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Reduction of antimony by nano-particulate magnetite and mackinawite

Published online by Cambridge University Press:  05 July 2018

R. Kirsch*
Affiliation:
Institute of Radiochemistry, FZD, Dresden, Germany, and ROBL at the European Synchrotron Radiation Facility (ESRF), BP220, 38043 Grenoble, France Laboratoire de Géophysique Interne et Tectonophysique (LGIT), BP 53, 38041 Grenoble, France
A. C. Scheinost
Affiliation:
Institute of Radiochemistry, FZD, Dresden, Germany, and ROBL at the European Synchrotron Radiation Facility (ESRF), BP220, 38043 Grenoble, France
A. Rossberg
Affiliation:
Institute of Radiochemistry, FZD, Dresden, Germany, and ROBL at the European Synchrotron Radiation Facility (ESRF), BP220, 38043 Grenoble, France
D. Banerjee
Affiliation:
Institute of Radiochemistry, FZD, Dresden, Germany, and ROBL at the European Synchrotron Radiation Facility (ESRF), BP220, 38043 Grenoble, France
L. Charlet
Affiliation:
Laboratoire de Géophysique Interne et Tectonophysique (LGIT), BP 53, 38041 Grenoble, France
*

Abstract

The speciation of antimony is strongly influenced by its oxidation state (V, III, 0, —III). Redox processes under anaerobic groundwater conditions may therefore greatly alter the environmental behaviour of Sb. Employing X-ray absorption and photoelectron spectroscopy, we show here that Sb(V) is reduced to Sb(III) by magnetite and mackinawite, two ubiquitous Fe(II)-containing minerals, while Sb(III) is not reduced further. At the surface of magnetite, Sb(III) forms a highly symmetrical sorption complex at the position otherwise occupied by tetrahedral Fe(III). The Sb(V) reduction increases with pH, and at pH values >6.5 Sb(V) is completely reduced to Sb(III) within 30 days. In contrast, at the mackinawite surface, Sb(V) is completely reduced across a wide pH range and within 1 h. The Sb(V) reduction proceeds solely by oxidation of surface Fe(II), while the oxidation state of sulphide is conserved. Independent of whether Sb(V) or Sb(III) was added, an amorphous or nano-particulate SbS3-like solid formed.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2008

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