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Incorporation of Cr, Mn and Ni into goethite (α-FeOOH): mechanism from extended X-ray absorption fine structure spectroscopy

Published online by Cambridge University Press:  09 July 2018

Balwant Singh ,
D. M. Sherman ,
R. J . Gilkes ,
M. A. Wells  and
J . F. W. Mosselmans
Balwant Singh*
Affiliation:
School of Land, Water and Crop Sciences, The University of Sydney, Sydney, Australia
D. M. Sherman
Affiliation:
Department of Earth Sciences, University of Bristol, Bristol, UK
R. J . Gilkes
Affiliation:
Department of Soil Science & Plant Nutrition, University of Western Australia, NedlandsAustralia
M. A. Wells
Affiliation:
Mineral Mapping Technology Group, CSIRO Exploration and Mining, Australian Resource Research Centre (ARRC), KensingtonWestern Australia
J . F. W. Mosselmans
Affiliation:
CCLRC, Daresbury Laboratory, WarringtonUK
*
*E-mail: [email protected]
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Abstract

The crystal-chemical mechanisms by which transition metals are associated with goethite are fundamental to our understanding of the solubility and bioavailability of micronutrients and heavy metals in soils, and in the formation of laterite ore deposits. Transition metals such as Cr, Mn and Ni may sorb onto goethite by forming surface precipitates, surface complexes or by replacing Fe3+ in the goethite structure. In the work reported here, we investigated the local coordination environment of Cr, Mn and Ni in synthetic goethite using EXAFS spectroscopy. We demonstrate the isomorphous substitution for Fe3+ by Cr3+ (up to 8 mol.%), Mn3+ (up to 15 mol.%) and Ni2+ (up to 5 mol.%). We find, however, that the next-nearest-neighbour coordination environment changes with composition. The perturbations are likely to be responsible for limiting the accommodation of Cr3+, Mn3+ or Ni2+ in the FeOOH structure.

Keywords

goethitemetal substitutionMnCrNiEXAFS
Type
Research Article
Information
Clay Minerals , Volume 37 , Issue 4 , December 2002 , pp. 639 - 649
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2002

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References

Binsted, N., Campbell, J.W., Gurman, S.J. & Stephenson, P.C. (1992) EXCURV92 Program.CLRC, Daresbury Laboratory, Warrington, UK.Google Scholar
Jr.Brown, G.E., Calas, G., Waychunas, G.A. & Petiau, J. (1988) X-ray absorption spectroscopy and its application in mineralogy and geochemistry. Pp. 431–512. in. Spectroscopic Methods in Mineralogy and Geology (Hawthorne, F.C., editor). Reviews in Mineralogy 18, Mineralogical Society of America, Washington, D.C.Google Scholar
Burns, R.G. (1970) Mineralogical Applications of Crystal Field Theory. Cambridge University Press, Cambridge.Google Scholar
Christensen, A.N., Hansen, P. & Lehmann, M.S. (1976) Isotope effects in the bonds of beta-CrOOH and beta- CrOOD. Journal of Solid State Chemistry, 19, 299–304.Google Scholar
Christensen, A.N., Hansen, P. & Lehmann, M.S. (1977) Isotope effects in the bonds of alpha-CrOOH and alpha-Cr. Journal of Solid State Chemistry, 21, 325–329.Google Scholar
Cornell, R.M. & Schwertmann, U. (1996) The Iron Oxides.VCH Publishers, New York.Google Scholar
Cornell, R.M., Giovanoli, R. & Schneider, W. (1992) The effect of nickel on the conversion of amorphous iron (III) hydroxide into more crystalline iron oxides in alkaline media. Journal of Chemical Technology and Biotechnology, 53, 73–79.Google Scholar
Eggleton, R.A. (1988) The application of micro-beam methods to iron minerals in soils. Pp. 165–201 in: Iron in Soils and Clay Minerals (Stuck, J.W.. et al., editors). NATO ASI Series C217. Reidel Publishing Co., The Netherlands.CrossRefGoogle Scholar
Fey, M.V. & Dixon, J.B. (1981) Synthesis and properties of poorly crystalline hydrated aluminous goethites. Clays and Clay Minerals, 29, 91–100.Google Scholar
Goodman, B.A. & Lewis, D.G. (1981) Mössbauer spectra of aluminous goethites (γ-FeOOH). Soil Science, 32, 351–363.Google Scholar
Gurman, S.J., Binsted, N. & Ross, I. (1984) A rapid, exact curved-wav e theory for EXAFS calculatio ns. Journal of Physics C, 17, 143–151.CrossRefGoogle Scholar
Kohler, T., Armbruster, T. & Libowitzky, E. (1997) Hydrogen bonding and Jahn-Teller distortion in groutite, alpha-(MnOOH) and manganite, gamma- (MnOOH), and their relations to the manganese dioxides ramsdellite and pyrolusit. Journal of Solid State Chemistry, 133, 486–500.Google Scholar
Lim-Nunez, R. & Gilkes, R.J. (1987) Acid dissolution of synthetic metal-containing goethites and hematites. Pp. 197–204 in: Proceedings of the International Clay Conference, 1985 (Schultz, L.G., van Olphen, H. & Mumpton, F.A., editors). Clay Minerals Society, Bloomington, Indiana.Google Scholar
Manceau, A. & Combes, J.M. (1988) Structure of Mn and Fe oxides and hydroxides: A topological approach by EXAFS. Physics and Chemistry of Minerals, 15, 283–295.Google Scholar
Manceau, A., Schlegel, M.L., Musso, M., Sole, V.A., Gauthier, C., Petit, P.E. & Trolard, F. (2000) Crystal chemistry of trace elements in natural and synthetic goethite. Geochimica et Cosmochimica Acta, 64, 3643 ­ 3661.Google Scholar
McKeague, J.A. & Day, J.H. (1966) Dithionite- and oxalate-extractable Fe and Si as aids in differentiating various classes of soils. Canadian Journal of Soil Science, 46, 13–22.CrossRefGoogle Scholar
Norrish, K. (1975) Geochemistry and mineralogy of trace elements. In: Trace Elements in the Soil-Plant- Animal System (Noholas, A.R. and Egan, D.J., editors). Academic Press, New York.Google Scholar
Norrish, K. & Taylor, R.M. (1961) The isomorphous substitution replacement of iron by aluminium in soil goethites. Journal of Soil Science, 12, 294–306.Google Scholar
Parfitt, R.L. (1989) Optimum conditions for extraction of Al, Fe and Si from soils with acid oxalate. Communicati ons in Soil Science and Plant Analysis, 20, 801–816.Google Scholar
Schulze, D.G. (1982) The identification of iron oxides by differential X-ray diffraction and the influence of aluminum substitution on the structure of goethite. PhD dissertation, Technische Universität München, Freising-Weihenstephan, Germany.Google Scholar
Schulze, D.G. & Schwertmann, U. (1984) The influence of aluminium on iron oxides: XIII. Properties of goethite synthesized in 0.3 M KOH at 25°C. Clay Minerals, 22, 83–92.Google Scholar
Schwertmann, U. (1964) Differenzierung der Eisenoxide des Boden durch Extraktion mit Ammoniumoxalat- Lösung. Zeitschrift für Pflanzenernährung Düngung und Bodenkunde, 105, 194–202.Google Scholar
Schwertmann, U. & Carlson, L. (1994) Aluminum influence on iron oxides: XVII. Unit-cell parameters and aluminum substitution of natural goethites. Soil Science Society of America Journal, 58, 256–261.Google Scholar
Schwertmann, U. & Taylor, R.M. (1989) Iron oxides. Pp. 379–438 in: Minerals in Soil Environments (Dixon, J.B. and Weed, S.B., editors). Soil Science Society of America, Madison, Wisconsin.Google Scholar
Schwertmann, U., Gasser, U. & Sticher, H. (1989) Chromium-for-iron substi tution in synthe tic goethites. Geochimica et Cosmochimica Acta, 53, 1293 ­ 1297.Google Scholar
Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica, A32, 751–767.Google Scholar
Singh, B. & Gilkes, R.J. (1992) Properties and distribution of iron oxides and their association with minor elements in the soils of south-western Australia. Journal of Soil Science, 43, 77–98.Google Scholar
Singh, B., Sherman, D.M., Gilkes, R.J., Wells, M. & Mosselmans, J.F.W. (2000) Structural chemistry of Fe, Mn and Ni in synthetic hematites as determined by extended X-ray absorption fine structure spectroscopy. Clays and Clay Minerals, 48, 521–527.Google Scholar
Stiers, W. & Schwertmann, U. (1985) Evidence for manganese substitutio n in synthetic goethite. Geochimica et Cosmochimica Acta, 49, 1909 ­ 1911.Google Scholar
Stucki, J.W., Goodman, B.A. & Schwertmann, U. (1988) Iron in soils and clay minerals. NATO ASI Series C217, Reidel Publishing Co., The Netherlands.Google Scholar
Szytula, A., Burewicz, A., Dimitrijevic, Z., Krasnicki, S., Rzany, H., Todorovic, J., Wanic, A. & Wolski, W. (1968) Neutron diffraction studies of γ-FeOOH. Physica Status Solidi, 26, 429–434.Google Scholar
Szytula, A., Murasik, A. & Balanda, M. (1987) Neutron diffraction study of Ni(OH)2. Physica Status Solidi, 43, 125–128.Google Scholar
Trolard, F., Bourrie, G., Jeanroy, E., Herbillon, A.J. & Martin, H. (1995) Trace metals in natural iron oxides from laterites: A study using selective kinetic extraction. Geochimica et Cosmochimica Acta, 59, 1285 ­ 1297.Google Scholar