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Structural insights from the study of Cs-exchanged smectites submitted to wetting-and-drying cycles

Published online by Cambridge University Press:  09 July 2018

J . Cuadros
J . Cuadros*
Affiliation:
Department of Mineralogy, The Natural History Museum, Cromwell Road, London SW7 5BD, UK
*
*E-mail: [email protected]
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Abstract

Six smectites of different tetrahedral and octahedral compositions (SAz-1, Chambers, Belle Fourche, two subsamples of nontronite 33B and SWy-1) were Cs-exchanged and submitted to 70 wetting-and-drying cycles. X-ray diffraction (XRD) of oriented and glycolated mounts of the resultant material showed non-expandable layer proportions ranging from 15 to 60%. They were also analysed by powder XRD at 200°C in vacuum. These patterns showed that 15 – 40% of the layers were not rotated relative to each other and the rest were randomly rotated (no rotations of the 60° and 120° types). All layers had a d-spacing of 11 Å, corresponding to collapsed layers with Cs in the cavities created by the hexagonal rings of the tetrahedral sheets. Analysis of the number of cavities available in relation to the layer rotation shows that the rotation angle must be close to 30° or its multiples 90, 150, 210, 270 and 330°. X-ray diffraction and thermal analysis detected the same proportion of cis-and trans-vacant sites in the smectites. The ideal bdimensions of the tetrahedral and octahedral sheets (the sheets are considered independently, without deformation) were calculated for the samples used in this work and for others from the literature, using the tetrahedral and octahedral compositions. These ideal bdimensions have a strong positive correlation. The cis/transvacant character of the smectites is related to the relative lateral dimensions of the ideal tetrahedral and octahedral sheets. A possible explanation of this fact is offered, in which the different configurations of hydroxyls and oxide ions in cis- and trans-vacant structures can affect octahedralsheet dimension.

Keywords

caesium exchangecis-trans occupancylayer rotationoctahedral-tetrahedral fitsmectitewetting-and-drying cycles
Type
Research Article
Information
Clay Minerals , Volume 37 , Issue 3 , September 2002 , pp. 473 - 486
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2002

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References

Besson, G. & Tchoubar, C. (1972) Determination du group de symmetry du feuillet elementaire de la beidellite. Comptes Rendus de l’Academie des Sciences de Paris, 275, 633–636.Google Scholar
Besson, G., Glaeser, R. & Tchoubar, C. (1983) Le cesium, revelateur de structure des smectites. Clay Minerals, 18, 11–19.CrossRefGoogle Scholar
Bonnin, D., Calas, G., Suquet, H. & Pezerat, H. (1985) Site occupancy of Fe3+ in Garfield nontronite. A spectroscopy study. Physics and Chemistry of Minerals, 12, 55–64.CrossRefGoogle Scholar
Christidis, G. & Dunham, A.C. (1993) Compositional variations in smectites: Part I. Alteration of intermediate volcanic rocks. A case study from Milos island, Greece. Clay Minerals, 28, 255–273.CrossRefGoogle Scholar
Čičel, B. & Machajdík, D. (1981) Potassium- and ammonium- treated montmorillonites . I . Interstratified structures with ethylene glycol and water. Clays and Clay Minerals, 29, 40–46.CrossRefGoogle Scholar
Čičel, B., Komadel, P., Lego, L., Madejová, J. & Vlčková, L. (1992) Iron-rich beidellite in the fine fraction of Stebno bentonite. Geologica Carpathica . Series Clays, 2, 121–124.Google Scholar
Cuadros, J. & Altaner, S.P. (1998) Compositional and structural features of the octahedral sheet in mixedlayer illite/smectite from bentonites. European Journal of Mineralogy, 10, 111–124.CrossRefGoogle Scholar
Cuadros, J., Sainz-Díaz, C.I., Ramírez, R. & Hernández-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., Drits, V.A. & Heifits, L.M. (1992) Computer simulation of cation distribution in dioctahedral 2:1 layer silicates using IR-data: application to Mössbauer spectroscopy of a glauconite sample. Clays and Clay Minerals, 40, 470–479.CrossRefGoogle Scholar
Drits, V.A., Plançon, A., Sakharov, B.A., Besson, G., Tsipursky, S.I. & Tchoubar, C. (1984) Diffraction effects calculated for structural models of Ksaturated montmorillonite containing different types of defects. Clay Minerals, 23, 541–561.Google Scholar
Drits, V.A., Besson, G. & Muller, F. (1995) An improved model for structural transformations of heat-treated aluminous dioctahedral 2:1 layer silicates. Clays and Clay Minerals, 43, 718–731.CrossRefGoogle Scholar
Drits, V.A., Dainyak, L.G., Muller, F., Besson, G. & 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., Salyn, A.L., Ylagan, R.F. and McCarty, D.K. (1998) Semiquantitative determination of trans-vacant and cis-vacant 2:1 layers in illites and illite-smectites by thermal analysis and X-ray diffraction. American Mineralogist, 83, 1188–1198.CrossRefGoogle Scholar
Eberl, D.D., Środoń, J. & Northrop, H.R. (1986) Potassium fixation in smectite by wetting and drying. Pp. 296–325 in. Geochemical Processes at Mineral Surfaces (Davis, J.A. & Hayes, K.F., editors). ACS Symposium Series 323. American Chemical Society, Washington, D.C.CrossRefGoogle Scholar
Grathoff, G.H. & Eisenhour, D.D. (1998) Random powder XRD analysis of seven commercial Ksaturated wetted and dried smectites. Proceedings of the 35th Clay Minerals Society Meeting, Cleveland, Ohio, p. 67.Google Scholar
Jr.Guthrie, G.D. & Jr.Reynolds, R.C. (1998) A coherent TEM- and XRD-description of mixed-layer illite/ smec tite. The Canadi an Mineralogi st, 36, 1421–1434.Google Scholar
Madejová, J., Komadel, P. & 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. & Stucki, J.W. (2000) Oxidation-reduction mechanism of iron in dioctahedral smectites: I. Crystal chemistry of oxidized reference nontronites. American Mineralogist, 85, 133–152.CrossRefGoogle Scholar
McCarty, D.K. & Jr.Reynolds, R.C. (1995) Rotationally disordered illite/smectite in Paleozoic K-bentonites. Clays and Clay Minerals, 43, 271–284.CrossRefGoogle Scholar
McCarty, D.K. & Jr.Reynolds, R.C. (2001) Threedimensional crystal structures of illite-smectite minerals in Paleozoic K-bentonit es from the Appalachian basin. Clays and Clay Minerals, 49, 24–35.CrossRefGoogle Scholar
Moore, D.M. & Jr.Reynolds, R.C. (1997) X-ray Diffraction and the Identification and Analysis of Clay Minerals, pp. 261–297. Oxford University Press, Oxford, UK.Google Scholar
Muller, F., Besson, G., Manceau, A. & Drits, V.A. (1997) Distribution of isomorphous cations within octahedral sheets in montmorillonite from Camp-Bertaux. Physics and Chemistry of Minerals, 24, 159–166.CrossRefGoogle Scholar
Muller, F., Drits, V., Plançon, A. & Robert, J. (2000) Structural transformation of 2:1 dioctahedral layer silicates during dehydroxylation-rehydroxylation reactions. Clays and Clay Minerals, 48, 572–585.CrossRefGoogle Scholar
Petit, S., Prot, T., Decarreau, A., Mosser, C. & Toledo-Groke, M.C. (1992) Crystallochemical study of a population of particles in smectites from a lateritic weathering profile. Clays and Clay Minerals, 40, 436–445.CrossRefGoogle Scholar
Jr.Reynolds, R.C. (1985) NEWMOD: A computer program for the calculation of one-dimensional diffraction powders of mixed-layer clays. 8 Brook Rd., Hanover, NH 03755, USA.Google Scholar
Jr.Reynolds, R.C. (1993) Three-dimensional X-ray powder diffraction from disordered illite: simulation and interpretation of the diffraction patterns. Pp. 44–78 in: Computer Applications to X-ray Powder Diffract ion Analysis of Clay Minerals (Reynolds, R.C. and Walker, J.R., editors). CMS Workshop Lectures, 5. Clay Minerals Society, Boulder, Colorado, USA.Google Scholar
Schroeder, P.A. (1993) A chemical, XRD, and 27Al MAS NMR investigation of Miocene Gulf coast shales with application to understanding illite/smectite crystal-chemistry. Clays and Clay Minerals, 41, 668–679.CrossRefGoogle Scholar
Shapiro, L. (1975) Rapid Analysis of Silicate, Carbonate, and Phosphate Rocks. US Geological Survey Bulletin 1401, Washington D.C., 76 pp.Google Scholar
Sposito, G. (1986) The polymer model of thermodynamical clay mineral stability. Clays and Clay Minerals, 34, 198–202.CrossRefGoogle Scholar
Šucha, V. & Širáńová, V. (1991) Ammonium and potassium fixation in smectite by wetting and drying. Clays and Clay Minerals, 39, 556–559.CrossRefGoogle Scholar
Tardy, Y., Duplay, J. & Fritz, B. (1987) Stability fields of smectites and illites as a function of temperature and chemical composition. Pp. 461–494 in : Geochemistry and Mineral Formation in the Earth Surface (Rodríguez-Clemente, R. and Tardy, Y., editors). Consejo Superior de Investigacio nes Científicas, Madrid, Spain.Google Scholar
Tchoubar, C. (1985) Quantitative determination of the fine structural features in clays by modelling of the X-ray diffra ction patterns. Mineralogica et Petrographica Acta, 29A, 35–54.Google Scholar
Tsipursky, S.I. & Drits, V.A. (1983) The distribution of octahedral cations in the 2:1 layers of dioctahedral smectites studied by oblique-texture electron diffraction. Clay Minerals, 19, 177–193.CrossRefGoogle Scholar
Weaver, C.E. & Pollard, L.D. (1973) The Chemistry of Clay Minerals. Elsevier, Amsterdam.Google Scholar
Ylagan, R.F., Altaner, S.P. & Pozzuoli, A. (2000) Reaction mechanisms of smectite illitization associated with hydrothermal alteration from Ponza island, Italy. Clays and Clay Minerals, 48, 610–631.CrossRefGoogle Scholar