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Clays and Clay Minerals

, Volume 56, Issue 2, pp 155–174 | Cite as

Surface area and layer charge of smectite from CEC and EGME/H2O-retention measurements

  • Jan Środoń
  • Douglas K. McCarty
Article

Abstract

The total specific surface area (TSSA) and smectitic layer charge (Qs) calculated from the structural formulae and unit-cell dimensions of 12 pure smectite samples were used as a reference in the design and evaluation of TSSA and Qs measurement techniques based on cation exchange capacity (CEC), H2O retention at 47% RH, and ethylene glycol monoethyl ether (EGME) retention. A thermogravimetric analysis-mass spectrometry (TGA-MS) technique was used to study the release of H2O from smectite on heating, and to introduce a correction for H2O remaining in the smectite after heating to 110°C, because the sample weight at this temperature has been used routinely as a reference in CEC and EGME sorption measurements. A temperature of 200°C was found to be the optimum reference for such measurements.

A good agreement between Qs from the structural formula and from CEC was obtained when this correction was applied. The TSSA of smectite was measured with similar accuracy (mean error of ±5–7%) by three techniques: (1) using mean H2O coverage; (2) using mean EGME coverage; and (3) using a combination of H2O coverage and CEC. A reduction of the mean error from 5–7% to 4% can be obtained by averaging these measurements, and a further reduction to 3% by introducing corrections for the dependence of H2O and EGME coverage on layer charge. The study demonstrates that Ca2+-smectite samples at 47% RH have H2O contents corresponding to 88–107% of the theoretical mass of a monolayer and offers an explanation of this variation.

Key Words

CEC Charge Density EGME Layer Charge Smectite Specific Surface Area Water Sorption 

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References

  1. Ammann, L., Bergaya, F., and Lagaly, G. (2005) Determination of the cation exchange capacity of clays with copper complexes revisited. Clay Minerals, 40, 441–453.Google Scholar
  2. Avena, M.J., Valenti, L.E., Pfaffen, V., and De Pauli, C.P. (2001) Methylene blue dimerization does not interfere in surface area measurements of kaolinite and soils. Clays and Clay Minerals, 49, 168–173.Google Scholar
  3. Bardon, C., Bieber, M.T, Cuiec, L., Jacquin, C., Courbot, A., Deneuville, G., Simon, J.M., Voirin, J.M., Espy, M., Nectoux, A., and Pellerin, A. (1983) Recommandations pour la determination experérimentale de la capacité d’échange de cations des milieux argileux. Revue de l’ Institut Français du Pétrole, 38, 621–626.Google Scholar
  4. Bergaya, F. and Vayer, M. (1997) CEC of clays: measurement by adsorption of a copper ethylendiamine complex. Applied Clay Science, 12, 275–280.Google Scholar
  5. Bigorre, F., Tessier, D., and Pedro, G. (2000) Contribution des argiles et des matiéres organiques á la rétention de l’eau dans les sols. Signification et role fondamental de la capacité d’échange en cations. Comptes Rendu Academy of Science Paris, Sciences de la Terre et des planetes, 330, 245–250.Google Scholar
  6. Blum, A.E. and Eberl, D.D. (2004) Measurement of clay surface areas by polyvinyl pyrrolidone (PVP) sorption and its use for quantifying illite and smectite abundance. Clays and Clay Minerals, 52, 589–602.Google Scholar
  7. Brindley, G.W. and Brown, G. (1980) Crystal Structures of Clay Minerals and their X-ray Identification. Monograph No. 5, Mineralogical Society, London.Google Scholar
  8. Carter, D.L., Heilman, M.D., and Gonzalez, C.L. (1965) Ethylene glycol monoethyl ether for determining surface area of silicate minerals. Soil Science, 100, 356–360.Google Scholar
  9. Cases, J.M., Berend, I., Francois, M., Uriot, J.P., Michot, L.J., and Thomas, F. (1997) Mechanism of adsorption and desorption of water vapor by homoionic montmorillonite: 3. the Mg2+, Ca2+, Sr2+ and Ba2+ exchanged forms. Clays and Clay Minerals, 45, 8–22.Google Scholar
  10. Chabra, R., Pleysier, J., and Cremers, A. (1975) The measurement of cation exchange capacity and exchangeable cations in soils. A new method. Proceedings of the International Clay Conference, 1975, Mexico, 439–449.Google Scholar
  11. Chiou, C.T. and Rutherford, D.W. (1997) Effects of exchanged cation and layer charge on the sorption of water and EGME vapors on montmorillonite clays. Clays and Clay Minerals, 45, 867–880.Google Scholar
  12. Chiou, C.T., Rutherford, D.W., and Manes, M. (1993) Sorption of N2 and EGME vapors on some soils, clays, and mineral oxides and determination of sample surface areas by use of sorption data. Environmental Science & Technology, 27, 1587–1594.Google Scholar
  13. Churchman, G.J., Burke, C.M., and Parfitt, R.L. (1991) Comparison of various methods for the determination of specific surfaces of subsoils. Journal of Soil Science, 42, 449–461.Google Scholar
  14. Ciesielski, H. and Steckerman, T. (1997) A comparison between three methods for the determination of cation exchange capacity and exchangeable cations in soils. Agronomie, 17, 9–16.Google Scholar
  15. Desprairies, A. (1983) Relation entre le parametre b des smectites et leur contenu en fer et magnesium. Application a l’etude des sediments. Clay Minerals, 18, 165–175.Google Scholar
  16. Dohrmann, R. and Echle, W. (1994) Eine kritische Betrachtung der Silber-Thioharnstoff-Methode (AgTu) zur Bestimmung der Kationenaustauschkapazitaet und Vorstellung eines neuen methodischen Ansatzes. Berichte der Deutschen Ton- und Tonmineralgruppe, 3, 213–222.Google Scholar
  17. Drits, V.A. and McCarty, D.K. (2007) The nature of structure-bonded H2O in illite and leucophyllite from dehydratation and dehydroxylation experiments. Clays and Clay Minerals, 55, 45–58.Google Scholar
  18. Dyal, R.S. and Hendricks, S.B. (1950) Total surface of clays in polar liquids as a characteristic index. Soil Science, 69, 421–432.Google Scholar
  19. Eberl, D.D., Środoń, J., and Northrop, H.R. (1986) Potassium fixation in smectite by wetting and drying. Pp. 296–326 in: Geochemical Processes at Mineral Surfaces (J.A. Davis and K.F. Hayes, editors). ACS Symposium Series 323, American Chemical Society.Google Scholar
  20. Emmerich, K. and Wolters, F. (2005) The role of crosschecks for the classification of montmorillonite. Berichte der Deutschen Ton- und Tonmineralgruppe, 11, 18–19.Google Scholar
  21. Ferrage, E., Lanson, B, Sakharov, B.A., and Drits, V.A. (2005a) Investigation of smectite hydration properties by modeling experimental X-ray diffraction patterns. Part I. Montmorillonite hydration properties. American Mineralogist, 90, 1358–1374.Google Scholar
  22. Ferrage, E., Lanson, B., Malikova, N., Plançon, A., Sakharov, B.A., and Drits, V.A. (2005b) New insights in the distribution of interlayer H2O molecules in bi-hydrated smectite from X-ray diffraction profile modeling of 001 reflections. Chemistry of Materials, 17, 3499–3512.Google Scholar
  23. Gates, W.P., Slade, P.G., Manceau, A., and Lanson, B. (2002) Site occupancies by iron in nontronites. Clays and Clay Minererals, 50, 223–239.Google Scholar
  24. Güven, N. (1988) Smectites. Pp. 497–559 in: Hydrous Phyllosilicates (S.W. Bailey, editor). Reviews in Mineralogy 19, Mineralogical Society of America, Washington D.C.Google Scholar
  25. Hendricks, S.B., Nelson, R.A., and Alexander L.T. (1940) Hydration mechanism of the clay mineral montmorillonite saturated with various cations. Journal of the American Chemical Society, 62, 1457–1464.Google Scholar
  26. Jackson, M.L. (1975) Soil Chemical Analysis — Advanced Course. Published by the author, Madison, Wisconsin, USA.Google Scholar
  27. Kaufhold, S. (2005) Influence of layer charge density on the determination of the internal surface area of smectites. Berichte der Deutschen Ton- und Tonmineralgruppe, 11, 20–26.Google Scholar
  28. Khoury, H.N. and Eberl, D.D. (1981) Montmorillonite from the Amargosa Desert, southern Nevada, USA. Neues Jahrbuch fur Mineralogie, 141, 134–141.Google Scholar
  29. Kodama, H. and Brydon, J.E. (1968) Dehydroxylation of microcrystalline muscovite. Transactions of the Faraday Society, 551, 3112–3119.Google Scholar
  30. Köster, H.M., Erlicher, U., Gilg, H.A., Jordan, R., Murad, E., and Onnich, K. (1999) Mineralogical and chemical characteristics of five nontronites and Fe-rich smectites. Clay Minerals, 34, 579–599.Google Scholar
  31. Lagaly, G. and Weiss, A. (1969) Determination of the layer charge in mica-type layer silicates. Proceedings of the International Clay Conference, Tokyo, 61–80.Google Scholar
  32. Laird, D.A. (1999) Layer charge influences on the hydration of expandable 2:1 phyllosilicates. Clays and Clay Minerals, 47, 630–636.Google Scholar
  33. MacEwan, D.M.C. and Wilson, M.J. (1980) Interlayer and intercalation complexes of clay minerals. Pp. 197–248 in: Crystal Structures of Clay Minerals and their X-ray Identification (G.W. Brindley and G. Brown, editors). Monograph No. 5, Mineralogical Society, London.Google Scholar
  34. Meier, L.P. and Kahr, G. (1999) Determination of the cation exchange capacity (CEC) of clay minerals using the complexes of copper(II) ion with triethylenetetramine and tetraethylenepentamine. Clays and Clay Minerals, 47, 386–388.Google Scholar
  35. Mermut, A.R. and Lagaly, G. (2001) Baseline studies of The Clay Minerals Society Source Clays: layer-charge determination and characteristics of those minerals containing 2:1 layers. Clays and Clay Minerals, 49, 393–397.Google Scholar
  36. Michot, L.J. and Villieras, F. (2006) Surface area and porosity. Pp. 965–978 in: Handbook of Clay Science (F. Bergaya, B.K.G. Theng and G. Lagaly, editors). Developments in Clay Science 1, Elsevier, Amsterdam.Google Scholar
  37. Moore, D.M. and Reynolds, R.C. (1997) X-ray diffraction and the Identification and Analysis of Clay Minerals. Oxford University Press, Oxford-New York, 378 pp.Google Scholar
  38. Nadeau, P.H., Wilson, M.J., McHardy, W.J., and Tait, J. (1984) Interstratified clays as fundamental particles. Science, 225, 923–925.Google Scholar
  39. Newman, A.C.D. (1983) The specific surface of soils determined by water sorption. Journal of Soil Science, 34, 23–32.Google Scholar
  40. Newman, A.C.D. (1987) The interaction of water with clay mineral surfaces. Pp. 237–271 in: Chemistry of Clays and Clay Materials (A.C.D. Newman, editor). Mineralogical Society Monograph No. 6, Longman, Essex, UK.Google Scholar
  41. Orsini, L. and Remy, J.-C. (1976) Utilisation du chlorure de cobaltihexammine pour la determination simultanee de la capacite d’echange et des bases echangeables des sols. Science du Sol, 4, 269–275.Google Scholar
  42. Quirk, J.P. and Murray, R.S. (1999) Appraisal of the ethylene glycol monoethyl ether method for measuring hydratable surface area of clays and soils. Soil Science Society of America Journal, 63, 839–849.Google Scholar
  43. Reichenbach, H. Graf V. and Beyer, J. (1994) Dehydration and rehydration of vermiculites: I. Phlogopitic Mg-vermiculite. Clay Minerals, 29, 327–340.Google Scholar
  44. Rinnert, E., Carteret, C., Humbert, B., Fragneto-Cusani, G., Ramsay, J.D.F., Delville, A., Robert, J.-L., Bihannic, I., Pelletier, M., and Michot, L.J. (2005) Hydration of a synthetic clay with tetrahedral charges: a multidisciplinary experimental and numerical study. Journal of Physical Chemistry B, 109, 23745–23759.Google Scholar
  45. Ristori, G.G., Sparvoli, E., Landi, L., and Martelloni, C. (1989) Measurement of specific surface areas of soils by p-nitrophenol adsorption. Applied Clay Science, 4, 521–532.Google Scholar
  46. 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.Google Scholar
  47. Slonimskaya, M.V., Drits, V.A., Finko V.I., and Salyn, A.L. (1978) The nature of interlayer water in fine-dispersed muscovites. Izvestiya Akademii Nauk SSSR, seriya geologicheskaya, 10, 95–104 (in Russian).Google Scholar
  48. Środoń, J., Elsass, F., McHardy, W.J., and Morgan, D.J. (1992) Chemistry of illite-smectite inferred from TEM measurements of fundamental particles. Clay Minerals, 27, 137–158.Google Scholar
  49. Theng, B.K.G., Ristori, G.G., Santi, C.A., and Percival, H.J. (1999) An improved method for determining the specific surface areas of topsoils with varied organic matter content, texture and clay mineral composition. European Journal of Soil Science, 50, 309–316.Google Scholar
  50. Tiller, K.G. and Smith, L.H. (1990) Limitations of EGME retention to estimate the surface area of soils. Australian Journal of Soil Research, 28, 1–26.Google Scholar
  51. Watanabe, T. and Sato, T. (1988) Expansion characteristics of montmorillonite and saponite under various relative humidity conditions. Clay Science, 7, 129–138.Google Scholar

Copyright information

© The Clay Minerals Society 2008

Authors and Affiliations

  • Jan Środoń
    • 1
  • Douglas K. McCarty
    • 2
  1. 1.Institute of Geological Sciences PANKrakowPoland
  2. 2.Chevron ETCHoustonUSA

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