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

¹ School of Land, Water and Crop Sciences, The University of Sydney, Sydney, Australia, ² Department of Earth Sciences, University of Bristol, Bristol, UK, ³ Department of Soil Science & Plant Nutrition, University of Western Australia, Nedlands, Australia, ⁴ Mineral Mapping Technology Group, CSIRO Exploration and Mining, Australian Resource Research Centre (ARRC), Kensington, Western Australia, and ⁵ CCLRC, Daresbury Laboratory, Warrington, UK

^* E-mail: b.singh{at}acss.usyd.edu.au

(Received 7 November 2001; revised 19 February 2002)

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: goethite, metal substitution, Mn, Cr, Ni, EXAFS

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