Vanadate Retention by Iron and Manganese Oxides.

Anthropogenic emissions of vanadium (V) into terrestrial and aquatic surface systems now match those of geogenic processes, and yet, the geochemistry of vanadium is poorly described in comparison to other comparable contaminants like arsenic. In oxic systems, V is present as an oxyanion with a +5 formal charge on the V center, typically described as H x VO4 (3-x)-, but also here as V(V). Iron (Fe) and manganese (Mn) (oxy)hydroxides represent key mineral phases in the cycling of V(V) at the solid-solution interface, and yet, fundamental descriptions of these surface-processes are not available. Here, we utilize extended X-ray absorption fine structure (EXAFS) and thermodynamic calculations to compare the surface complexation of V(V) by the common Fe and Mn mineral phases ferrihydrite, hematite, goethite, birnessite, and pyrolusite at pH 7. Inner-sphere V(V) complexes were detected on all phases, with mononuclear V(V) species dominating the adsorbed species distribution. Our results demonstrate that V(V) adsorption is exergonic for a variety of surfaces with differing amounts of terminal -OH groups and metal-O bond saturations, implicating the conjunctive role of varied mineral surfaces in controlling the mobility and fate of V(V) in terrestrial and aquatic systems.

Manganese, Arsenic, and Carbonate Interactions in Model Oxic Groundwater Systems.

Manganese and arsenic both threaten groundwater quality globally, but their chemical behavior leads to both co-contamination and separation of these contaminants from individual well to regional scales. Here we tested manganese and arsenic retention under conditions commonly found within aquifer redox fluctuating and transition zones where both arsenic and iron phases are present in oxidized forms, but manganese persists as reduced and soluble Mn(II). Analysis of column aqueous breakthrough data and characterization of solid-phase products using X-ray photoelectron (XPS) and absorption spectroscopies (XAS) show that the addition of bicarbonate increased manganese retention but decreased arsenic retention, while the presence of manganese and arsenic together increased both arsenic and manganese retention. In the presence of O2 arsenic remained oxidized as arsenate under all conditions measured; however, reduced Mn(II) was oxidized to an average Mn oxidation state of ∼3 in the absence of arsenate. The presence of arsenate partially inhibited Mn(II) oxidation likely by blocking ferrihydrite surfaces needed to catalyze Mn(II) oxidation by O2 and by stabilizing Mn(II) via ternary complex formation. These results highlight the interactions between reduced and oxidized contaminants that can contribute to the co-occurrence or physical separation of manganese and arsenic in groundwater systems under changing or stratified redox conditions.