O B O R I N G S
8.12.1 General
T h e S E M has played an i m p o r t a n t role in t h e study
of microborings in c a r b o n a t e substrates, since it
enables t h e three-dimensional forms of micron-sized
borings t o be examined in detail.
Bioerosion is now recognized as a most i m p o r t a n t
factor in t h e reduction of c a r b o n a t e grains a n d
substrates, particularly in t h e shallow m a r i n e en
vironment. G o l u b i c , Perkins & L u k a s (1975) re
viewed t h e history of t h e study of microborings and
provided an extensive reference list. T h e larger
borings p r o d u c e d by echinoids, g a s t r o p o d s , bivalves,
polychaetes a n d sipunculids ( s u m m a r y in W a r m e ,
1975) a r e n o t studied using t h e S E M , b u t detailed
features of t h e walls of t h e borings can provide
useful information. T h e smaller borings d u e t o
sponges (particularly Cliona) are of suitable size for
S E M examination of fine detail a n d of s e d i m e n t
p r o d u c e d , but t h e greatest contribution of t h e S E M
is in the study of algal, fungal and possible bacterial
borings in grains and rock surfaces. O t h e r small
borings such as s o m e of those due to cirripedes,
bryozoa and foraminifera can also b e usefully ex
amined with the S E M .
8.12.2 Methods
P r e p a r a t i o n m e t h o d s are described in Section 8.5.
Study of recent borings should involve identification
of t h e organism responsible, b u t iii d e a d and fossil
material all that remains is a cavity or filled boring
which must b e p r e p a r e d by a suitable impregnation
or etching t e c h n i q u e . Considerable t a x o n o m i c
p r o b l e m s exist with respect t o endolithic algae and
fungi which a r e beyond t h e scope of this w o r k .
8.12.3 Sedimentological f a c t o r s
Bioerosion is of the greatest i m p o r t a n c e in car
b o n a t e e n v i r o n m e n t s and o n coastlines with exposed
carbonate-rich rocks, b u t is by n o m e a n s confined
Fig. 8.21. (a) Resin pore-cast of interparticle porosity; carbonate aeolian dune sand, Pleistocene, Shark Bay, West
Australia.
(b) Resin pore cast of secondary oomoldic porosity in the same rock as in Fig. 8.20(b). Calcite has been dissolved, but a
dolomite rhomb remains within the pore cast at lower centre of picture.
Fig. 8.22. (a) Coarse dolomite with intercrystalline porosity containing books of kaolinite; small illite plates and ribbons
are also present on dolomite surfaces.
(b) Dolomite with oomoldic porosity due to dissolution of ooids, some intergranular porosity remains.
Both from Yellow Drum Formation, Upper Devonian, Canning Basin, West Australia.
to such situations. T h e organisms responsible for
microborings have specific ecological r e q u i r e m e n t s
and t h u s a zonation of such organisms can be recog
nized with respect to factors such as water d e p t h ,
tidal r a n g e , light p e n e t r a t i o n and climate. T h u s t h e
identification of borings can lead to interpretations
(Fig. 8.23) on the d e p t h ranges of boring algae and
fungi (Golubic et al., 1975; L u k a s , 1979). L i m e s t o n e
coasts are generally subject to intense bioerosion,
with distinctive zones of bioerosion leading to d e
velopment of features such as a biogenic notch w h e r e
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destruction is particularly great. Schneider (1976),

in a detailed study of an Adriatic limestone coast,
illustrates t h e borings found in t h e various zones of
t h e rocky shore. Such studies are of great value from
t h e ecological standpoint, and increase o u r knowl
e d g e of t h e d e p t h range of specific types of borings.
Endolithic algae (Fig. 8.24) which require very
little light occur as d e e p as 370 m ( L u k a s , 1979) but
are more characteristic of shallower depths to 100 m.
Fungi d o not require light and are found to much
greater d e p t h s . It appears (e.g. Fig. 8.23) that t h e r e
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N.H. TREWIN
cellular activity, thus only 2 - 3 % of the substrate is
dissolved, t h e rest contributing to sediment produc
tion. Typical sediment chips and wall features of t h e
boring are illustrated in Fig. 8.25. In early coloniza
tion stages N e u m a n n (1966) found that Cliona des
troyed 57 kg limestone m in 100 days, but since
Cliona ceases t o b o r e after reaching a particular
d e p t h this figure is well in excess of t h e n o r m a l r a t e
which Rutzler (1975) calculated to be 250 m g of
sediment p e r m p e r year in B e r m u d a , which can
account for up to 4 1 % of sediment in m u d pockets
within a coral framework. F u t t e r e r (1974) found
sponge excavated particles to constitute 3 0 % of
Fanning Island (Pacific Atoll) lagoonal sediments,
and 2 3 % of samples from t h e A r a b i a n Gulf and
t h e Adriatic. H e also illustrated typical grains and
showed how the edges b e c o m e r o u n d e d by abrasion.
A c k e r & Risk (1985) calculated rates of bioerosion
by Cliona caribbaea in t h e shallow terrace zones off
271
2
G r a n d C a y m a n ( B . W . I . ) to b e 8 k g limestone m
p e r a n n u m , most of which is rapidly transported
d o w n s l o p e . S E M p h o t o g r a p h s of fine fractions ( 3 4 c[>) w e r e used for estimation of a b u n d a n c e of
sponge-produced chips.
Fig. 8.23. Relative vertical

distribution of common marine
microboring algae superimposed on
an idealized coastal profile. The upper
limits above high-tide level are
controlled by water supply; the lower
limits by light penetration into the
water column.
(a) Coccoid eiplithiccyanophytes, (b)
Hormathonema luteobrunneum, H.
violaceo-nigrum, (c) Hormathonema
paulocellulare, (d) Solentia
foveolarum, Kyrtuthrix dalmatica, (e)
Hyella tenuior, (f) Mastigocoleus
testarum,
Gomontiapolyrhiza,
Phaeophila dendroides,
Conchocelis-st&ges of various
rhodophytes, (g) Hyella caespitosa,
Eugomontiasdcculata, (h\
Plectonema terebrans, Ostreobium
quekettii, (i) Fungi. Modified from
Golubic et al. (1975) and Lukas
(1979).
High t i d e /
A i
Low t i d e / ^
Light compensation depth
ENDOLITHIC ALGAE
Endolithic algae have b e e n r e p o r t e d to b o r e at rates
varying from 0.3 t o 36 um/day (data s u m m a r y in
L u k a s , 1979) but most can only reach a d e p t h of a
few millimetres d u e to light r e q u i r e m e n t s . Their
activity m a k e s t h e rock o r grain surface w e a k a n d
p o r o u s and thus m o r e subject t o mechanical erosion,
but it is t h e activities of grazing animals such as sea
urchins, gastropods, chitons and fish which rasp
away the algae infested rock which result in most
sediment production. Grazing activity r e m o v e s the
surface layer and allows t h e algae to b o r e d e e p e r
Table 8.2. Examples of processes, mechanisms, traces produced, and habitats of some organisms responsible for
bioerosion (modified from Schneider, 1976)
Microboring
organisms
is greater variety and a b u n d a n c e of microborings in

shallow waters and a m o r e precise d e p t h zonation
developed t h a n in d e e p e r water. A s indicated in
T a b l e 8.2, algae, lichens and fungi b o r e by corrosion
with a chemical mechanism and thus d o not directly
p r o d u c e sediment. T h e clionid s p o n g e s , h o w e v e r ,
release c a r b o n a t e particles which contribute signi
ficantly to sediment production.
Destruction process
Mechanisms
Algae, blue-green,
green,red
Boring, internal
corrosion
Chemical solution?
Lichens
Surface corrosion and

boring
Chemical solution by
organic acids
Fungi
Boring, internal
corrosion
Chemical solution
Sponges,
e.g. Cliona
Boring
Chemical loosening of
small chips of
15100 um size by
acids and enzymes
SPONGES
Fig. 8.24. Endolothic algal borings in mollusc shell,

several different morphologies and depths of boring extend
into the shell from its outer surface A - A (top of picture).
The finest borings are possibly of fungal origin. Borings
prepared by impregnation with resin and etching of a
polished surface.
T h e mechanism of boring of Cliona has been d e

scribed and well illustrated with S E M p h o t o s
(Rutzler & Rieger, 1973) to show t h e m e t h o d of
excavation which r e m o v e s 15100 um size chips of
substrate of characteristic s h a p e with etched sur
faces. M e a n dimensions of C7/ona-produced chips
are 56 x 47 x 32 um. T h e chips are excavated by t h e
production of crevices only 0.2 um wide etched by
Traces
Network of fine
Littoral to lower limit of
borings with specific
photic zone, mostly to
patterns. Up to 800
only 100 m depth,
urn deep. Tubes 1
extreme 370 m +
urn to 100 um but
most frequently
210 um. Various
rock surfaces
Various rock surfaces, Intertidal and supratidal
disintegration of
surface into small
particles
Very fine borings up to Intertidal and below to
2 mm deep.
1000 m +
Frequent 1-3 urn
hyphae with
sporangea 2 - 5 0 \im
but can be 812 urn
diameter tubes
From biological notch
Regular chamber
near low tide
system in rock with
downwards
openings to surface
http://jurassic.ru/
Jjjliil
Habitat
i i i liilh,
272
N.H. TREWIN

may also lead t o the production of micritized grain
surfaces.
ACKNOWLEDGMENTS
T h e a u t h o r wishes t o thank D r I.J. Fairchild for Fig.
8 . 8 ( a - c ) , A . H o g g , E . Sellier and Total C F P for
Fig. 8 . 8 ( d - f ) , A . T . Kearsley for Fig. 8 . 9 ( a - c ) , and
R . L . G a w t h o r p e for Fig. 8 . 9 ( d - h ) . Figs 8.17(c, d)
and 8.22(a, b) were taken by the author at the
Fig. 8.25. Cliona borings in the bivalve Tridacna. Heron Island lagoon, Great Barrier Reef, Queensland, Australia.
(a) Typical sculpture of wall of boring, with two chips excavated by Cliona lying on the surface and showing the
characteristic convex outer surface (wrt the sponge).
(b) Typical concave etched facets of the inner surface of a chip.
and so continue t h e bioerosion process. F a r r o w &
Clokie (1979) illustrated typical effects of grazing by
limpets and chitons on algal-infested shells and t h e
consequent production of sediment. T h e r a t e of
destruction of c a r b o n a t e rock surfaces in various
environments is of the order of 1 m m y r (Schneider,
1976). Algal endoliths Have a long history extending
at least to t h e late P r e c a m b r i a n ( C a m p b e l l , 1982).
Typical algal endolithic borings are illustrated in
Fig. 8.24. T h e rate of c a r b o n a t e dissolution by micro
boring organisms was investigated in t h e lagoon of
Davies Reef, Australia, by T u d h o p e & Risk (1985).
Using t h e S E M , and observing i m p r e g n a t e d b o r e d
grains, the p e r c e n t a g e of borings could b e point
counted within grains. E x a m i n a t i o n of t h e surface
uncoated and u n d e r a weak vacuum p r o d u c e d high
contrast between resin-filled borings and c a r b o n a t e ,
and simplified point-counting.
_ 1
Infestation of c a r b o n a t e s by endoliths also occurs

b e n e a t h t h e sediment/water interface, particularly in
organic-rich m u d . May & Perkins (1979) illustrate a
restricted assemblage of four forms found up to 1.6 m
below the surface in fine-grained reducing sediments.
T w o of t h e boring cell-like forms a r e considered to
represent unicellular prokaryotic blue-green algae or
bacteria. Such algae probably function as a n a e r o b i c
h e t e r o t r o p h s and can form chlorophyll in t h e d a r k if
a suitable organic carbon source is available.
FUNGI
Fungal borings are difficult to distinguish from algal
borings, t h e r e being n o simple criteria for their
separation and a distinct overlap in sizes of borings.

Zeff & Perkins (1979) described five distinct types of
fungal borings in d e e p water sediments (2101450 m)
from t h e B a h a m a s area. S o m e are identical to
shallow water forms but t h r e e are considered char
acteristic of d e e p aphotic e n v i r o n m e n t s . A s p o i n t e d
o u t by Zeff & Perkins t h e study of such borings has
sedimentological significance in the recognition of
aphotic zone sediments, source areas of turbidites,
and d e e p water c a r b o n a t e s .
MICRITE ENVELOPES
Boring by endolithic algae and fungi o n loose car
b o n a t e grains is responsible for the formation of
micrite envelopes (Bathurst, 1966,1975). A b a n d o n
ed borings are filled by fine aragonite or high-Mg
calcite. Margolis & R e x (1971) illustrated t h e rela
tion b e t w e e n endolithic algae and micrite envelope
formation in B a h a m i a n oolites. Endolithic algae can
extensively colonize new substrates in w e e k s or
m o n t h s ( L u k a s , 1979 for s u m m a r y ) and thus repeat
ed abrasion and grain-size reduciton must occur d u e
to t h e activities of sediment ingesting organisms in
c a r b o n a t e environments (e.g. fish, holothurians).
T h e r e is a great deal of scope for use of t h e S E M in
examination of c a r b o n a t e grain surface textures d u e
to endolithic borers and their destruction by organic
and physical processes. T h e production of micrite
envelopes by boring is frequently t a k e n t o b e a
shallow water p h e n o m e n o m , but t h e d e e p water
fungal borings described by Zeff & Perkins (1979)
http://jurassic.ru/
ii
iimiiii
273
W e s t e r n Australia Institute of Technology whose

technical assistance is acknowledged. AH o t h e r
figures were p h o t o g r a p h e d at A b e r d e e n University's
D e p a r t m e n t of Geology a n d Mineralogy using equip
ment purchased through generous research grants
to t h e author from Occidental P e t r o l e u m . Iain S.C.
Spark and R o b e r t A . D o w n i e assisted greatly with
machine operation. Barry Fulton assisted with draft
ing and the text was patiently word-processed and
edited by Sue Castle.
CHEMICAL ANALYSIS OF SEDIMENTARY ROCKS
Chemical analysis of sedimentary rocks
GENETIC
COMPONENTS
IAN FAIRCHILD, GRAHAM HENDRY,

MARTIN QUEST and MAURICE TUCKER
unmodified terrigeneous detritus

leached/chemically modified
chemical/biological
\ t e r r i g e n o u s detritus
precipitates in the
3
sedimentary environment
VJJ7"~~ authigenic phases
Examples of sediment and

sedimentary rock types
fT\
unmodified plus chemically

modified detritus
. g . river sand
e
fT\
9.1
INTRODUCTION
This c h a p t e r is written for sedimentologists n e w to

chemical analysis, or those seeking new ways of
tackling rock-based chemical
sedimentological
p r o b l e m s . Since several t e x t b o o k s would b e n e e d e d
to cover t h e details of t h e geochemical theory and
analytical techniques reviewed h e r e , t h e a p p r o a c h
has necessarily b e e n selective. W h e r e good descrip
tions of experimental details exist in readily-avail
able literature, then
is m a d e to those papers
and b o o k s . This
is not simply a recipelist,
b u t it
t o instil a philosophy
a p p r o a c h to
analysis, its objectives and t h e fundamental chemical
controls o n sediment composition. S o m e major
aspects of t h e chemistry, of s e d i m e n t a r y rocks a r e
o m i t t e d , notably organic geochemistry and t h e
analysis of radioactive isotopes, but these a r e n o t
usually studied by sedimentologists. A l t h o u g h t h e
solution-based techniques of chemical analysis d e
scribed in this c h a p t e r a r e c o m m o n to t h e analysis of
p o r e water a n d depositional w a t e r s , t h e specialized
tools and p r o c e d u r e s of t h e a q u e o u s analyst and t h e
experimentalists in crystal growth a n d dissolution
a r e n o t t o b e found h e r e (but see Whitfield, 1975;
Riley, 1975; M a n h e i m , 1976; P a m p l i n , 1980).
aims
reference
chapter
of
T h e r e a r e two key features of t h e chemistry of t h e

s e d i m e n t a r y cycle. First, t h e r e is t h e r o l e of w a t e r as
a solvent, a m e d i u m of t r a n s p o r t and source for
precipitating minerals. Second, t h e r m o d y n a m i c
equilibrium is often n o t obtained at t h e low t e m
p e r a t u r e s which concern u s . G e o l o g y g r a d u a t e s
often
a p o o r background in l o w - t e m p e r a t u r e
a q u e o u s geochemistry; h e n c e t h e n e e d for Section
9.2 which outlines t h e most relevant concepts and
discusses their usefulness in practice. T h o s e em
barking o n t h e acquisition and interpretation of
chemical d a t a a r e strongly advised to p u r s u e a pro
p e r understanding of these concepts by further study.
Sometimes interpretation m a y a p p e a r t o b e a m a t t e r
of p a t t e r n recognition by comparison of d a t a sets,
b u t this is only on a superficial level. G o o d geo
chemical research involves a clear understanding of
have
275
t h e limitations of t h e d a t a d u e t o t h e sampling
p r o c e d u r e and analytical techniques used and an
ability t o assess t h e feasibility of b o t h chemical a n d
geological processes.
as above, plus authiqenic
[y
..
VJ
rj
phases
e.g. sandstone
chemical/biological
e.g, shell gravel,
precipitates
primary evaporite
diagenetically transformed e.g. secondary
rock
dolostone
requires
Identification of component chemistry Interpretation
assumptions about
is straightforward
components' chemistry
TABLE OF ANALYTICAL
STRATEGIES
9.2 O B J E C T I V E S
Whole-rock
analysis
1
Objective
W h e r e a s basic chemical d a t a o n s e d i m e n t a r y rocks

have b e e n available for s o m e time ( C l a r k e , 1924)
a n d correct conclusions d r a w n a b o u t t h e origin of
m a n y c o m m o n sedimentary minerals, it is in t h e
fields of e c o n o m i c mineralization, a n d igneous a n d
m e t a m o r p h i c geology, that t h e results of chemical
analysis w e r e first fully exploited. T h e diverse ori
gins of sedimentary rocks in general, and of t h e
c o m p o n e n t s of individual specimens in particular,
m a k e t h e formulation of objectives, prior t o plan
ning t h e n a t u r e a n d extent of a p r o g r a m m e of
chemical analysis, of t h e utmost i m p o r t a n c e . Since
this is n o t normally explicitly treated in s e d i m e n t a r y
texts, an a t t e m p t at a general scheme of objectives is
given below.
Successful a p p r o a c h e s t o problem-solving by
chemical analysis of sedimentary rocks a r e illu
strated in Fig. 9 . 1 . T h e potential presence of four
is illustrated: unmodified terri
genous detritus, leached or otherwise chemicallyw e a t h e r e d terrigenous detritus, chemical o r biologi
cal precipitates in t h e sedimentary e n v i r o n m e n t , and
authigenic (diagenetic) phases. A rock with, all four
c o m p o n e n t s is shown as a circle, otherwise t h e
a p p r o p r i a t e quarter-circles a r e depicted.
In t h e tabular part of Fig. 9.1 t h e analysed portion
of each rock is r e p r e s e n t e d by a blacked-in region.
C o l u m n s 1 and 2 refer respectively to whole-rock
analysis ( e . g . by X-ray fluorescence s p e c t r o m e t r y )
and selective analysis (e.g. by m i c r o p r o b e or by
analysis of t h e solute after dissolution of a particular
mineral). It is assumed in these cases that the mine
rals p r e s e n t can b e obviously assigned t o o n e of t h e
four petrographic c o m p o n e n t s of the rock and that
t h e e l e m e n t s of interest a r e obviously sited in par-
genetic components
Selective
analysis
2
Whole-rock or
selective analysis
3
*>,
Source-rock
chemistry
Chemical parameters
and transformational
processes of
sedimentary
environment
c
VI /
Chemical/physical/
biological parameters
of depositional
environment
Chemistry of diagenetic
fluids and/or nature
of diagenetic
processes
Elemental
cycling
:F
f *7
to
1\
Fig. 9.1. Objectives of chemical analysis. See text for explanation.
ticular minerals. Q u i t e often, however, o n e has to

assume that this is probably, or largely s o , in o r d e r
to interpret the results. This is t h e situation r e p r e
sented by column 3. F o r e x a m p l e One might have t o
assume that diagenetic alteration of feldspars did
not occur in order to use the feldspar composition as
a guide-to p r o v e n a n c e . In column 3 the dashed lines
enclose c o m p o n e n t s of t h e rock whose contribution
to the analysed chemistry is h o p e d to be either
obvious o r else insignificant. T h e s e c o m p o n e n t s are

n o t blacked-in on t h e diagram since they may or
may n o t have been analysed. T h e column 3 a p
p r o a c h is of course a slippery slope, but as long as
o n e c o m p o n e n t d o m i n a t e s t h e aspects of t h e chemis
try that are being studied t h e n it is a perfectly
reasonable strategy.
T h e five rows in Fig. 9.1 d e n o t e five different
kinds of p r o b l e m s that may be tackled. Strategy A
274
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IIHIIH11
W H 1 W
276
I.J. FAIRCHILD ef al.
(row A ) assumes that terrigenous sediments have

inherited some aspects of source-rock chemistry un
altered (A1/A2) or still preserved as a clear signal
( A 3 ) in o r d e r t o m a k e deductions about the source
a r e a from which t h e sediments were derived.
Strategy B involves looking at the alteration pro
cesses in the sedimentary e n v i r o n m e n t such as char
acterizing t h e intensity of chemical weathering by
whole-rock analysis, o r t h e salinity of t h e deposi
tional e n v i r o n m e n t from analysis of trace elements
in clay minerals. B l and B2 are not shown because it
is extremely unlikely t h a t s o m e inheritance of ori
ginal chemistry, formation of new precipitates (such
as neoformed clays) in t h e depositional environ
m e n t s , or diagenetic alteration can be categorically
ruled out in such studies.
T h e r e is a wide variety of precipitates which could
be used to characterize p a r a m e t e r s of t h e deposi
tional environment (strategy C ) . E x a m p l e s include
t h e analysis of m i n o r elements or oxygen isotopes in
calcareous fossils t o estimate the chemical composi
tion and palaeotemperatures of ancient oceans; char
acterization of unusual sea water compositions near
spreading centres by study of metalliferous sedi
m e n t s ; elucidation of environmental setting o r stage
of evaporation of brines responsible for evaporite
deposits.
Strategy D involves t h e analysis of diagenetically
transformed rocks or t h e diagenetic c o m p o n e n t s of
sediments to ascertain p a r a m e t e r s such as t h e degree
of secondary alteration, or its timing, or the chemis
try of t h e diagenetic fluids, or t h e evolution of
porosity.
T h e understanding of the cycling of t h e elements
now and at various times in the E a r t h ' s history, is
t h e objective of strategy E . R e c e n t successful devel
o p m e n t s have concerned Sr analyses in calcareous
fossils as a monitor of Sr content of sea water,
strontium isotope studies, which can be used t o
assess changing patterns of tectonism and sea-level,
a n d carbon and sulphur isotope studies which have
major implications about changing depositional en
vironments with time. Bulk-rock analyses ( E l ) can
b e used ( G a r r e l s & M a c K e n z i e , 1971) even if the
origin of the rocks is not k n o w n . H o w e v e r , gener
ating geochemical d a t a in ignorance of t h e rock
petrology is not generally a good idea!
D a t a derived from strategies E 2 and E 3 (and
sometimes ( E l ) can also be used for strategies A
and C and vice-versa. Strategies in column 2 give
information vital to mineralogists. Whole-rock
analyses a r e essential for many industrial uses of
sedimentary materials b u t , in many cases, selective

analysis or sedimentologieal expertise wquld be of
great benefit in optimizing extraction o r t r e a t m e n t
procedures or predicting t h e extent of resources.
G o o d geochemical d a t a , with accompanying infor
mation on field relationships and p e t r o g r a p h y , often
d o prove multifarious in their application.
T h e purpose of this section has been to stimulate
thought about the aims of the research (although
Fig. 9.1 is necessarily generalized a n d i n c o m p l e t e ) .
Before asking how to get the d a t a , b e sure you
k n o w why you want t h e m !
277
Column in Periodic Table

IV
9.3 C H E M I C A L P R I N C I P L E S
Since only a skeletal t r e a t m e n t is possible h e r e ,
particularly of t h e m o r e standard physical chemistry,
t h e r e a d e r is referred to the following texts for
further enlightenment: Krauskopf (1979) or B r o w n low (1979) for general geochemical background and
m o r e specific d a t a on sedimentary geochemistry;
Raiswell et al. (1980) and O p e n University (1981)
for an introduction to surface geochemical pro
cesses; G a r r e l s & Christ (1965) for an extensive
introduction to t h e practical application of t h e r m o
dynamic relations in a q u e o u s systems; B e r n e r (1980)
for a most r e a d a b l e introduction t o chemical p r o
cesses occurring in early diagenesis together with a
m o r e advanced mathematical t r e a t m e n t ; B e r n e r
(1971) for a wider but m o r e concise overview of
chemical sedimentology (excluding most sedimen
tary petrological aspects). T h e chemistry of natural
waters are well reviewed by Holland (1978), D r e v e r
(1982), and the somewhat less r e a d a b l e advanced
text of S t u m m & M o r g a n (1981), while t h e p a s t s t a t e
of t h e oceans and a t m o s p h e r e is t h e subject of a
masterly book by Holland (1984). T h e practical pre
diction of mineral stability in a given solution can now
be u n d e r t a k e n most easily and precisely by using
interactive c o m p u t e r p r o g r a m s such as phreeqe
(pH-REdox-EQuilibrium-Equations) which was devel
oped at t h e U n i t e d States Geological Survey and is
freely available (Parkhurst, T h o r s t e n s o n & Plumm e r , 1980; Fleming & P l u m m e r , 1983; P l u m m e r &
Parkhurst, 1985).
A basic understanding of t h e behaviour of ele
ments can b e achieved by considering their ionic
potential (Fig. 9.2). This is t h e charge (z) of t h e
a p p r o p r i a t e positive ion of t h e element divided by
its radius (r). W h e r e zlr is less than 3 , t h e r e is
Soluble complex
anions
i
3
4
Ionic charge
Fig. 9.2. Ionic potential of elements (modified from Blatt et al., 1980).
relatively little affinity of the element for oxygen in
water molecules: the e l e m e n t forms simple cations
in solution surrounded by loosely-bound water mole
cules (water of h y d r a t i o n ) . With zlr between 3 and
12, the affinity for oxygen is greater and hydroxides
of t h e element readily form. W h e n zlr is greater
than 12, t h e affinity for oxygen is so great that
oxyanions result. B o t h t h e electropositive e l e m e n t s ,
forming hydrated cations, and the electronegative
elements forming anions, t e n d to remain in solution
at relatively high concentrations, whereas inter
m e d i a t e elements tend to be readily removed from
solution as hydroxides or m o r e usually by adsorp
tion on to solids (Li, 1981). W h e r e a s t h e elements
with very high or very low ionic potential tend to
occur in sediments as relatively soluble salts and
intermediate elements as unaltered or chemicallymodified detritus, all also occur as reactive metastable phases and b o u n d o n the surface of solids.
T h e behaviour of each element is therefore highly
variable, d e p e n d i n g on precisely which minerals and
dissolved species a r e p r e s e n t .
sample, results are expressed as a percentage of t h e

total sample weight (wt % ) for major elements or
parts p e r million ( p p m ) for m i n o r c o m p o n e n t s . Ex
pression in t e r m s of the equivalent oxide is normal
for silicate rocks. Conversion of an analysis from a
weight basis (e.g. wt % ) to a molecular basis (e.g.
mole % ) involves division of t h e analysis of each
species by its formula weight and normalizing (re
calculating t h e total to 1 0 0 % ) . Mineral analyses may
t h e n b e expressed in t e r m s of an equivalent formula,
e.g. Ki 5 ( S i A l / ) ( A l . F e . F e o . M g . ) O
( O H ) , a glauconite. F o r clay minerals this will
normally involve an assumption about oxygen and
hydroxyl stoichiometry since these c o m p o n e n t s are
often calculated by difference, being difficult to
analyse.
Analysis is usually in t e r m s of parts per thousand
of the solution ( % o or g k g ) or, for trace com
p o n e n t s , p p m (mg k g ) , or even parts per billion
(ppb, ug k g ) . A t standard t e m p e r a t u r e s and pres
sures g k g is equivalent to g l of dilute solutions.
T h e molarity ( M ) of a solution is the concentration
of a chemical in moles F" (i.e. g 1 divided by the
formula weight of t h e species c o n c e r n e d ) . F o r
theoretical calculations t h e molality (m) is used: it is
t h e concentration in moles per kilogram of solvent
(water). Unlike molarity, molality is i n d e p e n d e n t of
3 +
7:i
Chemical analysis generally yields results in terms of

weight concentrations of chemical species. In a rock
http://jurassic.ru/
- 1
- 1
- 1
- 1
- 1
9.3.1 Concentrations and activities
2 +
_ 1
2 0
278
CHEMICAL ANALYSIS OF SEDIMENTARY ROCKS 279
I.J. FAIRCHILD e t a l .
t e m p e r a t u r e and pressure, b u t at low t e m p e r a t u r e s

t h e two scales a r e virtually identical except in con
centrated brines. T h e conversion equation is:
w h e r e W = weight of t h e solution, w = weight of t h e

dissolved chemicals a n d = solution density. F o r
gases, t h e partial pressure (P) is used t o express
concentration.
Except for reactions in dilute solutions t h e para
m e t e r of concentration is~ i n a d e q u a t e t o account for
t h e b e h a v i o u r of chemical species because of inter
action between chemicals in solution. Oppositelycharged ions will attract o n e a n o t h e r which reduces
their ability t o participate in chemical reations. A l s o ,
a certain proportion will combine t o form ion-pairs
(both n e u t r a l , e.g. M g S O , a n d charged, e.g.
C a H C 0 ~ ) a n d ion-complexes dissolved in t h e solu
tion. T h e activity of a species i ( a ) is t h e effective
a m o u n t of / which is available t o t a k e p a r t in a
reaction,
0
a, = Y,m,
(2)
- 1
w h e r e m, h a s units of moles l a n d y,- is t h e activity

coefficient with units chosen t o b e 1 m o l e so that
activity is dimensionless.
A n essential concept involved with activity is that
of s t a n d a r d states. T h e standard state of a substance
is w h e n it has an activity of 1 at 25C a n d o n e
a t m o s p h e r e pressure. F o r a solid, liquid or ideal gas,
a = 1 w h e n it is p u r e a n d at this t e m p e r a t u r e a n d
pressure. F o r dissolved species t h e s t a n d a r d state
that h a s b e e n chosen assumes that , = y, =
= 1.
It is impossible t o m a k e such a solution since it
requires t h e ions t o b e h a v e ideally ( i . e . n o t t o
interact with o n e a n o t h e r ) y e t b e p r e s e n t a t t h e very
high concentration of 1 mole
T h e convenience
of this definition is t h a t in dilute solutions a is
numerically equal t o m, a n d hence concentrations
can b e used in calculations.
In dilute solutions, values of y,- allowing for ion
interactions ( b u t n o t ion-complex formation) a r e
readily calculated by t h e D e b y e - H u c k e l e q u a t i o n
(e.g. B e r n e r , 1980, p p . 1518) which quantifies t h e
deceasing y, with increasing charge of ions a n d in
creasing concentration of t h e solution. This concen
tration is expressed as t h e ionic strength (I):
- 1
7 = |Sm,(z,)
(3)
w h e r e i refers t o each ionic species in solution a n d
is t h e charge of t h e ion. In m o r e concentrated solu

tions, ion complexes must b e allowed for as well (to
give 'total' activity coefficients), b u t this is difficult
since these d e p e n d n o t only on / b u t also o n t h e
relative a b u n d a n c e of particular ions as t h e different
ion complexes vary greatly in stability. T h e elucida
tion of total ion activity coefficients in s e a water h a s
b e e n an obvious target for research ( G a r r e l s &
T h o m p s o n , 1962) a n d refinements continue to b e
m a d e , albeit with disagreement in s o m e i m p o r t a n t
details (Millero & Schreiber, 1982; P l u m m e r &
Sundquist, 1982; Nesbitt, 1984). M o r e concentrated
brines have p r o v e d rather intractable although it has
long been clear that activity coefficients rise t o
greater t h a n o n e (thus activities a r e numerically
greater than concentrations a good reason for n o t
assigning units of concentration t o activity as is d o n e
in s o m e introductory texts). A generalized explana
tion for this p h e n o m e n o n is that at high ionic
strengths cations lose their attached water molecules
and so a r e m o r e free t o t a k e part in chemical
reactions t h a n in t h e hypothetical standard state
condition (where t h e activity coefficient is o n e , b u t
cations a r e assumed to b e h y d r a t e d ) . Recently, fol
lowing theoretical advances by t h e chemist Pitzer,
considerable progress has been m a d e in u n d e r s t a n d
ing t h e chemistry of brines a n d h e n c e predicting t h e
precipitation of minerals from t h e m ( e . g . H a r v i e ,
Moller & W e a r e , 1984).
a p
= K
(5)
(11)
A G = -RT
In K
(6)
w h e r e A G " is t h e change in (Gibbs) free energy

accompanying t h e reaction ( t h e superscript denotes
that this is t h e standard free energy change corre
sponding t o t h e chemicals being in their standard
s t a t e ) , R is t h e gas constant a n d T is t h e absolute
t e m p e r a t u r e . A t 25C:
A G = AG = -1.364 log
10
(V)
w h e r e A G is expressed in kcal mole . F o r reaction

(4):
/ D
+ AG7
- AG
/ B
- AG
/ C
(8)
w h r e AGf is t h e free energy involved in forming D

from its elements in t h e standard state (standard
free energy of formation) a n d likewise for E , B a n d
C.
Values of A G / a r e tabulated in many texts,
although constantly subject t o revision. Values for K
can thus b e readily calculated for any reaction of
interest. A negative value of A G indicates that a
system starting with proportions of chemicals as
written in equation (4) will go t o t h e right t o reach
equilibrium. Conversely a positive value indicates a
leftward m o v e m e n t t o reach equilibrium.
In t h e special case of t h e dissolution-precipitation
reaction of a salt B C :
B,,C,.bB
(4)
i.e. b molecules pf species B react with c molecules

of C tQ ferm dof D and e of E (and vice-versa). T h e
Law of M a s s A c t i o n shows that:
= K
w h e r e K is t h e (activity) solubility
product.
In a given solution, t h e Ionic Activity
Product
( I A P ) can b e d e t e r m i n e d :
+ cC~
(9)
K =
(*B )(fi -)
C
(10)
Since t h e activity of a p u r e solid is o n e by definition,

then:
http://jurassic.ru/
IAP =
(a )(a -)
B
(12)
and c o m p a r e d with t h e solubility product by t h e

saturation index ( Q ) :
IAP
Q
or t h e %
(13)
saturation:
% saturation =
IAP
t
(14)
r~.
N B s o m e a u t h o r s define Q as l o g ( I A P / K ) . If
Q = 1, t h e solution is at equilibrium (the salt tend
ing neither t o dissolve n o r t o precipitate) a n d is
said t o b e just ( 1 0 0 % ) saturated. With Q > 1, then
t h e solution is s u p e r s a t u r a t e d a n d o u g h t t o b e p r e
cipitating t h e salt, conversely an u n d e r s a t u r a t e d
solution ( Q < 1) should b e dissolving t h e salt.
T h e correct formulation of a n equilibrium con
stant for solid solutions h a s b e e n u n d e r d e b a t e with
particular reference t o magnesian calcites and clay
minerals. T h r e e different approaches have been
p r o p o s e d . Using magnesian calcites as an example,
fractional e x p o n e n t s can b e used ( e . g . T h o r s t e n s o n
& P l u m m e r , 1977):
10
K,( M g ^ C a ' - ' C O j )
Chemical equilibrium refers t o a state of dynamic

balance between a b u n d a n c e s of chemical species. It
is rapidly attained for reactions involving only dis
solved species, b u t at low t e m p e r a t u r e s solids t e n d
t o remain o u t of equilibrium with t h e solution with
which they a r e in contact (except w h e r e this contact
is extremely p r o l o n g e d , e.g. Nesbitt, 1985). Never
theless, t h e concept of equilibrium is extremely
useful in that reactions will m o v e in t h e direction of
equilibrium. T h e r e f o r e t h e sense of change in a
system (e.g. dissolution or precipitation of a mineral)
can b e predicted.
T h e stoichiometry of a n equilibrium reaction can
b e written in a general way as:
bB + cC = dD + eE,
K = (a )(a -)
where a
= activity of D raised t o t h e p o w e r d e t c . ,
and K is t h e thermodynamic
equilibrium constant for
t h e reaction. K varies only with t e m p e r a t u r e a n d
pressure. Sometimes t h e relationship is formulated
in t e r m s of concentrations (K becomes K ), but K
will vary with solution composition a s well as t e m
p e r a t u r e and pressure.
E q u a t i o n (5) expresses t h e relative stability of t h e
chemical species: t h e degree t o which reaction (4)
goes t o t h e right or left. A second way of expressing
relative stabilities of chemicals is by t h e c h a n g e in
free energy accompanying t h e reaction. T h e free
energy of a substance is t h e energy it possesses t o d o
work. F o r any reaction:
AG" = A G
9.3.2 Equilibrium
a t
( a
2
C
(15)
y - * ( a
2
M
y ( a
2
C
- ) -
Alternatively it could b e assumed that equilibrium is

always reached for t h e C a C 0 c o m p o n e n t (e.g.
Wollast, G a r r e l s & M a c K e n z i e , 1980):
3
^ ( C a , M g ) C 0
( C a
) (
C O ,
^ s ( C a C O , ) -
Finally, activities of substituting ions could be a d d e d

( L i p p m a n n , 1977; G r e s e n s , 1981):
^ ( C a , M g ) C 0
M g
>co
2
3
--
(17)
D e s p i t e t h e theoretical objections t o t h e use of

fractional e x p o n e n t s ( L i p p m a n , 1977; G r e s e n s ,
1981), t h e formulation of equation (15) was t h e only
o n e t o fit t h e d a t a in t h e careful experiments of
Walter & Morse (1982). T a r d y & Fritz (1981) also
continued this approach in calculating clay mineral
solubilities.
F o r solid solutions a distinction (well reviewed by
M a c K e n z i e et al., 1983) must b e m a d e b e t w e e n true
t h e r m o d y n a m i c equilibrium of solid and contacting
280.
I.J. FAIRCHILD et al:
solution, and stoichiometric saturation (Thorstenson

& P l u m m e r , 1977). In the former case, crystals
equilibrating with a large reservoir of fluid have
their composition d e t e r m i n e d by the fluid, which
usually necessitates recrystallization. Since this is
often very slow in n a t u r e , stoichiometric saturation
describes the c o m m o n case of dissolution ceasing in
the absence of recrystallization (i.e. congruent dis
solution). T h e converse is incongruent dissolution:
the release of chemicals to solution in different p r o
portions to the solid composition. This occurs not
only with solid solutions but can also lead to the
transformation of o n e mineral t o a n o t h e r as in the
chemical weathering of silicates.
T h e dissociation of w a t e r is an equilibrium of
special importance:
H O ^ H
+ OH .
(18)
A t 25C and in dilute solutions:

1
- 1 .
(H XOH-)
+
OH
O H
pH = -log (fl ).
1 0
(20)
Therefore at 25C the p H of a neutral solution is 7,

lower values corresponding to acid solutions, higher
p H s to alkaline ones.
T h e relevance t o carbonates arises because the
c a r b o n a t e ion is m o r e a b u n d a n t at higher p H . It is
derived by the double dissociation of the weak acid
H C 0 (carbonic acid).
2
H C0
2
? H
HCO-T ^
+ HCCV
+
+ C0
2
3
(21)
".
Ac = m ~
+ 2m o "-
HCO
(23)
T h e figure two arises in equation (23) since C 0 ~

can react with two Ff ions. Knowing A , a ~
can
be calculated from a knowledge of K from equation
(22). T h e alkaline (high p H ) n a t u r e of a particular
solution should n o t b e confused with alkalinity: the
two p a r a m e t e r s are i n d e p e n d e n t variables. High
values of c a r b o n a t e alkalinity m e a n t h a t the solution
can receive much acid, input without markedly
changing its p H , since the excess H ions are re
moved by reacting with the weak bases. A n y solu
tion which resists" a change in p H by reacting with
H or O H ~ ions is said to be buffered and t h e
reactions are t e r m e d buffering reactions.
A l t h o u g h t h e relationship of p H t o mineral stabi
lity is normally clear, complications arise w h e n two
minerals a r e in competition. T a k e for example sedi
m e n t a r y calcium p h o s p h a t e and calcium c a r b o n a t e .
A l t h o u g h both are less soluble in alkaline solutions,
calcium c a r b o n a t e shows this m o r e intensely, and so
tends to win a Competition for calcium ions in alka
line solutions. In early marine diagenesis, calcium
p h o s p h a t e would thus b e expected t o form in neutral
to weakly acid pore waters ( N a t h a n & Sass, 1981).
In chemical reactions involving exchange of elec
trons t h e r e is a third measure of equilibrium (other
t h a n A G and K) which is the oxidation-reduction
potential ( E h ) . E a c h such reaction can b e b r o k e n
down into two half-reactions involving a n Oxidized
chemical reacting with electrons to form a r e d u c e d
chemical:
3
co
In m o r e concentrated solutions, a , is less than

o n e and is equivalent to the water v a p o u r pressure
a b o v e the solution at equilibrium relative to the
vapour pressure above pure water. T h e varying re
lative a b u n d a n c e s of H and O H ~ are extremely
i m p o r t a n t in n a t u r e for life processes and stability of
minerals, notably carbonates. W h e n a
a ~
( = 1 0 ~ at 25C), the solution is neutral. W h e n a
> A o h " , the solution is acid whereas w h e n a ~ >
a
the solution is alkaline. F o r convenience, a
logarithmic derivative ( p H ) of H is generally used
to express this property:
H
clear that the a m o u n t s of c a r b o n a t e ion are often a

limiting factor in c a r b o n a t e mineral formation.
T h e a m o u n t s of C 0 ~ cannot be m e a s u r e d
directly in solution but, by carrying o u t an acid
titration, the a m o u n t of chemicals (bases) that will
react with acids is easily c o m p u t e d . This is the
alkalinity of the solution. In most cases H C 0 ~ and
C 0 ~ are by far the d o m i n a n t weak bases present
so that the alkalinity approximates t o the carbonate
alkalinity (A ) w h e r e :
(22)
B ^ B"
n+
ne + C
B + C
+ ne
(half-reaction)
(24)
^ C
(half-reaction)
(25)
(overall reaction)
(26)
^ C + B "
Low a m o u n t s of H ( h i g h p H ) drive these equilib

ria to the right. K for (21) is 1 0 " so that the p H
has to rise to greater than 6.4 for a ~
to be
g r e a t e r than a , c o - K for (22) is 1 0 " , therefore
even in an alkaline solution like sea water (around
p H 8 ) , fl co = ( 1 0 - ) ( f l c o , ) " c o , " - T h u s it is
6 4
HCO
1 0 3
2-
w h e r e n is an integer and e stands for an electron.

Since each half reaction involves electron transfer it
is associated with a putative E M F (voltage), the
magnitude of which d e p e n d s on the free energy for
each half-reaction. U n d e r standard conditions (25C,
1 a t m o s p h e r e p r e s s u r e , unit activities of chemicals):
susceptibilities to dissolution, as discussed for quartz

by
H u r s t (1981). Crystal defects affect the incor
A G " = nFE
(27)
poration of some trace elements into minerals (see
w h e r e F is Faraday's n u m b e r (the charge of a mole
Section 9.3.5) and probably limit the size of clay
of electrons) and E" is the standard E M F for the
mineral crystals.
reaction. U n d e r n o n - s t a n d a r d conditions t h e voltage
Diagrams showing the stability of different
produced is the oxidation-reduction potential ( E h ) :
mineral phases and a q u e o u s species are commonly
used in chemical sedimentology and have a powerful
2-^
7?7"
"(oxidized chemical species)
En = IL + ~ In 7;
visual impact as an apparently precise guide to the
HP
" ( r e d u c e d chemical species)
conditions u n d e r which minerals have formed.
Garrels & Christ (1965) gave an excellent guide to
= E>
(28) their construction arid use. Figure 9.3 has been
deliberately badly presented to illustrate possible
"red
pitfalls in t h e use of stability diagrams. T h e lines
In practice, voltage can only be m e a s u r e d for
themselves have been constructed from equations in
pairs of half-reactions so that o n e half-reaction n e e d s
t e r m s of E h and/or p H resulting from substituting
to be arbitrarily defined as zero to enable values for
each half-reaction to be given. Reaction (29) is thus
free energy data into equation (8), together with
defined with E = 0 V .
(28), or (6) and (5). Values for A G are known with
greater or lesser precision and are constantly being
H ^ 2 H + 2 e .
(29)
revised (Helgeson etal., 1978; R o b i e , Hemingway &
This is equivalent to saying that the standard free
Fisher, 1978; W e a s t , 1983; W o o d s & G a r r e l s , 1987).
energy of formation of H is z e r o .
A n o t h e r source of imprecision is the m e a s u r e m e n t of
F o r any solution in n a t u r e t h e r e will b e a mixture
E h in natural waters which, as previously mentioned,
of various oxidizing and reducing agents which will
is difficult and not always meaningful (Hostettler,
react and tend towards equilibrium. By comparing
1984). T h e stability fields refer to regions w h e r e one
this solution with a standard electrode of k n o w n E h ,
phase is m o r e stable than a n o t h e r . W h e n a field is
the E h of the test solution can be d e t e r m i n e d . A
labelled for a dissolved p h a s e , it is saying ' n o solid
positive value for E h indicates that it is relatively
phase is stable h e r e ' . H o w e v e r , dissolved phases
oxidizing ('electron-grabbing'), likewise reducing
have variable activities, so that field boundaries with
for negative E h . E h is o n e of the less satisfactory
chemical concepts to apply to real solutions because
it is difficult to m e a s u r e , and in sedimentary systems
many redox reactions are irreversible and bacteriallymediated (Hostettler, 1984).
A complicating factor when considering equili
brium in n a t u r e is the physical condition of solid
materials. F o r e x a m p l e , very small particles have
excess free energy (surface free energy) arising from
unsatisfied bonds on their surface. This leads to the
p h e n o m e n o n of Ostwald's ripening (reviewed by
B a r o n n e t , 1982) w h e r e b y larger crystals may grow
in solution whilst very small ones dissolve. This is a
useful p h e n o m e n o n in experimental studies of cry
stal growth carried out at low growth rates (Lorens,
1981). Excessive surface area is also a property of
organic tests and complex crystal aggregates, and
Williams, Parks & C r e r a r (1985) illustrated how the
resulting increased solubility plays an i m p o r t a n t role
in silica diagenesis.
pH
Crystals that have been stressed or which contain
a larger proportion of dislocations t h a n o t h e r cry
Fig. 9.3. Thermodynamic stability relations of iron
stals of the same phase will dissolve preferentially.
species at 25C and 1 atmosphere total pressure. See text
E v e n different surfaces of single crystals differ in
for omissions!
+ ^4
http://jurassic.ru/
282
solids d e p e n d o n t h e choice of activity. In Fig. 9 . 3 ,

the boundary between the F e
and F e ( O H ) fields
is actually d r a w n in assuming a
= 1 ( T at t h e
b o u n d a r y , lower values for t h e activity would cor
r e s p o n d to moving t h e line parallel t o itself t o t h e
u p p e r right. T h e caption to Fig. 9.3 should state:
activities of F e
and F e
at field b o u n d a r i e s are
1CT . Choosing an a p p r o p r i a t e value for t h e limiting
activity of a dissolved phase requires s o m e geologi
cal j u d g e m e n t . F o r e x a m p l e , Curtis & Spears (1968)
decided that since a
< 1 0 " in sea w a t e r t h e n
A
= 1 0 ~ would be an a p p r o p r i a t e b o u n d a r y
condition for t h e F e
field in a diagram expressing
relationships in sea w a t e r , w h e r e a s in p o r e waters
a
= 1 0 ~ would be apposite since activities of
ferrous iron range u p t o this value t h e r e . A n o t h e r
p r o b l e m with Fig. 9.3 is that in o r d e r t o construct a
field b o u n d a r y for F e C 0 you n e e d t o k n o w t h e
total activity of t h e dissolved carboxy species
( H C G - , HCO3" a n d C O 3 " ) ; t h e caption for Fig.
9.3 should h a v e stated t h a t their total activity was
1 0 in this case. S o m e fields are missing in Fig. 9.3:
for e x a m p l e F e ( O H ) has a stability field b e t w e e n
F e and F e ( O H ) (e.g. G a r r e l s & Christ, 1965, fig.
714). T h u s o n e must b e certain that relevant equi
libria have not b e e n forgotten. T h e diagram also
implicitly assumes that activities of H S are negli
gible, otherwise pyrite would have a stability field
of substantial size. Silicates such as glauconite and
berthierine must also n o t be forgotten ( M a y n a r d ,
1986). Finally, it would be m o r e informative t o plot
E h against activity of H C 0 ~ o r HS~ because t h e s e
species vary m u c h m o r e than p H in practice (Curtis
& S p e a r s , 1968). A series of diagrams is n e e d e d t o
show t h e c o m p l e t e picture of t h e system.
2 +
2+
Fe
2 +
3 +
2+
Fe
increase solubility, but S reduces it because of t h e

reduction in a , o which destabilizes h y d r a t e d silica
in solution ( F o u r n i e r , 1983). T h e s e concepts can be
applied to p e r m e a b l e rocks in which convective flow
is occurring ( W o o d , 1986) and indicate that quartz
and c a r b o n a t e s can be transferred from o n e p a r t of
t h e rock mass t o a n o t h e r , often moving in opposite
directions and hence giving rise to replacive relation
ships.
F e
2 +
2+
Fe
- 2
2 +
3 +
G o o d e x a m p l e s of t h e utility of stability diagrams

in diagenetic studies a r e given by Davies et al.
(1979), H u t c h e o n (1981) and Curtis (1983).
W h e n considering systems far r e m o v e d from their
standard s t a t e , for e x a m p l e during burial diagenesis,
the effects of t e m p e r a t u r e , pressure and salinity
variations must be carefully considered. T a k e for
e x a m p l e t h e relative stability of c a r b o n a t e minerals
and silica. A p p a r e n t alternating silica-carbonate r e
placements h a v e b e e n explained simply in t e r m s of
p H variations ( W a l k e r , 1962), b u t t h e solubility of
silica shows little variation with p H until p H s of 9 o r
m o r e . Actually during steady burial, t e m p e r a t u r e
(T) pressure ( F ) , p H a n d salinity ( 5 ) will p r o b a b l y
all rise. F o r calcite t h e effects of T a n d p H a r e t o
d e c r e a s e solubility, w h e r e a s P (with constant P c o )
a n d 5 increase solubility. F o r q u a r t z , T, P and p H all
2
R = K(Q
- 1)"
(31)
w h e r e n > 1. For e x a m p l e , Mg-adsorption strongly

inhibits calcite growth, and a d s o r b e d humic and
fulvic acids and P 0 ~ inhibit t h e growth of aragonite
( B e r n e r et al., 1978). T h e i m p o r t a n c e of Mg as an
inhibitor lies in its a b u n d a n c e in natural waters. Ex
perimental studies ( M e y e r , 1984) on calcite growth
have shown t h a t n u m e r o u s inorganic and organic
species a r e m o r e effective inhibitors, with F e being
so by four o r d e r s of m a g n i t u d e . A d s o r p t i o n p h e n o
m e n a are also i m p o r t a n t in controlling crystal habit
(Boistelle, 1982).
3
2 +
9.3.3 Departures f r o m e q u i l i b r i u m
2 +
tion would probably b e c o m e ( B e r n e r , 1980, p . 105):
W h e r e sediments are out of equilibrium with their

contained fluids, this relates either to kinetic con
trols ( t h e slowness of chemical reactions o r m o v e
m e n t of chemicals) o r t o biological interference.
T h e most i m p o r t a n t kinetic control concerns t h e
b e h a v i o u r of crystal surfaces involved in dissolution
or g r o w t h , especially t h e latter. T h e presence of
a b u n d a n t early diagenetic minerals such as glau
conite or c a r b o n a t e fluorapatite only in slowlydeposited
m a r i n e calcareous sediments illustrates
t h e kinetic control on crystal growth. Conversely t h e
fact t h a t slowly-deposited detrital s e d i m e n t s exist at
all attests t o t h e i n c o m p l e t e dissolution of mineral
grains in u n d e r s a t u r a t e d waters.
Crystal growth in a clean, s u p e r s a t u r a t e d solution
is initially limited by a stage of nucleation,
since
nuclei b e l o w a certain critical size h a v e excess free
energy and are thus unstable. H o w e v e r , in t h e sedi
m e n t a r y e n v i r o n m e n t t h e r e will normally already b e
nuclei in t h e system which can b e o v e r g r o w n , even if
nucleus a n d overgrowth a r e different minerals (epi
taxial o v e r g r o w t h ) . W h e r e supersaturation is low [Q
(equation 13) close to 1] t h e critical nucleus size is
larger and the availability of nuclei could then be
rate-limiting, but such conditions also lead to slow
crystal growth anyway.
If surface reactions r a t h e r than m o v e m e n t of
chemicals limit t h e growth rate of crystals, t h e n t h e
m o d e of growth would b e expected to be by addition
to growth spirals a r o u n d screw dislocations occur
ring on t h e crystal surface, r a t h e r t h a n by t h e birth
and spreading of two-dimensional layers ( S u n a g a w a ,
1982). If Q is close to 1, t h e n :
R = K(Q
- l)
(30)
w h e r e R is t h e growth r a t e , frequently expressed in

t e r m s of a radial increase in crystal size, and K is a
constant. Often t h e real growth-limiting factor is
adsorption (see Section 9.2.4) of foreign ions on t h e
surface of t h e crystal. In this case t h e a b o v e e q u a -
lines ( B e r n e r , 1978a, 1980). T h e existence of

specifically di/jfaHow-controlled growth in sediments
and sedimentary rocks is d e m o n s t r a t e d by Liesegang ring p h e n o m e n a , such as iron oxide b a n d s
formed during w e a t h e r i n g , or concentric mineral
ogical banding in concretions ( D e Celles & Gutschick,
1983). This arises where inter-diffusion of two species
has led to precipitation of material at episodicallyshifting sites.
T h e m a g n i t u d e of a diffusional flux is given by
Fick's first law of diffusion. It relates the mass of
chemical c o m p o n e n t i transported p e r unit a r e a per
unit time (J) to its concentration gradient (dCldx)
across distance x:
For dissolution, we h a v e :
R = K(l
- Q ) " (cf. 31).
(32)
w h e r e R refers to t h e dissolution r a t e . Very slow

dissolution rates caused by ion-adsorption a r e com
m o n : for e x a m p l e t h e dissolution of calcite and
aragonite shells in u n d e r s a t u r a t e d sea water w h e r e n
= 45 (Keir, 1980), the reaction being limited by
adsorption of P 0
. H o w e v e r , inhibition of dis
solution of calcium c a r b o n a t e by organic materials is
generally related to physical covering, r a t h e r t h a n
adsorption p h e n o m e n a ( M o r s e , 1983).
B e r n e r (1978a, 1980) has shown that w h e r e dis
solution is controlled by surface reactions, the cry
stals have angular outlines with crystallographicallycontrolled etch pits: such surface-reaction control is
n o r m a l in soils and nearly all surface waters.
U n d e r s o m e circumstances the rate of crystal
growth or dissolution is controlled by t h e rate of
m o v e m e n t of chemicals in solution r a t h e r than by
reactions taking place on t h e crystal surface. This
only seems feasible within p o r e waters and w h e r e
precipitation or dissolution is unusually rapid (im
plying great supersaturation or u n d e r s a t u r a t i o n ) .
M o v e m e n t of chemicals in general may be by advection ( m o v e m e n t u n d e r forces, e.g. g r o u n d w a t e r flow
or t h e relative m o v e m e n t of grains and p o r e fluid
d u e to c o m p a c t i o n ) , dispersal by burrowing organ
isms or t u r b u l e n c e , or by molecular diffusion.
The
existence of a p p r o p r i a t e concentration gradients in
solutions away from sites of, for e x a m p l e , m a n g a n
ese oxide or iron sulphide precipitation in R e c e n t
sediments d e m o n s t r a t e s t h e i m p o r t a n c e of the trans
port-control m e c h a n i s m . G r o w i n g crystals in t h e s e
circumstances may b e restricted t o a very fine crystal
size, or show dendritic or spherulitic morphologies
( R o d r i g u e z - C l e m e n t e , 1982; Sunagawa, 1982); dis
solving crystals will exhibit s m o o t h l y - r o u n d e d out
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3 _
w h e r e D,- is t h e diffusion coefficient, specific to t h e

chemical c o m p o n e n t i (typically a r o u n d 1 0 ~ c m
s
for salts in w a t e r at 25C). In a s e d i m e n t ,
diffusion is slowed because of the effective increase
in p a t h length caused by the obstructions represen
ted by t h e sediment grains. T h u s t h e effective diffu
sion coefficient is smaller by a factor relating to t h e
sediment porosity (e.g. <j> w h e r e (j) is t h e fractional
porosity, L e r m a n , 1979). T h e r e is also s o m e varia
tion of D, with salinity of a solution (e.g. L e r m a n ,
1979, p . 81). S o m e t i m e s corrections are necessary to
allow for ion-pairing effects (Mangelsdorf & Sayles,
1982). T h e b e h a v i o u r of the diffusion gradient with
time is covered by Fick's second law (e.g. B e r n e r ,
1980, p p . 3233); diffusion acts to reduce t h e con
centration gradients b u t , if it is allowed to d o so, t h e
flux necessarily diminishes.
E n h a n c e d m o v e m e n t of chemicals, because of t h e
p r e s e n c e of o p e n b u r r o w s in a sediment, can be
modelled in a similar way, using a biodiffusion
coefficient o r , if c o m p l e t e bioturbation occurs, then
a ' b o x modelling' a p p r o a c h can b e used ( B e r n e r ,
1980, p p . 4 2 - 5 3 ) .
A n advective flux can be calculated as the product
of the concentration of t h e c o m p o n e n t ( C ) and t h e
velocity of flow (U),
5
_ 1
J = CU.
(34)
It is often useful to c o m p a r e the effectiveness of

diffusion with that of advective flow. If we imagine a
situation w h e r e a diffusive flux in o n e direction is
balanced by an advective flux in t h e o t h e r direction,
then:
-Di^f-
+ CU = 0.
(35)
284
I.J. FAIRCHILD et al.
If t h e concentration difference (dC) is of the same

o r d e r as t h e concentration (C) then:
Udx = Dj.
(36)
F o r a given diffusion coefficient, this equation shows

over what distance an advective flow of velocity U is
equally effective as diffusion. For example, for a typi
cal value of D, in a sediment at 25C of 100 c m y r
t h e n an advective flux would need t o exceed
1000 cm y r in o r d e r to balance diffusion across a 1
m m gradient, or only 1 cm y r over a distance of
1 m ( B e r n e r , 1980, p p . 1 1 7 - 1 1 8 ) . Unless t h e con
centration gradient is fixed by reactions occurring at
either end (such as rapid dissolution, precipitation
o r dispersal at an interface), diffusion will diminish
with time by Fick's second law. A way of conceiving
this ( L e r m a n , 1979, p p . 5860), again assuming
dC~C, is by use of the criterion that advection will
transport material in a time t over a distance ( L ) of
L = Ut whereas diffusion will transport material
o v e r a distance ( L ) = y/(D,-t). If t h e concentration
gradient is n o t fixed t h e n L = L is a criterion for
t h e time (r = D , / ( { / ) ) after which advection starts
t o b e c o m e m o r e effective t h a n diffusional t r a n s p o r t
(e.g. 14 days with ( / = ' l m y r and D = 1 0 " c m
s ) . In this way t h e most effective t r a n s p o r t process
m a y b e d e t e r m i n e d for a given situation.
2
_ 1
- 1
_ 1
_ 1
vertical section of deep-sea ooze with a 20C t e m

p e r a t u r e increase from t o p to b o t t o m . It is m o r e
difficult to assess diffusion coefficients in extremely
small p o r e s , b u t t h e effectiveness of diffusion along
intergranular b o u n d a r i e s during diagenesis is well
known from the pressure dissolution and mineral
ogical replacement p h e n o m e n a a b u n d a n t in sedi
m e n t a r y rocks:
A p a r t from kinetic effects, organisms have a p r o
found influence on the sedimentary e n v i r o n m e n t ,
causing widespread d e p a r t u r e s from equilibrium.
F o r e x a m p l e , t h e secretion of calcareous shells in
u n d e r s a t u r e d waters is well k n o w n . Siliceous organ
isms can reduce silica concentrations in solution to
vanishingly small a m o u n t s . T h e decomposition of
organic m a t t e r during early diagenesis is immensely
s p e e d e d - u p by the action of bacteria and this in turn
leads t o greatly accelerated mineral reactions, par
ticularly pyrite formation, and reactions involving
carbonates. Such activities, not forgetting t h e d e p o
sition of i m m e n s e quantities of reduced c a r b o n ,
h a v e obviously h a d a major effect o n t h e sedimen
tary cycling of e l e m e n t s . Vital effects on c a r b o n a t e
trace element chemistry and isotopic ratios a r e m e n
tioned in later sections.
_ 1
It is often stated (e.g. Pingitore, 1982) t h a t diffu

sion becomes m o r e i m p o r t a n t at higher t e m p e r a
t u r e s . Certainly D , increases steadily with increasing
t e m p e r a t u r e : d a t a (Weast, 1983) on equivalent con
ductance of ions (directly proportional t o diffusion
coefficients, Li & G r e g o r y , 1974) yield a rough
relationship to 150C:
A = Z> (l +
(37)
oi
w h e r e D is t h e diffusion coefficient for t h e ion at

0C and T is t e m p e r a t u r e in degrees Celsius. T h e
relationship with t e m p e r a t u r e is also definable in
t e r m s of fluid viscosity (T)) and absolute t e m p e r a t u r e
( 7 / ) such that:
oj
^r = constant
(38)
(Li & G r e g o r y , 1974; L e r m a n , 1979, p p . 8 6 - 8 9 ) .

R a t e s of diffusion will only increase with t e m p e r a
ture as long as t h e increase in D outweighs t h e
restriction d u e to decreasing porosity. For e x a m p l e ,
B a k e r , Gieskes & Elderfield (1982) indicated that
this is marginally so for S r
and C a
in a 500 m
t
2 +
2 +
co-ions which have respectively t h e opposite and t h e

same charge as the fixed layer. In a m o r e concen
trated solution t h e G o u y layer contracts (Fig. 9.4b).
T h e ions in t h e G o u y layer are described as adsorb
ed, b u t a r e readily exchanged for other ions if the
composition of the bulk solution changes. In Fig.
9.4(c), t h e fixed layer now comprises t h e solid sur
face together with strongly- ('specifically-') adsorbed
species (in this case positively-charged ions of two
different kinds). T h e overall charge of t h e fixed
layer in this instance has b e e n reversed so that the
G o u y layer now has an excess of negative ions. T h e
change from Fig. 9.4(b) to Fig. 9.4(c) could be
simply a function of t i m e , allowing two kinds of
process to occur. First, weakly-adsorbed species in
t h e G o u y layer m a y d e v e l o p a stronger b o n d with
t h e solid (e.g. by losing water of hydration). Second,
t h e solid may progressively scavenge any r a r e species
in the solution for which it has a great affinity,
particularly if solid and solution are in differential
motion.
A t h e r m o d y n a m i c a p p r o a c h (Parks, 1975) is help
ful in clarifying why adsorption occurs. A particular
species will adsorb if this will entail a loss of free
energy ( A G
is negative). A G
is the sum of a
series of possible processes. In many cases electro
static attaction of ions to a charged surface (with
associated A G i ) is t h e most important process,
b u t in o t h e r cases AG iec is smaller in m a g n i t u d e
than A G
(the formation of a specific chemical
b o n d of t h e a d s o r b e n t with t h e solid) o r A G
a d s
a d s
9.3.4 A d s o r p t i o n
e c
(changes in t h e size o r s h a p e of t h e hydration envel

o p e a r o u n d ions) or A G
(displacement of ions
from t h e solid by reaction with t h e a d s o r b e n t ) , or
s o m e combination of these.
r x h
W h e n A G i is d o m i n a n t , t h e adsorption process
is relatively non-specific, that is, it d e p e n d s m o r e on
t h e charge of t h e ions being adsorbed t h a n o n any of
their o t h e r properties. H e r e t h e G o u y layer concept
applies, for which t h e r e a r e various detailed m a t h e
matical models ( P a r k s , 1975; van O l p h e n , 1977).
W h e n AGeiec < s u b o r d i n a t e , t h e adsorption is
specific to the adsorbent and the solid concerned.
F o r e x a m p l e , s o m e large organic molecules a r e ad
sorbed because t h e process of V a n d e r Waal's bond
ing contributes m u c h loss of free energy. B o r o n is
k n o w n to adsorb strongly and specifically to illite,
presumably by chemical b o n d i n g of B ( O H ) ~ groups
to sites o n t h e mineral surface (Couch & G r i m ,
1968). I n fact any solute species which is capable of
forming particularly strong complexes in solution, or
insoluble c o m p o u n d s with s o m e c o m p o n e n t of t h e
solid, will potentially show strong adsorption. It
should b e emphasized t h a t all gradations exist b e
tween specific and non-specific adsorption.
T h e sign a n d m a g n i t u d e of t h e surface charge on
most solids d e p e n d s o n the solution chemistry. For
e x a m p l e , considering hydroxides, they will either
b e c o m e positively charge by reactions such as:
e
e c
A d s o r p t i o n is t h e process of accumulation of chemi

cal species at an interface: in our context at t h e
surface of a solid. It is a complex p h e n o m e n o n
( P a r k s , 1975; van O l p h e n , 1977; Yariv & Cross,
1979) which is sometimes r e n d e r e d confusing by
oversimplification. Parks (1975) provided an excel
lent review of t h e chemical concepts involved'with
detailed examples, and Cody (1971) discussed its
application t o p a l a e o e n v i r o n m e n t a l studies of shales.
T h e relevance of adsorption may be judged from t h e
statement of Li (1981) that it is t h e most i m p o r t a n t
removal mechanism for m o s t e l e m e n t s into sedi
m e n t s from sea water. T h e i m p o r t a n c e for crystal
growth and dissolution kinetics was m e n t i o n e d in
Section 9.3.3 a n d its relevance in coprecipitation
studies is dealt with in Section 9.3.5.
Figure 9.4(a) illustrates a solid whose surface has
developed a surface charge. T h e charge is neutral
ized by an electrical field in t h e solution featuring an
excess of (in this case) positive ions close to the
solid. T h e whole system m a k e s u p an electrical
double layer consisting of the fixed layer on t h e solid
a n d t h e diffuse o r Gouy layer of counter-ions and
MOH + H
MOH
+
2
c h e m
h y d
Solid
Gouy
layer
Gouy layer
o r negatively charged:
normal solution
fixed
layer
Gouy
layer
normal
solution
m m
0
0 O
0 0 0
o 0 0:
0
(a)
Gouy layer in dilute solution
(b)
Gouy layer in concentrated

solution
Gouy layer around

specific adsorbents in
concentrated solution
Fig. 9.4. Schematic illustration of adsorption processes. For simplicity, the surface charge of the solid is shown as if
owing to lattice substitutions (as in clays) rather than because of adsorption of potential-determining ions (see text).
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285
286

+
MOH MO" + H .
+
Excess of H ions, as in acid solutions, p r o m o t e s a

positive charge which decreases with increasing p H
until a point of zero charge (pzc), specific for each
substance, is r e a c h e d , followed by t h e d e v e l o p m e n t
of a negative charge at higher p H . Oxides b e h a v e in
a similar way, since their surface oxygens b e c o m e
hydroxyl groups adjacent t o a q u e o u s solutions. T h u s
for oxides and hydroxides, H determines t h e charge
and hence the electric potential of t h e surface: it is
t h e potential-determining
ion ( P D I ) . P D I s for salts
such as C a C 0 a r e its constituent ions, positive
charge being expected w h e n A
minus flco, in
t h e solution exceeds a critical level, b u t p H is rele
vant t o o since a o ~
d e p e n d s on it.
A s indicated on Fig. 9.4(c), the surface charge o n
a solid m a y b e nullified or reversed by specific
adsorbents. O n e i m p o r t a n t example of this is t h e
observation t h a t a variety of natural solids, regard
less of their charge in artificial sea w a t e r , show a
negative charge in natural sea water, probably d u e
to adsorption of organic molecules (Neihof & L o e b ,
1972).
Clay minerals a r e negatively-charged, b u t this
arises o u t of substitution of lower- for higher-valent
cations in t h e lattice a n d so is an intrinsic feature.
T h e charge is balanced by t h e adsorption of cations
b e t w e e n lattice layers a n d o n t h e flat basal surfaces
of clay particles. A n o t h e r effect present on t h e edge
of clay grains, and over t h e whole surface of some
clays (e.g. kaolinite), which display little altervalent
substitution, is a positive or negative charge devel
oped by reaction of H with S i O H or A l O H sites.
A s with o t h e r fine-grained materials, clays b e h a v e as
colloids in a q u e o u s solutions. A colloidal system has
particles of colloidal dimensions (between 1 0 ~ and
1 0 ~ m in at least o n e direction) dispersed in a
continuous phase of different composition (van
O l p h e n , 1977). Colloidal physical properties ( e . g .
settling behaviour) a r e d o m i n a t e d by surface elec
trostatic p h e n o m e n a .
T h e relationship b e t w e e n concentration of adsor
bent in solution a n d a m o u n t of adsorption can t a k e
different forms, b u t normally t h e main feature is
that adsorption reaches a m a x i m u m level correspon
ding t o a saturation of adsorption sites. Assuming
that t h e adsorbent molecules form a monolayer and
d o n o t interact with each o t h e r , then at equilibrium
t h e rate of adsorption (proportional to concentra
tion of adsorbent in bulk solution and n u m b e r of
available sites) will equal t h e rate of desorption
+
2+
2-
Ca
(proportional to t h e n u m b e r of sites occupied by the

a d s o r b e n t ) . This logic (e.g. Yariv & Cross, 1979, p p .
1 2 0 - 1 2 3 ) leads to a form of equation k n o w n as t h e
Langmuir
isotherm:
abC,,
Qd 1 + (aC )
K =
(flA
sol
w h e r e C is t h e concentration of adsorbed species

(per unit mass of solid), C is the concentration in
solution and a a n d b a r e constants, b being a mea
sure of t h e total n u m b e r of adsorption sites. T h e
assumptions involved a r e probably n o t valid in con
centrated solution w h e r e , for e x a m p l e , n e w adsorp
tion sites on clays may b e c o m e available ( C o d y ,
1971).
W h e r e adsorption sites a r e n o t saturated, an e m
pirical equation ( t h e Freundlich isotherm) often fits:
a d
s o l
Cad = K(C f"
(40)
sol
w h e r e n > 1 and K is a constant. A t low concentra

tions, a simplified form is often applicable:
Q d = KC .
(41)
sol
A d s o r b e d ions a r e m o r e o r less readily exchange

able. T h e total a m o u n t of exchangeable cations
(cation-exchange
capacity, C E C ) is m e a s u r e d in
t e r m s of milliequivalents (millimoles times charge)
of exchangeable cations p e r 100 g of dry substance,
and is highly d e p e n d e n t on its specific surface area.
Typical values r a n g e from 100 to 300 for organic
m a t t e r a n d zeolites, through 7080 for smectites,
1040 for illites and 3 - 1 5 for kaolinite ( L e r m a n ,
1979).
Ion-exchange t a k e s place readily when A G i

forms a large p r o p o r t i o n of A G . W i t h Gouy-layer
type adsorption all ions of t h e s a m e charge 'are
competing for t h e adsorption sites. If A G i w e r e
overridingly i m p o r t a n t then t h e relative concentra
tions (strictly activities) of t h e a d s o r b e d ions would
b e equal t o their relative concentrations (or activi
ties) in the bulk solution. In practice this is n o t so
a n d , using clays as a n e x a m p l e , adsorption affinity
decreases with decreasing hydrated ion radius, for
example from b o t t o m to t o p of columns I a n d II of
t h e periodic t a b l e . This can b e expressed in t e r m s of
an exchange reaction (between equally-charged ions,
as t h e simplest e x a m p l e ) :
e
e c
a d s
+ B
a d
^ B
+ A
ec
(42)
for which t h e equilibrium constant (K n o t equal to

o n e ) is:
(B )(Aad)
+
(43)
)(Bad)'
Since activity coefficients for adsorbed ions a r e

not readily estimated a n d often a p p e a r to b e close to
unity, mole fractions (x) a r e frequently used instead
of activities of a d s o r b e d species. If t h e system is
noticeably non-ideal (for e x a m p l e w h e n large varia
tions in compositions a r e being considered) t h e n
mole fractions may still b e used with a different
(empirical) form of e q u a t i o n :
X
Xft
= K'
(44)
B
w h e r e K' a n d p a r e constants for t h e pair of adsor

bents considered ( L e r m a n , 1979, p . 346).
Altervalent ion-exchange has b e e n found to b e an
important mechanism in experiments o n freshwater
clays exposed to sea water (Sayles & Mangelsdorf,
1977, 1979). E q u a t i o n s (42) a n d (43) can b e modi
fied to model this process (e.g. B e r n e r , 1980, p . 70)
and carry the i m p o r t a n t implication that the less
highly-charged ion will b e preferentially adsorbed in
solutions of progressively higher ionic strength b e
cause its activity coefficient in solution will fall m o r e
slowly. E x p e r i m e n t s on exposure of clays to sea
water also show t h a t C E C diminishes with time as
K becomes specifically sorbed on to degraded illites
(Russell, 1970). Ion-exchange reactions a n d specific
adsorption processes a r e also very i m p o r t a n t during
weathering a n d burial diagenesis.
Li (1981) considered adsorption as a mechanism
for controlling t h e ratios of concentrations of ele
m e n t s in oceanic pelagic sediments and in sea water
by plotting these ratios against equilibrium constants
for reactions involved in adsorption on O H sites on
solids. (These equilibrium constants correlate fairly
well with ionic potential.) Most elements fall within
a b a n d on such plots, consistent with adsorption
being a major control on their behaviour.
T h e complexing of trace metals to organic material
can b e extremely i m p o r t a n t as a m e a n s of intro
ducing elements to sediments even if later released
by organic decay a n d fixed in o t h e r ways. Unfortu
nately t h e mechanisms of complexation (e.g. by
specific adsorption, or alternatively by chelation, i.e.
b o n d e d to O , N or S a n d lying centrally in ring
structures) is not often k n o w n (Jackson, Jonasson &
Skippen, 1978), especially in sea water: Chelation is
well-known for example for V and Ni in petroleum
and oil shales (e.g. Riley & Saxby, 1982). A n u m b e r
+
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287
of elements a r e found t o correlate with organic

carbon in black shales (e.g. M o , Ni, C u , V , C o , U ,
Z n , H g and A s in t h e study of Leventhal & Hosterm a n , 1982) which is empirical evidence for t h e
importance of the association of organic molecules
and metals in sea water.
Nyffeler, Li & Santschi (1984) performed experi
m e n t s on the rates of adsorption processes to test
w h e t h e r particles r e m a i n e d long enough in sea water
to reach a state of equilibrium adsorption. W h e r e
particles only reside for a few days in the water
column it seems that equilibration may n o t b e com
plete a n d will certainly n o t b e so for certain elements
( B e , M n , C o and F e ) . H o w e v e r , for several of these
e l e m e n t s , removal of adsorption on to manganese
nodules will b e continuously available. In principle,
however, sedimentation rate and aspects of sedi
m e n t a r y e n v i r o n m e n t ( e . g . water d e p t h ) , even with
constant water chemistry, a r e liable to affect t h e
minor e l e m e n t (adsorbed species) composition of
sediments. Variations in salinity or organic carbon
flux to sediments will b e major controls on trace
element content.
W h e n considering use of adsorbed trace elements
to characterize t h e chemistry of depositional en
v i r o n m e n t s , specific adsorbents a r e required that
will n o t readily b e diagenetically-altered. Possible
problems a r e inheritance of trace elements in detri
tal p h a s e s , control of u p t a k e by several chemical
p a r a m e t e r s (e.g. p H , t e m p e r a t u r e and salinity), and
variations in mineralogical abundances and surface
properties even of individual minerals (Cody, 1971).
Success only seems likely w h e n making comparative
studies, within a geological unit, using selective
analyses, on a specific mineral species (see Section
9.8).
9.3.5 Lattice i n c o r p o r a t i o n of trace

elements
T h e object of studying trace elements in minerals is
normally to constrain the chemistry of the precipita
ting solution, or to assess t h e degree of chemical
exchange during diagenetic alterations (Brand &
Veizer, 1980; Veizer, 1983). Usually interpretations
are only possible when coprecipitation of t h e trace
element by substitution for a host (carrier) ion of
similar radius a n d electronegativity h a s occurred
( M c l n t y r e , 1963). Ions occupying interstitial lattice
positions m a y also b e a m e n a b l e to analysis and
interpretation (Ishikawa & Ichikuni, 1984), although
288
t h e a b u n d a n c e of these sites is related to t h e occur

rence of lattice defects (Busenberg & P l u m m e r ,
1985). In assuming t h a t lattice substitution has oc
c u r r e d , care should b e taken that inclusions of o t h e r
phases are absent ( A n g u s , R a y n o r & R o b s o n , 1979).
Bulk analysis will be useless if a trace e l e m e n t occurs
in significant a m o u n t s within solid or liquid inclu
sions in t h e host mineral. E v e n if lattice substitution
has occurred, sometimes t h e r e may be two possible
lattice sites which can be occupied: it is often as
sumed that an element is present in o n e site only: for
example in d o l o m i t e , F e and M n are t h o u g h t to
occupy dominantly M g sites r a t h e r than C a sites
because of their small ionic radius (like M g ) .
L u m s d e n & Lloyd (1984) showed that variations in
M n site-partitioning d o occur in different d o l o m i t e
samples: in t h e future such variations could b e use
ful in interpreting mineral genesis.
If a very small volume of solid is considered, in
which a trace element (Tr) is substituting for a
carrier element ( C r ) , precipitating from a large re
servoir of solution then at equilibrium:
2 +
2 +
2 +
2 +
2 +
(45)
K
m_
Cr
w h e r e S refers to t h e solid p h a s e and L t h e liquid

p h a s e . K is t h e partition coefficient or distribution
coefficient which is constant provided that: (1) tem
p e r a t u r e and pressure and constant, (2) t h e solutions
a r e dilute a n d (3) t h e ratio m lm ,
is low in t h e
solution and the solid.
So far we have considered a small volume of solid
with high surface area t o volume ratio such that all
parts of t h e crystal are effectively in contact with t h e
fluid and the solution reservoir is sufficiently large
that w / m in the solution has r e m a i n e d constant.
In the m o r e general case, crystals grow from solu
tions whose compositions change either because the
system is o p e n , or because the crystallizing solids in
a closed system a r e removing chemicals in a differ
ent ratio from their initial ratio in the solution. In
either case, two e n d - m e m b e r situations are possible.
First, the crystals could b e c o m e zoned during
growth so that e q u a t i o n (45) only applies t o t h e
o u t e r m o s t layer of the crystals. Theoretically this
'Doerner-Hoskins
behaviour applies w h e n diffusion
in t h e solid is slow and precipitation is either slow,
with constant degree of supersaturation, or else rapid
but with no recrystallization occurring ( M c l n t y r e ,
1963). T h e constant K is often symbolized X. in this
case and is known as the logarithmic distribution
TT
T r
C r
coefficient because it also appears in e q u a t i o n (46)

which relates initial (i) and final (f) fluid composi
tions of closed systems:
In
Xln
("&)'
(47), as has been d o n e for example by G a r r e l s &

Christ (1965, p p . 8 9 - 9 1 ) and Eriksson, M c C a r t h y &
Truswell (1975) t h e n K would be readily calculable.
Unfortunately, although t h e second term usually
approximates to o n e , t h e solid solution will normally
be far from ideal: K must be determined experi
mentally. Sverjensky (1984), however, has shown
that it is possible to calculate relative values of K for
two trace ions of similar ionic radius, at least in
carbonates.
(46)
{mcrY
T h e D o e r n e r - H o s k i n s behaviour can of course occur

in o p e n systems t o o , but e q u a t i o n (46) is n o t relevant
in that case.
Second, the crystals could remain h o m o g e n e o u s
in composition as t h e solution composition changes.
This could be d u e to r e p e a t e d crystallization of fine
grained crystals, but is also t h e expected result of
slow relief of supersaturation of a solution (Mclntyre,
1963). In this 'Berthelot-Nernsf behaviour, K is
referred to as D ( M c l n t y r e , 1963).
E x p e r i m e n t a l results (e.g. K a t z , 1973; Kushnir,
1980) indicate that in seidmentary systems o n e would
normally expect D o e r n e r - H o s k i n s behaviour, cer
tainly w h e n e v e r e u h e d r a l crystals w e r e being formed
from t h e outset. A l t h o u g h this is generally agreed,
authors (e.g. Veizer, 1983) commonly use D w h e n
referring t o partition coefficients. This usage arises
because of the convergence of Berthelot-Nernst and
D o e r n e r - H o s k i n s behaviour in t h e situation initially
described (equation 45). It would seem m o r e logical,
however, to use neither D n o r X. for situations
covered by this convergent behaviour, to avoid con
fusion (Dickson, 1985). T h u s K is used h e r e .
T h e t h e r m o d y n a m i c quantities contributing to K
can be seen if we consider an exchange reaction of
t h e type:
CrM(ss) + T r
m +
^ TrM(ss) + C r
m +
m +
^ C r M (YTr )
m +
K =
(exp(-Ap/i?r)
(47)
m +
^TrM ( Y C r )
T h e role of kinetic factors in controlling minor

element chemistry is a source of disagreement.
L o r e n s (1981) d e m o n s t r a t e d a clear kinetic effect for
the coprecipitation of Sr, M n , C o and Cd with
calcite as did B u s e n b e r g & P l u m m e r (1985) for Na
and S 0 in calcite, but no kinetic effects were found
for Sr in magnesian calcite by Mucci & M o r s e (1983)
or B a in calcite by Pingitore & E a s t m a n (1984). O n e
p r o b l e m in evaluating experimental work is that
a u t h o r s often d o not give potentially important in
formation such as the d e g r e e of supersaturation ( Q ) ,
precipitation rate in t e r m s of lattice layers p e r unit
t i m e , absolute concentrations rather than just ratios
of concentrations of reactants, and-growth form of
4
ar
where K
* d K-n-M are the solubility products of
t h e e n d - m e m b e r s of the solid solution, Y T r
and
Ycr
are t h e activity coefficients in a q u e o u s solu
tion, R is the gas constant, T t h e absolute t e m p e r a
ture and A p is a m e a s u r e of the d e p a r t u r e (in t e r m s
of free energy gain) of the real solid solution from
an ideal o n e .
If o n e could ignore the last two t e r m s in equation
CM
m+
m +
t h e precipitates. In looking at sedimentary rocks o n e

should not expect any reliable information to c o m e
from spherulitic or dendritic crystals since these
have grown relatively quickly. L o r e n s ' (1981) data
can be recast in a petrographically-meaningful way:
his slowest growth rate (actually rate of recrystal
lization by Ostwald's ripening) would roughly corre
s p o n d t o t h e growth of a 1 m m rhombic crystal from
a substrate in about 3000 years. K halved at
growth rates t e n times larger t h a n this, w h e r e a s K
showed no change until still higher growth rates
were reached.
M
Sr
E x p e r i m e n t a l work on determination of K for

evaporite minerals is summarized by Holser (1979)
to which should be a d d e d new work on gypsum
(Kushnir, 1980), anhydrite (Kushnir, 1982) and halite
( H e r r m a n n , 1980; McCaffrey, Lazar & Holland,
1987). F o r c a r b o n a t e s , Veizer (1983) gave an exten
sive bibliography which can be supplemented by the
experiments of F u c h t b a u e r (1980), F u c h t b a u e r &
H a r d i e (1980), Scherer & Seitz (1980), Mucci &
M o r s e (1983), Ishikawa & Ichikuni (1984), Pingitore
& E a s t m a n (1984, 1986), T a k a n o (1985) and
O k u r a m a & K i t a n o (1986). In o r d e r t o obtain some
estimates of K for dolomite, given t h e absence of
experimental w o r k except for Sr, Veizer (1983)
utilized the suggestion of Kretz (1982), that the
partitioning of t r a c e e l e m e n t s b e t w e e n d o l o m i t e
and calcite could be estimated solely by considering
ionic radii. K r e t z ' m o d e l m a k e s n o allowance for
t e m p e r a t u r e . A l t h o u g h t e m p e r a t u r e effects were
t h o u g h t theoretically not i m p o r t a n t e n o u g h to allow
for g e o t h e r m o m e t r y of calcitedolomite mineral pairs
(Jacobsen & U s d o w s k i , 1976), this is contradicted
by the work of, e.g. Bodine, Holland & Borcsik (1965),
Katz (1973) and Powell, Condliffe & Condliffe
(1984). Therefore t h e use of Kretz' (1982) model to
calculate K, even in t h e general way suggested by
Veizer (1983), should be regarded very cautiously.
m +
w h e r e M refers t o t h e part of t h e formula unaffected

by solid solution, CrM(ss) and TrM(ss) refer t o t h e
c o m p o n e n t s of, respectively, t h e carrier element
and t h e trace element in t h e solid solution and T r
and C r
a r e t h e ions in t h e fluid p h a s e . It can be
shown ( M c l n t y r e , 1963) that:
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F r o m t h e work of, for e x a m p l e , H e r r m a n n (1980),

Kushnir (1980), L o r e n s (1981) and B u s e n b e r g &
P l u m m e r (1985), it seems that o n e can generalize in
stating that K is n e a r e r to o n e at high precipitation
rates than at low rates. U n d e r conditions close to
equilibrium, t h e rates of ion adsorption and desorption (which control K) are much quicker than crystal
growth r a t e . A t high growth rates, however
(Kushnir, 1980), a d s o r b e d ions are accidentally in
c o r p o r a t e d because they d o not desorb quickly
e n o u g h t o avoid being incorporated into the crystal
lattice: thus t h e mineral Tr/Cr ratio m o r e nearly
resembles t h e solution T r / C r ratio.
T h e influence of solution chemistry on K can be
significant, particularly w h e r e t h e t r a c e and carrier
ions show different tendencies to form complexes
(as, e.g. Br~ versus Cl~ in Mg-Cl brines, H e r r m a n n ,
1980). This effect can b e minimized if K is formu
lated using activities rather than concentrations.
Effects of varying solid composition should generally
b e significant, for e x a m p l e , t h e increase in K for
Sr " " in calcite with increasing content of Mg (Mucci
& M o r s e , 1983) and M n ( T a k a n o , 1985).
W h e n t h e 'trace' c o m p o n e n t becomes a major
element in solution o n e would not expect K to
remain constant. Studies by F u c h t b a u e r & H a r d i e
(1980), F u c h t b a u e r (1980) and Mucci & Morse
(1983) for F e a n d M g in calcite, a r e illustrative. F o r
Mg in calcite, as t h e M g / C a ratio in solution rises,
t h e partition coefficient falls because of an increasing
saturation of adsorption sites for M g , adsorption
being a necessary precursor t o lattice incorporation.
K falls by much less t h a n an order of m a g n i t u d e ,
however, because of an opposing tendency to in
crease M g adsorption because of t h e affinity of M g
ions in solution for Mg already adsorbed (Mucci &
M o r s e , 1983).
T h e incorporation of N a and K into calcite is now
known to be an example of interstitial solid solution.
2
290
T h e experimental work of Ishikawa & Ichikuni

(1984) showed that t h e levels of these elements was
i n d e p e n d e n t of t h e C a
activity of t h e solution at
fixed N a and K activities, but actually follow a
Freundlich-type isotherm ( B u s e n b e r g & P l u m m e r ,
1985). Ishikawa & Ichikuni (1984) a t t e m p t e d to
calibrate this as a palaeosalinity indicator, but
B u s e n b e r g & P l u m m e r (1985) clearly showed that
N a incorporation was related to t h e speed of crystal
growth, fast crystal growth leading t o t h e formation
of m o r e lattice defects which are selected by N a .
A b s o l u t e levels of N a a r e n o t therefore useful as
salinity indicators, although N a variation within a
sample suite of similar origin may reflect salinity
variations ( Z h a o & Fairchild, 1987). O k u r a m a &
K i t a n o (1986) d e m o n s t r a t e d that the presence of M g
in t h e solution increased t h e a m o u n t s of alkali metals
(Li, N a , K, R b ) incorporated in calcite.
Pingitore & E a s t m a n (1986) provided p e r h a p s t h e
best example of t h e complexity of real chemical
systems by considering Sr incorporation in calcite
(Fig. 9.5). T h e y showed that Sr displays complex
behaviour best reconciled with a model in which
s o m e Sr could b e incorporated in defect sites as well
as substituting for C a . H e n c e the partition coeffi
cient (K) is higher at very fast growth rates w h e n
m o r e lattice defects would b e present. A t slower
growth rates, t h e r e would be a fixed n u m b e r of
defect sites which, w h e n filled, would cause a lower
ing in K since Sr would then only be entering C a
sites. T h u s K is lowered by increasing N a or B a
concentrations in t h e fluid (these elements prefer
entially fill defect sites), o r high absolute concentra
tion of S r
(equivalent to concentrations of Sr in
t h e solid of m o r e than a few h u n d r e d p p m ) .
Organisms precipitating calcareous shells may or
may not a d h e r e t o trace element concentrations
a p p r o p r i a t e for inorganic systems. G r e a t variations,
particularly in Sr and M g , are well k n o w n (Milliman,
1974). Sometimes growth r a t e , often coupled t o
t e m p e r a t u r e changes, has an effect (Moberly, 1968;
Kolesar, 1978) but in o t h e r cases K r e m a i n s constant
and different from t h e inorganic case regardless of
growth rate ( L o r e n s & B e n d e r , 1980). A different
composition of body fluids from t h e ambient fluid
explains s o m e , but not all, of these relationships
( L o r e n s & B e n d e r , 1980). Interpretation of ancient
water chemistry from shell chemistry obviously re
quires as a prerequisite a detailed knowledge of t h e
behaviour of the group being considered from studies
of m o d e r n organisms.
bonding is w e a k e r ( C o l e m a n , 1977). Kinetic frac

tionations occur additionally when t h e r e is insuffi
cient time for equilibrium to be obtained and in
general it is t h e lightest isotope that participates in a
chemical reaction t h e most readily.
T h e isotopic fractionation between two phases A
and B is expressed as a fractionation factor ( a )
3500 \r
2 +
2 +
3000
RA
RB'
w h e r e R A and R represent t h e ratio of a b u n d a n c e

of a heavier, r a r e r isotope t o the most a b u n d a n t
isotope (for o u r p u r p o s e s D / H , C / C , 0 / 0 a n d
S / S ) . F o r equilibrium processes, a corresponds
to t h e equilibrium constant for an isotope exchange
reaction b e t w e e n t h e two substances, written so that
only o n e a t o m is exchanged (Javoy, 1977, p . 612).
In practice, analysis of absolute a b u n d a n c e s is
imprecise so that results are normally expressed as
delta (5) values in %o w h e r e
B
1 3
3 4
0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20
1 2
1 8
1 6
3 2
b(x) = 1000
Fig. 9.5. Summary of the results of Pingitore & Eastman
(1986) concerning Sr incorporation in calcite. Low values
of partition coefficient K result from high Sr or addition
of Ba or Na to the solution (see paper for quantitative
aspects). Even with Na present in solution, a high value
for K can be restored by increasing growth rate.
(R
R )
ST<J
(50)
R. s t d
where R is t h e isotopic ratio of t h e sample and R a

is t h e same ratio in a s t a n d a r d for which R is known.
C o m p a r e d to t h e s t a n d a r d , samples with positive 5
values a r e enriched in t h e heavier isotope ( h e n c e ,
'heavy') w h e r e a s samples with negative 6 values are
described as isotopically 'light'.
Since values of a are very close to unity it is often
convenient t o express equilibrium fractionation in a
different way, as
X
2 +
2 +
(4a)
<*A-B
9.3.6 Stable isotope fractionation

T h e partitioning of the isotopes of a given element
between different phases during chemical or phy
sical processes is known as fractionation. Specific
environmental or diagenetic processes are charac
terized by particular fractionations which a r e often
identifiable in t h e rock record. Hoefs (1980),
A n d e r s o n & A r t h u r (1983), K a p l a n (1983),
Longstaffe (1983) and Veizer (1983) provided read
able accounts of t h e theory and application of iso
t o p e analysis.
In principle, both equilibrium and kineticallycontrolled isotope fractionations can be recognized
which a r e explicable in t e r m s of q u a n t u m theory (in
particular the vibrational frequencies of t h e mole
cules or lattices c o n c e r n e d ) . Differences in isotopic
composition between two phases a t equilibrium is
inevitable w h e n e v e r t h e element b o n d s differ in t h e
two phases: t h e lighter e l e m e n t , which tends to form
w e a k e r b o n d s , concentrates in the p h a s e w h e r e
s t
1000(a _
A
- 1) or
10001na _
6A -
or
(51)
(52)
(53)
T h e s e expressions yield very similar n u m b e r s

(essentially identical w h e n less than 10). T h e enrich
m e n t factor ( _ ) is defined as t h e quantity in
e q u a t i o n (51) whilst each of t h e these t h r e e expres
sions has b e e n used by different authors as a d e
finition of A _
(Hoefs, 1980; Schwarcz, 1981;
A n d e r s o n & A r t h u r , 1983). T h e a r g u m e n t for con
sidering 1000 l n a _ (Schwarcz, 1981) is that this
quantity has a special significance in that it expresses
t h e t e m p e r a t u r e - d e p e n d e n c e of the reaction (at geo
logically-relevant t e m p e r a t u r e s smooth curves are
obtained w h e n 1000 l n a _ is plotted against 1/T
w h e r e T is t h e absolute t e m p e r a t u r e ) . F r i e d m a n &
O'Neil (1977) presented a compilation of fractiona
A
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291
tion factors of geochemical interest and their varia

tion with t e m p e r a t u r e .
A special t y p e of equilibrium fractionation p r o
cess involves the r e p e a t e d removal of o n e p h a s e and
was originally treated mathematically by Rayleigh
(see H o e f s , 1980, p p . 1 0 - 1 2 ) . Partial distillation
and condensation of water v a p o u r is the most fami
liar of these 'Rayleigh processes'.
T h e following discussion outlines t h e specific frac
tionation mechanisms of i m p o r t a n c e in sedimentary
geology. T a b l e 9.1 summarizes the isotopes, t h e re
ference standards used a n d t h e ranges of isotopic
variation. Nitrogen isotopes a r e not discussed h e r e
but see Kaplan (1983).
CARBON
I 3
Bicarbonate dissolved in sea water (with 5 C around

O ) provides a convenient baseline, especially since
t h e r e is only a very small fractionation on C a C 0
precipitation at earth surface temperatures, although
calcified organisms show varying taxon-related d e
p a r t u r e s from inorganic equilibrium ( D o d d &
S t a n t o n , 1981; Veizer, 1983) and t h e r e are inorganic
kinetic effects too ( T u r n e r , 1982). Equilibrium is
approximately maintained between sea water bicar
b o n a t e and atmospheric C 0 with 6 C a r o u n d
-7%.
T h e most p r o n o u n c e d fractionations are related
to t h e fixation of carbon in organic m a t t e r by p h o t o
synthesis (summarized by D e i n e s , 1980 and A n d e r
son & A r t h u r , 1983). T h e organic carbon of plants
h a s 6 C in t h e r a n g e 10 to 30%o with variations
according to taxa, a n d , in the case of m a r i n e plank
ton, t e m p e r a t u r e . Kerogen derived by m a t u r a t i o n of
m a r i n e organic m a t t e r may show slight enrichment
or depletion of C c o m p a r e d to t h e original organic
m a t t e r . R e l e a s e of organic decay products into p o r e
waters during early diagenesis causes p r o n o u n c e d
shifts in 5 C and increases in c a r b o n a t e alkalinity
leading to t h e formation of authigenic carbonates
a n d p h o s p h a t e s with distinctive isotope signatures
(e.g. Irwin, Curtis & C o l e m a n , 1977; Pisciotto &
M a h o n e y , 1981; B e n m o r e , C o l e m a n & M c A r t h u r ,
1983; Nelson & L a w r e n c e , 1984). I m p o r t a n t in this
respect are bacterial sulphate-, iron- and manganesereduction which are t h o u g h t to produce b i c a r b o n a t e
with little carbon isotope fractionation. A t slightly
greater depths occurs bacterial fermentation which
3
J 3
1 3
1 3
1 3
292
I.J. FAIRCHILD ET AL.
leads to fractionation between simultaneouslyg e n e r a t e d C O ( 5 C say + 1 0 to + 15%,) and C H

( 6 C say - 5 5 to 70%o). S o m e t i m e s carbon from
such sources mixes with heavier bicarbonate derived
from dissolution of unstable carbonates ( C o l e m a n &
Raiswell, 1981).
In freshwater conditions, 5 C of bicarbonate (and
hence that of c a r b o n a t e precipitates) typically is
negative, but shows great variation d e p e n d i n g on
t h e size of input from organic carbon, a t m o s p h e r i c
C 0 and rock c a r b o n a t e . Heavier values accompany
equilibration with a t m o s p h e r i c C 0
in shallow,
agitated waters. A n additional possible mechanism
of fractionation arises when c a r b o n a t e precipitation
in an enclosed m a r i n e or continental water b o d y is
induced by C 0 loss. T h e residual bicarbonate is
heavy (Katz, Kolodny & N i s s e n b a u m , 1977). M o r e
e x t r e m e enrichment is possible in cave c a r b o n a t e s ,
a n d in brines, w h e r e rapid C 0 loss can lead t o an
additional, kinetic fractionation ( H e n d y , 1971;
D r e y b r o d t , 1982; Stiller, Rounick & Shasha, 1985).
1 3
1 3
1 3
HYDROGEN
l s
of O in initial condensates and progressive lower

ing of t e m p e r a t u r e , although the real system is
actually much m o r e complex than this m o d e l admits
( A n d e r s o n & A r t h u r , 1983). E v a p o r a t i o n into un
saturated air leads to an additional kinetic fraction
ation of oxygen isotopes. H o w e v e r , the positive
excursions of 5 0 of e v a p o r a t e d water bodies are
limited: first, by an oppositely-directed isotope ex
change effect which causes 6 O values to peak (at
a r o u n d 6%o S M O W in humid coastal areas) w h e n
t h e liquid is 1525% of its original mass a n d , second,
by t h e possibility of addition of freshwater during
evaporation (Lloyd, 1966).
P o r e waters of buried c a r b o n a t e sequences may
u n d e r g o 5 O e n r i c h m e n t in response to recrystal
lization of sedimentary carbonates at significantly
greater t e m p e r a t u r e s than those of s e d i m e n t a t i o n .
This process awaits detailed modelling. In terrigen
ous sediments e n r i c h m e n t of O can occur d u e to
clay m e m b r a n e filtration (see next section), although
this will be o p p o s e d by any dissolution of hight e m p e r a t u r e silicate minerals.
A s for oxygen, the water molecule is t h e d o m i n a n t

reservoir of h y d r o g e n . T h e large relative difference
in mass b e t w e e n H and deuterium is the cause of the
large isotopic variations in nature. T h e main fraction
ation mechanism is that of distillation-condensation
which, as for oxygen isotopes, causes considerable
isotopic lightening in the m o r e e x t r e m e fraction
ation products. Meteoric waters show linear co
variation on a 5 D 8 0 plot (meteoric water line of
Fig. 9.6). Figure 9.6 also shows t h e d e p a r t u r e of
waters in oilfields from t h e meteoric water line per
haps because of t h e effects of adsorption on to clay
m e m b r a n e s (Coplen & H a n s h a w , 1973) during p o r e
fluid flow. Inter-layer water in clay minerals shows
ready isotope exchange, b u t good estimates of t h e
isotopic composition of t h e mineral-forming fluids
can be obtained by isotopic analysis of structural
hydrogen and oxygen.
I 8
l s
1 8
l s
l s
Isotopic equilibrium can be d e m o n s t r a t e d for the

formation of clays during weathering. Figure 9.6
illustrates the fractionation involved in forming kao
linite from meteoric water at equatorial latitudes.
K n a u t h & B e e u n a s (1986) emphasized that a
combination of decreased 8 O and 8 D in highly
e v a p o r a t e d sea water (following the hook-like tra
jectory of Fig. 9.6) and mixing with meteoric water
may lead t o isotope signatures typical of m a n y for
mation waters, hitherto interpreted as flushed free
of, c o n n a t e brines. Isotope d a t a are thus equivocal
h e r e . O n t h e o t h e r h a n d , providing a p p r o p r i a t e
extraction techniques are employed, isotopic studies
oh fluid inclusions can provide invaluable informa
tion ( B u c h b i n d e r , Magaritz & G o l d b e r g , 1984;
K n a u t h & B e e u n a s , 1986).
OXYGEN
l s
Exchange of oxygen between water and dissolved

inorganic species is rapid, a p a r t from oxygen in t h e
sulphate radical (Chiba & Sakai, 1985). H e n c e , since
water molecules are by far t h e most a b u n d a n t species
in a q u e o u s solutions, the 5 O composition of t h e
water will d e t e r m i n e t h e oxygen isotope composi
tion of t h e precipitated minerals. A n exception may
be some examples of relatively rapid dissolutionprecipitation reactions in thin film micro-environ
ments (Veizer, 1983). Mineral-water fractionation
factors are strongly t e m p e r a t u r e - d e p e n d e n t (Fried
m a n & O'Neil, 1977) which, although holding
promise of p a l a e o t e m p e r a t u r e d e t e r m i n a t i o n s , in
practice leads to ambiguity of interpretation of iso
t o p e values since 8 0 values of natural waters show
great variation. Low t e m p e r a t u r e minerals are en
riched in O c o m p a r e d to water by considerable
a m o u n t s ; a b o u t 20 %o for p h o s p h a t e , low 20s %o for
clays, high 20s %o for carbonates and 35 %o for silica.
A t 25C water is enriched in 0 by about 0.8 %
c o m p a r e d to co-existing vapour because the greater
velocity of t h e H
0 molecule allows it to evapor
ate more easily. Application of a Rayleigh distillation
model predicts the observed progressive lightening
in isotopic composition of precipitation at higher
latitudes (Fig. 9.6) because of the selective removal
l s
SULPHUR
t h e speed of sulphur u p t a k e and complexing. R e

duction of this sort, h o w e v e r , usually yields only
m o d e s t fractionation (i.e. ~5%o).
O n e of the main effects of bacterial sulphate
reduction is t h a t o c e a n water is enriched in S
relative to primordial sulphur (e.g. meteorites) since
light sulphur is extracted in sediments through the
production of iron sulphides. In practice isotope
values for iron sulphides in particular cases are
variable d e p e n d i n g , for e x a m p l e , on t h e degree of
closure of t h e system for sulphur.
O t h e r sulphur fractionation mechanisms include
a fractionation of up to 6%o during the clay mem
b r a n e filtration process discussed in the hydrogen
section (Nriagu, 1974).
3 4
ISOTOPE REFERENCE
i 8
, s
l 8
- 2 0
- 1 0
18
S 0%o
+ 1 0
+ 2 0
SMOW
1 6
ls
Fig. 9.6. Variations in 8D and 8 O . Compiled from

various sources. The kaolinite line indicates the potential
range of equilibrium compositions of kaolinite forming
from meteoric waters.
http://jurassic.ru/
STANDARDS
Isotope laboratories normally use their own working

standard for routine isotope m e a s u r e m e n t s , but
quote their results relative to internationally-accepted
standards (summarized in T a b l e 9.1), which (until
exhausted) are used for inter-laboratory calibra
tions. Standards should of course be isotopically
h o m o g e n e o u s and easy to p r e p a r e and h a n d l e , but
should also lie in t h e mid-range of natural variations
(Hoefs, 1980), unless two standards are used. Sus
ceptibility to isotopic re-equilibration can cause
p r o b l e m s as in t h e case of the international standard
Solenhofen L i m e s t o n e (NBS-20) which, because of
its fine crystal size, exchanges oxygen with atmos
pheric moisture (Friedman & O'Neil, 1977). T o
eliminate such exchange, samples and standards
must be kept dry. If wetted by a chemical t r e a t m e n t
they should be washed with acetone rather than
being left to dry ( B a r b e r a & Savin, 1987).
: All carbon isotope data are reported relative to
t h e Chicago C 0 s t a n d a r d P D B , an U p p e r Cretace
ous belemnite. Since this is exhausted, secondary or
tertiary c a r b o n a t e and graphite standards are distri
buted by t h e National B u r e a u of Standards.
T h e S M O W standard (Craig, 1961a, b) is used for
8 O results of waters and silicates. Defined as a
hypothetical water with 8 0 close to average ocean
water, it has now b e e n supplemented by Vienna
S M O W ( V - S M O W ) which has t h e same zero point.
H y d r o g e n isotopes a r e also referable to S M O W , but
V - S M O W is about -1% 8 D relative to S M O W
( A n d e r s o n & A r t h u r , 1983).
For c a r b o n a t e oxygen, P D B is more commonly
used than S M O W . T h e conversion equations be2
Sulphur isotope variation has recently been review

ed by C o l e m a n (1977), Nielsen (1979) and Kaplan
(1983). T h e mechanism responsible for much of the
natural variation is biological sulphate reduction
Which yields light H S . This kinetic effect can usual
ly be seen to follow o n e of two pathways, each
producing characteristic fractionations: (a) Dissimilatory sulphate reduction occurs in anaerobic en
vironments w h e r e organisms use sulphur in place of
oxygen during respiration which r e s u l t s in fraction
ations of up to 60%o. (b) Assimilatory reduction
occurs when cells utilize sulphur in biosynthesis: the
effectiveness of this fractionation being governed by
293
l s
1 8
1
294
I.J.
F A I R C H I L D ef
al.
CHEMICAL ANALYSIS O F S E D I M E N T A R Y R O C K S
Table 9.1. Characteristics of stable isotopes important in sedimentary systems (data from Hoefs, 1980)
Element
Isotope
abundance
International reference
materials ('standards')
Ratio
used
'H 99.9844%
D = H 0.0156%
D/H
12
13
13
16
17
l s
32
33
34
36
C 98.89%
C1.11%
0 99.763%
0 0.0375%
O 0.1995%
S
S
S
S
12
C/ C
1 8
3 4
95.02%
0.75%
4.21%
0.02%
1 6
3 2
V-SMOW
(Vienna Standard Mean
Ocean Water)
PDB
Cretaceous Belemnite
SMOW or V-SMOW
(Vienna) Standard Mean
Ocean Water. PDB often
used for carbonates
CD troilite
(troilite from the Canon
Diablo meteorite)
tween t h e two scales have recently ( C o p l e n , Kendall

& H o p p l e , 1983) b e e n revised as:
1 8
8 0 - S M O W = 1-03091 8
1 8
1 8
p d b
+ 30.91
1 8
p d b
= 0.97002 5 0 - S M O W - 29.98.
V
H u d s o n (1977b) provided a useful review of t h e

subtleties of t h e interconversions between P D B and
SMOW
scales.
Sulphur data are referred t o sulphur from troilite

of t h e C a n o n D i a b l o m e t e o r i t e , which is used b e
cause of its great isotopic homogeneity c o m p a r e d t o
terrestrial sulphur. Recently the I A E A has distri
b u t e d alternative s t a n d a r d s of native sulphur, and
B a S 0 precipitated from sea water.
4
9.4 G E O L O G I C A L S A M P L E
COLLECTION
T h e starting point for t h e chemical analysis of any
geological material is t h e collection of t h e s a m p l e . If
this collection is not carefully planned and executed
any geological conclusions d r a w n from t h e analysis
are suspect and t h e errors introduced at t h e sampling
stage cannot be subsequently rectified, no m a t t e r
how skilled t h e analyst or sophisicated t h e equip
m e n t . T h e old c o m p u t e r aphorism of 'garbage in
garbage o u t ' applies equally well to geochemistry.
F r o m the point of view of sampling strategy, t h e r e
Range of variation
in sedimentary systems
8D = -430 to +50%o
,3
5 C = - 9 0 to + 2 0 %
18
5 0 = - 4 5 to + 4 0 % SMOW
8 S = - 4 0 to + 5 0 %
34
are two types of investigation: large scale and small

scale.
(1) Large-scale investigations in which chemical
variations a r e sought over an a r e a o r volume
that is extremely large in relation to t h e sample
size, e.g. bulk-rock chemical variations in a
major depositional unit. K n o w l e d g e of sampling
statistics is particularly vital in this case.
(2) Small-scale investigations are those w h e r e
chemical variations are studied o n a scale com
p a r a b l e to t h a t of t h e - s a m p l e s , e.g. studies of
c a r b o n a t e diagenesis where c o m p l e t e fossils and
whole regions of cements a r e analysed.
T h e overall aim of a geochemical research p r o
g r a m m e should, as far as possible, be defined before
any samples are collected. This allows t h e investi
gator t o identify t h e hypotheses t o be tested, to
choose a p p r o p r i a t e statistical tests and to select the
sampling schemes most suited to t h e tests /.Regretably, p e r h a p s t h e majority of geological p r o g r a m m e s
p r o c e e d on an ad hoc basis with t h e investigators
becoming aware of predictable p r o b l e m s only at a
late stage. T h e ideal is that t h e material should b e
collected bearing in mind all t h e investigation tech
niques that may subsequently be applied. F o r exam
ple a research p r o g r a m m e into lateral variations
within o n e sedimentary unit m a y initially b e thought
to require only optical microscopy and bulk m a j o r
e l e m e n t analyses. T h e s e results may show a n e e d for
trace e l e m e n t analysis followed by mineral separ-
ation and p e r h a p s isotopic analysis. F o r e t h o u g h t

during collection not only avoids the need for ex
pensive re-collection but also ensures that all tech
niques of analysis are applied to essentially the same
samples.
T h e sample s cheme a n d sample collection should
always be t h e responsibility of the field geologist
w h o o u g h t t o have t h e greatest k n o w l e d g e of t h e
material and its variability. In practice it is rarely
possible t o follow a rigorous s c h e m e , especially as
all the questions to be answered cannot be defined at
t h e start of t h e p r o g r a m m e . H o w e v e r a clear p l a n
can help to minimize t h e m o r e gross errors.
Sampling schemes have b e e n mainly developed by
statisticians working in t h e social sciences or in
biometrics. In these subjects the collection of an
a d e q u a t e statistical sample from t h e target popula
tion is relatively simple, unlike the geological
sciences w h e r e standard schemes can only be a p
plied in t h e few cases w h e r e t h e objectives are
clearly defined, for example in t h e geochemical
exploration for minerals. F o r t h e majority of geo
logical applications t h e p r o b l e m s are t o o varied for
general guidelines. K r u m b e i n & Graybill (1965),
K o c h & Link (1970) a n d G a r r e t t (1983) discussed
the p r o b l e m s and give a n u m b e r of specific examples,
b u t it is frequently necessary for a researcher t o
r e t u r n to first principles using a text such as C o c h r a n
(1977). Because t h e topic is so i m p o r t a n t a relatively
simple example is given to illustrate the questions
that must b e answered before geological samples a r e
collected. T h e p r o b l e m is p r e s e n t e d as a simplified
version of that a t t e m p t e d by H i c k m a n & Wright
(1983). T h e a u t h o r s wished to establish criteria to
distinguish quartzite units found in U p p e r Proterozoic rrtetasediments in t h e A p p i n area of t h e West
Highlands of Scotland, and to use t h e criteria to
identify the units in o t h e r areas.
Considering only two units, the TARGET
popu
lation is h e r e m a d e u p of two populations, the two
units, and is t h e total popul at i on. T h e
SAMPLED
p o p u l a t i o n is t h a t which w e succeed in sampling and
is m a d e u p of a n u m b e r of (large ~ 1 kg) hand
specimens, of which t h e TARGET
p o p u l a t i o n con
tains an essentially infinite n u m b e r . T h e first task is
t o define t h e t h e TARGET
p o p u l a t i o n from a n u m
b e r of possible alternatives, for e x a m p l e : (1) T h e
whole of t h e t w o units as deposited. (2) T h e whole
of the two units remaining after erosion. (3) T h e
units not covered by y o u n g e r rocks. (4) T h e units
currently exposed.
'.
http://jurassic.ru/
295
Clearly (1) is n o longer possible, while (4) is t h e

most likely and simplest alternative, but (2) is also a
possibility if t h e cost of drilling is justified.
Having established the TARGET
population, t h e
SAMPLED
population must then be defined with
considerable thought being given to geological as
well as statistical considerations. For example: (1)
A r e the outcrops (mainly on t h e tops of hills) pre
sent because these parts of the units are m o r e resis
tant to erosion? (2) D o changes in m e t a m o r p h i c
g r a d e affect the chemical composition? (3) Is the
geological interest only in t h e total variance of each
unit, or is m o r e detail of vertical and lateral varia
tion r e q u i r e d ?
Finally, before a sampling design can be p r o d u c e d
t h e scale a n d s h a p e of expected variations must b e
defined.
A t this stage it may b e c o m e a p p a r e n t that answers
are not available to s o m e of the questions, and that
it is necessary to conduct an orientation survey to
establish the final form of the SAMPLED
population.
9.4.1 Search techniques

Ideally geological samples should be collected ac
cording to s o m e p a t t e r n , with the spacing of indivi
dual points related t o t h e scale and s h a p e of t h e
overall chemical variations. In t h e example given it
might be expected t h a t t h e r e would b e vertical
changes in composition on a scale of a few centi
m e t r e s while lateral variations would be over many
h u n d r e d s of m e t r e s . T h u s t h e collection p r o g r a m m e
should contain a relatively widely spaced areal design
with closely spaced points along vertical sections
through t h e two units.
T h e simplest design is a systematic collection at
equally spaced points along vertical traverses located
at t h e intersections of s q u a r e , rectangular, triangular
or hexagonal grids (Fig. 9.7a). E v e n allowing for the
fact t h a t o u t c r o p s d o n o t generally coincide with a
regular grid this is an inefficient design.
A b e t t e r plan is t o collect a t points randomly
spaced along t h e traverses which are randomly
located areally (Fig. 9.7b). T h e r a n d o m n u m b e r s
may be t a k e n from published tables or m o r e con
veniently from t h e r a n d o m n u m b e r generator found
in s o m e scientific p o c k e t calculators ( C h e e n e y , 1983,
p . 136, described a very simple technique involving
p o k e r dice). E v e n this m e t h o d can be improved by
introducing stratification w h e r e the sites for traverses
a r e r a n d o m l y located within grid areas (cells) related
296
to the scale of variation. Points along t h e traverses

are also stratified (Fig. 9.7c).
F u r t h e r refinement can be a d d e d by using a nested
hierarchical system w h e r e the main cells are sub
divided and both sub-cells and the position of tra
verse points within sub-cells occupied randomly (Fig.
9.7d). Frequently a balanced sampling scheme is
a d o p t e d w h e r e sites are sampled in duplicate, often
with each sample t h e n being analysed in duplicate.
This leads to an excessive load both in collecting and
in analysis. A n unbalanced nested hierarchical de
sign (Fig. 9.7e) is m o r e efficient and can result, in
favourable circumstances, in a saving of up to 5 0 %
in samples analysed. F o r a large-scale study this
m e t h o d is only viable w h e n a c o m p u t e r p r o g r a m is
available to plan t h e design ( G a r r e t t & G r o s s , 1980).
Having decided on t h e collection plan it only
remains to identify t h e size of geological sample
required. This must obviously be large enough to
provide material for all envisaged p r o c e d u r e s , plus a
safety margin, after contaminated and altered areas
have been r e m o v e d . T h e a p p r o p r i a t e mass which is
required to provide a given statistical e r r o r in sam
pling mineral grains or fragments can be calculated
by t h e m e t h o d s covered* in detail in Section 9.5.2.
A reasonable approximation is given by E d e l m a n
(1962) w h o showed that for a rock with an even
grain size of 1.2 m m , a grab sample of 1 kg is n e e d e d
to represent adequately the rock for chemical anal
ysis. If the grain size is doubled the required sample
weight is increased by eight.
Such large samples may be impossible to collect
logistically, and for consolidated sediments, clearly
require a sledge h a m m e r to r e m o v e from t h e out
c r o p . If a decision is t a k e n to reduce t h e sample
mass t h e level of e r r o r introduced should b e quanti
fied and allowed for in subsequent d a t a analysis.
9.5 P R E P A R A T I O N F O R C H E M I C A L
ANALYSIS
F r o m t h e time a geological sample is chosen for
collection considerable care must be t a k e n to mini
mize contamination. This can be present locally
from industrial activity, agricultural chemicals, as
part of natural processes, for example from salt
water spray, from t h e tools used to r e m o v e t h e
sample or from the materials used for storage.
T h e containers used t o transport and store t h e
material may add or r e m o v e e l e m e n t s , especially

w h e n wet unconsolidated sediment is k e p t for a long
period. T h e c h e a p e r varieties of highly coloured
domestic plastic goods a r e especially p r o n e to add
high concentrations of exotic elements. Polythene or
polypropylene jars are preferable for field use, and
ideally should be soaked overnight in 5 0 % nitric or
hydrochloric acid and washed in distilled w a t e r to
r e m o v e c o n t a m i n a n t s , particularly zinc.
R o c k specimens are frequently labelled in t h e
field using paint or m a r k e r pens which again may
lead to contamination. W h e r e large n u m b e r s of
samples are collected, according to t h e type of sta
tistical scheme discussed a b o v e , laboratory n u m b e r s
a r e often randomly allocated (see Section 9.7.1) and
h e r e t h e containers will have been labelled already
with the grid co-ordinates and laboratory n u m b e r of
t h e sample before going into the field. T h e policy of
using p r e - n u m b e r e d bags or jars can also r e d u c e
confusion during less extensive sample collection.
T a b l e 9.2 lists t h e m o r e c o m m o n c o n t a m i n a n t s of
containers.
Unconsolidated sediments will generally require
drying. In geochemical exploration surveys this is
often d o n e in t h e field by sun drying in high wetstrength p a p e r bags. Most samples, h o w e v e r , will
first be r e t u r n e d t o t h e laboratory and must b e dried
at t e m p e r a t u r e s n o higher t h a n 65C otherwise clays
will b a k e h a r d and volatile c o m p o n e n t s , for example
mercury or carbon c o m p o u n d s , may b e lost. O n c e
dry t h e sample should b e disaggregated by gentle
p o u n d i n g in an agate pestle and m o r t a r .
>-
- 9 -
o-
<)
>
1>
<1
>
>
(1
<>
(>
-9
ee e
Traverse sampling
Traverse sampling
oo
1 'i
.
11
<>
(>
c'
(>
>
<1
<>
>
(a)
<>
<>
e
Areal sampling
<)
o
o
()
(b)
L2
CO
o
O
<)
o
o
tr
297
o
o
o
.
o o
Areal sampling
Traverse sampling
9.5.1 C r u s h i n g
In any subsequent processing of sediment or rock
samples, contamination is inevitable although it may
be possible t o reduce t h e effect t o insignificant levels.
T h e m e t h o d ( s ) chosen should b e dictated by t h e
type of chemical analysis and elements required,
and by any further investigations which may follow.
Areal sampling
(0
Fig. 9.7.(a) Example of traverse and areal sampling using a regular grid. The spacing is determined by the expected size
of the target.
ROCK SAMPLES
Different approaches are required d e p e n d i n g on
analytical strategy. W h e r e o n e spatial c o m p o n e n t of
the sample is to be analysed, sawing and thin section
ing should precede analysis. Whilst microbeam tech
niques m a k e use of polished sections, o t h e r m e t h o d s
require a p o w d e r e d sample which can be chipped or
drilled from sawn surfaces and then ground in an
(b) Example of simple random sampling along a traverse and over an area. There may be a clustering of sample sites in
parts of the area and gaps left elsewhere. Note that it is possible that one site will be sampled more than once.
(c) Stratified random sampling where a grid of pre-determined size is randomly placed over an area and samples
randomly drawn from each grid cell. This reduces the clustering effect of simple random sampling.
(d) Balanced sampling using a nested hierarchical technique with duplicates collected from each site. Sample site and
analytical variability can both be studied but it is not necessary for every level to be fully replicated. In this example 72
samples would be analysed in duplicate. : (e) Unbalanced sampling using a nested hierarchical design. This produces a considerable saving in analysis with only 36
samples collected. Only one of the field duplicates need be analysed in duplicate.
http://jurassic.ru/
298
I.J. F A I R C H I L D ef AL.
O
C H E M I C A L A N A L Y S I S OF S E D I M E N T A R Y R O C K S
oo
o o
0
oo
oo
o oo
o o
oo
oo
0
oo
oo
o
oo
oo
oo
oo
oo
oo
o
oo
oo
o o
oo
Coloured plastic:
Oils:
oo
oo
Containers:
Polypropylene
Polythene
PVC
Brown paper
White paper
Rubber
Crushing:
Steel, iron, hard alloys
Ceramic, alumina
W carbide
Agate
Saws:
Diamond
Abrasive
Sieves:
299
Table 9.2. Potential contamination

introduced during various stages of
sample preparation. This list is far
from comprehensive and all new
materials or new supplies should
ideally be checked before use
Ti
Ti, Zn, Ba, Cd
Ti, Zn, Na, Cd
Si
Ti, Ba
Zn
Fe, Co, Cr, Mn, Ni, V, Cu, Mo, Zr
Al, Ga, B, Ba, Co, Cu, Fe, Li, Mn, Zn, Zr
W, Co, T i , R E E , Hf,Ta, Cu
Si, Pb
Cu, Fe, Cr, Mn, Ni
Al, Fe
Cu, Zn, Pb, Sb, Sn
Fe, Ni, Cr, Pb, Sn, Sb
Various
Various, Mo
oo
(d)
o
o
o
o
o
o
o
o
o
0
o
o
o
o
o
o
o
o
o
o
(e)
oo
agate pestle and m o r t a r . W h e n the sampled com

p o n e n t s h a v e small areas a n d t h e analytical techni
ques require small sample weights (e.g. isotopes and
I C P ) , use of a fine drill creates a p o w d e r which
requires little o r n o further p r e p a r a t i o n . C o n t a m i n a
tion will b e similar to that described below. T h o u g h t
must of course be given to a sampling scheme to
ensure that the samples a r e representative of all
similar areas in t h e slice.
In the case w h e r e whole samples or large parts of
samples n e e d to be p r e p a r e d a m o r e complex pro
cess is required.
This will initially involve crushing t h e sample to
an a p p r o p r i a t e grain size after sufficient material has
b e e n retained for a h a n d specimen and for thin
sectioning. W e a t h e r e d material not t r i m m e d in t h e
field should first be r e m o v e d and the sample then
reduced to roughly 50 m m cubes using a hydraulic
splitter with h a r d e n e d steel knife e d g e s . V a l u a b l e
samples may be sliced with a d i a m o n d saw and
weathering removed by grinding although care should
b e t a k e n t o p r e v e n t m e t a l smearing from t h e b l a d e .
T h e fragments should t h e n be washed in distilled
water (unless t h e r e is a danger of leaching s o m e
c o m p o n e n t s ) , preferably with ultrasonic cleaning.
T o reduce t h e grain size of t h e sample further t h e
http://jurassic.ru/
most p o p u l a r device is a j a w crusher where frag

m e n t s a r e fed b e t w e e n moving steel jaws. Roller
crushers employing rotating eccentric ribbed hard
steel rollers a n d cone grinders w h e r e t h e fragments
a r e fed between two ribbed steel cones, o n e within
t h e o t h e r , a r e also used.
All these are efficient in quickly reducing frag
m e n t size, t h e last two d o w n to approximately 60 B S
mesh (250 u m ) , but in t h e process slivers of metal
a r e r e m o v e d from grinding surfaces into t h e sample
p o w d e r . In addition they a r e difficult t o clean and it
is generally necessary to crush and then discard
s o m e sample to prevent cross contamination. Some
crushers also have sieve trays to screen t h e sample,
providing a further source of contamination.
A simpler and c h e a p e r m e t h o d uses an industrial
'fly p r e s s ' or hydraulic press fitted with h a r d e n e d
steel or tungsten carbide plates. T h e straight crush
ing action introduces very little contamination, t h e
sample is visible at all times and t h e a p p a r a t u s is
simple t o clean. It is, h o w e v e r , comparatively t i m e
consuming to use.
All m e t h o d s will p r o d u c e a s a m p l e with a maxi
m u m size of 5 m m down to 250 um depending o n t h e
machine settings, b u t with 'fines' d o w n to a few
microns. Appropriate action is needed to avoid health
300
hazards associated with silicate dust and with rock

splinters. G o o d analytical practice also dictates that
fine dust should not be lost from t h e sample as this
will introduce bias into the analysis. C o n t a m i n a t i o n
of t h e sample at this stage will be from t h e e l e m e n t s
present in h a r d e n e d steel, and possibly from lubri
cating and hydraulic oil.
If t h e initial sample was relatively coarse grained a
mass of 1 kg or m o r e should have been crushed, in
which case s o m e form of blending is a p p r o p r i a t e .
This may involve simple r e p e a t e d 'cone and quar
tering' followed by re-combination, o r t h e use of
m o r e sophisticated mechanical blenders. T h e blen
ded 'coarse' p o w d e r may be required for a n u m b e r
of purposes, for example mineral separation, radio
metric dating o r ferrous iron d e t e r m i n a t i o n , all re
quiring different sample p r e p a r a t i o n , h e n c e an
a p p r o p r i a t e n u m b e r of 'splits' should be t a k e n , again
either by 'cone and q u a r t e r i n g ' or by using a propri
etary sample splitter.
F u r t h e r reduction in grain size to 'fine p o w d e r ' is
almost universally performed in a laboratory disc
mill of t h e Tema or Shatterbox t y p e . Providing
t h e initial p o w d e r is n o t t o o coarse a n d that t h e
manufacturer's instructions regarding m i n i m u m and
m a x i m u m volumes are followed (maximum ~ 6 0 c m
for a 100 c m mill) these mills will rapidly reduce
samples t o a m e d i a n grain size of a r o u n d 40 u m . T h e
major exceptions are platey minerals such as micas
which are little affected by crushing. If t h e mill is
overloaded s o m e coarse rock fragments will remain
n o m a t t e r h o w long t h e material is crushed.
A g a t e and tungsten carbide are t h e most com
monly used barrels. A g a t e is relatively fragile and
must b e run at slow speeds, extending crushing
times t o 25 min for a 60 c m load, b u t reducing t h e
welding of softer minerals to t h e mill. Silica is
introduced as a c o n t a m i n a n t but equally significant
is t h e introduction of lead from vugs of galena
generally contained in t h e agate. T u n g s t e n carbide
usually contains approximately 6 % cobalt as a binder
and b o t h elements will contaminate t h e s a m p l e . In
addition rare earth elements may be used in t h e
b i n d e r and t h e tungsten may contain Hf and T a
impurities. T h e heat g e n e r a t e d in a tungsten carbide
mill often causes aggregation of t h e sample grains
and may also encourage oxidation of ferrous iron t o
ferric iron a n d possibly lead t o t h e loss of volatile
organic c o m p o n e n t s and elements such as mercury
and c a d m i u m . T h e r e is also a slight possibility of
altering t h e mineralogical composition; B u r n s &
3
B r e d i n g (1956) r e p o r t e d the c h a n g e of calcite to

aragonite with prolonged grinding. In general t h e
agate mill is to be preferred for general crushing, but
it may b e necessary t o crush separate splits of coarse
powder in each mill if all elements are to b e analysed.
Loss of very fine dust must obviously be avoided by
maintaining t h e barrel seals in good condition.
M a x i m u m contamination levels should b e check
ed by grinding a h a r d , p u r e material such as clear
q u a r t z crystal or p u r e silica sand, r e m e m b e r i n g that
levels may c h a n g e with time as t h e barrels a r e e r o d e d
thus exposing pockets of o r e in t h e agate o r , for
e x a m p l e , the brazing at the edge of t h e carbide
inserts. T a b l e 9.2 shows c o m m o n c o n t a m i n a n t s and
T a b l e 9.3 t h e results of a routine contamination
tests.
Cross contamination of samples is always possible
and careful cleaning, and possibly crushing and dis
carding s o m e material, is essential. T h e level of such
cross contamination is generally low, for e x a m p l e if
0.1 g of sample containing 1000 p p m of an e l e m e n t is
carried over t o t h e next 60 g load in a swing mill only
2 p p m of that element will b e a d d e d t o t h e next
sample. It is, h o w e v e r , advisable to record t h e
sequence of sample crushing to isolate sources of
e r r o r . T h e crushing history of b o t h 'coarse' a n d
'fine' powders should also b e r e c o r d e d b o t h in
laboratory notes and on t h e sample containers. T h e
international reference sample T - l which was con
taminated with cassiterite during crushing should
serve as a salutary r e m i n d e r .
9.5.2 The statistics of sampling

U n d e r ideal circumstances t h e sample p r e s e n t e d for
chemical analysis would be totally representative of
t h e target but in t h e majority of cases this is an
unattainable ideal because of t h e essential i n h o m o geneity of geological materials. T h e m a g n i t u d e of
t h e e r r o r can, however, be quantified using very
simple statistical m e t h o d s and either r e d u c e d t o a n
acceptable level or allowed for when t h e chemical
d a t a a r e interpreted.
W h e n a bulk sample is to b e analysed a sufficient
ly large a m o u n t should b e collected in t h e field to
allow for variations in mineral o r clast composition.
T h e 'rule of t h u m b ' ( d u e to E d e l m a n , 1962, and
referred t o previously) shows t h a t t h e majority of
samples collected by geologist are t o o small to p r o
vide a 1% sampling error as many rocks have minerals
o r clasts exceeding 2.4 m m , and 8 kg samples a r e t h e
301
Table 9.3. Test of the contamination introduced during the crushing of an industrial silica sand in three separate Tema
swing mill barrels (ten 50 g samples in each). Milling time 1 min at high speed for W carbide and steel, 3 min for agate.
Analysis by XRF of duplicate 15 g powder pellets. Oxides as percentages, elements as ppm. The low value for Ni crushed
in carbide is caused by a W background interference. The difference in mean Zr values for carbide and agate can be
explained by sampling errors
W carbide
Fe 0 *
MnO
CaO
K 0
Ni
Cr
Zr
Sr
Pb
W
2
Agate
Range
Range
Range
0.259-0.284
0.002-0.004
0.156-0.209
0.107-0.137
1-2
14-23
48-107
12-13
2-4
751-1855
0.267
0.003
0.193
0.125
1.5
18
70
12.6
3.0
1430
0.01
0.001
0.03
0.01
0.6
3.8
25.6
0.6
0.7
457
0.233-0.994
0.002- 0.003
0.161-0.206
0.107-0.159
4-7
8-24
50-137
11-13
48-134
<2
0.268
0.003
0.195
0.133
4.8
15
88
12.0
90
0.02
0.001
0.02
0.02
1.3
6.3
33.6
0.7
37
0.290-0.344
0.003-0.006
0.176-0.202
0.119-0.146
4375-7163
629-962
84-126
11-14
2-4
<2
0.311
0.005
0.189
0.133
5588
775
102
12
2.8
0.02
0.001
0.01
0.02
1194
143
18
1.3
0.8
exception rather than t h e rule! E v e n when an ade

q u a t e a m o u n t of sample has been collected, crushed
and blended for analysis it is necessary to ensure
that the small sub-samples taken for analysis are
representative of the w h o l e , particularly when ac
cessory mineral phases containing the majority of
o n e element (e.g. zircon) are present.
A moderately extensive literature is available
which discusses t h e whole range of sample size from
m o u n t a i n to milligram, but it is largely ignored
except in commercial areas such as t h e assaying of
bulk ores (where p a y m e n t d e p e n d s on an accurate
knowledge of total composition), in t h e assay of
very low concentrations of precious metals present
in large quantities of ' g a n g u e ' , and in t h e supply and
evaluation of rock and mineral reference materials.
A general t r e a t m e n t is given by Wilson (1964)
w h o considered the real cases w h e r e elements are
distributed in major and minor proportions b e t w e e n
several minerals of differing density and size r a n g e .
All these a p p r o a c h e s work o n the principle that the
standard deviation of t h e a m o u n t present can be
calculated using a multi-nomial distribution, and t h e
confidence limits assigned. W h e r e there a r e a large
n u m b e r of particles of each mineral or clast species,
http://jurassic.ru/
Steel
a Gaussian distribution is a p p r o p r i a t e but when

minor or accessory minerals are considered t h e sam
ple is most likely to be r e p r e s e n t e d by a skewed
Poisson distribution. A n e x t r e m e example taken
from T h o m p s o n (1983) is illustrated in Fig. 9.8.
T h e m e t h o d below is t a k e n from M o o r e (1979)
w h o used t h e Poisson distribution to develop equa
tions to calculate t h e standard deviation for minor
mineral species. T h e simplified approach considers a
particulate material containing p p p m of uniformly
sized grains of an accessory mineral of weight x g. If
a r a n d o m sample of weight W g is taken it will
contain an average n u m b e r of accessory mineral
grains Wp/x. A s t h e particles are discrete they may
be expected to follow a Poisson distribution with
m e a n Wp/x. T h e sample may be considered as a
large n u m b e r of sub-samples for which there is a
small probability of including an accessory mineral
particle. T h e coefficient of variation (CV) of this
mineral content is:
CV = lOOV^Wp %
3
for particles of similar shape x = AqD

w h e r e D is the particle d i a m e t e r ( u m ) ,
c, is the particle density (g c m ) ,
- 3
302
303
Table 9.4. Errors introduced by sampling different masses and grain sizes of minerals of differing densities (g) using the
method of Moore (1979) (see Section 9.5.2). The 95% confidence limit is approximated to 2s. Note that the ranges are as
ppm of the mineral
60
x = 318
s = 313
Samples of 40 urn diameter containing 20 ppm of mineral
n = 388
0)
Zircon
ZrSi0
4.7
Cassiterite
Sn0
?7
Gold
Au
gl9.3
40
Apatite
Ca F(P0 )
3.2
cr
Fig. 9.8. Tin results obtained by

optical emission spectroscopy of a
reference sample of stream sediment
in 388 successive batches. There is
extreme deviation from the Normal
curve because of the small sample
size (15 mg), the particle size (100
um) and segregation of tin in
cassiterite (from Thompson, 1983).
CD
Mass
20
(g)
500
LU nnrin n
1000
o n
1500
Tin (fig g )
A is a constant = ir/(6 x 10 ) for spherical

particles,
H e n c e t h e variability of sampling t h e accessory

mineral increases with increasing density a n d dia
m e t e r and with decreasing sample size and a m o u n t
of mineral present. T a b l e 9.4 illustrates this for a
range of mineral species. Gold is chosen because of
its e x t r e m e density but also because it has been the
subject of many papers relating to its obvious com
mercial i m p o r t a n c e . Nichol (1986) gave an e x t e n d e d
account of t h e p r o b l e m s and showed that for a
content of A u at 64 p p b with particles at 62 um
d i a m e t e r an 800 g sample must b e analysed to give a
precision of 5 0 % at a 9 5 % confidence level.
Generally an i m p r o v e m e n t in sampling precision
will be m a d e either by decreasing t h e grain size, or
by increasing the analysed sample weight. In t h e first
case this may not always b e practicable, for example
where minerals resistant to crushing such as micas,
or malleable materials like gold are present.
W h e n the analytical m e t h o d involves dissolving
the sample it is usually possible to increase t h e mass
t a k e n but with s o m e solid sampling techniques, such
as X-ray fluorescence analysis of light e l e m e n t s , t h e
effective mass analysed may be extremely small.
T h e above t r e a t m e n t can b e extended t o cover
ranges of particle sizes, or the situation w h e r e t h e
accessory mineral is present with two size distribu
tions, for example as discrete large grains, and as
small grains within a n o t h e r mineral. In t h e latter
case if replicate analyses w e r e m a d e with small

sample weights o n e would obtain low but relatively
consistent results but with occasional high values. If
t h e sample weight is increased the replicates may b e
less consistent but will have a m e a n close t o t h e
' t r u e ' value. T h u s with a knowledge of t h e sample it
is possible to predict errors and to avoid mistakes in
the interpretation of chemical results.
It is surprising that in spite of the available infor
mation sampling errors are often not considered
even w h e r e highly accurate work is involved.
B e n e d e t t i et al. (1987), for e x a m p l e , found discre
pancies between published values obtained by dif
ferent laboratories w h e n analysing international rock
and mineral reference samples for gold at t h e p p b
level (e.g. 1.66.7 p p b for t h e sample Mica-Fe). F o r
s o m e results u n d e r 1 g of material had b e e n used!
T h e principle of applying confidence limits is ex
tremely valuable a n d should be a t t e m p t e d w h e r e v e r
possible if only to avoid false conclusions. A n inter
esting example is provided by the c o r r e s p o n d e n c e
concerning t h e occurrence of rare d e t r i t a l zircons
from M t N a r r y e r , Australia, which was claimed, o n
t h e basis of i o n - p r o b e analysis by F r o u d e et al.
(1983), to be older than 4000 M y r . T h e claim is
questioned by Scharer & Allegre (1985) w h o found,
after analysis of 32 grains by mass spectrometry, a
younger age. C o m p s t o n et al. (1985), however,
showed that as t h e original analysis found only 5
'old' grains in 260 t h e r e is a strong statistical p r o b
ability that Scharer & Allegre would not have found
'old' zircons in their small sample.
Simple statistical m e t h o d s can also b e used to
10
5
1
0.5
0.1
Cof V
%
5.7
8.0
18.0
25.4
56.8
Range at
95%
confidence
ppm
17.7
16.8
12.8
9.8
22.3
23.2
27.2
30.2
42.8
Cof V
%
3.4
4.8
10.8
15.3
34.3
Range at
95%
confidence
ppm
Cof V
%
18.6
18.1
15.7
13.9
6.3
21.4
21.9
24.3
26.1
33.7
2.8
4.0
8.9
12.6
28.1
561
88
52
48.7
31.1
26.6
21.5
1109
139
64
38
22.8
13.5
3.1
Range at
95%
confidence
PPm
CofV
%
Ran; *e at
95%
confidence
ppm
18.9
18.4
16.4
15.0
8.8
21.1
21.6
23.6
25.0
31.2
2.3
3.3
7.3
10.4
23.2
19.1
18.7
17.1
15.9
10.7
20.9
21.3
22.9
24.1
29.3
464
76
46
35.3
29.1
22.7
21.3
915
114
53
32
18.8
11.2
2.6
203
66
41
32.6
27.5
24.5
21.0
Samples of 1 g containing 20 ppm of mineral

Grain size
BS mesh
um
16
1000
60
250
150
100
150
106
200
75
300
53
20
2248
280
130
78
46
27.4
6.4
1.5
9.0
17.5
919
132
72
51
38.5
31.0
22.5
1354
169
79
47
27.8
16.5
3.8
1.3
8.9
13.4
18.5
consider t h e errors in sampling i n h o m o g e n e o u s or

z o n e d minerals.
9.5.3 Sample d e c o m p o s i t i o n
A l m o s t all m e t h o d s of chemical a n d isotopic analysis
require t h e initial decomposition of t h e sample,
either directly, for example by an electrical arc or
spark as in optical emission spectroscopy, or chemi
cally by acid attack or fusion. Only t h e m e t h o d s
using t h e excitation of characteristic X-rays ( X R F ,
electron p r o b e ) a n d radiation techniques (such as
instrumental n e u t r o n activation analysis, I N A A ) can
on a routine basis employ the finely g r o u n d sample
p o w d e r alone.
In general the samples are presented for analysis
as solutions (in t h e special case of major element
d e t e r m i n a t i o n by X R F as a solid solution in the form
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4.7
10.9
17.3
18.7
7.4
12.5
15.5
19.0
of a glass disc), either after 'total' decomposition by

acid attack a n d / o r fusion or after partial and selective
decomposition or extraction potentially involving a
wide r a n g e of r e a g e n t s . Total decomposition is ex
tremely difficult t o achieve, particularly where minor
elements a r e p r e s e n t in resistant accessary minerals.
Geologists are frequently guilty of following general
recipes without thinking of t h e chemical characteris
tics of t h e minerals in t h e sample. Discrepancies
b e t w e e n values p r o d u c e d by different m e t h o d s may
result from incomplete decomposition, a n d t h e
mineralogy of any residue should b e checked micro
scopically or by X-ray diffraction.
Decomposition m e t h o d s will also b e d e t e r m i n e d
by t h e final m e t h o d of analysis and such factors as
matrix effects, t h e solid c o n t e n t of flames and spec
tral interferences the latter being especially im
portant in multi-element analysis and w h e r e the
304
same solution is used both for chemical and isotopic

analysis.
Selective extraction a n d decomposition a r e im
p o r t a n t in t h e d e t e r m i n a t i o n of t h e organic com
p o n e n t s of a sediment, in t h e analysis of t h e readily
soluble c a r b o n a t e fraction of samples and in analy
sing t h e geochemically 'mobile' c o m p o n e n t s of un
consolidated sediments and soils.
T h e r e is an extensively literature on available
m e t h o d s for t h e dissolution of silicates and related
materials, h e n c e t h e m e t h o d s will only be summar
ized. F o r up-to-date reviews see Jeffery & Hutchi
son (1981) and Potts (1987) and for explorationrelated samples see Fletcher (1981).
T w o types of decomposition are generally used:
acid decomposition a n d fusion; both m e t h o d s a r e
greatly assisted by a finely ground s a m p l e .
D E C O M P O S I T I O N BY M I N E R A L A C I D S
Acid decomposition has b e e n widely used for m o r e
t h a n 30 years, both for major and minor e l e m e n t
analysis. It is now especially i m p o r t a n t for trace
analysis by atomic absorption and inductively cou
pled plasma m e t h o d s w h e r e t h e relatively low salt
c o n t e n t s of flame a n d plasma is a considerable ad
vantage. A further major advantage is t h e purity of
mineral acids. T h e m a x i m u m levels of each element
of interest in all analytical reagents should of course
be carefully checked. For trace analysis Analar
acids are the minimum purity, and it may be necess
ary to use the Aristar g r a d e or in e x t r e m e cases to
re-distill the most p u r e commercially available
material. Potts (1987) described t h e distillation
m e t h o d and lists impurities in nitric, hydrochloric
a n d hydrofluoric acids ( P o t t s , 1987, tables 1.21 and
1.22).
Decomposition vessels are possible sources of
contamination in trace level analysis and these should
be m o n i t o r e d . S o m e workers for e x a m p l e have been
t e m p t e d to use soda glass when digesting c a r b o n a t e s
in cold dilute HC1 only to find that alkali elements
are leached from t h e glass! E v e n borosilicate glass
may b e unsatisfactory and ideally P T F E o r , m o r e
cheaply, polyethylene or polycarbonate should b e
used (after rigorous cleaning). A d s o r p t i o n of s o m e
elements on t h e container walls may be a p r o b l e m
especially in t h e m o r e e x t r e m e decomposition pro
cedures discussed below.
Hydrochloric
acid Dilute hydrochloric acid, either
cold o r h e a t e d , will dissolve all c a r b o n a t e minerals

(other than t h e scapolites) and is generally used for
t h e decomposition of c a r b o n a t e rocks and t h e
separation of any silicate or oxide minerals (see
section on selective dissolution). S o m e sulphides
and calc-silicate minerals a r e also attacked at ele
vated t e m p e r a t u r e s .
T h e chlorides of A s , B , G e , H g , Sb and Sn are
volatile and m a y be lost from t h e solution.
Nitric acid C o n c e n t r a t e d nitric acid will d e c o m p o s e
carbonates and most sulphide minerals which are
oxidized to sulphates and is widely used in mineral
exploration geochemistry. A mixture of H N 0 and
HC1 ( 3 : 1 , a q u a regia) is also used as a powerful
solvent for t h e n o b l e metals and oxides as well as
sulphides. C a r b o n c o m p o u n d s may not be fully oxi
dized and may preclude t h e use of nitric acid disso
lution w h e r e organic-rich material is to b e analysed
by I C P .
3
Hydrofluoric acid This acid, combined with nitric o r

perchloric acids, is very widely used and is able to
d e c o m p o s e t h e majority of silicates as well as car
bonates b u t , w h e r e this is d o n e in o p e n vessels, acidresistant minerals such as zircon, rutile a n d tour
maline may not be attacked. Disadvantages a r e that
decomposition must t a k e place in P T F E (below
260C) or platinum crucibles and t h e highly hazard
ous n a t u r e of both hydrofluoric and perchloric acids.
A typical p r o c e d u r e is to w a r m a 0.5 g sample for
several h o u r s in a covered vessel with 15 ml H F and
4 ml H C 1 0 , the latter to ensure oxidizing conditions.
T h e solution is evaporated t o incipient dryness, re
moving t h e Si as the volatile silicon tetrafluoride
t o g e t h e r with o t h e r fluorides which m a y interfere
with s o m e determinations. It may b e necessary to
r e p e a t this evaporation a n u m b e r of times with
additions of perchloric acid. This acid is a very
strong oxidizing agent which, with organic carbon
and in particular oils in t h e sample, may explode
violently at t h e evaporation stage. It is b e t t e r with
such samples t o a d d H N 0 t o t h e HCIO4 (at least
4:1) allowing a slow oxidation of t h e organics. T h e
cooled residue is t h e n t a k e n u p in HC1 (4 ml) and
diluted t o an a p p r o p r i a t e v o l u m e with distilled
water.
A n alternative p r o c e d u r e , which has the advan
tage of retaining silicon, is to digest t h e sample with
hydrofluoric acid plus nitric acid or a q u a regia in a
sealed P T F E lined ' b o m b ' as originally described by
B e r n a s (1968). T h e attack at t e m p e r a t u r e s of u p to
180C for 1 h o u r will d e c o m p o s e most resistant
minerals but t h e r e is t h e disadvantage that elements
may be absorbed at pressure by the P T F E . C a r e
should be t a k e n to m o n i t o r t h e possible release of
such elements in subsequent samples. Excess boric
acid is then a d d e d to complex t h e fluoride and it is
preferable to re-heat in t h e ' b o m b ' for ten minutes
at pressure to prevent the formation of insoluble
fluorides. E v e n h e r e s o m e resistant minerals may
remain and the solution should be checked and if
necessary t h e residue fused. This m e t h o d has t h e
disadvantage of producing a solution high in solids
which m a k e s analysis by I C P spectrometry difficult.
It should b e n o t e d t h a t the b o r a t e complexed
solution will still attack glassware!
SAFETY NOTE
Hydrofluoric
acid produces serious burns
requiring
hospital treatment with even minor contact.
Users
must be familiar with all necessary precautions
and
should have their method of work approved by a
Safety
Officer.
Perchloric acid is an extremely powerful
oxidizing
agent and should not be allowed to come into contact
with organic material. In addition, it forms
explosive
metal perchlorates. A scheme of work must again be
followed and the acid only used in an approved
fume
hood with wash-down
facilities.
D E C O M P O S I T I O N BY F U S I O N
Classical gravimetric analysis initiated in t h e nine

teenth century and early coiorimetric schemes of
major e l e m e n t analysis d e c o m p o s e t h e sample by
fusing with sodium carbonate. M o r e recently lithium
borates have been widely employed both for solutionbased analysis and especially for X-ray
fluorescence
using fused cast beads. S o m e specific examples of
m e t h o d s are discussed below.
A major p r o b l e m of fusion is the relatively high
ratio of sample to flux (generally m o r e t h a n 1:3)
which produces a high solid content and also poten
tially introduces contaminants (see section on p r e
paration for X R F ) . F o r these reasons decomposition
by fusion is m o r e widely employed in major element
analysis or to attack any r e s i d u e after acid decom
position.
Fluxes are generally extremely reactive and fusion
must t a k e place in a p p r o p r i a t e -resistant vessels,
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305
normally platinum, silver o r nickel. T h e s e are them

selves attacked a n d have a limited life, t h e life being
further reduced by alloys forming between t h e cru
cible and metals within the sample. T h e s e elements
may b e t a k e n u p into subsequent fusions, hence the
use of crucibles should be carefully logged.
Sodium carbonate This material in t h e anhydrous
form will d e c o m p o s e all silicate rocks with fusion
times of about o n e h o u r at 1000C, although s o m e
accessory minerals may require an additional ten
minutes at 1200C. T h e ratio of sample to flux now
r e c o m m e n d e d is 1:5 in contrast to earlier reliance on
larger a m o u n t s of flux. S o m e analysts have further
reduced the ratio to 1:1 by sintering at 1200C. T h e
fusion is normally performed in platinum crucibles,
and care must b e taken t o avoid reducing condi
tions, which could cause alloying and so destroy t h e
crucible! A small a m o u n t of nitrate or chlorate can
be a d d e d to the flux, or where sulphide or carbon is
present t h e sample should be pre-roasted in air. A
small a m o u n t of iron from t h e sample normally
alloys with t h e crucible and this may be released if a
low iron sample is subsequently fused.
Alkali hydroxide Sodium and potassium hydroxide
are widely used for decomposition, often with the
addition of p e r o x i d e , and a p p e a r in a n u m b e r of
coiorimetric analysis schemes. T h e fusion tempera
tures are less t h a n for sodium c a r b o n a t e but again an
h o u r is n e e d e d to ensure total solution. Fusion is
performed in either silver or nickel and care must be
t a k e n to ensure that t h e melt does n o t ' c r e e p ' out of
t h e crucible.
Prolonged fusion of samples containing
may result in loss of silica.
fluoride
Alkali borates Sodium b o r a t e has been used as an

efficient flux for aluminium-rich materials and also
for slags from t h e ferrous and non-ferrous industries
(West, H e n d r y & Bailey 1974). H o w e v e r , much
m o r e widely used are lithium m e t a b o r a t e ( L i B 0 )
and lithium m e t a b o r a t e - t e t r a b o r a t e mixtures as they
allow t h e determination of sodium. T h o m p s o n &
Walsh (1983) r e c o m m e n d e d the m e t a b o r a t e as
a flux for major element determination by I C P
at a sample to flux ratio of 1:4 which ensures that
the final solid content does not exceed 2 % . T h e
sample and flux are h e a t e d , with swirling at 1000C
for 3 0 - 4 5 min in a Pt or P t / A u crucible and, w h e n
cool, t h e melt t a k e n up in nitric acid. Most silicates
2
306
a r e readily dissolved if they a r e finely ground ( < 6 0

u m ) but high concentrations of a n u m b e r of acces
sory minerals may leave a residue. Potts (1987, table
2.4) listed t h e minerals and t h e proportion remain
ing after fusion.
T h e greatest use of b o r a t e fluxes is in X-ray fluor
escence, details of which are given in the next sec
tion. Many of the problems associated w i t h t h e use of
such fluxes are also c o m m o n to atomic absorption
and I C P techniques and it is also possible t o dissolve
X R F beads after analysis for use in solution methods.
Lithium borate fusions for X-ray fluorescence anal

ysis T h e intensity of characteristic X-ray emission
lines for the lighter elements (Na-Fe) is n o t only
d e p e n d e n t on t h e concentration of t h e e l e m e n t but
also o n t h e grain size a n d mineralogical composition
of t h e sample. It is therefore essential to r e m o v e
grain effects and t h e most efficient m e t h o d is t o
present all samples to t h e spectrometer as a solid
solution in the form of a glass disc.
T h e flux(es) used must satisfy t h e following cri
teria: (a) a wide r a n g e of sample compositions must
ideally be t a k e n into solution; (b) fusion t e m p e r a
tures must be sufficiently low to p r o d u c e a fluid melt
using gas burners o r normal laboratory furnaces
( 1 0 0 0 - 1 2 0 0 C ) ; (c) the cooled melt must form a
stable glass disc without devitrification; (d) t h e glass
must be relatively resistant to attack by moisture
and atmospheric gases; (e) t h e flux should ideally
n o t contain elements which are t o be analysed in t h e
sample.
(a) B e n n e t t & Oliver (1976) considered the effic
iency of Li m e t a b o r a t e a n d Li t e t r a b o r a t e for t h e
decomposition of a wide range of silicate, c a r b o n a t e
and ceramic materials. T h e y showed that the former
flux is most effective for silica-rich samples (100%
silica80% alumina) and t h e latter for materials
rich in alkali and alkaline earth oxides and alumin
ous samples (100% alumina95% silica), and p r o
posed a fluxed c o m p o s e d of a 1 part Li t e t r a b o r a t e
and 4 parts Li m e t a b o r a t e (Johnson M a t t h e y Spectroflux 100B) to cover t h e widest possible range of
materials. This flux is extremely effective at a ratio
of 1 part sample to 5 parts flux and will d e c o m p o s e
most silicates with 20 min fusion at t e m p e r a t u r e s
b e t w e e n 1000 and 1200C. B e n n e t t & Oliver (1976)
also considered t h e fluxes and sample to flux ratios
n e e d e d t o p r o d u c e stable b e a d s for a wide range of
materials. Of particular i m p o r t a n c e to t h e analysis

of sedimentary rocks is their r e c o m m e n d a t i o n of
lithium m e t a b o r a t e (sample to flux 1:5) to decom
pose limestones and dolomites. Their major conclu
sion is that t h e r e is n o universal flux and that t h e
chemistry of t h e sample to b e dissolved must be
considered when choosing flux and sample dilution.
A s h o r t e n e d version of their findings is given in
T a b l e 9.5.
T h o m a s & H a u k k a (1978) r e c o m m e n d e d a 1:2
fusion with lithium m e t a b o r a t e to allow t h e deter
mination of both major and minor e l e m e n t s in t h e
same b e a d . T h e i r results are excellent but t h e r e
must b e s o m e d o u b t a b o u t t h e ability of this low
dilution to dissolve all minerals.
O n e flux which has b e e n widely used is lithium
m e t a b o r a t e with t h e addition of 1 6 % l a n t h a n u m
oxide. It was m a d e popular by Norrish in a multi
t u d e of papers and was designed t o reduce X-ray
matrix effects by t h e addition of L a O as a heavy
absorber. This gives t h e a d d e d b o n u s of increasing
t h e ability t o dissolve 'basic oxides' and also acting
as a glass-former t o p r o d u c e stable b e a d s . Recently
t h e r e has b e e n a decline in its popularity as t h e
characteristic L a lines interfere with s o m e deter
minations, its purity is comparatively p o o r and it is
m o r e expensive t h a n t h e n o r m a l lithium b o r a t e
fluxes.
(b) Lithium m e t a b o r a t e melts at 849C hence a
b u r n e r or muffle furnace at 1000C will p r o d u c e a
fluid melt with sufficient t h e r m a l agitation t o aid
Table 9.5. Recommended sample-to-flux ratios for

different sample types and the two common fluxes Li
metaborate and Li tetraborate. * indicates minimum
amount to give a clear stable bead. From Bennett &
Oliver (1976)
Parts of flux to 1 part ignited
sample
Silica-alumina range
Apatite
Zircon
Limestone
Dolomite
Magnesite
Li metaborate
Li tetraborate
4
0
4
0
0
0
1
3*
1
5*
5*
10
solution without t h e n e e d for continuous swirling.

Lithium t e t r a b o r a t e melts at 917C placing fluid
melts beyond the r a n g e of n o r m a l burners, while the
4:1 eutectic mixture of t h e two fluxes melts at 832C
combining t h e advantages of a fluid melt and d e
composition of a wide r a n g e of materials.
F o r most laboratories fusion is a labour intensive
operation using standard b u r n e r s or muffle furnaces,
with limited a u t o m a t i o n , e.g. a four sample swirling
system as described by B e n n e t t & Oliver (1976).
Expensive a u t o m a t e d fusion devices a r e available
based on either gas b u r n e r s or o n R F furnaces which
a r e mainly used in industrial process control w h e r e
the sample throughput justifies the cost. T h e s e may
o p e r a t e either t o p r o d u c e X R F b e a d s or samples for
I C P or atomic absorption.
In X R F , where a constant sample to flux ratio must
be m a i n t a i n e d , t e m p e r a t u r e control of t h e fusion
is critical, especially at t e m p e r a t u r e s a b o v e 1000C
w h e r e a significant p r o p o r t i o n of t h e flux will b e lost
( 0 . 0 0 5 % m i n " at 1200C). T h e alkali elements are
also lost, approximately 0.002% of t h e K 0 present
per m i n u t e at 1200C. A further problem when using
gas burners is that at high t e m p e r a t u r e s platinum
is porous to hydrocarbons in t h e flame which may
p r o d u c e reducing conditions in the m e l t , which in
turn may allow metals to alloy with t h e crucible.
(c) W h e n fusion is used as a precursor to acid
dissolution t h e only r e q u i r e m e n t is.total dissolution
of t h e sample. In analysis by X R F t h e b e a d is
presented t o t h e s p e c t r o m e t e r with a flat, polished
surface. Devitrification and shattering before, and
particularly during, analysis is most undesirable. If
t h e b e a d is well annealed this will generally n o t
occur unless undissolved mineral grains remain in
t h e glass t o act as nucleating centres. S o m e samples
may have insufficient glass-forming elements in which
case p u r e silica may b e a d d e d (and subtracted from
t h e analysis result) or B e O a d d e d . This is an espe
cially good m e t h o d for 'blank' beads but requires
considerable care as beryllium is a highly toxic
element.
1
(d) A t m o s p h e r i c moisture rapidly attacks sodium

b o r a t e glass, changing t h e composition of t h e bead
surface and producing large errors in the lighter
element analyses. Lithium b o r a t e glasses a r e affect
ed m o r e slowly b u t t h e deterioration is detectable
after a few h o u r s as t h e moist surface allows attack
by o t h e r gases, especially t h e sulphur oxides. This
can be a particular problem in industrial atmospheres
w h e r e b e a d s m a y sit in automatic sample loaders for
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11111
307
m a n y h o u r s . T h e increase in sulphur content of t h e

b e a d surface is detectable by X R F after two h o u r s .
It follows that beads should be stored in a desiccator
and exposed to the a t m o s p h e r e for as short a time as
possible, in particular for reference samples which
may be re-analysed a n u m b e r of times. Changes in
t h e chemical composition of b o r a t e glass u n d e r t h e
X-ray b e a m , in particular of Si and A l , have been
n o t e d by Le Maitre & H a u k k a (1973) and o t h e r
a u t h o r s ; h e n c e prolonged and r e p e a t e d exposure is
t o b e avoided.
(e) A t ratios of sample to flux of 1:3 and greater a
significant blank can be introduced for m a n y ele
m e n t s . T a b l e 9.6 lists typical m a x i m u m levels of
impurity specified by a n u m b e r of manufacturers for
t h e X-ray fluorescence grade of b o t h lithium metaand t e t r a b o r a t e fluxes. H i g h e r purity is available
with levels about an o r d e r of magnitude less, but
these grades are extremely expensive. It should b e
stressed that impurity levels will changes from batch
to b a t c h , and that frequent checking of blanks is
essential. T h e level of C a can b e t a k e n to illustrate
potential errors. If it is at t h e m a x i m u m specified
( 0 . 0 1 % ) , t h e a p p a r e n t C a O content of a blank
sample fused at a 1:5 ratio will be 0 . 0 7 % .
SELECTIVE DISSOLUTION OF
CARBONATES
Analysis of t h e c a r b o n a t e fraction of i m p u r e car
b o n a t e s usually involves a compromise b e t w e e n an
effective dissolution agent and one that does not simul
taneously leach t h e n o n - c a r b o n a t e c o m p o n e n t s . P.
R o b i n s o n (1980) reviewed previous work and found
that for s o m e Palaeozoic carbonates 1M HC1 caused
n o m o r e leaching of M n , Sr o r N a from t h e insoluble
residue t h a n did 0 . 1 M acetic acid, yet was much
m o r e effective in attacking dolomite. I r o n , however,
was m o r e strongly leached. Boyle (1981) found that
finely-divided FeMn oxides were leached even by
Table 9.6. Typical maximum levels of impurity (in %) in
Li metaborate and Li tetraborate fluxes used in X-ray
fluorescence
Si
Ti
Al
Fe
Mn
0.0050
0.0020
0.0050
0.0010
0.0020
Mg
Ca
Na
K
P
0.0020
0.0100
0.0040
0.0020
0.0030
CI
so
F
As
Pb
0.0020
0.0050
0.0020
0.0020
0.0020
308
an acetic acid solution buffered at p H 5.5 by excess

a c e t a t e . F o r his analyses of very low concentrations
of C d , Z n and B a in foraminiferal tests, dissolution
in distilled water in contact with a C 0 a t m o s p h e r e
was required to avoid leaching the n o n - c a r b o n a t e
fraction. W h e r e detection limits allow, electron
microbeam techniques are preferable (e.g. for Fe in
impure carbonates). Alternatively by plotting chemi
cal d a t a against percentage of insoluble residue,
s o m e estimate can b e m a d e of t h e degree of leaching
(Veizer etal., 1977, 1978). Veizer et al. (1978) found
a clear relationship of increasing solute ( 8 % v/v
HC1) potassium with insoluble residue c o n t e n t , b u t
for sodium in t h e same samples Veizer et al. (1977)
found that that positive correlation disappeared when
a priori hypersaline and n o r m a l marine samples
w e r e considered separately.
2
W h e r e analysis of t h e insoluble fraction is t h e

aim, acidic ion exchange resins can b e used ( F r e n c h ,
W a r n e & Sheedy 1984), although smectites show
s o m e leaching, and zeolites and simple salts tend to
dissolve.
Phosphoric acid residues from isotopic analysis
can be used for cation analysis: this m e t h o d is
evaluated in Section 9.6:5.
EXTRACTION OF ORGANIC MATERIAL

AND D E T E R M I N A T I O N OF O R G A N I C
CARBON
T h e details of the separation and analysis of organic
material is beyond t h e scope of this chapter. Extractants include m e t h a n o l , a c e t o n e , b e n z e n e and
chloroform, which will r e m o v e t h e 'bituminous frac
tion' for analysis by gas c h r o m a t o g r a p h y or infrared
spectrometry. NB most of these solvents present a
safety hazard!
A second 'humic acid' fraction may b e recovered
using sodium hydroxide solution. T h e remaining
insoluble c a r b o n a c e o u s material is t h e kerogen
fraction.
It is c o m m o n practice to d e t e r m i n e organic carbon
in sedimentary rocks, and t h e r e are C H N (carbonhydrogen-nitrogen) analysers available for this. Or
ganic carbon contents can be readily d e t e r m i n e d by
loss on ignition, although t h e results may not be very
accurate. If t h e r e is n o ' c a r b o n a t e c a r b o n ' present in
t h e rock, then t h e dried, weighed p o w d e r e d sample
can be heated in an oven at 8 0 0 - 1 0 0 0 C for 2 - 3
hours to oxidize t h e carbonaceous material. T h e
weight loss will give t h e organic carbon content. If
much pyrite is p r e s e n t , t h e oxidation of this will

introduce an error. F o r sandstones and m u d r o c k s ,
c a r b o n a t e carbon can be r e m o v e d first by acid diges
tion. Before the oxidation of the organic c a r b o n ,
samples should be dried at 105110C t o drive off
any water, and t h e n weighed. With limestones and
dolomites, the c a r b o n a t e can be dissolved o u t , the
residue dried (and weighed) and t h e n c o m b u s t e d at
8 0 0 - 1 0 0 0 C . F r e q u e n t l y , the weight loss is deter
mined on t h e whole p o w d e r e d limestone sample
(after drying), but t h e n the t e m p e r a t u r e is critical. If
it is t o o high, t h e c a r b o n a t e carbon will d e c o m p o s e .
A t e m p e r a t u r e of 550C is generally considered
sufficient to combust most of t h e organic c a r b o n , b u t
little of the c a r b o n a t e carbon. If t h e limestone sam
ple is then heated again, to 1000C for a further 23
h o u r s , the second weight loss will give the c a r b o n a t e
carbon content.
9.6 A N A L Y T I C A L T E C H N I Q U E S
9.6.1 Introduction
In this section, t h e p o p u l a r techniques for analysing
sedimentary rocks are discussed, notably those in
volving instruments rather than t h e 'classic', mostly
' w e t ' m e t h o d s of rock analysis. Analysis by electron
m i c r o p r o b e , X-ray fluorescence ( X R F ) , atomic ab
sorption spectrophotometry ( A A S ) , inductivelycoupled plasma spectrometry ( I C P ) , instrument
n e u t r o n activation ( I N A A ) and stable isotope mass
spectrometry are described, with t h e emphasis on
how sedimentary rocks are t r e a t e d , r a t h e r t h a n on
t h e details of the technique or instrument itself.
T h e r e are n u m e r o u s textbooks giving full explana
tions of all t h e various techniques (see Potts, 1987,
for o n e of t h e most r e c e n t ) , although these are often
written from t h e point of view of t h e hard-rock
geochemist, mostly concerned with silicate rocks.
Techniques which are not covered h e r e include flame
p h o t o m e t r y coiorimetric m e t h o d s , and those of or
ganic geochemistry, notably gas c h r o m a t o g r a p h y ,
mass spectrometry and pyrolysis.
9.6.2 Electron beam microanalysis

Following a period of rapid d e v e l o p m e n t in t h e
1960s and early 1970s, reliable and fairly standar
dized m e t h o d s of quantitative analysis on t h e micron
scale have b e c o m e widely available. T h e electron
m i c r o p r o b e is an instrument specifically designed for
such a p u r p o s e , but quantitative results are also

obtainable from a scanning electron microscope
( S E M ) or a scanning transmission electron micro
scope ( S T E M ) fitted with a suitable detection sytem.
In all cases, a focused b e a m of electrons in impinged
u p o n a specimen (Fig. 9.9) causing t h e generation of
an X-ray spectrum containing lines, characteristic of
each e l e m e n t , whose intensity is related to t h e con
centration of t h e e l e m e n t in t h e specimen.
T h e r e are several useful references for micro
probe, work including the lucid book by R e e d (1975)
and the c h a p t e r by L o n g (1977). Goldstein et a/.'s
(1981) b o o k covered nearly all aspects of S E M /
m i c r o p r o b e work, and Heinrich (1981) provided a
t h o r o u g h , but rather drier survey of the field. T h e
ion microprobe is not covered h e r e , but could have
s o m e i m p o r t a n t applications to carbonates in the
future ( M a s o n , 1987; Veizer etal., 1987).
MICROPROBE ANALYSIS: GENERAL

ASPECTS
Samples (usually polished thin sections) and stan
d a r d s are inserted into a specimen c h a m b e r which is
evacuated prior to analysis. Electron microprobes
and s o m e of t h e new generation of S E M s incorpor
ate an optical microscope to allow the ready location
of the areas to b e analysed.
T h e electron b e a m is g e n e r a t e d by heating a fila
m e n t , usually of tungsten, within a triode electron
gun. T h e b e a m is focused by two sets of magnetic
lenses. T h e first (the condenser) determines the
b e a m diameter whilst t h e second (the objective)
sharply focuses t h e b e a m . Accelerating voltages are
1030 kV corresponding to electron energies within
t h e range 1030 k e V . T h e b e a m can be kept station
ary on a spot or traverse along a line or scan (raster)
an area t o derive a point analysis, line scan or areal
distribution of an element as required.
A proportion of t h e electrons d o not p e n e t r a t e the
sample, but are backscattered. Since this effect in
creases with average atomic n u m b e r of t h e a r e a ,
irradiated backscattered electrons can b e used to
p r o d u c e 'atomic n u m b e r contrast' images ( C h a p t e r
8). Electrons penetrating t h e specimen show com
plex trajectories (Fig. 9.10) d u e to various forms of
interaction. T h e y spread o u t qVer a diffuse region
typically about 1 um d e e p (size d e p e n d i n g on acce
lerating voltage a n d atomic n u m b e r ) . A l t h o u g h t h e
incident electron b e a m can b e m a d e m u c h n a r r o w e r
than 1 u m , this spreading effect d e t e r m i n e s t h e
spatial limit of resolution in the m i c r o p r o b e . T h e
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309
Filament
Accelerating
anode
Objective
lens
Gas-proportional
counter
(WDS)
Fig. 9.9. Schematic illustration of the elements of an
electron microprobe.
interactions of electrons can be divided into elastic
scattering, which involves a change in direction with
minimal loss of energy, and inelastic scattering. T h e
latter covers a variety or processes leading to energy
loss. F o r example, excitation of lattice oscillations
leads to heat production which is important because
of t h e thermal instability of certain sedimentary
minerals. T h e ejection of low-energy ( < 5 0 e V )
secondary electrons from t h e o u t e r parts of elec
trons is a n o t h e r inelastic scattering process, obvi
ously important in forming specimen images in t h e
S E M . A n o t h e r process, i m p o r t a n t in s o m e materials,
is t h e release of long-wavelength p h o t o n s : c a t h o d o
luminescence ( C h a p t e r 6). Also t h e r e is t h e deceler
ation of electrons by charge interaction with a t o m s ,
leading to the production of X-ray p h o t o n s whose
310
= 10 keV
= 20 keV
30 keV
secondary
fluorescence
X-rays
Fig. 9.11. Schematic illustration of the regions in the
specimen within which electrons are emitted or reflected
and X-rays generated. Scale depends on accelerating
voltage, and average atomic number of specimen (see Fig.
9.10).
Fig. 9.10. Simulation (by a Monte Carlo procedure) of electron paths (above) and K X-ray photons (below) in copper.
Note the emergence of backscattered electrons. The effects of atomic number are illustrated by the fact that equivalent
diagrams (at 20 keV) for gold and aluminium resemble the left and right diagrams respectively. From Heinrich (1981).
energy varies u p t o a m a x i m u m corresponding t o t h e

energy of the incident electrons. A ' b a c k g r o u n d '
continuous X-ray spectrum is thus p r o d u c e d in which
low energy X-rays ( < 1 k e V ) are missing d u e t o
absorption by t h e specimen. O n this spectrum a r e
superimposed p e a k s corresponding t o specific elec
tronic transitions in t h e specimen. T h e s e p e a k s form
t h e characteristic spectrum a n d arise from decay of
electrons from an o u t e r t o an inner energy shell
following an initial excitation by an incident electron
(Fig. 9.11). In t h e energy range of interest (110
k e V ) elements of higher atomic numbeT a r e analysed
successively by study of K , L and M lines (Fig. 9.12).
Quantitative analysis is normally restricted to ele
m e n t s with a t o m i c n u m b e r > 1 1 unless special tech
niques are used. Energy-dispersive systems (see
below) have b e e n particularly limited in this respect,
but analysis down t o Z = 5 ( b o r o n ) is now available

( S t a t h a m , 1982) o n commercial systems.
D E T E C T O R SYSTEMS
T w o alternative m e t h o d s of analysing t h e X-ray
spectrum are available: wavelength-dispersive sys
tems ( W D S ) and energy-dispersive systems ( E D S ) .
T h e original, and most analytically-sensitive ar
r a n g e m e n t ( W D S ) is t o m a k e use of a Bragg spectro
m e t e r in which t h e X-rays are diffracted by a crystal
and h e n c e s e p a r a t e d by wavelength (see also C h a p t e r
7). T h e crystal has a curved surface t o i m p r o v e
intensities of X-rays. B r a g g ' s law applies:
2d sin 9 = rik
w h e r e d interplanar spacing of t h e
diffracting
crystal, 0 = angle of incidence of the X-rays, n = a

positive integer and X = wavelength of t h e X-rays.
R a y s satisfying this e q u a t i o n are r o t a t e d 28 degrees
in their angle of p r o p a g a t i o n . A detector is placed at
t h e 26 angle of interest for analysing t h e largest firsto r d e r reflection available for a given e l e m e n t , or can
be scanned through various 26 angles t o obtain t h e
whole spectrum. (The latter process is much m o r e
efficiently carried out by E D S , however.) X-ray
p h o t o n s of short wavelength can be analysed by a
solid-state detector as described below for E D S , but
normally in W D S the Bragg spectrometer is coupled
to a gas-proportional counter. H e r e each X-ray
p h o t o n causes ionization of the gas leading t o t h e
production of free electrons which a r e attracted to a
wire and give rise to a pulse of charge. A sealed
detector is used for shorter p h o t o n wavelengths, b u t
otherwise a continuously-flowing gas is used. F o r
qualitative analysis only the total n u m b e r of pulses
at a given 26 value n e e d be c o u n t e d . H o w e v e r , in
order to eliminate higher-order reflections and pulses
p r o d u c e d by inner-shell ionization of the counter
gas, t h e instrument is set u p only to count pulses
within a certain voltage r a n g e ( d e t e r m i n e d empiri
cally in each case) c o r r e s p o n d i n g to p h o t o n s of a
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311
given energy ( = given wavelength). A 26 scan in the

a r e a of interest reveals t h e form of t h e background
c o n t i n u u m . B a c k g r o u n d counts a r e m a d e o n either
side of t h e p e a k for each analysis. W h e n two spectro
m e t e r s a r e fitted, two elements can be d e t e r m i n e d
simultaneously.
T h e most widely used detection system is that of
E D S in which all t h e X-ray p h o t o n s are collected in
t h e s a m e place. T h e d e t e c t o r used is a solid-state
instrument containing a single-crystal slice of p-type
silicon whose resistivity has been increased by addi
tion of lithium: h e n c e lithium-drifted silicon (Si(Li)).
A s in t h e gas-proportional c o u n t e r , each X-ray
p h o t o n causes t h e generation of charged particles
which create an electrical pulse which, after amplifi
cation, is classified according to its amplitude. A
multi-channel analyser is used so that a histogram of
pulse intensities is built up which largely corresponds
t o t h e distribution of energies of t h e incoming p h o
t o n s . C o u n t s are accumulated over a period of typi
cally 2 min ( R e e d & W a r e , 1975) corresponding t o a
'live-time' (time w h e n t h e counter is not processing
a p h o t o n and thus able to accept a n o t h e r p h o t o n ) of
100 s. T h u s t h e overall chemistry of t h e analysed
area is rapidly appreciated, but t h e histogram con
tains spurious p e a k s and overlapping p e a k s which
complicate analysis.
In practice t h e energy-dispersive system is nor
mally used for r o u t i n e analyses because of its low
cost and the speed with which d a t a can b e obtained.
A wavelength-dispersive system is suitable when
only a few elements a r e t o be analysed or w h e r e
trace elements a r e to be d e t e r m i n e d since t h e detec
tion limits a r e significantly lower.
STANDARDS
T h e intensities of characteristic lines in t h e speci
m e n ' s X-ray spectrum a r e c o m p a r e d with line inten
sities from material of k n o w n composition in order
to obtain a quantitative analysis. Ideally t h e refer
ence materials (standards) would be of very similar
composition to t h e mineral analysed so that electron
b e a m - m i n e r a l interactions would b e t h e s a m e , eli
minating t h e need for a correction p r o c e d u r e . This
a p p r o a c h is impractical w h e r e various minerals are
to be analysed. Normally geological m i c r o p r o b e
laboratories utilize a set of reference materials (ele
m e n t s , oxides a n d silicates) which a r e used in con
junction with a correction p r o c e d u r e for silicate and
oxide analysis, and often c a r b o n a t e and sulphide
analysis as well. E x a m p l e s of suitable materials are
312
A n electrically-conducting coating, 2 0 0 - 4 0 0 A
thick, usually of carbon, is applied to avoid t h e build
u p of charge on the surface of non-conducting
materials. Standards m u s t h a v e t h e s a m e thickness
of coating as t h e specimens: this is most easily
obtained by coating both at t h e same time.
OPERATING CONDITIONS
10
Energy (keV)
Fig. 9.12. Plot of the energy of the X-ray emission lines observed in the range 0,75-10 keV by energy-dispersive X-ray
spectrometry (simplified from Fiori & Newbury, 1978). ESC indicates escape peak. An example of peak overlap would be
the KfJ peak for Mn (element 25) and the Ka peak for Fe (element 26): both have the same energy. If Mn abundance Fe,
then Mn K(5 will have a similar strength to Fe Ka.
SPECIMEN PREPARATION
periclase (for M g ) , quartz (Si), jadeite ( N a ) , wollastonite (Ca) and metals for first series transition
elements. Synthetic glasses are also used and are
particularly useful for r a r e r elements with which t h e
glass can be ' d o p e d ' , b u t care has t o b e t a k e n
because of decomposition u n d e r t h e electron b e a m .
M o r e accurate analysis should in principle b e
achievable by using e n d - m e m b e r s of solid-solution
series, e.g. p u r e siderite for F e in calcite (Moberly,
1968; Jarosewich & M a c l n t y r e , 1983). U s e of other
than t h e normal laboratory reference materials
should be ^considered for study of, for e x a m p l e ,
m i n o r elements in carbonates or minerals with un
usually high concentrations of u n c o m m o n e l e m e n t s .
It is obviously vital to ensure t h e reference material
is h o m o g e n e o u s on all scales for t h e e l e m e n t s of
interest.
T h e n o r m a l practice is to analyse highly-polished

thin sections of s t a n d a r d (30 um) thickness. Succes
sively finer abrasives are used, finishing o n \ u m
alumina. A final h a n d polish using a cloth with
0.050.1 um alumina is r e c o m m e n d e d :by Taylor &
R a d t k e (1965). A m o r e rapid m e t h o d is described
by Allen (1984) using only 0.3 um alumina. E x c e p
tionally, d i a m o n d m a y be required r a t h e r t h a n
alumina if contamination of soft or p o r o u s materials
by alumina occurs and Al-analysis is r e q u i r e d . T h e
necessity for a good polish arises since an u n e v e n
surface increases t h e statistical uncertainties of X ray analysis, whilst sharp steps or grooves can lead
t o widely inaccurate results. T h e quality of t h e
surface polish can be judged o n t h e m i c r o p r o b e by
specimen current imaging.
Routinely, an accelerating voltage within the range

1520 k V is used for analysis. H i g h e r voltages may
be used to increase t h e p e a k to background ratio for
trace element analysis, whilst voltages of 10 k V may
b e required for very unstable (glassy) materials. T h e
incident p r o b e current is an important variable and
needs to be m o n i t o r e d in s o m e way to check con
stancy of analytical conditions. Sometimes authors
r e p o r t t h e specimen current (the current from speci
m e n to e a r t h ) . H o w e v e r , this current d e p e n d s on
t h e a m o u n t of backscattering and secondary electron
generation and so varies with different materials.
Energy-dispersive analysis requires a p r o b e current
of only 1 n A w h e r e a s 1 0 - 1 0 0 n A is m o r e usual in
W D S . Since specimen heating is directly propor
tional t o current (as well as voltage), specimens
liable to thermal decomposition should preferably be
analysed on an E D S : this includes hydrous minerals
such as most clay minerals, halides, p h o s p h a t e s ,
carbonates a n d phases containing alkali metals (e.g.
alkali feldspar). Alternatively, using a W D S , d e
composition m a y b e reduced by defocusing t h e b e a m
to 20 (im or m o r e in diameter. Since spatial resolu
tion is i m p o r t a n t for clay mineral analysis, V e l d e
(1984) r e c o m m e n d e d use of a 5 um spot on an E D S
system with its associated low current and low coun
ting times for a complete analysis. A n o t h e r strategy
(Fairchild, 1980b), designed particularly for char
acterizing minor elements in zoned c a r b o n a t e s , is t o
allow sample decomposition to occur u n d e r a p r o b e
current, b u t to use chemically-similar standards since
these d e c o m p o s e to a c o m p a r a b l e degree. Totals a r e
normalized to allow for differential decomposition
(Moberly, 1968). This ensures a high p e a k to back
ground ratio. G o l d coating and use of continuous
scans r a t h e r than spot analyses were found to
i m p r o v e precision. T h e optimal coating material
would a p p e a r t o be silver, as its high t h e r m a l con
ductivity minimizes sample decomposition at high
values of p r o b e current (Smith, 1986).
T h e rapid p r o c e d u r e s of t h e E D S m e e t most
r e q u i r e m e n t s , but with a detection limit of t h e o r d e r
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313
of 1000 p p m (0.1 wt % ) , it is not a p p r o p r i a t e for

trace element analysis (e.g. N a or Sr in c a r b o n a t e s ) .
Detection limits using W D S , although variable, are
of t h e order of 100 p p m .
CORRECTION
PROCEDURES
T h e simplest case is a W D S w h e r e standards are

similar in composition to specimens. Following de
duction of t h e background c o u n t s , the ratio of X-ray
intensities are p r e s u m e d equal to the ratio of con^
centrations of specimen and standard. M o r e gener
ally in W D analysis a series of corrections have to b e
applied ( L o n g , 1977, p . 313). First, a 'dead-time
correction is m a d e which allows for p h o t o n s which
w e r e not counted because t h e proportional counter
was processing t h e previous p h o t o n : this is only
i m p o r t a n t at high count rates. T h e n t h e r e are cor
rections for atomic n u m b e r , absorption and fluore
scence differences b e t w e e n specimen and standard:
t h e Z A F corrections.
7
T h e atomic n u m b e r correction is t h e resultant of

two opposing tendencies: backscattering which in
creases with increasing atomic n u m b e r , and electronstopping p o w e r which decreases with increasing
atomic n u m b e r . T h e absorption correction arises
because t h e X-rays are g e n e r a t e d below the surface
of t h e specimen and particular wavelengths are then
preferentially a b s o r b e d by different a t o m s . T h e
fluorescence correction allows for t h e generation of
'secondary' X-rays by interaction of higher energy
X-ray p h o t o n s with a t o m s . T h e s e corrections are
applied iteratively until satisfactory convergence has
been reached.
A m o r e complex m e t h o d is required for an E D S
(Statham, 1981) because of t h e presence of spurious
p e a k s and c o m m o n overlapping p e a k s in t h e spec
t r u m : these must be r e m o v e d before carrying out
t h e Z A F corrections. ' E s c a p e ' peaks (caused by
ionization of Si inner shell electrons in t h e detector,
and displaced by t h e energy of t h e S i K transition
from t h e p a r e n t p e a k ) and sum peaks (caused by
simultaneous arrival of two photons) must clearly b e
r e m o v e d . In o r d e r t o separate peaks from back
g r o u n d , either a m o d e l for t h e shape of the back
ground can be generated or the peaks can be removed
in stages until n o n e r e m a i n . Overlapping peaks pro
vide t h e major p r o b l e m in E D S analysis. A major
element will g e n e r a t e several p e a k s , s o m e of which
may coincide with the main p e a k of a minor element.
T o separate p e a k s , an accurate idea of their s h a p e ,
a
314
either from a theoretical m o d e l , o r a 'library' of

standard shapes, is required. Potential p r o b l e m s
with p e a k overlap c a n b e j u d g e d from Fig. 9.12. In
severe cases (e.g. t h e analysis of small a m o u n t s of
F e in an M n m i n e r a l ) , quantitative analysis with an
E D S may n o t b e possible. It is thus i m p o r t a n t t o b e
a w a r e of t h e particular p r o b l e m s of E D correction
p r o c e d u r e s in o r d e r t o eliminate spurious results
although m a n y m o d e r n systems automatically advise
on possible overlaps.
A s a n alternative t o t h e Z A F p r o c e d u r e , many
a u t h o r s correct using empirical 'a-factors' ( B e n c e &
A l b e e , 1968) which summarize t h e effect of o n e
e l e m e n t o n t h e o t h e r s present. This process involves
less c o m p u t a t i o n t h a n t h e Z A F m e t h o d a n d can
obtain near-equivalent results, b u t is specific t o o n e
accelerating voltage a n d take-off angle (angle b e
tween electron b e a m a n d specimen surface).
Generally, results for unusual materials should,
wherever possible, b e checked against reference
materials of similar composition in case of deficien
cies in t h e specific p r o g r a m m e used.
A N A L i s i a USING AN SEM
In t h e past t h e r e h a s b e e n very little use of S E M s b y
sedimentologists for quantitative analysis. T h e p r o b
lem is t h a t t h e p r e - e m i n e n t design a i m h a s b e e n
spatial resolution rather t h a n analytical convenience.
Low take-off angles h a v e led t o high absorption
corrections being necessary a n d t h e lack of optical
microscope attachments have led t o difficulties in
specifying t h e area t o b e analysed. This situation has
now changed with t h e introduction of c o m b i n e d
S E M - m i c r o p r o b e s a n d t h e increasing u s e of backscattered electron imagery t o relate chemical a n d
p e t r o g r a p h i c features ( H u g g e t t , 1984a). If speci
m e n s a r e polished as for n o r m a l m i c r o p r o b e work
t h e n t h e situation is t h e s a m e as t h a t described in
t h e previous sections.
U s e of t h e S E M in qualitative analysis (and hence
identification) is widespread in sedimentological
studies a n d is striaghtforward if t h e alternatives a r e
k n o w n a n d chemically distinct. Otherwise m o r e care
is n e e d e d : a n excellent s u m m a r y of guidelines for
qualitative analysis is given in Goldstein et al. (1981,
chapter 6 ) . Often analysis is u n d e r t a k e n o n fracture
surfaces of rock chips: h e r e o n e must b e particularly
aware of possible stray X-rays g e n e r a t e d from ad
j a c e n t minerals or t h e sample holder.
ANALYSIS USING A STEM (SCANNING

TRANSMISSION ELECTRON MICROSCOPE)
This instrument enables analysis of areas as small as
510 n m in d i a m e t e r , since the electron-transparent
specimens required a r e s o thin that t h e r e is n o
spreading effect of t h e electron b e a m . A l s o , given a
negligible specimen thickness, t h e r e a r e n o absorp
tion o r fluorescence effects s o t h e correction p r o
c e d u r e is simplified. H i g h accelerating voltages, of
t h e o r d e r of 100 k V , a r e used usually in conjunction
with a Si(Li) detector (see review article by G o o d h e w
& C h e s c o , 1980).
Polished thin sections a r e m o u n t e d o n a metal
grid a n d thinned b y i o n - b e a m milling until holes
start t o a p p e a r ( P h a k e y , Curtis & O e r t e l , 1972). T o
b e certain that specimen thickness is negligible, areas
next t o holes are analysed (Ireland, Curtis & W h i t e m a n , 1983). T h e b e a m size must b e above a certain
m i n i m u m for each mineral t o avoid loss of volatiles
such a s alkali metals. T h e correction p r o c e d u r e
involves a k n o w l e d g e of t h e relative efficiencies of
X-ray generation of t h e e l e m e n t in question relative
t o , for e x a m p l e silicon, d e t e r m i n e d b y analysis o f
thinned standards (Cliff & L o r i m e r , 1975). T h e u s e
of a S T E M is powerful, n o t only because of t h e
spatial resolution of t h e analysis, b u t also because
T E M images c a n b e obtained t o illustrate t e x t u r e s ,
and selected-area diffraction patterns may b e obtain
ed from grains analysed: hence t e x t u r e , mineralogy
and crystal structure can b e d e t e r m i n e d o n s u b micron-sized grains. T h e S T E M can also b e used in
other kinds of ways: for example in t h e analysis of fine suspended s e d i m e n t , S T E M analysis of indivi
dual particles can allow t h e interpretation of 'bulk'
(100 u m a r e a ) analyses in t e r m s of mineralogical
percentages (Bryant & Williams, 1982).
9.6.3 X-ray fluorescence

X R F analysis is a s t a n d a r d technique in hard-rock
petrology a n d in soft-rock circles it is frequently
used for t h e whole-rock analysis of m u d r o c k s , less
often for sandstones a n d rarely for c a r b o n a t e s a n d
evaporites. T h e principle behind this t e c h n i q u e is
that w h e n a sample is b o m b a r d e d with high energy
X-rays, secondary radiation is e m i t t e d , with t h e
wavelengths a n d intensities d e p e n d e n t o n t h e ele
m e n t s present. M e a s u r e m e n t of t h e intensity of t h e
characteristic radiation for a particular element gives
a value reflecting its concentration in t h e sample.
T h e emission from standards is m e a s u r e d first t o

produce a calibration curve, against which t h e u n
k n o w n samples an be c o m p a r e d . Primary X-rays a r e
p r o d u c e d in a n X-ray t u b e , commonly with a rho
dium target, a n d t h e secondary radiation emitted is
passed through a collimator system. T h e various
wavelengths are then resolved by diffraction off L i F
or P E T crystals. T h e radiation passes t o a counter
system, with a flow p r o p o r t i o n a l c o u n t e r being used
for light elements ( < 2 2 ) a n d a scintillation counter
for heavy elements. T w o types of X R F system a r e
currently available: wavelength dispersive ( W D ) and
energy dispersive ( E D ) . E D systems a r e a m o r e
r e c e n t d e v e l o p m e n t (early 1970s) t h a n t h e W D units,
and have s o m e advantages in certain applications.
F o r e x a m p l e , E D is c h e a p e r a n d measures all ele
m e n t s , however, in general t h e detection limit is n o t
as low as with W D , a n d t h e r e a r e many instances of
spectral line overlap.
M a n y textbooks give details of t h e X R F techni
q u e ; see, e.g. Norrish & Chappell (1977), Jenkins &
de Vries (1970), Bertin (1975), J o h n s o n & Maxwell
(1981), T e r t i a n & Claisse (1982) a n d Potts (1987).
Samples for X R F analysis mostly consist of pow
d e r e d rocks m a d e u p into pressed pellets (briquettes)
or fused discs. F o r t h e pellets, t h e p o w d e r is mixed
with a commercially mixed binder, such as Mowoil,
and pressed t o 20,000 psi (1400 kg c m ) o r m o r e to
form a b r i q u e t t e . S t a n d a r d rocks a n d samples n e e d
to be p r e p a r e d in exactly t h e same m a n n e r t o achieve
t h e same packing density. Fused discs involve t h e
fusion of p o w d e r e d rock with lithium t e t r a b o r a t e o r
m e t a b o r a t e and t h e casting of t h e melt into a m o u l d .
W i t h this t e c h n i q u e , t h e s a m p l e is h o m o g e n i z e d ,
and synthetic standards can b e p r e p a r e d m o r e read
ily. A l s o , discs a r e d u r a b l e a n d can b e m a n y times.
O n e disadvantage is that trace constituents a r e di
luted further by t h e addition of t h e flux. T h e pre
paration of fusion discs is fully discussed in Section
9.5.3. In recent years, pressed pellets have b e c o m e
m o r e p o p u l a r t h a n t h e disc although discs a r e still
considered better for major elements.
9.6.4 A t o m i c a b s o r p t i o n analysis
A t o m i c absorption s p e c t r o p h o t o m e t r y ( A A S ) h a s
b e e n widely used as a technique for elemental analy
sis of rocks a n d minerals, a n d also w a t e r s , since t h e
1960s. M o r e than 50 useful elements can be detected
and t h e technique has b e e n popular since it is a
relatively simple p r o c e d u r e , t h e instruments a r e
generally sensitive a n d reliable, a n d a basic A A
machines is n o t t o o expensive. Information o n A A S
is presented by A n g i n o & Billings (1972), J o h n s o n
& Maxwell (1981), Potts (1987), a n d others, a n d
most instruction manuals supplied with A A instru
m e n t s give much useful background material, as
well as guidance. H o w e v e r , it is possible that in t h e
future A A S will b e c o m e less widespread in its use as
I C P (Section 9.6.5) becomes m o r e readily available.
T h e principle of A A S is t h e absorption of radiant
energy by ground state a t o m s . W h e n a substance is
dispersed as a n atomic v a p o u r , it possesses t h e pro
perty of absorbing particular radiations, identical in
wavelength t o those which t h e substance can emit,
as w h e n it is h e a t e d for e x a m p l e . If a parallel b e a m
of radiation of intensity I is incident o n a n atomic
v a p o u r , I is t h e intensity of transmitted radiation
a n d v is t h e frequency, t h e n
0
I =
I exp(-K l)
- 2
X R F is ideal for t h e determination of major a n d

m i n o r e l e m e n t s , such a s Si, A l , M g , C a , F e , K , N a ,
T i , S a n d P in siliciclastic rocks a n d also for trace
e l e m e n t s , such as metals P b , Z n , C d , C r a n d M n .
L i m e s t o n e s , on t h e o t h e r h a n d , a r e rarely analysed
with X R F since a p o w d e r e d sample will include t h e
clay fraction, and it is t h e e l e m e n t s in t h e c a r b o n a t e
fraction which a r e mostly being sought. X R F h a s
been very successfully used for t h e analysis of bro
mine (and o t h e r elements) in halite.
w h e r e K is t h e absorption coefficient a n d / is t h e
atomic vapour thickness. T h e absorption coefficient
is also p r o p o r t i o n a l t o t h e concentration of t h e free
a t o m s in t h e vapour ( B e e r ' s law):
v
K dv
v
mc
Nvf
w h e r e / i s t h e oscillator strength (i.e. average n u m

b e r of electrons p e r a t o m which can b e excited by
t h e incident radiation), N is t h e n u m b e r of atoms
p e r c m which a r e capable of absorbing in t h e fre
quently v t o dv, c is t h e velocity of light, m is t h e
electronic m a s s a n d e t h e electronic charge. F o r
absorption t o t a k e place, t h e atoms must b e in t h e
g r o u n d state, n o t excited. T h e fraction of total
a t o m s available which exist in t h e excited stated
b e c o m e s significant only a t high t e m p e r a t u r e s , or for
a t o m s which have low ionization potentials. T h e
spectral lines a b s o r b e d b y a t o m s in their ground
state a r e referred t o as resonance lines.
A A analysis involves passing t h e characteristic
spectrum of a n element t h r o u g h a flame in which
a t o m s a r e present. If t h e a t o m s a r e of t h e s a m e
e l e m e n t , t h e n t h e r e is a reduction in intensity, d u e
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316
317
t o absorption, of a particular wavelength (Fig. 9.13).

T h e a m o u n t of light absorbed d e p e n d s u p o n t h e
concentration of t h e element in t h e vapour ( B e e r ' s
law, a b o v e ) . Generally, other metal a t o m s in the
flame do not interfere, since t h e r e is no light of
suitable wavelength for t h e m to a b s o r b .
T h e A A i n s t r u m e n t requires a light source, a
flame, an atomizer and a photomultiplier t o m e a s u r e
t h e transmitted raditation (Fig. 9.14). A m o n o
c h r o m a t o r is inserted b e t w e e n t h e flame a n d t h e
detection device so t h a t any interfering light, such as
generated by emission from t h e flame itself, is ex
cluded. Hollow-cathode lamps supply t h e radiation,
with t h e c a t h o d e m a d e of the element whose spec
t r u m is required. Multi-element lamps a r e p o p u l a r ,
and save on time. R e s o n a n c e lines a r e emitted from
t h e lamps when a current is passed and t h e c a t h o d e
is b o m b a r d e d by ions from t h e filler gas, usually
argon o r n e o n . T h e characteristic wavelengths of t h e
e l e m e n t a r e e m i t t e d as excited-state a t o m s r e t u r n to
t h e g r o u n d state. M a n y lines a r e p r o d u c e d for o n e
e l e m e n t , and several p r o m i n e n t o n e s , n o t a b s o r b e d
or interfered with by t h e atoms of t h e filler gas, a r e
usually available for use in the analysis. T h e flame
(or furnace) is t h e h e a r t of t h e A A machine w h e r e
t h e sample is atomized and through which t h e light
from t h e spectral source is passed. T h e t e m p e r a t u r e
of t h e flame is i m p o r t a n t ; it must be o n e at which
dissociation of all molecules in the sample occurs,
but at which a m i n i m u m of ionization takes place.
T h e gases used in t h e flame a r e usually mixtures of
two gases from acetylene, air, nitrous o x i d e , oxygen
and hydrogen. Air-acetylene is used for m u c h w o r k ,
set t o give a t e m p e r a t u r e of a r o u n d 2350 K. T h e
gases and sample are generally mixed in a b u r n e r
c h a m b e r or nebulizer before entering t h e flame. F o r
analysing elements in very low concentration, a gra
phite furnace, consisting of a t u b e of graphite heated
by electrodes, can be used instead of a flame. Higher
concentrations of t h e atoms are obtained and t h e r e
is a m o r e precise control o n t e m p e r a t u r e .
After transmission through t h e flame, t h e spectral
line of interest is selected at the m o n o c h r o m a t o r and
t h e n its intensity m e a s u r e d at t h e photomultiplier.
T h e reduction in light intensity before and while t h e
sample is in t h e flame, i.e. t h e a b s o r b a n c e , is dis
played as a m e t e r reading, chart record o r digital
printout. While m e a s u r e m e n t s are being m a d e t h e
instrument must be stable, i.e. t h e t e m p e r a t u r e of
t h e flame must not change, nor the o u t p u t from t h e
l a m p . R a t e s of atomization of samples and standards
must also b e similar. M o d e r n instruments are quite
Monochromator
to
Detector
Flame
cathode
to
Hollow
cathode
lamp
Lens
Filter
Slit
anode
Cloud
chamber
Fuel gas =={
(b)
Oxidant gas
Output
Nebulizer
1
CD
Sample
Fig. 9.14. Basic features of an atomic absorption spectrometer.
Reference beam
(rj)
Wavelength
Sample beam
Fig. 9.13. Sketches to illustrate the principle of atomic

absorption analysis, (a) In the hollow-cathode lamp, a
spectrum of the element to be determined is produced.
(b) In the flame, if the element in question is present in
the atomic vapour of the sample then absorption takes
place, so that the intensity of the spectrum is 'reduced'.
(c) At the monochromator, only a narrow band of
wavelength is allo.wed to pass, that including the
resonance line of the element to be determined, (d) At
the detector, the reduced intensity of the resonance line is
measured.
complicated in o r d e r to o v e r c o m e these sorts of
p r o b l e m s . F o r e x a m p l e , m a n y instruments have a
d o u b l e - b e a m system, w h e r e b y t h e light is passed
alternately t h r o u g h the flame and r o u n d t h e flame
by a system of mirrors, and t h e ratio of t h e inten
sities is m e a s u r e d (Fig. 9.15).
Samples are presented to t h e A A m a c h i n e in
solution and t h e instrument is calibrated by running
standards, either p u r e , off-the-shelf solutions with
k n o w n concentrations of t h e e l e m e n t , o r solutions
of rocks of k n o w n composition. A range of s t a n d a r d
solutions is m a d e u p with different concentrations;
absorbances are measured and a calibration line is
constructed. This should b e a straight line, as p r e
dicted by B e e r ' s law, b u t at higher concentrations it
m a y b e a curve.
http://jurassic.ru/
Flame"
INTERFERENCE
In atomic absorption analysis, interference is not
generally a major p r o b l e m . Spectral interference
can arise w h e r e two e l e m e n t s h a v e r e s o n a n c e lines
at a similar wavelength, resulting in a positive error
as t h e two signals a r e a d d e d together. A n alternative
line t o m e a s u r e can usually be found. S o m e metals
have a low ionization potential so that a smaller
n u m b e r of atoms remain in t h e ground state w h e r e
they can a b s o r b their characteristic radiation. T h i s
ionization interference can be overcome by adding
certain elements to t h e solution to suppress t h e
ionization. Chemical interference results from ele
ments combining to form stable c o m p o u n d s which
do not break down in t h e flame to form ground state
a t o m s . Negative errors arise, or even no absorption
at all occurs. T o overcome this, an excess of a metal
is a d d e d which can c o m p e t e with t h e metal being
d e t e r m i n e d for combination with; t h e interfering
To monochromator
and detector
Fig. 9.15. Basic features of a doublebeam atomic absorption instrument

whereby light from the lamp is
alternately passed through and past
the flame.
element. Alkaline earth metals are p r o n e to inter

ference. C a
for e x a m p l e , shows t h e effect of
interference in t h e presence of S 0 ~ , P 0 ~ , Al
a n d Si, w h e n complexes like CaAl o r CaSi a r e
formed. T h e addition of large a m o u n t s of strontium
(in the form of S r C l ) or l a n t h a n u m ( L a C l . 6 H O )
can o v e r c o m e this source of error. M a n g a n e s e can
be interfered with by Si, and then C a
is added.
W i t h strontium, there is a problem of ionization
interference, especially in t h e presence of N a and
K , a n d so l a n t h a n u m o r potassium (KC1) is a d d e d .
T h e p r o b l e m of interference is dealt with at length in
A n g i n o & Billings (1972), J o h n s o n & Maxwell (1981)
and Potts (1987).
2 +
2 +
SAMPLE PREPARATION
A A S has b e e n widely used in t h e analysis of lime
stones and dolomites since t h e interests h e r e are
318
mostly in the elements contained within t h e car

b o n a t e lattice. T o obtain t h e solutions, p o w d e r e d
samples (0.2 g is a suitable weight) a r e dissolved in
acid which is sufficiently strong t o t a k e u p t h e car
b o n a t e , but not so strong that it completely dissolves
or leaches t h e insoluble residue (clays, o p a q u e s ,
etc.). F o r limestones, 3 % v/v cold acetic acid (25 ml
on 0.2 g) overnight is sufficiently strong, and t h e n
solutions can be m a d e u p t o 50 ml. B r a n d & Veizer
(1980) used 3 % ( 8 % v/v) HC1 for 5Vi h o u r s ; after
this length of time t h e insoluble residue was exten
sively leached. W i t h dolomites, stronger acid is re
quired and 10% HC1 at 60C for 4 h o u r s is widely
used. With dolomite-calcite mixtures s o m e trial and
e r r o r may be required since dolomite solubility does
d e p e n d on its ordering and stoichiometry. B u r n s &
B a k e r (1987) first leached a mixed s a m p l e with
acetic acid buffered with a m m o n i u m acetate ( p H = 5 )
for 30 minutes t o r e m o v e t h e calcite. After filtering
and rinsing, t h e r e m a i n i n g solid was leached in 1M
HC1 for 15 m i n u t e s to t a k e u p t h e d o l o m i t e .
O n c e solutions of p o w d e r e d rock have b e e n p r e
p a r e d t h e n aliquots can b e r e m o v e d and diluted as
a p p r o p r i a t e for t h e machine. Several dilutions m a y
b e necessary t o bring t h e u n k n o w n sample within
the r a n g e for t h e e l e m e n t in question in t h e instru
m e n t , b u t with a u t o m a t i c diluters this is neither time
consuming n o r likely to introduce e r r o r s .
T h e c o m m o n elements d e t e r m i n e d for c a r b o n a t e s
a r e C a , M g , Sr, N a , F e a n d M n . For s o m e of these it
will b e necessary t o add solutions to p r e v e n t inter
ference, as noted earlier. T h e quantity of r o c k fre
quently used in A A S (0.2 g) is not great, b u t m u c h
smaller weights can b e used if judicious use of t h e
solution is m a d e . This is particularly useful for car
b o n a t e s , w h e r e grains and different c e m e n t genera
tions can be extracted with a dental drill or scalpel
from thin sections. If a graphite furnace is available,
then sample weights as low as 10 m g can b e used.
A A S can also b e used for o t h e r sedimentary rocks,
sandstones, a n d m u d r o c k s for e x a m p l e , although Xray fluorescence can b e easier. A whole-rock t a k e u p is obviously necessary so that much stronger (and
m o r e dangerous) acids a r e required. A mixture of
H F and H C 1 0 (perchloric), 2 ml of each o n 0.2 g
p o w d e r , h e a t e d o n a h o t plate, will b r e a k d o w n t h e
rock. A mixture of H F , H S 0 and HC1 ( a q u a regia)
is also popular. B l a n k s a r e also m a d e in t h e s a m e
t a k e - u p p r o c e d u r e , as a r e s t a n d a r d r o c k s , if these
are being used.
4
elements present: atomic (or optical) emission spec

t r o m e t r y ( I C P - A E S or I C P - O E S ) and mass spectro
metry ( I C P - M S ) . T h e i n s t r u m e n t a t i o n for I C P - A E S
has been available since the late 1970s, w h e r e a s
I C P - M S is an early 1980s d e v e l o p m e n t . I C P - A E S is
related to A A S , w h e r e a s I C P - M S is m o r e related to
stable isotope analysis.
9.6.5 Inductively-coupled plasma

spectrometry
A plasma is a luminous volume of gas with a t o m s
and molecules in an ionized state. In I C P analysis
t h e gas used is usually argon. T h e plasma is formed
by passing the gas through a torch m a d e of q u a r t z
glass. A t e m p e r a t u r e of a r o u n d 10000 K is p r o d u c e d
by a radiofrequency generator connected to copper
work coils surrounding t h e torch (Fig. 9.16). T h e
plasma is constrained by the n a t u r e of t h e orifice of
t h e gas injector tube in t h e torch and t h e gas flow
rate so as to p r o d u c e a toroidal or d o u g h n u t s h a p e d
fireball. Nitrogen, or m o r e argon, is used as a coolant
gas to stabilize t h e plasma centrally in t h e torch a n d
to prevent t h e o u t e r glass j a c k e t of t h e t o r c h from
fusing or distorting. With t h e plasma established,
t h e s a m p l e , in acid-solution, is passed through a
nebulizer to form an aerosol a n d t h e n mixed with
t h e argon injector gas. In the fireball of t h e torch t h e
sample is completely atomized at t h e very high
temperatures there.
Inductively-coupled
plasma atomic emission
spectro
metry ( I C P - A E S ) works on the principle that when
atoms and ions are excited t h e n light is emitted, and
t h e wavelengths a n d intensities of t h e light reflect
the elements present in t h e sample. T h e emission
spectra from atomization in the plasma are analysed
with a high resolution s p e c t r o m e t e r within the wave
length range of 170780 n m . T h e general arrange
m e n t of an I C P - A E S machine is shown in Fig. 9.17.
O n e of t h e major advantages of I C P - A E S over A A S
is that many elements can be analysed simultane
ously; s o m e instruments have a polychromator spec
t r o m e t e r capable of a c c o m m o d a t i n g m o r e t h a n 50
spectral lines. O n e of t h e p r o b l e m s with I C P - A E S
has been spectral interferences from overlaps be
N o w t h a t t h e s a m p l e h a s b e e n atomized and
ionized, t h e r e a r e t w o completely different techni
q u e s for measuring t h e concentrations of t h e various
319
tween emission lines of different e l e m e n t s , so that

line selection and t h e identification and correction of
overlap interferences a r e i m p o r t a n t considerations.
A n o t h e r attraction of I C P - A E S is that for many
elements t h e detection limit is m u c h lower t h a n for
A A S , although for many metallic elements t h e de
tection limits are about t h e same a n d , for Z n , N a
and K , A A S is b e t t e r . A n o t h e r a d v a n t a g e is t h a t
calibrations are linear over 4 or 5 orders of magni
t u d e so that dilutions are generally unnecessary and
major, minor and trace elements can b e d e t e r m i n e d
in o n e run, lasting only a few minutes. Only a small
a m o u n t of solution is also necessary for I C P - A E S ,
0.52.0 ml typically, so that very small quantities of
sample, 1 10 m g , can b e used. P o w d e r e d rocks a r e
dissolved in acid and p r e s e n t e d t o t h e m a c h i n e in a
very dilute form. F o r c a r b o n a t e s , w h e r e I C P analysis
is increasing in popularity, a scheme of solution pre
paration is p r e s e n t e d later in this I C P section. Stan
dard solutions can be p r e p a r e d with a similar matrix
to t h e samples (see P o t t s , 1987, p . 180 for recipes) or
they can be bought off the shelf. Sample solutions
a r e frequently spiked with an internal standard to
Fixed diffraction
grafting
Entrance slits
to
mass spectrometer
for ICP-MS analysis
MS or AES
/
To
emission spectrometer
for ICP-AES analysis
t
Tailflame
Radio frequency
generator
Diffracted lines
Sample
capillary
Fixed exit
slit assmbly
Sample
solution
11
Cloud
chamber \
Waste (-97%)
Fig. 9.16. Schematic representation of the inductivelycoupled plasma instrument.
Fig. 9.17. Schematic representation

of inductively-coupled plasma atomic
emission spectrometer (ICP-AES).
Mirror
http://jurassic.ru/
I
1
I.
320
c o m p e n s a t e for variations in instrument sensitivity,

matrix effects, electronic drift, e t c . Identical con
centrations of an e l e m e n t n o t present in t h e samples
a r e a d d e d to all solutions and then t h e ratio of each
m e a s u r e m e n t t o t h e intensity of t h e internal stan
d a r d will permit d e t e r m i n a t i o n of any error.
Inductively-coupled
plasma mass spectrometry ( I C P M S ) is p e r h a p s t h e most exciting d e v e l o p m e n t on
t h e analytical front in d e c a d e s . T h e t e c h n i q u e has all
t h e advantages of I C P - A E S : rapid, multi-element
trace analysis, but with much lower detection limits
(ppb-level), including t h e d e t e r m i n a t i o n of indivi
dual isotope ratios. In I C P - M S , t h e inductivelycoupled argon plasma is used as a source of ions and
their mass spectrum is m e a s u r e d using a q u a d r u p o l e
mass spectrometer. T h e argon plasma is p r o d u c e d in
t h e same way as in I C P - A E S (Fig. 9.16) and t h e
sample in solution is nebulized into t h e p l a s m a ,
although t h e torch is now in an horizontal position.
A t the very high t e m p e r a t u r e s of t h e I C P , t h e sample
is very efficiently atomized and ionized, and t h e r e
a r e few interferences. T h e ion b e a m emerging from
t h e torch is collimated by cones and skimmers and
focussed by a n u m b e r of plates set at particular
potentials (see Fig. 9.18). T h e b e a m is t h e n trans
mitted through t h e q u a d r u p o l e mass filter w h e r e t h e
mass p e a k s of t h e ions a r e m e a s u r e d in an electron
channel multiplier ion d e t e c t o r , on t h e basis of their
mass to charge ratio. T h e pulses are amplified a n d
stored in a multi-channel analyser and quickly p r o
cessed by m i c r o c o m p u t e r .
I C P - M S could well be t h e routine instrument for
geochemical analysis in t h e years to c o m e , with its
detection limits lower t h a n most o t h e r t e c h n i q u e s ,
t h e rapidity of multi-element analyses and relatively
simple sample p r e p a r a t i o n . Much I C P - M S d a t a will
b e forthcoming in t h e next few years and it is possible

t h a t particular e l e m e n t s will b e found t o have en
vironmental and diagenetic significance.
T w o potentially exciting d e v e l o p m e n t s with I C P S
are in t h e use of lasers on thin sections of rock a n d in
the study of fluid inclusions. T h e energy of a laser
b e a m can be used t o vaporize material so t h a t it is
possible to zap a rock slice and h a v e t h e volatilized
material carried into an I C P m a c h i n e for analysis
( T h o m p s o n , G o u l t e r & Sieper, 1981). Fluid inclu
sions can be analysed by heating t h e crystals con
taining t h e m until t h e inclusions b r e a k and t h e n
having t h e contents carried in a s t r e a m of argon into
t h e I C P instrument for analysis ( T h o m p s o n et al.,
1980).
Inductively-coupled plasma techniques a r e treat
ed at length in T h o m p s o n & Walsh (1983) and Potts
(1987) and a review is given by T h o m p s o n (1986).
In making up standards in practice it proves convenient to use commercially

available cation solutions wherever possible, otherwise solid salts. The quoted
levels of impurities for elements to be analysed must be carefully checked to
see if they intrude significantly on background levels. For Ca, only Specpure
grade solid C a C 0 is sufficiently free of Sr for this purpose
3
Name of
standard
Acid-blank
2C
1C
0.5C
0.1C
1.5CM
1CM
0.5CM
0.1CM
CI
C2
C3
C4
Dl
D2
D3
D4
D5
ICP-AES
Carbonate workers are likely to want to use I C P - A E S
in preference to o t h e r solution-based techniques
w h e n e v e r it is available: b o t h because of its rapid
sample t h r o u g h p u t and capability for simultaneous
analysis of m a n y e l e m e n t s , and because of t h e small
sample size (1 10 mg) required. Microsampled
powders can t h u s be analysed for both cations and
isotopes. Since t h e r e is little published on techni
q u e s specific to c a r b o n a t e s , a detailed account is
given h e r e . It also serves to illustrate m o r e generally
an a p p r o a c h t o standardization of chemical analysis
a n d correction of results.
A l t h o u g h d a t a can b e o b t a i n e d using generalp u r p o s e s t a n d a r d s designed for silicate rocks,, con
siderable e r r o r s a r e likely t o result b e c a u s e of t h e
Ion
detector
Pulse
amplifier
ICZH
ICP
torch
Sampling cone
and skimmer
Table 9.7. Equivalent concentrations of standards solutions for calcite and

dolomite analysis by ICP-AES. The figures represent the model concentrations
of an element expressed as if it were a solid carbonate. For example, calcite
contains 400,000 ppm Ca and is modelled by standards 1C, and CI to C4.
Stoichiometric dolomite contains 200,000 ppm Ca and 120,000 ppm Mg and is
modelled by standards 1CM, and D l to D5. When the samples are dissolved,
there will be a dilution factor, for example 10 mg solid in 10 g (about 10 ml)
solution corresponds to a dilution factor of 1000. In this case the actual
concentrations of Ca and Mg in standard solutions would be 1/1000 of those
given in the table.
ANALYSIS OF CARBONATES USING
Ion extraction
electrodes
Quadrupole m a s s
filter
Multichannel
analyser
and display
Fig. 9.18. Schematic representation of the inductively-coupled plasma mass spectrometer (ICP-MS).
321
Ca
Mg
Sr
Fe
ppm ( u g g )
Mn
_
800,000
400,000
200,000
40,000
300,000
200,000
100,000
20,000
400,000
400,000
400,000
400,000
200,000
200,000
200,000
200,000
200,000
50
200
500
4,000
50
200
500
2,000
2,000
120,000
80,000
40,000
8,000
200
400
1,000
5,000
120,000
120,000
120,000
120,000
120,000
200
400
1,000
5,000
200
1,000
5,000
20,000
100,000
different acid matrix and major cation compositions

of samples and standards. Instead, synthetic stan
d a r d s , closely matching t h e samples in terms of
major-ion composition and acid type and strength
should b e p r e p a r e d . T a b l e 9.7 illustrates a possible
r a n g e of standards. T h e acid-blank is a solution
containing impurity-free acid of the same concentra
tion as in samples and all standards and is used to
m o n i t o r t h e baseline for background levels. T h e
series 2 C , 1C, 0.5C, 0.1C provides a Ca calibration,
t h e t o p standard having twice t h e Ca concentration
expected in a p u r e c a r b o n a t e sample. A l t h o u g h a
http://jurassic.ru/
Na
- 1
200
400
1,000
5,000
.200
400
1,000
2,000
2,000
40
200
500
2,000
40
200
2,000
10,000
10,000
linear calibration b e t w e e n concentration and output

voltage from the instrument is expected this should
be directly tested; deviations from a straight-line
relationship are likely at high concentrations (Fig.
9.19a). This series of standards additionally allows
t h e effect of major element (Ca) interference on the
background of a minor element to be quantified
(line C on Fig. 9.19b). T h e C M series a r e for Ca and
Mg calibrations for dolomites, 1CM being the ap
p r o p r i a t e strength for a stoichiometric dolomite
sample. T h e effects on backgrounds are shown as
line C M in Fig. 9.19b; combining data from lines C
322
a n d C M allows the s e p a r a t e effects of C a and M g o n

background t o be quantified. Solutions C I t o C 4 a r e
mixed standards designed t o calibrate m i n o r ele
m e n t s across their likely r a n g e in calcites; likewise
D l to D 5 for dolomites, D 5 being included for
ankerites. M o r e extensive Fe-rich s t a n d a r d s would
be required for siderites. O t h e r minor elements such
as B a , P b , C u and Z n might well n e e d t o be included
in other investigations.
D o l o m i t e samples and calcite samples should b e
run separately to simplify t h e process of calibration
and possible p r o b l e m s of machine drift with t i m e .
D o l o m i t e samples should b e p r e c e d e d by t h e full set
of dolomite-matching standards and every tenth sam
ple followed by a mixed dolomite-matching s t a n d a r d
(e.g. D 4 ) and an acid-blank t o monitor drift in
b a c k g r o u n d values or sensitivity (Fig. 9.19c).
A correction p r o c e d u r e could be written into t h e
instrumental o u t p u t , b u t t h e c a r b o n a t e w o r k e r can
d o it personally with t h e advantage of a full under
standing of t h e corrections m a d e and potential
sources of e r r o r . It is not particularly difficult given
t h e availability of c o m p u t e r s p r e a d s h e e t software o n
which t h e calculations >can b e laid out. A l s o t h e r e
a r e only a few major elements for whose interference
effects m i n o r e l e m e n t concentrations h a v e t o b e
corrected.
A spreadsheet is a table o r matrix of material
typically consisting partly of text, partly of input
d a t a and partly of t h e results of calculations. T h e
instructions for carrying o u t calculations a r e ' h i d d e n '
in matrix cells. It is m u c h easier t o learn h o w t o
write a spreadsheet to carry o u t a series of correc
tions to results t h a n to write a c o m p u t e r p r o g r a m ,
and i n t e r m e d i a t e steps are m o r e easily seen. T h e
examples given h e r e were written using Microsoft
C o r p o r a t i o n ' s Multiplan speadsheet software.
A data spreadsheet is created of all t h e o u t p u t
voltages for the elements of interest for each sample
and standard. A second spreadsheet file (e.g. T a b l e
9.8) contains correction factors. Calculations for
each element in turn a r e performed o n s e p a r a t e
spreadsheets (e.g. T a b l e 9.9) which copy in d a t a and
correction factors as required from t h e o t h e r files.
A n o t h e r s p r e a d s h e e t then copies t h e results of these
calculations, totals t h e m , normalizes t h e m , a n d cal
culates m o l a r percentages.
A c o m p a r a t i v e study of t h e analysis of HC1 a n d
H3PO4 solutes was m a d e on 50 samples of calcite
a n d d o l o m i t e . A table of results is given in Fairchild
& Spiro (1987).
Output
voltage
(peak
minus
background)
Table 9.8. Example of a spreadsheet with factors used to

correct data to concentrations. The analysis numbers
identify which block of samples have similar correction
factors (as identified on plots like that of Fig. 9.19c) and
so can be corrected together by the factors in this table.
Stdwt is the standard weight (e.g. 10 mg of carbonate)
assumed to be dissolved. Cabkd is the Ca background in
volts, Cacorr is the inverse slope of the line in a plot like
that of Fig. 9.19(a), Cadrift is the rate of change of
Cacorr per analysis derived from a plot like that of Fig.
9.19(c). For Mg similar factors apply except that there is a
correction to apply to the Mg background because of the
presence of major Ca (CacorrMgbkd is equal to the slope
of plots like that of C in Fig. 9.19(b). For the other
elements similar factors apply except that for dolomites
there is also a magnesium correction for the background
representing the difference in slope per unit Ca of lines
CM and C o n Fig. 9.19(b)
region of
ine curvation
Element concentration
(a)
Background
level of
output
voltage
for minor
element
(b)
Output voltage (major element)

standard
(drift)
Output
voltage
for a
given
element
(c)
(no drift)
rapid drift (may have to

discard analyses)
acid-blank
10
20
30
40
50
Analysis number (time axis)

Fig. 9.19. Schematic illustrations of plots used to
calculate correction factors for ICP-AES analysis of
carbonates. CM and C refer to series of standards (Table
9.7).
T h e HC1 residues were o b t a i n e d by dissolving a
dried a n d accurately-weighed sample (in t h e r a n g e
5 - 4 0 mg) in 8 ml 1 0 % v/v Aristar-grade HC1. E a c h
sample was d e c a n t e d into a n e w vial w h e n e v e r t h e r e
was a discernable insoluble r e s i d u e . T h e insoluble
residue was weighed after twice dilution and decantation of t h e acid and evaporation o n a hotplate at
100C. T h e results show detection limits of 3.5 p p m
(Sr) t o 70 p p m ( F e ) calculated by t h e m e t h o d s of
Date
User
Analysis nos
Stdwt
Cabkd
Cacorr
Cadrift
Mgbkd
CacorrMgbkd
Mgcorr
Mgdrift
Febkd
CacorrFebkd
MgcorrFebkd
Fecorr
Fedrift
Mnbkd
CacorrMnbkd
MgcorrMnbkd
Mncorr
Mndrift
Srbkd
CacorrSrbkd
MgcorrSrbkd
Srcorr
Srdrift
Nabkd
CacorrNabkd
MgcorrNabkd
Nacorr
Nadrift
30/10/86
ijf
17-44
10
70
49.8
0
82
0.0068
4.6
0
86
0
0.0005
5.1
0
103
0
0.0005
1.17
-0.0028
115
0.023
0
0^0354
-0.000056
175
0.0050
0.0025
1.36
-0.002
323
T h o m p s o n & Walsh (1983) or 1 - 5 p p m calculated

using t h e less rigorous definition that detection limits
a r e t h r e e times t h e standard deviation of the
background.
T h e phosphoric acid solutes resulted from sample
dissolution for isotopic analysis. Because of t h e high
viscosity of 100% H3PO4, dilution to 12% H P 0 by
weight was required, even though this gives a high
dilution factor (w/w of t h e original c. 10 mg car
b o n a t e solid in final solution) of a b o u t 1:6000. T h e
proportion of insoluble residue was t a k e n to be t h e
same for each p o w d e r as d e t e r m i n e d by HC1 dis
solution. D e t e c t i o n limits were of t h e o r d e r of 2000
p p m for F e , 100 p p m for M n , and greater t h a n 40
p p m for Sr. N a analysis was essentially impossible
because of high N a impurity from P2O5, used to
increase t h e concentration of H P 0 , and difficult
to buy in sufficiently p u r e form. H o w e v e r , the ac
curacy of major element results was as good as for
t h e HC1 residues. It should b e concluded that as
long as a few milligrams of sample can be spared for
I C P E S analysis by HC1 dissolution, this will be
preferable to analysing phosphoric acid residues,
especially given t h e physical difficulties in handling
H P 0 , but for m i n u t e samples t h e latter might be
a p p r o p r i a t e . W h e r e m i n o r element and isotopic
variation occurs on a very fine scale the phosphoric
acid m e t h o d could also c o m e into its own (M.
C o l e m a n , 1986, p e r s . c o m m . ) , although this would
d e p e n d o n t h e d e g r e e of crushing of the sample. T h e
deliberate r e p e a t e d analysis of an i n h o m o g e n e o u s
sample crush, with an intimate mixture of two com
p o n e n t s differing in m i n o r element and isotopic
composition, could be used t o find t h e composition
of o n e end m e m b e r if t h e composition of t h e o t h e r is
k n o w n by o t h e r m e a n s .
3
T h e handling of small samples does create diffi

culties as is shown by analytical totals for the HC1
residues of Fairchild & Spiro (1987) which d o not
closely cluster a r o u n d 100% (Fig. 9.20). Normalized
analyses of reference materials in the same sample
batch a r e closely c o m p a r a b l e with results using o t h e r
analytical m e t h o d s , suggesting that t h e correction
factors used a r e generally valid. A n exception may
be t h e consistently low totals obtained on dolomites
with high sample weights (Fig. 9.20) which could be
d u e to i n a d e q u a t e allowance for line curvature of
t h e type shown in Fig. 9.19(a). O t h e r contributory
factors to totals deviating from 100% are errors in
weighing such small samples (variable water content
if insufficiently d r i e d ) ; errors in measuring insoluble
http://jurassic.ru/
lllllUliU
324

Table 9.9. Example of a spreadsheet used to correct output voltages (in this
case for Fe) to concentrations. The first four columns and column 15 are
automatically input from a data file. Columns 5 to 7, 10, 11 and 15 are
automatically input from the file of correction factors (Table 9.8). The first
steps are to compute the background Fe value allowing for the interference of
Ca and Mg; the final background (column 8) is then subtracted from the Fe
value output to give peak minus background in column 9. The Fe correction
(column 10) is then modified for any drift (column 11, see also Table 9.8) to
give a final correction (column 12) by which column 9 is multiplied to give the
Fe value in column 13. This value must then be corrected by the ratio of the
actual weight of carbonate minerals dissolved (column 14: total sample weight
minus insoluble residue) to the standard sample weight (column 15) to yield Fe
ppm (column 16)
1
2
3
4
5
6
7
8
9
10
11
1
Sample
bcs368v
f6962a
f6975a
f6989b
f6890a
m4208b
m3852
f6890b
f6963b
m3855
2
Ca
3731
4112
4858
2865
1287
5917
4102
4910
4314
2282
8
Fin bkd
98
97
102
94
89
103
96
99
98
92
9
p-b
207
5827
5897
10439
2467
3069
5392
6621
2272
6094
15
Stdwt
10
10
10
10
10
10
10
10
10
10
16
Feppm
1090
27263
26616
69141
41932
11950
31247
30979
12200
54529
5
4
3
Febkd
Fe
Mg
86
305
23300
86
22250 5924
86
31330 5999
86
16141 10533
86
6768 2556
86
33200 3172
86
20770 5488
86
26130 6720
86
23070 2370
86
11191 6186
10
Fecorr
5.1
5.1
5,1
5.1
5.1
5.1
5.1
5.1
5.1
5.1
:
11
Fedrift
0
0
0
0'
0
0
0
0
0
0
. - 17
FeCC-3
0.23
5.66
5.52
14.34
8.70
2.48
6.48
6.43
2.53
11.31
6
CacorrFebkd
0
0
0
0
0
0
0
0
0
0
12
Fin corr
5.1
5.1
5.1
5.1
5.1
5.1
5.1
5.1
5.1
5.1
7
MgcorrFebkd
0.0005
0.0005
0.0005
0.0005
0.0005
0.0005
0.0005
0.0005
0.0005
0.0005
13
Fe value
1057
29717
30076
53239
12580
15654
27497
33767
11590
31081
14
Weight
9.7
10.9
11.3
7.7
3
13.1.
8.8
10.9
9.5
5.7
. . I
Dolomite
x Calcite
85
90
95
100
Analytical total (%)
residues; minor dilution or evaporation of samples.

T h e s e factors will n o t affect t h e accuracy of normal
ized results. E v e n s o , t h e calculation of analytical
totals (necessarily involving weighing insoluble re
sidues) is an i m p o r t a n t part of t h e analytical pro
cedure a n d will allow errors t o be readily spotted.
9.6.6 Instrument neutron activation

analysis
This t e c h n i q u e is mostly used t o d e t e r m i n e t h e con
tents of rare earth elements ( L a , C e , N d , S m , E u ,
T b , Y b a n d L u ) , a n d u r a n i u m , t h o r i u m , hafnium
a n d t a n t a l u m ( a n d s o m e o t h e r trace elements) in a
variety of rock-types. T h e basis of N A A is that w h e n
material, in this case p o w d e r e d rock, is irradiated by
nuclear particles in a reactor, some of t h e atoms in
the sample interact with b o m b a r d i n g particles and
are converted into radioactive isotopes. T h e induced
radioactivity is separated, identified and m e a s u r e d
relative t o k n o w n standards. T h e elements a r e iden
tified by t h e characteristic energy ( g a m m a rays)
emitted during t h e radioactive decay. A gamma-ray
spectrometer is used as a detector, measuring t h e
energies and intensities of various y-ray p e a k s above
b a c k g r o u n d , which e m a n a t e from an activated sam
ple. Complicated mathematical processing of t h e
data is required t o separate t h e complex spectrum
into c o m p o n e n t s that correspond t o individual
radioactivities.
N A A is mostly used by hard-rock penologists for
r a r e earth a n d o t h e r e l e m e n t s , which a r e generally
present at t h e level of tens of ppb.- T h e technique
has b e e n used t o d e t e r m i n e R E E in s a n d s t o n e s and
http://jurassic.ru/
105
Fig. 9.20. Plot of sample weights

against analytical totals for HC1
residues of Fairchild & Spiro (1987).
110
m u d r o c k s , and data from A r c h e a n and Proterozoic

sediments h a v e b e e n used t o discuss t h e origin of
continental crust (see Taylor & M c L e n n a n , 1985)
and t h e a m o u n t of recycling which has taken place.
T h e r e a r e few studies of R E E in c a r b o n a t e rocks,
but Tlig & M ' R a b e t (1985) have recently shown that
typical R E E distribution p a t t e r n s a r e preserved
during dolomitization, although total a m o u n t s a r e
reduced. T h e decrease correlates with Sr a n d 8 O
a n d is related t o lower salinity (meteoric-marine
mixed) dolomitizing fluids. R E E determinations can
also be m a d e by I C P .
l s
9.6.7 Stable isotopes

T h e main variations in technique arise from t h e
mineralogical siting of t h e isotope concerned a n d so
the text is divided u p accordingly. Covered here a r e
sulphur and oxygen isotopes in sulphates, sulphate
isotopes a n d sulphides, c a r b o n a n d oxygen isotopes
in carbonates a n d oxygen isotopes in silica. T h e
r e a d e r is referred t o t h e following references for
analyses of o t h e r minerals. F o r t h e preparation of
organic carbon in its various forms: see D u n b a r &
Wilson (1983) for coal, Jackson, Fritz & D r i m m i e
(1978) and Schopf (1983) for kerogen a n d extractable organic m a t t e r , a n d Schoell (1980) for m e t h a n e .
T h e extraction of oxygen from phosphatic shell
material for 5 O determinations is covered by
T u d g e (1960), while C a r o t h e r s & K h a r a k a (1980)
deal with t h e m e a s u r e m e n t of 5 C on dissolved
H C 0 3 ~ ! Finally, t h e standard reference for 5 O
w o r k o n w a t e r s is t h e C 0 equilibration m e t h o d of
Epstein & M a y e d a (1953).
l s
1 3
l s
326
C o l e m a n & M o o r e (1978) outlined a further im

p r o v e m e n t by mixing their sulphate sample (15 mg)
with c u p r o u s oxide ( C u 0 , 200 mg) a n d p u r e q u a r t z
sand (600 mg, < 7 5 um) and heating the mixture
u n d e r v a c u u m to 1120C. A l t h o u g h they w e r e un
sure of t h e exact reaction involved, r e p e a t e d use
proved yields of 99.8 1.3% and gave 5 S values
on a laboratory reference s a m p l e , virtually identical
to those o b t a i n e d via t h e t e c h n i q u e of reduction and
s u b s e q u e n t oxidation.
Magnet
MASS S P E C T R O M E T R Y
In simple terms a mass s p e c t r o m e t e r m a y b e t h o u g h t
of as an instrument to m e a s u r e relative differences
in t h e a b u n d a n c e of certain isotopes of a given
e l e m e n t . In all cases t h e sample is i n t r o d u c e d as a
gas (e.g. C 0 , S O 2 ) via an inlet system designed t o
allow t h e rapid comparison of t h e sample with a
reference gas p r e p a r e d at t h e s a m e time (Fig. 9.21).
O n c e inside t h e i n s t r u m e n t t h e gas is ionized by
electrical b o m b a r d m e n t in t h e 'source r e g i o n ' , the
ions are accelerated in an electrical field a n d collim a t e d t o e m e r g e as an ion b e a m . T h e ions within
this b e a m a r e then s e p a r a t e d according to their mass
by passage t h r o u g h a magnetic field, e m e r g i n g as a
series of b e a m s , each with a given mass a n d a
c h a r g e . Collectors for e a c h m a s s , usually a r r a n g e d
in t h e form of a metal c u p or F a r a d a y cage, are
placed at t h e a p p r o p r i a t e spot to collect particular
i o n s , which t h e n discharge o n t o t h e m . T h e strength
of t h e discharge, p r o p o r t i o n a l to t h e n u m b e r of ions
of each mass p r e s e n t , is t h e n registered electroni
cally and displayed as a ratio or, normally, trans
ferred automatically for s t o r a g e in a m i c r o c o m p u t e r .
3 4
To high-vacuum
system
a n c
j amplifier
Fig. 9.21. Schematic representation of mass spectrometer

(from Dodd &,Stanton, 1981).
Generally t h e p r e p a r a t i o n t e c h n i q u e s for m e a s u r i n g
sulphur isotope ratios seek t o yield p u r e sulphur
dioxide ( S 0 ) , although s o m e a u t h o r s prefer S F as
a n e n d - p r o d u c t . Sulphides a r e c o n v e r t e d t o S 0 by
reaction with a suitable oxidizing agent such as
C u 0 or V 0 , while sulphates h a v e b e e n tradi
tionally c o n v e r t e d first t o t h e sulphide b y a variety of
chemical m e a n s , a n d t h e n oxidized in a similar m a n
ner. Since a b o u t 1970, h o w e v e r , a variety of t h e r m a l
decomposition m e t h o d s h a v e b e e n d e v e l o p e d which
allow t h e direct reduction of sulphates t o S 0 .
2
B a S 0 - B a O + ?0
4
+ SO .
1 9
2FeS + 10BrF
2
4SF + 2FeF + 5Br .
T h e reaction p r o d u c t s are sufficiently distinct chemi

cally to allow t h e easy separation and purification of
SF .
6
T h e a p p a r e n t lack of any widespread acceptance

of SF6 in sulphur isotope w o r k in t h e face of its
obvious advantages m a y b e related to t h e toxicity of
B r F ~ B r F and their high cost. M o r e o v e r , sul
p h a t e s still require reduction to metal sulphide be
fore reaction to S F so that t h e direct reduction
m e t h o d to S 0 is still m o r e convenient.
5
O X Y G E N I S O T O P E S IN S U L P H A T E S
T h e r e are two possible objectives: the analysis of
0 / 0 in t h e sulphate or that associated with inter
stitial w a t e r of crystallization.
In the former case, t h e m o s t widely used p r e p a r a
tion t e c h n i q u e is the graphite reduction m e t h o d of
Rafter (1967). E a r l i e r w o r k by Rafter (1957) had
proved t h e general feasibility of producing C 0 by
reduction with carbon according to t h e reaction:
1 8
1 6
BaS0
+ 2C ^
BaS + 2 C 0
S0
V E R S U S SI
D e s p i t e t h e chemical stability of S O , , it d o e s cause

s o m e p r o b l e m s ( R e e s , 1978). INTER-laboratory cor
relations are m a d e difficult by t h e t e n d e n c y of S 0
2
but at t h e t e m p e r a t u r e s involved ( 9 0 0 - 1 0 0 0 C ) a
C 0 - g r a p h i t e reduction reaction also occurred which
c o n v e r t e d some of the C 0 to C O . H e therefore
developed a modified t e c h n i q u e in which t h e first
a p p e a r a n c e of C O caused a pressure change in t h e
vacuum line which induced a high voltage electrical
discharge across two e l e m e n t s ; converting C O to
2
http://jurassic.ru/
T h e B a O fused with t h e silica a n d p u r e S 0 was

collected in a nitrogen cold t r a p . Yields w e r e re
p o r t e d as 100 1 % . T h e r e w a s a little c o n t a m i n a
tion by C 0 from c a r b o n residues on t h e v a c u u m
line which was r e m o v e d by a 1:1 solution of H F .
Sample weights ranged from 20 t o 50 m g . Bailey &
Smith (1972) modified the m e t h o d by introducing
c o p p e r m e t a l t o t h e system a n d reducing t h e t e m
p e r a t u r e of reaction to 800C which allowed a b e t t e r
control over t h e generation of S 0 , k e e p i n g p r o d u c
tion of SO3 to a m i n i m u m . T h e y also p o i n t e d o u t
that p o w d e r e d silica n e e d not b e a d d e d since t h e r e
was sufficient o n t h e walls of t h e v a c u u m line.
2
T h e t r e a t m e n t of sulphates may b e conveniently

divided into t h r e e steps: (a) purifying the s a m p l e
s u l p h a t e , (b) r e d u c t i o n to sulphide-sulphur a n d (c)
oxidation to S O . T h e last step is essentially t h e
s a m e as that for sulphides and will b e outlined u n d e r
that heading.
(a) Isolation of p u r e sulphate is usually achieved
by dissolution of solid sulphates (in HC1 or N a C l
solutions for calcium s u l p h a t e ) a n d precipitation as
PURIFICATION AND REDUCTION

PROCEDURES FOR SULPHATES
T h e p r e p a r a t i o n p r o c e d u r e is relatively straight
forward for a p u r e s a m p l e , requiring only the oxida
tion of t h e sample to yield S 0 . U s e of oxygen as t h e
oxidizing agent ( T h o d e et al., 1961) required ex
tremely high t e m p e r a t u r e s (1350C) to hinder frac
tionation by S 0 p r o d u c t i o n , and to avoid formation
of A g S 0 from A g S ( R o b i n s o n & K u s a k a b e , 1975).
N e i t h e r p r o b l e m arises if a solid oxidant is used, as is
now normal.
A range of solid materials a r e utilized including
C u O (Ripley & Nicol, 1981), C u 0 ( R o b i n s o n &
K u s a k a b e , 1975; Kiyosu, 1980) a n d V 0 ( M a k e l a
& V a r t i a i n e n , 1978; G a v e l i n et al., 1960) a n d at
significantly reduced t e m p e r a t u r e s ; generally in t h e
range 6 0 0 - 8 5 0 C . R o b i n s o n & K u s a k a b e (1975)
carried o u t their reactions at 800C producing yields
of 99100% in approximately 10 minutes with con
taminating C 0 being r e m o v e d via an - p e n t a n e liquid nitrogen t r a p .
A pre-concentration step is needed for the analysis
of disseminated sulphide in a s a m p l e . Ripley &
Nicol (1981) dissolved their s a m p l e in c o n c e n t r a t e d
acid a n d used T h o d e solution (a boiling mixture of
H I , H P 0 and H C 1 , T h o d e et al., 1961) to convert
t h e sulphur to H S , a n d subsequently A g S . Sasaki
et al. (1979) stressed that Kiba r e a g e n t (a mixture of
tin I I a n d H3PO4) was far m o r e rapid than T h o d e
solution in extracting sulphide from pyrite. C a m e r o n
(1983) used Kiba r e a g e n t , but found that since this
also extracted organic S a n d S in B a S 0 a sulphidespecific dissolution stage was n e e d e d first ( D i n u r ,
Spiro & A i z e n s h t a t , 1980).
2
SULPHATES AND SULPHIDES
t h e insoluble salt B a S 0 by addition of B a C l solu

tion (Longinelli & Craig, 1967; Claypool etal., 1980;
Sakai et al., 1980; Cortecci et al., 1981). W h e r e
i m p u r e sulphates a r e t o b e analysed for oxygen
isotopes, t h e additional p r e c a u t i o n of passing t h e
solute t h r o u g h a n ion-exchanger prior t o addition of
B a C l is desirable to avoid coprecipitation of metal
oxides with t h e B a S 0 (Claypool et al., 1980).
( b ) T h e rapid quantitative r e d u c t i o n of s u l p h a t e
requires powerful reducing a g e n t s , a variety of which
h a v e b e e n found satisfactory. Usually A g S is d e
signed t o b e t h e e n d - p r o d u c t of t h e process. Details
are given in T h o d e , M o n s t e r & D u n f o r d (1961),
G a v e l i n , Parwel & R y h a g e (1960), Sasaki, A r i k a w a
& Folinsbee (1979), Sakai et al. (1980) and Kiyosu
(1980).
Direct-reduction of s u l p h a t e t o S 0 (thus elimin
ating t h e sulphide stage altogether) was a d v o c a t e d
by H o l t & E n g e l k e m e i r (1970). T h e y h e a d e d B a S 0
coated in pulverized q u a r t z t o 1400C in vacuo:
4
to stick in the inlet system, causing m e m o r y effects.

A l s o , corrections n e e d to be m a d e for mass interfer
ences in t h e s p e c t r o m e t e r d u e to the presence of
several isotopes of oxygen. T h e alternative is S F :
chemically inert, insensitive to m o i s t u r e , not p r o n e
to adsorb on t o t h e v a c u u m line and needing no
corrections for interference effects since F is the
only stable isotope. T h e intensity of the S F
beam
can b e m e a s u r e d readily as it occurs in a mass region
free of instrument b a c k g r o u n d (Puchelt, Sables &
H o e r i n g , 1971).
R e e s et al. (1978) p r o d u c e d S F from A g S by
reaction with B r F , while Puchelt et al. (1971) p r e
ferred B r F because it was less d a n g e r o u s ; although
it is still very toxic, fumes in moist air a n d reacts
violently with w a t e r a n d organic matter! D e s p i t e
these p r o b l e m s , they m a i n t a i n e d that elemental sul
p h u r a n d m a n y metallic sulphides react rapidly and
completely with B r F according to the reaction:
6
ANALYSIS OF SULPHIDE-SULPHUR
327
328
CO

by t h e reaction:
2 C O -> C 0
+ C.
According to Sakai (1977) this reaction p r o c e e d s to

the right if t h e C 0 formed is continuously con
d e n s e d o n to a glass wall cooled by liquid air. Rafter
(1967) also showed that the intimate mixing and fine
grinding of sample ( B a S 0 ) and graphite allowed
t h e reaction t e m p e r a t u r e t o b e l o w e r e d , diminishing
t h e formation of C O . Sakai & K r o u s e (1971) modi
fied this technique slightly by using internally h e a t e d
reaction cells with cooled quartz walls rather t h a n
t h e externally h e a t e d q u a r t z tube of Rafter (1967).
This eliminated m e m o r y effects caused by oxygen
isotope exchange b e t w e e n t h e hot q u a r t z walls and
C O . O t h e r examples of t h e use of graphite reduc
tion include Longinelli & Craig (1967), Claypool
et al. (1980) and Cortecci et al. (1981).
T h e m e a s u r e m e n t of 0 / 0 associated with t h e
water of crystallization of sulphates is a relatively
simple affair (Sofer, 1978; H a l a s & K r o u s e , 1982).
T h e basic t e c h n i q u e involves heating t h e s a m p l e
in vacuo and collecting any expelled w a t e r in a cold
t r a p . T h e oxygen isotopic composition of this water
is t h e n d e t e r m i n e d using a standard C 0 equilibra
tion m e t h o d (Epstein & M a y e d a , 1953).
2
1 8
1 6
329
ly process milligram-sized samples (e.g. 0.30.5 mg

at t h e University of Michigan, Given & L o h m a n n ,
1986) if very small petrographic c o m p o n e n t s (Given
& L o h m a n n , 1986) or hand-picked microfossils
(Shackleton, Hall & B o e r s m a , 1984; Fig. 9.22) are
to b e analysed. W h e n t h e v o l u m e of evolved C 0 is
very small it m a y be necessary t o u s e 'cold finger'
a t t a c h m e n t which allows all t h e gas t o be introduced
to t h e machine. F o r p u r e calcium c a r b o n a t e t h e time
allowed t o elapse before collection of t h e C 0 will
d e p e n d very much on t h e degree of a u t o m a t i o n
incorporated within t h e p r e p a r a t i o n line-mass spec
t r o m e t e r system; that is, crudely, o n t h e age of the
assembly. S o m e of t h e older mass s p e c t r o m e t e r s are
only semi-automatic and require 'setting-up' by t h e
o p e r a t o r prior to analysing each sample and hence
t h e n u m b e r of gases that can be m e a s u r e d in a day is
limited. In this case t h e sample and acid mixture is
usually p r e p a r e d , left overnight in a water b a t h at
25C and t h e C 0 collected and m e a s u r e d t h e fol
lowing day. H o w e v e r , because t h e reaction itself
will go to completion in a m a t t e r of tens of m i n u t e s ,
m o d e r n fully a u t o m a t e d systems allow batches of
samples t o b e p r e p a r e d and m e a s u r e d m o r e o r less
continuously. In this latter case s o m e laboratories
react their carbonates with H P 0 at 50C to hasten
t h e evolution of C 0 (e.g. Fig. 9.22).
2
CARBONATES
1 8
1 6
1 3
1 2
B o t h 0 / 0 a n d C / C ratios can b e d e t e r m i n e d
in o n e operation by t h e evolution of C 0
from
c a r b o n a t e s . M c C r e a (1950) laid t h e basis for t h e
technique now used. M e a s u r e m e n t s of the ratios of
C 0 with mass 44 ( C 0 ) 45 ( C 0 ) and 46
( C 0 0 ) allows t h e two ratios to b e d e t e r m i n e d
since C and
0 are by far the most a b u n d a n t
isotopes. Successful mass spectrometry of C 0 thus
required a quantitative a n d reproducible extraction
p r o c e d u r e , lacking impurities in t h e mass range 44
46, as well as a lack of opportunity for oxygen
isotope exchange. M c C r e a (1950) found that thermal
decomposition did not give reproducible results, and
e x p e r i m e n t e d with various acids. T h e use of 100%
phosphoric acid ( H P 0 ) at 25C was found to be a
reliable technique for C a C 0 . T h e reaction takes
place in vakuo and t h e gas should be passed through
a cold t r a p of dry ice and m e t h a n o l (safer than dry
ice/actone) t o r e m o v e impurities (particularly H 0 )
before C 0 is frozen in a collection vessel i m m e r s e d
in liquid nitrogen. T h e sample size required will
typically be 10 m g o r less. S o m e laboratories routine
2
1 2
1 6
1 2
1 3
1 8
1 6
B e c a u s e of t h e relatively small quantities of p h o s

phoric acid c o n s u m e d annually, t o o u r knowledge
it is n o t available commercially in t h e desired purity.
Individual laboratories therefore usually p r e p a r e
their own according to their n e e d s ; adding p h o s
p h o r o u s p e n t o x i d e ( P O ) to o r t h o p h o s p h o r i c acid
( 8 5 - 8 8 % ) to p r o d u c e 100% H P 0 .
2
1 2
1 6
Fig. 9.22. Reaction system used in the laboratory of N.J. Shackleton to generate C 0 from foraminifera for isotopic
analysis. The whole region illustrated is kept at 50C. Orthophosphoric acid is dropped on to the foraminifera which have
previously been cleaned and vacuum-roasted in the sample thimble within container A. The acid is replenished monthly
and kept pumped so that it does not take up moisture (from Shackleton et al., 1984, with permission of the Ocean Drilling
Program, Texas A & M University).
2
1 6
ISOTOPIC CORRECTIONS
N o a t t e m p t will b e m a d e h e r e to provide a t h o r o u g h
account of t h e various corrections t h a t may b e a p
plied to ' r a w ' isotopic d a t a , since a good n u m b e r are
concerned with machine errors (e.g. inlet valve
leakage) or interference effects which a r e , strictly
speaking, outside t h e scope of this discussion; but
see Craig (1957), D e i n e s (1970) and B l a t t n e r &
H u l s t o n (1978). Since t h e processing of raw d a t a is
usually d o n e by c o m p u t e r , all necessary corrections
may be incorporated within the p r o g r a m and applied
automatically t o yield the adjusted delta value. It is
r e c o m m e n d e d that all correction factors should be
q u o t e d when publishing isotopic d a t a t o g e t h e r with
an approximation of t h e total analytical e r r o r (i.e.
the preparation and machine error combined).
O n e correction factor that n e e d s particular j u d g e

ment is that in respect of isotopic fractionation during
p h o s p h o r i c acid digestion. A l t h o u g h all t h e sample
m a y b e c o n s u m e d , only a b o u t 6 6 % of t h e total
oxygen finds its way into t h e C 0 ; the r e m a i n d e r
reacting with H ions to form water. This imparts a
fractionation factor ( a ) of the form;.
2
lK
( 0/' 0)co.
~ r n/ rv>
l8
l6
v
'-Vcarbonale.
which results in t h e uncorrected 6 b value being
approximately 10% t o o heavy. This fractionation
1 8
http://jurassic.ru/
liiiiimiimiiiiiiifliiiiif
mechanism is t e m p e r a t u r e - d e p e n d e n t , hence it is
i m p o r t a n t always t o perform the acid decomposition
reaction at the same temperature (e.g. 25C or 50C).
S h a r m a & Clayton (1965) provided an account of
this particular correction, while T a r u t a n i , Clayton &
M a g e d a (1969) and R u b i n s o n & Clayton (1969)
outlined additional corrections for Mg calcites and
a r a g o n i t e . R o s e n b a u m & S h e p p a r d (1986) provided
t h e best compilation of d a t a on F e - and Mg-bearing
carbonates at varying t e m p e r a t u r e s . D o l o m i t e poses
particular p r o b l e m s since t h e r e is n o a g r e e m e n t o n
its fractionation factor with phosphoric acid. Most
330
authors after 1965 followed Sharma & Clayton (1965)

in applying a correction that approximates t o 0.8%o
with respect to calcite. L a n d (1980) n o t e d that cor
rections applied w e r e varied, a n d often n o t stated.
B o t h he and R o s e n b a u m & S h e p p a r d (1986) found a
substantially larger correction most likely in t h e light
of their experimental evidence, although Land (1980)
r e c o m m e n d e d treating all carbonates effectively as
calcites in this respect until t h e m a t t e r is resolved.
Clearly it is very i m p o r t a n t to state the phosphoric
acid correction factor used in published r e p o r t s .
PREPARATION OF CARBONATES OTHER
THAN C a C 0 AND MIXED CARBONATE
SAMPLES
3
T h e standard p r e p a r a t i o n m e t h o d of M c C r e a (1950)
outlined a b o v e was designed specifically t o c o p e
with calcium c a r b o n a t e , either as calcite o r aragonite
which react readily with phosphoric acid at r o o m
t e m p e r a t u r e . With o t h e r c a r b o n a t e species, how
ever, t h e reaction at 25C is very much slower a n d
can considerably lengthen t h e time to process each
sample. B e c k e r & Clayton (1972) p r e p a r e d samples
of calcite, dolomite, ankerite and siderite at 25C
a n d found t h a t while t h e calcite reaction was c o m
plete in 24 h o u r s , periods of o n e w e e k , two weeks
and two t o t h r e e m o n t h s respectively w e r e required
for t h e r e m a i n d e r . N o t only a r e such e x t e n d e d
periods of reaction inconvenient in routine work but
t h e r e is always a d a n g e r that t h e reaction vessel m a y
leak while not being actively p u m p e d , leading t o
contamination with atmospheric C 0 . F i n e grinding
of t h e sample t o increase t h e total surface a r e a can
b e used to speed u p t h e reaction but such t r e a t m e n t
is time-consuming and may cause isotopic exchange
with the a t m o s p h e r e . M u c h m o r e convenient is t o
increase t h e reaction t e m p e r a t u r e . G o u l d & Smith
(1979), for e x a m p l e , working with siderite, initially
mixed sample a n d acid at 80C and t h e n allowed t h e
mixture to react at 25C for 72 h o u r s . S t a n d a r d cal
cites treated in t h e s a m e m a n n e r showed n o change
in 5 C although 5 0 values were found t o b e t o o
light by 1.2%o and h e n c e all oxygens w e r e corrected
by this a m o u n t (see also G a u t i e r , 1982). Raising t h e
reaction t e m p e r a t u r e is particularly useful w h e n
working with dolomites, which at 50C react t o
completion overnight. B e a r i n g in mind t h e tem
perature-related changes in t h e phosphoric acid cor
rection factor, t h e standards should b e run at t h e
same temperature.
2
1 3
1 8
Mixtures of c a r b o n a t e s , particularly calcite and

d o l o m i t e , often n e e d to be analysed. If t h e composi
tion of only o n e of t h e minerals is n e e d e d , it m a y b e
possible to r e m o v e it physically (see microsampling
section), otherwise a chemical p r e - t r e a t m e n t is re
quired. Videtich (1981) g r o u n d the sample t o < 3 um
and selectively leached t h e calcite with E D T A
( G l o v e r , 1961) in o r d e r t o analyse t h e d o l o m i t e , but
w a r n e d that this m e t h o d was not suitable for calcian
dolomites which dissolve m o r e readily in E D T A .
W a d a & Suzuki (1983), seeking t o analyse calcite in
dolomitic m a r b l e s , ground samples t o <50- um and
used a heavy-liquid m e t h o d to separate t h e calcite.
O t h e r techniques include that of Magaritz & Kafri
(1981) w h o r e m o v e d calcite by dissolution in 3 %
HC1 and L a n d (1973) w h o used a dilute acetic acid
digestion, b o t h sets of a u t h o r s using X R D tech
niques to p r o v e t h e purity of t h e remaining d o l o m i t e .
W h e n it is necessary t o k n o w t h e isotopic composi
tion of both minerals present, and physical separation
is n o t possible, chemical m e t h o d s are again necess
ary. T h e most favoured m e t h o d of separation
(although not without its critics) m a k e s use of t h e
variable reaction rates of calcite and d o l o m i t e with
p h o s p h o r i c acid; a technique originally p i o n e e r e d by
E p s t e i n , Graf & D e g e n s (1964) and D e g e n s &
E p s t e i n (1964). In their e x p e r i m e n t s , mixtures of
calcite and dolomite having first b e e n g r o u n d t o < 5 0
pm were reacted with phosphoric acid at 25C and
t h e C d p r o d u c e d in t h e first h o u r (assumed t o b e
principally from t h e m o r e reactive calcite p h a s e )
analysed o n t h e mass spectrometer. T h e reaction
was t h e n allowed t o p r o c e e d for a further three'
h o u r s during which time t h e C 0 formed was p u m p
ed away, while t h e r e m a i n d e r of t h e gas p r o d u c e d
from t h e fourth h o u r u p t o a m a x i m u m of 72 .hours
was assumed to represent t h e dolomitic fraction.
H e n c e , they believed that by using this d o u b l e col
lection p r o c e d u r e it was possible to d e t e r m i n e t h e
isotopic composition of b o t h minerals with minimal
cross c o n t a m i n a t i o n ; although they suggested it w a s
unsuitable for samples in which t h e two phases
differed greatly in isotopic composition or w h e r e t h e
ratio of o n e mineral to t h e o t h e r was large. M o r e
recently W a l t e r s , Claypool & C h o q u e t t e (1972) have
pointed o u t t h a t unless close bracketing of grain size
is a t t e m p t e d by sieving, t h e large r a n g e of grain sizes
will introduce errors into this technique because of
t h e variable solubility in H P 0 . D e s p i t e these
p r o b l e m s many w o r k e r s have m a d e use of t h e dou
ble collection p r o c e d u r e and a n u m b e r of modifica2
tions have been m a d e to m e e t specific needs. Clayton

et al. (1968) altered their reaction times to cope with
very fine-grained samples while B e c k e r & Clayton
(1972) used t h e m e t h o d to separate ankerite and
siderite.
331
not suited to aragonite samples since s o m e conver

sion of t h e unstable p h a s e to calcite is likely u n d e r
t h e high t e m p e r a t u r e conditions.
MICROSAMPLING
REMOVAL OF ORGANIC MATTER
T h e presence of organic carbon in samples of car
b o n a t e leads to t h e introduction of volatile sub
stances into t h e mass s p e c t r o m e t e r which form a
variety of reaction products in t h e ionization cham
b e r and interfere with t h e weak mass 45 and 46 ion
beams.
A l t h o u g h p r e - t r e a t m e n t s for t h e removal of
organic m a t t e r a r e most relevant to R e c e n t skeletal
aragonite, which h a s a very high organic content,
it repays to give s o m e t h o u g h t to t h e effect on
ancient c a r b o n a t e s . Charef & S h e p p a r d (1984) n o t e d
that sulphur-rich organic material is particularly
troublesome.
By far t h e simplest technique for removing organic
carbon involves soaking t h e sample in a solution of
sodium hypochlorite ( N a C 1 0 , clorox) or hydrogen
peroxide ( H 0 ) to oxidize t h e organic material
(e.g. Wefer & B e r g e r , 1981; Cummings & M c C a r t y ,
1982). A m o r e e l a b o r a t e p r o c e d u r e was developed
by Epstein et al. (1953) and involved 'roasting' t h e
sample in a continuous stream of helium which
swept away t h e decomposition products of t h e heat
ed organic materials and preserved t h e sample in an
inert a t m o s p h e r e . W e b e r et al. (1976), L a n d , L o n g
& B a r n e s (1977), Durazzi (1977) and Weil et al.
(1981) a r e a m o n g t h o s e t h a t h a v e a t t e m p t e d experi
mental work to quantify the effectiveness of each of
these techniques and any isotopic fractionation ef
fects they may h a v e . T h e general consensus is that
neither t h e c l o r o x / H 0 t r e a t m e n t s n o r high tem
p e r a t u r e roasting a r e capable of removing all organic
carbon and t h e r e is considerable evidence that t h e
former will impart s o m e e r r o r to t h e m e a s u r e d
isotopic value; although provided all samples are
p r e p a r e d in t h e same m a n n e r any errors will be
systematic. B e c a u s e of t h e possibility of some or
ganic carbon remaining even after t h o r o u g h pret r e a t m e n t , W e b e r et al. (1976) devised a rejection
p r o c e d u r e b a s e d o n a careful examination of t h e
reference and sample chart recorder traces that
allowed a n excessive input from organic m a t t e r t o b e
recognized. It should also be n o t e d that roasting is
http://jurassic.ru/
In c o m m o n with chemical analyses discussed else

w h e r e , t h e effectiveness of isotope studies o n car
b o n a t e s is often greatly e n h a n c e d by being able to
resolve differences b e t w e e n individual rock com
p o n e n t s such as grain and c e m e n t types ( H u d s o n ,
1977a).
O n e of t h e most p o p u l a r m e t h o d s of micro
sampling c a r b o n a t e rocks is t o u s e a dental drill
modified to accept very small drill bits which ideally
n e e d to be < 0 . 5 m m in diameter. Prezbindowski
(1980) outlined s o m e of t h e r e q u i r e m e n t s of such a
sampling p r o c e d u r e and described a miniature verti
cal milling machine developed for such a role and
capable of both vertical and horizontal (furrow)
cutting m o v e m e n t s .
A precise, but m o r e time-consuming alternative is
to use a scalpel or razor blade to cut out particular
c o m p o n e n t s of interest from a thin-section. Dickson
& C o l e m a n (1980) used multiple 40 p m thin sections
cut from a single hand specimen which had been
m o u n t e d in L a k e s i d e 70 and stained. Samples of > 5
m g were cut from each thin section using a scalpel
a n d binocular microscope a n d they were able t o
p r o v e that neither t h e m o u n t i n g glue n o r t h e stain
affected the m e a s u r e d isotopic composition of t h e
carbonate.
SILICATES
Techniques designed for crystalline rocks have been
a d a p t e d for sedimentary silicates. 0 / 0 a n d D / H
ratios are t h e only i m p o r t a n t ones; see D o u t h i t t
(1982) for silicon isotopes.
1 8
1 6
O X Y G E N IN S I L I C A T E S
O x y g e n i s o t o p e ratio m e a s u r e m e n t s a r e performed
exclusively o n C 0 in preference t o 0 because it
lies in a mass region relatively free of background
interference. M o r e o v e r , C 0 is less reactive t h a n 0
and thus less likely to be involved in chemical re
actions with substances within t h e p r e p a r a t i o n linemass spectrometer assembly which could introduce
an isotope fractionation effect. H e n c e , t h e m e t h o d
2
332
I.J. FAIRCHILD ef a l .
of sample p r e p a r a t i o n is usually a two-step process

involving t h e extraction of 0 from t h e sample fol
lowed by its quantitative conversion to C 0 for
m e a s u r e m e n t on t h e mass spectrometer.
T h e initial liberation of 0 from t h e silicate struc
t u r e requires oxidation with a suitable r e a g e n t , t h e
two most commonly in use being F (Taylor &
E p s t e i n , 1962) and B r F (Clayton & M a y e d a , 1963);
which have largely superseded t h e high t e m p e r a t u r e
carbon reduction m e t h o d of Baertschi & Schwander
(1952), which is p r o n e to contamination.
B r o m i n e pentafluoride ( B r F ) at r o o m t e m p e r a
ture is highly corrosive to glass although it may b e
handled safely w h e n cooled by liquid nitrogen; while
at typical reaction t e m p e r a t u r e s (400600C) nickel
is t h e only suitable material for handling t h e sub
stance. According t o Clayton & M a y e d a (1963) a
five-fold excess of B r F over stoichiometric require
ments was desirable, sample size ranging from 5 to
30 mg which yielded 1 0 0 - 4 0 0 pmol of 0 . O n
completion of t h e reaction, 0 was collected via a
liquid nitrogen cold-trap (Fig. 9.23) which r e m o v e d
u n w a n t e d p r o d u c t gases (e.g. B r F , B r , S i F and
H F ) . T h e extraction of 0 using F follows similar
lines to t h e B r F technique with most published
accounts quoting Taylor & Epstein (1962) as t h e
definitive t r e a t m e n t . A minor modification to this
m e t h o d was suggested by Savin & Epstein (1970)
w h o used hot mercury in addition to a K B r trap to
r e m o v e excess F and o t h e r contaminants from t h e
oxygen.
O n c e p u r e 0 has been isolated from o t h e r p r o
duct gases the next step is to convert t h e 0 to C 0
quantitatively, and in both t h e F and B r F examples
cited above this was achieved by passing t h e gas over
an electrically h e a t e d graphite rod. T h e C 0 p r o
duced is t h e n m e a s u r e d in t h e conventional way with
standard corrections (Craig, 1957), while Taylor &
Epstein (1962) pointed o u t that 0 introduced with
fluorine in their m e t h o d required a correction of
0.10.2%o. Pisciotto (1981) provided an account of
how t o calculate t h e 5 O value for opal C T from an
opal CT/quartz mixture.
positive pressure of dry nitrogen. This p r o c e d u r e is

less complex and providing the reaction vessel is
o p e n for n o m o r e than o n e minute t h e a m o u n t of
water vapour that enters is negligible and has n o
a p p a r e n t effect on t h e m e a s u r e d 0 / 0 ratio.
In recent years t h e r e has b e e n s o m e a t t e m p t to
find a cheaper alternative t o B r F , which has b e c o m e
prohibitively expensive for routine 0 isotope w o r k
as supplies have dwindled. Borthwick & H a r m o n
(1982) examined t h e suitability of a variety of p o t e n
tial oxidation reagents and concluded that C1F had
t h e most desirablecharacteristics, being easily flush
ed from t h e p r e p a r a t i o n line while its ability to
freeze completely in liquid nitrogen p r e v e n t e d con
tamination of evolved 0 . T h e y also provided a
short description of their analytical p r o c e d u r e to
highlight t h e small differences c o m p a r e d with con
ventional m e t h o d s .
Sedimentary rocks often require p r e - t r e a t m e n t to
r e m o v e c a r b o n a t e s , organic carbon and oxides which
provide a source of non-silicate oxygen. M c M u r t y ,
C h o n g - H o W a n g & Y e h (1983) r e m o v e d calcium
c a r b o n a t e with an acetic acid solution buffered with
sodium acetate to p H 5. Organic m a t t e r can be
oxidized with 3 0 % hydrogen peroxide ( H 0 ) or
sodium hypochlorite 'clorox' ( N a C 1 0 ) adjusted t o
p H 9.5 with I N HC1. I r o n and possibly m a n g a n e s e
oxides can b e r e m o v e d using t h e sodium citratedithionite solution buffered with sodium b i c a r b o n a t e
developed by M e h r a & Jackson (1960). In s o m e
cases it may also be necessary to analyse specific
grain-size fractions. L e R o u x , Clayton & Jackson
(1980), for e x a m p l e , isolating the 1 10 urn portion
of their samples by a combination of s e d i m e n t a t i o n
and centrifuge techniques (see also J a c k s o n , 1979).
T h e y also isolated quartz from t h e r e m a i n d e r of t h e
sediment using a modified form of t h e sodium pyrosulphate fusion-hexafluorosilicic acid t e c h n i q u e of
Syers, C h a p m a n & Jackson (1968) developed by
Sridhar, Jackson & Clayton ( 1 9 7 5 ) ; a n d J a c k s o n ,
Sayin & Clayton (1976). Pisciotto (1981) used this
technique to r e m o v e clays and feldspars from silice
ous m u d r o c k s .
T h e only substantial modification to either of the

above techniques to date involves t h e m e t h o d of
sample entry into the reaction vessel. While Clayton
& M a y e d a (1963) o p e n e d their reaction vessels in a
P 0 dry-box to prevent entry of water v a p o u r ,
F r i e d m a n & Gleason (1973) and Labeyrie & Juillet
(1982) suggested loading the sample directly u n d e r a
A l s o of crucial i m p o r t a n c e is the removal of interlayer or a d s o r b e d water from clays without affecting

H / D or 0 / 0 ratios of structural H and O . Savin &
Epstein (1970) suggested that clays for 5 0 analysis
should be k e p t in a P 0 dry-box for at least 24
h o u r s prior to oxidation, while Y e h & Savin (1977)
replaced t h e a t m o s p h e r e in their dry-box with dry
l s
1 8
High vacuum
High vacuum
1 6
Reaction tubes
BrF cylinder
5
High
vacuum
1 8
From
BrF line
6
ft
Manometer
scale
Sample
tube
Calibrated
volume
^C0
CO
converter
2
t r a
v*4>
Manometer
1 6
Toepler pumps
1 8
Fig. 9.23. Top: apparatus for reaction pfoxygen compounds with bromine pentafluoride. Bottom: apparatus for
collection of oxygen and conversion to carbon dioxide (from Clayton & Mayeda, 1963).
http://jurassic.ru/
334
nitrogen two h o u r s after t h e sample h a d been intro

d u c e d . T h e small a m o u n t of water vapour remaining
after 24 hours was n o t expected to effect t h e mea
sured 6 0 value by m o r e t h a n a few tenths per mil.
Particular care should b e t a k e n when p r e p a r i n g
smectitic clays which have t h e ability to adsorb
relatively large a m o u n t s of water a n d may require
m o r e thorough drying.
F o r H / D m e a s u r e m e n t s preliminary out-gassing
needs to b e much m o r e intensive. Savin & Epstein
(1970) r e c o m m e n d e d heating t h e sample u n d e r
vacuum at 1 0 0 - 2 5 0 C for 24 hours or m o r e , while
Y e h (1980) dried his samples at b e t w e e n 250 a n d
300C for not less that t h r e e hours followed by
storage in a nitrogen filled P2O5 dry-box. B o t h
m e t h o d s should b e capable of removing virtually all
a d s o r b e d a n d inter-layer water.
1 8
D/H R A T I O M E A S U R E M E N T S ON
SILICATES
T h e m e a s u r e m e n t is p e r f o r m e d on hydrogen gas
which is p r e p a r e d by a fairly standard t e c h n i q u e .
T h e initial step after out-gassing is to extract h y d r o
gen from t h e silicate structure as molecular w a t e r by
heating t h e sample u n d e r vacuum at high t e m p e r a
t u r e , anywhere b e t w e e n 900C (Savin & E p s t e i n ,
1970) and 1 5 0 0 - 1 7 0 0 C (Godfrey, 1962). Since s o m e
h y d r o g e n is also liberated in t h e molecular form this
is converted to water by reaction with C u O . This
water m a y t h e n b e quantitatively converted to H by
reaction with h o t u r a n i u m (400700C) or h o t zinc
after which it is collected via a liquid nitrogen cold
t r a p (Bigeleisen, Perlman & Prosser, 1952; Craig,
1961a, b ; Godfrey, 1962; C o l e m a n etal., 1983). T h e
evolved H is m e a s u r e d isotopically against a suit
able reference with a correction being m a d e for t h e
H
ion interference effect ( F r i e d m a n , 1953). B e
cause of t h e frequently large deviation from the
s t a n d a r d , 6 D values may b e q u o t e d in p e r cent
r a t h e r than parts p e r mil w h e n necessary.
2
3 +
9.7 A N A L Y T I C A L Q U A L I T Y
9.7.1 Accuracy a n d precision
W h e n chemical concentrations have b e e n o b t a i n e d
it is desirable to know b o t h their internal consistency
and their relation to the ' t r u e ' concentration.
If a single t e c h n i q u e is used to analyse r e p e a t e d l y

a perfectly h o m o g e n e o u s geological material t h e n a
range of results will be obtained for t h e elemental
concentration(s). T h e variation arises because of t h e
small e r r o r s introduced at all stages of t h e p r e p a r a
tion a n d m e a s u r e m e n t of the s a m p l e , and if sufficient
replicates a r e plotted as a frequency diagram they
will generally follow a Gaussian distribution. T h e
results can t h u s b e described by t h e m e a n (x) a n d
t h e standard deviation (s), t h e latter t e r m being
known as t h e repeatability (reproducibility is often
used synonymously b u t it m a y also b e used for t h e
specific m e a n i n g of t h e variation b e t w e e n labora
tories which have analysed that sample by t h e s a m e
m e t h o d ) . Relative repeatability is m o r e convenient
than s t a n d a r d deviation with t h e terms relative stan
dard deviation (rsd = six), coefficient of variation
(C = s / x . 1 0 0 % ) a n d precision ( P = 2s/*. 1 0 0 % )
being used. Precision is often used loosely instead of
repeatability.
Accuracy is t h e extent to which t h e m e a n a p
proaches t h e ' t r u e ' concentration a n d bias t h e dif
ference b e t w e e n the m e a n or m e d i a n and t h e ' t r u e '
value. F o r geological materials t h e t r u e concentra
tion is u n k n o w a b l e and is a p p r o x i m a t e d by a con
sensus 'usable v a l u e ' (see Section 9.7.2).
T h e properties of t h e N o r m a l distribution allow
an analyst t o predict t h e p r o p o r t i o n of t h e total
n u m b e r of m e a s u r e m e n t s which lie b e t w e e n t h e
given ranges (for a Gaussian distribution 6 8 . 3 % of
observations lie in t h e range x s). This allows
criteria for t h e rejection of results which m a y b e in
e r r o r , the rejection limit usually being set at 9 5 %
confidence (strictly this is 1 . 9 6 s b u t is usually a p
proximated t o 2s). It should b e stressed that 5 % of
valid results will b e rejected a n d possibly s o m e
e r r o n e o u s results accepted. T h e observations in e r r o r
are usually t e r m e d 'fliers' a n d arise from unusual
situations, for example t h e misreading of a balance
o r transient electrical ' n o i s e ' . T h e y can usually b e
detected w h e r e t h e r e a r e a large n u m b e r of repli
cates b u t w h e n , for e x a m p l e , only triplicate m e a
surements a r e available t h e rejection limits in t e r m s
of j b e c o m e very large (x 10s) ( H a r v e y , 1974).
W h e r e fliers a r e p r e s e n t t h e median m a y b e a b e t t e r
estimator of central tendency t h a n t h e m e a n . T h e
repeatability c a n b e illustrated by frequency dia
g r a m s o r , m o r e usefully, by control charts w h e r e t h e
individual observations in order of analysis a r e plot
ted against the deviation from t h e m e a n .
T h e precision of a m e a s u r e m e n t varies as a hyper-
bolic function with the concentration reaching a

level, the detection limit, below which a value can
n o t b e d e t e c t e d . This theoretical limit is usually
defined as being greater than two standard devia
tions of the m e a s u r e m e n t s t a k e n at zero concentra
tion. It should b e stressed that this is a theoretical
limit with t h e practical limit of determination being
35 times t h e detection limit. It follows that when
precisions a r e being q u o t e d they should b e given for
t h e range of concentrations being studied.
9.7.2 Practical quality c o n t r o l

T h e r e a r e t h r e e b r o a d areas of a n analysis w h e r e it is
desirable to have information regarding repeatability.
(a) T h e r e p e a t e d analysis of a single prepared
sample as in analyses of a solution by I C P or of a
powder pellet by X R F . T h e s e , assuming t h e sample
stays unaffected, give an estimate of t h e instrumen
tal p e r f o r m a n c e over t h e period of t h e test (short- or
long-term drift). T h e overall coefficient of variation
is a combination of errors introduced by individual
c o m p o n e n t s , for example a series of m e a s u r e m e n t s
by X R F could include g e n e r a t o r and tube variation
(1), sample changer reset (2) and g o n i o m e t e r reset
(3), all contributing small errors to t h e total w h e r e :
Qotal
Vc
Cf
C3.
This type of e x p e r i m e n t is especially valuable w h e r e

an instrument malfunction is suspected as individual
functions can b e tested a n d their contribution to t h e
total e r r o r isolated.
T h e use of mini a n d microcomputers attached to
a u t o m a t e d analytical instruments allows such infor
m a t i o n to b e readily collected a n d stored, and statis
tical evaluation software is usually provided by the
manufacturer. Stable samples such as pressed
p o w d e r pellets for X R F may be r e - m e a s u r e d for
several years, giving a very comprehensive m e a s u r e
of instrument p e r f o r m a n c e , w h e r e a s solutions used,
for e x a m p l e , in I C P a n d A A S have a relatively
limited life. T h e sophistication of instrumental hard
ware and software varies from t h e ability to m e a s u r e
o n e o r m o r e references at fixed intervals t o a p r o
gram w h e r e the samples a r e selected within a r a n d o m
sequence. C o m p u t e r control also allows automatic
repetition of samples until a required precision of
m e a s u r e m e n t is reached.
T h e above information is also desirable w h e r e less
a u t o m a t e d e q u i p m e n t is used although it is much
http://jurassic.ru/
m o r e time consuming to p r o d u c e . It should b e stress

ed that only the instrument repeatability is being
tested and that t h e precision figure represents the
best possible case.
(b) T h e second a n d m o r e i m p o r t a n t m e a s u r e m e n t
is the repeatability of sample preparation which
should b e tested for each analytical m e t h o d a n d
sample type. Unfortunately this is time consuming
and frequently ignored. Ideally it should b e estab
lished by preparing a relatively large n u m b e r (10 or
m o r e ) of replicates from t h e same h o m o g e n e o u s
bulk sample, either from t h e analysts collection o r
an 'in h o u s e ' reference material. T h e factors con
cerning sample h o m o g e n e i t y discussed in Section
9.5.2 should b e very carefully considered. It is likely
that t h e bulk samples, a n d especially 'in house'
references, will have a smaller grain size t h a n rou
tine samples a n d consequently will b e m o r e readily
decomposed during sample p r e p a r a t i o n . This will
t e n d to give an optimistic view of t h e repeatability of
sample p r e p a r a t i o n . T h e value for routine samples
can b e obtained from duplicates included in the
batches. T h e variation m e a s u r e d will of course b e a
combination of t h e total instrumental e r r o r and t h e
sample p r e p a r a t i o n variation. It should b e stressed
t h a t t h e physical a n d chemical characteristics of
rocks a n d minerals can strongly influence the effi
ciency of sample p r e p a r a t i o n ; hence each major
sample type should b e tested.
(c) Finally, it is rare for a large collection of
samples to b e p r e p a r e d a n d m e a s u r e d at the same
time. Normally they a r e split into batches and hence
m a y b e p r e p a r e d with different reagents or analysed
with different instrumental calibrations. It follows
that s o m e check must be m a d e of the overall consis
tency of results during t h e period of t h e project.
First, t h e within batch variation should b e tested,
t h e precise m e t h o d d e p e n d i n g on t h e analytical
technique used. Instrumental drift may b e checked
a n d corrected with m o n i t o r samples or s t a n d a r d
solutions preferably introduced randomly. In addi
tion, 'in h o u s e ' reference samples should b e pre
p a r e d a n d analysed, again r a n d o m l y , a n d preferably
'blind'. This last r e q u i r e m e n t is obviously m o r e
simple t o a r r a n g e w h e r e analysis is p e r f o r m e d by an
external laboratory. A n average of o n e reference
p e r t e n u n k n o w n s inserted at r a n d o m in each batch
is ideal with at least two reference samples with
chemical compositions near t h e t o p and b o t t o m of
the range of t h e u n k n o w n s plus o n e blank. T h e
choice of such reference samples is especially diffi-
336
cult where multi-element analytical m e t h o d s a r e

used as it is unlikely that t h e range of elemental
concentrations will be covered in just two o r t h r e e
samples.
A further test of analytical reproducibility can b e
provided by analysing a n u m b e r of u n k n o w n sam
ples in duplicate, t h e duplicates again being spread
randomly within t h e batch. Between batch variation
can b e tested by following the same p r o c e d u r e with
t h e s a m e reference samples.
In large-scale surveys, w h e r e the u n k n o w n sam
ples' n u m b e r s a r e r a n d o m i z e d t o avoid systematic
analytical errors being interpreted as geochemical
t r e n d s , n u m b e r s a r e also allocated t o duplicates a n d
to reference samples (Plant et al., 1975; H o w a r t h ,
1977).
T h e schemes described obviously increase effort
and cost by adding to t h e n u m b e r of samples b u t this
is offset by t h e improved knowledge of t h e quality of
results and by early indications of systematic bias.
A n absolute m i n i m u m is t o analyse 'in h o u s e ' refer
ence samples w h e n e v e r reagents or calibrations a r e
changed.
Accuracy is finally j u d g e d by comparison with
international reference materials which a r e discuss
e d in Section 9.7.2. Because of their very high value
they should n o t b e used as replicates in t h e above
schemes, particularly in analytical m e t h o d s which
destroy t h e sample. Instead, t h e 'in h o u s e ' refer
ences should have b e e n calibrated against interna
tional samples, a n d t h e latter on r a r e occasions
t r e a t e d as u n k n o w n s within a batch.
9.7.2 Standardization
All t h e analytical techniques previously described
require calibration, that is comparison of their in
strumental response with that of k n o w n concen
trations of t h e element(s) of interest. Broadly t h r e e
m e t h o d s can be used for calibration: (1) Standard
ization against known weights of extremely p u r e
elements or c o m p o u n d s . (2) Standard addition or
spiking. (3) C o m p a r i s o n with geological reference
materials.
T h e distinction should b e clearly m a d e between
standards and reference materials. T h e former a r e
usually simple c o m p o u n d s of known stoichiometry
and chemical composition, whereas the latter a r e
natural materials for which consensus concentration
values a r e available. D e s p i t e the c o m m o n practice
of referring to t h e m as 'geostandards' o r 'inter

national s t a n d a r d s ' they a r e n o t primary standards
and strictly their t r u e composition can never b e
known!
(1) This m e t h o d is generally used w h e r e t h e
sample is presented for analysis as a solution. Potts
(1987, table 5.4) listed suitable standard materials
for all e l e m e n t s in the periodic table. Such com
p o u n d s must b e available in a very p u r e form (gen
erally 99.999% or b e t t e r ) , b e stoichiometric a n d
generally be stable in air t o allow for accurate weigh
ing. Finally, they must b e readily soluble in water or
dilute acids, a n d these solutions should b e stable
over a reasonable period of time. Particular care is
n e e d e d in drying t h e substances before weighing as
t o o high a t e m p e r a t u r e m a y cause s o m e to decom
pose partially while others m a y retain water or car
bon dioxide even at high t e m p e r a t u r e s ( e . g . L a 0
may retain s o m e 2 0 % C 0 below 700C). Such
standard solutions a r e used for initial calibration
but also t o m o n i t o r drift of calibration lines. In tech
niques such as I C P multi-element standard solutions
are n e e d e d and it is necessary t o establish t h a t in
dividual elements d o n o t precipitate or polymerize
in t h e presence of o t h e r s . Potts (1987) identified N b ,
T a , M o a n d W as particularly difficult. S t a n d a r d
solutions a r e available commercially (usually at
concentrations of 1000 \ i g m l ' ) and similar pre
cautions should b e taken if these a r e mixed.
Finally it is usually necessary to 'matrix-match'
standards to u n k n o w n s in terms of major e l e m e n t
levels and salt or acid content. This may cause
p r o b l e m s if acids or fluxes a r e not sufficiently p u r e (Table 9.6) or if t h e matrix elements a r e n o t added
as p u r e Compounds. F o r e x a m p l e , in t h e analysis of
Sr in carbonates t h e matrix C a must b e a d d e d as
Specpure or equivalent c a r b o n a t e as Analar
material can contain in excess of 0 . 0 6 % Sr. Such
considerations a r e also i m p o r t a n t w h e r e t h e multi
element standards a r e used to d e t e r m i n e interfer
ence effects (Table 9.7).
T h e same m e t h o d can also b e used to standardize
t h e fused bead technique in X R F analysis. H e r e
oxides a r e generally used a n d t h e possible loss of
elements at high fusion t e m p e r a t u r e s must b e con
sidered (Oliver, 1979).
In general the set of standards with concentrations
covering the whole range of t h e calibration should
b e individually p r e p a r e d from t h e ' m a s t e r ' solution
to avoid propagation of errors.
(2) Standard addition is used mainly in areas
2
w h e r e the matrix of the u n k n o w n must be exactly

matched with that of t h e calibration standards, for
example in flame p h o t o m e t r y . T h e u n k n o w n sol
ution is divided into a minimum of six aliquots, five
of which a r e spiked with increasing a m o u n t s of the
element to b e analysed. A graph is then m a d e of
a d d e d concentration against instrument response,
t h e negative concentration intercept giving the value
of t h e unspiked sample. A similar m e t h o d can be
employed to calibrate p o w d e r samples in X R F and
I N A A . H e r e standards can b e a d d e d for a range of
e l e m e n t s , as p o w d e r e d oxides, as a q u e o u s solutions
or as organo-metal solutions. G r e a t care is n e e d e d
to ensure h o m o g e n e i t y , usually involving further
grinding and mixing of t h e samples. A l t h o u g h good
(linear) calibration lines a r e generally produced they
may n o t provide true concentrations because of dif
fering analytical response between the element in a
mineral and the same element in a simple laboratory
chemical. This is particularly so for t h e analysis of
lighter elements by X R F .
(3) Geological reference materials a r e unfortu
nately increasingly being used for standardization.
This practise should be avoided wherever practi
cable and t h e reference materials used only as a
m e a n s of comparing sets of samples analysed in dif
ferent laboratories, or by different m e t h o d s which
have b e e n calibrated by primary m e t h o d s . O n e
great danger in using comparative standardization is
t h e propagation of errors in each new reference
material whose 'consensus' concentrations may re
late to a very few original ' s t a n d a r d s ' analysed by
primary m e t h o d s .
9.7.3 Geological reference materials

O v e r t h e past 25 years a large n u m b e r of geo
logically related reference materials have b e e n
p r o d u c e d . T h e most comprehensive list of those
available is that of Flanagan (1986) w h o detailed
m o r e than 830 samples for use as chemical, isotopic
or m i c r o p r o b e references. Unfortunately t h e greater
p r o p o r t i o n of these a r e of igneous materials, a n d
even w h e r e natural sedimentary samples a r e avail
able the quality of information is generally inferior
to that for igneous samples.
T h e most recent compilation of values is d u e to
Govindaraju (1984) in a special issue of Geo
standards Newsletter w h e r e 'working values' for a
http://jurassic.ru/
wide range of elements in 170 reference samples a r e

listed. This journal is the major source of infor
mation on G R S with periodic updates of values for
existing material plus the a n n o u n c e m e n t of new
samples.
W o r k i n g values a r e generally obtained by distri
buting samples for analysis to interested laboratories
and the large a m o u n t s of data independently re
turned a r e statistically treated to remove outliers
before arriving, with a greater or lessee degree of
subjectivity, at an accepted ' r e c o m m e n d e d ' , 'certi
fied', 'best' or 'working' value. If the original results
are studied there is usually a considerable spread,
even after the removal of outliers, and the user of
G R M s is advised to study these before making use
of compiled ' r e c o m m e n d e d ' values. It should b e
obvious that analytical m e t h o d s whose calibration
relies on these consensus values should not be used
to provide values for new reference samples, or
those values should b e t r e a t e d with caution. T h e r e
are m a n y examples in t h e literature w h e r e t h e r e has
b e e n extensive extrapolation of calibrations, and
w h e r e m a n y analysts use the same m e t h o d and
comparative calibration samples a consistent but
biassed 'working value' m a y b e obtained. A good
example is t h e analysis of Z r w h e r e most values a r e
obtained by X R F .
Most reference materials a r e distributed free of
charge by their producers, usually national geo
logical surveys or similar organizations. H o w e v e r ,
they a r e extremely costly to produce a n d analyse
and so should be used sparingly. Indeed the supplies
of a n u m b e r of early reference samples were exhaus
ted before reliable working values were reached.
T h e main p u r p o s e of a G R M is to allow users (and
suppliers) of analytical d a t a to j u d g e its reliability,
and hence the results of geochemical analyses
should be accompanied by equivalent d a t a on refer
ence materials of similar composition and analysed
by t h e same m e t h o d s . This particularly allows the
efficiency of sample preparation to be tested.
T h e aim should b e t o employ a reference only
when an analytical technique is essentially proven
and for each laboratory to provide its own 'in-house'
references for day to day quality control and for
m e t h o d d e v e l o p m e n t . This is particularly important
for all m e t h o d s which destroy the original material.
Users of G R M s and in particular those provided
free of charge should b e prepared to provide the issu
ing organization with reliable data on the samples
within a reasonable time.
338
I.J. FAIRCHILD ef AL.
Reporting a n d d o c u m e n t a t i o n
9.7A
Geochemical d a t a from sedimentary rocks are re

ported in several forms, and there are many ways in
which the data can be presented to illustrate t r e n d s ,
patterns and variations in distribution. In addition,
data are frequently examined statistically to deter
mine m e a n s , standard deviations, correlation coeffi
cients and other p a r a m e t e r s .
Analyses of major and some minor elements in
siliciclastic rocks are usually q u o t e d in percentages
as the oxides. This is the convention a d o p t e d in
hard-rock petrology, a n d it is useful since it d o e s
give an indication of the completeness of the analysis.
M a n y of the less c o m m o n metals and o t h e r elements
present in only trace quantities are expressed as the
elemental form in p p m o r p p b . With carbonates it is
usual t o give t h e results in elemental form, as % or
p p m , although for limestones the acid-soluble Mg
content is often quoted as the mole % M g C 0
present in the calcite lattice. With dolomites, the Ca
and Mg values are often recalculated to give the
mole % of each c a r b o n a t e in 100% dolomite, so that
the stoichiometry is obvious.
W h e r e limestones in an analysed suite have a
variable insoluble residue, t h e n direct comparison of
trace element (and major element) values b e t w e e n
samples is difficult. T o get round this p r o b l e m ,
analyses of the acid-soluble fraction of limestones
and dolomites are frequently recalculated to give
insoluble residue-free values (i.e. 100% soluble
carbonate).
Insoluble Residues ( I R ) are frequently d e t e r m i n e d
for carbonate rocks, as they give a value for t h e
purity of the rock. In addition, o n e can see if t h e r e is
any positive correlation b e t w e e n I R and trace ele
ments in the acid-soluble fraction (notably F e ,
M g , A l and M n ) , which would indicate leach
ing from the insoluble residue. After acid digestion,
the I R is r e m o v e d by filtering and t h e n it is weighed
after ashing the filter p a p e r at, say, 900C for 2
hours. If organic carbon is present, then this would
be oxidized and r e m o v e d along with the p a p e r on
ashing.
T h e validity of the interpretation of geochemical
data depends on the quality of those data, and it is
therefore necessary for an author to provide the
reader with sufficient information to m a k e a judge
ment. It follows that such information should also
be fully d o c u m e n t e d in the laboratory before
publication.
3
2 +
2 +
3 +
2 +
A brief description of collection and crushing

p r o c e d u r e s should be given together with sample
p r e t r e a t m e n t (for example the drying t e m p e r a t u r e
before analysis). T h e m e t h o d of analysis should be
decribed, and if this is modified from a published
technique any deviations o r i m p r o v e m e n t s should
be indicated. Sample weights and the m e t h o d of
calibration used are especially important. T h e aim
should be to allow the r e a d e r to repeat the m e t h o d
of analysis exactly. Reference materials q u o t e d
should have been analysed by the same m e t h o d .
Steele (1978) has listed the essential information
which an analyst should provide when reporting on
values of reference materials; this list is an excellent
m o d e l for the reporting of all analytical data. W h e r e
extensive use is m a d e of unpublished primary data
(for example through lack of journal space) the full
set and analytical information should be available on
request.
T h e precision and accuracy of analyses are often
given in m e t h o d s sections of papers and here it is
normal to q u o t e the reference materials used and a
figure for accuracy and instrumental and analytical
precision in relative per cent. W h e r e no indiation of
the uncertainty is given t h e n , in terms of the n u m b e r
of significant figures for an e l e m e n t in an analysis, it
is generally held that the last figure is correct to 2
or 3 ; that is, a figure of 3 5 . 2 % m e a n s the actual
value is probably b e t w e e n 35.5 and 3 4 . 9 % ; with
35.24, it would lie between 35.21 and 35.27.
Geochemical data are frequently displayed as
scatter plots of one element against a n o t h e r . With
limestones, N a v. Sr, N a or Sr v. M n , M n v. F e , 5 C
v. 8 0 and N a or Sr v. 8 0 are frequently shown
(see e.g. A l - A a s m & Veizer, 1982; T u c k e r , 1986).
In s o m e instances two elements are a d d e d t o g e t h e r
and plotted against a third; e.g. Fe + Mn v. Sr. Fe
and Mn are normally low in marine c a r b o n a t e pre
cipitates (Sr is high) and they are picked u p during
diagenesis (Sr is lost), so that Fe + Mn,<y. Sr will
reflect the degree of diagenetic alteration. Ratios of
elements are also used, e.g. 1000 Sr/Ca, which allows
for variations in Ca content b e t w e e n samples. B r a n d
& Veizer (1980) used a plot of 1000 Sr/Ca v. M n to
show the a m o u n t of alteration of fossils during
diagenesis.
In limestones, as most rocks, the trace element
contents are log-normally distributed. T o clarify
chemical trends in c a r b o n a t e s , data are frequently
plotted on log scales.
Geochemical data can be treated at length statis-
tically, especially now that data manipulation can be

u n d e r t a k e n by computer. Necessary values, such as
m e a n , standard deviation, precision and accuracy
are easily calculated. It is c o m m o n to go further than
this and u n d e r t a k e tests of significance, analysis of
variance and calculations of correlation and regres
sion. Correlation coefficients are useful and allow
o n e t o find meaningful relationships between the
different p a r a m e t e r s . Significant correlations can
help in the interpretation of the data. For example,
with dolomites a positive correlation b e t w e e n 5 C
and 8 O or Sr and 8 0 can support a mixing-zone
origin for t h e dolomitization. A s n o t e d earlier,
negative correlations of Sr and M n , or N a and M n ,
reflect degrees of diagenetic change. Mn and F e
normally co-vary, as do N a and Sr, and Ca and Mg.
M o r e elaborate statistical techniques can be used
and include factor analysis, to identify the reasons
for variations in the measured elements and discri
m i n a n t analysis, t o distinguish b e t w e e n different
suites of samples. Factor analysis was used by B r a n d
& Veizer (1980) a n d A l - A a s m & Veizer (1982) to
account for the variations of trace elements in vari
ous c o m p o n e n t s of Silurian and Mississippian lime
stones, and in rudist bivalves. W a l t e r s et al. (1987)
used discriminant analysis to separate J u r a s s i c Cretaceous shales of marine a n d non-marine origin.
Details of these and o t h e r m e t h o d s of statistical
analysis are contained in the many textbooks on this
subject.
1 3
l s
1 3
1 3
1 8
1 8
9.8
EXAMPLES
In this section, a few of the applications of chemical

analysis of sedimentary rocks are p r e s e n t e d , roughly
in the o r d e r of the objectives A to E outlined in
Section 9 . 1 .
9.8.1 Provenance and weathering

T h e s e two topics (objective A and part of objective
B ) are t r e a t e d t o g e t h e r because of the difficulty in
establishing that weathering effects were minimal in
provenance determinations. Chemical analysis has
m u c h ground t o m a k e u p on purely mineralogical
studies in these areas. F o r e x a m p l e , the precise
interpretation of provenance f r o m heavy mineral
studies has b e e n long established, as are interpreta
tions of the tectonic significance of the source and
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339
depositional areas deduced from the modal percen

tages of the main minerals; the climatic significance
of the clay mineralogy of detrital sediments is also
well known. In many cases, therefore, the direct
r o u t e to the objective is by purely mineralogical
rather than chemical study, but some notable excep
tions are given below.
Blatt, Middleton & M u r r a y (1980) reviewed exam
ples w h e r e knowledge of mineral chemistry, partic
ularly of heavy minerals, can be used to reconstruct
p r o v e n a n c e . G a r n e t is a n o t a b l e e x a m p l e because of
its chemical variability in the source area and chemi
cal stability ( M o r t o n , 1985). A m o n g major consti
t u e n t s , feldspar has particular promise. T r e v e n a &
N a s h (1981) argued that microprobe analysis of d e
trital feldspars should be m o r e widely used in pro
venance determinations, a n d they spelt out the
significance of feldspar chemistry in terms of source
rocks. In contrast to whole-rock work, only fresh,
unweathered grains are chosen for analysis. Although
weathering is not a p r o b l e m in this approach ( p r o viding s o m e fresh grains are p r e s e n t ) , diagenetic
alteration must be carefully evaluated.
If o n e considers t h e whole-rock analytical ap
proach, only in glacially-transported sediments can
it b e realistically supposed t h a t minimal chemical
weathering has occurred. Unless inert chemical
c o m p o n e n t s are studied, such analyses are likely to
reveal m o r e a b o u t chemical weathering processes
t h a n source rock chemistry. T h e study of Nesbitt,
Markovics & Price (1980) on granodiorite weather
ing in an 'average' climate illustrates the varying
susceptibility of cations to the combination of leach
ing and adsorption processes operating h e r e . Their
results are consistent with adsorption theory and the
leachate has very similar e l e m e n t ratios to worldaverage river w a t e r . Applying this a p p r o a c h t o t h e
Early Proterozoic H u r o n i a n S u p e r g r o u p , Nesbitt &
Y o u n g (1982) r e a s o n e d t h a t m u d r o c k s would give a
good index of possible changes in intensity of chemi
cal w e a t h e r i n g with time. Using a chemical altera
tion index (Fig. 9.24) they w e r e apparently able to
d e m o n s t r a t e climatic changes b e t w e e n (i) a regime
of active chemical weathering at the t o p and b o t t o m
of the studied section and (ii) the glacial G o w g a n d a
F o r m a t i o n in the central part of the section in which
chemical weathering effects w e r e small, particularly
in the matrix of diamictites. This approach is worthy
of further d e v e l o p m e n t , which will be helped by
theoretical a n d experimental studies (e.g. Nesbitt &
Y o u n g , 1984).
7
340
ing processes on these elements. It will not usually

be possible to tackle t h e p r o b l e m in t h e elegant
fashion of Tieh, L e d g e r & R o w e (1980), who used
fission-track images t o d e m o n s t r a t e t h a t U w a s lost
only from intergranular sites during weathering of
granites. Nesbitt (1979) showed in a study of granodiorite weathering that R E E elements were leached
in acid, u p p e r portions of soils and precipitated or
a d s o r b e d , in accordance with theoretical predic
tions, as p H increased to neutral down t h e soil
profile. H e argued that Ti will b e t h e most inert
e l e m e n t h e r e . In a similar study, b u t on a m o r e
reactive volcanogenic s a n d s t o n e , D u d d y (1980) c a m e
to similar conclusions, but by using microprobe
analyses was able to show that vermiculite was a
major repository of r a r e e a r t h s , in quantities suffi
ciently large (up to 10%!) to indicate siting within
t h e lattice rather t h a n by adsorption. T h u s little of
t h e R E E find their way into solution, and a r e t h e r e
in similar p r o p o r t i o n s t o t h e host rocks anyway
(Piper, 1974). Taylor, M c L e n n a n & McCulIoch
(1983), in testing loess as a sampling agent for t h e
composition of t h e u p p e r crust, found R E E p a t t e r n s
Residual clays _
Amazon cone muds
Average shale _
Pleistocene varved clays
I
Pleistocene glacial clays

I
Pleistocene tills (loca
Archaean
shield.
NW Ontario
(source rocks)
Bar River Fm
Gordon Lake Fm
(but not o t h e r elemental a b u n d a n c e s ) very constant.

This testifies to t h e inert n a t u r e of R E E , but also
illustrates their imprecision as source indicators.
B a s u , Blauchard & B r a n n o n (1982) found that
weathering climate was irrelevant to R E E patterns
(but not absolute a b u n d a n c e s ) , b u t indicated that
s o m e variation with rock type may occur. Neverthe
less, R E E may be m o r e useful in assessing t h e
terrigenous contribution to a sediment r a t h e r t h a n
specifying p r o v e n a n c e . T h e study of Tlig & Steinberg
(1982) is instructive in illustrating t h a t this will n o t
be possible in sediments with complex mixtures of
chemical c o m p o n e n t s . In their sediments, a bland
whole-rock R E E p a t t e r n , similar to that of typical
shales, is seen to consist of a mixture of two patterns:
o n e with a negative Ce-anomaly in t h e coarser,
biogenic size fractions (similar to t h e R E E pattern
of sea w a t e r ) and a p a t t e r n with a positive C e anomaly, associated with authigenic smectite in the
finer size fractions (Fig. 9.25).
T h e possibilities of using geochemical p a r a m e t e r s
to estimate t h e size of t h e terrigenous c o m p o n e n t in
sediments has been exploited to good effect by
Sample/shale
(log scale)
Mineralogy
i i
Fig. 9.24. Plot of 'chemical index of

alteration' of sedimentary rocks from
the Huronian Supergroup compared
with Quaternary clays and the
Archaean source rocks for the
Huronian Supergroup. Note that
CaO* refers to silicate Ca, i.e. the
data are whole-rock data on a
carbonate-free basis. For
comparison, CIAs for basalts are
3 0 - 45, and for granites 4 5 - 5 5 . High
CIAs denote greater chemical
weathering (after Nesbitt & Young,
1982).
i i
341
size fraction
/xm
Opal
>35
Feldspar
Quartz
20-35
Bulk clay
5-20
Kaolinite
2-5
Illite
Chemical index of alteration =
1.00 A I Q
Na 0 + K 0
A l , 0 + CaO*
2
Bulk sample
T h e device of using inert chemical c o m p o n e n t s to
m o n i t o r provenance has been explored by various
authors. Strontium has b e e n advocated as an evaluator of t h e geographic siting and type of terrigen
ous input by P a r r a , Puechmaille & Carrkesco (1981).
H o w e v e r , their use of whole-rock analyses causes
p r o b l e m s since t h e r e is a b u n d a n t Sr sited in biogenic
carbonates in their studied sediments. T h e y esti
m a t e d the Sr content of the n o n - c a r b o n a t e fraction
1-2
Smectite
as t h e intercept on plots of Sr versus C a C 0 con

t e n t . It would h a v e b e e n m o r e straightforward t o
have analysed carbonate-free insoluble residues.
R a r e - e a r t h elements ( R E E ) and certain o t h e r
trace elements such as T h a r e r e g a r d e d as t h e m o s t
reliable elemental inert c o m p o n e n t s in t h e sedimen
tary cycle (Piper, 1974; Bhatia & Taylor, 1981;
M c L e n n a n , 1982; Pacey, 1984). Relatively little work
has b e e n d o n e , however, on t h e effects of weather-
BS
0.5-1
0.2-0.5
<0.2
La Ce Nd Sm Eu Tb
Yb Lu
Fig. 9.25. Rare earth element patterns and mineralogical variation for different size fractions of a Recent sediment from
a site in the Indian Ocean. BS = bulk sample (after Tlig & Steinberg, 1982).
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Hti
342
Sugisaki (1984) w h o used ratios of M n , C o and Ni to

Ti as an expression of the relative a b u n d a n c e of
authigenic oxide precipitates to terrigenous sedi
m e n t . T h e s e ratios correlate well with sedimentation
rate which in turn correlates with distance from
source of terrigenous detritus. This allows distinc
tion of pelagic from arc sediments in ophiolite suites.
H i c k m a n & Wright (1983), in an empirical study,
have shown t h a t whole-rock geochemical d a t a can
allow stratigraphic correlations to be m a d e in d e
formed terrains for slates, c a r b o n a t e s , and even
s o m e quartzites. W h e n combined with selective
analysis and petrographic d a t a , this could prove to
be a powerful tool.
9.8.2 Environmental parameters

T h e s e are t h e objectives of strategy C and some
times strategy B (Fig. 9.1). T h e r a n g e of material
studied is very considerable but only two topics a r e
covered h e r e , both classics of sedimentary geo
chemistry: boron palaeosalinity studies on clays, and
geochemical studies o n calcareous shells.
T h e following a r e useful reviews and recent not
able p a p e r s on other* applications: t h e geochemistry
of metalliferous oceanic deposits and m a n g a n e s e
nodules (e.g. C r o n a n & M o o r b y , 1981; M o o r b y ,
C r o n o n & Glasby, 1984; and a special issue of
Geochimica
cosmochimica
Acta, M a y 1984); the
geochemistry of phosphorites (e.g. M c A r t h u r et al.,
1986); isotopic m e t h o d s for measuring sedimenta
tion rates (e.g. Special Issue of Chemical
Geology,
V o l u m e 44, parts 1/3, 1984); t h e geochemistry of
marine-authigenic silicates (e.g. articles in B u r n s ,
1979; H a r d e r , 1980; Cole & Shaw, 1983; BergM a d s e n , 1983); t h e origin of brines responsible for
evaporite deposits ( H a r d i e , 1984).
BORON PALAEOSALINITY STUDIES
It follows, therefore, that for an element to be of

use as an index of salinity it must m e e t certain
criteria: (a) It must be widespread in c o m m o n sedi
m e n t s and a b u n d a n t enough to be detected and
m e a s u r e d with a reasonable d e g r e e of precision, (b)
Its concentration should d e p e n d as far as possible on
salinity and not on any o t h e r factors, (c) Equili
brium should exist b e t w e e n its concentration in the
sediment and t h e solution from which t h e sediment
was deposited, (d) Diagenetic, m e t a m o r p h i c and
weathering processes should have n o effect o n t h e
concentration of t h e e l e m e n t .
T h o s e elements which broadly satisfy these- re
q u i r e m e n t s include V , Cr, G a , N i , R b , B a n d Li;
although with t h e exception of boron most of these
are treated with scepticism today. D e g e n s , Williams
& Keith (1957) a n d P o t t e r , S h i m p & W i t t e r s (1963)
a r e a m o n g t h e few authors w h o have successfully
applied such a b u n d l e of elements to specific palaeoenvironmental p r o b l e m s .
M o r e commonly it is to b o r o n that most geologists
have turned in the h o p e of arriving at credible salinity
interpretations. H o w e v e r , even with b o r o n relative
ly few a t t e m p t s have been m a d e to apply t h e tech
nique to real p r o b l e m s directly. M a n y researchers
have concentrated instead on validating t h e b o r o n salinity relationship using as guides sediments with
good faunal-salinity data. This is in large p a r t d u e t o
t h e wide range of factors that can affect its m e a s u r e d
concentration (i.e. it does n o t strictly conform with
( b ) ' a b o v e ) . In this respect b o r o n is a good example
of how" an apparently simple geochemical relation
ship b e c o m e s complicated w h e n a t t e m p t i n g t o use it
to solve geological p r o b l e m s (Walker, 1975).
T h e concentration of b o r o n in natural waters is
primarily linked t o salinity via t h e ability of certain
dissolved salts t o p r o m o t e t h e dissociation of boric
acid (H3BO3). H e n c e in sea water t h e presence of
C a , N a , K and M g salts increases t h e n u m b e r of
b o r o n anion groups (e.g. B ( O H ) ~ ) being liberated
into solution and thus available for adsorption by
clays. Conversely t h e r e d u c e d concentration of these
salts in river water inhibits t h e dissociation process
and explains t h e low values for dissolved b o r o n in
such solutions (i.e. 0.013 p p m c o m p a r e d t o 4.8
p p m ) . F r o m this relationship it may b e r e a s o n e d
that marine clays will contain m o r e b o r o n t h a n
freshwater clays, and indeed this is w h a t t h e earliest
research found (e.g, Goldschmidt & Peters, 1932;
L a n d e r g e n , 1945; Frederickson & R e y n o l d s , 1960).
H o w e v e r , in the intervening years it has b e c o m e
clear that this simple boron-salinity relationship is
complicated by a r a n g e of o t h e r natural p h e n o m e n a .
N o t all clay minerals fix b o r o n at an equal r a t e ,
most research showing that the element has a strong
affinity for illite (Hingston, 1964; Fleet, 1965). H e n c e
it is the concentration of boron in illite that is usually
d e t e r m i n e d , while since grain size also affects t h e
a m o u n t of b o r o n a d s o r b e d it is usual to confine all
m e a s u r e m e n t s t o a single particle size o r r a n g e (e.g.
< 2 u m ) . This also removes the possibility of intro
ducing b o r o n as tourmaline. T o complicate m a t t e r s ,
s o m e research has shown that smectitic clays are
capable of adsorbing as much or m o r e boron than
illite (Tourtelot, Schultz & Huffman, 1961; L e r m a n ,
1966), while successful palaeosalinity interpretations
have been m a d e using kaolinite (Couch, 1971).
Poorly crystallized illites are capable of adsorbing
more boron than well crystallized varieties (Porrenga,
1967), a p h e n o m e n o n apparently reflecting t h e divi
sion of each particle into a 'structurally coherent
silicate c o r e ' with little or n o vacant sites, surround
ed by an ' i n c o h e r e n t rind' or 'frayed e d g e ' with
a b u n d a n t adsorbing sites (Jackson, 1963; G a u d e t t e ,
G r i m & Metzger, 1966; Fig. 9.26). H e n c e , as crystal
linity improves, t h e silicate core occupies a larger
p r o p o r t i o n of t h e illite particle a n d less b o r o n can b e
fixed. T h e reverse is true for poorly crystallized
particles.
E v e n w h e n apparently p u r e illite is isolated, com
positional variations can affect t h e u p t a k e of b o r o n .
C . T . W a l k e r (1962) used t h e concentration of K 0
in illite to d e t e r m i n e t h e n u m b e r of muscovite-type
layers p r e s e n t , deriving what he t e r m e d 'adjusted'
2
Structurally coherent
silicate core
E n v i r o n m e n t a l discrimination based on trace ele

m e n t analysis is founded o n t h e assumption that
t h e r e is s o m e link b e t w e e n t h e m e a s u r e d concentra
tion of an element in a sediment and its concentra
tion in solution at t h e time of deposition. In o t h e r
w o r d s , 'the chemical composition of detrital clay
minerals . . . is affected by the chemistry of their
a q u e o u s depositional e n v i r o n m e n t ' ( C o d y , 1971).
This definition is equally applicable to sandstones,
limestones and shales since it is in t h e clay fraction
that elements of use in palaeosalinity work a r e
encountered.
Incoherent 'rind' or
'frayed edge'
Fig. 9.26. The 'core-rind' model of boron incorporation
in illite.
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343
b o r o n . This correction was refined by W a l k e r &

Price (1963) because 'adjusted' b o r o n was found to
b e d e p e n d e n t o n t h e potassium content. T h e i r
'equivalent' b o r o n they suggested was capable of
resolving small salinity variations.
Spears (1965), while accepting the validity of 'ad
j u s t e d ' b o r o n , rejected 'equivalent' b o r o n because it
was based on u n i q u e empirical d a t a which could
not b e expected to be applicable to all sedimentary
basins. Spears went further, however, and a p p e a r e d
to reject b o t h corrections; believing that t h e boron/
K 0 ratio was not solely influenced by the chemistry
of t h e depositional solution but was greatly affected
by weathering of source rocks, boron being m o r e
stable t h a n potassium.
T h e concentration of organic m a t t e r in solution
can also affect t h e fixation process, B a d e r (1962)
showing t h a t clays h a v e t h e potential t o adsorb
350% of their own mass of colloidal organic carbon
from solution, h e n c e forming a 'protective skin'
( L a n d e r g r e n & Carvajal, 1969) a r o u n d each clay
particle, t h u s retarding o r even stopping t h e adsorp
tion of b o r o n .
Purely detrital organic matter has a simple dilutant
effect, as does C a C 0 and S i 0 , such that t h e fluc
tuating concentration of these substances through a
sedimentary sequence will p r o d u c e changes in b o r o n
unrelated to salinity, unless corrected for.
Sedimentation rate is also important since t h e
second step in t h e fixation mechanism after initial
adsorption is t h e diffusion of b o r o n into t h e clay's
interior (Couch & G r i m , 1968) which is slow at
surface t e m p e r a t u r e s a n d pressures. H e n c e alterna
tions of limestone (slowly deposited) and sandstone
(rapidly deposited) may also p r o d u c e spurious b o r o n
variations.
T h i s t e n a c e o u s bonding of b o r o n t o illite via
structural incorporation has profound consequences
for t h e use of b o r o n as a salinity tool because it
introduces t h e p r o b l e m of element re-cycling. It is
this p r o b l e m of 'inherited' b o r o n which has dogged
t h e technique and which t e m p e r e d much of the early
enthusiasm for t h e m e t h o d .
L a n d e r g r e n & Carvajal (1969) defined inherited
b o r o n in terms of 'relic (detrital)' b o r o n which did
not reflect t h e existing set of environmental condi
tions but nevertheless belonged to t h e same deposi
tional episode a n d 'recycled o r redeposited' b o r o n
which had u n d e r g o n e o n e or m o r e sedimentary
cycles.
E x p e r i m e n t a l work by Fleet (1965) and Couch &
G r i m (1968) revealed t h a t illites with an inherited
2
344
b o r o n concentration of u p to 500 p p m w e r e still

capable of fixing fresh b o r o n from solution, while
Spears (1965) convincingly showed that m u c h of the
b o r o n work o n C o a l M e a s u r e sediments from t h e
north of England was invalid because of t h e strong
source control. This p r o b l e m of recycled b o r o n
clearly hinges o n t h e acceptance that illites cannot
b e d e g r a d e d by n o r m a l weathering processes a n d
forced to lose their b o r o n . H o w e v e r , B o h o r &
G l u s k o t e r (1973), while accepting t h e great resilience
of illite to chemical attack, nevertheless believed
that surface processes w e r e capable of achieving this
aim and that as a c o n s e q u e n c e , ' o u r rivers are full of
d e g r a d e d illites'. Couch (1971) s u p p o r t e d this view,
pointing out that u n d e r m o d e r a t e to humid climates
appreciable leaching of b o r o n occurs during soil
formation.
R e c e n t work by o n e of us ( Q u e s t , 1985) on t h e
Purbeck B e d s ( U p p e r JurassicLower C r e t a c e o u s )
of D o r s e t a p p e a r s to confirm that syn-sedimentary

leaching of b o r o n is possible. Illite in these beds is
t h o u g h t t o have been derived from erosion of t h e
underlying m a r i n e K i m m e r i d g e Clay and thus should
give t h e whole sequence a m a r i n e signature, while
faunal studies ( C l e m e n t s , 1973) record a fluctuating
salinity regime from hypersaline t o near fresh w a t e r .
F r o m an examination of approximately 30 beds
chosen on t h e basis of their fauna as belonging to
o n e of four salinity groups (hypersaline, m a r i n e ,
brackish and freshwater), Q u e s t was able to show
that b o r o n in illite was a realistic m e a s u r e of p a l a e o
salinity and t h a t b o r o n recycling w a s u n i m p o r t a n t
(Fig. 9.27). Leaching of boron from t h e m a r i n e
Kimmeridge source rocks must have occurred prior
to deposition. Smith & Briden (1976) suggested a
palaeolatitude of about 36N for the D o r s e t P u r b e c k
and thus appreciable chemical weathering in t h e
warm humid climate would be expected.
SKELETAL GEOCHEMISTRY
345
in their study of PlioPleistocene invertebrates from
sisted of sandstones, siltstones and claystones with

local conglomerates deposited in a m a r i n e embaym e n t which b e c a m e gradually isolated until lacu
strine and fluvial environments were established.
H e n c e relatively large-scale salinity
fluctuations
could b e expected while t h e r e was evidence for a
gradual cooling t o w a r d s the early Pleistocene. Fossil
invertebrates were a b u n d a n t and well preserved
with extant varieties for comparison.
P a l a e o t e m p e r a t u r e estimates were m a d e using t h e
concentration of Sr in the o u t e r calcitic layer of
Mytilus shells. All analyses were performed o n the
s a m e species of bivalve t o avoid phylogenetic effects.
Estimating the Sr/Ca ratio in t h e depositional waters
proved difficult because of t h e restricted n a t u r e of
t h e p a l a e o e n v i r o n m e n t a n d a variable freshwater
input. Extensive diagenetic modification w a s , how
ever, ruled out because ontogenetic Sr variations
could be recognized.
T h e Sr p a l a e o t e m p e r a t u r e d a t a they p r o d u c e d
were found to be in b r o a d agreement with faunal
interpretations with n o systematic variations. U n
fortunately t h e authors failed to include an explana
tion of how t h e Sr concentrations w e r e converted to
p a l a e o t e m p e r a t u r e s , this information being p r o
vided by D o d d (1966). H e found t h a t t h e concentra
tion of Sr expressed as mol % S r C 0 in the calcite
layer of m o d e r n Mytilus shells was related to tem
p e r a t u r e over t h e range 1220C by t h e equation:
t h e K e t t l e m a n Hills, central California. T h e p u r p o s e
T = 347Sr - 32.9.
A good introduction to this topic was provided in

t h e text by D o d d & S t a n t o n (1981) w h o detailed t h e
chemical properties of fossils as tools in palaeoenvironmental reconstruction, concentrating o n
skeletal mineralogy, trace chemistry and isotopic
techniques. T h e y suggested that t h e main factors
controlling skeletal chemistry (physical-chemical,
e n v i r o n m e n t a l , physiological a n d diagenetic) can b e
regarded as t h e four corners of a t e t r a h e d r o n (Fig.
9.28), with t h e actual trace e l e m e n t or isotopic com
position of t h e shell plotting as a point whose posi
tion is d e t e r m i n e d by the relative i m p o r t a n c e of
each factor. Clearly shells with much diagenetic
alteration need t o b e avoided (see D o d d & S t a n t o n ,
1981, and o t h e r works reviewed in Section 9.8.3).
T h e y believed that t h e study of biogeochemistry can
help in t h e solution of four major types of geological
p r o b l e m : (a) general c a r b o n a t e geochemistry, (b)
c a r b o n a t e diagenesis, (c) element recycling within
t h e crust and (d) p a l a e o e n v i r o n m e n t a l interpreta
tion. N u m e r o u s examples of such applications are
provided including an examination of oxygen isotope
palaeothermometry.
Upper
A particularly good example of the combined use

of trace e l e m e n t and isotope geochemistry was pro
vided by the same a u t h o r s (Stanton & D o d d , 1970)
of this w o r k , a m o n g o t h e r things, was to c o m p a r e
Middle
and contrast faunal and geochemical m e t h o d s for

reconstructing p a l a e o e n v i r o n m e n t s a n d , in partic
ular, t e m p e r a t u r e and salinity. T h e sediments con-
Physical
Diagenetic
W h e n attempting to apply oxygen isotope d a t a to

an understanding of palaeosalinity, the authors had
to concede that only crude t r e n d s in salinity could b e
d e d u c e d because t h e 0 / 0 ratio for t h e Kettlem a n e n v i r o n m e n t was not k n o w n d u e to t h e uncer
tain influence of inflowing fresh water. This also
ruled out p a l a e o t e m p e r a t u r e work, although they
suggested that if t h e Sr p a l a e o t e m p e r a t u r e and t h e
oxygen isotopic composition of t h e shell were p u t
into t h e p a l a e o t e m p e r a t u r e equation of Epstein
et al. (1953), t h e n it could be solved to give t h e 0 /
0 ratio of t h e water in which t h e shell grew.
Diagenetic alteration was once again found to be
u n i m p o r t a n t d u e to t h e lack of any significant light
ening of the m e a s u r e d 5 0 values. Oxygen isotope
palaeosalinities also corresponded well to those de
duced faunally.
T h e authors concluded that the interpretative value
of a combined faunal and geochemical study was
very strong because t h e two m e t h o d s c o m p l e m e n t e d
1 8
1 6
1 8
1 5
Lower
Fig. 9.27. Concentration of boron in

< 2 um illite for the Purbeck at
Durlston Bay (data of M. Quest).
Faunal/salinity classification scheme
after Clements (1973).
freshwater
brackish
marine
hypersaline
120 m
total
1 8
Environmental
100
200
300
400 ppm
Fig. 9.28. Schematic representation of the factors

controlling the chemistry of skeletal components (from
Dodd & Stanton, 1981).
http://jurassic.ru/
346
CHEMICAL ANALYSIS OF SEDIMENTARY ROCKS 3 4 7
I . J . FAIRCHILD ef al.
each other. Geochemistry allowed t h e quantification

of t e m p e r a t u r e a n d salinity while t h e structure and
composition of t h e fauna provided an estimate of
the degree of isolation from t h e sea. In addition t h e
a g r e e m e n t between geochemistry and palaeon
tology was thought t o b e a good indication of a lack
of diagenetic alteration although i n d e p e n d e n t petro
graphic verification of lack of alteration is preferable.
In a later p a p e r , D o d d & Stanton (1975) were
able t o provide palaeosalinity contours for t h e
Kettleman region in two stratigraphic zones. T h e y
-assumed that during t h e deposition of each zone t h e
t e m p e r a t u r e at which calcification occurred was
m o r e o r less t h e same such that t h e 0 / 0 ratio in
the water ( a n d h e n c e in t h e shell) was a function of
salinity alone. By analysing known marine a n d
freshwater bivalves they were able t o establish endm e m b e r s for their salinity spectrum. T h u s a shell
with a 5 0 i n t e r m e d i a t e b e t w e e n these points
would correspond t o a given a m o u n t of mixing of
marine a n d fresh waters. Using this technique they
w e r e able t o identify t h e m o u t h of t h e e m b a y m e n t
and t h e points of inflow of river water.
Most theoretical discussions of oxygen isotope
palaeothermometry assume that t h e skeletal material
being analysed is derived from fully mixed o p e n
m a r i n e conditions. A s t h e a b o v e example shows,
1 8
1 6
1 8
berg, 1986); this will be particularly useful when

combined with analytical techniques (such as I C P )
that use minimal sample. Alternatively, preserved
aragonite can yield valuable information, even using
the mobile element N a ( B r a n d , 1986). B r a n d &
Morrison (1987) provided a good review of fossil
skeletal geochemistry.
however, this m a y n o t b e t h e case since m a n y inver

tebrates inhabit marginal near-shore regions with an
input of light 0 that is difficult t o quantify. M o o k
(1971) overcame this problem in his study of molluscs
from four D u t c h estuaries. H e found that w h e n t h e
isotopic composition of t h e shell c a r b o n a t e from
these estuaries was plotted on a graph of 5 0 v.
5 C they each described a straight line (Fig. 9.29).
This relationship arose because t h e isotopic composi
tion of t h e brackish water in which t h e organisms
calcified was related linearly t o t h e 8 O a n d 8 C
c o n t e n t of t h e mixed m a r i n e a n d fresh waters a n d
their dissolved bicarbonate. T h e fact that molluscs
from each estuary plotted o n s e p a r a t e lines w a s
because t h e freshwater source in each case w a s
isotopically distinct. Since all four estuaries contain
ed some marine water of c o m m o n isotopic composi
tion, M o o k found that t h e data for each converged
on a point equivalent t o t h e 8 0 a n d 8 C content
of marine c a r b o n a t e . Since t h e 0 / 0 ratio of sea
water is k n o w n , a p a l a e o t e m p e r a t u r e could b e cal
culated for t h e estuaries.
T h e s e studies a r e precise because of t h e younger
age of t h e studied material. In older rocks, material
which has suffered minimal alteration is h a r d e r t o
find. Cathodoluminescence can help t o select un
altered portions of shells ( P o p p , A n d e r s o n & Saud1 6
1 8
1 3
l s
1 8
1 8
9.8.3 Diagenesis
1 3
1 3
1 6
+4r
+2h
0 o
-VP
cr--
p~-2 o
to
13
Fig. 9.29. Relation between 5 C

and 6 O of skeletal carbonate for
four Netherland estuaries: Western
Schelde (W), Eastern Schelde (E),
Mouth of the Rhine (R), ZuiderzeeWaddenzee (Z). The line with the
temperature scale indicates the
isotopic composition of fully marine
carbonates formed at those
temperatures (after Mook, 1971).
-4_
l s
Chemical analysis has played a full part in t h e

revolutionary advances in t h e understanding of dia
genesis t h a t h a v e t a k e n place in recent years, yet w e
are far short of t h e goal of predictive, rather than
deductive, diagenesis. M o s t space will b e d e v o t e d
here t o c a r b o n a t e rocks because of t h e special im
pact of chemical rather than merely mineralogical
analysis.
Whilst most c a r b o n a t e workers have carried o u t
integrated field-petrographic-geochemical studies on
individual stratigraphic units, an alternative a p
proach, s p e a r h e a d e d by Veizer and co-workers in
n u m e r o u s publications, seeks to characterize chemi
cal diagenetic processes in a m o r e general way by
the empirical geochemical study of m o r e widelyd r a w n samples, or by focussing o n diagenetic altera
tion of particular depositional c o m p o n e n t s . This
alternative a p p r o a c h is reviewed first.
T h e study of Veizer (1974) o n t h e diagenesis of
certain Jurassic belemnites is illustrative and partic
ularly apposite given t h e choice of a belemnite as t h e
isotopic ( P D B ) s t a n d a r d , presumably in t h e h o p e
that it was both h o m o g e n e o u s and unaltered in
composition. Veizer (1974) found that although t h e
Sr (Fig. 9.30a) a n d M g contents of belemnite rostra
were fairly constant, M n (Fig. 9.30b) and F e were
m u c h m o r e variable. T h e chemical composition of
the p h r a g m a c o n e septa (originally aragonitic) was
nearly identical t o t h e c a r b o n a t e in t h e host rock.
Veizer inferred that t h e rostra must have b e e n partly
recrystallized or h a d h a d internal pores c e m e n t e d
(or both) and deduced t h e degree of this diagenetic
alteration from t h e approach of t h e M n content t o
the host rock value (Fig. 9.30b). T h e secondary
calcite must have contained m u c h m o r e F e a n d M n
t h a n t h e original rostra, b u t differed little in Sr and
Mg. T h o s e rostra with slightly m o r e negative 8 0
values also have high M n contents, invalidating
previous conclusions of p a l a e o t e m p e r a t u r e varia
tions in t h e Jurassic seas supposedly evidenced by
8 0 values. S o m e points from this study that have
1 8
8
'
~~ ^ ^
-8
-6
-4
-2
50 (%o)
+2
+4
18
1 8
http://jurassic.ru/
been found t o b e generally valid are (1) c a r b o n a t e

rocks a r e chemically h e t e r o g e n e o u s with original
mineralogy having an important control on chemical
diagenetic changes, (2) diagenetic alteration m a y
not b e detectable by a single chemical p a r a m e t e r
and (3) t h e direction of diagenetic change of minor
elements can b e predicted from partition coefficients
(e.g. Sr decreases, M n a n d F e increase).
Empirical observations suggest that solid-state
diffusion a n d consequent e n h a n c e d exchange of ions
with p o r e fluid is insignificant in c a r b o n a t e rocks
even for oxygen isotopes ( H u d s o n , 1977a; B r a n d ,
1982). Neither does repeated recrystallization by
dissolution-reprecipitation occur (Veizer, 1977). A
contrary opinion regarding isotope d a t a is some
times expressed by isotope geochemists working on
burial diagenesis (e.g. Longstaffe, 1983) and indeed
little empirical evidence is available t o check t h e
experimental studies of A n d e r s o n (1969) which
quantified t h e increasing a m o u n t of oxygen isotope
exchange in calcite with increasing t e m p e r a t u r e .
C a r b o n isotopes and minor elements would b e less
susceptible to e x c h a n g e ; Fairchild (1980b, 1985)
showed that fine chemical zones in dolomite (but n o t
calcite) survived regional m e t a m o r p h i s m with tem
p e r a t u r e s attaining 450C, a n d T u c k e r (unpublished
data) has found oxygen isotope data from massive
dolomites in t h e same geological setting t o show a
similar range as u n m e t a m o r p h o s e d ones of similar
age elsewhere.
T h e evidence for different geochemical pathways
for different original c a r b o n a t e minerals has been
summarized by Veizer (1977,1983). B r a n d & Veizer
( 1 9 8 0 , 1 9 8 1 ) carried o u t a particularly sophisticated
study of this type in which they recognize three
different diagenetic trends on SrMn plots, corre
sponding to original calcite, aragonite and Mg-calcite,
allowing original mineralogy t o b e determined as
long as diagenetic alteration is in t h e lesser half of
the studied samples. A l - A a s m & Veizer (1982) and
B r a n d (1981a, b , 1982) confirmed t h e small degree
of recrystallization apparently n o r m a l for calcific
bioclasts a n d illustrated t h e preservation in special
circumstances of arguably original chemistry of pre
served metastable carbonates, although Brand (1983)
recognized t h e importance of later cementation of
p o r e s within bioclasts. Veizer (e.g. 1977) a n d Pingi
t o r e (1976,1978,1982) have stressed t h e importance
in n e o m o r p h i s m of a 'thin' or 'messenger' a q u e o u s
film, b e t w e e n dissolving a n d precipitating crystals,
of different chemistry t o t h e bulk pore fluid. T h u s ,
348
I.J. FAIRCHILD e t a l .
graphy, will clearly help interpretations. W h e n com

p o n e n t s are physically mixed, factor analysis of d a t a
(e.g. B r a n d & Veizer, 1980,1981) can be e m p l o y e d ,
but is clearly a less direct m e t h o d . T h e r e is also t h e
danger of over-interpreting the results: of assuming
that every factor represents a single physical p h e n o
m e n o n (such as salinity variations). This need not be
so (see G o u l d , 1980, for a lucid explanation of this).
Interpretations of N a d a t a (e.g. Veizer et al., 1977,
1978; R a o , 1981) need t o b e r e t h o u g h t in t h e light of
t h e work of B u s e n b e r g & P l u m m e r (1985). Finally
t h e explicit assumption t h a t stabilization only occurs
in meteoric waters (Veizer 1977, 1983) needs eva
luation. Possible stabilization in marine-derived
fluids should b e considered and modelled.
10" ppm
ppm
10
10
,o\
Chemical characteristics of m a r i n e cements in

m o d e r n and ancient carbonates a r e not discussed
h e r e , b u t see Milliman (1974), Bathurst (1975) and
J a m e s & C h o q u e t t e (1983).
Following earlier controversy about the extent to
which r a w carbon isotope d a t a can tell us about t h e
prevalence of m e t e o r i c water diagenesis ( H u d s o n ,
1975; Allan & M a t t h e w s , 1977; Bathurst, 1980),
Allan & M a t t h e w s (1982) have provided useful ex
amples of t h e characteristics of isotope profiles across
ancient e x p o s u r e surfaces, interpreting their results
by analogy with Q u a t e r n a r y sections on B a r b a d o s .
A m o n g other points m a d e a r e t h e observations that
t h e variability in oxygen isotope ratios is much less
t h a n that of carbon isotopes w h e n diagenesis is by a
single fresh g r o u n d w a t e r system, that a b r u p t de
creases in 5 C are likely across exposure surfaces
and t h a t covariance of C and O is t o b e expected
w h e n diagenesis in the freshwatermarine water
mixing z o n e occurs. Figure 9.31 (from Allan &
M a t t h e w s , 1982) illustrates a Mississippian profile
which can b e interpreted in this way. It ought t o b e
said, however, that since so little of the stratigraphic
column has been studied by detailed isotopic pro
files, chemical data alone are insufficient t o b e
conclusive.
E l e m e n t a l characters of meteoric c a r b o n a t e
cements are variable. V a d o s e cements will be ironfree; also Benson (1974) d e m o n s t r a t e d , by micro
p r o b e analysis, a zonation with successive M g and Sr
p e a k s corresponding to t h e successive stabilization
of Mg-calcite and of aragonite in t h e aquifer. Since
meteoric lenses change in response to seasonal and
longer-term climatic changes, phreatic cements
should be expected t o show complex zonation
(Steinen, M a t t h e w s & Sealy, 1978), as is apparently
1 3
Calcite w
F
Fig. 9.30. (a) Sr and (b) Mn analyses

of Jurassic belemnites from SW
Germany (from Veizer, 1974).
C a l c i t e and Calcite indicate
compositions in equilibrium with sea
water and average fresh water
respectively. In (b) the percentage
figures indicate calculated degree of
recrystallization from an original
content of 15 ppm in rostra.
sw
Calcitesw
FW
*~
'
rostra
+ p.septa
0%
<1
10
Mn in enclosing rocks
10
ppm
(b)
neomorphfc or replacive carbonates can retain s o m e

m e m o r y of the chemistry of their precursor, t h e
m o r e so the m o r e 'closed' the system. Veizer et al.
(1978) expressed this concept in t e r m s of the per
centage of ions in t h e thin film derived from t h e
dissolving solid p h a s e ; this illustrates t h e important
point that the system will be m o r e ' o p e n ' to s o m e
c o m p o n e n t s (particularly oxygen isotopes) t h a n

others.
Veizer (1983) reviewed future d e v e l o p m e n t s in
t h e a p p r o a c h t o chemical diagenesis of c a r b o n a t e s .
M o r e physical separation of c o m p o n e n t s , or avail
ability or use of microanalytical techniques, together
with use of conventional and luminescence p e t r o -
http://jurassic.ru/
349
Lime
mudstone
Subaerial
and
crust
palaeosol
Vadose
Lime
mudstone
Mixing
zone
13
8 C
Skeletal
packstone
-7
-6 -5
-4
-3 - 2 - 1
8%o PDB
Fig. 9.31. Isotope profiles across a Mississippian emersion

surface (Newman Limestone, Kentucky). Top five samples
below exposure surface are depleted in O and C .
Deeper samples show covariant increase in 6 C and 5 O
thought to indicate diagenesis in marine-meteoric mixing
zone. After Allan & Matthews (1982).
l s
13
13
l s
d e m o n s t r a t e d in Mississippian limestones of N e w
Mexico (Meyers, 1978). Complexly zoned c e m e n t s
and replacements h a v e , h o w e v e r , also b e e n argued
to originate by burial diagenetic processes (Fairchild,
1980b; W o n g & O l d e r s h a w , 1981).
M a n y studies have d e m o n s t r a t e d geochemical
differences between depositional components, earlier
and later c e m e n t s , allowing assignment of the later
cements to burial diagenesis. Dickson & Coleman
(1980) provided a particularly convincing example
on Dinantian limestones from the Isle of M a n ,
E n g l a n d w h e r e a sequence of zoned calcite cements
followed by dolomite and kaolinite cements display
increasingly negative 5 0 values corresponding to
progressively higher t e m p e r a t u r e s (coupled with an
u n k n o w n degree of isotopic evolution of the p o r e
fluid).
Chemical analyses of calcareous oozes have pro
vided i m p o r t a n t evidence supporting t h e prevalence
of pressure solution-reprecipitation as t h e process
of lithification. T h u s Scholle (1977) showed that
5 0 values of Cretaceous Chalks systematically
lighten in m o r e deeply buried, less p o r o u s Chalks
1 8
1 8
350

site 305. Modelling (by I J F ) indicates that t h e Sr and
M g d a t a from site 305 is satisfied by a n u m b e r of
combinations of K values and p e r c e n t a g e closure of
t h e system with respect to the minor e l e m e n t s . T h e
i m p o r t a n c e of explicitly considering t h e d e g r e e of
closure of a system has often b e e n stressed (Pingi
t o r e , 1978, 1982; Veizer et al., 1978). Chalks with
low porosity ( 2 0 % ) d o not show depth-related 6 O
changes. This arises not from a diagenetic microe n v i r o n m e n t isolated from bulk p o r e fluid ('closed'
system referred to a b o v e ) , but as a cumulative result
of dissolution-precipitation reactions: t h e p o r e fluid
b e c o m e s so enriched in 6 O that n o further reduc
tion in rock 5 0 occurs despite increased t e m p e r a
t u r e s (Jorgensen, 1987).
since the reprecipitated calcite crystallized at elevated

t e m p e r a t u r e s . C h a l k s which w e r e c e m e n t e d o n the
seafloor ( h a r d g r o u n d s ) show a w e a k e r , similar t r e n d
with h i g h e r <5 0 values as their residual porosity is
diminished. Killingley (1983) proposed that burial
recrystallization could a c c o u n t for t h e a p p a r e n t
climatic cooling t r e n d d e d u c e d from isotopic study
of Tertiary oozes, b u t this suggestion h a s not yet
b e e n rigorously assessed. M i n o r e l e m e n t changes,
notably loss of Sr and gain of M g (Fig. 9.32),
accompanying the burial diagenesis of oozes h a v e
b e e n well d o c u m e n t e d by B a k e r et al. (1982) w h o
studied p o r e water a n d sediment chemical d a t a .
Particularly significant is their d e m o n s t r a t i o n t h a t ,
w h e n diffusion is allowed for, t h e r e can b e a major
e x p o r t of Sr from sediments (particularly w h e n sedi
mentation rates are slow, see Fig. 9.32); m e t e o r i c
diagenesis n e e d not be invoked for Sr-depleted lime
stones! B a k e r et al. (1982) further c o n s i d e r e d t h a t
their d a t a constrain K
for calcite to b e a r o u n d
0.04, consistent with t h e e x p e r i m e n t a l w o r k of K a t z ,
Sass & Starinsky (1972) w h e r e a s
a p p e a r e d to
be 8.1 x 1 0 ~ , 60 times smaller than experimentally
d e t e r m i n e d (Katz, 1973). In fact this conclusion
d e p e n d s o n t h e assumption of a n o p e n diagenetic
system a n d it is also inconsistent with t h e d a t a from
18
l s
8 7
l s
1 8
G e o c h e m i c a l interpretation of dolomitization is
particularly complicated by major uncertainties in
partition coefficients as well as the question of t h e
d e g r e e of isotopic a n d m i n o r e l e m e n t interference
from precursor c a r b o n a t e s (if a n y ) . Veizer et al.
(1977', 1978) showed for some Palaeozoic examples
h o w high N a and Sr concentrations a p p e a r t o cor
relate with early dolomitization from m o r e con
tinental waters. G e n e r a l l y , absolute a m o u n t s of N a
a n d Sr a r e liable t o vary particularly given t h e com
plexly variable chemistries of potential dolomitizing
Sl
fluids. L a n d (1980) has critically reviewed these

topics. Bein & Land (1983) stressed that a simplistic
interpretation of o n e geochemical p a r a m e t e r (e.g.
Sr in terms of salinity) is certainly to b e avoided (see
also Sass & K a t z , 1982 a n d Z h a o & Fairchild, 1987).
W h e r e a s in p u r e c a r b o n a t e sediments t h e effects
of n o n - c a r b o n a t e c o m p o n e n t s a r e insignificant, re
active silicates o r organic m a t t e r , w h e r e p r e s e n t ,
h a v e a major impact. E v e n small a m o u n t s of altera
tion of reactive volcanic material can b e detected by
S r / S r analysis of recrystallized c a r b o n a t e (Elderfield & G i e s k e s , 1982). M o r e widely recognized n o w
in c a r b o n a t e minerals in terrigenous rocks a r e carbon
isotopic signatures indicative of carbon derivation
from particular bacterial reactions (e.g. Irwin et al.,
1977; Pisciotto & M a h o n e y , 1981; Marshall, 1981).
A n o t h e r d e v e l o p m e n t has b e e n t h e recognition that
c a r b o n a t e s of extremely variable chemical composi
tion a r e very c o m m o n (e.g. Curtis, P e a r s o n &
Somogyi, 1975; M a t s u m o t o & Iijima, 1981; Tasse &
H e s s e , 1984). M a t s u m o t o & Iijima's (1981) study is
instructive in correlating t h e chemistry of authigenic
c a r b o n a t e s with p o r e fluid chemistry as controlled
by depositional setting, whilst Tasse & H e s s e (1984)
h a v e utilized a particularly effective m o d e of d a t a
8 6
CaC0
0
1
0.2
2
0.4
3 Mg/Ca x 10
0.6
0.8
1.0
351
p r e s e n t a t i o n (Fig. 9.33). M a t s u m o t o & Matsuhisa

(1985) not only describe t h e elemental variation of
N e o g e n e authigenic c a r b o n a t e s from t h e J a p a n
t r e n c h , but elegantly place t h e m in burial context by
oxygen isotope analysis. D o l o m i t e formation in
sulphate-bearing p o r e w a t e r s is just o n e of t h e m a n y
interesting inferences that can b e m a d e from their
data.
A s for c a r b o n a t e s , t h e t r u e chemical variability of
clay minerals is now becoming a p p a r e n t , aided par
ticularly by m i c r o b e a m analysis. Glauconitic clays
are a m e n a b l e to wet chemical analyses because pel
lets can b e physically s e p a r a t e d : O d i n & M a t t e r
(1981) summarized these d a t a . A l t h o u g h they dis
tinguish two s e p a r a t e families: high-Fe glauconitic
minerals a n d low-Fe illites, B e r g - M a d s e n (1983), on
t h e basis of m i c r o p r o b e results, showed that interm e d i a t e - F e , high-Al glauconites occur and p r o p o s e d
a cool-water origin for t h e m . In contrast, Ireland
et al. (1983), in p r e s e n t i n g S T E M analyses of clays,
n o t e d t h e association (also p r e s e n t in B e r g - M a d s e n ' s
clays) of high-Al glauconite with pyrite and pro
posed a diagenetic origin for t h e clay chemistry.
Clearly, d e v e l o p m e n t of o u r u n d e r s t a n d i n g of the
n a t u r e and origin of clay-mineral chemical varia-
1.2
t
1.4
r~i
1.6
1.8 Sr/Ca x 1 0
1A~~r
100
200
300
400
500
O
600
A
A
700
Fig. 9.32. Variations in composition
with depth of pelagic carbonates
from two DSDP drill sites. Data
replotted from Baker et al. (1982).
Site 305 has the slower rate of
sedimentation.
800
900
1000
Mg/Ca site 305

* Sr/Ca site 305
Sr/Ca site 289
Fig. 9.33. Compositional fields of siderite (S), dolomite (D) and rhodochrosites (R) of concretions from Cretaceous black
shales of the western Alps projected on toeach face of the CaC0 -FeC0 TMnC0 -MgC03 tetrahedron. Straight lines
are regression lines calculated for the most elongated fields (simplified from Tasse & Hesse, 1984).
3
http://jurassic.ru/
352
tions is most likely to be rapidly advanced by com

bined microchemical-microstructural studies.
Isotopic studies on silicates have b e e n relatively
few because of the complexity of the t e c h n i q u e , but
have yielded s o m e extremely useful results (review
ed by Longstaffe, 1983). Particularly appealing is
t h e prospect of t h e possibility of using co-existing
minerals to tie down p a l a e o t e m p e r a t u r e s , irrespec
tive of isotopic values of t h e p o r e fluid (Elsinger,
Savin & Y e h , 1979).
9.8.4 Elemental c y c l i n g
T h e geological cycle involves transfer of sediments
between several reservoirs which, on t h e simplest
level, a r e the a t m o s p h e r e , continental waters, sea
water and sediments and rocks. Models of t h e kine
tics of these processes (e.g. G a r r e l s & M a c K e n z i e ,
1971; Veizer & J a n s e n , 1979; B e r n e r , Lasaga &
G a r r e l s , 1983) d e p e n d on the existence of reliable
chemical and mineralogical d a t a from rocks of vari
ous ages. Possible secular changes in t h e composi
tion of these reservoirs are of interest from m a n y
points of view.
A n a l y s e s of terrigenous material should provide
evidence of the composition of t h e u p p e r crust.
Obtaining average estimates of t h e chemical c o m
position of sedimentary sequences of various ages is,
of c o u r s e , r e p l e t e with pitfalls. Schwab (1978) m a d e
an extensive compilation of 'terrigenous' composi
tions and correctly excluded the c a r b o n a t e fraction,
but he did not disregard o t h e r chemical sediments.
A n o t h e r criticism ( M c L e n n a n , 1982) is that h e placed
t o o much emphasis on glacially t r a n s p o r t e d , chemi
cally u n w e a t h e r e d sediments in early Proterozoic
sections (Fig. 9.24). W h e n this is allowed for it is clear
that t h e ArchaeanProterozoic b o u n d a r y m a r k s the
most significant change in t h e sedimentary record
with changes in N a 0 / K 0 , T h , light R E E / h e a v y
R E E (and e m e r g e n c e of a negative E u a n o m a l y in
R E E patterns normalized to chondrites) correspon
ding t o a change from a m o r e mafic t o a m o r e felsic
u p p e r crust (Veizer & J a n s e n , 1979; M c L e n n a n ,
Taylor & Eriksson, 1983; M c L e n n a n , 1982).
Considerable attention continues to be given to
possible changes in oceanic chemistry with t i m e .
B e i n g for most purposes and at most times wellmixed, sea water provides a sensitive indicator of
changes in p a t t e r n s of cycling b e t w e e n o t h e r reser
voirs and itself. P e r h a p s t h e most i m p o r t a n t putative
change was an increase in oxidation state accom
2
panied by increased oxygen accumulation in t h e

a t m o s p h e r e , largely during t h e Proterozoic. It is
very difficult to provide chemical d a t a from m a r i n e
sediments to constrain this. F o r e x a m p l e , it is clear
that t h e Fe and M n content of dolostones decreased
during t h e P r e c a m b r i a n (whole rock d a t a of Veizer,
1978; for microprobe data and a review of whole
rock d a t a for p u r e finely crystalline dolostones see
Fairchild, 1980a), which could b e explained by a n
increasing E h of surface e n v i r o n m e n t s . This c a n n o t
be readily p r o v e n , however, because of t h e great
variation in chemistry at any o n e time d u e to p a l a e o geographic considerations, and potential variability
in t h e timing of formation of t h e d o l o m i t e . Less
equivocal evidence comes from chemical analyses of
palaeosols ( a n d studies o n t h e survivability of easily
oxidized detrital minerals in placers) which constrain
atmospheric C 0 / 0 ratios ( H o l l a n d , 1984).
T h e proposition that seawater chemistry can b e
treated in equilibrium t e r m s (Sillen, 1967) has given
way to the view that kinetic factors (fluxes in and o u t
of sea water) p r e d o m i n a t e , although H o l l a n d (1972,
1984) showed that the mineralogy of preserved sedi
m e n t s constrained t h e possible past excursions in
oceanic chemistry within half an o r d e r of m a g n i t u d e
limits of a b u n d a n c e of m a n y individual e l e m e n t s , at
least in the Phanerozoic. Establishing t h e major
element composition of sea water at different times
within these limits is extremely difficult. In s o m e
circumstances, minor elements are tractable. F o r
e x a m p l e ; G r a h a m et al. (1982) d e m o n s t r a t e d small,
b u t significant variations in oceanic Sr/Ca by analy
sing well-preserved Tertiary planktonic foraminifera
and utilizing their well-known partition coefficient
for Sr.
E v e n if aspects of t h e composition of sea water
w e r e k n o w n , establishing t h e n a t u r e of t h e tem
porally-changing kinetic processes is a m o r e impor
tant, yet m o r e r e m o t e objective. F o r e x a m p l e , t h e
m o d e l of B e r n e r et al. (1983) of t h e control of t h e
carbonate-silicate geochemical cycle for t h e last 100
million years illustrates t h e complexity of t h e con
trols o n oceanic p H a n d a b u n d a n c e of C a
and
M g , and conversely t h e difficulty in finding geo
chemical p a r a m e t e r s that give information a b o u t
few (preferably only two) kinetic processes. T h e r e
are certain p a r a m e t e r s that m e e t this r e q u i r e m e n t ,
however: notably Sr/Ca, S / S , C / C and S r /
S r . F o r e x a m p l e , G r a h a m et al.'s (1982) results
cited above can be i n t e r p r e t e d in t e r m s of two
processes: seafloor spreading r a t e (affecting C a re2
m o v e d by h y d r o t h e r m a l action) and aragonite pre

cipitation r a t e (removing material with high Sr/Ca).
Strontium isotope variation reflects the balance of
input of Sr in solution with relatively high S r / S r
(derived from the u p p e r continental crust) and input
by interaction with basaltic oceanic crust (with low
S r / S r ) . T h e composition of carbonates in equili
brium with sea water readily yields information o n
Sr isotopes in sea water since t h e r e is n o fractiona
tion during c a r b o n a t e precipitation. By analysis of
t h e c a r b o n a t e fraction of carbonate-rich sediments,
major d a t a sets have b e e n compiled by Veizer &
C o m p s t o n (1974, 1976), B u r k e et al. (1982) and
Veizer et al. (1983). Samples with low Sr a b u n d a n c e ,
or which may have been c o n t a m i n a t e d by a b u n d a n t
S r in a high insoluble residue ( B u r k e etal., 1982),
or low Ca/Sr or high M n indicative of diagenetic
alteration (Veizer et al., 1983) are rejected. T h e
curve of B u r k e et al. (1982) (Fig. 9.34) is t h e best
available d a t a set covering t h e whole of t h e P h a n e r
ozoic for any chemical p a r a m e t e r , because of t h e
precision b o t h of t h e analyses and of the strati
graphic age of t h e samples. Realization of t h e full
potential of this a p p r o a c h requires m o r e careful
screening of samples, using b o t h the valuable geo
87
87
353
chemical approach of Veizer et al. (1983), and m o r e

integration with petrography.
C a r b o n and sulphur isotope variations in car
b o n a t e s and sulphate evaporites respectively have
been well d o c u m e n t e d . Despite the cruder agegrouping, particularly of the carbon isotopic d a t a ,
antipathetic variation is clearly shown (Veizer,
Holser & Wilgus, 1980) illustrating a coupling of C
and S cycles by an overall reaction such as:
86
86
15CH 0 + 8CaS0 + 2 F e 0 + 7MgSi0 =

4FeS + 8 C a C 0 + 7 M g C 0 + 7SiO + 15H 0.
2
T h e geological consequences are very interesting

( B e r n e r & Raiswell, 1983) as are t h e short-term
violations of this relationship ( A n d e r s o n & A r t h u r ,
1983). Because of t h e heterogeneity of carbon iso
t o p e values in c a r b o n a t e rocks at any o n e time, t h e r e
is much scope for refinement of t h e sampling p r o
c e d u r e , particularly for examining shorter-term
variations. Magaritz et al. (1983) have d e m o n s t r a t e d
an extraordinarily rapid rise in 5 C of 8.5%o in only
4000 years in t h e U p p e r P e r m i a n of Texas that
correlates with o t h e r rapid rises world-wide. Like
wise, Claypool et al. (1980) showed that s o m e 5 S
rises are very rapid and postulate that sudden de-
8 7
1 3
3 4
.7100
.7095
y
.7090
.7085
C/J
%. .7080
CO
CO
<J
i '
.7075
.7070
2 +
2 +
3 4
3 2
1 3
1 2
87
.7065
.7060
V
qI
Tertiary
Cretaceous
100
Jurassic
Triassic Permian Penn Miss.
200
Devonian Silurian
300
Myr
400
Ordovician
500
Cambrian
Pc.
600
86
Fig. 9.34. Plot of Sr isotope variation with age of 744 samples of marine carbonates, evaporites and phosphorites (from
Burke et al., 1982). Data points scatter above the line because of diagenetic alteration and short-lived positive excursions
(e.g. Cretaceous-Tertiary boundary. Hess, Bender & Schilling, 1986).
http://jurassic.ru/
1 1 1 1 It
354
stratification of an ocean basin is the only mechanism

t h a t can explain t h e m .
Secular variation in t h e oxygen isotope composi
tion of c a r b o n a t e s , cherts and phosphorites takes
t h e form of a progressive decrease in average 6 O
in older rocks (Veizer & H o e f s , 1976; K n a u t h &
L o w e , 1978; A n d e r s o n & A r t h u r , 1983). T h e cause
of this variation, w h e t h e r increased total recrystal
lization with age, t e m p e r a t u r e c h a n g e , or secular
variation in seawater isotopic composition, is hotly
disputed, although t h e s t r o n g buffering of sea w a t e r
5 0 by interaction with new ocean crust is increa
singly evident (Holland, 1984). T h e careful analysis
of little-altered portions of Palaeozoic b r a c h i o p o d
shells ( P o p p et al., 1986; Veizer, Fritz & J o n e s ,
l s
1 8
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area (abstract). Soc. econ. Paleont. Miner. Ann. Midyear
Meeting Abstr. 3, 121.
Abney hand level, use of 24-25,25

albite, X-ray diffraction of 208
alteration
fabrics
128,130,159,159,160
timing of 160,164-165,167
anhydrite
cement formation by 151,152
optical properties of 112-113
staining for 98
ankerite, preparation of 330
apatites, cathodoluminescence
microscopy of 188
aragonite
staining for 98
X-ray diffraction of 207
atomic absorption analysis 315-318,
316,317
interference 317
sample preparation 317318
attapulgite, X-ray diffraction of 219
authigenic minerals 109,258,
260-261,260,341
backscattered electron imagery 235,

237,238,239-240,241
balloon diagrams, plotting of
orientations on 120
baryte, optical properties of 112113
Batschelet chart, in presentation of
palaeocurrent data 45,46
bedding
description of 17-21,18,19,20
bed geometry 21
bedform hierarchies 4 6 - 48,47,48,49
bedsets 19-20
biotite
diagenetic processes in 133
optical properties of 112113
bitumens, optical properties of
112-113
boron, palaeosalinity of 342-344,
343,344
calcite
cathodoluminescence microscopy
of 182,183,755,186
cement formation by 139,148-149,
152,264-265
iron content of 183,186
magnesium content of 186
manganese content of 186
preparation of 330
scanning electron microscopy of
236
staining for 99-100
Mg-calcite 99
calcite-dolomite mixtures 224,
226-227,227
carbon
isotope fractionation of 290-291
stable isotopes 294
carbonates
analysis of by inductively-coupled
plasma atomic emission
spectrometry 320-325,321,
322,323,324,325
of 183,184,186-187
chemical analysis of 328-330
examination of slices from 88-89,
89
mixed, preparation of 330-331
recording of 26
selective dissolution of 307-308
stable isotope analysis of 328,329,
330
X-ray diffraction of 220-227
226-227,227
dolomites
221,222-226,224,
225,226
magnesium in calcite 220221,
221
mixtures of calcium carbonate
minerals 221-222,222,223,
224
see also calcite, chalks, dolomites,

limestones
cathodoluminescence microscopy 3,
139,174-190
application of 182,183,184,185
comparison of with backscattered
electron imagery 237
equipment 176-179,177
microscopes for
cathodoluminescence
178-179,178
operation 177'-178,178
radiation precautions 179
interpretation and description of
results 180-182
quantification 181 182
photographic recording of 189-190
physical explanation of
luminescence 174176
excitation factors 174175
luminescence centres 175176
sample preparation 179-180
use of in sedimentology 183,
186-188
carbonate rocks 183,186-187
sandstones 185,187-188
see also electron beam
microanalysis
celestite, optical properties of
112-113
cements 109,110,139-156,140,141
burial
148-149,151,152,156
carbonate 265-266,267
of185,188
grain overgrowth 139,142,143,
144,150
vadose and shallow marine
carbonate 146-147,152
cement stratigraphy, application of
cathodoluminescence to 184,
186-187
chalcedony, X-ray diffraction of 228
chalks
diagenesis in 350
microscopical examination of slices
87-88
387
http://jurassic.ru/
388
INDEX
INDEX
thin sections 95
porosity of 123
266-267
chamosite
chemical analysis of sedimentary
rocks 3 - 4 , 2 7 4 - 3 5 4
analytical quality 334-339
accuracy and precision 334335
geological reference materials
337
practical quality control 335336
reporting and documentation
338-339
standardisation 336-337
analytical techniques
atomic absorption analysis
315-318,3/6,3/7
electron beam microanalysis
3 0 8 - 3 1 4 , 3 0 9 , 3 / 0 , 3 / / , 312
inductively-coupled plasma
spectrometry 318-325,318,
319,320,322,322,323,324,
325
instrument neutron activation
analysis 325
stable isotopes 325-334,326,
329,333
X-ray fluorescence 314-315
applications 339-354
diagenesis 347-352,348,349,
350,351
elemental cycling 352-354,353
environmental parameters
342 -347,343,344,345,346
provenance and weathering 182,
185,339-342,340,341
chemical principles 274-294,277
adsorption 284-287,285
concentrations and activities
277-278
departures from equilibrium
282-284
equilibrium 278-282,281
isotope reference standards
293-294,294
lattice incorporation of trace
elements 287-290,290
stable isotope fractionation
290-293,292
geological sample collection
294-296
search techniques 295-296,
297-298
objectives of 274 -276,275

preparation for 296,299-308, 299
crushing 296,299-300,299, 301
sample decomposition 303308,
306,308
statistics of sampling 300-303,
302, 302
cherts
chlorite
cement formation by 139
258,259
X-ray diffraction of 207,218,219,
220
clasts
in conglomerates 10,11,12,13
orientation of 37 - 38,38
day minerals
cement formation by 139,148,149,
152
staining for 100
X-ray diffraction of 209-220
illite crystallinity 218
mudrocks 218-220,220
preparation 211-213, 212
qualitative analysis 213,214, 215,
216-217
quantitative analysis 214,
216-217
separation 210-211,211, 212
see also mudrocks
coals
microscopical examination of
slices 87-88
thin sections 95
collophane, optical properties of
112-113
colour, recording of 15,17
compaction 124,126-127,129-139
by mechanical processes 124,
126-127,129,130
:estimation of amount of 139
solution between individual grains
127,131-133,131,132,134
solution in cemented sediments
133-139,133-136,137,138
conglomerates, identification and
description of 6 - 1 0 , 7, 8 - 9 ,
10,11,12
corrensite, X-ray diffraction of 206,
219,220
depositional fabrics 110-121

grain identification 110-111,
112-113
grain morphology 116
grain orientation 120,121
grain size and sorting
measurements 118-120,118,
119,120
modal composition 111, 114-115,
114,114,115
abuses and uses 114-115,118
point counting techniques 111,
116
visual estimation techniques 114,
117
provenance studies 120121, /22,
122
quartz provenance studies 121,
124,125
see also grain size, determination
and interpretation of
detrital grains 109,110,258,
260-261,260
diagenetic fabrics 123-173,125
alteration and replacement
alteration
128,130,159,160-161
individual mineral replacement
125,159-160,160-161,162
large scale replacement 160,163
timing of dissolution, alteration
and replacement 160,
164-165,167
application of chemical analysis to
347-352,348,349,350,351
ofl82,/6>4
cementation 139-156,140,141
burial cements 148-149,151,
152,156
grain overgrowth cements 139;
142,143,144,150
vadose and shallow marine
carbonate cements 146147,
152
compaction 124,126-127,129,139
by mechanical processes 124,
126-127,729,130
estimation of amount of 139
solution between individual
grains 127,131-133,131,132,
134
solution in cemented sediments
133-139,133,136-137,138
diagenetic potential 166,167
dissolution fabrics 153,156158
corrosion fabrics 154-155,

157-158
penetrative dissolution fabrics
154-155,156-157,158
nomenclature of 123-124
diagenetic environments 123,
126,127
porosity nomenclature 123-124,
128
see also cements, porosity and
permeability, sandstone
diagenesis 153,156-158
dissolution 154-155
corrosion fabrics 156157, 158
sandstones 260, 261
timing of 160,164-165,167
dolomites
of 182,183,186
152
determination of organic carbon in
308
identification and description of
10-12
iron content of 186
magnesium content of 186
manganese content of 186
preparation of 330
244
staining for 98
X-ray diffraction of 208,221,
222- 226,224,225,226
2 2 6 - 227,227
echinoderm fragments, overgrowth

cements on 143,144
308-314,309
analysis using scanning electron
microscope 314
analysis using scanning
transmission electron
microscope 314
correction procedures 312,
313-314
detector systems 310-311
feldspar 339
microprobe analysis 309310,310,
311,312
operating conditions 313
specimen preparation 312-313
standards for 311312

see also cathodoluminescence
microscopy
elemental cycling, application of
chemical analysis to 352354,
353
endolithic microborings
268-273
endolithic algae 270,271-272
fungi 270, 271
methods 268
micrite envelopes 272273
sponges 270-271,271,272
environmental parameters
application of chemical analysis to
3 4 2 - 347,343,344,345,346
boron palaeosalinity studies
342-344,343,344
skeletal geochemistry 345-347,
345,346
Epoxy resins, use of in slide
preparation 93-94,248
etching 96-97, 96,244
evaporites
identification and description of 12
slices 87-88
thin sections 95
facies relationships 52,53

feldspar
of 182,183,188
cement formation by 139,142,143
diagenesis 133
dissolution of grains of 261
microprobe analysis of 339
overgrowths 259,261
replacement of by kaolinite 261,
263
235,258-259,259
staining for 97-98
field data, collection and analysis of 2,
5-62
palaeocurrent data 27,3032,34
37-50
interpretation of results 4650,
-47,48,49,50,51
measurement of directional
;
http://jurassic.ru/
lIliiiMi
389
structures 31-32, 34, 3 7 - 4 1 ,

37,38,39,40
presentation of 43 46,43,44,
45,46,47
removal of tectonic effects
41-43,41,42
recording in the field
bedding 17-21,18,19,20
colour 15,17
fossil and trace fossil content
22-23,24
graphic logs 2 5 - 2 7 , 2 6 , 2 8 - 3 1 ,
32,33-34
induration and degree of
weathering 17
lateral relations 27,35,36
lithology identification and
description 6 - 1 2 , 6, 7, 8 - 9 ,
10-12
measurement of stratigraphic
sections 2 3 - 2 5 , 2 4 , 2 5
sedimentary structures 21 - 2 2 ,
21,22
texture 13-15,13,13,14,15,16
sedimentary facies and sequence
analysis 5062
erection and use of facies 5052
Markov chains 52-58,54,55,56,
56,57,58,61
non-Markov techniques 59, 60,
61,62
see also geological sample
collection
flexural folding 42
flute marks 38
fluvials, recording of 26
fossils
of 182,184,185
recording of 2 2 - 2 3 , 23,24
geological reference materials 337

geological sample collection 294-296
containers for 296
contaminants of 296, 299
search techniques 295-296,
297-298
see also field data, collection and
analysis of
gibbsite, X-ray diffraction of 218
glauconite
cement formation by 151, 152
390
INDEX
INDEX
goethite, X-ray diffraction of 207

gold, coating of SEM samples with
249
graded concrete aggregates, grain size
0(83,84,85
grain morphology 116117
grain orientation 120,121
grain size, determination and
interpretation of 2, 13-14,13,13
14,63-85
analysis of lithified sediments
7 2 - 73, 73
Coulter counter 72
direct measurement of grain size
65
environmental interpretation from
grain size data 8 0 - 8 5 , 8 1 , 8 2 ,
83,84
grain size analysis 7 3 - 8 0
alternative grain size distribution
79-80
curve characterization by
statistical methods 7 6 - 7 8 , 7 8
graphic presentation 7 4 - 7 5 , 75,
76
moment methods 7 8 - 7 9
scales of size 7 3 - 7 4 , 74, 74
sample preparation 6 4 - 6 5
sieving 6569,66,67
dry sieving 66, 68
wet sieving 6869
size analysis by sedimentation
methods 6 9 - 7 2
pipette method 6 9 - 7 1 , 7 0 , 70
sedimentation tube 7 1 - 7 2
sorting measurements 118-120,
118,119,120
see also texture
graphic logs
use of 25 - 2 7 , 2 6 , 2 8 - 3 1 , 3 2
presentation 2 7 , 3 3 - 3 4
gypsum
staining for 98
hematite
152
halite
cement formation by 139,151,152
halloysite, X-ray diffraction of 218
hematite, X-ray diffraction 208
hydrochloric acid, sample

decomposition by 304
hydrofluoric acid
sample decomposition by 304305
use of in etching 9 6 - 9 7 , 96
hydrogen
isotope fractionation of 293
in silicates 334
stable isotopes 294
illites
boron absorption by 343
258,259
smectite-illite transformation 261,
263
X-ray diffraction of 206, 218, 219,
220
individual mineral replacement
fabrics 125, 159-160, 76/, /62
inductively-coupled plasma atomic
emission spectrometry
319-320,3/9
analysis of carbonates by 320325,
309,322,323,324,325
inductively-coupled plasma
spectrometry 318-325,318
induration and weathering, recording
of 17
instrument neutron activation analysis
325
Jacob staff, use of 2 4 - 2 5 , 2 5

jadeite, as Na standard for electron
beam microanalysis 312
kaolinite
replacement of by illite 261
236,259
X-ray diffraction of 207,218,219,
220
large-scale replacement fabrics 160,

163
lateral relations, recording of 27,35,
36
lepidocrocite, X-ray diffraction of 207
limestone diagenesis 266-267
limestones
material and solvents 101

procedure 102-103,102
stained peels 101-102
processing samples 86,87
sedimentary petrography 2,
108-173
components and petrofabrics
109-110,770
depositional fabrics 110-121,
112-113,114,774,115,116,
117,118,119,120,121,722,
122,124,125
diagenetic fabrics 123-167,125,
126,127,128-132,133,
134-138,140-151,153,
154-166
recording of data 167-173,
168-171,172,173
techniques and tools 108-109,
709
slices 2 , 8 6 - 8 9
examination of cut faces 8889,
89
preparation of 8788
staining 2,97-101
aragonite 98
calcite 99-100
clay minerals 100
dolomite 9 8 - 9 9
feldspars 9 7 - 9 8
gypsum and anhydrite 98
Mg-calcite 99
polysaccharide stain for
bioturbation 100-101
thin section preparation 8996
high quality section-making
process 9 0 - 95, 97, 92, 93, 95
non-standard rocks 9596
requirements for thin sections
89-90,90
montmorillonite, X-ray diffraction of
206,219
mudrocks
chemical weathering of 339,340
308
grain size determination in 14
porosity of 123
244
Munsell Colour System 15,77
muscovite
diagenesis 133
bedding of 19,20
308
dolomitization of 268,269
etching of 97, 243
identification and description of
10-12
scanning electron microscopy 244
slices 8 8 - 8 9 , 5 9
thin sections 95
carbonate grains 265
cementation of carbonates
265 - 266,267
diagenesis-carbonate porosity
2 6 7 - 268
dolomitization 268,269
limonite, cement formation by
148-149, 152
lithofacies codes, use of 6 , 8 - 9 , 10
lithium metaborate
sample decomposition by 305306
use of in X-ray fluorescence
306-307,306, 307
lithology, identification and
description of 612
conglomerates 6 - 1 0 , 7,89,10,
11,12
evaporites 12
limestones and dolomites 1012
mudrocks 6
sandstones 6
lussatite, see opal-CT
magnetite, optical properties of

112-113
Markov chains 5 2 - 5 8 , 5 4 , 5 5 , 5 6 , 5 6 ,
61
mica diagenesis 133
micas, optical properties of 112-113
microcline, optical properties
112-113
microscopical techniques
etching 96-97,96
limestones 97
examination of microscopical
preparations 103106
low power examination and
drawing 105-106,105
petrological microscope 106
photographic map 104-105,104
photomicrography 106
peels 2, 101-103
http://jurassic.ru/
nitric acid, sample decomposition by

304
non-porous rocks, scanning electron
microscopy of 244
opal-A, X-ray diffraction of 227,229

opal-CT, X-ray diffraction of
227-228
othoclase
oxygen
in silicates 331 - 334,333
stable isotopes 294
palaeocurrent data, collection and

analysis of 27,30-32,34,
37-50
interpretation of results 4 6 - 5 0
bedform hierarchies 46-48,47,
48,49
palaeocurrent patterns 4950,57
relationship of sedimentary
structures to environment 49,
50
use of variability in
environmental interpretation
48-49
measurement of directional
structures 3 1 - 3 2 , 3 4 , 3 7 - 4 1
cross-stratification 32,34,37
flute marks 38
imbrication and clast orientation
37-38,35
linear structures 31-32
sampling 3941
slump folds 3 8 - 3 9 , 3 9 , 4 0
presentation of data 4346,43,44,
45, 46, 47
removal of tectonic effects 4 1 - 4 3 ,
41,42
palygorskite, X-ray diffraction of 218,
219,220
peels 2,101-103
material and solvents for 101
preparation of 101-103
applying film 102-103,702
drying 103
etching smoothed face 102
orientation of specimen 102
preparation of film 102
preparing cut face 102
taking the peel 103
391
trimming and mounting 103

washing prepared sample 102
staining of 101-102
use of in description of carbonate
rocks 10
see also slices, thin sections,
preparation of
penninite, X-ray diffraction of 207
periclase, as Mg standard for electron
beam microanalysis 312
petrological microscope 106
phosphates
cement formation by 139,75/, 152
photomicrography 106
plagioclase
polar stereographic projections, in
presentation of palaeocurrent
data 43,44
pore spaces 110
porosity and permeability 15,84,85,
259,260,264,269
carbonates 267-268,269
nomenclature 123-124,128-129
porous rocks
241-243
air-dried samples 242
critical-point drying 243
freeze drying 243
oil-saturated samples 242243
potassium hydroxide, sample
Powder Diffraction Index for
Minerals (JCPDS) 204-205
provenance studies 120-121,122,
122,339-342,340,341
use of cathodoluminescence
microscopy in 182,755
pyrite
quartz
as Si standard for electron beam
microanalysis 312
of 185,187-188
cement formation by 139,742,144,
152,167
236,258,259
392
INDEX

quartz grain surface textures
252-258
ancient deposits 257
experimental work 256257
processes, textures and
procedures 253 256,253,254,
255
quartz overgrowths 258,259, 261
Rayleigh test, in presentation of

palaeocurrent data 45
rectorite, X-ray diffraction of 206
red beds 259,263
replacement
individual mineral 125,159-160,
161,162
large-scale 160,163
timing of 160,164-165,167
replacive minerals 109
rose diagrams
in presentation of palaeocurrent
data 43,46
plotting of orientations on 120
sandstone diagenesis 167

258-264
detrital and authigenic phases
258,260,261
diagenetic sequence 262263
dissolution and replacement of
grains 260,261
dissolution at grain contact 260,
261
'freshwater' sandstones 259,
263-264
identification of minerals 258,
259
'marine' sandstones 259,263
mechanical deformation 261
order of diagenetic events 262
porosity and permeability 259,
260,264,269
red beds 259, 263
sandstones
of 755,187-188
308
flute marks in 38
grain size determination in 13-14,
13,14
INDEX
slices 88
thin sections 9091
243
see also feldspar, quartz
saponite, X-ray diffraction of 206
scanning electron microscopy 3,
229-273
ancillary equipment and techniques
232-238
alpha-numeric displays 234
analytical equipment 234-235,
235,236,239-240
back scattered electron detectors
235,239-240
charge-free anticontamination
system 235,238
image analysis 238
photography 232-234,233
endolithic microborings 268273
sedimentological factors
268 - 273,269,270,271,272
examples and reviews 252
function and operation of SEM
230-232,230
cathodoluminescence mode 232,
237-238
emission and reflection modes
231-232,257
X-ray mode 232
limestones and dolomites 264-268,
265,267
problems of SEM operation
250-252
poor photographs 251-252,257
poor screen image 250251
quartz grain surface textures
252-258
ancient deposits 257
experimental work 256-257
processes, textures and
procedures 253-256,253,254,
255
sample collection 238241
subsurface material 241
surface material and outcrops
238,241
sample mounting
coating and storage 247-250
coating specimens 235 236,249
mounting of grains and loose
sediments 248-249,249
mounting rock chips and slices
247-248,245
storage and handling of stubs

249-250
sample treatment 241-247
impregnation of pores and
borings 245 -247,245,269,270
see also thin sections, preparation
of
mudrocks and fine grained
sediment 244-245
non-porous rocks 244
porous rocks viewed on fractured
surfaces 241-243
sedimentary grains 245
sandstone diagenesis 258-264
applications of SEM to
sandstones 259,262-264
practical considerations
258-262,259,260
sedimentary facies and sequence
analysis 5062
erection and use of facies 5052
Markov chains 5 2 - 5 8 , 5 4 , 5 5 , 5 6 ,
56,61
data presentation and
interpretation 5 7 - 5 8 , 5 7 , 5 8 ,
61
non-Markov techniques 59,60,61,
62
sedimentary grains
245
sedimentary petrography 2,108-173
components and petrofabrics
109-110,770
depositional fabrics 110121
grain identification 110111,
112-113
grain morphology, size, sorting
measurements and orientation
115-120,775,779, 720,727
modal composition 111,
114-115,114,774,115,116,
777,775
:
provenance studies 120121,
722,122,724,725
diagenetic fabrics 122167, 725
cementation 139-156, 740, 74/,
742, 743, 744, 745,146-147,
148-149,150,151,153
compaction fabrics 124,
126-127,729,750,131-139,
131,132,133,134-135,
136-137,138
diagenetic potential 766,167
dissolution fabrics 154155,
156-167,156-157,158,159,
160-161,162-163,164-165
nomenclature 123-124, 726, 127,
725
recording of data 167173,
168-171,172,173
techniques and tools 107-109, 709
sedimentary structures, recognition
and recording of 21 - 2 2 , 21,22
sepiolite, X-ray diffraction of 218,220
shales
preparation of slices from 8788
preparation of thin sections from 95
siderite
preparation of 330
237
silica minerals, X-ray diffraction of
227 -228,229
silicates
D/H ratio measurements in 334
isotope analysis of 331
oxygen in 331-334,355
siliciclastics
chemical analysis of 337
microscopical examination of 101,
102
slices 2, 86-89
definition of 86
examination of cut faces 88-89
carbonate rocks 8 8 - 8 9 , 5 9
sandstones and siltstones 88
preparation 8788
see also peels, thin sections,
preparation of
smectite
authigenic 347
replacement of by illite 261, 263
258
X-ray diffraction of 206,218, 219,
220
sodium borate, sample decomposition
by 305
sodium carbonate, sample
sodium hydroxide, sample
solution seams, formation of
133-139,736-757,755
stable isotopes, use of in chemical
analysis 325-334
http://jurassic.ru/
analysis of sulphide-sulphur 327

carbonates 328,329
D/H ratio measurements in silicates
334
isotopic corrections 328330
mass spectrometry 326
microsampling 331
oxygen in silicates 331-334,333
oxygen isotopes in sulphates 328
preparation of mixed carbonate
samples 330-331
purification and reduction
procedures for sulphates
326-327
removal of organic matter 331
silicates 331
S 0 versus SF 327
sulphates and sulphides 326
staining 2, 97-101
aragonite 98
calcite 99-100
clay minerals 100
dolomite 98-99
feldspars 97-98
gypsum and anhydrite 98
Mg-calcite 99
polysaccharide stain for
2
bioturbation 100-101
stereonets, plotting of orientations on
120
stratigraphic sections, measurement
of 23-25,24,25
stylolites, formation of 133-139,
136-137,138
sulphur
stable isotopes 294
tectonic effects, correction for in

recording of palaeocurrent
data 41-43,47,42
texture
of 182,753
determination of 1315
fabric 15
grain shape 1415, 75, 76
grain size 13-14,13, 73, 14
porosity and permeability 15
sorting 15, 76
quartz grain surface, scanning
electron microscopy of 252258,
253,254,255
see also grain size, determination
and interpretation of
393
thin sections, preparation of 8996

high quality section-making process
90-95
bonding slice to glass slide 93-94
covering 95
cutting and trimming 9193,92
finishing 9 4 - 9 5 , 95
first face lap 95
glass slide preparation 93
labelling 95
preparation 90-91,91
pre-section cutting 94
requirements 89-90, 90
see also peels, slices
thuringite, X-ray diffraction of 207
translucent rocks, examination of
slices from 89
turbidites, recording of 25,26
Udden-Wentworth grain size scale 73,

74
ultra-violet fluorescence microscopy
174
vermiculite, X-ray diffraction of 206,

218
volcanic rock, diagenetic processes in
133
weathering 17, 339-342,340,547

whole rock samples, X-ray diffraction
of 195-197,796, 797
wollastonite, as Ca standard for
312
X-ray diffraction of sediments 3,

191-228
analysis 195-209
qualitative 197-205,198-203,
204,206-208
quantitative 205,208-209,209,
210 .
whole rock 195-197,196,197
carbonate analysis 206-208,
220-227
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http://jurassic.ru/
t>6
Thes techniques available for the study of sediments and sedimentary rocks form the focus of this
book. While field aspects are included, greater emphasis is placed on the laboratory examination
of sediments. Each chapter provides introductory background material and then proceeds to a
discussion of technique, the equipment, and its limitations. Examples are included of how the
techniques can be used to solve sedimentological problems. Techniques in Sedimentology
will
be an unrivalled textbook for undergraduate and postgraduate students and of great use to many
other geologists.
Some titles of related interest

Sedimentary Environments and Facies
H.G. Reading
Second Edition. 1986. 628 pages, 564 illustrations
This book describes present day sedimentary
environments and discusses the recognition of ancient
analogues. It emphasizes processes and their products,
the useof facies, facies associations and sequences in
the interpretation of ancient rocks. It has been designed
for final year undergraduates, postgraduates and
professional geologists, especially those working on
industrial problems.
Deformation of S e d i m e n t s a n d S e d i m e n t a r y
Rocks
Special Publications of the Geological Society No. 29
Edited by M.E. Jones and R.M.F. Preston

1987. 358 pages, 275 illustrations
This text reports the proceedings of an international
conference held at University College, London, in April
1985. It contains theoretical and field studies and gives
descriptive accounts of areas as well as the mechanisms
of sediment deformation. It will be of great use to
sedimentologists and structural geologists in academic
institutions, in the field and in the oil industry.
Foreland B a s i n s
Special Publications of the International Society of
Sedimentologists No. 8
S e d i m e n t a r y P e t r o l o g y : a n Introduction
Edited by P.A. Allen and P. Homewood

The outcome of a symposium held in Friburg,
Switzerland, this book represents a collection of casestudies covering a wide range of basin types and
tectonic and stratigraphic settings. The text will be of
special interest to teachers, researchers and petroleum
geologists concerned with the relationships between
tectonics and sedimentation.
M.E.Tucker
Some 70% of the rocks at the earth's surface are
sedimentary in origin, yet only recently have their
formation processes been appreciated. This book
concentrates on up-to-date information and a concise
account of sedimentary petrology. Each rock group is
examined in turn, with composition, petrography,
sedimentary structures and diagenesis being discussed.
This is a welcome addition to textbooks for first- and
second-year undergraduates.
P a l e o s o l s : their R e c o g n i t i o n a n d
Interpretation
Edited by V.P.Wright
This book contains selected reviews and case studies on
paleopedology, including the geological history of soils,
time resolution in alluvial stratigraphy, and Quaternary
pedogenesis. Case studies illustrating the various
approaches to paleosols and their uses in archaeology,
stratigraphy, sedimentology and basin analysis are also
included.
BLACKWELL SCIENTIFIC
P U B L I C A T I O N S LTD
Osney Mead, Oxford 0>
8 John Street, London i
23 Ainslie Place, Edinb
3 Cambridge Center,
Massachusetts 02142, USA
107 Barry Street, Carlton, Victoria 3053, Australia
http://jurassic.ru/
Geoscience Texts, Volume 3
Carbonate Sedimentology
M.E. Tucker and V.P. Wright
Early 1990. 496 pages, 394 illustrations
This book covers the generation, sedimentation and
subsequent diagenesis of carbonate sediments in every
major environmental setting. The aim is to explain the
principles underlying the processes which control
carbonate rock generation. Primarily an undergraduate
textbook, it will also be invaluable to teachers and to
geologists in industry.
ISBN
0-b3E-D1375-T
l l
780632"013722

1988 Techniques in Sedimentology

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List of contributors vii

X-ray powder diffraction of sediments 191

Chemical analysis of sedimentary rocks 2 7 4

Use of the scanning electron microscope in sedimentology 2 2 9

Microscopical techniques: II. Principles of sedimentary petrography 108

Microscopical techniques: I. Slices, slides, stains and peels 8 6

Grain size determination and interpretation 6 3

Collection and analysis of field data 5

D e p a r t m e n t of Geological Sciences, T h e University, Birmingham B15 2 T T .

D e p a r t m e n t of Geology, Trinity College, D u b l i n , E i r e .

D e p a r t m e n t of Geologial Sciences, T h e University, D u r h a m D H 1 3 L E .

D e p a r t m e n t of Geology, T h e University, Newcastle upon T y n e N E 1 7 R U .

D e p a r t m e n t of Geological Sciences, T h e University, Birmingham B15 2 T T .

G r a n t Institute of Geology, T h e University, E d i n b u r g h E H 9 3JW.

D e p a r t m e n t of Geological Sciences, T h e University, Birmingham B15 2 T T .

Sedimentologists a r e keen t o discover t h e processes, conditio

these d a t a can b e analysed a n d presented. T h e follow; ' ,

T h e study of sediments and sedimentary rocks has

increasingly used to analyse t h e rocks and their

COLLECTION AND ANALYSIS

In C h a p t e r 2, John G r a h a m examines t h e rationale

T h e rock thin section is t h e basis of much routine

This chapter is presented by John Miller and de

MICROSCOPIC TECHNIQUES II:

This chapter is by Gill H a r w o o d and follows on from

Fine-grained siliceous rocks are often difficult to

In many branches of sedimentology, chemical ana

important principles of sedimentary geochemistry:

TECHNIQUES NOT INCLUDED

facies and diagenesis. It does not cover techniques

This b o o k describes most of the techniques currently

Collection and analysis of field data

M u c h of t h e information preserved in sedimentary

mineralogy/composition and colour of

Field notes: T h e s e a r e written descriptions of

important principles of sedimentary geochemistry:

TECHNIQUES NOT INCLUDED

facies and diagenesis. It does not cover techniques

This b o o k describes most of the techniques currently

Collection and analysis of field data

Much of t h e information preserved in sedimentary

mineralogy/composition and colour of

Field notes: T h e s e are written descriptions of

COLLECTION AND ANALYSIS OF FIELD DATA

Table 2.1. Scheme for nomenclature of fine-grained clastic

1 Sorting size distribution

even in thin section (Blatt, 1982), but it is often

Diamictite: a non-genetic term referring to any

Intraformational: a t e r m to describe clasts from

Oligomict: a term to describe conglomerates w h e r e

Description can be e n h a n c e d by using the d o m i n

COLLECTION AND ANALYSIS OF FIELD DATA

Massive, matrixsupported gravel

Table 2.2. Use of concise lithofacies

Dmm with evidence of

Dms with evidence of

Initially appears structureless but

Dms with evidence of

(b) Diagnostic criteria for recognition of common matrix-supported diamict

Dmg with evidence