Model-Based Interpretation of Groundwater Arsenic Mobility during in Situ Reductive Transformation of Ferrihydrite

Arsenic (As) release and mobility in groundwater is coupled to the iron (Fe) cycling and the associated transformation of Fe-oxides present in sediments. Recent in situ experiments have provided observations on arsenic mobilization and co-occurring reductive mineral transformation when placing As-loaded ferrihydrite-coated sand for 80 days in wells of an As-contaminated aquifer of Northern China. However, the complex temporal change in solid-associated arsenic and the multiple geochemical processes occurring when the flowing groundwater contacts the As-loaded ferrihydrite-coated sand hamper a detailed evaluation of the experimental data set. In this study, we develop a modeling approach that allows a quantitative interpretation of arsenic release and ferrihydrite transformation observed during the in situ experiments. The model accounts for the interplay of abiotic and biotic geochemical processes (i.e., surface complexation, reductive dissolution, formation of secondary iron minerals, and arsenic sequestration into the newly formed minerals) involved in the transformation of Fe-oxides and controlling arsenic mobility. The results show the capability of the proposed approach to reproduce the temporal trends of solid arsenic and ferrihydrite concentrations, as well as the spatial variability of mineral transformation, observed in different wells using a common set of surface complexation parameters and kinetic rate constants. The simulation outcomes allowed us to disentangle the specific contribution of the different mechanisms controlling the release of arsenic. It was possible to identify an initial rapid but minor release of As (13-23% of the initial surface concentration) due to desorption from ferrihydrite, as well as the reduction of adsorbed As(V) to As(III) upon contact with the flowing anoxic groundwater. Successively, reductive dissolution of ferrihydrite caused the decrease of the amount of the Fe mineral phase and led to a major depletion of solid-associated arsenic. The produced Fe(II) catalyzed the ferrihydrite conversion into more crystalline Fe(III) oxides (i.e., lepidocrocite and goethite) through Ostwald ripening, and resulted in the formation of siderite and mackinawite upon reaction with carbonates and sulfides naturally present in the groundwater. The model results also showed that, whereas the decrease in surface sites during reductive dissolution of ferrihydrite promoted arsenic mobilization, the mineral transformation limited As release through its sequestration into the newly formed secondary mineral phases.