A closed coal ash impoundment case study characterized the effects of field redox conditions on arsenic and selenium partitioning through monitoring of porewater and subsurface gas in conjunction with geochemical speciation modeling. When disposed coal ash materials and porewater were recovered for testing, oxidation led to lower arsenic and higher selenium concentrations in leaching test extracts compared to porewater measurements. Multiple lines of evidence suggest multiple mechanisms of arsenic retention are plausible and the concurrent presence of several redox processes and conditions (e.g., methanogenesis, sulfate reduction, and Fe(III)-reduction) controlled by spatial gradients and dis-equilibrium. Geochemical speciation modeling indicated that, under reducing field conditions, selenium was immobilized through the formation of insoluble precipitates Se(0) or FeSe while arsenic partitioning was affected by a progression of reactions including changes in arsenic speciation, reduction in adsorption due to dissolution and recrystallization of hydrous ferric oxides, and precipitation of arsenic sulfide minerals.
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