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Further titles in this series

1 . 1 . L . ELLIOTT and W.K. FLETCHER


GEOCHEMICAL E X P L O R A T I O N 1 9 7 4

2.P.M.D. BRADSHAW
C O N C E P T U A L M O D E L S IN E X P L O R A T I O N G E O C H E M I S T R Y
The Canadian Cordillera and Canadian Shield

3 . G.J.S. GOVETTand M.H. GOVETT


W O R L D M I N E R A L SUPPLIES
Assessment and Perspective

4.R.T. SHUEY
SEMICONDUCTING O R E M I N E R A L S

5. J.S. SUMNER
PRINCIPLES O F I N D U C E D P O L A R I Z A T I O N F O R G E O P H Y S I C A L
EXPLORATION

6. R.A. RICH, H.D. HOLLAND and U. PETERSEN


HYDROTHERMAL URANIUM DEPOSITS
D e v e l o p m e n t s in E c o n o m i c G e o l o g y , 7

NUCLEAR METHODS IN MINERAL


EXPLORATION AND PRODUCTION

Edited b y

J E R O M E G. M O R S E

Deputy Director, Colorado Energy Research Institute, Golden, Colorado, U.S.A.

Adjunct Associate Professor of Physics, Colorado School of Mines, Golden,


Colorado, U.S.A.

ELSEVIER SCIENTIFIC PUBLISHING COMPANY


Amsterdam — Oxford — N e w York 1977
ELSEVIER SCIENTIFIC PUBLISHING COMPANY
335 Jan van Galenstraat
P.O. B o x 2 1 1 , Amsterdam, The Netherlands

Distributors for the United States and Canada:

ELSEVIER NORTH-HOLLAND INC.


52, Vanderbilt Avenue
N e w York, N.Y. 1 0 0 1 7

Library of Congress Cataloging in Publication Data

Nuclear methods in minerals exploration and pro-


duction.

(Developments in economic geology ; v. 7)


Bibliography: p.
Includes index.
1 . Radioactive prospecting. 2 . Oil well
logging, Radiation. 3- Radioactive s u b s t a n c e s -
I n d u s t r i a l a p p l i c a t i o n s . I . Morse, Jerome G.
II. Series.
TN269.N8 622'.15 77-23866
ISBN 0 - W - U 5 6 7 - X

ISBN 0-444-41250-6 (series)


ISBN 0-444-41567-X (vol.7)

© Elsevier Scientific Publishing Company, 1 9 7 7


All rights reserved. N o part of this publication may be reproduced, stored in a
retrieval system or transmitted in any form or by any means, electronic, mechan-
ical, photocopying, recording or otherwise, without the prior written permission
of the publisher, Elsevier Scientific Publishing Company, P.O. B o x 3 3 0 , Amsterdam,
The Netherlands

Printed inTheJNetherlands
To my wife Elizabeth
PREFACE

Nuclear m e t h o d s n o w provide t h e basis for rapid identification of a b o u t


two-thirds of t h e earth's naturally occurring chemical e l e m e n t s . The broad
application of these techniques t o exploration and p r o d u c t i o n of minerals
has b e e n s l o w in developing. This unfortunate state o f affairs m a y be d u e
largely t o a lack of awareness b y t h e e x p l o r a t i o n geologist and p r o d u c t i o n
engineer of t h e burgeoning t e c h n o l o g i e s in this segment of applied nu-
cleonics.
T h e thrust of this b o o k is t o describe t h e current status of t h o s e appli-
cable nuclear t e c h n i q u e s w h i c h lend themselves t o field u s e , in m o b i l e labora-
tories or as portable devices. S o m e of t h e latter are designed as d o w n h o l e
probes for identifying and quantifying elemental c o m p o s i t i o n s of rocks, dis-
crete mineralogical deposits or delineating lithological features, all o f w h i c h
m a y lead t o better definition o f subsurface ore deposits. Others find use in
control of mining o p e r a t i o n , in beneficiation and recovery processes. S o m e
of these t e c h n i q u e s are n o w in field use, and t h e data presented are intended
t o provide a basis for assessing their advantages, as well as their disadvantages,
in contrast with t h o s e of a more traditional nature.
The subject matter derives from interdisciplinary lecture series, presented
b y the editor t o graduate students and faculty at t h e Colorado S c h o o l of
Mines. A u d i e n c e s comprised t h e disciplines of g e o l o g y , g e o c h e m i s t r y , geo-
physics and physics. The considerable growth in literature related t o this
specialized application area of nuclear science virtually m a n d a t e d inviting
contributions from a m o n g t h o s e productively active in their current fields. It
is intended that t h e b o o k will find use a m o n g t h o s e professional engaged in
t h e search for and p r o d u c t i o n of metalliferous minerals, as well as bulk
deposits of coal, oil, natural gas, p h o s p h a t e , e t c .
A n u m b e r of p e o p l e contributed t o t h e preparation of this b o o k and
appreciation is expressed t o all o f t h e m . Particular thanks are given t o Drs.
F.E. Senftle and A . B . Tanner ( U . S . Geological Survey), Dr. J. Miskel, L. Ger-
main, L.L. Schwartz, J. Hearst (Lawrence Livermore Laboratory), Dr. J. Bur-
n e t t (Colorado S c h o o l of Mines) and R e b e c c a Vories (Colorado Energy
Research Institute) for reviewing portions o f t h e manuscript.

J.G. MORSE
LIST O F C O N T R I B U T O R S

A.K. BAIRD Department of Geology, Pomona College, Claremont, Calif-


ornia, U.S.A.
B.C. CLARK Planetary Science Laboratory, Martin Marietta Aerospace,
Denver, Colorado, U.S.A.
D.W. HILCHIE Department of Petroleum Engineering, Colorado School of
Mines, Colorado, U.S.A.
K. KEIL Department of Geology and Institute of Meteoritics, Uni-
versity of New Mexico, Albuquerque, New Mexico, U.S.A.
J.G. MORSE Colorado Energy Research Institute, Golden, Colorado, and
Department of Physics, Colorado School of Mines, Golden,
Colorado, U.S.A.
S.S. NARGOLWALLA Nuclear Applications Research Laboratory, Scintrex Ltd.,
Concord, Ontario, Canada
N.D. N G U Y E N Nuclear Applications Research Laboratory, Scintrex Ltd.,
Concord, Ontario, Canada
A.U. REHMAN * Nuclear Applications Research Laboratory, Scintrex Ltd.,
Concord, Ontario, Canada
H.J. ROSE, Jr. U.S. Geological Survey, Reston, Virginia, U.S.A.
M. SLAUGHTER Department of Chemistry and Geochemistry, Colorado
School of Mines, Golden, Colorado, U.S.A.
H A . TEWES Lawrence Livermore Laboratory, University of California,
Los Angeles, California, U.S.A.
J. TOMAN Lawrence Livermore Laboratory, University of California,
Los Angeles, California, U.S.A.
P. TOULMIN, III U.S. Geological Survey, Reston, Virginia, U.S.A.
H A . WOLLENBERG Lawrence Berkeley Laboratory, University of California,
Berkeley, California, U.S.A.

* N o w with Ontario Hydroelectric Commission, Nuclear Studies and Safety Department,


Toronto, Ontario, Canada.
Chapter 1

INTRODUCTION

JEROME G. MORSE

"Accuse not nature, she hath done her part: do thou thine. . ."
John Milton, Paradise Lost

Exploration for n e w mineral resources is b u t o n e of the alternatives avail-


able t o man t o satisfy his continuing and growing n e e d for non-renewable
raw materials. There are also other o p t i o n s w h i c h merit our serious concern
n o w and into t h e forseeable future. T h e y include measures t o conserve and
reduce our use of these materials, improved processing t e c h n i q u e s for more
effective recovery, reclamation and recycling of used materials, substitutions,
etc., but it is t o t h e subjects of exploration and p r o d u c t i o n that this b o o k is
addressed. All o p t i o n s , however, require intensive s t u d y and in-parallel
pursuit, and with significant shortages n o w anticipated w o r l d w i d e , a reorder-
ing of m a n y national priorities m a y well b e inevitable.
We recognize that t h e viability of our civilization requires a steady supply
of minerals as these substances virtually t o u c h u p o n every facet of our lives.
In fact, it has b e e n said that w i t h o u t minerals and materials, w e w o u l d have
n o gross national product. Further, the w o r l d w i d e e c o n o m i c and p o p u l a t i o n
growth, as reflected in increasing affluence, urbanization and industrializa-
tion signals such forecasts for the period 1 9 6 8 — 2 0 0 0 of cumulative mineral
values from $ 2 . 0 t o 2 . 9 trillion (in the U.S.) and from $ 6 . 8 t o 9.6 trillion
(worldwide) in c o n s t a n t of 1 9 6 8 dollars ( U . S . Bureau of Mines, 1 9 7 0 ) . The
magnitude of these numbers staggers the imagination. A l t h o u g h t h e y are
estimates o n l y , refinements in these data m u s t include inflation w i t h escalat-
ing costs of energy for extraction and processing of these minerals. Energy
costs will increase particularly in view of t h e n e e d t o recover resources of
lower quality, and t h o s e costs necessary t o return t h e disturbed environment
t o a regionally acceptable state.
The energy-minerals shortage is n o w a reality a c c e p t e d within t h e borders
of virtually all of t h e world's industrialized nations. A t t e n t i o n currently is
being drawn nationally and internationally t o a rapidly approaching n o n -
energy-minerals shortage. For e x a m p l e , t h e U . S . Geological Survey ( 1 9 7 5 )
stated that in 1 9 7 4 , t h e United States was more than 9 0 % d e p e n d e n t o n
imports of such primary materials as manganese, c h r o m i u m , t i t a n i u m , nio-
b i u m , strontium and sheet mica; 75—90% o n a l u m i n u m , p l a t i n u m , tin, tan-
2

talum, bismuth, fluorine, asbestos and mercury; 50—75% o n zinc, gold,


silver, tungsten, nickel, selenium and potassium. This d e p e n d e n c y can be
e x p e c t e d t o increase with time unless other measures are taken, such as t h o s e
n o t e d earlier.
S o l u t i o n s t o these serious p r o b l e m s , as o n e w o u l d e x p e c t , are n o t simple.
A t a m i n i m u m , there is an urgent n e e d t o expand t h e continuing search for
n e w mineral deposits using all t e c h n o l o g i e s available t o man t o m a x i m u m
advantage. It is t h e o p i n i o n of m a n y that this is n o t n o w being d o n e on a
broad e n o u g h basis t o p u t available b o d i e s of k n o w l e d g e t o effective use.
Reluctance t o a d o p t change, particularly that inspired b y technological
advance, is often greatest a m o n g t h o s e industries least technology-oriented,
and, unfortunately, this includes m a n y of t h o s e involved w i t h minerals. The
National A c a d e m y o f Sciences ( 1 9 7 6 ) r e c o m m e n d e d recently, and rather
strongly, the initiation of intensive research directed towards t h e lessening of
U . S . ' vulnerability t o overseas supplies of vital materials. Included were tech-
niques t o be d e v e l o p e d which run t h e gamut from exploration t o recovery,
along with the important consideration of using substitute materials where
possible.
The techniques n o t e d above will, of necessity, involve the evolutionary
d e v e l o p m e n t of n e w instrumentation for measuring selected properties of
minerals (or their elemental c o n s t i t u e n t s ) , b o t h existing and induced. We
believe their performance in achieving effective use in geochemistry, geo-
physics and recovery will embrace t h e following criteria:

Exploration
(1) Speed of analysis — sufficiently rapid t o enable a large number of
analyses within a relatively short period of t i m e .
(2) Amenability t o field use — small, c o m p a c t , light weight and stable
under field c o n d i t i o n s .
(3) Sensitivity — able t o d e t e c t and accurately measure l o w concentrations
of t h e elements being sought.
(4) Reproducibility of data.
( 5 ) Reasonably l o w in cost.
( 6 ) Simple t o operate and maintain in the field.

Mining
(1) Compatibility with the mining environment, particularly with the
newer rapid and more efficient mining t e c h n o l o g i e s , in order t o provide on-
the-spot assessments of t h e c o n s t i t u e n t s t o be recovered.
(2) Versatility allowing t h e m t o be inserted as probes i n t o sample holes,
drilled in a predetermined grid pattern, t o delineate a three dimensional
m o d e l of the ore b o d y , using computer-derived analyses, as appropriate.
Optimally, analyses will b e d o n e entirely in t h e field obviating t h e n e e d for
sample retrieval and off-site analysis.
3

Processing
Capability of in-situ m e a s u r e m e n t in beneficiation and processing in such
a w a y t h a t rapid analyses m a y be c o u p l e d t o c o m p u t e r c o n t r o l o f reagent
input t o o p t i m i z e the upgrading or recovery t e c h n i q u e .
Since 1 9 6 5 , t h e International A t o m i c Energy A g e n c y , recognizing t h e
growing b o d y of nuclear t e c h n o l o g y w h i c h could be applied t o t h e areas of
minerals exploration and recovery, h o s t e d a n u m b e r of conferences o n this
subject, t h e intent of w h i c h was t o further and e x c h a n g e relevant n e w infor-
m a t i o n ( I A E A , 1 9 6 9 , 1 9 7 1 ) . G r o w t h in this area of nuclear applications m a y
be attributed largely t o t h e t e c h n o l o g i e s derived from national and interna-
tional programs in t h e space and nuclear fields.
Nuclear m e t h o d s have already d e m o n s t r a t e d m a n y advantages over their
non-nuclear counterparts, where specific applicability has b e e n obtained.
There are also s o m e disadvantages t o nuclear t e c h n i q u e s and these will be
identified. The f o l l o w i n g discussion briefly describes a variety of t h e tech-
niques dealt w i t h in this b o o k .
Exploration for n e w mineral deposits, their evaluation, d e v e l o p m e n t and
recovery are expensive and time c o n s u m i n g undertakings. Nuclear m e t h o d s ,
where applicable (and their applicability is growing), have b e e n s h o w n t o be
significantly faster and often at least as accurate as c o n v e n t i o n a l analytical
m e t h o d s . B o t h factors reflect chances for lower operating costs accrued in
field work.
For e x a m p l e , Chapter 2 describes t h e use of d o w n - h o l e s p e c t r o s c o p y in
t h e characterization of uranium deposits. It reduces the need for sample
recovery and subsequent laboratory analyses in t h e vital e x p l o r a t i o n phase.
Other demonstrated approaches t o uranium exploration are also reviewed.
Many chemical e l e m e n t s m a y be identified qualitatively and quantitatively
d o w n - h o l e , in core samples, o n site in the field by using X-ray fluorescence
(Chapter 3) or radioactivation (Chapter 5) m e t h o d s . Further, radioactivation
is n o w in commercial use for d o w n - h o l e surveillance. All m e t h o d s n o t e d
above are n o w in or available for field service, although growth in usage has
been slow.
A specific X-ray fluorescence spectrometer is described in Chapter 4 as an
e x a m p l e of a ''space age" instrument t o d o geochemistry o n a planetary sur-
face (Mars). E m b o d y i n g sophisticated advanced t e c h n o l o g i e s , such develop-
m e n t s o f t e n pave t h e w a y for earth-bound usage.
The oil industry for m a n y years has b e e n making considerable use of
nuclear well logging and Chapter 6 reviews their current techniques.
Chapter 7 treats an interesting potentially useful m e t h o d , currently latent
in t h e U . S . but active in t h e U.S.S.R., for t h e recovery o f shale-locked gas
and oil through nuclear stimulation.
The exploration m e t h o d s covered in the first chapters are n o t c o n f i n e d
solely t o this purpose, but are adaptable also t o mineral recovery through
beneficiation and processing. In m a n y cases, t h e y are f o u n d in current indus-
4

trial use because rapid, accurate information at the site of the recovery oper-
ation will provide significant cost savings.
To assist t h o s e readers s o m e w h a t removed from nuclear terminology and
t e c h n o l o g y , a refresher or background chapter o n the fundamentals of
a t o m i c and nuclear physics is included as an appendix.
The disadvantages of nuclear m e t h o d s are few in number. They include:
( 1 ) A single approach, such as thermal neutron activation will address a large
and discrete number of chemical e l e m e n t s , but n o t the entire periodic chart.
Prior k n o w l e d g e of local geochemistry will enable proper instrument selec-
t i o n , and more than o n e m a y be required. (2) The use of radioactive mate-
rials in t h e field necessitates observing specific safety precautions plus
adherence t o t h e requirements o f t h e local nuclear regulatory authorities.
This may involve the use of c u m b e r s o m e and heavy shields against radiation,
monitoring of personnel t o minimize radiation e x p o s u r e , reporting exposure
data, etc. (3) Skills necessary for t h e operation of instruments and interpre-
tation of the results obtained may n o t be f o u n d normally in m a n y man-
p o w e r p o o l s of the mineral industry. T h e y are, however, readily obtained
through t h e normal marketplace.

SUMMARY

It will be s h o w n that in t h e relatively recent past nuclear techniques have


made considerable progress in addressing the problems o f mineral explora-
t i o n and recovery, even surpassing t h o s e of a more conventional nature.
Although t h e nuclear approach is evolving rapidly and m a n y specific instru-
m e n t s are n o w b o t h available commercially and in active field use, this
approach m a y n o t provide t h e final or o n l y answer. T o attack t h e problem
of worldwide mineral shortages, judicious application of all pertinent meth-
o d s must c o n t i n u e t o be d e v e l o p e d and used t o enable effective progress
toward a solution.

REFERENCES

International Atomic Energy Agency, 1 9 6 9 . Nuclear Techniques and Mineral Resources.


IAEA Proceedings. Vienna.
International Atomic Energy Agency, 1 9 7 1 . Nuclear Techniques for Mineral Exploration
and Exploitation. IAEA Proceedings. Vienna.
National Academy of Sciences, 1 9 7 6 . Mineral Resources and the Environment. National
Academy of Sciences—National Research Council, Washington, D.C.
U.S. Bureau of Mines, 1 9 7 0 . Mineral facts and problems. U.S. Bur. Mines. Bull, 6 5 0 .
U.S. Geological Survey, 1 9 7 5 . Mineral resource perspectives, 1 9 7 5 . U.S. Geol. Surv.,
Prof. Paper, 9 4 0 .
Chapter 2

RADIOMETRIC METHODS

HAROLD A. WOLLENBERG

INTRODUCTION

This chapter will deal with m e t h o d s t o measure g a m m a radioactivity,


primarily from t h e natural radioelements, U,
2 3 8
T h , and K . In seeking
2 3 2 4 0

uranium resources it is necessary t o characterize b y its c o n s t i t u e n t s t h e total


gamma-radiation field observed, so that tell-tale ratios indicating, for e x a m -
ple, above-normal c o n c e n t r a t i o n s of uranium, can be discerned. Similarly,
radiometric m e t h o d s can be used t o d e t e c t t h e preponderance of other radio-
e l e m e n t s , such as potassium in alteration z o n e s associated w i t h base metal
mineralization.
Superimposed o n t h e natural radioelement field are g a m m a radiations
from fission p r o d u c t fallout, t h e longest lived and, therefore, t h e m o s t
ubiquitious being 1 3 7
C s . Autoradiographic t e c h n i q u e s t o d e t e r m i n e t h e loca-
t i o n and abundance of U and Th within t h e mineral matrix of rock samples
will also be discussed, as will d e t e c t i o n of R n , a gaseous d e c a y p r o d u c t of
2 2 2

the 2 3 8
U series, and o f t e n an indicator o f d e e p l y buried uranium concentra-
tions.
T o furnish t h e reader an idea of t h e breadth of variation in natural radio-
e l e m e n t c o n t e n t s , average abundances of U , T h , and K in s o m e representa-
tive rock t y p e s are listed in Table 2-1. Of t h e igneous rocks, r a d i o e l e m e n t
c o n t e n t s are listed for the intrusives; values are comparable for their extru-
sive counterparts. The relative abundances of these radioelements are illus-
trated o n a ternary diagram (Fig. 2-1), within w h i c h there are characteristic
fields for broad categories of rock t y p e s (Wollenberg and S m i t h , 1 9 6 8 , 1 9 6 9 ;
Wollenberg e t al., 1 9 6 7 ) . Most acidic and intermediate igneous rocks fall i n t o
sector A, as d o m o s t siliceous clastic sedimentary rocks. Ultrabasic t o basic
igneous rocks o c c u p y a field w h i c h parallels t h e K-Th edge o f t h e triangle,
and ranges from sector C for t h e ultrabasics t o sector A for t h e basic t o inter-
mediate rocks. The carbonate sedimentary rocks o c c u p y a region parallel t o
t h e U-Th edge, ranging from sector B for t h e pure carbonates t o sector A for
carbonates m o r e c o n t a m i n a t e d b y siliceous material. Superimposed o n these
usual fields are rocks wherein o n e of t h e radioelements is c o n c e n t r a t e d : feld-
spar-rich pegmatites where K strongly p r e d o m i n a t e s , m o n a z i t e - and thorite-
rich veins, monazite-rich sandstones, and s o m e peralkaline igneous rocks
where Th strongly p r e d o m i n a t e s and, finally, t h e targets m o s t s o u g h t after
6

TABLE 2-1
Mean values of radioelement contents of typical crustal rocks

Description U Th K Reference
(ppm) (ppm) (%)

Igneous rocks
Acidic 6 20 3.2
Intermediate 3 11 2.1 Wollenberg and Smith, 1 9 6 8
Basic 1.5 4 1.4

Metamorphic rocks
Granulite facies 0.6 2.5 2.5
High amphibolite facies 1.2 9.4 2.0
Heier and Adams, 1 9 6 5
Epidote amphibolite t o
low amphibolite facies 3.5 26.5 3.4
Glaucophane schist
Wollenberg et al., 1 9 6 7
and eclogite 0.5 1.4 0.5

Sedimentary rocks
Siliceous elastics 2.2 7.0 1.5
} Wollenberg and Smith, 1 9 6 9
Carbonates 0.7 1.0 0.2

b y radiometric m e t h o d s , i g n e o u s and sedimentary r o c k s w h e r e U strongly


predominates.
A l s o s u p e r i m p o s e d o n t h e s e natural a b u n d a n c e patterns are t h e relative

Th

xlO -4
50
Fig. 2-1. Relative abundances of radioelements in different rock types. The field for ura-
nium-rich rocks is near the U corner of sector B.
7

radioactivities of t h e natural radioelements, normalized o n t h e basis of


c o u n t s per m i n u t e (in t h e gamma-ray energy region above ~ 0 . 1 M e V ) per
gram of e l e m e n t : K : Th : U = 1 : 3 . 3 X 1 0 : 8 . 0 5 X 1 0 . Therefore, in a
3 3

"normal" siliceous rock where relative abundances of K : Th : U m a y be


1 : 5 X 1 0 " : 1.5 X 1 0 " , t h e contributions o f U and Th t o t h e samples' total
4 4

gamma radioactivity m a y be respectively 1.2 and 1.6 that o f K.

GAMMA-RAY SPECTROMETRY

The radiometric t e c h n i q u e m o s t useful in t h e d e t e c t i o n and assessment of


radioelement resources is gamma-ray s p e c t r o m e t r y . It involves t h e d e t e c t i o n
of gamma rays of varying energy b y scintillation or solid-state d e t e c t o r s ,
c o l l e c t i o n , sorting, and storage of energy spectra b y single- or multi-channel
pulse-height analyzers, and treatment of t h e spectral data, o f t e n b y c o m -
puters, t o yield abundances of t h e individual radioelements. Gamma-ray
spectrometers for field use are n o w available commercially. T o illustrate t h e
features o f gamma-ray spectra w e shall use spectra, generated in t h e labora-
t o r y , of standard radioelement m i x t u r e s . T h e subject of gamma-ray spectrom-
etry, discussed necessarily briefly in this chapter, is covered at length b y a
recently published b o o k b y A d a m s and Gasparini ( 1 9 7 0 ) .

The gamma-ray spectrum

In its m o s t general application, a gamma-ray spectrometer consists of a


thallium-activated sodium-iodide [ N a l ( T l ) ] scintillation d e t e c t o r , its a c c o m -
panying photomultiplier, c o u p l e d t o a single- or multi-channel pulse-height
analyzer which stores t h e accumulated c o u n t s , and delimits discrete portions
of t h e gamma-ray energy spectrum. The electronics of t h e spectrometer
s y s t e m are normally adjusted so that the spectrum e n c o m p a s s e s gamma-ray
energies from t h e region o f a few t e n t h s u p t o 3—4 M e V . This energy region
contains t h e m a n y characteristic g a m m a rays of t h e U and
2 3 8
T h decay
2 3 2

series, as well as t h e single gamma ray at 1 . 4 6 MeV o f K . Spectra from U, 4 0

T h , and K standard materials are c o m p a r e d in Fig. 2 - 2 . The 4 0 0 - c h a n n e l


spectra here e n c o m p a s s t h e energy region 0.2—4 M e V . T h e y were obtained
from measurement of ~ 1 0 0 0 - g samples 6 inches ( 1 5 . 2 c m ) in diameter and
1.5 inches ( 3 . 8 c m ) thick, encased in plastic b o x e s , and centered o n an
8-inch-diameter ( 2 0 . 3 c m ) b y 4-inch-thick ( 1 0 . 2 c m ) N a l ( T l ) d e t e c t o r .
In the U spectrum, p r o m i n e n t peaks from B i , at 0 . 6 1 , 1 . 1 2 , and 1.76
2 1 4

MeV are often used for analysis of U . Counts in channel intervals spanning
t h e 2 . 6 2 - M e V peak o f T 1 , a d e c a y p r o d u c t o f
2 0 8
T h , are m o s t o f t e n used
2 3 2

for analysis of that e l e m e n t , while t h e p r o m i n e n t 1.46-MeV peak of K is 4 0

singularly diagnostic of K. In t h e cases of t h e U and Th d e c a y series, it is


generally assumed that t h e daughter p r o d u c t s , u p o n which t h e analyses are
8

2 3 MeV
Relative counts per channel (log scale)

(Channel no.) Channel number

Fig. 2-2. Gamma-ray spectra for U, Th, and K standard materials.

Fig. 2-3. Observed, natural (solid lines), and fallout (open circles) gamma-ray spectra trom
a soil sample, background subtracted. Solid circles: a gamma-ray spectrum of dried weeds.
(From Wollenberg et al., 1 9 6 9 . )

based, are in secular equilibrium with their parent radioelements. Equilib-


rium c o n d i t i o n s are assumed t o exist in samples of m o s t rocks and soils.
However, in m a n y instances this is n o t t h e case; disequilibrium is often
present in t h e U d e c a y series, especially in uranium ore minerals. Disequilib-
rium is difficult t o discern w i t h a N a l ( T l ) s y s t e m , because o n e c a n n o t resolve
relatively low-energy peaks o f t h e first five m e m b e r s o f t h e U d e c a y series,
w h o s e ratios are diagnostic o f equilibrium c o n d i t i o n s . Much better resolution
of low-energy gamma-ray peaks is afforded b y a s y s t e m based o n a lithium-
drifted germanium [ G e ( L i ) ] d e t e c t o r , permitting determination of t h e status
o f secular equilibrium b e t w e e n parent radioelements and their d e c a y
products.
In m a n y cases, gamma-ray spectra o f rocks or soils contain contributions
from fission products, d e p o s i t e d in fallout from atmospheric nuclear b o m b
tests. The longest-lived (half-life ~ 2 8 years) and therefore t h e m o s t ubiqui-
9

t o u s gamma-emitting fission p r o d u c t is C s , w i t h an energy of 0 . 6 6 MeV.


1 3 7

Also present, d e p e n d i n g o n p r o x i m i t y o f t h e sample l o c a t i o n t o t h e site of


atmospheric nuclear testing, in t i m e and space, m a y be t h e g a m m a activity
from N b - Z r ; an energy of 0 . 7 6 MeV. This peak will initially partially
9 5 9 5

mask that of C s , b u t will decay relatively quickly (the effective half-life of


1 3 7

9 5
N b - Z r is approximately 5 0 d a y s ) leaving t h e 0 . 6 6 MeV peak o f
9 5 1 3 7
C s as
t h e sole fallout contributor. The effect of fallout o n t h e 100-channel gamma-
ray spectrum of a sample of soil from California, collected in 1 9 6 3 (Wollen-
berg et al., 1 9 6 9 ) is s h o w n in Fig. 2 - 3 . The set of o p e n circles is t h e fallout
c o m p o n e n t , the upper solid curve t h e total spectrum, t h e l o w e r solid line t h e
"natural" spectrum w i t h o u t t h e fallout c o m p o n e n t . The set of solid circles
near the b o t t o m of t h e diagram is t h e fallout d e p o s i t e d o n a c l u m p of dried
w e e d s ; the o n l y activity in t h e w e e d s is from fission p r o d u c t s . A t present,
t h e effect of fallout is t o o n l y add a f e w percent t o t h e total gamma-ray
c o u n t i n g rate measured in t h e field.

Data reduction

The m o s t straightforward and m o s t c o m m o n l y used m e t h o d t o quantita-


tively determine radioelement c o n t e n t s from gamma-ray spectra, is t o c o m -
pare directly t h e sample spectra w i t h t h o s e o f standards, containing k n o w n
a m o u n t s of t h e individual radioelements. In t h e laboratory, where hundreds
of channels of pulse-height analyzer data are available and c o m p u t e r s are at
hand, sample spectra can b e compared channel b y channel w i t h standard
spectra, using least-squares fitting t e c h n i q u e s , t o yield highly accurate assays
of U, Th, and K. In t h e field, and also in t h e laboratory, where hundreds of
channels are usually n o t available in pulse-height analyzers, relatively broad
intervals spanning diagnostic peaks in standard and sample spectra Eire used
[ m e t h o d s and applications of field gamma-ray spectrometry are discussed
later, and are covered in detail in articles b y L0vborg e t al. ( 1 9 6 8 , 1 9 7 1 ) ] .
Most c o m m o n l y , t h e energy regions e x a m i n e d are t h o s e centered at 2 . 6 2
MeV, t h e T 1 peak of t h e Th d e c a y series; t h e 1.76-MeV peak of
2 0 8
B i in 2 1 4

t h e U decay series; and t h e region encompassing t h e 1.46-MeV peak o f K . 4 0

A portable g a m m a spectrometer, t h e Scintrex G A M - 1 , is s h o w n in Fig. 2-4.


It utilizes a single-channel analyzer w i t h rate-meter display. The d e t e c t o r
s h o w n has a 2-inch-diameter b y 2-inch-thick N a l ( T l ) crystal; detectors of
varying sizes as well as o n e for borehole logging are available.
In laboratory analyses, pulse-height analyzer data m u s t first be corrected
for background: t h e nearly featureless gamma-spectral c o n t i n u u m u p o n
w h i c h t h e gamma-ray energy peaks of t h e samples are superimposed. The
peak areas are integrated b y s u m m i n g their c o u n t s . After background c o u n t s
are subtracted from each interval, t h e n e t c o u n t i n g rates are treated as fol-
l o w s . Three simultaneous e q u a t i o n s are solved for T h , U, and K; in this case
t h e c o u n t i n g rates proportional t o t h e abundances of t h e three radioele-
10

Fig. 2-4. The Scintrex GAM-1 portable gamma-ray spectrometer system.

ments:

N = CxTh
x

N = C Th + C U
2 2 3

N = C Th + C U + C K
3 4 5 6

where c,- are constants d e t e r m i n e d b y calibrations with standards, and JVj,


iV , and AT are n e t c o u n t i n g rates (after background is subtracted) in t h e
2 3

energy intervals spanning t h e 2 . 6 2 - M e V T 1 , 1.76-MeV


2 0 8 B i , and 1.47-MeV
2 1 4

K peaks, respectively. The simultaneous e q u a t i o n s are required because t h e


4 0

n e t c o u n t i n g rate from t h e gamma-activity of t h e sample (or from t h e effec-


tive sample v o l u m e in t h e case of field measurements) within each o f t h e
energy intervals, contains a c o m p o n e n t from g a m m a rays of higher energy.
11

Thus, for e x a m p l e , t h e p r o m i n e n t K peak contains c o u n t s from scattering


4 0

of t h e U series gamma rays of 1 . 7 6 , 2 . 2 , and 2 . 4 M e V , as well as c o u n t s from


scattered 2.62-MeV gamma rays of t h e Th series. In field measurements it is
usually assumed that there is n o c o n t r i b u t i o n from radioelements other than
t h o s e of t h e Th d e c a y series in t h e N interval, centered at 2 . 6 2 MeV. A c t u -
x

ally, there is a small c o n t r i b u t i o n t o this interval from high-energy "tails" of


t h e 2 . 2 - and 2.4-MeV peaks of t h e U series; this c o n t r i b u t i o n is normally
taken into a c c o u n t in high-precision analyses in t h e laboratory.
A simple c o m p u t e r program for calculation o f U, T h , and K c o n t e n t s from
three-interval data is normally e m p l o y e d . Inputs are weight of sample, length
of run, and the interval c o u n t s from t h e 2 . 6 2 - , 1.76-, and 1.46-MeV peaks.
The c o u n t s are converted t o c o u n t rates, corrected for background, three
simultaneous equations solved incorporating n e t c o u n t rates and calibration
constants, and sample weight applied t o yield radioelement c o n t e n t s . Errors
are calculated, based o n c o u n t i n g statistics of t h e interval totals. Therefore,
t o achieve statistically significant results (errors d u e t o c o u n t i n g statistics are
less than 5% for each radioelement) in a m i n i m u m a m o u n t of t i m e , o n e must
o p t i m i z e length of run and the n u m b e r of c o u n t s accumulated in t h e inter-
vals for each sample (or, in the case of field m e a s u r e m e n t s , for each loca-
t i o n ) . The sequence of calculations is listed in Table 2-II.
Laboratory standards, u p o n w h i c h t h e calculations are based, are easily
made b y blending equilibrium U- and Th-rich materials (for e x a m p l e , pre-
cisely analyzed diluted pitchblende ores and m o n a z i t e furnished b y t h e N e w
Brunswick Laboratory of t h e U . S . Energy Research and D e v e l o p m e n t
Administration) w i t h a matrix of l o w radioelement c o n t e n t , such as finely
ground ultramafic rock. Potassium standard material m a y be a chemically
pure salt such as KC1. Standards t o provide calibration constants for field
measurements m a y consist of large c o n c r e t e slabs within w h i c h o n e radio-
e l e m e n t predominates (L0vborg et al., 1 9 7 1 ) . If such standards are n o t
readily available, field calibration constants can be derived, based o n data

TABLE 2-II
Sequence in calculation of radioelement abundances

1. Inputs: weight, time, counts in three-channel intervals encompassing 2.62-, 1.76-, and
1.46-MeV peaks
2. Counts converted to counting rates, and background subtracted in the three intervals
3. Grams of U, Th, and K calculated, using three simultaneous equations incorporating
constants based on standards
4. Concentrations calculated: Th, U, in ppm, K in %. Element ratios calculated
5. Errors in concentrations calculated, based on counting statistics
6. Results: Th, error; U, error; K, error; T h / U
12

from radioelement analyses of samples collected at m a n y field measurement


sites.

Detector systems

The N a l ( T l ) and Ge(Li) d e t e c t o r s y s t e m s will be briefly described and


c o m p a r e d . As m e n t i o n e d under "The gamma-ray s p e c t r u m " t h e detectors
m o s t used for gamma spectrometry of geologic materials are N a l ( T l ) scintil-
lation crystals. Gamma rays ( p h o t o n s ) interacting with the d e t e c t o r material
produce light flashes (scintillations) which are in turn d e t e c t e d b y a p h o t o -
multiplier t u b e optically c o u p l e d t o the crystal. The amplitudes of the
voltage-pulse o u t p u t s o f the p h o t o m u l t i p l i e r are directly proportional t o the
energy e x p e n d e d in t h e d e t e c t o r b y t h e interacting p h o t o n s . A pulse-height
analyzer is t h e n used t o d e t e c t , classify, and store t h e pulse heights and, on
c o m m a n d , t o present the stored information in the form of a gamma-ray
spectrum. The m o s t w i d e l y used N a l ( T l ) crystals are cylindrical, and are
available in several sizes, ranging from a few centimeters in diameter b y a
f e w centimeters thick u p t o tens of centimeters in diameter and thickness.
Also widely used are well-shaped crystals, permitting insertion of t h e sample
so that it is nearly surrounded b y t h e d e t e c t o r material. This configuration
furnishes higher c o u n t i n g efficiency than a cylindrical d e t e c t o r , for a given
d e t e c t o r v o l u m e . The configuration of the sample should be o p t i m i z e d with
the size and shape of t h e available d e t e c t o r , t o achieve t h e best efficiency
m o s t e c o n o m i c a l l y . Therefore, for e x a m p l e , a large flat cylindrical sample
best suits a large cylindrical d e t e c t o r , while an equidimensional or elongate
cylindrical sample best suits a well-type d e t e c t o r . Sodium-iodide detectors
for portable field gamma spectrometers are limited b y size and weight o f the
apparatus, and generally d o n o t e x c e e d 3 inches ( 7 . 6 c m ) in diameter b y
3 inches thick.
With appropriate sample-detector configurations, N a l ( T l ) s y s t e m s may
have absolute peak-detection efficiencies of 20—40%, for gamma-rays of t h e
order of 1 MeV. As s h o w n in Fig. 2 - 5 , peak-detection efficiency decreases as
gamma-ray energy increases above ~ 0 . 2 MeV.
A laboratory s y s t e m , e m p l o y i n g an unusual sample-detector g e o m e t r y ,
was developed for c o n t i n u o u s or step-scanning for U, Th, and K c o n t e n t s in
d i a m o n d drill cores (L^vborg et al., 1 9 7 2 ) . Cores are placed o n a movable
tray which passes b e t w e e n t w o 2-inch b y 3-inch ( 5 . 1 c m b y 7.6 c m ) N a l ( T l )
crystals. Output from t h e d e t e c t o r s ' photomultipliers is s u m m e d , and sent t o
a multi-channel pulse-height analyzer, where radioelement c o n t e n t s are
determined. Resulting c o m p u t e r plots are compared with lithologic and
d o w n h o l e gamma logs in Fig. 2-9.
Over the past d e c a d e , t h e advent and increasing use of high-resolution
lithium-drifted germanium or silicon [Ge(Li), or Si(Li)] s e m i c o n d u c t o r
detectors has had p r o f o u n d effects o n gamma-ray spectrometry. The greatest
13

"840 - 1 1 6 0 key

I0 l

channel
(tl
efficiency

per
1
Absolute

Counts
1

10"
10 100 1000
r-ray energy Channel number

Fig. 2-5. Comparison of absolute peak detection efficiencies for a 1 0 - c m Ge(Li) and an
3

8-inch-diameter by 4-inch-thick Nal(Tl) gamma-ray spectrometer detector. (From Smith


and Wollenberg, 1 9 7 2 . )

Fig. 2-6. Comparison of spectral shapes from Nal(Tl) and Ge(Li) gamma-ray spectrometers,
showing portion of a gamma-ray spectrum o n an expanded energy scale. (From Smith and
Wollenberg, 1 9 7 2 . )

advantage o f these d e t e c t o r s is that resolutions o f gamma-ray peaks are at


least an order o f magnitude higher than t h o s e o f N a l ( T l ) , disclosing fine
detail in t h e structure o f gamma-ray spectra. A comparison o f N a l and
Ge(Li) resolutions is illustrated in Fig. 2 - 6 . A disadvantage is t h e relatively
l o w absolute peak d e t e c t i o n efficiency o f Ge(Li) with respect t o N a l ( T l ) .
Efficiencies o f an 8-inch ( 2 0 . 3 c m ) diameter N a l and a 1 0 - c m Ge(Li) are 3

compared in Fig. 2 - 5 . A larger Ge(Li) w o u l d have s o m e w h a t greater effi-


ciency than t h e 1 0 - c m d e t e c t o r , especially for t h e higher g a m m a energies,
3

but N a l ( T l ) efficiencies w o u l d still b e over an order o f magnitude greater


than t h o s e o f Ge(Li). A n e x c e l l e n t review o f Ge(Li) gamma-ray spectrometry
was written b y Heath ( 1 9 6 9 ) ; t h e article emphasizes a s y s t e m c o m b i n i n g a
small c o m p u t e r for data c o l l e c t i o n and analysis. A discussion o f high-resolu-
tion gamma spectrometry o f Th and U d e c a y series has b e e n recently p u b -
lished (Smith and Wollenberg, 1 9 7 2 ) .
Instead o f using scintillations in t h e d e t e c t o r such as N a l , t h e principle o f
operation o f s e m i c o n d u c t o r detectors is t o collect t h e electric charge
released in t h e solid m e d i u m b y t h e absorption o f g a m m a rays. T h e drifting
of lithium into silicon or germanium crystals, under an electric field at t e m -
peratures o f 1 0 0 — 4 0 0 ° C, provides a sensitive v o l u m e t o permit their use in
gamma spectrometry. Ge(Li) d e t e c t o r s m u s t operate at liquid nitrogen tern-
14

peratures t o minimize the leakage current from thermal e x c i t a t i o n o f elec-


trons. Because of its significantly higher d e n s i t y and a t o m i c mass number,
Ge has a higher absorption coefficient than Si; t h u s , Ge is better suited t o
g a m m a spectrometry than Si.
A Ge(Li) s y s t e m is comprised of a d e t e c t o r , ranging in size from a f e w t o
over 1 0 0 c m , c o o l e d in a v a c u u m b y its a c c o m p a n y i n g cryostat, a field-
3

effect transistor preamplifier (usually c o o l e d in t h e same enclosure as t h e


d e t e c t o r ) , and an a c c o m p a n y i n g pulse-height analyzer. Because of their large
bulk, Ge(Li) s y s t e m s d o n o t lend themselves as readily t o m o b i l e field opera-
t i o n as d o t h e more c o m p a c t N a l ( T l ) s y s t e m s . However, car- and truck-
m o u n t e d Ge(Li) s y s t e m s are used especially t o measure, b y virtue o f their
high resolution, g a m m a rays o f relatively l o w energy in t h e region 1 0 0 — 3 0 0
keV (Anspaugh et al., 1 9 7 2 ) .

Field applications

Surface measurements
Probably the m o s t w i d e l y used and readily available s y s t e m s for assess-
m e n t o f U and Th resources in t h e field are portable single- or multi-channel
gamma spectrometers, c o u p l e d t o N a l ( T l ) d e t e c t o r s . Such a s y s t e m was
described briefly in a previous s e c t i o n , and illustrated in Fig. 2-4. T o achieve
statistically significant U and Th analyses from on-the-outcrop measure-
m e n t s , o n e m u s t consider t h e source-detector g e o m e t r y ; in other words, t h e
effective sample measured b y t h e d e t e c t o r . But first o n e m u s t d e c i d e if o n e
is t o use a d e t e c t o r collimated b y an effective shield against extraneous
gamma rays, such as lead ( w h i c h m a y inhibit m o b i l i t y in t h e field), or if field
c o n d i t i o n s warrant use of t h e d e t e c t o r u n c o l l i m a t e d ( A d a m s and Fryer,
1 9 6 4 , discussed a collimated d e t e c t o r for field surveys). D e t e c t o r s m a y be
used uncollimated at locations where terrain is relatively featureless over
several square meters where t h e rock surface is well e x p o s e d , grain size fairly
regular, and radioelements e x p e c t e d t o be distributed rather h o m o g e n e o u s l y .
A t locations where o n e or m o r e of these factors is significantly n o t m e t , o n e
should consider collimating t h e d e t e c t o r . For e x a m p l e , t h e c o u n t i n g rate in
an uncollimated d e t e c t o r placed at t h e base of a sharp step-like break in
terrain, m a y be half again as great (for material o f given radioelement c o n -
t e n t ) as t h e c o u n t i n g rate measured b y t h e d e t e c t o r placed o n a flat surface.
On very coarse-grained or pegmatitic surfaces, c o u n t i n g rates, especially in
t h e 1.46-MeV interval, m a y vary b y factors of t w o from p o s i t i o n t o p o s i t i o n ,
because of t h e presence of large feldspar p h e n o c r y s t s containing abundant
potassium.
Serious t h o u g h t has b e e n given t o the c o n c e p t of effective sample, e x e m -
plified b y t h e work of L0vborg et al. ( 1 9 7 1 ) . In that paper t h e effective
sample was defined as t h e v o l u m e of rock in which t h e variance (the square
of t h e standard deviation) of a particular radioelement ( w h o s e c o n c e n t r a t i o n
15

is considered a random variable w i t h c o n s t a n t m e a n value; Matheron, 1 9 6 3 ) ,


is equal t o t h e estimation variance of a gamma-ray spectrometric determina-
t i o n of that radioelement. Fig. 2-7 s h o w s a cross-section of t h e effective
sample v o l u m e s for a collimated and u n c o l l i m a t e d isotropic d e t e c t o r w h o s e
center is ~ 5 c m above t h e surface. The v o l u m e o f material comprising t h e
effective sample contributes approximately 6 0 % of t h e measured gamma
rays; it is roughly 1 / 1 0 t h e v o l u m e w h i c h contributes 90%. Table 2-III sum-
marizes t h e mass of the effective sample (Af ), its surface radius ( i 2 ) , and
0 0

m a x i m u m vertical e x t e n s i o n (Z) for energies o f 1 . 7 6 and 2 . 6 2 M e V , for colli-


m a t e d and u n c o l l i m a t e d d e t e c t o r s w h o s e centers are 5 c m above t h e surface.
This comparison indicates that the effective mass sample is significantly
larger for t h e u n c o l l i m a t e d case, b u t that t h e vertical e x t e n s i o n s are nearly
t h e same for collimated and u n c o l l i m a t e d geometries.
Field surveys incorporating on-site gamma-ray s p e c t r o m e t r y for t h e
natural radioelements have b e e n c o n d u c t e d o n e x p o s e d rock surfaces at
m a n y locations. N o t e w o r t h y studies were c o n d u c t e d b y Richardson ( 1 9 6 4 )
and colleagues at Rice University o n t h e C o n w a y Granite, N e w Hampshire;
b y D o i g ( 1 9 6 8 ) in t h e Canadian Shield; b y M o x h a m e t al. ( 1 9 6 5 ) and Davis
and Guilbert ( 1 9 7 3 ) in hydrothermally altered z o n e s associated primarily
w i t h porphyry c o p p e r d e p o s i t s ; and surveys in s o u t h Greenland, described
b y L^vborg et al. ( 1 9 6 8 , 1 9 7 1 ) . Fig. 2-8 s h o w s a field m e a s u r e m e n t for U
and Th in this latter s t u d y , o n peralkaline rocks of s o u t h Greenland. A Pb
collimator, surrounding t h e sides of t h e 3-inch-diameter b y 3-inch-thick
Nal(Tl) d e t e c t o r , was used for these measurements, primarily because of the
coarse granularity of t h e rock, e x p e c t e d d i s h o m o g e n e i t y of radioelements,
and abrupt changes o f relief o n t h e rock surface. The d e t e c t o r is c o n n e c t e d

Scintillation d e t e c t o r

Fig. 2-7. Vertical cross-section showing calculated effective samples obtained by a col-
limated (dashed curve) and uncollimated (solid curve) detector placed o n a flat rock
surface. Parameters: E = 2.62 MeV, fi = 0 . 1 1 1 c m . (From L 0 v b o r g et al., 1 9 7 1 . )
y
- 1
16

TABLE 2-III
Mass, surface radius, and depth of effective sample measured by collimated and uncolli-
mated detectors in the configuration shown in Fig. 2-7

Ey (MeV) M 0 (kg) R0 (cm) Z (cm)

Uncollimated Nal detector 1.76 37 40 12


2.62 49 42 14
Collimated Nal detector 1.76 14 16 11
2.62 21 17 13

t o a single-channel pulse-height analyzer, w i t h scaler readout. Such a s y s t e m ,


measuring o n closely spaced intervals, can obtain scores of analyses per day,
furnishing data for c o n t o u r maps of radioelement c o n t e n t s . In t h e case of

Fig. 2-8. A typical field setup on an exposed bedrock surface. (From L^vborg et al.,
1971.)
17

t h e s o u t h Greenland m e a s u r e m e n t s , U and Th c o n t e n t s were at least several


hundred parts per million, permitting statistically significant analyses from
c o u n t i n g times of 5 0 — 1 0 0 s e c o n d s . L o w e r c o n t e n t s w o u l d , of course,
require proportionately longer c o u n t i n g times, using a comparable field
spectrometer s y s t e m . L0vborg ( 1 9 7 3 ) calculated c o u n t i n g t i m e s required t o
obtain a standard deviation of 15% in a field U m e a s u r e m e n t o n rock in
which the T h / U ratio ~ 3 . Using a 3 X 3 N a l crystal, 1 0 m i n u t e s is required
for U c o n t e n t s o f ~ 1 p p m , and 1 m i n u t e if U ~ 3 0 p p m .

Subsurface measurements
D o w n h o l e radiometric logging, s o m e t i m e s incorporating gamma-ray spec-
trometry of drill h o l e s , is quicker and significantly less expensive than coring
and subsequent laboratory r a d i o e l e m e n t analysis. In its simplest f o r m , radio-
metric logging utilizes a geiger t u b e or N a l ( T l ) d e t e c t o r s y s t e m o n a cable
attached t o a w i n c h and d e p t h counter, t o furnish gross-gamma c o u n t i n g
rates, measured b y a c o u n t rate-meter at t h e surface. The e x c e l l e n t c o n -
cordance b e t w e e n in-hole g a m m a c o u n t rates and U and Th is illustrated in
Fig. 2-9 (L^vborg et al., 1 9 7 2 ) . There is a great t i m e advantage t o d o w n h o l e
logging; t h e g a m m a log s h o w n in Fig. 2-9 t o o k a f e w hours t o measure, while
t h e a c c o m p a n y i n g U and Th core scans required eleven d a y s .
It is preferred that t h e h o l e be uncased for logging, and essentially free o f
drilling m u d or other c o n t a m i n a n t s , t h o u g h t h e relatively high-energy g a m m a
rays o f t h e U and Th series are detectable through normal steel casing thick-
nesses. Where significant anomalies are furnished solely b y U , measurements
of total g a m m a activity are adequate t o define, if n o t a b s o l u t e l y , at least t h e
relative abundances of t h e radioelement. H o w e v e r , as in t h e case of field
gamma s p e c t r o m e t r y , o n e m u s t assume that secular equilibrium exists
b e t w e e n parent U and its daughters. With proper calibrations, based either
o n analyses of cores f r o m drill h o l e s , or o n measurements in h o l e s in full-
scale standards ( D o d d and Eschliman, 1 9 7 2 ) , abundances of equivalent U or
uranium o x i d e can be calculated from gross-gamma c o u n t rates. The relation-
ship b e t w e e n g a m m a activity and grade of uranium mineralization has b e e n
determined empirically ( D o d d and Eschliman, 1 9 7 2 ) : G T = KA, where G
y y

is t h e average grade in percent U O , T is t h e thickness of mineralization, K


3 g

is a c o n s t a n t determined b y instrument characteristics, and A is t h e area


under t h e gamma-ray log curve.
G a m m a spectrometry o f d o w n h o l e radiometry is m o r e definitive, and
more useful in terranes where U m a y n o t be t h e p r e d o m i n a n t radioelement.
Single- or multi-channel pulse-height analyzers, used for field g a m m a spectrom-
etry in surface m e a s u r e m e n t s , are also useful for d o w n h o l e spectrometry
(for e x a m p l e , t h e Scintrex s y s t e m , s h o w n in Fig. 2-4, and t h e Ris0 analyzer,
s h o w n in Fig. 2-8). R e c e n t l y , Sprecher and R y b a c h ( 1 9 7 4 ) described a well-
packaged b o r e h o l e gamma-ray spectral logging s y s t e m for h o l e s o f diameter
greater than 2 . 5 c m . Calibration for this s y s t e m was furnished b y measure-
18

Th(ppm) U(ppm) Th/U Gamma-ray log


1000 5000 200 1000 1 5 1000 5000cp
' I 1 1 1 1 1—J=r-1 1 1 1 1 i i i », i i > < |

20

10

11

12i

131

141

15<

16(

17(

18(

19C

20C

'<;>] Medium-to coarse-grained lujavrife °o| Naujaite


0

HH Fine-grained lujavrite | Syenite

^""j L a v a / l a v a sheared

Fig. 2-9. Geologic, radioelement, and logging diagram of a borehole in the Ilimaussac
intrusion. Radioelement diagrams are based on continuous scans of 1-m-long core sec
tions. (From L^vborg et al., 1 9 7 2 . )
19

m e n t s in standards of k n o w n U c o n t e n t , and confirmed b y U c o n t e n t s of


analyzed drill cores.
Gamma spectrometry o f borehole radioelements is c o m p l i c a t e d b y t h e
accentuation of t h e C o m p t o n c o n t i n u u m in t h e energy region b e l o w 1 M e V .
This results from gamma rays having b e e n scattered within t h e large mass of
material effectively sampled, before t h e y reach t h e d e t e c t o r . Thus, t h e ratio
of c o u n t s in t h e low-energy region t o t h o s e in the region greater than 1 M e V ,
is enhanced in comparison w i t h a spectrum obtained in a laboratory c o u n t -
ing configuration. Experience has s h o w n ( D o d d and Eschliman, 1 9 7 2 ) that
t h e enhanced C o m p t o n c o n t i n u u m strongly masks any full-energy peak in
t h e region b e l o w 1 MeV. However, this p h e n o m e n o n m a y be turned t o
advantage, because t h e ratio of t h e low-energy t o high-energy p o r t i o n s of t h e
spectrum m a y be diagnostic of equilibrium c o n d i t i o n s in t h e U d e c a y series.
In z o n e s of ore c o n c e n t r a t i o n ( 0 . 2 % U 0 or greater) t h e relatively high
3 8

equivalent a t o m i c n u m b e r (Z) of t h e ore z o n e material, c o m p a r e d t o t h e Z


of c o m m o n rocks (in t h e range 1 0 — 2 0 ) , has an attenuating effect o n gamma
rays, especially t h o s e with energies less than 0 . 4 MeV. The error in determin-
ing d o w n h o l e U c o n c e n t r a t i o n s caused b y this so-called Z-effect is, therefore,
greatest in gamma probes m o s t sensitive t o low-energy g a m m a rays. D o d d
and Eschliman ( 1 9 7 2 ) indicate that such errors increase w i t h grade of t h e
ore, from approximately 10% in ores of 1% U O t o over 2 0 % in 2.5% ores.
3 s

As in other facets of gamma-ray s p e c t r o m e t r y , d o w n h o l e spectral logging


requires that t h e s y s t e m be stabilized t o prevent drift in channels or spectral
w i n d o w s assigned t o specific g a m m a energies. A gain-stabilization s y s t e m for
borehole spectral logging has b e e n described recently b y K e y and Eschliman
( 1 9 7 4 ) . A M n source provides a g a m m a peak o f 0 . 8 3 5 M e V , w h i c h is used
5 4

as the " b e n c h m a r k " for stabilization. This energy was c h o s e n because it is


b e l o w the energy region usually e x a m i n e d for t h e natural radioelements
(>1.3MeV).
D o d d and Eschliman ( 1 9 7 2 ) p o i n t o u t the value o f c o m b i n i n g information
from gamma-ray logs with logs of other parameters. Especially useful are
comparisons of gamma-ray, resistance, and s p o n t a n e o u s potential logs, w h i c h
accurately define lithologic units in sedimentary sequences. There is also
increasing utilization of n e u t r o n logs, w h i c h respond t o changes in h y d r o g e n
c o n t e n t , reflecting the abundance of water and, indirectly, porosity. Mag-
netic susceptibility logs m a y disclose t h e inverse relationship b e t w e e n this
parameter and s o m e occurrences of uranium. Because uranium-bearing fluids
may alter magnetic minerals, localized negative magnetic anomalies m a y be
associated with uranium ore z o n e s .

Airborne measurements
Considerable exploration for uranium has e m p l o y e d , and is presently
e m p l o y i n g , airborne gamma-ray surveys as t h e primary surveying m e t h o d . In
t h e early days of uranium e x p l o r a t i o n , small, single-engine aircraft, carrying
20

a geiger c o u n t e r or primitive scintillation detectors "flew t h e r i m s " o f the


c a n y o n s o f the s o u t h w e s t e r n U n i t e d States, occasionally d e t e c t i n g outcrops
of ore (and n o t infrequently failing t o clear t h e rims). T o d a y , m u c h more
sophisticated airborne g a m m a systems, incorporating v o l u m e s of several
t h o u s a n d cubic inches of N a l ( T l ) , survey in multi-engine aircraft o n evenly
spaced flight lines, 1 5 0 — 2 0 0 m above ground surface (Darnley, 1 9 7 2 , 1 9 7 3 ) .
For more detailed surveys at l o w e r altitudes and slower speeds, helicopter-
m o u n t e d s y s t e m s of smaller N a l v o l u m e are o f t e n e m p l o y e d ( A d a m s , 1 9 6 8 ) .
As w i t h large-area surveys o n t h e surface, t h e m o s t up-to-date airborne
m e t h o d s incorporate spectral analyses, measuring the regions encompassing
the K (1.46 MeV),
4 0
B i ( 1 . 7 6 M e V ) , and
2 1 4
T 1 ( 2 . 6 2 M e V ) peaks. Four
2 0 8

" w i n d o w s " centered o n each of these peaks, and o n e spanning nearly the
entire spectrum are o f t e n e m p l o y e d . Data concurrently obtained includes
altitude (by radar altimeter), p o s i t i o n (by doppler radar, inertial navigation,
or c o n t i n u o u s imaging of t h e ground b y video or p h o t o g r a p h y ) and, o f t e n ,
a c c o m p a n y i n g geophysical sensors, such as a m a g n e t o m e t e r . G a m m a spectral
and ancillary data are stored o n multi-track magnetic tape for processing b y
on-board c o m p u t e r , or b y ground s y s t e m s , subsequent t o t h e flight.
Airborne g a m m a surveys lend themselves t o several stages of an explora-
t i o n program. Large-area regional surveys are best carried o u t b y air, espe-
cially over inaccessible terrain. Reconnaissance surveys m a y utilize t h e total
gamma spectrum, o n comparatively w i d e l y spaced flight lines, w i t h follow-
u p surveys over areas of interest o n closer spaced lines, incorporating spectral
interval data. Even more detailed surveys m a y b e d o n e b y helicopter, permit-
ting a geologist t o land and c o n d u c t ground radiometry and sampling.
Parameters considered m o s t important b y Darnley ( 1 9 7 3 ) are t h e ratios
U / T h and U / K . These ratios can be calculated in "real t i m e " b y an on-board
c o m p u t e r , or from t h e t h r e e - w i n d o w interval data at t h e c o n c l u s i o n o f t h e
flight. A n e x a m p l e of results from such a s y s t e m is s h o w n in Fig. 2 - 1 0 (from
Darnley, 1 9 7 2 ) . Calibration of g a m m a spectrometers b y flights over terrain
of k n o w n radioelement c o n t e n t , or b y positioning t h e aircraft o n concrete
pads of given c o n t e n t , permits actual concentrations o f U, T h , and K t o be
calculated from airborne spectral c o u n t rates (Grasty and Darnley, 1 9 7 1 ) . If
such absolute assays are required, it is o f t e n necessary t o e m p l o y ground-
truth t e a m s , sampling rocks and soils for moisture c o n t e n t and typical radio-
e l e m e n t values, concurrently w i t h flight operations.
Operational parameters specified b y t h e Geological Survey of Canada
(Darnley, 1 9 7 3 ) are considered necessary t o achieve statistically significant
c o u n t i n g rates t o differentiate b e t w e e n U, Th, and K over terrain of
"normal" radioelement c o n t e n t : For a m e a n flying height o f 4 0 0 ft ( 1 2 3 m )
and an air speed of 6 0 m p h ( 9 7 . 5 k m / h o u r ) , t h e v o l u m e of N a l ( T l ) crystals
m u s t total approximately 1 5 0 0 c u . inches ( 2 4 5 8 1 c m ) ; for an air speed of
3

1 2 0 m p h ( 1 9 8 k m / h o u r ) total crystal v o l u m e should be approximately 3 0 0 0


c u . inches ( 4 9 1 6 1 c m ) . D e t e c t o r s are stabilized for single-channel analyzer
3
21

Ul O Ul o o o o o o o o o o o o o Ul o ui o o o o o
Lake Athabasca survey 1 9 6 9
CD

l i n e 21 - N o r t h
oooo o o o o o o o o o o o o oooo o o o o
(U/TH)x1000 (U/K)x1000 (TH/K)X1000 height ( f t )

<J>
w
roUi^O
(Ji O oi o ro w
M w ^
Thorium

J
_i_.ro

13 12 11 10 9 8 7 6 5 4 3 2 1
Uranium

K 0) 00
oooo oooo
oooo oooo

13 12 11 10 9 8 7 6 5 4 3 2 1
Potassium

v y ,v . Jv ,N . . J v.
Ui O ui o
Integral

Miles

Fig. 2-10. Airborne gamma spectral plots from a survey over the Canadian Shield. The
uranium anomaly is essentially hidden in the integral plot. (From Darnley, 1 9 7 2 . )

operation, and individual crystals should b e n o smaller than 5 inches ( 1 2 . 7


c m ) i n diameter b y 4 inches ( 1 0 . 2 c m ) thick. A lower-flying, slower helicop-
ter-borne s y s t e m m a y e m p l o y a considerably smaller d e t e c t o r v o l u m e . In
comparing t h e effectiveness o f different s y s t e m s , Darnley ( 1 9 7 3 ) e m p l o y s as
t h e figure o f merit t h e square r o o t o f t h e normalized c o u n t i n g rate o f each
s y s t e m . Then d e t e c t o r v o l u m e s , ground speed, and altitude are directly
related t o t h e figure o f merit.
Before data reductions are c o m p l e t e , corrections are m a d e for t h e cosmic-
ray contribution t o t h e gamma spectrum (based primarily o n flights over
22

water in t h e survey region), and t h e abundance of atmospheric R n . Several


2 2 2

m e t h o d s have been a t t e m p t e d t o correct for R n : o n e e m p l o y s an upward-


looking set of N a l d e t e c t o r s , shielded from t h e ground contribution b y a
layer of lead, w h o s e s u m m e d c o u n t rate is subtracted from that of t h e d o w n -
ward-looking d e t e c t o r s (C. Jupiter, EG & G Inc., private c o m m u n i c a t i o n ) .
A n o t h e r Rn correction m e t h o d involves periodically collecting an air sample
and counting it o n board t h e aircraft for Rn daughters (Burson et al., 1 9 7 2 ) .
A third m e t h o d , presently being tested (P. D o d d , private c o m m u n i c a t i o n )
incorporates the c o l l e c t i o n of Rn daughters o n a charged wire c o n t i n u o u s l y
circulating outside t h e aircraft, and c o u n t i n g its g a m m a radioactivity as the
wire is w o u n d around a take-up spool.

AUTORADIOGRAPHY OF URANIUM A N D THORIUM

For m a n y decades alpha-track and, more recently, fission-track autoradio-


graphic techniques have b e e n utilized t o determine the location of radio-
active minerals in thin or polished sections of rock.

Alpha autoradiography

Alpha particles radiating from U- and Th-bearing z o n e s near t h e surface of


a thin section are registered o n an overlying photographic e m u l s i o n . When
t h e emulsion is d e v e l o p e d , sites o f radioactivity are located and their alpha
activity quantitatively determined. B o w i e ( 1 9 5 4 ) described geologic applica-
tions of alpha radiography while, more recently, Ragland ( 1 9 6 4 ) presented
an e x c e l l e n t review article o n t h e technique and its applications. Though it is
effective in registering radioactive mineral grains, a drawback of the alpha
radiographic m e t h o d is the long t i m e required t o obtain results. Minerals
with relatively high radioactivity (several hundred t o several thousand parts
per million U or Th) require exposure t i m e s of t h e order of t e n d a y s t o yield
statistically significant numbers of countable alpha tracks for quantitative
determination of radioelements.
Furthermore, in a p o p u l a t i o n of alpha tracks it is very difficult t o differ-
entiate b e t w e e n t h o s e from the Th d e c a y series and t h o s e from t h e U decay
series. A l s o , it is possible that secular equilibrium d o e s n o t exist b e t w e e n
U and its daughters which are t h e principal alpha-particle emitters. There-
2 3 8

fore, unless t h e ratios of Th t o U within t h e radioactive minerals are k n o w n ,


either through i n d e p e n d e n t measurements, or are successfully assumed,
alpha-particle autoradiography d o e s n o t furnish i n d e p e n d e n t determinations
of t h e radioelements.

The fission-track method

This m e t h o d , d e v e l o p e d in t h e mid 1 9 6 0 ' s b y Fleischer et al. ( 1 9 6 5 ) ,


permits determination of the location and abundances of U and, under favor-
23

able c o n d i t i o n s , Th, in thin or polished sections after short exposures


(generally a f e w m i n u t e s ) t o reactor neutrons. Over t h e past several years,
geologists have applied t h e m e t h o d t o study U c o n t e n t s , ranging from tens t o
thousands of parts per million, in thin and polished sections containing
accessory and rock-forming minerals — see, for e x a m p l e , Kleeman and
Lovering ( 1 9 6 7 ) , B o w i e et al. ( 1 9 7 2 ) , and Wollenberg ( 1 9 7 2 ) . U c o n t e n t s as
l o w as a f e w tens of parts per billion have b e e n measured in finely p o w d e r e d
preparations of w h o l e rock ultramafic samples (Fisher, 1 9 7 0 ) .
The basic procedure t o obtain fission tracks from U a n d / o r Th is quite
simple. Solid-state track d e t e c t o r s , usually mica or plastic, are m o u n t e d on a
series o f samples and standards, which are t h e n e x p o s e d t o reactor neutrons.
On c o m p l e t i o n of t h e e x p o s u r e , the detectors are r e m o v e d and e t c h e d in t h e
appropriate reagents. The resulting tracks are t h e n viewed and c o u n t e d with
t h e aid of a m i c r o s c o p e . (Fig. 2-11 is an e x a m p l e of a fission-track field.) In
c h o o s i n g the neutron e x p o s u r e appropriate for the e x p e c t e d c o n c e n t r a t i o n
of uranium, o n e e m p l o y s the e q u a t i o n which governs density of fission
tracks in a d e t e c t o r placed directly o n the flat surface of material containing
U, and irradiated w i t h n e u t r o n s :

p = (froEn [1]
where p is t h e track density in tracks c m " , 0 is t h e integrated neutron flux
2

in c m " , o is the neutron-induced fission cross-section ( 5 8 0 barns for thermal


2

neutron fission of U; 1 barn = 1 0 " c m ) , E is the efficiency o f d e t e c t i o n ,


2 4 2

and n is t h e n u m b e r of U nuclei per square centimeter of thin section


2 3 5

surface within the effective range of fission fragments. In t h e usual case of a


flat detector-sample interface, E is i n d e p e n d e n t of materials, and is 0 . 5 ; half
of the fission events will register in the d e t e c t o r . For fragments from t h e
fission of U and Th the effective range in m o s t silicate and p h o s p h a t e
minerals is -^3 mg c m " . T h u s :
2

n = (3Ca/A)XlO" 3
[2]
where C is t h e c o n c e n t r a t i o n of radioelement in grams per gram, a is Avo-
gadro's n u m b e r , and A is t h e a t o m i c mass n u m b e r of t h e radioelement.
In c h o o s i n g a fission-track d e t e c t o r , o n e m u s t weigh t h e advantages and
disadvantages o f different materials. The t w o d e t e c t o r s m o s t c o m m o n l y used
in geologic applications are high-quality muscovite mica and polycarbonate
plastic (Lexan or Makrofol). These are compared briefly in Table 2-1V, and
their tracks illustrated in Fig. 2 - 1 2 . Tracks in mica are easier t o recognize
than t h o s e in plastic. H o w e v e r , Lexan's principal advantage is that it has
essentially n o background U, whereas t h e highest quality mica has a back-
ground of tracks from t h e s p o n t a n e o u s and induced fission of its inherent
U c o n t e n t . Therefore, if a l o w c o n t e n t of U is e x p e c t e d in t h e sample, it
2 3 8

m a y be preferred t o use a Lexan d e t e c t o r , or e x p o s e a mica d e t e c t o r "blank"


t o obtain the effective background value.
24

Fig. 2-11. Enrichment in U ( 2 5 0 0 — 3 0 0 0 ppm) at margin of an opaque grain (hematite?)


in fluoritized fault-zone breccia, east Greenland. The upper portion of the figure is a
photomicrograph of the grain, the lower portion shows the matching fission tracks. Field
diameter, 0.88 mm. (From Wollenberg, 1 9 7 2 . )
25

Fig. 2-12. Fission-track etch pits in muscovite (top) and Lexan polycarbonate ( b o t t o m ) .
Track density, 2.25 X 1 0 tracks c m " . Mica was etched in 48% HF for ~ 1 hour, the
s 2

Lexan in 6N KOH at 6 0 ° C for 15 minutes. (From Wollenberg, 1 9 7 2 . )


26

TABLE 2-IV
Comparison of detector materials

Natural muscovite Polycarbonate plastic

Very durable Surface scratches easily


Tracks easy to recognize, readily distin- Tracks perpendicular to surface appear as
guished from scratches small dots, easily confused with scratches
Etching time, \ — 4 hours Etching time, 10—15 minutes
Track size regulated by varying etching Surface removed readily as etching pro-
time without danger of appreciable sur- gresses; not possible t o enlarge tracks
face loss after 10—15 minutes
U content plus geologic age yield back- Essentially no background tracks, detec-
ground tracks from spontaneous and tion limit governed by neutron exposure
induced fission. This governs detection
limit (1—5 ppm U)

Exposure, processing, and etching c o n d i t i o n s for different U concentra-


tions are summarized in Table 2-V. The c h o i c e of irradiation c o n d i t i o n s
d e p e n d s u p o n the e l e m e n t t o be determined and its c o n c e n t r a t i o n . If U
alone is desired, thermal neutrons are e m p l o y e d for the essentially exclusive
fission of 2 3 5
U . The samples are e x p o s e d in t h e thermal c o l u m n of the
reactor (a position outside the core, surrounded b y graphite t o e x c l u d e fast
neutrons), where t h e ratio of thermal t o fast neutrons is highest. Conversely,
a fast-neutron irradiation is used t o d e t e c t T h . The sample-detector package
is placed as close as possible t o t h e core of t h e reactor, and is encased in at
least a 3-mm thickness of c a d m i u m t o permit as pure a flux of fast neutrons
as possible. In t h e flux estimate for a T h irradiation, o n e m u s t include t h e
large contribution t o t h e observed track density from U . The estimated
2 3 8

TABLE 2-V
Exposure, processing and observation conditions for various evenly distributed uranium
concentrations

U content Neutron exposure Track density Etching time Magnifi- Tracks/


(ppm) (n c m ) - 2
(tracks c m " ) 2
(hours) cation field

50 2 X 10 3
1.2 X 10 4
3-4 X 36 -500
500 1 X 10 3
6 X 10 4
2-3 X 80 -450
5000 1 X 10 3
6 X 10 s
1-2 X 270 -400

* Etching of high-quality muscovite mica in 40—48% HF at room temperature.


27

integrated n e u t r o n flux is t h e n :

0 = plEio^n^ + auttu) 13]


where p is t h e desired track d e n s i t y , E t h e efficiency of d e t e c t i o n , a and x h

Ou t h e fast n e u t r o n fission cross sections for T h ( 0 . 3 barn) and 2 3 2


U (~1.12 3 8

barn) respectively, and n and n are t h e estimated c o n c e n t r a t i o n s of T h


Th v

and U nuclei.
2 3 8

If t h e T h / U ratio of a mineral is great e n o u g h , t h e use o f fast neutrons


permits a d e t e r m i n a t i o n o f Th c o n t e n t . Since practically all Th-bearing
minerals also c o n t a i n s o m e U, it is necessary first t o d e t e r m i n e U b y a

13 -

12 -

11 -

10 -

9 -

8 -

7 -
z>
_:
t—

6 -

5 -

4 -

3 -

2 -

1 -

N I i i ' • i 1—. 1 1 '


u
10 20 30 40 50 60 70 80 90
0»- Relative Error in T h ( ° / o )

Fig. 2-13. T h / U ratio versus relative error in Th for typical exposure and counting condi-
tions. (From Wollenberg, 1 9 7 2 . )
28

thermal neutron e x p o s u r e . T h e n t h e sample, w i t h a n e w d e t e c t o r and U and


Th standards is e x p o s e d t o a fast neutron flux. The resulting track density is
from t h e fission o f U and
2 3 8
T h , b u t k n o w i n g t h e U c o n t e n t , and having
2 3 2

simultaneously e x p o s e d a U standard, t h e U track contribution is determined.


The contribution from Th is t h e n the difference b e t w e e n t h e total track
density and that from U.
The main difficulty of this m e t h o d of Th determination is t h a t t h e relative
errors d u e t o c o u n t i n g statistics are rather large; t h e cross-section ratio for
fast neutrons favors U over Th b y nearly a factor of 3 . Fig. 2 - 1 3 relates T h / U
ratios and relative errors for typical exposure and c o u n t i n g c o n d i t i o n s of
accessory-mineral samples. Relative errors are ^-25% if T h / U is greater than
~ 3 ; for ratios < 3 t h e errors increase rapidly and are unacceptably high
(~ 40%) for T h / U < 1 .

RADON DETECTION

R n , a gaseous d e c a y product of t h e
2 2 2
U series, has been successfully
2 3 8

used as a diagnostic parameter for locating U beneath a thickness o f cover


which w o u l d otherwise conceal the ore from d e t e c t i o n b y surface or air-
borne gamma-ray surveys.

Physical parameters

Because it is an inert gas, Rn diffuses from its source sites, mineral grains
containing abundances of parent 2 3 8
U , w i t h o u t chemical interaction with
constituents of rock or soil. The Rn daughter i s o t o p e of t h e T h series,
2 3 2

R n (termed t h o r o n ) , has a m u c h shorter half-life ( 5 5 seconds) than


2 2 0
Rn
2 2 2

( 3 . 8 d a y s ) . Therefore, t h e U series daughter travels significantly farther in


the soil before decaying, and is c o n s e q u e n t l y present at or near t h e earth's
surface in greater abundance than t h o r o n .
A parameter termed the e m a n a t i o n coefficient, the ratio of R n emanated
b y a mineral t o t h e R n actually produced in the mineral, varies widely for
given minerals and their physical character (Barretto et al., 1 9 7 2 ) . Rn losses
of 1—20% are n o t u n c o m m o n for rock materials crushed t o identical grain
size fractions, and values of 10—50% were observed for soils. Accessory
minerals with high U c o n t e n t s have relatively l o w e m a n a t i o n coefficients; Rn
loss d e p e n d s u p o n w h e t h e r t h e mineral grains are fresh or badly damaged b y
alpha particles, weathering, or other factors. By virtue of closing pore spaces
through w h i c h Rn m a y m o v e , soil moisture tends t o inhibit diffusion and
exhalation. The m o v e m e n t of Rn can, however, be enhanced b y groundwater
flow (Tanner, 1 9 6 4 ) .
Israel ( 1 9 5 8 ) defined t h e exhalation rate of a radioactive gas from the
ground: E = a(D/X) , 1/2
where a is t h e rate of generation of gas a t o m s i n t o soil
29

pore spaces in Ci c m ~ s , D is t h e bulk diffusion coefficient through t h e


3 _ 1

porous m e d i u m in c m s ~ \ and X is t h e radioactive d e c a y c o n s t a n t in s" .


2 1

Megumi and Mamuro ( 1 9 7 4 ) list exhalation rates of R n and t h o r o n for


various size fractions of soil originating from weathered granite. Calculated
exhalation rates for Rn were approximately seven t i m e s greater for minus
2 0 0 - m e s h sizes than for t h e 5—10-mesh fraction of a granite-derived soil.
2 2 2
Rn d e c a y s through its daughters t o P b , w i t h t h e emission of 3 alpha
2 1 0

particles o f 5 . 4 8 , 6 . 0 , and 7 . 6 9 M e V , each distinguishable b y alpha spectro-


s c o p y . Within t h e d e c a y series, P b and B i e m i t g a m m a rays detectable in
2 1 4 2 1 4

t h e energy regions e n c o m p a s s e d b y normal gamma-ray s p e c t r o m e t r y .

Sampling and analysis

Most instruments for R n measurement, t o d a t e , have b e e n d e v e l o p e d for


assessment of t h e element's environmental effects. A valuable c o m p e n d i u m
of information o n t h e s e measurement systems has b e e n prepared b y Budnitz
( 1 9 7 3 ) . In b o t h t h e environmental and prospecting applications, Rn assess-
m e n t utilizes primarily, alpha-particle c o u n t i n g . A relatively n e w m e t h o d ,
described s u b s e q u e n t l y , e m p l o y s solid-state alpha-track d e t e c t o r s .

Alpha counting
Field instrumentation for on-site m e a s u r e m e n t of Rn in soil gas incor-
porates extraction of the gas and i m m e d i a t e c o u n t i n g of its alpha activity.
Such a lightweight, portable instrument, an alpha p r o b e , is described in a
review article b y Miller and Ostle ( 1 9 7 3 ) . A sharp-pointed bar is driven 6 0
c m into t h e ground t h e n withdrawn. The suction of withdrawing t h e t u b e
forces soil air i n t o t h e h o l e , w h i c h is t h e n cased. Insertion of t h e alpha probe
t h e h o l e forces air i n t o the measuring chamber. Alphas are c o u n t e d b y inter-
action w i t h silver-activated zinc sulfide, a p h o s p h o r - c o a t e d d e t e c t o r , v i e w e d
b y a photomultiplier t u b e . The total alpha radioactivity of R n and its
daughters is measured, and results are normally expressed as c o u n t i n g rates.
Other s y s t e m s utilize p u m p i n g o f soil gas from uncased h o l e s , through an
alpha counter. A portable p u m p i n g s y s t e m , t h e Scintrex E T R - 1 , w h i c h
measures alpha activity in an ionization chamber, is s h o w n in Fig. 2 - 1 4 .
S o m e p u m p e d s y s t e m s e m p l o y closed c y c l e s , where the e x h a u s t from t h e
d e t e c t o r chamber is circulated back i n t o the capped h o l e , others e x h a u s t t h e
gas from t h e chamber t o t h e atmosphere. The latter draw gas from a v o l u m e
considerably larger than t h e h o l e . Pumping s y s t e m s m a y introduce appreci-
able dust and moisture, thus t h e y require filtration w h i c h m a y remove s o m e
Rn daughters w h i c h adhere t o dust particles.
Because Rn daughters adhere t o dust particles, d e t e c t o r chamber c o n -
tamination levels build up with successive measurements, despite flushing
w i t h atmospheric air. This c o n t a m i n a t i o n requires that ZnS detectors be
30

Fig. 2-14. The Scintrex ETR-1 Emanometer for analysis of soil-gas 2 2 2 Rn.

changed frequently. Filtering reduces, b u t d o e s n o t c o m p l e t e l y prevent,


accumulation o f daughters.
Field soil-gas m e a s u r e m e n t s y s t e m s range in size from the afore-mentioned
p r o b e , t o systems e m p l o y i n g vehicle-mounted augering and p u m p i n g equip-
m e n t . Results o f measurements are generally expressed as alpha c o u n t rates,
rather than absolute Rn c o n c e n t r a t i o n s . In areas where 2 3 2 T h is abundant,
R n ( t h o r o n ) m a y be an important c o n s t i t u e n t of soil gas. Its effect can be
2 2 0

m i n i m i z e d b y retaining t h e air sample in t h e d e t e c t o r chamber for several


half-lives ( ~ 1 0 m i n ) before c o u n t i n g , allowing t h o r o n t o d e c a y .
Rn c o n t e n t s of stream and lake waters m a y be indicators of nearby U
mineralization ( D y c k , 1 9 7 2 ) . R n is extracted from t h e water sample b y
bubbling air or an inert gas through t h e sample, and collecting t h e gas-Rn
mixture in a ZnS-coated cell for alpha counting. If a low-background gamma-
c o u n t i n g s y s t e m is close at h a n d , water samples can b e analyzed directly for
31

R n using t h e p r e d o m i n a n t
2 2 2 B i g a m m a rays (Wollenberg, 1 9 7 4 ) . Results
2 1 4

of water analyses are normally expressed as picocuries per liter ( 1 0 ~ Ci T ) . 1 2 1

Alpha-track detectors
The registration o f alpha particles in plastics has b e e n successfully applied
t o t h e search for U in recent years. The basic c o n c e p t — called Track Etch

Fig. 2-15. Plastic cup with alpha-track detector attached. (From Gingrich, 1 9 7 5 . )
32

because it e t c h e s t h e alpha tracks in t h e plastics — was discovered b y scien-


tists at t h e General Electric Research and D e v e l o p m e n t Laboratory (Fleischer
et al., 1 9 7 2 ) . It was subsequently m o d i f i e d and patented b y scientists of the
Terradex Corporation t o d e t e c t alpha particles from t h e d e c a y of Rn 2 2 2

Alter e t al., 1 9 7 2 ) .
Inverted plastic cups w i t h a specially treated dielectric alpha-track d e t e c -
t o r attached inside (Fig. 2-15) are placed, each in an approximately 0.5-m-
d e e p h o l e , in arrays o f varying e x t e n t . The walls o f t h e c u p are thick e n o u g h
t o e x c l u d e alpha particles from R n in t h e air outside t h e c u p and other alpha
emitters in t h e soil surrounding t h e c u p ; t h e o n l y c o n t r i b u t i o n is from t h e
R n i m m e d i a t e l y inside t h e c u p . After exposure o f several w e e k s , t h e cups are
retrieved, t h e d e t e c t o r s r e m o v e d and e t c h e d revealing track densities propor-
tional t o t h e emanating R n flux. A major advantage o f t h e Track Etch
m e t h o d is this l o n g e x p o s u r e w h i c h averages t h e large variations ( s o m e t i m e s
as large as 1 0 0 - f o l d in 2 4 h ) that o c c u r in R n levels. Fig. 2 - 1 6 s h o w s a Rn
c o n t o u r m a p based o n this t e c h n i q u e (Gingrich, 1 9 7 5 ) where subsequent
drilling led t o t h e discovery of a sizeable o r e b o d y w h i c h w o u l d have other-
wise g o n e u n d e t e c t e d b y surface gamma-ray surveys.
T h e principal advantage of t h e track d e t e c t o r m e t h o d over t h e direct
measurement on-site o f R n , is that the track m e t h o d integrates over a
2 2 2

period o f t i m e , and therefore s m o o t h s o u t effects o f fluctuations in emana-


t i o n d u e primarily t o atmospheric p h e n o m e n a .
Quite recently, a n e w m e t h o d o f field R n d e t e c t i o n has b e e n d e v e l o p e d b y

f i l l 1 1 / \
SCALE
0 500 1000 1500
FEET
Fig. 2-16. Radon track-etch contours (in tracks m m ) , over a potential uranium resource
2

area. (From Gingrich, 1 9 7 5 . )


33

E x x o n Eastern Inc., and Alpha-Nuclear C o m p a n y . A plastic c u p w i t h a


silicon-semiconductor d e t e c t o r is placed in a h o l e , similar t o t h e track-etch
detectors. Alpha particles from t h e d e c a y of R n in t h e c u p are registered
2 2 2

o n t h e s e m i c o n d u c t o r , w h o s e pulses are stored b y an electronic unit, also in


t h e h o l e . The integrated c o u n t s are t h e n read o u t periodically b y a separate,
portable unit. T h o u g h initial costs greatly e x c e e d t h o s e of t h e track-etch
cups, t h e electronic R n d e t e c t i o n units can be reset and used indefinitely,
making t h e m cost-effective over a long period.

CONCLUSIONS

Radiometric m e t h o d s are applicable t o all aspects o f t h e search for ura-


nium resources, t h e definition of reserves, and their d e v e l o p m e n t . A three-
phase program incorporating radiometric m e t h o d s is generally e m p l o y e d :
exploration for target areas; evaluation o f targets, leading t o definition of
reserves; f o l l o w e d b y d e v e l o p m e n t and p r o d u c t i o n . Table 2-VI lists t h e
radiometric m e t h o d s w h i c h fit i n t o these categories. It is e m p h a s i z e d that
data from radiometric m e t h o d s a l o n e , are n o t a sufficient base u p o n w h i c h
t o decide t h e course o f a resource d e v e l o p m e n t program. Of great impor-

TABLE 2-VI
Radiometric methods applicable to phases of uranium resource development

1. Exploration for target areas:


Airborne total gamma and gamma-spectral surveys
Groundborne field gamma spectrometry on broad-scale surveys, and laboratory gamma
spectrometry of selected samples
Soil and water 2 2 2
Rn surveys over large areas

2. Evaluation of targets:
Detailed field total gamma and gamma spectral surveys over target areas
Laboratory gamma spectrometry of specimens from intensely samples areas
Rn alpha-track surveys of target areas
Downhole total gamma and gamma-spectral measurements of targets delineated by sur-
face surveys
Autoradiography of selected thin or polished sections

3. Development and production of resource areas:


Downhole total gamma and gamma-spectral measurements for grade control
Field total gamma and gamma-spectral measurements of working faces, benches, and
stockpiles, and laboratory gamma spectrometry of samples from these areas
34

tance are e c o n o m i c considerations and a strong k n o w l e d g e o f t h e geologic


setting, c o u p l e d w i t h a t h o r o u g h understanding o f non-radioactive g e o c h e m -
ical and geophysical parameters. These, t h e n , c o m b i n e d with information
from radiometric m e t h o d s , furnish a firm basis for evaluation o f uranium
resource potential.

REFERENCES

Adams, J.A.S., 1 9 6 8 . Total and spectrometric gamma-ray surveys from helicopters and
vehicles. In: Symposium on Use of Nuclear Techniques for Prospecting and Developing
Mineral Resources, Buenos Aires. IAEA, Vienna.
Adams, J.A.S. and Fryer, G., 1 9 6 4 . Portable gamma-ray spectrometer for field determina-
tion of thorium, uranium, and potassium. In: J.A.S. Adams and W. Lowder (Editors),
The Natural Radiation Environment. University of Chicago Press, Chicago, 111.
Adams, J.A.S. and Gasparini, P., 1 9 7 0 . Gamma-Ray Spectrometry of Rocks. Elsevier,
Amsterdam, 2 9 5 pp.
Alter, W. et al., 1 9 7 2 . Radon detection using track-registration materials. U.S. Patent No.
3,665,194 (issued May 2 3 , 1 9 7 2 ) .
Anspaugh, L.R., Phelps, P.L., Gudiksen, P.H., Lindeken, C.L. and Huckabay, G.W., 1 9 7 2 .
The in-situ measurement of radionuclides in the environment with a Ge(Li) detector.
In: J.A.S. Adams, W. Lowder and T. Gessell (Editors), The Natural Radiation Environ-
ment II. U.S. ERDA Rep. Conf, 7 2 0 8 0 5 - P 2 .
Barretto, P.M.C., Clark, R.B. and Adams, J.A.S., 1 9 7 2 . Physical characteristics of
radon-222 emanation from rocks, soils and minerals: its relation to temperature and
alpha dose. In: J.A.S. Adams, W. Lowder and T. Gessell (Editors), The Natural Radia-
tion Environment II. U.S. ERDA Rep. Conf, 7 2 0 8 0 5 - P 2 .
Bowie, S.H.U., 1 9 5 4 . Nuclear emulsion techniques. In: H. Faul (Editor), Nuclear Geology.
Wiley, N e w York, N.Y., pp. 148—174.
Bowie, S.H.U., Simpson, P.R. and Rice, C M . , 1 9 7 2 . Application of fission-track and
neutron activation methods to geochemical explorations. In: M. Jones (Editor), Geo-
chemical Exploration, 1972. Institution of Mining and Metallurgy, London.
Budnitz, R., 1 9 7 3 . Radon-222 and its daughters. In: Instrumentation for Environmental
Monitoring. Lawrence Berkeley Lab. Rep., LBL-1.
Burson, Z.G., Boyns, P.K. and Fritzsche, A.E., 1 9 7 2 . Technical procedures for character-
izing the terrestrial gamma radiation environment by aerial surveys. In: J.A.S. Adams,
W.M. Lowder and T.F. Gessell (Editors), Natural Radiation Environment II. U.S.
ERDA Rep. Conf, 7 2 0 8 0 5 - P 2 .
Darnley, A.G., 1 9 7 2 . Airborne gamma-ray survey techniques. In: S.H.U. Bowie et al.
(Editors), Uranium Prospecting Handbook. Institution of Mining and Metallurgy,
London, pp. 174—211.
Darnley, A.G., 1 9 7 3 . Airborne gamma-ray survey techniques — present and future. In:
Uranium Exploration Methods. IAEA, Vienna, pp. 67—108.
Davis, J.D. and Guilbert, J.M., 1 9 7 3 . Distribution o f the radioelements potassium, ura-
nium, and thorium in selected porphyry copper deposits. Econ. Geol, 6 8 : 145—160.
Dodd, P.H. and Eschliman, D.H., 1 9 7 2 . Borehole techniques for uranium exploration and
evaluation. In: S.H.U. Bowie et al. (Editors), Uranium Prospecting Handbook. Institu-
tion of Mining and Metallurgy, London, pp. 244—276.
Doig, R., 1 9 6 8 . The natural gamma-ray flux: in-situ analysis. Econ. Geol., 3 3 : 311—328.
Dyck, W., 1 9 7 2 . Radon methods of prospecting in Canada. In: S.H.U. Bowie et al.
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(Editors), Uranium Prospecting Handbook. Institution of Mining and Metallurgy,


London.
Fisher, D.E., 1 9 7 0 . Homogenized fission track determination of uranium in whole-rock
geologic samples. Analyt. Chem., 4 2 : 414—416.
Fleischer, R.L., Price, P.B. and Walker, R.M., 1 9 6 5 . Tracks of charged particles in solids.
Science, 1 4 9 : 3 8 3 — 3 9 3 .
Fleischer, R.L., Alter, H.W., Furman, S.C., Price, P.B. and Walker, R.M., 1 9 7 2 . Particle
track etching. Science, 1 7 8 : 255—263.
Gingrich, J., 1 9 7 5 . Results from a new uranium exploration method. Trans. Soc. Min.
Eng., Am. Inst. Min. Eng., 2 5 8 : 61—64.
Grasty, R.L. and Darnley, A.G., 1 9 7 1 . Calibration of gamma-ray spectrometers for
ground and airborne use. Geol. Surv. Can. Paper, 71-17.
Heath, R.L., 1 9 6 9 . Gamma-ray spectrometry and automated data analysis systems for
activation analysis. In: J.R. D e V o e (Editor), International Conference on Modern
Trends in Activation Analysis, 2. Natl Bur. Stand. (U.S.), Spec. Publ, 3 1 2 .
Heier, K.S. and Adams, J.A.S., 1 9 6 5 . Concentration of radioactive elements in deep
crustal material. Geochim. Cosmochim. Acta, 2 9 : 53—61.
Israel, H., 1 9 5 8 . Die Naturliche Radioaktivitat in Boden, Wasser, und Luft. Beitr. Phys.
Atmos., 3 0 : 177—188.
Key, B.N. and Eschliman, D.H., 1 9 7 4 . Preliminary evaluation of a spectral logging meth-
od for the borehole. Unpublished report, Lucius Pitkin Inc. for E R D A Resource
Division.
Kleeman, J.D. and Lovering, J.F., 1 9 6 7 . Uranium distribution in rocks by fission-track
registration in Lexan plastic. Science, 1 5 6 : 512—513.
L^vborg, L., 1 9 7 3 . Future development in the use of gamma-ray spectrometry for ura-
nium prospecting on the ground. In: Uranium Exploration Methods. IAEA, Vienna.
L^vborg, L., Kunzendorf, H. and Rose-Hansen, J., 1 9 6 8 . Use of field gamma spectrom-
etry in the exploration of uranium and thorium deposits in South Greenland. In:
Nuclear Techniques and Mineral Resources. IAEA, Vienna, pp. 1 9 7 — 2 1 1 .
L^vborg, L., Wollenberg, H., Sorensen, P. and Rose-Hansen, J., 1 9 7 1 . Field determination
of uranium and thorium by gamma-ray spectrometry, exemplified by measurements in
the Ilimaussaq alkaline intrusive, South Greenland. Econ. Geol, 6 6 : 3 6 8 .
L^vborg, L., Wollenberg, H.A., Rose-Hansen, J. and Leth Nielsen, B., 1 9 7 2 . Drill-core
scanning for radioelements by gamma-ray spectrometry. Geophysics, 37: 675—693.
Matheron, G., 1 9 6 3 . Principles of geostatistics. Econ. Geol, 5 8 : 1 2 4 6 — 1 2 6 6 .
Megumi, K. and Mamuro, T., 1 9 7 4 . Emanation and exhalation of radon and thoron gases
from soil particles. J. Geophys. Res., 7 9 : 3 3 5 7 — 3 3 6 0 .
Miller, J.M. and Ostle, D., 1 9 7 3 . Radon measurement in uranium prospecting. In: Ura-
nium Exploration Methods. IAEA, Vienna.
Moxham, R.M., F o o t e , R.S. and Bunker, C M . , 1 9 6 5 . Gamma-ray spectrometer studies of
hydrothermally-altered rocks. Econ. Geol, 6 0 : 6 5 3 — 6 7 0 .
Ragland, P., 1 9 6 4 . Autoradiographic investigations of naturally occurring materials. In:
J.A.S. Adams and W. Lowder (Editors), The Natural Radiation Environment. Univer-
sity of Chicago Press, Chicago, 111.
Richardson, K.A., 1 9 6 4 . Thorium, uranium and potassium in the Conway Granite, N e w
Hampshire, U.S.A. In: J.A.S. Adams and W. Lowder (Editors), The Natural Radiation
Environment. University of Chicago Press, Chicago, 111.
Smith, A.R. and Wollenberg, H.A., 1 9 7 2 . High-resolution gamma-ray spectrometry for
laboratory analysis of the uranium and thorium decay series. In: J.A.S. Adams, W.
Lowder and T. Gessell (Editors), The Natural Radiation Environment II. US. ERDA
Rep. Conf, 7 2 0 8 0 5 - P 2 .
Sprecher, C. and Rybach, L., 1 9 7 4 . Design and field test of a scintillation probe for
gamma-logging of small siameter boreholes. Pageoph, 1 1 2 : 564—570.
36

Tanner, A., 1 9 6 4 . Radon migration in the ground: a review. In: J.A.S. Adams and W.
Lowder (Editors), The Natural Radiation Environment. University of Chicago Press,
Chicago, 111.
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minerals. In: M. Jones (Editor), Geochemical Exploration 1972. Institution of Mining
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Wollenberg, H., 1 9 7 4 . Radioactivity of Nevada hot spring systems. Geophys. Res. Lett.,
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Wollenberg, H.A. and Smith, A.R., 1 9 6 8 . Radiogeologic studies in the central part of the
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Wollenberg, H.A. and Smith, A.R., 1 9 6 9 . Radioactivity and radiogenic heat production in
prebatholithic rocks of the central Sierra Nevada. J. Geophys. Res., 7 5 : 431—438.
Wollenberg, H.A., Smith, A.R. and Bailey, E.H., 1 9 6 7 . Radioactivity of Upper Mesozoic
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Chapter 3

X - R A Y A N A L Y S I S IN M I N E R A L E X P L O R A T I O N

M. SLAUGHTER

INTRODUCTION

Mineral exploration is the art of finding and defining e c o n o m i c a l l y desir-


able natural resources. When e x e c u t e d logically, mineral exploration e n c o m -
passes a narrowing sequence of deductive and inductive predictions of
presence, quality and quantity of ore. The entire e x p l o r a t i o n process from
regional geological analysis t o detailed chemical analysis rests o n an analyt-
ical base. Mineral exploration is a c o m p l e x art requiring m a n y t y p e s of ana-
lytical t o o l s . T w o of t h e t o o l s t o determine chemical c o m p o s i t i o n and
mineral c o n t e n t of rocks and ores are X-ray fluorescence analysis and X-ray
diffraction analysis. B o t h m e t h o d s of X-ray analysis add vital information t o
a p o o l of k n o w l e d g e necessary for mineral finding and e x p l o i t a t i o n .
X-ray fluorescence analysis determines chemical c o m p o s i t i o n . A n X-ray
source excites X-ray emission in a s p e c i m e n . X-rays emanating from t h e
specimen indicate its elemental c o m p o s i t i o n . X-ray fluorescence analysis is
particularly suited t o mineral exploration because it determines m a n y
e l e m e n t s in rocks and ores simultaneously, rapidly and accurately as well as
determining e l e m e n t s that are difficult or expensive t o measure b y other
means.
X-ray diffraction analysis uses X-rays t o determine mineralogical c o n t e n t
of a specimen. An X-ray source impinges X-rays on a s p e c i m e n w h i c h dif-
fracts t h e m m u c h as light diffracts through a fine wire m e s h , t h e angles of
diffraction d e p e n d i n g o n t h e minerals in t h e s p e c i m e n .
X-ray fluorescence and X-ray diffraction analysis, although powerful t o o l s
for mineral e x p l o r a t i o n , serve best in a particular niche of t h e e x p l o r a t i o n
s e q u e n c e . Out of their n i c h e , b o t h m e t h o d s give b u t supporting help t o t h e
exploration process and m a y n o t be useful at all. H o w are these m e t h o d s
used in mineral e x p l o r a t i o n ? We shall try t o s h o w t h e e x p l o r a t i o n niche of
b o t h m e t h o d s of analysis b y developing a simplified e x a m p l e o f e x p l o r a t i o n
for uranium. A p p l i c a t i o n of t h e X-ray m e t h o d s is similar in exploration for
all t y p e s of metal and non-metal ores.
The geologist begins l o o k i n g for a uranium d e p o s i t perhaps b y c h o o s i n g an
area in sedimentary rocks flanked b y a granitic terrain. He k n o w s that ura-
nium frequently c o n c e n t r a t e s in sedimentary rocks from a source in granites.
Should t h e literature lead him t o a promising area, h e m a y initiate field
38

inspection for potential ore sites. The geologist might c h o o s e t o l o o k for


b o t h suitable source and h o s t rocks for his initial investigation. He might
visually analyze potential source-rock lithology for a likelihood of containing
uranium. He might sample run-off waters from the potential source rock or
sample t h e source rock itself for m i n u t e quantities of uranium or related
daughter products using gamma-ray spectrometry. Normally the geologist
w o u l d n o t use surface radiometry because of l o w concentration of radio-
active e l e m e n t s .
During this preliminary phase of source-rock inspection chemical and
mineralogical analyses by X-ray m e t h o d s have limited use. The geologist
specifies analytical m e t h o d s t o determine chemical concentration in parts
per billion or parts per trillion, o u t o f t h e useful range of X-ray fluorescence
analysis. Selected spot samples, subjected t o chemical analysis by X-ray
fluorescence and qualitative mineralogical analysis b y X-ray diffraction,
might help t o establish a chemical and mineralogical framework of the
potential source rocks.
Concurrently with source investigation, t h e geologist might investigate
surface rock exposures t o find a suitable lithology for uranium transport and
concentration. Again the geologist analyzes the rocks visually. Should he
find a sedimentary sequence where a not-too-pervious sandstone is over- and
underlain b y impervious shales, having t h e granite as a s e d i m e n t source, he
m a y proceed t o analyze for uranium indications d o w n - d i p from the sediment
source. He m a y analyze t h e surface using radiometric surveys, radon analysis,
or trace e l e m e n t analysis t o d e t e c t leakage t o t h e surface of daughter prod-
ucts or "pointer" e l e m e n t s from a subsurface uranium deposit. He may even
analyze plants for radiometric e l e m e n t s or trace e l e m e n t s such as m o l y b -
d e n u m w h i c h may b e associated with a uranium d e p o s i t . Should these
indications, c o u p l e d w i t h analyses of sediment nearer the source, s h o w
relative depletion of uranium and daughter products, a n e w phase of e x p l o -
ration begins — exploration drilling.
The beginning of the drilling phase o f exploration marks a transition in
the usefulness of X-ray analytical m e t h o d s . Initial investigation of potential
uranium accumulation sites use trace e l e m e n t analysis, radiometric measure-
m e n t s of various sorts and visual analysis. Neither X-ray diffraction nor
fluorescence contributes e x c e p t perhaps for occasional analyses t o determine
s o m e indirectly useful rock parameter.
From the beginning of t h e drilling phase of exploration or its equivalent
for other minerals t o the c o m p l e t i o n of drilling prior t o mining, X-ray
fluorescence and X-ray diffraction analysis can contribute systematically t o
t h e finding and definition of orebodies. For e x a m p l e , during the drilling
phase of exploration of a given site, o n e c o m p a n y submitted 1 0 0 , 0 0 0
samples for X-ray analysis t o help find and define its ore. X-ray fluorescence
defined metal pointer e l e m e n t s , rock-forming e l e m e n t s and uranium.
The exploration t e a m begins drilling t o l o o k for ore. Rotary drilling holes
39

spaced relatively w i d e l y allow the uranium geologist a small w i n d o w t o t h e


subsurface. Through this w i n d o w he determines stratigraphy, structure,
lithology, t e x t u r e , p o r o s i t y , permeability, alteration products of migrating
groundwater solutions, uranium indicator e l e m e n t s , and uranium itself. He
might find in o n e h o l e that a potential ore-bearing bed had insufficient
permeability t o carry ore-bearing solutions. If sufficiently permeable he
might find zeolites b y X-ray diffraction analysis t o tell h i m that leaching
solutions carrying uranium had n o t reached his drill h o l e . Conversely,
mineralogical analysis b y X-ray diffraction could s h o w an abundance o f
kaolinite and n o zeolites indicating acid groundwater leaching up-dip from a
potential deposit. Closer t o a uranium deposit, chemical analysis provides a
framework leading t o ore. X-ray fluorescence analysis m a y determine
anomalously high copper or vanadium a m o u n t s and m a y d e t e c t and quantify
uranium itself.
Systematic X-ray diffraction and X-ray fluorescence analyses o f samples
from each h o l e provide a mineralogical and chemical framework t o , at first,
s u p p l e m e n t and t h e n t o supplant visual analysis and d o w n h o l e logging
m e t h o d s . B o t h analytical X-ray m e t h o d s give a basis for quantitative map-
ping as did radiometric surveys during the previous exploration phase. Subtle
indicators of a uranium d e p o s i t or the direction t o a d e p o s i t can b e m a p p e d
b y X-ray analysis even w i t h c o n t a m i n a t e d cuttings from rotary drilling.
The geologist having f o u n d a uranium o r e b o d y n o w enters t h e final phase
of exploration. With a c o m b i n a t i o n of core and rotary drilling h e defines t h e
boundaries, quantity and quality of ore. During earlier phases of exploration
h e used analyses of various t y p e s t o find ore. During this phase he uses
analyses t o establish t h e ore inventory and t h e lithologic and structural
framework preliminary t o mining. X-ray fluorescence and X-ray diffraction
b e c o m e very powerful analytical t o o l s during this final phase. The combina-
t i o n of m e t h o d s can quantitatively d o c u m e n t t h e m o s t important e l e m e n t s
and lithologies inexpensively and accurately, providing a g o o d three-dimen-
sional m o d e l of t h e o r e b o d y . The d e p o s i t m a y n o w be m i n e d .
From t h e i n c e p t i o n of e x p l o r a t i o n , X-ray fluorescence and X-ray diffrac-
tion analysis have progressively more importance in the exploration process.
A t first neither m e t h o d has m u c h application. Later b o t h m e t h o d s serve
occasionally t o help correlate chemical or mineral c o m p o s i t i o n w i t h visual or
other m e t h o d s of analysis. Finally in t h e later stages o f e x p l o r a t i o n b o t h
X-ray fluorescence and X-ray diffraction analysis can contribute significantly
t o mineral exploration and o r e b o d y definition. Either or b o t h m e t h o d s can
be the m o s t powerful laboratory analysis m e t h o d s for the final phase of
exploration drilling.
The purpose of this chapter is t o d e v e l o p t h e t h e o r y , instrumentation and
application of X-ray analysis t o mineral e x p l o r a t i o n . As with m o s t analytical
m e t h o d s , c o m p l i c a t i o n s and limitations require sophistication and c o m p e -
tence for the analyst and a reasonable degree of k n o w l e d g e for t h e explora-
40

t i o n team t o k n o w w h e n and h o w t o use each t e c h n i q u e . We therefore


present the t h e o r y of X-ray fluorescence and X-ray diffraction in sufficient
detail t o serve as a primer for t h e user t o select and judge t h e kind and
quality of results he needs. X-ray instrumentation n o t o n l y serves various
purposes in exploration analysis, but different instruments give different
kinds, qualities and rates of analyses. To aquaint t h e potential X-ray user of
these differences, w e present short sections o n X-ray instrumentation. Finally
w e introduce t h e reader t o selected applications of X-ray analysis t o raw
materials exploration. Where appropriate, w e m e n t i o n strengths, weaknesses
and pitfalls e n c o u n t e r e d w h e n analyzing rock and ore materials.
For more c o m p l e t e treatments of X-ray fluorescence analysis m e t h o d
refer t o an e x c e l l e n t short t e x t b y Jenkins ( 1 9 7 4 ) or t o a comprehensive
reference t e x t b y Bertin ( 1 9 7 5 ) . X-ray diffraction analysis is treated c o m -
prehensively b y Klug and Alexander ( 1 9 7 4 ) .

X-RAY FLUORESCENCE ANALYSIS

X-ray fluorescence analysis determines t h e chemical c o m p o s i t i o n of solids


and the partial chemical c o m p o s i t i o n of liquids. The basic principle of X-ray
fluorescence analysis is simple. A n X-ray source generates a range of wave-
lengths o f X-ray p h o t o n s m u c h as an incandescent bulb generates w h i t e light,
a range of p h o t o n s wavelengths in t h e visible region of t h e electromagnetic
spectrum. The X-ray p h o t o n s impinge o n a s m o o t h specimen surface where
t h e y cause ejection of electrons from a t o m s in t h e s p e c i m e n . To maintain
electrical neutrality other electrons re-occupy t h e vacant sites in t h e speci-
m e n a t o m s , emitting n e w X-ray p h o t o n s characteristic of each a t o m . A
p h o t o n d e t e c t i o n s y s t e m measures t h e numbers and wavelengths of p h o t o n s
emanating from the s p e c i m e n . The wavelengths and numbers of p h o t o n s
d e t e c t e d translate into a t o m i c kind and a m o u n t .
In t h e following sections w e d e v e l o p the X-ray fluorescence analysis
process beginning with X-ray generation and ending with m e t h o d s of trans-
lating raw X-ray p h o t o n c o u n t s i n t o chemical analyses of rock and mineral
materials.

Generation of X-rays

The continuous spectrum


A very simple X-ray-generating tube produces primary X-rays used t o
e x c i t e secondary X-rays in an analyte sample. Fig. 3-1 s h o w s t h e construction
of the X-ray tubes. A low-voltage (7—14 V ) , high-current circuit heats a
tungsten filament t o cause emission of thermal electrons. A large potential,
usually b e t w e e n 3 0 and 7 5 k V , accelerates the thermal electrons e m i t t e d
from t h e filament c a t h o d e toward a target a n o d e . A metal cup b e l o w t h e
41

X-RAYS
ANODE
X-RAYS

CATHODE-

a b
b
Fig. 3-1. X-ray fluorescence tube (a) and diffraction tube (b). Arrows indicate direction
of accelerated electrons. Cones indicate beams passing through windows.

filament traps thermal electrons m o v i n g in t h e direction o p p o s i t e t h e target.


Electrons accelerated toward t h e metal target material strike t h e target w i t h
an energy E = Ve where V is t h e voltage and e is t h e charge o n t h e electron
(1.602 X 1 0 " C ) . 1 9

The electrons, u p o n entering t h e metal target material, accelerate as t h e y


pass through t h e force fields of t h e a t o m i c nuclei and t h e diffuse electron
clouds a b o u t t h e nuclei. The accelerating (slowing) electrons in t h e field of
nuclei and electron c l o u d s lose all or part of their energy w i t h emission of
o n e or more p h o t o n s of energy hv. Ve establishes t h e upper limit of energy
loss or e m i t t e d p h o t o n energy, that is:

E = Ve = hv max

where h is Planck's c o n s t a n t ( 6 . 6 2 5 6 X 1 0 ~ J s) and v is t h e frequency of t h e


3 4

e m i t t e d energy. If t h e electron accelerates t o zero v e l o c i t y instantaneously:

^max —
^/^-min

where c is t h e speed o f light ( 2 . 9 9 8 X 1 0 m s" ) and X


8 1
= hc/Ve = 1 2 4 0 0
m i n

A / y . A n y electron striking a target thus produces a m i n i m u m wavelength of


p h o t o n radiation w h e n it loses all its energy at o n c e .
Most electrons d o n o t lose all their energy at o n c e but in increments pro-
ducing a distribution of p h o t o n energies. This distribution, a f u n c t i o n of
accelerating voltage, is pictured in Fig. 3-2a. The spectral distribution
resembles black-body radiation and a derivation similar t o Planck's derivation
of black-body radiation explains t h e distribution. The wavelength of maxi-
m u m intensity of p h o t o n s emanating from t h e target is a b o u t 1.5—2.0 t i m e s
^ m i n - We term this spectral distribution t h e " w h i t e " or c o n t i n u o u s spectrum.
The c o n t i n u o u s spectrum radiates from t h e water-cooled target material
in all directions b u t passes from the t u b e through a berylium w i n d o w t o t h e
analyte s p e c i m e n . The c o n t i n u o u s spectrum striking t h e sample e x c i t e s elec-
trons in t h e a t o m s t o generate a characteristic spectrum.
42

INTENSITY ( A R B I T R A R Y UNITS)
INTENSITY

WAVELENGTH (A) WAVELENGTH (A)


Fig. 3-2. Intensity distribution versus wavelength of the X-ray spectrum, (a) Continuous
distribution of tungsten radiation at several voltages, (b) A portion of continuous and
characteristic spectrum of molybdenum.

The characteristic spectrum


The electrons in a t o m s o f analyte material o c c u p y specific and more or
less well-defined energy levels. We designate these energy levels b y a set of
numbers called q u a n t u m numbers. Each electron energy b e c o m e s a f u n c t i o n
o f t h e designating q u a n t u m numbers.
Specifying t h e pertinent q u a n t u m numbers w e have :
n = principal q u a n t u m number; specifies t h e total electronic energy exclu-
sive of orbital m o m e n t u m and electron spin; values are 1 , 2 , ... in a
hydrogen-like a t o m .
/ = specifies orbital angular m o m e n t u m ; values 0 , 1 , 2 , . . . n.
m = specifies t h e spin angular m o m e n t u m o f t h e electron; values are ± \ cor-
s

responding t o spin in o n e direction or t h e other.


We m a y c o m b i n e t h e orbital and spin terms t o obtain a n e w q u a n t u m
number wliich contains b o t h orbital angular m o m e n t u m and spin in t h e same
term (total angular m o m e n t u m ) , t h u s j = I + m = I ± \. A f u n c t i o n o f t h e
s

n e w set o f numbers n, /, j also specifies t h e total electron energy. Fig. 3-3


s h o w s energies o f electrons in a first-row transition e l e m e n t .
If w e impinge a c o n t i n u o u s spectrum o n a t o m s containing t h e energy
levels o f Fig. 3 - 3 , p h o t o n s m a y eject (excite) electrons from energy levels of
t h o s e a t o m s . A p h o t o n from t h e c o n t i n u o u s spectrum w h o s e energy is equal
t o or greater than t h e negative o f t h e energy o f an a t o m i c electron can eject
an atom's electron, losing its o w n energy in t h e process. When an X-ray
43

K L. L.| L j . .
LEVEL n I j STATE
3 2 5/2 A
k. j 3d
3 2 3/2 3d
M
3 1
1 3 // 2
3 2 3p
3 1
1 1/2
1/2 3p

3 0 1/2 3s

2 1 3/2 f 2p
2 1 1/2
2p
L
2s

2 0 1/2

>f \f > f > 1s

K > K, K K

Fig. 3-3. Electronic excitations and transitions yielding a characteristic spectrum of a


hypothetical first-row transition element. Arrows pointed downward represent transi-
tion energies. Arrows pointed upward represent excitation energies.
K 1 0 1/2

p h o t o n e x c i t e s an electron from an a t o m , an electron from a higher energy


level in the same a t o m enters t h e vacated level generating a n e w p h o t o n . The
n e w l y e m i t t e d p h o t o n will have energy E = hv — hv that is, t h e difference
2 u

b e t w e e n the energies of t h e t w o levels.


Empirical selection rules govern allowed transitions from higher energy
levels t o l o w e r levels and simplify the e m i t t e d spectrum:

Arc = 0; A/ = ± l ; A/' = ± l o r O .
The arrows in Fig. 3-3 s h o w allowed electron transitions within that a t o m .
The length of the arrows are roughly proportional t o the a m o u n t of energy
of t h e transition, h e n c e energy of t h e e m i t t e d p h o t o n s . P h o t o n s e m i t t e d as a
result of these transitions comprise the characteristic spectrum. Fig. 3-2b
s h o w s part of t h e characteristic spectrum from the target material of an
X-ray tube superposed o n its c o n t i n u o u s spectrum where accelerated elec-
trons eject a t o m i c electrons.
Each e l e m e n t has a differently charged nucleus and each has electrons
o c c u p y i n g different energy levels, c o n s e q u e n t l y t h e characteristic spectrum
of each e l e m e n t differs from t h e spectrum o f all other e l e m e n t s . Table 3-1
s h o w s e x a m p l e s of energies required t o eject electrons from different a t o m s
w i t h energies of p h o t o n s e m i t t e d from t h e different a t o m i c transitions. C o m -
plete lists of energies are given b y Bertin ( 1 9 7 5 ) .
The X-ray p h o t o n flux from an X-ray t u b e provides t h e energy for X-ray
fluorescence analysis or X-ray diffraction. If w e wish t o analyze for the ele-
m e n t s in a specimen w e use t h e spectrum w i t h o u t m o d i f i c a t i o n . If w e wish
4^

TABLE 3-1
X-ray excitation energies, mean emission energies and fluorescent yields for c o m m o n rock- and ore-forming elements

Element Excitation energy ( k e V ) Emission energy ( k e V ) Fluorescent yield

L
K Li Ln III K a

c 0.283 — — — — 0.279 * — — 0.001 —


Na 1.080 0.055 0.034 0.034 — 1.041 — — 0.013 —
Mg 1.303 0.063 0.050 0.049 — 1.255 — — 0.019 —
Al 1.559 0.087 0.073 0.072 1.55 1.487 — — 0.026 —
Si 1.838 0.118 0.099 0.098 1.838 1.739 — — 0.036 —
P 2.142 0.153 0.129 0.126 2.142 2.014 — — 0.047 —
S 2.470 0.193 0.164 0.163 2.468 2.307 — — 0.061 —
K 3.607 0.341 0.297 0.294 3.589 3.312 — — 0.118 —
Ca 4.038 0.399 0.352 0.349 4.012 3.690 0.344 0.341 0.142 0.001
Ti 4.964 0.530 0.460 0.454 4.931 4.508 0.458 0.452 0.197 0.001
V 5.463 0.604 0.519 0.512 5.427 4.949 0.519 0.510 0.227 0.002
Cr 5.988 0.679 0.583 0.574 5.947 5.411 0.581 0.571 0.258 0.002
Mn 6.537 0.762 0.650 0.639 6.494 5.895 0.647 0.636 0.291 0.003
Fe 7.111 0.849 0.721 0.708 7.059 6.400 0.717 0.704 0.324 0.003
Co 7.709 0.929 0.794 0.779 7.649 6.925 0.790 0.775 0.358 0.004
Ni 8.331 1.015 0.871 0.853 8.265 7.472 0.866 0.849 0.392 0.005
Cu 8.980 1.100 0.953 0.933 8.907 8.041 0.948 0.928 0.425 0.006
Zn 9.660 1.200 1.045 1.022 9.572 8.631 1.032 1.009 0.458 0.007
Mo 20.002 2.884 2.627 2.523 19.633 17.443 2.395 2.164 0.749 0.039
U 115.991 * 21.753 20.943 17.163 111.786 * 97.143 * 17.218 13.000 0.960 0.478

* Values not attainable or measurable with standard equipment.


** Emission from M I V
t o Lj levels for all but U.
v V
*** Emission from M , M j to L J U levels for all but U.
45

t o identify minerals b y X-ray diffraction w e m o n o c h r o m a t i z e the X-ray


spectrum eliminating almost all radiation e x c e p t t h e characteristic K radia- a

t i o n from t h e target.

Secondary X-rays — fluorescence


X-ray p h o t o n s of a given wavelength passing into a material eject electrons
from t h e a t o m s of that material because p h o t o n s have m o m e n t u m :

mc = h/\ = hvjc
Like electrons, X-ray p h o t o n s t o eject an electron from an a t o m m u s t
have energy equal t o or greater than t h e electron's energy. If a p h o t o n ejects
an electron, an electronic transition occurs as in t h e target of the X-ray t u b e .
If there is a distribution of p h o t o n energies, electronic ejection f o l l o w e d b y
electronic transitions in t h e specimen material produces all lines of t h e
characteristic spectrum o f t h e a t o m o f t h e specimen material. P h o t o n s have
n o electrical charge and c a n n o t interact with the electrical field of s p e c i m e n
a t o m s , therefore, c a n n o t generate a c o n t i n u o u s s p e c t r u m . The spectrum so
generated is called t h e fluorescent spectrum and is t h e basis for X-ray
spectrometric analysis.
Considering only fluorescence, the n u m b e r of X-ray p h o t o n s of a specific
electronic energy transition e m i t t e d from a specimen e l e m e n t w o u l d be
proportional t o t h e weight fraction of t h e e l e m e n t in t h e sample. We should
have o n l y t o compare t h e intensity of a characteristic spectral line of an ele-
m e n t from t h e s p e c i m e n , J , , w i t h the same radiation from a k n o w n
( u )

a m o u n t of the same e l e m e n t in a standard, 7 , t o accurately estimate t h e


I ( s )

a m o u n t of t h e e l e m e n t in t h e u n k n o w n s p e c i m e n :

mJJCU) = w,-<.) 7— (!)


1
Ks)

The weight fraction of e l e m e n t i in t h e u n k n o w n and standard respectively


are w and w
i{u) . i { s )

Absorption and secondary fluorescence

A l t h o u g h equation (1) is s o m e t i m e s a g o o d a p p r o x i m a t i o n for estimating


a m o u n t s of e l e m e n t s in a sample, usually it is n o t . S o m e X-rays e m i t t e d from
an e l e m e n t in a specimen have e n o u g h energy t o eject electrons from another
a t o m of t h e same s p e c i m e n . These X-rays can be absorbed. A b s o r p t i o n
decreases the intensity of X-rays from t h e emitting e l e m e n t . On t h e other
hand, t h e e l e m e n t w h o s e electron is ejected by t h e p h o t o n e m i t t e d from
another e l e m e n t also e m i t s a p h o t o n resulting in "secondary fluorescence".
Secondary fluorescence enhances t h e intensity of X-ray lines caused b y
p h o t o n s from t h e X-ray t u b e .
46

The X-ray absorption spectrum


Lambert in 1 7 9 2 found that t h e fraction of radiation absorbed, dl/I, pass-
ing through a thin layer of matter is proportional t o the thickness of material:

dl/I = —fa dx

For finite thicknesses:

dl

io

or:

///o = e~ * M l
(2)
T h e linear absorption coefficient, n , d e p e n d s o n the state of matter. We m a y
Y

substitute a n e w coefficient JJL* that is i n d e p e n d e n t of t h e solid, liquid or


gaseous state:

M*=Mi/P (3)

where p is t h e density of t h e material. Equation (2) b e c o m e s :

I/Io^e-f* (4)

Absorption of a p h o t o n of a given wavelength d e p e n d s in equation ( 4 ) o n JJL*


for that wavelength, t h e density of t h e absorbing e l e m e n t and t h e thickness
o f t h e absorber.
The quantity, called t h e mass absorption coefficient, varies with the
wavelength of radiation. Fig. 3 - 4 s h o w s a p l o t of fx* against wavelength for
platinum. Absorption is at a local m a x i m u m w h e n t h e p h o t o n striking the
material has just e n o u g h energy t o eject an electron from a particular shell of
the absorbing e l e m e n t . Absorption is at a local m i n i m u m w h e n t h e p h o t o n
has slightly less energy than e n o u g h t o eject an electron from a particular
shell. The probability that a p h o t o n will eject an electron decreases the more
t h e p h o t o n energy e x c e e d s t h e ejection energy. We k n o w t h e mass absorp-
tion coefficients as a f u n c t i o n of wavelength fairly accurately for all b u t t h e
very light e l e m e n t s . Therefore, if w e k n o w each o f t h e other parameters in
equation ( 4 ) , w e can accurately predict the a m o u n t of absorption in a mate-
rial for any given wavelength of impinging radiation.

Secondary fluorescence
Elements in a specimen absorbing either the primary b e a m or radiation
from other a t o m s in t h e specimen m u s t re-emit radiation. When radiation
from o n e e l e m e n t o f a s p e c i m e n causes absorption and re-emission from
another e l e m e n t o f a s p e c i m e n , t h e s e c o n d e l e m e n t is said t o be secondarily
fluorescing. K radiation from copper in a specimen is absorbed b y iron and
a

t h e iron a t o m s re-emit i r o n - K radiation. The c o p p e r - K intensities are


a a
47

300 1 1 1 T i 1 i i i 1— i i r i

200

L
III

100

K
i i i
0 •fWi i 1 1 1 1 1 1 i

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5
o
Wavelength (A)
Fig. 3-4. The mass absorption coefficient, j U * , versus wavelength for platinum showing K
and L absorption edges.

diminished b y iron absorption while t h e i r o n - K intensities are enhanced b y a

secondary fluorescence. B o t h effects are illustrated in Fig. 3-5 in comparison


w i t h the e x p e c t a t i o n o f e q u a t i o n ( 1 ) .
A fairly simple order exists in t h e periodic table t o predict w h i c h e l e m e n t
will absorb and fluoresce K-radiation. In t h e first and s e c o n d rows of t h e

i i • i

0 50
ATOMIC PERCENT 100

Fig. 3-5. Relative X-ray intensities versus atomic percent for a copper-iron mixture
showing relative effect of absorption of copper radiation by iron and absorption and
secondary fluorescence of iron radiation by copper.
48

periodic table an e l e m e n t strongly absorbs K-radiation from an e l e m e n t o n e


higher in a t o m i c number. A l u m i n u m strongly absorbs silicon K-radiation and
silicon strongly absorbs sulfur K-radiation. In turn, t h e aluminum fluoresces
K-radiation from absorption o f silicon and sulfur K-radiation. In t h e third
r o w of the periodic table of e l e m e n t s , an e l e m e n t absorbs very strongly t h e
K-radiation from an e l e m e n t t w o higher in a t o m i c number. T w o or three ele-
m e n t s successively l o w e r in a t o m i c numbers than t h e very strongly absorbing
e l e m e n t also absorb strongly. Cobalt very strongly absorbs copper K-radia-
t i o n w i t h iron, c h r o m i u m and manganese successively less strongly absorbing
t h e copper K-radiation. In t h e fourth-row e l e m e n t s t h e relation is similar
e x c e p t the m o s t strongly absorbing e l e m e n t is three d o w n in a t o m i c number
from t h e fluorescing e l e m e n t . The absorbing e l e m e n t emits K-radiation as
secondary fluorescence. The a m o u n t of e m i t t e d secondary radiation is less
than t h e absorbed radiation because s o m e o f the absorbed radiation ejects L,
M, etc., electrons.
Lighter e l e m e n t s absorb and re-emit less strongly than heavier e l e m e n t s .
However, the distribution o f primary X-rays from an X-ray t u b e yields a
relatively small number of p h o t o n s t o e x c i t e light e l e m e n t s so any absorp-
tion of t h e radiation from light e l e m e n t s p r o f o u n d l y limits analytical sen-
sitivity o f t h e light e l e m e n t s from aluminum d o w n . A b s o r p t i o n o f light-
e l e m e n t radiation effectively limits detectable radiation t o that e m i t t e d from
very near t h e surface of a s p e c i m e n .

Qualitative fluorescence analysis

Obviously, for g o o d exploration analysis results, t h e exploration analyst


must a c c o u n t for t h e several interrelated physical processes that p r o d u c e his
analytical determinations: fluorescence, absorption and secondary fluores-
c e n c e . It is t h e quantitative accounting (or lack of it) of these processes that
determines t h e utility and quality of fluorescence analysis in mineral
exploration. Because t h e physical processes c o n d i t i o n results so c o m p l e t e l y ,
w e proceed b y explaining qualitative analysis f o l l o w e d b y a more precise
d e v e l o p m e n t o f quantitative analysis using the physical g e o m e t r y of t h e
qualitative analysis. Quantitative analysis is t h e primary use of X-ray fluores-
c e n c e in mineral e x p l o r a t i o n .
Qualitative X-ray fluorescence analysis for major and minor elements in
rocks and ores is rapid and simple. T w o t y p e s o f instruments furnish t h e
exploration analyst w i t h his analytical t o o l s .
Fig. 3-6a schematically illustrates t h e scanning crystal X-ray spectrometer.
In this instrument the X-rays emanating from t h e X-ray t u b e strike t h e
sample causing X-ray fluorescence in t h e s p e c i m e n . Part o f t h e radiation
from t h e specimen passes through a collimator t o p r o d u c e a parallel X-ray
b e a m . The collimated b e a m of X-rays strikes an "analyzing" crystal surface
where it diffracts i n t o a s e c o n d collimator, t h e n c e into a d e t e c t o r . Diffrac-
49

DETECTOR! I
DETECTOR

DIFFRACTED ,
X-RAYS— 0 A
FLUORESCENT-/

FLUORESCENT $

SAMPLE

Fig. 3-6. T w o types of X-ray spectrometer geometry, (a) Scanning or "crystal" spectrom-
eter, (b) Energy dispersive spectrometer.

t i o n from the analyzing crystal f o l l o w s t h e e q u a t i o n :

nX = 2d { sin 6 (5)

(See section "X-ray diffraction analysis" for derivation of this e q u a t i o n . ) If


t h e analyzing crystal is rotated a b o u t an axis at one-half t h e speed of rota-
t i o n of t h e d e t e c t o r assembly a b o u t its axis, w e m a y measure diffraction
m a x i m a corresponding t o values of X or nX, where n is a positive integer. We
choose d , t h e spacing of a particular plane in a tabular crystal t o allow
c r y s t

measurement of a range of wavelengths. Each instrument has a selection of


collimators, analyzing crystals and d e t e c t o r s t o cover all wavelength ranges.
Target material of the X-ray t u b e s can also be selected for m o s t efficient
operation over a particular e l e m e n t or wavelength range. For e x a m p l e ,
c h r o m i u m or r h o d i u m targets are efficient for general rock analysis (lighter
e l e m e n t s ) whereas tungsten or platinum targets are efficient for lead, copper,
or zinc ores. Spectra from a scanning spectrometer analysis resemble t h e
spectrum s h o w n in Fig. 3-7. Values of 2 0 for each line can be correlated
through e q u a t i o n ( 5 ) w i t h t h e wavelength of t h e radiation. Tables o f radia-
t i o n wavelengths (White and J o h n s o n , 1 9 7 0 ) for each e l e m e n t identify ele-
mental kind as in Fig. 3-7a. The scanning fluorescence spectrometer, t h e m o s t
widely used t y p e of X-ray spectrometer, gives t h e best spectral sensitivity,
resolution, and flexibility of all X-ray spectrometers for e x p l o r a t i o n analysis.
Fig. 3-6b illustrates schematically a s e c o n d t y p e of X-ray spectrometer,
usually called an energy dispersive X-ray spectrometer. The g e o m e t r y of this
spectrometer is simpler than t h e scanning spectrometer. Typically an X-ray
t u b e impinges a b e a m o f X-rays o n a s p e c i m e n . The s p e c i m e n emits fluores-
c e n t X-rays w h i c h pass through a collimator t o eliminate stray radiation. T h e
collimated X-rays t h e n pass into a solid-state d e t e c t o r (usually lithium-
drifted silicon) maintained at liquid nitrogen temperatures. For each p h o t o n
t h e d e t e c t o r gives a pulse w h o s e voltage is proportional t o t h e energy of t h e
50

b
/

Fig. 3-7. X-ray spectra of elements each with 0.8% concentration, (a) Spectrum from scanning spectrometer, lithium fluoride ana-
lyzing crystal and scintillation detector, 4 0 kV. (b) Spectrum from energy dispersive spectrometer redrawn t o scale of (a), 3 0 kV.
Each scanned the same length of time.
51

p h o t o n . A n analogue t o digital converter converts t h e pulse t o digital form


and t h e digital signal is accumulated in a multi-channel analyzer according t o
voltage. When pulses have accumulated for a f e w s e c o n d s or m i n u t e s , t h e
entire elemental energy spectrum can be displayed, printed or otherwise
s h o w n t o t h e analyst (Fig. 3 - 7 b ) .
The energy dispersive spectrometer has several advantages for exploration
analysis. It is fast — u p t o ten t i m e s the analysis speed of t h e scanning spec-
trometer. It is less expensive t o purchase than scanning spectrometers. It is
mechanically simpler than scanning spectrometers. Lines of higher value o f n
than o n e in equation (5) d o n o t clutter t h e spectrum. T o balance the advan-
tages, energy dispersive spectrometers have disadvantages t o o . Energy dis-
persive X-ray spectrometry can resolve energies t o an average of a b o u t 1 5 0 eV
while crystal X-ray spectrometry can resolve t o a b o u t 3 e V . T h e poorer
resolution of t h e energy dispersive spectrometer frequently requires elaborate
mathematical unfolding of the spectrum t o r e m o v e line overlaps for e l e m e n t s
in t h e c o m m o n ore minerals, making qualitative and quantitative analysis less
precise. A l t h o u g h t h e entire spectrum is being collected simultaneously, the
d e t e c t o r allows a m a x i m u m linear p h o t o n c o u n t rate of a b o u t 1 0 t i m e s less
than detectors used in scanning crystal spectrometers, again necessitating
elaborate correction for d e t e c t o r " d e a d - t i m e " at t h e c o s t of analytical sen-
sitivity and precision. Finally, a supply of liquid nitrogen m u s t be available
to continuously cool the detector.
There are other n o t e w o r t h y aspects of b o t h t y p e s of spectrometers. Quan-
titative analytical sensitivity under normal operating c o n d i t i o n s ranges at
best from a b o u t 1 p p m for heavier e l e m e n t s in a light-element matrix t o
0.05—0.1 wt. % for light e l e m e n t s in a light-element matrix. As t h e matrix
elements b e c o m e heavier, sensitivity decreases. First-row transition e l e m e n t s
in m o s t rocks usually can be d e t e c t e d d o w n t o a b o u t 1 0 p p m and light ele-
m e n t s such as F and Na can be d e t e c t e d t o only a b o u t 0.5—1%. Special
instrumentation configurations and scanning procedures are required t o
attain the best sensitivity. Equation ( 1 ) permits qualitative estimates of t h e
a m o u n t of each e l e m e n t in a s p e c i m e n , but the accuracy of the estimates can
range from an error of a f e w percent o f t h e a m o u n t of t h e e l e m e n t in a
specimen t o t w o or three orders of magnitude of t h e a m o u n t of the e l e m e n t .
It is hazardous t o p u t m u c h reliance o n quantitative estimates of elemental
a m o u n t s in exploration samples unless t h e analyst has experience w i t h b o t h
X-ray t h e o r y and geological materials. One special qualitative analysis
m e t h o d is useful o n automatic scanning spectrometers. A u t o m a t i c spectrom-
eters can l o o k for specific e l e m e n t s and at t h e same t i m e give g o o d intensity
measurements for t h o s e elements.
Qualitative analysis, although useful in mineral e x p l o r a t i o n , usually serves
t o establish data for quantitative analysis. Quantitative analysis provides t h e
data u p o n which the geologist can m a k e exploration and e x p l o i t a t i o n
decisions.
52

Quantitative fluorescence analysis

Quantitative X-ray fluorescence analysis has proved a very powerful,


precise and accurate analytical t o o l in t h e minerals p r o d u c t i o n and process-
ing industries. H o w e v e r , accurate quantitative analyses for geological
exploration i m p o s e m o r e stringent c o n d i t i o n s than typical in mineral
p r o d u c t i o n and processing. Exploration specimens vary w i d e l y and fre-
quently unpredictably in c o m p o s i t i o n from sample t o sample. T h e more dif-
ficultly measurable l o w - a t o m i c - n u m b e r e l e m e n t s c o n s t i t u t e major c o m -
p o n e n t s . S p e c i m e n character, such as particle size and shape, introduces
special problems, usually requiring specific and m o r e elaborate procedures
for maintaining accuracy. T h e problems n o t withstanding, a u t o m a t i c X-ray
fluorescence analysis using rapid semi-automatic sample preparation,
automatic data collection and c o m p u t e r correction programs requiring f e w
analytical standards, makes possible l o w - c o s t accurate exploration analysis.
The discussion following emphasizes t h e more stringent restrictions o f X-ray
analysis o f geological samples and t h e use o f c o m p u t e r a u t o m a t i o n tech-
niques and features t o o v e r c o m e exploration analysis problems.

Line intensities with absorption and fluorescence corrections


Mass absorption coefficients signify more than just h o w an absorbing
e l e m e n t diminishes t h e intensity o f t h e radiation from t h e X-ray t u b e or
from another emitting e l e m e n t . If w e separate t h e curve o f Fig. 3-4 into t h e
mass absorption coefficients for each electronic shell K, L, M, e t c . , each o f
the separated curves / z * , J U * , e t c . , w o u l d b e proportional t o t h e probabil-
K L i

ity that a p h o t o n o f a given wavelength o f radiation will eject an electron


from a particular shell. Should a p h o t o n eject an electron from a level and a
transition occur, t h e a m o u n t o f radiation leaving t h e a t o m from a particular
transition is cog. The term co, t h e fluorescent yield (Table 3-1), defines t h e
fraction o f p h o t o n s leaving an a t o m after t h e series o f transitions t o a given
level such as t h e K-level. We define g as t h e relative intensity o f a line in its
series. Neglecting absorption and secondary fluorescence in t h e sample, for
t h e /th e l e m e n t kind:

dI ,\
i J = kI i*jG) g dt
ttXpl J Pi (6)
where I is t h e intensity o f t h e primary beam from t h e t u b e at a d e p t h t in
tfX

t h e sample (Fig. 3 - 8 ) .
P

Substituting Q for t h e constants in e q u a t i o n ( 6 ) :

Qi = kuljwjg
With t h e g e o m e t r y o f Fig. 3 - 8 :

It,\ p =V \ p e x p - (/i* pt c o s e c 0)
p

where I 0%K is t h e intensity o f a given wavelength o f t h e primary b e a m


53

Fig. 3-8. Geometry of secondary excitation in a specimen.

impinging o n t h e s p e c i m e n . The emerging intensity:

d/ U j = dI tfXj exp - Pt cosec i//)

=
QiPiIo,\ p e x p pt(M* c o s e c 0 + /xj^ c o s e c \//) d£
p

Since c o s e c 0, c o s e c i//, J U * and /z*^ are c o n s t a n t for a given instrument


and s p e c i m e n w e m a y set:

Jx = (/i^ c o s e c 0 + J U ^ c o s e c
p

Equation (7) b e c o m e s :

<Ui.\j = QiPih,\ p exp - dipt) dt (8)


Integrating e q u a t i o n ( 8 ) :

= = [1 - (exp - iipt)].
MP

If w e permit t t o b e c o m e very large, that is, an infinitely thick sample, t h e n :

hxj = (QiPiio^vap O)
For an infinitely thick sample, w h i c h for m o s t e l e m e n t s is less than a f e w
millimeters t h e intensity of a b e a m scattered from s p e c i m e n is given b y equa-
tion (9).
We m a y p r o c e e d from e q u a t i o n ( 9 ) along several paths t o p r o d u c e correc-
t i o n m e t h o d s for quantitative analysis. We l o o k at t w o , each of w h i c h is
typical of correction procedures suitable for e x p l o r a t i o n analysis.

Linear correction method


A l l o w i n g fx o f e q u a t i o n ( 9 ) t o be defined b y a s u m o f linear coefficients
with each term representing t h e effect o f absorption and secondary fluores-
c e n c e of e l e m e n t j o n e l e m e n t /:

P=Sa y (10)
54

Since p =_^p where p is t h e density o f e l e m e n t i in t h e sample. Then


t f

Q,-P//o,\ MP 2 a p / and a - = 1, so that for pure /:


p
= =
l 7 fI

QiPiWhoot =
<tuPi-

Therefore:
O i l Pi +
0 ; P 2
2
+
- +
t 1 _ /
100//^]Pf - + <*inPn = 0 (11)

where and i i o o / are analyte line intensities of e l e m e n t / from t h e specimen


and pure e l e m e n t i respectively.
Since p /p - w equation ( 1 1 ) b e c o m e s :
t iy

n
£ dijWi + (1 - RdWi = 0, i # j (12)
7=1

w i t h Ziooi/^i = Ri-
Equation ( 1 2 ) gives t h e basis for quantitative absorption and secondary
fluorescence corrections. If ten e l e m e n t s are t o be analyzed in a sample, at
least ten standards m u s t have t e n e l e m e n t s in differing proportion t o deter-
m i n e t h e coefficients a j. All e l e m e n t s in a specimen e x c e p t trace or very
(

minor e l e m e n t s m u s t be included in the equation for accurate results.


The m e t h o d outlined, d u e t o Lucas-Tooth and P y n e ( 1 9 6 4 ) , although quite
simple and often powerful, has a fundamental weakness. Equation ( 1 0 ) is
b u t an approximation because t h e preceding equations d o n o t explicitly
a c c o u n t for secondary fluorescence. In geological specimens, secondary
fluorescence can be appreciable, especially in metal ore materials. For e x a m -
ple, w h e n analyzing for titanium in t h e presence of iron and calcium, the
error in t h e a m o u n t o f titanium reported can be as great as 50%, w i t h o u t
secondary fluorescence corrections. Analysts avoid such errors b y requiring a
limited range of c o m p o s i t i o n s of the analyte specimen and having the stan-
dards closely approximate t h e c o m p o s i t i o n of t h e analytes. A l m o s t all cor-
rection m e t h o d s useful for exploration samples proposed before 1 9 7 0 are
similar t o t h e Lucas-Tooth and Pyne m e t h o d and have similar weaknesses.
Rasberry and Heinrich ( 1 9 7 4 ) proposed equations t o explicitly correct for
secondary fluorescence:

(13)

The fundamental difference b e t w e e n previous m e t h o d s and t h e Rasberry-


Heinrich m e t h o d is t h e s e c o n d s u m m a t i o n in e q u a t i o n ( 1 3 ) w h i c h approxi-
mately fits t h e form of e n h a n c e m e n t o f an analyte line b y secondary fluores-
c e n c e . This i m p r o v e m e n t should give better accuracy and wider c o m p o s i -
tional range of applicability than simpler m e t h o d s .
Fundamental parameters method
We m a y m a k e corrections for absorption and secondary fluorescence using
55

fundamental parameters t o define e x c i t a t i o n , absorption and secondary


fluorescence (Criss and Birks, 1 9 6 8 ) . If w e derive a set o f e q u a t i o n s in a
similar manner t o e q u a t i o n s (6) through ( 9 ) , b u t n o w assume a distribution
o f X-ray wavelengths from t h e t u b e similar t o t h e distribution in Fig. 3-2a,
taking into a c c o u n t e n h a n c e m e n t o f an X-ray line of e l e m e n t i b y other ele-
m e n t s in t h e sample, w e have the following e q u a t i o n :

(14)

The variables in e q u a t i o n ( 1 4 ) are defined as f o l l o w s :


weight fraction o t analyte e l e m e n t i
Wj weight fraction of matrix e l e m e n t j
has value 1 if X is short e n o u g h t o e x c i t e X or Xj and value 0
p L

for longer wavelengths


8i f u n c t i o n of absolute intensity from e l e m e n t i
Kj [ 1 — 1/r] Co for spectral line of e l e m e n t ; that e x c i t e s X of
L

element /
intensity of analyte line of e l e m e n t i
intensity o f t h e primary b e a m in t h e interval A X P

i,j analyte and matrix e l e m e n t respectively


M s p e c i m e n matrix including i
r absorption edge j u m p ratio, t h e ratio of t h e local high t o t h e
adjacent l o w in Fig. 3-4
AX P
:
increment of primary spectrum
wavelength of a spectral line from e l e m e n t j capable of excit-
ing X f

\ :
wavelength at analyte line of e l e m e n t i
:
o n e wavelength of primary beam
Mi 5 My 5 MM
:
mass absorption coefficients of analyte /, matrix e l e m e n t j and
matrix respectively
:
angles of Fig. 3-8
CO
:
fluorescent y i e l d , related t o Q of e q u a t i o n ( 7 ) .
t

The fundamental parameters m e t h o d requires k n o w i n g t h e distribution of


radiation from the t u b e , mass absorption coefficients as a f u n c t i o n of wave-
length and t h e fluorescent yield. From tables of these and related values w e
can determine all values in t h e previous list and e q u a t i o n ( 1 4 ) . Equation ( 1 4 )
56

c a n n o t be solved for w explicitly and interative converging procedures must


t

find the final values o f Wf. The m e t h o d , while very powerful, requires a
c o m p u t e r of larger size than for the previously discussed m e t h o d s .
The fundamental parameters m e t h o d has several advantages in exploration
analysis. Pure e l e m e n t standards or a single multi-element standard is suf-
ficient for m a n y t y p e s o f analyses. For practical rock analyses, perhaps 20—
3 0 standards are necessary for analyzing any t y p e of rock, whereas 2 0 0 or
more standards are required for t h e linear equation m e t h o d s t o cover t h e
same elemental ranges. A l t h o u g h o n e multi-element standard is all that is
necessary in the fundamental parameters m e t h o d , the mass absorption coef-
ficients and fluorescent yields for t h e lighter e l e m e n t s are n o t accurate and
multiple standards must cover a range of elemental concentrations. For
e x a m p l e , t o analyze a shale-sandstone s e q u e n c e , four standards might prove
adequate; a granite, a t o n o l i t e , a basalt and a granite spiked with quartz. The
fundamental parameters m e t h o d allows inclusion in t h e equations of ele-
m e n t s determined b y other m e t h o d s . Carbon m a y b e analyzed b y t h e r m o -
gravimetric analysis and s o d i u m and magnesium analyzed b y a t o m i c absorp-
tion. The results of carbon, s o d i u m and magnesium analysis can be included
in the correction e q u a t i o n s for t h e elements actually analyzed for b y X-ray
spectrometry. The linear e q u a t i o n m e t h o d d o e s n o t have the same flexibil-
ity. Like the linear e q u a t i o n m e t h o d all elements in a s p e c i m e n , e x c e p t o n e
e l e m e n t b y difference and trace e l e m e n t s , must be determined for accurate
analytical values.

Heavy matrix method


This m e t h o d is useful for measuring o n e or a few e l e m e n t s in exploration
specimens. The m e t h o d m a y also be used w h e n n o c o m p u t e r is available for
absorption and fluorescence corrections.
We m a y express t h e efficiency of excitation of an analyte line of a
specimen as:

(15)

with
analyte line intensity of t h e ith e l e m e n t of t h e specimen
7
o,\ p
incident b e a m intensity
W h Wj analyte and / t h c o m p o n e n t weight fraction respectively
mass absorption coefficient of ith e l e m e n t for primary beam
mass absorption coefficient of ;th e l e m e n t for primary beam
and analyte X-ray line respectively
c o n s t a n t for ith e l e m e n t related t o Q of equation (7)
t

A c o n s t a n t geometric f u n c t i o n .
57

We can e x p a n d e q u a t i o n ( 1 5 ) t o :

(16)

where t h e subscript h refers t o a highly absorbing additive and d refers t o a


diluent.
If w e m a k e either t h e heavy absorber or the diluent term in e q u a t i o n ( 1 6 )
large b y adding say o n e gram of heavy absorber and t e n grams of diluent t o
o n e gram of s p e c i m e n , a change in the matrix e l e m e n t s of t h e sample affects
t h e d e n o m i n a t o r of e q u a t i o n ( 1 6 ) very little. I
s i b e c o m e s proportional t o
Wf. This is t h e simplest of m e t h o d s that have proved effective w i t h geological
exploration samples.

Evaluation of correction methods


B o t h t h e fundamental parameters m e t h o d and t h e linear e q u a t i o n
m e t h o d s and their near relatives are t h e m o s t suitable for total rock analysis.
B o t h m e t h o d s require analysis of all but o n e non-trace e l e m e n t in each
s p e c i m e n . T h e fundamental parameters m e t h o d is proving t h e best for explora-
t i o n analysis. It has great flexibility and requires few standards. One variation
of t h e fundamental parameters m e t h o d called C O R S E T ( S t e p h e n s o n , 1 9 7 1 ) has
been proved in several laboratories o n b o t h scanning and energy dispersive
spectrometers. The linear equation m e t h o d is fast and accurate in its correc-
tions over a limited range of c o m p o s i t i o n s . For mineral exploration analysis,
t h e large n u m b e r of standards and standard measurements partially cripples
t h e linear e q u a t i o n m e t h o d . The heavy matrix m e t h o d is g o o d w h e n analyz-
ing rocks for a f e w e l e m e n t s . However, t h e heavy matrix m e t h o d causes sig-
nificant loss of sensitivity and an increase in m e a s u r e m e n t t i m e t o achieve
desired statistical accuracy. This m e t h o d also requires m o r e c o s t l y and t i m e
c o n s u m i n g sample preparation w i t h at least three weighings per s p e c i m e n .
The heavy-matrix m e t h o d is perhaps t h e best rock analysis m e t h o d w h e n n o
c o m p u t e r is available. We can c o m b i n e features of the heavy matrix m e t h o d
t o increase the correctable range of c o m p o s i t i o n s and t h e accuracy of t h e
fundamental parameters and linear e q u a t i o n m e t h o d s . Mixing s o m e diluent
w i t h t h e specimen material reduces differential absorption and secondary
fluorescence effects in t h e s p e c i m e n making correction m o r e accurate over
wider c o m p o s i t i o n ranges. The price for more accurate correction is, of
course, loss of sensitivity and analytical speed.

Sample preparation (quantitative analysis)

T o obtain intermediate- t o high-accuracy analyses b y X-ray fluorescence


analysis, samples m u s t be prepared w i t h a t t e n t i o n t o detail. Poor sample
preparation abrogates t h e quality o f present-day spectrometers and correc-
58

t i o n m e t h o d s . The nature o f geological specimens c o m p l i c a t e s sample


preparation. Differences in shape, c o m p o s i t i o n and size of rock particles
effect analytical results t o such an e x t e n t that every effort m u s t be made t o
m i n i m i z e these effects. Geological samples usually require t h e measurement
of light e l e m e n t s where absorption prevents light-element radiation from all
b u t t h e surface of t h e s p e c i m e n . G o o d mixing and s m o o t h sample surfaces
are necessary.
Exploration samples fall into t w o categories: samples where o n l y a f e w
e l e m e n t s are of interest and samples where a total rock analysis is necessary.
For b o t h t y p e s of specimens, e c o n o m i c restrictions d e m a n d fast inexpensive
m e t h o d s capable of analysis of large numbers of samples w i t h relatively high
accuracy. Samples should be processed and analyzed for from $ 5—$ 2 5 each
depending o n the number of elements determined and desired accuracy.
Sample preparation procedure, therefore, m u s t be relatively simple. The
procedure must apply t o all t y p e s of rock samples.

Fused pellets
Fusion is the best m e t h o d of preparation of silicate rock materials for
accurate analysis. Ground specimens with a c o n s t a n t proportion of a mixture
o f lithium tetraborate and lithium carbonate flux w i t h , say, 1 part specimen
t o 2—8 parts o f flux are fused in a carbon or p l a t i n u m / g o l d crucible. If the
matrix dilution m e t h o d is used, a heavy absorber such as lanthanum o x i d e
can be added. The resulting glass b u t t o n s m a y be polished or used directly.
Fusion realizes several necessary or desirable specimen attributes. Fusion
removes particle size and shape effects w h i c h reduce accuracy. Fusion affects
g o o d sample mixing and presents a s m o o t h specimen surface necessary for
light e l e m e n t measurement. Fusion also introduces a diluent making absorp-
t i o n and secondary fluorescence corrections less consequential. Fusion
eliminates carbonates and water from t h e s p e c i m e n , w h i c h m u s t be measured
b y other m e t h o d s w h e n d o i n g total rock analysis. Finally, fusion a c c o m -
plished with a u t o m a t i c fusion devices, is actually faster and cheaper than
other m e t h o d s suitable for high-accuracy quantitative analysis.

Briquettes
Briquettes are suitable for sulfide ores and other rocks where fusion m a y n o t
be appropriate. T h e specimen is ground t o pass a 3 2 5 - m e s h sieve and m i x e d
w i t h a binder in c o n s t a n t p r o p o r t i o n . The ratio o f binder t o sample m a y vary
from 0 . 1 5 t o 1 0 . A press capable of 1 0 , 0 0 0 — 2 5 , 0 0 0 psi makes a c o h e r e n t
pellet of the specimen-binder m i x . Binder serves several purposes besides
holding t h e sample together. Binder makes t h e mass absorption coefficient
o f t h e matrix m o r e uniform from s p e c i m e n t o s p e c i m e n requiring less drastic
absorption and e n h a n c e m e n t corrections and aids forming a s m o o t h
specimen surface. The binder helps eliminate d e n s i t y , particle shape and
particle size differences a m o n g specimens and standards. For the matrix dilu-
59

tion m e t h o d w e might use proportions of 1 : 1 : 1 0 of s p e c i m e n , heavy


binder (e.g., cesium i o d i d e ) , light binder (boric acid). For total rock analysis
w e eliminate t h e heavy binder w h e n possible and m a x i m i z e t h e ratio of
specimen t o binder.
For rock analysis, t h e briquette m e t h o d w i t h m i x e d binder is s o m e t i m e s
discouraging. Mixing is t h e major p r o b l e m . Mixing o f rock samples t o get a
uniform specimen is o f t e n difficult because o f t h e h y g r o s c o p i c nature o f
m a n y rock forming minerals. A n o t h e r disadvantage of t h e briquette m e t h o d
is that non-measurable e l e m e n t s such as carbon and h y d r o g e n remain in t h e
sample and m u s t b e a c c o u n t e d for in t h e correction programs.
S o m e t i m e s , w h e n specimens and desired accuracy permit, briquettes m a y
be made w i t h t h e binder as a backing for the sample. Boric acid is p o u r e d
into an a l u m i n u m c u p with sample poured over it and pressed. This m e t h o d ,
requiring n o weighing, gives m a x i m u m sensitivity, b u t poorer accuracy than
the fusion m e t h o d . It is rapid and inexpensive. The m e t h o d is a particularly
appropriate sample preparation t e c h n i q u e for e x p l o r a t i o n drill cuttings
where high accuracy is n o t necessary because of sample c o n t a m i n a t i o n .

X-RAY DIFFRACTION ANALYSIS

X-ray diffraction analysis determines t h e mineral c o m p o s i t i o n o f rocks. A


m o n o c h r o m a t i c b e a m of X-rays from an X-ray t u b e impinges o n a flat
sample surface o f ground rock or mineral p o w d e r . The minerals in t h e
p o w d e r comprise well-ordered arrays of a t o m s w h o s e arrangement describe
families of planes in each mineral particle. The a t o m i c arrangements charac-
terize the spacing of t h e planes, w h i c h in turn characterize t h e mineral.
" R e f l e c t i o n " o f impinging X-rays from t h e planes occurs as an angular
function of t h e interplanar spacing. The n u m b e r of p h o t o n s reflecting from a
plane and t h e reflection angle identify and quantify each mineral in t h e
specimen.
In t h e hands of a c o m p e t e n t e x p l o r a t i o n analyst, X-ray diffraction can be
o n e of t h e m o s t powerful t o o l s for mineral e x p l o r a t i o n . X-ray diffraction
m e t h o d s allow t h e mineralogist t o identify minerals and quantitatively deter-
mine a m o u n t s of minerals in rocks and ores. The mineralogist can identify
and quantify minerals quickly and inexpensively w h e t h e r t h e rocks are fine-
or coarse-grained.

X-ray diffraction theory

If t h e spectrum from an X-ray t u b e w i t h an appropriate target, say


copper, is passed through nickel foil t h e o u t p u t of t h e t u b e is a nearly m o n o -
chromatic b e a m of wavelength 1 . 5 4 A corresponding t o c o p p e r - K radiation.
a

If n o w a g e o m e t r y o f a spectrometer and a collimated X-ray beam is c o n -


60

structed as in Fig. 3 - 9 , X-ray diffraction can occur. X-ray diffraction occurs


because X-ray p h o t o n s cause an electron in an a t o m o f a crystal t o act as a
secondary source, emitting p h o t o n s of t h e same wavelength as t h e incident
p h o t o n s . All electrons in all a t o m s e m i t t h e same w a y . Each electron acts as
a source with waves emanating from it spherically.
Every crystal has families of planes w h o s e a t o m i c environment is the same
around each plane. Fig. 3 - 1 0 s h o w s t w o such families of planes. There are an
infinite n u m b e r of families o f planes in each crystal. Each family of planes in
a particular crystal or mineral has a definite distance b e t w e e n the members
of t h e family. When X-rays impinge o n electrons, diffraction will o c c u r if t h e
path difference b e t w e e n spherical waves from electrons associated w i t h
successive planes is an integral number^of wavelengths.
Since t h e e n v i r o n m e n t a b o u t all planes in a family is identical, w e can
assume that the planes themselves reflect (diffract) the X-rays as in Fig. 3-9b.
Referring t o t h e g e o m e t r y o f Fig. 3 - 9 b , X-rays impinge w i t h t h e wave front
SS
t 2 and are reflected f r o m t h e planes t o give t h e diffracted wave front P\P , 2

Diffraction occurs o n l y if t h e path difference b e t w e e n S i OP! and S AP 2 2 is

b
Fig. 3-9. X-ray diffraction geometry, (a) Diffractometer instrument geometry, (b) Geom-
etry of diffraction from one family of planes from one specimen particle.
61

Fig. 3-10. Representation of a crystal showing t w o families of planes.

o n e X-ray wavelength so that:

X = S^AP 2 - S^OP x =NA+ AM = 2d sin 0

Thus diffraction occurs w h e n t h e f o l l o w i n g e q u a t i o n is satisfied:

X = 2d sin 0 (17)
where d is t h e spacing b e t w e e n a particular set o f planes. E q u a t i o n ( 1 7 ) , t h e
Bragg e q u a t i o n , is t h e basis for all X-ray diffraction analysis.

Qualitative analysis

Each mineral has a different chemical c o m p o s i t i o n and arrangement of


a t o m s in its structure. Differences in a t o m i c arrangement or c o m p o s i t i o n
cause t h e families of planes t o b e spaced differently, causing diffraction t o
occur at different angles for e a c h mineral. Each mineral will have diffraction
occurring at angles characteristic o f that mineral. Since each grain of each
mineral diffracts individually, t h e pattern of diffraction from a mixture of
t w o minerals w o u l d appear as in Fig. 3 - 1 1 , a diffraction pattern o f calcite
( C a C 0 ) and quartz ( S i 0 ) .
3 2

The different c o m p o s i t i o n s and arrangements o f a t o m s in minerals also


p r o d u c e different a m o u n t s of diffraction from each plane. Each mineral
therefore n o t o n l y has its o w n set of characteristic spacings b e t w e e n planes
and c o n s e q u e n t diffraction angles, b u t also has a characteristic intensity for
each line, giving us t w o sets o f criteria for mineral identification: d-spacing
and line intensity.
A file maintained originally b y American S o c i e t y for Testing and Materials
and n o w maintained b y J.C.P.D.S. (Joint C o m m i t t e e for P o w d e r Diffraction
Standards) (Berry et al., 1 9 7 1 ) , catalogue t h e characteristic spacings and
relative intensities of diffraction lines of over 2 0 , 0 0 0 inorganic, organic and
62

Fig. 3-11. Diffraction spectrum of quartz and calcite mixture.

mineral c o m p o u n d s . This i n d e x e d and cross-referenced file allows identifica-


t i o n of m o s t mineral species.

Quantitative analysis

Quantitative mineral analysis b y X-ray diffraction is simple and relatively


straightforward in principle. S u p p o s e a mineral is ground t o a p o w d e r and
placed in t h e g e o m e t r y of Fig. 3-9. S u p p o s e t h e specimen in Fig. 3-9 is
rotated a b o u t its axis at a v e l o c i t y co and t h e d e t e c t o r is rotated a b o u t t h e
same axis at 2 GJ. T h e b e a m , s p e c i m e n , and d e t e c t o r will always have t h e same
angular g e o m e t r y w i t h respect t o b e a m , sample surface and d e t e c t o r as t h e
specimen in Fig. 3-9. A n y particle, o n e of w h o s e planes has t h e orientation
o f Fig. 3 - 9 , will diffract.
The intensity o f radiation from a given diffraction line is proportional t o
t h e v o l u m e fraction of t h e mineral in t h e sample if there is n o t differential
absorption of X-rays. The intensity o f any diffraction line will be propor-
tional t o t h e v o l u m e o f particles oriented t o diffract, that is, oriented t o
satisfy equation ( 1 7 ) . If w e reduce t h e v o l u m e of a mineral's diffracting
particles b y adding a s e c o n d c o m p o n e n t , t h e intensity will be reduced
proportionally t o t h e reduction in v o l u m e of t h e c o m p o n e n t .
63

Absorption and intensity of diffraction


The o n l y effect o n t h e intensity o f an X-ray line diffracted from a well
ground p o w d e r , other than changing the v o l u m e o f particles of a given
mineral, is absorption of X-rays, usually different for each different mineral
in t h e sample. We can express t h e mass absorption coefficient of a mineral as:

n
juf = Wilif
1
1=1

where Wi is t h e weight fraction and //* is t h e mass absorption coefficient of


the ith e l e m e n t in t h e mineral. The mass absorption coefficient o f a sample
of N mineral c o m p o n e n t s is:

where Xj is t h e weight fraction of the / t h mineral.


The intensity of a given line from t h e ; t h mineral is proportional t o t h e
v o l u m e fraction f. The intensity decreases as t h e linear absorption JJ = (Jl*/p)
o f the sample increases:

The v o l u m e fraction f is simply:

where p is t h e density of t h e j t h c o m p o n e n t , and:


;

giving:

(18)

We can use e q u a t i o n ( 1 8 ) for an iV-component s p e c i m e n b y regarding t h e


sample as consisting of just t w o c o m p o n e n t s , t h e analyzed c o m p o n e n t , ; = 1 ,
and the sum of all other c o m p o n e n t s , t h e matrix, M. The mass absorption
coefficient o f t h e matrix is:
64

Equation ( 1 8 ) b e c o m e s :

(19)

Equation ( 1 9 ) relates relative intensity of o n e c o m p o n e n t t o absorption


b y that c o m p o n e n t and t h e matrix. Fig. 3 - 5 illustrates equation ( 1 9 ) for t h e
c o n d i t i o n s JJL* < / / M > M I M M and jut > ju , represented b y lower, middle and
=
M

upper lines respectively with percent c o m p o n e n t 1 as t h e abscissa.

All-component method
If w e have pure c o m p o n e n t 1 , w h o s e intensity is:

/
i
lo ~ *
0
PiM*
we m a y ratio t h e intensity o f a c o m p o n e n t 1 in an u n k n o w n sample:

(20)

Equation ( 2 0 ) is the working equation for quantitative analysis o f minerals


in an iV-component s y s t e m . One pure standard must be measured for each
c o m p o n e n t . Particle shape, size and orientation effects generally require that
I be determined b y extrapolation from standards m a d e from t h e u n k n o w n s .
0

If we use equation ( 2 0 ) t o determine x in an iV-component s p e c i m e n , all N


x

c o m p o n e n t s must be measured and determined. Since w e c a n n o t solve for x x

explicitly, w e must determine it b y iterative c o m p u t a t i o n a l procedures. The


m e t h o d outlined b y equation ( 2 0 ) , although requiring a c o m p u t e r , is fast,
simple and requires n o introduction of standard materials i n t o t h e sample.

Internal-standard method
Suppose an internal standard mineral(s) is added in k n o w n and constant
a m o u n t t o a sample with fraction ft of c o m p o n e n t t h e n :

ij = Kjfj/ji, i =
s Kfm
s s

and

Solving for x' the weight fraction of the ; t h c o m p o n e n t including the


h

internal standard as part o f the s p e c i m e n :


65

so that:

x
< rhr
=K
s ( 2 D
F r o m e q u a t i o n ( 2 1 ) w e see that if an internal standard is added in c o n -
stant a m o u n t t o a series of standard samples w i t h k n o w n a m o u n t s of t h e jth
mineral, a linear curve always results w h e n Ij/I is p l o t t e d against x
s jt

This m e t h o d is simple, fast and effective w h e n o n e or m o r e c o m p o n e n t s


are t o be determined.

Sample preparation

Samples are usually prepared for qualitative analysis b y X-ray diffraction


as loose powders or oriented-grain m o u n t s . Samples should be ground t o
—325 mesh t o insure m i n i m u m particle orientation and p r o d u c e m a x i m u m
intensity and reproducibility. For consistent results, geological materials
require that each sample be p u t into t h e sample holders in t h e same w a y ,
preferably b y t h e same person. Clay minerals in e x p l o r a t i o n samples o f t e n
require special preparation t o enhance diffraction lines from planes parallel
t o their platy shape. Exploration analysis, however, often precludes elabo-
rate sample handling procedures. One simple procedure t o orient clay
minerals and micas for qualitative X-ray diffraction uses a small a m o u n t of
the sample t o make a slurry with water. The preparer t h e n smears a glass
slide with a thin layer of t h e slurry. As t h e slide dries, flat particles orient
parallel t o t h e slide.
G o o d quality quantitative analyses require s p e c i m e n m o u n t s w i t h uniform
density, packing, and usually require rotation in t h e X-ray b e a m t o average
sample i n h o m o g e n e i t i e s . We have f o u n d that t h e best procedure for prepar-
ing almost all t y p e s of exploration samples for quantitative mineral analysis
is the following. We grind the sample t o —325 m e s h . A d d internal standard
and mix if t h e internal standard m e t h o d is used. Press the sample at 1 0 , 0 0 0 —
2 5 , 0 0 0 psi i n t o an X-ray fluorescence analysis aluminum cup t o produce a
l | - i n c h diameter s p e c i m e n . We find that for suites of e x p l o r a t i o n samples t h e
pressed m o u n t produces consistent and reproducible grain orientation, inten-
sities and sensitivities. The pressed specimens m a y be kept as l o n g as neces-
sary because t h e y are in their o w n holders.

Accuracy and sensitivity

The l o w e s t d e t e c t i o n limit for minerals determined b y X-ray diffraction


analysis ranges from 1 t o 5 vol. % in l o o s e p o w d e r samples and 0.2—2 vol. %
for pressed samples. A highly absorbing matrix increases t h e d e t e c t i o n limit.
For e x a m p l e , c o p p e r - K radiation impinging o n an iron-rich matrix results in
a

absorption b y the iron t o decrease d e t e c t i o n limits t o ten v o l u m e percent. In


66

such instances, radiation such as c o b a l t - K must be used t o minimize absorp-


a

tion.
With careful specimen preparation, accuracies will range around ± 1 0 % of
t h e a m o u n t of a major mineral present in the specimen w h e n using a l o o s e
p o w d e r . Pressed pellets can give accuracies of a b o u t ±4% of t h e a m o u n t of a
mineral present in t h e sample. O p t i m u m accuracy is a b o u t ±2%.

INSTRUMENTATION

X-ray fluorescence

Scanning spectrometers
X-ray fluorescence instruments have four essential c o m p o n e n t s , a genera-
tor and X-ray t u b e , the spectrometer, X-ray d e t e c t i o n electronics, display
and control e q u i p m e n t .
The generator transforms line voltage and current t o produce a high
voltage and a l o w current t o p o w e r the X-ray tube located in t h e spectrom-
eter. The generator and t h e X-ray t u b e c o n s t i t u t e t h e X-ray source. Fig. 3-12
s h o w s a typical X-ray generator. X-ray generators have controls t o adjust
voltage and current b e t w e e n t h e X-ray tube's c a t h o d e and a n o d e . Generators
for high-precision fluorescence analysis provide internally stabilized, c o n -
stant-potential voltage and stabilized current. Switches allow resetting
voltage and current precisely each time t h e unit is turned o n .
Modern X-ray spectrometers (Fig. 3 - 1 3 ) , although having the essential
g e o m e t r y depicted in Fig. 6a, have m a n y more features t o measure all pos-
sible wavelengths with precision and sensitivity. Crystal changers with up t o
six crystals allow changing wavelength ranges. Collimators with different slit
widths allow the operator t o c h o o s e b e t w e e n resolution and intensity. T w o
detectors, a scintillation c o u n t e r and a gas-flow proportional counter permit
d e t e c t i o n of higher- and lower-energy X-rays respectively. A heater heats the
spectrometer t o a c o n s t a n t temperature t o k e e p analyzing crystals spacings
and other geometries constant. V a c u u m s y s t e m s evacuate the spectrometers,
t o eliminate absorption of long wavelengths. S o m e spectrometers such as the
o n e s s h o w n in Fig. 3 - 1 3 have sample changers holding m a n y samples and
capable of either automatic or manual operation.
D e t e c t i o n electronics comprises several c o m p o n e n t s . The detectors, a
scintillation counter for short wavelengths and a flow-proportional counter
for longer wavelengths, and their preamplifiers produce pulses w h o s e voltage
is roughly proportional t o t h e energy of t h e X-ray p h o t o n s entering t h e m .
Pulses, o n e for each p h o t o n d e t e c t e d , pass into an amplifier w h i c h amplifies
and shapes t h e m . The shaped signal passes i n t o a pulse-height selector which
acts as a pass-band filter t o eliminate u n w a n t e d energies. F r o m t h e pulse-
height selector, t h e signal m a y be used in t w o different w a y s . A pulse
67

Fig. 3-12. Typical X-ray generator containing high-voltage transformer, inside voltage con-
trols (lower left), current controls (lower right), switching (lower center) and X-ray tube
housing (vertical housing in upper left).

counter accumulates individual pulses. The pulses m a y also pass i n t o an RC


time-constant circuit w h i c h averages t h e m and converts t h e averages t o an
analog signal for display o n a recorder.
68

Fig. 3-13. Scanning X-ray spectrometers, (a) Spectrometer showing scintillation counters
on scanning arm. Drum with window contains analyzing crystals and gas flow propor-
tional counter. Sample cassette with specimen holders (front center), (b) Modern auto-
mated spectrometer in enclosure; geometry of spectrometer similar to (a).
69

Fig. 3 - 1 4 s h o w s an electronic panel of an X-ray spectrometer. The spec-


trometer c o m p o n e n t s described are c o m m o n t o b o t h a u t o m a t i c and manual
spectrometers. A u t o m a t i c spectrometers also have a c o m p u t e r , interfacing
electronics and peripheral devices such as a t e l e t y p e , card reader or disk drive

Fig. 3-14. Electronic control and signal detection panel. Right side contains detection
electronics. Left side contains computer system.
70

for subsidiary data and program storage. Fig. 3 - 1 4 also s h o w s a u t o m a t i o n


c o m p o n e n t s of an automatic spectrometer s y s t e m .
Exploration analysis requires high sample throughput at l o w cost. Cost
and high sample analysis rates m a k e automatic fluorescence spectrometers
necessary or very desirable t o service extensive exploration programs.
A u t o m a t e d X-ray fluorescence analysis can deliver u p t o fifty high-quality
total rock analyses per d a y on a scanning spectrometer. If, h o w e v e r , lower-
quality analyses are acceptable or f e w elements are required, sample through-
p u t rate can be as great as o n e hundred samples per day.
C o m p l e t e automatic analysis b y X-ray fluorescence uses a c o m p u t e r t o
insert a specimen then t o slew t h e spectrometer t o each element's emission
line, determine proper measurement t i m e , find t h e peak, position t h e line,
measure the line, measure nearby backgrounds and store the measured data.
Before and after measurement, t h e c o m p u t e r m a y calibrate the spectrometer
and check the calibration. When all lines are measured t h e c o m p u t e r t h e n
processes the data with quantitative data correction programs and prints the
analyses in whatever form required b y t h e operator. The c o m p u t e r then
inserts the n e x t specimen and c o n t i n u e s with analysis. B o t h spectrometers
s h o w n in Fig. 3 - 1 3 are automatic units. The control s y s t e m for these units is
s h o w n in Fig. 3 - 1 4 .

Energy dispersive spectrometers


The X-ray generator and X-ray t u b e are similar in c o n c e p t , if n o t physical
f o r m , t o t h o s e of t h e scanning spectrometer. The function of the energy
dispersive spectrometer has been described earlier. Fig. 3-15 s h o w s an energy
dispersive spectrometer. The s y s t e m as illustrated can d o qualitative and
quantitative analysis. A small c o m p u t e r allows data collection and data
processing b y programs which separate overlapping spectral lines and cal-
culate p h o t o n c o u n t s under a peak. Other programs correct data and present
results of analyses as in t h e scanning spectrometer.

X-ray diffractometry

X-ray diffraction instruments are simpler than X-ray fluorescence instru-


m e n t s . The same or a slightly simpler X-ray generator used for fluorescence
analysis powers an X-ray diffraction t u b e . Ordinarily t h e generator has few
stabilizing circuits and frequently d o e s n o t operate at c o n s t a n t potential b u t
w i t h full-wave rectification.
The X-rays emanate from an X-ray t u b e , similar in function t o t h e fluores-
cence tube, but different in t h e g e o m e t r y of construction. The X-rays pass
from the tube through a filter which m o n o c h r o m a t i z e s the b e a m , filtering
m o s t non-Ka radiation. A sealed proportional counter or a scintillation
counter d e t e c t s the diffracted signal. Signal d e t e c t i o n and display electronics
are the same as those of a scanning X-ray fluorescence spectrometer. Fig.
71

Fig. 3-15. Energy dispersive spectrometer. Console on left contains multichannel analyzer
in upper portion with computer hidden below. X-ray chamber is on table. (Courtesy
Colorado School of Mines Research Institute.)

3-16 s h o w s a typical X-ray diffractometer w i t h t u b e and generator. There are


n o portable field X-ray diffractometers b u t there is a small 1 2 0 - V X-ray
diffractometer that c o u l d be m o u n t e d in a van for field u s e . This small
instrument has limited flexibility but could be a u t o m a t e d for quantitative
analysis.
A u t o m a t e d diffractometers use the same generator, g o n i o m e t e r and
c o u n t i n g electronics as manual m o d e l s . A u t o m a t i c diffractometers have
stepping m o t o r s replacing t h e s y n c h r o n o u s drive m o t o r s in t h e g o n i o m e t e r .
A n a u t o m a t i c sample changer and a c o n t r o l c o m p u t e r c o m p l e t e s t h e
automatic hardware. The e l e c t r o n i c / c o m p u t e r panel s h o w n in Fig. 3 - 1 4
serves an a u t o m a t i c diffractometer sis well as an a u t o m a t i c X-ray s p e c t r o m -
eter. Standard-sized a u t o m a t i c as well as manual diffractometers m a y consti-
tute instruments in a m o b i l e e x p l o r a t i o n laboratory as d e p i c t e d in Fig. 3 - 1 7 .
For s o m e t y p e s of exploration analysis, manual diffractometers suffice for
quantitative mineral analysis, while for other t y p e s an a u t o m a t i c diffrac-
t o m e t e r is desirable. We define quantitative analysis in t w o w a y s . In t h e c o n -
ventional sense, w e define quantitative analysis as t h e quantitative deter-
mination of o n e or m o r e mineral c o n s t i t u e n t s in a sample. We also define
72

Fig. 3-16. X-ray diffractometers; manual (left), automatic (right).

quantitative analysis as t h e quantitative measurement of any diffraction


parameter representing t h e attribute of o n e or m o r e minerals in a specimen
such as width of a diffraction peak.

Special instrumentation

Mobile exploration laboratories


The object of X-ray fluorescence analysis, X-ray diffraction analysis and
73

other t y p e s of analysis is t o give t h e e x p l o r a t i o n geologist information he


c a n n o t otherwise o b t a i n . The c o m p e t e n t and experienced geologist can
estimate visually m a n y parameters of potential ore rocks. Exploration
analysis m u s t , therefore, give him qualitative and quantitative definition and
accuracy b e y o n d his capability. Such definition and accuracy d e m a n d s
proper procedures and e q u i p m e n t . At present, this implies use of a conven-
tional laboratory.
The U . S . Geological Survey in Denver, Colorado, has successfully
m o u n t e d standard laboratory direct-reading emission spectrometers in vans.
The vans go t o t h e field site, where t h e analyst performs analyses as the
geologist collects samples. Other groups (Australian Mining, 1 9 7 0 ; Kinson
and Belcher, 1 9 7 0 ; L y n c h and D u r h a m , 1 9 6 6 ; H o l m a n and D u r h a m , 1 9 6 6 )
have built and operated m o b i l e e x p l o r a t i o n laboratories for several years.
Most have b e e n emission s p e c t r o g r a p h s laboratories and all s e e m t o have
worked well after solving problems associated with m o b i l i t y .
Mineral e x p l o r a t i o n programs cost m u c h t i m e and m o n e y . T h e y will cost
more in t h e future as e x p l o r a t i o n drilling b e c o m e s deeper and t h e predomi-
nant exploration m e t h o d . A simple c o n c e p t of m o v i n g analytical e x p l o r a t i o n
services t o t h e field w i t h t h e geologists, if e x e c u t e d properly, should substan-
tially shorten exploration time and save e x p l o r a t i o n drilling and large-team
exploration costs. A l o n g with field analytical services, t h e geologists should
have very fast interactive mineral logging and chemical mapping during
surface and drilling phases o f minerals e x p l o r a t i o n .
Typically, t h e geologist collects e x p l o r a t i o n samples or e x e c u t e s a drilling
program and m u s t wait w e e k s or m o n t h s for analytical results w i t h w h i c h t o
make exploration decisions. T o save costs t h e geologist c o u l d have such
data available t o h i m during e x p l o r a t i o n . Frequently h e m u s t revisit the
exploration site w i t h a drilling rig for additional data. Often h e m u s t collect
and analyze more samples or drill more holes than necessary t o insure that
there will be e n o u g h information for future decisions. The samples the
geologist has already c o l l e c t e d or the h o l e s h e has drilled should tell h i m h o w
he should collect t h e m o s t significant n e w samples or drill t h e n e x t h o l e s .
During the drilling program t h e geologist frequently has limited k n o w l e d g e
of trends, gradients and quality o f ore until analyses can b e c o m p l e t e d at
later dates.
A g o o d rock analysis s y s t e m w i t h special data presentation and synthesis
capabilities brought t o or near the exploration site w o u l d add t o exploration
and profit t h e exploring group in t i m e and m o n e y . The geologist w o u l d have
almost i m m e d i a t e analyses t o guide his n e x t c o l l e c t i o n s or drilling. H e could
collect more efficiently, spend m o r e t i m e l o o k i n g for trends or indications
and collect fewer b u t more significant samples. He w o u l d m i n i m i z e recollec-
t i o n . With i m m e d i a t e analysis of samples t h e geologist could d e t e r m i n e t h e
best drilling strategy. Moreover, if t h e service laboratory accumulated data
and p l o t t e d m a p s , sections, ore pointers and preliminary o r e b o d y m o d e l s ,
74

rapid exploration decisions w o u l d be e x p e d i t e d .


We have e x a m i n e d t w o e c o n o m i c deposits and f o u n d , in retrospect, that
an on-site mobile laboratory could have significantly reduced exploration
drilling.
A ciay deposit constituted the first study. The area was drilled on a close
grid. N o analyses were d o n e o n cores at t h e time of drilling. Later, maps of
mineralogical, chemical and ceramic tests defined t h e deposits. The impor-
tant tests were ceramic and mineralogical properties. Correlating results with
core spacing and drilling d e p t h , w e found that on-site analysis could allow
initial drilling at t w i c e t h e grid spacing, that is, one-fourth t h e n u m b e r of
holes o f t h e actual drilling program. T o present clay distribution t o t h e
accuracy available from t h e original cores, only a b o u t one-half t h e holes
drilled w o u l d have b e e n necessary. A b o u t 50% of t h e drilling and subsequent
sample analysis could have b e e n saved.
The second study was also after t h e fact. We analyzed cores from lead
deposits. We analyzed t h e cores chemically b y several m e t h o d s and miner-
alogically b y X-ray diffraction and binocular m i c r o s c o p e . The d e p o s i t was
irregularly shaped w i t h narrow elongate mineralized z o n e s . We estimate that
on-site analysis w o u l d have saved a b o u t 25% o f t h e coring and associated
analyses. A part of this saving was t h e result of a discovery during analysis
that the magnesium c o n t e n t of the carbonate wall rock " p o i n t e d " t o the
ore.
Speeding mineral exploration with immediate on-site analytical service
w o u l d yield other, less quantifiable benefits. Land costs w o u l d be reduced.
Faster exploration w o u l d give more c o n t i n u i t y t o an exploration program,
minimizing effects of changing personnel, short field seasons, and short-term
changes in e c o n o m i c climate.
A m o b i l e laboratory n e e d s t o m e e t just a f e w criteria t o be e x t r e m e l y
useful. The instruments m u s t have t h e capability t o analyze for major, minor
and trace e l e m e n t s with b o t h speed and accuracy. The mobile laboratory
m u s t have t h e capability t o analyze mineral c o n t e n t o f rocks b o t h qualita-
tively and quantitatively. F e w instruments m u s t d o the analyses and each
instrument m u s t be a u t o m a t e d t o attain the necessary speed and accuracy.
Fig. 3-17 illustrates o n e possible version o f a m o b i l e laboratory. E x c e p t
for a u t o m a t i o n , each instrument c o n f o r m s t o conventional laboratory-based
specifications. The X-ray fluorescence instrument d o e s major and minor
e l e m e n t analysis of rocks. X-ray diffraction d o e s mineral analysis. A plasma-
source emission spectrometer analyzes trace e l e m e n t s and s o m e minor ele-
m e n t s . Thermogravimetric analyses determine C 0 and H 0 . T h e c o m p u t e r
2 2

controls the instruments, determines elemental concentration and collates


data from each instrument. The c o m p u t e r s y s t e m , in addition t o instrument
control and data processing, integrates analyses geographically and strati-
graphically, presenting t h e data as stratigraphic sections and three-dimensional
c o n t o u r maps.
75

Fig. 3-17. Mobile exploration laboratory. Preparation r o o m : 1 = balance, 2 = chair, 3 =


grinder, 4 = sink, 5 = refrigerator, 6 - drying oven, 7 = furnace, 8 - seats, 9 = table, 10 -
press, 11 - h o o d , 12 - work benches. Instrument r o o m : 13 = plasma source direct-reading
emission spectrometer, 14 = argon tanks for plasma, 15 = chair, 16 = X-ray generator,
17 = diffractometers (automatic), 18 = card file, 19 = desk, 20 = typewriter/microscope,
21 = waste, 22 = teletype, 23 = electronics and computer system, 24 = card reader, 2 5 =
plotter, 2 6 = X-ray spectrometer, 2 7 = PlO gas tank for spectrometer, 28 = thermogravi-
metric analyzer, 29 = bath. Utilities and power in underneath compartments.

Portable field spectrometers


X-ray f l u o r e s c e n c e analysis i n s t r u m e n t s have b e e n d e s i g n e d for field u s e .
S o m e i n s t r u m e n t s are very portable and o t h e r s are transportable in a v e h i c l e .
O n e o f t h e m o s t portable o f such i n s t r u m e n t s measures a b o u t 1 2 X 9 X 8
76

inches and weighs a f e w p o u n d s . For strictly portable instruments, an iso-


t o p e b u t t o n such as P u produces gamma-rays w h i c h e x c i t e X-ray fluores-
2 3 8

c e n c e in a s p e c i m e n . The specimen m a y be a normally prepared sample or an


unprepared sample such as a rock or soil in-situ. The fluorescent X-rays from
t h e specimen pass through a pair of thin foil filters, eliminating s o m e
u n w a n t e d radiation b y absorption. A scintillation counter d e t e c t s the
filtered X-rays. Scintillation counters produce electrical pulses of voltage
approximately proportional t o p h o t o n energy allowing a pulse-height selec-
tor t o further eliminate u n w a n t e d energies. A pulse-counter c o u n t s and dis-
plays p h o t o n s from t h e analyte line.
Portable units usually measure o n e or t w o e l e m e n t s , b u t can measure
more if their energies are sufficiently well separated. Absorption o f X-rays
by air, t h e inefficiency of t h e scintillation c o u n t e r at long wavelengths, t h e
absorption of X-rays b y t h e filter and the high energy o f the gamma-ray
source permits m e a s u r e m e n t o f e l e m e n t s o f a t o m i c n u m b e r higher than
chromium.
A second t y p e o f portable X-ray fluorescence unit, o n t h e market for
s o m e years, has a m o r e nearly conventional spectrometer configuration. A
single crystal-spectrometer measures fluorescent X-rays from a specimen. X-
rays are produced b y a small l o w - p o w e r generator and t u b e . This t y p e of
spectrometer has t h e advantage of g o o d p h o t o n energy resolution but is
more bulky than t h e radioactive-source scintillation-counter t y p e of unit.
Fig. 3 - 1 8 illustrates a portable unit.

Fig. 3-18. Portable X-ray spectrometer box measures 12 inches across. Source and detec-
tor in detachable assembly on right. (Courtesy Columbia Scientific Industries Corp.)
77

There are a f e w e x p l o r a t i o n applications where t h e portable analyzer as


described above can serve usefully. A portable unit gave a reasonably g o o d
estimate of iron c o n t e n t in Precambrian t a c o n i t e b e d s in W y o m i n g . The
estimates were better than visual (hand lens) estimates because o f t h e dif-
ficulty of visually quantifying a m o u n t s of particles in differently t e x t u r e d
dark matrixes. Application of a portable fluorescence unit proved useful in
exploration of copper-bearing black shales. Wollenberg et al. ( 1 9 7 1 ) very
effectively used a portable X-ray spectrometer t o explore for n i o b i u m ,
zirconium and lanthanium plus cerium in Greenland. Fig. 3 - 1 9 illustrates
part o f their analytical results across five rock units. R h o d e s ( 1 9 7 1 , 1 9 7 4 )
summarized the status of portable X-ray analyzer applications.
Before t h e e x p l o r a t i o n geologist rushes t o b u y a portable unit for use o n
t h e o u t c r o p or o n a drill-core sample, he should realize that usually a f e w
accurate analyses o f selected materials will give h i m comparative information
t o visually estimate elemental c o n t e n t adequately for early exploration
needs. A portable unit m a y serve usefully where visual discrimination fails.

Downhole spectrometers
If w e use t h e c o n c e p t of t h e first-described portable X-ray fluorescence
spectrometer w i t h a radioactive i s o t o p e source, place t h e measuring device
and source in a cylinder w i t h appropriate cabling, w e have a primitive d o w n -
h o l e X-ray spectrometer.
The d o w n h o l e spectrometer b e c o m e s a simple logging device. T h e oper-


Zr
4-
' (%)

\
3-

2-

V-
^ •
0-

La+
Ce

0.7 -
0.5-
0.3-
0.1 -
I

ROCK U N I T S

Fig. 3-19. Profiles of zirconium and lanthanum plus cerium measured by portable X-ray
fluorescence analyzer, across four rock unit boundaries (vertical lines). (After Wollenberg
et al., 1 9 7 1 . )
78

ator lowers it into a drill h o l e , logging t h e spectrum while t h e spectrom-


eter measures at fixed intervals d o w n the h o l e . The spectrometer can, if
configured with o n e or m o r e scintillation counters, measure a few elements
at a t i m e .
Since t h e d o w n h o l e spectrometer requires a van t o carry the spectrometer,
electronics, cables, etc., w e m a y make t h e spectrometer m o r e sophisticated
than a portable X-ray unit. The scintillation c o u n t e r pulses m a y pass into a
multichannel analyzer as d o t h e pulses from energy dispersive detectors. A
c o m p u t e r m a y t h e n mathematically strip the energy spectrum stored in the
multichannel analyzer allowing d e t e c t i o n and s o m e quantification of several
e l e m e n t s simultaneously.
A l t h o u g h still in t h e experimental stages t h e d o w n h o l e spectrometer, like
t h e portable X-ray fluorescence spectrometers described above for surface
use, d o e s have potential utility. The d o w n h o l e spectrometer gives informa-
tion t o t h e geologist h e c o u l d n o t get otherwise because h e c a n n o t go d o w n
the h o l e t o l o o k at the rocks. If a d o w n h o l e spectrometer can give g o o d
information in t h e particular exploration situation, the a m o u n t of drilling
and e x p e n s e can be reduced.

Future trends

Future trends in X-ray instrumentation as used b y mineral exploration are


difficult t o predict. One trend that is certain is t h e e v o l u t i o n t o more auto-
m a t i o n in b o t h fluorescence and diffraction. A u t o m a t i o n speeds t h e ana-
lytical process making it e c o n o m i c a l l y feasible t o use X-ray m e t h o d s routine-
ly. Instrumentation seems t o evolve from manual t o automatic in predictable
stages w i t h t h e manual instrument increasing in c o m p l e x i t y w i t h automatic
functions making a primitive d e b u t . As a u t o m a t i o n proceeds, t h e instrument
b e c o m e s simpler while t h e c o m p u t e r d o e s more and more decision making
and work.
The final stage is an a u t o m a t i c instrument from which a m o d e r a t e l y well-
trained operator can extract useful analyses easily. X-ray instruments are
n o w a b o u t in the middle of the evolutionary stage. When e v o l u t i o n c o m -
pletes, X-ray analysis will be able t o accomplish almost all the quantitative
analyses of solids in mineral exploration e x c e p t l o w levels of concentration
of trace e l e m e n t s .
As a u t o m a t i c instruments evolve, b e c o m i n g more simple and more
c o m p a c t , it will be possible t o m o v e t h e m into t h e field. The m o b i l e labora-
tory c o n c e p t as s h o w n in Fig. 3-17 uses presently available e q u i p m e n t .
However, a c o m p a c t suitably m o n i t o r e d high-frequency generator could sub-
stitute for the traditional generator. Using a fully a u t o m a t e d energy dis-
persive X-ray analyzer w o u l d reduce size and weight of X-ray diffraction and
fluorescence instruments t o less than one-half that of Fig. 3-17 allowing
t h e m t o b e c o m e t h e hand-maidens o f field e x p l o r a t i o n .
79

APPLICATION OF X-RAY A N A L Y S I S

Reporting of systematic applications o f X-ray analysis t o mineral explora-


tion s e l d o m appears in t h e literature for several e c o n o m i c reasons. Further,
e x c e p t for diffraction, m o s t m o d e r n X-ray instrumentation and m e t h o d s
discussed in this chapter date from 1 9 6 4 , or later precluding extensive
reporting from any but t h e m o s t recent literature. Finally, t h e application of
X-ray analysis t o mineral exploration is broad e n o u g h t o preclude c o m -
prehensive review. Therefore, this s e c t i o n elucidates s o m e of t h e kinds of
applications rather than reporting systematic studies.

Non-metallic minerals

Limestone and dolomite


The carbonate producing industry, including l i m e s t o n e for c e m e n t
manufacture, steel p r o d u c t i o n and other uses, requires k n o w l e d g e of t h e
c o n t e n t o f Ca/Mg ratios, quartz c o n t e n t and other contaminating impurities
such as clay minerals, e t c . B o t h X-ray fluorescence and X-ray diffraction
analysis can provide m u c h of t h e information n e e d e d t o determine quality of
deposit. Quantitative X-ray diffraction gives very g o o d estimates o f calcite
( C a C 0 ) , d o l o m i t e [ ( C a , M g ) C 0 ] and quartz c o n t e n t in u n m e t a m o r p h o s e d
3 3

and m e t a m o r p h o s e d d e p o s i t s . Silicate impurities can also lend themselves t o


quantitative determination in marbles and t o a lesser e x t e n t in u n m e t a m o r -
p h o s e d l i m e s t o n e and d o l o m i t e . X-ray fluorescence gives accurate estimates
of Ca, Mg, F e , Si and Al.
Both the linear equation and the fundamental parameters m e t h o d s of
correction give g o o d results since C 0 d o m i n a t e s t h e matrix. It is possible t o
2

define any e c o n o m i c carbonate d e p o s i t using o n l y X-ray fluorescence and X-


ray diffraction c o u p l e d w i t h supplementary use of other analytical tech-
niques.

Bauxite and laterite ores


Bauxite and laterite ores conscitute t h e chief source of a l u m i n u m and o n e
of the main sources of nickel. Ores of this t y p e are particularly amenable t o
exploration analysis b y X-ray fluorescence and t o a lesser e x t e n t b y X-ray
diffraction.
X-ray fluorescence gives g o o d analytical values for Al, Si, F e , Ti and Ni in
bauxites and laterites. Exploration analysis is fast and relatively accurate.
When c o u p l e d with weight-loss-on-ignition, extractable A 1 0 and S i 0 by 2 3 2

w e t extraction, X-ray fluorescence analysis almost c o m p l e t e s the chemical


data needed for exploration decisions. Furthermore, it is n o t difficult t o
analyze 1 0 0 samples per day with a scanning X-ray spectrometer, allowing
analysis t o coincide w i t h e x p l o r a t i o n .
Quantitative X-ray diffraction can provide g o o d estimates of mineral and
80

chemical c o n t e n t of b a u x i t e ores. Frequently, t h e aluminum-bearing minerals,


gibbsite [ A l ( O H ) ] and related species have well-defined X-ray diffraction
3

lines and t h e a m o u n t s of each mineral can b e estimated accurately. T h e iron-


bearing minerals of b a u x i t e , although hydrated, tend also t o have well-
defined diffraction peaks and estimation o f a m o u n t is n o t difficult. On t h e
other hand, residual quartz has its peak masked b y gibbsite and its measure-
m e n t is more difficult.
E m p l o y i n g X-ray diffraction t o outline nickelferous laterite and other
laterites can be very difficult. Frequently t h e iron minerals are variously
hydrated and d o n o t s h o w well-defined diffraction lines, rendering quan-
titative diffraction analyses impossible.

Clays
Ceramic clay minerals are primarily kaolinite and halloysite ( A 1 0 • 2 2 3

S i 0 • 2 H 0 ) , t w o minerals o f nearly t h e same c o m p o s i t i o n b u t slightly


2 2

different structure. Bauxitic clay deposits m a y also contain hydrated


aluminum o x i d e minerals such as gibbsite [ ( A l ( O H ) ] and related minerals
3

b o e h m i t e , bayerite, e t c . Toward the o p p o s i t e c o m p o s i t i o n a l t y p e , clay


deposits m a y c o n t a i n illite (a muscovite-like clay mineral) a d m i x e d w i t h t h e
kaolinite. Quartz, anatase ( T i 0 ) and other minerals are o f t e n present as
2

contaminants.
A l t h o u g h standard ceramic tests provide necessary information o n ceramic
behavior, a c o m b i n a t i o n of b o t h X-ray diffraction and X-ray fluorescence
analysis yield important e x p l o r a t i o n information. For m o s t deposits diffrac-
t i o n analysis is t h e m o s t comprehensive m e t h o d o f identifying and quantify-
ing t h e clays mineralogically. With special standard and s p e c i m e n preparation
t e c h n i q u e s , mineralogical analysis can give quantities of t h e various t y p e s of
clays and other minerals w i t h an error a b o u t ±7—10% of t h e a m o u n t present.
Special characteristics of t h e clay minerals such as crystalline disorder w h i c h
often areally indicates changes in c o m p o s i t i o n o f t h e clay minerals and
a m o u n t s o f fluxing e l e m e n t s m a y b e quantified b y X-ray diffraction.
X-ray fluorescence analysis gives g o o d estimates of a l u m i n u m , silicon, and
iron o x i d e s ift clay deposits. Perhaps as important as determining t h e more
abundant e l e m e n t s , X-ray fluorescence can give g o o d analyses o f t h e fluxing
e l e m e n t s N a , K, Mg, and Ca. Where t h e latter group of e l e m e n t s are t h e only
e l e m e n t s of interest, other instrumental m e t h o d s w o u l d be superior t o X-
ray fluorescence analysis.

Other non-metallic minerals


Exploration for other non-metallic materials such as glass sands, b e n t o n i t e ,
zeolites, p h o s p h a t e s , g y p s u m , e t c . , effectively use t h e c o m b i n a t i o n of X-ray
diffraction and X-ray fluorescence analysis t o define t h e quality and useful
limits of a deposit.
81

Energy materials

Coal
The use o f X-ray diffraction and X-ray fluorescence in coal e x p l o r a t i o n is
minimal. There is s o m e potential for use b u t t h e potential remains undevel-
o p e d . Coals comprise organic material and subsidiary mineral c o n t a m i n a n t s .
Kaolinite, illite, pyrite, small quantities of quartz, a f e w resistant detrital
minerals and g y p s u m comprise the subsidiary suite of minerals that even-
tually b e c o m e s ash. Sulfur, an environmental c o n t a m i n a n t w h e n t h e coal
burns, occurs in t h e organic fraction, in sulphates and in sulfides (mainly
pyrite). B.T.U., ash, sulfur and water c o n t e n t s constitute t h e m o s t important
non-geological or industrial parameters t o d e t e r m i n e coal quality.
X-ray diffraction analysis is unable t o d e t e r m i n e any o f t h e industrial
parameters directly. Diffraction analysis can determine mineral, sulphate and
pyrite c o n t e n t if the coal is ashed at l o w temperatures. The value of l o w -
temperature ashing f o l l o w e d b y diffraction analysis o n routine exploration
samples is questionable. Eastern U . S . coals, h o w e v e r , frequently have suf-
ficient pyrite and occasionally sufficient g y p s u m t o allow inorganic sulfur
determination in t h e raw coals b y diffraction m e t h o d s .
Research b y t h e U . S . Bureau o f Mines (Berman and Ergun, 1 9 6 8 ) has
s h o w n that X-ray fluorescence analysis can determine total sulfur and total
ash c o n t e n t of coals very accurately. X-ray fluorescence analysis determines
total sulfur c o n t e n t directly. D e t e r m i n a t i o n of ash c o n t e n t b y X-ray fluores-
c e n c e requires correlation o f chemical c o n t e n t w i t h mineral c o n t e n t t h e n c e
with ash c o n t e n t . A l t h o u g h an indirect m e t h o d of finding ash c o n t e n t m a y
seem less useful than direct m e t h o d s , there are advantages. B o t h sulfur and
ash are determined simultaneously, ash materials can be d e d u c e d accurately,
sample preparation is simple and measurement is rapid.
Other factors limit t h e value o f X-ray analysis o f coals. The cost o f X-ray
analysis e q u i p m e n t prohibits investment b y t h e smaller c o m p a n i e s unless t h e
e q u i p m e n t can also serve quality control in an operating m i n e . Low-sulfur,
low-ash coals o f t h e western U . S . can b e analyzed b y less expensive instru-
mental m e t h o d s than X-ray diffraction and X-ray fluorescence.

Petroleum
The p e t r o l e u m industry has m a d e t h e m o s t sophisticated exploration use
of X-ray analysis of all industries. T h e y have used X-ray m e t h o d s in spite of
t h e fact that X-ray m e t h o d s d o n o t usually lead directly t o finding oil or
defining reserves and give o n l y supplementary data t o t h e information bank
necessary for comprehensive e x p l o r a t i o n . The p e t r o l e u m industry research
groups have d o n e m o s t of t h e exploration analysis partly because t h e y have
adequate laboratory facilities and partly because t h e y also have t h e special
c o m p e t e n c e required. Three t y p e s o f X-ray analysis d o m i n a t e p e t r o l e u m
exploration and correlation studies: stratigraphic definition, facies analysis
82

and uepositional e n v i r o n m e n t definition. Most exploration studies have


centered around X-ray diffraction analysis because diffraction analysis can
differentiate fine-grained sediments and carbonates. X-ray fluorescence has
had limited use in p e t r o l e u m e x p l o r a t i o n .
Unfortunately m u c h of the e x c e l l e n t w o r k using X-ray diffraction analysis
as an exploratory t o o l remains unpublished and in c o m p a n y files. T w o
e x a m p l e s of exploration analysis b y X-ray diffraction were c o n d u c t e d s o m e
years ago b y W.T. Caneer.
Preliminary exploration drilling off t h e coast of Santa Barbara C o u n t y ,
California, presented a thick sequence of sediments from several formations.
T h e formations, comprising sandy siltstones and m u d s t o n e s , were very
difficult t o differentiate using drill cuttings. Faulting c o m p l i c a t e d the nearly
impossible task of stratigraphic correlation.
X-ray diffraction analysis allowed differentiation of t h e formations and
approximate stratigraphic correlation. Table 3-II summarizes the results. The
e x a m p l e is interesting because t h e rocks were so fine-grained that o n l y X-ray
diffraction could provide diagnostic mineral determinations.
In another oil e x p l o r a t i o n program d o n e b y Caneer, exploration analysis
o f a shale and carbonate sequence of southern Canada f o u n d that the minor
mineral chlorite as defined b y X-ray diffraction b e c a m e less iron-rich near
ancient oil-bearing reefs. T w o measured parameters, t h e ratio of t h e ( 0 0 1 ) t o
( 0 0 2 ) diffraction peaks and t h e X-ray diffraction behavior of t h e chlorite
after heating t o 6 0 0 ° C indicated t h e relative distance from t h e reefs.
Examination of samples from exploration drilling over a geographic area
located direction and distance t o isolated reefs. Closer t o reefs, changes in

TABLE 3-II
Summary of mineralogical analyses by X-ray diffraction, Ventura Basin, California

Formation and member Illite/kaolin ratio Diagnostic minerals

Pico and Repetto 1.2-3.2 microcline


0.9-1.1 microcline
Upper Sisquoc 0.5-0.9 —
1.0 —
1.1-1.3 —
1.6 —

Lower Sisquoc 1.1-1.4 cristobalite


1.6-2.5 cristobalite
1.7 cristobalite + microcline
Basal Sisquoc 0.7 —
(laminated) 1.0-2.4 plagioclase + cristobalite
Monterey 5.5 cristobalite
mica, no clay cristobalite
83

t h e d o l o m i t e / c a l c i t e ratio as determined b y X-ray diffraction further defined


the reef edges. Wells drilled as a result of the X-ray analysis produced oil.
X-ray fluorescence analysis has m u c h m o r e limited value than X-ray
diffraction for p e t r o l e u m e x p l o r a t i o n . The reason is simple, m o s t sedimen-
tary rocks are less distinctive chemically than t h e y are mineralogically or
texturally. Only special chemical characteristics of rocks m a k e fluorescence
analysis w o r t h while in p e t r o l e u m e x p l o r a t i o n . For e x a m p l e , s o m e black
shales or z o n e s in black shales have unusually high copper or zinc concentra-
tions. X-ray fluorescence easily quantifies such anomalies, which can t h e n
serve as k e y stratigraphic horizons. In carbonate sequences, X-ray fluores-
cence analysis can define trends in such e l e m e n t s as barium and strontium
w h i c h , like the chlorite e x a m p l e cited above, might help locate p o r o u s oil-
bearing z o n e s .

Uranium
A b o u t 9 5 % of e c o n o m i c uranium deposits and reserves are in sedimentary
formations and m o s t are in sandstones (Saum and Link, 1 9 6 9 ) . Most sedi-
mentary deposits result from leaching of a sandstone b y groundwater with
reconcentration in e c o n o m i c mineral quantities. U d e c a y leads t o m a n y
2 3 8

radioactive daughter products a m o n g t h e m Th, Bi, Pb, R n and K. Each of


these daughter products emits gamma radiation of characteristic energy
measurable radiometrically. Frequently M o , Cu, Ag, Se, Co and V migrate
with the uranium t o t h e ore site. Quick-test m e t h o d s can d e t e c t m o s t of
these emigrant e l e m e n t s .
Radiometrics, tests for " p o i n t e r " e l e m e n t s and geologic features of
uranium deposits make systematic analysis b y X-ray diffraction and fluores-
cence usually unnecessary until t h e drilling phase of e x p l o r a t i o n .
The drilling program begins w h e n samples of subsurface materials are
n e e d e d . These samples will be of o n e of t w o t y p e s . The m o s t expensive and
m o s t useful samples are taken b y t h e core drill. The samples are long cylin-
ders of rock and t h e geologist is able t o e x a m i n e t h e l i t h o l o g y , mineral c o n -
tent, etc., in detail. Samples taken w i t h the core drill are m u c h more reliable
than t h o s e acquired in other w a y s because t h e core is enclosed within the
steel core barrel in the drill h o l e and n o c o n t a m i n a t i o n occurs. Usually core
drilling is used in the final phase of an exploration program and c o n t i n u e s
during mine d e v e l o p m e n t . The m o s t c o m m o n and inexpensive drilling
m e t h o d s c u t chips from the b o t t o m of the drill hole and use air or m u d t o
carry these chips t o the surface. A l t h o u g h samples obtained this w a y are of
less value t o t h e geologist, the c o s t is o n l y one-tenth that of core-drilling.
Drilling programs fall into three categories: ( 1 ) information or reconnais-
sance drilling in w h i c h t h e h o l e is p u t d o w n t o determine geologic information
about the area, and h o p e f u l l y , t o make a uranium discovery; (2) outline
drilling which is used t o determine the outline of a discovery and e x t e n t of
mineralization; and ( 3 ) sample or core drilling t o obtain information o n
84

exactly h o w m u c h ore of w h a t grade can be reliably c o u n t e d o n for planning


a mine.
Reconnaissance drilling o n r a n d o m centers spaced more than a mile apart
is c o m m o n in uranium e x p l o r a t i o n in the sedimentary basins. When uranium
or altered h o s t rocks are located b y a reconnaissance drilling program, out-
line drilling is begun. Outline drilling delineates lithologic units, buried
stream channels, and other favorable hosts for t h e ore material. Emphasis is
placed o n obtaining information o n t h e nature of t h e ore d e p o s i t rather than
a t t e m p t i n g t o detail t h e entire deposit.
A t t h e o u t s e t of drilling, X-ray fluorescence and diffraction can serve use-
fully in t h e exploration process. S u p p o s e exploration for uranium with t h e
c o n d i t i o n s stated above, that is, reconnaissance drilling for t h e "roll" t y p e of
deposit schematically d e p i c t e d in Fig. 3 - 2 0 . During t h e information or
reconnaissance drilling phase, h o l e s A through D of Fig. 3 - 2 0 might be
drilled. Table 3-III lists s o m e of t h e features f o u n d in each drill h o l e . In
Table 3-III, t h e letters F for fluorescence and D for diffraction indicate t h e
application of each t o o l for defining particular parameters. Interestingly X-
ray diffraction powerfully addresses determination o f several useful param-
eters during t h e exploration drilling, b u t is little used e x c e p t b y companies
w h o had used diffraction t o find other t y p e s of energy sources.
Fluorescence analysis has g o o d sensitivity for t h e pointer e l e m e n t s
because t h e matrix (sandstone) has l o w absorption coefficients. Outside t h e
o r e b o d y , fluorescence o f t e n has insufficient sensitivity t o measure uranium
e x c e p t with use of special preparation m e t h o d s . In t h e o r e b o d y uranium
c o n t e n t is easily measured.
When core drilling begins, X-ray m e t h o d s supply systematic mineral and
chemical data t o define t h e n e w discovery.

Fig. 3-20. Typical uranium roll ore deposit in sandstone. (After Adler and Sharp, 1 9 6 7 . )
85

Metals

B o t h X-ray diffraction and X-ray fluorescence analysis have great p o w e r as


t o o l s in metals exploration. As w i t h uranium e x p l o r a t i o n , t h e usefulness of
b o t h m e t h o d s occurs mainly during the later stages or ore finding w h e n t h e
systematic definition and use of physical chemical parameters might indicate
t h e presence of ores or the direction t o ores and t h e definition of quality and
quantity of ore after t h e b o d y is f o u n d .
The metals mining industry has for s o m e years used X-ray fluorescence
analysis very effectively for quality c o n t r o l in mines. S o m e m i n e operations
have used modern c o m p u t e r controlled s y s t e m s t o give g o o d analyses of ore
and gangue e l e m e n t s t o m o n i t o r m i n e operation. T h e y use X-ray fluores-
cence analysis t o systematically map t h e mining operation as it proceeds and
make projections for future m i x i n g of ores for beneficiation. S o m e c o m -
panies use c o n t i n u o u s l y operating "on-stream" X-ray fluorescence analyzers
t o help control t h e entire beneficiation process. Most mining operations use
X-ray diffraction less than X-ray fluorescence.
A l t h o u g h X-ray m e t h o d s receive wide use in m i n e and mill, for a plethora
o f reasons ranging from legitimate financial and technical considerations t o
considerations based o n less appealing reasons, X-ray fluorescence and X-ray
diffraction analysis have n o t contributed their full potential in metals
exploration even after t h e metals prospecting phase is over and during
systematic e x p l o r a t i o n of a local area. The speed and comprehensive c h e m -
ical and mineralogical analytical capability of b o t h m e t h o d s can characterize
an ore b o d y easily and inexpensively relative t o other costs of exploration.
Because X-ray fluorescence and diffraction analysis, w h e n properly
e x e c u t e d , can be so universally applicable in metals exploration w e elucidate
e x a m p l e s of t h e weakness of each m e t h o d in metals e x p l o r a t i o n rather than
dwelling o n strengths.
X-ray fluorescence analysis frequently gives p o o r analytical results on
s o m e by-product e l e m e n t s . For e x a m p l e , X-ray fluorescence analysis indi-
cated n o or incorrect a m o u n t s of Co in Pb ore from southeast Missouri lead
district. However, electron microprobe analysis s h o w e d a Co-rich phase c o n -
centrated around ore-mineral grains. Calculation based on t h e premise that
t h e electron microprobe samples were representative indicated Co could be
extracted e c o n o m i c a l l y as a by-product. During X-ray fluorescence analysis,
m o s t of t h e cobalt radiation was absorbed b y the highly absorbing Pb-Cu-Zn
matrix. Cd, A u , M o and Ag frequently are n o t always analyzable w h e n in b y -
product quantities. Se and Ge, by-products of Cu and Zn processing, are also
n o t easily quantified in t h e raw ores. In general, minute-quantity by-prod-
ucts are n o t easily analyzed b y fluorescence analysis.
Native metals such as A u and Cu are difficult t o analyze w i t h o u t special
treatment. X-ray fluorescence also proves t o o insensitive for m o s t metals in
t h e water samples frequently collected for analysis during prospecting or
preliminary e x p l o r a t i o n .
00

TABLE 3-III
Mineralogical and chemical characteristics of uranium ore rolls of Fig. 3-20 *

Drill hole A Drill hole B Drill hole C Drill hole D


Eh- Eh- Eh+ Eh+
unoxidized zone ore roll (unoxidized) oxidized zone oxidized zone
unaltered sand ore and "protore" barren interior barren
altered sand altered sand

Color: light gray drak gray light gray, greenish yel- light gray, greenish yel-
low, bleached, brownish low, bleached brownish
reddish reddish
Pyrite: present, local abundant; subhedral present, scarce absent or sparse; cor-
aggregates or euhedral roded where scarse; un-
tarnished euhedral where
sparse
Uranium: trace F concentrated ore absent or trace absent or trace
Molybdenum: F low (< 10 p p m ) F high ( 1 0 0 p p m ) F very high (1000— low ( < 1 0 p p m )
10,000 ppm)
Vanadium: F low (1—10 p p m ) F moderate to high F moderate ( 1 0 0 0 p p m ) F low (10—20 p p m )
(500—2000 ppm)
Copper: F variable ( < 2 0 p p m ) F low ( 2 0 p p m ) F low (10 ppm) F l o w (<1—2 p p m )
Selenium: F low ( < 0 . 5 p p m ) F moderate to high F very high ( 2 0 0 — 1 2 0 0 F moderate (10—60
(2—200 ppm) ppm) ppm)
2 + 3 +
Fe /Fe : 2 >2 <2 1
Heavy opaques: present absent or scarce scarce scarce
Calcite: D scarce D abundant D sparse D absent or sparse
Clay: D low-iron mont. ** D low-iron mont. D high-iron mont. D high-iron mont.
kaolinite/mont. kaolinite/mont. D kaolinite/mont. kaolinite/mont.
sharp (00/) lines sharp (00/) lines broad (00/) diffrac- broad ( 0 0 / ) diffrac-
tion lines tion lines
Limonite: D absent D usually absent D present D sometimes abundant
Hematite: D absent in reduzate D usually absent or D present sometimes D sometimes predomi-
facies localized in ore abundant nant
Zeolites: D present D present D absent D absent
Sulfate: moderately abundant high low very low

* Based only on available data, primarily applicable to rolls in Tertiary sandstones; selected to indicate promising exploratory
guides from Harshman ( 1 9 7 2 ) ; Adler and Sharp ( 1 9 6 7 ) and W.T. Caneer (personal communication); Granger et al. ( 1 9 6 1 ) .
** Mont. = montmorillonite.

00
88

X-ray diffraction analysis, although a very powerful exploration t o o l ,


occasionally suffers similar deficiencies t o X-ray fluorescence analysis. X-ray
diffraction has a sensitivity limit ranging upward from a b o u t 0 . 2 5 % for a
given mineral. A sensitivity o f 1% is typical and w i t h a highly absorbing
matrix, as m a n y ores might have, t h e analyst can find a sensitivity limit as
high as 4%. Poor sensitivity means that e c o n o m i c a l l y valuable mineral phases
could be missed or at best, p o o r l y quantified.

Lead
We present o n e e x a m p l e o f t h e application o f X-ray analysis t o explora-
t i o n o f metals. In southeast Missouri Pb occurs in mineralized z o n e s in t h e
Cambrian Bonneterre F o r m a t i o n , a d o l o m i t e . Fluorescence and diffraction
analysis, easily able t o quantify t h e elemental and mineral richness o f t h e
mineralized z o n e s , c o u l d also serve t o indicate direction t o ore during
exploration drilling. Within t h e sensitivity range o f X-ray fluorescence,
elemental analysis o f Bonneterre d o l o m i t e s h o w e d little relation b e t w e e n
such e l e m e n t s as Cu, F e , Zn, Mn and Cd in t h e c o u n t r y rock and nearness t o
t h e mineralized z o n e s .
However, t h e Bonneterre F o r m a t i o n , although regionally d o l o m a t i z e d ,
3
MOLE PERCENT Mg C0

i I
0 1000
d I
FEET
Fig. 3 - 2 1 . Plot of maximum, mean and minimum mole percent M g C 0 content of core
3

samples along an east-west traverse across a mineralized zone in the Bonneterre Forma-
tion, Missouri (After Briceno, 1 9 7 5 . )
89

a b

Fig. 3-22. (a) Diffractogram showing the positions for the d ( 1 0 4 ) reflections for calcite
( C a C 0 ) and dolomite ( C a , M g ) C 0 . (b) Plot for d ( 1 0 4 ) versus mole percent M g C 0 for
3 3 3

Ca-Mg carbonates. (After Goldsmith and Graf, 1 9 5 8 . )

contained higher concentrations o f Mg near t h e ores, t h e relative Mg enrich-


m e n t being partly d e p e n d e n t o n the original lithologic character o f t h e rock.
Fig. 3 - 2 1 illustrates t h e variation of Mg w i t h respect t o Ca in t h e wall rock
z o n e s , showing h o w t h e e l e m e n t c o n c e n t r a t i o n can be used t o indicate ore
z o n e s . Variation b e t w e e n m a x i m u m and m i n i m u m can b e related partly t o
textural parameters of individual facies of t h e original biogenic l i m e s t o n e .
Diffraction gave t h e results o f Fig. 3 - 2 1 , although fluorescence analysis
w o u l d have yielded t h e same results. Fig. 3 - 2 2 illustrates t h e m e t h o d of
determination o f t h e m o l e percent M g C 0 o f Fig. 3 - 2 1 . Similar relationships
3

b e t w e e n m o l e percent M g C 0 and mineralized z o n e s were f o u n d b y Klug-


3

man et al. ( 1 9 6 2 ) in Colorado.

CONCLUSIONS

Quantitative analysis is t h e primary f u n c t i o n of b o t h X-ray fluorescence


and diffraction in e x p l o r a t i o n analysis. Each m e t h o d has strengths and
weaknesses. For multi-element total rock analysis at high sample rates and
l o w c o s t per sample, X-ray fluorescence is perhaps t h e single m o s t powerful
instrumental m e t h o d for e x p l o r a t i o n analysis. Fluorescence analysis is
particularly g o o d w h e n A l , Si, Ti and Fe c o n s t i t u t e analyte e l e m e n t s .
Fluorescence has sufficient sensitivity for metals of the first-row transition
e l e m e n t s for almost all e x p l o r a t i o n n e e d s .
On t h e other hand, X-ray fluorescence analysis w i t h standard instrument
configurations s h o w s analytical w e a k n e s s , as d o o t h e r t y p e s of instruments
for individual e l e m e n t s , if there are overlapping lines such as s h o w n b y ura-
90

nium in the presence of strontium. Special instrument configurations can


often abrogate specific analytical weakness. For e x a m p l e , a special X-ray
tube and v a c u u m s y s t e m allows measurement of certain low-energy lines of
uranium rather than the higher-energy lines, reducing overlap and back-
ground. However, special instrument configurations or modifications are
expensive and require special care. Fluorescence analysis is inadequate for
routine trace-element analysis b e l o w 1—50 p p m for metals and b e l o w
higher levels for lighter e l e m e n t s . R o u t i n e fluorescence analysis is incapable
of analyzing e l e m e n t s b e l o w Na.
X-ray diffraction and microscopic analysis give t h e best results for general
mineral analysis o f any m e t h o d s n o w in use. B o t h m e t h o d s yield g o o d results
for m o s t coarse-grained rocks. For fine-grained rocks, X-ray diffraction
yields better values than microscopic analysis. The character of t h e analyte
specimen generally limits accuracy.
Quantitative analysis b y X-ray diffraction is usually fast and inexpensive.
Quantitative diffraction t e c h n i q u e s are very g o o d for analyzing carbonate
rocks, igneous and m e t a m o r p h i c rocks and sandstones w h e n peaks d o n o t
overlap. Diffraction provides t h e best m e t h o d for analyzing shales and mud-
stones. However, clay minerals, fine-grained iron and aluminum oxides,
certain carbonates and a f e w other rock-forming minerals, have poorly
defined structures and c o m p o s i t i o n s , creating difficulties in characterizing
t h e m in standards and specimens. T o analyze these minerals quantitatively
o f t e n require special c o m p e t e n c e and experience.
X-ray fluorescence and X-ray diffraction analysis as used b y t h e mineral
industry for exploration has had a history marked with b o t h success and
failure. T w o factors have a c c o u n t e d for success or failure. Technological
reasons a c c o u n t for s o m e failures. Until a b o u t eight years ago fluorescence
e q u i p m e n t did n o t have sufficient sophistication t o m e e t t h e requirements of
flexibility and speed t o satisfactorily serve an exploration program. Earlier
e q u i p m e n t had insufficient stability, t o o f e w analyzing crystals in the
spectrometers t o cover t h e wavelength range necessary for general explora-
tion analysis, e t c . Operators had t o attend instruments at all times during
measurement and d o primitive corrections b y hand calculation or use large
r e m o t e c o m p u t e r s . If t h e operator wished t o avoid corrections, sample
preparation b e c a m e m o r e c o m p l i c a t e d . In short, primitive e q u i p m e n t
precluded extensive use of fluorescence analysis for general mineral explora-
t i o n . Where fluorescence analysis had success it was brought a b o u t b y c o m -
p e t e n t and determined analysts.
The use of X-ray fluorescence analysis in mineral processing and material
p r o d u c t i o n caused d e v e l o p m e n t of better e q u i p m e n t c o i n c i d e n t with advent
of improved transistor and integrated circuit electronics and inexpensive
control c o m p u t e r s . E q u i p m e n t is n o w g o o d e n o u g h for exploration require-
ments.
Personnel c o m p e t e n c e has caused s p o t t y success for exploration analysis
91

using X-ray fluorescence. Many c o m p a n i e s have charged untrained personnel


w i t h their X-ray fluorescence analysis programs. For e x a m p l e , o n e c o m p a n y
brought a y o u n g m a n , recently graduated from high s c h o o l , from o n e of its
mines t o operate an X-ray fluorescence and diffraction analysis program. The
analysis program failed and t h e e q u i p m e n t sat idle. On t h e other h a n d , a
certain very c o m p e t e n t commercial analyst, using ancient cast-off equip-
m e n t , obtains enviable e x p l o r a t i o n analyses accurately, rapidly and inex-
pensively.
The history of X-ray diffraction analysis has suffered similarly but less
p r o f o u n d l y than X-ray fluorescence analysis. Diffraction analysis has proved
itself in m a n y specific exploration programs. E x c e p t in t h e hands of a f e w
specialists, diffraction has served primarily as a qualitative and semiquan-
titative analysis t o o l . T i m e , e x p e n s e , l o w accuracy of quantitative mineral
determinations have precluded wide-spread use of diffraction as a quantita-
tive exploration m e t h o d . Many exploration problems such as locating and
characterizing orebodies call for special experience and c o m p e t e n c e . S o m e
c o m p a n i e s have been willing t o c o m m i s s i o n t h e special c o m p e t e n c e neces-
sary t o m a k e effective use of X-ray diffraction, m a n y have n o t .
Unlike X-ray fluorescence e q u i p m e n t , basic diffraction e q u i p m e n t , has
changed little in more than t w e n t y years e x c e p t for i m p r o v e m e n t s in c o u n t -
ing electronics. Present e q u i p m e n t w i t h additions for a u t o m a t i o n , if desired,
is adequate t o serve exploration analysis. The major problem associated with
measurement remains what is has b e e n , t h e character and preparation of
samples. Usually experience and initiative can s u r m o u n t difficulties with
sample preparation and analytical c o n s i s t e n c y and reproduceability.
Modern X-ray spectrometry and diffraction, primarily d u e t o recently
improved e q u i p m e n t and a u t o m a t i o n , are taking their place as major t o o l s of
mineral exploration. The trend will c o n t i n u e and probably accelerate over
t h e n e x t t w e n t y years. Sophisticated a u t o m a t i c control and data processing
c o u p l e d w i t h relatively simple hardware will deliver large quantities of
accurate analyses and aleviate the n e e d for highly skilled analysts. The draw-
back of l o w sensitivity for s o m e e l e m e n t s and c o m p o u n d s is n o t likely t o be
o v e r c o m e in t h e near future, preventing X-ray analysis from b e c o m i n g t h e
analytical panacea for mineral e x p l o r a t i o n . Despite this drawback, X-ray
analysis is an e x t r e m e l y powerful t o o l and should always b e considered as
o n e o f t h e potential analytical m e t h o d s in any mineral e x p l o r a t i o n program.

REFERENCES

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92

Berman, M. and Ergun, S., 1 9 6 8 . Analysis of mineral matter in coals by X-ray fluores-
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Chapter 4

X - R A Y F L U O R E S C E N C E GEOCHEMICAL A N A L Y S I S O N THE
SURFACE OF MARS

BENTON C. CLARK, A.K. BAIRD, PRIESTLEY TOULMIN, III, H A R R Y J. ROSE, Jr.


and KLAUS KEIL

INTRODUCTION

With the advent of t h e space age, it has b e c o m e technically feasible t o


begin the geochemical exploration of t h e planets and satellites of our solar
s y s t e m , and t e c h n i q u e s e m p l o y i n g nuclear or a t o m i c radiation have already
contributed p r o m i n e n t l y t o that e x p l o r a t i o n . The first in-situ analysis of the
inorganic chemical c o m p o s i t i o n of Martian surface material e m p l o y s a highly
miniaturized, energy dispersive X-ray fluorescence spectrometer. This experi-
m e n t is o n t w o Viking spacecraft launched b y Titan III-C rockets late in t h e
summer o f 1 9 7 5 and landed o n t h e surface of Mars in July and S e p t e m b e r of
1 9 7 6 . In t h e sections w h i c h f o l l o w , w e discuss in detail t h e X-ray e x p e r i m e n t
w e have sponsored for the Viking mission and provide brief reviews of past
usages of spaceborne nuclear geochemical t e c h n i q u e s .

THE VIKING MISSION TO MARS

After 1 0 m o n t h journeys of s o m e 7 0 0 million kilometers through space,


the t w o Viking spacecraft reached the vicinity of Mars, retro-rockets fired
and the spacecraft were injected into elliptical orbits a b o u t t h e planet. A t
this p o i n t in the mission, the scientific study of Mars began, using t e c h n i q u e s
of r e m o t e sensing. Dual telescopic vidicon cameras photograph t h e surface
with overlapping frames t o provide c o n t i g u o u s coverage w i t h a resolution at
closest approach of 5 0 m per picture e l e m e n t . A multichannel infrared
radiometer m a p s reflected solar radiation and thermal emissions from areas
as small as 5 km in diameter. From these data can be d e d u c e d t h e surface
thermal inertia, emissivity, and a l b e d o , w h i c h are f u n c t i o n s of n o t only grain
size distribution and bulk d e n s i t y , but c o m p o s i t i o n . With a visible-light
channel and five channels covering the range 6—35 jum (Kieffer e t al., 1 9 7 2 ) ,
it m a y be possible t o characterize t h o s e areas with p h y s i o c h e m i c a l similar-
ities and recognize geographical dissimilarities m o r e subtle than m o r p h o l o g -
ical differences. In addition, a fixed-grating infrared spectrometer tuned t o
94

t h e 1.4-/xm absorption band of water m o l e c u l e s is mapping the water vapor


c o n t e n t of the Martian atmosphere.
When sufficient data had been accumulated b y the orbiter science experi-
m e n t s t o allow final selection of o p t i m u m landing sites, a signal from ground
controllers o n earth initiated t h e c o m p l e x series of steps w h i c h led t o separa-
t i o n of the Viking-1 Lander from t h e Viking-1 Orbiter. Only after t h e land-
ing and performance of primary mission objectives of Lander-1 was a similar
c o m m a n d signal sent t o Viking-2.
The Viking Lander (Fig. 4-1) has been described as the m o s t sophisticated
and c o m p l e x a u t o m a t e d spacecraft ever built. There are m a n y reasons for
this, a m o n g w h i c h t h e f o l l o w i n g are s o m e of t h e more important:
( 1 ) Since t h e landing from orbit t o o k place within a 5- t o 10-min period, a
time short compared t o t h e radio link travel t i m e t o earth (up t o 2 0 m i n ) ,
t h e landings had t o be fully a u t o m a t i c .
(2) The atmosphere o f Mars was n o t c o m p l e t e l y k n o w n (pressure; argon
c o n t e n t ; winds) and there was an uncertainty in the height of the terrain at
the landing site, w h i c h required an adaptive landing flight.

Fig. 4-1. The Viking Mars Lander, with science experiment equipment.
95

(3) The science c o m p l e m e n t included 1 3 separate e x p e r i m e n t s , o n l y o n e


of w h i c h has b e e n f l o w n previously; t w o e x p e r i m e n t s ( b i o l o g y and organic
chemistry) m o s t likely surpass in sophistication and technical c o m p l e x i t y all
past space science hardware.
(4) In accordance with an international treaty limiting t h e c o n t a m i n a t i o n
of Mars w i t h viable organisms from earth, b o t h lander spacecraft were
sterilized b y heating in a dry nitrogen atmosphere at 1 1 2 ° C for 4 0 h prior t o
launch.
A central c o m p u t e r inside the Lander controlled all aspects o f t h e landing
d e s c e n t as well as all operations of e q u i p m e n t after t h e landing was c o m -
pleted. To initiate d e s c e n t , separation nuts were fired, retrorockets were
p o w e r e d o n , and pulsed-burns were m a d e t o maintain correct orientation for
entry. A n ablative aeroshell p r o t e c t e d t h e lander against t h e heat of entry.
A n inertial reference unit, containing gyros and accelerometers and t w o
separate radar s y s t e m s provided t h e c o m p u t e r w i t h t h e information required
t o control t h e d e s c e n t profile. Final deceleration was provided in t w o incre-
m e n t s — first b y a parachute o p e n e d at 6 . 4 k m and jettisoned at 1.2 k m , and
finally b y three terminal propulsion retro-rockets. The rockets utilized
unique 18-nozzle engines fueled b y ultrapure hydrazine, w h i c h provided for
minimal alteration of the physical and chemical properties of t h e landing
site.
Once landed, Viking began a u t o m a t i c e x e c u t i o n o f a s e q u e n c e o f engineer-
ing f u n c t i o n s and scientific e x p e r i m e n t s . The sequence is modified as desired
by updating the program stored in the central c o m p u t e r ; this is a c c o m p l i s h e d
b y transmitting from earth t o the on-board S-band c o m m u n i c a t i o n s s y s t e m .
Scientists are able t o interact in an adaptive manner w i t h their e x p e r i m e n t s ,
changing sequences and instrument operating parameters. Scientific experi-
m e n t s c o n d u c t e d o n the landers include t h e search for life forms (biology
investigation), multispectral imagery of t h e landscape b y dual facsimile
cameras, c o l l e c t i o n of meteorological data (temperature, w i n d v e l o c i t y , and
pressure), seismic m o n i t o r i n g for Marsquakes, analysis of t h e soil for mag-
netic c o m p o n e n t s and physical properties, assay for organic c o m p o u n d s b y
c o m b i n e d gas c h r o m a t o g r a p h y / m a s s s p e c t r o m e t r y , and lastly, analysis of soil
and pebble-sized fragments b y X-ray fluorescence s p e c t r o m e t r y using t h e
instrument described b e l o w . For additional information concerning Viking,
its mission and scientific results, the reader is referred t o t h e f o l l o w i n g issues
of Science: V o l . 1 9 3 , N o . 4 2 5 5 ; V o l . 1 9 4 , N o . 4 2 6 0 ; and V o l . 1 9 4 , N o . 4 2 7 1
(1976).

DESIGNING A N INSTRUMENT FOR SPACE

With the e x t r e m e constraints i m p o s e d u p o n t h e instrument designer, it is


n o t surprising that virtually n o n e of t h e spaceborne geochemical experiments
96

are simply derivatives o f already existing instruments. The first and f o r e m o s t


objectives in design o f an instrument for space are miniaturization, rugged-
ness, and reliability. Obviously, these three objectives c a n n o t necessarily be
o p t i m i z e d i n d e p e n d e n t l y , and tradeoffs m u s t be m a d e . F o r t h e designer w h o
is also t h e scientist, as usually is t h e case, a greater conflict arises: h o w t o
obtain t h e greatest quantity and quality of scientific information, y e t satisfy
t h e applicable engineering requirements. This, indeed, is the justification and
t h e necessity for d e e p involvement b y the scientist during all phases of
design.
Planetary missions provide even m o r e constraints than usual, for the
e q u i p m e n t must face n o t o n l y t h e harsh environments of d e e p space but the
entry and landed environments as well. Table 4-1 summarizes the environ-
m e n t s e n c o u n t e r e d in a Mars mission and lists s o m e of t h e characteristics of
each environment w h i c h m u s t be considered. The specifications matrix
resulting from crossing the right- and left-hand c o l u m n s of Table 4-1 is, of
course, quite formidable.
In designing t h e X-ray fluorescence e x p e r i m e n t for Mars (Clark and Baird,
1 9 7 3 a ) w e were c o n f r o n t e d w i t h a design requirement unique t o Viking, viz.,
that all c o m p o n e n t s b e heat sterilizable. This rendered impractical our first
c h o i c e for t h e X-ray sensor, t h e high-resolution Si solid-state detector,
because of its susceptibility t o degradation b y any c o n t a m i n a n t s released
from its housing during heating and because o f t h e difficulty in providing t h e
requisite cryogenic temperature for low-noise operation. The n e x t best
sensor, in terms of resolution of fluorescent X-rays from low-atomic-number
a t o m s is t h e gas-filled proportional counter. When properly designed and
constructed the performance o f this c o u n t e r is unaffected b y heat steriliza-
tion.
Reliability considerations also greatly influenced t h e design. Originally,
t h e c o n c e p t for sample handling was placing t h e soil in a shallow c u p ,
s m o o t h i n g w i t h a knife e d g e , and t h e n m o v i n g t h e c u p i n t o p o s i t i o n for
analysis. It was also planned t o k e e p t h e soil inlet covered w i t h a solenoid -

TABLE 4-1
Environments for a Mars mission

Types of environments Environment components

Transportation, handling Shock, vibration, acceleration


Prelaunch Vacuum/pressure
Launch and boost Temperature (including heat sterilization)
Interplanetary cruise Humidity
Mars orbit Electromagnetic interface
Deorbit and entry Acoustics
Landing Atmospheric composition, wind, dust
Martian surface Solar flare and cosmic radiation
97

actuated lid t o m i n i m i z e convection-current heat losses. B o t h o f these ideas


were rejected, h o w e v e r , o n t h e basis that a failure in either m e c h a n i s m could
ruin t h e entire e x p e r i m e n t . The alternatives selected were t o ( 1 ) provide a
fixed sample-holding cavity with thin plastic w i n d o w s o n t w o of its vertical
walls, and a trap d o o r at the b o t t o m (see "Instrument d e s c r i p t i o n " b e l o w ) ,
and (2) eliminate t h e inlet-lid and tolerate t h e relatively m i n o r additional
temperature excursions.
Since our e x p e r i m e n t was added t o Viking more than a year after t h e
other e x p e r i m e n t s were selected and t h e spacecraft detailed design was
well u n d e r w a y , t h e instrument had t o be designed t o fit w i t h i n an available
" g a p " b e t w e e n t h e life-detection e x p e r i m e n t and data processor unit, result-
ing in a packaging arrangement far from that w h i c h w o u l d b e o p t i m u m for
ease of assembly and maintainability.
Electronic design was governed b y several factors, including t h e selection
of c o m p o n e n t s from o n l y a narrow range of approved devices w i t h proven
reliability; a prescribed all-digital interface w i t h the data s y s t e m ; and require-
m e n t t o minimize p o w e r drain b y p o w e r switching certain portions of cir-
cuitry. This latter requirement is o f critical importance since t h e entire
p o w e r source for t h e Viking lander is only 7 0 w a t t s , i.e., o n e light-bulb
equivalent of p o w e r t o operate t h e c o m p u t e r , m e c h a n i s m s , c o m m u n i c a t i o n s
systems, and all science experiments on-board the spacecraft. The p o w e r
sources are t w o thermoelectric converter units with t h e heat provided b y
S N A P - 1 9 units containing p l u t o n i u m o x i d e fuel.
In t h e preceding discussion, w e have emphasized o n l y a f e w of t h e m a n y
technical c o m p l e x i t i e s that c o n f r o n t e d t h e instrument design t e a m . A more
c o m p l e t e list is provided in Table 4-II. Before describing t h e instrument as it

TABLE 4-II

Design criteria for flight instruments

Scientific performance versus


Weight and volume available Age-sensitive elastomeric compounds
Type and amount of power available Malfunction isolation and test points
Sterilization heat soak Quality assurance factors
Radiation safety Cleanliness control
Reliability RTG radiation environment
Failure detection Operating and useful life
Interchangeability Emissions, outgassing, and vapor pressure
Attachment points Workmanship implementation
Electrical connectors Mandatory parts, materials, and processes
Operating safety Identification, standardization and traceability
Dissimilar metals Experiment's radioisotope environment
Stress corrosion Electrical ground system
Electromagnetic compatibility Packaging against amplification
Thermal dissipation
98

was finally d e v e l o p e d , t h e c o n t e x t of this e x p e r i m e n t in t h e history of


exploration of planetary surfaces will be briefly reviewed.

PREVIOUS NUCLEAR GEOCHEMICAL MEASUREMENTS OF P L A N E T A R Y


SURFACE

The first proposal for a spaceborne nuclear technique for geochemical


exploration is that b y Arnold ( 1 9 5 8 ) a scant t w o years after t h e opening of
the space age b y t h e first successful launch of an artificial satellite, Sputnik I.
Arnold proposed passive gamma-ray s p e c t r o s c o p y of t h e lunar surface t o
d e t e c t emissions o f natural radioactivity in the soil, including K , Th, and U,
4 0

and radioactive nuclides of other elements produced b y nuclear reactions


with t h e incident c o s m i c ray flux. In 1 9 6 2 , three spacecraft, Ranger 3 , 4 ,
and 5, carried 32-channel gamma-ray spectrometers t o perform this proposed
experiment. Each spectrometer consisted o f a 7-cm X 7-cm Csl scintillator
crystal surrounded b y a plastic scintillator, b o t h viewed b y t h e same p h o t o -
multiplier, w h o s e o u t p u t pulses were analyzed b y the " p h o s w i c h " pulse-rise-
time discrimination t e c h n i q u e t o reject c o s m i c ray events originating in b o t h
scintillators and t o accept gamma-ray events in the Csl crystal. Although the
Ranger craft did n o t pass sufficiently close t o t h e m o o n t o allow d e t e c t i o n
of lunar gamma rays, an important result was t h e experimental demonstra-
t i o n of the high background of secondary gamma rays produced in the space-
craft structure b y c o s m i c rays, and that its interference was reduced t o a
negligible value by d e p l o y m e n t of the spectrometer away from the space-
craft by a 2-m b o o m (Arnold e t al., 1 9 6 2 ) .
In 1 9 6 6 , gamma-ray spectrometers were f l o w n on the Soviet lunar orbiters,
Luna 1 0 and 1 1 . These spectrometers were also of t h e p h o s w i c h t y p e , like
t h e Ranger instruments, b u t the central d e t e c t o r was a 3-cm X 4-cm Nal(Tl)
crystal, and t h e e x p e r i m e n t was m o u n t e d inside t h e spacecraft rather than
o n a b o o m (Adler and Trombka, 1 9 7 0 ) . Although the emissions were n o t
correlated t o levels of specific e l e m e n t s , Vinogradov et al. ( 1 9 6 7 ) c o n c l u d e d
that t h e natural radioactivity of the lunar maria corresponds t o that of
terrestrial basalts.
The landmark e x p e r i m e n t in r e m o t e geochemical analysis was performed
by t h e alpha-particle instrument m o u n t e d on t h e Surveyor 5 spacecraft
which softlanded o n t h e m o o n in September, 1 9 6 7 . This e x p e r i m e n t , as well
as the basic m e t h o d of chemical analysis b y spectrometry of Rutherford
scattering of alpha particles, was d e v e l o p e d b y Turkevich ( 1 9 6 1 ) . In this
t e c h n i q u e , t h e sample is irradiated at normal incidence b y a tightly colli-
mated beam of 6.11-MeV alpha particles from six C m sources. Alpha
2 4 2

particles scattered directly backwards ( 1 8 0 ° scattering angle) suffer an


energy loss which is greater for scattering b y light nuclei than heavy nuclei.
Each e l e m e n t produces a characteristic energy loss, so that for a thick sample
99

of a pure e l e m e n t the energy spectrum of backscattered alphas is virtually


constant u p t o t h e critical energy, t h e n decreases t o zero. A sample contain-
ing m a n y e l e m e n t s p r o d u c e s a staircase s p e c t r u m , w i t h each step indicative
of t h e presence and relative c o n c e n t r a t i o n of s o m e e l e m e n t . In addition,
s o m e e l e m e n t s , such as N , F, Na, Mg, Al, and Si undergo nuclear reactions
w i t h alpha particles t o produce p r o t o n s having distinctly characteristic
spectra w h i c h provides additional identification. Silicon solid-state d e t e c t o r s ,
b o t h Li-drifted and surface barrier t y p e s , were used t o measure t h e resulting
alpha and p r o t o n spectra. E l e m e n t s d e t e c t e d during t h e Surveyor missions
were O, N a , Mg, Al, Si, (K + Ca), Ti, and Fe (Franzgrote e t al., 1 9 7 0 ) . The
outstanding achievement of t h e alpha-backscatter e x p e r i m e n t in providing
the first chemical analyses of t h e lunar surface was capped b y its success in
s h o w i n g that t h e c o m p o s i t i o n was very similar at sites o n t w o lunar maria
(Surveyors 5 and 6 ) , but distinctly different from that at a highlands site
(Surveyor 7 ) . Further, analyses o f returned samples ( A p o l l o and Luna
programs) verified t h e chemical conclusions reached from t h e alpha-back-
scatter e x p e r i m e n t .
In late 1 9 7 0 , t h e Soviet a u t o m a t e d m o o n rover L u n o k h o d - 1 carried
" R I F M A " , an X-ray fluorescence spectrometer e x p e r i m e n t m o u n t e d 3 0 c m
above ground level, and accumulated spectral data from t h e local terrain
b o t h while t h e rover was stationary and during traverses. Kocharov et al.
( 1 9 7 1 ) report that t h e e x p e r i m e n t e m p l o y e d t w o tritium-containing X-ray
sources, several side-window proportional counters, and selective filters. A
64-level pulse-height digitizer provided t h e spectral analysis. Several hundred
spectra were obtained during t h e course of rover operations. Concentrations
for Mg, Al, Si, Ca, and Fe have b e e n given, and upper limits have b e e n
placed o n K and Ti.
In S e p t e m b e r , 1 9 7 1 and April, 1 9 7 2 , a special integrated geochemical
e x p e r i m e n t (Metzger et al., 1 9 7 3 ) was f l o w n as part o f the A p o l l o 1 5 and 1 6
astronaut missions t o t h e m o o n . This package remained w i t h t h e orbiting
c o m m a n d service m o d u l e o f A p o l l o and thus was able t o view t h e lunar
surface from an altitude o f 1 1 0 k m . One instrument in t h e e x p e r i m e n t was
an improved version of previous gamma ray spectrometers, this t i m e includ-
ing a 7-cm X 7-cm N a l crystal and an optically isolated plastic scintillator
equipped with its o w n photomultiplier t u b e . The plastic was operated in anti-
c o i n c i d e n c e with the crystal, rather than in t h e p h o s w i c h m o d e , for rejec-
t i o n o f cosmic ray-charged particles. A n e x t e n d e d b o o m placed t h e spectrom-
eter 7.6 m from t h e spacecraft. High-resolution 5 1 2 - c h a n n e l spectra were
transmitted in real t i m e directly t o earth. Collimation was impractical, so t h e
mapping distance was defined by t h e spacecraft altitude, with one-half o f t h e
d e t e c t e d gamma rays originating within a 2 4 0 - k m diameter circle o n t h e lunar
surface. T h e e x p e r i m e n t observed gamma-ray lines from t h e naturally radio-
active elements (K, U, Th) and from inelastic scattering events o f neutrons
(cosmic ray secondaries) with nuclei of c o n s t i t u e n t s of t h e lunar regolith.
100

Comparing t h e spectra obtained over areas for w h i c h "ground t r u t h " is avail-


able from A p o l l o and Luna sampling missions, it has been possible for the
experimenters t o obtain empirical calibration factors and t h u s d e d u c e c o n -
centrations o f K, (Th + U ) , F e , Ti, Si, and O over the lunar surface ( T r o m b k a
et al., 1 9 7 5 ) . D a t a analysis still in progress should yield maps o f U also, and
possibly s o m e information concerning Ca and Al distribution.
A s e c o n d e x p e r i m e n t in t h e A p o l l o geochemical package was an X-ray
fluorescence analyzer e x p e r i m e n t based u p o n t h e very imaginative c o n c e p t
of searching for the fluorescent X-rays e m i t t e d from the lunar surface as a
result of e x c i t a t i o n b y natural X-ray emissions of t h e sun. Instrumentation
included three large-area, collimated, beryllium-window proportional
counters, t w o of which had selective filters (Mg and Al foil, respectively). A
fourth d e t e c t o r viewed away from the lunar surface toward the sun t o
m o n i t o r t h e sometimes-variable solar X-ray flux. A n 8-channel pulse-height
analyzer produced spectra every 8 seconds. When integrated over a 6 0 -
second time period t o improve statistics, these covered a ground area approx-
imately 1 1 0 k m b y 1 5 0 k m . (Adler et al., 1 9 7 2 . ) A l t h o u g h an earlier a t t e m p t
at a similar measurement o n Luna 1 2 obtained little data o n c o m p o s i t i o n ,
Adler e t al. ( 1 9 7 3 ) have n o w mapped t h e Mg/Si and Al/Si ratios over nearly
25% of the lunar surface. E l e m e n t s of a t o m i c number higher than Si are n o t
efficiently e x c i t e d because of t h e relative paucity of solar X-rays at higher
energies.
The o n l y successful measurement t o date pertaining t o t h e chemical
c o m p o s i t i o n of a planetary surface other than t h e m o o n is that of Vinogradov
et al. ( 1 9 7 3 ) , from t h e Venera 8 and 9 spacecraft w h i c h landed o n t h e
surface of V e n u s in July 1 9 7 2 and October 1 9 7 5 , respectively. The instru-
m e n t , consisting of a 6.3-cm X 6.3-cm N a l ( T l ) crystal with a 60-channel
pulse-height analyzer, was m o u n t e d within the temperature-controlled
interior of the spacecraft. On Venera 8 , t h e e x p e r i m e n t accumulated t w o
spectra over a total period of 4 2 min before t h e spacecraft s u c c u m b e d t o the
e x t r e m e l y hostile ( 5 0 0 ° C , 1 0 0 atmospheres pressure) environment. Rela-
tively high levels of K, U, and Th were d e t e c t e d quite similar t o average
granites o n earth. The K / U ratio was also close t o values typical of terrestrial
crustal materials. Venera 9 reportedly measured lower values of K, U, and Th
at its landing site.

INSTRUMENT DESCRIPTION

The Viking X-ray fluorescence spectrometer ( X R F S ) is constructed in t w o


parts, w h i c h are assembled i n t o t h e final configuration during installation in
t h e spacecraft. The first part is t h e funnel-inlet unit, consisting of a conical
funnel, wind spoiler, and delivery t u b e . For sample delivery, t h e Viking sur-
face sampler arm is p o s i t i o n e d w i t h its s c o o p nestled d o w n into t h e X R F S
101

wind spoiler, w h i c h provides a mechanical barrier t o minimize sweeping


away of fines b y w i n d . Normal delivery is b y vibratory sieving through 2-mm
circular openings in t h e b o t t o m of t h e sampler s c o o p , into t h e X R F S funnel,
and t h e n c e by gravity feed through a 2.5-cm diameter t u b e into t h e sample
analysis cavity. A n alternate delivery m o d e is t o first sieve o u t t h e fines w i t h
the s c o o p p o s i t i o n e d over t h e local terrain and t h e n deliver t h e residual frag-
m e n t s b y inverting t h e s c o o p while over t h e X R F S funnel. A screen w i t h 1.2-
c m square openings is m o u n t e d over the funnel t o prevent jamming o f t h e
delivery tube b y large sample pieces.
The s e c o n d part o f t h e X R F S assembly is t h e main unit, a rectangular b o x
2 4 c m X 1 5 c m X 7.6 c m and weighing 2 . 1 kg, w h i c h contains t h e X-ray
sources, d e t e c t o r s , sample chamber, and all necessary electronics. The t w o
parts are m o u n t e d t o a c o m m o n e q u i p m e n t - m o u n t i n g plate, o n e from above
and the other from b e l o w (Fig. 4-2) w i t h t h e circular delivery t u b e posi-
t i o n e d directly over t h e sample holding chamber.
A typical sample q u a n t i t y delivered b y t h e s c o o p is 3 5 c m . In Fig. 4 - 3 ,
3

t h e sample chamber is filled w i t h a sample of this a m o u n t , w h i c h is approx-


imately 4 0 % m o r e than that required t o fill t h e chamber t o a level above t h e
ports through w h i c h t h e X-ray analysis is m a d e . These ports ( o n l y o n e is
depicted in Fig. 4 - 3 ; t h e s e c o n d is perpendicular t o t h e first) are 2 . 2 c m in
diameter. The port w i n d o w s are very thin plastic films reinforced b y metal
grids ( T o u l m i n et al., 1 9 7 3 ) w h i c h have high transmission for t h e e x c i t a t i o n
and fluorescent X-rays. R a d i o i s o t o p e sources provide t h e stimulus X-rays.

Soil Delivery Tube

Equipment Mounting

Sample Analysis Proportional


Chamber Counter

Soil Dump Cavity

Soil Dump Valve


XRFS
€lectronic
Compartments

Fig. 4-2. The X-ray fluorescence spectrometer ( X R F S ) ; cutaway view from the side. The
hatched area is the location of insulation material which protects the inside of the lander
from the extreme cold (as l o w as — 1 2 0 ° C ) during the Martian night.
102

Fig. 4-3. Sample analysis chamber, showing one of the four proportional counter detec-
tors and one of the t w o radioisotope X-ray sources.

T w o nuclides are e m p l o y e d : F e , emitting 5.9-keV X-rays ( M n K ) and


5 5
a

C d , emitting 2 2 . 2 - k e V X-rays ( A g K ) . Half-lives of the sources are 2 . 6 0


1 0 9
a

and 1 . 2 4 years, respectively. Accelerator grade material w i t h high specific


activity and virtually n o c o n t a m i n a t i o n b y extraneous radionuclides is used
for b o t h sources. When t h e e x p e r i m e n t was landed o n Mars, source strengths
were 2 7 0 mCi of F e and 5 5 mCi of C d . The C d source holder, s h o w n
5 5 1 0 9 1 0 9

in Fig. 4 - 3 , is a c o m p o s i t e of tungsten and silver layers designed for strong


absorption of the 8 7 . 7 - k e V gamma-ray from C d , and for collimation of
1 0 9

t h e source such that t h e X-rays are allowed t o impinge o n l y u p o n the sample


w i n d o w . Less-tight collimation was e m p l o y e d for t h e F e source in order t o
5 5

provide t h e desired level of count-rate and c o n s e q u e n t l y there is s o m e im-


p i n g e m e n t of source X-rays o n t h e sample holder. T o prevent t h e p r o d u c t i o n
of extraneous Al fluorescence signals from t h e holder, a thin electro-coating
of Ni was applied. When Ni is e x c i t e d by an F e source, o n l y t h e L lines are
5 5

produced and their energies are t o o l o w for d e t e c t i o n .


Four different proportional c o u n t e r (PC) t u b e s are included, each opti-
mized for a specific region of t h e fluorescent X-ray energy spectrum by
selection of w i n d o w material, gas filling, and inner liner. A description of the
selected properties has been given elsewhere (Toulmin et al., 1 9 7 3 ) .
Analysis proceeds b y taking pulse-height spectra from t h e four PC tubes.
Insufficient weight and v o l u m e were available for a multi-channel analyzer,
so a stepping single-channel analyzer circuit is used t o scan the fluorescent
103

X-ray peaks. The c o n t r o l logic has b e e n designed so that t h e scan m a y be


initiated at any of 1 6 equally spaced channels within t h e 128-channel spec-
trum, w i t h dwell t i m e s adjustable from 8 t o 4 9 2 s e c o n d s per channel. A pro-
grammable high-voltage bias supply also permits t h e setting of s y s t e m gain in
increments of 5% over a d y n a m i c range o f 1 0 , 0 0 0 t o 1 b y c o m m a n d from
earth.
As with all analyses b y t h e t e c h n i q u e of X-ray fluorescence, t h e observed
signals for t h e light e l e m e n t s originate from only a very shallow surface layer
because of strong absorption w i t h i n t h e sample. T h e "half-thickness" value
for an X-ray is t h e 50% transmission p o i n t for that X-ray energy in t h e mate-
rial specified (Table 4-III). Alternatively stated, 50% of t h e X-rays will have
originated in t h e region b e t w e e n t h e surface and a d e p t h equal t o t h e half-
thickness value, w h e n measured along t h e path of t h e X-ray (45° t o t h e sur-
face normal for our instrument). F r o m the simple e x p o n e n t i a l absorption
law, it f o l l o w s that 9 0 % of the signal originates b e t w e e n t h e surface and 3 . 3
t i m e s the half-value d e p t h , and 9 9 % from surface t o 6.7 t i m e s t h e half-value
d e p t h . The values of Table 4-III m a k e it clear that for soils devoid of a clay-
sized fraction, t h e fluorescent X-rays for t h e light e l e m e n t s will originate
almost exclusively from the single-grain layer adjacent t o t h e sample cham-
ber w i n d o w .
U p o n analyzing the spectra obtained o n a given sample, and deciding it is
sufficient and c o m p l e t e , a signal is sent t o c o m m a n d a trap d o o r t o o p e n in
t h e b o t t o m of t h e sample chamber. A cycling solenoid will o p e n / c l o s e t h e
trap d o o r 4 t i m e s per s e c o n d for a period of o n e m i n u t e t o d u m p t h e sample
into a " d u m p c a v i t y " within t h e X R F S (Fig. 4 - 2 ) . This cavity can contain
6 8 8 c m of sample material, or from 5 t o 2 0 samples, d e p e n d i n g o n average
3

sample size.

TABLE 4-III
Half-thickness values for key elements in typical matrices

Element X-ray Half-value thickness (fdm)


energy
(keV) quartz rhyolite basalt ultramafic calcite

Mg 1.25 1.5 1.2 1.0 1.0 1.0


Al 1.49 2.4 1.9 1.5 1.2 1.7
Si 1.74 3.6 2.2 1.8 1.7 2.5
K 3.31 5.9 5.5 6.0 6.1 15.2
Ca 3.69 8.0 6.6 7.7 8.1 20.6
Ti 4.51 14.1 11.3 10.6 10.7 7.0
55p 5.90 30.5 24.0
e
21.8 21.8 14.5
Fe 6.40 38.9 30.5 27.6 27.7 18.3
Sr 14.16 423.7 284.4 175.0 166.2 178.6
1 0 9
Cd 22.16 1415.2 930.2 555.8 526.5 569.6
104

METHODS OF D A T A INTERPRETATION

The basic o u t p u t of t h e X R F S instrument is spectra w i t h n u m e r o u s peaks


corresponding t o t h e presence of fluorescent X-rays from particular ele-
m e n t s . In Fig. 4-4, t h e spectra of 7 pure e l e m e n t s as recorded in PC-2 are
superimposed u p o n a spectrum of t h e backscatter peak produced b y t h e F e 5 5

source. As will be our c o n v e n t i o n for this paper, this p l o t has t h e ordinate


(counts per channel) p l o t t e d logarithmically so that for t h o s e spectra includ-
ing trace e l e m e n t s , b o t h major and minor peaks will be revealed. Elements of
adjacent a t o m i c n u m b e r overlap quite strongly d u e t o t h e limited resolution
attainable with t h e PC t u b e . Careful analysis using c o m p u t e r techniques is
required t o determine a small c o n c e n t r a t i o n of o n e e l e m e n t in t h e presence
of large concentrations of its nearest-neighbor or n e x t nearest-neighbor ele-
ment.
S o m e spectra of geological materials for PC-2 are s h o w n in Fig. 4-5. Each
spectrum has b e e n multiplied b y an appropriate factor so that t h e same
number of c o u n t s are in t h e backscatter peak. Simple inspection of the
curves in this figure allows the ranking of each specimen for relative Si, S, K,
and Ca c o n t e n t . The situation for Ti is often less clear and requires more
quantitative analysis. That different rock t y p e s produce significantly dif-
ferent spectra is evidenced b y the c o l l e c t i o n of PC-2 spectra presented in Fig.
4-6, a group w h i c h includes a sequence of igneous rocks as well as quartz and
a l i m e s t o n e (highest Ca p e a k ) .
N o t only are the major e l e m e n t s apparent in these spectra, but certain

I0 F 4
pi
5
C0UNTS

ro
5

5

Fig. 4-4. Spectra of pure elements and a backscatter spectrum ( F e ) , as recorded in PC-2.
5 5
105

I0 E 4

Si K Ca Ti Fe-55

-Quartz
o
-

-Chattanooga Shale
i ii i 1 1

-Pikes Peak Granite


Columbia River Basalt
COUNTS
1—i
1
o
-
—i—i i i i i 1 1

4° CHANNEL 8 0 1 2 0

Fig. 4-5. PC-2 spectra tor four distinctly different rock types. Quartz produces only t w o
peaks, i.e., silicon and backscatter. N o t e the indicated levels for S, K, Ca, and Ti in the
other rocks.

trace e l e m e n t s can be identified as well. Fig. 4-7 s h o w s spectra from three


specimens taken w i t h t h e PC-3 t u b e and t h e C d source. Besides t h e ubiqui-
1 0 9

t o u s Fe peak, peaks are clearly seen for t h e e l e m e n t s R b , Sr, and Zr, w h i c h


are present at levels of 0.1—0.3% in their respective sample. Such concentra-
tions for these three e l e m e n t s are rather atypical, b u t a w i d e variety of
5
I
C0UNTS

'
5
1
1 1 1
1
1 1
v

CHANNEL
Fig. 4-6. Spectra for nine different rocks are overlaid in this graph t o indicate the relative
uniqueness of rock signatures.
106

I0 E 4

L Co Fe Rb Zr Cd-109
5
5 C0UNTS

Fig. 4 - 7 . These spectra, taken with PC-3, illustrate detection of the important trace ele-
ments, Rb, Sr, and Zr.

terrestrial rocks, and lunar samples as well, contain levels of trace elements
w h i c h are readily d e t e c t e d . S o m e e x a m p l e s are s h o w n in Fig. 4-8.
The foregoing discussion of spectra was intended t o demonstrate t h e dis-
criminatory p o w e r o f t h e instruments. It also serves t o indicate t h e ultimate
approach t o interpretation of the data received from Mars: t h e m e t h o d of
CM
5
C0UNTS

PO
5

0 4 0 CHANNEL 8 0 1 2 0

Fig. 4 - 8 . PC-3 spectra of specimens with a range of Fe content and typical trace element
concentrations.
107

analogues, or w h a t is k n o w n as "signature analysis". The X R F S flight instru-


m e n t s have each been tested w i t h 2 5 rock t y p e s as well as standards of pure
elements. These spectra are stored in a c o m p u t e r library and c o m p a r e d t o
t h e spectra telemetered from the Martian surface. A series o f laboratory
studies using other rock standards, soils, and contrived mixtures will later be
undertaken w i t h t h e t w o remaining flight instruments. These studies will
c o n t i n u e until an analogue is f o u n d or synthesized w h i c h m a t c h e s , within
statistical limits, t h e spectra data obtained.
Other m e t h o d s of analysis were n e e d e d t o s u p p l e m e n t t h e signature anal-
ysis t e c h n i q u e , particularly during the mission w h e n decisions are required
o n a timeline n o t consistent w i t h a systematic laboratory study. F o r this, a
mathematical m o d e l was d e v e l o p e d (Clark, 1 9 7 4 ) w h i c h includes theoretical
corrections for matrix absorption and e n h a n c e m e n t effects, theoretical cal-
culations of backscatter intensity, PC-tube response f u n c t i o n s , and empirical
correction factors obtained from laboratory tests. With this m o d e l , spectra
can be calculated for rocks of any specified c o m p o s i t i o n .
An algorithm e m p l o y i n g an iterative series approach t o spectrum matching
(Fig. 4-9) has been programmed and successfully used t o calculate e l e m e n t
concentrations in k n o w n s and in blind samples (Clark and Baird, 1 9 7 3 a , b ) .
A l t h o u g h studies are still in progress, it is clear that t h e e l e m e n t s in t h e
periodic table can be classified i n t o eight distinct groups for w h i c h t h e X R F S
has different analytical capabilities. A discussion of these groups f o l l o w s .

io E 4

Detector: PC-2
Sample: Biotite Peridotite
-Measured Spectrum
-Calculated Spectrum

I0 t 3
COUNTS

IO b- z

1 0
0 40 CHANNEL 8 0
'20
Fig. 4 - 9 . The computer program to calculate element concentrations matches the mea-
sured spectrum with a theoretical spectrum derived from the deduced composition. This
figure indicates the accuracy of match that can be achieved.
108

Elements 1—10 (H to Ne). The first 1 0 e l e m e n t s of t h e periodic table c a n n o t


be identified directly b y our t e c h n i q u e because t h e fluorescent X-rays t h e y
p r o d u c e are of such l o w energy that t h e y d o n o t effectively penetrate t h e
PC-tube entrance w i n d o w s or soil chamber w i n d o w s . However, t h e presence
o f elements within this group can be d e t e c t e d b y the intensity of the back-
scattered X-ray signal since t h e y strongly influence t h e bulk absorption and
scattering properties of t h e sample material.

Elements 11—13 (Na to Al). The elements Na, Mg, and Al e m i t very soft
X-rays ( 1 . 0 4 — 1 . 4 9 k e V ) w h i c h penetrate t h e 5-jum aluminum w i n d o w of
PC-1. However, t h e fluorescent yields for these e l e m e n t s (1—3.5%) are l o w ,
and s o m e interference occurs d u e t o t h e generation o f extraneous Al signal
b y fluorescence of t h e w i n d o w itself b y higher-energy X-rays. Our present
evaluation of m i n i m u m d e t e c t i o n limits:
N a — n o t detectable in igneous rocks
Mg — 2.0% b y w e i g h t in ultra-basic matrix
Al — 1.0% b y weight in basalt.

Elements 14—23 (Si to V). Included in this group are the important rock-
forming e l e m e n t s Si, P, S, K, Ca, and Ti. E l e m e n t 2 3 ( V ) is t h e highest ele-
m e n t in the periodic table w h i c h can be efficiently e x c i t e d b y the F e 5 5

source, and all e l e m e n t s in this group are d e t e c t e d in PC-2 (see Figs. 4-4 t o
4-6).
The m i n i m u m d e t e c t i o n limit for Si is o f n o concern for m a n y geological
samples, but is of considerable importance if t h e specimen is say, limonite or
l i m e s t o n e . For these cases, t h e Si d e t e c t i o n limit is slightly less than 1.0% b y
weight. Accuracy of Si determination w h e n at levels of 20—30% is of t h e
order of ± 1 . 5 % b y weight at a c o n f i d e n c e level of 75%. Analysis for P is p o o r
in m o s t cases because o f interference b y high levels of Si. The same is par-
tially true for S, although t h e sulfur in certain chondrites has b e e n d e t e c t e d
readily, and t h e 4.6% S in Chattanooga Shale is obvious from t h e spectrum
(Fig. 4-5). Sensitivity for the e l e m e n t s K and Ca is quite g o o d , but t h e y d o
interfere with o n e another. In a K-free d u n i t e matrix, t h e m i n i m u m detec-
t i o n limit for Ca has been established as 0.02%, and for a Ca-free quartz sand
containing minor K-feldspar, t h e detectable limit for K is also 0.02%. On the
other hand, in a high-Ca basalt, t h e limit for K b e c o m e s 0.15%. The diag-
nostic geochemical ratio of K/Ca has previously b e e n demonstrated t o b e
measurable w i t h useful accuracy over at least t h e range 0.1—10.0 (Clark and
Baird, 1 9 7 3 a ) . For t h e e l e m e n t Ti, n o interference occurs from the presence
o f large quantities of Fe because t h e F e source d o e s n o t e x c i t e the latter.
5 5

The F e backscatter peak and Ca peak interfere with Ti t o s o m e e x t e n t , b u t


5 5

all analyses for Ti t o date have been well within t h e accuracy desired for
petrologic interpretation. The L lines from Ca d o , however, overlap t h e Ti
emission.
109

Elements 24—30 (Cr to Zn). The e l e m e n t s w i t h a t o m i c n u m b e r 2 4 through


3 0 include Fe ( 2 6 ) , and other geochemically significant e l e m e n t s such as Mn,
Co, Ni, Cu, and Zn. Sensitivity for Fe is quite satisfactory (0.03%) and
limited chiefly b y fluorescence from t h e stainless-steel edges of t h e PC-tube
entrance w i n d o w . D e t e r m i n a t i o n of t h e levels o f other e l e m e n t s in this group
is usually difficult or impossible w i t h t h e X R F S because of t h e interference
b y t h e relatively higher c o n c e n t r a t i o n s o f Fe itself. In a granitic matrix c o n -
taining 2% F e , t h e d e t e c t i o n limits for Ni, Cu, and Zn are roughly 0 . 8 , 0 . 4 ,
and 0.2% respectively.

Elements 31—46 (Ga to Pd). E x c e l l e n t sensitivity for A s , R b , Sr, Zr, M o , and


other e l e m e n t s in this group has b e e n achieved. Under typical c o n d i t i o n s ,
30—60 p p m of these e l e m e n t s can be d e t e c t e d . The trio R u , R h , Pd at t h e
upper end can b e d e t e c t e d less easily because of overlap w i t h t h e C d back-1 0 9

scatter peak.

Elements 47—57 (Ag to La). E l e m e n t s such as Ag, Cd, S n , and Ba have K-


shell absorption thresholds b e y o n d the 2 2 . 2 - k e V Cd
1 0 9
X-ray and t h u s can
b e fluoresced only in t h e L-shell. This is accomplished efficiently b y F e ,
5 5

b u t t h e resultant L-lines ( 2 . 9 8 — 4 . 4 7 k e V ) are generally obscured b y t h e K-


lines from m u c h higher concentrations of K, Ca, and Ti.

Elements 58—75 (Ce to Re). Consisting o f t h e rare earths, and Ta, W, and R e ,
this group of elements also can o n l y be fluoresced in t h e L-shell b y t h e
X R F S sources. In this case, their emissions (4.7—8.7 k e V ) are obscured b y
t h e omnipresent F e signal.

Elements 76—100 (Os to Fm). The L-lines from this group, w h i c h includes
A u , P b , T h , and U fall in t h e high-sensitivity energy range 8.9—16.4 k e V .
Characteristic and diagnostic d o u b l e peaks (L and L^) are produced b y each
a

o f these e l e m e n t s . In s p e c i m e n s free o f interfering concentrations of R b , Sr,


e t c , m i n i m u m d e t e c t i o n limits of 5 0 and 8 0 p p m are indicated for Pb and U ,
respectively.
The above discussion serves t o illustrate t h e capabilities and limitations of
t h e Viking X R F S . Confident identification o f e l e m e n t s through peak anal-
ysis rests, of course, u p o n accurate k n o w l e d g e o f t h e pulse-height spectrum
energy scale. T o determine this scale while t h e X R F S is o n Mars, a number
o f calibration standards, including samples o f t h e e l e m e n t s Al, Ca, and Zn
are built into the instrument.

MARS RESULTS

The Viking-1 Lander successfully t o u c h e d d o w n o n t h e surface of Mars o n


July 2 0 , 1 9 7 6 in t h e region Chryse Planitia. Lander-2 was d e p l o y e d t o t h e
110

surface s o m e 4 4 d a y s later at U t o p i a Planitia, a m o r e northerly site o n t h e


o p p o s i t e side o f t h e planet. With t h e sole e x c e p t i o n of the seismic monitor-
ing instrument o n V i k i n g - 1 , all scientific instruments have operated at or
above e x p e c t e d performance levels and c o m p l e t e d the primary mission
objectives in w h a t has b e e n hailed as t h e m o s t successful planetary explora-
t i o n mission t o date. Interim results for t h e X R F S e x p e r i m e n t have b e e n
published elsewhere (Clark et al., 1 9 7 6 a , b; T o u l m i n et al., 1 9 7 6 ; Baird et al.,
1 9 7 6 ) and can b e summarized as f o l l o w s :
(1) F r o m a geochemical standpoint, the fines ( < 2 - m m size fraction) are
remarkably similar at b o t h lander sites, in spite of a distance of 6 5 0 0 k m
b e t w e e n t h e t w o landing sites (a separation of 1 7 8 ° in longitude and 25° in
latitude).
(2) The fines are predominately c o m p o s e d o f o n e or more silicate minerals
(bulk SiQi = 4 5 ± 5% b y weight w i t h a high c o n t e n t of iron ( F e 0 equivalent
2 3

= 1 9 ± 3%).
(3) Sulfur c o n t e n t is u n e x p e c t e d l y high, approximately 1 0 0 times higher
than t h e average for t h e earth's crust. A duricrust (hardpan) observed b y the
lander cameras contains higher sulfur than t h e l o o s e fines, and m a y be
c e m e n t e d b y a magnesium sulfate salt comprising approximately 10% of t h e
total sample.
(4) Potassium is less than 0.25%, at least five t i m e s lower than t h e average
for t h e earth's crust. If this result is also representative of t h e Mars average
crustal potassium c o n t e n t , t h e n t h e l o w c o n t e n t of A r observed in t h e
4 0

Martian atmosphere m a y reflect the dearth o f source material ( K ) rather 4 0

than a lower degree o f planetary outgassing o n Mars as compared t o t h e


earth.
(5) If an iron o x i d e coating exists over all mineral grains (as proposed b y
s o m e ) , such a coating m u s t be e x t r e m e l y thin ( < 0 . 2 5 / m i ) , or highly discon-
tinuous.
(6) The bulk density o f fines after delivery t o the X R F S is 1 . 1 0 ± 0 . 1 5
g c m " , implying a bulk soil p o r o s i t y of 6 0 ± 15%.
3

ACKNOWLEDGEMENTS

Translating this e x p e r i m e n t c o n c e p t i n t o an engineering reality has largely


d e p e n d e d u p o n superb m a n a g e m e n t b y t w o individuals: A.J. Castro, w h o
directed t h e detailed design and fabrication o f t h e flight instruments, and
W.C. Kelliher, w h o directed its i m p l e m e n t a t i o n o n t h e Viking spacecraft.
T.L. Steinborn made t h e spectral measurements of Figs. 4-4 t o 4-9.

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TT F-14, 9 1 1 ) .
Chapter 5

RADIOACTIVATION METHODS

SAM S. NARGOLWALLA, NOI D. N G U Y E N and AZIZ-UR-REHMAN

INTRODUCTION

In t h e continuing search for energy sources such as gas and oil, test holes
are drilled often d o w n t o m a n y thousands o f feet. Probes or logging t o o l s are
introduced into these holes t o measure properties o f the geological strata
intersected b y t h e m . Recording instruments located o n t h e surface provide a
c o n v e n i e n t m e t h o d of measuring t h e digital or analog responses c o m m u n i -
cated from t h e probe sensor via t h e logging cable. The m o s t c o m m o n
procedure for obtaining drill-hole information pertinent t o t h e c o m p o s i t i o n
of t h e geological matrix involves t h e extraction of drill cores w h i c h are sub-
sequently analysed in t h e laboratory. The analytical data are used t o deter-
mine t h e viability of t h e o r e b o d y in t h e exploration stage, and grade control
in t h e d e v e l o p m e n t stage of mining operations. By and large t h e core extrac-
t i o n t e c h n i q u e c o n s t i t u t e s a major portion o f t h e mineral prospecting and
exploration budget, since it involves t i m e - c o n s u m i n g operations and t h e use
of sophisticated drilling and extraction e q u i p m e n t . The c o s t can be consider-
ably magnified if drilling and core sampling is d o n e at considerable d e p t h .
Inasmuch as t h e drilling of boreholes and extraction of core samples are
fundamental t e c h n i q u e s for exploration o f mineral d e p o s i t s , t h e develop-
m e n t of n e w geological prospecting m e t h o d s , t h e impact of nuclear tech-
niques o n geophysical well logging, advances in electronics, a u t o m a t i o n and
c o m p u t e r reduction of data, and i m p r o v e m e n t s in general mining t e c h n o l o g y
have dictated totally n e w c o n c e p t s for t h e definition of w h a t actually can be
considered t o be a "profitable d e p o s i t " . A graphic d e m o n s t r a t i o n of the
importance of defining a profitable ore d e p o s i t with serious e c o n o m i c over-
t o n e s is given b y Chapman ( 1 9 7 0 ) . Taking a very large low-grade copper
deposit as a test case, Chapman s h o w s that deleterious financial effects can
be experienced, should the c o p p e r eventually recovered from t h e mining
operation be 15—20% l o w e r than that predicted from drill-core analysis data.
Furthermore, the necessity for accurate grade evaluation together w i t h t h e
distribution of metals in t h e total ore mass m u s t also be considered. Wide
variations in t h e grade of t h e feed t o a mill introduces c o m p l e x and costly
undertakings. Perhaps t h e principal cause o f this difficult p r o b l e m lies in t h e
fact that laboratory chemical and instrumental analyses can be confidently
related only t o t h e sample analyzed, and d o n o t necessarily represent t h e
114

"true" in-situ ore distribution, resulting quite o f t e n in serious grade control


problems and tonnage estimation. Since the analytical information is s e l d o m
obtained immediately o n site, costly delays occur in t h e exploration and
d e v e l o p m e n t programs often leading t o t h e drilling of m a n y unnecessary
holes.
Recognizing the disadvantages of existing m e t h o d s for obtaining composi-
tional information, t h e mining c o m m u n i t y has repeatedly expressed a dire
need for totally instrumental and in-situ m e t h o d s for elemental analysis in
boreholes. The availability o f reliable logging data o n a c o n t i n u o u s or
incremental basis o n site w o u l d alleviate m u c h o f t h e c o s t and t h e drilling of
waste drill h o l e s . Such dependable logging techniques w o u l d permit the use
of cheaper percussion or rotary drilling operations at usually a m u c h l o w e r
cost than that for diamond-drilled h o l e s , or other sophisticated drilling
m e t h o d s used t o maintain t h e integrity of t h e core sample.
In contrast t o t h e currently popular core extraction-chemical analysis
process, nuclear m e t h o d s of analysis have t h e potential for in-situ elemental
determinations. D u e t o t h e inherent penetrating characteristics of nuclear
radiation, and d e p e n d i n g u p o n t h e nature o f radiation utilized, these tech-
niques can permit a m o r e realistic evaluation o f the mineral c o n t e n t of a
given deposit.
A t t e m p t s t o utilize basic nuclear physics in well logging were initiated as
early as 1 9 4 0 w h e n t h e natural gamma-ray activity in boreholes was mea-
sured. A classic dissertation o n t h e use of neutrons as a m e t h o d for well
logging was presented b y t h e f a m o u s atomic scientist Bruno Pontecorvo in
S e p t e m b e r o f 1 9 4 1 . A considerable i m p e t u s was also given t o neutron
experiments b y t h e discovery of neutron fission o f t h e uranium nucleus. It
was n o t until 1 9 5 9 that d e v e l o p m e n t o f nuclear techniques as applied t o
petroleum logging was appropriately d o c u m e n t e d b y Caldwell and Mills
( 1 9 5 9 ) , Y o u m a n s and Zimmerman ( 1 9 5 9 ) , and Y o u m a n s e t al. ( 1 9 5 9 ) . With
t h e availability o f l o w - c o s t medium-intensity neutron sources, such as t h o s e
generated from sealed-tube neutron generators, and isotopic and spontane-
o u s fission sources, considerable interest for t h e application of nuclear tech-
niques, such as radioactivation, for t h e characterization of boreholes was
expressed. R e c e n t l y s o m e e x c e l l e n t reviews b y K e y s and B o u l o g n e ( 1 9 6 9 ) ,
and Czubek ( 1 9 7 1 ) discussing t h e general applicability of nuclear techniques
for in-situ borehole analysis demonstrate radioactivation m e t h o d s for the
identification and/or analysis for such elements as H, Be, B, O, F, Na, Mg,
Al, Si, P, CI, Ca, Ti, Cr, Mn, F e , C o , Ni, Cu, Ag, Cd, In, W, and A u .
This chapter a t t e m p t s t o summarize only t h o s e nuclear geophysical
m e t h o d s that can b e classified as radioactivation m e t h o d s . As such, tech-
niques w h i c h provide o n l y lithologic information b y the use of nuclear
scattering reactions are e x c l u d e d . On the other hand, if t h e nuclear scattering
principle is e m p l o y e d for elemental determinations, e.g. gamma-gamma
scattering analysis for lead and zinc, such techniques are classified a m o n g t h e
115

radioactivation t e c h n i q u e s and discussed. A concise description of radio-


activation principles and m e t h o d s as applied t o mineral exploration are
covered in s o m e detail. Comparisons b e t w e e n various radioactivation
m e t h o d s are also drawn. A section o f this chapter is d e v o t e d t o theoretical
c o n c e p t s utilized for t h e evaluation of analytical m e t h o d s for borehole
logging. A listing and description of appropriate radiation sources applicable
t o mineral exploration are presented w i t h a view t o o p t i m i z a t i o n of basic
logging systems for single or multi-element determinations. T o assist the
reader in proper planning of field s y s t e m s , a detailed a c c o u n t o f t h e proper-
ties o f useful neutron and gamma-ray sources is also given.
Application o f radioactivation m e t h o d s as currently practiced and ongoing
research activities form an important part of this chapter. Selected opera-
tions and studies are described in s o m e detail. A critical evaluation of field
data and case histories is also m a d e . Comparisons b e t w e e n radioactivation
m e t h o d s are made in an effort t o present a proper perspective t o t h e state-of-
the-art.
Finally, the impact of radioactivation t e c h n i q u e s o n general mineral
exploration operations is discussed. E x t e n s i o n s t o these t e c h n i q u e s t o n e w
fields of venture such as oceanographic applications are presented.

THEORETICAL CONSIDERATIONS

In general, nuclear m e t h o d s e m p l o y e d for t h e characterization of geolog-


ical samples can be classified under t w o principal groups: (1) t e c h n i q u e s
utilizing gamma-radiation measurements w i t h or w i t h o u t artificial gamma-
ray sources, and ( 2 ) t e c h n i q u e s in w h i c h n e u t r o n sources serve as a basis of
measurement. A discussion of these techniques in terms of their applicability
t o mineral exploration f o l l o w s :

Gamma group

Natural gamma-ray measurement


This process is used for t h e d e t e c t i o n o f g a m m a rays from t h e d e c a y of
natural radioactive e l e m e n t s such as uranium, t h o r i u m and p o t a s s i u m . The
application o f m e t h o d s based o n such emissions is described in Chapter 2 .

Gamma-gamma scattering method


These techniques have b e e n extensively used for t h e determination of
in-place density of geological strata, and w i t h s o m e modifications also
applied t o t h e determination of e l e m e n t s in certain t y p e s of ore deposits.
The principle of this m e t h o d is based o n t h e m e a s u r e m e n t of scattered
gamma radiation from the geologic matrix irradiated w i t h artificial gamma-
ray sources. A schematic view of a typical d o w n h o l e m e a s u r e m e n t s y s t e m is
116

30"

HIGH VOLTAGE SUPPLY CS RADIOACTIVE SOURCE(10m CURIES)


AND /
PRE-AMPLIFIER PLUG IN SODIUM IODIDE /
MODULE SCINTILLATION DETECTOR / SOURCE

HOIST, POWER and


SIGNAL CABLE BUNDLE

DETECTOR SHIELD
(LEAD)

Fig. 5-1. Gamma-gamma backscattering logging system.

s h o w n in Fig. 5 - 1 . In t h e logging t o o l itself, t h e gamma-ray source is


separated from a d e t e c t o r b y a suitable shield. As a result o f photoelectric
absorption and C o m p t o n scattering events in t h e matrix, a spectrum of
gamma-ray energies is measured b y the d e t e c t o r . T w o main factors influence
t h e probe (or s o n d e ) response. T h e s e are: ( 1 ) t h e in-place density of t h e scat-
tering m e d i u m , and (2) t h e effective or equivalent a t o m i c number of the
scattering matrix. According t o Czubek ( 1 9 7 1 ) , t h e equivalent a t o m i c n u m -
ber, Z , can be c o m p u t e d w i t h g o o d results for gamma-energy measure-
e q

m e n t s above t h e K-edge, from t h e formula:

(1)

where P is the weight fraction of an e l e m e n t of a t o m i c weight, A


t and
i9

a t o m i c n u m b e r , Z . E x c e p t for t h e restrictive case o f an ore containing a


t

heavy e l e m e n t where o n e c a n n o t establish a discrete value for Z , for t h e


e q

entire p h o t o n energy spectrum, t h e above formula d o e s provide satisfactory


results. A simple graph (Fig. 5-2), abstracted from Czubek's ( 1 9 7 1 ) review,
illustrates four spectra for t w o different bulk densities and for t w o different
Z . These spectra result from t h e C o m p t o n scattering and photoelectric
e q

absorption o f a m o n o e n e r g e t i c gamma-ray e x c i t a t i o n source. As can be seen,


t w o distinct regions occur. In o n e energy region ( > 2 0 0 k e V ) t h e t w o differ-
117
LOGARITHM OF SPECTRAL PHOTON INTENSITY

Z
eql .
Region of bulk-density
measurement

/ Z
e q 2 \ J
Z
eq 1 < Z
eq 2
/ /'""\'»
Pl< ?2

// Zeql
1 \ - ? l
,
f \ »
/ eq 2 \
Z
!

/
// N
1

/
;

/ Region of j
i
/ the selective ] \ !
gamma-gamma J NJ
IE =200keV'
measurements j p |

E
P
ENERGY
Fig. 5-2. Scattered gamma-ray spectra as a function of the density and chemical composi-
tion of the medium (Czubek, 1 9 7 1 ) .

e n t densities can b e clearly separated. In this region t h e gamma-gamma


density m e t h o d is applied. In t h e energy region b e l o w 2 0 0 k e V t h e total
response is influenced b y b o t h t h e density and chemical c o m p o s i t i o n of t h e
geological matrix. This region is used for t h e selective gamma-gamma
m e t h o d , usually referred t o as t h e X-ray fluorescence m e t h o d . E x c e p t for a
very limited n u m b e r o f applications, d e n s i t y logging c a n n o t b e easily applied
for the d e t e r m i n a t i o n o f discrete e l e m e n t s , and is mainly e m p l o y e d in oil,
gas and coal e x p l o r a t i o n . On t h e other hand, selective gamma-gamma logging
is applied t o elemental determinations. H o w e v e r , its application till n o w is
principally restricted t o t w o - c o m p o n e n t s y s t e m s .
In selective gamma-gamma logging, a very low-energy gamma-ray excita-
t i o n source is used. T h e i s o t o p e s S e (E = 0 . 2 6 4 5 , 0 . 1 3 5 9 M e V , T = 120 7 5
y 1 / 2

days), T m (E = 0 . 0 8 4 2 6 M e V , T1 7 0
= 1 2 7 d a y s ) and
y H g (E = 0 . 2 7 9 1 7 1 / 2
2 0 3
y

MeV, T = 4 6 . 5 9 days) are o f t e n used. These energies are photoelectrically


l/2

absorbed in t h e rock matrix t o yield low-energy g a m m a responses in t h e


d e t e c t o r . Since t h e p h o t o e l e c t r i c effect varies rapidly w i t h t h e a t o m i c n u m b e r
of the absorber, a differentiation can be m a d e . T h e m e t h o d is generally
applied t o t h e d e t e r m i n a t i o n of heavy e l e m e n t s such as Hg, P b , Bi, Sb and Ba
118

in h o s t rock of a reasonably c o n s t a n t density. Because of the very l o w energy


of the measured radiation, t h e b o r e h o l e s have t o be relatively s m o o t h and
w i t h o u t t h e presence of drilling m u d . In reality, it is essentially a surface
analytical m e t h o d .
As m e n t i o n e d earlier, d e n s i t y logging in s o m e cases can be related t o the
elemental abundance. D o n h o f f e r ( 1 9 6 8 ) , in his concise description o f the
determination of zinc in a lead-zinc deposit, s h o w s h o w this effect can be
used for zinc determinations. His detailed study is w o r t h y o f further discus-
sion. In this s t u d y , t h e principal interaction events measured are gamma
energies b e t w e e n 0.3—2 M e V from C o m p t o n scattering in the matrix. Since
for medium-Z elements b e t w e e n Z = 1 0 and 3 0 , the macroscopic scattering
cross-section is directly proportional t o the density of t h e m e d i u m and t h e
ratio Z\A is approximately c o n s t a n t , t h e macroscopic scattering cross-section
is therefore a direct function of d e n s i t y . Thus a determination of density
permits a direct relationship w i t h t h e elemental c o n t e n t o f t h e m e d i u m .
Furthermore, the influence of t h e photoelectric effect, which varies as the
fifth p o w e r o f Z, is n o t significant if l o w ore concentrations are considered.
The probe response as a function of source strength, source-detector distance,
density and chemical c o m p o s i t i o n of t h e matrix can be theoretically cal-
culated using the p h o t o n transport t h e o r y as given b y Tittman and Wahl
( 1 9 6 5 ) . A n approximation t o the solution of the differential equation for a
cylindrical s y s t e m is in g o o d agreement with t h e semi-empirical formula:

/ = Ap exp(—jupd) (2)
as given b y Bulashevich et al. ( 1 9 6 2 ) , where p is t h e d e n s i t y , /x t h e mass
absorption coefficient of t h e m e d i u m , d t h e source-detector distance, and A
is a proportionality factor w h i c h includes t h e source strength and the g e o m -
etry. D o n h o f f e r has evaluated this formula t o obtain Fig. 5-3 for t h e entire
density range, and for a s o n d e using a C s irradiation source separated from
1 3 7

a d e t e c t o r b y 3 0 c m . For t h e density range o f interest, i.e. b e t w e e n 2 . 5 and


4 . 0 g c m " , an increase in density results in a corresponding decrease in the
3

probe response, thereby providing a means for density determinations. Thus,


assuming a t w o - c o m p o n e n t s y s t e m , a simple relation b e t w e e n t h e in-place
density and the c o n c e n t r a t i o n o f o n e c o m p o n e n t can be established. This
calibration curve can be used for estimating t h e e l e m e n t of interest in a
similar geologic matrix from gamma-ray backscattered intensity measure-
ments.

Resonance gamma method


Essentially this m e t h o d is an e x t e n s i o n of the Mossbauer effect as applied
t o t h e field. In a discussion of the advantages for mineral exploration,
S o w e r b y ( 1 9 7 3 ) has given an exhaustive description of this t e c h n i q u e and
suggested s o m e possible applications for mineral exploration. The resonance
scattering m e t h o d s e m p l o y the use of a radioactive nuclide decaying b y
119

0.15

p exp(-^ipd)
for ^ - 0 . 0 7 77 cm /g
2

d«30 cm
INTENSITY (I )

5
o
g
o

0 1.0 2.0 3.0 4.0


DENSITY (g/cm ) 3

Fig. 5-3. Dependence of the intensity of scattered radiation on the density of surrounding
material (Donhoffer, 1 9 6 8 ) .

gamma emission through a stable i s o t o p e o f t h e e l e m e n t o f interest. This


gamma radiation is scattered from like nuclei in t h e matrix. The recoil
energy loss is c o m p e n s a t e d b y imparting m o t i o n t o nuclei of t h e primary
gamma source. Several m e t h o d s for providing this c o m p e n s a t i n g m o t i o n have
been used. It is d o n e either mechanically, thermally or b y utilizing the
recoil energy following radioactive d e c a y . The reader is directed t o Sower-
by's dissertation for additional information regarding this t e c h n i q u e .
Application of this t e c h n i q u e requires a careful selection of parameters for
its success in t h e field. In t h e writers' o p i n i o n a viable field application of
this technique that will c o m p e t e w i t h existing exploration m e t h o d s , b o t h in
e c o n o m i c s and analytical accuracies, appears t o b e still in t h e future. H o w -
ever, this m e t h o d e x p l o i t s a rather unique approach t o elemental analysis
and under certain controlled c o n d i t i o n s , such as t h o s e existing in mineral
processing plants, its application for on-stream m o n i t o r i n g of geological
materials definitely s h o w s promise.

Photonuclear methods
This m e t h o d has limited application and is almost exclusively used for t h e
exploration of t h e e l e m e n t beryllium. If stable high-energy g a m m a e x c i t a t i o n
sources were available, additional e l e m e n t s w o u l d be amenable t o this tech-
nique. Berzin et al. ( 1 9 6 6 ) , have described s o m e of t h e basic principles
governing this t e c h n i q u e . When a l o w activation threshold e l e m e n t for
incident gamma radiation is irradiated by gamma rays of energies higher than
t h e threshold, t h e ( 7 , n) reaction takes place. A measurement of t h e e m i t t e d
neutrons can then be related t o t h e elemental c o m p o s i t i o n . In general, t h e
120

p h o t o n e u t r o n threshold for m o s t e l e m e n t s is in excess of 6 M e V , an energy


n o t available from t h e highest gamma-emitting artificial radioisotope. T h e
d e v e l o p m e n t of exploratory t o o l s capable of generating g a m m a energies of
this order for d o w n h o l e applications is m o s t difficult. If e c o n o m i c s and
other mechanical factors, such as speed and ease of operation, are c o n c e r n e d ,
this technique for e l e m e n t s other than beryllium b e c o m e s overly cumber-
s o m e and c o s t l y . The e l e m e n t beryllium differs from all other elements in
t h e fact that t h e threshold energy for interaction w i t h g a m m a radiation is
e x t r e m e l y l o w , i.e. 1.67 M e V . Therefore, artificial radioisotope sources such
as N a and
2 4 1 2 4
S b can be used t o induce t h e ( 7 , n ) reaction w i t h beryllium
nuclei. In particular, t h e i s o t o p e 1 2 4
S b has been extensively used for this
purpose. This i s o t o p e e m i t s g a m m a energies of 1.69 MeV (46%) and 2 . 0 9
MeV (7%). T h e average energy of p h o t o n e u t r o n s e m i t t e d from this interac-
tion is of the order o f 0 . 0 2 4 MeV. Since t h e activation cross-section for t h e
( 7 , n) reaction is a b o u t 1.5 mbarns at 1.7 M e V incident g a m m a energy, an
acceptable sensitivity for t h e determination of this e l e m e n t results. The
p h o t o n e u t r o n s e m i t t e d are c o u n t e d b y B - e n r i c h e d B F counters or scintilla-
10
3

t i o n counters. It is estimated that using a source strength of a b o u t 2 0 — 1 5 0


mCi of 1 2 4
S b , beryllium in beryllium-bearing strata, can be determined at
levels o f a f e w hundredths o f a percent.

Neutron group

This group includes t e c h n i q u e s w h i c h perhaps have been m o s t e x p l o i t e d


for geological e x p l o r a t i o n . A s s u c h , t h e theoretical treatment of the
fundamentals involved will b e fairly thorough so that t h e reader m a y have an
adequate basis for assessing t h e application o f o n e or more of t h e techniques
discussed herein. The specific m e t h o d s within t h e s c o p e of this chapter are:
( 1 ) fast neutron activation, ( 2 ) fast neutron inelastic scatter, ( 3 ) resonance
neutron activation, ( 4 ) thermal neutron activation, ( 5 ) thermal neutron
capture, and ( 6 ) delayed fission neutron c o u n t i n g . M e t h o d s related t o t h e
determination of radiation life-times, such as die-away e x p e r i m e n t s , are n o t
included since t h e y are generally used t o obtain gross lithological informa-
t i o n rather than t o specifically determine elements of interest. In the
broadest terms, all of t h e above m e t h o d s can be generally classified as
n e u t r o n activation analysis and as s u c h , t h e t h e o r y o f activating particles o n
nuclei t o obtain radioactive and detectable products is applied. Several t e x t s
dealing w i t h these fundamentals have been written b y K o c h ( 1 9 6 0 ) , B o w e n
and G i b b o n s ( 1 9 6 3 ) , L y o n ( 1 9 6 4 ) , Taylor ( 1 9 6 4 ) , Lenihan and T h o m s o n
( 1 9 6 5 ) , Kruger ( 1 9 7 1 ) , D e S o e t e et al. ( 1 9 7 2 ) , and Nargolwalla and Przyby-
lowicz ( 1 9 7 3 ) ; and t h e reader is referred t o these for this information.
Suffice it t o m e n t i o n t h a t t h e activity induced in a nuclide, B, can b e
expressed as a function o f t h e operational parameters of t h e t e c h n i q u e in t h e
121

f o l l o w i n g manner:

A = DCN o (j>
B B (3)

where
A = the measured c o u n t rate at t i m e t ( c o u n t s s" )
d
1

D = t h e branching ratio o f t h e emission t o b e measured


C = t h e d e t e c t i o n efficiency of t h e c o u n t i n g assembly
N =B t h e n u m b e r o f target nuclei of t h e b o m b a r d e d e l e m e n t B
a =B t h e activation cross-section of t h e specific reaction w i t h e l e m e n t , B,
at t h e incident particle energy ( c m ) 2

0 = t h e particle flux o f c o n s t a n t energy and intensity (particles c m " s" )


2 1

^ = irradiation t i m e
td = d e c a y t i m e from t h e termination of irradiation t o start o f c o u n t
T = t h e half-life of t h e p r o d u c t nuclide.
m

In practice t h e factors, C, o and 0 are n o t specifically evaluated and a


B

simple comparative m e t h o d is used. In this approach a sample and a standard


are simultaneously irradiated, and t h e e l e m e n t , B, in t h e u n k n o w n sample is
determined b y comparing its radioactivity w i t h that generated in t h e same
e l e m e n t in t h e standard. The simple relation:

[Weight B ] ^ ^ 0 ^ = [weight B] (4)

is u s e d .
The five principal neutron-nuclei interactions w h i c h are c o m m o n l y used
for t h e quantitative evaluation o f e l e m e n t s are described b e l o w .

Radiative capture (n,y)


A nucleus w h i c h captures a neutron p r o d u c e s g a m m a rays instantaneously
from t h e d e - e x c i t a t i o n of certain e x c i t e d energy levels in t h e resulting
c o m p o u n d nucleus. This reaction occurs at a significant rate o n l y w i t h
thermal and epithermal neutrons for m o s t e l e m e n t s that comprise rock or
ore d e p o s i t s . T h e g a m m a transition energies of interest w h i c h are m o s t
important from t h e aspect of spectral identification are high (2—10 M e V ) . It
is t h e c o m p l e x i t y and t h e lesser range of t h e lower-energy capture g a m m a
rays that have so far m a d e t h e m n o t useful in t h e p r o m p t gamma-ray tech-
nique. The identifying transitions for m a n y base metals m a y b e distinguished
from t h o s e from c o m m o n rock b y t h e fact that t h e y occur within t h e energy
range of 6—10 M e V .

Activation process (n, y)


Most of t h e nuclei formed b y (n, 7 ) reactions are unstable and subsequent-
ly undergo radioactive d e c a y w i t h a characteristic half-life. The g a m m a rays
e m i t t e d during d e c a y are nearly all b e l o w 2 MeV in energy. B o t h the
122

characteristic g a m m a emissions and t h e half-life m a y be used for their


unambiguous analysis.

Inelastic scattering (n, riy)


This reaction is important o n l y for incident neutron energies above 2 MeV;
t h e threshold for m o s t e l e m e n t s being higher than this energy. T h e nucleus
involved in t h e collision process is left in an e x c i t e d state and i m m e d i a t e l y
returns t o t h e ground state w i t h the emission of a neutron and gamma rays.
In s o m e favourable c o n d i t i o n s there is a significant cross-section for an iden-
tifying transition.

Particle reactions (n, 2n), (n, oc) (n, p) y

These t y p e s o f reactions are initiated b y high-energy n e u t r o n s o n l y . Ele-


mental identification m a y be accomplished b y examining t h e characteristic
gamma radiation p r o d u c e d in t h e subsequent d e c a y of the product radio-
nuclide.

Delayed neutron counting


This t e c h n i q u e has b e e n recently adapted for t h e borehole exploration of
fissionable i s o t o p e s occurring naturally, i.e. i s o t o p e s o f uranium and thorium.
Of all fissions in U b y thermal n e u t r o n b o m b a r d m e n t a b o u t 9 9 . 3 6 % yield
2 3 5

fission neutrons within 1 0 " s e c o n d and are called p r o m p t neutrons. In the


1 2

0.64% of the fission events, a limited n u m b e r ( ~ 9 ) o f radioactive fission


products w i t h short half-life (1—55 s e c o n d s ) , d e c a y b y beta emission. S o m e
of t h e m h o w e v e r leave a p r o d u c t nucleus with energy in excess of its neutron
separation energy. In these cases neutrons are e m i t t e d w i t h half-life c o m -
parable t o t h e preceding b e t a d e c a y s . These n e u t r o n s form d e l a y e d neutron
groups. A m e a s u r e m e n t o f such n e u t r o n energy groups offers a unique
m e t h o d for t h e exploration for U . The longest-lived delayed neutron
2 3 5

emitter, t h e 5 5 . 6 - s e c o n d B r provides n e u t r o n energies o f a b o u t 0 . 3 MeV.


8 7

The basic principle involves irradiation of t h e geological matrix with a fast


neutron isotopic or accelerator source f o l l o w e d b y a measurement of the
delayed n e u t r o n emission b y a d e t e c t o r separated from t h e irradiation source
by a suitable spacer.
In borehole logging for minerals, t h e measurement t o o l generally consists
of a suitable isotopic (e.g. A m - B e ) or fission (e.g. C f ) neutron source of
2 4 1 2 5 2

s o m e acceptable o u t p u t separated from a gamma-ray d e t e c t o r , such as a


N a l ( T l ) scintillator or Ge(Li) solid state assembly, b y a l o w n e u t r o n capture-
high gamma-ray attenuating shield. This shield protects t h e d e t e c t o r and
associated electronics from direct n e u t r o n and gamma-ray e x p o s u r e from t h e
primary n e u t r o n source. The matrix solid angle s u b t e n d e d at t h e d e t e c t o r
d e p e n d s u p o n such mechanical parameters such as t h e source-detector
distance and t h e ratio of t h e shield and d e t e c t o r diameters. If these param-
eters are carefully selected, and if t h e materials used for t h e construction of
123

t h e s o n d e are optimally c h o s e n for their unfavourable nuclear activation


characteristics, t h e n t h e s o n d e itself will behave as a quantitative t o o l for t h e
measurement o f t h e activated geological matrix.
Ideally, in any nuclear activation m e t h o d , t h e m e a s u r e m e n t of character-
istic gamma rays can be directly related t o t h e elemental c o m p o s i t i o n . This
situation is o n l y true if such parameters as t h e neutron flux distribution at
effective l o c a t i o n s in t h e matrix, t h e neutron flux absorption in t h e matrix,
t h e bulk density o f t h e matrix and its moisture c o n t e n t , and t h e e x t e n t o f
h e t e r o g e n e i t y of t h e e l e m e n t in t h e matrix, are assumed t o be constant. In
practice, however, all of t h e above parameters are subject t o variation, and
their effect o n t h e sensitivity of a given e l e m e n t irradiated w i t h a c o n s t a n t
o u t p u t neutron source w i t h respect t o s o m e fixed source-detector g e o m e t r y ,
can be severe. T o understand t h e effect of these environmental c o n d i t i o n s o n
t h e sensitivity, s o m e t h o u g h t is given t o w a r d a study of neutron and gamma-
ray transport in a geological m e d i u m irradiated w i t h neutrons. F o r reasons of
simplicity, t h e interposing d e t e c t o r shadow-shield has b e e n r e m o v e d from
theoretical m o d e l s t o be described. Furthermore, o n l y a d e t e c t o r and a
source have been considered w i t h o u t regard t o perturbations w h i c h m a y
result from t h e presence o f other materials w h i c h comprise t h e probe
housing, e t c .

Neutron-gamma transport

In t h e s t u d y of neutron-gamma b o r e h o l e logging, t h e calculation o f t h e


n e u t r o n flux (created b y t h e radioisotopic n e u t r o n source) in b o t h t h e
borehole and the matrix is very important in t h e e s t i m a t i o n o f t h e total
gammas p r o d u c e d in the matrix and measured b y t h e d e t e c t o r . Moreover,
t h e calculated n e u t r o n and gamma-ray fluxes have b e e n used in t h e optimiza-
t i o n o f t h e experimental design parameters such as t h e size and configuration
of t h e neutron-source/gamma-ray d e t e c t o r probe and t h e o p t i m u m experi-
mental b o r e h o l e size.
Using any of t h e fundamental theories such as diffusion, transport, or
Monte Carlo, t h e n e u t r o n flux distribution can be o b t a i n e d . T o determine
thermal n e u t r o n flux distribution in a b o r e h o l e , three approaches can b e
considered. The first approach (Glasstone and E d l u n d , 1 9 5 2 ) assumes a
p o i n t thermal n e u t r o n source of unit strength located in an infinite m e d i u m
o f silica. T h e s e c o n d approach (Glasstone and E d l u n d , 1 9 5 2 ) assumes a fast
n e u t r o n p o i n t source of 5-MeV energy w h i c h are s l o w e d d o w n according t o
Fermi t h e o r y t o thermal energy. The third approach, as described b e l o w ,
gives a more realistic representation of the source-detector arrangement in
t h e b o r e h o l e logging environment. This approach provides adequately
acceptable e s t i m a t i o n of analytical parameters used in t h e prediction of
experimental measurements. Using t h e two-group and two-region neutron
diffusion t h e o r y t o take i n t o a c c o u n t t h e b o r e h o l e diameter effects and t h e
124

source-detector distance, t h e thermal and fast n e u t r o n fluxes can be calcu-


lated. After the thermal neutron flux in t h e matrix is determined, b o t h t h e
gamma p r o d u c t i o n rate and t h e p r o m p t or delayed gammas returning t o t h e
d e t e c t o r can be c o m p u t e d .
N e u t r o n diffusion t h e o r y in its m o s t fundamental form assumes a thermal
n e u t r o n p o i n t source, and a single energy group. In t h e multi-group diffusion
t h e o r y , a fast neutron p o i n t source is assumed and the neutrons are slowed
d o w n t o thermal energies. In t h e fast energy region, t h e neutrons are clas-
sified into several energy groups depending u p o n t h e sophistication and
accuracy of t h e results desired. It is f o u n d b y Allen e t al. ( 1 9 6 7 ) that t h e
assumption of a single fast group and a thermal group (two-group diffusion
t h e o r y ) , furnishes accuracies comparable t o the e x p e c t e d precision of t h e
analytical measurements.

One-group diffusion theory


Tittle ( 1 9 6 1 ) used one-group neutron diffusion t h e o r y t o study t h e slow-
ing d o w n of neutrons from a fast neutron p o i n t source centered in an infi-
nite c o n t i n u o u s m e d i u m , for a single cylinder, and for concentric cylinders
representing a fluid-filled borehole and t h e surrounding formation. N e u t r o n s ,
while diffusing through the media, are b o t h absorbed and scattered b y t h e
matrix.
The one-group neutron balance differential equation in a s y s t e m described
b y Tittle ( 1 9 6 1 ) is:

fl.V<.-£ + S -*J ,5)

where 0 = neutron flux (n c m s" ); X = absorption mean free path ( c m ) ;


- 2 1
a

D = diffusion coefficient ( c m ) ; S = source term (n c m " s " ) ; n = neutron


3 1

density (n c m " ) ; and t = t i m e (s). In t h e case of a p o i n t source w i t h spherical


3

g e o m e t r y , t h e n e u t r o n flux, 0, is related t o t h e neutron density and t h e neu-


tron speed, u b y :
9

<p = nv (6)

w h i c h is also o f t e n referred t o as t h e flux density or fluence rate.


In a steady-state s y s t e m , where the changes in neutron density are
assumed t o be zero, and since S is a p o i n t source, it is zero everywhere
e x c e p t at the origin; therefore S = 0 in equation ( 5 ) . The equation for t h e
epithermal n e u t r o n flux at all different p o i n t s in t h e c o n t i n u o u s m e d i u m is
then:

(7,

Since t h e diffusion length, L, is defined as:

L = VKfi (8)
125

equation ( 7 ) reduces t o :

V 2 0 _ 0 _ = o ( )
9

L 2

Since Tittle ( 1 9 6 1 ) applied one-group diffusion t h e o r y in t h e slowing


d o w n region, he assumed t h e s l o w i n g - d o w n length, L , analogous t o L, o w i n g
s

t o t h e fact t h a t t h e n u m b e r o f n e u t r o n s r e m o v e d b y s l o w i n g d o w n is equiva-
lent t o that b y absorption. H e n c e e q u a t i o n ( 9 ) is rewritten as:

V </.-i-=0
2
(10)
L 2

The slowing-down length, L , m a y be best obtained from t h e experimentally


s

derived relation from Feld ( 1 9 5 3 ) :

6L s
2
= r = 2

(ii)

where r is t h e mean square distance of t h e slowing d o w n distribution. The


2

integrals are evaluated numerically from experimental data.


The solution o f e q u a t i o n ( 1 0 ) for a p o i n t source in infinite m e d i u m is
reported b y Glasstone and Edlund ( 1 9 5 2 ) and Feld ( 1 9 5 3 ) as f o l l o w s :

where t h e epithermal flux, 0, is related b y Hughes ( 1 9 5 3 ) t o t h e slowing-


d o w n d e n s i t y , q, b y :

q = W\ s (13)

D = L, 2
*A. (14)

The relation, D = Z/s£/X , is n e e d e d b y t h e normalization c o n d i t i o n that t h e


s

total n u m b e r o f neutrons in t h e m e d i u m , s l o w e d d o w n through the epi-


thermal energy, E, per s e c o n d , m u s t equal t h e source strength, Q, since n o n e
o f these neutrons are assumed lost through absorption. In e q u a t i o n s ( 1 2 ) and
( 1 3 ) , £ and X are evaluated at t h e final epithermal energy, E.
s

Tittle ( 1 9 6 1 ) c o m p a r e d t h e results from e q u a t i o n ( 1 2 ) w i t h t h e experi-


mental values and t h e age t h e o r y , in Fig. 5-4. Curve A is t h e prediction o f
equation ( 1 2 ) and the experimental p o i n t s obtained b y measurements in a
large water tank b y the use of a Ra-Be n e u t r o n source and epithermal
neutron d e t e c t o r s , i.e. cadmium-covered indium foils. The source strength, g,
126
_
0, n/cm sec. U
2

r, cm

Fig. 5-4. Comparison of diffusion and age theories with experiment. The neutron source
is 3 0 0 mCi of Ra-Be. Experimental points are based on measurements of the indium
resonance neutron flux at 1.45 eV by Dacey et al. ( 1 9 4 9 ) . Curve A: one-group diffusion
theory with L = 6.8 cm, £ / A = 1.41 c m " . Curve B: age theory, using same values of L ,
s s
1
s

and £ / A . In the unit for epithermal neutron flux n c m


s s" U the symbol U stands for
- 2 1
t

the neutron lethargy (In E /E ). It is t o be interpreted as "per unit lethargy interval'' in


0

the specification of the unit of flux (Tittle, 1 9 6 1 ) .

was 4 . 5 X 1 0 n s ~ \ L was 6 . 8 c m , and £/X = 1 . 4 1 . Curve B is t h e prediction


6
s s

o f t h e age t h e o r y (Glasstone and Edlund, 1 9 5 2 ) . A g r e e m e n t w i t h experimental


results is p o o r because of t h e large h y d r o g e n c o n t e n t of water. However,
there seems t o be g o o d agreement b e t w e e n e x p e r i m e n t and t h e diffusion
t h e o r y , e x c e p t at p o s i t i o n s near t h e source.
Encouraged b y these results, Tittle ( 1 9 6 1 ) applied this approach t o a
cylindrical region and also t o t w o concentric cylinders. For an infinite
cylindrical m e d i u m and assuming t h e c o n d i t i o n o f g e o m e t r y , t h e neutron
balance equation [ e q u a t i o n ( 1 0 ) ] in cylindrical co-ordinates (r, z) can b e
written as:

(15)
127

The solution of e q u a t i o n ( 1 5 ) is:

0(r, z) = AJ (Cr) 0 exp(-Fz)

where A, C and F are constants and F = ( C + L ~ ) 2 2 1 / 2


.
Then:

0 (r, 2 ) = A J ( C „ r ) e x p ( - F * )
n n 0 n (16)

where t h e subscript n is introduced because there are several values of C,


which will satisfy e q u a t i o n ( 1 6 ) and each value of C has a particular value of
F, A and 0. The general s o l u t i o n of e q u a t i o n ( 1 5 ) will b e :

0 = £ 0„ = £ A </ (<V) e x p ( - F „ 2 )
n 0 (17)

where:

(18)

and:

(19)

in which x are t h e values at w h i c h J = 0 periodically.


n 0

The c o m p l e t e s o l u t i o n t o calculate t h e epithermal n e u t r o n flux in a


cylinder b y one-group diffusion t h e o r y is given b y :

(20)

where:

1/2
(21)

The flux e q u a t i o n ( 2 0 ) neglects t h e effect of t h e b o r e h o l e . The applica-


tion of one-group t h e o r y t o t h e concentric cylinders is o m i t t e d in favour of
t h e two-group diffusion t h e o r y t o f o l l o w .

Two-group, two-region diffusion theory


Glauberman and Talianskyi ( 1 9 5 8 ) and Kulinkovich ( 1 9 6 5 ) used t h e t w o -
group, two-region diffusion t h e o r y t o calculate thermal and fast n e u t r o n fluxes
in t h e borehole and t h e surrounding f o r m a t i o n . Their expressions for t h e
neutron fluxes are in t h e form of infinite integrals and, therefore, rather
tedious t o work w i t h . Their approach is similar t o that used b y Allen et al.
( 1 9 6 7 ) . Allen et al. using t h e t w o - g r o u p , two-region diffusion t h e o r y have
128

Borehole Axis

Region A ^
(Borehole)
»—Detector

Region B
(Matrix)
•— Neutron
Source

o
a
4
w

-
Fig. 5-5. Theoretical model for neutron flux calculations (Nargolwalla et al., 1 9 7 3 ) .

derived an expression for t h e thermal n e u t r o n flux in t h e borehole o n l y .


Their expression for t h e n e u t r o n flux is in t h e form o f an infinite series and
is easily adapted for c o m p u t e r calculations.
Nargolwalla et al. ( 1 9 7 3 ) e x t e n d e d t h e m e t h o d used b y Allen et al. ( 1 9 6 7 )
t o derive expressions for thermal and fast n e u t r o n fluxes in t h e borehole as
well as in t h e surrounding matrix.
Assume a p o i n t n e u t r o n source, S (i.e. 2 5 2
C f w i t h an average neutron
energy o f 2—3 M e V ) , o f strength Q ( 1 0 n s" ) is placed at t h e origin o f t h e
6 1

r-z coordinate a x e s , w h i c h is at t h e center o f t w o concentric cylinders of


radii a, and b (Fig. 5-5). A p o i n t d e t e c t o r , D, is l o c a t e d at a distance z
directly above t h e source, S. The t w o concentric cylinders, representing the
borehole of radius a, and t h e effective irradiated matrix region of radius 6,
contain 2 different media, i.e. water and t h e matrix ( S i 0 ) , respectively. The
2

height o f t h e cylinders is assumed t o be 2ft. It is further assumed that t h e


flux in t h e axial direction is symmetrical.
The neutron balance e q u a t i o n s , as s h o w n b y Glasstone and Edlund
( 1 9 5 2 ) , in t h e t w o regions, for fast and thermal n e u t r o n s , are expressed as
129

follows:

D S/ <t> (r,z)-<l> (r,z)X +S(r,z)


1A
2
1A 1A 1A = 0, 0 < r < a (22)

D A^ 4>2A(r z)-if> (r,z)


2
2
t iA 2 M +<t>i (r,z)
A 2 1 A = 0, 0 < r < a (23)

^IBV 0 2
1 B (V,2)-0i (R,2)2 B 1 B =0 , a < r < 6 (24)

D BV <l>2B( ,z)-<t>2B(r,z)
2
2 r
2 B 2
+
=0, a< r< 6 (25)

where
S(r, z) = S'5(r) 8 ( 2 ) , where 5(r) and 8 ( 2 ) are Dirac delta f u n c t i o n s
S f
= t h e rate o f n e u t r o n d e n s i t y p r o d u c t i o n (n c m s" ) - 3 1

D = diffusion coefficient ( c m )
0 = neutron flux (n c m " s" ) 2 1

1 d e n o t e s fast n e u t r o n s
2 d e n o t e s thermal n e u t r o n s
V 2
= Laplacian operator
21 = m a c r o s c o p i c removal cross-section for neutrons from fast to
thermal energy
2 2 = macroscopic thermal absorption cross-section,
can be readily calculated f r o m :
_pN o 0 i

in which p = t h e density of t h e material (g c m " ) , N = Avogadro's n u m b e r 3


0

( 6 . 0 2 3 X 1 0 a t o m s / g - a t o m ) , A = a t o m i c w e i g h t ( g / g - a t o m ) , and o = cross-
2 3
0 t

s e c t i o n of e l e m e n t i ( c m ) ; A d e n o t e s b o r e h o l e region containing water, and


2

jB, effective irradiated matrix region containing S i 0 . 2

T h e analytical solutions o f equations ( 2 2 ) t o ( 2 5 ) , from Tittle and Allen


( 1 9 6 6 ) , are as f o l l o w s :

I (a r)
0 n eos(A z) n (26)

•Jo(0„r) cos(X„r) (27)


130

<PIB = S G K (y r)
n 0 n cos(A„z) (28)
n

02B = S L K (8 r)
n 0 n cos(A„z) + S 0 3 1 B (29)
n

where:

S 3 = s ••4

LIB = [£WZ 1 B p/2 ; L 2 B = [Z) 2 B /2 2 B ]i/2

7* = [XJ ^ r i J 1 / 2
; a n = [ A 2 + L r i ] 1 / 2

n = l , 3, t>,...

and:

=- / ( 0 a ) - K tf a)
o n 0 n + (1 - P ) K ( „ a ) 0 7

in w h i c h :

R = D 8 aK (5 a)
2B n 1 n K (y a)
0 n + K (p a)0 n - K (a a)
0 n

- ( g * ) / ( a „ a ) ] -K (8 a)
0 0 n i D ^ a P ^ K ^ ^ )

D 2A ^aK^a) - a ^ K ^ a ) - /^a)}] ]
131

P =

The values for 0 1 A 0 2 A > a n


in e q u a t i o n s ( 2 6 ) t o ( 2 9 ) can be
d

solved b y c o m p u t e r . &ome parameters, such as t h e thermal diffusion coef-


ficient, D , the fast diffusion coefficient, D t h e slowing d o w n length, L ,
2 u s

and the diffusion length, L , are given b y Glasstone and Sesonske ( 1 9 6 3 —


fast group parameters for water); A N L - 5 8 0 0 (thermal group parameters c o m -
piled b y Argonne National Laboratory, 1 9 6 3 ) ; and B N L - 3 2 5 (the scattering
cross-section for silicon for t h e fast group is averaged over t h e energy range
o f interest from the cross-section energy curve reported b y Hughes and
Schwartz, 1 9 5 8 ) .
The c o m p u t e r program F L U X was used b y Nargolwalla et al. ( 1 9 7 3 ) t o
calculate t h e flux distribution in a simulated b o r e h o l e in t h e laboratory.
This c o m p u t e r program for solving equations ( 2 6 ) t o ( 2 9 ) was written in a
manner such that t h e convergence occurred w h e n three consecutive terms in
t h e series did n o t differ from each other b y a fraction greater than 1 0 " . 6

Theoretical model for prompt gamma rays returning to the detector


Once t h e thermal neutron flux 0 2 B ( > ) from e q u a t i o n ( 2 9 ) in t h e matrix
r
z

is evaluated, the g a m m a p r o d u c t i o n rate, P , can be easily d e t e r m i n e d .


7

Gamma transport — one region. Assuming that each n e u t r o n absorbed in t h e


matrix nuclei produces a single p r o m p t g a m m a p h o t o n o f a specific energy,
t h e n , from Fig. 5-6, t h e g a m m a flux, P , returning t o t h e p o i n t d e t e c t o r can
T

be determined b y :

(30)

z =0 plant

Fig. 5-6. Theoretical model for one-region gamma transport (Nargolwalla et al., 1 9 7 3 ) .
132

z = 0 plane

Fig. 5-7. Theoretical model for two-region gamma transport (Nargolwalla et al., 1 9 7 3 ) .

where ji is t h e linear absorption coefficient o f s o m e discrete gamma-ray


energy, and is assumed t o be t h e same for b o t h the matrix and t h e borehole
materials; p is t h e d e n s i t y (g c m " ) ; M t h e gram molecular weight of the
3
0

matrix material; and N t h e Avogadro's number. Here o is t h e effective


0

microscopic cross-section o f t h e matrix material as a w h o l e .

Gamma transport — two region. For practical calculation, expression ( 3 0 )


can be simplified. C o m p l e x i t y of integration increases w h e n t h e source and
t h e d e t e c t o r are separated b y s o m e finite distance and appropriate attenua-
t i o n coefficients are a d o p t e d for matrix and borehole material (Fig. 5-7).
Numerical integration is necessary in this very c o m p l e x situation.
T o be d e t e c t e d as a full energy ray b y a d e t e c t o r at t h e l o c a t i o n D, a
gamma p h o t o n produced at a p o i n t P(r, z) in t h e borehole has t o traverse a
distance PE = t in t h e matrix region and a distance DE = s in t h e borehole
(water) region, in a straight p a t h . Neglecting g a m m a p r o d u c t i o n in the
b o r e h o l e , t h e g a m m a flux P returning t o t h e d e t e c t o r from t h e total matrix
y

can be written as:

• exp(-ju s) exp(-M0
w (31)

where J U is t h e g a m m a absorption coefficient for water and p


w t h e effec-.
eff

tive d e n s i t y o f matrix material t o a c c o u n t for changes in porosity. A l s o :


133

[r + ( z - d ) ]
2 2 1 / 2

To evaluate the absorption coefficient for a c o m p o u n d or a m i x t u r e , ju can


be replaced b y :

(32)

where p = partial density o f e l e m e n t i (g c m " ) , and (ju/P)/ mass absorption


t
3 =

coefficient for e l e m e n t / ( c m g " ) .


2 1

The values (ju/p); for e l e m e n t s Si, H, and O are given b y S t o r m and Israel
( 1 9 6 7 ) and Grodstein ( 1 9 5 7 ) for the g a m m a energies investigated.
To simplify t h e calculations further in t h e case o f a single e l e m e n t in the
matrix, w e can write:

Py ~ Peff - <I>2B (r, *) exp(—JU S) W exp(—pt) (33)

A c o m p u t e r program G A M U X was written t o perform this integration for


the e l e m e n t Si, for various source d e t e c t o r distances, d, p o r o s i t y , p ff and
e

gamma energy E.
It m u s t b e n o t e d that e q u a t i o n ( 3 3 ) represents o n l y t h e attenuation o f
gamma p h o t o n s o f energy E b y the matrix and borehole material irradiated
b y t h e thermal n e u t r o n flux distribution, 0 e( > )> It d o e s n o t i m p l y that
2j
r z

gammas of energy E are actually p r o d u c e d and s u b s e q u e n t l y d e t e c t e d b y the


d e t e c t o r D. For e x a m p l e , g a m m a p h o t o n s o f energy E = 1 0 MeV are n o t
produced b y n e u t r o n absorption in t h e silicon matrix.

Theoretical results

Neutron flux distribution. In t h e theoretical s t u d y described b y Nargolwalla


et al. ( 1 9 7 3 ) , the b o r e h o l e is assumed t o be full of water and the matrix
silica sand ( S i 0 ) o f theoretical density 2 . 6 5 g c m " , i.e. porosity = 0. The
2
3

porosity is increased b y t h e introduction o f air (dry case) or water ( w e t case).


The calculated results (Figs. 5-8 and 5-9) s h o w the thermal neutron flux
distribution. A n analogous p l o t for t h e case of a dry matrix is s h o w n in Fig.
5-10. The effect of water in the matrix indicates an e n h a n c e m e n t in the
neutron flux close t o t h e b o r e h o l e and a sharp decrease away from t h e bore-
h o l e . As such, the effective v o l u m e of the matrix decreases with the increase
in t h e moisture. A s can be e x p e c t e d for equivalent porosities, t h e neutron
flux in t h e dry matrix is considerably higher.

Gamma-ray intensity returning to the detector. The n u m b e r of gammas


returning t o the d e t e c t o r d e p e n d s o n the moisture c o n t e n t , borehole size and
134

,o 5
0th,n. cm" sec"'
2

10 I u l l i I I

0 20 40 60
DISTANCE FROM THE SOURCE,CM
Fig. 5-8. Calculated thermal neutron flux in z = 0 plane for a water-filled borehole (9 cm
radius) and wet (W) matrix of porosity 0—10% (Nargolwalla et al., 1 9 7 3 ) .

t h e source-detector distance as described in the following.


The total number of gammas of energies 2 , 3 , 5, 6 , 8 and 1 0 MeV return-
ing t o t h e d e t e c t o r in t h e dry and w e t matrix as a f u n c t i o n of porosity are
s h o w n in Figs. 5-11 and 5-12. G a m m a flux at t h e d e t e c t o r D increases w i t h
increasing porosity in t h e w e t matrix. However, w e e x p e c t all the curves t o
fall t o zero in t h e limit o f 1 0 0 % p o r o s i t y , in w h i c h case pefi will be zero.
N o t e t h e overall reduction in sensitivity with increase in t h e source-detector
distance. From an experimental v i e w p o i n t the selection of an o p t i m u m
source-detector distance can reduce t h e error d u e t o t h e porosity effect. The
effect of increasing t h e borehole diameter results in a decrease in t h e gamma-
ray intensity as seen b y t h e d e t e c t o r .
In interpretation of t h e s e calculated results, it m u s t be remembered that
t h e shield normally separating t h e source and d e t e c t o r has n o t been con-
sidered. In practice h o w e v e r , a considerable distortion in t h e theoretical
gamma-ray pattern occurs. The design o f an o p t i m u m probe d e p e n d s t o a
135
0 th, n. cm" sec"'
2

DISTANCE FROM THE SOURCE ,CM

Fig. 5-9. Calculated thermal neutron flux in z = 0 plane for a water-filled borehole (9 cm
radius) and wet (W) matrix of porosity 15—60% (Nargolwalla et al., 1 9 7 3 ) .

large e x t e n t o n t h e diameter of t h e shield w i t h respect t o t h e d e t e c t o r , as


well as t h e length o f t h e shield.

Pulsed neutron logging


Pulsed neutron logging finds particular application for t h e use o f inelastic
scattering reactions t o t h e determination of certain e l e m e n t s . Essentially,
h o w e v e r , t h e object of pulsed n e u t r o n logging is t h e determination of
fundamental n e u t r o n parameters such as, 2 , t h e macroscopic absorption
a

cross-section; £>, t h e diffusion coefficient and t h e like. In logging, t h e


changes in such parameters from t h e k n o w n values can assist in t h e identifi-
cation of e l e m e n t s o f interest.
Denisik et al. ( 1 9 6 3 ) used t h e M o n t e Carlo m e t h o d for t h e calculation of
t h e space-time distribution of n e u t r o n s in a S i 0 matrix of varying porosities.
2

The agreement b e t w e e n t h e o r y and e x p e r i m e n t was excellent. Rezvanov et


136
1
0 th. n. cm" sec
2

DISTANCE FROM THE SOURCE , CM

Fig. 5-10. Calculated thermal neutron flux in z = 0 plane for a water-filled borehole (9 cm
radius) and dry (D) matrix of porosity 0—50% (Nargolwalla et al., 1 9 7 3 ) .

al. ( 1 9 6 8 ) have s h o w n results of a mathematical m o d e l o f space-time thermal


neutron distribution in a two-layer m e d i u m w i t h a cylindrical interface.
Using t h e diffusion a p p r o x i m a t i o n of the neutron transport t h e o r y ,
Caldwell e t al. ( 1 9 6 6 ) calculated t h e neutron distribution in space and t i m e
for t h e borehole g e o m e t r y . A c o m p u t e r c o d e called " C U N L A P " ( A n o n y -
m o u s , 1 9 6 5 ) was used t o solve t h e t i m e - d e p e n d e n t , three-group diffusion
equations. This c o d e has t h e capacity of accepting u p t o 3 9 different time-
step sizes. Furthermore, it is also possible for t h e c o m p u t e r c o d e t o select its
o w n time-step size based o n t h e rate of change o f t h e neutron flux. The
alternate direction implicit t e c h n i q u e reported b y Wachpress and Habetler
( 1 9 6 0 ) is used t o achieve spatial convergence o f t h e finite difference expres-
sions for t h e neutron fluxes.
T o provide experimental verification for t h e theoretical c o m p u t a t i o n s , a
limestone m o d e l was used. The die-away of thermal neutrons and capture
137
GAMMA FLUX AT DETECTOR (JT/cm /sec)

GAMMA FLUX AT DETECTOR U/cm /sec)


2

POROSITY, PERCENT POROSITY, PERCENT


Fig. 5-11. Calculated gamma-ray flux at the detector for source-detector distance of 30
c m for a water-filled borehole (9 cm radius). Solid curves: dry matrix; dashed curves: wet
matrix (Nargolwalla et al., 1 9 7 3 ) .

Fig. 5-12. Calculated gamma-ray flux at the detector for source-detector distance of 6 0
cm for a water-filled borehole (9 cm radius). Solid curves: dry matrix; dashed curves: wet
matrix (Nargolwalla et al., 1 9 7 3 ) .

g a m m a rays from a pulsed 14-MeV n e u t r o n source were measured b y a H e 3

and N a l ( T l ) d e t e c t o r , respectively. A comparison o f t h e c o m p l e t e theoretical


n e u t r o n and gamma-ray d e c a y curves w i t h experimental measurements is
s h o w n in Fig. 5 - 1 3 . The experimental data was obtained for a 7-inch diam-
eter b o r e h o l e . The gamma-ray c o u n t s measured were t h o s e above 1.5 M e V
energy. During each n e u t r o n burst from t h e pulsed n e u t r o n source, t h e
p h o t o m u l t i p l i e r t u b e was gated off. T h e data as s h o w n have b e e n corrected
for t h e t i m e analyzer d e a d t i m e and for background.
As can be observed that, for t h e n e u t r o n curves, there is a large discrep-
ancy b e t w e e n t h e theoretical and experimental t i m e distribution immedi-
ately f o l l o w i n g t h e burst. Possible reasons for this discrepancy have b e e n
attributed t o ( 1 ) t h e inability of t h e calculation t o properly a c c o u n t for t h e
central air c o l u m n in t h e b o r e h o l e , and ( 2 ) the effects of thermal-neutron
flight time across t h e air c o l u m n . It m a y also b e observed that t h e gamma-
ray curves are a l m o s t e x p o n e n t i a l over a longer t i m e scale than t h e neutron
curves. The theoretical gamma-ray d e c a y curve was calculated b y spatially
integrating over the c o m p u t e d neutron distribution. B o t h single scattered
and u n a t t e n u a t e d radiation were included.
138
COUNTS

TIME yjs)

Fig. 5-13. Comparison of experimental and theoretical time distributions (Caldwell et al.,
1966).

In later sections o f t h e chapter dealing w i t h t h e d e v e l o p m e n t of borehole


exploration t e c h n i q u e s , use is made o f t h e theoretical c o n c e p t s given above.
A l t h o u g h t h e theoretical approach is a simple t r e a t m e n t of neutron and
p h o t o n physics, a general feeling for t h e important parameters controlling
t h e analytical sensitivity and possible means for t h e minimization o f sys-
tematic errors is indicated.

RADIOACTIVATION SOURCES

Irradiation sources used in t h e radioactivation m e t h o d s in mineral explora-


t i o n can be classified i n t o four main categories ( 1 ) radioisotopic neutron
sources, (2) s p o n t a n e o u s fission n e u t r o n sources, ( 3 ) accelerators and
neutron generators, and ( 4 ) gamma sources. D e p e n d i n g o n t h e t y p e of
neutron source u s e d , fast, epithermal or thermal neutrons can be p r o d u c e d .
The c h o i c e o f an appropriate source d e p e n d s mainly o n t h e applications t o
be pursued. A f e w criteria that m u s t be considered in t h e proper selection
are (a) t h e cost, (b) t h e d i m e n s i o n , shape and shielding required, (c) t h e
requirement of source handling, (d) source strength, and (e) space available.
139

Radioisotopic neutron sources

The principal sources o f neutrons are t h o s e from nuclear reactions that


emit a high flux of neutrons. S o m e naturally occurring and s o m e artificial
alpha and g a m m a emitters have b e e n c o u p l e d with a particular low-mass
e l e m e n t having a l o w neutron binding energy and suitable cross s e c t i o n t o
produce n e u t r o n s . Until recently the m o s t w e l l - k n o w n radioisotopic neutron
sources have b e e n mainly t h e ( a , n) and t h e ( 7 , n) sources. These consist of
alpha- and gamma-emitting radionuclides m i x e d w i t h a target e l e m e n t . The
( a , n ) sources utilizing alpha-emitting i s o t o p e s are m i x e d with a beryllium
target, t o p r o d u c e neutrons w i t h a w i d e range of energies. The principal
alpha emitters used w i t h a beryllium target are Ra,
2 2 6
Po,
2 1 0
Ac, Pu,
2 2 7 2 3 8

2 4 1
A m and C m . T h e ( 7 , n ) sources involve a g a m m a emitter, such as
2 4 2
Sb, 1 2 4

8 8
Y , N a , and
2 4
L a , surrounded b y a beryllium or a deuterium o x i d e target.
1 4 0

S o m e of these neutron sources can be designed t o turn t h e n e u t r o n o u t p u t


" O F F " and " O N " . A survey o f a f e w c o m m o n l y used ( a , n ) and ( 7 , n)
sources w i t h their principal nuclear reactions, reaction energy Q, neutron
energy and n e u t r o n y i e l d , is s h o w n in Table 5 - 1 .
In practice t h e principal advantages o f i s o t o p i c neutron sources are their
stability and c o m p a c t size. Their neutron o u t p u t s diminish w i t h t h e d e c a y of
t h e gamma-emitting and alpha-emitting nuclides, d e p e n d i n g o n t h e half-lives
of t h e nuclides. These neutron sources have certain disadvantages; i.e. ( 1 ) t h e
insufficient intensity for neutron activation analysis; this s h o r t c o m i n g can
be corrected b y using large samples or b y irradiating and c o u n t i n g repeatedly
t o improve t h e precision of t h e result and, ( 2 ) inability for turning off t h e
neutron o u t p u t easily.

(a, n) Sources
More than 2 0 principal alpha-emitting nuclides are utilized in t h e fabrica-
t i o n o f these sources as described b y Ansell and Hall ( 1 9 7 1 a , b ) .
The alpha particles e m i t t e d b y t h e d e c a y o f a naturally occurring or
artificially produced radioisotope react with t h e nuclei of a low-atomic-
number e l e m e n t of suitable threshold and cross-section t o p r o d u c e neutrons.
The alpha emitters m o s t o f t e n used are Po,
2 1 0
Am,
2 4 1
P u , and2 3 9
Pu 2 3 8

(Table 5 - 1 ) , and typical target materials invariably include H and B e . In t h e2

early d a y s t h e radium i s o t o p e s and their daughters m i x e d w i t h a beryllium


target, were a b o u t t h e o n l y t y p e s of isotopic neutron source available for
well logging. H o w e v e r , t h e n u m b e r of ( a , n) sources rapidly increased with
t h e introduction of the smaller P o - B e source giving more n e u t r o n s , a
2 1 0

relatively c o m p a c t P u - B e and other useful sources such as P u - B e and


2 3 8 2 3 9

A m - B e . In t h e selection of a suitable target material in t h e n e u t r o n produc-


2 4 1

t i o n , beryllium is t h e m o s t favorable since t h e n u m b e r of neutrons e m i t t e d


per alpha particle bombarding this target material is t h e largest (i.e. 7 7 n / 1 0 6

alpha particles) in comparison w i t h t h e yield of neutrons b y other target


140

TABLE 5-1
(a, n) and ( 7 , n ) neutron sources

Type Source Main Q Average Neutron yield Half-life


1 1
reaction (MeV) neutron (n s" C i " ) of alpha-
energy emitting
(MeV) nuclide

2 4 2 9 1 2 6
(a,n) Cm-Be Be(a, n ) C 5.65 4 4 X 10 163 days
2 4 4 6
Cm-Be — 5.65 4 3 X 10 18.1 yr
2 4 1 9 1 2 6
A m - B e mixture Be(a, n) C 5.65 4 2.2 X 10 433 yr
2 2 6 9 1 2 7
R a - B e mixture Be(a, n) C 5.65 3.6 1.5 X 10 1602 yr
2 1 0 9 1 2 6
P o - B e mixture Be(a, n) C 5.65 4.3 2.5 X 10 138 days
2 3 9 9 1 2 6
P u - B e mixture Be(a, n) C 5.65 4.5 2 X 10 24,360 yr
2 2 7 9 1 2 7
Ac-Be Be(a, n) C 5.65 4 2.4 X 10 21.8 yr
2 2 8 7
Th-Be — 5.65 4 2.8 X 10 1.9 yr
2 3 8 6
Pu-Be — 5.65 4 2.8 X 10 89 yr
2 4 9 8 s
(7, n)* Na-Be Be(7, n) Be —1.67 0.2 1.4 X 10 15 h
2 4 2 5
Na-D 0 2 H(7,n)*H -2.23 0.8 2.9 X 10 15 h
8 8 9 8 s
Y-Be Be(7, n) Be -1.67 0.16 1 X 10 108 days
8 8 2 1 3
Y-D 0 2 H(7,n) H -2.23 0.3 3 X 10 108 days
1 2 4 9 8 s
Sb-Be Be(7, n) Be -1.67 0.02 1.9 X 10 60 days
1 4 0 9 8 3
La-Be Be(7, n) Be -1.67 0.6 2 X 10 40.2 h
1 4 0 2 1 3
La-D O 2 H(7,n) H -2.23 0.15 7 X 10 40.2 h

* Neutron yields are those for a 1-g Be or heavy water target at 1 c m from the gamma source of 1 Ci.
141

materials under t h e same c o n d i t i o n s (Strain and L y o n , 1 9 6 5 , p p . 2 4 5 — 2 5 8 ) .


H o w e v e r , B , Li, and F are e m p l o y e d as target material w h e n e v e r t h e activa-
t i o n b y a thermal n e u t r o n flux is specifically required.
Owing t o t h e short range of alpha particles, a c h i e v e m e n t o f t h e highest
possible n e u t r o n yield requires t h e alpha-emitting i s o t o p e t o b e intimately
m i x e d w i t h t h e beryllium target t o form a p o w d e r m i x t u r e , or an alloy,
depending o n t h e i n t e n d e d application w h i c h d e m a n d particular shapes and
proper encapsulation or shielding. H o w e v e r , neutron source alloys (e.g.
Pu-13Be,
2 3 9
C m - 1 3 B e and A m - 1 3 B e ) have a higher n e u t r o n yield than
2 4 2 2 4 1

that produced b y p o w d e r mixtures (e.g. P u 0 + metallic B e ) . 2

In t h e selection o f a n e u t r o n source t o b e used for a specific purpose, t h e


size and shape of t h e encapsulating container, t h e n e u t r o n o u t p u t , and t h e
gamma radiation e m i t t e d b y t h e alpha-emitting radioactive nuclide are t h e
main criteria that m u s t be considered. A l t h o u g h m a n y alpha-emitting
i s o t o p e s , such as R a , have l o n g half-lives c o m p a r e d w i t h t h o s e o f other
2 2 6

i s o t o p e s , such as P o , and have m o r e intensive neutron o u t p u t s from ( a , n )


2 1 0

reactions; t h e gamma-ray intensity e m i t t e d b y long-lived nuclides (e.g. Ra 2 2 6

and T h ) is so high that t h e g a m m a interference in t h e gamma-ray spectro-


2 2 8

metric measurements and t h e n e e d for shielding makes t h e use o f other


relatively shorter half-lived nuclides (e.g. P u - B e and A m - B e ) more 2 3 8 2 4 1

attractive. Comparing a f e w ( a , n ) sources in Table 5-1, C m - B e is n o t easily 2 4 4

available and P u - B e has s o m e user restrictions since


2 3 9
P u is a fissile 2 3 9
RELATIVE NEUTRON INTENSITY

J I I I I L

0 0.2 0.4 0.6 0.8 1.0 1.2

NEUTRON ENERGY(MeV)
Fig. 5-14. Neutron spectrum of 2 1 0
P o - L i (a, n) source.
142
INTENSITY
RELATIVE NEUTRON

0 2 4 6 8 10 12
NEUTRON ENERGY, MeV

Fig. 5-15. Neutron spectrum of 2 3 9


P u - B e (a, n) source.

16
RELATIVE NEUTRON INTENSITY

0 2 4 6 8 10

NEUTRON ENERGY, MeV


Fig. 5-16. Neutron spectrum of 2 4 1
Am-Be (a, n) source.
143
RELATIVE NEUTRON INTENSITY

0 2 4 6 8 10

NEUTRON ENERGY, MeV


Fig. 5-17. Neutron spectrum of Ra-Be (a, n) source.

i s o t o p e . The n e u t r o n energy spectra o f s o m e of t h e more useful ( a , n )


sources are given in Figs. 5 - 1 4 t o 5-17. T h e n e u t r o n yield o f A m - B e can be 2 4 1

improved significantly w h e n irradiated for 3 0 d a y s at a n e u t r o n flux of


2 X 1 0 n c m " s" in a nuclear reactor. In mineral analysis this source is o n e
1 4 2 1

of t h e m o s t useful low-intensity n e u t r o n producers. Other long-lived sources,


i.e. T h - B e and C m - B e , prepared b y the irradiation o f
2 2 8 2 4 2
R a and 2 2 6

A m o x i d e , respectively, at a flux of 1 0 n c m " s" have a relatively


2 4 1 1 4 2 1

high neutron o u t p u t of a b o u t 1 0 n s ~ C i " . Other sources, i.e. ^ C m -


8 1 1

Be, A c - B e and P u - B e , incorporate alpha emitters o f very high specific


2 2 7 2 3 8

activity, w h i c h are principally m a d e in reactors. The 22-year half-life Ac 2 2 7

has a high n e u t r o n o u t p u t per unit v o l u m e and a l o w gamma-ray o u t p u t


from t h e source c o m b i n a t i o n A c - B e . A by-product from t h e reprocessing
2 2 7

of nuclear fuel is t h e 18-year half-life C m which, when combined with Be,


2 4 4

has b e e n used for high sensitivity analysis of small samples.


In practice t h e ( a , n ) sources are used for fast and thermal n e u t r o n activa-
t i o n analysis and are quite popular for t h e analysis of b o r e h o l e s . N e u t r o n
activation data using these sources, such as ( 1 ) t h e d e t e c t i o n sensitivities of
e l e m e n t s irradiated w i t h a fast neutron flux (Wing and Wahlgren, 1 9 6 7 , p p .
8 5 — 8 9 ) , and ( 2 ) t h e gamma-ray spectra (Wing and Wahlgren, 1 9 6 6 ) are avail-
able. However, d e t e c t i o n sensitivity data for various e l e m e n t s irradiated b y
thermal neutrons can be d e t e r m i n e d from published data b y Anders ( 1 9 6 0 ) ,
Wing and Wahlgren ( 1 9 6 5 ) , and Yule ( 1 9 6 5 ) . The sources described can be
used for t w o principal t y p e s o f analyses, i.e. thermal n e u t r o n activation-
delayed gamma-ray m e a s u r e m e n t and thermal neutron-capture gamma-ray
144

analysis. T h e latter in m o s t cases is interference-free from t h e high-energy


gammas of 4 . 4 3 and 2 . 2 3 MeV resulting from the use of such sources d u e
t o t h e Be target and t h e h y d r o g e n c o n t e n t of moderators, respectively. Con-
centrations of e l e m e n t s such as F e , Cu, Sr, Ti, N i , and m a n y others can be
determined w i t h these sources as described by Christell and Ljunggren
( 1 9 6 5 ) , and Gijbels ( 1 9 7 3 ) .

Gamma-neutron sources
These sources use t w o target nuclei, Be and D 0 , and t h e bombarding 2

gamma rays are obtained from t h e d e c a y o f nuclides such as N a , M n , G a , 2 4 5 4 7 2

Y,
8 8
Sb, L a , R a and T h . Important characteristics o f s o m e o f these
1 2 4 1 4 0 2 2 6 2 2 8

sources are given in Table 5-1. The ( 7 , n ) threshold for Be and deuterium are
1.67 and 2 . 2 3 M e V , respectively. T o yield high n e u t r o n yields, these sources
m u s t have very thick targets.
Generally, t h e ( a , n) sources are m o r e w i d e l y used for mineral exploration
for t h e f o l l o w i n g reasons: ( 1 ) the n e u t r o n yield per curie is higher than for
( 7 , n ) sources, and ( 2 ) t h e ( 7 , n) sources p r o d u c e m o r e interfering radiation
from t h e gamma-emitting nuclides used in t h e source and also t h e y have
short half-lives (see Table 5-1). However, ( 7 , n ) sources have t h e advantage of
being smaller in size, b u t are m o r e difficult t o handle.
Perhaps t h e m o s t useful ( 7 , n ) source is t h e S b - B e , because of its l o w 1 2 4

c o s t , its ability o f being regenerated b y irradiating it in a high flux reactor,


and its relatively high o u t p u t o f 2 X 1 0 n s" Ci" . However, o w i n g t o its 6 1 1

relatively short half-life and l o w n e u t r o n o u t p u t energy of a b o u t 2 4 k e V , its


use has b e e n o n t h e d o w n trend. A n e u t r o n spectrum from this source is
s h o w n in Fig. 5-18. For m o s t ( 7 , n) sources, t h e highest-energy neutrons
e m i t t e d are still b e l o w normal threshold for inducing reactions such as (n, a ) ,
NEUTRONS PER ENERGY INTERVAL
(arbitrary units)

20 25 30

NEUTRON ENERGY, KeV


Fig. 5-18. Neutron spectrum of 1 2 4
S b - B e ( 7 , n) source.
145

(n, 2 n ) and ( n , p ) . In practice a thermal n e u t r o n shield, such as U fission 2 3 5

foil, in front of t h e source is used t o shield o u t t h e thermal c o m p o n e n t .

Isotopic spontaneous fission neutron source


In t h e isotopic s p o n t a n e o u s fission process, neutrons are e m i t t e d . S o m e
transuranic e l e m e n t s , disintegrating t o a significant degree b y s p o n t a n e o u s
fission, are c o p i o u s sources of energetic neutrons. S o m e of these sources and
their emission characteristics are s h o w n in Table 5-II abstracted f r o m Kruger's
treatise ( 1 9 7 1 ) . Currently h o w e v e r , m o s t o f t h e heavy e l e m e n t s listed in
Table 5-II are p r o d u c e d in m i n u t e quantities from t h e irradiation of fuel
elements in very high flux reactors for a n u m b e r of years. Their availability
till very recent t i m e s was e x t r e m e l y limited. In t h e future t h e s e heavy ele-
m e n t s m a y be produced as by-products from controlled thermo-nuclear
e x p l o s i o n s . These events produce heavy radioelements b y successive n e u t r o n
capture processes t o generate beta-unstable products. After several beta
d e c a y s t h e unstable nuclide d e c a y s b y s p o n t a n e o u s fission and alpha d e c a y ,
t o p r o d u c e high fluxes of n e u t r o n s w i t h a distribution comparable t o that
obtained from t h e thermal n e u t r o n fission of U . If problems, such as heat
2 3 5

dissipation from t h e sources are solved, these s p o n t a n e o u s fission sources


will be e x t r e m e l y useful for t h e analysis of minerals. A m o n g these sources
C f is t h e m o s t popular and useful. It is of rugged c o n s t r u c t i o n , small in
2 5 2

size, provides a stable flux for a reasonable period o f t i m e (half-life 2 . 6 4 6


years) and has flexibility in terms of encapsulation. In Tables 5-III t o 5-V
and Figs. 5-19 and 5-20 are given data pertinent t o this source. The source is
generally encapsulated in stainless steel, platinum-rhodium alloy, zircaloy
or certain t y p e s o f ceramics. T h e source is manufactured b y t h e U . S . A t o m i c
Energy C o m m i s s i o n ( n o w E R D A ) and costs $ 1 0 per microgram. T h e encap-

TABLE 5-II
Spontaneous fission neutron sources

Nuclide Alpha decay Fission Fissions Neutrons


Ty (yr)
2
Ti (yr)
/2
per 1 0 a's 6
per fission

238u 4.5 X 10 9
6.5 X 10 1 5
5.6 X 10" 1

236p u
2.85 3.5 X 10 9
8.1 X 10" 4
1.89 ± 0.20
2 38p u
86.4 4.9 X 10 1 0
2.3 X 10~ 3
2.04 ± 0.13
240p u
65.8 X 10 2
1.3 X 10 1 1
5.4 X 10~ 2
2.09 ± 0.11
242p u
3.8 X 10 s
7.1 X 10 1 0
5.3 2.32 ± 0.16
244p u
7.6 X 10 7
2.5 X 10 1 0
3.0 X 10" 3

2 4 2
Cm 0.45 7.2 X 10 6
6.2 X 10" 2
2.33 ± 0.11
2 4 4
Cm 17.6 1.3 X 10 7
1.3 2.61 ± 0.13
252 C f
2.6 85 3.3 X 10 4
3.51 ± 0.16
254 C f
long 0.17 large —
146

TABLE 5-III
Neutrons from 2 5 2
C f spontaneous fission

Energy (MeV) Abundance (n s 1


mg 1
)

10.00 - 1 4 . 9 2 8.28 X 10 6

6.42 x 1 0
6.70 - 1 0 . 0 0 7

8.19 X 1 0
5.49 - 6.70 7

1.26 X 1 0
4.49 - 5.49 8

1.68 X 1 0
3.68 - 4.49 8

2.00 X 1 0
3.01 - 3.68 8

4.36 X 1 0
2.02 - 3.01 8

6.98 X 1 0
0.91 - 2.02 8

3.36 X 1 0
0.41 - 0.91 8

1.56 X 1 0
0.11 - 0.41 8

2.74 x 1 0
0 . 0 1 5 - 0.11 7

0.0 - 0.015 0

Total 2.3 X 10 9

sulation o f sources in t h e range of 1 0 0 fig costs in t h e region of $ 1 0 0 0 and


a further investment of approximately $ 1 0 0 0 is necessary t o provide an
adequate shipping or storage container. T h e cost of larger shields is of course
m u c h higher. When high source strength is n e e d e d w i t h o u t adding t o t h e
weight of t h e i s o t o p e , a uranium blanket (Californium-252 Information
Center, 1 9 7 4 ) is used t o b o o s t t h e neutron o u t p u t . B o o s t i n g factors ap-
proaching a factor of 3 5 have b e e n obtained in such a manner. Concise
information regarding t h e purchase, encapsulation and research d o n e with
this source are f o u n d in regular C f bulletins issued by t h e
2 5 2
C f Informa-
2 5 2

t i o n Center of t h e U n i t e d States Energy Research and D e v e l o p m e n t Ad-


ministration ( E R D A ) in A i k e n , S o u t h Carolina. E x c e p t for its half-life t o
a certain e x t e n t , this source possesses ideal characteristics for moderately
long-term use in t h e field for mineral exploration.

TABLE 5-IV
Gamma rays from 2 5 2
C f alpha decay process

Energy (MeV) Abundance (photons s" m g " ) 1 1

0.043 2.8 X 10 6

0.100
2.0 X 10 6

0.156
4.0 X 10 s
147
RELATIVE NUMBER OF NEUTRONS PER UNIT OF ENERGY

2 3 4 5

NEUTRON ENERGX MeV


Fig. 5-19. Fission neutron spectrum of 2 5 2
C f source.
RELATIVE GAMMA INTENSITY

GAMMA ENERGY, MeV

Fig. 5-20. Gamma spectrum of 2 5 2


C f source.
148

TABLE 5-V
Gamma rays from 2 5 2
C f spontaneous fission

Energy Prompt Gamma rays Total


(MeV) gamma rays from equilibrium (photons s" m g " ) 1 1

(photons s" m g " ) 1 1


fission products
(photons s" m g " )1 1

0 -0.5 3.3 X 10 9
1.3 X 10 9
4.6 X 10 9

0.5-1.0 1.7 X 10 9
4.0 X 10 9
5.7 X 10 9

1.0-1.5 7.7 X 10 8
9.1 X 10 8
1.7 X 10 9

1.5-2.0 4.2 X 10 8
3.5 X 10 8
7.7 X 10 8

2.0-2.5 2.2 X 10 8
2.2 X 10 8

2.5-3.0 1.1 X 10 8
1.1 X 10 8

3.0-3.5 5.6 X 10 7
5.6 X 10 7

3.5-4.0 3.0 X 10 7
3.0 X 10 7

4.0—4.5 1.7 X 10 7
1.7 X 10 7

4.5-5.0 8.2 X 10 6
8.2 X 10 6

5.0-5.5 4.9 X 10 6
4.9 X 10 6

5.5-6.0 1.8 X 10 6
1.8 X 10 6

6.0-6.5 1.0 X 10 6
1.0 X 10 6

Total 6.6 X 10 9
6.6 X 10 9
1.3 X 10 1 0

Accelerator neutron sources

Neutron generators
Miniature n e u t r o n generators have b e e n w i d e l y used in activation analysis
o f minerals and for e x p l o r a t i o n . The commercial instruments are scaled-
d o w n charged-particle accelerators producing moderate fluxes of 1 4 - and
3-MeV neutrons b y exoergic (d, n ) reactions such as H ( d , n ) H e and 3 4

2
H ( d , n ) H e . Principally a neutron generator is c o m p o s e d of an ion source,
3

an accelerating t u b e or chamber and a target. Ions generated in t h e ion


source are accelerated through a potential difference of 6 0 — 1 5 0 k V in t h e
accelerator t u b e w h i c h is maintained at pressures o f 1 0 " t o 1 0 " m m Hg. 4 6

The accelerated i o n s t h e n strike t h e target t o p r o d u c e high-energy neutrons


w h i c h are approximately isotropic in emission. These neutrons can be
m o d e r a t e d b y p o l y e t h y l e n e or paraffin w a x t o generate thermal neutrons
w h i c h can be used for activation purposes. Certain minerals are more
amenable t o analysis via their threshold reactions. In such cases, t h e moder-
ating m e d i u m is eliminated from t h e measurement device. A recent treatise
o n t h e use of neutron generators for activation analysis (Nargolwalla and
P r z y b y l o w i c z , 1 9 7 3 ) describes t h e application and mechanical aspects o f this
t y p e o f accelerator. The section o n sealed-tube generators applicable t o
borehole analysis is also given. The reader is advised t o refer t o this t e x t for
149

discussions pertinent t o t h e operation and maintenance o f t h e accelerator.


The application of this t y p e o f n e u t r o n source has t h e f o l l o w i n g advantages:
( 1 ) t h e neutron b e a m can be turned off b y simply de-exciting t h e high
voltage, and ( 2 ) threshold reactions o f t e n provide a unique s o l u t i o n t o
certain nuclear interference p r o b l e m s , n o t possible w i t h thermal n e u t r o n
activation. On t h e other hand t h e instrument also presents s o m e p r o b l e m s in
terms of accurate flux monitoring of t h e primary n e u t r o n emission from t h e
target and t h e mechanical difficulties associated w i t h t h e generation o f high
voltages o f that magnitude inside small devices lowered i n t o b o r e h o l e s . S o m e
applications that have f o u n d success using this t y p e of n e u t r o n source are
discussed in t h e s e c t i o n "The radioactivation m e t h o d s for mineral explora-
tion".

Other accelerator neutron sources


Limited use has also b e e n m a d e o f other accelerator t y p e n e u t r o n sources.
In a f e w cases a t t e m p t s have b e e n m a d e t o use a Van d e Graaff generator in
t h e borehole e n v i r o n m e n t . This m e t h o d requires an e x t r e m e l y high degree of
instrument sophistication and d o e s n o t appear t o have reached a state w h e n
it can be c o n v e n i e n t l y used for mineral e x p l o r a t i o n in d o w n h o l e devices.

Gamma-ray sources

These sources are principally used for gamma-gamma devices for mineral
characterization. Four useful sources e m p l o y e d in various devices are Cs, 1 3 7

Co,
6 0
R a and S e . For selective g a m m a logging t h e sources described
2 2 6 7 5

earlier are r e c o m m e n d e d . G a m m a sources are cheap and easily procured. The


experimenter has a great deal of flexibility in his c h o i c e of t h e specific activ-
ity and encapsulation. Since these sources d o n o t activate t h e s o n d e or t h e
irradiated matrix, t h e analysis is m o r e c o n v e n i e n t and straightforward.
S o m e properties of such sources are listed in Table 5-VI.

TABLE 5-VI
Nuclear properties of gamma-ray sources

Source Mean Half-life Mass absorption


gamma energy coefficient ( c m 2

(keV)
CaC0 3 ZnS

7 5
Se 224 120 days 0.1223 0.1353
1 3 7
Cs 662 30 yr 0.0777 0.0741
6 0
Co 1250 5.3 yr 0.0577 0.0546
2 2 6
Ra 186 1602 yr — —
150

RADIOACTIVATION METHODS FOR MINERAL EXPLORATION

Introduction

The application of radioactivation m e t h o d s for t h e analysis of mineral


samples has been well d o c u m e n t e d in literature. Single- and multi-element
studies are discussed in several hundred publications. The general activation
analysis bibliography c o m p i l e d b y Lutz et al. ( 1 9 7 1 ) issued b y t h e National
Bureau of Standards in 1 9 7 1 lists over 4 0 0 references related t o t h e analysis
of mineral samples. However, b y far the majority of this research has been
carried o u t in highly controlled laboratory environments. Despite t h e fact
that m a n y of these studies purport direct applications t o t h e mineral indus-
try, very f e w have b e e n tested under typical field c o n d i t i o n s . Furthermore,
o f t h e limited n u m b e r of such tests, o n l y a handful are actually being utilized
for mineral exploration and m i n e d e v e l o p m e n t . Reasons for t h e rather
meagre success i n d e x are m a n y . S o m e of the principal causes for t h e dif-
ficulties experienced b y researchers in attempting t o "sell" their individual
d e v e l o p m e n t s t o the mining industry are:
(1) The general reluctance o n the part of prospective users t o displace or
c o m p l e m e n t existing chemical and non-nuclear instrumental m e t h o d s in
current use for t h e characterization of minerals. The chemical analyses of
drill-core, chips, cuttings and other t y p e s of recovered geological samples still
form t h e basis of o r e b o d y evaluation and mineral e x p l o r a t i o n .
(2) Insufficient e x a m i n a t i o n o n the part of t h e researcher of t h e specific
needs of a particular exploration or prospecting t e c h n i q u e . In all fairness, it
might b e emphasized that these requirements change radically for a given
t y p e of mineral deposit operated by t w o different m i n e developers. For
e x a m p l e , in drill-hole logging for nickel laterites and porphyry copper, o n e
mining organization m a y o n l y be interested in t h e principal e l e m e n t s , i.e.
nickel and copper; o n t h e other hand, another c o m p a n y w o u l d require
c o m p o s i t i o n a l k n o w l e d g e of subsidiary e l e m e n t s , such as iron and silicon,
since the particular mineral process it uses is e x t r e m e l y sensitive t o these
matrix elements. Only under these c o n d i t i o n s w o u l d it consider a n e w
m e t h o d as a viable alternative t o t h e current chemical and instrumental
methods employed.
( 3 ) A n investigation i n t o the "field" analytical speed of a developed radio-
activation m e t h o d in t h e laboratory is often neglected. In mining circles, this
factor is o f u t m o s t i m p o r t a n c e , and almost always is directly proportional t o
t h e ultimate cost o f e x p l o r a t i o n .
(4) The researcher often overlooks t h e fact that instrumentation used t o
analyze samples in t h e laboratory m a y n o t function in t h e hostile environ-
m e n t so s y n o n y m o u s of field c o n d i t i o n s . Enough forethought in this area is
often n o t given, w i t h t h e result that b o t h electronic and mechanical hard-
ware fail miserably during the early stages of perhaps a hard-to-organize and
costly field test.
151

( 5 ) The high degree of sophistication built i n t o radioactivation m e t h o d s


often acts as a deterrent for its acceptance b y field geologists acclimatized t o
t h e day-to-day routine of core e x t r a c t i o n , bag sampling and m i n e laboratory
analyses.
(6) The researcher often develops a technique under t h e best possible
c o n d i t i o n s w h i c h d o n o t allow for a sufficient degree of flexibility t o
research t h e effects of various physical and mechanical constraints usually
imposed b y field c o n d i t i o n s .
It is t h e general experience of t h e f e w researchers w h o have f o u n d success
that, before a research study is initiated, a full understanding o f a single
application be t h o r o u g h l y e x p l o r e d , t o satisfy t h e n e e d s of a single user;
rather than d e v e l o p a s y s t e m w h i c h claims t o have a general application in
t h e mining industry. A n y additional benefits derived from a successful field
t e c h n i q u e can always be applied t o strengthen t h e case in favor of similar
requirements expressed b y another m i n e developer o f a similar ore deposit.
In this s e c t i o n , an a t t e m p t has b e e n m a d e t o select radioactivation
m e t h o d s w i t h a potential for their application t o t h e mineral exploration
industry. As s u c h , o n l y t h o s e applications having a direct bearing o n explora-
t i o n and m i n e d e v e l o p m e n t , have b e e n considered. However, m e n t i o n of
techniques w h i c h are considered t o have potential for future applications
have also b e e n discussed. A short t r e a t m e n t o f t h e significance of assay data
t o t h e evaluation of ore deposits is given. The i n t e n t i o n in this chapter is n o t
t o list applications o n an e l e m e n t - t o - e l e m e n t basis, b u t rather t o emphasize
o n radioactivation t e c h n i q u e s that have broken ground w i t h demonstrations
of successful field case histories. In this respect, t h e authors have exercised
their o w n j u d g m e n t in forming selection criteria for t h e inclusion o f success-
ful studies. As far as possible, nuclear data information, such as sensitivity,
cross-section and t h e like, have b e e n e x c l u d e d , and t h e reader is referred t o
pertinent references for such information. Finally, on-going research into
radioactivation m e t h o d s pertinent t o geological exploration is briefly
described. In this regard, t h e authors have offered s o m e extrapolations i n t o
the future for these t e c h n i q u e s and their importance t o t h e mining industry
from e c o n o m i c and analytical v i e w p o i n t s .

Significance of borehole analysis for deposit evaluation

In t h e mineral evaluation of ore d e p o s i t s , it is necessary t o k n o w t h e ore


grade of t h e mineralized layers located b e t w e e n any t w o sampling points
from the wide-spaced drilling and sampling in t h e exploration stage of
mining. The delineation of an area of influence in an assay is thus important
for grade estimation in underground m i n e sections, and for reporting daily
grades and tonnages for p r o d u c t i o n scheduling.
In t h e statistical analysis applicable t o mine sampling, e x p l o r a t i o n , grading
of deposits or ore occurrences, special techniques are used in t h e data anal-
152

ysis. T w o such t e c h n i q u e s , i.e. the mean-square-successive-difference test and


linear correlation, are applied t o designate an area of influence t o a particular
assay and c o n t i n u i t y of assays o b t a i n e d , and mineral d e p o s i t samplings.
Hazen ( 1 9 6 7 ) applied t h e mean-square-successive-difference and linear
correlation t e c h n i q u e s t o investigate t h e area o f influence and t h e c o n t i n u i t y
of assays. The linear correlation technique is used t o relate a series of mea-
surements of t w o variables, e.g. s e q u e n c e of assays in o n e drill h o l e t o that in
an adjacent drill h o l e in order t o establish ore c o n t i n u i t y , ore grade b e t w e e n
holes and t w o samples in layered deposits. The mean-square-successive-
difference t e c h n i q u e is used t o provide an indication of t h e difference
b e t w e e n successive assays o f successive samples and is used as a standard test
procedure for both long- and short-range trends or fluctuations. A brief
description o f t h e t w o statistical procedures f o l l o w s .

Linear correlation
In this t e c h n i q u e , t h e linear correlation coefficient, r, is related t o N, the
number of items in each set of data, i.e. X values being individual items in
o n e set of data and Y values being individual items in t h e s e c o n d set of data,
as f o l l o w s :

(34)

The linear correlation, r, m a y be expressed in terms o f t h e variance, based o n


t h e assumption that t h e correlation b e t w e e n Y and X values is linear and
that variation in X is related t o variation in Y. The a m o u n t of variation is
expressed b y r . 2

The residual variation, (1 — r ) , is often considered as a random e l e m e n t in


2

the t w o data sets.

Mean-square-successive difference
This difference, 5 , w h i c h relates t h e ith assay X t h e successive (i + l ) t h
2
i9

assay X i+i9and t h e number of assay i t e m s , N is obtained b y taking t h e


9

mean of the square of t h e (N — 1) difference b e t w e e n t w o successive assays,


or!

(35)

The variance of t h e assays is d e p e n d e n t o n t h e ith assay X and t h e mean of


t

all assays X as f o l l o w s :

(36)
153

The comparison b e t w e e n 5 and s is that t h e value o f 5 is based o n t h e


2 2 2

difference b e t w e e n t w o successive assays, whereas t h e value o f s is depen- 2

d e n t o n t h e deviates of each assay from t h e m e a n of all assays. When N > 2 5 ,


the formula for t h e m e a n square succession difference, Z, is used ( B e n n e t t
and Franklin, 1 9 5 4 ) :

(37)

where:

e = l - (38)

For long-period fluctuation in t h e assay data, e will be positive w h e n t h e


ratio 5 / s = r? is less than 2 . However, for short-period fluctuation in t h e
2 2

assay data, e will b e negative for values greater than 2. T h e s e positive and
negative values of e Eire useful in t h e mean-square-successive-difference test in
determining t h e i n d e p e n d e n c e and non-randomness b e t w e e n successsive
assays, and also t o differentiate b e t w e e n t h e t y p e s of fluctuations in t h e assay
data as well as t h e prediction o f trend in t h e assay data.
A process, referred t o as Kriging, o f finding optimal weighting factor for
sample grades used in the estimation of b l o c k s of ore has been recently
described b y D o w d ( 1 9 7 5 ) . This procedure uses a cathode-ray display screen
in t h e conversational m o d e w i t h t h e operator. The m e t h o d of Kriging in a
two-dimensional s y s t e m and t h e use o f t h e variogram, a major t o o l of g e o -
statistics, is applied t o basic mining p r o b l e m s . The variogram is a f u n c t i o n
w h i c h represents the variance of samples w i t h respect t o t h e differences
b e t w e e n t h e m . Several e x a m p l e s of this t e c h n i q u e in w h i c h t h e operator is
intimately involved in t h e e s t i m a t i o n process via t h e C R T display are given.
The use of such c o m p u t e r techniques are necessary t o bring operators in
close t o u c h w i t h t h e p r o b l e m , rather than d e p e n d o n t h e service o f expert
c o m p u t e r specialists w h o are s e l d o m aware of t h e m a n y variables affecting
t h e estimation of ore grades in a c o m p l e x g e o l o g y .

Application of radioactivation methods

A l t h o u g h t h e p e t r o l e u m industry has b e e n using nuclear t e c h n i q u e s for


well logging of oil-bearing formations since t h e 1 9 3 0 ' s , t h e mineral industry,
o n t h e other hand, has b e e n rather s l o w t o take advantage o f such t e c h n i q u e s .
Consequently applications and appropriate d o c u m e n t a t i o n o f field case
histories have b e e n meagre t o d a t e . In t h e literature, it is difficult t o search
for such applications for specific e l e m e n t s since t h e m e t h o d s themselves are
generally classified according t o t h e nuclear principles u s e d . A recent review
b y S c o t t and Tibbetts ( 1 9 7 4 ) summarizes nuclear m e t h o d s for mineral
deposit evaluation. The radioactivation m e t h o d s as applied t o t h e determina-
154
TABLE 5-VII
Radioactivation methods in well logging

Logging technique Metals

gen- Al Sb Be B Cu Fe Pb-Zn Mn Hg Ni Ag-Au Sn W U


eral

Natural gamma ray X X X X


Gamma-ray spectral X
Gamma-gamma ray X X X X X X X
Selective gamma-gamma ray X X X X X X X
X-ray fluorescence X X X X X X X X
Neutron absorption X X X X
Neutron activation X X X X X X X
Photoneutron X
Resonance gamma absorption X
Neutron fission X

Non-metals

general coal evaporites fluorspar oil shale rock salt s


Natural gamma ray
Gamma-ray spectral
Gamma-gamma ray
Selective gamma-gamma ray
X-ray fluorescence
Neutron absorption
Neutron activation
Photoneutron
Resonance gamma absorption
Neutron fission
155

t i o n of e l e m e n t s b y well logging t e c h n i q u e s are abstracted from this review


and tabulated (Table 5-VII).
These t e c h n i q u e s are within t h e general s c o p e o f this chapter and there-
fore described. In order t o reduce t h e c o m p l e x i t y of this discussion, an
a t t e m p t is made t o classify applications in terms of t h e nuclear process
described in t h e s e c t i o n "Theoretical considerations". Furthermore, since
t h e utilization of instruments, logging devices, m o b i l e laboratories, and other
logging hardware are closely tied in w i t h their individual applications t o t h e
determination of specific e l e m e n t s , such descriptions are included in t h e
discussion of pertinent applications. Properties of special materials used for
t h e construction o f logging devices or s o n d e s are given t o aid in t h e design
and fabrication of similar measuring t o o l s . Such discussions are again
restricted t o the application in q u e s t i o n . An a t t e m p t is m a d e t o m i n i m i z e t h e
inclusion of large tabulations of nuclear data, sensitivity and t h e like. As far
as possible t h e sources of such information have b e e n referenced and o n l y
appropriate abstractions from such sources have b e e n tabulated. It is h o p e d
that t h e approach described above will be less confusing t o t h e reader and
still maintain c o n t i n u i t y of discussion relevant t o application o f radioactiva-
tion t e c h n i q u e s t o mineral e x p l o r a t i o n . It m a y also be recalled that t h e selec-
t i o n of t e c h n i q u e s is based o n t h e authors' j u d g e m e n t as t o w h i c h t e c h n i q u e
had b e e n adequately researched and had p r o d u c e d , or had t h e potential of
producing satisfactory field case histories. Before discussing t h e application
of individual radioactivation t e c h n i q u e s t o mineral e x p l o r a t i o n , t h e reader's
attention is drawn t o s o m e e x c e l l e n t reviews b y Berzin et al. ( 1 9 6 6 ) , K e y s
and B o u l o g n e ( 1 9 6 9 ) , Czubek ( 1 9 7 1 ) , and Gjibels ( 1 9 7 3 ) , w h i c h summarize
applications; and t o sources o f nuclear data c o m p i l e d b y G r e e n w o o d and
R e e d ( 1 9 6 5 ) , B r o o k h a v e n National Laboratory ( 1 9 6 0 — 1 9 6 6 ) , Rasmussen et
al. ( 1 9 6 9 ) , D u f f e y et al. ( 1 9 7 0 ) , and Nargolwalla and P r z y b y l o w i c z ( 1 9 7 3 ) ,
applicable t o radioactivation m e t h o d s of elemental analysis.

Gamma-gamma techniques
A s m e n t i o n e d earlier, t h e gamma-gamma backscattering t e c h n i q u e has
been used for e l e m e n t determinations b y three possible m e t h o d s : ( 1 ) density
logging, ( 2 ) selective gamma logging, and (3) spectrometric gamma-gamma
logging.
Perhaps o n e o f t h e best e x a m p l e s of t h e utilization o f this general tech-
nique is d o c u m e n t e d b y D o n h o f f e r ( 1 9 6 8 ) . The evaluation in a horizontal
drill h o l e concerns t h e analysis of zinc in a zinc-lead deposit. Because of t h e
special g e o l o g y in t h e m i n e operated b y Bleiberger Bergwerksunion, Austria,
calibration curves relating density t o the zinc c o n t e n t were d e v e l o p e d for an
o p t i m u m source-detector g e o m e t r y and an o p t i m a l l y selected primary
gamma-ray energy source. The backscatter probe used b y D o n h o f f e r is
shown in Fig. 5 - 2 1 . A family of calibration curves was d e v e l o p e d for
various source-detector geometries and source t y p e s using fundamental
156

SCATTERED

GAMMA-RAY

PRIMARY

Nal CRYSTAL BORE HOLE


WALL

P M TUBE 8 PREAMR

PROBE CASING SOURCE

Fig. 5-21. Schematic view of backscatter probe (Donhoffer, 1 9 6 8 ) .

gamma-ray transport principles applied t o a t w o - c o m p o n e n t s y s t e m . The


particular g e o l o g y investigated was a g o o d e x a m p l e o f a t w o - c o m p o n e n t
s y s t e m . The zinc ore occurs mainly as t h e sulphide in a l i m e s t o n e matrix.
Lead concentrations were generally of an order of magnitude less than that
o f zinc. T h e analysis was c o n d u c t e d in 48-mm-diameter boreholes. For c o m -
parison purposes fourteen h o l e s , s o m e o f w h i c h were 5 0 m long, and for
w h i c h core analyses were available, were selected. T h e total length of bore-
h o l e s logged w a s a b o u t 9 4 0 m .
The probe (Fig. 5-21) consisted of a source holder in which three t y p e s of
gamma-ray sources were used. These were S e , C s and C o . A 14-cm-long
7 5 1 3 7 6 0

lead shield separated t h e source from a 0.75-inch b y 0.75-inch N a l ( T l ) scin-


tillation d e t e c t o r . The distance b e t w e e n t h e source and d e t e c t o r could be
varied b y introducing acrylic spacers. The overall diameter o f t h e probe was
3 6 m m . The probe was e n c l o s e d in a close-fitting plastic t u b e of 4 2 m m out-
side diameter, so that t h e probe was essentially centered in the b o r e h o l e .
A ratemeter with a t i m e c o n s t a n t of 1 5 s e c o n d s was e m p l o y e d t o measure
c o u n t rates u p t o 2 0 0 0 c o u n t s per s e c o n d . Incremental logging in 0 . 2 5 - m
steps was performed. This distance corresponded t o t h e linear length o f t h e
sensitive v o l u m e scanned b y t h e probe. N o m i n a l l y t h e scans were d o n e at a
speed of 2 5 m per hour. T h e logging data were normalized t o measurements
m a d e o n o n l y t h e rock matrix. These data were obtained from the scanning of
boreholes in w h i c h o n l y t h e matrix was present. This so-called zero value (I ) 0

was f o u n d t o be essentially constant. Plotting I/I against t h e mineral c o n -


0

t e n t , D o n h o f f e r obtained results as s h o w n in Figs. 5-22 t o 5 - 2 4 . Based o n his


studies, D o n h o f f e r c o n c l u d e d that a 37-mCi C s g a m m a source separated
1 3 7

from t h e d e t e c t o r b y 3 0 c m n o t o n l y gave almost an o p t i m u m sensitivity,


but the probe was also insensitive t o o t h e r interferences from anomalies.
Several conclusions are drawn from t h e results: ( 1 ) if zinc was the only
157

GAMMA-MEASUREMENT CHEMICAL
ANALYSIS
^ A I J I J A UCAOIIDCMCMT
GAMMA-MEASUREMENT
CHEMICAL
ANALYSIS
DEPTH OF BORE HOLE (m)

0.5 10 0 20 10 0 0 10
%Zn %Zn
RELATIVE INTENSITY l / l % Z n % Z n

RELATIVE INTENSITY l / l 0
Q

Fig. 5-22. Borehole profile, showing high ore concentration at the end (Donhoffer, 1 9 6 8 ) .

Fig. 5-23. Borehole profile with strong anomalies (Donhoffer, 1 9 6 8 ) .

GAMMA-MEASUREMENT
DEPTH OF BOREHOLE (m)

0.5 1.0 4 0 20 0 4020 0 4 0 20 0


%0RE %Zn % P b

RELATIVE INTENSITY l/l 0

Fig. 5-24. Borehole profile with high-grade zinc- and lead-bearing zone (Donhoffer, 1 9 6 8 ) .
158

e l e m e n t present in t h e matrix, ore concentration in t h e range of 1—10% Zn


could be analyzed t o an accuracy within ± 1 % Zn; ( 2 ) if lead is present s o m e
k n o w l e d g e o f P b / Z n ratios is necessary; (3) t h e m e t h o d has t h e capability of
analyzing a m u c h larger ore sample than that used for core analysis; and (4)
the technique offers distinct advantages in terms of t h e speed of analysis and
t h e almost instantaneous data retrieval.
In assessing t h e merits of Donhoffer's s t u d y , it can be said the presence of
lead can have a very serious effect o n zinc determinations. The sensitivity for
lead determinations is of t h e order of 3—5 t i m e s that for zinc. The possibil-
ity of determining b o t h lead and zinc also exists. In this case t w o sources,
C s and S e , are used. The primary source energies essentially straddles the
1 3 7 7 5

K-edge of lead. B y using a very short source-detector distance t h e response


from each e l e m e n t can be measured. However, such experiments are still in
t h e laboratory stage.
The use of density gamma-gamma and selective gamma-gamma m e t h o d s
have been m a d e for t h e determination o f iron. Czubek ( 1 9 7 1 ) , reporting on
the success o f several investigations in this area, describes a m e t h o d e m p l o y -
ing the two-source principle. The logging s o n d e contains a S e and a 7 5
Cs
1 3 7

source. For qualitative identification of ore z o n e s , the total scattered


gamma-ray intensity is measured. Ore z o n e s containing iron are characterized
b y m i n i m u m intensity as measured b y t h e d e t e c t o r s y s t e m . Since a total
intensity measurement is n o t adequate for an iron correlation, t w o
approaches are taken: (1) developing a relationship b e t w e e n t h e metal c o n -
centration and t h e average a t o m i c n u m b e r of t h e matrix, Z e q (for iron there
appears t o be a g o o d correlation), and ( 2 ) developing a correlation b e t w e e n
the in-place density and t h e iron c o n t e n t . Results reported b y Czubek for
the latter t e c h n i q u e are s h o w n in Fig. 5-25. However, Czubek points o u t that
if n o correlation b e t w e e n t h e metal c o n t e n t and t h e in-place density exists, a
relative spectral intensity measurement m e t h o d can b e used. In this case t h e
ratio of soft t o t h e hard scattered c o m p o n e n t s is correlated with t h e e l e m e n t
concentration. A n e x a m p l e of this application for the determination of iron
is s h o w n in Fig. 5-26. It should be recognized that logging instrumentation
required for this t y p e o f operation is considerably m o r e sophisticated and
in t h e d e v e l o p m e n t stage.
Recalling Donhoffer's study ( 1 9 6 8 ) it was emphasized that t h e presence
of lead in t h e d e p o s i t w o u l d influence determinations for zinc, and the pos-
sibility of using t h e two-source principle for determining a correction for t h e
Pb/Zn ratios was considered. Czubek's report ( 1 9 7 1 ) describing the S e - 7 5

B a s y s t e m is encouraging. B y c h o o s i n g an o p t i m u m source-detector
1 3 3

distance expressed in g c m " , t h e e q u a t i o n :


2

r R =f(rp)
2
yy (39)
can be used t o design a probe w h i c h is relatively insensitive t o changes in t h e
in-place density of t h e rock matrix. In t h e above expression, r, is t h e source-
159
°9|o INTENSITY IN THE ORE LAYER/
( BACKGROUND INTENSITY \
L

IRON PERCENT

Fig. 5-25. Correlation between the logarithm of the amplitude of the selective gamma-
gamma anomaly and iron content (Czubek, 1 9 7 1 ) .
_ HIGH ENERGY SCATTERED PHOTONS
~ LOW ENERGY SCATTERED PHOTONS
P

IRON CONTENT, PERCENT

Fig. 5-26. Correlation between the P value and iron content (Czubek, 1 9 7 1 ) .
160

d e t e c t o r distance, R ,
yy the measured intensity of scattered p h o t o n s , and p is
t h e rock d e n s i t y . The m e t h o d used t o obtain Fig. 5-25 can n o w be used t o
interpret t h e results. Such an approach is particularly successful for t h e
determination of lead in t h e presence of zinc and iron. However, for t h e
technique t o be c o m p l e t e l y i n d e p e n d e n t from density effects, supplemental
gamma-gamma density logs are necessary. The uncertainty in lead determina-
tions using t h e selective gamma-gamma m e t h o d is o f t h e order of 14% with a
d e t e c t i o n limit of a b o u t 0.2—0.3% Pb. In t h e Soviet U n i o n and Czechoslovakia,
lead determinations are routinely carried o u t b y this m e t h o d and have
afforded a 10% savings in t h e total c o s t o f p r o d u c t i o n of t h e m i n e . S i m o n
( 1 9 6 9 ) has described a s y s t e m o f Czechoslovakian manufacture in which a
probe 3 4 m m in diameter is used. The primary gamma source is C o . The 6 0

d e t e c t o r system uses a Geiger-Muller t u b e . This battery-operated device is


capable of making point-to-point measurements in 2 5 - c m steps. A 3 0 - m
borehole can be logged in six hours. Quadruplicate measurements each o f
three-minute duration are taken at each meter. This s y s t e m has undergone
exhaustive tests in t h e Czechoslovakian tin deposits. F r o m 1.5 t o 3 mCi o f
C o and from 1.5 t o 2 mCi of S e are used as e x c i t a t i o n gamma-ray
6 0 7 5

sources.
In order t o reduce t h e systematic errors in t h e gamma-gamma t y p e mea-
surements, a t t e m p t s have b e e n m a d e t o reduce t h e effect of a changing
borehole diameter, uneveness of t h e borehole walls and t h e effect of drilling
m u d o n t h e measurements. Special efforts have b e e n m a d e t o properly
collimate b o t h t h e source and t h e d e t e c t o r , t o reduce s o m e of t h e above
sources o f error. T o d a y t h e state-of-the-art offers e q u i p m e n t w h i c h is stable
even at temperatures u p t o 1 5 0 ° C . B l y u m e n t s e v and F e l d m a n ( 1 9 6 2 ) have
developed an instrument w h i c h adequately corrects for the effect of drilling
m u d . Their s y s t e m is essentially a t w o - d e t e c t o r s y s t e m , each d e t e c t o r is o f a
different size and is situated at different and adjustable distances from the
gamma-ray source. The larger d e t e c t o r response is converted i n t o rock
density values. B y analog c o m p u t i n g devices (constructed from t h e small
d e t e c t o r measurements), a correction curve is generated. This curve is added
t o , or subtracted from (in the case of heavy s o l u t i o n s ) , t h e density curve.
Such e q u i p m e n t has b e e n k n o w n t o operate under a pressure of 1 4 0 0 kg
c m " and at temperatures u p t o 2 0 0 ° C and provide logging speeds of 5 5 0 m
2

per hour. However, t h e s o n d e requires a m i n i m u m b o r e h o l e diameter of at


least 5 inches.
Experimental c o n d i t i o n s pertinent t o selective gamma-gamma logging
include c o m p e n s a t o r y parameters, t o reduce t h e effect of changing borehole
diameter. Experimentally it has b e e n established that for a 3 2 - m m diameter
s o n d e e m p l o y i n g t w o sources, o n e of w h i c h is S e , n o effect is observed for
7 5

a b o r e h o l e diameter change b e t w e e n 4 0 — 2 3 0 m m w h e n t h e o p t i m u m
distance of S e sources from t h e d e t e c t o r are 1 9 0 m m and 1 9 m m , for an
7 5

activity ratio of 2 5 : 1. These parameters are so c h o s e n that as t h e borehole


161

diameter varies t h e r e d u c t i o n in scattered radiation from o n e source is c o m -


pensated b y an increase in intensity from the other. Furthermore, it has b e e n
established that t h e d o u b l e probe is essentially i n d e p e n d e n t of density
within a substantial range o f 1.5—3.0 g c m " . A l t h o u g h t h e " d o u b l e p r o b e "
3

c o n c e p t provides comparable sensitivities t o t h o s e obtained from normal


probes, t h e rock penetration is approximately o n e half w h e n c o m p a r e d t o
that of t h e normal probe.
In spectrometric gamma-gamma logging, the spectral analysis o f scattered
p h o t o n s makes it possible t o determine t h e d i s c o n t i n u i t y of t h e spectrum
d u e t o the K-absorption edge. S o m e advantages realized b y this approach
include high sensitivity, differentiation of C o m p t o n scattering events and less
susceptibility t o t h e effect of cavities than m e t h o d s in w h i c h o n l y integral
intensity measurements are m a d e . A n important consideration in coal mining
is t h e determination of t h e ash c o n t e n t . In t h e 0—30% ash c o n t e n t range, t h e
accuracy for its d e t e r m i n a t i o n , using spectrometric gamma-gamma logging,
is of t h e order of 1—15%. In this specific application carried o u t b y U t k i n
( 1 9 6 5 ) , spectral ratios of c o u n t s recorded in a channel set at 6 0 keV and the
other at 1 4 0 keV are c o m p u t e d ; t h e band w i d t h of b o t h channels is a b o u t
2 5 k e V . T h e instrument included a source ( T 1 , 4 0 mCi) separated from a
2 0 4

d e t e c t o r b y o n l y 1 0 c m . Spectrometric instrumentation that can be used in


b o r e h o l e s u p t o 1 5 0 0 m in d e p t h , has b e e n d e v e l o p e d .

Gamma-ray resonance scattering


S o w e r b y and Ellis ( 1 9 7 3 ) , in an elegant d e m o n s t r a t i o n o f t h e gamma-ray
resonance scatter p h e n o m e n o n , s h o w e d a promising application o f this tech-
nique t o plant-stream monitoring of certain base metals in t h e mineral
processing industry. A n o t h e r possible application is t h e b o r e h o l e analysis for
t h e elements copper and nickel. Inferences drawn from laboratory studies
carried o u t in simulated media indicated that gaseous sources o f Z n I and 6 5
2

C o B r could be used for t h e determination of c o p p e r and nickel, respec-


6 0
2

tively. Borehole diameters from 7.5—20 c m c o u l d be used w i t h o u t inducing


significant e x c e s s errors. T h e sensitivity of t h e m e t h o d for copper analysis was
4 c o u n t s per s e c o n d per 1% Cu in t h e p h o t o p e a k for a 10-Ci Z n I source and
6 5
2

a N a l ( T l ) d e t e c t o r . A t this sensitivity t h e background under t h e p h o t o p e a k


was also 4 c o u n t s per s e c o n d . Similar data were obtained for t h e e l e m e n t
nickel. It was c o n t e n d e d from their results that logging speeds of a b o u t 0.5—
1.0 m per m i n u t e were possible in b o r e h o l e s > 1 4 c m in diameter. U n d e r these
c o n d i t i o n s 0.5% Cu or N i could be determined with a relative accuracy of
20%. Advantages of this m e t h o d over t h e diamond-core drilling process
included a 50% c o s t saving and analysis of samples t w e n t y t i m e s larger than
equivalent core samples.
In t h e comparison o f this m e t h o d with other t e c h n i q u e s , S o w e r b y ( 1 9 7 3 )
is perhaps u n d u l y harsh, since t h e gamma resonance scatter t e c h n i q u e d o e s
n o t appear t o have g o n e past simulated borehole testing. Furthermore,
162

several m e t h o d s criticized have already proven themselves in p r o d u c t i o n


logging under severe environmental c o n d i t i o n s . Moreover, t h e object of using
a high activity o f gaseous sources for borehole work m a y raise difficult
questions in terms of health physics precautions and radioactivity licensing
administrations in various countries. However, t h e intrinsic advantages of
this t e c h n i q u e under well-controlled c o n d i t i o n s , such as plant-stream
monitoring in t h e process industry are significant. The t e c h n i q u e is probably
t h e m o s t specific for c o p p e r and nickel. The application is unique, and with
time will find a significant place in t h e analytical arsenal.

Photonuclear methods
As emphasized in t h e section "Theoretical considerations", p h o t o n e u t r o n
logging is limited t o the determination of beryllium. Currently this technique
is used t o re-evaluate k n o w n beryllium deposits, t o e x t e n d t h e thickness of
these deposits and re-determine t h e d e p t h s . Prior t o logging, standardization
of beryllometers is necessary. Normally this is performed b y calibrating the
instrument using an experimental m o d e l m a d e u p o f a mixture of beryllium
o x i d e and paraffin. In t h e field, high-speed scans at rates up t o 1 5 0 m per
h o u r are carried o u t . Interesting ore regions isolated are carefully e x a m i n e d at
a m u c h reduced rate of ca. 20—40 m per hour. Berzin e t al. ( 1 9 6 6 ) define a
relationship in saturated strata b e t w e e n t h e area S of t h e a n o m a l y , the true
thickness of t h e ore b o d y H, and t h e beryllium c o n t e n t g b y t h e e q u a t i o n :
S = KHg (40)

where K is a proportionality coefficient w h o s e value d e p e n d s o n t h e param-


eters of t h e b o r e h o l e s o n d e , e.g. source-detector separation, d e t e c t o r g e o m -
etry and efficiency, source strength, drilling c o n d i t i o n s , density and c o m p o -
sition o f t h e rock, e t c . Should t h e o r e b o d y contain high neutron-absorbing
elements such as B, Li, etc., t h e gamma-gamma or neutron-neutron logging is
used t o s u p p l e m e n t t h e gamma-neutron beryllium log. E x c e p t for t h e
environmental factors, t h e t e c h n i q u e is specific for beryllium. A t t h e thresh-
old energies used, beryllium is t h e o n l y e l e m e n t w h i c h will undergo t h e
( 7 , n ) reaction. The present beryllometers, as compared t o the 1 9 5 0 m o d e l s ,
have n o t really changed t o o m u c h . The sensitivity of t h e m e t h o d is of the
order o f 0 . 0 0 1 % BeO w h e n an irradiation source strength o f 10—20 mCi of
S b and a H e neutron d e t e c t o r are used. Beryllometers incorporating
1 2 4 3

source strengths u p t o 5 0 mCi of 1 2 4


S b have b e e n used t o determine beryl-
lium with purported accuracies of 0 . 0 0 3 % with a logging speed of about
20—30 m per h. Much of t h e d e v e l o p m e n t of beryllometers is d o n e b y Soviet
researchers (Saltsevich et al., 1 9 6 8 a , b) w h o s e work is highly r e c o m m e n d e d
for interested log analysts.

Neutron methods
Of all t h e nuclear techniques applied t o in-situ elemental determination in
163

boreholes, t h e n e u t r o n activation and t h e neutron-capture-gamma m e t h o d s


are considered m o s t promising. Basically, these t e c h n i q u e s involve t h e
irradiation of the b o r e h o l e walls and surrounding matrix with neutrons.
U p o n interaction, several t y p e s of nuclear reactions can be induced. The
m o s t frequently used in neutron activation analysis is t h e (n, 7 ) reaction.
Measurements of characteristic g a m m a radiation resulting from this reaction
can be made simultaneous (i.e. p r o m p t g a m m a emissions from t h e de-excita-
t i o n of t h e c o m p o u n d nucleus) or subsequent (i.e. g a m m a emissions from
t h e p r o d u c t nuclide d e c a y i n g with a characteristic half-life). B y and large,
applied research in neutron-gamma m e t h o d s has b e e n limited t o t h e measure-
m e n t s of gamma emissions from d e c a y i n g product nuclide (i.e. delayed
gamma-ray measurements). C o n s e q u e n t l y , t h e logging process can be
severely hampered b y t h e e x i s t e n c e of nuclear interferences, environmental
background difficulties, and relatively s l o w and u n e c o n o m i c a l logging
speeds. On t h e other h a n d , t h e use of p r o m p t g a m m a emissions for analytical
purposes has b e e n neglected. R e c e n t l y , however, t h e w o r k o f Senftle et al.
( 1 9 7 1 b ) generated considerable interest in t h e application of this t e c h n i q u e t o
t h e borehole logging of base metals. In this semi-quantitative s t u d y , Senftle
et al. determined t h e e l e m e n t nickel in ore samples b y a m e a s u r e m e n t o f t h e
single and d o u b l e escape fractions of t h e primary ( 8 . 5 3 M e V ) p r o m p t emis-
sion from thermal neutron capture in nickel nuclei. A high-resolution solid-
state d e t e c t o r was used in their laboratory s t u d y . Results obtained in a test
borehole indicated t h e feasibility o f t h e t e c h n i q u e . In comparing t h e above
t e c h n i q u e w i t h t h o s e in w h i c h delayed activation products have b e e n mea-
sured b y Eisler et al. ( 1 9 7 1 ) , H o y e r and L o c k e ( 1 9 7 2 ) , Landstrom e t al.
( 1 9 7 2 ) , and M o x h a m e t al. ( 1 9 7 2 ) , s o m e general c o n c l u s i o n s can be drawn
(Table 5-VIII).

TABLE 5-VIII
Comparison of in-situ gamma measurement techniques

Analytical property Analysis technique, dry matrix


(density = 2 g c m ) - 3

prompt gamma, delayed gamma,


Ey — 7 MeV Ey = 2 MeV

Useful sample radius 40—50 cm 4—6 cm


Effective sample volume ~ 1 0 cm
6 3
~ 1 0 cm
3 3

Borehole effects minimal significant


Inhomogeneity effects minimal significant
Density effect (1.5—2.0 g c m ) - 3
minimal significant
Moisture effect significant significant
Logging speed fast, 5 0 - 1 0 0 ft/h slow, 5—10 ft/h
Environmental radioactivity interference not pertinent severe
164

Neutron-gamma m e t h o d s used in mineral exploration have d e p e n d e d u p o n


isotopic (e.g. A m - B e ) , fission (e.g. C f ) and accelerator (e.g. sealed-tube
2 4 1 2 5 2

14-MeV neutron generators) n e u t r o n sources. The detectors used are essen-


tially o f t w o t y p e s , i.e. s o d i u m iodide scintillator and the lithium-drifted
germanium detector. Properties and operation of these d e t e c t o r s , in con-
j u n c t i o n w i t h nuclear pulse-handling s y s t e m s can b e f o u n d in a t e x t b y
Krugers ( 1 9 7 3 ) . T o date there are several exploration case histories devel-
o p e d from the use of t h e s o d i u m iodide detector. A n adequate p r o d u c t i o n
logging case history (Fanger e t al., 1 9 7 3 ) , based o n t h e use o f t h e Ge(Li)
d e t e c t o r , has b e e n reported. R e c e n t d e v e l o p m e n t s concerning long-term
field use of t h e Ge(Li) d e t e c t o r described b y Lauber and Landstrom ( 1 9 7 2 ) ,
Tanner et al. ( 1 9 7 2 ) , and Fanger et al. ( 1 9 7 3 ) , are being actively pursued
and it is h o p e d that in t h e very near future this t y p e of d e t e c t o r with accept-
able efficiency will be available for operation o n a c o n t i n u o u s day-to-day
basis in p r o d u c t i o n logging. T h e applications of neutrons as a base for mineral
explorations are classified according t o t h e nuclear reactions being utilized
for elemental analysis.

Inelastic neutron scattering — prompt gamma-ray measurement This m e t h o d


possesses serious limitations for its direct application t o borehole explora-
t i o n . Studies carried o u t for t h e d e v e l o p m e n t o f this m o d e o f analysis are
essentially of an exploratory nature. T o construct a viable borehole s o n d e t o
include a high-energy pulsed neutron source presents considerable fabrica-
t i o n and analytical problems. Normalization and calibration of such devices
in terms o f t h e incident neutron flux delivered per burst t o t h e matrix, give
data that is at best within ± 2 0 % in accuracy. This discrepancy in t h e prin-
cipal controlling activation parameter thus affects t h e final result according-
ly. Caldwell et al. ( 1 9 6 0 ) measured t h e inelastic gamma-ray spectra of nine
elements representing t h e c o m m o n earth. E x c e p t for s o m e of t h e light ele-
m e n t s (i.e. C, O, Mg, Si and P), t h e majority o f g a m m a rays resolved were
b e l o w 2.5 MeV. The neutron source used consisted of a Van de Graaff
accelerator in w h i c h 3 2 5 - k e V deuterons were allowed t o impinge u p o n a
thick zirconium-tritium target. The gamma-ray measurements were made
w i t h a 2-inch diameter b y 2-inch long N a l ( T l ) crystal. Stinner ( 1 9 6 1 ) c o n -
d u c t e d an extensive feasibility study t o assess the potential of this technique
for lunar exploration. A high-energy pulsed n e u t r o n source and a cylindrical
1.75-inch diameter b y 2-inch l o n g N a l ( T l ) scintillator were used t o generate
and measure t h e inelastic gamma-ray spectra, respectively.
A summary of Stinner's study in which t h e m i n i m u m d e t e c t a b l e abun-
dance of nine c o m m o n earth e l e m e n t s is tabulated in Table 5-IX. A time
diagram illustrating t h e basis o f t h e inelastic scattering t e c h n i q u e is s h o w n in
Fig. 5-27. In this s t u d y , n o m e n t i o n of instrumental difficulties or probable
errors t o be e x p e c t e d has b e e n m a d e . A m o r e elaborate study m a d e b y
Waggoner and K n o x ( 1 9 6 8 ) is w o r t h y of n o t i c e . In this research, a great deal
165

TABLE 5-IX
Analysis of c o m m o n lunar elements by nuclear inelastic scattering

Possible elements Principal Isotopic Prominent Minimum detect-


found on the isotope abundance energy level able abundance
m o o n surface (%) (MeV) (%)

Iron 5 6 F e
91.5 0.84 0.1
Silicon 2 8
Si 92.3 1.78 0.5
Magnesium 2 4
Mg 78.6 1.37 0.3
Aluminum 2 7
A1 100 2.20 2.0
Oxygen 16Q
99.8 6.14 3.7
(triple peak)
3 9
Potassium K
93 2.15 1.0
Calcium 4 0
Ca 97 0.77 1.2
Sodium 2 3
Na 100 0.63 1.3
Nickel 5 8 N i
67.8 1.45 1.0

of effort was e x p e n d e d in developing a suitable fast n e u t r o n generator w h i c h


w o u l d potentially f u n c t i o n o n t h e lunar surface. The total weight o f the
instrument was just 1 4 p o u n d s including a pulsed source of 1 4 - M e V n e u t r o n s ,
a 512-channel gamma-ray spectrometer and associated electronics. Special
a t t e n t i o n has b e e n given t o d e t e c t o r shielding requirements. Readers
interested in this m o d e of analysis will find this report very useful.

Fast neutron-induced reactions. T o fully appreciate t h e significance o f prin-


cipal fast neutron interactions, i.e. (n, p ) , ( n , a ) and (n, 2 n ) , as applied t o

Fig. 5-27. Time spectrum of gammas from a pulsed neutron source (Stinner, 1 9 6 1 ) .
166

mineral exploration, o n e m u s t compare their merits with the operational


parameters of b o t h standard chemical and non-nuclear instrumental tech-
niques, and t o similar considerations pertinent t o other m o d e s of nuclear
analysis. Activation analysis w i t h fast neutrons, c o n t i n u o u s or pulsed, is
principally c o n d u c t e d w i t h portable sealed-tube accelerators described
extensively b y Nargolwalla and P r z y b y l o w i c z ( 1 9 7 3 ) . D u e t o t h e high
incident neutron energy, t h e m o s t probable nuclear reactions are those
in which particles are e m i t t e d . The basic m e t h o d is highly selective, partic-
ularly for t h e light e l e m e n t s , and t h e neutron source, through a c h o i c e of
different target materials, can provide c o p i o u s fluxes of intermediate-energy
( ~ 3 MeV) or high-energy ( ~ 1 4 M e V ) neutrons. With t h e rapid advancement
in electronic t e c h n o l o g y , it is possible t o construct measurement devices that
can b e introduced i n t o boreholes o f o n l y 3 inches in diameter.
In its application t o mineral analysis, Senftle and H o y t e ( 1 9 6 6 ) have dis-
cussed t h e use of a fast neutron accelerator source for elemental determina-
tions. Their research s h o w s that w h e n exploring for e l e m e n t s of e c o n o m i c
interest, the neutron-producing reaction H ( d , n ) H e (3-MeV neutrons) is
2 3

more practical than 14-MeV neutrons produced from t h e H ( d , n ) H e reac-3 4

t i o n . F r o m their feasibility s t u d y , analytical conclusions regarding t h e use


of 14-MeV neutrons for mineral explorations are s h o w n in Table 5-X. Con-
siderable interest in t h e use of accelerator neutrons for prospecting has been
sponsored b y Australian research organizations. Wylie and Eisler ( 1 9 6 9 ) used
a sealed-tube accelerator manufactured b y Philips, and c o n d u c t e d carefully
controlled laboratory studies. F r o m t h e results o b t a i n e d , requirements for a
viable t e c h n i q u e applicable t o b o r e h o l e exploration were expressed. These
requirements included a desired rapid scanning logging speed up t o 2 5 0 m
per hour, f o l l o w e d b y a m o r e detailed e x a m i n a t i o n of interesting sections of
t h e b o r e h o l e . A suggested d e t e c t o r system favoured t h e selection of t h e
N a l ( T l ) scintillator over t h e high-resolution Ge(Li) detector. The importance
of shielding the d e t e c t o r with a blanket of B or Li was emphasized t o
1 0 6

reduce t h e measurement of g a m m a p h o t o n s created b y neutrons scattered


i n t o t h e d e t e c t o r itself. This work was subsequently f o l l o w e d u p by a
study c o n d u c t e d b y Eisler et al. ( 1 9 7 1 ) concerning t h e analysis of copper.
In this study, experimental m o d e l s w h i c h simulate boreholes were used.
The measurement of t h e strong annihilation peak d u e t o positron d e c a y of
t h e activated species produced from C u ( n , 2 n ) C u ( T = 9 . 8 min) and
6 3 6 2
1 / 2

6 3
C u ( n , 7 ) C u ( T = 1 2 . 8 h ) , respectively, were used for t h e analysis of
6 4
1 / 2

copper. According t o Dibbs ( 1 9 7 0 ) , t h e elements which interfere in this


m e t h o d are tabulated in Table 5-XI. Eisler et al. ( 1 9 7 1 ) used a 2-inch diam-
eter b y 2-inch long N a l ( T l ) scintillator with a resolution o f 8% for t h e 0 . 6 6 2 -
MeV gamma emission from C s . This spectral quality was maintained at the
1 3 7

e n d of a 3 5 - m logging cable. The neutron t u b e was operated at a continuous


o u t p u t of 1 0 n s" . Spectra were recorded b y a 400-channel pulse-height
8 1

analyzer, and digital gain stabilization was used t o maintain spectral integrity
167

TABLE 5-X
The counting rates * for some of the nuclides ** most easily activated by 14-MeV neu-
trons ( 1 0 n c m " s"" ) after 2-minute irradiation and a 5-second delay time (Senftle and
9 2 1

Hoyte, 1 9 6 6 )

Parent Reaction Daughter Half-life Counting rate (cps/g) Major 7


nuclide nuclide after radiation
(MeV)
2-minute followed by
irradiation 5-second
delay time

2 3
Na n, a 20p 11.2 s 5.8 X 10 s
5.1 X 10 s
1.63
n, p
2 3
Ne 40.2 s 8.0 X 10 4
7.3 X 10 4
0.44
19p 19Q 29.4 s 4.2 10 s
3.7 10 5
1.37, 0.20
n, p X X
16Q 16 7.35 s 3.5 10 s
2.2 10 s
7 . 1 , 6.1
n, p N
X X
2 8
Si n, p A1
2 8
2.27 min 2.0 X 10 s
1.9 X 10 s
1.78
2 9
Si n,p A1
2 9
6.56 min 5.0 X 10 4
4.9 X 10 4
1.28, 2.42
n
B n, a Li
8
0.83 s 1.5 X 10 s
2.3 X 10 3
4.43
31p n, a A1
2 8
2.27 min 1.4 X 10 s
1.4 X 10 s
1.78
109 A g
n, 2n ios A g 2.3 min 1.0 X 10 s
1.0 X 10 s
0.44
7 9
Br n, 2n 78 B r
6.4 min 9.5 X 10 4
9.4 X 10 4
0.11, 0.049
2 5 M g
n, p 2 5
Na 60 s 8.5 X 10 4
8.0 X 10 4
1.37, 2.75
n, a 34p 12.4 s 7.8 10 5.9 10 2.1
C1
4 4
37
X X
6 3
Cu n, 2n Cu
6 2
9.8 min 4.5 X 10 4
4.5 X 10 4
0.66 (weak)
1 0 3
Rh n, a ioo T c 15.7 s 3.6 X 10 4
2.9 X 10 4
0 . 5 4 , 0.60
2 7
A1 n,p Mg
2 7
9.5 min 2.4 X 10 4
2.4 X 10 4
0 . 8 4 , 1.02
2 6
Mg n, a Ne
2 3
40.2 s 2.0 X 10 4
1.8 X 10 4
0.436
34g 34p 12.4 s 6.5 10 3
4.9 10 3
2.1
n,p X X
5 4
Fe n, 2n 5 3 F e
8.9 min 1.2 X 10 3
1.2 X 10 3
0.38

* Based on 10% counting efficiency, flux of 1 0 n c m " s"* . 9 2 1

** Calculations based on amount of parent nuclide in 1 g of element having normal nu-


clidic abundance.

A p p r o x i m a t e l y 5 s e c o n d s were n e e d e d t o d u m p t h e analyzer m e m o r y , thus


releasing t h e m e m o r y for t h e c o l l e c t i o n of subsequent spectra. The measure-
m e n t of t h e delayed gammas was d o n e b y first irradiating t h e matrix for
a b o u t 2 0 min and f o l l o w e d b y t h e rapid insertion of t h e d e t e c t o r t o the loca-
t i o n of t h e irradiated area. A n evaluation o f this work indicated that t h e
sensitivity for copper determinations was increased b y allowing interfering
elements such as A 1 from t h e S i ( n , p ) A l reaction t o d e c a y o u t . The anal-
28 2 8 2 8

ysis of t h e 0.51-MeV peak was d o n e b y integrating it b e t w e e n t w o selected


channels. The n e u t r o n flux normalization t e c h n i q u e used involved t h e sum-
m a t i o n of c o u n t s under t h e N a ( 2 . 7 5 - M e V ) p h o t o p e a k . The i s o t o p e N a is
2 4 2 4

produced from N a ( n , 7 ) N a , A l ( n , a ) N a , and M g ( n , p ) N a . It was


2 3 2 4 2 7 2 4 24 2 4

assumed that t h e concentrations of these e l e m e n t s in t h e simulated ore were


constant. In Table 5-XII are given t h e results of this study. In view of t h e
168

TABLE 5-XI
List of positron emitters produced by fast-neutron (n, 2n) activation that could cause
interference in copper determination (Dibbs, 1 9 7 0 )

Target Isotopic Product Half-life Positron Other gamma


nuclide abundance isotope emission energies (MeV)
(%) (%)

31p 30p
100 2.53 min 100
39 98.08 38
R R
7.7 min 100 2.16 (100%)
5 4
Fe 5.82 5 3
Fe 9.0 min 98 0.38 (32%)
14 99.63 1 3 10 min —
N N
100
1 2 1
Sb 57.25 1 2 0
Sb 15.7 min 43 1.17 (1.3%)
35
C1 75.53 34m 32.4 min
c l
50 1.17 (12%), 2.12
(38%), 3.3 (12%)
6 4
Zn 48.89 6 3
Zn 38.1 min 93 0.67 (8%), 0 . 9 6 2
(6%), 1.42 (0.9%)

large n u m b e r of potential sources of error, it is difficult t o assess t h e accu-


racy of this m e t h o d for copper analysis.
Much of the d e v e l o p m e n t in fast activation logging has emanated from
research groups in industry. Sophisticated logging s o n d e s , and associated
pulse sorting and data processing devices, have resulted. Several c o m p a n i e s ,
predominantly in t h e United States, offer contract services in m a n y areas of
nuclear logging. Most of these services have resulted from m a n y years of
research in t h e field, and t h e final products bear t h e evidence of concise
thinking and innovative instrument design. Even t h o u g h t h e accelerator
neutron source was d e v e l o p e d b y a f e w major electronic c o m p a n i e s , t h e
source w h i c h c o u l d be profitably used was d e v e l o p e d b y industries involved
in providing contract services. Wichmann ( 1 9 7 2 ) describes several applica-
tions in w h i c h fast neutron interactions were used t o produce adequate case
histories. The e l e m e n t s amenable t o fast activation analysis are o x y g e n ,
silicon and aluminum. In Table 5-XIII are given pertinent activation data.

TABLE 5-XII
Copper content of samples (Eisler et al., 1 9 7 1 )

Estimated least-squares Cu value determined by


fitted Cu value (%) chemical analysis (%)

0.52 0.53
1.11 1.04
1.86 1.98
3.79 3.76
169

TABLE 5-XIII
Nuclear data for fast activation analysis with 14-MeV neutrons (Wichmann, 1 9 7 2 )

Element Reaction E (MeV) Half-life

Oxygen "Ofn.ppN 6.1 7.2 s


Silicon 2 8
Si(n, p) Al2 8
1.78 2.3 min
Aluminum 2 7
Al(n, p) Mg 2 7
0.84, 1.01 9.5 min

The activation b u i l d u p o f t h e irradiated p r o d u c t s as a f u n c t i o n o f activation


t i m e is s h o w n in Fig. 5 - 2 8 . T h e logging d e v i c e described b y W i c h m a n n ( 1 9 7 2 )
is s h o w n in Fig. 5 - 2 9 . A standard 1 2 - f o o t s o u r c e - d e t e c t o r spacing is u s e d t o

i CABLE HEAD

35-*-
^8
GAMMA RAY
ADAPTOR 8
DETECTOR

ELECTRONICS

12

COLLAR LOCATOR
PERCENT OF ACTIVITY

DETECTOR

ION ACCELERATOR

VAN D E G R A A F F
.GENERATOR

ACCELERATOR
' ELECTRONICS

I 2

TIME (MINUTES)
Fig. 5-28. Activation buildup of o x y g e n , silicon and aluminum (Wichmann, 1 9 7 2 ) .

Fig. 5-29. Instrument configuration for activation logging (Wichmann, 1 9 7 2 ) .


170

log t h e above e l e m e n t s . This distance is optimally suited for silicon, and in


v i e w o f t h e half-life o f N , o x y g e n logs have t o be performed at speeds faster
1 6

than operationally derived. T o m a k e this instrument capable o f logging for


o x y g e n u n a m b i g u o u s l y , a rather high-energy gamma discrimination level has
t o be used, w i t h the result that t h e sensitivity for o x y g e n drops off signifi-
cantly. T o d e t e r m i n e t h e o p t i m u m logging speed w i t h respect t o c o u n t rate
for any activation product, Wichmann gives t h e e q u a t i o n :

T / _ 0.693 L
" -m (41)
1/2
1

where V is t h e o p t i m u m logging speed in feet per m i n u t e ; L t h e source-


0

d e t e c t o r distance in feet; and T 1 / 2 t h e half-life of t h e measured nuclide in


m i n u t e s . T h e o p t i m u m logging speed w i t h a 6-foot source-detector spacing is
approximately 3 4 feet per m i n u t e . Wichmann drew a t t e n t i o n t o t h e fact that
o x y g e n logs for oil-water differentiation were n o t totally successful, since
o x y g e n is a significant part of all major reservoir rock t y p e s . Therefore,
anomalies indicated b y t h e logs are o f t e n difficult t o interpret. Silicon logging,
o n t h e other hand, is commercially used. These logs are obtained unambigu-
ously b y allowing t h e N activity induced from fast activation of o x y g e n
1 6

nuclei t o d e c a y o u t . Interference from t h e 9.5-min activity resulting from


2 7
A l activation is apparently absorbed in t h e error of analysis. T h e o p t i m u m
c o n d i t i o n s for silicon logging include a 1 2 - f o o t source-detector spacing and a
logging speed of 3.6 feet per m i n u t e ; h o w e v e r , such speeds are considered
u n e c o n o m i c a l . A c c e p t a b l e logs can be obtained at speeds u p t o 1 2 feet per
m i n u t e . Logging for aluminum d o e s n o t appear t o be t o o satisfactory d u e t o
t h e very l o w o p t i m u m speed of ^ 1 f o o t per m i n u t e , and a background sub-
traction is necessary after irradiating a given section of t h e borehole for
several m i n u t e s . This background is created b y t h e d e c a y o f o t h e r matrix ele-
m e n t s . For all of t h e three cases described a b o v e , it m u s t b e emphasized that
these logs are essentially ''element i d e n t i f i c a t i o n " t y p e s , and d o n o t give
quantitative results. H o w e v e r , these d e v e l o p m e n t s d o demonstrate t h e
potential of fast neutron accelerator sources for t h e determination of light
e l e m e n t s . Furthermore, these "identification" logs provide significant infor-
m a t i o n regarding instrumentation and hardware applicable for d o w n h o l e
operation, and form t h e basis for quantitative determinations in t h e future.
The possibility of applying a fast neutron accelerator source for silver
exploration was investigated b y H o y t e et al. ( 1 9 6 7 ) . A truck-mounted
positive ion accelerator s y s t e m was used. The applicability of b o t h 1 4 - and 3-
MeV neutrons t o this p r o b l e m was assessed in t h e field. The high-energy
neutrons were m o d e r a t e d t o thermal energies and t h e reaction A g ( n , 7 ) A g
1 0 9 1 1 0

was utilized for silver determinations. Even at d e p t h s d o w n t o 2 6 c m , pulse-


height spectra of 1 1 0
A g obtained clearly resolved t h e 0.66-MeV g a m m a emis-
sion. The e q u i p m e n t consisted o f a n e u t r o n generator and a scintillation
d e t e c t o r m o u n t e d rigidly o n either side of a moderating shield. A sensitivity
171

Fig. 5-30. Experimental silver detector showing 3-MeV neutron generator on the tailgate
assembly which is lowered and in position for irradiation (Hoyte et al., 1 9 6 7 ) .

for silver d o w n t o 1 o u n c e per t o n was predicted. The experimental s y s t e m


including t h e 3-MeV irradiation s y s t e m is s h o w n in Fig. 5 - 3 0 .
Field application of an accelerator source of n e u t r o n s t o c o p p e r analysis
was investigated b y H o y e r and L o c k ( 1 9 7 2 ) . Proceeding from laboratory
studies, t h e d e v e l o p e d t e c h n i q u e was tested in t w o b o r e h o l e s . T w o t y p e s of
neutron sources were used. A P u - B e low-energy i s o t o p i c source of a b o u t
2 3 9

1 0 n s" o u t p u t or a (d, T) accelerator source producing 1 0 n s" o f 1 4 -


7 1 8 1

MeV neutrons was incorporated in t h e field s y s t e m s h o w n schematically in


Fig. 5 - 3 1 . The purpose of using t w o t y p e s of sources was t o distinguish
b e t w e e n t h e C u ( n , 2 n ) C u reaction induced b y 1 4 - M e V n e u t r o n s and t h e
6 3 6 2

C u ( n , 7 ) C u reaction w h i c h is p r e d o m i n a n t l y propagated b y thermal


6 5 6 6

neutron capture processes. The p r o d u c t i o n o f C u can of course o c c u r b y


6 4

fast neutrons, e.g. C u ( n , 2 n ) C u , and also b y thermal activation, e.g.


6 5 6 4

C u ( n , 7 ) C u . H o w e v e r , t h e nuclear activation parameters did n o t permit a


6 3 6 4

significant contribution from C u . 6 4

The d e t e c t o r in this field s y s t e m was a 2 inches in diameter b y 2 inches


long N a l ( T l ) scintillator c o u p l e d t o a 512-channel pulse-height analyzer. The
field operation involved a survey of t h e borehole f o l l o w e d b y stationary
activation analysis. The results obtained were generally disappointing, in that
t h e t e c h n i q u e was n o t consistent in locating z o n e s o f mineralization. Back-
ground problems resulting from t h e activation of S i and A l were experi-
2 8 2 7
172

SINGLE SINGLE SINGLE SINGLE


H AMPLIFIER CHANNEL CHANNEL CHANNEL CHANNEL
ANALYZER ANALYZER ANALYZER ANALYZER

RATEMETER RATEMETER RATEMETER RATEMETER

COUNT RATES
r
MULTICHANNEL IN PRESELECTED
DOWN ANALYZER ENERGY INTERVALS
HOLE

GAMMA
SONDE RAY
DETECTOR

SPACER
GAMMA RAYS FROM PREVIOUS
NEUTRON IRRADIATION BEING DETECTED
SOURCE WHILE NEUTRONS BOMBARD
NEXT DEPTH TO BE EVALUATED

Fig. 5-31. Schematic of logging system (Hoyer and Lock, 1 9 7 2 ) .

e n c e d . T h e presence o f natural radiation presented additional difficulties.


In t h e stationary runs t h e neutron source was p o s i t i o n e d o p p o s i t e a z o n e of
interest and irradiated for a 5- or 10-min t i m e period. The d e t e c t o r was t h e n
m o v e d o p p o s i t e t o t h a t same z o n e and measurements m a d e in sequence.
After waiting for a period o f 2 m i n gamma-ray spectra were collected for
2 and 3 min each. After a further delay of 2 m i n , measurements for t w o
additional 5-min t i m e periods were m a d e . D e s p i t e t h e g o o d effort p u t o u t
in this test, t h e conclusions were discouraging in terms of t h e application of
delayed gamma c o u n t i n g for copper determination in a b o r e h o l e . Perhaps an
important fact t o be considered here is that despite t h e o p t i m i z a t i o n of
instrumentation, t h e practical logging speed that c o u l d be e x p e c t e d , is a b o u t
2 m per hour. S u c h speeds w o u l d require considerable e c o n o m i c justification
for t h e acceptance of this particular t e c h n i q u e b y industry.
In t h e present d a y and age, t h e availability of sufficient energy is of prime
concern t o m o s t countries. The difficult oil situation in particular has led t o
a burst of concentrated effort o n t h e part of m a n y governments t o find ore
reserves for t h e e l e m e n t uranium. The recent activity in airborne surveys will
very likely be f o l l o w e d u p b y detailed ground evaluations and drill-hole
logging. A l t h o u g h t h e applications of pulsed neutron logging techniques as
an e c o n o m i c m e t h o d for quantitative elemental analysis are limited, t h e ele-
m e n t uranium is o n e w h i c h can be analyzed b y such m e t h o d s . An e x c e l l e n t
173

investigation reported b y Czubek ( 1 9 7 2 ) discusses t h e theoretical c o n c e p t s


and practical implications of this t e c h n i q u e as applied t o b o r e h o l e logging
for uranium. The m e t h o d e m p l o y e d t h e m e a s u r e m e n t o f t h e t i m e distribu-
tion of neutrons after a burst of fast neutrons. Czubek d e v e l o p e d a time- and
energy-dependent t h e o r y , b u t i n d e p e n d e n t from space, for t h e four distribu-
t i o n s resulting f r o m t h e p r o m p t thermal fission of U and d e l a y e d fission
2 3 5

o f uranium. Theoretical derivations are included in this s t u d y . F r o m t h e


experimental verification o f the t h e o r y the following c o n c l u s i o n s were
d e d u c e d : (1) t h e application of p r o m p t fission neutrons in t h e epithermal
region requires a short- and high-frequency neutron burst, and ( 2 ) a l o n g
low-frequency neutron burst is necessary if a m e a s u r e m e n t of d e l a y e d fast or
thermal fission neutrons is t o be m a d e . This t e c h n i q u e , at least in t h e labora-
t o r y , appears t o have g o o d potential for t h e borehole analysis of uranium. Its
success in t h e field, h o w e v e r , is y e t t o be d e m o n s t r a t e d .

Thermal neutron absorption. R e c e n t l y , the s p o n t a n e o u s fission n e u t r o n


source C f w a s m a d e available for sale b y t h e U . S . A t o m i c Energy C o m m i s -
2 5 2

sion ( n o w E R D A ) . This d e v e l o p m e n t has resulted in increasing a t t e n t i o n t o


t h e use of this source in logging s o n d e s . Reference is m a d e t o several
investigations carried o u t b y Philbin et al. ( 1 9 7 1 ) , Senftle et al. ( 1 9 7 1 b ) ,
Lauber and Landstrom ( 1 9 7 2 ) , and Tanner e t al. ( 1 9 7 2 ) , w h i c h discuss the
properties of materials with a v i e w t o their selection for s o n d e c o n s t r u c t i o n .
Pertinent details abstracted from these investigations are included in t h e dis-
cussion of m e t h o d s t o f o l l o w .
For t h e determination of copper b y thermal n e u t r o n activation, Land-
strom et al. ( 1 9 7 2 ) c o n d u c t e d field tests similar t o t h o s e carried o u t b y
H o y e r and L o c k ( 1 9 7 2 ) . Tests were performed in b o t h 4 6 - m m diameter
diamond-core drilled h o l e s and 2 5 0 - m m diameter p r o d u c t i o n h o l e s . Aside
from t h e fact t h a t Landstrom et al. ( 1 9 7 2 ) used a 10-Ci P o - B e neutron 2 1 0

source exclusively, and that their logging s o n d e included a device consisting


of an inflatable rubber cylinder t o preclude t h e m e a s u r e m e n t o f radon, b o t h
investigations have m u c h in c o m m o n . A schematic o f t h e s o n d e is s h o w n in
Fig. 5 - 3 2 . The important c o n c l u s i o n s drawn from this test were that a high-
resolution Ge(Li) d e t e c t o r be used in future w o r k in c o n j u n c t i o n w i t h a neu-
tron source a b o u t five t i m e s greater in source strength. H o w e v e r , for t h e
boreholes investigated the log (Fig. 5-33) s h o w s evidence of satisfactory cali-
bration b e t w e e n C u ( 0 . 5 1 M e V ) c o u n t s and t h e core chemical analysis. T h e
6 4

regions of mineralization are clearly defined. However, as emphasized earlier,


t h e utilization of this t e c h n i q u e for low-abundant (0.2—1.5%) c o p p e r ore
d o e s n o t project a g o o d e c o n o m i c viability, even w i t h t h e m o d i f i c a t i o n s sug-
gested in this test. This s t a t e m e n t is clarified b y e x a m i n i n g t h e o u t c o m e of
another test c o n d u c t e d b y Lauber and Landstrom ( 1 9 7 2 ) in w h i c h a Ge(Li)
d e t e c t o r s y s t e m was e m p l o y e d . The fabricated s o n d e was 8 . 9 c m in diameter
and 1 6 0 c m long. A 2 2 - c m coaxial Ge(Li) d e t e c t o r , c o o l e d b y liquid nitro-
3
174

CARRIER-WIRE

AIR HOSE

LOCK

BAR

PROBE

DETECTOR

RUBBER BAG

Fig. 5-32. Logging sonde showing arrangement with rubber device (Landstrom et al.
1972).

gen, had a hold t i m e of a b o u t 1 0 h. The energy resolution o f t h e d e t e c t o r


was 2 . 3 k e V for 1 2 2 - k e V g a m m a rays and 2 . 6 k e V for 1.33-MeV p h o t o n s . A
schematic of this p r o b e is s h o w n in Fig. 5 - 3 4 . Field tests w i t h t h e s y s t e m
demonstrated t h e g o o d performance of t h e d e t e c t o r s y s t e m in a borehole
environment. A s t o w h e t h e r a Ge(Li) d e t e c t o r s y s t e m can stand t h e rigorous
o f day-to-day p r o d u c t i o n logging over several m o n t h s in t h e field w i t h o u t
expensive d o w n times is an important factor in t h e e c o n o m i c s of neutron
activation logging.
The application o f b o t h delayed and p r o m p t gamma-ray measurements t o
borehole analysis for e l e m e n t s o f interest has b e e n o f special interest t o t h e
research t e a m o f t h e U . S . Geological Survey. These workers have placed a
great emphasis o n t h e use of t h e Ge(Li) d e t e c t i o n s y s t e m and have pioneered
175

GAMMA INTENSITY
CORE ANALYSIS OF 6 4
C u ( 0 . 5 l MeV).
0 10 2 0 %Cu 0 200 400 6 0 0 COUNTS
n—i—i—i—r — PER
"T" n—r &o MINUTE

6.0
n
DEPTH (m)

7.0
1
1

8.0
1

9.0
1

10.0 IRRADIATION POSITIONS


—i

(ARROWS INDICATE)

Fig. 5-33. Comparison between core analyses and borehole measurements of induced
activity in copper ( 0 . 5 1 MeV from C u ) after irradiation in 2 5 0 - m m borehole (Land-
6 4

strom et al., 1 9 7 2 ) .

m u c h of t h e hardware d e v e l o p m e n t for its d o w n h o l e application. Tanner e t


al. ( 1 9 7 2 ) have described a borehole s o n d e incorporating such a s y s t e m of
d e t e c t i o n . A p p l y i n g t h e principle o f a melting cryogen like propane, hold
t i m e s as l o n g as 1 0 h have b e e n achieved. The c h o i c e of t h e c r y o g e n w a s
made from commercially available fluorocarbon refrigerants. The ultimate
selection was restricted t o t h e use of instrument-grade propane ( > 9 9 . 5 % ) .
The melting p o i n t o f solid propane ( — 1 8 7 . 6 9 ° C ) is t h e closest t o that o f liq-
uid nitrogen (—195.8°C) c o m m o n l y used for Ge(Li) detectors in t h e labora-
t o r y . T h e borehole s o n d e was 7 . 3 c m in diameter and a b o u t 2 m long. T h e
modular c o n s t r u c t i o n of t h e device permits easy access t o t h e important
c o m p o n e n t s such as t h e source holder for t h e C f n e u t r o n source, shield,
2 5 2

cryostat h o l d i n g t h e Ge(Li) d e t e c t o r and electronics. During storage and


refreezing periods, t h e cryostat s e c t i o n was d e t a c h e d from t h e p r o b e , held in
a vertical p o s i t i o n and c o o l e d d o w n b y a 14-liter liquid nitrogen reservoir in
t h e conventional manner. T h e total weight o f t h e s o n d e was a b o u t 1 6 kg
( 3 5 p o u n d s ) , e x c l u d i n g t h e shield and t h e source-holder filling material. The
source holder itself w a s m a d e from epoxy-filled fibreglass t o provide
mechanical strength and m i n i m u m swelling d u e t o water absorption. The
neutron source was m o u n t e d in a short acrylic rod and inserted in t h e
annular source holder. The s h a d o w shield was a tungsten rod w h i c h was
m o u n t e d coaxially w i t h t h e source. B y introducing plastic spacers, t h e
source-detector distance c o u l d be varied b e t w e e n 3 3 and 1 2 0 c m . For field
176

WIRE PLASTIC TUBE


WITH CABLES

OUTER CYLINDER

PREAMPLIFIER

GE(LI) DETECTOR
CRYOSTAT

NITROGEN CONTAINER

COLD FINGER

Fig. 5-34. Ge(Li) borehole probe (Lauber and Landstrom, 1 9 7 2 ) .

application a 3 0 0 m long cable was attached t o t h e probe.


A portion of a p r o m p t gamma-ray spectrum measured b y this s o n d e is
s h o w n in Fig. 5-35. T h e d e v e l o p m e n t of this p r o b e w a s based o n findings b y
Senftle et al. ( 1 9 7 1 b ) . This research laid t h e basic f o u n d a t i o n for t h e success-
ful application o f this t e c h n i q u e t o nickel exploration o n a p r o d u c t i o n basis.
Interesting laboratory e x p e r i m e n t s c o n d u c t e d b y Senftle e t al. ( 1 9 7 1 b ) are
f o u n d in t h e report.
M o x h a m et al. ( 1 9 7 2 ) pursued t h e early d e v e l o p m e n t carried o u t b y
Senftle et al. ( 1 9 7 1 b ) described above and c o n d u c t e d field tests in copper-
and nickel-bearing gabbro. T h e e l e m e n t s Al, Mn, Na, Mg, Cu and V were
readily d e t e c t e d in t h e d e l a y e d g a m m a spectra. The e l e m e n t s H, F e , Si and
Ni were identified from t h e p r o m p t g a m m a response in t h e higher energy
regions of t h e spectra. Table 5-XIV, abstracted from M o x h a m e t al. ( 1 9 7 2 ) ,
contains nuclear parameters pertinent t o this test. The d e l a y e d and p r o m p t
gamma-ray spectral analysis indicated a better sensitivity for c o p p e r w i t h t h e
z _
00 H

8.0 8.5 9.0 9.5

Capture 7-ray energy (MeV)

Fig. 5-35. Part of the spectrum of radiative-capture gamma rays detected by borehole sonde from ore containing about 1% Ni
2 5 2
during 4 | h irradiation by a 0.9 fig C f source in a simulated borehole, (f), (s), and (d) denote full-energy, single-escape, and
177

double-escape gamma-ray photopeaks (Tanner et al., 1 9 7 2 ) .


178

TABLE 5-XIV
Gamma-ray emission from copper and nickel isotopes (Moxham et al., 1 9 7 2 )

Target Isotopic Cross- Product Gamma-•ray emission Half-life


abundance section
(%) (barns) full- inten- single double
energy sity escape escape
peak (%) (keV) (keV)
(keV)

Neutron-capture gamma rays


6 3
Cu 69.17 4.4 6 4
Cu 7916 27.3 7405 6894
7637 14.9 7126 6615
7307 9.3 6796 6285
7176 2.7 6665 6154
5 8Nj 67.88 4.4 59 j N
8999 41.6 8488 7977
8533 18.74 8022 7511
6837 11.91 6326 5815

Delayed gamma rays


6 3
Cu 69.17 4.4 6 4
Cu 511 19 12.8 h
1343 0.5
6 5
Cu 30.83 2.17 6 6
Cu 1039 9.0 5.1 min
828 0.25
Ni 1.08 1.52 65 1480
6 4
N i
25.0 2.56 h

delayed t e c h n i q u e . Experiments carried o u t in t h e laboratory s h o w e d that


for delayed gamma measurement using t h e 1.78-MeV A l p h o t o p e a k as an
2 8

i n d e x , an infinite sample was achieved w h e n t h e vertical thickness of t h e


rock layer was ^ 2 0 c m and a horizontal thickness from t h e borehole walls
was ~ 1 0 c m . H o w e v e r , it should be borne in mind that in t h e case of copper,
the o p t i m u m energy w h i c h was being measured was less than 1 M e V . Gamma-
ray transport for such energies w o u l d indicate a significant decrease in t h e
size of t h e infinite sample although t h e sensitivity w o u l d n o t be unduly
affected. S o m e critical information gathered from this report indicated that
t h e m a x i m u m probe response was obtained w h e n t h e ratio D /D ^ 2.5,
h d

where D was t h e b o r e h o l e diameter, D was the d e t e c t o r diameter, and t h e


h d

annulus was considered t o be full of water. When this ratio approached ^-3.2,
t h e centering of t h e s o n d e in t h e borehole was f o u n d t o be unnecessary.
The effect of water in t h e matrix increased t h e peak intensity of C u 6 6

( 1 . 0 3 9 M e V ) . This increase was further augmented w h e n t h e borehole was


also filled with water. It was suggested therefore that s o m e means for cor-
recting for t h e presence of water, e.g. a measurement of t h e p r o m p t 2 . 2 3 -
179

MeV emission from h y d r o g e n , w o u l d be necessary for quantitative determi-


nations for copper.
In t h e field a source-detector distance o f 7 3 . 6 c m was u s e d . The source
strength of 2 5 2
C f was ~ 8 5 /ig (i.e. 2 X 1 0 n s" ). In t h e borehole (diameter
8 1

~ 1 2 . 7 c m ) t h e matrix was irradiated for a b o u t 1 7 m i n and f o l l o w e d u p w i t h


a 17-min c o u n t . Estimates of t h e c o p p e r c o n t e n t at t h e 0 . 9 1 % Cu level were
made. Because of t h e p o o r response from c o p p e r in t h e p r o m p t gamma-ray
energy region, t h e use of t h e N a l ( T l ) d e t e c t o r was considered t o be futile.
However, it should b e realized that such d e d u c t i o n s are b y n o m e a n s general
and perhaps apply o n l y t o t h e d e t e c t o r s y s t e m used and t h e data analysis
m e t h o d s e m p l o y e d . The c o m m o n l y applied m e t h o d of peak integration in
certain cases places restrictions w h i c h automatically preclude t h e analysis of
e l e m e n t s w h o s e peaks are n o t visible, even t h o u g h t h e gamma-ray contribu-
t i o n from such an e l e m e n t m a y be substantial for its d e t e r m i n a t i o n . M o x h a m
et al. ( 1 9 7 2 ) indicated that a sensitivity of 0.5% Cu or Ni could be o b t a i n e d
using t h e delayed and p r o m p t gamma-ray m e a s u r e m e n t t e c h n i q u e s , respec-
tively.
The natural o u t g r o w t h of t h e above test was an a t t e m p t t o compare t h e
t w o techniques. Senftle et al. ( 1 9 7 2 ) produced an extensive table in an effort
t o derive comparison b e t w e e n t h e t w o t e c h n i q u e s for a large n u m b e r of ele-
m e n t s . This table is helpful in preliminary assessments of feasibility. H o w -
ever, caution m u s t be exercised in such assessments. Furthermore, care should
be taken in examining all assumptions m a d e in arriving at t h e tabulation.
A t this stage it is necessary t o pause and reflect o n t h e applications
described thus far. Several observations can be m a d e , and pertinent questions
raised. It is o b v i o u s that e x t r e m e l y f e w d e v e l o p m e n t s have advanced t o t h e
p o i n t of active consideration b y t h e mineral e x p l o r a t i o n industry. It is true,
however, that s o m e studies and field case histories (as limited as t h e y have
been) offer considerable potential. Nevertheless, t h e acceptance o f such tech-
niques b y industry requires a greater degree o f field testing particularly o n a
p r o d u c t i o n logging basis. Most important, h o w e v e r , it is necessary t o
demonstrate that t h e nuclear t e c h n i q u e p r o p o s e d n o t o n l y satisfies t h e ana-
lytical parameters, b u t is also e c o n o m i c a l w h e n c o m p a r e d t o t h e core extrac-
tion—chemical analysis procedures c o m m o n l y used for o r e b o d y evaluation.
Industry c a n n o t b e e x p e c t e d t o grasp n e w sophisticated t e c h n i q u e s w i t h o u t
adequate and extensive d e m o n s t r a t i o n s , b o t h in terms of its analytical
capability and mechanical ruggedness. The b o r e h o l e e n v i r o n m e n t in t h e best
field c o n d i t i o n s is a far cry from t h e air-conditioned laboratory in w h i c h
"ideal" samples are analyzed. Gross h e t e r o g e n e i t y , large d e n s i t y variations,
irregular borehole c o n d i t i o n s , and the presence o f moisture, are part and
parcel of almost all geological strata. If a nuclear m e t h o d based o n radio-
activation b y neutrons is t o f u n c t i o n t o t h e satisfaction of exploration
geologists, it is imperative that t h o u g h t s be given t o t h e sources of analytical
error created b y t h e changing hostile borehole environment. Essentially t h e
180

above picture, as pessimistic as it appears, faced a Canadian research t e a m in


1 9 7 0 . This t e a m was charged w i t h t h e responsibility o f developing and
fabricating a viable borehole analysis s y s t e m for t h e analysis of Cu in
porphyry copper, and N i , Fe and Si in a lateritic matrix. Many discussions
carried o u t w i t h exploration experts s o o n m a d e it apparent that laboratory
studies, if any, w o u l d have t o b e c o n d u c t e d under very closely simulated
field c o n d i t i o n s . F r o m t h e literature abounding at that t i m e , t h e strong c o n -
census of o p i n i o n was that Ge(Li) detectors were " i n " and N a l ( T l ) scintil-
lators were " o u t " . It w a s also o b v i o u s at that t i m e that Ge(Li) detectors
could ultimately present a very serious set back; because it was assessed that
a d e t e c t i o n s y s t e m based o n this principle w o u l d n o t be suitable or accept-
able b y t h e mining industry, and despite t h e pioneering efforts described b y
Lauber and Landstrom ( 1 9 7 2 ) and Tanner et al. ( 1 9 7 2 ) , it w o u l d n o t be o n
t h e horizon in a state o f d e v e l o p m e n t sufficient for its routine and long-
term use b y mineral explorationists. Furthermore, a s y s t e m developed
around t h e Ge(Li) d e t e c t o r w i t h peak amplitude-type analysis w o u l d n o t
provide adequate sensitivities, t o determine low-grade cut-off levels. T o add
t o t h e difficulty, t h e d e l a y e d g a m m a measurement t e c h n i q u e d o e s n o t
provide results reflecting t h e response from a large e n o u g h sample v o l u m e .
The end result from these observations at least for t h e base metals, F e , Ni
and Cu, was that if t h e mining c o m m u n i t y was t o b e fully c o n v i n c e d , any
techniques d e v e l o p e d m u s t satisfy t h e following criteria.
( 1 ) U n a m b i g u o u s analysis in t h e actual environment.
( 2 ) The overall experimental error from statistical and systematic c o n -
siderations be < ± 1 5 % relative at t h e 0.5% Cu level w i t h a d e t e c t i o n limit
approaching 0 . 1 % Cu; and < ± 5 % , < ± 1 0 % , and < ± 1 5 % for t h e e l e m e n t s Ni,
Fe and Si in nickel-bearing strata as typified b y t h e laterite m e d i u m .
( 3 ) The analysis m u s t b e reported o n a dry weight basis.
( 4 ) T h e logging speed ( c o n t i n u o u s or incremental) b e reasonably fast
( > 2 5 m per hour for c o n t i n u o u s logging and at least 5 m per hour for fine
structure incremental logging).
(5) The m e t h o d should provide analytical information that represents a
m u c h larger ( 5 0 — 1 0 0 t i m e s ) t h e v o l u m e of rock w h e n c o m p a r e d t o drill-core
samples.
( 6 ) The logging s y s t e m , w h e t h e r it b e hand-carried or installed in a m o b i l e
laboratory, be e x t r e m e l y rugged and fully adaptable t o general field condi-
tions.
With these goals in m i n d , t h e Canadian team embarked o n a five-year
research and d e v e l o p m e n t s t u d y . In early 1 9 7 5 t h e y (Nargolwalla, 1 9 7 5 )
demonstrated t h e application of the first field p r o d u c t i o n logging system for
t h e simultaneous analysis of Ni, Fe and S i 6 in a nickel laterite mining
2

property. This matrix possesses all t h e qualifications w h i c h make quantita-


tive determinations subject t o error. T h e m o b i l e laboratory (Figs. 5-36 and
5 - 3 7 ) , called t h e "Metalogger", was put through every required test, t o prove
181

that t h e nuclear t e c h n i q u e was ready t o replace t h e core extraction m e t h o d


w i t h substantial long-term savings t o t h e lateritic nickel industry.
A n entirely original m e t h o d o f gamma-ray spectral analysis was d e v e l o p e d
for general application. This m e t h o d takes i n t o a c c o u n t environmental
effects w h i c h perturb t h e sensitivity o f t h e e l e m e n t s and, therefore, t h e final
results. The effects o f h e t e r o g e n e i t y and density variations are absorbed in
t h e overall experimental error. The m e t h o d is based o n t h e p r o m p t gamma-
ray measurement process. Design o f t h e s o n d e was such as t o provide anal-
yses for these e l e m e n t s averaged over a p p r o x i m a t e l y 6 8 0 kg o f ore per deter-
mination. In t h e laterite application, an average logging o u t p u t o f ~ 4 0 m per
8-h day was maintained for almost 6 0 0 — 7 0 0 m of p r o d u c t i o n logging.
Results for all three c o m p o n e n t s are provided o n an incremental basis for
every meter of b o r e h o l e , almost instantaneously. The field geologist can,
therefore, assess t h e quality o f t h e h o l e being logged, and is in a p o s i t i o n t o
m a k e decisions as t o w h e t h e r t o c o n t i n u e logging a particular h o l e or n o t .
The analytical criteria set forth earlier were all satisfied.
In regard t o c o p p e r analysis in t h e porphyry matrix, t h e N a l ( T l ) d e t e c t o r
was used. Copper determinations as l o w as ~ 0 . 2 % Cu were m a d e w i t h an
overall relative experimental error o f < ± 1 5 % at t h e 0.2% Cu level. The tech-
n i q u e is simple and reliable in extracting t h e c o n t r i b u t i o n of t h e p r o m p t
emissions from thermal neutron capture processes in c o p p e r nuclei from t h e
gross spectra. Logging speeds u p t o 1 0 0 feet per h o u r were achieved. T h e

Fig. 5-36. The Scintrex Metalogger.


182

Fig. 5-37. Rear view of Metalogger showing sonde and tripod setup.
183

theoretical study described in t h e s e c t i o n * 'Theoretical considerations" aided


in t h e design o f t h e field s o n d e . Details of this design and t h e c o m p l e t e m e t h -
o d of analysis are currently under patent consideration. Photographs showing
t h e "Metalogger" in various stages of operation in t h e lateritic d e v e l o p m e n t are
s h o w n in Figs. 5-38 and 5-39. Calibration curves, reported b y Nargolwalla
( 1 9 7 5 ) , and Nargolwalla and Robertshaw ( 1 9 7 5 ) , for t h e e l e m e n t s F e , Ni
and Si (as S i 0 ) are s h o w n in Figs. 5-40 t o 5 - 4 2 . The m e t h o d i n d e e d cor-
2

relates better w i t h t h e bulk sample than w i t h t h e core analysis as is d e m o n -


strated in Table 5-XV. A n interesting feature of t h e m e t h o d is illustrated
in Fig. 5 - 4 3 . In this figure, t h e data were obtained b y carefully logging at
very small intervals in an artificial pit o f 6 - f o o t diameter containing t w o
grades of laterite ore. T h e sharp physical interface is clearly identified b y
t h e measurement. A region of influence o f a b o u t 7 0 c m m a y be observed.

Fig. 5-38. Lowering sonde in laterite borehole for production logging.


184

Fig. 5-39. Logging of lateritic nickel with the Metalogger.

The e l e m e n t iron was used as an i n d e x for this determination.


The test also included an evaluation o f t h e reproducibility o f t h e Metalog
measurements, b o t h in terms of c o u n t i n g statistics and t h e ability for accu-
rate positioning o f t h e s o n d e ; relogging o f h o l e s t o c h e c k t h e overall repro-
ducibility; and t h e logging of water-filled b o r e h o l e s . In t h e generation o f t h e
calibration curves, chemical analysis of t e n s o f t o n s o f bulk samples with-
drawn from a b o u t 0.5 m radius o f t h e b o r e h o l e were chemically analyzed t o
assess the full capability o f t h e m e t h o d . Currently t h e s y s t e m is building u p
an impressive list o f field case histories w h i c h will be o p e n t o active consider-
ation b y t h e mineral exploration industry.

Delayed neutron measurement. During t h e past three decades, t h e search for


uranium has d e p e n d e d heavily o n t h e use o f t h e Geiger m o n i t o r and t h e
Nal(Tl) scintillator for t h e m e a s u r e m e n t o f g a m m a radiation e m i t t e d from
the daughter products o f t h e uranium series. B o t h U and
2 3 8 2 3 5 U are p o o r
gamma emitters, while m o s t of their daughter products b e y o n d R n are
2 2 2

strong emitters. Since 2 2 2R n is a gas, it can migrate through a gas permeable


environment. In this migration, daughter products are continually being
created. A m e a s u r e m e n t o f migrated daughter products, therefore, gives a
false indication as t o t h e l o c a t i o n of t h e uranium itself. Such deposits are
said t o be in disequilibrium. If, o n t h e other hand, t h e R n d o e s n o t escape,
2 2 2

t h e d e p o s i t is considered t o be in equilibrium. C o n s e q u e n t l y a measurement


of t h e gamma activity of t h e radon daughters d o e s provide a quantitative
185

5 , 0
LINEAR FIT: CORRELATION COEFFICIENT 0.9715
8
>
PREDICTED ERROR: 5 . 0 2 % ( A L L Fe) /
4 g _ 3.47 % ( F e > 10%) • /
NORMALIZED IRON PEAKS(XI0"')

i.o U

0.5 -

0 10 20 30 40 50 60 70
BULK % IRON

Fig. 5-40. Calibration curve for iron (Nargolwalla and Robertshaw, 1 9 7 5 ) .

determination for uranium. In v i e w of such geological c o n d i t i o n s , there have


b e e n c o n t i n u o u s d e m a n d s for in-situ t e c h n i q u e s w h i c h will quantify t h e
fissionable i s o t o p e s o n l y . With t h e availability o f C f , t h e possibility o f in- 2 5 2

situ determinations for uranium b y t h e delayed neutron c o u n t i n g t e c h n i q u e


was thoroughly investigated.
As is well k n o w n from the nuclear fission process, b o t h U and U 2 3 8 2 3 5

produce six groups o f delayed neutrons of comparable half-lives. Perhaps t h e


m o s t successful application of this t e c h n i q u e was d e m o n s t r a t e d b y t h e Kerr-
McGee research group (Californium-252 Information Center, 1 9 7 2 , N o . 1 2 ) .
For the initial evaluation of t h e t e c h n i q u e , a 1-mg C f neutron source 2 5 2

( ~ 2 X 1 0 n s" ) was used t o d e v e l o p a t e c h n i q u e with a capability of logging


9 1

at a rapid rate o f 1 2 0 feet per m i n u t e . A rugged field logging s y s t e m was


built and operated in t h e field for several m o n t h s . During this t i m e over
1 0 0 , 0 0 0 feet of b o t h d e l a y e d n e u t r o n and natural g a m m a logs were o b t a i n e d .
Several of the boreholes investigated had b e e n previously cored and c h e m -
186
NORMALIZED NICKEL PEAK (XIO" )
2

Fig. 5-41. Calibration curve for nickel (Nargolwalla and Robertshaw, 1 9 7 5 ) .

LINEAR FIT; CORRELATION COEFFICIENT-0.9299


PREDICTED ERROR 5.60%(ALL SiOg)
2.40%(SI0 >I5%)
2
(XI0~ )
2
NORMALIZED SILICON PEAK

0 10 20 30 40 50 60 70

BULK % SILICA (SI0 ) 2

Fig. 5-42. Calibration curve for silica (Nargolwalla and Robertshaw, 1 9 7 5 ) .


187

TABLE 5-XV
Comparison of correlation coefficients

Sample size * Correlation coefficient


(axial length,
cm) element metalog metalog
vs. core vs. bulk

100 Fe 0.912 0.962


Ni 0.837 0.858
Si0 2 0.812 0.903
66 Fe 0.916 0.971
Ni 0.854 0.876
SiQ 2
0.811 0.930

* Chemical analysis of core (3-inch diameter) averaged over the axial borehole length.
For bulk sample correlation, a cylindrical sample approximately 1 m in diameter and of
the given axial length was withdrawn, mixed and chemically analyzed. Total weight of the
sample was approximately 6 8 0 kg for the 100-cm sample.

3.6631-
3.563 h

3.363

3.163

2.863 -
DEPTH OF PIT C, mttars

NORMALIZED IRON
Fig. 5-43. Experimental region of influence (ROI) of prompt gammas from iron (Nargol-
walla and Robertshaw, 1 9 7 5 ) .
188

ically analyzed. T o perform this impressive task, Kerr-McGee d e v e l o p e d a


w h o l e n e w s y s t e m o f operations and e q u i p m e n t so that operators c o u l d be
adequately p r o t e c t e d from t h e high-intensity neutron source and also m e e t
t h e relevant transport licensing regulations. The d e v e l o p m e n t o f this tech-
nique can be f o l l o w e d in chronological sequence b y a review of Californium-
2 5 2 Progress Reports (Californium-252 Information Center, 1 9 7 1 , N o . 7;
1972, No. 10).
In t h e field s y s t e m t h e C f source holder, confined in a large shielding
2 5 2

flask, is lowered several feet d o w n t h e borehole and clamped. The d e t e c t o r


section containing a gamma-ray d e t e c t o r and a He-filled n e u t r o n c o u n t i n g
3

74.75*
- Gamma Crystal
Centre

30.0"

-Neutron Detector
1.75" Centre

S-G
i
S
I
S-N

3.75*

252.
Cf Source
4
± T
Fig. 5-44. Uranium logging sonde using 2 5 2
C f (Californium-252 Information Center,
1 9 7 2 , No. 12).
189

TABLE 5-XVI
Borehole logging sonde configurations used with 2 5 2
Cf

Spacer Source-to-neutron detector Source-to-gamma detector Total


length length
(inch) separation time * separation time * (inch)
(inch) (s) (inch) (s)

95.25 141.5 23.5 171.5 28.5 212.5


56.25 102.5 17.0 132.5 22.0 173.5
39.0 85.25 14.2 115.25 19.2 156.25
30.0 76.25 12.7 106.25 17.7 147.25
25.0 71.65 11.8 101.25 16.8 142.25
0.0 46.25 7.7 76.25 12.7 117.25

* Time between irradiation and detection using logging speed of 3 0 feet per minute.

t u b e is a t t a c h e d t o t h e t o p o f t h e source h o l d e r . In Fig. 5 - 4 4 (Californium-


2 5 2 I n f o r m a t i o n Center, 1 9 7 2 , N o . 1 2 ) is s h o w n a s c h e m a t i c v i e w o f t h e
s o n d e . T h e length o f t h e s o n d e can be easily adjusted b y i n t r o d u c i n g spacers
b e t w e e n t h e source h o l d e r and t h e d e t e c t o r s e c t i o n . Various s o n d e c o n -
figurations t e s t e d are given in Table 5 - X V I . T h e c o n s e q u e n c e o f varying
t h e s e parameters is d e m o n s t r a t e d in t h e d e c a y curves (Fig. 5 - 4 5 ) . E x a m i n a -
DELAYED NEUTRON ACTIVITY(Arbltrary units)

CM

TIME AFTER IRRADIATION, s«c.

Fig. 5-45. Decay curves for the delayed neutron activity produced b y U when irradi- 2 3 5

ated with C f ; logging speeds of 2 0 , 3 0 , 6 0 and 1 2 0 feet per minute and source-detector
2 5 2

separations of 4 , 6, 8, and 1 0 feet (Californium-252 Information Center, 1 9 7 2 , N o . 1 2 ) .


190

t i o n o f these curves indicate that t h e source-detector distance should be as


short as possible w i t h o u t p i c k u p of t h e scattered neutrons from t h e source
itself. For o p t i m u m operation, a logging speed of 3 0 feet per m i n u t e using a
source-detector distance o f 7 6 inches is suggested.
A thorough description of other parameters which influence t h e delayed
neutron c o u n t is given in t h e report (Californium-252 Information Center,
1 9 7 2 , N o . 1 2 ) and should be studied b y log analysts interested in fabricating
their individual s y s t e m s . A comparison o f delayed neutron results with
chemical analyses of t h e core can be gauged from Table 5-XVII. Despite t h e
very encouraging results, t h e Kerr-McGee group felt t h e necessity of further
improvements in t h e t e c h n i q u e . Areas in w h i c h further investigations were
n e e d e d included:
( 1 ) Increasing t h e sensitivity b y a factor of t e n . This increase could be
realized b y utilizing a higher neutron source strength (2—3 m g C f ) and 2 5 2

enlarging t h e v o l u m e o f t h e H e d e t e c t o r b y a factor o f 3—4.


3

(2) Investigating in greater d e p t h t h e i n d e p e n d e n t roles of fast, epithermal


and thermal fission as a f u n c t i o n of t h e d e p t h of ore penetration b y t h e
neutron from t h e C f source.
2 5 2

TABLE 5-XVII
Wyoming core analyses results vs. neutron count rates (Californium-252 Information Cen-
ter, 1 9 7 2 , N o . 12)

Bore- Run Zone Core Average n s 1


Average nft' 1

holes thick- chemical n s" 1


= 1% u 3 o 8
n ft" 1
= 1% U 0 3 8

ness grade
(ft) (%U 0 )
3 8

1 1 25 0.088 5.71 64.9 8.5 96.6


2 25 0.088 6.0 68.2 9.0 102.3
1 12.5 0.082 6.0 73.2 9.5 115.8
2 12.5 0.082 5.6 68.3 8.8 107.3
2 1 3 0.0264 2.2 83.3 3.5 132.6
2 3 0.0264 2.8 106.1 4.2 158.0
1 5 0.095 4.3 45.2 7.1 74.7
2 5 0.095 6.0 63.2 9.4 98.9
1 20 0.0725 4.4 60.7 7.3 100.7
3 1 1 0.291 15.0 51.5 25.0 85.9
2 1 0.291 19.5 67.0 32.5 111.7
1 2 0.064 2.75 43.0 4.8 75.0
2 2 0.064 3.25 85.4 5.4 84.3
4 1 15 0.096 7.9 82.3 12.5 130.2
2 15 0.096 6.4 66.7 10.1 105.2

Average conversion factors from all data: n s 1


= 1% e U 0 3 8 = 6 7 ; n ft 1
=1% eU O 3 g -
106.
191

( 3 ) Evaluating t h e effect of high neutron absorbers such as B , Gd, S m , Eu


and D y .
( 4 ) Continuing core vs. delayed neutron correlations, so that w i t h adequate
sampling statistics, a better correlation b e t w e e n t h e t w o m e t h o d s could be
established.
Further w o r k (Californium-252 Information Center, 1 9 7 3 , N o . 1 5 )
reported by this group incorporated s o m e of t h e i m p r o v e m e n t s indicated
above, and was highly successful. The region of influence for this m e t h o d
e x t e n d e d a b o u t 6—12 inches from t h e b o r e h o l e face. For a 6-inch d e p t h of
influence, t h e ore analyzed was a b o u t 5 0 t i m e s that for a corresponding
length of core.
This t e c h n i q u e still requires further investigation. T h e effect of t h e rare
earth c o n t a m i n a n t s has y e t t o b e evaluated. Furthermore, t h e presence of
t h o r i u m c o u l d c o n f u s e t h e interpretation of delayed n e u t r o n c o u n t s . H o w -
ever, t h e Kerr-McGee group is t o be highly c o m m e n d e d for breaking ground
in a highly c o m p l e x matrix for t h e in-situ b o r e h o l e logging for uranium. The
full-scale industrial application o f this t e c h n i q u e as a routine quantitative
m e t h o d o f ground f o l l o w - u p from airborne spectrometric anomalies appears
t o be o n l y a matter of t i m e .

ONGOING A N D F U T U R E DEVELOPMENTS

Perhaps t h e m o s t exciting d e v e l o p m e n t s in t h e application of radioactiva-


t i o n m e t h o d s for mineral exploration are t h o s e concerned w i t h t h e analysis
o f ocean b o t t o m s . Research i n t o t h e fabrication o f analytical devices w h i c h
operate at considerable d e p t h s have taken a n e w d i m e n s i o n . A l t h o u g h
predictions o f p o p u l a t i o n growth m a y e x c i t e considerable and controversial
d e b a t e , t h e global d e m a n d for an ever increasing requirement for mineral
resources and raw materials is a matter of fact. Since t h e oceans cover 70%
of t h e earth's surface, exploration of even a minimal area o f t h e sea bed
could conceivable o p e n u p mineral resources t o satisfy t h e d e m a n d of man-
kind for years t o c o m e . In t h e long run, t h e technological world will b e faced
w i t h t h e acute p r o b l e m of mining either t h e d e p l e t e d terrestrial mineral
resources w i t h very efficient m e t h o d s or a t t e m p t t o tap t h e rich marine
sources, utilizing very expensive ore recovery devices. It is far t o o early t o
make such decisions at t h e present t i m e . If t h e inherent technological dif-
ficulties pertinent t o marine e x p l o r a t i o n are solved, appropriate decisions
will automatically e n s u e . Exploratory studies m a d e thus far indicate that
mining for manganese n o d u l e s o n t h e ocean floor at t h e rate of 5 0 0 0 —
1 0 , 0 0 0 t o n s per day m a y be possible and reap reasonable benefits.
Fanger and Pepelnik ( 1 9 7 4 ) , in their recent review emphasizing t h e
exploration of marine ore deposits, have classified such deposits into three
main categories:
( 1 ) "Heavy minerals" (p > 2 . 9 g c m " ) in shelf regions. The heavy mineral
3
192

fractions in these regions are of t h e order o f 3—6% and c o n t a i n ilmenite


( F e T i 0 ) , rutile ( T i 0 ) , zircon ( Z r S i 0 ) , tinstone ( S n 0 ) , m o n a z i t e [(Ce,La,
3 2 4 2

Y , T h ) P 0 ] and traces of d i a m o n d , platinum and gold. Concentrations of Ti


4

and Zr in the range 1—2% and 0.3—0.6%, respectively, can b e e x p e c t e d .


( 2 ) H y d r o thermal ore slime o f t h e R e d Sea-type sediments. These sedi-
m e n t s occur at approximately 2 0 0 0 m o n t h e ocean floor. Concentrations of
1% Cu, 5% Zn, 30% F e , 0 . 1 % Pb, 2 0 0 p p m Cd, Co and M o , and 1 0 0 p p m Ag
are f o u n d in such d e p o s i t s .
( 3 ) Deep-sea ores such as manganese n o d u l e s . These deposits are f o u n d at
depths b e t w e e n 4 0 0 0 and 6 0 0 0 m o n t h e ocean b e d . Typical concentrations
of elements in manganese n o d u l e s f o u n d o n t h e Pacific o c e a n floor are 1%
Ni, 0.5% Cu, 0.2% C o , 2 5 % Mn, and 10% F e . O r e b o d y evaluation of t h e
Pacific ocean bed is estimated at 1 0 t o n s . A n interesting observation can be
1 2

m a d e b y e x a m i n i n g t h e Ni and Cu concentrations. In 1 9 7 0 t h e yearly c o n -


s u m p t i o n of these e l e m e n t s was o f t h e order of 7 X 1 0 t o n s (Cu) and 5 X 1 0
6 s

t o n s ( N i ) . Conservative estimates of these e l e m e n t s o n t h e sea beds are o f t h e


order of 1 0 t o 1 0 t o n s . This fact i m m e d i a t e l y sets u p a situation that is
9 1 0

m o s t attractive for investigation at t h e e x p e n s e of other t y p e s o f mineral


deposits.
The facts presented above have b e e n instrumental in initiating funda-
mental research in this area b y various groups, as presented in Californium-
2 5 2 Progress reports (Californium-252 Information Center, 1 9 7 0 , N o . 2 ;
1 9 7 1 , N o . 6; 1 9 7 1 , N o . 7; 1 9 7 2 , N o . 1 2 ) , and also described b y Senftle et al.
( 1 9 6 9 ) , Senftle ( 1 9 7 0 ) , Perkins et al. ( 1 9 7 1 ) , B e c k m a n n and Abdullah
( 1 9 7 3 ) , Wogman et al. ( 1 9 7 3 ) , Fanger and Pepelnik ( 1 9 7 4 ) , and Senftle et al.
( 1 9 7 5 ) . In order t o organize a feasibility s t u d y , certain discrete steps must be
considered. First, a general k n o w l e d g e of t h e d e p o s i t m u s t be acquired b y
rough prospecting m e a n s . These include such t e c h n i q u e s as deep-sea televi-
sion, p h o t o g r a p h y , dredging and grab sampling. S e c o n d l y , s o m e m e t h o d of
exploration is applied t o estimate t h e ore reserves o n a quantitative basis. In
t h e case o f manganese n o d u l e s this b e c o m e s a strictly two-dimensional case
since t h e n o d u l e s are essentially a mono-granular layer o n the sea bed. H o w -
ever, tonnage variations in t h e mineral c o n t e n t of n o d u l e s n e e d t o b e quan-
titatively evaluated. This information can be c o m b i n e d with t h e nodule
density, t o estimate ore reserves. S o m e c o n c e p t s e x p l o i t e d or considered are
depicted in Figs. 5-46 t o 5-49. S o m e of these c o n c e p t s are already at t h e
field testing stage. Fanger and Pepelnik ( 1 9 7 4 ) described a p i l o t device s o o n
t o be tested in t h e Pacific. This device will concentrate o n t h e analyses of
manganese n o d u l e s . Disregarding capital costs, these workers have estimated
a c o s t of a b o u t 8 5 D e u t s c h Marks for t h e analysis of a b o u t 3 0 kg of sample.
According t o t h e m such c o s t s are considered t o be e c o n o m i c .
A n o t h e r area where a great deal o f emphasis is being applied is in t h e
uranium exploration industry. Nuclear p o w e r reactors are springing u p quite
rapidly and t h e d e m a n d for electrical energy is acute. R e c e n t l y t h e oil crisis
193

compressor

Fig. 5 - 4 6 . Scheme of the technical concept for in-situ (n, 7 ) analysis of manganese nodules
(Fanger and Pepelnik, 1 9 7 4 ) .

has spurred industry i n t o investing funds i n t o e x p l o r a t i o n for uranium. As


described in t h e previous s e c t i o n , t h e d e l a y e d n e u t r o n m e a s u r e m e n t
t e c h n i q u e is being improved and will h o p e f u l l y accelerate uranium explora-
t i o n . It is w o r t h m e n t i o n i n g , h o w e v e r , that another t e c h n i q u e , i.e. nuclear
track c o u n t i n g , c o u l d have g o o d potential as reported b y Carpenter ( 1 9 7 0 )
and Carpenter ( 1 9 7 2 ) , for t h e analysis o f such e l e m e n t s as uranium, thorium
and b o r o n . H o w e v e r , in t h e laboratory high fluxes of thermal neutrons are
necessary for t h e feasibility of this m e t h o d . Such fluxes are e x t r e m e l y
difficult t o generate in situ. Furthermore, t h e etching and optical c o u n t i n g
194

D r u m filled with

fresh water

Cf sources
Ge(U) ^ t o f l l
d

Fig. 5-47. Sketch showing a proposed improved probe using multiple 2 5 2 C f sources in a
more efficient array (Senftle et al., 1 9 7 5 ) .

t e c h n i q u e for track determination could present s o m e difficulty. T h e deter-


m i n a t i o n of uranium b y t h e fission-track m e t h o d is k n o w n t o analyze
uranium d o w n t o t h e sub-ppb levels.
Insofar as t h e borehole analysis o f other minerals o f geologic interest is
c o n c e r n e d , t h e present state-of-the-art allows quantitative determination o f
o n l y a f e w e l e m e n t s . There is a dire n e e d t o e x p a n d t h e application of
radioactivation m e t h o d s t o other minerals, in particular, gold. A l t h o u g h the
determination o f gold in t h e laboratory is relatively simple, in-situ measure-
m e n t s w h i c h are b o t h e c o n o m i c a l and specific for gold present unique prob-
lems in data processing. Sophisticated c o m p u t e r c o d e s are necessary t o
extract spectral information relevant t o gold. A typical gamma-ray spectrum
obtained from t h e irradiation o f a geologic matrix is generally s w a m p e d w i t h
u n w a n t e d p h o t o n responses. It is o n l y b y using certain nuclear properties of
t h e e l e m e n t s , e.g. irradiation and d e c a y t i m e s , energy discrimination e t c . , t o
the fullest advantage that o n e can m a k e reasonable quantitative determina-
tions. The p r o b l e m o f gold determinations in t h e p p m range is therefore
compounded.
195

Fig. 5-48. Proposed experiment arrangement of 2 5 2 C f source and Ge(Li) detector for
marine use (Senftle et al., 1 9 6 9 ) .

Fig. 5-49. Sketch showing similar equipment as shown in Fig. 5-48 except on a sub-
mersible, to provide greater flexibility of operation (Senftle, 1 9 7 0 ) .
196

The overall picture for t h e application of radioactivation techniques t o


mineral exploration is certainly very encouraging. The principal challenges
are obvious. It is n o w i n c u m b e n t u p o n t h e mineral exploration industry t o
invest in t h e d e v e l o p m e n t o f such t e c h n i q u e s , since t h e benefit gained from
their successful application is invariably e n j o y e d b y the industry itself.

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Chapter 6

N U C L E A R WELL L O G G I N G F O R P E T R O L E U M

DOUGLAS W. HILCHIE

INTRODUCTION

Well logging as used in t h e p e t r o l e u m industry has several separate objec-


tives w h i c h are c o m b i n e d t o give the overall final result of finding hydro-
carbons in t h e p o r o u s and permeable rocks. Wells are logged either in " o p e n -
h o l e " in w h i c h case t h e h o l e is filled with s o m e drilling fluid, usually ben-
tonite-water m i x t u r e , or are logged in "cased-hole" in w h i c h t h e h o l e has
iron casing in it w h i c h m a y or m a y n o t have b e e n c e m e n t e d in place. Most of
the logging that takes place is d o n e in o p e n - h o l e although there is consider-
able cased-hole logging.
At t h e t i m e of logging in o p e n - h o l e t h e p o r o u s and permeable beds that
contain hydrocarbons are o f t e n invaded b y t h e drilling fluids and t h e h y d r o -
carbons t o be d e t e c t e d are n o t close t o t h e wellbore. In cased-hole situations
there is usually n o invasion of drilling fluids b u t t h e iron casing and t h e
annulus that m a y be filled w i t h c e m e n t interfere w i t h t h e measurements,
introducing u n k n o w n s .
A t present t i m e in o p e n - h o l e logging nuclear t o o l s are used almost exclu-
sively for t h e determination of rock t y p e and porosity (the capacity of t h e
rock t o contain fluids). These measurements are used in c o n j u n c t i o n w i t h
electrical resistivity measurements t o d e t e c t t h e presence and v o l u m e of
hydrocarbons present.
In cased-hole applications nuclear t o o l s are used t o d e t e c t t h e rock t y p e
and t h e presence and v o l u m e o f hydrocarbons.
Nuclear logging in this t e x t is t h e well logs classified as natural and
induced.

N A T U R A L RADIATION

Natural gamma-ray log

One of t h e prime nuclear measurements is t h e m e a s u r e m e n t of natural


gamma-ray activity o f t h e formations. The g a m m a rays, primarily from K 4 0

although significant contributions are m a d e from t h e t h o r i u m and t h e ura-


nium-radium series. The energy o f t h e K c o n t r i b u t i o n as s h o w n in Fig. 6-1
4 0
202
DISINTEGRATION

POTASSIUM
PER

THORIUM SERIES
EMISSION

ii 1 J I I i i_
OF
PROBABILITY

URANIUM- RADIUM SERIES

Mil LI I | 1 III ,1 I I I , I I
0 .5 I 1.5 2 2.5 3

GAMMA-RAY ENERGY (MEV)

Fig. 6-1. Energy spectra of three components making up t o natural gamma-ray log.

is 1 . 4 6 M e V . The radioactive materials in t h e formations are generally asso-


ciated w i t h t h e shales although other rock t y p e s are radioactive o n a local
basis. T h e gamma-ray l o g is considered a shale log. Using this general charac-
teristic t h e formations m a y t h e n b e separated i n t o shales and non-shales. The
non-shales generally being t h e potential hydrocarbon-bearing formations.
Most gamma-ray logging devices use s o d i u m i o d i d e crystals (thallium-
activated) and photomultipliers with t h e w h o l e assembly kept in a dewar
flask. In e x t r e m e l y h o t or rugged operations Geiger-Mueller counters are
generally used.
In s o m e areas it is difficult t o correlate b e t w e e n o n e formation and
another or t h e z o n e s o f interest are radioactive and a spectral natural gamma-
ray log is used. This device breaks u p t h e g a m m a rays being measured i n t o
their three basic energy classifications, p o t a s s i u m , thorium series, and ura-
nium-radium series. This is d o n e o n a energy-selective basis. T h e T 1 peak 2 0 8

occurs at 2 . 6 2 M e V , B i occurs at 1 . 7 6 M e V , and t h e K peak occurs at


2 1 4 4 0

1.46 M e V . Fig. 6-2 s h o w s a gamma-ray l o g and a spectral gamma-ray l o g run


in t h e same h o l e .
The spectral gamma-ray l o g is n o t a routinely used device as it is primarily
used in areas where correlation is a problem or in areas where t h e formation
is radioactive and better information is n e e d e d .
203

INDUCED LOGS

The induced radioactivity logs fall i n t o t h o s e run w i t h n e u t r o n sources


and t h o s e run w i t h gamma-ray sources.
204

Fig. 6-3. Schematic of a compensated formation density logging tool.

Induced gamma-ray logs

The o n l y induced gamma-ray l o g being commercially run is the density


log. The t o o l consists of a 1 3 7
C s source and t w o ( c o m m o n l y scintillation)
detectors as s h o w n in Fig. 6 - 3 . The long-spaced c o m b i n a t i o n measures deeper
i n t o t h e formation whereas t h e shorter space is more influenced b y m u d
cake and other materials that exist b e t w e e n t h e pad (containing t h e source
and detectors) and the f o r m a t i o n . A p l o t of typical laboratory results s h o w -
ing t h e response of t h e long- and short-spaced c o u n t rates is s h o w n in Fig.
6-4. In Fig. 6-4 t h e solid line is t h e response with n o material b e t w e e n t h e
pad and t h e formation. As t h e pad is held away from t h e rock the data
points shift off t h e primary "spine" and f o l l o w t h e "rib" curves. The direc-
tion (left or right) d e p e n d s o n t h e density of t h e m u d cake relative t o t h e
formation density. A c o m p u t e r is used t o make t h e correction for t h e mate-
rial b e t w e e n t h e pad formation ( m u d cake) and t h e log reads o u t in apparent
density.
The process that is measured is primarily C o m p t o n scattering. The source
has sufficiently l o w energy t o effectively eliminate pair p r o d u c t i o n and the
detectors are set so that t h e y d o n o t see gamma rays with energies that sig-
nificantly are affected b y p h o t o e l e c t r i c effects.
205
RATE
COUNTING
DETECTOR
SPACING
LONG

SHORT SPACING DETECTOR COUNTING RATE

Fig. 6-4. A compensated formation density log "spine and ribs" chart showing the effect
of mud cake o n the short- and long-spaced counting rates.

In effect w h a t is being measured is electron d e n s i t y . The relation b e t w e e n


electron density and bulk density is apparent in e q u a t i o n ( 1 ) :

P E = 2 E I (1)

where p = electron density, Z = t h e a t o m i c n u m b e r , A = t h e a t o m i c weight,


e

and p = t h e bulk d e n s i t y .
b

For m o s t reservoir t y p e rocks, for e x a m p l e sandstone, l i m e s t o n e , and


d o l o m i t e , Z/A is equal t o 0 . 5 and t h e relationship b e t w e e n bulk d e n s i t y and
electron density is apparently t h e same. U n f o r t u n a t e l y , t h e Z/A is n o t equal
t o 0 . 5 for water b u t b y calibrating t h e density l o g in l i m e s t o n e filled w i t h
water this effect is eliminated s o that t h e relationship b e t w e e n electron den-
sity and bulk density is further modified b y e q u a t i o n ( 2 ) :

p = 1.07 p - 0 . 1 8 8
b e (2)
The density log readings are converted t o p o r o s i t y , 0 , using e q u a t i o n ( 3 ) :

PB ~ PMA
=
(3)
PF — PMA
206

Fig. 6-5. A compensated formation density log presentation.

where p m a = t h e d e n s i t y of t h e solid rock, usually 2 . 6 5 g c m " for sandstone,


3

2 . 7 1 for l i m e s t o n e , and a b o v e 2 . 8 5 for d o l o m i t e ; and pf = fluid density.


Fig. 6-5 is an e x a m p l e o f a d e n s i t y log. The additional d o t t e d curve o n t h e
right-hand side of t h e density log is t h e a m o u n t o f correction ( A p ) applied
by t h e c o m p u t e r t o t h e long-spaced reading t o obtain t h e final bulk density.

Neutron logs

T w o t y p e s of n e u t r o n logs are run in t h e oilfield. The t w o basic classifica-


tions o f neutron logs used in t h e oil business are: ( 1 ) steady-state sources,
207

and ( 2 ) pulsed sources. The former are used primarily as a p o r o s i t y t o o l


whereas t h e pulsed source t o o l s are used t o d e t e c t t h e e x i s t e n c e of hydro-
carbons, usually in cased-hole environments.

Neutron logs (steady-state)


Most steady-state n e u t r o n logs, hereafter called just n e u t r o n logs, used
either Am-Be or Pu-Be sources. The d e t e c t o r s are p r e d o m i n a t e l y epithermal
or thermal n e u t r o n d e t e c t o r s . T w o particular t y p e s o f n e u t r o n logs pre-
d o m i n a t e t o d a y although a third is evident in m a n y areas. The m o s t popular
and n e w e s t is t h e c o m p e n s a t e d neutron log w h i c h has a source and t w o
detectors located o n a mandrel. The near and far d e t e c t o r c o u n t rates are
ratioed and give a linear response o n semi-log p l o t similar t o t h a t s h o w n in
Fig. 6-6. This s h o w s a considerable r e d u c t i o n in b o r e h o l e effects over n e u -
tron logs using o n l y o n e d e t e c t o r . The c o m p e n s a t e d neutron logs all measure
thermal neutrons although s o m e experimental t o o l s being d e v e l o p e d d o
measure epithermal n e u t r o n s .
The s e c o n d n e u t r o n log of n o t e is t h e side-wall n e u t r o n . This is a pad t y p e
device. The neutron source and d e t e c t o r are located o n a pad w h i c h is
POROSITY — P E R C E N T

BOREHOLE DIAMETER". 12" 10" 8"6" 4"

.I ; i ' i ' ' ' • ' 1 1


i 1 I
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
THERMAL NEUTRON RESPONSE j> ( 9 0 ) 7 ^ ( 7 0 ) PERCENT

Fig. 6-6. Porosity response for a laboratory dual spaced neutron log.
208

pushed against the side o f t h e h o l e in t h e same manner as w i t h t h e density


log. Side-wall neutrons devices all measure epithermal neutrons.
The side-wall neutrons are systematically being replaced with t h e c o m p e n -
sated devices.
T h e third neutron log s y s t e m , truly o b s o l e t e b u t n o t y e t been totally
replaced, is t h e single source and single d e t e c t o r o n a mandrel. These are gen-
erally n o t calibrated in terms of porosities as are t h e other n e u t r o n logs d u e
t o t h e inability t o define t h e e x a c t l o c a t i o n in the borehole at any given
time.
N e u t r o n logs are used primarily for porosity b u t also gain very w i d e use as
a gas finding t o o l . Water and oil have very m u c h t h e same h y d r o g e n c o n t e n t
and thus t o t h e neutron l o g l o o k the same, as t h e reactions are primarily
b e t w e e n t h e h y d r o g e n and neutrons. In gases the h y d r o g e n c o n t e n t is l o w
and accordingly gas s h o w s u p as l o w p o r o s i t y . Fig. 6-7 s h o w s an e x a m p l e of
a n e u t r o n and density log run simultaneously and recorded o n compatible
porosity scales. The separation that occurs is d u e t o t h e natural gas in t h e
sandstone formation. Separation also occurs in shales b u t these are generally
n o t considered gas reservoirs.

Pulsed neutron logging


T w o different pulsed neutron logging t e c h n i q u e s are in use in t h e petro-
l e u m business. The first measures t h e d e c a y rate o f thermal neutrons
(thermal neutron life-time) in t h e formation and the other measures the
inelastic collisions o f carbon and o x y g e n in t h e f o r m a t i o n . The former will

Fig. 6-7. An example of a simultaneous density ( D ) and neutron ( N ) log. Depth is in


arbitrary units. G/O indicates the gas/oil contact.
209

be referred t o as a pulsed n e u t r o n capture (PNC) log and t h e s e c o n d will be


called c a r b o n - o x y g e n logging. B o t h of these t e c h n i q u e s are used in case h o l e s
and are used for direct l o c a t i o n of h y d r o c a r b o n s . U n f o r t u n a t e l y t h e data
alone are n o t sufficient t o make definitive decisions as l i t h o l o g y , and
porosity logs m u s t b e run for an interpretation.
B o t h systems use high-voltage p o w e r supplies and accelerators. The neu-
trons are created by deuterium ions striking a tritium target. T h e p o w e r
supplies range from classical Van der Graaf generators t o solid-state p o w e r
supplies. It should b e remembered that all these logging t o o l s are roughly 3 |
inches in diameter and a g o o d portion o f this diameter is a steel pressure
housing, so that the electronic c o m p o n e n t s o c c u p y s o m e t h i n g less than 3
inches in diameter.

Pulsed neutron capture logs. Pulsed n e u t r o n capture logs w h i c h run under


t h e trade names of neutron life-time and thermal d e c a y - t i m e logs measure
the macroscopic thermal neutron absorption cross-section o f t h e materials
which controls t h e life-time o f thermal neutrons in a material. T h e source is
pulsed and t h e g a m m a rays of capture are measured during t h e off-period of
the source. Immediately f o l l o w i n g t h e cessation of n e u t r o n p r o d u c t i o n ,
there is a period of thermal neutron d e c a y w h i c h is a b o r e h o l e signal and
after a b o u t 4 0 0 micro-seconds, t h e decay is controlled primarily b y t h e
formation characteristics (Fig. 6-8). The rate of thermal d e c a y is made
during this latter part of t h e die-away so as t o effectively b o r e h o l e c o m p e n -
sate for t h e measurement.
The m e a s u r e m e n t o f macroscopic thermal neutron absorption capture
cross-section (cross-section) is related t o porosity and water saturation as
s h o w n in equation ( 4 ) :

2 = 0(Z*S w + 2 S ) + (1 - 0 ) 2
h h m a (4)
where 2 m a = t h e cross-section of t h e solid rock; 0 = t h e porosity; 2 , 2 = h W

the cross-section of t h e hydrocarbons and water, respectively; S , S = t h e h w

saturation of t h e h y d r o c a r b o n s and water, respectively; and 2 = t h e forma-


t i o n cross-section.
The variation in Z is a function of t h e salinity of t h e water with distilled
w

water and oil having a b o u t t h e same capture cross-section ( 2 2 c m " X 1 0 " ) . 1 3

It can be seen that t h e effectiveness o f t h e m e a s u r e m e n t relies o n a signifi-


cant difference b e t w e e n t h e water and h y d r o c a r b o n cross-sections. In oil
z o n e s , this is accomplished b y having salty waters and in gas z o n e s this is
present in all cases as t h e natural gases have very l o w cross-sections relative
t o either fresh or salty water. The matrix cross-sections for various forma-
tions are very close t o being t h e same w i t h field clean sandstones being in t h e
9—12 sigma unit range, l i m e s t o n e s 8—11 and d o l o m i t e s 1 0 — 1 2 . Shales have
very high capture cross-sections and thus are easily distinguished from other
rocks.
210
RATE
COUNTING
RELATIVE

TIME {fi sec) AFTER NEUTRON BURST

Fig. 6-8. Thermal neutron die-away curve obtained with PNC log.

The interpretations of t h e PNC logs is d e p e n d e n t o n k n o w i n g t h e forma-


tion water salinity, p o r o s i t y , and t h e e x p e c t e d hydrocarbon (gas or oil).
These m u s t be obtained from other sources.
The newer PNC logs have t w o detectors and simultaneously measure cap-
ture cross-section and t h e ratio o f t h e far and near d e t e c t o r c o u n t rates. This
ratio is relatable t o p o r o s i t y . In oil z o n e s this significantly helps t h e inter-
pretation. In gas z o n e s where n e u t r o n logs see gas as l o w porosity it has b e e n
f o u n d that b y presenting the c o u n t rate from t h e near and far detectors, as
s h o w n in Fig. 6-9, the presence o f gas can be observed b y t h e relative posi-
t i o n of t h e t w o curves. This is a purely empirical t e c h n i q u e .
PNC logs are used t o find hydrocarbons in old wells t h a t have never b e e n
logged and t o m o n i t o r t h e producing z o n e s t o determine t h e efficiency of
p r o d u c t i o n and t o help evaluate p r o d u c t i o n p r o b l e m s where it is uncertain
w h e t h e r t h e well has b e c o m e d e p l e t e d or is mechanically being obstructed
from producing hydrocarbons.

Carbon-oxygen logging. In formations where the water is fresh t h e PNC logs


c a n n o t distinguish b e t w e e n oil and water. T o cover this special c o n d i t i o n t h e
carbon-oxygen log was d e v e l o p e d . A pulsed source similar t o that used for
PNC logs is used. The g a m m a rays produced b y inelastic scattering of t h e 1 4 -
211

I
GAMMA RAY
60 30 0
80 T 480
NEAR cps
BACKGROUND 4000 N, 0
0 £ 3 1 0 0 0 6 f A J L ° _ _ _ i § i * _ F
* F , C
- l - J ?

) f — G R

V S

/RATIO^ i

1 T
ITOP OFFLUID
SG.
£ IN C

<8 5/8'CSG RATIO/j^"


j FRESH MUD
5 £
Fig. 6-9. An example of a PNC log with t w o detectors.

MeV n e u t r o n s are d e t e c t e d b y a scintillation spectrometer. The role o f t h e


instrument is t o d e t e c t t h e c a r b o n / o x y g e n ratio in sandstones w h i c h is
directly related t o t h e relative abundances o f h y d r o c a r b o n s and water. T h e
measurement o f c a r b o n / o x y g e n ratio is recorded o n a station b y station
level. The stationary measurements are for periods u p t o 1 0 m i n . The station
by station m e a s u r e m e n t is m a d e necessary b y t h e l o w c o u n t i n g rates and t h e
n e e d for very precise numbers. For e x a m p l e , in a water z o n e t h e measured
c a r b o n / o x y g e n ratio is typically around 1.65 and if t h e same z o n e is h y d r o -
carbon-producing t h e n u m b e r ranges from 1.7 t o 1 . 8 5 .
Fig. 6-10 s h o w s a spectra o f frequency versus gamma-ray energy for a tank
filled with oil versus a tank filled w i t h water. The carbon, o x y g e n and t h e
escape peaks are o b v i o u s and t h e approximate w i n d o w w i d t h used is s h o w n .
212
N U M B E R / 0 04 MtV INTERVAL

W I C J ^ 3 O f
GAMMA RAY ENERGY (M«V)
Fig. 6-10. Carbon-oxygen spectra in tanks of oil and water. DE = dual escape peak; SE =
single escape peak.

This is an e x t r e m e case in that it w o u l d represent a f o r m a t i o n w i t h 1 0 0 %


porosity and 1 0 0 % either oil or water saturation. Typically w e are looking at
10—30% porosity and water saturations in the 20—100% range. Real
formation spectra s h o w considerably less separation b e t w e e n oil and water.
The o n l y commercial c a r b o n - o x y g e n log available t o d a y uses a thallium-
activated s o d i u m i o d i d e crystal in a dewar flask. T h e p h o t o m u l t i p l i e r is
rigorously stabilized and t h e gating circuits are severely limited t o be sure
that high-quality pulse data is transmitted over t h e very long cable.
The c a r b o n - o x y g e n log at t h e present t i m e is n o t usable in carbonates, i.e.,
l i m e s t o n e or d o l o m i t e , because of t h e carbon in t h e rock material itself. It is
necessary t o be able t o identify t h e t y p e o f l i t h o l o g y o f t h e formation being
investigated if it is n o t already k n o w n from geological drill cuttings. T o
accomplish this end a silicon/calcium ratio is run w i t h t h e carbon-oxygen
log. The silicon and calcium are measured either from g a m m a rays from
thermal neutron capture interactions or from inelastic n e u t r o n interactions.
T h o s e that are run with thermal n e u t r o n capture interactions are salinity
sensitive as t h e chlorine in calcium spectral shapes overlap. The putting
together of t h e silicon/calcium ratio and t h e c a r b o n / o x y g e n ratio allows for
t h e identification of sands and sands with small a m o u n t s o f calcite c e m e n t
and t h e identification of t h e fluids inside. Fig. 6-11 s h o w s a p l o t based o n
t h e use o f b o t h ratios.
213
C/O RATIO

1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1

Si/Ca R A T I O

Fig. 6 - 1 1 . Method for predicting fluid content of limy sandstones using carbon/oxygen
and silicon/calcium ratios. WOR = water/oil ratio.

CONCLUSIONS

Nuclear well logging t e c h n i q u e s play a major and very necessary role in


well logging for p e t r o l e u m .

REFERENCES

Culver, R.B., Hopkinson, E.C. and Youmans, A.H., 1 9 7 3 . Carbon-oxygen (C/O) logging
instrumentation. 48th Annu. Soc. Pet. Eng., AIME Meet., September, Las Vegas, Nev.,
SPE 4 6 4 0 .
Hilchie, D.W., undated. Neutron Lifetime Log Interpretation. Dresser Atlas, Houston,
Texas.
Hilchie, D.W., 1 9 7 4 . Neutron accelerator logging. Conf. on Neutron Accelerators, October,
North Texas State University, Denton, Texas.
Hilchie, D.W., 1 9 7 5 . Nuclear well logging. Am. Nucl. Soc. Meet, June, New Orleans, La.
Schlumberger Log Interpretation, I. Principles. Schlumberger Ltd., N e w York, N.Y. ( n o
date).
Schlumberger Log Interpretation, II. Applications. Schlumberger Ltd., N e w York, N.Y.,
( n o date).
Schultz, W.E. and Smith, H.D., 1 9 7 3 . Laboratory and field evaluation of a carbon-oxygen
well logging system. 48th Annu. Soc. Pet. Eng., AIME Meet, September, Las Vegas,
Nev., SPE 4 6 3 8 .
Wichman, P.A., McWhirter, V.C. and Hopkinson, E . C , 1 9 7 5 . Field results of natural
gamma-ray spectralog. Soc. Prof. Well Log Analysts, 16th Annu. Symp., June, New
Orleans, La.
Chapter 7

THE P O T E N T I A L O F P L O W S H A R E F O R R E S O U R C E D E V E L O P M E N T

JOHN TOMAN and HOWARD A. TEWES

INTRODUCTION

It was o n l y natural that success in d e v e l o p m e n t of nuclear explosives


should lead t o investigations i n t o practical use for these highly c o m p a c t
explosive sources. The 1 9 5 6 war over t h e Suez Canal, f o u g h t b y Britain,
France, and Israel against E g y p t , provided t h e m o t i v a t i o n for initiation of
studies i n t o non-military uses of nuclear explosives. The possibility of
excavating an alternate canal through Israel w i t h nuclear explosives was dis-
cussed at t h e "First Plowshare S y m p o s i u m " c o n v e n e d at t h e Livermore
installation of t h e University of California Radiation Laboratory ( n o w t h e
Lawrence Livermore Laboratory, or LLL) in February 1 9 5 7 . In July 1 9 5 7
Project Plowshare was formally established at t h e LLL t o investigate indus-
trial uses of nuclear explosives. F r o m 1 9 5 7 t o 1 9 7 0 , t h e major thrust o f t h e
effort centered o n excavation and t h e feasibility of excavating a sea-level
canal across t h e Isthmus of Panama (Atlantic-Pacific Interoceanic Canal
S t u d y C o m m i s s i o n , 1 9 7 0 ) . A summary o f cratering e x p e r i m e n t s carried o u t
as part of t h e Plowshare Program, as well as possible industrial applications
of nuclear cratering are given b y T o m a n ( 1 9 7 0 a , b ) .
American industrial interest in Plowshare was concentrated o n under-
ground or c o m p l e t e l y contained applications o f nuclear explosives because
of the lack o f commercially attractive nuclear excavation projects within t h e
Continental U . S . The potential applications w h i c h appeared t o be e c o n o m i -
cally attractive w h e n c o m p a r e d w i t h conventional t e c h n o l o g y included t h e
use of nuclear cavities for underground storage of natural gas and hydro-
carbon liquids, stimulation of natural gas reservoirs b y rock breakage, the
p r o d u c t i o n o f shale oil b y t h e in-situ retorting c o n c e p t , and chemical mining
of d e e p l y buried deposits of c o p p e r ore.
The m o s t simple and straightforward application is that of storage, b u t n o
U.S. experiments have been c o n d u c t e d for this specific purpose. While gas
well stimulation is inherently a more c o m p l e x application o f peaceful nuclear
e x p l o s i o n s (PNEs), three experiments have been carried o u t in this branch
of the t e c h n o l o g y . Analysis of t h e results from these e x p e r i m e n t s has indi-
cated that w i t h careful planning, this application could be commercially
attractive.
216

A substantial calculational and laboratory effort has b e e n e x p e n d e d t o


assess t h e feasibility of in-situ retorting o f shale oil w i t h i n a nuclear c h i m n e y ;
a program of similar s c o p e has been carried o u t in c o n j u n c t i o n w i t h industry
t o assess t h e e c o n o m i c and technological characteristics o f nuclear chemical
copper mining. These t w o potential resource recovery applications o f PNEs
are technically c o m p l e x , and n o full scale field tests have b e e n c o n d u c t e d .
At t h e present t i m e , t h e Plowshare Program is o n l y very m o d e s t l y funded
b y t h e Federal government, probably d u e mainly t o t h e current socio-politi-
cal climate. C o n s e q u e n t l y , n o field experiments are currently planned. It
appears that, for Plowshare t e c h n o l o g y t o be applied on any scale t o
resource extraction in t h e U n i t e d States, it m u s t display very significant
e c o n o m i c superiority over any c o m p e t i n g conventional t e c h n o l o g y . In t h e
event that social attitudes change in t h e n e x t decade or s o , or if t h e energy
crisis b e c o m e s so severe that all potential energy resource recovery m e t h o d s
are pursued, t h e use of PNE t e c h n o l o g y m a y be reevaluated. The following
overview of t h e use of nuclear explosives for resource d e v e l o p m e n t is an
a t t e m p t t o place t h e potential o f this t e c h n o l o g y in perspective. The refer-
ence list presented at t h e end o f this chapter is n o t intended t o be exhaustive
b u t is adequate for a n y o n e desiring t o perform additional background
research.

PHENOMENOLOGY

The large yield of energy produced b y an explosive w i t h a relatively small


v o l u m e is t h e major factor favoring t h e use o f nuclear explosives for indus-
trial rock crushing or earth m o v i n g applications. As an e x a m p l e , a 1 0 0 - k t
nuclear explosive designed for contained (non-cratering) applications has a
v o l u m e of less than 1 m , while t h e chemical explosive such as T N T required
3

t o produce the same energy release has a v o l u m e o n t h e order o f 5 0 , 0 0 0 m . 3

In this brief discussion o f nuclear explosives, w e will c o n f i n e ourselves t o


their utilization for contained applications. While t h e Soviets have p r o p o s e d
using nuclear explosives t o remove t h e overburden from d e e p l y buried ore
bodies (see section " U . S . S . R . program"), w e will n o t deal w i t h this p r o p o s e d
m e t h o d of explosive utilization in this s e c t i o n .

Cavity and chimney formation (Rawson, 1966)

In order t o illustrate t h e effects of a contained nuclear d e t o n a t i o n , w e


shall consider a particular e x a m p l e in w h i c h a 1 0 0 - k t explosive is d e t o n a t e d
at a depth of 9 0 0 m . The schematic representation s h o w n in Fig. 7-1 indi-
cates t h e d e v e l o p m e n t of t h e e x p l o s i o n effects resulting from such a detona-
tion.
In less than a m i c r o s e c o n d f o l l o w i n g the d e t o n a t i o n , t h e total energy of
217

JL

FINAL CONFIGURATION

Fig. 7-1. Cavity growth and collapse history of contained nuclear explosions.

4.2 X 1 0 2 1 ergs is released. A p p r o x i m a t e l y 6 0 0 0 — 9 0 0 0 t o n n e s o f rock, as


well as t h e explosive itself, are vaporized. The temperature and pressure of
this sphere of "rock g a s " are initially o n t h e order of 1 3 , 0 0 0 , 0 0 0 ° K and
1 0 TPa, respectively ( J o h n s o n and V i o l e t , 1 9 5 8 ; J o h n s o n e t al., 1 9 5 9 ) . A
strong spherical s h o c k front m o v e s radially outward from this gas bubble
d e e p underground — melting, crushing, displacing and cracking t h e surround-
ing rock. Well over 90% o f t h e energy of this shock wave is d e p o s i t e d locally
in t h e form o f heat and w o r k o n t h e surrounding rock — typically, a total of
a b o u t 1 0 0 , 0 0 0 t o n n e s o f rock eventually are m e l t e d a n d / o r vaporized. The
fraction of t h e total e x p l o s i o n energy w h i c h is eventually manifested as an
elastic or seismic wave ranges from a b o u t 1% t o as l o w as a f e w hundredths
of a percent.
The original bubble of "rock gas" e x p a n d s , forming a cavity. The expan-
sion phase c o n t i n u e s until t h e gas pressure is a p p r o x i m a t e l y equal t o t h e
overburden pressure (in this e x a m p l e , a b o u t 2 2 . 5 MPa). Cavity growth is
c o m p l e t e d in a f e w hundred milliseconds t o a radius of a b o u t 4 5 m. A t this
t i m e , t h e walls o f t h e cavity are lined w i t h t h e 1 0 0 , 0 0 0 t o n n e s o f m e l t e d
rock (as n o t e d a b o v e ) , and t h e cavity gas temperature is a f e w t h o u s a n d
degrees Kelvin.
The cavity persists for a period o f t i m e w h i c h is s o m e w h a t d e p e n d e n t o n
t h e mechanical properties of t h e rock overburden; during this t i m e interval,
218

t h e "rock gas" c o n d e n s e s , t h e temperature and pressure d r o p , and the


m o l t e n rock lining t h e cavity flows d o w n t o form a puddle at t h e b o t t o m of
t h e cavity. Finally, t h e fractured rock above the explosion-generated cavity
collapses into t h e spherical v o i d , resulting in a roughly cylindrical c o l u m n of
broken rock w h i c h is referred t o as t h e " c h i m n e y " .
If the rock in w h i c h t h e explosive is d e t o n a t e d is relatively tight and c o m -
pact, collapse leads t o r a n d o m packing o f t h e rock fragments with a conse-
q u e n t reduction of t h e bulk density of the rock " b e d " in the c h i m n e y
region, t o g e t h e r w i t h a corresponding increase in t h e effective porosity and
permeability of t h e rubble c o l u m n . On t h e other hand, if the d e t o n a t i o n
environment can be characterized as a p o r o u s and c o m p a c t a b l e rock (such as
t h e tuffaceous alluvium o f t h e Nevada Test Site), little or n o decrease in bulk
density occurs with collapse. When the roof of t h e cavity collapses, t h e over-
lying rock c o n t i n u e s t o fail progressively upward until t h e void v o l u m e is
translated t o t h e ground surface and a subsidence crater is formed. The roofs
of cavities in plastic unfractured rock (such as exists in m a n y kinds o f
layered salt or in salt d o m e s ) are m o r e stable and collapse very s l o w l y , if at
all.
The observed values for cavity radius and c h i m n e y height vary as a func-
tion of explosive y i e l d , d e p t h of burial, rock t y p e and overburden density.
Assuming that the cavity is f o r m e d b y adiabatic e x p a n s i o n o f high-pressure
gas t o overburden pressure, cavity radii can be calculated b y using the
approximate relation (Boardman et al., 1 9 6 4 ) :

r c = c r / 3
/ ( P / i ) l / 4
, ( i )

where R = cavity radius ( m ) ; C = c o n s t a n t (appropriate t o t h e d e t o n a t i o n


c

m e d i u m ) ; W = energy yield o f e x p l o s i o n ( k t ) ; p = average overburden density;


and h = d e p t h of overburden ( m ) .
On t h e basis of data from a large n u m b e r of nuclear d e t o n a t i o n s in differ-
e n t media (including such dissimilar substances as tuff, granite, d o l o m i t e and
salt), C displays an average value of a b o u t 6 6 (individual values of C range
from 5 5 t o 8 2 ) . Cavity size is thus seen t o be relatively insensitive t o rock
type.
The c h i m n e y height observed where t h e d e t o n a t i o n m e d i u m is c o m p e t e n t
(i.e., where collapse d o e s n o t c o n t i n u e upward t o t h e ground surface) can be
expressed b y t h e simple relation :
H = kR c (2)
where H = c h i m n e y height ( m ) , measured from t h e original l o c a t i o n o f the
nuclear explosive t o t h e a p e x o f t h e c h i m n e y ; k = c o n s t a n t (which ranges
from a b o u t 3 t o 6 ) .
C h i m n e y collapse and t h e resultant c h i m n e y characteristics are m u c h
more variable than is t h e cavity radius, R , since c h i m n e y size and shape are
c

strongly influenced b y i n h o m o g e n e i t i e s in t h e rock mass, such as bedding


219

planes, fracture frequencies, and jointing characteristics.


N o t e also that e q u a t i o n ( 2 ) d o e s n o t apply t o d e t o n a t i o n s taking place in
a plastic m e d i u m , such as salt, where c h i m n e y s appear t o be minimal or n o n -
existant.
In t h e rock outside t h e cavity-chimney region, the d e t o n a t i o n - i n d u c e d
shock wave characteristically produces a z o n e of increased permeability in
t h e rock environment. It has b e e n calculated that this z o n e of e n h a n c e d per-
meability should e x t e n d t o a distance as great as 4 i ? , as measured from the
c

d e t o n a t i o n p o i n t . Because this region displaying greater permeability than


the surrounding rock can o n l y be characterized with great difficulty (requir-
ing t h e drilling of several exploratory wells surrounding t h e nuclear cavity-
c h i m n e y s y s t e m ) , it has n o t as y e t been possible t o physically measure t h e
increase in permeability as a f u n c t i o n of distance from t h e s h o t p o i n t . It
should b e emphasized that t h e e x t e n t of this z o n e of increased permeability
is critical t o t h e e c o n o m i c evaluation of t h e potential of peaceful nuclear
e x p l o s i o n s (especially for t h e recovery of natural gas). Based o n m o d e l i n g gas
flow from nuclear c h i m n e y s in natural gas reservoirs, enhanced permeability
appears t o e x t e n d t o a lateral distance of 3 R . c

Seismic effects (Holzer, 1 9 7 1 )

From t h e i n c e p t i o n of t h e Plowshare Program it has b e e n recognized that


understanding and predicting the ground m o t i o n generated b y a nuclear
e x p l o s i o n and any associated building or structural damage was necessary if
nuclear e x p l o s i o n s for peaceful purposes were t o achieve their m a x i m u m
usefulness and e m p l o y m e n t (Griggs, 1 9 5 8 ) . Over t h e past d e c a d e , m e t h o d s
have been d e v e l o p e d that enable us t o estimate, with reasonable accuracy,
t h e ground m o t i o n from single, relatively high y i e l d , d e t o n a t i o n s . Ground
m o t i o n parameters w h i c h appear t o best correlate with damage have b e e n
identified.
The approach used has involved t h e generation of a response spectrum
( N a d o l s k y , 1 9 6 9 ) w h i c h represents t h e structure response t o a particular
ground displacement. The simplifying assumption is m a d e that t h e response
of a structure t o such a ground d i s p l a c e m e n t can b e a p p r o x i m a t e d b y t h e
envelope formed b y t h e m a x i m u m response of a series o f simple harmonic
oscillators w h i c h are t u n e d t o different frequencies and d a m p e d t o a fixed
fraction of t h e critical value (Clough, 1 9 6 7 ) . The generation of this response
spectrum can be carried o u t using a digital c o m p u t e r ; a typical spectrum is
s h o w n in Fig. 7-2 w h i c h also s h o w s t h e approximate period intervals in
w h i c h buildings o f various heights have been f o u n d t o resonate.
For o n e - or t w o - s t o r y buildings, t h e value o f t h e pseudo-absolute accelera-
tion ( P S A A ) * in t h e 5—20 Hz range (periods o f 0.2—0.05 s e c o n d ) s e e m s t o

* PSAA is a function of both the displacement of a building by a seismic pulse and the
square of the natural response frequency of the building.
220

Debeque Canyon, hard rock, station R18, distance 33.5 km

oP.o*

% X
Pseudo relative velocity — cm/sec

?
V
%

/
Period — sec

Fig. 7-2. Sample spectrum, with regions of building response.

correlate better w i t h observed damage than a n y other m o t i o n parameter


( N a d o l s k y , 1 9 6 9 ) . T h e ground m o t i o n measurements m a d e o n t h e Rulison
gas stimulation e x p e r i m e n t ( U . S . A t o m i c Energy C o m m i s s i o n , 1 9 6 9 b ) ,
together w i t h t h o r o u g h structural o r architectural seismic damage d o c u m e n -
tation ( U . S . A t o m i c Energy C o m m i s s i o n , 1 9 7 1 ) has empirically established
this correlation.
This Rulison experience (Rizer, 1 9 7 0 ; F a r h o o m a n d and Scholl, 1 9 7 1 ) is
summarized in Fig. 7 - 3 , t o g e t h e r w i t h s o m e results from t h e S a l m o n experi-
m e n t and also from several d e t o n a t i o n s carried o u t at t h e Nevada Test Site.
This figure s h o w s that at P S A A o f lg in t h e frequency range of 5—20 H z ,
221
Building damage — %

PSAA at 0 . 0 5 - 0 . 2 sec, g

Fig. 7-3. Correlation between damage and pseudo-absolute acceleration.

over 50% of o n e - or two-story structures can be e x p e c t e d t o sustain s o m e


damage. A t a b o u t O.Olg, damage will be sporadic; at l o w e r g loadings, little
or n o damage should be anticipated. T h u s , Fig. 7-3 can be used as a quick
and c o n v e n i e n t aid in estimating building damage for one- or two-story struc-
tures in t h e vicinity of a planned nuclear d e t o n a t i o n , provided that t h e
response spectra of these structures can b e predicted.
222

Radioactivity production, distribution, and transport ( T e w e s e t al., 1 9 7 4 ;


Levy, 1 9 7 2 )

T h e specific radionuclides p r o d u c e d b y a nuclear d e t o n a t i o n used for


underground resource d e v e l o p m e n t are m u c h t h e s a m e irrespective o f t h e
design o f t h e nuclear e x p l o s i v e w h i c h is u s e d ; h o w e v e r , t h e relative a m o u n t s
of t h e various radioactivities f o r m e d is critically d e p e n d e n t o n t h e fission-to-
fusion ratio o f t h e e x p l o s i v e . Table 7-1 s h o w s t h e fission p r o d u c t radioactiv-
i t y present 1 8 0 d a y s after t h e d e t o n a t i o n o f a 1 0 0 - k t all-fission e x p l o s i v e .
S h o u l d a 1 0 0 - k t t h e r m o n u c l e a r e x p l o s i v e w i t h a 5-kt fission trigger b e e m -
p l o y e d , t h e a m o u n t s o f all t h e radionuclides s h o w n in Table 7-1 s h o u l d be
r e d u c e d t w e n t y f o l d . With regard t o t h e radioactive p r o d u c t s f o r m e d w h e n

TABLE 7-1
Radionuclide source at D + 1 8 0 days after detonation of a 100-kt all-fission explosive
(assumes U fission) 2 3 5

Nuclide Fission products Predominant location


of radioactivity
half-life activity (Ci)

85 K r
10.8 yr 2200 gas
8 9
Sr 52 days 220,000 chimney — o n rock surfaces
9 0
Sr 28 yr 15,000 chimney — o n rock surfaces
9 i Y 59 days 360,000 chimney — o n rock surfaces
9 5
Zr 65 days 440,000 melt — in vitreous matrix
9 5
Nb 35 days 800,000 melt — in vitreous matrix
1 0 3 R u * 40 days 105,000 chimney — on rock surfaces
1 0 6 R u * 1.0 yr 38,000 chimney — o n rock surfaces
115m C d
43 days 120 chimney — o n rock surfaces
1 2 3
Sn 125 days 600 chimney — o n rock surfaces
1 2 4
Sb 60 days 50 chimney — on rock surfaces
1 2 5
Sb 2.7 yr 6000 chimney — o n rock surfaces
l25m T e
58 days 1100 chimney — on rock surfaces
12 7 m T e * 109 days 7000 chimney — o n rock surfaces
129nvpe * 34 days 1700 chimney — o n rock surfaces
137 * C s
30 yr 18,000 chimney — on rock surfaces
140B a * 12.8 days 900 chimney — on rock surfaces
1 4 1
Ce 33 days 130,000 melt — in vitreous matrix
143p r
13.6 days 1600 melt — in vitreous matrix
144 C e * 284 days 360,000 melt — in vitreous matrix
Pm
1 4 7
2.6 yr 70,000 melt — in vitreous matrix
^Sm 87 yr 500 melt — in vitreous matrix
Eu
1 5 5
1.8 yr 3000 melt — in vitreous matrix

* Relatively short-lived radioactive daughters are in transient equilibrium with these fis-
sion products; however, the total activity (in curies) listed for these fission products
represents only that from the parent nuclide.
223

TABLE 7-II
Soil activation products (assumes Hardhat granite with 1 wt.% FeS2, 1 wt.% C u F e S , and 2

5 wt.% H 0 ) 2

Nuclide Half-life Activity (Ci) Predominant location


of radioactivity
3
H 12 < 2 0 0 0 ** water
14 5730 7 gas
C
yr
32p 14 days 170 chimney — on rock surfaces
35 g
88 days 15,000 chimney — o n rock surfaces
3 7
Ar 35 days 7200 gas
3 9
Ar 270 yr 8 gas
4 5
Ca 155 days 20,000 melt — in vitreous matrix
4 6
Sc 84 days 1400 melt — in vitreous matrix
5 4
Mn 303 days 180 melt — in vitreous matrix
5 5 F e
2.6 yr 49,000 melt — in vitreous matrix
5 9
Fe 45 days 1700 melt — in vitreous matrix
6 0
Co 5.3 yr 120 melt — in vitreous matrix
6 5
Zn 245 days 1000 melt — in vitreous matrix
8 5
Sr 64 days 160 melt — in vitreous matrix
89 S r * 52 days 550 melt — in vitreous matrix
95 Z r * 65 days 90 melt — in vitreous matrix
9 5 N b * 35 days 150 melt — in vitreous matrix
1 3 4
Cs 2 yr 1500 chimney — on rock surfaces
141 C e * 33 days 130 melt — in vitreous matrix
1 5 2
Eu 12 yr 600 melt — in vitreous matrix
160 X b
72 days 830 melt — in vitreous matrix
1 7 0
Tm 130 days 2900 melt — in vitreous matrix
192 I r
74 days 900 melt — in vitreous matrix

* Also formed as a fission product.


** Published values for gas-stimulation fission explosive detonated in Wagon Wheel
environment.

n e u t r o n s e m i t t e d f r o m t h e e x p l o s i v e are captured in t h e surrounding r o c k ,


t h e a m o u n t s o f t h e s e p r o d u c t s are i n f l u e n c e d b o t h b y t h e c o m p o s i t i o n o f
t h e rock and b y t h e n u m b e r of n e u t r o n s escaping f r o m t h e nuclear e x p l o s i v e .
Since b o t h fission and t h e r m o n u c l e a r e x p l o s i v e s e m i t * a p p r o x i m a t e l y
2 X 10 n e u t r o n s per k i l o t o n of y i e l d (Lessler et al., 1 9 7 1 ) , t h e s a m e
2 3

a m o u n t s o f t h e various activation p r o d u c t s are p r o d u c e d for a given t o t a l


y i e l d , irrespective o f t h e t y p e o f e x p l o s i v e . T h u s , t h e list o f radioactivities
given in Table 7-II represents r o c k activation p r o d u c e d b y either a fission or
a t h e r m o n u c l e a r e x p l o s i o n . T h e o n e radioactive species s h o w n in Table 7-II

* Assuming that the explosives do not employ neutron "shields" to diminish the number
of neutrons released into the surroundings.
224

which is sensitive t o t h e t y p e o f explosive used is H (tritium). Since approx-


3

imately 2 g of this nuclide is f o r m e d per k i l o t o n o f thermonuclear yield


( T e w e s , 1 9 6 8 ) , use of a fusion explosive o f t h e t y p e previously n o t e d (5-kt
fission trigger) w o u l d produce s o m e 2 , 0 0 0 , 0 0 0 Ci of tritium, as against t h e
less than 2 0 0 0 Ci produced in a typical gas-well e n v i r o n m e n t b y t h e specially
designed gas-stimulation explosive (Rubin et al., 1 9 7 2 ) . (It is necessary t o
minimize t h e tritium p r o d u c t i o n associated with a nuclear e x p l o s i o n used t o
enhance t h e recovery o f a p e t r o l e u m p r o d u c t , inasmuch as s o m e fraction of
t h e tritium will be chemically incorporated i n t o t h e p e t r o l e u m p r o d u c t . )
It should b e n o t e d t h a t t h e radioactive species formed b y n e u t r o n absorp-
tion w h i c h are listed in Table 7-II represent o n l y t h o s e resulting from activa-
t i o n of t h e rock surrounding t h e explosive. Additional radioactivity can be
p r o d u c e d b y neutron activation of the materials used in t h e construction of
the explosive itself. The large a m o u n t s of such nuclides as W , W , and 1 8 1 1 8 8

1 8 2
T a w h i c h have b e e n observed in debris from nuclear cratering e x p e r i m e n t s
( N o r d y k e and Williamson, 1 9 6 5 ; T e w e s , 1 9 7 0 ; Lessler, 1 9 6 8 ) indicate that
care m u s t be used in t h e design o f a thermonuclear explosive t o prevent t h e
formation of radionuclides w h i c h could adversely affect t h e feasibility of
certain mineral resource recovery projects.
The distribution of t h e various radioactive nuclides formed b y a nuclear
d e t o n a t i o n is d e p e n d e n t o n t h e chemical characteristics of each o f these spe-
cies at t h e t i m e during w h i c h c h i m n e y f o r m a t i o n takes place (Borg, 1 9 7 3 ) .
That is, t h o s e radioactive substances w h i c h act in a refractory manner will
largely be f o u n d in t h e so-called "puddle glass" or rock m e l t at t h e b o t t o m
of the c h i m n e y , while t h o s e which display s o m e degree o f volatility will be
found t o a greater or lesser e x t e n t t o be d e p o s i t e d o n t h e surfaces o f t h e
c h i m n e y rubble or in t h e void v o l u m e b e t w e e n t h e rubble fragments. Table
7-III gives a simple categorization of various typical radionuclides which
c o u l d b e f o u n d in debris from a nuclear d e t o n a t i o n .
T h o s e radioactive i s o t o p e s that are described as volatile appear t o behave
as such because either t h e y themselves or o n e o f their precursors in a radio-

TABLE 7-III
Chemical behavior of selected radioactive species

Volatile Non-volatile

Fission products 8 9
Sr, 9 0
Sr, 9 1
Y 9 5
Zr, Nb, Zr
9 5 9 7

103 R U ) 1 0 6 R u
1 4 4
Ce
1 3 7
Cs 1 4 7
Nd, Sm 1 5 1

Activation products 32p 4 5


Ca, 5 4
Mn
5 6
Mn, 5 5
Fe, 5 9
Fe
Fusion products 3
H
225

active d e c a y chain exists in a volatile chemical form for s o m e t i m e during t h e


distribution process. T h e former situation m a y b e e x e m p l i f i e d b y such spe-
cies as R u or H while t h e latter is typified b y t h e mass-90 d e c a y chain:
1 0 3 3

9o ^ 9o
f i r ^ 9oK r 9o
R b S l % w hcourse, t h e K r is a n o b l e gas and t h e
e r e > o f
9 0

B r and R b m a y be volatile under t h e c o n d i t i o n s prevailing at t h e t i m e of


9 0 9 0

cavity collapse.
The refractory radioactive substances, in an analogous w a y , m u s t t h e m -
selves be refractory in nature or m u s t be t h e e n d p r o d u c t o f a radioactive
decay chain all t h e m e m b e r s of w h i c h are also refractory.
On t h e basis of this chemical differentiation, t h e p r e d o m i n a n t l o c a t i o n of
t h o s e nuclides listed in Tables 7-1 and 7-II — within t h e glass matrix or o n
t h e rubble surface — can b e established as s h o w n in t h e fourth c o l u m n of
these tables.
Regarding t h e q u e s t i o n o f groundwater transport o f radionuclides present
in t h e cavity-chimney s y s t e m resulting from a contained underground
nuclear d e t o n a t i o n , t h e radioactive species remaining in t h e m e l t region will
be either chemically part o f t h e m e l t or o c c l u d e d in it. The m e l t will t e n d t o
protect t h e radioactivity from leaching o u t appreciably, at least until temper-
atures and pressures are reached that w o u l d break d o w n t h e m e l t matrix. On
the other hand, t h e radioactivity in the c h i m n e y rubble region will have c o n -
densed o n t h e rock surfaces and be more readily accessible t o leaching b y
groundwater. This has b e e n borne o u t experimentally.
In a f l o o d e d nuclear c h i m n e y t h e c o n c e n t r a t i o n in s o l u t i o n o f a particular
radioactive species will d e p e n d n o t o n l y o n its physical availability for leach-
ing b u t also o n its behavior in t h e prevailing chemical e n v i r o n m e n t . Such fac-
tors as t h e temperature and pressure, t h e c o m p o s i t i o n o f t h e groundwater
(including its p H ) , t h e solubility o f t h e chemical forms in w h i c h t h e given
species is present, and t h e ion-exchange behavior b e t w e e n t h e given species
and the c h i m n e y rubble m a y all be important in determining t h e ultimate
concentration of the species in solution in t h e c h i m n e y .
The radioactive species tritium is of special interest w i t h respect t o ground-
water c o n t a m i n a t i o n . Tritium will exchange with t h e normal h y d r o g e n in
water and, therefore, tritium will b e in t h e groundwater as part of t h e water
molecules.
Because o f t h e slowness o f m o s t groundwater m o v e m e n t , o n e rarely has t o
consider radioactive species with half-lives less than a f e w m o n t h s t o a year
in evaluating t h e p r o b l e m of radioactive c o n t a m i n a t i o n . In addition, w h e n a
contained nuclear e x p l o s i o n occurs b e l o w t h e water table, rock is displaced
outward from t h e region o f t h e e x p l o s i o n , creating more void space in t h e
e x p l o s i o n region and resulting in a depression being f o r m e d in t h e p o t e n t i o -
metric surface. * Until equilibrium is restored in t h e p o t e n t i o m e t r i c surface,

* The potentiometric surface is the maximum elevation at which ground water can be
found, and is defined by the height to which water will rise in a well under hydrostatic
pressure.
226

the water f l o w will be inward toward t h e e x p l o s i o n z o n e , minimizing chances


of radioactive c o n t a m i n a t i o n of t h e nearby groundwater. When t h e water-
table level is restored, normal groundwater f l o w will resume. The restoration
of t h e water-table level m a y take m a n y m o n t h s or even years. In a Plowshare
application in w h i c h t h e c h i m n e y might be deliberately f l o o d e d , this time
scale can be considerably s h o r t e n e d . However, it is unlikely that o n e could
n o t afford t o wait until t h e short-lived activities d e c a y e d ( a b o u t six m o n t h s )
before flooding t h e c h i m n e y .
The parameters that affect t h e transport o f radioactive c o n t a m i n a t i o n in
t h e groundwater s y s t e m are n u m e r o u s and can e x t e n d over a very large range
of values under field c o n d i t i o n s . Thus, in order t o m a k e a realistic evaluation
of t h e groundwater radioactive problem for a given Plowshare site, it is
necessary t o m a k e a thorough study of t h e groundwater chemistry and of
t h e h y d r o l o g y of t h e water-bearing formations in t h e vicinity of t h e pro-
p o s e d project. Whether or n o t sorption plays an important role, ultimately
t h e fate o f any radioactive species that is present in the groundwater d e p e n d s
o n t h e f l o w of the groundwater, where it goes, w h a t paths it takes, h o w fast
it m o v e s , e t c .
Formation t y p e s in w h i c h it is especially difficult t o predict radionuclide
dispersion include: ( 1 ) aquifers that contain narrow sections of very high
permeability, (2) formations w i t h strongly anisotropic permeability where
t h e principal direction of f l o w m a y tend away from t h e regional hydraulic
gradient and instead t e n d in t h e direction o f m a x i m u m permeability (i.e.,
along local induced gradients), and ( 3 ) aquifers w i t h more or less c o n t i n u o u s
variation o f f l o w parameters a n d / o r h e t e r o g e n e o u s sections, resulting in large
dispersive effects or simply a n o m a l o u s f l o w patterns. Unless such deviations
from ideal behavior are measured and properly taken into a c c o u n t , radio-
active c o n t a m i n a t i o n either ( 1 ) m a y arrive where it is e x p e c t e d b u t m u c h
sooner than e x p e c t e d , (2) m a y arrive where it is n o t e x p e c t e d at all, or (3)
m a y spread and travel in a m u c h broader band than e x p e c t e d . In t h e latter
case, although t h e c o n c e n t r a t i o n front m a y arrive sooner than e x p e c t e d , t h e
radioactivity c o n c e n t r a t i o n will be lower, due t o spreading over a larger vol-
u m e of water.
For a given groundwater f l o w rate, t h e transport of a radioactive contami-
nant can be affected quite differently, depending o n w h e t h e r the f l o w is
through a h o m o g e n e o u s p o r o u s m e d i u m or principally through m a n y very
small fractures. F l o w through small fractures is more likely t o have a greater
velocity variance, resulting in m o r e of a dispersive effect. A l s o , in f l o w
through fractures, sorption and desorption takes place along t h e surfaces of
t h e fractures, w h i c h will o f t e n have sorptive characteristics different from
t h o s e of t h e bulk rock. Unless experimental c o n d i t i o n s are carefully c h o s e n ,
the fraction of a radioactive species sorbed on rock relative t o that remaining
in a solution in c o n t a c t w i t h t h e rock, as measured o n t h e bulk rock in
laboratory e x p e r i m e n t s , m a y be quite different from that prevailing under
field c o n d i t i o n s .
227

Such peaceful applications o f nuclear e x p l o s i o n s as waste disposal and in-


situ ore leaching, because of t h e chemical reactions occurring in t h e c h i m -
n e y , m a y p o s e problems t h a t are n o t e n c o u n t e r e d in c h i m n e y s w i t h ordinary
groundwater. The chemistry o f t h e c h i m n e y e n v i r o n m e n t is likely t o have a
bearing o n w h e t h e r or n o t radioactive c o n t a m i n a t i o n o f t h e groundwater is a
serious p r o b l e m .
A l t h o u g h s o m e w o r k has b e e n d o n e o n t h e groundwater c o n t a m i n a t i o n
p r o b l e m , m u c h remains t o be d o n e t o improve t h e base from w h i c h w e may
treat t h e problem in e x p e r i m e n t s where c o n d i t i o n s are outside our e x p e -
rience.

SUMMARY OF PNE CONTAINED U N D E R G R O U N D EXPERIMENTS CONDUCTED


THROUGH 1 9 7 5 *

The current capabilities for predicting the effects of d e e p l y buried nuclear


e x p l o s i o n s have b e e n basically derived from data on several hundred tests
c o n d u c t e d at the Energy Research and D e v e l o p m e n t Agency's (formerly
AEC) Nevada Test Site as part of t h e nuclear w e a p o n s test program. A
number of nuclear explosive e x p e r i m e n t s c o n d u c t e d specifically t o address
industrial applications have added t o this wealth o f data.
Project G n o m e ( R a w s o n , 1 9 6 3 ) t h e first Plowshare e x p e r i m e n t , was c o n -
d u c t e d D e c e m b e r 1 0 , 1 9 6 1 , near Carlsbad, N e w M e x i c o . A 3.1-kt explosive
d e t o n a t e d at a d e p t h of 3 6 1 m in a b e d d e d salt formation p r o d u c e d a par-
tially standing cavity w i t h a radius o f a b o u t 1 7 . 4 m . Project Handcar (Werth,
1 9 7 0 ) was an e x p e r i m e n t at the Nevada Test Site t o study t h e effects of a
nuclear d e t o n a t i o n in a carbonate rock. A 1 2 - k t explosive d e t o n a t e d at a
d e p t h of 4 0 2 m o n N o v e m b e r 5 , 1 9 6 4 , p r o d u c e d a c h i m n e y w i t h a radius of
2 1 m and a height of 7 1 m .
Three nuclear tests (Projects Gasbuggy, Rulison, and Rio Blanco) have
been e x e c u t e d t o evaluate t h e potential of P N E s for stimulating t h e flow of
natural gas ( m e t h a n e ) from submarginal reservoirs. Project Gasbuggy
(Holzer, 1 9 7 0 ) used an explosive with a yield o f 2 9 kt buried at a d e p t h o f
1 2 9 2 m in t h e San Juan Basin o f N e w M e x i c o . It was d e t o n a t e d o n D e c e m -
ber 1 0 , 1 9 6 7 and produced a c h i m n e y w i t h a radius o f approximately 2 5 m
and a height of 1 0 2 m. Production data indicate that rock was fractured
laterally o u t t o a distance o f a b o u t 9 0 m from t h e explosive l o c a t i o n . Since
this was t h e first test in a gas reservoir, its primary purpose was t o determine
t h e effect of t h e c h i m n e y and fractured rock b e y o n d t h e c h i m n e y o n t h e
a m o u n t and quality of gas p r o d u c e d .
The Project Rulison ( R e y n o l d s , 1 9 7 2 ) explosive with a yield o f 4 3 kt was

* Scientific experiments, such as those used to produce very heavy isotopes, will not be
treated in this discussion.
228

d e t o n a t e d o n S e p t e m b e r 1 0 , 1 9 6 9 , at a d e p t h of 2 5 6 8 m in t h e Piceance
Basin of Colorado. A primary objective was t o e x t e n d t h e k n o w l e d g e of
stimulation effects t o t h e deeper reservoirs w h i c h are typical of t h e R o c k y
Mountain basins. Rulison was t h e m o s t d e e p l y buried nuclear e x p l o s i o n t o
have ever taken place in t h e U n i t e d States. Data from this event verified the
validity o f extrapolating predictive t e c h n i q u e s for estimating cavity and
c h i m n e y d i m e n s i o n s t o d e t o n a t i o n d e p t h s far b e y o n d existing experience. It
is estimated that a c h i m n e y was formed with a radius o f 2 3 m and a height
of 8 2 m . C o m p u t e r m o d e l i n g o f t h e c h i m n e y and reservoir t o m a t c h gas
p r o d u c t i o n test data required that increased permeability t o gas f l o w e x t e n d
t o a range of a b o u t 7 0 m . This is assumed t o be t h e range o f rock fracturing.
A basic q u e s t i o n relative t o nuclear fracturing is whether t h e fractures
produced b y t h e d e t o n a t i o n permanently increase t h e m e d i u m permeability
or whether t h e great lithostatic pressures in d e e p reservoirs s o o n e r or later
seal whatever fractures are f o r m e d . Modeling o f t h e chimney/reservoir sys-
t e m has n o t indicated a reduction in permeability or t h e sealing of fractures.
A recognized n e e d for using multiple explosives t o fracture t h e 6 0 0 — 1 2 0 0
m thick vertical gas-bearing intervals f o u n d in t h e R o c k y Mountain reservoirs
was first investigated w i t h Project R i o Blanco (Luetkehans e t al., 1 9 7 5 ) . Three
explosives with yields of 3 0 kt each were d e t o n a t e d simultaneously in a
single well at d e p t h s o f 1 7 8 0 m , 1 8 9 9 m , and 2 0 3 9 m . The site was located
in R i o Blanco C o u n t y , Colorado, and t h e d e t o n a t i o n date was May 1 7 , 1 9 7 3 .
D i m e n s i o n s of t h e c h i m n e y s and t h e e x t e n t o f fracturing were as e x p e c t e d
for three individual explosives o f t h e yield e m p l o y e d , b u t there is n o evi-
d e n c e of enhanced fracturing from t h e d y n a m i c interaction b e t w e e n t h e
explosion-generated s h o c k waves. The reservoir m o d e l i n g t e c h n i q u e , iden-
tical t o that used for t h e Rulison evaluation, gave results c o n s i s t e n t w i t h a
z o n e o f e n h a n c e d permeability t o a range of 3 cavity radii laterally from t h e
explosive location o n t h e basis of gas p r o d u c t i o n test data. This ratio is
similar t o that d e t e r m i n e d for b o t h Gasbuggy and Rulison. However, there
is n o vertical f l o w o f gas b e t w e e n t h e three c h i m n e y s as was predicted. The
reason for this behavior is y e t t o be established, b u t is n o t critical t o t h e
technical and e c o n o m i c feasibility of gas stimulation w i t h nuclear explosives.
D e v e l o p m e n t s were incorporated in t h e R i o Blanco test t o prepare for a
commercial t e c h n o l o g y . The e x p e r i m e n t used a nuclear explosive s y s t e m
w h i c h , for t h e first t i m e , was designed specifically for industrial applications.
The outside diameter o f t h e explosive canister was slightly less than 2 0 c m ,
and incorporated design features t o allow its use in a hostile temperature and
pressure environment. A l s o , t h e monitoring and firing o f the explosives was
accomplished from a r e m o t e l o c a t i o n using a microwave relay s y s t e m rather
than electrical cable. A single coaxial cable from t h e wellhead t o d e p t h was
used t o m o n i t o r t h e status of c o m p o n e n t s in each of t h e three explosive
canisters and t o d e t o n a t e t h e explosives. The l o w p r o d u c t i o n o f tritium was
a major advance over previously used nuclear explosives. In contrast t o
229

Gasbuggy and Rulison, w h i c h produced a b o u t 4 0 , 0 0 0 Ci and 1 0 , 0 0 0 Ci


respectively, less than 1 0 0 0 Ci were produced b y each of t h e three Rio
Blanco explosives.

DESCRIPTION OF POTENTIAL APPLICATIONS RELATED TO E N E R G Y


RESOURCES *

Storage

The construction and use of nuclear cavities for storage o f natural gas or
liquid hydrocarbons is t h e simplest and m o s t straightforward application of
nuclear e x p l o s i o n s . Unlike resource extraction applications in w h i c h the
location of t h e resource dictates where explosives m u s t be d e t o n a t e d , storage
locations are more flexible, b u t will tend t o be as close t o market areas as
seismic damage considerations will allow. The primary and least expensive
storage for natural gas is in d e p l e t e d oil and gas fields, b u t b y t h e mid-
1 9 6 0 ' s , m o s t of this storage was in use. In comparison t o o t h e r conventional
storage possibilities such as above-ground tanks, nuclear cavities appear t o be
very attractive. In fact, t h e o n l y other c o n v e n t i o n a l storage w h i c h appears t o
compare favorably w i t h nuclear cavities from an e c o n o m i c s t a n d p o i n t is
storage in w a s h e d - o u t salt cavities. The o b v i o u s disadvantage t o t h e preferred
conventional storage t e c h n i q u e s of d e p l e t e d reservoirs and w a s h e d - o u t salt
cavities is that there is n o t m u c h flexibility in l o c a t i o n . In 1 9 6 7 , a feasibility
s t u d y , Project K e t c h ( U . S . A t o m i c Energy C o m m i s s i o n , 1 9 6 7 ) c o n d u c t e d b y
Columbia Gas S y s t e m s , Inc., t h e Lawrence Livermore Laboratory, and t h e
A E C gave favorable results, and e x e c u t i o n o f a field e x p e r i m e n t was planned.
Project sponsors were n o t prepared for t h e public o p p o s i t i o n w h i c h was
generated w h e n p e o p l e w i t h technical credentials raised o b j e c t i o n s relative t o
public safety. After extensive public hearings, t h e initial objectors stated
publicly t h a t t h e y believed t h e e x p e r i m e n t c o u l d b e c o n d u c t e d safely. H o w -
ever, by this time it was t o o late — public o p p o s i t i o n c o n t i n u e d and t h e
project was a b a n d o n e d at t h e request of Columbia Gas Corporation.
For several years f o l l o w i n g t h e a b a n d o n m e n t of Project K e t c h , very little
industrial interest was s h o w n in storage. In 1 9 7 0 , t h e El Paso Natural Gas
C o m p a n y c o n d u c t e d a feasibility s t u d y of nuclear gas storage for a site in
Arizona in w h i c h t h e e c o n o m i c s were again s h o w n t o b e favorable
( R a n d o l p h , 1 9 7 1 ) . The project was n o t pursued because of the i m m i n e n t
perceived shortage of natural gas.

* While it has been proposed to use PNE for the deep underground disposal of high-level
nuclear wastes from the operation of commercial nuclear reactors (Cohen et al., 1 9 7 1 ;
Cohen et al., 1 9 7 4 ) , this application is not directly related to energy resource develop-
ment, and will not be discussed in this presentation.
Only applications which have been studied by the U.S. are discussed in this section.
230

TABLE 7-IV
Comparison of different refinery feed-stock storage methods (Van der Harst and Knutson,
1969)

Method Cost * (U.S. $/bbl)

Concrete sea-bottom oil storage 11.00-14.00


Mined caverns 5.00-11.00
Leached salt cavities 1 . 0 0 - 2.50
Steel tanks and offshore platforms 2 . 0 0 - 5.00
Steel tanks, onshore 2 . 0 0 - 4.00
Nuclear cavities 0 . 7 7 - 1.70

* 1 9 7 0 dollars.

Currently, t h e critical status of energy availability and t h e threat of future


OPEC embargoes m a y argue for t h e large-scale storage of crude oil for
national security reasons. Refineries maintain o n l y a f e w w e e k s supply of
feed-stocks or finished products o n hand. If t h e U.S. were t o maintain a
three-month stored reserve of refinery feed-stock, storage v o l u m e for about
1.5 billion barrels w o u l d b e required, based o n current c o n s u m p t i o n .
D e v e l o p m e n t of large off-shore storage facilities t o a c c o m m o d a t e "super-
tankers" m a y also b e c o m e a requirement in t h e n e x t d e c a d e . Nuclear storage
m a y be t h e m o s t e c o n o m i c solution as s h o w n in Table 7-IV above, devel-
o p e d b y the CER Geonuclear Corporation (Van der Harst and K n u t s o n ,
1 9 6 9 ) . It is n o t believed that inflationary factors will alter these relative
costs w h i c h are expressed in 1 9 7 0 dollars. There are several unique advan-
tages t o nuclear storage. One is that t h e cavities w o u l d be d e e p l y buried and
virtually i m m u n e t o e n e m y attack. For liquified natural gas ( L N G ) , storage
in a nuclear cavity offshore appears t o be desirable from a safety standpoint.
LNG is dangerous t o handle and an e x p l o s i o n aboard a ship in port or in
onshore storage facilities could be disastrous in a highly p o p u l a t e d area.
There are n o major technical questions w h i c h have t o be resolved prior t o
undertaking a full-scale test of nuclear storage o f liquid hydrocarbons. The
degree t o w h i c h stored products b e c o m e c o n t a m i n a t e d with specific radio-
nuclides can be investigated in such a test, b u t c o n t a m i n a t i o n is likely t o be
very small. * The integrity of t h e c h i m n e y through a n u m b e r of loading-
unloading c y c l e s , t h e nature of w e t t i n g of t h e c h i m n e y rubble b y water and
fuel, t h e transport of fine particles, and t h e growth of bacteria are other
areas w h i c h need t o be investigated.

* This is borne out by Soviet statements (Kedrovskiy et al., 1 9 7 5 ) .


231

Oil shale

The fact that a petroluem-like p r o d u c t c o u l d be obtained b y heating a


certain t y p e o f rock has b e e n k n o w n for hundreds of years. Significant
deposits of this rock, n o w called oil shale, exist in t h e U . S . and s o m e 2 3
foreign countries. Within t h e U . S . , t h e Green River F o r m a t i o n in Colorado,
U t a h , and W y o m i n g is estimated t o c o n t a i n 1.8 trillion barrels o f shale oil.
For comparison, t h e discovered U . S . oil in place is 4 3 3 billion barrels of
w h i c h 1 5 5 billion barrels has already b e e n p r o d u c e d . Considering t h e oil
which is y e t t o b e discovered, t h e total a m o u n t o f future recoverable oil is
estimated t o b e 2 5 0 billion barrels. In o t h e r w o r d s , one-third o f U . S . oil has
been produced and a b o u t two-thirds is left. With these reserves and an
aggressive drilling program, d o m e s t i c p r o d u c t i o n c o u l d reach a b o u t 1 7 mil-
lion barrels per d a y in t h e 1 9 9 0 ' s b u t w o u l d t h e n decline precipitously. The
difference b e t w e e n supply and d e m a n d w o u l d m a k e t h e d e v e l o p m e n t of
these oil shales a critical issue if t h e U . S . is t o maintain a high degree of
i n d e p e n d e n c e from foreign oil. Conservation, d e v e l o p m e n t o f nuclear p o w e r
reactors, solar energy, and geothermal energy, as well as increased use o f coal
will help s o m e w h a t , b u t t h e transportation sector c o n s u m e s the majority o f
oil. It is unlikely that there will be a drastic reduction in t h e use o f auto-
m o b i l e s , since m o s t vehicle miles are dedicated toward earning a living or
family business. Only a b o u t 3 3 % of vehicle miles are used for social and
recreational purposes. It appears t h e o n l y real alternative t o massive exploita-
t i o n o f t h e oil shale is t h e d e v e l o p m e n t of vehicles w h i c h either are grossly
more e c o n o m i c a l or use alternate fuels such as m e t h a n o l (produced from
coal) or h y d r o g e n .
Oil shale is a fine-grained n o n - p o r o u s sedimentary rock w h i c h is more
similar t o l i m e s t o n e than shale. T h e organic material in t h e oil shale ( w h i c h
is called kerogen) yields p e t r o l e u m h y d r o c a r b o n s u p o n destructive distilla-
tion at temperatures o f approximately 5 0 0 ° C . Oil shale is graded according
t o t h e a m o u n t of shale oil w h i c h it contains. Commercial surface retorting
processes generally utilize oil shales in t h e 3 0 — 3 5 gal/t category. The basic
m e t h o d s of producing shale oil include: ( 1 ) surface or underground mining
f o l l o w e d b y retorting in above-ground facilities, ( 2 ) breaking t h e oil shale in
place (in situ) and retorting in this below-ground configuration. In general,
mining and surface retorting will be more expensive than in-situ processes
and will have t h e additional significant environmental p r o b l e m of disposing
of large v o l u m e s of spent shale. In o n e in-situ process called RISE ("rubble
in-situ e x t r a c t i o n " , R o t h m a n , 1 9 7 5 ) , a large underground c o l u m n o f rubble
is produced conventionally b y mining and block caving t e c h n i q u e s , and
retorted in place using c o m b u s t i o n in an air stream. A b o u t 2 0 % o f t h e rock
will have t o b e m i n e d and brought t o t h e surface t o provide t h e necessary
v o l u m e for t h e rubble w h e n it bulks. This m i n e d material c o u l d b e retorted
in surface facilities if desired. With a nuclear c h i m n e y , t h e void v o l u m e is
232

TABLE 7-V
Comparison of estimated costs for various oil shale recovery methods (Rothman, 1 9 7 5 )

Method Cost Capital investment


(U.S.$/bbl) for 1 0 0 , 0 0 0 bbl/day *
(U.S.$ 1 , 0 0 0 , 0 0 0 )

Mining and surface retorting 12 1000-1500


Rubblization by mining and in-situ 8 600
retorting (RISE)
Nuclear fracturing and in situ retorting 5 300

* Cost (in 1 9 7 5 dollars) includes upgrading to refinery feed-stock standards. Current costs
are probably significantly higher, but relative costs would be unchanged.

formed b y compressing t h e surrounding rock and slightly displacing t h e


ground surface. The resulting c h i m n e y o f rubble w h i c h forms could t h e n be
retorted in situ w i t h o u t t h e n e e d for any underground mining. Estimated
costs ( R o t h m a n , 1 9 7 5 ) for various oil shale recovery m e t h o d s are s h o w n in
Table 7-V.
In comparing the environmental c o n s e q u e n c e s of recovering oil from oil
shale for a 1 million barrels per day industry, a 20-mile X 30-mile region in
the northern part of t h e Piceance Basin of Colorado was evaluated. This is
o n e of t h e thickest and richest sections of t h e Green River Formation and
contains 7 2 0 billion barrels in oil shale thickness greater than 1 2 0 m of
which 6 0 0 billion barrels is in oil shale greater than 2 5 0 m in thickness. This
area of 6 0 0 square miles is a small fraction of t h e 4 3 , 0 0 0 k m underlain b y
2

t h e Green River F o r m a t i o n . Table 7-VI compares t h e resource in this area


amenable t o t h e various m e t h o d s o f recovery, as well as s o m e k e y environ-
mental factors.
A major difficulty facing any recovery m e t h o d used in this area involves
groundwater. The large v o l u m e s of highly saline groundwater in the region of
t h e shale deposits obviously c a n n o t be disposed of b y p u m p i n g into streams.
Possible solutions include reinjecting this saline water back underground, or
possibly even building a pipeline t o t h e Great Salt Lake. The in-situ m e t h o d s
are n o t y e t d e v e l o p e d for commercial use, b u t studies and small-scale tests
are proceeding o n variants o f this process. A l t h o u g h there are m a n y technical
and e c o n o m i c issues which m u s t be resolved for the in-situ processes in
general, d e v e l o p m e n t of a commercial process w o u l d resolve m a n y issues
directly applicable t o t h e nuclear m e t h o d . There w o u l d still remain s o m e
significant technical uncertainties in t h e nuclear m e t h o d w h i c h can be
evaluated only b y a full scale field test. These uncertainties include t h e size
and shape of the c h i m n e y , t h e distribution o f rubble size, t h e m i n i m u m
spacing allowable b e t w e e n c h i m n e y s t o maintain the integrity of each
233

TABLE 7-VI
Comparison of the major methods that have been considered for recovering oil from oil
shale for production of 1 million barrels per day

Recovery method and Oil shale resource Environmental impact


shale preparation
grade oil ( 1 0 9
bbl) annual population water
(gal/t) disposal influx use
in recover- required (10 ) 3
( 1 0 acre-ft)
3

place able ( 1 0 t)
9

Surface
Underground mining, 30 100 54 0.5 130 176
room and pillar

Open-pit mining 20 700 660 1.2 140 173

In situ
Mining rubblization 20 700 350 0.23 100 96
(RISE process)
Nuclear fracturing 20 650 200 none 55 65

c h i m n e y during t h e retorting phase, and t h e pressure of residual gases in t h e


c h i m n e y ( s ) w h i c h were p r o d u c e d b y thermal d e c o m p o s i t i o n o f carbonate-
containing rocks. Preliminary studies of ground m o t i o n and t h e fate of t h e
radionuclides associated w i t h a nuclear c h i m n e y indicate that o c c u p a t i o n a l
and public safety can be maintained b y conservative engineering design of
t h e project. However, n o e x p e r i m e n t s have b e e n c o n d u c t e d t o date and n o n e
are c o n t e m p l a t e d in t h e near future because of prevailing attitudes regarding
nuclear t e c h n o l o g y . T h e primary deterrents t o mining and surface retorting
are t h e high cost o f t h e operation, t h e large capital investment, and the
environmental c o n s e q u e n c e s of disposing o f very large v o l u m e s o f s p e n t oil
shale. A l t h o u g h t h e c o s t per barrel is comparable t o foreign oil, t h e industry
could be seriously affected b y a d r o p in foreign oil prices if it were n o t
protected b y g o v e r n m e n t price guarantees.

Gas stimulation

Measured reserves of natural gas in t h e U . S . a m o u n t t o a b o u t 2 6 6 trillion


cubic feet (TCF) with an additional 3 8 0 T C F indicated and inferred from
geologic evidence. The current c o n s u m p t i o n is a b o u t 2 3 T C F per year. The
above reserves are t h o s e w h i c h are e c o n o m i c a l l y recoverable at current prices.
A n o t h e r source of natural gas w h i c h is indicated and inferred from geologic
evidence, but for w h i c h recovery is s u b e c o n o m i c at current prices, is that
within tight gas sands located in Colorado, Utah and W y o m i n g . The esti-
234

Fig. 7-4. Nuclear gas-reservoir stimulation. The reservoir is modeled after the Green River
Basin in Wyoming.

m a t e d a m o u n t o f gas in place is 6 0 0 T C F of w h i c h 3 0 0 TCF m a y be pro-


d u c e d w i t h advanced t e c h n o l o g y . These resources as identified b y t h e FPC
Natural Gas T e c h n o l o g y Task Force (Federal P o w e r C o m m i s s i o n , 1 9 7 3 )
were considered t o be amenable t o stimulation b y either nuclear explosive or
hydraulic fracturing t e c h n i q u e s . In general, these reservoirs are very d e e p
( b e t w e e n 1 5 0 0 and 5 0 0 0 m ) , c o n t a i n alternating layers or lenses of sand-
stones and shale in thick s e q u e n c e s ( 6 0 0 — 1 2 0 0 m ) , t h e gas-bearing sand-
s t o n e s have very l o w permeabilities (less than 1 5 microdarcies compared t o
several millidarcies in e c o n o m i c a l l y - p r o d u c e d reservoirs), t h e pay sands are
n o t interbedded w i t h high-permeability aquifers, and t h e reservoirs are in
r e m o t e areas.
The c o n c e p t for nuclear stimulation is s h o w n in Fig. 7-4. Multiple e x p l o -
sives, each 1 0 0 kt in y i e l d , w o u l d be placed in a single wellbore and spaced
so that all of the gas-bearing sandstones are fractured w i t h i n a reservoir as
thick as 9 0 0 — 1 2 0 0 m . The explosives w o u l d be d e t o n a t e d sequentially from
the b o t t o m - u p w i t h a sufficient t i m e delay t o insure that t h e m a x i m u m
ground m o t i o n generated is that e x p e c t e d from a single 1 0 0 - k t explosive.
The large nuclear c h i m n e y or wellbore a c c o u n t s for 6 0 % o f t h e stimulation
effect and fracturing of t h e reservoir rock outside t h e c h i m n e y a c c o u n t s for
235

40%. If the spacing of t h e sequentially d e t o n a t e d explosives results in g o o d


vertical permeability, reentry t o t h e t o p of t h e t o p c h i m n e y w o u l d be suffi-
cient t o produce t h e natural gas from all of t h e c h i m n e y s . Otherwise, a
separate p r o d u c t i o n well must be constructed alongside t h e c h i m n e y s in t h e
fractured region. T o d e v e l o p a reservoir adequately, nuclear wells w o u l d be
spaced at 320-acre intervals or t w o per square mile.
The alternate m e t h o d for e x p l o i t i n g t h e submarginal natural gas reservoirs
is termed "massive hydraulic fracturing" ( M H F ) . Hydraulic fracturing has
b e e n used b y industry for over 2 0 years t o o v e r c o m e wellbore damage
caused b y drilling fluids plugging t h e pores o f t h e rock and preventing gas
f l o w into t h e wellbore. Fractures a f e w meters long are adequate t o c o m p l e t e
a commercial well in a producing reservoir. The creation of vertical fractures
which e x t e n d a b o u t 1 5 0 m radially from t h e wellbore and span t h e 9 0 0 —
1 2 0 0 m thick reservoirs were d e e m e d t o be feasible b y t h e FPC Natural Gas
T e c h n o l o g y Task Force. In fact, fractures greater than 1 5 0 0 m in length have
been produced b y A m o c o in t h e Wattenberg field o f Colorado. In this case a
single gas-bearing sand a b o u t 1 2 m thick was successfully stimulated in this
reservoir. The major technical uncertainty in this m e t h o d is t h e m i n i m u m
spacing b e t w e e n individual fractures t o span t h e desired vertical interval of
6 0 0 — 1 2 0 0 m. If successive fractures are t o o close, t h e s e c o n d m a y break
i n t o t h e first and result in n o n e w stimulation; if t o o far apart, m a n y sand-
s t o n e lenses w o u l d be by-passed and a sizeable fraction of t h e resource m a y
be left in place. A n o t h e r uncertainty w h i c h requires additional field testing
is t h e selection of a suitable fracturing fluid. S u c h a fluid m u s t have adequate
viscosity t o carry t h e proppant o u t t o t h e extremities of the fracture; must
n o t chemically or physically damage t h e gas-bearing sands; m u s t have t h e
l o w e s t practical viscosity so as t o minimize t h e energy wasted in forcing t h e
crack t o o p e n wider than necessary; and can be produced o u t o f t h e fracture
(i.e., removed so as n o t t o interfere w i t h gas f l o w through t h e crack).
Wells p r o d u c e d b y massive hydraulic fracturing will probably n o t be
spaced closer than 80-acre intervals t o p r o d u c e t h e o p t i m u m percentage of
recoverable gas per s e c t i o n .
A comparison of wellhead gas costs for either t h e nuclear stimulation
m e t h o d or massive hydraulic fracturing is s h o w n in Table 7-VII for t h e
Piceance, Uinta, and Green River Basins. The costs are for 1 9 8 0 using 1 9 7 2
dollars escalated at 3.5% per year. The inflationary factors are n o w k n o w n t o
be inadequate, but overall these costs are believed t o b e t h e best available.
The greatest uncertainty m a y n o t be t h e use of u n d e v e l o p e d t e c h n o l o g i e s ,
but rather m a y be in t h e quality of reservoirs w h i c h are assumed t o exist in
t h e three R o c k y Mountain basins. A major c o n c l u s i o n from Project R i o
Blanco is that these reservoirs are highly variable and that conventional tech-
niques of reservoir evaluation m a y n o t be adequate t o describe t h e quality of
reservoirs w i t h very l o w permeabilities. The reservoir capacity (permeability
times thickness of gas-bearing sands) established b y p r o d u c t i o n o f gas from
236

TABLE 7-VII
Comparison of wellhead gas costs (cents/MCF * at wellhead) (Federal Power Commission
1973)

Discounted cash flow rate of return * *

10% 15% 20%

N *** H*** N H N H

High production case


Uinta Basin 1980 19 20 25 23 31 26
1990 26 27 34 31 42 35
2000 36 37 46 42 56 47
Piceance Basin 1980 36 33 45 38 54 42
1990 49 45 61 51 73 57
2000 65 61 81 69 98 77
Green River Basin 1980 52 54 66 63 80 72
1990 71 73 90 85 108 97
2000 95 98 121 114 145 130

Low production case


Uinta Basin 1980 45 37 55 43 65 49
1990 60 50 74 58 87 66
2000 81 67 99 78 117 89
Piceance Basin 1980 79 62 93 72 107 82
1990 107 84 127 97 144 110
2000 144 113 170 131 194 148
Green River Basin 1980 52 54 66 63 80 72
1990 71 73 90 85 108 97
2000 95 98 121 114 145 130

* MCF = million cubic feet.


** Current-dollar basis, escalation included.
*** N = nuclear, H = hydraulic.
Principal e c o n o m i c factors incorporated into these projections are:
cost escalation factors: 4.0%/yr through 1 9 7 5 , 3.5%/yr 1 9 7 6 — 1 9 8 0 , 3.0%/yr after
1980,
ad valorem tax rate 5.5%, severance tax 1%,
federal income tax 48%, depletion allowance 22%, royalty rate 12.5%.
An approximate lOc/MCF field processing charge for treating gas from nuclear-stimulated
wells is n o t in these wellhead costs.

t h e nuclear well at R i o B l a n c o is 6 t o 1 0 t i m e s l o w e r than w a s e s t i m a t e d pre-


s h o t in t h e vicinity o f t h e t o p e x p l o s i v e . In t h e v i c i n i t y o f t h e b o t t o m Rio
B l a n c o e x p l o s i v e , t h e reservoir c a p a c i t y is j u d g e d t o b e a b o u t \ o f t h e pre-
s h o t e s t i m a t e . H o w e v e r , t h e lateral e x t e n t o f t h e gas bearing s a n d s t o n e lenses
appears t o b e very l i m i t e d . T h e reservoir c a p a c i t y and t h e size o f t h e gas-
237

bearing lenses are k e y factors in t h e v o l u m e of gas w h i c h m a y be produced


from a well over a reasonable period of t i m e . The use o f a nuclear c h i m n e y
as a t e c h n i q u e for determining reservoir characteristics m a y be its m o s t
important use in t h e foreseeable future.
MHF well c o m p l e t i o n tests b y t h e El Paso Natural Gas C o m p a n y in t h e
Pinedale unit in t h e northern part of t h e Green River Basin in W y o m i n g have
produced similar disappointing results ( R a n d o l p h , 1 9 7 6 ) . When data from
these e x p e r i m e n t s are extrapolated t o t h e p r o t o t y p e M H F wells envisioned
in t h e Federal P o w e r C o m m i s s i o n s t u d y , t h e t o t a l 25-year gas p r o d u c t i o n is a
factor of 4 t o 5 b e l o w that calculated b y the natural gas survey for this
basin, d u e mainly t o t h e fact that t h e reservoir capacity is less than had b e e n
previously estimated.

U.S.S.R. PROGRAM ( N o r d y k e , 1975)

Over t h e past several years, through a series of international meetings


sponsored b y t h e International A t o m i c Energy A g e n c y ( I A E A ) , bilateral
meetings b e t w e e n U.S.S.R. and U . S . scientists, and in a n u m b e r o f publica-
tions ( U . S . A t o m i c Energy C o m m i s s i o n , 1 9 6 9 a ; Kedrovskiy, 1 9 7 0 a , b ) , t h e
Soviet U n i o n has disclosed an active program for developing uses for peace-
ful nuclear e x p l o s i o n s in their national e c o n o m y . T h e results of 1 5 experi-
mental and industrial e x p l o s i o n s have b e e n described (see Table 7-VIII
and 7-IX); these projects were designed t o d e v e l o p seven different appli-
cations in t h e p e t r o l e u m , gas and minerals industries, as well as for water
resources d e v e l o p m e n t .
That the Soviet P N E program is even m o r e active than that indicated in
Tables 7-VIII and 7-IX can b e c o n c l u d e d o n t h e basis of t h e large n u m b e r of
unidentified seismic events that have b e e n reported since 1 9 6 5 o u t s i d e of t h e
normal nuclear-weapon test areas (see Table 7-X).
A brief discussion o f past e x p e r i m e n t s and p r o p o s e d applications of PNE
reported b y t h e Soviets will be given in t h e f o l l o w i n g subsections.

Excavation experiments and applications (Table 7-VIII; Myasnikov e t al.,


1 9 7 0 ; Kirlev et al., 1 9 7 5 )

The Soviet PNE excavation program includes b o t h water resource develop-


m e n t and d e v e l o p m e n t of underground orebodies b y m e a n s of overburden
removal. H o w e v e r , experimental d e t o n a t i o n s have b e e n reported o n l y in t h e
first of these t w o areas of interest.
T w o p r o t o t y p e crater lip d a m s have b e e n c o n s t r u c t e d , w i t h t h e first
(designated " 1 0 0 3 " ) n o t located o n a watercourse and presumably designed
primarily t o collect data o n t h e configuration of a nuclear crater. The s e c o n d
of these e x p e r i m e n t s , h o w e v e r , was planned as a practical d e m o n s t r a t i o n of
238

TABLE 7-VIII
Soviet excavation PNE applications

Application Explosive yield Comments

Water resource development


1003 1.1-kt cratering shot in siltstone
1004 -125-kt crater in river produced two
lakes, 1.7 X 1 0 m ( 1 3 , 0 0 0 acre-
7 3

ft); "proven t e c h n o l o g y "


Proposed reservoir t w o 150-kt t o form 3 X 1 0 m
7 3
( 2 4 , 0 0 0 acre-
ft) reservoir
T-l 0.2-kt cratering shot in sandstone, cali-
bration for T-2
T-2 three 0.2-kt row-charge cratering shot "model
of Pechora-Kama"
Proposed Pechora-Kama Canal 2 5 0 explosives divert Pechora River into Kama
River and thence to Caspian Sea
Pechora-Kama row crater three 15-kt experiment at southern end of
Pechora-Kama Canal alignment
to gain data on cratering charac-
teristics and stability in saturat-
ed, alluvial medium
Overburden removal
Proposed mining project - 1-Mt row charge will remove 9 X 1 0 m of over-
8 3

burden at 5 kopecks per cubic


meter

t h e use of a nuclear crater as a d a m (see Fig. 7-5). A s e c o n d Soviet use o f


PNE for water resource d e v e l o p m e n t has b e e n in t h e area of canal construc-
t i o n . As in t h e case of t h e crater lip d a m application, c o n s t r u c t i o n of a work-
ing p r o t o t y p e was preceded b y experimental verification of t h e c o n c e p t . In
this case, t h e verification was provided b y t w o e x p e r i m e n t s , b o t h of which
used nuclear explosives w i t h individual yields o f 0 . 2 kt. The first o f these
involved t h e d e t o n a t i o n of a single charge, while t h e s e c o n d used three
charges t o create a short channel in a sandstone m e d i u m .
A working p r o t o t y p e canal c o n s t r u c t i o n project has b e e n recently reported
b y t h e Soviets, and is intended t o serve as a small portion o f t h e large ( 1 1 2
k m long) Pechora-Kama Canal. Fig. 7-6 s h o w s a picture o f a portion o f this
canal cut, and Fig. 7-7 indicates t h e l o c a t i o n of t h e p r o p o s e d canal.
While t h e Soviets have described a very large overburden removal project
for t h e mining of an extensive nonferrous metal d e p o s i t , there is n o indica-
t i o n t o date that any p r o t o t y p e d e t o n a t i o n s have b e e n carried o u t . The scale
239

INNER RESERVOIR
LIP H E I G H T - 2 0 - 3 5 m
UP DIAMETER-520m
AREA - 0.14 k m 2

VOLUME - 7 , 0 0 0 , 0 0 0 m 3

Fig. 7-5. Aerial view of " 1 0 0 4 " crater and reservoir.

Fig. 7-6. View of prototype Pechora-Kama Canal nuclear cut.


240

Fig. 7-7. Location of Soviet Pechora-Kama Canal.

of t h e project is e x t r e m e l y large, with a total overburden of 2 . 3 X 1 0 m 9 3

w h i c h m u s t be r e m o v e d ( 9 X 1 0 m are t o b e r e m o v e d using nuclear e x p l o -


8 3

sives).
241

TABLE 7-IX
Soviet contained PNE applications

Application Explosives Comments

Control of runaway wells


Urtabulak 30-kt $ 7 5 million worth of gas lost
over 3 years prior to nuclear
explosion
Nearby gas field 40-kt "proven technology"

Oil stimulation
Field A t w o 2.3-kt and U.S. e c o n o m i c analysis indi-
one 8-kt cates 26% internal rate of return
Field B t w o 8-kt "proven t e c h n o l o g y "
Proposed Field C three 20—30-kt designed to break barrier so un-
derlying water will push oil out

Gas stimulation
Un described statement that such an applica-
tion was carried out
Proposed gas condensate field three 40-kt expect gas production increase
of about 1 0 0 MCF */day

Underground storage of oil or gas


Salt dome A 1.1-kt salt dome — leaked water and
radioactivity
Salt dome B 25-kt 1 0 - b b l storage at one-sixth the
6

cost of surface gas storage and


one-third the cost of washed
cavities
Unidentified cavity — tested with oil and gas at 6 MPa
( 6 0 atm)
Gas condensate storage facility 15-kt 300,000-bbl storage facility in
industrial use at a gas conden-
sate deposit — working pressure
8 MPa ( 8 0 atm)
Proposed — layered salt t w o 35-kt 2 X 1 0 - b b l storage for gas con-
6

densate
Proposed — tuff under permafrost three 40-kt 2.5-BCF ** storage for gas at 7
MPa ( 7 0 atm)

Mineral development
"Granddaddy s h o t " — granite shot similar to Hardhat
Proposed ore breaking 1.8-kt will break 1 0 m 6 3
of ore in situ

* MCF = million cubic feet.


** BCF = billion cubic feet.
242

Contained experiments and applications (Table 7-IX; Kirlev e t al., 1 9 7 5 ;


Kedrovskiy e t aL, 1 9 7 5 )

Soviet contained P N E applications can be divided i n t o five categories,


each o f w h i c h will be briefly discussed b e l o w .

Well N o . 1-C
Cretaceous

<

Fig. 7-8. Section of Urtabulak runaway gas well control project.


243

Control of runaway gas wells


The Soviets have reported t h e successful control of t w o runaway gas wells;
in b o t h cases, a nuclear d e t o n a t i o n was used t o seal t h e wellbore d e e p under-
ground. For this t e c h n i q u e t o be successful, it is necessary t o d e t o n a t e t h e
nuclear explosive in a relatively plastic m e d i u m (such as salt or clay) w h i c h
will d e f o r m rather than crack or rupture, and will t h u s transfer t h e pressure
generated b y t h e nuclear e x p l o s i o n t o t h e wellbore requiring closure. In b o t h
instances where this t e c h n i q u e was u s e d , the nuclear explosive was placed
less than 4 0 m from t h e casing of t h e runaway well. The configuration used
in the first well control project ("Urtabulak") is s h o w n in Fig. 7-8. N o t e that
this application has never been considered under t h e U . S . Plowshare Program,
possibly because of t h e e x i s t e n c e o f a relatively sophisticated c o n v e n t i o n a l
runaway well c o n t r o l t e c h n o l o g y in this c o u n t r y .

Oil stimulation
A goal of t h e Soviet p e t r o l e u m industry is t h e recovery of at least 50% of
t h e in-place oil in producing fields. Generally, this goal has n o t b e e n achieved,
even w h e n secondary recovery t e c h n i q u e s , such as water f l o o d i n g , have b e e n
applied. In an a t t e m p t t o achieve their recovery goals, o n t w o o c c a s i o n s t h e
Soviets have turned t o nuclear d e t o n a t i o n s t o alter t h e characteristics of t h e
p e t r o l e u m reservoir.
In t h e first instance, t h e so-called "Field A " , a total of three nuclear
e x p l o s i o n s were carried o u t t o increase p r o d u c t i o n from a gas drive reservoir.
F o l l o w i n g t h e d e t o n a t i o n s , n o t o n l y did t h e f l o w o f oil increase b y almost
35%, b u t also t h e recovered oil contained significantly less dissolved gas than
had been observed prior t o t h e e x p l o s i o n s . A n e c o n o m i c analysis of t h e
"Field A " project (using S o v i e t data, b u t e m p l o y i n g U . S . oil pricing and
explosive service costs) indicates that t h e internal rate of return should be on
t h e order of 30% for such a project w h e n routinely c o n d u c t e d . It is of
interest t o n o t e that t h e Soviets have reported fracturing o f t h e reservoir
m e d i u m at distances as m u c h as 1 0 t o 2 0 t i m e s t h e cavity radii away from
t h e d e t o n a t i o n sites. This is significantly larger than t h e 3 t o 4 cavity radii
reported from U . S . e x p e r i m e n t s , and n o reason for this apparent discrepancy
has been suggested. The s e c o n d field t o be stimulated b y nuclear d e t o n a t i o n s
(designated "Field B") was a carbonate reef d e p o s i t w h i c h was being pro-
d u c e d b y water injection. T w o nuclear explosives, d e t o n a t e d a b o u t a w e e k
apart, apparently succeeded in enhancing t h e p r o d u c t i o n from this field b y
s o m e 30—60%. In b o t h oil stimulation products, t h e Soviets reported that
t h e a m o u n t of radioactivity present in t h e oil p r o d u c e d after t h e respective
d e t o n a t i o n s was "insignificant", and t h e recovered oil is in general use.
In addition, a third oil stimulation project has b e e n p r o p o s e d w h i c h will
use three 20—30-kt explosives t o fracture an acquitard, allowing t h e under-
lying water t o rise under an existing oil d e p o s i t and drive t h e oil from the
formation.
244

TABLE 7-X
Presumed nuclear events in the Soviet Union occurring away from normal test sites (through 1 9 7 3 only)

NEIS or SIPRI data * Event identified Location


— — — as presumed
Identifi- date origin Lat. Long. Magni- Depth explosion by:
cation time °N °E tude (km)
No. (GMT) Mb SIPRI USAEC

1 65-01-15 05:59:59 49.89 78.97 6.0 0 no yes Semipalatinsk area **


2 66-04-22 02:58:04 47.86 47.72 4.9 0 yes no north of Caspian
3 66-09-30 05:59:53 38.8 64.5 5.1 33 yes no Bukhara
4 67-10-06 07:00:03 57.69 65.27 4.7 N yes no east of Urals
5 68-05-21 03:59:12 38.916 65.159 5.4 13 yes no Bukhara
6 68-07-01 04:02:02 47.922 47.950 5.5 N yes yes north of Caspian
7 69-09-02 04:59:57 57.415 54.860 4.9 0 yes no Urals region
8 69-09-08 04:59:56 57.365 55.108 4.9 0 yes yes Urals region
9 69-09-26 06:59:56 45.890 42.472 5.6 0 yes yes west of Caspian
10 69-12-06 07:02:57 43.832 54.783 5.8 0 yes yes east of Caspian

11 70-06-25 04:59:52 52.201 55.692 4.9 0 yes no north of Caspian


12 70-12-12 07:00:57 43.851 54.774 6.1 0 yes yes Caspian region
13 70-12-23 07:00:57 43.827 54.846 6.1 0 yes yes Caspian region
14 71-03-23 06:59:56 61.287 56.466 5.6 0 yes yes northern Urals
15 71-07-10 16:59:59 64.168 55.183 5.3 0 yes yes western slope of Urals
16 71-09-19 11:00:07 57.777 41.098 4.5 N yes no Urals region
17 71-10-04 10:00:03 61.613 47.116 5.1 13 ± 2 9 yes no western Russia
18 71-10-22 05:00:00 51.575 54.536 5.3 6 ± 18 yes yes southern Urals
19 71-12-22 06:59:56 47.872 48.222 6.0 0 yes yes north of Caspian

20 72-07-09 — 49.9 35.2 5.0 —


yes no north of Black Sea
21 72-07-14 — 55.8 47.4 3.5 — yes no north of Caspian
22 72-08-20 02:59:58 49.462 48.179 5.7 0 yes yes north of Caspian
23 72-09-04 07:00:04 67.689 33.445 4.6 7 ± 30 yes no western Russia
24 72-09-21 09:00:01 52.127 51.994 5.1 28 ± 19 yes yes southern Urals
25 72-10-03 08:59:58 46.848 45.010 5.8 0 yes yes northwest of Caspian
26 72-11-24 09:00:08 52.779 51.067 4.7 N yes no western Russia
27 72-11-24 09:59:58 51.843 64.152 5.2 0 no yes southeastern Urals
28 73-08-15 01:59:58 42.711 67.410 5.3 0 *** yes northwest of Tashkent
29 73-08-28 02:59:58 50.550 68.395 5.3 0 *** yes northern Kazakh Desert
30 73-09-19 02:59:57 45.635 67.850 5.2 0 *** yes central Kazakh Desert
31 73-09-30 04:59:57 51.608 54.582 5.2 0 *** yes southern Urals
32 73-10-26 05:59:58 53.656 55.375 4.8 0 *** yes southern Urals

* NEIS = National Earthquake Information Service (formerly N O A A and USC&GS); SIPRI = S t o c k h o l m International Peace Re-
search Institute.
** This event was near the Semipalatinsk testing area but fell well outside the area of all previous Soviet events at the time it
occurred. Significant amounts of atmospheric radioactivity were reported in association with this event leading t o speculation that
it was a PNE nuclear cratering event.
* * * Date of event is after publication of SIPRI report.
245
246

Gas stimulation
On several occasions, Soviet P N E experts have stated that t h e y have car-
ried o u t a nuclear gas well stimulation e x p e r i m e n t , but n o details have been
m a d e available. In addition, t h e Soviet U n i o n has proposed t o use three
4 0 - k t explosives t o stimulate p r o d u c t i o n in a gas/gas condensate field.

Underground storage of petroleum products


The Soviets have expressed a great deal of interest in this P N E application,
and have e x p e n d e d a large fraction of their effort in t h e overall experimental
program t o bring this application t o fruition as a proven industrial usage of
P N E . Their e c o n o m i c analyses have indicated that gas c o n d e n s a t e can be
stored in nuclear cavities at o n e sixth t h e cost required for surface storage,
and at o n e third t h e cost of storage in washed cavities (constructed in
bedded salt or in salt d o m e s ) .
In preliminary e x p e r i m e n t s , t w o cavities in salt have b e e n constructed,
o n e using a 1.1-kt e x p l o s i v e , and t h e other using a 2 5 - k t explosive. The
experimental results are schematically s h o w n in Figs. 7-9 and 7-10, respec-
tively. In b o t h cases, t h e d e t o n a t i o n s were extensively instrumented and a
n u m b e r o f p o s t e v e n t exploratory drill h o l e s were used t o confirm cavity
sizes and t h e e x t e n t of fracturing.
In addition t o these t w o e x p e r i m e n t s , t w o p r o t o t y p e industrial gas c o n -
densate storage cavities have been constructed. The yield of t h e nuclear
explosive used t o p r o d u c e t h e first of these was n o t revealed; however, a
15-kt e x p l o s i o n was used in t h e s e c o n d project. In b o t h cases, t h e cavities are
reported t o be in routine industrial use, and t h e radioactive c o n t a m i n a t i o n of
t h e stored c o n d e n s a t e is " b e l o w t h e level of concern".
T h e Soviets have also p r o p o s e d t w o other storage projects, o n e for gas
c o n d e n s a t e and t h e s e c o n d for natural gas. The former w o u l d use t w o 35-kt
explosives d e t o n a t e d in layered salt, while the latter application calls for t h e
d e t o n a t i o n o f three 4 0 - k t explosives in a tuffaceous e n v i r o n m e n t overlain b y
permafrost. There is n o indication t o date that either o f these t w o projects
has been carried o u t .

Mineral development
In order t o determine t h e characteristics of a nuclear cavity-chimney sys-
t e m , t h e Soviets d e t o n a t e d a low-yield nuclear explosive a n u m b e r o f years
ago in granite. The resulting structure was extensively e x p l o r e d , with the
fracture z o n e being thoroughly investigated. The e x p e r i m e n t apparently
resembled in m a n y w a y s the U.S. Project Hardhat (a 5-kt explosive d e t o n a t e d
in granite).
The Soviets have also proposed an ore-breaking project which w o u l d
utilize a 1.8-kt nuclear explosive t o fracture a 60—80 m thick o r e b o d y which
dips into a mountainside at a 25° t o 35° angle. A vertical and horizontal
latticework grid of m i n e d drifts t o reflect t h e s h o c k wave and enhance ore
breakage has been planned for this p r o t o t y p e industrial project.
247

Depth, m A-B C-D


Or _,,,, T r SITE PLAN

17^77) Sandy loam w i t h pebble limestone


F ^ Rock s a l t u n a f f e c t e d by the e x p l o s i o n
\y M V i o l e t rock s a l t
K f r ^ Rubble m a t e r i a l
Fused m a t e r i a l
\ ^ I Radial f r a c t u r e s with glide planes
Ir^J Horizontal fracturing
kSK'ti Crushed zones
r U I Changes i n hole diameter
O O Anomalies noted i n c a l i D e r log

Fig. 7-9. Cross-section of 1.1-kt storage experiment in salt.


248

Projection in plane I - I
Hole G G - 2 Hole G G - 1 Hole PO-1 Hole G G - 1 1

_ 2 _ J I \™' °- l\
f 2

Fig. 7-10. Profile of 25-kt explosion in a salt dome.


249

OBSTACLES TO THE DEVELOPMENT OF A COMMERCIAL PLOWSHARE


PROGRAM IN THE U.S. (Crump, 1 9 7 5 ; Gahin, 1 9 7 3 )

A n u m b e r o f problems exist w i t h respect t o d e v e l o p m e n t of a viable c o m -


mercial industry in t h e U . S . w h i c h is based o n Plowshare t e c h n o l o g y . H o w -
ever, these can be generally placed i n t o three categories: e c o n o m i c , b o t h
from t h e s t a n d p o i n t o f funding o f experimental programs and of t h e evalua-
tion of a mature t e c h n o l o g y ; political, in t h e sense o f regulatory constraints
o n t h e rate of t e c h n o l o g y d e v e l o p m e n t ; and social, from t h e s t a n d p o i n t of
safety and environmental p r o b l e m s as perceived b y at least a s e g m e n t o f t h e
public. These areas will be briefly discussed in t h e f o l l o w i n g subsections;
however, it should b e emphasized that t h e presentation is n o t i n t e n d e d t o be
comprehensive.

Economic obstacles

Prior t o its dissolution early in 1 9 7 5 , it had b e e n t h e p o l i c y of t h e A t o m i c


Energy C o m m i s s i o n ( A E C ) t o require t h e participation o f an industrial part-
ner in Plowshare resource d e v e l o p m e n t experiments c o n d u c t e d away from
t h e Nevada Test Site. As an e x a m p l e of t h e t y p e o f arrangement w h i c h was
required b y t h e A E C , for t h e R i o Blanco project t h e A E C furnished t h e
nuclear explosives, together w i t h everything n e e d e d t o d e t o n a t e t h e m and t o
ensure their security prior t o firing. The A E C was also responsible for radio-
logical safety, while t h e industrial partner was responsible for everything
else, including drilling of e m p l a c e m e n t and exploratory wells, installation of
required utilities, e t c . S h o u l d t h e division of financial responsibility for t h e
construction of t h e p r o t o t y p e liquid metal fast breeder reactor ( L M F B R ) be
made in an analogous w a y , E R D A ' s contribution might include o n l y the
fabrication of t h e fuel e l e m e n t s and t h e fielding and operation of a radiologi-
cal monitoring n e t w o r k — w i t h t h e electric utilities being required t o pay all
other engineering and c o n s t r u c t i o n costs. Under these circumstances, it is
likely that t h e d e v e l o p m e n t of t h e L M F B R w o u l d p r o c e e d at even a slower
rate than w e are experiencing at t h e present t i m e . Thus, A E C fiscal p o l i c y
has n o t b e e n especially encouraging t o industry w i t h regard t o Plowshare
experimental projects.
A s e c o n d e c o n o m i c problem grows o u t of t h e first. With relatively meager
p r o t o t y p e experimental project experience o n w h i c h t o base extrapolation
t o a large scale industrial application, t h e projections of e c o n o m i c viability
b e c o m e s o m e w h a t shaky, despite encouraging results of paper studies.
Clearly, more extensive field e x p e r i e n c e is required in order that valid e c o -
n o m i c analyses of Plowshare resource recovery t e c h n o l o g i e s can be m a d e .
A final problem is o n e w h i c h also can be categorized as a political obsta-
cle: d u e t o t h e n e e d t o safeguard nuclear explosive design i n f o r m a t i o n , it is
n o t possible t o publish a firm estimate of explosive costs — either for single
250

explosives or for t h e large numbers w h i c h w o u l d b e n e e d e d for commercial


applications. Thus, a part o f t h e basic data n e e d e d for a realistic e c o n o m i c
evaluation of commercial Plowshare applications is n o t generally available.

Political obstacles

These include t h e lack of required federal legislation, t h e presence of regu-


latory roadblocks, and t h e lack of firm decisions o n t h e as y e t unresolved
q u e s t i o n s relating t o federal, state and local spheres of interest. While it is
n o t possible t o explore all these areas in d e p t h , e x a m p l e s of each can be
given t o indicate t h e nature of t h e existing obstacles. In t h e case of n e e d e d
federal legislation, under existing law, E R D A d o e s n o t have t h e authority t o
provide nuclear explosives and firing services for commercial ventures. Legis-
lation correcting this deficiency has b e e n introduced in several sessions of
Congress, b u t has never b e e n passed. Concurrent with this is t h e fact that, as
n o t e d above, t h e costs of t h e nuclear explosive and firing services will have
t o b e established b y statute (or t h e responsibility for this will have t o be
appropriately delegated t o E R D A ) .
F r o m t h e standpoint of potential regulatory roadblocks, o n e such problem
involves t h e fact that there n o w exists n o provision for t h e sale of industrial
products containing small a m o u n t s of residual radioactivity from a c o m m e r -
cial Plowshare application. In order for such products t o be legally salable
w i t h o u t each purchaser having t o obtain a license t o receive radioactive
material, t h e Nuclear Regulatory C o m m i s s i o n ( N R C ) w o u l d have t o c o n d u c t
rulemaking hearings as provided b y law, and publish t h e product standards
for radioactivity in t h e Federal Register. The c o m p l e t e procedure from appli-
cation t o published rule can take as m u c h as several years.
Finally, t h e role and s c o p e of individual states and local governments in
regulating t h e application of Plowshare t e c h n o l o g i e s must be resolved. As an
e x a m p l e of this area o f c o n c e r n , in N o v e m b e r 1 9 7 4 t h e voters o f Colorado
passed a constitutional a m e n d m e n t w h i c h requires a state-wide referendum
t o approve t h e d e t o n a t i o n of a nuclear explosive within t h e borders o f t h e
state. The constitutionality of this action is still o p e n t o q u e s t i o n , b u t w o u l d
have t o b e resolved before a commercial Plowshare project could take place
in Colorado.

Social obstacles

The problems in this sector can be exemplified b y t h e passage of t h e


a m e n d m e n t t o t h e Colorado c o n s t i t u t i o n , discussed above. The public per-
c e p t i o n of danger from peaceful nuclear explosives is almost visceral in
nature, since t h e vision of t h e m u s h r o o m cloud elicited b y a vocal o p p o s i t i o n
is a s y m b o l o f d e a t h and disaster.
However, Project R i o Blanco was c o n d u c t e d (May 1 7 , 1 9 7 3 ) w i t h t h e sup-
251

port of a majority o f t h e local p o p u l a c e as a result o f repeated public infor-


mational meetings and close c o n t a c t w i t h t h e project sponsors. Polls c o n -
d u c t e d b y t h e Grand J u n c t i o n Sentinel, b o t h pre- and p o s t - d e t o n a t i o n ,
s h o w e d that m o s t of t h e p e o p l e responding favored c o n t i n u i n g investigations
t o d e v e l o p t h e t e c h n o l o g y . The importance o f public dissemination of fac-
tual information can be seen in t h e passage in N o v e m b e r 1 9 7 4 of t h e Colo-
rado a m e n d m e n t t o require referendum approval of future nuclear e x p l o -
sions. Environmental groups in Denver framed t h e a m e n d m e n t and main-
tained a well organized drive t o gain public support. There w a s , h o w e v e r , n o
organized group t o provide factual information regarding t h e environmental
and safety issues being raised a b o u t Plowshare projects. G o v e r n m e n t e m -
p l o y e e s (of E R D A and o f t h e University of California, Lawrence Livermore
Laboratory) were prohibited b y law from engaging in "political" activities in
t h e State o f Colorado. Major oil c o m p a n i e s were reluctant t o b e c o m e
involved publicly because their public image at this t i m e was already tar-
nished. The o u t c o m e of t h e statewide v o t e was o b v i o u s long before t h e elec-
tion.
The experience from Project R i o Blanco s h o w s clearly that public accep-
tance o f Plowshare t e c h n o l o g i e s is possible if t h e public is well informed and
financially p r o t e c t e d from damage.
The lack of g o v e r n m e n t support ( b o t h legislative and e x e c u t i v e ) and
industrial reluctance t o b e c o m e involved in a controversial t e c h n o l o g y makes
it improbable t h a t advances will be m a d e in d e v e l o p m e n t of Peaceful Nuclear
E x p l o s i o n s in t h e near future. It w o u l d appear that o n l y an e x t r e m e shortfall
of mineral and energy resources can provide t h e necessary i m p e t u s for
increasing public acceptance of Plowshare t e c h n o l o g i e s .

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Appendix

F U N D A M E N T A L S O F ATOMIC A N D N U C L E A R PHYSICS

JEROME G. MORSE

A l t h o u g h elementary in nature for nuclear-oriented geologists and engi-


neers, this brief review is intended t o augment t h e background o f t h o s e
distant from this field and aid in t h e understanding of t h e preceding chap-
ters. E x t e n d e d treatments o f this subject are available elsewhere (Glasstone,
1 9 5 0 ; Evans, 1 9 6 5 ; Lapp and A n d r e w s , 1 9 7 2 ; Bowler, 1 9 7 3 ) .

ATOMIC STRUCTURE

A n a t o m is c o m p o s e d o f a positively charged nucleus surrounded b y nega-


tively charged particles, called electrons, w h i c h are sufficient in n u m b e r t o
balance t h e positive nuclear charge. In terms of t h e classical c o n c e p t , a par-
ticle is a relatively c o n c e n t r a t e d structure w h i c h has inertia, or resistance t o
any change in its v e l o c i t y . Mass is a measure of this inertia. A t o m i c diameters
are o f t h e order o f a f e w angstroms ( 1 A = 10"* c m ) . Virtually all o f an
8

atom's mass is f o u n d in its n u c l e u s , w h o s e diameters approximate 1 0 " A. 4

With its mass concentrated in so small a v o l u m e , nuclear d e n s i t y is an


e x t r e m e l y large n u m b e r . For e x a m p l e , if nuclei were closely p a c k e d side b y
side, t h e density of matter w o u l d b e a b o u t 1 0 g c m " ( 5 0 0 million t o n s per
1 2 3

cubic c e n t i m e t e r ) .

The nucleus

A t o m i c nuclei are c o m p o s e d o f t w o t y p e s o f primary particles, called pro-


t o n s and neutrons. T h e p r o t o n , w h i c h has a mass o f 1 . 0 0 7 2 8 a t o m i c mass
units ( a m u ) , carries a single unit positive charge w h i c h is equal in magnitude
t o t h e negative electronic charge of 4 . 8 0 2 5 X 1 0 " electrostatic units (esu).
1 0

The simplest nucleus is that o f t h e h y d r o g e n a t o m , w h i c h contains o n l y a


single p r o t o n . N e u t r o n s have n o electric charge; t h e mass of this particle is
1 . 0 0 8 6 7 a m u . There are also secondary nuclear particles o f lesser mass, such
as m e s o n s , e t c . , b u t t h e s e play little or n o role in t h e subjects treated in this
book.
All nuclei, other than t h o s e o f h y d r o g e n , contain a m i x t u r e of n e u t r o n s
and p r o t o n s , w i t h t h e p r o p o r t i o n o f n e u t r o n s generally increasing w i t h t h e
atomic weight of t h e e l e m e n t . The total n u m b e r o f n u c l e o n s ( p r o t o n s plus
256

neutrons) in an a t o m i c nucleus is t h e mass n u m b e r , o f t e n designated A. The


atomic n u m b e r of an e l e m e n t is equal t o t h e n u m b e r o f p r o t o n s , or n e t posi-
tive charges, contained in its nucleus, and this is called Z. If X is t h e normal
chemical s y m b o l of a given e l e m e n t , in nuclear parlance, t h e nucleus o f X is
described as For e x a m p l e , t h e largest naturally occurring e l e m e n t is
uranium, written as H\J. Z is equal t o 9 2 , indicating its n u m b e r of protons.
2

Since A equals 2 3 8 , t h e n 2 3 8 — 9 2 = 1 4 6 , w i t h t h e latter representing the


n u m b e r of neutrons in its nucleus.
R e c e n t b u t n o t y e t fully confirmed data suggest t h e e x i s t e n c e o f p l u t o -
n i u m which m a y have resulted from a naturally occurring nuclear reactor in
Africa.
A t o m i c numbers of e l e m e n t s range from 1 t o 1 0 6 , although lawrencium
( 1 0 3 ) is t h e last o n e n a m e d formally.
Using t h e above m e t h o d o l o g y , o n e can predict that t h e mass o f t h e helium
nucleus ( H e ) is t w i c e that of t h e p r o t o n plus t w i c e t h e mass of t h e n e u t r o n .
4

However, t h e measured mass o f t h e h e l i u m nucleus was f o u n d t o be 4 . 0 0 1 5


a m u , t h e a t o m i c mass less t h a t of t w o electrons, with each of t h e latter c o n -
tributing 0 . 0 0 0 5 5 a m u . Performing a simple calculation, o n e finds (Ameri-
can Institute of Physics, 1 9 7 2 ) :

mass of protons = 2 ( 1 . 0 0 7 2 8 ) = 2 . 0 1 4 5 6 amu


mass of neutrons = 2 ( 1 . 0 0 8 6 7 ) = 2 . 0 1 7 3 4 amu

4 . 0 3 1 9 0 amu
mass of He nucleus 4 . 0 0 1 5 1 amu
mass defect 0.03039

This discrepancy, or d e f e c t , e x c e e d s possible instrument errors in measure-


m e n t and is explained b y Einstein's law w h i c h defines t h e equivalence of
mass and energy. In t h e process of fusing t w o p r o t o n s and t w o neutrons t o
form this nucleus, radiant or heat energy has b e e n liberated w i t h t h e a m o u n t
equivalent t o t h e mass d e f e c t . Conversely, t h e energy input required t o
remove c o n s t i t u e n t particles from t h e nucleus is called t h e binding energy,
and it will be treated shortly.
T h e energy equivalent of t h e mass d e f e c t is calculated from Einstein's
equation:
E = mc 2
(1)
where c = t h e v e l o c i t y o f light ( 2 . 9 9 8 X 1 0 c m s *), m = mass d e f e c t in a m u ,
1 0

and 1 amu = 1 . 6 6 0 X 1 0 ~ g. The energy equivalent is: E = ( 0 . 3 0 3 9 a m u ) X


2 4

( 1 . 6 6 0 X 1 0 " g / a m u ) ( 2 . 9 9 8 X 1 0 c m s " ) = 4 . 5 3 4 X 1 0 " erg.


2 4 1 0 1 2 5

The electron volt ( e V ) and million electron volts ( M e V ) are useful energy
units in nuclear science w i t h t h e former defined as t h e a m o u n t of energy
acquired b y an electron w h e n accelerated through a potential difference of
1 volt.
257

> 1
BINDING ENERGY PER NUCLEON = E (MeV)

,„. 32 - - 238
Kr 92

If
w

1 36 196
Pt
b

78

j IK
p 1
L i

•iHe

>
20 40 60 80 100 120 140 160 180 200 220 240

MASS NUMBER (A)

Fig. A - l . Variation of binding energy per nucleon with mass number (Lapp and Andrews,
1972).

1 e V = 1 . 6 0 2 X 1 0 " erg, and therefore t h e energy d e f e c t for t h e helium


1 2

nucleus is 2 8 . 3 M e V .
Since there are four n u c l e o n s in t h e He nucleus, t h e binding energy per
n u c l e o n , w h i c h offers a comparative measure of nuclear stability is 2 8 . 3 / 4 or
7.1 MeV. Binding energies for other nuclei can b e calculated in a similar
manner. The average binding energy per n u c l e o n , as seen in Fig. A - l , varies
from 6 t o 8 MeV t h r o u g h o u t t h e periodic table, e x c e p t for a f e w o f t h e light-
est nuclei. The higher t h e energy per n u c l e o n , t h e m o r e stable t h e nucleus. In
t h e process o f nuclear fission, large a m o u n t s o f energy are liberated w h e n t h e
heavy nuclei are b r o k e n d o w n i n t o t h o s e o f m e d i u m mass. Even greater
a m o u n t s of energy are released in nuclear fusion w h e n light nuclei, such as
h y d r o g e n , are c o m b i n e d i n t o heavier particles as occurs in regions o f t h e sun,
as seen in t h e above e x a m p l e .

Electrons

This subject is treated m o r e extensively in the chapter o n X-ray tech-


niques (Chapter 3 ) and is covered here o n l y briefly. A n electron is a nega-
tively charged particle w h o s e mass is 1 / 1 8 2 0 of that of t h e p r o t o n , or
0 . 0 0 0 5 5 a m u . Since t h e a t o m is electrically neutral, t h e n u m b e r of electrons
m u s t equal t h e n u m b e r o f p r o t o n s . Electrostatic forces maintain electrons in
orbital configurations at varying distances from t h e n u c l e u s . Chemical prop-
erties of t h e e l e m e n t s are determined largely b y t h e n u m b e r o f electrons and
their arrangement.
258

ISOTOPES A N D RADIOACTIVITY

T h e a t o m i c n u m b e r (Z) o f an e l e m e n t defines t h e n u m b e r o f p r o t o n s in its


nucleus, t h e n u m b e r of orbital electrons and h e n c e its chemical identity.
When a t o m s of a given e l e m e n t (same Z ) have different mass numbers (^4),
t h e y are called i s o t o p e s o f this e l e m e n t . Varying A at c o n s t a n t Z, indicates a
change in t h e n u m b e r of neutrons in t h e nucleus. A l t h o u g h t h e chemical
behavior o f i s o t o p e s o f a given e l e m e n t is t h e same for e a c h , nuclear behavior
is often quite different. The e l e m e n t uranium occurs in nature in at least
three isotopic forms, having mass numbers of 2 3 4 , 2 3 5 , and 2 3 8 . Their abun-
dances are given in Table A-I.

Radioactivity

The majority o f e l e m e n t s in their naturally occurring forms are stable;


that is, their nuclei are unaffected in normal chemical processes. Nuclear
instability was first reported b y Becquerel in 1 8 9 6 after he discovered that
e m a n a t i o n s from uranium salts caused blackening o f photographic plates,
even w h e n t h e latter were p r o t e c t e d from visible and ultraviolet light. Later,
it was s h o w n that t h e nucleus was t h e source of these radiations. It was also
s h o w n that e l e m e n t s w h o s e Z is greater than 8 3 ( P o , Ra, T h , e t c . ) consist
almost entirely of unstable or radioactive i s o t o p e s .
Radioactivity is a s p o n t a n e o u s process in w h i c h t h e nucleus undergoes
d e c a y at a definite rate. This d e c a y is a c c o m p a n i e d generally b y t h e emission
of an electrically charged particle or electromagnetic radiation or b o t h .
Often t h e products of d e c a y are also radioactive and therefore, a series of
disintegrations m u s t take place before an a t o m i c species is formed having a
stable nucleus. The latter is called t h e ground state and is t h e end result of
energy emission.
In addition t o naturally occurring radioactive substances, radioactivity
m a y be induced artificially b y b o m b a r d m e n t of stable e l e m e n t s with charged
particles, neutrons, e t c . This area is covered in t h e chapter "Radioactivation
M e t h o d s " (Chapter 5) and is also treated here in section " C o m p o u n d n u c l e u s "
and onwards.

TABLE A-I

Isotopic composition of natural uranium

Isotope Abundance (%)


2 3 4
U 0.006
9 2 U
2 3 5
U 0.712
92 U

2 3 8

92
U
U 98.28
259

Half-life

The rate of radioactive d e c a y f o l l o w s a simple law. For a given radio-


nuclide, each nucleus has a definite probability of d e c a y i n g in a unit of t i m e .
This probability has a c o n s t a n t value w h i c h is characteristic of t h e particular
radioisotope. A t any p o i n t in t i m e , it m a y be said that a c o n s t a n t fraction of
t h e radioactive nuclei is disintegrating. This c o n s t a n t fraction of d e c a y is
peculiar t o each individual species and is i n d e p e n d e n t of t h e chemical or
physical state o f t h e e l e m e n t at all readily accessible temperatures and pres-
sures. Control or alteration of t h e d e c a y rate d o e s n o t s e e m t o be possible.
A t a given instant of t i m e , t h e rate of d e c a y is directly proportional t o t h e
n u m b e r of radioactive a t o m s o f t h e i s o t o p e present (AT), and is given b y :

—d/V/df = XN (2)

where t is t h e t i m e and X is t h e proportionality or d e c a y c o n s t a n t of t h e spe-


cies. Rearranging t h e e q u a t i o n :

dN/N = —Xt (3)

and integrating b e t w e e n N = N 0 at t = 0 , and N = N at t i m e t:

\og (N /N)
e 0 = Xt

or:
N =N 0 e~ xt
(4)

F r o m t h e above it is seen that radioactive d e c a y is an e x p o n e n t i a l process


with t h e actual rate d e t e r m i n e d b y t h e d e c a y c o n s t a n t (X) and t h e n u m b e r of
radionuclei present (see Fig. A - 2 ) . ( N o t e : although t h e dN/dt n o t a t i o n is
used here, it actually refers t o very large values of N. The A n o t a t i o n ,
AN/AT, describes t h e situation m o r e precisely.)

Illustrative example
A platinum sample, in w h i c h radioactivity w a s i n d u c e d , has a measured
activity of 1 0 disintegrations per s e c o n d (dps). Calculate t h e activity o f the
3

sample 1 d a y later.

Solution — A s s u m e sample measured is 1 9 7


Pt:

t\/2 18 h =

from e q u a t i o n ( 3 ) , X = 0 . 6 9 3 / 1 8 h = 0 . 0 3 8 5 h" 1

from e q u a t i o n ( 4 ) , N/N = e~ 0
xt

Xt = ( 0 . 0 3 8 5 h ) ( 2 4 h ) = 0 . 9 2 4
_ 1

( N o t e : units used for t m u s t be consistent)

e~ = 0.397
xt

N = 1 0 dps
0
3
260
i3ionNOiava ONiNivwab d O O N -ivisioi±ovad

CM
1
T
1
00
1
(O
1
CMf
IT

—I 1 1 1 1 1
1 2 3 4 5 6
NUMBER OF HALF LIVES

Fig. A-2. Half-life expressed as exponential function of radioactive decay.

Answer: N = 4 X 1 0 dps
2

( N o t e : if o n e half-life ( 1 8 h ) h a d elapsed, t h e activity w o u l d have been


5 X 1 0 dps.) 2

PROPERTIES OF R A Y S A N D PARTICLES EMITTED B Y RADIONUCLIDES

The radioactive d e c a y o f primary interest here is emission from t h e


nucleus o f alpha particles ( a ) , beta particles (j3), and/or gamma rays ( 7 ) . T h e
first o f these are helium nuclei, t h e second are electrons and t h e third c o n -
sists o f quanta o f electromagnetic radiations w h o s e energies are usually
greater than t h o s e o f X-rays. A description o f their properties f o l l o w s .
261

Alpha radiation (a)

Many of t h e heavy radioelements s p o n t a n e o u s l y e m i t these i o n s (jHe)


b e c o m i n g other elemental species. These processes are generally a c c o m p a n i e d
b y t h e release o f electromagnetic energy, and s o m e e x a m p l e s are:
2
l\\J -> ,*Th + *He
23

2 2
8 8 lta- 2 2 2
3 n + «He

N o t e that in t h e emission of an a particle, Z reduces b y 2 and A b y 4 in


t h e product nuclide. T h e alpha particle is ejected from t h e nucleus at high
velocities, o f t e n as great as 1 0 c m s" , or 9 0 % of t h e v e l o c i t y o f light.
9 1

A l t h o u g h t h e y are heavy and energetic, t h e y penetrate o n l y short distances


in matter removing electrons from this matter t o b e c o m e h e l i u m a t o m s . T w o
rules o f t h u m b are: ( 1 ) m o s t alphas are s t o p p e d b y a sheet o f paper; (2) their
range in air is a b o u t 1 c m for each MeV of energy. There is a rough inverse
relationship b e t w e e n t h e half-life of t h e radionuclide and its energy (and
therefore t h e range of alpha particles). The shorter t h e half-life, t h e further is
t h e alpha particle range.

Beta radiation ((3)

Electrons ejected b y radioactive nuclei are called b e t a particles and these


are e m i t t e d at velocities approaching that of light. Their origin within t h e
nucleus results from t h e transformation of a n e u t r o n t o a p r o t o n and an elec-
tron, and this emission increases Z of t h e p r o d u c t b y 1 w i t h n o change in A:

0 n - } H + _?e

E x a m p l e s are:
23
,STh -> ,?Pa + 23
>
2
8 2Pb+ 2
8 ^ B i + _?e

T o a c c o u n t for t h e conservation of energy in this process, Pauli postulated


that a neutrino a c c o m p a n i e s t h e emission of a beta particle, w i t h this n e w
particle containing almost negligible mass and n o electrical charge. The neu-
trino, as seen in Fig. A-3 carries a b o u t two-thirds of t h e total energy released
in beta d e c a y . The penetrating p o w e r of betas is generally m u c h greater than
that of the alpha particle, but t h e y are usually absorbed in a f e w millimeters
of metal, such as a l u m i n u m . Table A-II lists their ranges in air, w h i c h as
e x p e c t e d are energy-dependent.
Positive beta particles (|3 or e ) called positrons also exist and t h e y behave
+ +

in a manner similar t o negative betas. Within a short t i m e of its emission,


however, a positron will probably c o m b i n e with an electron of w h i c h a pre-
262

E average 1/3 E max


NO. OF BETA PARTICLES

Fig. A-3. Energy spectrum of beta particles.

ponderance exists largely in t h e orbit o f t h e nucleus. The attraction o f these


o p p o s i t e l y charged particles f o r each other leads t o electrical neutralization
and annihilation. T h e energy liberated is called annihilation radiation, and its
value is calculated using t h e Einstein relationship given earlier. With t h e total
mass o f t h e electron and t h e positron taken as 0 . 0 0 1 1 0 a m u , t h e energy
released is 1 . 0 2 M e V . T o conserve m o m e n t u m , t w o p h o t o n s o f electromag-
netic radiation are formed m o v i n g in o p p o s i t e directions, each w i t h energy
o f 0 . 5 1 M e V , and w i t h t h e properties o f g a m m a radiation.
When electrons o f energy greater than 1 M e V pass through matter, c o n -
t i n u o u s X-rays are p r o d u c e d . These are called bremsstrahlung (German for
"slowing d o w n " radiation) and t h e efficiency o f conversion o f electron
kinetic energy into these X-rays increases w i t h b o t h electron energy and t h e

TABLE A-II
Approximate ranges of beta particles in air

Energy (MeV) Ranges ( m )

0.1 0.11
0.5 1.5
1.0 3.7
2.0 8.5
3.0 13
263

5 9
Co(n, ) Y
6 0
Co 1 9 7
Au(n, ) Y
1 9 8
Au

6 0
Co(5.3y) 1 9 8
Au(2.7d)

stable 6 0
Ni

Fig. A-4. Decay schemes (simplified) of beta-gamma emitters.

a t o m i c n u m b e r of t h e matter traversed. The bremsstrahlung energy spectrum


derived from a m o n o e n e r g e t i c source is c o n t i n u o u s and it e x t e n d s from t h e
energy of t h e initial electron d o w n t o zero.

Gamma rays (y)

These radiations are t h e same physically as X-rays in that t h e y are quanta


(of discrete energy values) or p h o t o n s o f electromagnetic radiation; g a m m a
rays, h o w e v e r , arise from energy changes originating within t h e nucleus. For
e x a m p l e , nuclei resulting from alpha or beta emission are o f t e n left in an
e x c i t e d state, and t h e e x c e s s energy is t h e n liberated as g a m m a radiation, as
s h o w n in Fig. A - 4 . Further, X-ray energy is of t h e order of t h o u s a n d s of elec-
tron volts ( k e V ) but m o s t gammas are of t h e order o f millions o f electron
volts (MeV) in m a g n i t u d e .
G a m m a p h o t o n s have considerably greater penetrating p o w e r than d o t h e
particulates m e n t i o n e d earlier. A s e c o n d important difference is that these
p h o t o n s have n o true range. R e d u c t i o n in intensity o f a stream of g a m m a
p h o t o n s incident o n a slab of material such as lead, is described b y an e x p o -
nential relationship:

Wo = (5)
where I = t h e initial intensity of t h e gamma b e a m ; J = t h e intensity of t h e
0

b e a m traversing a m e d i u m o f thickness x ( c m ) ; and /z = t h e linear absorption


coefficient (a f u n c t i o n of t h e 7 energy and t h e m e d i u m ) .
The thickness o f matter n e e d e d t o halve t h e intensity is:
/// = -=e-^i/2
0 2 (6)

* i / 2 = log 2/ju = 0.693//Xe (7)


264

TABLE A-III
Linear absorption coefficients, jLt ( c m ) , and half-thicknesses, x
- 1
l/2 (cm), of c o m m o n
materials

Energy Water Aluminum Iron Lead


(MeV)
M *l/2 #1/2 A*
x
l/2 X 1/2

0.5 0.090 7.7 0.23 3.0 0.63 1.1 1.7 0.40


1.0 0.067 10.3 0.16 4.3 0.44 1.6 0.77 0.90
2.0 0.048 14.4 0.12 5.8 0.33 2.1 0.51 1.36
3.0 0.038 18.2 0.09 7.7 0.30 2.3 0.47 1.47

Illustrative example
A situation arises in a field exploration program wherein t h e measurement
o f a sample's activity m u s t b e m a d e in an area o f relatively high background
gamma radiation. Thin lead sheet is available t o shield b o t h t h e sample and
t h e d e t e c t o r so that t h e measurement can be made under c o n d i t i o n s o f
reduced interference. If t h e background g a m m a source is k n o w n t o have an
energy level o f 0.5 M e V , h o w thick a lead shield is n e e d e d t o reduce t h e
background flux b y a factor o f 10?

Solution — Using equation (5) in logarithmic f o r m , w e have:

log (/// ) =
e 0

when:

x =
X\/2 > I/Io 0.5
=

x = *i/io , I/h = 0.1


writing o n e equation for each value o f x, w e have:
l o g 0.5 =
e —px V2

l o g 0.1 =
e io
eliminating JJL b e t w e e n t h e equations, w e find:

*i/io = * i ( l o g 0 . 1 / l o g 0 . 5 )
/2 e e

Answer: F r o m Table A-III, x = 0.40 c m for E = 0.5 M e V and x


1/2 = 1.33 1/10

cm.
( N o t e : 0.4-cm-thick sheet o f lead will reduce t h e flux t o 50%; a s e c o n d
0.4-cm sheet reduces t h e flux t o 25%; a third 0.4-cm sheet reduces t h e flux
t o 12.5%; etc.)
Three o f t h e m o r e important w a y s in which gamma p h o t o n s interact with
an absorbing material are: t h e p h o t o e l e c t r i c effect, t h e C o m p t o n effect and
265

The photoelectric process. The y -ray


is completely absorbed. An electron is
ejected with the y -rays energy minus
the electron's binding energy.

The Compton recoil process. A y -ray of


lower energy proceeds in a new direction.
An electron is ejected with the energy
difference.

The pair production process. A y -ray


is annihilated. An electron and a
positron are created and share the y -ray's
energy minus 1.02 Mev.

Fig. A-5. Gamma photons interacting with matter.

pair p r o d u c t i o n . These will be described briefly b e l o w and are illustrated in


Fig. A - 5 .

Photoelectric effect. T h e p h o t o e l e c t r i c effect involves t h e interaction of a


gamma-ray p h o t o n w i t h an orbital electron. If t h e p h o t o n energy e x c e e d s
t h e electron binding energy and this energy is transferred t o t h e electron, t h e
latter will be ejected from t h e a t o m . The kinetic energy o f t h e ejected elec-
tron is a p p r o x i m a t e l y t h e difference b e t w e e n t h e initial p h o t o n energy and
t h e binding energy. T h e p h o t o e l e c t r o n p r o d u c e d behaves as a beta particle
and it m a y lead t o t h e ionization of other a t o m s . Photoelectric absorption of
266

gamma radiation is i m p o r t a n t at energies less than 1 M e V , and for absorbers


o f high Z.

Compton effect. The s e c o n d t y p e of interaction is the C o m p t o n effect,


which also involves a p h o t o n hitting an orbital electron of t h e absorbing
material, but here t h e collision is elastic, analogous t o t h e impact o f o n e
billiard ball on another. On colliding, b o t h m o m e n t u m and energy are c o n -
served. Part of t h e energy of t h e incident p h o t o n is transferred t o the elec-
tron, and t h e p h o t o n is scattered or deflected from its original path. The
magnitude of t h e effect is d e p e n d e n t o n t h e number of orbital electrons in
t h e absorber, therefore, it is directly proportional t o Z, and like t h e p h o t o -
electric effect, it is m o r e significant for materials of high a t o m i c number.
The important difference b e t w e e n t h e t w o is that in t h e photoelectric effect,
t h e p h o t o n is c o m p l e t e l y absorbed, whereas in t h e C o m p t o n process, t h e
p h o t o n is scattered and reduced in energy. After suffering several C o m p t o n
collisions, t h e p h o t o n ultimately m a y be absorbed through photoelectric
interaction. The C o m p t o n effect b e c o m e s d o m i n a n t at g a m m a energies of
0 . 6 - 4 MeV.

Pair production. Pair p r o d u c t i o n obtains w h e n a g a m m a p h o t o n with energy


greater than 1 . 0 2 MeV passes near t h e atomic nucleus. The p h o t o n may be
annihilated in this strong electrical field w i t h t h e subsequent formation of an
electron-positron pair. This process b e c o m e s d o m i n a n t at higher p h o t o n
energies, particularly at t h o s e in e x c e s s of 5 M e V , whereas t h e photoelectric
and C o m p t o n effects decrease w i t h increasing p h o t o n energies. Pair produc-
t i o n , like t h e p h o t o e l e c t r i c effect, results in t h e absorption o f t h e gamma
p h o t o n , b u t it also gives rise t o the formation of t w o 0.51-MeV p h o t o n s
from t h e annihilation reaction.

UNITS OF RADIOACTIVITY

The curie

The m o s t frequently used unit is t h e curie, w h i c h is defined as 3.7 X 1 0 1 0

disintegrating a t o m s per s e c o n d . Early work based this n u m b e r o n t h e d e c a y


rate o f 1 gram of radium, later s h o w n t o be in error, b u t t h e original n u m b e r
is accepted as t h e basic d i m e n s i o n o f t h e curie.
It is of interest t o c o m p u t e t h e actual d e c a y rate of ggRa from its half-
2

life:
t U 2 = 1 6 2 0 yr
X = 0 . 6 9 3 / ( 1 6 2 0 y r ) ( 3 6 5 d a y s / y r ) ( 2 4 h / d a y ) ( 6 0 m i n / h ) ( 6 0 s/min)
= 1.36X10- s' 1 1 1
267

A =226

n u m b e r of a t o m s Avogadro's n u m b e r 6.02 X 1 0 2 3

gram atomic weight A 226

disintegration rate = — d N / d t = Xt
= 1.36 X 1 0 " X 6.02 X 1 0 / 2 2 6
1 1 2 3

= 3 . 6 1 X 1 0 dps 1 0

Specific activity is o f t e n expressed as t h e ratio o f t h e n u m b e r o f radio-


active a t o m s t o t h e total n u m b e r of a t o m s of t h e e l e m e n t in t h e sample
(curies per gram o f material), and it is also a useful t e r m .
Mention is m a d e of t h e r o e n t g e n , defined as t h e quantity of X- or g a m m a
radiation producing in 0 . 0 0 1 2 9 3 g of air ( 1 c m at standard temperatures 3

and pressures, STP), i o n s carrying 1 esu of charge of either sign. Recall that
t h e charge o n an electron is 4 . 8 X 1 0 " esu. The roentgen relates primarily
1 0

t o t h e effect produced b y radiation.

Decay series

When the products of radioactive d e c a y are also radioactive, a series or


family o f radioelements m a y exist simultaneously. If t h e parent nuclide in a
chain has a relatively l o n g half-life compared w i t h that of its daughter, t h e
a m o u n t of daughter (or daughters) present will be c o n s t a n t after a period of
t i m e . This p h e n o m e n o n is called a steady state, as t h e p r o d u c t e l e m e n t s will
decay as fast as t h e y are f o r m e d .
A B -> C ... -+ X , is an e x a m p l e of a d e c a y chain in w h i c h a steady
state, or secular equilibrium m a y be established.
Since —dN/dt = XN for all radioactive d e c a y , and since t h e rate o f d e c a y
of A is equal t o the rate of formation o f B, etc., in t h e above e x a m p l e , or
~~dN /dt
A = diV /d£, o n e can write: X N
B A = XN
A = XN = XN,
B B e t c . It C C B U

must be n o t e d that t h e e q u a t i o n that diN /dt = XN


B — XN describes t h e
A A B B

n e t rate of change o f B w i t h t i m e . The first term o f t h e right represents t h e


rate of formation of B and t h e s e c o n d term, t h e rate of d e c a y of B. A similar
relationship applies t o C through X .
In natural radioactive series, such as t h o s e of uranium, t h o r i u m , e t c . , t h e
very long parent half-life permits t h e assumption that N is virtually c o n - A

stant. A c o n d i t i o n eventually obtains w h e n X N = XN, A so that the n e t


A B B

rate of change of B is zero. Then A d e c a y s t o form B at t h e same rate B


decays t o form C, and that t h e quantity of B in t h e s y s t e m is c o n s t a n t . This
is called a state of secular equilibrium. If t h e a m o u n t of parent nuclide
remains essentially u n c h a n g e d , all m e m b e r s of such a series e x c e p t t h e last,
will be in equilibrium w i t h each other w i t h t h e lapse of sufficient t i m e .
268

THE N E U T R O N

The existence of t h e neutron was first verified experimentally b y Chad-


wick w h e n h e b o m b a r d e d beryllium with high-energy alpha rays, giving t h e
reaction:

^Be + H e +
4 1 2
C + Jn

This m a y be written:

»Be(a,n)»C
H y d r o g e n a t o m s in a paraffin target, o n being struck b y neutrons, were c o n -
verted t o p r o t o n s , dislodged and d e t e c t e d .
N e u t r o n s are particularly effective in engaging in reactions w i t h nuclei b y
virtue of their lack o f electrical charge, w h i c h enables passage through t h e
electrostatic fields of t h e a t o m . T h e y can m o v e through matter for long dis-
tances w i t h o u t being s t o p p e d . Electrical or magnetic fields externally applied
have n o effect o n their m o t i o n . This m o t i o n or energy is described in terms
of electron volts.
Consider t h e case of high-energy neutrons ( > 1 M e V ) passing through a
v o l u m e of heavy water ( D 0 ) . T h e y lose energy d u e t o multiple collisions
2

w i t h the deuterium nuclei t o t h e e x t e n t that their energies will b e c o m e that


o f t h e m e d i u m , and t h e y will be in thermal equilibrium w i t h t h e heavy
water. Called thermal neutrons, their kinetic energy can be calculated. In a
m e d i u m such as heavy water, their v e l o c i t y at r o o m temperatures is a b o u t
2 2 0 0 m s" . Taking t h e neutron mass as 1.6 X 1 0 ~ g, its kinetic energy is:
1 2 4

E = mv /2 2
= (1.66 X 10" )(2.2 X 10 )/2
2 4 5

4.0 X 1 0 " 1 4
erg = 0 . 0 2 5 e V
Reactions can take place w i t h thermal ( 0 . 0 2 5 e V ) or higher-energy neu-
trons in several w a y s , of w h i c h t h e four m o s t c o m m o n are: neutron absorp-
t i o n or capture, transmutation, scattering, and fission. All of these are
treated in greater d e p t h in Chapter 5.
Since neutrons are p r o d u c e d o n l y b y nuclear reactions, sources of neu-
trons arise from t h e following:
(1) Using selected target nuclei, interactions w i t h alpha or gamma radia-
t i o n from radionuclides, or charged particles or g a m m a radiation from accel-
erating devices.
( 2 ) Nuclear fission or fusion under controlled or uncontrolled c o n d i t i o n s .

COMPOUND NUCLEUS

The c o n c e p t of t h e c o m p o u n d nucleus was advanced b y Bohr in 1 9 3 6 t o


explain nuclear reactions in t h e M e V region, a detailed discussion o f this is
269

b e y o n d t h e s c o p e of this s e c t i o n . Here w e shall consider briefly reactions


which result w h e n nuclei are bombarded w i t h radiation, such as p h o t o n s ,
neutrons and i o n s , and these reactions take place in a series of steps.
First, t h e incident particle, having finite kinetic energy, penetrates the
potential barrier, strikes a nucleus and transfers s o m e or all of its energy t o
it. S e c o n d , t h e kinetic and binding energies o f t h e particle are added t o t h e
structure of t h e nucleus, resulting in a redistribution o f its internal energy
and it achieves an e x c i t e d state. This is t h e c o m p o u n d nucleus. Third, this
e x c i t e d nucleus n o w e m i t s either electromagnetic or particulate radiation, or
b o t h , or it m a y fission yielding these radiations along w i t h fission fragments.
The lifetime of a c o m p o u n d nucleus is approximately 1 0 " t o 1 0 " s e c o n d , 1 2 1 4

w h i c h is considerably longer than that required for a particle t o m o v e o n e


nuclear diameter, estimated as 1 0 " s e c o n d .
2 1

CROSS-SECTION

When incident particles of sufficient energy collide w i t h a nucleus, t h e


probability that a nuclear reaction will o c c u r is a f u n c t i o n of: t h e flux or
number of particles per s e c o n d ; t y p e and energies; and t h e n u m b e r o f target
nuclei within t h e sample. This probability term is called t h e reaction cross-
section and it is seen as t h e ability of a substance t o r e m o v e particles from a
beam of radiation. Cross-section data are readily available in t h e literature
and are tabulated b y reaction t y p e , such as absorption, capture, scattering or
fission, nature of t h e particle and its energy. The unit of cross-section, called
a barn, is equivalent t o 1 0 ~ c m . It derives from t h e expression "hitting t h e
2 4 2

side of a barn", w i t h 1 barn t h e average geometric nuclear cross-section.


For neutron-induced nuclear reactions of a given energy level, t h e a m o u n t
of radioactive species f o r m e d m a y b e calculated f r o m :

R = ocl)n(l-e~ )
xt
(8)

where R = activity o f t h e p r o d u c t (dps); o = cross-section ( c m ) ; 0 = flux of 2

bombarding particles (number c m " s" ); n = number of target nuclei per


2 1

sample; X = d e c a y c o n s t a n t of t h e p r o d u c t radionuclide; and t = exposure


time.

Illustrative examples
(1) A n ore contains an estimated c o p p e r value of 1%. If a 10-g sample is
e x p o s e d t o a thermal n e u t r o n flux of 1 0 n c m " s" ( 1 0 0 m g C f source)
1 1 2 1 2 5 2

for 3 0 m i n u t e s , w h a t is t h e resulting activation induced in t h e copper?


Solution — Consider t h e reaction C u ( n , 7 ) C u . The n u m b e r (n) of C u
6 3 6 4 6 3

nuclei are: natural abundance of C u = 0 . 6 9 1 ; a t o m i c w e i g h t = 6 3 . 5 ; n u m -


6 3

ber of a t o m s per gram a t o m i c w e i g h t = 6 . 0 2 X 1 0 . Using e q u a t i o n ( 8 ) :


2 3
270

n = 10 g (0.01)(0.691)6.02 X 10 /63.5 2 3

= 6.55 X 1 0 atoms 2 0

a = 4 . 5 barns = 4 . 5 X 1 0 ~ c m thermal n e u t r o n cross-section 2 4 2

0 = lO ncm n
s" _ 2 1

T= 1 2 . 9 h (half-life o f C u ) 6 4

t =0.5h
X = l o g 2 / T = 0 . 6 9 3 / 1 2 . 8 = 0 . 0 5 4 h"
e
1

Xt = 0 . 0 2 7
( l - e ' ) = 0.03
- A

R = a<l>n(l-e~ ) xt

= 4.5 X 1 0 X 1 0 X 6.55 X 1 0 X 0.03


- 2 4 1 1 2 0

Answer: R = 8.8X 1 0 dps


6

( 2 ) Conversely, a 10-g crushed rock sample, taken from an o r e b o d y w i t h


k n o w n manganese h o r i z o n s , is e x p o s e d t o a thermal n e u t r o n flux o f 1 0 n 1 0

c m " s for a 1 0 - m i n u t e period. For purposes o f illustration, o n l y t h e man-


2 - 1

ganese is activated. Nuclear measurements attribute a d e c a y rate t o M n of s 6

6 . 4 X 1 0 dps. Calculate t h e percentage o f manganese b y w e i g h t in t h e sam-


7

ple.

Solution — Consider t h e reaction S 5


Mn(n,7) Mn: S 6

R = 6 . 4 X 1 0 dps 6

M n = 1 0 0 % naturally abundant
5 5

a = 1 3 . 3 barns = 1 3 . 3 X 1 0 cm - 2 4 2

<t> = 1 0 n c n T s" 1 0 2 1

T = 2 . 6 h (half-life o f M n ) 5 6

t = 1 0 min = 0.167 h
Xt = 0 . 0 4 5
( l - e ~ ) = 0.044
X f

Using e q u a t i o n ( 8 ) , and / = fraction of Mn b y weight in t h e sample:

_ sample w e i g h t X (f) X 6 . 0 2 X 1 0 2 3

a t o m i c w e i g h t o f Mn
= .R/o<A(l-e ') - x

= 6.4 X 1 0 / ( 1 3 . 3 X 1 0 - ) ( 1 0 ) ( 0 . 0 4 4 )
6 2 4 1 0

= 1.09X10 2 1

/ = (1.09 X 10 )(55)/(10)(6.02 X 1 0 ) = 0.00996


2 1 2 3

Answer: f=l% 5 5
Mn

ARTIFICIAL RADIOACTIVITY

Transmutation, t h e dream o f a l c h e m y t o convert base metals i n t o gold, or


o n e e l e m e n t i n t o another, was e f f e c t e d b y Rutherford in 1 9 1 9 w h e n he
271

bombarded nitrogen w i t h alpha particles and p r o d u c e d an i s o t o p e of o x y g e n .


In the shorthand n o t a t i o n indicated earlier, t h e reaction was N ( a , p ) 0 . 1 4 1 7

Rutherford's discovery is basic t o s o m e of t h e t e c h n i q u e s described in this


b o o k , in that t h e process o f transmutation, n o w n o longer a dream, a stable
e l e m e n t can be converted i n t o a radioactive species, with t h e latter detect-
able d o w n t o very l o w concentrations. A f e w e x a m p l e s involving transmuta-
t i o n are:

^B(a,n) 1 3
N ( N : |3 emitter, t
1 3
l/2 = 10 min)
2 7
Al(a,n) °P 3
( P : positron emitter; t
3 0
l/2 = 2.5 m i n )
1
^Pd(n,p) ^Rh 1
( 1 0 6
R h : 0 emitter, t 1/2 = 3 0 s)

Alternatively, t h e p r o d u c t nuclei m a y result as radioactive w i t h o u t trans-


m u t a t i o n , such as:
2 3
Na(n,7) Na 2 4
( N a : 0 emitter; t
2 4
l/2 = 1 5 h)

^Co(n,7)^Co ( C o : j3,7 emitter; t


6 0
1/2 = 5.3 yr)

A f e w e x a m p l e s of activation reactions are included b e l o w t o s h o w their


general utility in field w o r k .
(1) Use of thermal n e u t r o n s :

^Aufn^^Au ( 1 9 8
A u : 0 , 7 emitter; t l/2 = 6 4 . 8 h)
2 3
Na(n,7) Na 2 4
( N a : |3 emitter; t
2 4
V 2 = 1 5 h)

(2) Fast n e u t r o n s :
2 7
Al(n, p) Mg 2 7
( M g : |3 emitter; t
27
V 2 = 1 0 min)

^B(n,a) Li 8
( L i : ]3,7 emitter; t
8
V 2 = 0 . 8 3 s)

(3) Photoactivation:

n g(7,P)nNa
M
( N a : ]3,7 emitter; t
2 5
1/2 = 1 min)

STATISTICAL CONSIDERATIONS IN MEASUREMENT OF RADIOACTIVITY

Brief m e n t i o n is m a d e regarding t h e importance o f c o u n t i n g statistics in


radioactivity measurements in order t o reduce errors in data interpretation.
Radioactive nuclei d e c a y in a r a n d o m manner and therefore this d e c a y is
governed b y t h e laws of probability w h i c h are used t o determine error limits
in measured data. For field use in particular, t h e s e laws will enable t h e
worker t o o p t i m i z e t h e c o u n t i n g t i m e so that errors will be m i n i m i z e d .
272

N u m e r o u s t e x t s o n radioactivity m e a s u r e m e n t s and c o u n t i n g statistics are


available for detail o n this subject (Chase and R a b i n o w i t z , 1 9 6 7 ) .

REFERENCES

American Institute of Physics, 1 9 7 2 . American Institute of Physics Handbook. McGraw-


Hill, N e w York, N.Y., 3rd ed.
Bowler, M.G., 1 9 7 3 . Nuclear Physics. Pergamon Press, Oxford.
Chase, G.D. and Rabinowitz, J.L., 1 9 6 7 . Principles of Radioisotope Methodology. Bur-
gess Publishing Co., Minneapolis, Minn., Chapters 3 , 4 and 5.
Evans, R . D . , 1 9 6 5 . The Atomic Nucleus. McGraw-Hill, N e w York, N.Y.
Glasstone, S., 1 9 5 0 . Sourcebook on Atomic Energy. Van Nostrand, N e w York, N.Y.
Lapp, R.E. and Andrews, H.L., 1 9 7 2 . Nuclear Radiation Physics. Prentice-Hall, Engle-
w o o d Cliffs, N.J.
SUBJECT INDEX

Absorption, 4 6 Canal, 2 1 5 , 2 3 8 , 2 3 9 , 2 4 0
linear coefficient of, 4 6 Panama, 2 1 5
mass coefficient of, 4 6 Pechora-Kama, 2 3 8 , 2 3 9 , 2 4 0
Accelerator, neutron generators, 1 4 8 CER Geonuclear Corporation, 2 3 0
Accuracy (diffraction), 6 5 , 6 6 Cesium-137, 5, 9
Activation process (n, 7 ) , 121 Characteristic spectrum, 4 2
Airborne radiometric surveys, 19—22 Chemical mining, copper, 2 1 5 , 2 1 6
All-component method (diffraction), 6 4 Chemistry, Mars surface, 1 0 9 , 1 1 0
Alpha autoradiography, 2 2 Collimation of gamma detectors, 1 4 , 1 5 ,
Alpha-neutron sources (see also Neutron, 16
sources), 1 3 9 Columbia Gas Systems, Inc., 2 2 9
Alpha-particle counting, 29 Compound nucleus, 2 6 8
Alpha probe for 2 2 2
R n , 29 Compton continuum, 19
Alpha-track detectors for 2 2 2
R n (see also Computer program for calculation of U,
Lexan detectors), 31 Th and K, 11
Alpha tracks from U and Th, 2 2 Continuous spectrum, 40—42
American Oil Company ( A m o c o ) , 2 3 5 Conway granite, 15
Applications of X-ray analysis (see also X- Copper, chemical mining, 2 1 5
ray), 79—89 Corrections (X-rays), 52—57
Aquifers, transport of radioactivity in, absorption, 52—57
2 2 5 , 2 2 6 , 227 fluorescence, 5 4 , 5 5
Artificial gamma-ray sources, 1 3 8 Cosmic ray contribution to the gamma-
Artificial radioactivity, 2 7 0 ray spectrum, 21
Atlantic-Pacific Interoceanic Canal Study Count-rate meter, 17
Commission, 2 0 5 Counting statistics, 271
Atmospheric radon-222, 22 Crater lip dams, 2 3 7 , 2 3 8 , 2 3 9
Atomic Energy Commission, 2 2 9 , 2 4 9 , Cratering, nuclear, 2 1 5 , 2 1 6 , 2 3 7 , 2 3 8 ,
250,251 239,240
Atomic structure, 2 5 5 applications, general, 2 1 5 , 2 1 6
Autoradiographic techniques, 5, 2 2 in Soviet Union, 2 3 7 , 2 3 8 , 2 3 9 , 2 4 0
Cross-section, 2 6 9
Background gamma radiation, 9 Crystal planes, 6 0
Beryllium, 1 1 9 , 1 3 8 - 1 4 5 , 1 6 2
Binding energy, 257 Data correction method (X-rays), 5 3 , 5 4 ,
Bismuth-214, 7, 9, 1 0 , 2 0 , 2 9 , 31 5 6 , 57
Borchok logging, 9, 17 all-component (diffraction), 6 4
Borehole analysis, 1 5 1 , 1 6 6 evaluation of (spectrometry), 57
Bragg equation, 4 9 , 6 0 , 6 1 fundamental (spectrometry), 5 4
derivation of, 6 0 , 61 internal standard (diffraction), 6 4 , 6 5
Buildings, response t o seismic shock, 2 1 9 , linear (spectrometry), 5 3
220, 221 Data interpretation, X-ray spectrometer,
104-109
Calibration constants, 10 Dams, crater lip, 2 3 7 , 2 3 8 , 2 3 9
Canadian Shield, 15 Decay series, 2 6 7
274

Delayed gamma-ray measurement, 1 6 3 , Energy materials


164,174 coal, 8 1
Delayed neutron counting, 1 2 2 , 1 8 4 , 1 9 1 petroleum, 8 1 , 8 3 , 201—213
Density gamma-gamma technique, 115— uranium, 5—34, 83—87
118 Energy Research and Development Ad-
Deposit evaluation, 151 ministration, see A t o m i c Energy
linear correlation method, 1 5 2 Commission
mean-square-successive-difference, 1 5 2 Energy resources, application of PNE to
Design, space instruments, 95—98 (see also Explosions, nuclear, Peace-
Design criteria, space instruments, 97 ful nuclear explosions), 229—237
(Table 4-II) Environments, Mars mission, 96 (Table
Detectors (see also Gamma-ray spectro- 4-1)
scopy) 1 1 6 , 1 2 3 , 1 6 4 - 1 6 6 , 1 7 1 , Equilibrium, secular, 8, 17, 2 6 7
1 7 3 - 1 7 6 , 180 Errors
neutron detector, 1 2 0 in calculated radioelement concentra-
Detection sensitivity, 1 4 3 tions, 11
Detector systems, 12 relative, Th by fission-track method,
Diffraction 27, 28
absorption and intensity of, 6 3 , 6 4 Evaluation of ore deposits, 3 3 , 1 5 0 , 1 5 1 ,
accuracy of, 6 5 153,155
process, 59—61 Excitation energies, 4 4
purpose, 37 Exhalation rate o f 2 2 2
R n , 2 8 , 29
sample preparation, 6 5 Exploration methods, 37—39, 79—91,
sensitivity, 6 5 1 1 9 , 1 5 6 , 1 6 4 , 170
spectrum, 6 2 Explosions, nuclear, 215—253
theory of, 59 cannister size, 2 2 8
Diffractometer, description of, 70—72 cavity and chimney, formation of, 2 1 6 ,
Diffusion theory, 124—131 217, 218, 219
one-group diffusion, 1 2 4 cavity, flooding of, 2 2 5
two-group diffusion, 127 contained applications of, 215—253
Downhole application, 1 1 5 , 1 2 0 , 1 5 6 , cratering, applications of, 2 1 5 , 2 1 6 ,
1 6 8 , 1 7 0 , 1 7 9 , 181 237, 238, 239, 240
D o w n h o l e measurement systems, 1 1 5 , design, 2 4 9 , 2 5 0
156, 168, 170, 179, 181 firing system, 2 2 8
Downhole spectrometer, 77, 78 growth and collapse, history of, 2 1 6 ,
217, 2 1 8 , 2 1 9
Effective sample, 1 4 , 15, 16 permeability increase produced by,
Efficiency for gamma-peak detection, 12, 2 1 9 , 2 2 8 , 234, 235
13 phenomenology, 216—227
El Paso Natural Gas Company, 2 2 9 , 237 radioactivity, produced by, 2 2 2 , 2 2 3 ,
Electric logs, 19 2 2 4 , 2 2 5 , 2 2 6 , 227
Electron, 2 5 7 seismic effects from, 2 1 9 , 2 2 0 , 2 2 1
acceleration, 4 1 size, 2 1 8
excitation, 4 2 Extrusive rocks, 5
Electronic energy, 41—44
Electronic panel, 6 9 Fallout, radioactive, 5, 8
Electronic transitions, 4 3 Fast activation logging, 1 6 5
Elemental sensitivity, X-ray spectrometer, Fast neutron accelerator, 1 6 6
107-109 Fast neutron-induced reactions, 1 6 5
Emanation coefficient, R n , 28
2 2 2
Federal Power Commission, Natural Gas
Emission energies, 4 3 , 4 4 Technical Task Force, 2 3 4 , 2 3 5 ,
Energy levels, atomic, 4 3 236,237
275

Field gamma-ray surveys, 14 scintillation detectors, 7


Fission cross-section solid-state detectors, 7
of U , 23
2 3 5
subsurface, 17, 18, 19
of Uand
2 3 8 2 3 2
T h , 27 surface, 1 4 , 15, 1 6 , 17
Fission products, 5, 8, 9 Gamma-ray spectroscopy, passive, 9 8
Fission-track m e t h o d , 22—28 spectrum, 7
Fluorescence analysis — of U, Th and K, 8
geometry, 4 9 — of standards, 9
Mars surface, 93—110 Gamma transport
purpose, 37 one-region, 1 3 1
qualitative, 48—51 two-region, 1 3 3
quantitative, 52—57 Gas stimulation, 2 2 7 , 2 2 8 , 2 4 1 , 2 4 6
spectra, 5 0 , 104—107 Soviet, 2 4 1 , 2 4 6
Fluorescence, secondary, 4 6 U.S. (see also Natural gas), 2 2 7 , 2 2 8
Fluorescent yields, 4 4 — Gasbuggy, 2 2 7 , 2 2 8
Fracturing, hydraulic, of gas formations, — Rio Blanco, 2 2 7 , 2 2 8 , 2 3 5 , 2 3 6
235, 236, 237 — Rulison, 2 2 0 , 2 2 1 , 2 2 2 , 2 2 8
Fundamental parameters method (spec- Gasbuggy, 2 2 7 , 2 2 8
trometry), 54—56 Geiger tube, 17
Fundamentals, atomic and nuclear phys- Generator, X-ray, 67
ics, 255—272 Geochemical analysis, Mars, 9 3
Gnome, 2 2 7
Gain stabilization of gamma-ray spectrom- Grade of mineralization, 17
eter system, 19 "Granddaddy", 2 4 6
Gamma-gamma techniques, 115—118 Granite, nuclear explosions in, 2 4 1 , 2 4 6
Gamma group, 1 1 5 Soviet, 2 4 1 , 2 4 6
gamma-gamma scattering m e t h o d , 1 1 5 Green River Basin, 2 3 4 , 2 3 5
natural gamma-ray measurement, 5— Green River Formation (see also Oil
34,115 shale), 2 3 1 , 2 3 2
photonuclear methods, 1 1 9 Ground shock, from nuclear explosions,
resonance gamma m e t h o d , 1 1 8 219, 220, 221
Gamma-neutron sources, 1 4 4 Groundwater, 2 2 5 , 2 2 6 , 2 2 7 , 2 3 2 , 2 3 3
Gamma production rate, 1 3 1 in Piceance Basin, 2 3 2
Gamma radioactivity of natural radio- and oil shale processing, 2 3 3
elements, 6, 7 radioactivity in, 2 2 5 , 2 2 6 , 227
Gamma-ray intensity, 1 3 3 , see also 5—34
Gamma-ray logs, 17, 201—203 Half-life, 2 5 9
Gamma-ray measurement, 1 1 5 , 155—161 function of radioactive decay, 2 6 0
natural gamma rays (see also Gamma Handcar, 227
group), 1 1 5 Hardhat, 2 4 6
prompt gamma rays, 1 6 3 , 1 6 4 Heavy matrix method (spectrometry), 5 6 ,
Gamma-ray resonance, scattering applica- 57
tion, 1 6 1 Helicopter-mounted systems, 2 0 , 21
Gamma-ray sources, 1 4 9 , 201—203 History, geochemical measurements, 98—
Gamma-ray spectrometers (see also 100
Gamma-ray measurement) Hydraulic fracturing, gas formations, 2 3 5 ,
portable, 9, 10 236,237
pulse-height analyzers, 7, 9, 1 2 Hydro thermally altered zones, 15
Gamma-ray spectrometry (see also Gam-
ma-ray spectrometers), 7 Induced logs, petroleum, 2 0 3
airborne, 19—22 carbon-oxygen logging, 2 1 0
detector systems, 7, 1 2 , 1 3 , 14 compensated formation density, 2 0 4
276

density t o porosity, 2 0 5 Linear correction method (spectrometry),


neutron logs, steady state, 2 0 6 , 207 5 3 , 54
pulsed neutron logs, 2 0 8 , 2 0 9 Linear correlation, 1 5 2
short spacing detector counting, 2 0 5 Lithium-drifted germanium detectors (see
Inelastic neutron scattering, 1 2 2 , 1 3 5 , also Detectors), 1 2 , 1 3 , 14, 1 7 6
163 Lithium-drifted silicon detectors, 12
prompt gamma-ray measurement, 1 6 3 Logging, 1 1 7 , 1 7 0 - 1 7 2 , 2 0 1 - 2 1 3
Inelastic scattering (n, n ' 7 ) , 1 2 2 density, 1 1 7 , 1 1 8 , 1 5 6 , 1 5 8
Igneous rocks, 5, 6 fast activation, 165
Intensities photo neutron, 1 6 2
diffraction, 6 3 , 6 4 selective gamma, 155—161
spectrometry, 5 2 , 53 spectrometric gamma-gamma, 1 5 6
Internal standard m e t h o d (diffraction), well, 1 5 3 - 1 5 7 , 2 0 1 - 2 1 3
64, 65
International A t o m i c Energy Agency, 3 , Manganese-54, 19
237 Mars surface chemistry, 109—110
Instrumentation Mass absorption coefficient
radioactivation, 113—196 elemental, 4 6 , 47
radiometric methods, 5—34 mineral, 6 3
trends, 7 8 Massive hydraulic fracturing (MHF), of
well logging, petroleum, 201—213 gas formations, 2 3 5 , 2 3 6 , 237
X-ray, 3 7 - 9 1 , 9 3 - 1 1 0 Mean-square-successive difference meth-
— diffraction, 70—72 od, 1 5 2
— fluorescence, 66—70, 93—103 Metals exploration, 8 5 , 8 8 , 8 9 , 162—187
Instrumentation criteria, 2 lead, 8 8 , 8 9
advantages and disadvantages, 3 , 4 Metamorphic rocks, 6
exploration, 2 Mineral imports, U.S., 1, 2
mining, 2 Mineral values, 1
processing, 3 Minerals, non-metallic, 79—81
Instruments, space bauxite and laterite, 79—80
alpha-particle spectroscopy, 9 8 clays, 8 0
gamma-ray spectroscopy, 9 8 , 9 9 limestone and dolomite, 79
X-ray fluorescence spectroscopy, 9 9 , other, 8 0
100-103 Mining, chemical, copper, 2 1 5 , 2 1 6
Intrusive rocks, 5 nuclear experiments, 2 3 8 , 2 3 9 , 2 4 1 ,
Ionization chamber, 29 246
Isotopic spontaneous fission neutron — Soviet, ore breaking, 2 4 6
sources, 1 2 2 , 1 4 5 , 1 7 3 overburden removal, 2 3 8 , 2 4 0 , 241
Model, borehole
Ketch, 2 2 9 experimental, 1 6 6
theoretical, 133—135
Laboratory, mobile (see also Mobile labo- Mobile laboratory
ratory), 72—75 configuration, 7 5 , 1 7 1 (Fig. 5-30), 181
Lawrence Livermore Laboratory, 2 1 5 , (Fig. 5-36), 1 8 2 (Fig. 5-37), 1 8 3
229,251 (Fig. 5-38), 1 8 4 (Fig. 5-39)
Lawrence Radiation Laboratory, see function, 7 2 - 7 4 , 1 7 0 - 1 8 5
Lawrence Livermore Laboratory Muscovite mica fission-track detector, 2 3 ,
Lead-210, 2 9 2 5 , 26
Lead-214, 2 9
Lexan detector, fission tracks (see also Natural gamma-ray logs, 18, 2 0 1 , 2 0 2 ,
Track-etch m e t h o d ) , 2 3 , 2 5 , 26 203
Linear absorption coefficient, 4 6 , 2 6 3 , Natural gamma-ray measurement, 18,
264 115,201
277

Natural gas (see also Gas stimulation), Nuclear explosions, see Explosions,
215, 227, 228, 229, 233, 234, 235, nuclear
236, 237, 241, 246 Nuclear power reactors, 2 4 9
prices of, 2 3 3 , 2 3 4 , 2 3 5 , 2 3 6 Nuclear Regulatory Commission, 2 5 0
production of, computer simulation, Nucleus, 255
228
reserves, U.S., 2 3 3 , 2 3 4 Oil, production, U.S., 2 3 1
storage, 2 1 5 , 2 2 9 reserves, U.S., 2 3 1
from tight reservoirs, 2 3 3 , 2 3 4 , 2 3 5 , shale, 2 1 5 , 2 3 1 , 2 3 2 , 2 3 3
236,237 — costs of processing, 2 3 2 , 2 3 3
Navigation systems for airborne gamma — rubblizing, using nuclear explosives,
surveys, 20 215, 216, 231, 232, 233
Neutron, 2 6 8 stimulation, using nuclear explosives,
absorption, 1 7 3 241,243
energy spectra, 140—144 Soviet, Field A, 2 4 1 , 2 4 3
exposure for fission tracks, 23 Soviet, Field B, 2 4 1 , 2 4 3
flux distribution, 1 2 3 , 1 2 4 , 131—133 One-group diffusion theory, 1 2 4
generators, 1 4 8 "1003", 237, 238
logs, 19, 2 0 6 , 2 0 7 , 2 0 8 , 2 0 9 , 2 1 0 "1004", 238, 239
measurement, 1 8 4
Operational parameters for airborne
reactions, 120—122, 2 6 8 , 2 7 1
gamma systems, 20
sources, 138—149
yield, 1 4 0 Passive gamma-ray spectroscopy, 14, 15,
Neutron-gamma transport, 1 2 3 16, 17, 9 8
one-group diffusion theory, 1 2 4 Particle reactions, 1 2 2
two-group diffusion theory, 127 Peaceful nuclear explosions (see also
one-region gamma transport, 1 3 1 Explosions, nuclear), 215—253
two-region gamma transport, 1 3 2 application to energy resources, 229—
gamma-ray intensity, 1 3 3 237
neutron flux distribution, 1 3 3 economics, 2 4 9 , 2 5 0
theoretical model, 131 for gas stimulation, 2 2 7 , 2 2 8 , 2 4 1 ,
Neutron group 246
activation process (n, 7 ) , 1 2 1 , 268— regulation of, 2 5 0
271 runaway gas well control, 2 4 1 , 2 4 2 ,
delayed fission neutron counting, 120 243
delayed neutron counting, 1 2 2 Soviet, program for, 2 4 1 , 2 4 8
fast neutron activation, 1 2 0 storage, 2 1 5 , 2 2 9 , 2 3 0 , 2 4 1 , 2 4 6 , 2 4 7 ,
fast neutron inelastic scattering, 1 2 0 248
inelastic scattering (n, n ' 7 ) , 1 2 2 Peralkaline rocks, 15
particle reactions, 1 2 2 Piceance Basin, 2 2 8 , 2 3 5
radiative capture (n, 7 ) , 121 Photographic emulsion for alpha tracks,
resonance neutron activation, 120 22
thermal neutron activation, 1 2 0 , 2 6 8 Photo nuclear applications, 1 6 2
thermal neutron capture, 1 2 0 , 2 6 8 methods, 1 1 9
Neutron methods and applications, 1 6 2 , Planetary surfaces, geochemical measure-
268-271 ments, 98—100
inelastic neutron scattering, 1 6 4 Plowshare, see Peaceful nuclear explo-
delayed neutron measurement, 1 8 4 sions
fast neutron-induced reactions, 1 6 5 PNE, see Peaceful nuclear explosions
thermal neutron absorption, 1 7 3 multiple simultaneous, 2 3 4 , 2 3 5
Niobium-95, 9 obstacles to development in U.S., 2 4 9 ,
Nevada Test Site, 2 1 8 250,251
Nuclear cratering, see Cratering, nuclear oil stimulation, 2 4 1 , 2 4 3
278

oil shale processing, 2 1 5 , 2 1 6 , 2 3 1 , Radiative capture (n, 7 ) process, 121


232,233 Radioelements, 5, 6, 7, 222—229, 2 5 8
public relations problems, 2 5 0 , 2 5 1 Radioisotope sources (see also Neutron
Porphyry copper deposits, 15, 1 7 1 sources, Gamma-ray sources), 1 0 1 ,
Potassium-40, 5—12, 2 0 , 21 102
Primary X-rays, 4 0 , 4 1 Radioisotopic neutron sources, 138—149
Probe, 17, 1 1 5 , 1 3 5 , 1 5 6 - 1 6 1 (a, n), 1 3 9
Prompt gamma-ray measurement, 1 6 4 , ( 7 , n), 1 4 4
171,174 isotopic fission, 1 4 5
Properties of rays and particles, 2 6 0 Radon-220, (thoron), 28
alpha radiation, 2 6 0 Radon-222, 5, 2 2 , 28—33
beta radiation, 2 6 1 , 2 6 2 , 2 6 3 contour map, 3 2
Compton effect, 2 6 6 detection, 28—33
gamma rays, 2 6 3 Reaction ( 7 , n), 1 1 9
pair production, 2 6 6 Reactors, nuclear, 2 4 9
photoelectric effect, 2 6 5 Relative radioactivities of U, Th and K, 7
Proportional counter tubes, 1 0 2 Resolution of gamma detector systems,
PSAA, 2 1 9 , 2 2 0 , 2 2 1 12, 1 3 , 1 6 0 - 1 6 3
Pulse-height analyzer, 7, 9, 1 2 , 1 3 5 Resonance gamma method, 1 1 8
Pulsed neutron logging (see also Neutron, Resonance scattering methods, 1 1 8
logs), 135 Resources, development of, by Plowshare
Pulsed neutron source, 1 3 6 , 2 0 8 , 2 0 9 technology, 215—253
energy, application of Plowshare tech-
Qualitative analysis, X-ray nology to, 229—237
diffraction, 6 1 , 6 2 Rio Blanco, 2 2 7 , 2 2 8 , 2 4 9 , 2 5 0 , 2 5 1
fluorescence, 48—51, 104—110 Rulison, 2 2 0 , 2 2 1 , 2 2 7 , 2 2 8
Quantitative analysis, X-ray Runaway gas wells, control of, by nuclear
diffraction, 6 2 , 65 explosions, 2 4 1 , 2 4 2 , 2 4 3
fluorescence, 52—57, 104—110
Quantum numbers, 4 2 Salmon, 2 2 0
Salt, nuclear explosions in, 2 1 8 , 2 1 9 ,
Radioactivation methods, 1 5 0 , 269—271 220, 229, 241
applications, 1 5 3 Sample preparation, X-ray analysis
gamma-gamma techniques, 155 diffraction, 6 3 , 65
gamma-ray resonance scattering, 161 spectrometry, 57—59
neutron methods, 1 6 2 San Juan Basin, 227
photonuclear methods, 1 6 2 Secondary X-rays, 4 5
Radioactivation sources (see also Neutron, excitation geometry, 53
sources), 138—149 fluorescence, 4 6 , 107
Radioactivity, 222—229, 2 5 8 Sedimentary rocks, 5
activation products, 150—162, 2 2 3 , radioelement content of carbonates, 6
224, 2 6 8 - 2 7 1 of elastics, 6
chemical behavior of, 2 2 4 Seismic effects from nuclear detonations,
fission products, 2 2 2 2 1 9 , 2 2 0 , 221
groundwater transport of, 2 2 5 , 2 2 6 , from Rulison, 2 2 0 , 2 2 1
227 Selection rules, 4 3
physical characteristics of, 2 2 4 , 2 2 5 , Selective gamma logging, 9, 15, 155—161,
258 201-203
product standards for, 2 5 0 Semiconductor gamma detectors (see also
production by nuclear explosions, 2 2 2 , Gamma-ray spectrometers, Gamma-
223, 224 ray spectrometry, Detectors), 13
tritium, 2 2 3 , 2 2 4 , 2 2 5 , 2 2 8 , 2 2 9 Sensitivity (diffraction), X-ray, 6 5 , 6 6
279

Shale oil, see Oil shale Detectors, Gamma-ray spectrom-


Shield, radiation, 1 2 2 , 1 2 3 , 1 3 5 , 1 4 5 , etry), 1 2 , 1 4 - 1 7 , 2 0 , 2 2
165, 188 Thermal neutrons, 2 0 6 — 2 1 1 , 268—271
Silicon-semiconductor alpha detector, 33 absorption, 1 7 3
Space instrument design, 95—98 activation, 1 7 3
Spectra Theoretical model for prompt gamma
examples, 5 0 , 1 0 4 (Fig. 4-4), 1 0 5 (Figs. rays, 131
4-5, 4-6), 1 0 6 (Figs. 4-7, 4-8), 107 one-region gamma transport, 1 3 1
(Fig. 4-9), 177 two-region gamma-transport, 1 3 2
of samples ( 7 ) , 9 Thorium-232, 5 - 1 2 , 14, 15, 17, 18, 2 0 -
of standards ( 7 ) , 9 23, 2 6 - 2 8 , 30
Spectral distribution, 8, 4 1 , 4 2