Abstract
Widespread contamination of groundwater with geogenic arsenic is attributed to microbial dissolution of arsenic-bearing iron (oxyhydr)oxides minerals coupled to the oxidation of organic carbon. The recharge sources to an aquifer can influence groundwater arsenic concentrations by transport of dissolved arsenic or reactive constituents that affect arsenic mobilization. To understand how different recharge sources affect arsenic contamination-in particular through their influence on organic carbon and sulfate cycling-we delineated and quantified recharge sources in the arsenic affected region around Hanoi, Vietnam. We constrained potential end-member compositions and employed a novel end-member mixing model using an ensemble approach to apportion recharge sources. Groundwater arsenic and dissolved organic carbon concentrations are controlled by the dominant source of recharge. High arsenic concentrations are prevalent regardless of high dissolved organic carbon or ammonium levels, indicative of organic matter decomposition, where the dominant recharge source is riverine. In contrast, high dissolved organic carbon and significant organic matter decomposition are required to generate elevated groundwater arsenic where recharge is largely nonriverine. These findings suggest that in areas of riverine recharge, arsenic may be efficiently mobilized from reactive surficial environments and carried from river-aquifer interfaces into groundwater. In groundwaters derived from nonriverine recharge areas, significantly more organic carbon mineralization is required to obtain equivalent levels of arsenic mobilization within inland sediments. This method can be broadly applied to examine the connection between hydrology, geochemistry and groundwater quality.