Abstract
Partial stabilization of Fe(II) in chemically reduced smectite, which normally readily undergoes reoxidation in air, was achieved. The purpose of this study was to determine if Fe(II) can be stabilized in reduced smectites by Li fixation upon heating. More than 80% of total Fe in ferruginous smectite SWa-1 was reduced to Fe(II) using the citrate-bicarbonate-dithionite (CBD) method while purging the clay dispersion with N2. The reduced smectite was Li-saturated, washed free of excess ions, freeze-dried, and heated in N2 atmosphere at 260°C for 24 h to produce Li-fixation. This treatment caused partial stabilization of Fe(II) in the clay structure. Chemical analysis, Mössbauer spectroscopy, and Fourier transform infrared (FTIR) spectroscopy proved that <20% of total Fe was Fe(II) after reoxidation with oxygen in a water dispersion, a treatment which causes complete reoxidation of Fe(II) in reduced Na-smectites. Decomposition of the OH-stretching band evident in the IR spectra indicated migration of Li into the vacant octahedra. Some of the OH groups in the reoxidized smectite were found in local trioctahedral configurations, associated with the AlFe(II)Li or Fe(III)Fe(II)Li groupings of central atoms in the octahedral sheet.
Similar content being viewed by others
References
Alvero, R., Alba, M.D., Castro, M.A., and Trillo, J.M. (1994) Reversible migration of lithium in montmorillonite. Journal of Physical Chemistry, 98, 7848–7853.
Besson, G. and Drits, V.A. (1997a) Refined relationships between chemical composition of dioctahedral fine-grained mica minerals and their infrared spectra within the OH stretching region. Part I: Identification of the OH stretching bands. Clays and Clay Minerals, 45, 158–169.
Besson, G. and Drits, V.A. (1997b) Refined relationships between chemical composition of dioctahedral fine-grained mica minerals and their infrared spectra within the OH stretching region. Part II: The main factors affecting OH vibrations and quantitative analysis. Clays and Clay Minerals, 45, 170–183.
Breen, C., Zahoor, F.D., Madejová, J., and Komadel, P. (1997) Characterisation and catalytic activity of acid treated, size fractionated smectites. Journal of Physical Chemistry B, 101, 5324–5331.
Bujdák, J. and Slosiariková, H. (1994) Dehydration and de-hydroxylation of reduced-charge montmorillonite. Journal of Thermal Analysis, 41, 825–831.
Bujdák, J., Slosiariková, H., Nováková, L’., and Číčel, B. (1991) Fixation of lithium cations in montmorillonite. Chemical Papers, 45, 499–507.
Bujdák, J., Petrovičová, I., and Slosiariková, H. (1992a) Study of water-reduced charge montmorillonite system. Geologica Carpathica Series Clays, 43, 109–111.
Bujdák, J., Slosiariková, H., and Číčel, B. (1992b) Interaction of long chain alkylammonium cations with reduced charge montmorillonite. Journal of Inclusion Phenomena and Molecular Recognition, 13, 321–327.
Bujdák, J., Slosiariková, H., and Číčel, B. (1993) Sorption of hexadecylammonium ions on reduced charge montmorillonite. Chemical Papers, 47, 85–87.
Calvet, R. and Prost, R. (1971) Cation migration into empty octahedral sites and surface properties of clays. Clays and Clay Minerals, 19, 175–186.
Gates, W.P., Stucki, J.W., and Kirkpatrick, R.J. (1996) Structural properties of reduced Upton montmorillonite. Physics and Chemistry of Minerals, 23, 535–541.
Goodman, B.A., Russell, J.D., and Fraser, A.R. (1976) A Mössbauer and IR spectroscopic study of the structure of nontronite. Clays and Clay Minerals, 24, 53–59.
Greene-Kelly R. (1953) The identification of montmorillonoids in clays. Journal of Soil Science, 4, 233–237.
Farmer, V.C. (1974) Layer silicates. In Infrared Spectra of Minerals, V.C. Farmer, ed., Mineralogical Society, London, 331–363.
Hofmann, U. and Kiemen, R. (1950) Verlust der Austauschfähigkeit von Lithiuminonen an Bentonit durch Erhitzung. Zeitschrift für Anorganische und Allgemeine Chemie, 262, 95–99.
Komadel, P. and Stucki, J.W. (1988) The quantitative assay of minerals for Fe2+ and Fe3+ using 1,10-phenanthroline: A rapid photochemical method. Clays and Clay Minerals, 36, 379–381.
Komadel, P., Lear, P.R., and Stucki, J.W. (1990) Reduction and reoxidation of nontronite: Extent of reduction and reaction rates. Clays and Clay Minerals, 38, 203–208.
Komadel, P., Madejová, J., and Stucki, J.W. (1995) Reduction and reoxidation of nontronite: Questions of reversibility. Clays and Clay Minerals, 43, 105–110.
Komadel, P., Bujdák, J., Madejová, J., Šucha, V, and Elsass, F. (1996a) Effect of non-swelling layers on the dissolution of reduced-charge montmorillonite in hydrochloric acid. Clay Minerals, 31, 333–345.
Komadel, P., Madejová, J., Janek, M., Gates, W.P., Kirkpatrick, R.J., and Stucki, J.W. (1996b) Dissolution of hectorite in inorganic acids. Clays and Clay Minerals, 44, 228–236.
Lim, C.H. and Jackson, M.L. (1986) Expandable phyllosilicate reactions with lithium on heating. Clays and Clay Minerals, 34, 346–352.
Madejová, J., Komadel, P., and Cícel, B. (1994) Infrared study of octahedral site populations in smectites. Clay Minerals, 31, 319–326.
Madejová, J., Bujdák, J„ Gates, W.P., and Komadel, P. (1996) Preparation and infrared spectroscopic characterization of reduced-charge montmorillonite with various Li content. Clay Minerals, 31, 233–241.
Manceau, A., Drits, V.A., Lanson, B., Chateigner, D., Wu, J., Huo, D., Gates, W.P., and Stucki, J.W. (1999) Oxidation-reduction mechanism of iron in dioctahedral smectites. 2. Structural chemistry of reduced Garfield nontronite. American Mineralogist, in press.
McBride, M.B., and Mortland, M.M. (1974) Copper (II) interactions with montmorillonite: Evidence from physical methods. Soil Science Society of America Proceedings, 38, 408–415.
Robert, J.L. and Kodama, H. (1988) Generalization of the correlations between hydroxyl-stretching wavenumbers and composition of micas in the system K2O-MgO-Al2O3-SiO2-H2O: A single model for trioctahedral and dioctahedral micas. American Journal of Science, 228A, 196–212.
Rouxhet, RG. (1970) Hydroxyl stretching bands in micas: A quantitative interpretation. Clay Minerals, 8, 375–388.
Rozenson, I. and Heller-Kallai, L. (1976) Reduction and oxidation of Fe3+ in dioctahedral smectite. I.: Reduction with hydrazine and dithionite. Clays and Clay Minerals, 32, 271–282.
Russell, J.D. (1979) An infrared spectroscopic study of interaction of nontronite and ferruginous montmorillonites with alkali metal hydroxides. Clay Minerals, 14, 127–137.
Russell, J.D. and Fraser, A.R. (1994) Infrared methods. In Clay Mineralogy: Spectroscopic and Chemical Determinative Methods, M.J. Wilson, ed., Chapman & Hall, London, 11–67.
Shen, S. and Stucki, J.W. (1994) Effects of iron oxidation state on the fate and behavior of potassium in soils. In Soil Testing: Prospects for Improving Nutrient Recommendations, J.L. Havlin, J. Jacobsen, P. Fixen, and G. Hergert, eds., Soil Science Society of America Special Publication 40, Soil Science Society of America, Madison, Wisconsin, 173–185.
Shen, S., Stucki, J.W, and Boast C.W (1992). Effects of structural iron reduction on the hydraulic conductivity of Na-smectite. Clays and Clay Minerals, 40, 381–386.
Slonimskaya, M.V., Besson, G., Danyak, L.G., Tchoubar, C., and Drits, V.A. (1986) Interpretation of the IR spectra of celadonites and glauconites in the region of OH-stretching frequencies. Clay Minerals, 21, 115–149.
Stucki, J.W. (1988) Structural iron in smectites. In Iron in Soils and Clay Minerals, J.W. Stucki, B.A. Goodman, and U. Schwertmann, eds., D. Reidel, Dordrecht, 625–675.
Stucki, J.W. and Roth, C.B. (1976) Interpretation of infrared spectra of oxidized and reduced nontronite. Clays and Clay Minerals, 24, 293–296.
Stucki, J.W, Golden, D.C., and Roth, C.B. (1984) The preparation and handling of dithionite-reduced smectite suspensions. Clays and Clay Minerals, 32, 191–197.
Stucki, J.W, Bailey, G.W., and Gan, H. (1996) Oxidation-reduction mechanisms in iron-bearing phyllosilicates. Applied Clay Science, 10, 417–430.
Theng, B.K.G., Hayashi, S., Soma, M., and Seyama, H. (1997) Nuclear magnetic resonance and X-ray photoelectron spectroscopic investigation of lithium migration in montmorillonite. Clays and Clay Minerals, 45, 718–723.
Vedder, W (1964) Correlations between infrared spectrum and chemical composition of mica. American Mineralogist, 49, 736–768.
Von Goldstein, S., Wolf, D., and Uhlig, J. (1995) Infrared spectroscopic studies on natural Li-Fe-Al micas. Chemie der Erde, 55, 46–60.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Komadel, P., Madejová, J. & Stucki, J.W. Partial Stabilization of Fe(II) in Reduced Ferruginous Smectite by Li Fixation. Clays Clay Miner. 47, 458–465 (1999). https://doi.org/10.1346/CCMN.1999.0470407
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1346/CCMN.1999.0470407