Hostname: page-component-cd9895bd7-q99xh Total loading time: 0 Render date: 2024-12-27T14:10:28.416Z Has data issue: false hasContentIssue false
  • English
  • Français

Interpretation of infrared spectra of dioctahedral smectites in the region of OH-stretching vibrations

Published online by Cambridge University Press:  01 January 2024

Bella B. Zviagina ,
Douglas K. McCarty ,
Jan Środoń  and
Victor A. Drits
Bella B. Zviagina*
Affiliation:
Geological Institute RAS, Pyzhevsky per. 7, Moscow, 119017, Russia
Douglas K. McCarty
Affiliation:
ChevronTexaco Inc., 3901 Briarpark, Houston, TX 77042, USA
Jan Środoń
Affiliation:
Polish Academy of Sciences, Institute of Geological Sciences, Senacka 1, Krakow 31-002, Poland
Victor A. Drits
Affiliation:
Geological Institute RAS, Pyzhevsky per. 7, Moscow, 119017, Russia
*
*E-mail address of corresponding author: zviagina@ginras.ru
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

Dioctahedral smectite samples of a wide range of compositions (beidellites, montmorillonites, nontronites, Fe-rich montmorillonites and Al-rich nontronites) were studied by infrared (IR) spectroscopy. A special sample-preparation technique was used to eliminate the contribution of molecular water. The OH-stretching regions of the spectra were decomposed and curve-fitted, and the individual OH-stretching bands were assigned to all the possible types of OH-bonded cation pairs that involve Al, Mg and Fe. The integrated optical densities of the OH bands were assumed to be proportional to the contents of the specific types of OH-linked cation pairs with the absorption coefficients being the same for all individual OH bands. Good agreement between the samples’ octahedral cation compositions calculated from the IR data and those given by crystal-chemical formulae was obtained for a representative collection of samples in terms of a unique set of individual OH-band positions that vary within narrow wavenumber intervals. This has allowed us to minimize the ambiguity in spectra decomposition caused by the poor resolution of smectite spectra and confirmed the validity of the resulting band identification.

The bands associated with specific OH-bonded cation pairs in the spectra of smectites are, on the whole, shifted to greater wavenumbers with respect to the corresponding bands in micas. In addition to OH bands that refer to the smectite structure, AlOHAl and AlOHFe bands of the pyrophyllite structural fragments were identified. The band-position variation ranges overlap in a few cases (AlOHFe and MgOHMg; AlOHAl of smectite and AlOHFe of pyrophyllite-like component).

Unambiguous interpretation of the OH-stretching vibrations was found to be possible only for smectite samples with known chemical compositions, so that IR data cannot be used for quantitative determination of octahedral cation composition of mixtures of dioctahedral 2:1 phyllosilicates. In the case of the studied monomineral smectites with known chemical compositions, IR data provided information on the short-range order/disorder in the distribution of octahedral cations along cation-OH-cation directions. This information can be employed, in conjunction with the data of other spectroscopic and diffraction techniques, in the analysis of short-range octahedral cation distribution.

Keywords

Cation DistributionDioctahedral SmectiteIR SpectroscopyOH-stretching VibrationsShort-range Order/Disorder
Type
Research Article
Information
Clays and Clay Minerals , Volume 52 , Issue 4 , August 2004 , pp. 399 - 410
Copyright
Copyright © The Clay Minerals Society 2004

References

Besson, G. and Drits, V.A., (1997) Refined relationships between chemical composition of dioctahedral fine-dispersed mica minerals and their infrared spectra in the OH stretching region. Part I. Identification of the stretching bands Clays and Clay Minerals 45 158–169.CrossRefGoogle Scholar
Besson, G. and Drits, V.A., (1997) Refined relationship between chemical composition of dioctahedral fine-dispersed mica minerals and their infrared spectra in the OH stretching region. Part II. The main factors affecting OH vibration and quantitative analysis Clays and Clay Minerals 45 170–183.CrossRefGoogle Scholar
Chekin, S.S., (1973) Lower Mesozoic Weathering Crust of Irkutsk Region Moscow Nauka 155 pp.Google Scholar
Čičel, B. Komadel, P. and Bartels, J.M., (1994) Structural formulae of layer silicates Quantitative Methods in Soil Mineralogy Wisconsin Soil Science Society of America, Madison 114–136.Google Scholar
Cuadros, J. and Altaner, S.P., (1998) Compositional and structural features of the octahedral sheet in mixed-layer illite-smectite from bentonites European Journal of Mineralogy 10 111–124.CrossRefGoogle Scholar
Cuadros, J. Sainz-Diaz, C.I. Ramirez, R. and Hernandez-Laguna, A., (1999) Analysis of Fe segregation in the octahedral sheet of bentonitic illite-smectite by means of FTIR, 27Al MAS NMR and reverse Monte-Carlo simulations American Journal of Science 299 289–308.CrossRefGoogle Scholar
Dainyak, L.G. and Kheifits, L.M., (1999) The improved equation for the Fe3+ quadrupole doublet assignment and computer simulation of cation distribution in trans-vacant dioctahedral micas EUROCLAY 1999 program with Abstracts Krakow Institute of Geological Sciences PAN 72.Google Scholar
Dainyak, L.G. Drits, V.A. and Heifits, L.M., (1992) Computer simulation of cation distribution in dioctahedral 2.1 layer silicates using IR data. Application to Mossbauer spectroscopy of a glauconite sample Clays and Clay Minerals 40 470–479.CrossRefGoogle Scholar
Decarreau, A. Grauby, O. and Petit, S., (1992) The actual distribution of octahedral cations in 2:1 clay minerals: results from clay synthesis Applied Clay Science 7 147–167.CrossRefGoogle Scholar
Drits, V.A. Dainyak, L.G. Muller, F. Besson, G. and Manceau, A., (1997) Isomorphous cation distribution in celadonites, glauconites, and Fe-illites determined by infrared, Mössbauer and EXAFS spectroscopies Clay Minerals 32 153–179.CrossRefGoogle Scholar
Drits, V.A., Lindgreen, H., Sakharov, B.A., Jakobsen, H.J and Zviagina, B.B. (2004) The structure and origin of clay minerals at the Cretaceous/Tertiary Boundary, Stevns Klint (Denmark). Clay Minerals (in press).CrossRefGoogle Scholar
Eberl, D.D., Środoń, J. and Northrop, H.R. (1986) Potassium fixation in smectite wetting and drying. Pp. 296–326 in: Geochemical Processes at Mineral Surfaces (Davis, J.A. and Hayes, K.F., editors). ACS Symposium Series, 323, American Chemical Society.Google Scholar
Farmer, V.C. and Farmer, V.C., (1974) The layer silicates Infrared Spectra of Minerals London Mineralogical Society 331–363.CrossRefGoogle Scholar
Farmer, V.C. and Russell, J.D., (1964) The infrared spectra of layer silicates Spectrochimica Acta 20 1149–1173.CrossRefGoogle Scholar
Fialips, C.I. Huo, D. Yan, L. Wu, J. and Stucki, J.W., (2002) Effect of Fe oxidation state on the IR spectra of Garfield nontronite American Mineralogist 87 630–641.CrossRefGoogle Scholar
Fialips, C.I. Huo, D. Yan, L. Wu, J. and Stucki, J.W., (2002) Infrared study of reduced and reduced-reoxidized ferruginous smectite Clays and Clay Minerals 50 45–469.CrossRefGoogle Scholar
Foster, M.D., (1953) Geochemical studies of clay minerals. II Relation between ionic substitution and swelling in montmorillonite American Mineralogist 38 994–1006.Google Scholar
Gates, W.P. (2003) Infrared spectroscopy and the chemistry of dioctahedral smectites. In: Vibrational Spectroscopy of Layer Silicates and Hydroxides (Kloprogge, T., editor). Clay Minerals Society Workshop Series, 14, Boulder (in press).Google Scholar
Gates, W.P. Slade, P.G. Manceau, A. and Lanson, B., (2002) Site occupancies by iron in nontronite Clays and Clay Minerals 50 223–239.CrossRefGoogle Scholar
Jackson, M.L., (1985) Soil Chemical Analysis — Advanced Course Madison, Wisconsin Published by the author 895 pp.Google Scholar
Madejová, J. Putyera, K. and Čičel, B., (1992) Proportion of central atoms in octahedral layers of smectites calculated from IR spectra Geologica Carpathica Series Clays 43 117–120.Google Scholar
Madejová, J. Komadel, P. and Čičel, B., (1994) Infrared study of octahedral site populations in smectites Clay Minerals 29 319–326.CrossRefGoogle Scholar
Manceau, A. Lanson, B. Drits, V.A. Chateigner, D. Gates, W.P. Wu, J. Huo, D. and Stucki, J.W., (2001) Oxidation-reduction mechanism of iron in dioctahedral smectites: 1. Crystal chemistry of oxidized reference nontronites American Mineralogist 85 133–152.CrossRefGoogle Scholar
McCarty, D.K. and Reynolds, R.C. Jr., (1995) Rotationally disordered illite-smectite in Paleozoic K-bentonites Clays and Clay Minerals 43 271–284.CrossRefGoogle Scholar
Mering, J. and Glaeser, R., (1954) Sur le rôle de la valence des cations échangeables dans la montmorillonite Bulletin de la Société Françaisede Minéralogie et Cristallographie 77 519–530.CrossRefGoogle Scholar
Petit, S., Robert, J.L., Decarreau, A., Besson, G., Grauby, O. and Martin, F. (1995) Contribution of spectroscopic methods to 2:1 clay characterization. Pp. 119–147 in: Structure et Transformation des Argiles dans les Champs Pétroliers et Géochimiques. Elf-Aquitaine Production, 19.Google Scholar
Petit, S. Caillaud, J. Righi, D. Madejová, J. Elsass, F. and Köster, H.M., (2002) Characterization and crystal chemistry of an Fe-rich montmorillonite from Olberg, Germany Clay Minerals 37 283–297.CrossRefGoogle Scholar
Russell, J.D. Fraser, A.R. and Wilson, M.J., (1994) Infrared methods Clay Mineralogy: Spectroscopic and Chemical Determinative Methods London Chapman & Hall 11–67.CrossRefGoogle Scholar
Sainz-Diaz, C.I. Cuadros, J. and Hernandez-Laguna, A., (2001) Analysis of cation distribution in the octahedral sheet of dioctahedral 2.1 phyllosilicates by using inverse Monte Carlomethods Physics and Chemistry of Minerals 28 445–454.Google Scholar
Sainz-Diaz, C.I. Timon, V. Botella, V. Artacho, E. and Hernandez-Laguna, A., (2002) Quantum mechanical calculations of dioctahedral 2:1 phyllosilicates: Effect of octahedral cation distributions in pyrophyllite, illite and smectite American Mineralogist 87 958–965.CrossRefGoogle Scholar
Slonimskaya, M.V. Besson, G. Dainyak, L.G. Tchoubar, C. and Drits, V.A., (1986) The interpretation of the IR spectra of celadonites and glauconites in the region of the OH stretching frequencies Clay Minerals 21 377–388.CrossRefGoogle Scholar
Środoń, J. Morgan, D.J. Eslinger, E.V. Eberl, D.D. and Karlinger, M.R., (1986) Chemistry of illite-smectite and end-member illite Clays and Clay Minerals 34 368–378.CrossRefGoogle Scholar
Strens, R.G. Jr. and Farmer, V.C., (1974) The common chain, ribbon and ring silicates Infrared Spectra of Minerals London Mineralogical Society 305–330.CrossRefGoogle Scholar
Vantelon, D. Pelletier, M. Michot, L.J. Barres, O. and Thomas, F., (2001) Fe, Mg and Al distribution in the octahedral sheet of montmorillonites. An infrared study in the OH-bending region Clay Minerals 36 369–379.CrossRefGoogle Scholar