Reductive dissolution of Mn oxides in river-recharged aquifers: a laboratory column study

River-recharged aquifers are developed for drinking water supplies in many parts of the world. Often, however, dissolved organic carbon (DOC) present in the infiltrating river water causes biogeochemical reactions to occur in the adjacent aquifer that create elevated Mn and Fe. Mn concentrations in groundwater from some of the production wells installed in the aquifer at Fredericton, New Brunswick exceed the Canadian Drinking Water Guideline of 9.1x10(-4) mmol/l by up to 5.5x10(-2) mmol/l. It has previously been hypothesized that the influx of DOC from the Saint John River is causing bacterially mediated reductive dissolution of Mn oxides in the aquifer system, leading to elevated aqueous Mn concentrations. Previous work was limited to the collection of water samples from production wells and several observation wells installed in the glacial outwash aquifer. The objective of this study was to investigate the biogeochemical controls on Mn concentrations using sand-filled columns. One column was inoculated with bacteria while a second column was treated with ethanol in order to decrease the microbial population initially present in the system. Both columns received the same influent solution that contained acetate as a source of DOC. The results of the experiments suggested that the two main controls on Mn concentrations in the columns were microbially mediated reductive dissolution of Mn oxides and cation exchange. The conceptual model that was developed based on the experimental data was supported by the results obtained using a one-dimensional reactive-transport model. The reductive dissolution of Mn oxides in the aquifer sands could be adequately simulated using dual-Monod kinetics. Similar trends are observed in the experimental data and field data collected from Production Well 5, located in the Fredericton Aquifer. From the experiments, it is evident that cation-exchange reactions may be an important geochemical control on Mn concentrations during the initial stages of pumping; however, the reductive dissolution of Mn oxides may represent a long-term source of Mn in the drinking water supply.