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The accurate crystal chemistry of ferric smectites from the

lateritic nickel ore of Murrin Murrin (Western Australia). II.
Spectroscopic (IR and EXAFS) a....

Article  in  Clay Minerals · December 2004

DOI: 10.1180/0009855043940147

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Clay Minerals (2004) 39, 453–467

The accurate crystal chemistry of ferric

smectites from the lateritic nickel ore of
Murrin Murrin (Western Australia). II.
Spectroscopic (IR and EXAFS) approaches
A . G AUDIN1 , 3 , * , S . P ETIT2 , J . R OSE3 , F . M ARTIN4 , A . D ECARREAU2 , Y . N OACK3
3
AND D . B ORSCHNECK

1
UMR CNRS 6112, Laboratoire de Planétologie et Géodynamique, Faculté des Sciences et Techniques, Université de
Nantes, BP-92208, 44322, Nantes Cedex 03, 2 UMR CNRS 6532, HydrASA, Université de Poitiers, 40, avenue du
Recteur Pineau, 86022 Poitiers Cedex, 3 CEREGE, UMR CNRS 6635 Université Aix-Marseille III, Europôle
Méditerranéen de l’Arbois, BP 80 F-13545 Aix-en-Provence Cedex 04, and 4 L.A.S.E.H., Faculté des Sciences et
Techniques, Université de Limoges, 87060 Limoges Cedex, France

(Received 27 February 2003; revised 2 February 2004)

AB ST R ACT : Fe-rich smectites from lateritic weathering profiles have previously been studied by
XRD, ICP-AES, SEM-EDX and TEM-EDX analyses (Gaudin et al., 2004). These smectites exhibit
intermediate chemistries between five end-members: Al-Fe beidellites, Al-Fe montmorillonites and
Mg+Ni-saponite. The spectroscopic study by FTIR and XAS of these smectites reveals that:
(1) tetrahedral Fe3+ is near or below the detection limit (0.05 cation for 4Si); (2) the large chemical
variability is due to substitution of the three major cations (Fe, Al, Mg) within adjacent octahedra;
(3) Ni is not concentrated in another clay phase such as Ni-kerolite and is located in the octahedral
sheets of smectite; (4) octahedral cations are not randomly distributed but ordered in separated Fe,
Al, Mg, Ni clusters; (5) the Mg-Ni saponite end-member actually appears as small trioctahedral
clusters of Mg and Ni distributed within the dioctahedral smectite.

KEYWORDS: smectites, infrared spectroscopy, Ni, laterite, Murrin Murrin, Australia.

Smectites from the smectite zone of Murrin Murrin
(M.M.) weathering profiles (Western Australia),
developed on serpentinized peridotites (Camuti &
Gifford, 1997), were previously investigated from
macroscopic to clay-particle scale (Gaudin et al.,
2004). The mineralogy and crystal-chemistry of
smectites were studied by XRD and chemical
analyses (ICP-AES, SEM and TEM-EDX). The
results from this previous study were that M.M.
smectites are dioctahedral, Fe3+ being the predomi-
* E-mail: anne.gaudin@chimie.univ-nantes.fr
DOI: 10.1180/0009855043940147
nant octahedral cation, more or less substituted by
Al3+, Mg2+, Ni2+ and Cr3+. Chemical variations
arise from (Mg+Ni) for (Fe3++Cr) and Al for
(Fe3++Cr) substitutions within the smectite layers,
leading to chemistries intermediate between five
end-members: Al- and Fe-beidellites, Al- and Fe-
montmorillonites and Mg-Ni saponite. The main
result was that natural Fe-montmorillonites are
more common than reported in the literature as
suggested by Petit et al. (2002), and that a chemical
continuity exists between the Fe-nontronite and the
Fe-montmorillonite end-members.
In phyllosilicates, the degree of the short-range
order-disorder in the distribution of isomorphous

# 2004 The Mineralogical Society

 454

TABLE 1. Structural formulae of Murrin Murrin smectites studied (after Gaudin et al., 2004).

‘Plasma-smectites’ ‘Fissure-smectites’
Samples 5-19 5-23 5-25 5-36 5-37 5-43 5-19F 5-36F 5-37F 5-44F 5-46F 2-17F 2-19F 2-21F 2-22F

IV Si4+ 3.79 3.79 3.85 3.82 3.89 3.75 3.69 3.82 3.84 3.89 3.81 3.85 3.79 3.81 3.80
IV Al3+ 0.21 0.21 0.15 0.18 0.11 0.25 0.31 0.18 0.16 0.11 0.19 0.15 0.21 0.19 0.20
VI Al3+ 0.08 0.10 0.19 0.12 0.17 0.26 0.47 0.18 0.91 0.51 0.62 0.55 0.49 0.63 0.36
VI Fe3+ 1.30 1.34 1.30 1.39 1.28 1.37 0.87 1.31 0.60 1.02 0.94 0.96 0.98 0.96 1.19
VI Mg2+ 0.58 0.57 0.45 0.32 0.48 0.20 0.72 0.45 0.39 0.19 0.26 0.30 0.36 0.22 0.29
VI Cr3+ 0.05 0.02 0.03 0.09 0.06 0.08 0.09 0.07 0.06 0.12 0.14 0.13 0.08 0.08 0.09
VI Ni2+ 0.12 0.13 0.15 0.16 0.11 0.14 0.10 0.10 0.12 0.17 0.12 0.18 0.23 0.17 0.13

Inter. Ca2+ 0.26 0.22 0.19 0.23 0.20 0.22 0.19 0.19 0.20 0.22 0.17 0.14 0.18 0.22 0.22
A. Gaudin et al.

SVIR 2.13 2.16 2.12 2.07 2.10 2.05 2.25 2.12 2.09 2.01 2.08 2.12 2.15 2.05 2.06
VI
Al/SVIR 0.04 0.05 0.09 0.06 0.08 0.13 0.21 0.08 0.44 0.25 0.30 0.26 0.23 0.31 0.17
Total charge 0.52 0.43 0.38 0.45 0.40 0.44 0.39 0.39 0.40 0.44 0.33 0.29 0.35 0.44 0.44
Octa. char.% 59 51 61 61 71 43 20 54 61 75 44 46 41 56 45

Octa. char.: octahedral charge

Inter.: interlayer
 Spectroscopic study of ferric smectites
cations, both in octahedral and tetrahedral sheets, is
highly variable. The spectroscopic methods probe
local atomic environments and they are used to
study the distribution of cations within the
phyllosilicate sheets. Thus, the distribution of
octahedral cations was studied mainly by IR
(infrared) and EXAFS (Extended X-ray
Absorption Fine Structure) spectroscopies in:
micas (Slonimskaya et al., 1986, Besson et al.,
1987; Manceau et al., 1990; Besson & Drits,
1997a,b; Drits et al., 1997); smectites (Decarreau
et al., 1987; Madejova et al., 1994; Muller et al.,
1997; Manceau et al., 2000a; Vantelon et al.,
2001); (Ni-Mg)-talc, kerolite and lizardite (Wilkins
& Ito, 1967; Manceau & Calas, 1985, 1986;
Manceau, 1990; Decarreau et al., 1992; Ducloux
et al., 1993). In some phyllosilicates, a random
distribution of cations was observed (Wilkins & Ito,
1967; Decarreau et al., 1992; Ducloux et al., 1993),
but in many others the distribution of octahedral
cations appears at least somewhat ordered. The
degree of the short-range order-disorder in the
distribution of isomorphous cations can be used as
indicators of the conditions of crystallization of
phyllosilicates and more particularly as geotherm-
ometers. Indeed, from Mg-Ni kerolite and talc
synthesized at different temperatures, Decarreau et
al. (1992) showed that, for trioctahedral Mg-Ni
phyllosilicates, ‘‘when the temperature of synthesis
decreases, a tendency to clustering is observed and
is more marked for Ni atoms’’. This is consistent
with the large Ni-clusters observed in (Ni-Mg)-
phyllosilicates formed at low temperature in
lateritic weathering profiles (Manceau & Calas,
1985, 1986; Decarreau et al., 1987) and with the
random cation distribution observed in hydro-
thermal (Ni-Mg)-phyllosilicates (Ducloux et al.,
1993). On the other hand, the crystal-chemistry of
nickel in dioctahedral phyllosilicates has never been
studied, and M.M. smectites provide the opportu-
nity to study it. Moreover, little is known about the
crystal chemistry and the actual distribution of
octahedral cations in dioctahedral smectites formed
by the weathering of serpentinized peridotites.
Therefore, the aims of this study were to
determine the actual distribution of octahedral
cations in the M.M. smectites, and to compare
them with those of the Fe-montmorillonite from
Ölberg described as a weathering product of
peridotite nodules in Oligo-Pliocene basalts from
Rhineland-Palatinate (Germany) (Köster et al. 1999;
Petit et al., 2002).
455
MATERIALS AND METHODS
Accurate locations for weathering profiles of M.M.
smectite samples (<2 mm) were presented by
Gaudin et al. (2004). Briefly, the studied M.M.
smectites are either ‘plasma-smectites’ or ‘fissure-
smectites’. Their respective structural formulae are
presented in Table 1.
The SAz montmorillonite was used as a reference
sample. Its interlayer cations were previously
exchanged by Ni2+ cations using a solution of
NiCl2. The suspension of the sample was obtained
by agitation and was left to stand for 2 h. After
centrifugation, this process was repeated to achieve
complete Ni2+ exchange. The excess Ni salt was
carefully washed out with ethanol.
Fourier transform infrared (FTIR)
spectroscopy
A Nicolet 510 FTIR spectrometer was used to
record FTIR spectra at 4 cm 1 resolution in the
4000 400 cm 1 (MIR) region. The spectrometer
was purged continuously with dry air during
scanning of the transmission spectra. The KBr
pellets were prepared by mixing 1 mg of sample
with 150 mg of KBr and heated overnight at 110ºC
in order to evacuate the hygroscopic water.
X-ray absorption spectroscopy (XAS)
The XAS experiments were performed at the
LURE synchroton (Orsay, France) using the X-ray
beam emitted by the DCI storage ring on the D21
beamline. Spectra of M.M. smectite samples were
collected in transmission mode, at the Fe-K and
Ni-K edges. A Si(311) monochromator was used to
scan energy from 7000 to 8000 eV for the Fe-K
edge and from 8240 to 9000 eV for the Ni-K edge.
Spectra were recorded with 0.2 eV steps in the
X-ray absorption near edge structure (XANES)
region and 2 eV steps in the EXAFS region. The
Fe-K pre-edge part was extracted from the XANES
region and was normalized by fitting the photo-
electric background above the absorption with a
second-order polynomial function.
A standard procedure for data reduction was used
to analyse the measured Fe-K and Ni-K EXAFS data.
This was done using a series of programs developed
by Michalowicz (1991). The EXAFS oscillations
were normalized to the absorption jump and
extracted from the absorption spectrum. The resulting
456 A. Gaudin et al.
normalized EXAFS data w(E) were converted from
energy to wave vector w(k) by reference to threshold
energy E0. This function is the summation of the
elementary contributions to the EXAFS spectra of the
very first atomic shells surrounding the absorbing
atom. The EXAFS spectra were then Fourier
transformed to real space (R) using a Kaiser
apodization window with t = 2.5 (Bonnin et al.,
1985; Manceau & Combes, 1988). The resulting
radial distribution functions (RDF) are uncorrected
for phase shift leading to a shift of the peaks by
0.3 0.4 Å from the actual distances depending on
the considered atomic pair (absorber neighbouring
atoms). The locations of the peaks in the RDFs
represent the distances between the absorber and
successive shells of neighbouring atoms. The RDFs
of octahedral cations in 2:1 phyllosilicates exhibit a
first intense peak attributed to the oxygen coordina-
tion sphere and, a second intense peak which
corresponds to the summation of the second and
third coordination spheres, composed of nearest
octahedral cations (between 3 and 6 cations) and
nearest tetrahedral cations (4 (Si4++Al3+)), respec-
tively (Manceau & Calas, 1986; Manceau, 1990).
The backtransform of a given structural peak yields
the partial EXAFS spectrum of the atomic shell(s)
attached to this peak. Least-squares fitting of these
partial EXAFS spectra provide structural parameters,
such as average interatomic distances (r), Debye-
Waller factor (s) that accounts for static and
dynamic disorder, and the nature and number (N)
of neighbours.
The present study focuses on the cationic
environment of Fe and Ni atoms in the smectites,
thereby only the second RDF peak was treated. The
strong overlap of scattering contributions from the
nearest tetrahedral and octahedral cations implies
that we need to take into account these two
contributions when fitting partial EXAFS spectra
from the second peak (Manceau, 1990). Scattering
factors depend strongly on the atomic number of
atoms, therefore for equivalent interatomic
distances, the contributions of Fe, Ni and Cr
neighbours (‘heavy’ atoms) or Si, Al and Mg
neighbours (‘light’ atoms) are indistinguishable
from EXAFS analysis. Moreover, because: (1) the
number of independent parameters was too small to
allow the use of three atomic shells during the
fitting procedure and (2) the contribution of
octahedral ‘light’ atoms (Al and Mg) is very
difficult to quantify when the contribution of
octahedral ‘heavy’ atoms (Fe, Cr and Ni) is
strong, the Fe-K and Ni-K partial EXAFS spectra
of Fe-rich M.M. smectites were adjusted using only
two atomic pairs which correspond to the octahe-
dral ‘heavy’ atom contribution and the tetrahedral
contribution (Fe-Fe and Fe-Si for Fe-K data and Ni-
Ni and Ni-Si for Ni-K data). The contribution of
octahedral ‘light’ neighbours (Al and Mg) was
ignored. The strategy adopted to ignore it was to fit
partial EXAFS spectra allowing the quality of the
adjustment at high k values (8 12 Å) for which the
contribution of octahedral Al and Mg neighbours on
the spectra is very weak. Phase shift and amplitude
functions used for the modelling were obtained
using mineral reference compounds with well-
known structures for the Fe-Fe and Ni-Ni atomic
pairs (lepidocrocite and bunsenite), and, theoretical
functions of McKale et al. (1988) for the Fe-Si and
Ni-Si atomic pairs. During modelling of experi-
mental EXAFS spectra of M.M. samples, the
adjusted parameters of the fit were Ni, Ri, si and
DE0 (difference between the threshold energy value
of the investigated element and the value fixed
during extraction of the EXAFS signal). A
combination of 4 Si at 3.25 Å was assumed for
the tetrahedral contribution (Fe-Si or Ni-Si), and the
gi (electron mean free path) values were kept fixed
(Manceau & Calas, 1986; Muller et al., 1997). This
fitting method allowed us to quantify only the
average numbers of octahedral ‘heavy’ atoms
nearest to central Fe or Ni atoms.
RESULTS
FTIR spectroscopy
In the OH-bending region (Fig. 1a), three major
absorption bands at 821, 874 and 920 cm 1 are
observed, and attributed to dFe 3+ Fe 3+ &-OH,
dAlFe3+&-OH and dAlAl&-OH vibrations, respec-
tively (e.g. Farmer, 1974; Bishop et al., 2002a),
where & is a vacant site. Less resolved absorption
bands near 767 and 785 cm 1 are also observed, the
latter being prevalent for samples having high VIAl
contents (Fig. 1a). The 785 cm 1 band is classically
observed in IR spectra of nontronites and assigned
to dFe3+Mg&-OH (Goodman et al., 1976; Bishop
et al., 2002a). The 767 cm 1 band was attributed to
the same environment in Fe-montmorillonites (Petit
et al., 2002) and in Fe-Al-Mg-montmorillonites
(Bishop et al., 2002a). These two bands were also
observed in IR spectra of synthetic Fe-Mg smectites
(Grauby et al., 1994). The 785 cm 1 and 767 cm 1
 Spectroscopic study of ferric smectites 457

FIG. 1. FTIR spectra of M.M. samples in the OH-bending (600 1000 cm 1) and in the OH-streching
(3450 3750 cm 1) regions. For VIFe and VIAl/SVIR values, see Table 1.

bands were tentatively attributed by these authors to
dFe3+Mg-OH occurring in dioctahedral and triocta-
hedral environments, respectively. Supporting these
assumptions, the 767 cm 1 is more intense for the
M.M. samples showing the highest octahedral
occupancy (Table 1). In the 600 750 cm 1
region, the occurrence of only one absorption
band at 687 cm 1, assigned to Fe3+-O out-of-
plane vibration (e.g. Russell & Fraser, 1994;
Bishop et al., 2002a,b), is noted for all smectite
samples. For sample 5-19 a large asymmetrical
band at 668 cm 1 is observed and can be related to
the occurrence of small amounts of chlorite (Gaudin
et al., 2004) which generally exhibits a strong band
at 667 cm 1 due to dOH components from the 2:1
layer and the hydroxide sheet (Russell et al., 1970;
Russell & Fraser, 1994).
The variations in the relative band intensities are
consistent with the octahedral chemistries of
smectites. Indeed, the increase in VIAl contents is
accompanied by: (1) a decrease in the relative
intensity of dFe3+Fe3+&-OH and Fe3+-O bands, (2)
an increase of the dAlFe3+?-OH band and (3) the
appearance of the dAlAl&-OH band. Thus,
‘plasma-smectites’ being Fe-rich and with VIAl
contents varying from only 0.08 to 0.26 (Table 1),
their IR spectra are similar and exhibit intense
dFe3+Fe3+&-OH and -Fe3+-O bands. On the other
hand, ‘fissure-smectites’, which present a larger
range of VIAl contents (0.18 0.91), show large
variations in relative intensities of dAlAl&-OH,
dAlFe3+&-OH, dFe3+Fe3+&-OH and Fe3+-O bands.
Despite the relatively small VIAl contents of
‘plasma-smectites’, the dAlFe3+&-OH band at
874 cm 1 always appears intense. This could be
explained by the occurrence, at about the same
frequency, of other OH vibrations, e.g. coordinated
with Cr atoms.
In the OH-streching region, a broad asymmetrical
band shifts in relation to the octahedral composition
458 A. Gaudin et al.
of smectites (Fig. 1b). Indeed, the increase of VIAl
is accompanied by a progressive shift of the
maximum towards the higher wavenumbers and a
broadening of this band. In fact, this large band is
due to the overlapping of several components,
particularly nFe 3+ Fe 3+ &-OH, nFe 3+ Mg&-OH,
nAlFe 3+ &-OH and nAlAl&-OH located at
~3550 cm 1, 3575 cm 1, 3585 cm 1 and
3620 3640 cm 1, respectively (Farmer, 1974;
Goodman et al., 1976; Madejová et al., 1994;
Petit et al., 2002).
The study of OH vibrations in the M.M.
smectites provides information about the distribu-
tion of cations within the octahedral sheets. The
occurrence of dAlFe3+&-OH bands indicates that
Fe and Al atoms are mixed in the octahedral sheets
in accordance with the previous XRD studies of the
(06-33) reflections (Gaudin et al., 2004), showing
that Fe3+ and Al cations are not segregated into
different layers. As only dFe3+Mg&-OH bands are
observed whereas dAlMg&-OH band is not, even
for sample 5-37F which has a larger VIAl content,
Mg cations are probably preferentially distributed
within the dioctahedral sheet of smectites. However,
although structural formulae showed an octahedral
occupancy slightly >2 (Table 1) no dRRR-OH
trioctahedral bands (with R = Mg, Ni,...) were
detected. According to structural formulae, local
trioctahedral environments would be in small
amounts, and then trioctahedral absorption bands
like dMgMgMg-OH and dNiNiNi-OH located at
FIG. 2. Lattice vibrations for the FTIR spectra of M.M. ‘fissure-smectites’.
668 cm 1 (Russell et al., 1970) and 710 cm 1
(Decarreau et al., 1987) would be hidden by the
Fe3+-O vibration at 687 cm 1. If they exist, the
extended trioctahedral domains would imply
numerous RRR-OH environments and then strong
dRRR-OH trioctahedral bands. As this is not
observed in IR spectra of M.M. samples, we can
conclude that Mg and Ni atoms are not segregated
in condensed Ni-phases like Ni-kerolite or Ni-
hydroxides nor in extended trioctahedral domains in
M.M. smectites.
The nSi-O-Si, dSi-O-Si and dSi-O-VIR absorption
bands are progressively shifted towards the higher
wavenumbers with the increase of VIAl contents of
smectites (Fig. 2). The position of the dSi-O-VIR
band is given by the equation: Si-O-VIR (cm 1) =
45*[VIAl/VI(Al+Fe)] + 488 (Fig. 3a). According to
this equation, for VIAl/VI(Al+Fe) = 0 and 1 the
calculated wavenumbers of the dSi-O-VIR band are
488 and 533 cm 1, respectively. These values are
consistent with those reported in the literature for
nontronite (490 cm 1; Goodman et al., 1976) and
beidellite (532 cm 1; Russell & Fraser, 1994).
According to the literature, the position of the
intense nSi-O-Si band near 1022 1035 cm 1 is
correlated with either the tetrahedral Fe3+ content of
smectites (Goodman et al., 1976) or the b unit-cell
parameter (Oinuma & Hayashi, 1968), these two
factors being commonly linked. For M.M. smec-
tites, a negative correlation is observed between the
position of the nSi-O-Si band and the b parameter
 Spectroscopic study of ferric smectites 459

FIG. 3. Relationships between the dSi-O-VIR position and the VIAl/VI(Al+Fe) ratio (a) and between the nSi-O-Si
position and b unit-cell parameters (b) of M.M. smectites.

values (Fig. 3b). As structural formulae (Table 1) probably because a [Si(331)] monochromator was
indicate quite similar Si for Al tetrahedral used for the Garfield nontronite (Manceau et al.,
substitutions, and no Si for Fe substitutions 2000) improving the spectral resolution. After a
(confirmed by XAS spectroscopy, see below, multi-technique study of Fe-site occupancies of
Fig. 4), b-dimension values increase with the nontronites, Gates et al. (2002) concluded that, for
VI
(Fe+Mg) content of M.M. smectites, and thus, Garfield nontronite, the Si for Fe tetrahedral
decrease with their VIAl content (VIFe and VIAl substitution is in the range 0 0.05 (for 4Si). The
being negatively correlated). Consequently the Si- pre-edge intensities of M.M. samples and Garfield
O-Si bands are shifted towards the higher nontronite are identical; so, in agreement with the
wavenumbers when the VIAl contents of smectites previous Mössbauer results (Gaudin et al., 2004),
increase (Figs 2 and 3b). the IVFe3+ amounts in M.M. samples are near or
below the detection limit, and all the Fe3+ cations
XAS spectroscopy
XANES at the Fe-K edge. The intensity and shape
of X-ray pre-edge spectra are dependent on the
symmetry of electronic states within the atom, and
thus on the coordination environments of cations in
phyllosilicates (Manceau & Gates, 1997; Manceau
et al., 2000; Gates et al., 2002). Normalized pre-
edge spectra of the M.M. samples were compared
to octahedral reference (Garfield nontronite) and
tetrahedral (FePO4) Fe3+ reference spectra reported
by Manceau et al. (2000) (Fig. 4). The amplitude of
pre-edge spectra for tetrahedral Fe3+ appears 10
times greater than for octahedral Fe3+. Pre-edge
spectra of M.M. samples (Fig. 4) show very similar
intensities, positions and shapes: the Fe3+ environ- FIG. 4. Normalized Fe-K pre-edge spectra for M.M.
ment is then the same in all samples. Pre-edge samples compared to references of VIFe3+ (Garfield
spectra of M.M. smectites and Garfield nontronite nontronite) and of IVFe3+ (FePO4) (in Manceau et al.,
have equivalent intensities but different shapes, 2000).
460 A. Gaudin et al.

occur in octahedral sites (the tetrahedral Fe3+
detection limit by XANES being 3% of total Fe3+
(Manceau et al., 2000)).
EXAFS at the Fe-K edge. Radial distribution
functions at the Fe-K edge of M.M. samples are
compared in Fig. 5a. Intensities of the 2nd peaks are
lower for 5-46F, 2-17F and 2-21F samples which
have the lowest (Fe+Ni+Cr)/(Mg+Al) ratio (except
sample 2-19F). Since the contribution of the
tetrahedral sheets is the same for all smectites
(four nearest Si, Al atoms near to 3.25 Å), the
observed changes depend essentially on disorder
(s) in the first cationic shell and on the
NFe-(Fe,Ni,Cr)/NFe-(Mg,Al) ratio. Indeed Fe-Mg and
Fe-Al EXAFS oscillations are in opposite phase
with Fe-Ni, Fe-Fe and Fe-Cr EXAFS oscillations
(Manceau, 1990). Partial EXAFS spectra corre-
sponding to these 2 nd peaks exhibit similar
frequencies but differ slightly in their amplitude
(Fig. 5b). At low-k values, the amplitude of the
spectra of 5-23, 5-36 and 5-43 are greater than
those of spectra of samples 5-46F, 2-17F, 2-19F and
2-21F. In the low-k region the effect of the s
parameter on the spectra amplitude is small. The
amplitude of the spectra is essentially controlled by
the NFe-(Fe,Ni,Cr)/NFe-(Mg,Al) ratio.
Good fits of these partial EXAFS spectra are
obtained for k values >7 Å using Fe-Si and Fe-Fe
atomic shells and assuming four Si atoms at
distances of 3.25 Å (Table 2 and Fig. 5b). The
number of ‘heavy’ octahedral neighbours
(NFe-(Fe,Cr,Ni)) is in agreement with the above
interpretation of the amplitude variations of the
partial EXAFS spectra at low k values. NFe-(Fe,Cr,Ni)
values are displayed vs. (Fe+Ni+Cr) octahedral
contents of M.M. smectites in Fig. 6. In dioctahe-
dral phyllosilicates, since only 2/3 of octahedral
sites are occupied, each octahedral cation is
surrounded by three cations in the first cationic
shell. Straight lines corresponding to models of
random distribution (I) and total segregation (II) of
octahedral ‘heavy’ (Fe, Cr, Ni) and ‘light’ (Al, Mg)
cations in dioctahedral smectites are reported in
Fig. 6. Except for samples 5-46F and 2-21F, M.M.
smectites exhibit partial up to complete segregation
of heavy octahedral cations. A NFe-(Fe,Cr,Ni) value
>3 for sample 5-43 is consistent with its structural
formula (Table 1) showing an octahedral occupancy
slightly above 2, inducing local trioctahedral
occupancies. In this case, Fe can be surrounded
by Ni atoms in small trioctahedral clusters. For
samples 5-43 and 5-36, the dFe3+Mg&-OH and

FIG. 5. k3-weighted Fe-K RDFs for M.M. samples (a) and, experimental and calculated partial EXAFS spectra
corresponding to the 2nd peaks of the FDRs (b).
 Spectroscopic study of ferric smectites 461

TABLE 2. EXAFS structural parameters of the Fe local environment.

Sample Atomic pair N r (Å) s (Å) G (Å 2) w2

5-23 Fe-(Fe,Cr,Ni) 2.7 3.08 0.089 0.97*

Fe-Si 4* 3.25* 0.071 1* 1.37
5-36 Fe-(Fe,Cr,Ni) 3.0 3.09 0.090 0.97*
Fe-Si 4* 3.25* 0.073 1* 2.41

5-43 Fe-(Fe,Cr,Ni) 3.2 3.09 0.096 0.97*

Fe-Si 4* 3.25* 0.06 1* 1.53
5-46F Fe-(Fe,Cr,Ni) 2.0 3.10 0.093 0.97*
Fe-Si 4* 3.25* 0.058 1* 1.05
2-17F Fe-(Fe,Cr,Ni) 2.6 3.10 0.086 0.97*
Fe-Si 4* 3.25* 0.075 1* 1.13
2-19F Fe-(Fe,Cr,Ni) 2.4 3.10 0.086 0.97*
Fe-Si 4* 3.25* 0.070 1* 0.34
2-21F Fe-(Fe,Cr,Ni) 1.7 3.09 0.081 0.97*
Fe-Si 4* 3.25* 0.069 1* 0.64

N: number of nearest neighbouring cations (3 3.3 Å)

r: interatomic distance
s: Debye-Waller parameter
g: Mean free path of the photoelecton (gFe-Si fixed to 1 Å 2 (Manceau & Calas, 1986;
Muller et al., 1997) and gFe-Fe value was determined on lepidocrocite)
*: Fixed parameters
For all spectra DE0 varied from 2 eV to 2 eV
Precision on N: 15%
w2 factor indicates fit quality (Michalowicz, 1991)

dFe3+Al&-OH absorption bands were observed in
IR spectra (Fig. 1). These data indicate that Fe
atoms are not clustered in very large clusters of
heavy cations. For the majority of M.M. smectites a
trend of the segregation of ‘heavy’ (Fe, Cr, Ni)
cations and more probably ‘light’ (Al, Mg) cations
FIG. 6. Heavy neighbours NFe-(Fe,Cr,Ni) of Fe vs.
octahedral (Fe+Cr+Ni) contents of M.M. smectites.
is observed and more pronounced for ‘plasma’
smectites.
EXAFS at the Ni-K edge. In Fig. 7a, M.M.
smectites RDFs at the Ni-K edge are compared to
that of a synthesized Ni-kerolite (Decarreau et al.,
1987) and of the SAz-montmorillonite with Ni2+ as
interlayer cation. The SAz RDF shows that only
one peak appears when Ni2+ cations are located
within the smectite interlayer. M.M. smectite RDFs
exhibit two peaks, proving the location of Ni atoms
within the octahedral sheets. The intensities of the
2nd peaks of M.M. RDFs are similar for all samples
(except for the 2-21F sample showing a slightly
weaker intensity) and are clearly lower than that of
the Ni-kerolite, in which Ni atoms have six Ni
atoms and four Si atoms in their nearest cationic
environment (3 3.3 Å). This suggests lower
NNi-(Fe,Ni,Cr) values for M.M. smectites than for
Ni-kerolite. Consequently, according to the
chemical data obtained at the SEM and TEM
scale (Gaudin et al., 2004) and IR data, EXAFS
data prove that Ni cations are not trapped in
462 A. Gaudin et al.

FIG. 7. k3-weighted Ni-K RDFs for M.M. samples compared with those for the Ni-kerolite and the Ni-saturated
SAz (a) and, experimental and calculated partial EXAFS spectra corresponding to the 2nd peaks of the FDRs (b).

condensed phases like Ni-kerolite or Ni-hydroxides,
because of the low intensity of the 2nd RDF peak
(Manceau & Calas, 1985, 1986). The partial
EXAFS spectra corresponding to the 2nd peaks of
the RDFs are presented in Fig. 7b. The attenuation
of signal amplitudes at high k values is more
pronounced for M.M. samples than for Ni-kerolite:
the local disorder (s) around Ni atoms is then
greater for M.M. smectites. In the low-k range, the
amplitudes of EXAFS oscillations of samples 5-36
and 5-43 are more intense than those of other
smectite samples, suggesting a higher NNi-(Fe,Ni,Cr)/
NNi-(Mg,Al) ratio.
Good fits of partial EXAFS spectra were
obtained using 4 Ni-Si neighbours at distances of
3.25 Å, and Ni-Ni atomic shells (Fig. 7b and
Table 3). The results are in agreement with the
amplitude variations previously observed on the
partial EXAFS spectra. The number of ‘heavy’ (Ni,
Fe, Cr) octahedral atoms nearest to Ni atoms
(N N i - ( N i , F e , C r ) ) are displayed in Fig. 8 vs.
(Fe+Ni+Cr) octahedral contents of smectites. For
all the samples, NNi-(Ni,Fe,Cr) values obtained from
EXAFS data are greater than NNi-(Ni,Fe,Cr) values
calculated assuming a random distribution of Ni
atoms within dioctahedral sheets. For samples 5-36
and 5-43, NNi-(Ni,Fe,Cr) values of 4.7 and 3.7,
respectively, imply a segregation of Ni atoms in
trioctahedral domains. These results are consistent
with the large numbers of ‘heavy’ cations
surrounding Fe atoms observed for smectites 5-36
and 5-43 (see above). NNi-(Ni,Fe,Cr) values for
samples 2-17F, 2-19F and 2-21F are smaller but
still indicate a strong segregation of ‘heavy’ cations.
As for these samples, octahedral occupancies are >2
(Table 1), it is more likely that Ni atoms are also
clustered into local trioctahedral clusters, but with
smaller sizes than for samples 5-43 and 5-36.
DISCUSSION AND CONCLUSION
The chemical study of M.M. smectites (Gaudin et
al., 2004) revealed structural formulae intermediate
between five end-members: Al and Fe-beidellites,
Al and Fe-montmorillonites and Mg+Ni-saponite.
According to XANES results obtained at the Fe-K
edge, the tetrahedral charge of these smectites
arises only by Si-for-Al substitutions, the amounts
of Fe3+ in tetrahedral sites being below or near the
detection limit. The Fe2O3 contents of M.M.
 Spectroscopic study of ferric smectites 463

TABLE 3. EXAFS structural parameters of the Ni local environment.

Sample Atomic pair N r (Å) s (Å) G (Å 2) w2

Ni-kerolite Ni-(Ni,Fe,Cr) 6.20 3.06 0.070 0.66*

Ni-Si 4* 3.25* 0.110 1* 1.93
5-36 Ni-(Ni, Fe,Cr) 4.70 3.06 0.108 0.66*
4* 3.25* 0.110 1* 0.50
5-43 Ni-(Ni, Fe,Cr) 3.70 3.04 0.095 0.66*
Ni-Si 4* 3.25* 0.098 1* 0.20
2-17F Ni-(Ni, Fe,Cr) 2.73 3.06 0.082 0.66*
Ni-Si 4* 3.25* 0.110 1* 0.18
2-19F Ni-(Ni, Fe,Cr) 2.80 3.08 0.079 0.66*
Ni-Si 4* 3.25* 0.110 1* 0.14
2-21F Ni-(Ni, Fe,Cr) 2.45 3.07 0.089 0.66*
Ni-Si 4* 3.25* 0.110 1* 0.22

N: number of nearest neighbouring cations (3 3.3 Å)

r: interatomic distance
s: Debye-Waller parameter
g: Mean free path of the photoelecton ( gFe-Si value fixed to 1 Å 2 (Manceau & Calas,
1986; Muller et al., 1997) and gNi-Ni value was determined on bunsenite)
*: Fixed parameters
For all spectra DE0 varied from 2 eV to 2 eV
Precision on N: 15%
w2 factor indicates fit quality (Michalowicz, 1991)

smectites are in the range 18.8 32.7% (ignited
basis) (Gaudin et al., 2004). Consistent with results
obtained by Gates et al. (2002) on nontronites,
tetrahedral Fe3+ does not occur in smectites
containing <33% Fe2O3.
Chemical data obtained on M.M. smectites
(Gaudin et al., 2004) showed large chemical
variability at different scales (from macroscopic
samples to the clay-particle scale) leading, notably,
FIG. 8. Heavy neighbours NNi-(Fe,Cr,Ni) of Ni vs.
octahedral (Fe+Cr+Ni) contents of M.M. smectites.
to important variations in the ratio of the three main
Al, Fe3+ and Mg octahedral cations. In IR spectra,
the presence of the Fe3+Mg&-OH and
Fe3+Al&-OH vibrations indicates that Fe3+ and Al
cations or Fe3+ and Mg cations do occur in the
same octahedral sheets and occupy adjacent
octahedral sites. Thus, in agreement with the XRD
and chemical data (Gaudin et al., 2004), IR data
prove that octahedral chemical variations arise from
cationic substitutions within the smectite layers.
In the OH-bending region, only dioctahedral
dM1M2&-OH bands are observed. This is consis-
tent with structural formulae (Table 1) showing
octahedral occupancies only slightly >2. Even for
samples with the greater octahedral occupancies (up
to 2.19), no trioctahedral dOH and nOH bands were
observed, probably because of their lower absorp-
tion coefficient than the dioctahedral equivalents
(Farmer, 1974). Ferric smectites from M.M. exhibit
at both macroscopic scale (chemistry and XRD
data) and short-range order scale (IR data) a
dominant dioctahedral character.
The EXAFS data at the Fe-K edge show
tendencies to a non-random distribution of octahe-
464 A. Gaudin et al.

dral cations in M.M. smectites. ‘Heavy’ cations (Fe,
Cr and potentially Ni) are clustered in medium-
sized clusters. In consequence, ‘light’ cations (Al,
Mg) would be also more or less clustered. As no
dMg-Al&-OH absorption band was detected in IR
spectra of M.M. smectites, it is more probable that
Al and Mg atoms are not clustered together. Even
for the most clustered samples (5-43, 5-36), the
number of Fe heavy octahedral neighbours is 3 or
slightly above. These data confirm the predominant
dioctahedral site occupancy of M.M. smectites.
Another major aim of this paper was to study the
crystal-chemistry of Ni. The FTIR and EXAFS data
at the Ni-K edge are consistent: (1) Ni is not
trapped in condensed Ni-phases like Ni-kerolite or
Ni-hydroxide; (2) Ni is substituted to other octahe-
dral cations in M.M. smectites. More precisely,
EXAFS data also show a tendency to the clustering
of ‘heavy’ cations (Ni, Fe, Cr) around Ni. For two
samples (5-43, 5-36), clusters are clearly trioctahe-
dral. In this case, it is more likely that the Ni
neighbours are predominantly Ni cations.
Figure 9 presents a model of cation distribution
in the octahedral sheet of sample 5-36, compatible
with the experimental data. Since Fe 3+ -rich
dioctahedral smectites generally have the octahedral
trans site vacant (Tsipursky et al., 1978, 1985;
Besson et al., 1983; Tsipursky & Drits, 1984;
Sakharov et al., 1990; Petit et al., 1992), we
assumed that it is the same for M.M. smectites.

FIG. 9. Model of cation distribution in the octahedral sheet of sample 5-36. The model is based on the
experimental IR and EXAFS data and on the structural formula of sample 5-36. Each Fe atom located on the
edge of the model is surrounded by 3 cations.
 Spectroscopic study of ferric smectites
According to the structural formula, the model,
composed of 50 unit cells, contains 141 Fe, 11 Al,
37 Mg, 12 Ni, 8 Cr and presents 22 octahedral
negative charges (experimental data = 21). In this
model, NFe-(Fe,Ni,Cr) and NNi-(Ni,Fe,Cr) are equal to 2.9
and 4.7, respectively, and are thus almost identical
to the EXAFS values (3.0 and 4.7). In accordance
with qualitative IR data, FeFe&-OH, FeAl&-OH
and FeMg&-OH environments are present.
Although there are no visible RRR-OH environ-
ments in the IR spectra of sample 5-36, they appear
in small amounts in the model; their occurrence is
assumed to be below the IR detection limit. The
model illustrates the Al, Mg, Ni cation clustering in
small dioctahedral or trioctahedral domains within
the Fe-rich dioctahedral sheets. In other words, the
distribution of the cations and negative charges
within octahedral sheets of ‘plasma-smectite’ layers
is heterogeneous.
The Mg-Ni saponite end-member, deduced from
chemistries of M.M. smectite particles which
indicate slight over octahedral occupation (Gaudin
et al., 2004) (Table 1), appears due to small
trioctahedral clusters of Mg and Ni atoms.
The TEM-EDX chemical analyses performed on
individual particles of each M.M. smectite revealed
a chemical heterogeneity at the clay-particle scale
(Gaudin et al., 2004). The present spectroscopic
approach indicates that, for all M.M. smectites, a
chemical heterogeneity also exists within the
octahedral sheet (Fig. 9) due to a preferential
distribution of octahedral cations. The M.M.
samples provided the opportunity to compare the
distribution of octahedral cations in smectites
formed in two kinds of microsite: plasma and
fissure. In ‘plasma-smectites’, the distribution of
cations is similar from one sample to another i.e.
with an equivalent segregation of ‘heavy’ (Fe, Ni,
Cr) cations (Fig. 6), and, a clear segregation of Ni
atoms in small trioctahedral domains (Figs 8 and 9).
On the contrary, in ‘fissure-smectites’, although the
cation distribution also presents some similarities
with plasma smectites (no AlMg& environments,
equivalent NNi-(Ni,Fe,Cr) values), some differences
are noted between the samples: after Fe-K XAS
data the distribution of ‘heavy’ (Fe, Ni, Cr) cations
appears random for samples 5-46F and 2-21F and
non-random for samples 2-17F and 2-19F, and the
clustering of Ni atoms is less pronounced (Fig. 8).
The conditions of smectite formation (pH, oxygen
fugacity, fluid composition...) being more variable
in fissure microsites (open microsystem) than in
465
plasma microsites, this could explain the greater
variability of the cation distribution observed for
‘fissure-smectites’.
M.M. smectites, especially ‘plasma-smectites’,
show numerous similarities with the Fe-mont-
morillonite from Ölberg (Köster et al., 1999; Petit
et al., 2002). Indeed, like M.M. smectites, the Fe-
rich Ölberg smectite has a significant octahedral
charge and local trioctahedral magnesian clusters
within dioctahedral Fe-rich layers (Petit et al.,
2002). Since both M.M. and Ölberg smectites are
issued from the weathering of serpentinized
peridotites, such structural characteristics appear
as specific features of this origin.
Large Ni clusters were identified in all previously
studied trioctahedral (Manceau & Calas, 1985,
1986; Manceau, 1990) or tri-dioctahedral (Fe-Mg-
Ni)-phyllosilicates (Decarreau et al., 1987) formed
at low temperature in lateritic weathering profiles,
even in Ni-poor phyllosilicates (Manceau, 1990).
Until now, the distribution of Ni atoms within
dioctahedral smectite layers has never been studied.
The present XAS data reveal that Ni atoms are
effectively segregated, but in clusters much smaller
than previously reported in the literature. It is
probably the dioctahedral structure of M.M.
smectite layers which limits the segregation of Ni
atoms in trioctahedral domains. Indeed, the
dioctahedral lattice of smectites would not support
the important distortions implied by large trioctahe-
dral Ni clusters. Consistent with smectites from
weathering profiles having an Mg 1.47 Ni 0.48
Fe0.5Al0.17 octahedral chemistry (Decarreau et al.,
1987), divalent and trivalent cations are demixed in
extended domains or layers.
ACKNOWLEDGMENTS
This study has been supported by GDR Metallogeny of
CNRS. The authors thank M. Wells, C. Butt and
E. Ramanaidou (CSIRO, Perth, Australia) for their help
in the field and Anaconda Nickel NL for assistance in
providing access to collect the samples. They also thank J.
Bishop and A.M. Karpoff for their reviews of the paper.
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