Hostname: page-component-586b7cd67f-t8hqh Total loading time: 0 Render date: 2024-11-28T09:45:00.111Z Has data issue: false hasContentIssue false
  • English
  • Français

Redox Properties of Structural Fe in Ferruginous Smectite. A Discussion of the Standard Potential and its Environmental Implications

Published online by Cambridge University Press:  01 January 2024

Fabienne Favre ,
Joseph W. Stucki  and
Pascal Boivin
Fabienne Favre
Affiliation:
Laboratory of Soil Science, LPE-ISTE-ENAC, Swiss Federal Institute of Technology, 1015 Lausanne, Switzerland
Joseph W. Stucki
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, W-321 Turner Hall, 1102 South Goodwin Avenue, Urbana, IL 61801, USA
Pascal Boivin*
Affiliation:
IRD, Laboratoire d’étude des Transferts en Hydrologie et Environnement LTHE, Université J. Fourier, B.P. 53, 38041 Grenoble Cedex 9, France
*
*E-mail address of corresponding author: [email protected]
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

The aim of this study was to compare the redox properties of oxides and smectite structural Fe (FeStr). Structural Fe in smectite often accounts for about half of the Fe pool in soils and sediments, and is naturally reduced by indigenous bacteria. This reaction is, however, seldom taken into account in environmental studies. The equation for the oxidation-reduction of FeStr and its application to the calculation of the standard electrode potential of FeStr, E0, are discussed on the basis of literature review. The resulting redox properties were used in a new analysis of previously reported field monitoring data. This agreed well with experimental observations that remained unexplained, and showed that if equilibrium conditions prevail, the FeStr pool in soils will reduce prior to the Fe in oxides. The FeStr pool is, therefore, likely to play a major role in controlling the bio-geochemistry of temporarily water-logged soils, and this reaction should be taken into account in further studies.

Keywords

GoethiteOxidesReductionSmectiteStandard PotentialStructural Fe
Type
Research Article
Information
Clays and Clay Minerals , Volume 54 , Issue 4 , August 2006 , pp. 466 - 472
Copyright
Copyright © 2006, The Clay Minerals Society

References

Amonette, J.E. and Fitch, A., (2002) Iron redox chemistry of clays and oxides: environmental applications Electrochemical Properties of Clays Aurora, Colorado The Clay Minerals Society 89–147.Google Scholar
Boivin, P. Favre, F. Hammecker, C. Maeght, J.L. Delariviere, J. Poussin, J.C. and Wopereis, M.C.S., (2002) Processes driving soil solution chemistry in a flooded rice-cropped vertisol: analysis of long-time monitoring data Geoderma 110 87–107 10.1016/S0016-7061(02)00226-4.CrossRefGoogle Scholar
Cervini-Silva, A. Wu, J. Larson, R.A. and Stucki, J.W., (2000) Transformation of chloropicrin in the presence of iron-bearing clay minerals Environmental Science & Technology 34 915–917 10.1021/es990900j.CrossRefGoogle Scholar
Cervini-Silva, J. Larson, R.A. Wu, J. and Stucki, J.W., (2002) Dechlorination of pentachloroethane by commercial Fe and ferruginous smectite Chemosphere 47 971–976 10.1016/S0045-6535(02)00056-5.CrossRefGoogle ScholarPubMed
Cervini-Silva, J. Kostka, J.E. Larson, R.A. Stucki, J.W. and Wu, J., (2003) Dehydrochlorination of 1,1,1-trichloroethane and pentachloroethane by microbially reduced ferruginous smectite Environmental Toxicology and Chemistry 22 1046–1050 10.1002/etc.5620220511.Google ScholarPubMed
Clark, W.M., (1972) Oxidation Reduction Potentials of Organic Systems New York, and Krieger, R.E., Baltimore Huntington.Google Scholar
Cornell, R.M. and Schwertmann, U., (1996) The Iron Oxides. Structure, Properties, Reactions, Occurence and Uses Weinheim, Germany VCH.Google Scholar
Drits, V.A. and Manceau, A., (2000) A model for the mechanism of Fe3+ to Fe2+ reduction in dioctahedral smectites Clays and Clay Minerals 48 185–195 10.1346/CCMN.2000.0480204.CrossRefGoogle Scholar
Egashira, K. and Ohtsubo, M., (1983) Swelling and mineralogy of smectites in paddy soils derived from marine alluvium, Japan Geoderma 29 119–127 10.1016/0016-7061(83)90036-8.CrossRefGoogle Scholar
Ernstsen, V., (1996) Reduction of nitrate by Fe2+ in clay minerals Clays and Clay Minerals 44 599–608 10.1346/CCMN.1996.0440503.CrossRefGoogle Scholar
Favre, F. Ernstsen, V. Tessier, D. and Boivin, P., (2002) Short scale changes in soil properties due to structural iron reduction Geochimica et Cosmochimica Acta 66 A226–A226.Google Scholar
Favre, F. Tessier, D. Abdelmoula, M. Genin, J.M. Gates, W.P. and Boivin, P., (2002) Iron reduction and changes in cation exchange capacity in intermittently waterlogged soil European Journal of Soil Science 53 175–183 10.1046/j.1365-2389.2002.00423.x.CrossRefGoogle Scholar
Favre, F. Jaunet, A.M. Badraoui, M. Boivin, P. and Tessier, D., (2004) Changes in clay organisation due to structural iron reduction in a flooded vertisol Clay Minerals 39 123–134 10.1180/0009855043920125.CrossRefGoogle Scholar
Fialips, C.I. Huo, D.F. Yan, L.B. Wu, J. and Stucki, J.W., (2002) Effect of Fe oxidation state on the IR spectra of Garfield nontronite American Mineralogist 87 630–641 10.2138/am-2002-5-605.CrossRefGoogle Scholar
Foster, M.D., (1953) Geochemical studies of clay minerals: II. Relation between ionic substitution and swelling in montmorillonites American Mineralogist 38 994–1006.Google Scholar
Gan, H. Stucki, J.W. and Bailey, G.W., (1992) Reduction of structural iron in ferruginous smectite by free radicals Clays and Clay Minerals 40 659–665 10.1346/CCMN.1992.0400605.CrossRefGoogle Scholar
Gates, W.P. Stucki, J.W. and Wilkinson, H.T., (1991) Reduction of structural iron(III) in smectites by bacteria: Effect on clay swelling Agronomy Abstracts 1991 365.Google Scholar
Hofstetter, T.B. Schwarzenbach, R.P. and Haderlein, S.B., (2003) Reactivity of Fe(II) species associated with clay minerals Environmental Science and Technology 37 519–528 10.1021/es025955r.CrossRefGoogle ScholarPubMed
Khaled, E.M. and Stucki, J.W., (1991) Iron oxidation-state effects on cation fixation in smectites Soil Science Society of America Journal 55 550–554 10.2136/sssaj1991.03615995005500020045x.CrossRefGoogle Scholar
Kostka, J.E. Stucki, J.W. Nealson, K.H. and Wu, J., (1996) Reduction of structural Fe(III) in smectite by a pure culture of Shewanella putrefaciens strain MR-1 Clays and Clay Minerals 44 522–529 10.1346/CCMN.1996.0440411.CrossRefGoogle Scholar
Kostka, J.E. Wu, J. Nealson, K.H. and Stucki, J.W., (1999) The impact of structural Fe(III) reduction by bacteria on the surface chemistry of smectite clay minerals Geochimica et Cosmochimica Acta 63 3705–3713 10.1016/S0016-7037(99)00199-4.CrossRefGoogle Scholar
Kostka, J.E. Stucki, J.W. and Dong, H., (2002) Microbial reduction of Fe(III) bound in clay minerals: Laboratory investigations of growth and mineral transformation Abstracts of Papers of the American Chemical Society 223 046–GEOC.Google Scholar
Kostka, J.E. Dalton, D.D. Skelton, H. Dollhopf, S. and Stucki, J.W., (2002) Growth of iron(III)-reducing bacteria on clay minerals as the sole electron acceptor and comparison of growth yields on a variety of oxidized iron forms Applied and Environmental Microbiology 68 6256–6262 10.1128/AEM.68.12.6256-6262.2002.CrossRefGoogle ScholarPubMed
Lear, P.R. and Stucki, J.W., (1985) The role of structural hydrogen in the reduction and reoxidation of iron in nontronite Clays and Clay Minerals 33 539–545 10.1346/CCMN.1985.0330609.CrossRefGoogle Scholar
Lear, P.R. and Stucki, J.W., (1989) Effects of Fe oxidation state on the specific surface area of nontronite Clays and Clay Minerals 37 547–552 10.1346/CCMN.1989.0370607.CrossRefGoogle Scholar
McBride, M.B., (1994) Environmental Chemistry of Soils New York Oxford University Press.Google Scholar
Ponnamperuma, F.N., (1972) The chemistry of submerged soils Advances in Agronomy 24 29–96 10.1016/S0065-2113(08)60633-1.CrossRefGoogle Scholar
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 10.1346/CCMN.1992.0400402.CrossRefGoogle Scholar
Sorensen, K. Stucki, J.W. Warner, R.E. and Plewa, M.J., (2004) Alteration of mammalian cell toxicity of pesticides by structural iron(II) in ferruginous smectite Environmental Science and Technology 38 4383–4389 10.1021/es035151r.CrossRefGoogle Scholar
Sorensen, K.C. Stucki, J.W. and Plewa, M.J., (2005) Comparative quantitative analysis of agricultural chemicals using a microplate mammalian cell cytotoxicity assay Bulletin of Environmental Contamination and Toxicology 70 1083–1088 10.1007/s00128-003-0093-2.CrossRefGoogle Scholar
Stucki, J.W., Stucki, J.W. Goodman, B.A. and Schwertmann, U., (1988) Structural iron in smectites Iron in Soils and Clay Minerals Dordrecht, The Netherlands D. Reidel 625–675 10.1007/978-94-009-4007-9_17.CrossRefGoogle Scholar
Stucki, J.W., Bergaya, F. Theng, B.K.G. and Lagaly, G., (2006) Properties and behaviour of iron in clay minerals Handbook of Clay Science Amsterdam Elsevier 423–475 10.1016/S1572-4352(05)01013-5.CrossRefGoogle Scholar
Stucki, J.W. and Lear, P.R., (1989) Variable oxidation states of iron in the crystal structure of smectite clay minerals American Chemical Society Symposium Series 415 330–358 10.1021/bk-1990-0415.ch017.CrossRefGoogle Scholar
Stucki, J.W. and Roth, C.B., (1977) Oxidation-reduction mechanism for structural iron in nontronite Soil Science Society of America Journal 41 808–814 10.2136/sssaj1977.03615995004100040041x.CrossRefGoogle Scholar
Stucki, J.W. Golden, D.C. and Roth, C.B., (1984) Preparation and handling of dithionite-reduced smectite suspensions Clays and Clay Minerals 32 191–197 10.1346/CCMN.1984.0320306.CrossRefGoogle Scholar
Stucki, J.W. Golden, D.C. and Roth, C.B., (1984) The effect of reduction and reoxidation on the surface charge and dissolution of dioctahedral smectites Clays and Clay Minerals 32 350–356 10.1346/CCMN.1984.0320502.CrossRefGoogle Scholar
Stucki, J.W. Low, P.F. Roth, C.B. and Golden, D.C., (1984) Effects of oxidation state of octahedral iron on clay swelling Clays and Clay Minerals 32 357–362 10.1346/CCMN.1984.0320503.CrossRefGoogle Scholar
Stucki, J.W. Bailey, G.W. and Gan, H.M., (1996) Oxidation-reduction mechanisms in iron-bearing phyllosilicates Applied Clay Science 10 417–430 10.1016/0169-1317(96)00002-6.CrossRefGoogle Scholar
Stucki, J.W. Wu, J. Gan, H. Komadel, P. and Banin, A., (2000) Effects of Fe oxidation state and organic cations on smectite hydration Clays and Clay Minerals 48 290–298 10.1346/CCMN.2000.0480216.CrossRefGoogle Scholar
Tor, J.M. Xu, C.F. Stucki, J.M. Wander, M.M. and Sims, G.K., (2000) Trifluralin degradation under microbiologically induced nitrate and Fe(III) reducing conditions Environmental Science and Technology 34 3148–3152 10.1021/es9912473.CrossRefGoogle Scholar
Xiang, Y. and Villemure, G., (1995) Electrodes modified with synthetic clay minerals: evidence of direct electron transfer from structural iron sites in the clay lattice Journal of Electroanalytical Chemistry 381 21–27 10.1016/0022-0728(94)03629-H.CrossRefGoogle Scholar
Xu, J.C. Stucki, J.W. Wu, J. Kostka, J.E. and Sims, G.K., (2001) Fate of atrazine and alachlor in redox-treated ferruginous smectite Environmental Toxicology and Chemistry 20 2717–2724 10.1002/etc.5620201210.Google ScholarPubMed
Yan, L.B. and Bailey, G.W., (2001) Sorption and abiotic redox transformation of nitrobenzene at the smectite-water interface Journal of Colloid and Interface Science 241 142–153 10.1006/jcis.2001.7735.CrossRefGoogle ScholarPubMed