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Reduction and Reoxidation of Nontronite: Questions of Reversibility

Published online by Cambridge University Press:  28 February 2024

Peter Komadel ,
Jana Madejova  and
Joseph W. Stucki
Peter Komadel
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, 842 36 Bratislava, Slovakia
Jana Madejova
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, 842 36 Bratislava, Slovakia
Joseph W. Stucki
Affiliation:
Department of Agronomy, University of Illinois, Urbana, Illinois 61801
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Abstract

Redox cycles are common in nature and likely have a profound effect on the behavior of soils and sediments. This study examined a key component of redox cycles in smectites, namely, the reoxidation process, which has received little attention compared to the reduction process. Unaltered (oxidized) and reoxidized ferruginous smectites (nontronites) were compared using infrared and Mössbauer spectroscopies, and thermal gravimetric analysis. The infrared and thermal gravimetric data revealed that the structural OH content of reduced-reoxidized clay is about 15 to 20% less than in the original (oxidized) sample, indicating that the structure remains partially dehydroxylated even after reoxidation. Mössbaner spectra of reoxidized samples consisted of larger quadrupole splitting for Fe(III) doublets than in the unaltered samples, suggesting that the environment of Fe(III) is more distorted after the reduction-reoxidation treatment.

Keywords

DehydroxylationFerricFerrousHydroxylationInfrared spectroscopyIronMössbauer spectroscopyNontroniteOxidationReductionReoxidationSmectiteThermal gravimetric analysisX-ray diffraction

Information

Type
Research Article
Information
Clays and Clay Minerals , Volume 43 , Issue 1 , February 1995 , pp. 105 - 110
Copyright
Copyright © 1995, The Clay Minerals Society

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References

Amonette, J. E., Khan, F. A., Scott, A. D., Gan, H., and Stucki, J. W. Quantitative oxidation-state analysis of soils. In Quantitative Methods in Soil Mineralogy. Amonette, J. E., and Zelany, L. W., 1994 eds. SSSA Misc. Pub. Madison, Wisconsin: Soil Science Society of America, 83–113.CrossRefGoogle Scholar
Cardile, C. M., 1987. Structural studies of montmorillonites by 57Fe Mössbauer spectroscopy. Clay Miner. 22: 387–394.CrossRefGoogle Scholar
Cardile, C. M., 1989. Tetrahedral iron in smectite: A critical commentary. Clays & Clay Miner. 37: 185–188.CrossRefGoogle Scholar
Cardile, C. M., and Johnston, J. H. 1985 . Structural studies of nontronites with different iron contents by 57Fe Mössbauer spectroscopy. Clays & Clay Miner. 33: 295–300.CrossRefGoogle Scholar
Cardile, C. M., and Johnston, J. H. 1986 . 57Fe Mössbauer spectroscopy of montmorillonites: A new interpretation. Clays & Clay Miner. 34: 307–313.CrossRefGoogle Scholar
Cardile, C. M., Childs, C. W., and Whitton, J. S. 1987 . The effect of citrate/bicarbonate/dithionite treatment on standard and soil smectites as evidenced by 57Fe Mössbauer spectroscopy. Aust. J. Soil Res. 25: 145–154.CrossRefGoogle Scholar
Chen, S. Z., Low, P. F., and Roth, C. B. 1987 . Relation between potassium fixation and the oxidation state of octahedral iron. Soil Sci. Soc. Am. J. 41: 82–86.CrossRefGoogle Scholar
Farmer, V. C., 1974. The Infrared Spectra of Minerals. London: The Mineralogical Society, 331–363.CrossRefGoogle Scholar
Gates, W. P., Wilkinson, H. T., and Stucki, J. W. 1993 . Swelling properties of microbially reduced ferruginous smectite. Clays & Clay Miner. 41: 360–364.CrossRefGoogle Scholar
Goodman, B. A., Russell, J. D., Fraser, A. R., and Woodhams, F. W. D. 1976 . A Mössbauer and IR spectroscopic study of the structure of nontronite. Clays & Clay Miner. 24: 53–59.CrossRefGoogle Scholar
Heller-Kallai, L., and Rozenson, I. 1980 . Dehydroxylation of dioctahedral phyllosilicates. Clays & Clay Miner. 28: 355–368.CrossRefGoogle Scholar
Khaled, E. M., and Stucki, J. W. 1991 . Effects of iron oxidation state on cation fixation in smectites. Soil Sci. Soc. Am. J. 55: 550–554.CrossRefGoogle Scholar
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 & Clay Miner. 36: 379–381.CrossRefGoogle Scholar
Komadel, P., Lear, P. R., and Stucki, J. W. 1990 . Reduction and reoxidation of nontronite: Extent of reduction and reaction rates. Clays & Clay Miner. 38: 203–208.CrossRefGoogle Scholar
Lear, P. R., 1984. The use of tritium as a label to evaluate the redox mechanism of iron in nontronites: M.S. thesis. University of Illinois, Urbana.Google Scholar
Lear, P. R., and Stucki, J. W. 1985 . The role of structural hydrogen in the reduction and reoxidation of iron in nontronite. Clays & Clay Miner. 33: 539–545.CrossRefGoogle Scholar
Lear, P. R., and Stucki, J. W. 1989 . Effects of iron oxidation state on the specific surface area of nontronite. Clays & Clay Miner. 37: 547–552.CrossRefGoogle Scholar
Lear, P. R., Komadel, P., and Stucki, J. W. 1988 . Mössbauer spectroscopic identification of iron oxides in nontronite from Hohen Hagen, Federal Republic of Germany. Clays & Clay Miner. 36: 376–378.CrossRefGoogle Scholar
Luca, V., 1991. Detection of tetrahedral Fe3+ site in nontronite and vermiculite by Mössbauer spectroscopy. Clays & Clay Miner. 39: 467–477.CrossRefGoogle Scholar
Luca, V., and Cardile, C. M. 1989 . Improved detection of tetrahedral Fe3+ in nontronite SWa-1 by Mössbauer spectroscopy. Clay Miner. 24: 555–560.CrossRefGoogle Scholar
Murad, E., 1987. Mössbauer spectra of nontronites: structural implications and characterization of associated iron oxides. Z. Pflanzenernähr. Bodenk. 150: 279–285.CrossRefGoogle Scholar
Rozenson, I., and Heller-Kallai, L. 1976 . Reduction and oxidation of Fe3+ in dioctahedral smectite. 1: Reduction with hydrazine and dithionite. Clays & Clay Miner. 24: 271–282.CrossRefGoogle Scholar
Russell, J. D., Goodman, B. A., and Fraser, A. R. 1979 . Infrared and Mössbauer studies of reduced nontronites. Clays & Clay Miner. 27: 63–71.CrossRefGoogle Scholar
Schneiderhöhn, P., 1965. Nontronit vom Hohen Hagen und Chloropal vom Meenser Stainberg bei Göttingen. Tschermaks Min. Pet. Mitt. 10: 385–399.CrossRefGoogle Scholar
Scott, A. D., and Amonette, J. E. Role of iron in mica weathering. In Iron in Soils and Clay Minerals. Stucki, J. W., Goodman, B. A., and Schwertmann, U., 1988 eds. Dordrecht: D. Reidel, 537–623.CrossRefGoogle Scholar
Stubican, V., and Roy, R. 1961 . New approach to assignment of infrared absorption bands in layer structure silicates. Z. Krist. 115: 200–214.CrossRefGoogle Scholar
Stucki, J. W., 1988. Structural iron in smectites. In Iron in Soils and Clay Minerals. Stucki, J. W., Goodman, B. A., and Schwertmann, U., eds. Dordrecht: D. Reidel, 625–675.CrossRefGoogle Scholar
Stucki, J. W., and Roth, C. B. 1976 . Interpretation of infrared spectra of oxidized and reduced nontronite. Clays & Clay Miner. 24: 293–296.CrossRefGoogle Scholar
Stucki, J. W., and Roth, C. B. 1977 . Oxidation-reduction mechanism for structural iron in nontronite. Soil Sci. Soc. Am. J. 41: 808–814.CrossRefGoogle Scholar
Stucki, J. W., and Lear, P. R. Variable oxidation states of iron in the crystal structure of smectite clay minerals. In Structures and Active Sites of Minerals. Coyne, L. M., Blake, D., and McKeever, S., 1989 eds. Washington, D. C.: American Chemical Society, 330–358.Google Scholar
Stucki, J. W., and Tessier, D. 1991 . Effects of iron oxidation state on the texture and structural order of Na-nontronite. Clays & Clay Miner. 39: 137–143.CrossRefGoogle Scholar
Stucki, J. W., Golden, D. C., and Roth, C. B. 1984a . The preparation and handling of dithionite-reduced smectite suspensions. Clays & Clay Miner. 32: 191–197.CrossRefGoogle Scholar
Stucki, J. W., Golden, D. C., and Roth, C. B. 1984b . Effects of reduction and reoxidation of structural iron on the surface charge and dissolution of dioctahedral smectites. Clays & Clay Miner. 32: 350–356.CrossRefGoogle Scholar
Walker, G. F., 1949. The decomposition of biotite in the soil. Mineral. Mag. 28: 693–703.Google Scholar