Distributed microbially- and chemically-mediated redox processes controlling arsenic dynamics within Mn-/Fe-oxide constructed aggregates

The aggregate-based structure of soils imparts physical heterogeneity that gives rise to variation in microbial and chemical processes which influence the speciation and retention of trace elements such as As. To examine the impact of distributed redox conditions on the fate of As in soils, we imposed various redox treatments upon constructed soil aggregates composed of ferrihydrite- and birnessite-coated sands presorbed with As(V) and inoculation with the dissimilatory metal reducing bacterium Shewanella sp. ANA-3. Aeration of the advecting solution surrounding the aggregates was varied to simulate environmental conditions. We find that diffusion-limited transport within high dissolved organic carbon environments allows reducing conditions to persist in the interior of aggregates despite aerated advecting external solutes, causing As, Mn, and Fe to migrate from the reduced aggregate interiors to the aerated exterior region. Upon transitioning to anoxic conditions in the external solutes, pulses of As, Mn and Fe are released into the advecting solution, while, conversely, a transition to aerated conditions in the exterior resulted in a cessation of As, Mn, and Fe release. Importantly, we find that As(III) oxidation by birnessite is appreciable only in the presence of O2; oxidation of As(III) to As(V) by Mn-oxides ceases under anaerobic conditions apparently as a result of microbially mediated Mn(IV/III) reduction. Our results demonstrate the importance of considering redox conditions and the physical complexity of soils in determining As dynamics, where redox transitions can either enhance or inhibit As release due to speciation shifts in both sorbents (solubilization versus precipitation of Fe and Mn oxides) and sorbates (As).