Biotic and Abiotic Mechanisms of Manganese (II) Oxidation in Lake Erie

Abstract

Manganese (Mn), an element sensitive to redox conditions in aquatic environments, plays a role in numerous biogeochemical cycles. Although the speciation of Mn in lakes largely tracks the availability of dissolved oxygen, direct oxidation of Mn by molecular oxygen occurs slowly and, instead, the majority of Mn oxidation occurs via biotic and abiotic mechanisms involving microbes, organic matter, light, reactive oxygen species, and mineral surfaces. While each of these mechanisms is either known or likely to occur in freshwater, the relative balance and interaction among these biogeochemical pathways in an intact plankton system remains uncertain. We investigated potential abiotic and biotic mechanisms contributing to Mn oxide formation in Lake Erie, which experiences seasonal hypoxia and accumulation of Mn during seasonal stratification. Overall, Mn oxidation rates were much higher in the shallow and highly productive western basin (up to 1.5 μmoles L−1 d−1) compared to the deeper and less productive central basin, where we observed very little Mn oxidation over 7 days. Our experiments suggest that abiotic mechanisms involving mineral surfaces played a larger role than biotic mechanisms, particularly in the light where Mn oxidation was highest. Reactive oxygen species exhibited antagonistic roles: hydrogen peroxide acted as a net reductant for manganese oxides and completely masked oxidation of Mn by the superoxide free radical. These findings show that multiple mechanisms may exert control over the fate of Mn and suggest that Mn released from sediments during hypoxia can potentially remain dissolved in the water for an extended period of time. Since the severity of Lake Erie hypoxia has increased in recent years, and we are becoming increasingly aware of the health effects of Mn in drinking water sources, these findings should help inform efforts to predict when and where Mn will accumulate in the lake water.