Arsenic Mobilization through Bioreduction of Iron Oxide Nanoparticles

Arsenic sorbs strongly to the surfaces of Fe(III) (hydr)oxides. Under aerobic conditions, oxygen acts as the terminal electron acceptor in microbial respiration and Fe(III) (hydr)oxides are highly insoluble, thus arsenic remains associated with Fe(III) (hydr)oxide phases. However, under anaerobic conditions Fe(III)-reducing microorganisms can couple the reduction of solid phase Fe(III) (hydr)oxides with the oxidation of organic carbon. When ferric iron is reduced to ferrous iron, arsenic is mobilized into groundwater. Although this process has been documented in a variety of pristine and contaminated environments, minimal information exists on the mechanisms causing this arsenic mobilization. Arsenic mobilization was studied by conducting controlled microcosm experiments containing an arsenic-bearing ferrihydrite and an Fe(III)-reducing microorganism, Geobacter metallireducens. Results show that arsenic mobility is strongly controlled by microbially-mediated disaggregation of arsenic-bearing iron nanoparticles. The most likely controlling mechanism of this disaggregation of iron oxide nanoparticles is a change in mineral phase from ferrihydrite to magnetite, a mixed Fe(III) and Fe(II) mineral, due to the microbially-mediated reduction of Fe(III). Although arsenic remained associated with the iron oxide nanoparticles and was not released as a hydrated oxyanion, the arsenic-bearing nanoparticles could be readily mobilized in aquifers. These results have significant implications for understanding arsenic behavior in aquifers with Fe(III) reducing conditions, and may aid in improving remediation of arsenic-contaminated waters.