Antimony mobility in reducing environments: The effect of microbial iron(III)-reduction and associated secondary mineralization

Abstract

Antimony is an environmental contaminant, whose mobility in soils, sediments and groundwater systems is strongly influenced by interactions with Fe(III) oxide minerals. When exposed to reducing conditions, these minerals can undergo reductive dissolution via the activity of Fe(III)-reducing microorganisms, thereby potentially liberating previously retained Sb. In addition, microbial Fe(III)-reduction and the consequent production of Fe(II) can induce the formation of secondary Fe(III)- and Fe(II)-bearing minerals, which may alter the speciation and partitioning of Sb. In this study, we examined Sb behaviour during (1) the microbially-mediated reduction and transformation of Sb(V)-bearing ferrihydrite by the dissimilatory Fe(III)-reducing bacterium, Shewanella putrefaciens (strain CN32), and (2) during the associated abiotic Fe(II)-catalyzed transformation of Sb(V)-bearing ferrihydrite. Antimony K-edge XANES spectroscopy showed negligible reduction of Sb(V) to Sb(III) in both experiments, reflecting the redox stability of Sb(V) under these conditions. X-ray diffraction and Fe K-edge EXAFS spectroscopy revealed that both microbially-mediated Fe(II) production as well as the experimental addition of aqueous Fe(II) under abiotic conditions triggered rapid transformation of the initial ferrihydrite to feroxyhyte (δ′-FeOOH) and goethite (α-FeOOH). Goethite has been widely observed as a product of the Fe(II)-catalyzed transformation of ferrihydrite. However, the present study is the first to document the formation of feroxyhyte via this pathway, with feroxyhyte formation appearing to be favored by the presence of Sb(V). The formation of these secondary Fe(III) oxides was associated with substantial decreases in aqueous Sb concentrations and in the amount of surface-bound Sb (as defined via extractions with 1 M PO43−). This is consistent with the incorporation of Sb(V) into the newly formed feroxyhyte and goethite via substitution for Fe(III). The results of this study provide new perspectives on coupling between Sb geochemistry and Fe mineralogy by showing that microbial Fe(III)-reduction and associated secondary Fe(III)-oxide formation can help to immobilize Sb(V) in reducing environments.