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Far-Infrared Study of the Influence of the Octahedral Sheet Composition on the K+-Layer Interactions in Synthetic Phlogopites

Published online by Cambridge University Press:  01 January 2024

Magali Diaz ,
Jean-Louis Robert ,
Paul A. Schroeder  and
Rene Prost
Magali Diaz
Affiliation:
INRA, Unité de Science du Sol, route de Saint Cyr, 78026 Versailles CEDEX, France
Jean-Louis Robert
Affiliation:
ISTO, UMR 6113, 1A, rue de la Férollerie, 45071 Orléans CEDEX 02, France
Paul A. Schroeder*
Affiliation:
Department of Geology, University of Georgia, Athens, GA 30602-2501, USA
Rene Prost
Affiliation:
INRA, Unité de Science du Sol, route de Saint Cyr, 78026 Versailles CEDEX, France
*
* E-mail address of corresponding author: [email protected]
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Abstract

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Far-infrared (FIR) analysis of synthetic Mg-, Ni-, Co-, and Fe-phlogopites coupled with structural data from X-ray diffraction revealed that the K interlayer environments are directly related to octahedral sheet composition and geometry. The general phlogopite formula, KM32+(Si3Al)O10(OH)2, was varied according to octahedral compositions, where M2+ = Mg2+, Fe2+, Co2+, and Ni2+. Octahedral substitutions have a direct effect on the b lattice parameter, which is related to the tetrahedral-octahedral sheet misfit and manifested by change in the tetrahedral rotation angle (α). The ditrigonal interlayer cavity geometry and the potential for retention of the compensating cations therefore varies according to the ionic size and the types and oxidation state of octahedral cations. These structural features appear as frequency shifts on FIR spectra. When Mg2+ is replaced by a smaller cation, Ni2+, the b parameter decreases and the tetrahedral rotation angle, α, increases, inducing the collapse of the ditrigonal ring. When this happens, the local anisotropy of the interlayer site increases, resulting in every other six out of 12 K-O bonds becoming shorter and the in-plane K-O vibration band shifts slightly to greater wavenumbers. Synthetic phlogopites with octahedral substitutions by cations of larger ionic radii (i.e. Co2+ and Fe2+) exhibit b parameter increases, where in the case of the annite end-member, α decreases to almost 0°. As α decreases, compensating cation sites become more hexagonal like and the nearest K-O bond increases in length. The K-O vibration bands move toward much smaller wavenumbers. Far infrared offers the potential for a new approach to study the retention of interlayer cations in other phyllosilicates and the mechanisms by which they are altered, such as heating or by weathering reactions in the environment.

Keywords

AnniteBiotiteCompensating CationFar-infrared SpectrometryK+-layer InteractionsOctahedral SubstitutionsPhlogopiteSyntheticTetrahedral Rotation
Type
Article
Information
Clays and Clay Minerals , Volume 58 , Issue 2 , April 2010 , pp. 263 - 271
Copyright
Copyright © Clays and Clay Minerals 2010

References

Badreddine, R. Le Dred, R. and Prost, R., 2002 A far infrared study of K+ ions during K+ ⇌ Ca2+ exchange in vermiculite Clay Minerals 37 59–70 10.1180/0009855023710017.CrossRefGoogle Scholar
Badreddine, R. Le Dred, R. and Prost, R., 2002 Far infrared study of K+, Rb+ and Cs+ during their exchange with Na+ and Ca2+ in vermiculite Clay Minerals 37 71–81 10.1180/0009855023710018.CrossRefGoogle Scholar
Bailey, S.W., Bailey, S.W., 1984 Crystal chemistry of the true micas Micas 13–60 10.1515/9781501508820-006.CrossRefGoogle Scholar
Washington, D.C. and Diaz, M., 1999 Etude des interactions cations compensateurs/feuillets dans les argiles: contribution à la connaissance des mécanismes de rétention sélective .Google Scholar
Diaz, M. Farmer, V.C. and Prost, R., 2000 Characterization and assignment of far infrared absorption bands of K+ in muscovite Clays and Clay Minerals 48 433–438 10.1346/CCMN.2000.0480403.CrossRefGoogle Scholar
Diaz, M. Huard, E. and Prost, R., 2002 Far infrared analysis of the structural environment of interlayer K+, NH+4, Rb+ and Cs+ selectively retained by vermiculite Clays and Clay Minerals 50 290–300 10.1346/000986002760832883.CrossRefGoogle Scholar
Donnay, G. Donnay, J.D.H. and Takeda, H., 1964 Trioctahedral one-layer micas. II. Prediction of the structure from composition and cell dimensions Acta Crystallographica 17 1374–1381 10.1107/S0365110X64003462.CrossRefGoogle Scholar
Eugster, H.P., 1957 Stability of annite Carnegie Institution of Washington Yearbook 1956-1957 161–164.Google Scholar
Eugster, H.P. and Wones, D.R., 1962 Stability relations of the ferruginous biotites annite Journal of Petrology 3 82–126 10.1093/petrology/3.1.82.CrossRefGoogle Scholar
Farmer, V.C. and Farmer, V.C., 1974 The layer silicates The Infrared Spectra of Minerals London Mineralogical Society 331–338 10.1180/mono-4.15.CrossRefGoogle Scholar
Fripiat, J.J. and Fripiat, J.J., 1981 Application of far infrared spectroscopy to the study of clay minerals and zeolites Advanced Techniques for Clay Minerals Analysis Amsterdam Elsevier 191–210.Google Scholar
Hamilton, D.L. and Henderson, C.M.B., 1968 The preparation silicate composition by a gelling method Mineralogical Magazine 36 832–838 10.1180/minmag.1968.036.282.11.CrossRefGoogle Scholar
Harris, D.C. and Bertolucci, M.D., 1989 Symmetry and Spectroscopy: An Introduction to Vibrational and Electronic Spectroscopy New York Dover Publications.Google Scholar
Hazen, R.M. and Burnham, C.W., 1973 The crystal structure of one-layer phlogopite and annite American Mineralogist 58 889–900.Google Scholar
Hazen, R.M. and Wones, D.R., 1972 The effect of cation substitutions on the physical properties of trioctahedral micas American Mineralogist 57 103–129.Google Scholar
Ishii, M. Shimanoushi, T. and Nakahira, M., 1967 Far-infrared absorption spectra of layer silicates Inorganica Chimica Acta 1 387–392 10.1016/S0020-1693(00)93207-9.CrossRefGoogle Scholar
Laperche, V., 1991 Etude de l’état et de la localisation des cations compensateurs dans les phyllosilicates par des méthodes spectrométriques .Google Scholar
Laperche, V. and Prost, R., 1991 Assignment of the far infrared absorption bands of K in micas Clays and Clay Minerals 39 281–289 10.1346/CCMN.1991.0390308.CrossRefGoogle Scholar
McCauley, J.M. and Newnham, R.E., 1971 Origin and prediction of ditrigonal distortions in micas American Mineralogist 56 1626–1638.Google Scholar
McKeown, D.A. Bell, M.I. and Etz, E.S., 1999 Raman spectra and vibrational analysis of the trioctahedral mica phlogopite American Mineralogist 84 970–976 10.2138/am-1999-5-633.CrossRefGoogle Scholar
Prost, R. and Laperche, V., 1990 Far infrared study of potassium in micas Clays and Clay Minerals 38 351–355 10.1346/CCMN.1990.0380403.CrossRefGoogle Scholar
Radoslovitch, E.W. and Norrish, K., 1962 The cell dimensions and symmetry of the layer-lattice silicates. I. Some structural considerations American Mineralogist 45 599–616.Google Scholar
Redhammer, G.J. Dachs, E. and Amthauer, G., 1995 Mössbauer spectroscopic and X-ray powder diffraction studies of synthetic micas on the join Annite KFe3AlSi3O10(OH)2-Phlogopite KMg3AlSi3O10(OH)2 Physics and Chemistry of Minerals 22 282–294 10.1007/BF00202768.CrossRefGoogle Scholar
Redhammer, G.J. Beran, A. Dachs, E. and Amthauer, G., 1993 A Mössbauer and X-ray diffraction study of annites synthesized at different oxygen fugacities and crystal chemical implications Physics and Chemistry of Minerals 20 382–394 10.1007/BF00203107.CrossRefGoogle Scholar
Rousseaux, J.M. Nathan, Y. Vielvoye, L.A. Herbillon, A., Serratosa, J.M., 1972 The vermiculitisation of trioctahedral micas. II. Correlations between the K level and crystallographic parameters Proceedings of the International Clay Conference in Madrid 449–446.Google Scholar
Schroeder, P.A. Kim, J.G. and Melear, N.D., 1997 Mineralogical and textural criteria for recognizing remnant Cenozoic deposits on the Piedmont: Evidence from Sparta and Greene County, Georgia, U.S.A Sedimentary Geology 108 195–206 10.1016/S0037-0738(96)00054-1.CrossRefGoogle Scholar
Schroeder, P.A., 1992 Far infrared study of the interlayer torsional-vibrational mode of mixed-layer illite/smectite Clays and Clay Minerals 40 81–91 10.1346/CCMN.1992.0400109.CrossRefGoogle Scholar
Schroeder, P.A., 1990 Far infrared, X-ray powder diffraction and chemical investigation of potassium micas American Mineralogist 75 983–991.Google Scholar
Scott, A.D. Ismail, F.T. Locatis, R.R., Serratosa, J.M., 1972 Changes in interlayer potassium exchangeability induced by heating micas Proceedings of the International Clay Conference 467–479.CrossRefGoogle Scholar
Shannon, R.D., 1976 Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Acta Crystallographica A32 751–767 10.1107/S0567739476001551.CrossRefGoogle Scholar
Takeda, H. and Morosin, B., 1975 Comparison of observed and predicted structural parameters of mica at high temperature Acta Crystallographica B31 2444–2452 10.1107/S0567740875007777.CrossRefGoogle Scholar
Tateyama, H. Shimoda, S. and Sudo, T., 1977 Estimation of K-O distance and tetrahedral rotation angle of K-micas from far-infrared absorption spectral data American Mineralogist 62 534–539.Google Scholar
Tuttle, O.F., 1949 Two pressure vessels for silicate-water studies Geological Society of America Bulletin 60 1727–1729 10.1130/0016-7606(1949)60[1727:TPVFSS]2.0.CO;2.CrossRefGoogle Scholar
Velde, B. and Couty, R., 1985 Far-infrared spectra of hydrous layer silicates Physics and Chemistry of Minerals 12 347–352 10.1007/BF00654345.CrossRefGoogle Scholar