Biogeochemistry of Antimony(V) in Microcosms under Sulfidogenic Conditions

Abstract:

As the mining and use of antimony continues to increase, environmental concerns involving the element have grown. Antimony(V) and (III) are the two most environmentally-relevant oxidation states, but little is known about the redox transitions between the two in natural systems. To better understand the behavior of antimony in anoxic environments, we examined the transformations of Sb(V) under Fe(III)- and sulfate-reducing conditions in aqueous suspensions that contained 2 mM KSb(OH)₆, 50 mM Fe(III) (as ferrihydrite), 10 mM sulfate, and 10 mM lactate, and were inoculated with sediment from a wetland on the campus of Argonne National Laboratory in Argonne, Illinois. Samples were collected over time to track changes in the concentrations of Sb, Fe(II), sulfate, and lactate, as well as the composition of the microbial community as determined by 16S rRNA gene inventories. We also examined the interaction of Sb(V) with pure Fe(II) mineral phases in aqueous suspensions containing 2 mM KSb(OH)₆ and 50 mM Fe(II) as either magnetite, sideritre, vivianite, green rust, or mackinawite. X-ray absorption fine-structure spectroscopy was used to determine the valence state of Sb and its chemical speciation. Lactate was rapidly fermented to acetate and propionate concomittant with a bloom of Veillonellaceae. Utilization of propionate for dissimilatory sulfate reduction (DSR) was accompanied by an increase in Desulfobulbaceae. Sb K-edge X-Ray absorption near edge structure (XANES) analysis showed reduction of Sb(V) to Sb(III) within 4 weeks, concurrent with DSR and the formation of FeS. We observed variable responses in the ability of specific Fe(II) minerals to reduce Sb(V). No reduction was observed with magnetite, siderite, vivianite, or green rust. In the presence of mackinawite (FeS), however, Sb(V) was reduced to Sb(III) sulfide. These results suggest that the reduction of Sb(V) to Sb(III) is not likely under solely Fe(III)-reducing conditions, but is expected in sulfidogenic environments.