Vibrational Spectroscopy 52 (2010) 122–127

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Vibrational Spectroscopy
journal homepage: www.elsevier.com/locate/vibspec

Spectroscopic characterization of natural chrysotile

G. Anbalagan a,*, G. Sivakumar b, A.R. Prabakaran c, S. Gunasekaran c
a
P.G. and Research Department of Physics, Presidency College, Kamaraj Salai, Chepauk, Chennai 5, India
b
CISL, Department of Physics, Annamalai University, Chidambaram 2, India
c
P.G. and Research Department of Physics, Pachaiyappa’s College, Chennai 30, India

A R T I C L E I N F O A B S T R A C T

Article history: Chrysotile, a variety of serpentine mineral was investigated by vibrational and magnetic resonance
Received 30 June 2009 spectroscopic methods. The SEM photograph of the sample shows that chrysotile is made up of thin and
Received in revised form 27 November 2009 flexible fibrils, classified as asbestos. The calculated lattice parameters were a = 5.1961  0.0053 Å,
Accepted 28 November 2009
b = 9.2365  0.0107 Å, c = 14.6208  0.0039 Å; b = 90.15  0.198; Z = 4, with space group C2/m. Three bands
Available online 5 December 2009
observed in the highest wavenumber region (3689 and 3648 cm 1) originate from the stretching vibrations
of the two crystallographically different OH groups. The Raman spectrum shows bending vibrations of the
Keywords:
SiO4 tetrahedra at 390 and 348 cm 1. Substitution of the Si ions in SiO4 tetrahedra by Al ions leads to low-
Chrysotile
field shifts in the 29Si NMR spectrum and the resonance line corresponding to Q3 (1 Al) was observed at
FT-IR
FT-Raman 89 ppm. This result was supported by the resonance line at 57 ppm in 27Al NMR spectrum.
EPR ß 2009 Elsevier B.V. All rights reserved.
29
Si NMR
27
Al NMR

1. Introduction
Chrysotile, a fibrous variety of serpentine with chemical
formula 2[Mg3Si2O5(OH)4] is the most important source of
commercial asbestos. It is a hydrous secondary mineral, resulting
from the alteration of magnesium silicates, especially olivine,
pyroxene and amphibole. It may also occur as a replacement of the
original mineral forming a pseudomorph or it may be deposited
elsewhere in the mineral openings or as replacing some other
mineral. Chrysotile, a two-layered silicate, is composed of one
tetrahedral and one octahedral layer. The first layer is a hexagonal
net of silicon–oxygen tetrahedral, in which three of the four ions
are linked. The second layer is like a brucite octahedral layer with
Mg2+ ions in octahedral environment of 2O2 and 4(OH) ions
instead of 6(OH) in brucite [1]. The bonds between the packets are
of van der Waals type [2]. In the case of chrysotile the mismatch
between a brucite type layer and an undistorted Si2O5 sheet with
hexagonal rings is resolved by a continuous bending of the
structure into the cylindrical tubes [3]. High magnification electron
micrographs have shown the existence of such a tube-like
structure for the layers. The lattice parameters of chrysotile are
a = 5.1961 Å, b = 9.2365 Å, c = 14.6208 Å; b = 90.15; Z = 4, with
space group C2/m. The survey of literature indicates that there is
* Corresponding author. Tel.: +91 44 26602331; fax: +91 44 28510732.
E-mail address: anbu24663@yahoo.co.in (G. Anbalagan).
only one type of octahedral site. Fe, Ni and Cr may substitute to
some extent for Mg and Al for some Si. The substitution of Mg2+ by
impurities like Fe2+, Mn2+, etc., shows that they must be also
present in octahedral site symmetry in the mineral in high spin
environment. The octahedral site symmetry of these ions is further
confirmed by the data reported earlier by Heller-Kalai et al. [4],
which states that in almost all serpentines Fe2+ and Fe3+ are only in
octahedral coordination. The release and retention of plant foods,
the stockpiling of water in the soil from wet to dry seasons, and the
accessibility of the soil to atmospheric gases and organism depend
in large part on the properties of the sheet silicates. There is a
continuing interest in the investigation on chrysotile because of
the health hazards associated with asbestos, of which chrysotile
accounts for 95% of world production [5,6]. The main purpose of
this work is to study the effect due to hydroxyl stretching modes
and to determine the site symmetry of iron and other impurities
present in the mineral chrysotile.
2. Experimental data
2.1. Samples
Serpentine mineral used in the present investigation, was
collected from Salem, Tamil Nadu, India. The crystals were
mechanically separated from the ore and used in a powdered
form for vibrational measurements.

0924-2031/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.vibspec.2009.11.007
 G. Anbalagan et al. / Vibrational Spectroscopy 52 (2010) 122–127 123

2.2. Instrumentation Table 1

Elemental analysis of natural chrysotile.

XRPD analysis was performed with a SEIFERT X-ray diffractom- Element wt.%
eter with Cu Ka radiation (l = 1.54 Å), Cu filter on secondary Mg 40.47
optics, 45 kV power and 20 mA current. The morphological study Si 56.84
was performed with a Jeol JSM-6360 SEM. The sample was glued Ti 0.67
onto aluminum tubes with colloidal graphite and then coated with Cr 0.27
Mn 0.46
a carbon film approximately 400 Å in thickness.
Fe 1.01
Perkin Elmer spectrum one FT-IR spectrometer was used, and Al 0.30
the samples were analyzed in KBr pellets. Spectra were traced in
the range 4000–400 cm 1, and the band intensities were expressed
in transmittance (%).
Bruker IFS FT-IR spectrometer with FRA Raman attachment was enhanced by the iso-orientation of the constituting crystals. The
used and Nd:YAG laser of wavelength 1064 nm was used as the calculated unit cell parameters are compiled in Table 2.
source. The spectra were traced in the range 3500–50 cm 1 with
500 scans at 0.1 cm 1 resolution. Both infrared and Raman analysis 3.2. Infrared spectral analysis
permitted the identification of the main molecular groups present
in the samples. IR spectrum of chrysotile presented in Fig. 3 exhibits three
A part of the powdered sample is taken into a quartz tube for well-defined spectral regions. The first group of bands appears in
EPR recordings on a Varian E-112 EPR spectrometer operated at X- the 3800–3600 cm 1 region, the second in the 1200–800 cm 1 and
band frequency having a 100 kHz field modulation and a phase the third region includes the bands below 800 cm 1. Two bands
sensitive detector to obtain a first derivative signal. DPPH is used as observed at 3689 cm 1 (strong) and 3648 cm 1 (weak) (Fig. 3) are
an internal standard (g = 2.0036). Approximately 2 mg of pow- assigned to in-phase outer and inner Mg–OH stretch, respectively
dered sample was used to acquire the 29Si and 27Al NMR spectra [8–11]. These two bands could be attributed to the presence of two
under magic-angle spinning (MAS) conditions. The spectrometer
used was DSX 300. Spectra were obtained at a frequency
59.62 MHz for 29Si and 78.19 MHz for 27Al. Rapid (8–9 kHz)
sample spinning at the magic angle to the external magnetic field
was used. In most cases, conventional FT NMR with 7 ms radio
frequency pulses and 5 s time intervals was used.

3. Results and discussion

3.1. Powder X-ray diffraction analysis

The morphology of the sample represented in Fig. 1 shows that

chrysotile is made up of thin and flexible fibrils, classified as
asbestos. The chemical composition of the sample obtained by
energy dispersive analysis is given in Table 1. X-ray powder
diffraction analysis shows that chrysotile is composed of bundles
of parallel fibers and each individual fiber is elongated parallel to
one crystallographic direction (Fig. 2). The peak positions of the
observed pattern match those reported on the ICDD file no. 25-
0645. The principal reflections occurring at the d-spacing 7.3110,
4.5287, 3.6548, 2.4460 and 1.5325 Å confirm the presence of
chrysotile as a major mineral phase in the sample [7]. The intensity Fig. 2. Powder X-ray diffraction pattern of natural chrysotile studied.
of peaks at the d-spacings 3.6548, 2.4460 and 1.5325 Å was

Fig. 1. SEM image of the chrysotile shows constituent fibers. Fig. 3. Infrared spectrum of chrysotile recorded at room temperature.
124 G. Anbalagan et al. / Vibrational Spectroscopy 52 (2010) 122–127

Table 2
Crystallographic data on chrysotile mineral.

Mineral Formula Space group Cell constants

a (Å) b (Å) c (Å) b (8) V (Å)3

Chrysotile 2[Mg3Si2O5(OH)4] C2/m; Z = 4 5.1961  0.0053 9.2365  0.0107 14.6208  0.0039 90.15  0.19 701.707

Table 3
Band assignments in the powder infrared spectrum of natural chrysotile.

This work Viti and Mellini [13] Farmer [16] Foresti et al. [17] Sontevska et al. [9] Tentative assignments [12,13,19]

3689 s 3688 s 3697 s 3697 s 3688 s n(OH)

3648 w 3640 w 3651 w 3650 w 3646 w n(OH)
3444 m, br – – – – H2O stretcha
1635 m – – – – H2O benda
1079 s 1072 m 1079 s 1080 s 1078 s n(Si–O–Si)
1018 m 1020 w 1022 m 1020 m 1022 sh n(Si–O–Si)
n(Si–O–Mg)a
965 s 956 vs 957 vs 965 vs 961 vs n(Si–O–Si)
– 635 sh 654 sh – – –
610 s 608 s 604 s 610 s 611 s d(OH)
556 sh 560 sh 550 sh 560 s 556 vw Out-of-plane bending mode of Si–Ob
482 vw 490 sh 481 w – – Out-of-plane bending mode of the Mg octahedrab
– – 450 sh 460 vw 455 sh –
– 437 vs 432 vs 440 vs 438 vs d(Si–O–Si)
– 425 vw – 415 w 405 w –

s, strong; w, weak; m, medium; sh, shoulder; v, very; br, broad.

a
According to Falini et al. [19].
b
According to Viti and Mellini [13] and Suquet [12].

crystallographically distinct OH groups in the chrysotile structure
[9]. Two broad bands observed at 3444 and 1635 cm 1 are due to
the stretching and bending vibrations of water molecules adsorbed
to the chrysotile tubes [11,12]. Three bands at 1079, 1018 and
965 cm 1 are registered in the 1200–800 cm 1 region and
prescribed to the vibrations of the SiO4 tetrahedra (Table 3).
Precisely, the first band (1079 cm 1) is attributed to the Si–O–Si
stretching vibrations, perpendicular to the basal plane, whereas
the shoulder at 1018 cm 1 and the most intensive band at
965 cm 1 arise from the Si–O–Si vibrations in the basal plane
[9,13]. The occupancy of the octahedral sheet in both 1:1 or in 2:1
minerals strongly influences the position of the OH bending bands.
Thus dioctahedral minerals absorb in the 950–800 cm 1 region
while the OH absorption of trioctahedral minerals is shifted to
lower frequencies in the 700–600 cm 1 range [14] corresponding-
ly a strong band is observed at 610 cm 1 in the present study. A
weak band observed at 482 cm 1 being attributed to the bending
vibrations of SiO4 tetrahedral, respectively [9,13,15–17]. The
sharpness of OH absorptions at 3648 and 610 cm 1 indicates that
chrysotile has a relatively ordered structure. Kraineva et al. [18]
used infrared spectroscopy to distinguish chrysotile of normal
strength, fractured and weathered specimens. In the fractured
material, there is a new band at 1045 cm 1, while the 1020 cm 1
band occurs as a shoulder. In the weathered specimens, these two
bands fuse into a broad shoulder on the 960 cm 1 band. The
infrared spectrum of chrysotile obtained in the present study
indicates that the specimen is not a fractured or weathered one.
Kraineva et al. [18] attributed that the change in the IR spectra is
due to the reduction in the point-group symmetry of Si2O5 from C3v
to C2v. The vibrations of H2O are seen as broad bands in the regions
3600–3200 cm 1 (stretching modes) and 1500–1650 cm 1 (defor-
mation modes). Kraineva et al. [18] further suggested that these
bands are not very prominent for the fractured and weathered
chrysotile, particularly in the region of the stretching vibrations.
The water contents of these specimens were less than those for
chrysotile of normal strength. Fig. 2 exhibits broad bands at 3444
and 1635 cm 1 which also confirms that the chrysotile studied in
the present work is not a fractured or weathered one.
3.3. Raman spectral analysis
The Raman spectrum of chrysotile is presented in Fig. 4. The
observed bands and their vibrational assignments given in Table 4
are in agreement with the corresponding literature data [8–10,19–
24]. The Raman bands present in the frequency range at about 1082
and 956 cm 1 are typical for Si–O–Si stretching vibration of the silica
network. The highest frequency band in the SiO4 region observed at
1105 cm 1 arise from the antisymmetric stretching vibrations of the
Si–Onb–Si groups (nb – non-bridging oxygen) [9]. The most intense
bands which lie usually near 690 and 390 cm 1 are assigned,
respectively, to symmetric stretching modes (ns) of the Si–Ob–Si
linkages and to bending modes n5(e) of the SiO4 tetrahedra,
respectively [9,20,21]. According to Kloprogge et al. [21], the band
around 625 cm 1 appears from the Mg–OH stretching mode. The
Raman band observed at 464 cm 1 ascribed to Si–O bending
vibration associated with an Mg–OH translation vibration. The
bands observed near 348,325 and 304 cm 1 are in agreement with
the literature data [20,21]. These bands arise from the SiO4 bending
vibrations [20,21]. The band observed at 232 cm 1, according to
Rinaudo et al. [20] is due to the vibrations of the Onb. . .H–O groups.
The band at 205 cm 1 arises from the stretching Mg–O mode (with
A1g symmetry) of the distorted MgO6 octahedra [21].
Fig. 4. FT-Raman spectrum of chrysotile recorded with excitation wavelength
1064 nm.
 G. Anbalagan et al. / Vibrational Spectroscopy 52 (2010) 122–127 125

Table 4
1
Wavenumber position (cm ) for vibrational bands observed in the Raman spectrum: excitation wavelength 1064 nm.

This work Sontevska et al. [9] Rinaudo et al. [20] Kloprogge et al. [21] Bard et al. [22] Tentative assignment [20,21]

1105 1106 m 1105 m 1102 1105 nas(Si–Onb–Si)

692 692 vs 692 vs 692 692 n(Si–O–Si)
622 626 m 620 m 629 623 n(Mg–OH)
464 – – 466 465 Mg–OH translation + n6(e)SiO4
438 – – 432 432 Antisymmetric Mg–OH translation
390 392 vs 389 vs 388 – Symmetric n5(e)SiO4
348 348 m 345 m 345 345 Bending of SiO4
325 320 w – 318 321 Bending of SiO4
304 306 w – 304 304 Bending of SiO4
232 235 s 231 s 231 – Onb


H–O vibrations
180 206 w – 199 – n(Mg–O)
s, strong; w, weak; m, medium; sh, shoulder; v, very; br, broad.

A strong band observed at 390 cm 1 indicates that this mineral
is Mg bearing phyllosilicates [24]. Rinaudo et al. [20] assigned the
band observed at 622 cm 1 to OH–Mg–OH translation modes,
however, Farmer [16] attributed the strong bands observed in the
infrared spectrum in the region 611–646 cm 1 to inner and surface
hydroxyl groups of the layers. Most trioctahedral phyllosilicates
have strong bands around 230 and 200 cm 1and hence chrysotile
spectrum exhibits a strong band at 232 cm 1. In trioctahedral
phyllosilicates, the occupancy of almost all the octahedral sites by
divalent cations prevents the formation of an O–H–O isosceles
triangle which changes the symmetry of the group consequently
only one band is observed in the 200–300 cm 1 range in the Raman
spectrum of the trioctahedral phyllosilicates [20] studied.
3.4. Near infrared spectral analysis
The NIR spectrum of chrysotile contains three overtones and
combination bands near: (a) 1481 nm, (b) 1927 nm, and (c)
2311 nm (Fig. 5), corresponding to (a) O–H vibrations in hydroxyl,
(b) H–O–H vibrations in crystalline structure, and (c) M–OH
vibrations in clay minerals (M = metals, Mg2+ in this case). The
absorptions at 1481, 1927, and 2311 nm can be attributed to the
presence of Mg-rich TOT clay mineral [25]. The sharp and well
resolved OH combination bands in the 2200–2500 nm regions
provide unique fingerprints for specific minerals. According to
Bishop et al. [26], Al-rich phyllosilicates exhibit OH combination
bands near 2200 nm, while these bands are observed near 2290–
2310, 2330–2340 nm and near 2350–2370 nm for Fe3+-rich, Mg-
rich and Fe2+-rich phyllosilicates, respectively. In the present study
the combination bands observed at 2311 and 2344 nm indicate the
sample under study is Mg-rich phyllosilicate. The spectral band
near 2311 nm is strongest with a doublet present in chrysotile as
reported by King and Clark [27] attributed to Mg–OH [28]. The
chrysotile secondary combination bands were observed at 2395
and 2474 nm. Further Gionis et al. [29] attributed an overtone
band at1383 nm and several combination bands are indicative of a
trioctahedral Mg3OH component. The first overtone (2nOH) bands
appear at wavenumbers 1383 nm (7231 cm 1) less than twice those
of the fundamental bands (nOH = 3689 cm 1), due to the anharmonic
character of vibrations, X = W2nOH/2 WnOH, with X being the
anharmonicity constant [30]. Petit et al. [30] used talc samples with
various crystal chemistries to solve the equation and the experi-
mental data are well fitted with X = 85.6 cm 1. Petit et al. [30]
further suggested that the anharmonicity constant remains almost
unchanged for several types of clay samples. The calculated
X = 73.5 is close to that reported by Petit et al. [30]. The high
anharmonicity also accounts for the relatively high intensity of these
bands in the NIR spectrum because these overtones would not be
detectable if the OH vibrations in chrysotile were harmonic [10].
29
3.5. Si NMR spectral analysis
The room temperature 29Si NMR spectrum of chrysotile sample is
given in Fig. 6. The 29Si NMR spectrum shows a sharp resonance at

29
Fig. 5. Near infrared spectrum of chrysotile. Fig. 6. Si NMR spectrum of chrysotile.
126 G. Anbalagan et al. / Vibrational Spectroscopy 52 (2010) 122–127
Fig. 7. Powder X-band EPR spectrum of natural chrysotile.
89 ppm of layer structured phyllosilicate (Q3) minerals. The
observed peak at 89 is attributed to isolated silanol groups that are
present in the internal tridimite layer [31]. The chemical shift of the
single Si resonance ( 89 ppm) is in reasonable agreement with the
one reported value of 93 ppm for serpentine of unspecified
morphology [32]. The only crystalline phase detectable in this
sample is chrysotile, which is also evident from the resonance at
89 ppm. Magi et al. [32] suggested that increasing degree of
condensation of the SiO4 tetrahedra leads to high-field shifts and
substitution of the Si ions in SiO4 tetrahedra by Al ions leads to low-
field shifts. The second trend is observed in the present study and
resonance line observed at 89 ppm is assigned to Q3 (1 Al). This
assignment is in agreement with that reported by Lippmaa et al.
[33]. The presence of a single line indicates the existence of a unique
environment for Si.
The EPR spectrum of the chrysotile sample of Fig. 7 shows
intense ferromagnetic (or super paramagnetic) absorptions [34].
This result strongly indicates that the spinning sidebands observed
in many natural aluminosilicates may be due not to chemical shift
anisotropy, but rather to the presence of large magnetic
susceptibility broadenings [35]. A narrow width of the resonance
observed is the characteristic of most highly siliceous system.
When no aluminum is present, the line broadening is removed.
Further, when aluminum is present in a symmetrical environment
(in which case the quadrupole moment is small) a very narrow line
is observed. Clearly, the line broadening mechanism involves the
aluminum atoms in the lattice [36].
27
Fig. 8. Al NMR spectrum of chrysotile.
27
3.6. Al NMR spectral analysis
27
Al NMR spectrum of chrysotile sample shown in Fig. 8
consists in general of a strongly broad central band accompanied at
both sides by one or two symmetrically located peaks of low
intensity which represent spinning side bands. According to the
previous work [37,38] the central line at 57 ppm must assign to
octahedral Al ions. These assignments are in agreement with the
structural composition of these samples. The spectrum shows that
Al is in tetrahedral coordination and the Al appears to be
disordered in the tetrahedral coordination, as indicated by the
broad resonance at 57 ppm.
4. Conclusions
The SEM micrograph of the sample shows that chrysotile is
made up of thin and flexible fibrils, classified as asbestos. Infrared
spectrum indicates the presence of two crystallographically
distinct OH groups in the chrysotile structure. The spectrum
exhibits broad bands at 3444 and 1635 cm 1 which also confirms
that the experimental chrysotile is not a fractured or weathered
one. The Raman spectrum is characterized by the main bands
observed at 1105, 692 and 622 cm 1and these bands assigned
according to the description of the vibrational bands in the infrared
spectrum of phyllosilicates. The spectra of clay minerals show Si–O
stretching and bending absorptions in the region 1300–400 cm 1.
The three bands were observed at 1079, 1018 and 965 cm 1 and
are attributed to Si–O stretching modes. The presence of a single
line at 89 ppm in 29Si NMR spectrum indicates the existence of a
unique environment for Si Q3 (1 Al). The EPR spectrum of the
chrysotile sample shows intense ferromagnetic absorptions. The
27
Al NMR spectrum shows that Al is in tetrahedral coordination. A
narrow width of the resonance observed is the characteristic of
most highly siliceous system.
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