Hostname: page-component-cb9f654ff-r5d9c Total loading time: 0 Render date: 2025-09-10T11:16:03.233Z Has data issue: false hasContentIssue false

Trans-vacant and cis-vacant 2:1 layer silicates: Structural features, identification, and occurrence

Published online by Cambridge University Press:  01 January 2024

Victor A. Drits
Affiliation:
Geological Institute of the Russian Academy of Science Pyzhevsky per. 7 119017 Moscow Russia
Bella B. Zviagina*
Affiliation:
Geological Institute of the Russian Academy of Science Pyzhevsky per. 7 119017 Moscow Russia

Abstract

A comprehensive study of clay minerals should include determination of the vacancy pattern of the dioctahedral sheet. The purpose of this report is to consider the advantages and limitations in various diffraction and non-diffraction methods for the determination of the layer types in clay minerals. Identification of trans-vacant (tv) and cis-vacant (cv) clay minerals reported here is based on powder X-ray diffraction (XRD) patterns calculated for different polytypes consisting of either tv or cv layers, on the simulation of experimental XRD patterns corresponding to illite or illite fundamental particles in which tv and cv layers are interstratified, and on the semi-quantitative assessment of the relative content of the layer types in the interstratified structures by generalized Méring’s rules. A simple and effective method for identification of tv and cv layers in dioctahedral 2:1 layer silicates employs thermal analysis and is based on different dehydroxylation temperatures for tv and cv illite and smectite layers.

Crystal chemical analysis of various dioctahedral 2:1 layer silicates consisting of tv and cv layers indicates that compositional control is present in the distribution of octahedral cations over trans- and cis-sites. In dioctahedral smectites the formation of tv and cv layers is related to the layer composition and local order-disorder in the distribution of isomorphous cations. Dioctahedral 1M micas with abundant Fe3+ and Mg occur only as tv varieties. In contrast, 1M-cv illite, as well as cv layers in illite fundamental particles of I-S, can form only as Fe- and Mg-poor varieties. In illites and illite fundamental particles of I-S consisting of tv and cv layers, cv layers prevail when the amounts of Al in octahedra and tetrahedra are >1.55 and >0.35 atoms per O10(OH)2, respectively.

The main factors responsible for the stability of cv and tv illites have been established. Monomineral cv 1M illite, its association with tv 1M illite, and interstratified cv/tv illite occur around ore deposits, in bentonites, and in sandstones mostly as a result of different types of hydrothermal activity. The initial material for their formation should be Al-rich, and hydrothermal fluids should be Mg- and Fe-poor.

Tv and cv smectites of volcanic origin differ in terms of octahedral cation composition and distribution of isomorphous octahedral cations. Mg-rich cv smectites have random distribution of isomorphous octahedral cations, whereas in Mg-bearing tv smectites octahedral Mg cations are dispersed so as to minimize the amount of Mg-OH-Mg arrangements.

Information

Type
Article
Copyright
© The Clay Minerals Society 2009

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Article purchase

Temporarily unavailable

References

Altaner, SP Ylagan, RF, Comparison of structural models of mixed-layer illite-smectite and reaction mechanisms of smectite illitization Clays and Clay Minerals 1997 45 517533 10.1346/CCMN.1997.0450404.CrossRefGoogle Scholar
Bailey, SW, Bailey, SW, Crystal chemistry of the true micas Micas 1984 Washington, D.C. Mineralogical Society of America 1366 10.1515/9781501508820-006.CrossRefGoogle Scholar
Besson, G Glaeser, R Tchoubar, C, Le cesium revelateur de structure des smectites Clay Minerals 1983 18 1119 10.1180/claymin.1983.018.1.02.CrossRefGoogle Scholar
Brigatti, MF Guggenheim, S, Mottana, A Sassi, FE Thompson, JB Jr. Guggenheim, S, Mica crystal chemistry and the influence of pressure, temperature and sold solution on atomistic models Micas: Crystal Chemistry and Metamorphic Petrology 2002 Roma, Italy Mineralogical Society of America with the Accademia Nazionale dei Lincei 197.Google Scholar
Cuadros, J, Structural insights from the study of Cs-exchanged smectites submitted to wetting-and-drying cycles Clay Minerals 2002 37 473486 10.1180/0009855023730046.CrossRefGoogle Scholar
Cuadros, J Altaner, SP, Characterization of mixed-layer illite-smectite from bentonites using microscopic, chemical and X-ray methods: constraints on the smectite-to-illite transformation mechanism American Mineralogist 1998 83 762774 10.2138/am-1998-7-808.CrossRefGoogle Scholar
Cuadros, J Altaner, SP, Compositional and structural features of the octahedral sheet in mixed-layer illite-smectite from bentonites European Journal of Mineralogy 1998 10 111124 10.1127/ejm/10/1/0111.CrossRefGoogle Scholar
Dainyak, LG Zviagna, BB Rusakov, VS Drits, VA, Interpretation of the nontronite dehydroxylate Mössbauer spectrum using EFG calculations European Journal of Mineralogy 2006 18 753764 10.1127/0935-1221/2006/0018-0753.CrossRefGoogle Scholar
Drits, VA, Structural and chemical heterogeneity of layer silicates and clay minerals Clay Minerals 2003 38 403432 10.1180/0009855033840106.CrossRefGoogle Scholar
Drits, VA Kossovskaya, AG, Clay Minerals: Micas and Chlorites 1991 Moscow Nauka 175 pp. (in Russian).Google Scholar
Drits, VA McCarty, DK, A simple technique for a semi-quantitative determination of the trans-vacant and cis-vacant 2:1 layer contents in illites and illite-smectites American Mineralogist 1996 81 852863 10.2138/am-1996-7-808.CrossRefGoogle Scholar
Drits, VA Sakharov, BA, Potential problems in the interpretation of powder X-ray diffraction patterns from fine-dispersed 2M 1 and 3T dioctahedral micas European Journal of Mineralogy 2004 16 99110 10.1127/0935-1221/2004/0016-0099.CrossRefGoogle Scholar
Drits, VA Tchoubar, C, X-ray Diffraction of Disordered Lamellar Structures. Theory and Application to Microdivided Silicates and Carbons 1990 Berlin Springer Verlag 242 pp.Google Scholar
Drits, VA Plançon, A Sakharov, BA Besson, G Tsipursky, SI Tchoubar, C, Diffraction effects calculated for structural models of K-saturated montmorillonite containing different types of defects Clay Minerals 1984 19 541562 10.1180/claymin.1984.019.4.03.Google Scholar
Drits, VA Weber, F Salyn, A Tsipursky, S, X-ray identification of 1M illite varieties: Application to the study of illites around uranium deposits of Canada Clays and Clay Minerals 1993 41 389398 10.1346/CCMN.1993.0410316.CrossRefGoogle Scholar
Drits, VA Besson, G Muller, F, Structural mechanism of dehydroxylation of cis-vacant 2:1 layer silicates Clays and Clay Minerals 1995 43 718731 10.1346/CCMN.1995.0430608.CrossRefGoogle Scholar
Drits, VA Salyn, AL Sucha, V, Structural transformations of interstratified illite-smectites from Dolna Ves hydrothermal deposits: dynamics and mechanisms Clays and Clay Minerals 1996 44 181190 10.1346/CCMN.1996.0440203.CrossRefGoogle Scholar
Drits, VA Dainyak, LG Muller, F Besson, G Manceau, A, Isomorphous cation distribution in celadonites, glauconites and Fe-illites determined by infrared, Mössbauer and EXAFS spectroscopy Clay Minerals 1997 32 153180 10.1180/claymin.1997.032.2.01.CrossRefGoogle Scholar
Drits, VA Sakharov, BA Lindgreen, H Salyn, A, Sequential structural transformation of illite-smectite-vermiculite during diagenesis of Upper Jurassic shales from the North Sea and Denmark Clay Minerals 1997 32 351372 10.1180/claymin.1997.032.3.03.CrossRefGoogle Scholar
Drits, VA Lindgreen, H Salyn, AL Ylagan, R McCarty, DK, 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 1998 83 3173.CrossRefGoogle Scholar
Drits, VA Sakharov, BA Dainyak, LG Salyn, AL Lindgreen, H, Structural and chemical heterogeneity of illite-smectites from Upper Jurassic mudstones of East Greenland related to volcanic and weathered parent rocks American Mineralogist 2002 87 15901607 10.2138/am-2002-11-1209.CrossRefGoogle Scholar
Drits, VA Lindgreen, H Sakharov, BA Jakobsen, HJ Zviagina, BB, The detailed structure and origin of clay minerals at the Cretaceous/Tertiary boundary, Stevns Klint (Denmark) Clay Minerals 2004 39 367390 10.1180/0009855043940141.CrossRefGoogle Scholar
Drits, VA McCarty, DK Zviagina, BB, Crystal-chemical factors responsible for the distribution of octahedral cations over trans- and cis-sites in dioctahedral 2:1 layer silicates Clays and Clay Minerals 2006 54 131152 10.1346/CCMN.2006.0540201.CrossRefGoogle Scholar
Drits, VA Lindgreen, H Sakharov, BA Jakobsen, HJ Fallick, AE Salyn, AL Dainyak, LG Zviagina, BB Barfod, DN, Formation and transformation of mixed-layer minerals by Tertiary intrusives in Cretaceous mudstones, West Greenland Clays and Clay Minerals 2007 55 261284.CrossRefGoogle Scholar
Ey, F, Un exemple de gisement d’uranium sous discordance: les minéralisations protérozoiques de Cluff Lake, Saskatchewan, Canada 1984 Strasbourg 1, France Thèse de doctorat, Université Louis Pasteur.Google Scholar
Gavrilov, YO Tsipursky, SI, Clay minerals from low- and middle-Jurassic deposits of different structural and facial zones of the central Caucasus Litologia and poleznye iskopaemye 1988 6 5772 (in Russian).Google Scholar
Guggenheim, S Chang, HY van Koster Groos, AE, Muscovite dehydroxylation: high-temperature studies American Mineralogist 1987 72 537550.Google Scholar
Halter, G, Zonalité des altérations dans l’environnement des gisements d’uranium associés à ladiscordance du Protérozoique moyen (Saskatchewan, Canada) 1988 Strasbourg 1, France Thèse de doctorat, Université Louis Pasteur.Google Scholar
Heller-Kallai, L Farmer, VC Mackenzie, RC Mitchell, BD Taylor, HEW, The dehydroxylation and rehydroxylation of triphormic dioctahedral clay minerals Clay Minerals Bulletin 1962 5 5672 10.1180/claymin.1962.005.28.02.CrossRefGoogle Scholar
Horton, D, Argillitic alteration associated with the amethyst vein system, Creede Mining District, Colorado 1983 Urbana-Champaign, Illinois, USA University of Illinois.Google Scholar
Jennings, S Thompson, GR, Diagenesis of Plio-Pleistocene sediments of the Colorado River delta, Southern California Journal of Sedimentary Petrology 1986 56 8998.Google Scholar
Lanson, B Beaufort, D Berger, G Baradat, J Lacharpaque, JC, Illitization of diagenetic kaolinite-to-dickite conversion series: Late-stage diagenesis of the Lower Permian Rotliegend sandstone reservoir, offshore of the Netherlands Journal of Sedimentary Research 1996 66 501518.Google Scholar
Lantenois, S Muller, F Beny, J-M Mahiaoui, J Champallier, R, Hydrothermal synthesis of beidellites: characterization and study of the cis- and trans-vacant character Clays and Clay Minerals 2008 56 3948 10.1346/CCMN.2008.0560104.CrossRefGoogle Scholar
Lee, M. (1996) 1M(cis) illite as an indicator of hydrothermal activities and its geological implication. 33rd Annual meeting of the Clay Minerals Society, program and abstracts. 15–20 June, 1996, Gatlinburg, Tennessee, USA, p. 106.Google Scholar
Lindgreen, H Surlyk, F, Upper Permian-Lower Cretaceous clay mineralogy of East Greenland: provenance, palaeoclimate and volcanicity Clay Minerals 2000 35 791806 10.1180/000985500547241.CrossRefGoogle Scholar
Lindgreen, H Drits, VA Sakharov, BA Salyn, AL Wrang, P Dainyak, LG, Illite-smectite structural changes during metamorphism in black Cambrian Alum shales from the Baltic area American Mineralogist 2000 85 12231238 10.2138/am-2000-8-916.CrossRefGoogle Scholar
Lindgreen, H Drits, VA Sakharov, BA Jakobsen, H Salyn, AL Dainyak, LG Kroyer, H, The structure and diagenetic transformation of illite-smectite and chlorite-smectite from North Sea Cretaceous-Tertiary chalk American Mineralogist 2002 87 429450.Google Scholar
Mamy, J Gaultier, JP, Les phenomenes de diffraction de rayonnements X et electonique per les reseaux atomiques: application é l’étude de l’ordre dans les mireraux argileux Annual Agronomiques 1976 27 116.Google Scholar
Manceau, A Lanson, B Drits, VA Chateigner, D Gates, WP Wu, J Huo, D Stucki, JW, Oxidation-reduction mechanism of iron in dioctahedral smectites. I. Crystal chemistry of oxidized reference nontronites American Mineralogist 2000 85 133152 10.2138/am-2000-0114.CrossRefGoogle Scholar
McCarty, DK Reynolds, RC Jr., Rotationally disordered illite-smectite in Paleozoic K-bentonites Clays and Clay Minerals 1995 43 271284 10.1346/CCMN.1995.0430302.CrossRefGoogle Scholar
McCarty, DK Reynolds, RC Jr., Three-dimensional crystal structures of illite-smectite minerals in Paleozoic K-bentonites from the Appalachian basin Clays and Clay Minerals 2001 49 2435 10.1346/CCMN.2001.0490102.CrossRefGoogle Scholar
McCarty, DK Sakharov, BA Drits, VA, Early clay diagenesis in Gulf Coast sediments: new insights from XRD profile modeling Clays and Clay Minerals 2008 56 359379 10.1346/CCMN.2008.0560306.CrossRefGoogle Scholar
Mering, J, L’interférence des rayons X dans las systèmes à stratification désordonnée Acta Crystallographica 1949 2 371377 10.1107/S0365110X49000977.CrossRefGoogle Scholar
Méring, J Oberlin, A, Gard, JA, Smectites The Electron-Optical Investigation of Clays 1971 London Mineralogical Society 193229.CrossRefGoogle Scholar
Morgan, DJ, Simultaneous DTA-EGA of mineral and natural mineral mixtures Journal of Thermal Analysis 1977 12 245263 10.1007/BF01909481.CrossRefGoogle Scholar
Muller, F Drits, VA Plançon, A Besson, G, Dehydroxylation of Fe3+, Mg-rich dioctahedral micas: (I) structural transformation Clay Minerals 2000 35 491504 10.1180/000985500546963.CrossRefGoogle Scholar
Muller, F Drits, VA Tsipursky, SI Plançon, A, Dehydroxylation of Fe3+, Mg-rich dioctahedral micas: (II) cation migration Clay Minerals 2000 35 505514 10.1180/000985500546972.CrossRefGoogle Scholar
Muller, F Drits, VA Plançon, A Robert, J-P, Structural transformation of 2:1 dioctahedral layer silicates during dehydroxylation-rehydroxylation reactions Clays and Clay Minerals 2000 48 572585 10.1346/CCMN.2000.0480510.CrossRefGoogle Scholar
Reynolds, RC Jr., Reynolds, RC Walker, J, Three-dimensional X-ray diffraction from disordered illite: simulation and interpretation of the diffraction patterns Computer Applications to X-ray Diffraction Methods 1993 Bloominton, Indiana, USA The Clay Minerals Society 4478.Google Scholar
Reynolds, RC Jr. Thomson, CH, Illites from the Postam sandstone of New York, a probable noncentrosymmetric micastructure Clays and Clay Minerals 1993 41 6672 10.1346/CCMN.1993.0410107.CrossRefGoogle Scholar
Sainz-Diaz, CI Hernandez-Laguna, A Dove, MT, Theoretical modeling of cis-vacant and trans-vacant configurations in the octahedral sheet of illites and smectites Physics and Chemistry of Minerals 2001 28 322331 10.1007/s002690100156.CrossRefGoogle Scholar
Sokolova, TN Drits, VA Sokolova, AL Stepanov, SS, Structural and mineralogical characteristics and conditions of formation of leucophyllite from salt-bearing deposits of Inder Litologia and poleznye iskopaemye 1976 6 8095 (in Russian).Google Scholar
Sokolova, TN Sakharov, BA Drits, VA, Mixed-layer leucophyllite-montmorillonite minerals Litologiya i Poleznye Ikopayemye 1978 6 87101 (in Russian).Google Scholar
Srodon, J, Nature of mixed-layer clays and mechanisms of their formation and alteration Annual Reviews in Earth and Planetary Science 1999 27 1953 10.1146/annurev.earth.27.1.19.CrossRefGoogle Scholar
Takahashi, T Kanehashi, K Saito, K, First evidence of multiple octahedral Al sites in Na-montmorillonite by 27Al multiple quantum MAS NMR Clays and Clay Minerals 2008 56 520525 10.1346/CCMN.2008.0560505.CrossRefGoogle Scholar
Tsipursky, SI Drits, VA, The distribution of octahedral cations in the 2:1 layers of dioctahedral smectites studied by oblique-texture electron diffraction Clay Minerals 1984 19 177193 10.1180/claymin.1984.019.2.05.CrossRefGoogle Scholar
Ufer, K Kleeberg, R Bergmann, J Dohrmann, R, Rietveld phase quantification of mixed-layer structures 4th Mid-European Clay Conference 2008 MECC’08, 22–27 September, 2008, Zakopane, Poland 2008 33 169 (K. Gorniak, T. Szydlak, M. Kasina, M. Michalik, and B. Zych-Habel, editors). Mineralogia, Special Papers.Google Scholar
Velde, B Iijima, A, Comparison of clay and zeolite mineral occurrences in Neogene age sediments from several deep wells Clays and Clay Minerals 1988 36 337342 10.1346/CCMN.1988.0360407.CrossRefGoogle Scholar
Velde, B Vasseur, G, Estimation of the diagenetic smectite to illite transformation in time-temperature space American Mineralogist 1992 77 967976.Google Scholar
Warshaw, CM, Experimental studies of illites Clays and Clay Minerals 1959 7 303316 10.1346/CCMN.1958.0070121.Google Scholar
Ylagan, RF Altaner, SP Pozzuoli, A, Reaction mechanisms of smectite illitization associated with hydrothermal alteration from Ponza island, Italy Clays and Clay Minerals 2000 48 610631 10.1346/CCMN.2000.0480603.CrossRefGoogle Scholar
Zhukhlistov, AP Dragulesku, EM Rusinov, VL Kovalenker, VA Zvyagin, BB Kuz’mina, OV, Sericite with non centrosymmetric structure from gold-silver-polymetallic ores of Banska Stiavnica deposit (Slovakia) Zapiski Vserossiyskogo Mineralogicheskogo Obshchestva 1996 125 4754 (in Russian).Google Scholar
Zvyagin, BB Rabotnov, VT Sidorenko, OV Kotelnikov, DD, Unique micaconsisting of non-centrosymmetric layers Izvestiya Akademii Nauk S.S.S.R, Seriya Geologicheskaya 1985 35 121124 (in Russian).Google Scholar
Zviagina, BB Sakharov, BA Drits, VA, X-ray diffraction criteria for the identification of trans- and cis-vacant varieties of dioctahedral micas Clays and Clay Minerals 2007 55 467480 10.1346/CCMN.2007.0550502.CrossRefGoogle Scholar