Dissolution of hausmannite (Mn 3O 4) in the presence of the trihydroxamate siderophore desferrioxamine B

Abstract

That microbial siderophores may be mediators of Mn(III) biogeochemistry is suggested by recent studies showing that these well known Fe(III)-chelating ligands form very stable Mn(III) aqueous complexes. In this study, we examine the influence of desferrioxamine B (DFOB), a trihydroxamate siderophore, on the dissolution of hausmannite, a mixed valence Mn(II, III) oxide found in soils and freshwater sediments. Batch dissolution experiments were conducted both in the absence (pH 4–9) and in the presence of 100 μM DFOB (pH 5–9). In the absence of the ligand, there is a sharp decrease in the extent of proton-promoted dissolution above pH 5 and no appreciable dissolution above pH 8. The resulting aqueous Mn 2+ activities were in good agreement with previous studies, indirectly supporting the accepted two-step mechanism involving the formation of manganite and reprecipitation of hausmannite. Desferrioxamine B enhanced hausmannite dissolution over the entire pH range investigated, both via the formation of a Mn(III) complex and through surface-catalyzed reductive dissolution. Above pH 8, non-reductive ligand-promoted dissolution dominated, whereas below pH 8, dissolution was non-stoichiometric with respect to DFOB. Concurrent proton-promoted, ligand-promoted, reductive, and induced dissolution was observed, with Mn release by either reductive or induced dissolution increasing linearly with decreasing pH. The fast kinetics of the DFOB-promoted dissolution of hausmannite, as compared to iron oxides, suggest that the siderophore-promoted dissolution of Mn(III)-bearing minerals may compete with the siderophore-promoted dissolution of Fe(III)-bearing minerals.