Hostname: page-component-7dd5485656-bt4hw Total loading time: 0 Render date: 2025-10-31T08:30:00.980Z Has data issue: false hasContentIssue false
  • English
  • Français

Determination of Layer-Charge Characteristics of Smectites

Published online by Cambridge University Press:  01 January 2024

G. E. Christidis  and
D. D. Eberl
G. E. Christidis*
Affiliation:
Technical University of Crete, Department of Mineral Resources Engineering, 73100 Chania, Greece
D. D. Eberl
Affiliation:
US Geological Survey, 3215 Marine St., Suite E-127, Boulder, Colorado, 80303-1066, USA
*
*E-mail address of corresponding author: christid@mred.tuc.gr
Get access Rights & Permissions [Opens in a new window]

Abstract

A new method for calculation of layer charge and charge distribution of smectites is proposed. The method is based on comparisons between X-ray diffraction (XRD) patterns of K-saturated, ethylene glycol-solvated, oriented samples and calculated XRD patterns for three-component, mixed-layer systems. For the calculated patterns it is assumed that the measured patterns can be modeled as random interstratifications of fully expanding 17.1 Å layers, partially expanding 13.5 Å layers and non-expanding 9.98 Å layers. The technique was tested using 29 well characterized smectites. According to their XRD patterns, smectites were classified as group 1 (low-charge smectites) and group 2 (high-charge smectites). The boundary between the two groups is at a layer charge of −0.46 equivalents per half unit-cell. Low-charge smectites are dominated by 17.1 Å layers, whereas high-charge smectites contain only 20% fully expandable layers on average. Smectite properties and industrial applications may be dictated by the proportion of 17.1 Å layers present. Non-expanding layers may control the behavior of smectites during weathering, facilitating the formation of illite layers after subsequent cycles of wetting and drying. The precision of the method is better than 3.5% at a layer charge of −0.50; therefore the method should be useful for basic research and for industrial purposes.

Keywords

Charge DistributionExpandable LayersK-saturationLayer ChargeLayerCharge ProgramProfile ModelingSmectiteX-ray Diffraction

Information

Type
Research Article
Information
Clays and Clay Minerals , Volume 51 , Issue 6 , December 2003 , pp. 644 - 655
Copyright
Copyright © 2003, The Clay Minerals Society

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

Christidis, G. and Dunham, A.C., (1993) Compositional variations in smectites derived from intermediate volcanic rocks. A case study from Milos Island, Greece Clay Minerals 28 255–273 10.1180/claymin.1993.028.2.07.10.1180/claymin.1993.028.2.07CrossRefGoogle Scholar
Christidis, G. and Dunham, A.C., (1997) Compositional variations in smectites. Part II: Alteration of acidic precursors. A case study from Milos Island, Greece Clay Minerals 32 255–273 10.1180/claymin.1997.032.2.07.10.1180/claymin.1997.032.2.07CrossRefGoogle Scholar
Christidis, G. and Scott, P.W., (1996) Physical and chemical properties of the bentonite deposits of Milos Island, Greece Transactions of the Institute of Mining and Metallurgy B 105 B165–B174.Google Scholar
Čičel, V. and Machajdik, D., (1981) Potassium- and amnoniumtreated montmorillonites. I. Interstratified structures with ethylene glycol and water Clays and Clay Minerals 29 40–46 10.1346/CCMN.1981.0290106.10.1346/CCMN.1981.0290106CrossRefGoogle 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 10.2475/ajs.299.4.289.CrossRefGoogle Scholar
Decarreau, A. Colin, F. Herbillon, A. Manceau, A. Nahon, D. Paquet, H. Trauth-Badeaud, D. and Trescases, J.J., (1987) Domain segregation in Ni-Fe-Mg-smectites Clays and Clay Minerals 35 1–10 10.1346/CCMN.1987.0350101.CrossRefGoogle Scholar
Drits, V.A. Lindgreen, H. Salyn, A.L. Ylagan, R. and McCarty, D.K., (1998) Semi quantitative detrmination of trans-vacant and cis-vacant 2:1 layers in illites and illitesmectites by thermal analysis and X-ray diffraction American Mineralogist 83 1188–1198 10.2138/am-1998-11-1207.CrossRefGoogle Scholar
Eberl, D.D., (1980) Alkali cation selectivity and fixation by clay minerals Clays and Clay Minerals 28 161–172 10.1346/CCMN.1980.0280301.CrossRefGoogle Scholar
Eberl, D.D. and Christidis, G., (2002) LayerCharge: A computer program for calculation of layer charge and charge distribution of smectites Boulder, Colorado USGS.Google Scholar
Eberl, D.D. Środoń, J. Northrop, R., Davis, J.A. and Hayes, K.F., (1986) Potassium fixation in smectite by wetting and drying Geochemical Processes at Mineral Surfaces Washington, D.C. American Chemical Society 296–326 10.1021/bk-1987-0323.ch014.Google Scholar
Eberl, D.D. Šrodoń, J. Mingchou, L. Nadeau, P.H. and Northrop, R.H., (1987) Sericite from the Silverton caldera, Colorado: Correlation among structure, composition, origin and particle thickness American Mineralogist 72 914–934.Google Scholar
Goodman, B.A. Nadeau, P.H. and Chadwick, J., (1988) Evidence for the multiphase nature of bentonites from Mössbauer and EPR spectroscopy Clay Minerals 23 147–159 10.1180/claymin.1988.023.2.03.CrossRefGoogle Scholar
Güven, N. and Bailey, S.W., (1988) Smectite Hydrous Phyllosilicates Washington, D.C. Mineralogical Society of America 497–559 10.1515/9781501508998-018.CrossRefGoogle Scholar
Inglethorpe, S.D.J., Morgan, D.J., Highley, D.E. and Bloodworth, A.D. (1993) Industrial Minerals laboratory manual: bentonite. British Geological Survey Technical Report WG/93/20.Google Scholar
Iwasaki, T. and Watanabe, T., (1988) Distribution of Ca and Na ions in dioctahedral smectites and interstratified dioctahedral mica/smectites Clays and Clay Minerals 36 73–82 10.1346/CCMN.1988.0360110.CrossRefGoogle Scholar
Jackson, M.L., (1985) Soil Chemical Analysis — Advanced Course 2nd Madison, Wisconsin Published by the author 895 pp.Google Scholar
Lagaly, G., (1981) Characterization of clays by organic compounds Clay Minerals 16 1–21 10.1180/claymin.1981.016.1.01.10.1180/claymin.1981.016.1.01CrossRefGoogle Scholar
Lagaly, G. and Mermut, A.R., (1994) Layer charge determination by alkylammoniumions Layer Charge Characteristics of 2:1 Silicate Clay Minerals Boulder Colorado The Clay Minerals Society 2–46.Google Scholar
Lagaly, G. and Weiss, A. (1975) The layer charge of smectitic layer silicates. Proceedings of the International Clay Conference Mexico, 157–172.Google Scholar
Laird, D.A. and Mermut, A.R., (1994) Evaluation of the structural formula and alkylammonium methods of determining layer charge Layer Charge Characteristics of 2:1 Silicate Clay Minerals Boulder Colorado The Clay Minerals Society 80–103.Google Scholar
Laird, D.A. Scott, A.D. and Fenton, T.E., (1989) Evaluation of the alkylammonium method of determining layer charge Clays and Clay Minerals 37 41–46 10.1346/CCMN.1989.0370105.CrossRefGoogle Scholar
Lim, C.H. and Jackson, M.L., (1986) Expandable phyllosilicate reactions with lithium on heating Clays and Clay Minerals 34 346–352 10.1346/CCMN.1986.0340316.10.1346/CCMN.1986.0340316CrossRefGoogle Scholar
MacEwan, D.A.C. Wilson, M.J., Brindley, G.W. and Brown, G., (1984) Interlayer and intercalation complexes of clay minerals Crystal Structures of Clay Minerals and their X-ray Identification London Mineralogical Society 197–248.Google Scholar
Machajdik, D. and Čičel, V., (1981) Potassium- and ammonium-treated montmorillonites. II. Calculation of characteristic layer charges Clays and Clay Minerals 29 47–52 10.1346/CCMN.1981.0290107.10.1346/CCMN.1981.0290107CrossRefGoogle Scholar
Maes, A. and Cremers, A., (1977) Charge density effects in ion exchange. Part 1. Heterovalent exchange equilibria Faraday Transactions of the Royal Society of Chemistry 73 1807–1814 10.1039/f19777301807.CrossRefGoogle Scholar
Maes, A. Stul, M.S. and Cremers, A., (1979) Layer chargecation-exchange capacity relationships in montmorillonite Clays and Clay Minerals 27 387–392 10.1346/CCMN.1979.0270510.CrossRefGoogle Scholar
Moore, D.M. and Reynolds, R.C. Jr., (1997) X-ray Diffraction and the Identification and Analysis of Clay Minerals 2nd New York Oxford University Press.Google Scholar
Nadeau, P.H. Farmer, V.C. McHardy, W.J. and Bain, D.C., (1985) Compositional variations of the Unterrupsroth beidellite American Mineralogist 70 1004–1010.Google Scholar
Newman, A.C.D. Brown, G. and Newman, A.C.D., (1987) The chemical constitution of clays Chemistry of Clays and Clay Minerals London Mineralogical Society 1–128.Google Scholar
Olis, A.C. Malla, P.B. and Douglas, L.A., (1990) The rapid estimation of the layer charges of 2:1 expanding clays from a single alkylammonium ion expansion Clay Minerals 25 39–50 10.1180/claymin.1990.025.1.05.10.1180/claymin.1990.025.1.05CrossRefGoogle Scholar
Reynolds, R.C. Jr., (1985) NEWMOD©, a computer program for the calculation of one-dimensional diffraction patterns of mixed-layer clays Hanover, NH 03755 R.C. Reynolds, Jr., 8 Brook Dr..Google Scholar
Sakharov, B.A. Lindgreen, H. Salyn, A. and Drits, V.A., (1999) Determination of illite-smectite structures using multispecimen X-ray diffraction profile fitting Clays and Clay Minerals 47 555–566 10.1346/CCMN.1999.0470502.10.1346/CCMN.1999.0470502CrossRefGoogle Scholar
Sato, T. Watanabe, T. and Otsuka, R., (1992) Effects of layer charge, charge location and energy change on expansion properties of dioctahedral smectites Clays and Clay Minerals 40 103–113 10.1346/CCMN.1992.0400111.10.1346/CCMN.1992.0400111CrossRefGoogle Scholar
Schultz, L.G., (1969) Lithium and potassium adsorption, dehydroxylation temperature and structural water content of aluminous smectites Clays and Clay Minerals 17 115–149 10.1346/CCMN.1969.0170302.CrossRefGoogle Scholar
Środoń, J., (1980) Precise identification of illite/smectite interstratifications by X-ray powder diffraction Clays and Clay Minerals 28 401–411 10.1346/CCMN.1980.0280601.CrossRefGoogle Scholar
Stul, M.S. and Mortier, W.J., (1974) The heterogeneity of the charge density in montmorillonites Clays and Clay Minerals 22 391–396 10.1346/CCMN.1974.0220505.10.1346/CCMN.1974.0220505CrossRefGoogle Scholar
Talibudeen, O. and Goulding, K.W.T., (1983) Charge heterogeneity in smectites Clays and Clay Minerals 31 37–42 10.1346/CCMN.1983.0310106.10.1346/CCMN.1983.0310106CrossRefGoogle Scholar
Tettenhorst, R. and Johns, W.D., (1966) Interstratification in montmorillonite Clays and Clay Minerals 15 85–93.Google Scholar
Velde, B., (1984) Electron microprobe analysis of clay minerals Clay Minerals 19 243–247 10.1180/claymin.1984.019.2.11.10.1180/claymin.1984.019.2.11CrossRefGoogle Scholar
Walker, G.G., Brindley, G.W. and Brown, G., (1961) Vermiculite minerals The X-ray Identification and Crystal Structures of Clay Minerals London Mineralogical Society 297–324.Google Scholar
Warren, E.A. and Ransom, B., (1992) The influence of analytical error upon the interpretation of chemical variations in clay minerals Clay Minerals 27 193–209 10.1180/claymin.1992.027.2.05.CrossRefGoogle Scholar
Weaver, C.E. and Pollard, L.D., (1973) The Chemistry of Clay Minerals Amsterdam. The Netherlands Elsevier 55–77.Google Scholar