Eur. J. Mineral.

1996,8, 115-127

Standardized clay mineral crystallinity data from the very

low-grade metamorphic facies rocks of southern New Zealand
LAURENCE N. WARR

Geologisch-Paläontologisches Institut, Ruprecht-Karls-Universität, Im Neuenheimer Feld 234,

D-69120 Heidelberg, Germany

Abstract: X-ray diffraction determined clay mineral crystallinity data, standardized to the Crystallinity Index
Standard (CIS) scale, is presented for illite (white mica) and chlorite-bearing pelitic rocks of the zeolite,
prehnite-pumpellyite, pumpellyite-actinolite and the greenschist facies. Good correlations exist between both
illite and chlorite crystallinity and crystallite size data, with respect to the mineral (metabasite) facies con-
ditions, using both the Full-Width-at-Half-Maximum and a Siemens Single-Line Fourier method, while
calculations employing the Warren-Averbach method yielded unacceptably high degrees of error, and hence
poor correlations. These preliminary data conform with the commonly held view that the diagenetic-, anchi-,
and epi-zones of Kiibler's illite crystallinity boundary limits, adopted by the CIS, correspond with the zeolite,
prehnite-pumpellyite plus pumpellyite-actinolite, and greenschist facies, respectively. The CIS scale is there-
fore considered a reliable indicator of metamorphic grade, when adequate attention is given to the calibration
of the experimental data and the selection of suitable peak reflections. The air-dried Sr- or Ca-saturated illite
002 and chlorite 003 peak combination are recommended as two useful reflections for accurate and rapid XRD
grade determinations in very low-grade metamorphic rocks.
Key-words: Crystallinity Index Standard (CIS) scale, very low-grade metamorphic facies, southern New
Zealand.

Introduction form to a general pattern with the diagenetic zone

In the field of very low-grade metamorphism, a
large number of studies have compared the degree
of X-ray determined illite (white mica) crystal-
linity (IC) with other indicators of metamorphic
conditions, such as mineral facies data, coal rank,
fluid inclusion data, conodont coloration, and iso-
topic information, from a range of similar and
contrasting geological settings (see review of
Kisch, 1987).
Traditionally, correlations with the mineral
(metabasite) facies divisions of the lower grades
of metamorphism have played an important role
in the interpretation of IC data; the definition of
Kiibler's (1967) anchizone/epizone boundary was
originally based on the occurrence of greenschist
facies minerals. Subsequently, a wide range of
such comparisons have been drawn from numer-
ous areas, which, according to Kisch (1987), con-
corresponding to the zeolite facies, the anchizone
to the prehnite-pumpellyite and pumpellyite-
actinolite facies, and the epizone either to the
pumpellyite-actinolite or greenschist facies. A
number of apparent discrepancies to this scenario
have also been reported, such as epizone values
occurring with prehnite-pumpellyite facies assem-
blages (Robinson & Bevins, 1986; Bevins & Ro-
binson, 1993), anchizone values with zeolite
facies assemblages (Durney, 1974; Aprahamian et
al., 1975) and even diagenetic values reported
with prehnite-pumpellyite facies assemblages
(Bril & Thiry, 1976; Kiibler et al., 1979; Arkai,
1983; Robinson & Bevins, 1986).
Such inconsistencies in the data are usually
taken to be geologically meaningful and a range
of explanations have been put forward. Kisch
(1987) suggested three possible reasons, namely,
the non-diagnostic nature of the mineral facies

0935-1221/96/0008-0115 $ 3.25
) 1996 E. Schweizerbart'sche Verlagsbuchhandlung. D-70176 Stuttgart
116 L. N. Warr
assemblages, the inhibition of clay mineral growth
by induration during a prior metamorphism, and
the influence of rock strain enhancing IC. Further-
more, Arkai (1991) proposed varying amounts of
detrital micas in the pelites as a principal cause for
such discrepancies.
Differences between IC data and mineral
facies assemblages may also be anticipated by
considering the reaction mechanisms involved.
The mineral facies concept is one based on the
laws of thermodynamics, in which mineral reac-
tions are reversible and equilibrium assemblages
are attained within given P-T fields, ideally inde-
pendent of the P-T-t path involved. As a result, pe-
trogenetic grids based either on experimental
studies of mineral stabilities (Liou et al, 1985) or
internally-consistent thermodynamic data, have
been successfully used for establishing P-T condi-
tions from mineral assemblages in metamorphic
rocks (Frey et al, 1991). On the other hand, the
IC concept is based on continuous, structural and
chemical transformations which occur within the
prograde illite-muscovite series (Hunziker et al,
1986). These kinetically controlled and irre-
versible transformations are considered to take
place through a series of metastable phase transi-
tions governed by Ostwald ripening processes
(Eberl et al, 1990). The IC method, hence, pro-
vides a measure of reaction progress which is pre-
dictively more dependent on the time function of
the P-T-t path than the thermodynamically con-
trolled minerals facies. A universal correlation be-
tween these two metamorphic indicators would
only be expected if P-T-t paths in very low-grade
metamorphic rocks are everywhere relatively con-
sistent, which is clearly not the case (Robinson,
1987).
The main restriction in drawing purposeful
correlations between IC studies, and which apply
to clay mineral crystallinity investigations in gen-
eral, is that the numerical data produced by labo-
ratories are frequently incompatible, due to insuf-
ficient standardization practices (Kisch & Frey,
1987; Warr & Rice, 1994; Krumm et al, 1994;
Krumm et al, in press). Although many labora-
tories have compared differences due to variations
in machine conditions, using polished rock chip
standards (Kisch, 1990), inconsistencies arising
from sample preparation effects have not been
sufficiently calibrated (Krumm et al, in press).
Similar problems are encountered when com-
paring clay mineral crystallite size data between
research groups, which is further complicated by
the wide range of measurement methods, saturat-
ing cations and peak reflections used for analysis.
Crystallite sizes have been calculated by the
Scherrer equation, based on the air-dried illite 001
peak (Weber et al, 1976; Kiibler, 1984; Merriman
et al, 1990; árodori & Elsass, 1994), the Wilson
method (Wilson, 1963), on the air-dried illite 001
(Arkai & Toth, 1983) or illite 002 reflection (Nie-
to & Sanchez-Navas, 1994), and the Warren-Aver-
bach (W-A) method (Warren & Averbach, 1950),
on the glycolated Sr-saturated illite 002-005 com-
bination (Eberl & árodori, 1988; Eberl et al,
1990; Warr & Rice, 1994), or the Ca-saturated air-
dried illite 002 peak (Eberl & Blum, 1993). As the
ac- curacy and precision of these methods are still
poorly tested, comparisons against other quantita-
tive methods of analysis are critical in order to es-
tablish their suitability as indicators of the condi-
tions of metamorphism.
In order to facilitate a single compatible data
base and thus enable more effective comparisons
between clay mineral crystallinity and crystallite
(domain) size studies, Warr (1993) and Warr &
Rice (1994) recently introduced a calibration ap-
proach to the standardization of data using a set of
available rock chip standards. This allows data
sets to be directly and quantitatively compared,
despite differences in analytical procedures adopt-
ed. A standardized scale of measurement was in-
troduced, called the Crystallinity Index Standard
(CIS), which was equated as closely as possible to
the original scale of Kiibler (1967) by calibration,
using the polished interlaboratory standards of
Kisch (1990).
The purpose of this paper is to present a range
of standardized clay mineral crystallinity and
crystallite size data for illites and chlorites, based
on the analysis of 14 pelitic samples selected from
the well studied very low-grade metamorphic
facies of southern New Zealand. The applicability
of various XRD methods, as indicators of the con-
ditions of low temperature metamorphism, are ex-
plored, and some preliminary P-T constraints for
the CIS scale, presented.
Geology and sample description
The South Island of New Zealand consists of a se-
ries of accreted litho-tectonic terranes (Coombs et
al, 1976) which were extensively deformed and
metamorphosed during the Jurassic-Cretaceous
Rangitata Orogeny (Fleming, 1970). Continuous
and widespread transitions in metamorphic grade
 Clay mineral crystallinity and very low-grade metamorphism 117

and deformational intensity are well exposed
within the Torlesse (zeolite to amphibolite facies),
Caples (zeolite to greenschist facies), Murihiku
(zeolite facies), and Brook Street (greenschist fa-
cies) terranes, making it a classical area for both
low temperature metamorphic and structural stud-
ies.
The largest and most extensively studied of
the terranes is that of the Torlesse, consisting
mostly of Permian to early Cretaceous interbed-
ded greywacke and argillite lithologies, which
grade into schist toward the south (Otago Schist)
and the west (Alpine Schist). The greywacke-suite
was derived from a dominantly plutonic-metamor-
phic provenance with a lesser volcanic and sed-
imentary component (MacKinnon, 1983), depos-
ited along the Pacific Margin of Gondwana. Well
defined metamorphic and textural zones have
been mapped across the Torlesse transition into
Otago Schist (Bishop, 1972; Norris & Bishop,
1990). Although isograd and isotect boundaries
are often locally oblique, a general correlation be-
tween metamorphism and deformation has been
recognized in greywacke sandstone lithologies.
Undeformed rocks of textural zone 1 are typically
of zeolite or prehnite-pumpellyite facies, textural
zone 2 (weakly to well cleaved) are commonly of
the prehnite-pumpellyite or pumpellyite-actinolite
facies, and textural zones 3 and 4 (phyllitic to
schistose) are usually of the greenschist facies.
Peak metamorphism was characteristically one of
a high pressure facies series as indicated by the
white mica b0 values of Sassi & Scolari (1974),
with temperatures of 400-450 °C (Yardley, 1982)
and pressures ca. 4.5kbar (Jamieson & Craw,
1987).
These well exposed very low-grade meta-
morphic terranes provide an ideal study area for
correlating mineral facies assemblages against clay
mineral crystallinity data. Firstly, the relatively
porous and permeable greywacke lithologies were
particularly susceptible to regional metamorph-
ism, with abundant intermediate and mafic igne-
ous fragments favoring the development of hydrous
Ca-Al silicate assemblages. Secondly, the grey-
wackes are frequently interbedded with fine-
grained clay-rich pelites and tuffs suitable for clay
mineral crystallinity studies. Thirdly, there was

Table 1. Summary of the 14 pelitic samples used in the study, showing locations, the stop numbers listed in Coombs
& Cox (1991), textural zones, reported mineral (metabasite) facies, minerals identified in the < 2 µm fraction by XRD,
and illite intensity ratio (Ir) data by the method of árodori (1984). Numbers greater than 1 indicate the presence of
interlayered smectite.

Sample Locality Stop Textu- Mineral facies < 2 µm assemblage Ir

ral
zone

NZ29 Rocky Point Quarry, Mossburn 4 1 Zeolite IU/Mus, Chi, Kin, Ab, Kfs, Qtz,
Lmt, Sm 1.5
NZ8 Benmore Dam (Shore platform) 1.3C 1 Zeolite Ill/Mus, Chi, Ab, Kfs, Qtz 1.2
NZ4 Deep Creek (Waimate Gorge) 1.1 1 Prh-pmp Ill/Mus, Chi, Qtz 1.5
NZ9 Dalrachnie Bridge (Longslip Creek) 1.4 2A Prh-pmp Ill/Mus, Chi, Ab, Kfs, Qtz, Sm 1.0
NZ11 Longslip Creek 1.5 2B Prh-Act Ill/Mus, Chi, Ab, Kfs, Qtz 1.0
NZ41 Watsons Beach 5.4 2 Pmp-bearing# Ill/Mus, Chi, Kin, Ab, Sm 1.0
NZ42 Taieri Mouth 5.5 2 Pmp-bearing# Ill/Mus, Chi, Kin, Ab, Kfs, Sm,
Stp, Pmp 1.0
NZ45 Lake Hawea to Lake Wanaka road
section - 3A Greenschist Ill/Mus, Chi, Ab, Kfs, Sm 1.0
NZ23 Remarkables 2.6 3 Greenschist Ill/Mus, Chi, Ab, Kfs 1.0
NZ15-P Lindis River (south of Goodger Road) 1.7 3 Greenschist Ill/Mus, Chi, Ab, Kfs 1.0
NZ15-S Lindis River (south of Goodger Road) 1.7 3 Greenschist Ill/Mus, Chi, Ab, Kfs, Stp 1.0
NZ46 Lake Hawea to Lake Wanaka road
section - 3B Greenschist Ill/Mus, Chi, Ab, Kfs 1.0
NZ17 Shotover River Bridge 2.1 4 Greenschist Ill/Mus, Chi, Ab, Kfs 1.1
NZ43 Lake Hawea to Lake Wanaka road
section - 4 Greenschist Ill/Mus, Chi, Ab, Kfs 1.0
P = phyll ite, S = schist, # = non-diagnostic mineral facies
118 L. N. Wan-
only minor igneous activity during metamorph-
ism, so the effects of local contact metamorphism,
which may complicate correlations, can be avoid-
ed.
Locality and mineralogical information for
the 14 pelitic samples used in this study, com-
prising mudstones, phyllites and schists selected
from across the region, are summarized in Table
1. Full details of the collection sites are given in
the field guide of Coombs & Cox (1991), from
which most of the following summary is drawn.
The samples cover the range of zeolite to green-
schist facies metamorphism, and span all of the
four textural zones defined by Bishop (1972).
Two uncleaved (textural zone 1) hard silty
mudstones of the zeolite facies were collected, the
first (NZ29) from Rocky Point Quarry, Mossburn,
and the second from the shore platform of the
Benmore Dam (NZ8). Laumontite-bearing assem-
blages have been described from the Rocky Point
Quarry, and were detected in the <2µm fraction
of sample NZ29, along with traces of discrete
smectite. Also recorded from this locality is a
vitrinite reflectance value of 0.94 %Rm oil
(Kisch, 1981), indicating a maximum temperature
of about 150°C (using the equation from Barker
& Goldstein, 1990). At the Benmore Dam locality,
metamorphic conditions were near the zeolite to
prehnite-pumpellyite facies transition, as laumon-
tite is partly replaced along small fractures by
prehnite and quartz. Five pelitic samples from tex-
tural zones 1 and 2 consist of two weakly cleaved
silty mudstones (NZ4 and NZ9) both of prehnite-
pumpellyite facies, a phyllite (NZ11) from a pum-
pellyite-actinolite facies locality, and two tuf-
faceous samples (NZ41 and NZ42), from local-
ities with non-diagnostic pumpellyite-bearing
assemblages. The remaining seven samples come
from textural zones 3 and 4, and consist of green-
schist facies grade phyllites (NZ45, NZ15-P,
NZ46, NZ43) and schists (NZ23, NZ17 and
NZ15-S).
In order to make a preliminary assessment of
the expandable nature of the illites, the intensity
ratio method of árodori(1984) was applied (Table
1), which showed small amounts of illite/smectite
mixed-layering to be present in only three samples
(Ir values between 1.2-1.5). All other pelites
yielded Ir values close to 1, indicative of non-ex-
pandable illites.
Analytical methods and data calibration
Samples were prepared and analyzed following
the methods outlined in Warr & Rice (1994),
using thick (>3mg/cm 2 ), sedimented, Sr-saturat-
ed clay fractions, with measurements made using
a Siemens D5000 diffractometer at 40 kV and 30
mA and CuKα radiation, aperture diaphragms all
1°, detector diaphragm 0.05°, graphite monochro-
mator and a time constant of 1 s. Three XRD slide
preparations from each sample were scanned both
in the air-dried and glycolated conditions from 2
to 50°, at a scan-rate of 0.6°29/min and a step-
width of 0.01°. All data presented are mean values
based on measurements of three slide preparations
per sample (n = 3).
Baosal illite 001 (-10-Å), 002 (»5-Å), 003
(«3.3-Å) and 005 («2-Å) reflections and chlorite
001 (-14-Å), 002 (*7-Å), 003 (-4.7-Å), 004
(-3.5-Å) reflections were fitted using the program
FIT (Siemens version 3.0) by the following treat-
ment of the raw data file. A linear background
level was removed and selected reflections fitted
using a Split Pearson VII function. Various peak-
fitting trials were performed in order to establish
the most reliable peak-fitting requirements, which
satisfactorily modelled both the peak profile and
background level. Although Kα 2 was retained for
peak-breath measurements at low 20 angles (to
maintain better counting statistics), the influence
of this reflection was subtracted by peak fitting
prior to crystallite size calculations. Suitably fitted
profiles were transferrred to the WIN-CRYSIZE
(version 1.0) program and calculations made from
single peaks and peak-pair combinations, using
both the Warren-Averbach (W-A) method and a
Siemens Single-Line (S-L) Fourier method.
Further details about these methods are given in
the Siemens WIN-CRYSIZE (1991) handbook
and in Eberl & Blum (1993).
The W-A method (Warren & Averbach, 1950)
is considered to be the more ideal method for
calculating the crystallite size of clay minerals, as
it can yield a crystallite size distribution from the
modelled diffraction profile (Eberl & árodori,
1988; Eberl & Blum, 1993). In summary, it sepa-
rates the crystallite size coefficient (AL*), which is
independent of the order of reflection, and the dis-
tortion (microstrain) coefficient (ALD), which is a
function of the order of reflection, from the Fou-
rier coefficients (An) of at least two basal reflec-
tions (Warren & Averbach, 1950; Warren, 1959;
Klug & Alexander, 1974). The method can also be
 Clay mineral crystallinity and very low-grade metamorphism
used on single reflections, if the broadening effect
is assumed to arise from one effect only (e.g. crys­
tallite size). The Single-Line (S-L) method (Sie­
mens WIN-CRYSIZE, 1991) also uses the Fourier
Transform of the pure broadening function, but it
assumes that small crystallites cause peak broad­
ening in the form of a Lorentzian curve, and that
strain causes peak broadening in the form of a
Gaussian curve (Warren-Averbach, 1950). Al­
though the S-L method works with only one peak
reflection, and is intended from peaks which are
broadened both by crystallite size and microstrain
effects, calculations were notably more precise
and faster (over six times quicker) than the W-A
method.
All crystallite size calculations were made
using the machine broadening profiles determined
on the single-crystal mica standard (MF1C) of
Warr & Rice (1994) for which the basal reflection
FWHM data is available. As no suitable single-
crystal chlorite flake could be found, and attempts
to produce sufficiently narrow reflections using
coarsely crystallite chlorite-bearing samples
proved unsuccessful, a "chlorite" standard was as­
sembled by modification of a MF1C fitted data
file. The nearest neighbor basal mica reflection
was used, to reduce any 20 dependant differences,
and the peak positions were adjusted to corre­
spond with the chlorite reflections of a natural
sample (NZ45), displaying rationally spaced re­
flections with the minimal of peak interference,
the highest peak intensities and the narrowest
peak-widths. This standard is considered realistic,
as the machine broadening profile should be simi­
lar for both muscovite and chlorite, regardless of
the difference in d-spacing. It also discounts any
discrepancies that may be introduced by using dif­
ferent mineral standards, which can be variably
influenced by factors other than the machine
broadening.
Experimental data was converted to calibrat­
ed CIS data using the procedure and standards of
Warr & Rice (1994). Clay mineral crystallinity,
measured as the Full-Width-at-Half-Maximum
(FWHM), was calibrated using the regression data
shown in Fig. 1. The excellent linear fit of exper­
imental to calibrated values yielded a R2 value of
0.996, based both on air-dried and glycolated
preparations. Crystallite (domain) size (L) data did
not require any conversion as no difference was
detected between experimental runs and the pub­
lished standardized L values for the CIS samples,
when using compatible measurement methods.
119
0.8 j
°Δ26
-o °-4 t f
ω I *[
.Q I f
% 0.2 I >*
==>
I s
0 I r 1 1 i 1
0 0.2 0.4 0.6 0.8
Calibrated (CIS) data (FWHM) °Δ2B
Fig. 1. Data used to convert experimental FWHM data
to calibrated Crystallinity Index Standard data: CIS data
= (uncalibrated data/1.0377) + 0.04634, R2 = 0.996.
Results
Diffraction characteristics and measurement
precision
Clay mineral crystallinity and crystallite size data
for the basal reflections of illite and chlorite are
shown in Table 2. Overall, the FWHM data from
glycolated (GY) slides are similar to air-dried
preparations (within the limits of error), except
from the following differences. The three least
metamorphosed samples (NZ29, NZ8 and NZ4),
show slight reductions in illite 001 peak-widths
(10-14% narrower) due to the presence of small
quantities of interlayered smectite. All other samples
showed no significant narrowing of this peak,
confirming the absence of mixed-layered smec­
tite, as indicated by the preliminary expandability
data presented in Table 1. Samples containing
small amounts of discrete smectite (NZ29, NZ9,
NZ41 and NZ45), show significant narrowing of
the chlorite 001 peak-width upon glyeolation, as
the 001 smectite reflection shifts from around
6°20 in the air-dried state to about 5.2 °26 when
glycolated. The presence of smectite in these sam­
ples is most likely due to the effects of secondary
low temperature hydrothermal alteration or recent
weathering.
During glycolation of three greenschist facies
samples (NZ23, NZ15-P and NZ46), significant
increases in peak-breadths were incurred at low
two theta angles, affecting both illite and chlorite
reflections. This uncommon feature is most prob-
120 L. N. Wan-

Table 2. Clay mineral crystallinity and crystallite size data for the 14 pelitic samples from southern New Zealand.
Symbols used: # denotes two non-diagnostic pumpellyite-bearing samples; FWHM = Full-width-at-half-maximum;
W-A = Warren-Averbach method; S-L = Single-Line method; GY = Glycolated. All FWHM values are given in units
of °Δ2β, in contrast to W-A and S-L crystallite size thickness (L), which are expressed in nm. * marks peak reflections
in which Kcc2 radiation was retained during analysis.

Mineral Fades Zeolite Prh-Pmp and Pmp-Act Greenschist

NZ29 NZ8 NZ4 NZ9 NZ11 NZ41# NZ42# NZ45 NZ23 NZ15-P NZ15-S NZ46 NZ17 NZ43 % error
n=30
lllite

001 FWHM* 0.62 0.51 0.28 0.32 0.27 0.31 0.23 0.18 0.17 0.19 0.25 0.19 0.23 0.25 6
002 FWHM* 0.50 0.43 0.28 0.30 0.25 0.31 0.20 0.17 0.16 0.18 0.20 0.18 0.20 0.20 10
003 FWHM* 0.56 0.46 0.22 0.28 0.21 0.33 0.21 0.17 0.17 0.18 0.22 0.18 0.20 0.20 7
005 FWHM 0.76 0.70 0.34 0.33 0.19 0.32 0.19 0.14 0.15 0.13 0.19 0.14 0.14 0.15 5

001 F W H M * G Y 0.56 0.46 0.24 0.31 0.26 0.30 0.23 0.18 0.25 0.21 0.24 0.27 0.21 0.22 7
002 F W H M * G Y 0.58 0.51 0.25 0.31 0.25 0.32 0.21 0.18 0.21 0.21 0.23 0.23 0.20 0.20 7
003 F W H M * G Y 0.38 0.38 0.23 0.33 0.20 0.30 0.18 0.18 0.20 0.20 0.20 0.21 0.19 0.19 6
005 F W H M G Y 0.80 0.68 0.33 0.32 0.18 0.33 0.17 0.14 0.17 0.14 0.18 0.15 0.16 0.15 4

001 W-A 8 7 39 21 22 26 42 31 19 24 26 21 18 21 27
002 W-A 28 22 38 24 48 44 36 74 59 58 46 53 43 52 22
003 W-A 32 24 60 39 58 35 146 110 66 64 121 83 49 59 16
005 W-A 11 9 23 23 23 32 46 130 64 107 35 89 61 72 21

001 S-L 13 13 28 25 33 27 37 60 55 55 35 50 38 34 7
002 S-L 16 17 32 27 36 27 53 86 73 72 40 70 57 52 11
003 S-L 27 18 44 22 33 27 92 133 118 108 72 105 89 80 10
005 S-L 12 12 28 27 58 28 71 170 125 189 64 151 129 115 7

001-002 W-A 7 7 31 31 19 24 43 26 16 20 23 18 15 18 26
001-003 W-A 9 7 39 39 21 26 40 29 18 23 25 20 17 20 23
001-005 W-A 7 7 39 39 24 27 42 31 19 25 27 21 18 22 23
002-003 W-A 25 23 33 33 40 50 24 59 54 54 31 41 39 46 28
002-005 W-A 32 24 42 42 51 45 36 69 59 54 47 50 41 49 22
003-005 W-A 154 39 92 92 56 36 190 103 69 54 143 81 46 54 20
All peaks W-A 15 11 42 42 39 35 50 46 30 36 15 32 26 31 19

Chlorite

001 FWHM* 0.66 0.42 0.48 0.31 0.41 0.45 0.37 0.18 0.19 0.24 0.19 0.26 0.38
002 FWHM* 0.44 0.59 0.31 0.35 0.30 0.34 0.33 0.18 0.18 0.20 0.24 0.20 0.22 0.24
003 FWHM* 0.44 0.44 0.31 0.37 0.27 0.29 0.24 0.16 0.17 0.18 0.24 0.19 0.21 0.23
004 FWHM* 0.45 0.44 0.34 0.36 0.26 0.22 0.17 0.19 0.18 0.18 0.23 0.18 0.21 0.20

001 F W H M * GY 0.59 0.44 0.37 0.29 0.20 0.21 0.25 0.22 0.21 0.29 0.25 0.37 10
002 F W H M * GY 0.49 0.45 0.30 0.38 0.30 0.35 0.32 0.18 0.25 0.20 0.24 0.27 0.21 0.22 8
003 F W H M * GY 0.44 0.53 0.22 0.39 0.27 0.30 0.26 0.18 0.22 0.20 0.22 0.24 0.19 0.20 7
004 F W H M * GY 0.44 0.41 0.37 0.26 0.28 0.17 0.18 0.21 0.20 0.23 0.21 0.18 0.19 4

001 W-A 16 19 17 28 20 53 38 18 32 28 24 32 36
002 W-A 19 19 40 20 22 27 24 48 27 45 42 37 34 23 13
003 W-A 8 13 15 12 27 10 33 56 27 54 40 44 29 14 26
004 W-A 30 26 7 21 68 19 29 93 41 81 51 65 47 38 27

001 S-L 13 16 15 26 16 32 54 47 48 38 47 33 16
002 S-L 19 17 26 16 29 24 34 68 57 58 37 56 38 36 11
003 S-L 18 15 25 20 33 25 39 80 66 67 43 65 45 41 11
004 S-L 18 17 20 17 39 22 36 120 97 95 49 97 61 75 13

001-002 W-A 14 18 20 29 19 61 35 16 30 26 22 31 40
001-003 W-A 15 20 15 28 21 57 37 17 31 28 23 32 34
001 -004 W-A 14 19 18 27 13 56 37 17 31 29 24 31 35
002-003 W-A 26 25 44 7 20 35 21 43 27 40 54 33 35 32 23
002-004 W-A 16 17 48 8 19 30 25 42 24 40 56 33 31 21 22
003-004 W-A 5 10 35 4 15 4 48 38 19 39 54 31 19 38
All peaks W-A 13 15 11 10 14 35 38 19 34 35 27 31 27
 Clay mineral crystallinity and very low-grade metamorphism
ably the result of a significant loss in the degree of
preferred particle orientation incurred during gly-
colation, which could give rise to small amounts
of additional broadening as a result of diverging
beam conditions in the incident X-rays. This ef­
fect is only resolvable in the more coarsely crys­
talline samples, where peak-broadening effects
due to crystallite size are small.
The progressive narrowing of the clay min­
eral peaks with increasing order of reflection was
a characteristic observed in XRD profiles of the
higher-grade metamorphic samples (ICooi<0.3
°Δ20). This feature, which is reflected in both the
FWHM values and the increasing values of L with
increasing 20 (Table 2), is considered to be a con­
sequence of the strong size grading which occurs
during sedimentation of the clay specimen
(Krumm & Buggisch, 1991). This effect is less
pronounced in diagenetic grade samples because
they contain a much narrower range in grain size
and particle thickness than that recorded from
more metamorphosed samples (Cashman & Ferry,
1988; Eberl et al, 1990). However, attempts at
producing more homogeneous preparations by the
filter transfer method of Moore & Reynolds
(1989), resulted in rather poorly orientated prepa­
rations, yielding markedly reduced peak intensi­
ties and unacceptable levels of measurement
precision. Results from sedimented (or centri-
fuged) clay preparations should therefore be con­
sidered as representing minimum estimates of the
true average crystallite size of a homogeneous
< 2 µm fraction, particularly when dealing with
more metamorphosed samples.
Overall, results from all illite and chlorite
peaks record an increase in the effective crystallite
size with prograde metamorphic conditions,
marked by decreasing FWHM values, and in­
creasing L dimensions calculated both by the W-A
and S-L methods. The precision of measurement
varies widely with the method applied. The most
reproducible measurements were made by the
FWHM (5-10% errors) and S-L (7-11% errors)
methods, while the highest levels of uncertainty
were incurred during calculations employing the
W-A method (13-40% error range), on both
single reflections and peak-pair combinations.
Illite and chlorite peak correlations
Regression analysis between all the various illite
and chlorite peak reflections listed in Table 2 were
carried out, in order to establish which peak com­
121
binations and measurement methods show the
highest level of correlation, and better reflect me­
tamorphic grade. Correlations between FWHM
data of illite and chlorite produced good linear or
logarithmic best fit curves ranging from R2 =
0.811 to 0.886. Similarly, excellent linear correla­
tions exist when plotting L calculated by the S-L
method for illite and chlorite, yielding R2 values
between 0.852 and 0.955. This high degree of
precision and correlation between illite and chlo­
rite characterizing the FWHM and S-L methods is
also accompanied by a good correspondence with
the mineral facies assemblages. In contrast, how­
ever, the lower precision of the W-A method data
produced very poor linear regression results be­
tween illite and chlorite, (R2 values between 0.111
and 0.588) and hence a poor correspondence to
the mineral facies.
The most useful combinations are shown in
Fig. 2 as log-log graphs, which were used in pref­
erence to linear plots as they presented a more
even spread of the data points in respect to meta­
morphic grade. The regression data presented is,
however, the same as that determined on linear
graphs. Fig. 2 a shows an excellent linear correla­
tion (R2 = 0.974) between peak-widths of illite
001 and illite 002 reflections, the latter of which is
usually narrower. The slope of the linear fit is,
however, slightly lower than that recorded from
similar grade samples of southern Spain (Nieto &
Sanchez-Navas, Fig. 2, 1994), which is probably
the result of not using an automated slit in the dif­
fraction setup (Nieto, pers. comm.). The best
peak-width correlations between illite and chlorite
reflections are shown in Fig. 2b and 2 c. A good
logarithmic correlation (R2 = 0.886) exists be­
tween illite 001 and chlorite 002 FWHM data, al­
though, if the samples containing small amounts
of mixed-layered smectite are excluded, the best
fit regression is a 1:1 linear curve (R2 = 0.791)
which is plotted on Fig. 2 b. A plot of illite 002
against chlorite 003 also shows a good (R2 =
0.830) 1:1 linear fit without the exclusion of ex­
pandable illites. Crystallite size results from the
chlorite 001 or 002 reflections have not been plot­
ted due to the interference by the smectite peak at
15-Å and the kaolin (terminology of Ehrenberg et
al., 1993) peak at 7-Å, present in some of the
samples (Table 1). The highest degree of correla-
tion between illites and chlorites was recorded
from L data calculated by the S-L method on the
illite 002 and chlorite 003 reflections (Fig. 2d).
An excellent linear regression curve (R2 = 0.955)
122 L. N. Warr

X
w

o
o

o
u

l°Δ26 0.1 ΓΔ29

Illite 001 (FWHM) Illite 001 (FWHM)

1°Δ20 c) 100 nm d)

jo
U

1°Δ26 100 nm

Illite 002 (FWHM) Illite 002 (L)

• Epizone

A
• Greenschist facies

Pumpellyite-actinolite facies

B Anchizone
Δ Prehnite-pumpellyite facies 1

π Diagenetic zone D
*
Zeolite facies

Non-diagnostic pumpellyite
bearing assemblages

Fig. 2. Useful peak combinations plotted as log-log graphs, a) Illite 001 FWHM vs illite 002 FWHM, with a best fit
linear regression expressed as: y = 0.0354 + 0.774x, R 2 = 0.974. b) Illite 001 FWHM vs chlorite 002 FWHM. The
best fit curve is logarithmic, expressed as y = 0.5835 + 0.52045*LOG(x), R 2 = 0.886. The linear regression y =
-0.0161 + 1.1438x, R 2 = 0.791, shown on the graph, is the best fit if the two zeolite facies samples are not considered,
c) Illite 002 FWHM vs chlorite 003 FWHM. y = -0.00536 + 1.0903x, R 2 = 0.830. d) Illite 002 L vs chlorite 003 L
determined by the Single-Line method, y = -0.992 + 0.9056x, R 2 = 0.955.
 Clay mineral crystallinity and very low-grade metamorphism 123

for these data, does not show a 1:1 trend, as
shown by FWHM data for these peaks, but sug­
gests the chlorites have slightly smaller crystallite
sizes than grade-equivalent illites.
Employing the ICQOI anchizonal boundary
limits of Kiibler (1967), which are adopted by the
CIS scale, the equivalent boundary limits for the
other peak reflections are presented in Table 3,
based on the regression data given in the caption
of Fig. 2. As the CIS crystallite size limits of the
anchizone presented in Warr & Rice (1994) were
determined from the less accurate W-A calcula­
tions on the glycolated illite 002-005 combina­
tions, these limits are considered an approxima­
tion only.
All selected boundary limits show a good
correspondence between clay mineral crystallinity
data and mineral facies assemblages (Fig. 2 a - d ) .
The two zeolite facies samples correspond with
the diagenetic zone, the prehnite-pumpellyite and
pumpellyite-actinolite facies with the anchizone,
and the greenschist facies samples with the epi-
zone. Within the boundary limits presented in
Table 3, over 90% of the 65 measurements plotted
in Fig. 2 a - d correspond with the expected min­
eral facies conditions. The position of the two
non-diagnostic pumpellyite-bearing samples would
suggest that NZ41, which is of middle to upper
anchizonal grade, is of pumpellyite-prehnite
facies, and NZ42, which falls around the upper
anchizone/epizone boundary, is of pumpellyite-
actinolite facies.
Also shown in Fig. 2d, is the relationship be­
tween illite and chlorite crystallite size thick­
nesses and the assigned textural zones (1-4).
Overall, larger L is commonly associated with the
increasing intensity of deformation (as recorded in
the greywacke units), with textural zone 1 sam­
ples corresponding mostly to the diagenetic grade,
textural zone 2, mostly to the anchizone, and tex­
tural zones 3 and 4, largely to the epizone. The re­
lationship is, however, not mutually exclusive,
with a textural zone 1 sample occurring in the an­
chizone, and a textural zone 2 sample occurring
near the anchizone/epizone boundary, along side
textural zone 4 schists.
Discussion

Procedures for determining clay mineral

Table 3. Preliminary correlation of the anchizonal
boundary limits for both illite and chlorite crystallinity
crystallinity and crystallite size
(FWHM in °Δ26) and crystallite size (L in nm), adopting Ideally, the most suitable basal reflections for
the ICooi limits of Kiibler (1967), presented for
measuring clay mineral crystallinity and crystal­
comparative purposes only. All other limits presented are
based on linear or logarithmic (*) regression of the data
lite size are those which are broadened minimally
shown in Fig. 2 a - d . by effects other than crystallite size (the X-ray
scattering domain size), and can be precisely meas­
Illite 001 Illite 002 Illite 002 ured. Therefore, the narrower, symmetrical, higher
(FWHM) (FWHM) (L)
intensity basal reflections, which show minimal
Low-grade anchi­ interference by other mineral phases, and allow
zonal boundary 0.42 0.36 23 precise fitting of both the peak profile and the
High-grade anchi­ background level, are preferred. Realistically,
zonal boundary 0.25 0.23 52 however, these criteria are rarely satisfied, and the
optimum reflections will vary with the mineralogy
Chlorite 002 Chlorite 003 Chlorite
(FWHM) (FWHM) 003 (L) of samples.
The illite 001 air-dried peak has been tradition­
Low-grade anchi­
ally used for crystallinity studies, following the
zonal boundary 0.42 0.36 20
work of KÜbler (1967, 1968, 1984, 1990). How-
High-grade anchi­ ever, while this relatively intense reflection has
zonal boundary 0.25 0.23 46
proven adequate for the general assignment of
Chlorite 002 metamorphic grade, in illites with significant
(FWHM)* swelling properties, it is strongly broadened
Low-grade anchi­ (asymmetrically) by the presence of interlayered
zonal boundary 0.39 smectite (Moore & Reynolds, 1989; Stern et al.,
High-grade anchi­ 1991; Nieto & Sanchez-Navas, 1994). More
zonal boundary 0.27 recently, Eberl & Blum (1993) and Nieto & San-
chez-Navas (1994) suggest that the air-dried Ca-
124 L. N. Warr
or Sr-saturated illite 002 peak is a more suitable
reflection for analysis, which is not interfered by
the presence of interlayered smectite with two
water layers (d=15-Å) when expandibilities are
less that 20%. Although not very common in very
low-grade metamorphic pelites, peak interference
will occur in the presence of interlayered smectite
containing one water layer (d= 12.5-Å). In the lat-
ter case, K-saturated samples may be used to in-
duce collapse of the smectite layers to approxi-
mately 10-Å (Eberl et al., 1987).
With respect to chlorite, the most commonly
used peak is the intense chlorite 002 air-dried re-
flection (e.g. Dandois, 1981; Braukmann, 1984;
Arkai, 1991), which usually allows good fitting of
the background level. However, this peak is strong-
ly overlapped by the presence of kaolin (001 re-
flection), which is commonly encountered in very
low-grade metamorphic samples. For this reason,
the chlorite 003 peak was preferred in this study
for crystallite size calculations.
Use of the illite 002 and chlorite 003 peaks
(Fig. 2) gave the highest degree of correlation (R2
= 0.955) in comparison to other basal illite and
chlorite peak combinations (R2 range of 0.811-
0.951), despite their significantly lower intensities
in comparison with the more commonly used illite
001 and chlorite 002 peaks. The illite 002/chlorite
003 combination also showed an excellent corre-
lation with the mineral facies assemblages. These
two adjacent reflections can be accurately meas-
ured by an ultra-precise (very slow) high resolu-
tion scan of less than 6°Δ20, from which both
peaks can be simultaneously fitted. The proximity
of these two reflections has the advantage that 20
related differences are minimized, but the dis­
advantage that the peak-tails overlap on broad re­
flections.
Comparisons between FWHM and Fourier
determined L data, calculated from illite 002 and
chlorite 003 peaks, may also yield important in­
formation about the type of broadening, and hence
the nature of the X-ray scattering domains. This is
illustrated in the regression data of Fig. 2 c, d,
where FWHM data suggests a 1:1 relationship be­
tween illite and chlorite, in contrast to the S-L
data which indicate that chlorites are, on the
whole, slightly smaller in domain thickness than
grade equivalent illites. As FWHM measurements
are less sensitive to broadening in the tails of the
profiles, than are the S-L and W-A methods, these
differences are probably reflective of more diffuse
Lorentzian type broadening in the limbs of the
chlorite peaks which may arise due to the pres­
ence of planar defects such as stacking faults (Er-
gun, 1970; Moore & Reynolds, 1989). Careful ex­
amination of scaled and superimposed illite and
chlorite peak profiles confirmed the presence of
slightly broadened chlorite tails in 9 of the 14
samples. Another potential source of peak broad­
ening is that of microstrain, but as no significant
levels of strain were recorded by either the W-A or
S-L methods, this effect is largely discounted.
The W-A method (the preferred method of
Eberl et al, 1988; Eberl & Blum, 1993; Warr &
Rice, 1994), proved to be a slow, imprecise and
inaccurate procedure for determining crystallite
size in polymineralic samples, probably a result of
its sensitivity to peak fitting errors and back­
ground corrections. This method is therefore only
recommended for more in depth study of mono-
mineralic samples, when the crystallite size distri­
bution is required, and where peak-fitting errors
can be minimized. The preferred method of this
study was the S-L Fourier method, which pro­
duced faster, more precise and apparently more
accurate results than the W-A method. This is des­
pite the reservations mentioned in the Siemens
WIN-CRYSIZE handbook, which states that the
S-L method should only be used when both crys­
tallite size and microstrain effects are present.
Preliminary constraints for the Crystallinity
Index Standard scale
CIS data from the very low-grade metamorphic
rocks of southern New Zealand conform to a gen­
eral pattern in which diagenetic grades correspond
to the zeolite facies, anchizone mostly to the preh-
nite-pumpellyite and pumpellyite-actinolite facies,
and epizone to the greenschist facies (Fig. 2). Al­
though there are too few samples to draw more
accurate boundary limits, the greenschist to pum-
pellyite-prehnite facies transition appears to lie
around ICooi 0.25-0.27 °Δ20, ChC002 0.24-0.31
°Δ20, while the boundary with the zeolite facies
occurs in the range ICooi 0.32-0.51 °Δ20, CI1C002
0.35-0.44 °Δ20. These correlations correspond
well with the original anchizonal boundary limits
of Kiibler (IC00i 0.25 and 0.42 °Δ20) which
are adopted by the CIS scale. Employing the pe-
tro- genetic grid of Frey et al. (1991), and the cor­
relations presented in Fig. 2, some general P-T
constraints can be presented for the anchizonal
range of metamorphism presented in this study.
Although the mineral facies overlap considerably
 Clay mineral crystallinity and very low-grade metamorphism
(Fig. 10 of Frey et al., 1991), correlating the
anchizone with the prehnite-pumpellyite facies
indicates a P-T field from about 175 to 280 °C
and 0.5 to 4.5 kbar, while inclusion of the pum-
pellyite-actinolite facies extends the temperature
field up to a maximum of about 320 °C at pres-
sures below < 4 kbar.
Further correlations for both crystallinity and
crystallite size values, based on regression anal-
ysis of the illite 001, 002 and chlorite 002, 003 re-
flections (Table 3) are preliminary, and intended
for comparative purposes only. Correlation of the
peak breadths of illite 001 against chlorite 002
show a proportional relationship, as recorded by
Duba & Williams-Jones (1983), in contrast to the
studies of Dandois (1981), Braukmann (1984) and
Arkai (1991), which reported narrower chlorite
peaks. Such differences may simply reflect vary-
ing amounts of mixed-layered smectite which
broadens the illite 001 in respect to the chlorite
002 peak, or alternatively such differences may
also arise from variations in growth rates of the
restrictive phyllosilicate minerals. A third alterna-
tive may be related to the density of planar defects
within the minerals. While correlations between
different minerals do yield more crystal-chemical
information than considering one mineral alone
(Arkai, 1991), and more mineralogical informa-
tion is obtained by employing a wider range of ba-
sal reflections and measurement methods, caution
is required when comparing metamorphic bound-
ary limits between different sample groups which
may vary in both mineralogy and P-T-t history.
Conclusions
1. A pilot study of the clay mineral crystallinity
and crystallite size of illites and chlorites from 14
pelitic samples of known mineral facies condi-
tions, suggest that the Crystallinity Index Stand-
ard (CIS) scale is a reliable indicator of metamor-
phic grade. However, before more accurate com-
parisons can be drawn between studies, adequate
attention needs to be given to, A) calibration of
the experimental data, and B) selection of suitable
peak reflections.
2. The illite 002 and chlorite 003 peaks proved
the two most useful peak reflections in this study
as they are broadened only by crystallite size ef-
fects, are minimally influenced by 20 dependent
differences, and are less effected by other overlap-
ping mineral phases.
125
3. The Siemens Single-Line method provided
a more rapid and more precise measure of crystal-
lite size than the Warren-Averbach method, as it is
not so sensitive to peak-fitting errors.
4. The anchizonal range of illite and chlorite
crystallinities (and crystallite sizes) from southern
New Zealand, measured by the CIS scale, corre-
sponds to mineral facies with stability ranges be-
tween 175 to 320 °C and 0.5 to 4.5 kbar. Differen-
ces between kinetically controlled clay mineral
crystallinity and thermodynamically based min-
eral facies assemblages are anticipated to exist be-
tween very low-grade metamorphic rocks of con-
trasting P-T-t histories.
Acknowledgements: Thanks to J. árodoh (Kra-
kow) and an anonymous referee for reviewing this
paper, and to W. V. Maresch for his editorial com-
ments. Also thanks to D. S. Coombs (Dunedin), S.
C. Cox (Dunedin), M. Frey (Basel), H. J. Kisch
(Negev), F. Nieto (Granada), A. H. N. Rice (Hei-
delberg), and W. B. Stern (Basel) for comments
and discussion on earlier versions of the manu-
script. This paper is a contribution to IGCP 294.
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Received 20 September 1994
Modified version received 25 July 1995
Accepted 13 September 1995