Beruflich Dokumente
Kultur Dokumente
practica! Identification
of clay minerals
A HANDBOOK FOR TEACHERS AND STUDENTS
IN CLAY MINERALOGY
1976
Editions G. LELOTTE
B 4820 DISON (Belgique)
PREFACE
The present author, in designing this short student handbook, had in mind the basic
needs of students and teachers in clay mineralogy and clay geology, who both have
to face routine X-ray diffraction analysis of clay minerals or to have periodic refreshment
of the basic knowledge in this topic.
The present author has already published a Laboratory Handbook in order to allow and
faciltate the best and accurate determination of phyllosilicates and clay minerals by
X-ray diffraction technique for both the oriented aggregates and the random powder
mounts. (THOREZ, 1975).
The clay fraction of sediments, soils and weathering producs is usually composed of
polymineralic associations, where both phyllosilicates and related minerals, and non
phyllosilicates are present (quartz, feldspar, zeolites, carbonates, amorphous etc...). It
is rather difficult and even impossible to seprate the phyllosilicates and clay minerals
from one anofher. For the purpose to identify the different components as in details
as possible without an artificial separation, it is thus desirable firstly to recognize and
confirm the composition of the different components of the mixture, after various treat-
ments, by oriented aggregates (the technique that allows an enhancement of the (001)
reflections), and by random powder mounts. As a consequence the reader will have
to use in simultaneity if necessary the two handbooks, (THOREZ, 1975) and the present
one, following his needs in the accuracy of the determination.
Jacques Thorez
Mineralgica! Instituto
Lige State University.
VI
TABLE OF CONTENTS
IV-C-4 '. " Crystallinity and varieties of Hites . . 12 VI C 3 : Behaviour of regularly interstratified mine-
rals upon treatments 45
IV-D. PYROPHYLLITE AND TALC 16
VI-C4 : Gritera for the reoogniton of regularly inter-
Remark : differentiation between pyrophyllite-talc, and stratified minerals 46
brittle micas and paragonite 16
VI-D : Randomly mterstratified structures . . . . 48
IV-E. SMECTITES 16
VI-D-1 : Generalities 48
IV-E-1 : Generalices 16
Vl-D-2 : Criteriaforthe recognition of randomly mter-
I V - E - 2 : Non-smectitic composition of a 1 7 glyco- stratified structures 48
lated material 17
VI-D-3 : Degrees of disorder and consequences . 49
IV-E-3 : Crystallinity of smectites (dioctahedral) 18
VI-D-4 : Proposed notations for randomly nterstrati-
IV-E 4 : Identification o f species . . . . 21 fied structures 51
IV-E-4a : Smectites with high and low charges 21 VI-D-4a : Randomly interstratified structures with
14c and 14y 52
IV-E-4b : Genetic differentiation between smec-
tites : low charge, high charge, authigenic, and mica- V|-D-4b : Randomly interstratified structures with
derived smectites 21 14c and 14|y 52
Vil
X. ALPHABETICAL LIST OF CURREN! CLAY MINERALS IN- XI. INCREASING (060) OF PHYLLOSILICATES AND CLAY
CLUDING MIXED LAYERS WITH THEIR d(001) VALES IN , MINERALS 79
AND THE CORRESPONDING INTENSITIES OUT TO THE 3
REGIN OF THE DIFFRACTOGRAM (oriented aggregate, na- XII. GLOSSARY OF PHYLLOSILICATES AND CLAY MINERALS 80
tural state) . 76
SELECTED BIBLIOGRAPHICAL REFERENCES 87
INDEX OF TABLES
Table 1. - Classification scheme for layer silicatos . 1 Table 19. - Observed X-ray powder data for sepiolite (after
CAILLERE, n GIESEKING, 1975) : data provided only out
Table 2. - Explanation of the motifs and symbols. . 3-4 to the 3 regin of the X-ray diffractogram 37
Table 3. - Routine differentiation for kaolinite minerals (X-ray Table 20. - Progressive shifting of the 12 sepiolite reflec-
powder pattern) - (data kindly provided to the author by tion towards 10 upon heating treatment from 300 to
Dr SIEFFERMAN) 800"C, with possible simultaneous occurrence of both the
reflections at certam temperatures (after LUCAS. 1963). 37
Table 4. - Comparison between the charactenstic reflections
(peculiar, common, supplementary) of kaolinie, dicktite and Table 21. - Vales of the basal reflection, in d(A), for the cur-
nacnte (after DOUILLET and NICOLS, 1969). . rent clay minerals, after the classical identification essays
(N = natural, untreated sample ; EG = ethylene glycol ;
Table 5. - Reaction types of kaolinite group minerals accordmg 500 = heating to 500C) 38
to heir behaviour towards hydrazine, hydrazine+waer, and
ethylene glycol leachings (after RANGE et a / , 1969) 7 Table 22. - Vales in d() of the charactenstic reflections of
the series (OOI) of curren! clay minerals, after various
Table 6. - Behaviour of kaolinite, and kaolinite types, towards diagnostic treatments (N, EG. 500 and 550"C) ( after
the treatment with K-acetate (ALIETTI, 1966). . 7 LUCAS, 1963) 39
Table 7. - d(001) and d(060) for minerals of the serpentine Table 23. - Vales in d() of the basal (001) reflection of
group (after BROWN, 1971, and THOREZ, 1975). . 7 curren! clay minerals (without, and with cation-saturations
with K+, Ca++, Mg ++) (after QUATERNAAT, 1968) . 40
Table 8. - (hkl) reflections in d(), and corresponding inten-
sities, for polymorph varieties of Hites and hydrous micas Table 24. - Coloured key for the routine identificaron of cur-
(after LEVINSON, 1955) 11 rent clay minerals, based on the behaviour of the basal (001)
reflection after different treatments (after THOREZ, 1975). 41
Table 9. - Charactenstic (hkl) reflections for the polymorph
varieties o f Hites (d-spacngs n ) . . . . . . 12 Table 25. Possible types of intersratification for binary com-
bmations of the various layers of simple clay minerals
Table 10. - Mixture of Hite polymorph varieties : intensities of (after THOREZ, 1975) 42
the specific reflections (after KODAMA, 1962) 12
Table 26. - Classification and combinations of interstratitied
Table 11, - Expansin of synthetic beidellite and montmoril- layers in all the actually known mixed layers (after STOCH,
lonite [(vales of (001) in d()] (after HARWARD and 1971, modified by the present author) 43
BRINDLEY, 1964) 23
Table 27. - Examples of the variability in layer composition for
Table 12. - Differentiation between montmorillomtes, beidel- regularly interstratified minerals (after THOREZ, 1975). . 45
lites and vermiculites on the basis of the saturatmg catin,
moisture conditioning, and solvation method (after HARWARD Table 28. - Position, m d(), and behaviours of the (002) re-
et al., 1969) 23 flection in some of the main types of regularly interstratified
minerals after glycolation and heating (to550C).. . . 46
Table 13. - Distinction between Cheto-, Wyoming-, and iron-
rich montmorillonites after catin saturations (K, Mg) (after Table 29. - Highest d-spacmg m A of the (001) reflection for
GRIM and KULBICKI, 1961). 24 regularly interstratified minerals (after VIVALDI and Mac
EWAN, 1960 ; LUCAS, CAMEZ. and MILLOT, 1959 ; Mac
Table 14. - Classification of Mg-, Al- and Fe-chlorites EWAN and RUIZ-AMIL m GIESEKING, 1975; THOREZ,
(after WARSHAW and ROY, 1961) . 31 1975) 46
Table 15. - Summary of one-layer polytypes in chlorites (after Table 30. - Coloured key for the routine identification of cur-
BAILEY, m GIESEKING, 1975) 35 rent regularly interstratified minerals, based on the behaviour
of the (002) reflection after different treatments. (after
Tablo 16. - Correspondence between chlorite species, and THOREZ, 1975) 64
the vales of the intensities ratio l(002) + (004)/l(003), and
l(003)/l(005) (after POST and PLUMMER, 1972). 36 Tables 31-35. - Routine identification keys (N, EG, 500C)
for current clay minerals, randomly and regularly mixed
Table 1 7. - (OOI) reflections for soil chlorites : Clinochlore, layers, taking into consideration the variations in the shapes
Prochlonte, Corundophilite, Leuchtenbergite, and Thurin- of the basal (001) reflection (simple clay minerals), or of
gite, for the untreated and the heated (to 550C) samples : the (002) reflection of mixed layers 65
positions of the (OOI) reflections n d(), and oorresponding
intensities (after MARTIN, 1955, modified in THOREZ, Table 36. - Classification of phyllosilicates (after BRINDLEY,
1975) 36 1962), and the recommendations of the AIPEA Nomen-
clature Committee, Madrid, 1972). 80
Table 18. - d-spacings and observed intensities of the Atta-
pulgus palygorskite (X-ray pattern out the 3 rea) (after
BRADLEY, 1940) 36
VIII
INDEX OF THE SHORT TABLES - Vermiculite 26
Figure 1. - Crystallinity orders n kaolinite (after MURRAY and Figure 7. Characterization of the Hite Crystallinity" or
LYONS, 1956) 9 sharpness ratio of WEAVER (1960), and DUNOYER de
SEGONZAC, (1969) 14
Figure 2. - Schematic Debye-Scherrer X-ray monogram of well-
crystallized kaolinite, fire-clay and halloysite (hydrokaoli- Figure 8. - Ilute characterization by the acute n d e x and
mte) ( after BRINDLEY and ROBINSON, 1948) . . . 9 the Al2O3/FeO+MgO compositon of the octahedral layer
(after ESQUEVIN, 1969, and DUNOYER de SEGONZAC,
Figure 3. - Crystallinity ndex for kaolmite (after HINCKLEY; 1969). Evolution of the crystallnity and compositon of the
RANGE ef al., 1969) 10 Hite from the diagenetc or weathering zone toward the
epizone . . . . . . . . . . 1 5
Figure 4. - X-ray powder diffraction patterns of monomineralic
kaolin minerals. (A) : well-crystallized, well-formed platy Figure 9. - Diagrammatic representaron of the Hite evoluton
material, enhanced basal reflections (kaolinite) ; (B) : platy during the weathering (after THOREZ, 1973). Vertical axis :
material with b-axis disordered sequence, enhanced basal Al2O3/FeO + MgO ESQUEVIN's ratio n the octahedral
reflections (disordered kaolinite) ; (C) : layer sequence layer based on the ntensities ratio (002)7(001) ; horizontal
partially disordered with respect to both a- and b-axies, axis : subdivisions of the acute ndex la of the ilute, based
little enhancement of basal reflections, rolled form (hal- on the thckness of the 10A reflection at half-height above
loysite) ; (D) : highly disordered layer sequence, no en- background : Hite with acute peak Ip A. with l a -3mrn ;
hancement of basal reflections, tubular form (halloysite) Hite with enlarged foot (lp.|.) with l a =6mm ; open ilute,
(after BRINDLEY and DE SOUZA SANTOS, 1963, repro- with la equal or above 10mm. (A)= domain of ilutes with
duced in DIMANME, RASSEL, TARTE and THOREZ, 1974). 10 a muscovite composiion ; (B)- domain of Hites with a
phengite composition ; (C)= ilute with a muscovite+bo-
Figure 5. - ESQUEVIN's method of fixmg the composition n tite compositon ; (D)= ilutes with a biotite compostion at
Al2O3/FeO+MgO in the octahedral layer of Hites, based the level of the octahedral layer (ESQUEVIN, 1969) . . 15
o n t h e ratio o f t h e ntensities o f (002)7(001) . . . 10
Figure 10. - - opening state of Hite after MELLIERES and
Figure 6. - Schematic representaron of the (001) Hite reflection PEREZ-NIETO (1973), n sedimentary Hites :
at 10 n the case of open varieties : IQ, ly, and IM ST-SI
(LUCAS, 1963). Comparison of the shape after the glyco- E 0 =100^
lation and heating. Minerals related to ilutes (Van der ST= total surface of the 10 reflection above background
MAREL, 1961) 13
IX
S|= surface of the normal reflection of the (well-crystal- Figure 23. - Types of (OOI) sequences of clay minerals (styli-
lized) Hite centered on the 10A: the surface s limited, sed X-ray diffraction patterns, providing the shapes of the
on the high angle side of the diffractogram, by the des- harmonio reflections). a) simple clay mineral, well-crystal-
cending curve of the reflection ; on the low angle side, lized, with symmetrical and intense reflections ; b) mixture of
the shape of the reflection s delimited by drawing the simple clay minerals ; c) regulary interstratified minerals the
symmetrical branch of the high angle side of the reflection. (OOI) reflections of which have d(A) positions intensities
Sample pretreated with C a , a n d glycolated . . . 15 and shapes according tothe same charactersforthe simple
clay minerals the layers of which are interstratified ; d)
Figure 11. - Interference of the (002) of pyrophyllite at 9.1, randomly interstratified structure charactenzed by badly-defined
with the (001) of ilute at 10 during the evaluation of the reflections, with a plateau shape in many cases and an irrational
acute ndex la of the latter mineral by DUNOYER de sequenceof (OOI) reflections ;thesuperlatticestructureisordinarily
SEGONZAC's method of characterization the crystallinity. missing ; e) aspect of a mixture of a simple clay mineral and of a
(A) : case of a mixture where the basal reflection (002) of randomly interstratified structure ; f)degraded mineral (i. e. illite) with
pyrophyllite s not apparent and causes an enlargement of asymmetrical reflections (tailing reflections) . . . . 42
the Hite reflection towards the high angle side ; (B) :
case of a mixture composed of pyrophyllite and ilute ; their Figure 24. - Illustrating the way n which each reflection
basal reflections are very closed, causing an enlargement of migrates and changes shape in randomly interstratified
the low part of the reflections while two distinct peaks struciure. The further apart the mxima for the pur phases
appear in the high part of the reflections respectively at are n reciprocal space, the more the curve of the reflec-
9.1A (pyrophyllite), and at 10A (Hite) 16 tion movement levis out for intermedate compositons, at
the same time as the reflecton becomes diffuse (after
Figure 12. - v/p ratio ( valley >/ peak height ratio) for the Mac EWAN and RUIZ-AMIL n GIESEKING, 1975) . 47
characterization of the crystallinity of smectites (after
BISCAYE, 1965). The measurement s achieved on the 1 7 Figure 25. - Eight types of interstratificaton of A- and B-layers.
peak of the glycolated material. p is measured below Regularly interstratified minerals (alternating ABAB :
the apex of the 1 7 reflection, above the background ; AABBAA : AAABBB ; ABBABB ; AABBBAABBB ; segrega-
" v s measuring the importance of the depression ( val- ted material : alternating AAAABBBB ; randomly interstrati-
ley ) towards the low angle side of the 1 ?A reflection. fied structures ; alternating ABABBAAB, and ABAABBBetc... 47
(A) : well-crystallized smectite ; (B) and (C) badly-crystal-
lized smectites 18 Figure 26. - Schematic representaron of the reflection zones
of an interstratified structure formed of A- and B-types of
Figure 13. - Empirical crystallinity classes of smectitic layers (LUCAS, 1963) 48
materials based on : 1) the shape, symmetry, ntensity of
the 1?A reflection ; 2) on the occurrence/absence and shape Figure 27. - Schematic representaron of the composition of
of the (002) at about 8A, and (003) at about 5.4. (THOREZ). 19 a system consisting of interstratified particles, and possible
X-ray diffraction curve aspect for difieren! mixed layers
Figure 14. - Relationship between the crystallinity ndex v/p composed of A- and B-layers (interlayers). Cl = degree of
of BISCAYE (1965), and the crystallinity classes of interstratification (vales from O to 1 ) ; n = number of
THOREZ (1974, unpublished data), allowng the charac- partiles with a given a (modified after KUBLER, 1961 ;
terzaton of the smectite evolution durng weathering or LUCAS, 1973; in THOREZ, 1975) 49
in a sedimentary nterval of sediments rich in smectites.
This relationship can be provided independently of the Figure 28. - WEAVER's method for the analysis on the X-ray
smectite composition . . . 19 diagram of an nterstratified mineral 50
Figure 15. - Differentiation between smectites (montmoril- Figure 29. Schematic representaron for the reflections of
lonites) vaneties after selective treatments (after THOREZ, mixed layers relatively to the position and intensities of the
1975). 20 pur phases (n this case montmorillonite and muscovite)
(after BYSTRM, 1956) 50
Figure 16. - Effects of amorphous material during the Li-test
of GREENE-KELLY, (1953) for the distinction between mont- Figure 30. - First-order apparent spacings for the three com-
monllonite and beidellite (after MURAVYOV, 1970, and ponent interstratifications that can be formed from 1 O, 1 2.4,
THOREZ, 1975) 22 14, and 15.4 spacings (after JOAS and BROWN, 1959,
also reproduced in GIESEKING, 1975) . . . . 51
Figure 1 7. - Basal reflection (001) n for vermiculite minerals
treated with water or glycerol as affected by the nature Figure 31. - Position in d() of the (001) and (002) reflections
of nterlayer catin and the method of sample preparation for regularly interstratified minrals : (C-V), (C-M), Cg-m),
(after BARSHAD, 1958, i n THOREZ, 1975) . . . 27 (Cg-V) and (M-V) after diagnostic treatments (ethylene
glycol and heating) 55
Figure 18. - Basal reflection (001) in for glycerolated mont-
morillonite minerals as affected by the catin exchange Figure 32. - Behaviour of the " basal " reflecion of random
capacity, the nature of the nterlayer catin, and the method mixed layers (14Q-14v) upon diagnostic treatments (ethy-
of sample preparation (with prevention of drying) (after lene glycol and heating) 56
BARSHAD, 1958, n THOREZ, 1975) 28
Figure 33. - Schematic presentation of the characteristic beha-
Figure 19. - Differentiation between vermiculite varieties -beha- viour and shape of the basal > reflection of random mixed
viour of the d(001) upon treatments (THOREZ, 1975). 29 layers (140-14^) upon diagnostic treatments (ethylene
glycol and heating) 57
Figure 20. - Chiorite species boundaries according to HEY
(1954) for the orthochlorite (A), and oxidized chlorites (B). Figure 34. - Schematic presentation of the characteristic beha-
Abbreviation symbols : pThur ~ pseudothuringie, Corun = viour and shape of the basal reflection of random mixed
corundophilite ; Daph = daphnite ; Ripi = ripidolite ; Sher = layers (14Q-14Q) upon diagnostic treatments (ethylene
sheridanite ; Bruns = brunsvigite ; Pycn = pycnochlorite ; glycol and heating) 58
Cuno clinochlore; Dia diabanite; Penn = penninite;
Talc-Chlo - talc-chlorite ; Thur = thuringite ; Klem = klemen- Figure 35. - Schematic presentation of the characteristic beha-
tite ; Cham = chamosite ; Deles = delessite . . . . 32 viour and shape of the basal reflection of random mixed
layers (10-14^) upon diagnostic treatments (ethylene
Figure 21. - Chiorite species boundaries according to FOSTER glycol and heating) 59
(1962) (U. S. Geol. Surv., Prof. Paper, 414, A-19).
Abbreviation symbols : Thur = thuringite ; Ripi = ripidolite ; Figure 36. - Schematic presentation of the characteristic beha-
Bruns = brunsvigite ; Cham = chamosite ; Diab = diaban- viour and shape of the " basal reflection of random mixed
tite 32 layers (10-14) upon diagnostic treatments (ethylene glycol
and heating) 60
Figure 22. - Schematic X-ray diffraction patterns of four chiorite
polytypes (based on data of BAILEY and BROWN, 1962, Figure 37. - Schematic presentation of the characteristic beha-
p. 839). The indexed, solid black bands are diagnostic for viour and shape of the " basal reflection of random mixed
each structure. The diagnostic (hol) bands of Ib (P=97) layers (10-14v) upon diagnostic treatments (ethylene
a r e broadened. (from HAYES, 1970, p . 288) . . . 35 glycol and heating) 61
INTRODUCTION
The problem of identifying the various existing clay minerals be combined : he (OOI) reflections allow a quick routine
has already been dealt with by several authors (BROWN, 1961 ; idenlificafion of he species or groups of minerals ; he powder
LUCAS, CAMEZ and MILLOT, 1959 ; WARSHAW and ROY, preparalion provides the enlire (hkl) specra for the concerned
1961 ; BRADLEY, 1945; LUCAS, 1963 (1968 in the English clay mineral, and s recommended when one has to deal
translation). Recently two other reference books have been with specific informations such as : the dioclahedral or Irioc-
published on the subjecl. lahedral characler, he polylypes, he crystallinily of the minerals,
the isomorphous subslilulion, etc...
The first one, edited by GIESEKING (1975), deals with the
identification of norganic soil components. Several well-known II is Ihus possible lo derive basic informafion firsl from fhe
scientists have contributed to that work which recalls traditional orientad aggregates of fhe clay minerals. A body of knowledge
data on the clay minerals, but also provides up-to-date and has now been buill up, for some decades and by several
past informations as well, all of them having been published aulhors, which enables he differenl clay mineral groups (and
in several papers since BROWN's book (1961). sub-groups) lo be recognized when he material occurs as
mono-mineralic componenl, or includes differenl componenls
The second one s by THOREZ (1975). Its objeclive is to in a mechanical mixlure.
provide to the clay scientists a series of identification keys
for clay minerals by X-ray diffraction analysis, both for oriented The majorily of clay minerals have layer slrucures consisling
aggregates and random powder preparations. The identification of parallel layers conlaining Si, Al, O and OH, somelimes
s conducted step-by-step on account of the wanted accuracy. combined wilh Mg, Fe and olher elemenls. The layers consisl
Emphasis has also been put on the effects of complementary of parallel sheets of atoms which are firmly bound logelher lo
tests (cation-saturations, glycolation, heating) in order to reach provide a more or less fairly sfable slruclure. Belween layers
a better identification. The work also contains : a series of he forces are usually weaker. So Ihal he sheels of aloms
stylised X-ray diffractogram patterns of oriented aggregates ; are bound logelher lo form layers. The layers are Ihen super-
the (hkl) reflections for about 420 varieties n both clay minerals posed lo form he cryslals. The classif icalion of fhe clay minerals
and phyllosilicates, and a general glossary. is largely based on slruclural consideralions for bofh the
composilional range within mineral groups, and the same order
The aim of the present handbook is to provide and recall to the belween groups.
teachers and students n clay mineralogy some basic X-ray
diffraction characters of clay minerals, including mixed layers, Two main types of layer appear in clay minerals : there are
in oriented aggregates. Some specific data are also presented he 1:1, and he 2:1 lypes. The former is made up by he
for the routine identification according to the X-ray patterns condensalion of one sheel of lelrahedrally coordinaled calions
of random powder preparation. The author recalls some basic wilh one sheel of oclahedrally coordinaled calions. The thickness
data, those usually used when one is concerned with the direct or elemenlary height of a single 1:1 layer is about 7.2 (as for
exploitation of diffractogram patterns. Therefore the conten of kandifes). The 2:1 lype which is he basic layer of micas (and
this handbook is to be beer considerad as a companion of the Hiles), chloriles, vermiculiles and smecliles, is made up by he
former laboraory handbook published by the author in 1975. condensalion of lwo telrahedrally coordinaled sheels of ca-
Its content can be easily combined with the one provided in lions, one on eilher side of oclahedrally coordinaled sheel.
THOREZ (1975). The Ihickness of a single 2:1 layer is aboul 9.3.
To define a clay mineral, its composition, and eilher is struc- In a wide sense he 1:1 lype layers are eleclrically neulral.
ture or some other properies tha are closely related to its The 2:1 layers oflen carry a negalive charge due lo isomor-
structure must be known. phous subtitulions. These negalive charges are balanced by
posilively charged aloms or groups of aloms which are silualed
As mostly clay minerals exist as partiles less han 1 micron and inlercalaled belween successive 2:1 layers. As a conse-
in diameer, and oflen occur in mixures, isolalion of pur quence he layer heighl for he 2:1 lype clay minerals depends
minerals is no easy. The slrucures of clay minerals can be on size of fhe posilively charged nlerlayer spaces. As an
sudied n a more or less direc way by X-ray diffracion method, example, in micas, K ions balance he charge on he 2:1 layers
particulary for he deermination of the aomic arrangement in and he elemenlary Ihickness of fhe mica layer is aboul 10.
crystals. The informations obtained from X-ray diffraction specra In vermiculite, moderalely hydraled calions are inlercalaled
can besubdivided inlo a wo-fold purpose : 1)lhe measurement belween lhe=2:1 layers, and he heighl of fhe vermiculite layer
of the geomerical disribution which corresponds tothegeome- s aboul 14. In smecliles, he balancing calions are more
try of atomic planes in the crysal (particularly at the level highly hydraled ; he layer heighl depends bolh on he precise
of he nerplanar spacings and nterplanar angles); 2) the nalure of he calion and on the humidity.
measuremen of he intensities of the reflections (he inensiies
are relaed lo he arrangemenl of aloms in planes). It s on the basis of he differenllhicknesses Ihatthe clay minerals
as single componenl or in mixlure are recognized by X-ray
Because of he nalure, size and cryslallinity grades n clay diffraction analysis. The X-ray pattern, since il allows a measure-
mineral particles, Ihere is a main difficully lo oblain easily he men of he distance between similar planes of atoms, provides
wanled informafions. Therefore I s indicaled to analyse the a direct measure of he heighl of the layers.
samples bolh as random powder preparalions, and as orienled
aggregates. The advanlage of he latter melhod is the enhance- The height of fhe layers, he nalure of he inlerlayered material,
menl of the infensilies of he basal reflecions, he so-called and he degree of hydrafalion in clay minerals can be usefully
integral series of he (OOI) reflecions which are alone repre- checked by fhe X-ray diffraclion in oriented aggregates of he
sentad in the X-ray patlern while he (hk) reflecions are nof clay fraclion (minus lwo-microns fraclion). The unlrealed (nalu-
reproduced. The lwo above quoled analytical melhods are lo ral : N) sample provides already some indicalions aboul he
XI
nature of the clay component(s). These indications can be The second aspect has some links with the first one just
further developed with complementary tests which are intro- presented. It concerns the quantitative (or semi-quanti-
duced n the analysis : effects on the basic spacings by the tative) evaluation of the clay mixture. It is clear that when a
solvation with ethylene glycol (EG) or giycerol (Gl), or by heating certain clay mineral is present n the mixture as a not very
treatments at various temperaturas (usually at about 490-550C). importan! component, there always is a risk not to detect it;
Also cation-saturations with Mg, Na, Ca, K, Li, etc..., combined if there are moreover overlapping effects for some of its
with glycolation (glycerolation) and heating, allow to reach, n reflections used for the evaluation, some misinterpretation
some cases, a better knowledge of the composition and may also occur.
structure of the material. As it will emphasized lateron, also of
interest are other tests which concern intercalations with organc A third aspect to be pointed out is the existence of mixed
and inorganic compounds such as hydrazine, K-acetate, DMSO. layers. There are cases where the combined layers of such
Some clay minerals do not resist to acid attack (HCI in instance). minerals are arranged in a regular way (cf. regular mixed
Thus f one proceeds to a cise examination of the behaviour layers) with respect to each type of layers. But there exists
of the basal reflections of clay minerals after the above cited randomly interstratified structures as well which are not true
tests, it is possible to reach the identificaron of the clay minerals. For the latter the disorder in their stacking of layers
components. But then further indications may sometimes be exists both in the structure and partiles. The interpretation
achieved f, n combination with the oriented aggregates, one of mixed layers, particularly the randomly ones named inter-
analyses a random powder mount of the same sample, and stratified structures, may sometimes be difficult. The difficulty
checks carefully some specific (hko) reflections (in both increases when such structures are engaged in mixture with
positions, and ntensities). other clay components.
In connection with the interpretaron of X-ray diffraction In an effort to reach a better differentiation between regularly
patterns of simple and mono-mineralic clays, there are also and randomly interstratified materials, a specific code has
three other aspects of the determination. been introduced and published by THOREZ (1975). Some of
these informations will be repeated here in the part of the
One concerns the recognition of the clay components into handbook devoted to these types of materials. The proposed
mixtures. In some cases there will be no problem at all method of transcription for mixed layers s not be considered
because the diffraction lines (reflections) of the components as a precise one. It serves the routine identificaron as it
are sufficiently separated one another n d-spacing and emphasizes more fully the characteristic behaviours of the
ntensities, and/or on account of their behaviour after certain combined layers on account of their behaviour upon deter-
dentification tests. mination tests (EG, Gl, heating, saturation, etc...). In fact, as
it will be illustrated in the coloured dentification keys, the
But there often occurs overlapping of reflections in certain aim of the proposed system of codificaron is to obtain first
parts of the X-ray pattern (i. e. the case of a mixture of some basic information about the composition before fur-
kaolinite and chlorite). Or some diagnostic reflections for ther and more precise data can be obtained by a more
a specific mineral are not readily available in the X-ray elaborated method of analysis (Fourier transform) of the real
pattern because of the masking effect by the reflections structure of the material.
(asymmetry, tailing) belonging to the other minerals which
are more or less degraded. Some care has to be taken when
such cases are encountered or suspected, and there is thus
indication to make detailed investigations.
XII
I. - TERMINOLOGY OF THE CLAY MINERALS
Terminology here used for clay minerals is based on the proposal An extensive comment about the content of this table exceeds the
classification for clay minerals and related phyllosilicates as issued scope of this chapter. It is however mportant to point out a decisin
by the Nomenclature Sub-Committee of the A. I. P. E. A. (BRINDLEY taken during the 1976 International Clay Conference, held in
1966, 1967 ; modified after the Madrid Clay Conference in 1972). Mxico ; its concerns the substitution of the group ame mont-
The classification scheme is here presented (table 1). morillonite-saponite by the ame smectites .
Layer type Interlayer Layer charge Group ames Subgroup ames Species
(octahedral layer)
Kaolinite- Di : Kaolinites
Kaolinite, Halloysite,
Serpentine Nacrite, Dicktite
1:1 Without 0 or
Kandites Tri : Serpentines Chrysotile, Lizardite,
Antigorite
Di : Vermiculites Vermiculite
~0.6<x<0.9 Vermiculites
Tri : Vermiculites Vermiculite
2:1
Dry or Di : Muscovites Muscovite, Paragonite
Hydrated x~1 Micas
Cations Tri : Biotites Biotite, Phlogopite
Di : Margante Margarite
x~2 Brittle Micas
Tri : Clintonite Seybertite, Xanthophyllite
In order to provide to the user a guick and simple guiding-mark (glycolation, glycerolation, heating), and to present this objective as
in the search of the position, n d(), and behaviours of the basal a mnemotechnical tool, the d-spacing vales and ranges of the
reflection of clay minerals upon different diagnostic treatments (001) reflections have been represented by colours and symbols.
d-spacing n for the (001) of clay d-spacing in for the (001) of clay
Symbols minerals & (002) of mixed layers Symbols minerals & (002) of mixed layers Symbols Signification
- No reflection
O 13,5-13,8 s~\ Broad reflection
7 ~7 13,9-14,3
r-i Diffraction band
% 9-9,7 *
14,6-15,3 OP Doublet
1 9,8-10,1
e 15,5-15,8
L
Asymmetry towards
low angles
A 10,3-10,5
o 16-16,5
Asymmetry towards
high angles
V 10,6-11
o 16,8-17,2 J
Reflection with
enlarged foot
A 11,2-11,7
17,3-18
. . > ^(*)
(#) Origin, n A, of
the tailing reflection
'
B V^ Diffraction band
+
Variation of the d-spacing
^r~1
12,5-13,3
[i.e. (11-14)] for the basal reflection
Each colour corresponds to a specific range of d-spacing in . The RED corresponds to intermedate d-spacings (with vales
The YELLOW corresponds to clay minerals whose basal reflections ranging between 11.9and 13.3).
are around 10-11, i. e. micas (these latter are generally white to The BLUE jecalls water, and is reserved for all the d-spacings
slightly yellow n natural samples). above 14.3. In particular it emphasizes the swelling of the basal
The GREEN corresponds to clay minerals with a basal spacing reflection upon solvation (with ethylene glycol and glycerol).
around 14, i. e. chlorites (ordinarily green n nature).
The first subdivisions of the d-spacngs ranges are mmediately This blackening is not chosen at random. It is progressively ob-
marked by a definitiva colour. These coloured ranges are further tained step-by-step n each of the symbols. For nstance, let us take
subdivided n narrower ones by different mnemotechnical symbols. the case pf the circle. The n creas i ng and the range of the d-spacings
In the choice of the latter, special attention has been drawn n in the circle are gradually indicated by : an open circle with a
order to provide a cise correspondence between these secondary central black point, a c/>c/e subdivided by an horizontal black Une,
subdivisions n the d-spacing ranges (limited by their proper colour} a circle subdivided into four sectors, two opposite being blackened,
and the appropriate symbols. In the choice of these symbols, the a solid black circle with a white central point, and finally a solid
number of sides and a gradatory blackening (that ncreases n black circle ; the gradation n the blackening of the circle -symbol
the same symbol) play their role to provide a complete sequence of s thus in relation with the different d-spacings : 14.6-15.3A;
symbols indica:.ing d-spacings increasing from 9.6A to 1 7. 15.5-15.8 ; 16-16.5A ; 16.8-17.2 and 17.3-18.
The selected symbols comprise : a dubbel "-like design , a narrow The most blackening for the different symbols has been managed
but vertically placed rectangle, a triangle, a square, an hexagone, to have spme _ strategic d-spacings emphasized : 10A; 12A;
a star, and a circ/e. 13.5-13.8, 14A, 17-18, because they are related to either specific
There exists a cise relationship between the definite range of clay minerals the (001) of which has a definite d() valu, or to the
d-spacings and the, shape and type of the corresponding symbol. behaviour of the d(001) upon treatments.
For instance, a 10A reflection will be represented by the rectangle All the d-spacings presented n figures and n the tables are ob-
(which has two sides) ; a 11.4, by a triangle (three sides) s. 16, tained for a Cu-anticathode, and a Ni-filter. Another set of mnemo-
by a circle (because of the swelling character, this symbol ndicates technical symbols can be used n parallel way and in association
the occurrence of an infinity of sides). with the just described ones. This complementary set (table 2)
is used n order to provide some further indications relatively to
Gradual blackening of these different symbols, exception for the the shape of the (001) reflection : doublet, broad reflection, dif-
dubbel -like and the rectangle ones, has also been ntroduced. fraction band, asymmetry etc...
Powder DISORDERED
diffractogram reas KAOLINITE METAHALLOYSITE
HYDRATED DEHYDRATED (80"C)
(d-spacing n A) sensu stricto KAOLINITE HALLOYSITE HALLOYSITE
3.36 weak
3.13 weak
3.09 weak
2.74 weak
2ole 3. - Routine differentiation for kaolinite minerals (X-ray powder pattern) (Data kindly provided to the author by SIFFERMAN)
Well-crystallized kao/inite s recognizable in powder preparation by Nacrite resembles dicktite n its X-ray powder pattern, but has
the numerous sharp reflections, the low background, and the generally fewer reflections, and shows perceptible differences both
presence of resolvable doublets and triplets at approximatively : n its d() positions and intensities. A characteristic reflection for
4.15. 3.80, 3.1 O, and 2.50. BRINDLEY (op. c/'.) considers the nacrite occurs at 2.43 (intensity : 6-7).
sharpness of all the (hkl) reflections, and the resolution of the (111) Disordered kaolinites display fewer reflections than the X-ray powder
and (111) reflections, and of the two triplets at 2.46-2.49 and pattern of kaolinite. Halloysite and hydrated halloysite have powder
2.38-2.28, as criteria for a perfect structural layer stacking (see patterns ressembng those of disordered kaolinite, but with broader
also paper by DIMANME e? al., 1974). series of (OOI) reflections, weaker intensities, and higher d-spacings
Dickite resembles kaolinite by its sharp resolvable reflections. than those of any kaolinite.
But there exists several reflections that have no parallel n kaolnite, Fre-clays show a complete set of kaolinite reflections but with a
and other reflections in similar positions to kaolinite but with decrease n intensities. The weakness of intensities reaches a
different intensities (see table 4 providing data from DOUILLET mximum n the case of hydrokaolinite for which the asymmetries of
and NICOLS, 1969). reflections become general, in particular for the (OOI) reflections.
The characteristic triplets of the kaolinite are more or less replaced IV - B - 3. - BEHAVIOUR OF KAOLINITES
by doublets in fire-clays, and by single but broad reflections in some
hydrokaolinite (DOUILLET and NICOLS, 1969 ; DIMANCHE ef al., WITH ORGANIC AND INORGANIC COMPOUNDS
1974).
It is also been proposed, by several authors, a complementary test
in the study of kandites. This test particularly displaces the basoal
(001) reflection at 7 to a position situated at higher vales in d(A).
characteristic KAOLINITE DICKTITE This test concerns the treatment with hydrazine, DMSO or K-acetate,
reflections d() I d() I combined or not with ethylene glycol or glycerol. Such a treatment
can be useful for the differentiation between kaolinite and entorile
4.18 5 4.27 3 in mixture because of the overlapping of the 7 and 3.5A reflections
3.84 4 3.95 2-3 in both the minerals. This overlapping is presented in the following
peculiar 3.74 2 table :
reflections 3.37 4 3.42 3
3.14 3 3.26 2 (OOI) reflections (001) (002) (003) (004)
2.75 3 2.79 2
Kaolinite 7 3.5
common reflec- 4.13 3 4.13 6-7 Chlorite 14 7 4.7 3.5
tions, but with 1.94 4-7 1.94 1-2
different 1.78 4-5 1.78 1-4
intensities 1.62 6-8 1.62 1 Hydrazine displaces the 7 (001) reflection to 10.4. The reaction
is reversible. Practically after 24 hours the treatment with pur
supplementary 2.29 8 2.93 1-2 hydrazine, at the temperatura of 60-65C, causes theoritically the
reflections 1.84 4 complete shift of the 7 to 10.4. But incomplete reaction often
occurs in fire-clays ; the treatment has to be prolonged several days
KAOLINITE DICKTITE NACRITE (up to 15 days sometimes) before the entire 7 reflection becomes
able to move. It has been shown, effectively, that the treatment
d. I d. I d. I works differentially by displacing very quickiy the largest partiles
of kaolinite while the very fine partiles (below 1 micron) are left
7.15 10 7.16 10 7.17 10 at the 7 position.
4.45 4 4.46 0.5 RANGE e a/., (1969) have proposed a classification scheme for
4.44 4 kaolinites which is based on degrees of lattice disorder by using
4.35 6 4.37 4 4.41 7 the effects of the reaction of the partiles with hydrazine water,
4.17 6 4.27 3 ethylene glycol, glyceroj. This sheme is concerned with the variable
4.12 3 4.13 7 4.12 3 displacement of the 7 reflection to 10.4. The behaviour of the
3.84 4 3.95 2 kaolinite after successive replacements and leachings allows a five-
3.734 2 3.795 6 fold classification which s hereafter represented : (table 5).
3.566 10 3.587 10 3.577 10
3.365 4 3.427 3
3.138 2 3.272 2
3,019 2 3.101 2 3.061 1 Other treatments, suoh as the one proposed by WADA (1961),
2.938 2 2.917 0.5 provide data for the recognition of kaolinite in a clay mixture. The
2.748 2 2.794 2 method indicated by WADA (op. c/'.) concerns the grinding of dry
2.553 8 2.560 4 2.576 3 kaolinite with potassium-acetate, which causes = an mtersalation
2.521 4 2.51 5
complex. The 7 reflection o moves towards 14A for an ordered
2.486 9 2.502 : 3 variety, while a doublet at 7 and 14 is characteristic for partially
2.374 7 2.40 1 2.438 i 7 and disordered varieties. In water solution the ammonium nitrate
2.331 10 2.322 9 2.33 2 displaces the potassium actate ; the effect results in the occurrence
2.284 9 of a 11.6A ammonium nitrate-kaolinite complex. But the reaction
2.182 3 2.212 2 2.237 ! 0.5 is not very often entirely quantitative : there can be found some
2.127 2 difficulty in the formation of the kaolinite-KCHsCOO complex with
1.985 7 1.975 5 1.982 0.5 the kaolinite because some natural clay material bears a ciment
1.935 4 1.937 1 1.921 2 richer in AI2O3 than SO2, which binds the kaolinite crystals and
1.892 2 1.898 2 makes difficult the intercalation of the salt (GOMES, 1967).
1.835 4 But by a reduction in the amorphous material conten [following
1.809 2 1.805 1 1.818 2 successive digestions with hot 5% Na2CO3 (MITCHELL and
1.778 5 1.785 1 1.792 3 FARMER, 1962)], a better development of the kaolinite-KCHsCOO
1.682 2 1.686 1 complex can be achieved. According to WADA (1963) the develop-
1.659 8 1 .652 5 1.668 3 ment of the kaolinite-salt complexes depends on the following
1.616 6 1.613 1 1.617 0.6 factors nherent to the kaolinite : 1) thickness, size and crystal-
1.581 4 1.586 1 linity of the partiles ; 2) presence of amorphous alumino-silicates
1.539 5 1.555 4 (allophane), and binding of the crystals by these materials ; 3) ana-
1.486 9 1.489 5 1.488 5 lytical errors.
ALIETTI (1966) provided some data for disordered kaolinites when
Table 4. Comparison between dicktite, kaolinite and nacrite re- the X-ray pattern of the powder preparation is examined n com-
flections (after DOUILLET and NICOLS, 1969). bination with the effects of the potassium actate (table 6).
Treatment Observed basal spacings in d()
Table 5. - Reaction types of kaolinite groups according to their behaviour towards hydrazine hydrated water,ethylene glycol leachings
(after RANGE et al., 1969).
Of course, of great interest is the electrn microscope examination antigorite (001) 7.30 1.541
of the trioctahedral 1:1 minerals. For nstance, hollow tubes and
fibers are characteristic for chrysotile while these structures are 6. layer (001) 7.33
also readily differentiated from those of halloysite. Antigorite occurs orthoserpentine 1.535
as plates and laths. Other serpentine minerals may have a X-ray
powder pattern similar to chrysotile, but their electrn micrographs Table 7. - d(001) and d(060) for the serpentine group (from BROWN,
resemble antigorite. 1961, and THOREZ, 1975).
IV - B - 5. - IDENTIFICATION OF KANDITES IN CLAY MIXTURES
The dentification concerns firstly kaolinite-halloysite, kaolinite- Hydrated ha/loysite is detected by a basal spacing of 7.3A or larger,
dicktite, mixture of trioctahedral (serpentina) minerals, and mixtures that shifts to smaller spacings when the sample s heated to 350C
of dioctahedral (kaolinite) and trioctahedral (serpentina) minerals. or less. Glycerol or ethylene glycol can expand the halloysite when
This objective can be achieved by the X-ray analysis of particularly the mineral s hydrated. When halloysite occurs n large amounts
the powder preparation in the regions between 4.4-3.5A, and the X-ray powder pattern shows- prominent broad and asymmetric
2.8-2.0 where the differences are mostly clearly occurring. reflections in the regin 4.6-3.5, and 2.8-2.4. Evaluation by elec-
tronic microscope provides further indications about the shape of
The distinction between kaolinite and haoysite can be obtained the partiles (tubular for halloysite, while platy and more or less
by a combination of different methods : X-ray analysis, DTA, electrn well hexagonal n kaolinite).
microscopy.
IV - B - 7. - CRYSTALLINITY OF KAOLINITE
Crystallinity indexes (or the order-disorder criterion) have been show a first perfectly and well-developed triplet while the other ones
attractive analytical tools and useful techniques for kaolinite, because have been substituted by single and enlarged reflections. These
of the importance of the minerals in ndustry. differences cannot be fully integrated into MURRAY and LYON's
MURRAY and LYON (1956) have proposed a set of 13 stylised classification scheme. It may be that such distorsin in the clas-
diffractogram patterns of random powder preparations, in which sification is in relationship with the genetic conditions of the kaolinite
a progressive decrease in crystallinity s shown (figure 1). Their materials analysed n Belgium.
classification is based on the changes n shapes and ntensities BRINDLEY and ROBINSON (1948) have published a schematic
of the (hkl) reflections, particularly with the enlargement of the chart for distinguishing between crystallized kaolinite, common
reflections, the replacement of triplets by doublet or by a single kaolinite, fire-clay and hydrokaolinite (figure 2).
but wide reflection. From such a gradation t would logically be HINCKLEY (1954) and RANGE [ef al. (1969)] have proposed a
accepted that t s easy to identify the degree of crystallinity. In crystallinity ndex. Their method is based on the ratio vales of
fact, if t s accepted that the decrease n crystallinity s based the intensities of the first triplet reflections (figure 3).
on the common and parallel substitution of the three characteristic
triplets by boublets, and finally by single reflections, the experience Comparison of the entire X-ray powder pattern of the kaolinite
by the present author for Belgian kaolins indcales the method to minerals provides a quick routine evaluation of the crystallinity
be somewhat invalid. For nstance, a monomineralic kaolinite may (figure 4) (data from BRINDLEY and DE SOUZA SANTOS, 1963).
060 igure 1. - Crystallinity orders in kaolinite (after MURRAY and LYONS.
Fig
1956).
0 o
Q,O^_
COI *
OJ^^ Ol 0 .
o i o
Well crystallzed
J|? i. 1 ,, , 1 1! i , . i i , , i . i ., 1 11
Common
_l I i I J l l l
Fire-clays
ll ll
Hydrokaolinites
i5
WELL ORYSTALLIZED KAOLINITE 002 001
002 111 110 002
26 25 24 23 22 21 20 19 26 25 24 23 22 21 20 19 26
HINCKLEY CRYSTALLINITY INDEX RANGE AND WEIS CRYSTALLINITY INDEX
IV- C - 1. - GENERALITIES
The dioctahedral muscovite and its derivative producs (such as (OOI) reflections; n muscovite the 5 s strong ; the ratio 1(001 )/l(002)
ilute) are recognized by their strong first and third order basal s between .7 and 1 ; n Hites, reflections at 4.97 (weak), and
reflections respectively at 10 and 3.3. The latter reflection may 4.47 (strong), occur while the 1(001)71(002) has a valu of 4/9.
coincide with the strongest quartz reflection when this mineral In Mg-rich ilutes, the 1(001)71(002) s weaker than 2 ; in Fe-rich
occurs n the clay fraction. ilutes, the ratio s higher than 3. The same ratio is n relationship
The basal spacing remains unaffected after glycolation (glycerola- with the K content (WHITE, 1962).
tion) and heating. ESQUEVIN (1969) has proposed to use the intensity ratio 1(002)71(001)
to provide, at first approximation, the AlaOs/FeO+MgO content n
This behaviour can be formulated as follows : the octahedral layer. The ratio vales can be correlated with the
AIsOs/FeO + MgO expressed in solid phase compositions as found
Treatments N EG 500C n biotite, phengite, muscovite, or in a mixture of biotite+muscovite
(see figure 5).
d(001) m d() 10 10 10
ratio vales 15 . 2 .3
Generally the ratio of the intensities for the 10 and 5 reflec- corresponding to
tions, hO/l5, s greater n dioctahedral than trioctahedral va- solid compositions biotite biotite phengite mus-
rieties. A high ratio s also associated with high ron conten of n the octahedral
the octahedral layer (GRIM ef al., 1951). layer of
In dioctahedral varieties a (002) reflection occurs at a d-spacing
of 5 while n trioctahedral varieties the 5 reflection s lacking Figure 5. - ESQUEVIN's method of fixing the composition m Al2O3/FeO+MgO
or of very weak mtensity (cf. biotite). n the ocahedral layer of Hites, based on the ratio of the intensities
In dioctahedral Hites the second order reflection at 5 remains of (002)/(001).
intense though weaker than for the muscovite. The latter mineral
usually presents narrow, intense and symmetnc reflections for the
10
I V - C - 2. - THE ILUTE TERM
The term ////fe is to be used as a co/lective ame for all the 10 with normal mica, but without swelling properties. The term hydro-
non-expanding clay material (GAUDETTE et al., 1966). Chemical muscovite, on the other hand, could be reserved for hydromica
analyses of dioctahedral ilutes, first described and named by GRIM formed by the degradation of muscovite ; the hydromica usually
ef al., 1937, show a lower K conten and a higher water conten shows a higher content of Al in the tetrahedral layer and can be
comparatively to muscovite. The lower substitution of Al for Si n assigned to 2M-| polytypic modification. Similarly ames such as
some of the ilutes, n comparison with that of muscovite, has led hydrobiotite and hydrophlogopite pertain the product of partial
GRIM ef al. (1937) to the conclusin that the former are not likely degradation of biotite and phlogopite, the crystalline structure of
to derive from micas. which retains a 10 spacing and does not show any swelling
It must be pointed out that commoner than typical micas as the properties. But one should have to recall that in some literatura
components of clayey rocks and of soils are minerals corresponding the term hydrobiotite is reserved to a regular mixed layer mineral
to i/lites (hydromicas). Apart the deficiency of K+, the electric charge built of biotite and vermiculite layers, and considerad as the product
is compensated by HsO+ introduced n the interlayer spaces ; there of the degradation of a biotite structure.
also occurs additional protons n the nterlayer spaces, and a partial In the mica (Hite) group one has to number glauconite and cela-
oxidation of Fe ++. So that the layer charge in the crystalline donite. However n the crystal lattice of glauconite it s usually
structure of ilutes is usually smaller than that n the structure of found swelling (montmorillonite behaving) interlayers as observed
micas. Normally the Hites do not exhibit any swelling properties. by BURST (1958) and HOWER (1961). As a consequence a sharp
There is however no sharp boundary between micas and hydro- boundary does not exist between glauconite, of the mica type
micas (Hites) as gradual transition between them is observed. structure, and montmonllonite. Celadonite s both structurally and
Detailed chemical composition are sometimes required for their chemically very similar to glauconite. Taking into consideration that
distinstion. For this reason it seems appropriate to include the ilutes the majority of glauconites and celadonites are structurally closer
into the mica group as a subgroup of the dioctahedral varieties. to Hites, these two species have been assigned to the subgroup
of dioctahedral mica too.
To describe hydromicas cise to muscovite, two ames are used :
////fe and hydromuscovite. As recalled by STOCH (1971), some authors In this handbook the term illite is .used for all the clay partiles
consider them as synonyms; other believe that Hite and hydro- that show a 10 layer spacing : the reflection apex s situated at
muscovite are different minerals. After GRIM ef al. (1937), ////fe is 10 while some tailing may occur towards the low angle side of
the ame for fine-grained authigenic micas occurring n clays, that the X-ray pattern, and is developed on the flank of the (001) reflec-
exhibit both a dficit of K+ and an excess of water n comparison tion.
IV - C - 3. - POLYTYPISM IN ILUTES
Dioctahedral illite shows a relatively sharp basal reflection which size, the kind of components with their relative amount, and the
may become slightly sharper after heating. Occurrence of a small the type of mixing (see chapter VI).
amount of expansible layers in the structure results n the development The asymmetry developed, n particular on the side of the (001)
of an asymmetry of the (OOI) reflection towards the low angle side reflection, s to be assigned t'hus to some expansible mterlayers,
for the (001), and towards the high angle side for the (003), while and corresponds to an open or degraded Hite.
the (002) becomes broader (BRADLEY, 1954; LUCAS, 1963;
KUBLER, 1962). The asymmetry is indicative of a transition to The polytypism (1M, 1Md, 2M) of lite is to be evaluated by some
mixed layer systems (REYNOLDS and HOWER, 1970; KODAMA definite (hkl) reflections.
et al., 1969) ; the analysis of such mixed layers involves the particle
Table 8. - (hkl) reflections in d() and corresponding intensities for polymorph varieties among ilutes and hydrous micas (after LEVINSON,
1955).
11
LEVINSON (1955) has published detailed data about the polymor- rassembled in THOREZ (1975).
phism of ilutes and hydrous micas, including the 3T(3-layer trigonal),
2M (2-layer monoclinic), 1M (1-layer monoclinic), and 1 Md (1-layer It often occurs that the polytypes are met in mixture, and in several
monoclinic disordered) (table 8). 2M and 1 Md polymorphs occur relative proportions. The distinction n mixture of 1 M, 1 Md and 2M
n sedimentary rocks ; 3T and 1M belong to non-sedimentary polytypes is not easy and remains a practical difficulty (WARSHAW,
environment, such as hydrothermal weathering. Complementary and 1960 ; VELDE and HOWER, 1963 ; MAXWELL and HOWER, 1967).
much detailed data about the (hkl) positions and intensities of the Each of the polytypes is characterized by a series of reflections
different polymorph varieties published in the literature have been which are presented n table 9.
2M : 4.48 4.29 3.89 3.74 3.66 3.54 3.33 3.21 3.01 2.87
2.08 2.55
1M : 4.48 3.66 3.33 3.07
2.58
1Md : 4.48 3.33
2.58
2M+1M : 2M 3.75 3.50 3.20 2.89
1M 3.66 3.07
Table 9 : characteristic reflections of the polymorph varieties among Hites,
(d spacings n ).
12
Figure 6. - Schemalic representaron of the (001) Hite reflection at 10A
m the case of open varieties : le, IV, and IM (LUCAS, 1963). Comparison
of the shape after the glycolation and heating. Minerals related to Hites
(Van der MAREL, 1961).
O
m m
co
o
oo
O
en
O
Oo
o
O O
14
Thickness of
the(001)at10 Using this crystallinity parameter DUNOYER de SEGONZAC, in
particular, has succeeded to fix a range of vales related to :
the diagenetic zone, the anchizone (anchimetamorphic zone),
and the epizone. The vales of the ndex can then be combined
10 with those provided by ESQUEVIN (1969) for the AlaOa/FeO+MgO
composition of the octahedral layer of ilute. A graphical presentation
s organized that allows the characterizaton of the Hite toward
and n the three above defined zones (figure 8). Such a presentation
of the crystallochemcal data s useful for nstance for the analysis
DIAGENETIC of a clay illitic-rich material whch has undergone an evoluton from
ZONE the diagenetic conditions toward those existing in the epizone ;
both the crystallinity and the composition of the Hite are taken into
consideraron. Many examples are provided in the work of DUNOYER
de SEGONZAC (1969) n the scope of several evolutions.
TRAUTH, SOMMER and LUCAS (1968) have fixed up some ap-
proaching vales of crystallinity for the ilute. They have proposed
an acuate ndex o based on the measurement (in mm) of the
thickness of the 10A reflection at half-height above the background.
::i ANCHIZONE Three varieties of illite are proposed : ////fe with an acuate peak
4 (Ip.a.) where the ndex has a valu equal or lower than 3 ; illite with
-VT-AM-:* ^.-.V.-.WT- large foot (or large peak) (lp.|.) with a correspondng ndex valu
xl;: ;:x -:'-^: <::: xxix of about 6 ; open illite (le, Iv, M varieties of LUCAS, 1963) where
3.5 the ndex has a valu equal or above 10.
THOREZ in several papers (1970 ; MULLER e al., 1973) has used
TRAUTH ef al. (1968) ndex and the ESQUEVIN's (1969) method
x:l:'.
EPIZONE n an attempt to fill up the evolution of the Hite during the weathering
of a sediment rch in ilute (figure 9). The ntensity of the weathering
can then be followed on account of modifications that take place
both n the octahedral layer, and in the crystallinity of the illite.
Other authors (CHAMLEY, 1967 ; WEBER, 1970, 1972) have also
l(
proposed comparable methods of analysis.
BIOTITE '( BIOTITE + ' i PHENGITE'l 1)
' MUSCOVITE ' ' MUSCOVITE MELLIERES and PEREZ-NIETO (1973) used another parameter for
the estimation of the crystallinity in sedimentary Hites. Their opening
Figure 8. - Illite characterization by the acule n d e x and the
Al2O3/FeO + MgO compostion of the octahedral layer (after ESQUEVIN, status" (figure 10) is measured by the ratio : Eo = 100
1969, and DUNOYER de SEGONZAC, 1969). Evolution of the crystallinty ST
and composition of the Hite from the diagenetic or weathering zone where ST is the total surface of the 10A reflection above the
toward he epizone. background, and S|, the surface of the normal reflection centered
on the 10A apex. The latter surface is measured after having fixed
up the symmetric branch of the reflection towards the low angle
IJ002) side comparatively to ts profile towards the high angle side of the
1(001) diffractogram. The measure is performed after Ca-saturation and
subsequent glycolation.
WEATHERING
.15
10 ACUTE INDEX
Figure 9. - Diagrammatic representaron of the Hite evolution during the Figure 10. - opening state of illite after MELLIERES and PEREZ-NIETO
weathering (after THOREZ, 1973). Vertical axis : Al2O3/FeO + MgO ESQUE- (1973), in sedimentary Hites :
VIN's ratio in the octahedral layer based on the intensities ratio (002)7(001) ; St-S|
horizontal axis : subdvisons of the acuate ndex la of the ilute, based on the EQ=100 ST
thickness of the 10 reflection at half-heght above background : Hite with Sj=total surface of the 10 reflection above background ; S| = surface of the
acute peak Ip.A.) with la3mm ; Hite wth enlarged foot (lp_|_)with Ig 6mm ; normal reflection of the (well-crystallized) illite centered on the 10 ; the
open illite, with la equal or above 10 mm. (A) = domain of Hites with a surface s limited, on the high angle side of the diffractogram, by the
muscovite composition ; (B) = domain of illites with a phengite compositon ; descendng curve of the reflection ; on the low angle side, the shape of the
(C) = ilute with a muscovite + biotte composition ; (D) = Hites with a biotite reflection is delimited by drawing the symmetncal branch of the high angle
compostion at the level of the octahedral layer (ESQUEVIN, 1969). side of the reflection. Sample pretreated with Ca, and glycolated.
15
Of course all these crystallinity ndexes are not to be considerad
as reliable measures with the crystallography of the mineral. But
they are useful when one has to deal with mportant series of
samples wherein sensitive modifications may appear in the shape
of the basal reflection of the ilute component, accordingly to certain
evolutions in the degree of the metamorphism or of the wea-
thering. In practice these measurements whathever the method
selected are easy to perform f the clay mixture comprises the
ilute as the main component. If interference effects ooccur in the
interested X-ray reas (for nstance : presence of the 14of chlorite,
vermiculite, mixed layers etc...) the measure cannot be readily
achieved. There is also the case where pyrophyllite occurs with
illite (figure 11).
-1/2 height
Figure 11. - Interference of the (002) of pyrophyllite at 9.1 A, with the (001)
of illite at 10A during the evaluation of the acule ndex l a of the latter
mineral by DUNOYER de SEGONZAC's method of characterization the
crystallinity. (A) : case of a mixture where the basal reflection (002) of
pyrophyllite is not apparent and causes an enlargement of the illite reflection
towards the high angle side ; (B): case of a mixture composed of pyrophyllite
and illite; their basal reflections are very closed, causing an enlargement
of the low part of the reflections while twq distinct peaks appear in the high
part of the reflections respectively at 9.1 (pyrophyllite), and at 10 (illite). BACKGROUND
These minerals are composed of layers structurally similar to the at least 1000C and can still be detected in the X-ray pattern.
micas except that they are electrically neutral, and that there are
no interlayer cations (BROWN, 1961, p. 469). The identification of one of these minerals in a clay fraction should
Pyrophyllite, tale and the allied mineral m/nnesota/te are o readily be verified by the examination of the whole X-ray pattern (oriented
distinguished on the basis of their (002) reflection at 9.16A (pyro- aggregate and powder preparation). These layer silicatos might be
phyllite), at 9.30 (tale) at 9.53-9.6 (minnesotaite)o. The other also easly confused on the basis of their (002) reflection with
reflections of the (OOI) series are situated at : 4.58 (004) and some platy zeo/ites, with britt/e micas (margarite, clintonite, seyber-
3.05 (006) for pyrophyl/ite ; at 4.65 (004) and 3.1 O (006) for tite, xantophyllite) or with paragonite (see table below).
tale ; 4.77 (004) and 3.1 7 (006) for minnesotaite.
These three minerals can be differentiated on the basiso of their ame (002) (004) (006) (060) n d ()
(060) reflection, respectively at 1.49, 1.54 and 1.57 : pyro-
phyllite is dioctahedral, the two others are trioctahedral. The (OOI) Willemseite 9.4 4.68 3.12 1.524
reflections are symmetric, narrow and relatively intense. The basal
reflection (002) s stable upon glycolation (glycerolation), and Paragonite 9.6-9.7 4.82 3.20 1.48
heating.
Margarite 9.56 4.78 3.19 1.48
The behaviour (002) reflection can be expressed as follows :
Clintonite 9.65 4.82 3.29 1.500
Treatments N EG 500C (001) (002) (003)
IV - E - SMECTITES
IV- E - 1. - GENERALITIES
The ame smectite (former montmorillonite-saponite group ame) confirmed during the last 1975 Clay Conference held n Mxico.
s a new group ame forexpanding clay minerals : montmorillonites Smectite will be taken as a group ame while montmorillonite,
(M), beide/lite (Bei), nontronite (Non) (dioctahedral); and saponite beidellite, nontronite as a species ame.
(Sap) (saponite -trioctahedral- group). The use of the ame smec-
tite for minerals of the montmorillonite-saponite group is in ac- The identification of smectites in an oriented aggregate is based
cordance with a suggestion emitted n 1968 by the A. I. P. E. A. on the characteristic expansin of the (001) to about 1 7 (with
Nomenclature Committee. This proposition has been definitively ethylene glycol) orto 18 (with glycerol) ( Mac EWAN, 1944, 1946).
16
A differentiation between montmorillonite and vermicu/ite can be reflection since osome smectites do not provide a distinct narrow
achieved by pretreated Mg-saturated and then glycerolated sam- reflection al 10, after Ihe Irealmenl but a broad reflection with
ples ; montmorillonite is still expandable after the treatment while a lower intensity compared lo Ihe basal refleclion in Ihe unlreated
vermiculite remains stable at 14. sample.
The X-ray patterns of smectite are generally of poor quality and The behaviour of the basal reflection upon trealments can be
the harmonio reflections other than the basal one are usually more formulated as follows :
or less diffuse. The most intense reflection, corresponding to the
basal one, occurs n the d-spacing range of 12-15. Some
varieties exhibit in the natural sample a prominent 14-15 Treatments N EG Gl 500"C
reflection with a diffuse range (tail) down to 10. This is probably
(001) n d() 12-15 17 18 9.6-10
n relation with the degree of the hydratation, or corresponds to
some random mixed layering involving smectite layers as well.
It is often written that a 12-montmorllonite corresponds to a Na- Generally speaking if the X-ray pattern of Ihe orienled smeclite
montmorillonite with one H2O molecule, while a 14-montmorillonite s relalively poor in refleclions n the untreatedsample, the distensin
belongs to the Ca-varieties with two H2O molecules ; but the of the lallice by polyalcools causes somelimes Ihe appearance of
hydration degrees range influences greatly the (001) basal spac- Ihe other harmonio reflections at 8.5 (002), 5.7 (003), 4.2 (004),
ing, and the chemical analysis must then be performed before one 3.4 (005). Moreover n the natural (untrealed) sample Ihere often
may decide if the mineral s a Na- or a Ca-rich one. occurs a 4.7 reflection which must not be confused with the (003)
The heating provokes a collapse of the first order, the mineral of a chlorite al the same d-spacing. In many varieties of smectites,
becoming anhydrous with a valu of the d-spacng o equal to 9.6-10. the X-ray pattern of oriented aggregate exhibits an intense 14-15
In a parallel way a reflection occurs near 3.1 7. In sedimentary (001 \ reflection while other reflections of very low intensity occur
smectites the d-spacng after heating s generally situated at 10. at 5A and 3.05. Dioctahedral smectites have a (060) between
When smectite is engaged into a mixture with ilute, it is not ndicated 1.49-1.52, while trioctahedral smectites have Iheir (060) between
to try after heating a semi-quantitative evaluation of the smectite 1.53-1.54.
conten on the basis of Ihe increased common 10A (Ilite+smectite)
17
IV - E - 3. - CRYSTALLINITY OF SMECTITES (dioctahedral species)
An evaluation and characterzation of the crystallinity of smecttes t s probably not entirely independen! of smectite abundance in
can be brought about n two complementary ways. When one deals the sample. This ratio is thus not a true measure of crystallinity, but
with important series of smectitic clays in sedimentary or strati- a good first approximation .
graphical problems, t is of nterest to fix up the trends of the (001)
as exh'ibited n the X-ray diffractogram patterns of glycolated The present author has uses this parameter n analyses of several
samples. Such an objective can be achieved ndependently of the hundreds of samples where smectite was a dominant componen!
real composition of the mineral f nodetailed analyses are completed. of the mixture ; he has obtained good correlations of this ratio with
In particular two methods enable the characterization of the crys- the stratigraphical position and depth of the samples as well with
tallinity (BISCAYE, 1965; THOREZ, 1974 and unpublished data). the diagenetic effects affecting these samples. BISCAYE's para-
meter can be combined with crystallinity classes developed by
A measure of the crystallinity of the smectite has been proposed THOREZ (1974 ; unpublished data).
by BISCAYE (op. cit.) as an additional and useful parameter n
routine even if empirical. It is an observation fact that the 1 7 (001) The five "crystallinity" classes developed by the present author are
reflection of an expanded smectite s often broad, and may exhibit schematized in figure 13. They are based on the shape of the 1 7 A
several patterns (or shapes). BISCAYE's parameter consists to reflection, and on the occurrence/lack, shapes and intensities of the
measure both the height of the 17A reflection above the background other (OOI) reflections for glycolated smectite. Emphasis s put
(the valu is indicated by the letter p , p for peak), and the depth on the manner the (002) is developed as well-shaped (class A),
of the val ley ( v ); the latter is shown moreor less well-developed badly-shaped reflection (class C), as shoulder (class B) or as foot
on the low angle side of the 17 reflection. (class D) ; the same gradation occurs n a parallel way with the (003)
A ratio v/p s then measured on the X-ray diffractogram pattern of of smectite. To reinforce through these classes the modification
the oriented aggregate. BISCAYE's comments are following : affecting the shape of the (002) and (003), figure 13 compares the
Because of the low angle position of the expanded smectite re- diffraction effects with those of the (OOI) -1001) and (002)- reflec-
flection (5.2 26), the depth of the valley (v) depends upon where tions of illite (figured as blackened reflections) and taken as nternal
the low-angle side of the reflection ntercepts and contributes to standard. This s shown on account of the ubiquitous character
the general background radiation which rises exponentially at low of illite n many mixtures where smectite also occurs. In a parallel
angles. The broadest the reflection is, the highest s the 29 angle way the v/p ratio by BISCAYE (op. cit.) s also represented.
at which t will contribute to the background trace, and the shal- Figure 14 shows the way these two parameters, v/p and crystal-
lowest s the valley between the reflection (at or near 1 7) and linity classes, may be used graphically. There appears a good
background. As a consequence a perfectly crystallized smectite correlation for the disposition of the representative points when
will have a v/p ratio approaching the unity (value = 1). Poor-crystal- important series of samples are analysed providing the smectites
lzed materials will correspond to small fraction of the ratio until show some variability both n the v/p and crystallinity classes.
v/p=^0 because there does not exist any valley and the reflection The method has been apphed to several problems by the present
at 5.2 26 is appearing just as a shoulder. author; it has been possible to reach a better presentaron and
For very poorly crystallinities, the ratio v/p will be represented by differentiation between the different samples, series, stratigraphical
increasingly large negativa fractions (see figure 12). As the ratio positions, weathering evolution etc...
v/p is based upon measurements of vertical reflection parameters,
A B
Figure 12. - v/p rallo (< valley / peak height ratio) for the characterization of the c r y s t a l l i n i t y of smectites
(after BISCAYE, 1965). The measurement s achieved on the 1 7 peak of the glycolated material, p is measured
below the apex of the 1 7 reflection, above the background: v is measuring the importance of the depression
(valley) towards the low angle side of the 1 7 reflection. (A) : well-crystallized smectite; (B) and (C) : badly-
crystallized smectites.
18
WELL-CRYSTALLIZED
17 (001)
CLASS A CLASS B CLASS C
v/p>0 v/p>0
Positive Positive
I
10
I (003)
5 M
ENLARGED
FOOT
\
BADLY CRYSTALLIZED
CLASS E
ILUTE
v/p<0 REFLECTIONS
Negativa
I
5 M
MONTMORILLONITE
REFLECTIONS
Figure 13. - Empincal crystallinity classes of smectitic materials based Wp RATIO (BISCAVE, 1965)
19
Figure 15. - Differentiation between smectites (montmonllonites) varieties after selective treatments
(after THOREZ, 1975).
20
IV - E - 4. - IDENTIFICATION OF SPECIES
There s a possibility to reach an accurate Identification of the VEEN (1970) considers it likely that authigenic smectite is concer-
different species represented n the smectite group : montmon- ned when the basal spacing contrais to 9.5 after heat treatment.
lonite, beidellite, low charge and high charge montmorillonites, When the basal spacing only collapses to about 10, this might
nontronite, montmorillonite with Al- or Fe-inter/ayers, etc... This point out to a mica-derived smectite, the larger contraction being
objective can be achieved by complementary tests involving cation- probably produced by the presence of K-ions located in the smec-
saturations, solvation by ethylene glycol and glycerol, heating tite layers as an inheritance effect from the parental mica structure.
treatments, variability n the RH conditions.
Figure 15, taken from THOREZ's (1975) Laboratory Handbook,
provides the necessary data for such a differentiation. These data IV - E - 4c. - INTERMEDATE SMECTITE-VERMICULITE
result from a synthesls of the available ones n the literatura. MINERALS
To allow a quick check of the variability of the behaviour of the
minerals upon the different tests, the d(001) n has been repre- In relationship with the considerations emitted above about the
sented by a mnemotechnic code (see table 2). The reader is in a authigenic or mica-derived character of smectites, ROBERT and
BARSHAD (1972) have pointed out the occurrence of expandmg
right position to reach a step-by-step differentiation and recognition
of the different and possible varieties n the smectite group (dioc- minerals intermedate between smectites and vermiculites (see fig-
tahedral species only). ure 15, separated column on the right hand). Referring to the
behaviour of these minerals after cation-saturations (with Ca"1""1",
Mg ++, L+, Na+, K + ), solvation (with ethylene glycol, glycerol,
IV - E - 4a. - SMECTITES WITH HIGH AND LOW CHARGES and water), and heating (to 110C), ROBERT and BARSHAD
(op. cit.) have demonstrated these minerals to show :
A significant difference between low-charge and high-charge smec- 1) smectite properties thanks to their expansin with ethylene glycol
tites can be obtained on the basis of the contraction of the mineral (with Mg and Na), or with glycerol (with Mg);
after K-saturation (WEAVER, 1958).
BARSHAD (1954) has stated that saturation causes an expanded 2) vermiculite properties (see detailed data for the vermiculite in
lattice with a high negative charge to contract to d(001)=10.4, the next chapter) because of the one layer swelling effect with
while a lattice with a low negative charge contrais tod(001) = 1 2.4. Na ; the mineral has also a vermiculite behaviour on account
Also HARWARD ef al. (1969) stated that at 45% RH, d(001)=12 of its irreversible contraction when K-saturated and heated to
for a K-saturated montmorillonite, and d(001)=11.6 for a K-satura- 110C.
ted beidellite with a relative high tetrahedrally located charge. 3) intermedate characters between smectite and vermiculite be-
cause of the swelling with water for the Mg- and Na-saturated
samp/es, or the lack of contraction for the K-saturated sample
IV - E - 4b. - GENETIC DIFFERENTIATION BETWEEN SMECTITES : treated with water or glycerol.
LOW-CHARGE AND HIGH-CHARGE SMECTITES, AU- The results obtained by ROBERT and BARSHAD (op. cit.) lead
THIGENIC AND MICA-DERIVED SMECTITES. to some important conclusions about the identification of such an
intermedate material, n particular if one refers only in practice
Interpretation of the occurrence of smectites has also to be based to a selected cation-saturation and to a single method of solvation.
on the difference between authigenic smectites and those originated Indeed, as demonstrated by these authors :
by the transformaron from other minerals and phyllosilicates. Often
this differentiation is by mostly difficult because two categories of 1) with ethylene glycol and Na- or Ca- or Mg-saturation, the mineral
smectite can only be differentiated after further and detailed inves- corres ponds to a smectite that different ates itself from low-charge
tigations (WIERSMA, 1970). This genetic differentiation has been vermiculite ;
too often disregarded (WEAVER, 1958 ; SCHWERTMANN, 1962). 2) with glycerol treatment, the mineral s a smectite when only
Smectites derived from Hite though transformaron might be indicated Mg-saturated, or a vermiculite f only Na-saturated ;
by high-charge minerals whereas a large part of the authigenic smec-
tites are of the type with a low-charge. SCHWERTMANN (1962) 3) the heating to 110C, and the air dried specimen show a
considers also that low-charge smectites may not only have been a variation within the expansin when the mineral is saturated
formed by the breakdown products of volcanic material, but also with monovallent cations. The Li-saturation cannot be used for
from the weathering of augite, hornblende, and feldspars, and from the identification of the beidellite composition. (see paragraph
hydrothermal solutions. IV-E-d).
WEAyER (1958) considered mica-derived smectite to collapse with As an immediate consequence the above authors recommend two
K-satration to a d(001) = 10.0-10.4, while authigenic smectite determination tests at least, which offer several possible results
(volcanic derived smectite, weathered augite, hydrothermal smectite) a) Na- then Mg-saturation, with subsequent glycerolation : vermicu-
has a d(001)= 10.4-1 2.4 after the same treatment. If this treatment lite will always give a single interlayer complex, while smectite
does not result into a contraction, WEAVER (op. cit.) has considered will always largely expand (two-layers complex). But smectites
the mineral to possess a low octahedrally located charge. generated by the transformation of previous minerals (cf. smectite
For authigenic smectite, GALLITELLI (1962) indicated a K-contrac- of transformation ) will only fix one layer with Na, and two layers
tion to d(001)=11.6-12; GORBUNOV and GRADUSOV (1966) with Mg during the glycerolation treatment;
indicated a valu of d(001)=12.5A for authigenic smectites, and b) if there exists a double layer swelling with glycerol after Mg-
d(001)=10-11 for a mica-derived smectite after a K-saturation saturation, there s an indication for a further investigaron : K-satu-
treatment. ration, and heating to 110C.
The smectites originated by the weathering of dioctahedral micas
It thus appears from those data (also those presented in figure will contract to 70/4 and maintain their contraction to 10 when
15) that high-charge smectites show a stronger K-contraction tp solvated with water, glycerol and ethylene glycol. True (neo-
a d(001)=10-11 than low-charge smectites where d(001)=12. formed, authigenic) smectites will swell after the K-saturation with
K-saturated mica-derived smectites treated with glycerol have, on water, glycerol, ethylene glycol.
the other hand, a d(001 ) = 10-14 while authigenic smectites expand
to 18A. For low-charge K-saturated smectites QUAKERNAAT The intermedate character of these materials have already been
(1968) stated o an expansin to d(001) = 1 7 with ethylene glycol, and shown by SCHWERTMANN (1962) by a comparison of the pro-
d(001) = 17.8 with glycerol. For high-charge K-smectites the same perties between standard (Wyoming-type) montmorillonite and
author stated a d(001 )=1 2.4-1 2.7A after glycolation, and d(001)= almost pur montmorillonite extracted from soil. The latter mineral
12.4-14A after glycerolation. has shown a greater contraction after K-saturation in spite of its
lower catin exchange capacity. WEAVER (1958) has suggested
But the degree of K-contraction can be sensibly affected by the that the K-fixation is related to an excess of negative charges
possible occurrence of nterlayer materials and ntergrades (RICH associated with tetrahedral layers.
and OBERSHAIN, 1955; WALKER, 1957; RICH, 1968), or by
organic materials, or by other factors (GEBHARDT et al., 1966).
21
Figure 16. - Effects o amorphous material during the Li-test of GREENE-KELLY (1953), for the
distinction between montmonllonite and beidelte (after MURAVYOV, 1970, m THOREZ, 1975).
How amorphous collodal substance in natural montmorillonite can affect the sorption
properties.
Li-test may fail to give conclusive results without prior removal of amorphous material.
IV - E - 4e. - DIFFERENTIATION BETWEEN BEIDELLITE, Some comments by HARWARD ef al. (op. c/f.) can be provided
MONTMORILLONITE AND VERMICULITE about table 1 2 content.
The montmorillonite expands to the equivalent two-layer complex
upon solvation by condensaron of ethylene glycol or glycerol
Montmorillonite is characterized by a lower charge compared to
vermiculite, and substitution of Mg for Al in the octahedral layer vapour. Beidellite exhibits the one-layer complex with glycerol
while vermiculite has a higher charge arising from substitution of vapour, and the two-layer complex with ethylene glycol. The vermi-
Al for Si n tetrahedral layer. HARWARD and BRINDLEY (1964) culite does not yield regular two-layer complexes regardness of
have provided conclusive data for the differentiation of beidellite saturating catin, prior to the moisture or the solvating agent
from montmorillonite on account of the results of experimental action. A number of different complexes of vermiculite are obtained
wo;ks conducted n synthetic materials with exchange capacities depending on conditions of solvation (spacings at 13.6A, 14.OA,
in the range 0.95-1.35 meq/gr. These two authors have shown that 14.3, 15A and 15.3).
oeidellite is intermedate between montmorillonite and vermiculite. K-saturated vermiculite and K-saturated smectites (montmorillonites
with respect to the expansin upon solvation (see figure 15). and beidellites) both exhibit collapsed layers n a dry atmosphere.
From HARWARD and BRINDLEY's (op. c/f.) experiments it is Hydratation of smectites occurs at humidities above 20%, and
clearly established that a distinction can be achieved between results n poorly ordered diffraction mxima of 11-12. The K-
montmorillonite and beidellite on the basis of the swelling behaviour saturated vermiculite tends to retain the collapsed lattice, and
.."en certain definite conditions are imposed. Solvation with ethy- exhibits diffraction mxima of 10-10.6, with integral higher orders.
"e glycol or with glycerol (liquid) offers no olear differentiation. Some hydratation occurs as evidenced by the reflection asymmetnc
3 _ t with glycerol vapours, and Mg- and Ca-saturation with drying shapes, or by the appearance of a small 14.3 reflection at higher
at 105C. before solvation, montmorillonite expands to about humidities, although the collapsed spacing predominates. The ten-
16.7-17.7, while beidellite expands only or remains at about dency of vermiculite to hydrate decreases as the exchange capacity
14.2-1 4.6. increases.
Treatments
M M Bei V
saturation moisture solvation d(001) m A d(001) n A d(001) in A
catin conditioning
23
IV - E - 4f. - AI-SMECTITES AND AI-VERMICULITES ; adsorbed into the interlayer surfaces of the montmorillonite formed
Fe-SMECTITES in situ, and in part translocated from the A horizon. By these
interlayering and subsequent altrnate dessication and wetting
RICH (1968) has emphasized the occurrence of smectites and processes, the silicate layers in the B horizon will become so
vermiculites in soils and sediments that are frequently and partially firmly constricted that the glycerol molecules cannot enter; an
inter/ayered o r chloritized. Dioctahedral expansible layer silicates agressive agent as 4M HCI must then be used to dissolve the Al
are those most frequently interlayered, and hydroxy-AI appears to and Fe compounds and allow a subsequent expansin upon gly-
be the principal componen! of the non exchangeable interlayer cerolation.
material. But the main problem which we were dealing with is to unable
Vermiculites with such nterlayers do not collapse readily after a distinction between a partially interlayered vermiculite or smectite
K-saturation. The basal spacings of smectites show a collapse on from a randomly interstratified vermiculite-chlorite (cf. the (14c~14v)
their side, after having been K-saturated ; this collapse depends following THOREZ's (1975) codificaron ; see chapter VI), or smec-
on the charge density, humidity conditions (SAYEGH et al., 1965), tite-chlorite mixed layer structure (14M-14c). Partial collapse should
and presence of nterlayer material. reveal non-integral higher orders of the nterstratified material,
As reported by RICH (1968), low-charge smectites placed in a but higher orders of the nterstratified material, may also not
moist atmosphere do not easily collapse on K-saturation even if been distinct n the preparation as well. For the ntergrade
nterlayers are absent. Interlayered expansible layer silicates may not material, there is an increase n central scattering (Mac EWAN,
expand with glycerol solvation (JAMURA, 1957, 1958), but mont- 1950), and a broadening of the 10 reflection on K-saturation
morillonite expands when nterlayers are first removed and the and subsequent 550C heating (JACKSON, 1963).
clay is then Mg-saturated and glycerolated. The relative intensities of the (001) and (002) reflections are also
Some parallel and interesting features have been published by indicative of interlayering ; as the interlayering ncreases in the
WIKLANDER and ALEKSANDROVIC (1969) about what they cali a structure, the intensities ratio (002)7(001) (cf. I7/I14) of the
crypto-montmorillonite found in Swedish Earths and Podzols. mixed layers increases as well. But caution must be taken n the
The behaviour of this particuliar mineral has also been recorded evaluation of this above ratio when kaolinite occurs n the clay
in the stylised diffractogram patterns by THOREZ (1975). In the fraction ; then the 1(003)71(001) may sometimes be more useful.
B horizon of the examined podzols no true montmorillonite occurs On another hand chloritization may not be uniform n all the
after glycerolation. On heating at 450 and 600C, the 14.2 s nterlayers.
replaced by a broad reflection at 11,3. If the clay s prepared
with 4M HCI, a distinct and large montmorillonite reflection appears
that expands to 18. The authors have demonstrated that the ap- IV - E - 4g. - WYOMING-, CHETO, AND IRON-RICH
pearance of the 18 reflection is not caused by swelling vermiculite MONTMORILLONITES
and/or chlorite as these minerals are normally dissolved in 4M HCI.
GRIM and KULBICKI (1961) have published some routine Gritera
By acid treatment, thus, hydroxy aluminum and ron adsorbed on for a X-ray diffraction distinguishing between Cheto- and Wyoming-
and oriented between the interplanar surfaces are dissolved. This type smectites, for a mixture of these two types, and a iron-rich
makes it possible the entrance and adsorption of glycerol molecules montmorillonite. It is of nterest to recall here the importan! works
on the inner surfaces. The montmorillonite has thereby been trans- completed by GRIM and KULBICKI (op. c/f.), and in Strasbourg's
formad from a non-expanding material with d(001) at 14 into Laboratory of Profs. MILLOT and LUCAS about the possibility of
an expanding one with d(001) at 18. WIKLANDER ef al. (1969) differentiation between the different smectites by the DTA method,
have also found that treatments with TAMM's oxalate solution and combined with TGA. But those methods are only accurate if the
ditionite solution do not induce expansin of the d-spacings n analysed material s made of a rather pur smectite. Otherwise
glycerol while the HCI does it. interferences are taking place in the DTA curves, and lead to some
TAMURA (1958) has made similar observations of expansin from discrepancies as well misinterpretations. The thermal accidents
14 to 16-18 with glycerol and Ca-saturation after treatment with may occur at least with 10% of another clay mineral present n the
Na-citrate at 100C for a clay from certain acid soils. This author mixture.
has concluded the unknown mineral to be of montmorillonite type, The Cheto-type montmorillonite is characterized by intense and
modified by weathering. About the mechanism involved in the sharp (001), but the higher orders are always of about uniform
formation of the crypto-montmorillonite WIKLANDER ef al. (op. low intensities (in both cases without and with solvation). The
c/r.) evoked the possible leaching of hydroxy -Al and -Fe from the Wyoming-type montmorillonite has a sharp (001) reflection, and
A horizon to the B horizon. These hydroxy -Al and -Fe are then intense and sharp higher orders too, up to about the (006) reflection.
24
These higher orders are mainly developed after glycerolation. MATSUIand YATSU (1969) have published some Identification data
When a mixture of the two types does occur, the X-ray pattern allowing a quick differentiation between Fe-saponite (trioctahedral),
presents sharp higher orders reflections as for the Wyoming-type, Fe-montmorillonite and nontronite (both dioctahedral). The three
but somewhat less intense reflections : the (004) and (006) are minerals yield of course a high amount of Fe (Fe2O3 + FeO) the
relatively weaker than the (002), (003) and (005). Such a character total of which reaching 13% n the iron-saponite, 15% n the Fe-
is more pronounced in the mixture of the two types than in the pur montmorillonite, and more than 30% n the nontronite.
Wyoming-type mineral. The dioctahedral and trioctahedral characters are established on
Further distnction can been achieved after K- and Mg-saturations the basis of the d(060) : 1.53 for the Fe-saponite, while near
as shown in table 13. 1.50 for the two dioctahedral species. The diagnostic behaviours
of the minerals upon treatments can be formulated as follows:
IV - E - 4h. - DISTNCTION BETWEEN SOIL MONTMORILLONITE,
MS, AND SOIL BEIDELLITE, BeS Treatments
d(001) n N EG 500C MH4NO30 HCl(")
So/7 montmorillonite MQ exhibits a broad 14.5 (001) reflection in
the untreated sample. The glyce/ol solvation provokes the expansin Fe-saponite 15.2 17.0 10.0 12.4 collapses
of the basal reflection to 1 7.9 (the resulting reflection remaining
as broad as n the untreated sample), while a clear reflection, of Fe-montmorillonite 12 g tends to
low ntensity, occurs at 8.9. K-saturation causes a collapse to and nontronite
16 6
' (w?thGI) 99
' collapse
12.4. The heating treatment is also indicative : at 350C there
occurs a diffraction band between 10 and 14.1, with two distinct (*) : 1N NH4NO3, boiled 10 min.; (**) : 6N HCI, 30 min.
reflections, at the above d-spacings and with a more or less well-
developed v a l l e y between them ; at 550C, the basal reflection
has its apex at 9.7 with a clear asymmetry (tail) towards the low MATSUI and YATSU (1969) indicated also that the Fe-saponite
angle side of the X-ray diffractogram pattern. heated to 200C shows a doublet at 10 (asymmetric towards the
These behaviour can be formulated as follows : low angle side, and intense), and at 14.7 (weak and relatively
symmetric). In comparison with the Fe-saponite behaviour upon
diagnostic treatments, it seems of interest to complete the data by
Treatments N Gl K 350C 550C providing those related to a normal" saponite. VENALE and van
der MAREL (1969) have published their observations on saponite.
d(001) n 14.5 b 17.9 b 12.4 b 10+14.1 d 9.7 as At the natural (untreated) state, the d(001) is situated at 14.4;
the reflection being particularly intense and well-defined. Upon
b = broad ; d = diffraction band ; as = asymmetric reflection. glycerolation, the (001) shifts to 1 7.4 (intense and narrow), while
a weak (002) reflection occurs at 8.8f\. K-saturation provokes a
Upon glycerolation, and after Mg-saturation, so;7 beidellite BeiQ collapse of the basal reflection to 11.9A. Heating to 350C does
such as the one described by ROSS and MORTLAND (1966), has not affect the basal reflection neither n position (still at 14.4)
a well-defined and intense reflection at 14.8, with a lower intense or in intensity; but the heating to 550C collapses the basal
reflection at 9.1 [cf. the d(002)]. K-saturation causes a contraction reflection to 9.6. These behaviours are formulated as follows :
of the lattice which shifts to give a d(001)=10.1. The same beha-
viour occurs with a K-saturated sample when heated to 500C.
Of interest is the expansin of the basal reflection to 17.7 with Treatments N Gl K 350 550
the GREENE-KELLY's test; but the basal reflection then becomes
broader, and the (002) reflection appears n the X-ray pattern as d(001) n
a diffraction band with its limits between 8.85 and 9.5A. saponite 14.4 17.4 11.9 14.4 9.6
These behaviour are formulated as follows :
n = narrow ; b = broad.
25
IV - F. - VERMICULITE : V
IV- F- 1. - GENERALITIES
The Identification of vermiculite is often a rather difficult problem new intensity of the 10 ref/ection. The collapse after and upon
because of its variable behaviours upon treatments. The term heating must be checked very carefully because the mineral
vermiculite has been used for numerous minarais which, underX-ray rehydrates very quickly even at room temperatures, and this pro-
diffraction examination, exhibit different properties. vokes heterogeneity of the X-ray diffraction pattern during the
collapsing phenomenon, or a misinterpretation of the real clay
An important character of the mineral, in particular at the level of
its (001)around 14A, is its dependence on the degree of hydratation. composition.
As a consequence it is indlcated for an accurate identificaron to On another hand, the collapse upon heating s not completely achie-
work under uniform and definite relative humidities. ved when the mineral incorporates some hydroxy nterlayered
WALKER (1957, 1958) has shown thatthe most reliable Information material. Particularly in soil clays, vermiculite may be engaged into
can be obtalned wlth Mg-saturated sample prior to the X-ray dif- mixtures with other clay components. As a consequence it often
fractiqn analysis as oriented aggregate. Then, the basal reflection occurs that the d-spacing of the basal reflection remains higher
at 14A in the natural sample remains stable over a wide range of than 10 after the heating. This effect is due to the interlayered
contaminan! which has not been removed by the treatment. It s
relative humldities at room temperature (BROWN, 1961). Mg-verm-
culite resists to expansin with glycerol (WALKER, 1950 ; BARSHAD, thus indicated to Mg-saturate the material, and then to proceed to
1950). However f Mg-saturated vermiculites are not expanding a step-by-step heating : t^ie 14 reflection s replaced by a 11.6
during solvation, certain natural and partially desaturated vermicu- one at 100C, and by a 10A at 300C. But these latter d-spacings
lites may incorprate two nterlayered sheets of glycerol or of must be absolutely measured before the complete cooling of the
ethylene glycol and, as a consequence, expand to 1 7A. That s sample which has to be kept in the oven as long as possible. This
the reason to have a Mg-saturation when vermicullte clay mineral is necessary because the vermiculite is very sensitive within a few
is suspected in a mixture. seconds or minutes to moisture n the laboratory atmosphere. If
these cautions are not taken the vermiculite might well be inter-
Magnesium vermiculite is defined by its sequence of (001) at (001) preted as a faulse chlorite.
14, (002) 7.1, (003) 4.7, and (004) 3.5. The first (or basal
reflection) s characterized by an intense and more or less broad
reflection, while the other (OOI) reflections are of very low ntensity
or even are lacking in the X-ray diffraction pattern. The intensities Treatments
N EG 500
of the (OOI) reflections are thus n contrast with those of a chlorite d(001) n
(see chapter IV-G).
normal, naturally
Heat treatment causes a shift of the 14 spacing to 9-1O. In so/7 or artificially 14 14 9.6-10
clay vermiculites this shifting is often accompagnied by a net Mg-saturated vermiculite
decrease of intensity ; the new reflection s usually broader relatively
to the 14 for the untreated sample. In many examples analysed desaturated vermiculite 14 expansin 1 0 broad
by the present author, t has been significant that the 10 reflection vermiculite with hydroxy
obtained after heating was of very low ntensity, the collapse being 14 variable 12-14
nterlayered matarais
not restricted to the d-spacing alone bul marking particular/y the
26
= Strong
= Medium
W=Weak
Figure 1 7. - Basal refleclion (001) n lor vermiculite mmerals treated with water or glyoerol as
affected by the nature of nterlayer catin and the method of sample preparation (after BARSHAD, 1 958.
m THOREZ. 1975).
CATIN: Na
GLYCERAT/Q/V
Figure 18. - Basal reflection (001) in A for glycerolated tnontmorillonite minerals as affected by tho
catin exchange capacity, tho nature of the interlayer catin, and Ihe rnethod of sample preparation
(with prevention of drymg) (after BARSHAD, 1958. m THOREZ, 1975).
Figure 19. - Differentiation between vermiculite varieties -behaviour of the d(001) upon treatments
(after THOREZ, 1975).
29
In particular n the clay-sized vermiculites, but also n the well- In the high-charge varieties a Mg-saturated sample remains stable
crystallized (macro)vermiculite, replacement of the Mg + + by K+ upon either glycolation or glycerolation. The data of WALKER
causes a sensitiva contraction of the c-dimension of the lattice. (1958) are to be compared with those provided by BARSHAD
When K-saturated, and subsequently dried at room temperature, (1958) (figure 19).
the basal spacing originally at about 14 n the untreated sample
s reduced to about 10-11. Many glycolated verrniculites give X-ray patterns with irregular
WEAVER (1958) considers that clay vermiculite derived from the layer sequences and with a d-spacing of 15.4. Such.a d-spacing
mica weathering has a relatively high charge character, and s is intermedate between the ones of a low-charge and of a high-
contracting to about 10A after the K-saturation. On the contrary, charge vermiculite. As a consequence this variety of vermiculite
clay vermiculites generated by the weathering of non phyllosilicates probably corresponds to a random nterlayering of 14.9 and 16.2
(such amphiboles) or from volcanic material, have a low charge, d-spacings.
and show a limited contraction after the same treatment. These
non-mica derived vermiculites show a basal spacing, n the K-satu- Other behaviours characterize verrniculites. Mg-saturated sample
rated sample, which ranges between 11 and 12.4, probably does not expand normally; But low-charge vermiculites (when Ca-
because of the interlayered materials and contaminants. The ubi- saturated) swell to 17.6 with glycerol (or to 15.5-15.8 with
quitous character of the nterlayer contaminants n the expanding ethylene glycol). On another hand, high-charge vermiculites (when
lattice of some clay soil minerals and of mixed layer structures Ca saturated) remain at 14.4 with glycerol, while expand to
has now been clearly established. For nstance Al-interlayers occur 16-16.5 with ethylene glycol. As a consequence, if care is not
as positively charged hydroxy-AI polymers. Gibbsitic or o brucitic taken, some confusin may arise in the identification between a
nterlayers tend to decrease the relative intensity of the 14 reflec- low-charge Ca-saturated vermiculite solvated with glycerol, and
tion too ; on the other hand, they enhance that of the subsequent smectites with both low-andhigh-charges treatedin the same conditions.
low-ordered reflections of the (OOI) series. Also a Al-smectite which becomes Ca-saturated and then solvated
Another consequence of the latter evoked situation is a deviation of with ethylene glycerol provides a basa/ spacing of 14.6-15.3,
the vermiculite interpretation to one of chlorite, because of the more a behaviour which can be easily confused with a high-charge and
or less stability of the 14 reflection upon heating. a low-charge Ca-vermiculite that have been glycero/ated.
Figure 19 displays detailed data to attempt an accurate differen- It s nteresting to notice the behaviour of what can be named a
tiation between the varieties of vermiculite. The elaboration of the ch/oritized vermiculite. The normal or other varieties of vermi;
figure and its informations are based on a review from the literature, culite have their first order reflection collapsed to about 10-11
These data concern : the vermiculite in general ; the low-charge upon K-saturation. A similar range of d-spacing occurs when the
(V<0), and high-charge (V>c) vermiculites, vermiculites with Al- and K-saturated samples have been heated to 100, 300 and 550C.
Fe-interlayers. Also provided for comparison are the characteristic In a chloritized vermiculite, the K-saturation maintains the d-spacing
behaviours of Al-interlayers and of a smectitic mineral with Al- of the (001) at about 14. The Mg-saturation, followed by a heating
interlayers. treatment at 350C, provokes, on the other Jiand, a partial collapse
with a diffraction band between 10 and 1 4.
Upon glycolation low-charg^e vermiculites may exhibit a rather large
d-spacings from 14 to 1 7A ; some have typically a d(001) = 16.2.
Mg-saturation induces ad(001)=14-15 in the untreated (N) sample
that remains at 14, or ranges between 14 and 15.5 upon gly-
colation (14 or 15.5 upon glycerolation). WALKER (1958) indicated
some reactions of the vermiculites upon Mg- and Ca-saturation
(with subsequent solvation) that can be recapituled as follows :
16.3 vermiculite
with a charge of 150 meq/100g.
Mg+EG
14 to 15 vermiculite
with a charge above 163 meq/100g.
IV - G. - CHLORITES : C
V - G - 1. - GENERALITIES
Well-crystallized chlorites exhibit an integral series of basal reflec- already be entirely decomposed at a temperature of 450C (GRIM
tions at : 14(001), 7(002), 4.7(003), 3.5(004) and 2.8(005). and JHNS, 1954). This latter situation s somewhat embarrassing
But the precise position and intensity of these (OOI) reflections are because one of the proposed identification and differentiation test
deeply depending of the kind of cations occupying both the between chlorite and kaolinite s effectively based on the result of
octahedral and tetrahedral positions (see further the discussion on the heating which, in the range of 450 to 500C, decomposes the
this problem). kaolinite.
The d-spacings are not affected by glycolation or glycerolation. Another characteristic behaviour of the chlorite upon heating to
Upon heating to 500C, the intensities of the (001) reflection are 500-550C is the more_or less complete disappearance of the even
enhanced o while its position s slightly shifted to a lower valu orders at 7 and 3.5, while the uneven ones, n particular the
(13.6-13.8) relatively to the original position in the untreated basal reflection near 14, remain more or less stable (excepted
sample. After the heating treatment, the other (OOI) reflections the slight shift towards the high angle side), and might moreover
decrease in intensity as the brucitic layer decomposes. But poorly be enhanced in intensity.
crystallized chlorites such as found n recent sediments, n soils, Chlorites occurring in the clay fraction (cf. clay-chlorte) are naturally
and in products of the weathering of chlorite-containing rocks, may and easily altered by weathering. As a consequence, defects occur
30
in the lattice that influence the relative ntensities of the (001) reflec- will deal with these peculiar mixed layers derived from the partial
tions. When the brucite layer becomes partly replaced by hydrated weathering of a chlorite structure.
cations during the weathering, the (001) reflection becomes dis-
placed towards the high angle side of the dffractogram after heating, The behaviour of a chlorite upon solvation and heating, can be
it may even not appear after heating because of the low thermal stability expressed as follows :
of the mineral. The easy collapse of the basal reflection might be
then confused with the one of vermiculite. Treatments N EG 550
More or less degraded chiorites, which show a 14 reflection n d(001) n A
the natural sample, that is not affected after solvation, may also
after the heating treatmentexhibit, n place of a single 14 reflection, well-crystallized
various scattering effects such as diffraction band (with ranges 14 14 13.8-14
chlorite
between 10 and 14), doublets, single but broad reflection at about
11, 12A, or 13. This behaviour indicates the occurrence n the soil-chlorite or
degraded chlorite various forms of collapse
chlorite lattice of unstable interlayer spaces which are similar to 14 14 that maintain the (001)
vermiculite. These unstable soil-chlorites are to be considerad, on with (vermiculite)
unstable nterlayers between 10 and 13
the basis of the heating treatment, more as random mixed layers
with residual chlorite layers (14c), and vermiculite inter/ayers (14v) ; collapsed (or decompo-
the representativo formula for such a random mixed layer can be soil-chlorite 14 14 sed at 450C)
shematized by : (14c~14v). Chapter V relative to the mixed layers
IV - G - 2. - VARIETS OF CHLORITE
According to the actual knowledge, chiorites group comprises Dioctahedral chlorite has been named sudofte by MLJLLER (1963) ;
trioctahedral, dioctahedral and di-trioctahedral minerals. After the the subgroup comprises also cookefte, wich is a Li-AI-rich chlorite.
recommendations of the A.I.P.E.A. Nomenclature Committee (Madrid Donbassite is considered as a di-trioctahedral chlorite.
1972), the layer of chiorites has to be considerad as one of the
2:1 type, but with hydroxyde layers in the nterlayer position. Usually the identificaron of the various species in the chlorite group
Representativo of the trioctahedral chiorites are Penninite, C/ino- is a difficult problem. There s a large variety of chiorites because
chlore. The nomenclature of trioctahedral chiorites is still characteri- of the wide possible range of ionic substitutions. Because of
zed by some arbitrariness. FOSTER (1962) has proposed a classi- extensivo solid solutions that occur n the group, there exist no
fication based on the crvstallochemical criteria. Other trioctahedral sharp boundaries between varieties even if some ames have been
chiorites comprise : Sheridanite, Ripidolite, Brunsvigite, Thuringite, used to define some of the species.
Chamosite, Kochubeite, Kmmererite, N imite. The classification of An effort to systematize the classification of chiorites has been
Cr-chlorites has been proposed by LAPHAM (1958); this author attempted by several authors (HEY, 1954; NELSON and ROY,
defines Kmmererite as a chlorite containing Cr3+ exclusively in 1958, and many others). Significant data have been provided by
the octahedral layer ; Kochubeite s considered as a chlorite in NELSON and ROY (1958) toward a systematization of chiorites
which Cr3+ s also localized in the tetrahedral layer. Ni-chlorite the results of which have also been published by WARSHAW and
has been named nimite (WAAL, 1970). ROY (1961).
Sheridanite Prochlorite
Daphnite
Ripidolite
Corundophyllite
Pseudo- Thuringite
thuringite
Amesite Amesite
Table 14. Classification of Mg-, Al-, and Fe-chlorites (after WARSHAW and ROY, 1961).
Rernark : classification based on studies by NELSON and ROY (1954, 1958), and HEY (1954).
Shuchardite is a nickeliferous normal chlorite ; Grovesite is a manganeso chlorite which may be either the 7 or 14 polymorph
Kmmererite s the Cr-chlorite where Cr substitutos for Al only n the octahedral positions.
31
It is difficult to achieve a comprehensive classification sheme for an excellent synthesis of all the available data. In 1972, BAILEY
chiorites because of the variety of chemical substitutions that are has published an importan! paper on the determinaron of chlorite
possible. Classifications are subject to change with advances in compositions by X-ray spacings and intensities. In particular this
our knowledge of the compositions, properties, and structures of author underlined the fact that the use of the (001) and (060) X-ray
chiorites noted BAILEY in GIESEKING (1975). Since TSCHERMAK's spacings, a method mentionned in the literature as empirical mea-
(1890) classification of chiorites there have been several other ones, sureof the tetrahedral and octahedral catin populations of chiorites,
the most used being, among the modern classifications, those by can show some pitfalls altough useful quantitative informations
HEY (1954) and by FOSTER (1962). (Figures 20 and 21.) obtained. On the other hand, relative (OOI) intensities yield, as
Several authors have also been dealt with the crystallochemical shown by BAILEY (1972), less reliable results that the spacing
aspects of the chiorites. BAILEY in GIESEKING (1975) provided method for octahedral compositions.
6.0
4.0
0.67 -
2.0
1.00
I
Th ur
Cham
0.8
Ripi Bruns Di ab
0.6
<M
o:
0.4
0.2
Sher Clino R;nn
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 4.0
Formula positions occupied by Si
Figure 21. - Chlorite species boundaries according to FOSTER (1962) (U. S. Geol. Surv., Prof Paper, 414, A-19).
Abbreviaion symbols : Thur - thunngite ; Ripi = ripidolite : Bruns = brunsvigite ; Cham = chamosite : Diab = diabantme.
Sher = sheridanite ; Clino = clinochlore ; Penn penmnite.
32
IV - G - 3. - X-RAY DIFFRACTION CHARACTERISTICS OF CHLORITES
The small sze of the partiles and their rather irregular crystal- 2) chiorites with two dioctahedral sheets : d(060)=1.49-1.50A ;
linity in c/ay-ch/or/tes provoke some diffuseness of the reflections, 3) less-crystallized layer silicates, compared to (1) and (2), with
and the absence of some ordinarily weak ones. Chiorites in which ncompletely developed nterlayer material.
the number of octahedral positions occupied by Fe-ions s not
exceeding 30% show mdium to strong intensities for the first A dioctahedral chlorite has been reported by HAYASHI and
five orders of the (001) series (BROWN, 1961). OINUMA (1964), with a d(060) at 1.509, and a d(001) at 14.18
Substitution of Fe for Mg in the octahedral layers provokes a which s table on heating and solvation ; the intensity of the basal
modification of the absolute as well of the relative intensities of the reflection is increased by a factor 5 to 6 on heating at 600C.
basal reflections (BROWN, 1955 ; BRINDLEY and GILLERY, 1956). the di-tri-chlorite category s represented by donbassite, but also
In a parallel way, increasing substitution of Al for Si displaces the by other types wherein the (060) is still at 1.49-1.50, and the d(001)
(001) reflection of macrocrystalline chlorite towards a higher angle. s stable upon solvation and heating. On heating this basal reflection
The (001) and (003) reflections are relatively weak in iron-rich increases in intensity, and s stable to temperatures of 550-600C.
chiorites as compared to the intensities n the magnesium-rich
chiorites. The even orders (002) and (004) are stronger. As pointed out by BAILEY ( n GIESEKING, 1975), during the past
In iron-rich chiorites the (001) reflection may lack because of its ten years, a large number of occurrences have been reported in
very low intensity. It also occurs n clay mixture that this basal sediments and soils of fine-grained, imperfectly crystallized diocta-
reflection s masked by the adjacent ones belonging to other clay hedral layer silicates that give a 14 basal spacing. These materials
components (as the asymmetric shape of an open Hite which is have been called : dioctahedral chlorite, dioctahedral vermiculite,
predominan! n the mixture relatively to the chlorite ; the occurrence swelling chiorites, intergradient chlorite-vermiculite, chlorite-like
of vermiculite, smectite, mixed layers the basal reflections of which mineral or 14-minerals, depending on their reactions to various
overlap the (001) of chlorite etc...). diagnostic tests. A majority among these materials appears to
On the other hand, Mg-rich chiorites have relatively equal intensities result from the precipitation of gibbsite-like or brucite-like sheets
n their (OOI) series of reflections. n the nterlayer spaces of preexisting degraded micas, or n
vermiculites, montmorillonites, or in' other mixed layers. The inter-
Sedimentar/ chiorites, as well those occurring n weakly metamor- layered material is often ncompletely developed as t is attested
phosed rocks, are ordinarily trioctahedral : with their d(060) at by their variable behaviour on heating, solvation and relative dis-
1.53-1.57. But dioctahedral chiorites have also been observed n solution. It s of nterest to note that such a 14 material may also
the nature, usually as^products of the hydrothermal weathering or be produced by reaction of a degraded mineral with organic matter
n some sedimentary environments and soils ; these dioctahedral when both present n the soil.
chiorites have their d(060) situated near 1.50, EGGLETON and
BAILEY (1967) have grouped the dioctahedral chiorites into three Two methods of study by X-ray diffraction can be used n order
different categones : to reach an accurate or possible identification. One s concerned with
1) chiorites with one dioctahedral sheet and one trioctahedral sheet: the oriented aggregates, the other, with random powder mounts.
d(060)= 1.49-1.51;
33
3) Sedimentary chiorite : found m sediments and of clay-sizes. The d(060) spacing at 1.49-1.50 is an important character of
It behaves rather as the two above described varieties. these dioctahedral chiorites.
4) Swelling chiorite (Cg) : the 14 reflection tends to become Dioctahedral chiorites exhibit an integral series of basal reflections
flatter and less pronounced than in normal chiorite.This isapparently of the (OOI) series such as the normal trioctahedral chiorites. Of
due to the fact that the layer tends to collapse somewhat between mterest is the fact that most of these dioctahedral chiorites have
the brucite columns. These swelling chiorites maintain a d-spacng a (003) reflection at 4.7 which s typically more intense that the
at about 14 but are slightly buckled, the reflections of these other reflections. The basal spacing remains stable upon glycolatio o n.
uneven planes being broader and weakened. Heating over 300C causes a gradual collapse of the 14.0A;
The basal reflection at 14 exhibits a broad base followed by a at 700C the d-spacing remains at 13.10. At an intermedate
small nflection near 1 2A. After glycolation, this reflection s replaced temperature of 500C it is noticed a marked increase in the intensity
by a large asymmetric reflection which culminates at 16.5 and of the basal reflection, and a reproduction in amplitude of the (002)
shows a gentle slope towards the high angle side. A clear defined reflection at 7/4. This behaviour is different than the one ordinarily
12 reflection may emerge from the background. On heating at observed for normal chiorites where occurs an increase in intensity
550C or after K-saturation,othe 1 4 reflection may be displaced of the 14A reflection accompagnied by a decrease in intensity for
to a lower valu (13.7-13.8) and exhibits a slightly asymmetric both the 7 (002), and 3.5A (004) reflections.
towards the high angle side as well. While trioctahedral chiorite s soluble in warm diluted HCI, diocta-
The asymmetry after the treatments s ndicative of the presence of hedral chiorite and kandites are relatively insoluble. GOMES (1967)
interstratified layers, some of them being more resistan! than the for a dioctahedral chloritegenerated bythe weathering of alepidolite,
others. Bucite islands remain in the interlayer spaces, and prevent has observed the extraordinary resistance of the mineral to HCI
a complete displacement of the basal spacing on heating ; this gives attack, even f the treatments were done with 1N, 6N and 12N HCI
rise to the slope towards the high angle side. solutions in a boiling water bath for varying periods of time.
The displacement of the reflection at 14 upon glycerolation (or PATTERSON and HOSTERMAN (1962) have also reported a highly
glycolation) proves the presence of some swelling layers. However aluminous chiorite that was not destroyed with 3N HCI. GOMES
the degree of swelling s less than for a fully swelling mineral (op. c/f.) has demonstrated that a Al-chlorite may be resistant to
such as a smectite. H u m p s observed between 10A and 7 treatment with 1N NaOH.
indcate a certain interstratification. The latter s more pronounced 9) Chamosites.
in true interstratified structures (regular, and random) mvolving Two types of chamosite have been recognized : a 2:1 chiorite,
chiorite and swelling chiorite layers (see chapter VI). and a 1:1 type (which should be called berthierine ) (BRINDLEY
5) So/7 chiorite (Cs) : such a mineral s characterized by a basal et al., 1968). BRINDLEY (1961) has discussed the structure of
reflection at 13.8-14 that remains stable upon glycerolation. After chamosite. BRINDLEY and YOUELL (1953) described ferrous and
K-saturation no change does occur, or only a slight decrease may ferric chamosites.
affect the basal reflection which collapse at about 13.4. On In nature there may occur mixtures of ferrous and ferric varieties,
heating there occurs a diffraction band between 10 and 13.8 as well of chlorite-type chamosite.
(350C), and a doublet 11+13.8A (550C). In the X-ray pattern only the basal (OOI) reflection usually shows
6) Swelling so/7 chiorite (Csg) : the basal reflection at about 13.2 rather diffuse shapes. But in rand_om powder mounts, a triplet of
becomes a doublet upon glycolation : a more intense reflection mdium intensity occurring at 2.40, 2.1 5 and 2.67A is diagnostic,
occurs at 1 7.8 with a hump or shoulder at 14. After K-satu- while a diffraction band is displayed at 4.5 that corresponds to
ration, or on heating an ill-defined reflection at about 12.8. the (02) une n disordered kaolinites.
Sometimes a remaining reflection occurs at 14A. After heat Chamosite s often associated with siderite, some of the d-spacings
treatment at 550C, the broad reflection is situated at 11.4 with of which coinciding with those of chamosite.
a remaining and less intense reflection at 13.8. Chamosite, an authigenic mineral (generally of the Ib chiorite poly-
type, see further in this chapter) exhibits a green colour (due to the
7) Chiorite with the behaviour of montmorillonite (C|\/|) (LUCAS, occurrence of the Fe ++)which is maintained n reducing conditions
1963) : in the natural (untreated) sample, the 14 reflection is very and in the presence of decomposed organic matter. On oxydation,
symmetric or slightly asymmetric towards the high angle side. Fe++ changes in Fe + + + : the diffractogram res m bles then that of a
The glycolation modifies the shape of the reflection while its apex disordered kaolinite. Chamosite has generally a rather poor crystal-
remains at the original d-spacing : the reflection becomes indeed line structure which is shown by only a 7 (001) reflection. The Ib
asymmetric, and broadens towards the small angle side. After chiorite polytype, n which Fe++ s found n appreciable amounts
heating, the asymmetry s reversed, the broadening being developed can be identified as either a disordered kaolinite or as a Ib chiorite.
towards the high angle side. The occurrence of an asymmetry, in In oriented X-ray pattern chamosite shows reflections at 7.07 and
this variety of chiorite, s related to the presence of certain inter- at 3.54A, as for a kaolinite. If one takes an X-ray pattern of a powder
layer spaces that are less stable, swell slightly upon glycolation, and mount, there occurs reflections at 4.54 (cf. (110) reflection), and
collapse in the same manner on heating. at 2.60 [cf. (130)] that distinguish the chamosite from the chiorite.
8) Dioctahedral chiorite (Co) the existence of dioctahedral chiorites If there also occur reflections at 2.60 and 2.44, the chamosite
has been comproved by several authors (BRYDON e al., 1961 ; can be mterpreted as of a ferric composition (BRINDLEY, n
MLLER, 1961; ENGELHARDT e a/., 1962; MLLER and BROWN, 1961).
KROMER, 1962 ; CAILLERE e al., 1962 ; HAYASHI and OINUMA, The d(060)=1.56 for ferrous chamosite, while =1.54 for ferric
1964; KOIZUMI and ROY, 1959; SUDO and HAYASHI, 1956; chamosite.
SUDO, 1963). AN the dioctahedral chiorites have been described The kaolin-type chamosite, on the other hand, gives an X-ray pattern
as Al-rich chiorites. The structural model of such silicates consists on natural and heated sample similar to kaolinite. The chlorite-type
of alternating pyrophyllite and gibbsite layers. MLLER (1963) has chamosite exhibits an X-ray pattern of a chiorite. That will say
proposed the ame sudoi'te for the dioctahedral chiorites. But there the kaolin-type structure of chamosite collapses at about 550C,
are also other chlorite-types, such as cookeite, which show struc- and becomes amorphous, while the chlorite-type structure shows an
tural characters between true dioctahedral members and true trioc- intensified 14 reflection, and does not collapse on heating.
tahedral members of the chiorite group.
IV - G - 5. - POLYTYPISM IN CHLORITES
It is not the topic of this handbook to deal with all the crystal- Asrecalled by BAILEY (n GIESEKING, 1975), there are 24 resultmg
lographic aspects of the chiorite group. The reader who whishes regular one-layer polytypes, designated la-1 through la-6,lb-1
to be nformed. in details on the subject should refer to several through lb-6, and so forth, depending on the type of nterlayer sheet
papers by BAILEY and BROWN (1962), BROWN and BAILEY (I or II), the position (a or b) of the nterlayer sheet on the initial 2:1
(1963), SHIROZU and BAILEY (1965, 1966), EGGLETON and layer, and the poston (1 through 6) of the repeatmg 2:1 layer on
BAILEY(1967), LISTER and BAILEY(1967), BAILEY (in GESIEKING. the interlayer sheet. Only 12 of these 24 structures prove to be
1975). truly different; the others are either enantiomorphic or equivalen!
34
by 180 rotation about Y. Two of the 12 unique polytypes are based 060
on a triclinic-shaped unit cell w t h a = 1 0 2 , and have triclinic 203 |+201
symmetry. Two are based on an orthorhombic-shaped unit cell with Si Hb
O - P - Y = 90, and have monoclinc symmetry. The remaining eight
polytypes are based on a monoclinic-shaped unit cell with P=97, 202
& 202
and include monoclinic symmetry and one triclinic symmetry repre-
sentative of each of the four structural unit types. Table 15 sum-
marizes details provided by BAILEY (m GIESEKING, 1975) for
S 204 005
II i Jl \, ,l
regular one-layer polytypes.
Equivallent Enantiomorphic
Symbol Space group Unique angle
structure structure
I
la-6 P = 97 la-4 - i 005
- -
lb-1
lb-2
lb-3
C2/m
Cm
C
P=90
P=97
a = 192
la-1
lb-5
-
-
! S |
lb-4
lb-5
C1
C
P=97
a=102
la-5
lb-3
lb-6
- ! 5 i S i, S i
lb-6 C1 P=97 la-3 lb-4 2.0 A 3.0A
llb-5
S i ii! * ; 1J I i "H
I lb-4 C P=97 llb-6 -
I lb-5 C 0 = 102 lla-4 llb-3
202
llb-6 C1 p=97 I lb-4 - 2.50
Ib (3=90)
i.
Table 15. Summary of one-layer polytypes in chlorites (after BAILEY
in GIESEKING, 1975).
J, ;H
Occurrence of structural units in natural chlorites (303 specimens
005
analysed by BAILEY and BROWN, 1962) :
Structure
llb-evon,
Ib-odd ,
p=97
p=90
Number of specimens observed
243
37 i
1.6
I
J I I I
2.0
I I I I i i i i |
3.0
Ib-even , p-97" 13
la-even , p-97 10 Figure 22. - Shematic X-ray diffraction paterns of four chlorite polytypes
lla-even, p=90" O (based on data of BAILEY and BROWN, 1962, p. 839). The mdexed, soid
lla-odd , P=97 O black bands are diagnostic for each structure. The diagnostic hoi bands
of Ib ( P=97) are broadened. (from HAYES, 1970, p. 288).
These polytypes are distinguishable by their (hOl) reflections in
the X-ray powder pattern. The differentiation between chlorite species can be achieved with
HAYES (1970) provides a sheme of diagnostic (hOl) reflections for DTA, and chemical analysis, both combined with X-ray diffraction
the four naturally occurring semi-random polytypes in sedimentary analysis (POST and PLUMMER, 1972). Each chlorite (Ripidolite,
rocks. As recalled by the latter author, the d-spacings and the Sheridanite, Clinochlore, Penninite) has a more or less distingui-
relativo intensities depend somewhat on the composition. It s rather shable set of reflections with definite intensities. POST and
easy to recognize polytypes by a visual examination and comparison PLUMMER (1972) have shown some good routme correlation
of the X-ray pattern given in figure 22 which has been based on between the above cited species on account of the 1(002)
data by BAILEY and BROWN (1962). HAYES (op. cit.) also empha- + 1(004)71(003) ratio, and the l(003)/l(005) (detailed data are given
sizes the difficulty of Identification of clay-size chlorites when they n the paper by POST and PLUMMER, op. cit.). As an example
become mixed with or are subordnate to other clay minerals, hereon, some of the results found by POST and PLUMMER (op.
principally micas and Hites, in a clay mixture. cit.) are here reproduced (table 16).
35
MARTIN (1955) has provided some data about chlorites identifi-
l(002)+l(004) 1(003) cation (Clinochlore, Proch/orite, Corundophilite, Leuchtenbergite,
Chiorite species 003] 1(005) Thuringite) found in soils. THOREZ (1975) has summarized
d n lowest highest lowest highest MARTIN's data and reproduced the positions and intensities of the
vales vales vales vales (001) reflections only both for the natural and the heated (550C/30
min.) samples (see table 1 7).
Ripidolite 4.79 6.53 2.23 3.20
Sheridanite 2.63 3.89 3.13 4.06
Clinochlore 2.15 3.16 3.10 5.43
Penninite 2.26 4.70
Cr-chlorte 2.25 6.66
Table 16. Correspondence between chiorite species, and the vales
of intensities ratio (after POST and PLUMMER, 1972).
N 550C/30min.
Chiorite species
d() I d() I
Table 17. (001) reflections : (positions in d(A) and intensities) of untreated and heated (to 550C)soil chlorites
[data after MARTIN (1955), modified by THOREZ, (1975)].
36
ascending section of the illite (001) reflection at 10A. It s conse- palygorskite ; 4) the same as 3) when mixed layers occur.
quently recognized with some difficulties when : 1) the amount But in these above problems there s always the possibility to
of palygorskite s small in the mixture ; 2) the other reflections of refer to an e/ectronic microscope examination which provides a
the mineral are not sufficiently pronounced to be observed, or are useful distinction between the fibrous and laths patterns of the
masked by those related to the associa;ed clay minerals ; 3) f palygorskite as compared with the usual irregular flakes of the
the 10A of a degraded Hite, with its asymmetric reflection towards illite.
the low angle side, nterferes with the reflection at 10.5 of the
IV - I. - SEPIOLITE : SEP
Sepiolte has a diagnostic reflection at 12 (cf.(110) reflection). Table 19 provides the d-spacings and corresponding intensities
Others reflections may be more or less pronounced at : 7.6, 5, of the X-ray pattern out to the 3 rea (data provided by HENIN
4.60, and 3.82. and CAILLERE, in GIESEKING, 1975) ; and CAILLERE and HENIN
The 12 reflection s stable after glycolation (or glycerolation), m BROWN, 1961).
with/without Ca- and K-saturation, and subsequent heating at 250C.
When the unsaturated sample is heated to 550C the 12A reflection
shifts to 10.
The behaviour of sepiolite upon diagnostic treatments can be
expressed as follows :
Table 19. Observed X-ray powder data for sepiolitejafter CAILLERE and HENIN, m BROWN (1961), and HENIN and CAILLERE in
GIESEKING, 1975) ; data are provided out to the 3 rea of the X-ray diffraction pattern.
LUCAS (1963) has indicated how to reach the identification of Table 20. Progressive shifting of the 12 sepiolite reflection to 10,
sepiolite when the heating treatment is proceeded step-by-step with possible simultaneous presence of both the two reflections at 12
(table 20). and 10A during the heating (LUCAS, 1963).
37
V. - SUMMARY OF BEHAVIOURS OF THE CLAY MINERALS
TOWARD IDENTIFICATION TREATMENTS
The results obtained by X-ray analysis after the three classical (glycolation or glycerolation, heating), may be relatively decisive for
determination tests for the basal reflections (001) of the current a gross identificaron. But it is indicated to proceed to a further
clay minerals are schematically presented n table 21. investigaron about the position in d() of the other (OOI) reflections.
Some data are summarized n table 22.
d-spacing in A
MINERAL SYMBOL 10 11 12 13 14 15 16 17
Kaolinite K N
EG
Chlorite C N
EG
500
Swelling Chlorite Cg N EG
500
Ilute I N
EG
500
Smectites M 500 EG
(Montmonllomtes)
Vermiculite 500 N
EG
Palygorskite PAL N
EG
500
Table 21. Vales of the basal reflection, n d(), for the current clay minerals, after the classical identification essays (N = natural,
untreated sample ; EG = ethylene glycol ; 500 = heating to 500C).
38
Vales (n ) of the characteristic reflections of simple clay minerals after
different treatments.
1 N 10 5 3,3 2,5
EG no changes
500
C
9 N 14 7-7,2 4,7 3,5 2,83
EG 17 8,85 5,85
500
550
same reactions as for normal chlorites
V N 14
(Mg-satured) EG 14 no changes
500 10
Table 22. Vales in d() of the characteristic reflections of the series (OOI) of current clay minerals, after various diagnostic treat-
ments (after LUCAS, 1963). (N = natural, untreated sample ; EG = ethylene glycol ; 500 and 550 = heating treatments).
39
UNTREATED SAMPLE d-spacing (in ) of the (001)
MINERAL COMPARED WITH
(Symbol) SATURATED SAMPLE 10 11 12 13 14 15 16 17 18
Untreated N
EG
500
I nr IWIi1)
Saturated with K or Mg N
EG
Gl
500
Untreated N
EG
500
Saturated with K or Mg N
EG
Gl
500
Untreated N EG
500
f~n
'-'Q
Saturated with K or Mg N EG
500
M .. r-f~\ p,|
Saturated with Ca 500
Saturated with K
500
500 N
Untreated
EG
\/<?v
(low charge) Saturated with K 500 N
Gl
Untreated 500 N
EG
\/-*>~
Table 23. Vales in d() of the basal (001) reflection of curren! clay minerals after treatments (without and with cation-saturations
with K + , Ca++ , Mg++ ) ( after QUAKERNAAT, 1968).
40
NATURAL-WITHOUT PRETREATMENTS Mg-SATURATION K-SATURATION
Ca-SATURATION
N EG GL 300
Vermcute
(high charge)
,,^
e
Vermiculite
(low charge)
^^
o *
Smectite c .
blT
(high charge)
M r
Smectite
(low charge)
Q
brT
,
^ L *j$
Table 24. - Coloured key for the routine Identification of current clay minerals, based
Beidelte BEI 1 on the behaviour of the basal (001) reflection after different treatments (after THOREZ,
1975).
*
VI. - QUALITATIVE DETERMINATION OF MIXED LAYERS
VI - A. - GENERALITIES
Simple clay minerals are composed of layers of one type. The Besides monomineralic clay samples (and mixtures of discreet clay
structure of a layer is the critenon for ts classification and iden- minerals) that exhibit their own series of (OOI) reflections (see figure
tification. The latter s generally concerned with the position of the 23), another type of mixture exists. It concerns the interstratification
basal reflections, and with ts possible alteration after various of clay minerals and corresponds to the interstratified or mixed layer
teatments. minerals and structures.
001 Mixed layers are usually built up by layers of two mineral types,
but some of them are characterized by the combination and inter-
004 003 002 stratification of three different types of layers as well. They have
MMBRALA
basically the same crystal structure as for simple clay minerals,
but they differ from these by amount and nature of the (inter)layer
populations.
Theoritically and practically the number of combinations (or possible
modes of interstratifications) in the mixed layers materials is very
large since any of the simple clay minerals (i////fe : I ; vermiculite :
V ; chlorite : C ; montmorillonite : M ; beidellite : Bei etc...) may
002 001 become interstratratified in binary systems of interstratification. It
MINERALS
B& C s less frequently encountered mixed layers nvolving more than two
components. Besides the nature and number of clay minerals
intervening in the interstratified clay minerals, one must take other
factors into account : the fypes of ordering, the proportions of
different layers, the degree of crystallization and the partile size
distribution of the components.
Mixed layers have occurrence and abundance that have not to be
003
recalled. They have been mostly recognized in soils, but also in
REGULARLY 02 sediments and as producs of the weathering (deuteric and hydro-
005 004
INTERSTRA-
TIFIED
thermal). They may be more or less easily produced artificially
MINERAL d u ring laboratory experiments through the weathering of well-cristal-
(B-C) lized simple clay minerals.
As reported by Mac EWAN (1949), three types of interstratification
occur n the nature : 1) regular (ordered) ; 2) random ; 3) with
segregation.
RANDOMLY Any nvestigator of an interstratified material hinges on the ability
INTERSTRA- to dentify it with the more accuracy as possible. But his ability
TIFIED is often limited thanks to an inadequate knowledge about the manner
"003"
,10Q2,,STRUCTURE
002
, the determination must be conducted, or because of the very large
(XB-YC) 01 range of combinations that exists n the mixed layers. In addition
to these two factors, there also occur structures the components
of which have a more or less distinct zonal distribution (GJEMS,
1967). As recalled by this authorthe layers ofmicrocrystals forming
the individual zones may be insufficient in number to give X-ray
MIXTURE reflections and will thus appear amorphous (JACKSON et al., 1952),
OF while phases similar to those in a mechanical mixture are shown
MINERAL (XB-YC)+C from the individual mineral components when the zones are very
C pronounced >>.
If one takes into account the nature of the components (layers)
that can become two by two nvolved in an interstratifieation, at least
13 main types are possible and found n the nature. Table 25
provides all the cases within a short formulation based on the
DEGRADED symbol of the mineral (see further the meaning of these formula).
MINERAL
high angle sde low angle sde - compositions K-Bio l-Bei M-V C-Cg
of thve mixed I-C M-Cg
Figure 23. - Types of (OOI) sequences of clay minerals (stylised X-ray
layers I-V
diffraction patterns, providing the shapes of the harmonio reflections). (binary combinations) l-Vg
a) simple clay mineral, well-crystallized, with symmetric and intense reflec-
tions ; b) mixture of simple clay minerals ; c) regulary interstratified minerals K = kaolinite ; I = Hite (micas) ; M = montmorillonite ; Bei = bei
the (OOI) reflections of which have d() positions intensities and shapes dellite ; Sm = smectite ; C = chlorite ; V = vermiculite ; Cg =
according to the same characters for the simple clay minerals the layers swelling chlorite ; Bio = biotite.
of which are interstratified ; d) randomly interstratified structure charac-
terized by badly-defined reflections, with a plateau shapes n many Table 25. Possible types of interstratification for binary combina-
cases and an irrational sequence of (OOI) reflections ; the superlattice tions of the various layers of simple clay minerals (after THOREZ,
structure is ordmarily missing ; e) aspect of a mixture of a simple clay
1975).
mineral and of a randomly interstratified structure ; f) degraded mineral
(i. e. Hite) with asymmetrical reflections (tailing reflecions).
42
The table 25 does not indcate of course the regular or random Data n table 26 are based on STOCH (1972), and are slightly
stacking, types for the degree of interstratification, or the law of modified after recent results provided by the literature. STOCH
repetition. In fac the above symbolism has been mtroduced here in (op. c/.) has attempted to represent all the combinations of two
place of long descriptions : kaolinite-montmorillonite ; kaolinite- different layers. The subdivisin considers the stacking character
biotite ; llite-montmorillonite, etc... Further in the text t will be (regular, random), and the di- or trioctahedral character of the
emphasized howan accurate descriptive notation of the mixed layers material. On the right-hand along the oblique line limiting the
can be presented for these of regular and random types of mixed diagram, are represented the layer structures composed of homo-
layers. topic layers with different interlayer cations. The latter selectively
fill the nterlayer spaces (interlayers); the homotopic layers may
STOCH (1971) has published a table (26) displaying a more comprise different amounts of water molecules between the layers
complete subdivisin of the known nterstratified clay minerals. themselves with the consequence that different vales n d-spacings
may also occur n the mixed layers. Interlayer spaces are either
occupied by simple cations only (micas), or by fairly hydrated cations
(smectites and vermiculites), or by a brucite-type layer (chlorites).
The character of the occupying cations determines the size of the
nterlayer space, while the binding forces between the layers
determine whether interlayer are more or less resistant to various
determinaron agents such as ethylene glycol, qlycerol, or heat.
As t has been recalled n the case of simple clay minerals, the
nterlayers alone unable the determination of the valu of the d-spac-
ing ; this valu s measured directly on the X-ray diffraction pattern
at the level of the reflections. The variations in the d-spacings are
taken into account for the determination of the mineral groups.
Such a procedure permits a rather quick distinction between
families of clay minerals, but not necessary between and among
the species being grouped into a specific family.
This brief review s represented here to show that there are no basic
a = crysalline structures
differences between simple and nterstratified minerals. The main
built up of heterotopic differences are in the mode of stacking ofstructura/ly identical layers,
layers. and in the nature of the cations occupying the various possib/e sites.
=
"~" b crystalne structures X-ray diffraction analysis makes it possible the determination of the
built upof homotopic
layers but with iner-
stacking of the layers within simple clay minerals, regularly nter-
layers filled n a dif- stratified minerals, and randomly nterstratfed structures :
ferent manner.
1) In simple clay minerals the stackmg s made of dentical layers
separated by identical interlayers ;
+ = structures confirmed but little studied 2) n regularly interstratified minerals, the stacking s made of
* = polymorphic or polytypic modiflcation
R = regular ordering dentical layers separated by nterlayer spaces of two types which
D - random ordering / altrnate regularly ;
? = posslble mixed layers 3) n randomly interstratified structures, the stackmg s made of
1 = corrensie ; 2 = montmorillomte-chlorlte mixed
layers including tosudite ; 3 = allevardlte (rectorite): identical or different layers separated by different interlayers
4 = tarasovlte (LAZARENKO and KOROLEV, 1970); which show no repetition in the period following the c axis (see
5 ' THIRY (1973). further).
LUCAS (1963) recalls that the differences between the clay minerals
Table 26. Classification and combinations of nterstratified layers can be explained by ionio substitution within a fixed framework.
n all the actually known mixed layers (after STOCH, 1971, modified This author compares the 2:1 clay minerals to houses the archi-
by the present author). tecture of which remains fixed but the tenants of which change.
The identification of the mixed layers has often to face theoritical ingly to the method the sample has been prepared in particular
and practical difficulties due to : with or without pretreatments, some discrepancies are observed
1)the search for an accurate defnition (description) of the nter- n the description of the material because crystallochemical modi-
stratified clay minerals with a simple notation system : after fications may have been induced in the analysed material.
having proceeded to the identification tests (so/vation, cation- 3) the large range of combinaisons in the mixed layers built on one or
saturations, heating), it often occurs that several notations exist two (sometimes three) components. These components are made
for the description of the same material n the literature ; that of different clay minerals (I, C, V, M, Bei, etc...) nterstratified n
leads to some confusions about the notation to take into consid- a regularly or n a randomly manner, with different degrees of
eration. There s thus a lack of the standardizaron for the interstratification of one component with the other.
description of the mixed layers. THOREZ (1975) has attempted One must also take into consideraron the variable degrees of
to offer a system of notations that unables this objective. It also crystallinity, the size distributions of the partiles, the relative
occurs that different descriptions are given fot the same material proportons of the components. All these factors may induce a
[(see Mac EWAN and RUIZ-AMIL, n GIESEKING, 1975 ; and van variability in the shapes, intensities and positions of the ref/ec-
der MAREL (1964)] i.e. for the synonyms in mixed layers built up tions belonging to the various interstratified clay minerals, n parti-
of chlorite layers). cular f moreover the effects of solvation, heating and cation-
2) the lack of uniformization during the sample preparation. Accord- saturations are considered as well.
43
4) an incompleta set ofdiagnost/c determination ofthe nterstratified exist presently several books and papers dealing with this subject,
materials. Classic tests as solvat/on and heating are not necessary and discussing the problem of the recognition and nomenclature
sufficient to unable an accurate Identification. It is often indicated (among the main authors to be cited are Mac EWAN and BROWN,
tooto perform complementary tests in particular cation-saturations 1949, 1950; Mac EWAN et al., 1961 ; WEAVER (1955, 1956),
(with subsequent so/vation and heating), acid attack etc... to reach LUCAS (1963). The bibliography in THOREZ (1975) provides
a better evaluation of the composition, mode of stacking, quan- a detailed list of references on the subject.
titative and reciproca! participations ofthe components. The d(060) The identification of mixed layers presents difficulties f one does
is also to be checked. not pay sufficiently attention to a series of criteria or aspects related
to them during the X-ray diffraction analysis.
The nterstratified clay minerals state genetic and nomenclature
problems similar or more difficult to solve relatively to those in The mixed ayer provides X-ray patterns of oriented aggregates, with
simple clay minerals. The complexity, variability and nomenclature definite series of (OOI) harmonio reflections that do not correspond to
of nterstratified clay minerals and structures have given rise to any simple clay minerals. The recognition of the nterstratified clay
numerous dscussions. The abundance of these materials in minerals is consequently based on :
different environments (soils, sediments, weathering) imposes to 1) the number of layers : a factor that ntervenes in the unit-cell,
the mineralogists, geologists, soil mechanicians and others, to and nfluences the basal spacing by displaying vales of the
achieve the most perfectly the practical and complete characteri- basal (001) reflection higher than 24 ;
zation. 2) the nature ofthe components (layers and interlayers) ;
It is however out of the scope of this chapter to provide the reader 3) the repartition of the layers (1:1, 2:1) which can be provided with
an exhaustive statement about the mixed layers structures. There more accuracy by the Fourier's transform method for nstance.
VI- C - 1. - GENERALITIES
The minerals are formed by the stacking of generally two layers The number of layers per un it ce 11 is given by the g reate r thickness
types. Each layer is characterized by the structure of a simple clay which s obtained by multiplying each of the d(A) valu of the (OOI)
mineral such as Hite (mica), chlorite, vermiculite, montmorillonite, reflections of the mineral by the serial number, i. e. f the (001) s
beidellite, swelling chlorite, thus moreover involving di- and/or equal to 28A, the series of harmonio reflections will be : (002) = 28/2
trioctahedral varieties. = 14, (003)=28/3 = 9.3, (004)=28/4 = 7, etc... . In practice the
The stacking is perfectly ordered, and gives rise in the X-ray numbering of the dfferent (OOI) reflections s achieved n this
diffractogram pattern of an oriented aggregate to a regular period manner. In a parallel way, the verification may be achieved by
perpendicular to the (OOI) plae (along the c axis). The period is multiplying the d(A) of the corresponding order (as measured in the
equal to the sum of the period of the composing layers that form X-ray pattern) by the serial number in order to check also f the
the theme of repetition. This can be expressed by: result of the multiplication s equal or near the d(A) of the (001)
reflection. The more regular nterstratified mineral the more identical
d(OOI)AB = d(OOI) A +d(OOI)B are the results of the multiplications for all the (OOI) reflections.
A and B designating the two layer components. When the thickness of the theme s established, it becomes easy
to calclate the number of composing layers having a defined thick-
The basal reflection (001) of the nterstratified clay minerals occurs ness of 10, 12, 14. However the calculation must be repeated
as a superlattice reflection with a d-spacing equal to the sum for solvated and heated samples at least, n order to get the most
of the d(001) of the A and B components as expressed in the accurate dentification of the layers. Stability, swelling and/or col-
formula: lapse of the (001) (superlattice reflection) and of (002) reflections
d(001 )AB = d(001 )A+d(001 )B are importan! both for the diagnose of the mineral and the measure
and verification of the X-ray pattern (where the other (OOI) reflec-
The regularity in the stacking is also indicated by the presence tions are exhibited). Complementary data about the composition
of a rational series of (OOI) reflections up to the 10th order in some of the mineral are sometimos indicated by reference to the results
cases. Each of the (OOI) reflections of the minerals corresponds, of complementary tests (cation-saturation).
for its d-spacing, to a d(A) position related to the submltiplos of It is also more or less difficult to assign only and firmly the
the basal (001) reflection, in other words, to 1/2, 1/3, 1/4, etc... of distribution of the different sheets and layers of the mineral on the
the thickness of the repetitivo motif as expressed m the formula : basis of a simple X-ray diffraction analysis ofthe oriented aggregate.
It s indicatd to refer to the calculated curves (Fourier transform)
d(002)AB=d(002)A+d(002)e ; d(003)AB = d(003)A+d(003)e ; etc...
by Mac EWAN ef al. (1 961)
44
the two appropriate letters are linked by a hyphen : (I-C) will thus being similar of a smectite. Differentiation between montmorillonite
mean a regular mixed /ayer llite-ch/orite. If t s need, species and beidel/ite can be achieved by complementary and appropriate
can be also described, such as (Ser-Su) for a regular mixed /ayer treatments such as those indicated n thechapter IV-E. By convention
composed of sericite and sudo/te /ayers. A further descripton may in the proposed notation system, the capital letter M will indcate
be completed by 1:1 designating the proportion of the component a smectite (group ame) or a montmorillonite (species ame) if the
layers. A letter D can be added to the formula : composition (beidellite, montmorillonite) is fixed. If the d(060)
(C-M)o desgnales a dioctahedral regular mixed ayer chlorite- indicates a trioctahedral or a dioctahedral smectite, the capital letter
montmorillonite. A peculiar chemical character will be designated will be respectively designated by : Sap and M.
in the formula by placing ts chemical symbol in front of the formula : V : the layer spacing of 14A is unaffected after glycolation (glyce-
Al (C-M) will desgnate the aluminous character of the mixed layer rolation) n the natural sample or after a preliminary Mg-saturation ;
mineral. By convention, f no D s added at the end of the formula, the layer spacing collapses to 10A on heating, being similar to a
t will signify that the mixed layer mineral is naturally trioctahedral, vermicu/ite.
all the composed layers being trioctahedral. However the fact the
proposed notations can be concise by the use of capital letters The nature of the layer components can be implicity referred to the
instead of a complete description [(I-M) referring to a regularly geological (or pedological) background . For nstance, if there are
interstratified llite-montmorillonite clay mineral] presents of course, indications that the parental rocks (or soils) contain a peculiar
at this step of determination, a lack about the relative proportion of mineral such as sappnite (Sap), biotite (Bio), sudote (Su), etc..-there
the two components ; i. e. a mica-chlorite interstratified mineral can might be some probabilities that the layer components engaged, in
be expressed either by (Mi-C) or (C-Mi) until the real proportion of the mixed layers, in the vicinity of the unweathered rocks have some
layers has been calculated. As far this complementary data s not composition similar. In this case, a formula such as (I-C) or (C-M)
provided, the descriptive notation as here designed for the shorten- can then be better differentiated and specified : (I-C) s replaced
ng of the description, does not preclude at all about the real by (Ser-Su); (I-V), by i. e. (Bio-V) ; (C-M), by (C-Sap); etc...
proport/ons of one component relatively to the other.
Pair combinations of these layer types provide different regularly
In the case of regular mixed layers minerals, f one excepts the interstratified minerals.
descriptive formula such as (Ser-Su) where the symbols refer to
definite layers of clay minerals (i. e. sericite = Ser; biotite = Bio ;
saponite = Sap ; montmorllonite = M ; beidellite = Be ; sudote = Su) d(A) of layer M
for the other representative formula, the symbols (I, M, Bei, etc...)
refer, on their side, to layers having the same or similar behav/ours minerals (I-C) (l-Cg) (I-M) (l-Bei) (I-V) (Mi-C) (Mi-Be)
(upon diagnostic treatments) as the corresponding simple clay (Mi-M) (M-V) (Phlog-V) (Ser-Su) (Bio-C) (Bio-V)
minerals. (C-Cg) (C-M) (C-M)o Al (C-M)o (C-V)
(Cg-M) (Talc-Sap) (Mi-ALL)
I : the layer spacing has a valu of 10A n the natural sample, and (Bei-hydrous Mi) (Bei-V) (C-Sap)
is not affected by either glycolation ( glycerolation) or heating. It
behaves as an ////fe (with not marked sweiling character). Table 27. Examples of the variability in layer composition for re-
Mi : the layer component has the behaviour of a mica (Mi), the 10 gularly interstratified minerals (after THOREZ, 1975).
basal spacing of which s stable upon treatments. I = Hite ; Mi = mica ; C = chiorite, Cg = sweiling chiorite ; M =
C : the layer spacing of 14 s stable upon glycolation (glycerolation) smectite (undifferentiated) or montmorillonite ; Bei = beidellite ;
and heating, being similar to a c/7/or/fe. The d(060) provides moreover V = vermiculite ; Phlog = phlogopite ; Ser = sericite ; Su = sudote ;
the dioctahedral or trioctahedral character. Bio = biotite ; Sap = saponite ; All = allevardite ; Hydrous Mi =
hydrous mica; D = dioctahedral.
Cg : the spacing of 14 in the natural sample increases to 16-1 7
upon glycolation (1 7-18 after glycerolation), but remains unaffected
on heating, being similar to a sweiling chiorite. If an interstratified mineral such as (I-C) is combined with simple clay
M or Bei : the layer spacing of 12-15 (generally ndicated by a minerals in a mixture, i. e. with ilute and chiorite, the notation ot the
d-spacing of 14Aforthe commodity of the notation) i n creases to 1 7 A association will be expressed by : I, C, (I-C). The comma separates
upon glycolation (glycerolation), and decreases to 10 on heating, the different components of the clay association.
45
MINERAL d(002)n 10 11 12 13 14 15 16 17
(I-C) N
EG
500
N
(l-Cg) EG
500
N
(I-V) 500 E Q
(I-M) 500
(C-V) 500 N
EG
N rr
(C-Cg)
500
(V-M) 500 N EG
(V-Cg) 500 N EG
(Cg-M) 500 N EG
Table 28. Position n and behaviours of the (002) reflection n some of the main types of regularly
interstratified mnerals after glycolation and heating to 500C.
d(001) i n
Composition
N EG 500C
(I-C) 24 24 24
(l-Cg) 24 31 24
(I-V) 24 24 20
(I-M) 24-25 27 20
(C-V) 28 28 24
(C-M) 28 31 24
(Cg-M) 28-29 35 24
(C-Cg) 24 31 28 Table 29. Highest d-spacing in A of the (001) for regularly inter-
(V-M) 28 31 20 stratified minerals (after VIVALDI and Mac EWAN, 1960; LUCAS,
(V-Cg) 28 30-31 24 CAMEZ and MILLOT, 1959 ; Mac EWAN and RUIZ-AMIL in GIE-
SEKING, 1975 ; THOREZ, 1975).
46
Thanks to the period of the structure it s possible to distinguish different types. adjacent to it. Then the sequence s expressed by
n regularly interstratified minerals, two mineral groups. AABBAABB or AAABBB (figure 25). As a consequence, it appears
The first group displays a structure wherein each layer A is for this different type of interstratification, that the number of
sandwhished between layers of type B (figure 25) ; the sequence dentical layers placed side by side must always be small enough,
can be expressed by ABABAS. Here the number of layers of type otherwise the structure would become one with regular segregation.
A is equal to half of the total number of all the layers constituting The second group of regularly interstratified minerals is characte-
the crystallite (the degree of interstratification of A with B equal rized by a degree of interstratification other than 50%, but still
50%). In the same group are also included mixed layers minerals produced within a regular repetition of a certain theme with a
whose degree of interstratification is still 50%, but n which the representative stacking like ABBABB or AABBBAABBB.
layers A may either have one or two other layers A, or a layer B of
100
%
A
A
O A
B
100 A A
B
B<
B
A
B
A A
A
100 A B
B
A
Figure 24. - Illustrating the way in which each rpflection migrates and Figure 25. - Eight types of mterstratification of A- and B-layers. Regularly
changes shape n randomly interstratified strucrure. The further apart the nterstratified minerals: alternating ABAB ; AABBAA : AAABBB ; ABBABB :
mxima for the pur phases are in reciproca! space, the more the curve AABBBAABBB ; segregated material : alternating AAAABBBB ; randomly
of the reflection movement levis out for intermedate compositions, at interstratified structures : alternating ABABBAAB, and ABAABBB, etc...
the same time as the reflection becomes diffuse (after Mac EWAN and
RUIZ-AMIL in GIESEKING, 1975).
47
VI - D. - RANDOMLY INTERSTRATIFIED STRUCTURES
VI - D - 1. - GENERALITIES
The materials are formed by the random stacking (not subdued to Then by connecting with a thick horizontal black line the two adja-
any law of repetition) of layers and (inter)layers of two or more types. cent reflections occurring at the closest position one to another
No rational series of (OOI) reflections s provided n the oriented ndependently of their serial number, t s possible to determine the
X-ray pattern. This s an mportant character : the materia/s are not regions of the X-ray pattern n which the diffraction effects are to be
true minera/s ; LUCAS (1 963) has proposed to have them designated found as single reflection, diffraction band or asymmetnc reflection.
by the terms interstratified structures (difices interstratifis, in In each of the determined point of the straight line there will occur
French). Moreover, it is not possible to give these nterstratified either a single reflection that belongs to the overlapping of these
structures a specific ame as for regularly interstratified minerals of the minerals A and B, or a narrow to enlarged diffraction zone
(corrensite, rectorite, tosudite, etc...). that replaces the two original but cise reflections of the minerals
The lack of periodicity along the c axis s expressed by the presence (layers) A and B. As the degree of interstratification of B with A
of irrational reflections (diffraction band and plateau, enlarged or ncreases from O to 1, the resulting reflection will shift from Si
asymmetnc reflections, ill-defined reflections of a rather low inten- toward 82, from 2Si toward 3S2 etc.
sity)of the (OOI)sequence.The first reflection, ntherange 10-17, Two remarks about this representation :
may be abnormal because of high intensity. In an nterstratified 1) In figure 26 the reflection zones 2S2 and 5S2 (belonging the
structure, the representative reflections take the place of the the component B of the nterstratified structure) are isolated. No
normal reflections that correspond to the two (or more) component shift does affect them ; only their shape and intensity will vary when
layers. the degree of interstratification (nameda) decreases from 1 to O,
giving rise to reflections that become flattened or that progres-
The determination of the interstratified structure s based on sively disappearing from X-ray pattern.
MERING's work (1949). The method concerns the plotting of the 2) The shift of a reflection s not linear. The curves representing
reciprocal vectors Si =1/di and S2=1/d2 on the same straight une the reflection shape and position n d(A) are in fact a function of a
(i. e. the sites of the reflections of the two simple minerals A and B) (that vares from O to 1), and can be calculated (BROWN and
on the X-ray diffractogram pattern (figure 26). Mac EWAN, 1951).
In a preliminary analysis, there will be not great error n assuming
that the peaks move linearly from the position for one pur compo-
nent toward the nearest position of the other component as the
proportions of the components alter (Mac EWAN, RUIZ-AMIL
and BROWN, 1961). This trend s expressed by the formula :
dm = dA+(dB-dA) (KUBLER, 1960)
Figure 26. - Schematic representation of the reflection zones of an inter- which allows a quick evaluation of the degree of interstratification
stratified structure formed of A- and B-types of layers (LUCAS, 1963). of B with A.
48
VI - D - 3. - DEGREES OF DISORDER AND CONSEQUENCES
Figure 27. - Schematic representation of the composition of a system consistmg of interstratified partiles,
and possible X-ray diffraction curve aspect for different mixed layers composed of A- and B-layers (interlayers).
d = degree of interstratification (vales from O to 1); n number of partiles with a given Q (modified
after KUBLER, 1961 : LUCAS. 1973 : in THOREZ, 1975).
Two cases of disorder can be considered (figure 27) : the disorder The summit of the reflection is at the dA position ; =10. but the
exists either m the particles or both in the partiles and n the clay resulting reflection shows a gentle slope (figure 27, 6) toward the
material itself. low angle side.
If the disorder exists only in the partiles, all of them give reflections It can be seen, on first analysis, how both the shape of the reflections
situated n the same d-spacing. The intensities of the resulting and the d-spacing can be provided by both the number of particles
reflections are high ;theirshapesare those of fairly narrow reflection occurring n the structure, and the degree of interstratification. For
types. Their d-spacings indcate the degree of mterstratification a comparison, if well-crystallized clay minerals are present in the
(figure 27, 4). In the case a constant degree of interstratification clay fraction, their (OOI) reflections are at a specific d-spacig, and
intervenes, the ntensity of the secondary reflections of the irrational the (001) exhibits a perfectly symmetric, narrow and intense reflec-
series (OOI) decreases rapidly from the lower to the higher terms tions (figures 27, 1 and 2) (i. e. at 1 O or at 14).
of the series. The greater the degree of disorder, the more rapid the
decrease. As a consequence, for highly disordered structures, The analysis of the asymmetry has been made by KUBLER (1961)
usually only the basal reflection will occur in the X-ray pattern. for randomly interstratified mica-montmorillonites (figure 27). As the
If the degree of order mcreases in the nterstratified structure, there distribution of the crystallites depends on the degrees of interstra-
should occur other reflections of the series (OOI), presenting an X-ray tification, different cases of shapes for the representative reflections
pattern of the interstratified structure with a progressive regularity can be observed. In figure 27, n represents the frequence of the
n the stacking of the components. There exists a continuous series crystallites, while a is the degree of interstratification or the number
of terms ranging from the complete disordered varieties toward of layers B interstratified with the layers A. Seven cases are discus-
the highly ordered ones ; the intermedate varieties can be termed sed by KUBLER (op. cit.) (figure 27, 1 to 7) :
almost regularly interstratified structures or minerals ". Figure 27, 1 :a = 0 ; unigue population of crystallites. The compo-
If the disorder exists both in the partiles and m the rock, the nen! A is only present (i. e. pur micas).
crystallites will show all the possible vales of the degree of Figure 27, 2 : a = 1 ; unique population of crystallites. The compo-
interstratification, and of the number of particles having the same nent B is only present (i. e. pur montmorillonite).
valu of a. Each partile will diffract for its own, and produces a Figure 27. 3 : a takes simultaneous all the vales between O and
d-spacing situated between those of the components A and B, at 1. and none population dommates the other.
d-spacings determined by a. Sin ce all the particles have a different Figure 27. 4 : 0<d<1 : unique population. Only one valu as for a
valu of a, none of the resulting reflections will become superposed. theoritical interstratified mineral.
No well-defined reflection does occur. All the radiations have rather Figure 27. 5 : 0<a<1 : the mximum population is statistical. If the
the same intensity, and a diffraction band (plateau) will be observed distribution s one of GAUSS type : m =true average.
instead of a single reflection. (Figure 27, 3). Figure 27, 6 : a m = 0 : the mximum population coincides with the
There are of course intermedate cases. Figure 27, 5 shows a pur component A.
particular distribution governed by a Gauss law : each partile Figure 27, 7 : a m ^1 ; the mximum population coincides with the
reflects for its own, but the ntensity of the radiation mcreases with pur component B.
the increase of the particles number with the same a. The resulting
effect is a reflection with an enlarged base, but with an apex In the case of randomly interstratified structures mica-montmoril-
dctcrmmed by the highest number of particles having the same lonites analysed by KUBLER (op. cit.), the asymmetries of the (001)
degree of interstratfcation. and (003) reflections are centrifuga! relatively to the (002). Upon
There are limited cases as for degraded Hites (KUBLER, 1961) glycolation, the reflection are not shifting, butthe change of intensity
where the partiles are formed by layers of a single type (micas). alters the shape of the reflections. These latter show a trend of
49
migration toward the low angle side. This can usually be demons-
trated by the decrease n ntensity of the (001) reflection, and by
the simultaneos increase of the background on the side of the Diffractogram
trace
low angles. In the mean time the (002) shows a hump ; the (003)
does not show any asymmetry, but s increased in ntensity. The
heating treatment collapses the asymmetries on the d-spacing
of the micas, with a parallel increase n the intensity relatively to
the original ones. Line diagram
1.8 L 45 005 M
B.9 0 03
mical composition, these authors conclude thatthere are three types 3.58 006
5 97
of interstratification : (1) random, (2) allevardite-like ordering, and 4. 51
i
13.44 2.97
(3) superlattice units consisting of three i/lite and one montmoril- 9.;3 I 3.0
lonite layers (IMII). By comparison of suites of calculated profiles I i
i
with the diffraction patterns of many samples of illite-montmorillo- 5.7 I 1
|
50
four possible three-component interlayer systems including the 15.4
10 (Hite), 12.4 (Na-montmorillonite), 14 (chlorite) and 15.4
(Ca-montmorillonte) spacings given by these layers at 50% RH.
Triangular diagram (figure 30) such as that proposed by JOAS
and BROWN (op. cit.) can be useful where multicomponent inter-
stratification s found along with short sequence of basal reflections.
For two-component systems, the edges of the triangle s used ;
for four-component systems a tetrahedron with four triangles is to
be used. This method s convenient for completely randomly inter-
stratification.
Figure 30. - First-order apparent spacings for the three componen! inter-
stratifications that can be formed from 10, 12.4, 14, and 15.4A spacings 154 15.4
(after JOAS and BROWN, 1959, also reproduced in GIESEKING, 1975). 0.9 0.8 07 0.6 0.5 0.4 0.3 0.2 0.114.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
A descriptivo codificaron for nterstratified structures has been reason the subscript O in IQ (designating the quality of the open
proposed by THOREZ (1967, 1973, 1975), a part of which being Hite) may be replaced by the subscripts C, V or M. This can be
nspired from LUCAS (1963). The nature of the layers and inter- done if the asymmetry and the foot of the reflection are not masked
layers is designated by different symbols which characterize and recall too much by the reflections devoted eventually to accompanying
the behaviour of the layers and nterlayers upon the diagnostic other clay minerals the basal reflections of which are situated n
treatments : the same d-spacing range as the f o o t of the 10A reflection. Three
types of degraded ilutes have been described by LUCAS (1963) :
1 ) 1 0 : nterlayer of 10 stable upon treatments, being similar in IC, IV and l|vl- They concern thus a form of random mixed layers
behaviour to Hite. that are intermediate between Hite (I), and more discrete random
2) 14c : interlayer of 14 stabie upon glycolation and heating being mixed layers llite-montmorillonites (figure 31).
similar in behaviour to chlorite.
3) 14Q or 14Cg : nterlayer of 14A ncreasing after glycolation, IC : The basal reflection at 10 in the natural sample exhibits an
but remaining stable on heating, being similar in behaviour asymmetry towards the low angle side, developed on the flank
to swe/ling chlorite. of the 10. This asymmetry remains stable after glycolation
4) 14y : nterlayer of 14, stable upon glycolation but collapsing and heating with its f o o t on the low angle side unchanged
after heat treatment, being similar in behaviour to vermiculite. and located at 14A. Because this foot remains stable at 14
5) 14M ( O r 14s) : nterlayer of 14 ncreasing after glycolation, and (and s closely related to the stability of the asymmetry), some
decreasing on heating, being similar in behaviour to montmoril- similitaries are proposed with the behaviour of a chlorite [(cf.
lonite. 14(N)-*14(EG)-14(500C)]. For this reason the subscript n
6) 7 : interlayer of 7 stable after glycolation, but destroyed on the ilute symbol, is specified as IQ. Indeed, this subscript C
heating, being similar n behaviour to kaolinite. does not indcate at all the presence of chlorite. If this .mineral
becomes associated in a mixture with IQ, it would be indicated
The above symbols indcate that the interlayers of the mixed layer by IQ, C (note the comma).
structures may have a behaviour like those of the corresponding IV : the asymmetry towards the low angle side and developed on
clay mineral Hite (I), chlorite (C), swelling chlorite (Cg), vermiculite the flank of the 10 reflection, remains stable upon glycolation,
(V), montmonllonite (M). When these symbols are used in a des- but is replaced by a narrow and symmetric reflection at the
criptive formula for an nterstratified structure, it does not preclude same d-spacing on heating. Because the foot of the asymmetry
that any discrete simple clay mineral is not present in the mixture provides some similitaries with the behaviour of a vermiculite
or even in the nterstratified structure : an nterstratified structure (cf. 14(NM4(EG)-10(500C) by the collapse on heating of the
might be generated by the weathering of a simple clay mineral ; distented interlayers, this variety of open Hite is designated
as a consequence some residual and intact particles might well by the symbol : IV-
still be preserved of the alteration while others are engaged n, and I|V] : the asymmetry on the lower angle side and developed on the
show n some nstances a modification of d-spacing due to the flank of the 10 reflection shows an ncrease of the background
distented process affecting the original layers of the mineral. and some swelling upon glycolation ; the asymmetry s
replaced by a narrow and symmetrical reflection on heating.
In the case of ////fe that undergoes an alteration the layers The movements of the 14A foot provide some similitaries with
become step by step intensively stripped of their original the ones of a montmorillonite (14(N)-swelling (EG) >10(500C).
K. A codificaron has been proposed by LUCAS (1963) that refers At the level of its distended interlayers, the open ilute behaves
explicitly to the opening character of the Hite chrystallites. The as a montmorillonitic material ; this is ndicated by the symbol :
stripping of the K determines the progressive displacement of some
of the interlayers from 10 to 14. The process provokes a modi- IM-
fication of the shape of the basal reflection at 10. The latter tends In the case of an nterstratified structure in which 10 layer
to become more and more asymmetric, with its foot situated near an/or 14A nterlayers (14c, 14y, 14Cg, 14|y|) are ntervening the
14 on the side of the low angles. The behaviour of the distended use of hyphen (outs/de and inside the parentheses), parentheses,
spaces after the treatments (glycolation, heating) allows to consider and the symbols : 14p, 14y, 14M, 14pg, 14|\/|, and I, C, V, M allows
and to compare the behaviour of the 14 foot reflection with similar to describe all the different types of inferstratified structures found
behaviours for chlorite, vermiculite, montmorillonite. There is the by several authors n natural clay samples. These latter comprise
51
clay material where the disorder may exist in the partiles or both 3)C-(140-14M)-M : The interstratified structure consists of :1) par-
in the partiles and n the material. Some examples, taken from tiles which are not affected by treatments ( = C) ; 2) partiles
THOREZ (1975) are here provided to Ilstrate how the notation all the interlayers of which expand to 1 7 ( = M) ; 3) interstratified
and description of the randomly mixed layers are constructed in partiles consisting of the above two types, with a degree of
a concise manner that emphasizes the type of stacking, the nature interstratification varying from O to 1.
and predominance of both the layers and inteHayers (figures 31 to 37).
52
VI - D - 4d. - RANDOMLY INTERSTRATIFIED STRUCTURES WITH asymmetries that modify the shape of the reflection. A similar
10 LAYERS AND 14M AND 14v INTERLAYERS situation intervenes with structure like (10-14v) where, also, the
basa/ reflection has its apex remaining at 10.
THOREZ (1967, 1973, 1975) has developed a specific notation for This first type of interstratified structures is of course more or less
the description of randomly interstratified structures composed by different n both their descriptivo transcription and X-ray pattern
Hite layers and swelling interlayers. The former are desgnated by than other mixed layers of the random type where the basal reflec-
the symbol 10, and the latter, because their similitude of behaviour tion is allocated, n the natural sample, at d-spacings higher than
with montmorillonite , are denoted 14(V|. If discrete Hite s present, 10. For nstance, there are some structures involving or composed
this will be ndicated by a separated symbol, I. Because there s of ////fe layers and montmorillonite (inter)layers that exhibit a basal
a rather continuous transition between stable Hite partiles, I, and spacing at about 12. On glycol this reflection splits into two
the nterstratified structure, the symbol I may be linked by a hyphen distnct reflections, one situated at about 10, the other at the low
to the representativo formula of the structure. angle valu. In this case it s rational to describe the material by a
somewhat different notation. The case is encountered in K-bentonites.
A complete sequence of transitional terms can be developed with If one must take into account the variation and relative amount of
defined notations : (10-14|\/|); lQi(10-14M), 10-(10-14|v|); 10-(1 14M interlayers in these structures, it s possible to adopt the system
10-(10-14M)-14M; (10-14M)-14M710-14M)-14M (figure 35). mtroduced by JEHL and LEIKINE (1968) : (|Q-14|y|), (10-14^),
From JLQ;(10-14|\/|) to (10-14|\/|)-J_4j\/|, there occurs a progressive (10-14M), (10-14[y|), (IO-MM). the underlining emphasizing the pre-
transition between structures where, firts, the ilute layers 10, are dominance of either the Hite layers or the montmorillonite inter-
largely predominant comparatively to the montmorillonite-like inter- layers.
layers, toward structures where these swelling interlayers are pre-
dominant.
Generally these structures exhibit in the natural sample a very asym-
metrical reflection toward the low angle side of the diffractogram REMARKS
pattern, but with its apex situated at 10 as for micas. On heating
this asymmetry is replaced by a narrow, more intense and more or As pointed out and shown in this chapter, randomly interstratified
less perfectly symmetrical 10A reflection. The different terms of the structures have a very wide range of compositions, diffraction
above quoted sequence of nterstratified structures are determined patterns, and behaviours upon the treatments. Such a situation is
by the characters pf the diffraction band that stretches on glycol possible, and s found in the nature, because each type of the
from 10 to 17 following the predominance of the inter- nterstratified structures is built up by two (or more) types of ele-
layers. mentary layers (and interlayers). Upon the different diagnostic
Of interest to note s the fact that Hite, I, can be associated to treatments, these interlayers behave like Hite (10), chlorite (14c),
the structure as well in the mixture. Such a character is shown by the treat- swelling chlorite (14cg), smectite (14|\/i), vermiculite (14v). Further-
ment with ethylene glycol, by a more narrow reflection at 10A (with more, there are different degrees of ordering in these materials.
a sensitively decreased intensity), that develops above or beside a Some of them are completely random, other tend to some regularity.
diffraction band related, on its side, to the interstratified structure. In the wide range of nterstratified structures, there are some of
Also smectite may occur in the sample, and may be identified by them which are composed of a clay mineral that undergoes different
a discrete 1 7 (on glycol), that is linked to the diffraction band. degrees of weathering. For these, the all weathering process is
based on the fact that progressively some of the layers become
Hlne PAQUET (1969) has found different terms in interstratified unstable and behave like montmorillonite or vermiculite, while the
structures where the ////fe layers, 10, are nterstratified with inter- parental clay s ilute (mica) or/and chlorite.
layers behaving like vermicu/ite , 14y. The sequence comprises
the following intermedate terms : l-(10-14\/)-V, (10-14v)-V, and An extensivo presentation of the variability among the mixed layers
|-(10-14v)-V. These interstratified structures are stylised in figure 37, exceeds the scope of this handbook or chaper. But the Laboratory
and are determined by the d-spacings, shapes and behaviour of Handbook published by the present author (THOREZ, 1975) has
the basal reflection (which d-spacing s situated at 10, 12, and 14) tried to provide a presentation of all the possible and noted cases
following the importance of the vermiculite interlayers n the inter- that exist n natural conditions. The reader, teacher or student, is
stratified structure. thus invited to refer to this Handbook to get an llustration of all
the characters shown by the variable mixed layers, both regular and
One can see the differences n both the notation system and dif- random. The combination of the present handbook with the pre-
fractogram patterns for the randomly interstratified structures. One viously published one provides a rational and didactic approach
type of structures is described with notations like i. e. 10-(10-14|\/|) to the problem of the X-ray diffraction analysis of the clay mineral,
or (10-14y)-14v because the geological or pedological conditions including the mixed layers minerals and structures. Mac EWAN and
have shown that these materials are generated after the weathering RUIZ-AMIL (n GIESEKING, 1975) have published complementary
of Hite or still show some parental links with Hite. In the case of data about the mixed layers, in particular some relative to the struc-
the (10-14M) structures, the main character s that the basal tural characters which has not be dealt here with n details in
reflection has always its d-spacing situated at 10 despite the order to not dupplicate the informations.
53
FORMULA
9 10 U 12 13 14 1? 20 25
REGULARLY d(OOI)=
INTERSTRATIFIED AB
MINERAL dA(ool)+dB(OOI)
2SA SB
u SA
J I I I J
54
FORMUL REGULAR MIXED LAYERS WITH C, C g , M V GENERAL
o
d(A) 8 9 10 11 12 13 14 17 20 25 30 3 9 10 11 12 13 14 17 20 25 30 ] 9 10 11 12 13 14 17 20 25 30
N 4 E(3 530
VS
A M
(C-V)R
2t}
28
W
24
1
i1
1', 15' ,5
-4
?
VS
s 21 31
B (C-M)R .
1 24
vw
W
|
1
<
4
14,5 12
VS
s 3
2t
34
24
c (Cg-M)R
1
W
vw
1
> i
14 1,5
vs
31
28
D 1 (Cg-V) R
1 1 24
W
vw
1 1
1<1,5 15,5
VS
2( 3 31
E M (M-V)R
vw
W
\
20
i
4-
KEY CODE MONOGR. N
REMARK:
IREFERENCE; VARIABLE 105
Figure 31. Position n d() of the (001) and (002) reflections for regularly nterstratified minerals :
(C-V), (C-M), (Cg-M), (Cg-V) and (M-V) after diagnostic treatments (ethylene glycol and heatmg). 55
FORMUU j (14C-14V)IRR VARIETS GlENERAL
0 .
d(A) 6 7 B 9 10 11 12 7 20 25 30 6 7 8 9 10 11 12 13 14 17 20 25 30
N OR EG 550 E
VS
c,v, (14C-14V)
s (14C-14V)
12 13
M
W
1
4
i1
550 14 A 550 F
VS
C* V, (14C-14V)
s
M 10 12
W
VW
ii
550
4
B 550 G
VS 14
C, V* V - (14C-14V)
S
L
M 10 12
W
VW
IM
550 _r
550 H
VS
C + (14C-14V) i C - (14C-14V) - V
s 2 14
LJ
M 10 14
W
VW
i
550 D 550
VS
C - (14C-14V) V*
s 12 Vt
M
]I
10
VW
~ I T
i
d(A) 8 9 10 11 12 13 14 1? 20 25 30 9 10 11 12 13 14 17 20 25 30 8 9 10 11 12 13 14 17 20 25 30
EG 550
14 15,5
14
12 14
C-(14C-14M)
14
vs 14 17 10
C-
(14C-14M) - M
d(A) 8 9 10 11 12 13 14 17 20 25 30 8 9 10 11 12 13 14 17 20 25 30 8 9 10 11 12 13 14 17 20 25 30
14
EG 550
vs
s
M
w
vw
15,5 14
vs
I
14
vs
- (14C-14G)
14
vs
c- 14 17
(14 C -14 G )-C G
w
vw
155
vs
12 14
I + (10-14M) - 14
I + 10 - (10-14M) (10-14M)-14M
10-(10-14M)-14M, M (10-14M)-14M,M
14 1? 20 25 30 14 1? 20 25 30 10 11 12 13 14 I/ 20 25 30
REFERENCE:
Figure 36. Schematic presentaron of the characteristic behaviour and shape of the < basal reflec-
60 tion of random mixed layers (10-14) upon dagnostic treatments (ethylene glycol and heating).
(10-14V) MIXED LAYERS VARIETIES
9 10 II 12 13 14 I/ 20 25 30 9 10 11 12 13 14 17 20 25 30 I 10 11 12 13 14 I/ - 20 25
12 PAQUET(1969)
(10-14V) - V
I - (10-14V) - V
62
SYMBOLS FOR THE TABLES 30-36
d-spacing m for the (001) of clay d-spacing in A for the (001) of clay
Symbols minerals & (002) of mixed layers Symbols minerals & (002) of mxed ayers Symbols Signifioation
^
- No reflection 13,5-13,8 S~\ Broad reflection
7 ~7 13,9-14,3
11 Diffraction band
OJ^
9-9,7
0
* 14,6-15,3 Doublet
1 9,8-10,1
e 15,5-15,8
L
Asymmetry towards
low angles
A 10,3-10,5
<x> 16 -16,5 A Asymmetry towards
high angles
Reflection with
V 10,6-11
0 16,8 17,2
J enlarged foot
A 11,2-11,7
17,3-18
*M#)
(#) Origin, n , of
the tailing reflection
3 i 12,5-13,3 v /*
^
/' '
Diffraction band
[i.e. (11-14)] + Variation of the d-spacing
for the basal reflection
63
NATURAL-WITHOUT PRETREATMENTS K-SATURATION
COMPOSITION 300 500
Table 30. Coloured key for the routine dentification of curren! regularly nterstratified
minerals, based on the behaviour of the (002) reflection after different treatments.
Comparison with the one of simple clay minerals (after THOREZ, 1975).
Composition Composition
EG 500 +(monogram n, in THOREZ 1975) EG 500 +(monogram n, in THOREZ 1975)
CHLORITE C
VERMICULITE V
CHLORITE + VERMICULITE C, V
(C-V)
**<)
C. (C-V)
C-(14 C -14 V )
V. (14 C -14 V )
+ (14Q-14 V )
V, (14 C -14 V ). C
SWELLING CHLORITE C
MONTMORILLONITE M
ic-c
(C-M)
(Cg-M)
C-(14 C -14 G )
C-(14 C -14 M )
C-(14Q-14 M )-M
Table 31 65
Composition Composition
EG 500 +(monogram n, n THOREZ 1975) EG 500 +(monogram n, n THOREZ 1975)
A PALYGORSKITE 24
v|) 85C
A
GLAU (20%M)21B
A 1 A (I-M) (20-25%M)
(10-14|v])-14M 89B
(10-14v) 70A
(10-14M) 95
(I-M) 98
(10-14^)870
JD)
D) k.(V)
I M 8 E / I + IM GLAU 19B
H M 84C
(10-14v-14M)
Tables 32 to 35 : Identification keys (after THOREZ, 1975).
1 T B.G. = Increase of back-ground.
I B.G. - Decrease of the ntensity.
66 Table 32
Composition Composition
EG 500 +(monogram n, n THOREZ 1975) +(monogram n, in THOREZ 1975)
(10-14 M ) / (10-14v-14M) /
10-(10-14M) 86 C
Table 33 67
Composition Composition
500 +(monogram n, in THOREZ 1975) EG 500 +(monogram n, in THOREZ 1975)
Ve 84 / (V-Mi)=(PHLOG-V) 151
Cs
2:1-2:2 Al(lnt.) g / Cs
(14c-14v) 113E
C-(14c-14\/) 113D
) 113C / C-(14c-14v)
CH2O
CM 54, 125A
C-(14C-14M)
OV^te I14C-14G)/C-(14C-14G)
(14 M -14 V )
C-(14 C -14 M )
Table 34
68
Composition Composition
500 +(monogramn,in THOREZ 1975) EG 500 +(monogram n, n THOREZ 1975)
e/ (C-M) 159
V / (not Mg-saturated)
(14C-14M)
(C-M)
(C-M) 121
C-(14c-14 M ) 128
(14c-14 M ) / (C-M)
) / (C-M) / Cq 53 /
C-(14 C -14 M ) 137
VAI / vFe
Cg + M / C+M
gs
(C-M)
SAP / M / BEI
(14)lEx / Ex(14)l g 13 / lg /
NON 20D, 41, 42 / Sm 38, 39 / BEI 40 /
GLAU 23 / NONFe 42 / Ms 43 /
BEIS 44 / SAP 46-48 / Bentonite 49
C gs 55, 56
Table 35 69
VIII. - DECREASING (001) IN d(A) OF PHYLLOSILICATES AND CLAY
MINERALS, AND (001) AND/OR (002) OF REGULAR MIXED LAYER
MINERALS - air dried state
71
d(A) : basal d() : basal
reflection Mineral ame reflecton Mineral ame
72
IX. - LIST OF THE (001) REFLECTIONS - (001) TO (006) - FOR CURRENT CLAY
MINERALS, INCLUDING MIXED LAYERS (Natural state)
43,75 (100) 21,8 (70) 10,55 (93) Tarasovite LAZARENCO & al. (1970)
30,5 15 7,37 6,06 (C-M)R SIAT & al. (1959)
30,5 (M) 14,5 (VS) 9.7 (W) 7,25 (W) (C-M)R EARLEY & al. (1956)
30,46 (90) 14,48 (100) 9,82 (25) 7,37 (55) 5,86 (5) (C-Cg)R STEINER (1968)
30,4 (320) 15,2 (240) 10,0 (3) 7,557 (20) 5.98 (3) Tosudite SHIMODA (1969)
30,2 (VS) 13,85 (VS) 9,45 (M) 7,09 (VW) 5,438 (W) (Mi-AII) MACHAJDIK & al. (1970)
30,0 (16) 15,0 (24) 9,96 (4B) 7,52 (4B) 6,01 (3B) Al, (M-O+R SUDO & al (1957)
30 (W) 14,4 (VS) (C-Cg) HECKROODT & al. (1965)
29,9 (48) 14,7 (100) 9,71 (8) 7.31 (10) 5,82 (3) (C-V)T SUDO & a l . (1969)
29,8 (10) 14,7 (15) 10,3 (4B) 7,18 (20) 4,95 (10) (C-M)R, Dioc, SUDO (1954)
29,7 (80) 14,4 (50) 9.66 (10) 7.3 (2) 5,72 (2) LI-AKM-OD BROWN & al. (1974)
29,6 (10) 14,7 (18) 9.8 (3) 7.32 (5) 5.99 (3) (C-M)p, Dioc. SUDO (1954)
29,6 (VW) 14,6 (VS) 9,8 (W) 7,18 (M) (C-Cg) VENALE & a l . (1969)
29,5 (S) 14,3 (VS) 7,12 (W) (C-M) SARKISYAN & al. (1972)
29,4 (M) 14,7 (VS) 7.4 (M) Corrensite PETERSON (1961)
29,4 (VS) 14,7 (VS) 9,8 (W) 7,30 (M) 5,8 (5) (C-SAP)R ALIETTI (1957)
29,2 (50) 14,6 (100) 9,73 7,3 (25) 5,9 (3) (M-C) BRADLEY & al. (1956)
29,2 (VW) 14,48 (VS) (Bei-V) HEYSTEK (1963)
29,0 (9) 14,6 (100) 7,26 (39) (C-V) JOHNSON (1964)
29,0 (100) 14,5 (71) 9,65 (8) 7,27 (6) (C-M) EGGLESTON & al. (1967)
29 14,2 9,7 7,3 5,9 (C-V) R BRADLEY & WEAVER (1956)
29 (30) 14 (100) 7,08 (60) (C-V)R BROWN B.E. (1967)
28,9 (M) 14,4 (VS) 9,6 (VW) 7,23 (M) (C-SAP)R VENALE & al. (1969)
28,8 14,3 9,5 7,14 5,76 Sangarite DRITS & al. (1963)
28.5 (21) 14,26 (100) 9,51 (7) 7,14 (46) 5,08 (3) (C-V), (Mg Saturated) JOHNSON (1964)
28,5 (W) 14,2 (VS) 9,43 (VW) 7,23 (W) (C-V)R WILSON (1973)
28,5 14,2 9,5 7,1 Corrensite LUCAS (1963)
28,5 (VW) 14 (VS) 7,1 (S) (C-V)R SARKISYAN & al. (1972)
28,44 (S) 8,08 (W) 5,94 (VW) 4,77 (W) (C-M)R + (C-Cg) ALIETTI & a l . (1963)
28,3 (M) 14,2 (S) 7,08 (W) 4,72 (M) 3,53 (S) Corrensite LIPPMAN (1954)
28,1 (W) 12,1 (VS) (Mi-M)R HAMILTON (1967)
28 (22) 16 (10) 11,5 (100) 8,43 (8) HyBio + 30%V FERLAJ & al. (1972)
28 (M) 14,27 (VS) 7,1 (M) (C-M) R FRANSOLET (1970)
27,6 (204) 14,1 (344) 9,72 (56) 7,15 (49) 5,75 (3) (C-EXP. Clay) 1:1 TETTENHORST & al. (1968)
27,3 (90) 12,4 (100) 5,06 ( 2 0 ) (Mi-M)R HAMILTON (1967)
26,77 12,45 5,06 (I-M) STEINER (1968)
26,3 (100) 13,4 (92) 9.1 (16) 5,2 (10) (Mi-Bei)R GALLEGO (1968)
26,1 (W) 12,8 (VS) (Bei-HyMi) HEYSTEK (1963)
25,8 (100) 12,6 (55) 8,49 6,32 5,02 (Mi-M)R SUDO & SHIMODA (1969)
25.8 (100) 12.4 (80) 4,3 (40) HEYSTEK (1954)
25,5 (100) 12,4 (100) 8.2 (30) 6.15 (10) 4,92 (60) HyBIO MIDGLEY & al. (1960)
25,2 (54) 12,25 (93) 8,33 (6) 4,95 (25) (Mi-V)R GRADUSOV (1971)
25.2 (30) 11,3 (100) 7,25 (2) 5,51 (5) 4,67 (4) (Mi-M) R HAMILTON (1967)
25 12,5 5 Rectorite
25 (S) 11,7 (VS) 5,03 (M) (I-M)R
24,8 (50) 12,4 (150) 8.3 (18) 5,0 (12) HyBIO EROSHCHEV-SHAK (1970)
d()l d()l d()l d()l d() I COMPOSITION REFERENCES
(001) (002) (003) (004) (005) (CODIFIED)
24,8 (VS) 12,5 (VS) 8,11 (W) 4,80 (VW) (SAP-TALC) ALIETTI (1956)
24,7 (100) 12,4 (50) 8 (5) Allevardite-Rectorite KOROLEV (1961)
24,7 (W) 12 (VS) 8,3 (VW) HyBIO VENALE & al. (1969)
24,5 (VS) 11,77 (S) 8,11 (M) 4,8 (M) (TALC-SAP)R ALIETTI (1960)
24,2 (VW) 12,36 (M) 8,01 (M) 6,09 (VW) 4,83 (VS) (Mi-Su)R SHIROZU & a l . (1971)
24 (25) 11,9 (100) 8,15 (4) 4,89 (18) HyBIO + 50% V FERLAJ Sal. (1972)
24 (VW) 12,6 (VS) 7,98 (S) 6,25 (W) 4,87 (S) (BIO-C)R EROSHCHEV-SHAK (1970)
24 11,2-12 ,4(100) 4,89-4,96 (20) Stevensite FAUST & al. (1953)
23,8 (VS) 11,8 (S) 8,1 (W) 6,09 (VW) 4,79 (VW) (TALC-SAP) VENALE & al. (1966)
23 (70) 12,3 (210) 8,03 (6) 4,87 (28) HyBIO EROSHCHEV-SHAK (1970)
22,8 (66) 11,04 (100) 5,22 (40) (Mi-Be)R GALLEGO & PREZ (1965)
15,85-14 ,05 (VS) 5,07 (W) 3,13-3,05(3) (Na-Ca)M ALIETTI & al. (1962)
15,4 (VS) 5,15 (M) 3,0 (W) Volchonskote 14M SARTORI (1967)
15,1 (100) 7.17 (20) 4,75 (66) 3,56 (31) Chlorite, (Dioc) : 1 4c : CD FUJII & a l . (1971)
14,8 (47) 7,325 (28) 4,844 (32) 3,59 (30) EXP. like Chlorite SHIMODA (1969)
14,4 (VS) 4,79 (VW) SAP
14,4 (M) 7,07 (VS) 4,714 (W) 3,535 (S) Ripidolite : 14c = RIPI POST & PLUMMER (1972)
14,38 (75) 7,18 (100) 4,79 (55) 3,60 (80) White penninite : 14c : PENN CERNY & al. (1965)
14,3 (60) 7,18 (180) 4,79 (100) 3,59 (100) Pennimte : 1 4c : PENN BRINDLEY (1961)
14,31 (68) 7,156 (103) 4,77 (74) 3,578 (64) Penninite : 14Q: PENN POST & PLUMMER (1972)
14,3 (35) 7,14 (65) 4,74 (40) 3,55 (15) Leuchtenbergite 14c : LEUCHT SAKAMOTO & SUDO (1958)
14,3 (70) 7,12 (100) 4,63 (70B) 3,56 (80) Clinochlore : 14Q: CUNO ASTM 19-749
14,2 (62) 7,14 (60) 4,72 (122) 3,54 (74) Al-Chlorite 14Q: (AI)C HAYASHI & al. (1964)
14,24 (64) 7,12 (100) 4,74 (48) 3,56 (68) Corundophyllite : 1 4Q : CORUN STEINFINK (1958)
14,2 (3) 7,1 (10) 4,68 (2B) 3,55 (8) Chlorite : 14c : o-hC SHIROZU (1958)
14,2 (7) 7,1 (10) 4,72 (7) 3,54 (10) Ilb-Fe-Mg Chlor 14c : (llb)(Fe-MG)C SHIROZU (1969)
14,2 (25) 7,1 (100) 4,74 (16) 3,55 (45) Nimite : 14c : NIM DEWAAL (1970)
14,2 (41) 7,13 (34) 4,86 (100) 3,53 (58) Sudoite : 14c: Su MULLER (1967)
14,2 (60) 7,14 (60) 4,72 (100+) 3,54 (74) Al-Chlorite: 1 4c : (AL) C HAYASHI & al. (1964)
14,19 (30) 7,094 (50) 4,73 (30) 3,547 (39) Clinochlore : 1 4c : CLINO POST & PLUMMER (1972)
14,16 (38) 7,08 (100) 4,72 (12) 3,54 (44) Ripidolite : 14p : RIPI SHIROZU & BAILEY (1965)
14,16 (84) 7,08 (100) 4,72 (21) 3,54 (59) Prochlorite : 14c : PROCHL STEINFINK (1958, 61, 62)
14,16 (78) 7,08 (147) 4,72 (72) 3,54 (96) Sheridanite: 14c: SHERID POST & PLUMMER (1972)
14,15 (35) 7,11 (95) 4,74 (90) 3,56 (95) Kochubete: 14Q: KOTSC BROWN (1961)
14,15 (8) 7,05 (10) 4,72 (6) 3,54 (10) llb Chlorite : 14c: MbC BROWN & al. (1962)
14,1 (60) 7,11 (70) 4,75 (50) 3,558 (50) Sheridanite: 14c: SHERID GILLERY - ASTM 7-77
14,13 (45) 7,13 (32) 4,71 (100) 3,517 (47) Chlorite, dioct. : 1 4 : CD VAN OOSTERWYCK (1968)
14,1 (7) 7,09 (9) 4,72 (8) 3,54 (10) Chlorite mono.: 1 4c : rnC SHIROZU (1958)
14,1 (90) 7,07 (100) 4,726 (30) 3,541 (60) Thurmgite : 1 4Q : THUR GILLERY - ASTM 7-78
14,1 (70) 7,07 (90) 4,72 (80) 3,54 (100) Leuchtenbergite: 1 4Q : LEUCHT SHIROZU (1958)
14,1 (10) 7,1 (10) 4,7 (10) 3,55 (10) Corundophyllite: 1 4c : CORUN GAUDEFROY & al. (1965)
14,1 (8) 7,05 (7) 4,7 (9) 3,52 (9) la Chlorite: 14c : (la) C BROWN & BAILEY (1963)
14,1 (50) 7,05 (100) 4,69 (50) 3,52 (90) Aphrosiderite : 1 4c : APHRO SHIROZU (1958)
14,1 (5) 7,05 (10) 4,69 (5) 3,52 (5) lb(90")Fe-Chlonte: 1 4c : (lb90")FeC SHIROZU (1969)
14,1 (5) 7,05 (10) 4,69 (5) 3,52 (9) Chlorite (orthohex.): 14c : o-h C SHIROZU (1958)
14,1 (8) 7,05 (7) 4,7 (10) 3,52 (10) Cookeite 14c : COOK BROWN & BAILEY (1963)
14 (90) 7,1 (100) 4,70 (70) 3,53 (100) Mg-Chamosite : 1 4c : (Mg) CHAM BANNISTER & al. (1945)
14 (S) 7,1 (VS) 4,69 (MS) 3,53 (VS) Mg-Chamosite : 1 4p : (Mg) CHAM JASMUND (1955)
14 (9) 7 (10) 4,6 (1) 3,53 (10) Mg-Chamosite : 14c : (Mg) CHAM BRINDLEY (1950)
14,0 (40) 7,08 (85) 4,75 (95) ,562 (100) Cr-Ni-Pennme : 1 4c : (Cr-Ni) PENN VARADARAJAN (1964)
13,7 (7) 7,04 (8) 4,68 (9) 3,51 (10) Sheridanite : 14c : SHERID JASMUND (1955)
13,6 (6) 7,02 (7) 4,7 (9) 3.525 (10) Sheridanite: 1 4Q : SHERID BRINDLEY & al. (1951)
13,6 (4) 6,9 (8) 4,65 (6) 3,48 (10) Prochlorite : 14Q : PROCHL JASMUND (1955)
13,6 (MS) 6,89 (VS) 4,62 (S) 3,48 (VS) Thuringite : 14c : THUR JASMUND (1955)
13,1 (6) 6,97 (9) 4,68 (9) 3,52 (10) Leuchtenbergite: 14Q: LEUCHT JASMUND (1955)
13,06 (VS) 6,18 (W) 3,83 (M) Na-Montmorillonite : 1 4|\/| : (Na) M ALIETTI & al. (1962)
12,4-11 ,2(10 + ) 3,5-3 (5) Stevensite : 14y : STEV BRINDLEY (1955)
12,36 (S) 8,01 (M) 6,09 (VW) 4,83 (VS) (Ser-Su) SHIROZU & al. (1971)
12,1-13(10) 4,78-5,2(1) Stevensite : 14|V| : STEV FAUST & al. (1959)
12,17 (100) 4,03 (8) 3,02 (M) Stilpnomelane: 12 : STILP GAY (1966)
d(A) I d() I d(A) l d(A) l d(A) I COMPOSITION KI u w N :;
(001) (002) (003) (004) (005) (CODIFIED)
11,2 (33) 5,06 (45) 4.50 (30) (Mi-M) SHIMODA & SUDO (1969)
11 (VS) 4,47 (M) (I-M) BOCCHI & al. (1965)
10,1 (VS) 5 (VVW) 3,3 (VS) Biotite : 10 : BIO
10,1 (80) 5,03 (60) 3,35 (80) Muscovite : 1 O : MU KODAMA (1962)
10,05 (VS) 5 (M) 3.3 (VS) Ilute : 10: I HOWER & MOWATT (1966)
9,91 (S) 4,98 (S) 3,33 (VS) Lepidolite: 10 : LEPI LEVINSON11953)
9,65 (S) 4,82 (MS) 3,21 (VS) Paragonite : 9 : PAR ZEN & ROSS (1964)
9,604 (VS) 4,818 (VS) 3,218 (VS) Margante, trigonal: 9 : MAR DIETRICH (1956)
9,34 (VS) 4,56 (S) 3,11 (S) Tale : 9 : TALC ROSS & al. (1968)
9,21 (VS) 4,58 (S) 3,08 (VS) Pyrophyllite : 9 : PYR KODAMA (1958)
9,14 (M) 4,57 (S) 3.04 (VS) Pyrophyllite : 9 : PYR MOLLOY & al. (1961)
7,43 (8) 3,66 (6) Pecoralte : 7 : PECOR FAUST & al. (1969)
7,36 (18) 3,65 (16) Lizardite : 7 : LIZ MU.CHI & al. (1968)
7,30 (10) 3,65 (9) Clmochrysotile: 7 : C H R Y S KRASTANOVIC & al. (1967)
7,30 (100) 3,63 (100) Antigorite : 7 ANTIG HESS & al. (1952)
7,30 (100) 3,62 (100) Orthoserpentine : 7 : o SERP JASMUND & SYLLA (1971)
7,25 (100) 3,65 (100) Orthochrysotile : 7 : o CHRYS MONTOYA & al. (1963)
7,25 (100) 3,62 (100) Nepouite : 7 : NEP MONTOYA & al. (1963)
7,24 (100) 3,619 (100) Antigorite (Clay) : 7 : ANTIG BRINDLEY & al. (1971)
7.21 (VS) 3,60 (S) Greenalite : 7 : GREEN
7,22 (VS) 3,59 (VS) Kaolinite (disordered) 7 : Kd
7,2 (VS) 3,59 (VS) Ball Clay: 7 : K(b.c) MURRAY (1954)
7,19 (80) 3,59 (100) Amesite : 7 : AMES MONTOYA & al. (1963)
7,16 (10) 3,587 (10) Dickite : 7 : DICK NEWMHAM & al. (1956)
7,13 (100) 3,566 (66) Kaolinite : 7 : K DRITS & al. (1960)
7,11 (100) 3,55 (64) Al-Serpentine : 7 : (AI)SERP JAHAMBAGLOO & al. (1968)
7,07 (10) 3,52 (10) Chamosite : 7 : CHAM BRINDLEY (1951)
7,05 (100) 3,527 (75) Nimesite : 7 : NIM MAKSIMOVIC (1972)
-o
o
X. - ALPHABETICAL LIST OF CURRENT CLAY MINERALS INCLUDING MIXED LAYERS,
WITH THEIR d(OOI) VALES IN , AND THE CORRESPONDING INTENSITIES OUT TO
THE 3 REGIN OF THE DIFFRACTOGRAM - oriented aggregate, natural state
It has seemend of nterest to group here some specific d(spamngs) and ntensities (ex. : mxed layers) or, on the contrary the list will only provide the (001) and
for the (001) harmonio sequence of reflections for different clay mnerals and (002) in d() for others (kandites).
mixed layers (regular).
Some sensitive differences may appear in the d(spacing) as well in the ntensities
The data are only provide up to the 3 zone of the diffractogram pattern ; that for specific minerals or mixed layers (regular) ; such a situation is due to the various
will say that may be related at least to the (005) reflection for some minerals authors references.
Kaolinite, ordered 7,13 (100) 3,56 (66) DRITS & al. (1960)
disordered 7,2 (VS) 3.59 (VS)
Kotschubete 14,15 (35) 7,11 (100) 4,74 (90) 3,56 (95) BROWN (1961)
Paragonite 9,65 (S) 4,82 (Ms) 3,21 (VS) ZEN & ROSS (1964)
Pecoraite 7,43 (VS) 3,66 (S) FAUST & al. (1969)
Penninite 14,31 (68) 7,156 (1007) 4,77 (74) 3,578 (64) POST & PLUMMER (1972)
14,2 (55) 7,13 (90) 4,74 (70) 3,57 (100) MONTOYA & BAUER (1963)
14,3 (60) 7,18 (100 + ) 4,79 (100) 3,59 (100) BRINDLEY (1961)
14,38 (75) 7,18 (100) 4,79 (55) 3,60 (80) CERNY & al. (1965)
Cr-Ni-Pennine 14,0 (40) 7,08 (85) 4,75 (95) 3,562 (100) VARADARAJAN (1964)
Prochlorite 14,16 (84) 7,08 (100) 4,72 (21) 3,54 (60) STEINFINK (1958, 61, 62)
13,6 (4) 6,9 (8) 4,65 (6) 3,48 (10) JASMUND (1955)
Pyrophyllite 9,21 (VS) 4,58 (S) 3,08 (VS) KODAMA (1958)
9,14 (40) 4,57 (50) 3,04 (100) MOLLOY & KERR (1961)
Rectorite 25 12,5
Ripidolite 14,16 (38) 7,08 (100) 4,72 (12) 3,54 (44) SHIROZU & BAILEY (1965)
14,4 (54) 7,07 (100+) 4,714 (43) 3,535 (89) POST & PLUMMER (1972)
Tale 9,34 (VS) 4.56 (S) 3,11 (S) ROSS & al. (1968)
Thuringite 14,1 (90) 7,07 (100) 4,726 (30) 3,541 (60) GILLERY, ASTM 7-78
13,6 (MS) 6,89 (VS) 4,62 (S) 3,48 (VS) JASMUND (1955)
Tarasovite 43,75 (100) 21,8 (70) - 10,55 (4) LAZARENKO & al. (1970)
Sangarite 28,8 14,3 9,5 7.14 7,14 5,76 DRITS & al. (1963)
Hydrobiotite + 30% V 28 (22) 11,5 (100) 8,43 (8) FERLAJ & al. (1972)
Hydrobiotite - (I-V) 25,5 (100) 12,4 (100) 8,2 (30) 6.15 6,15 4,92 (60) MIDGLRY & MIDGGLEY (1960)
24,8 (50) 12,4 (150) 8,3 (18) 5.0 (12) EROSHCHEV-SHAK (1970)
24,7 (W) 12 (VS) 8,3 (VW) VENALE & al. (1969)
23,0 (70). 12,3 (210) 8,3 (6) 4,87 (28) EROSHCHEV-SHAK (1970)
Hydrobiotite + 50% V 24 (25) 11,9 (100) 8,15 (4) 4,89 (18) FERLAJ & al. (1972)
(Mica-Vermicu lite) 25,2 (54) 12,25 (100) 8,33 (6) 4,95 (25) GRADUSOV (1971)
Stevensite 24 11,2-12,4(100) 4,89-4,96 (20) FAUST & al. (1 953)
(Talc-Saponite) 24,52 (58) 10,5-10,9 (92) GUENOT(1970)
24,5-24,8(92) 11,7-12,3(100) 4,80 (13) ALIETTI (1960)
23,8 (VS) 11,8 (S) (W) (W) 6,09 (VW) 4,79 (VW) VENALE & al. (1966)
(Mica-Beidellite) 22,8 (66) 11,04 (100) - 5,22 (40) GALLEGO & PREZ (1965)
(Mica-Montmorillonite) 25,2 (30) 11,3 (100) - 5.07 (10) HAMILTON (1967)
(Illite-Montmorillonite) 25 (S) 11,7 (S) - 5,03 (M) BOCCHI & al. (1969)
(Mica-Montmorillonite) 27,3 (90) 12,4 (100) - 5,06 (20) HAMILTON (1967)
(Mica-Montmorillonite) - 11,2 (33) - 5,06 (45) SHIMODA & al. (1969)
(Illite-Montmonllonite) 25 (S) 11,7 (VS) - 5,03 (M)
(Mica-Montmorillonite) 25,8 (100) 12,4 (80) - HEYSTEK (1954)
25,8 (100) 12,6 (55) 8,49 6,32 5,02 SUDO & SHIMODA (1969)
(Beidellite-hydromica) 26,1 (W) 12,8 (VS) - HEYSTEK (1963)
.(Mica-Beidellite) 26,3 (100) 13,4 (92) 9,1 (16) 5,20 (10) GALLEGO (1968)
(Illite-Montmorillonite) 26,77 12,45 - 5,06 STEINER (1968)
(Mica-Montmorillonite) 28,1 (W) 12,1 (VS) - HAMILTON (1967)
(Mica-Allevardite) 30,2 (VS) 13,85 (VS) 9,45 (M) 7,09 (VVJ) 5,438 (W) MACHAJDIK
(Sericite-Sudoite) 24,2 (VW) 12,36 (M) 8,01 (M) 6,09 (VW) 4,83 (VS) SHIROZU & al. (1971)
(Biotite-Chlorite) 24 (VW) 12,6 (VS) 7,98 (S) 6.25 (W) 4,87 (S) EROSHCHEV-SHAK (1970)
(Be idel lite-Vermicu lite) 29,2 (VW) 14,48 (VS) - HEYSTEK (1963)
(Chlorite-Vermiculite) 29 (30) 14 (100) - 7,08 (60) BROWN (1967)
29,9 (48) 14,7 (100) 9,71 (8) 7,31 (10) 5,82 (3) SUDO & SHIMODA (1969)
28,5 (VW) 14 (VS) - 7,1 (S) SARKISYAN & al. (1972)
28,5 (W) 14,2 (VS) 9,43 (VW) 7,23 (W) WILSON (1973)
29 14,2 9,7 7,3 5,9 BRADLEY & WEAVER (1956)
29,0 (9) 14,6 (100) - 7.26 (39) JOHNSON (1964)
Tosudite 30,4 (320) 15,2 (240) 10,0 (3) 7,557 (20) 5.98 (3) SHIMODA (1969)
(dioctah. Chlorite-Montmorill.) 31,5 (79) 14,7 (100) - SUDO & KODAMA (1969)
(Chlorite-Montmorillonite),Dioct. 29,6 (10) 14,7 (16) 9,8 (3) 7,32 (5) 5.99 (3) SUDO (1954)
Li-AI (Chlorite-Montm., Dioct. 29,7 (80) 14,4 (50) 9,66 (10) 7,3 (2) 5,72 (2) BROWN & al. (1974)
(Chlorite-IViontmorillonite), Dioct 29,8 (10) 14,7 (15) 10,3 (4B) 7,18 (20) SUDO (1954)
(Montmonllonite-Chlonte), Dioct 30,0 (16) 15,0 (24) 9,96 (4B) 7,52 (4B) 6.01 (3B) SUDO & KODAMA (1957)
(Montmorill.-Chlonte), Trioct. 30,5 (S) 14,5 (VS) 9,7 (M) 7,25 (M) EARLEY 4 al. (1956)
(Chlorite-Montmorillonite) 30,5 15,0 - 7,37 6,06 SIAT & al. (1959)
(Chlorite-Montmorillonite) 29,5 (S) 14,3 (VS) - 7,12 (W) SARKISYAN & al. (1972)
Corrensite : (C-M) 29,2 (50) 14,6 (100) 9,73 (12) 7,3 (25) 5,9 (3) BRADLEY & WEAVER (1956)
(Chlorite-Montmorillonite) 28 (M) 14,27 (VS) - 7,1 FRANSOLET (1970)
29,0 (100) 14,5 (71) 9,65 (8) 7,27 (6) EGGLESTON & al. (1967)
(Chlonte-Exp. Clay) 27,6 (204) 14,1 (344) 9,72 (56) 7,15 (49) 5,75 (3) TETTENHORST & al. (1968)
(Chlorite-Saponite) 28,9 (M) 14,4 (VS) 9,6 (VW) 7,23 (M) VENALE & al. (1969)
(Chlorite-Saponite) 29,4 (VS) 14,7 (VS) 9,8 (W) 7,3 (M) 5.8 (S) ALIETTI (1956)
Mixed layer Swelling Chlorite 30,46 (90) 14,48 (100) - 7,37 (55) STEINER (1968)
+ 11 (Chlonte-Montmo.) + 28,44 (S) - 8,08 (W) 5,94 (VW) ALIETTI & al. (1963)
(Chlorite-Swelling Chlorite)
(Chlorite-Swelling Chlorite) 30 (W) 14,4 (VS) HECKROODT & al. (1965)
29,6 (VW) 14,4 (VS) 9,8 (W) 7,18 (M) VENALE & al. (1969)
30,46 (90) 14,48 (100) 9,82 (25) 7,37 (55) 5,86 (51) STEINER (1968)
XI. - INCREASING (060) IN d() OF PHYLLOSILICATES AND CLAY
MINERALS
79
XII. - GLOSSARY OF PHYLLOSILICATES AND CLAY MINERALS
Pyrophyllite ~9
Di : Pyrophyllites Pyrophyllite
Without O
-Tale Tri : Tales Tale
Montmorillonite, Beidellite
Montmorillonites Di : Montmorillonies Saponite, Hectorite,
~0,25<x<~0,6 14M
or Smectites Tri : Saponitas Sauconite
Dry or
2/1 Hydrated
cations ~0,6<x<~0,9 Vermiculites Di : Vermiculites Vermiculite
14y
Tri : Vermiculites Vermiculite
Subgroup Structural
AME REMARKS GROUP (SUBGROUP) Octah. Layer type
80
Subgroup Structural
'.-'.'E REMARKS GROUP (SUBGROUP) Octah. Layer type
81
Subgroup Structural
AME REMARKS GROUP (SUBGROUP) Ootah. Layer type
82
Subgroup Sructural
AME REMARKS GROUP (SUBGROUP) Octah. Layer type
83
Subgroup Structural
AME REMARKS GROUP (SUBGROUP) Octah. Layer type
Palygorskite
Parabiotite A Biotite with a higher conten of H2O
Parachrysotile
Paragonite Micas (Muscovite) Di 2/1
Parahalloysite Similar to Halioysie in composition, and a silica-poor
Montmorillonite in Structure
Pennantite Fe-Mn Chlorite Chlorites Tri 2/1
Penninite Mg-Fe Chlorite Chlorites Tn 2/1
84
Subgroup Structural
.-VE REMARKS GROUP (SUBGROUP) Octah. Layer type
Radiophyllite = Zeophyllite
Rectorite = Allevardite = Mixed layer Illite-Montmorillonite Mixed layers
Ripidolite Chlorites Tri 2/1
Romannechite = Psilomelane
Roscoelite V-Mica Micas (Muscovite) Di 2/1
Xanthophyllite Mg-Ca Mica, variety of Seybertite Bnttle Micas (Clintonite) Tri 2/1
Xylotile Fe-bearing Palygorskited
Zedebassite = Saponite Saponites Tri 2/1
Zeophyllite Ca-F hydrated silicate
Zinalsite Zn- ; mixture of Sauconite and Berthierine
Zinc-Montmorillomte = Sauconite Saponites Tri 2/1
Zincsilite Montmorillonites
Zinnwaldite Lepidolite group Micas Tri 2/1
Zircophyllite X-ray analogue to Astrophyllite
Zn-Mica
85
SELECTED BIBLIOGRAPHY
ALIETTI A. (1966). - Identification of disordered kaolinites. Clay Min., BURST J. F. (1956). - Mineralgica! variability in glauconite-like pellets
Great Britain, 6, 229-231. application to stratigraphic interpretation. Am. Ass. Petrol. Geol. Bull, 42,
ANDREW R. W., JACKSON M. L, WADA K. (1960). - Intersalation as a 310-327.
schmque for differentiation el kaolinite from chloritic materials by X-ray BURST J. F. (1958). - Mineral heterogeneity of glauconite pellets.
diffraction. Soil Sc. Soc. Am. Proc., 24, 422-424. Amer. Mmer, 43, 481-497.
3AILEY S. W. and BROWN B. E. (1962). - Chlorite polyiypism : I. Regular BYSTRM A. M. (1954). - Mixed /ayer minerals from the Ordovician
and semi-random one -layer structures. Amer. Min,, 47, 819-850. bentonite beds at Kinnekulle, Sweden. Nature, 1 73, 783-784.
BAILEY S. W. (1963). - Polymorphism of the kaoln minera/s. Amer. Min., BYSTRM A. M. (1956). - Mineralogy of Ordovician beds at Kinnekulle,
48. 1196-1209. Sweden. Sveriges Geol. Undersokn, Arsbok, 48, 1-62.
3AILEY S. W. (1966). - The status of clay mineral structures. Clays Clay BYSTRM A. M. (1957). - The clay minerals in the Ordovician bentonite
Min.. 14. 1-23. beds in Bellingen, South-West Sweden. Geol. Fren, 79, 52-56.
BAILEY S. W. (1969). - Polytypism of trioctahedral 1:1 layer silicates. Clays CAILLERE S. and HENIN S. (1963). - Minralogie des Arges. Masson
Clay Min., 17, 355-371. et Ci, Paris, 355 p.
BAILEY S. W. (1972). - Determinaron of chlorite by X-ray spacings and CARSTEA D. D. (1968). - Formation of hydroxy-AI and Fe- interlayers in
intensities. Clays Clay Min., 20, 381-388. montmorillonite and vermiculite : influence of partile s/ze and temperature.
BARSHAD I. (1952). - Faciere affecting the nter/ayer expansin of vermi- Clays Clay Min, 16, 231-238.
culite and montmorillonite. Soil Sci. Am. Proc., 16, 176-182. CHAMLEY H. (1967). - Possibilit d'utilisation de la cristallinit d'un
BARSHAD I. (1954). - Catin exchange in micaceous minerals. 2. Replace- mineral argileux (illite) comme tmoin clim.atique dans les sediments reces.
ability of ammonia and potassium from vermiculite, biotite and montmoril- C. R. Acad. Sci, Paris, 265, 184-187.
lonite. Soil Sci, 78, 57-76. DIMANCHE F, RASSEL A, TARTE P. and THOREZ J. (1974). - The
BISCAYE P. E. (1964). - Distinction between kaolinite and chlorite n recent kaoln : mineralogy, deposits, uses. Minerals Sci. Engng, 6, 184-205.
sediments by X-ray diffraction. Amer. Min., 49, 1 281 -1 289. DIXON J. B. and JACKSON M. L. (1962). - Properties of intergradient
BISCAYE P. E. (1965). - Mineralogy and Sedimentaron of Recent Deep- chlorite-expansible layer silicates of soils. Soil Sci. Soc. Am. Proc, 24,
Sea Clay in the Atlantic Ocean and Adjacent Seas and Oceans. Geol. Soc. 358-362.
Amer. Bull, 76, 803-832. DOUILLET Ph. and NICOLS J. (1969). - Les minraux du kaoln -Histo-
BRADLEY W. F. (1940). - Attapulgte. Amer. Min., 25, 405-410. rique- Rflexions concernan les diverses classificaions e nomenclatures-
BRADLEY W. F. (1945). - Diagnostic Criteria for Clay Minerals. Amer. Proposition d'une nomenclature nouvelle. Bull. Soc. Fr. Cramique. 83,
Min.. 30, 704-713. 87-114.
BRADLEY W. F. (1954). - X-Ray Diffraction Criteria for the Characteriza- DUNOYER de SEGONZAC G. (1964). - Les arges du Crtac Suprieur
tion of Chlorite Material in Sediments. Clays Clay Mm, 2nd Nati. Conf. dans le bassin de Douala (Cameroun) : problemas de diagense. Bull.
1953, 324-334. Serv. Carte Geol. Ais. Lorr, Strasbourg, 17, 287-310.
BRINDLEY G. W. and ROBINSON K. (1948). - Structures of metahal- DUNOYER de SEGONZAC G. and KUBLER B. (1966). - La cristallinit de
loysite. Min. Mag, 28, 393-406. /'/'///fe. Mesures faites au Laboratoire de Gologie de la Facult des Sciences
de Strasbourg et au Centre de Recherche S.N.P.A. de Pau sur des forages
BRINDLEY G. W. and ROBINSON K. (1951). - The chlorite minerals, in : B.R.P. Bull. Techn. des Socits du Groupe E.R.A.P, 27, 16-41.
G. BROWN Ed. - The X-ray Identification and Crystal Structures o Clay
Minerals. Min. Soc, London', 173-198. DUNOYER de SEGONZAC G, PERRERO J. and KUBLER B. (1968). - Sur
la cristallinit de /'////'fe dans la diagense et l'anchimtamorphisme. Vil Congr.
BRINDLEY G. W. and YOUELL R. F. (1953). - Ferrous chamosite and
Intern. Sdim, Reading-Edinburg, 1967, and Sedimentology, 10, 137-143.
ferric chamosite. Min. Mag, 30, 57-70.
BRINDLEY G. W. and GILLERY F. M. (1956). - X-ray Identification of DUNOYER de SEGONZAC G. (1969). - Les minraux argileux dans la
chlorite species. Amer. Min, 41, 169-189. diagense - Passage au mtamorphisme. Mm. 29, Serv. Carte Geol. Ais.
Lorr, 320 p.
BRINDLEY G. W. (1961). - Kaoln, Serpentine, and kindred minerals in :
G. BROWN Ed. - The X-ray Identification and Crystal Structures of Clay EGGLETON R. A. and Bailey S. W. (1967). - Structural aspeis of dioc-
Minarais. Min. Soc, London. tahedral chlorite. Amer. Min, 52, 673-689.
BRINDLEY G. W, de SOUZA SANTOS, P. and H. (1963). - Mineralgica! ENGELHARDT W. (von), MULLER G. and KROMER H. (1962). - Dioc-
studies of kaolinite-halloysite clays. I. Identification problema. Amer. Min, taedrischer Chlorit (" Sudoit) in Sedimenten des Mitt/eren Keuper von
48. 897-910. Wrttemberg. Naturwissensch, 49, 205.
3RINDLEY G. W. (1961). - "Kaoln, serpentino and kindred minerals in : ESQUEVIN J. (1969). - Influence de la composition chirnique des ilutes
G. BROWN, Ed.- The X-Ray Identification and Crystal Structures of Clay sur la crsta/linit. Bull. Centre Rech. Pau-S.N.P.A, 3, 147-154.
Minerals. Min. Soc. London, 51-131. FOSTER M. D. (1962). - Interpretaron ofthe composition and aclassification
BRINDLEY G. W. and PHAM THI HANG (1973). - Structures, chemical of the chlorites. U.S. Geol. Surv, Prof. Paper n 414A, 27 p.
compositions and colour characteristcs. Clays Clay Mm, 21, 27-40. GALLITELLI P. (1962). - Remarques sur la gense de quelques minraux
BROWN G. (1953). - The dioctahedral analogue of vermiculite. Clay Min. argileux des Appenins de l'ltalie du Nord. In : Gense et Synthse des
Bull, 2. 64-70. Arges, Colloq. Intern. C.N.R.S, Paris, 191-195.
BROWN G. (1955). - The effects of isomorphous substitution on the GAUDETTE H. E, EADES J. L. and GRIM R. E. (1964). - The nature
n'.ensities of (001) ref/ections of mica- and chlorite-type structures. Min. of illite. Clays Clay Min, 13, 33-48.
Mag, 30, 657-665. GEBHARDT H, MEYER B. and SCHEFFER F. (1966). - Zwischenschicht-
BROWN G, Ed. (1961). - The X-ray Identification and Crystal Structures belegung und Expansion-verhalten von Dreischicht-Tonmineralen in CaCO3
of Clay Minerals. Min. Soc, London, 544p. gepufferten Hydrogencarbonatmilieu kalk-reicher Lockersedimentboden
(Beispiel Lss). Z. Pflanzenernachr. Dng. Bodenk, 114, 90-100.
BROWN G, BOURGUIGNON P. and THOREZ J. (1974). - A Lithium-
bearing aluminian regular mixed layer montmorillonite-chlorite from Huy, GIBBS R. J. (1967). - Quantitative X-ray diffraction analysis using clay
Belgium. Clay Min, 10, 135-144. mineral standards extracted from the samples to be ana/ysed. Clay Min,
BROWN B. E. and BAILEY S. W. (1962). - Chlorite polytypism. I. Regular 7, 79-90.
and semi-random one-layer structures. Amer. Min, 47, 819-850. GIESEKING J. E, Ed. (1975). - Soils Components. I/o/. 2. Inorganic
BROWN .B. E. and BAILEY S. W. (1963). - Chlorite polytypism. II. Crystal Components. Springer-Verlag Berlin-Heidelberg-New York, 684 p.
structure of one-layer Cr-chlorite. Amer. Min, 48, 42-61. GJEMS O. (1963). - A swelling dioctahedral clay mineral of vermiculite-
BRYDON J. E, CLARK J. S. and OSBORNE V. (1961). - Dioctahedral smectite type in the weathering horizons of podzols. Clay Min. Bull, 5,
chlorite. Caad. Mm, 6, 595-609. GJEMS O. (1967). - Studies on Clay Minerals and Clay Mineral Formation
BRURST J. F. (1956). - Mineralgica! variability in glauconite-like pellets in Soil Profiles in Scandinavia. Medd. Norske Skogf, 81, 302-415.
and its application in stratigraphic studies. Geol. Soc. Amer. Bull, 67, 1678. 183-193.
87
GOMES C. S. (1967). - Kaolinite displaying a particular behaviour on KUBLER B. (1 961). - Sur que/ques /nterstratifis irrguliers m/ca-montmoril-
KCHgCOO intercalation. Publ.Museu e Labor. Miner. e Geol., Univ. Coimbra lonite. Bull. Serv. Carte Geol. Ais. Lorr., 14, 173-178.
e Centro Estudos Geol., 3, 47-54. KUBLER B. (1964). - Les arges, indicateurs de mtamorphisme. Revue
GORBUNOV N. I. and GRADUSOV B. P. (1966). - Methods of determmmg Inst. Fr. Ptrole., 19, 1093-1112.
fine-grained minera/s. Soviet Soil ScL, 712-725. KUBLER B. (1966). - La cristallinit de /'////fe et les zones tout fait
GRIM R. E., BRAY R. H. and BRADLEY W. F. (1937). - The mica in suprieures de mtamorphisme. In : Col loque sur les Etages Tectoniques,
argil/aceous sediments. Amer. Min., 22, 813-829. la Baconnire, Neuchtel, Suisse., 105-122.
GRIM R. E., BRADLEY W. F. and BROWN G. (1951). - The mica clay KUBLER B. (1967). - Anchimtamorphisme et Schistosit. Bull. Centre
minerals in : BRINDLEY G. W., Ed., X-Ray Identification and Crystal Rech. Pau-S.N.P.A., 1, 259-278.
Structure of the Clay Minerals. Miner. Soc., London, 138-172. KUBLER B. (1968). - Evaluation quantitative du mtamorphisme par la
GRIM R. E. (1953). - Clay Mineralogy. Macgrew Hill, New York. cristallinit de /'////fe. - Etat des progrs raliss ees dermres annes.
GRIM R. E. and JOHNS W. D. (1954). - Clay mineral sediments in the Bull. Centre Rech. Pau-S.N.P.A., 2, 385-397.
Northern Gulf of Mxico. Clays Clay Min., Publ. 327, Nati. Acad. Sci. - LAPHAM D. M. (1958). - Structural chemical variations in chromium
Nati. Res. Counc., 81-103. chlorite. Amer. Min., 43, 921-956.
GRIM R. E. and KULBICKI G. (1961). - Montmori/lonite : high temperature LAZARENKO E. K. and LOROLEV Yu. M. (1970). - Tarasovite, a new
reactions and classification. Amer. Min., 46, 1329-1369. doctahedral ordered interlayered mineral. Zap. Vses. Mineral. Obsch., 99,
GUINER A. (1964). - Thorie et technique de a radiocristallographie. 214-224.
Dunod, Pars, 740 p. LEVINSON A. A. (1955). - Studies in the mica group : polymorphism
HAMILTON J. D. (1967). - Partially ordered mixed-layer mica-montmoril- among i/lite and hydrous micas. Amer. Min., 40, 41-49.
lonite from Maitland, New South Wales. Clay Min., 7, 63-78. LISTER J. S. and BAILEY S. W. (1967). - Chlorite polytypism : V. Regular
HARWARD M. E. and BRINDLEY G. W. (1965). - Swelling properties two-layer structures. Amer. Min., 52, 1614-1631.
of synthetic smectites in relation to lattice substitutions. Clays Clay Min., LUCAS J., CAMEZ T. and MILLOT G. (1959). - Determinaron pratique
Proa, 13th Nati. Conf. (1964), 209-222. aux rayons X des minraux argileux simples et nterstratifis. Bull. Serv.
HARWARD M. E., CARSTEA D. D. and SAYEGH A. H. (1968). - Properties Carte Geol. Ais. Lorr., 12, 21-33.
of vermiculites and smectites : expansin and collapse, Clays Clay Min., LUCAS J. and JEHL G. (1961). - Etude de l'action de la chaleur sur la
16, 437-447. chlorite et la kaolinite par diffraction des rayons X. - Application a la
MAYES J. B. (1970). - Polytypism of chlorite in sedimentary roete. Clays distinction de ees deux minraux. Bull. Serv. Carte Geol. Ais. Lorr., 14,
Clay Min., 18, 285-306. 159-172.
HAYASHI H. and OINUMA K. (1964). - Aluminum chlorite from Karnikita LUCAS J. (1963). La transformation des minraux argileux dans la
mine, Japan. Clay Sci., 2, 22-30. sedimentaron. Etudes sur les arges du Trias. Mm. Carte Geol. Ais. Lorr.,
23, 202 p.
HENDRICKS S. B. and JEFFERSON M. E. (1938). - Crystal structure of
vermiculite-ch/orite. Amer. Min., 23, 851. LUCAS J. (1968). - The transformation of clay minerals during sedimentation.
A study on Triassic Clays. Mm. Serv. Carte Geol. Ais. Lorr., 23, translated
HEY M. H. (1954). - A new review of the chlorites. Min. Mag., 30, 277-292 from Frenen, and Published by Israel Prog. Serv. Transiation., 203 p.
HINCKLEY D. N. (1954). - Variability in crystallinity" vales among the
Mac EWAN D. M. C. (1944). - Identification of Montmorillonite. Nature,
kaoln deposits of the coastal plain of Georgia and South Carolina. Clays
Clay Min., 11, 229-235. 154, 577-578.
Mac EWAN D. M. C. (1946). - The identfication and estimation of the
HOFMANN V., WEISS A., MEHLER A. and SCHOLZ A. (1956). -Intra-
montmorillonite group of minerals with special reference to so/7 c/ays.
crystalline swelling, catin exchange and anin exchange of minerals of
J. Soc. Chem. Ind., 65, 298-305.
the montmorillonite and of kaolinite. Clays Clay Min., 4, 273-287.
Mac EWAN D. M. C. (1949). - Some Notes on the Recording and Inter-
HOWER J. (1961). - Some factors concerning the nature and origin of pretation of X-Ray Diagrams of Soils Clays. J. Soil Sci., 1, 90-103.
glauconite. Amer. Min., 44, 19-32; Amer. Min., 46, 313-334; Amer. Min.
47, 886-896. Mac EWAN D. M. C. and BROWN G. (1949). - Interstrat/fication in clay
minerals. J. Soil Sci., 1, 239.
HOWER J. and MOWATT T. C. (1966). - The mineralogy of ilutes and
mixed layers illite-montmorillonites. Amer. Min., 51, 825-854. Mac EWAN D. M. C. and BROWN G. (1950). - Interstratified minerals in :
The X-ray Identification and Crystal Structures of Clay Minera/s. Min. Soc.,
HOWER J. (1967). - Order of mixed- layerng in illite-montmorillonites. London, 544 p.
Clays Clay Min., 27, 63-74.
Mac EWAN D. M. C. (1953). - Randomly stacked layers in clay minerals.
JACKSON M. L, HSEUNG Y., COREY R. B, EVANS E. J. and Van den
Nature, 171, 616.
HEUVEL R. C. (1952). - Weathering sequence of clay-size minerals in
so/te and sediments. II. Chemical weathering of ayer silicates. Soil Sci. Mac EWAN D. M. C. (1956). - Fourier transform methods. -LA direct
Soc. Amer., Proc., 16, 3-6. method of analysing Interstratified mixtures. Kolloidzschr., 149, 96-108.
JACKSON M. L. (1963). - Aluminum bonding in soi/s : a unfying principie Mac EWAN D. M. C. (1958). - Fourier transform for studying X-ray scat-
in so/7 sciences. Soil Sci. Soc. Amaer. Proc., 27, 1-10. tering from /amellar system. II. The calculation of the X-ray diffraction
effects for various types of interstratification. Kolloidzschr., 156, 61.
JACKSON M. L. (1963). - Interlayering of expansible layer silicates in soi/s
by chemical weathering. Clays Clay Mm., 11, 29-46. Mac EWAN D. M. C. and RUIZ-AMIL A. (1959). - Fourier transform
methods for studying X-ray diffraction from /amellar system. III. Kolloidzschr.,
JEHL G. and LEIKINE M. (1968). - Les minraux argileux des formations 162, 93.
secondaires du Massif des Bahors Occidentaux (Algrie) - Apport a la
connaissance de la Sdimentologie, de la Palogographie et de la Mac EWAN D. M. C., RUIZ-AMIL A. and BROWN G. (1961). - Interstra-
Tectonique. Bull. Serv. Carte Geol. Ais. Lorr., 21, 253-284. tified clay minerals in : G. BROWN, Ed. : The X-ray Identification and
Crystal Structures of Clay Minera/s. Min. Soc., London., 544 p.
JOHNS W. D., GRIM R. E. and BRADLEY W. F. (1954). - Quantitative
estimations of minerals by diffraction methods. J. Sed. Petrol , 24, 242-251. MALCOLM R. L., NETTLETON W. D. and Me CRACKEN R. J. (1968).
- Pedogenic formation of montmorillonite from a 2:1 - 2-2 intergrade clay
JOAS E. C. and BROWN B. E. (1959). - Three-component interstratifi- mineral. Clays Clay Min., 16, 405-414.
cations. J. Sed. Petrol., 29, 77-86.
MAREL H. W., van der (1950). - Identification of minerals in sos clay by
KODAMA H. (1962). - Interpretaron of X-ray powder patterns of some X-ray diffraction patterns. Soiil Sci., 70, 109-136.
hydromuscovite from Japan, with reference to their alkali contents. Clay
Sci., Japan, 1, 89-99. MAREL H. W., van der (1954). - Potassium fixation in Dutch sos :
mineralgica! analyses. Soil Sci., 163-179.
KODAMA H. and OINUMA K. (1963). - Identification of koalm minera/s in
c/ays by X-ray and infrared absorption spectra. Clays Clay Min., 11, 236-249. MAREL H. W., van der (1962). - Quantitative analysis of the clay seprate
of so/te. Acta Univ. Carolmae, Tchecosl., Geol. Suppl., 1, (1961), 23-82.
KODAMA H. and BRYDON J. E. (1966). - Interstratified montmoj-lonite-
mica c/ays from subsoils of the prairie provinces, Western Canad. Clays MAREL H. W., van der (1964). - Identification of chlorite and chlorite-
Clay Min., 13, 151-173. re/ated minera/s in sediments. Beitr. Mineral. Petrogr., 9, 462-480.
KODAMA H., SHIMODA S. and SUDO T. (1969). - Hydrous mica complexes: MAREL H. W., van der (1966). Quantitative analysis of clay minerals and
their structure and chemical composition. Proc. Intern. Clay Conf., Tokyo, their admixtures. Contr. Mineral. Petrol., 12, 96-138.
1969., 1, 185-196. MARTIN R. T. (1955). - Reterence chlorite characterization for chlorite
KOHYAMA N., SHIMODA S. and SUDO T. (1973). - Iron-r/ch sapomte Identification in so/7 c/ays. Clays Clay Min., Proc. 3rd, Nati. Conf. (1954),
(ferrous and ferric forms). Clays Clay Min., 21, 229-237. 117-145.
KOIZUMI M. and ROY R. (1959). - Synthetic montmorillonoids with MATSUI T. and YATSU E. (1969). - Iron-bearing montmorillonites from
variable exchange capacity. Amer. Min., 44, 788-805. pedosphere in North Japan. Clay Sci., 3, 116-125.
88
UAXWELL G. T. and HOWER J. (1967). - High-grade diagenesis and low ROSS C. S. and MORTLAND M. M. (1966). - A soil beidellite. Soil Sci.
yode metamorphism of i/lite in the Precambrian Belt. Amer. Min., 52, 843-857. Soc. Am. Proc., 30, 337-343.
1CLUERES F. and PEREZ-NIETO H. (1973). - Les minraux argi/eux des RUIZ-AMIL A., RAMREZ A. and Mac EWAN D. M. C. (1967). - X-Ray
adonsnrs recenta du Golfe de Cariaco (Venezuela). Bull. Gr. Fr. Argiles, Diffraction Curves for the Analysis of Interstratified Structures. Volturna Press,
XXV. 65-78. Talleres Grficos del C. S. I. C., Madrid.
ICR1NG J. 11949). - L'interfrence des rayons X dans les systmes a SAWHNEY B. L. (1968). - A/uminum interlayers in layer sil/cates. -Effect
HMilication dsordonne. Acta Cryst., 2, 371-377. o! OH/AI ratio of Al solution, time of reaction. and type of structure. Clays
ViLLER W. D. and KELLER W. D. (1963). - Differentiation between endel- Clay Min., 16, 157-163.
tte. halloysite and kaolinite by treatment with potassium actate and SAYEGH A. H., HARWARD M. E. and KNOX E. G. (1965). Humidity and
eOijkne glycol. Clays Clay Min., 10, 244-256. temperature interactions with respect to K-saturater expanding clay minerals.
MTTCHELL B. D. and FARMER V. C. (1962). - Amorohous clay minerals Amer. Min., 50, 490-495.
osme Scottish soil profiles. Clay Min. Bull., 5, 128-144. SCHWERTMANN U. (1962). - Eigenschaften und B/ldung aufweitbarer
--G " 9 6 1 ! . - Vorlnfige Mitteilung ber ein neues di-oktaedrischer (quellbarer) Dreischt-Tonminerale in Bden aus Sedimenten. Beitr. Minere.
Pbftasilikate mit chloritstruktur. N. Jb. Minerl., Mh. 5, 112-120. Petrogr., 8, 199-209.
1IULLER G. (1963). - Zur Kenntnis di-oktaedrischer vierschicht-phyllosi/i- SCHULTZ L. G. (1969). - Lithium and potassium absorption, dehydroxylation
kae fSudoit- reine der sudot-chlorit -gruppe). Proc. Intern. Clay Conf., temperature, and structural water conten of aluminous smectites. Clays Ciay
fcockhoim. 1, 121 130. Min., 17, 115-149.
MULLER G. (1967). - Sudoit (< dioktaedrischer Chloritl, Al-Chlorit") im SHIROZU H. (1958). - X-ray powder patterns and cell dimensions of some
irnberger Sanstein von Cornberg/Hessen. Contr. Mineral. Petrel., 14, chlorites in Japan, with a note on their interference colors. Min. Journal
-39 (Japan), 2, 209-223.
MULLER A.. PARTING H. and THOREZ J. (1973). - Caracfres sdimen- SHIROZU H. and BAILEY S. W. (1965). - Chlorite polytypism. III. Crystal
-es e minralogiques des couches de passage du Trias au Lias structure of an orthogonal ron chiorite. Amer. Min., 50, 868-885.
ijre Nnrd-Est du Bassin de Paris. Ann. Soc. Gol. Belgique. 96. SHIROZU H. and BAILEY S. W. (1966). - Crystal structure ot a two-layer
671 707. Mg-vermiculite. Amer. Min., 51, 1124-1143.
MURAVYOV V. I. (1970). - On the Identification of montmorillonite minerals SLAUGHTER M. and MILNE I. M. (1958). - The transformaron of chiorite
- -;-5ence of amorphous matarais. Sedimentology, 15, 199-203. -like Structures from montmorillonite. Clays Clay Min., Proc., 7th Nati. Conf.,
MURRAY H. H. and LYONS S. C. (1956). - Correlation of paper-coating 114-124.
gu&>r/ with degree of crystalline perfection of kaolinie. Clays Clay Min., 4, SMITH J. V. and YODER H. S. (1956). - Experimental and theoritical studies
. of the mica polymorphs. Min. Mag., 31, 209-235.
: - : . ' 3 W, and ROY R. (1954). - New data on the compostion and STEPHEN I. and Mac EWAN D. M. C. (1951). - Some chlor/tic clay minerals
- of chlorite. Clays Clay Min., Nati. Acad. Sci., Nati. Res. Counc., of unusual type. Clay Min. Bull., 1, 157-162.
:.. 327. 335-348. STOCH L. (1971). - On the classification and nomenclature of c/ay minerals.
- . ? ' . 3 W. and ROY R. (1958). - Synthesis of chlonte. and their Mineraloga Polonia, 2, 85-93.
:^d chemical constitution. Amer. Min., 43, 707-725. SUDO T. and HAYASHI H. (1956). - Types of mixed -layer minerals from
ORCEL J.. CAILLERE S. and HENIN S. (1950). - Nouvel essai de clas- Japan. Clays Clay Min., Nati. Acad. Sci., Nati. Res. Council, Publ. 456.
'ca.-'on des chlorites. Min. Mag., 29, 329-340. 389-412.
=
*QUET H. (1970). - Evolution gochimique des minraux argleux dans SUDO T. (1963). - Interstratified minerals from Japan, their geolgica!
es atrations et les sois des climats mditerranens tropicaux saisons behaviours and orgins. Proc. Intern. Clay Conf., Stockholm, 113-120.
r:-asfes. Mm. Serv. Carte Gol. Ais. Lorr., 30, 212 p. TAMURA T. (1956). - Physical, chemical and mineralgica! properties of
- - - " 3 S O N S. H. and HOSTERMAN J. W. (1962). - Geology and brown podzo/ic soils in Southern New England : Paxton and Merrimac
refractor/ clay deposits of the Haldeman and Wrigley Quadrangles, Ken- series. Soil. Sci., 81, 287-299.
ucky. U. S. Gol. Serv., Bull., 1122-F. TAMURA T. (1957). - Identification of the 14A mineral component. Amer.
^EDRO G. (1970). - A. E. I. P. E. A., Newsletter, 4, 4. Min., 42, 107-110.
PHAM THI HANG and BRINDLEY G. W. (1973). - The nature of gar TAMURA T. (1958). - Identification of clay minerals from acid soils. J. Soil
- e - : e s . ///. Thermal transformations. Clays Clay Min., 21, 51-57. Sci., 9, 141-147.
= ERCE J. W. and SIEGEL F. R. (1969). - Quantification in clay mineral THIRY M. (1973). - Les sediments de l'Eocne Infrieur du Bassin de Paris
s:jd/es in sediments and sedimentary rocks. J. Sed. Petrol., 39, 187-193. et leurs relations avec les paloaltrations de la Craie. (unpublished Thesis
= OST J. L. and PLUMMER C. C. (1972). - The chlonte series of Flagstaff of the Institute of Geology, University Louis Pasteur, Strasbourg, France,
Hillarea, California : a pre/imnaryinvestigation. Clays Clay Min., 20, 271 -283. 79 p.)
Z _ A K E R N A A T J. (1968). - X-ray analyses of clay minerals in some recent THOREZ J. and VAN LECKWIJCK W. (1 967). - Les minraux argileux et leurs
lluviatile sediments along the coastal of Central Italy. Publ. Fys. Geogr. altratons dans le Namurien infrieur de la Belgique (Synclinal de Namur).
Lab. Univ.. Amsterdam, 12, 105 p. Ann. Soc. Gol. Belgique, 90, B329-380.
TANGE K. J. and WEISS A. (1969). - Uber das Verhalten von Kaolimt THOREZ J. and VAN LECKWIJCK W. (1967). - Mmralogie des arges
bei hohen Drcken. Berichte Deuts. Keram. Gesells., 46, 231-239. dans une poche de disso/ution au contad du Viseen et du Namurien. Ann.
Soc. Gol. Belgique, 90, B381-394.
RANGE K. G., RANGE A. and WEISS A. (1969). - Fire-clay type kaolinite THOREZ J., BOURGUIGNON P. and PAEPE R. (1970). - Etude prlimmaire
or fire-clay mineral ? Experimental classification of kaolinite-halloysite mi- des associations de minraux argileux dans les loess p/istocnes en Belgique.
nerals. Ann. Soc. Gol. Belgique, 93, 265-285.
REYNOLDS R. C. (1967). - Interstratified clay Systems : calcu/at/on o THOREZ J. and BOURGUIGNON P. (1973). - Minralogie des arges de
the total one-dimensional diffraction function. Amer. Min., 52, 661-672. dissolution des calcaires dinantiens en Condroz (Belgique). Ann. Soc. Gol.
REYNOLDS R. C. and HOWER J. (1970). - The nature of interlayering in Belgique, 96, 59-85.
mixed-layer illite-montmorillonite. Ciays Clay Min., 18, 25-36. THOREZ J. (1975). - Phyllos/licates and Clay Minerals - A Laboratory
5 CH C I. and OBERSHAIN S. S. (1955). - Chemical and clay mineral Handbook for Their X-Ray Diffraction Analysis. G. LELOTTE, Ed., Dison,
properties of a red-yellow podzolic so/1 derived from muscovite schist. Belgique, 604 p.
Proc. Soil Sci. Am., 19, 334-339. TRAUTH N., LUCAS J. and SOMMER F. (1968). - Etude des minraux
RICH C. I. (1968). - Hydroxy inter/ayers in expansible layer silicates. Clays argileux du Palogne des sondages de Chaignes (Eure). Montjavoult
Clay Min.. 16, 15-30. (Oise), Mellot-le-Tillet (Oise), et Ludes (Mame). Mm. BRGM, 59, 11, 53-76.
ROBERSON H. E. and JOAS E. C. (1965). - Clay minerals intermedate VEEN A. W. L. (1970). - On geogenesis and pedogenesis in the od
between Hite and monmorillonite. Amer. Min., 50, 766-770. Coastal Plan of Surinam (South America). Publ. Fys. Geogr. Bodemk. Lab.
ROBERT M. (1972). - Transformation experimntale de glauconite et Univ., Amsterdam, n 14.
d'illites en smectites. C. R. Acad. Sci. Paris, 275, 1319-1322. VELDE B. and HOWER J. (1963). - Petrological significance of Hite
ROBERT M. and BARSHAD I. (1972). - Sur les proprits et la dtermination polymorphism in paleozoic sedimentary rocks. Amer. Min., 48, 1239-1254.
des minraux argileux 1/2 expansibles (vermiculites-smectites). C. R. Acad. VIVALDI J. M. L. and Mac EWAN D. M. C. (1959). - Triassic chlorites from
Sci.. Pars. 275, 1463-1465. the Jura and the Cataln Coastal tange. Clay Mm. Bull., 3, 179-189.
RODRGUEZ GALLEGO M. and PREZ L. J. A. (1965). - Regular Mtxed WADA K. (1961). - Lattice expansin of kaoln minerals by treatment with
Layer Micca-Beidellite. Clay Min,, 6, 119-122. potassium actate. Amer. Min., 46, 78-91.
^OSS C. S. (1969). - Review of the relation in the montmorillonite group WADA K. (1963). - Cuantitativo dtermination of kaolinite and halloysite
o clay minerals. Clays Clay Min., Proc., 7th Conf., 225-229. by NH4CI retention measurements. Amer. Min., 48, 1289-1299.
89
WADA K. (1965). - Intercalaron of water in kaoln minerals. Amer. Min., WEAVER C. E. (1958). - The effects and geologic signifiance of potassium
50, 924-941. fixation " by expandable clay minerals derived from muscovite, biotite,
WALKER G. F. (1950). - Vermiculite-organic complexas. Nature, 166, chlorite and volcanic material. Amer. Min., 43, 839-861.
695-696. WEAVER C. E. (1958). - Geologic interpretaron of argillaceous sedimente.
WALKER G. F. (1950). - Trioctahedral minerals in the soil-clays of North- Part I. Origin and significance of clay minerals in sedimentary rocks. Bull.
East Scotland. Min. Mag., 29, 72-84. Am. Assoc. Petrol. Geol., 42, 254-271.
WALKER G. F. (1957). - On the differentiation of vermiculites and smectites WEAVER C. E. (1960). - Possible uses of clay minerals in search for oil.
in clays. Clay Min. Bull., 3, 154-163. Bull. Am. Assoc. Geol., 44, 1505-1518 and Clays Clay Min., 8th Nati. Clay
Conf., (1959). 214-227.
WALKER G. F. (1958). - Reactions of expanding-lattice clay minerals with
glycerol and ethylene glycol. Clay Min. Bull., 3, 302-313. WEAVER C. E. (1961). - Clay minerals of the Onachita structural belt and
adjacent foreland. in : The Ouachita System. The Univ. Texas Publ. 6120,
WARSHAW C. M. (1960). - Experimental studies of illite. Clays Clay Min., Bureau Econ. Geol. Austin, 147-160.
Proc. 7th Nati. Conf., 303-316.
WHITE J. L. (1962). - X-ray diffraction studies on weathering of muscovite.
WARSHAW C. M. and ROY R. (1961). - Classification and a scheme for the Soil Sel. 93, 16-21.
Identification of ayer silicates. Geol. Soc. Amer. Bull., 72, 1455-1492.
WIERSMA J. (1970). - Provenance, gnesis and paleogeographical im-
WEBER K. (1970). - lllit-Krista/linitt und Metamorphose in Nordslichen plications on microminerals occurring in sedimentary rocks of the Jordn
Rheinischen Schiefergebirge. Vortrays -Kurzfassung, Nachr. dt Geol. Ges., I/a ley rea. Publ. Fys. Geogr. Bodemk. Lab. Univ., Amsterdam, n 15, 240 p.
2, 65-66.
WICKLANDER L. and ALEKSANDROVIC D. (1969). - Mineral Analysis of
WEBER K. (1972). - Notes on determination of illite crysta/linity. N. Jb. Swedish Soils. I. Brown Earths and Podzols. Lantbr. hogsk, Annle 35,
Miner. Abh, 46, 267-276. 895-819.
WEAVER C. E. (1955). - The distribution and identificaron of mixed-layer ZVYAGIN B. B. and NEFEDOV E. I. (1954). - Cookeite. Doklady Akad Nauk
clays in sedimentary rocks. Proc. 4th. Nati. Clay. Conf., 385-386 and Amer. SSSR, 95, 1305-1308.
Min., 43, 202-221.
90
Achev d'imprimer en avril 1976, sur les presses de
la S.P.R.L. Imprimerie G. Lelotte, Dison (Belgique).
Maquettes et dessins d'Edouard Rusinowski.
Tous droits de traduction, d'adaptation ou de reproduction par tous
procedes, y compris la photographie, reserves pour tous pays.