Natural attenuation of arsenic by sediment sorption and oxidation.

Arsenic sorption onto aquifer sediments was investigated in anaerobic laboratory batch and column uptake experiments and characterized by As, Fe, and Mn X-ray absorption spectroscopy (XAS) to estimate the extent and mechanism of abiotic sorption and oxidation of As(III). Batch experiments at pH 6 showed that the amount of As(III) or As(V) sorption from synthetic background porewaterto sediments was similar as a function of total As concentration, but slightly more As(V) was sorbed than As(III) with increasing As concentrations. Column experiments with As(III) solutions in the absence and presence of dissolved Fe2+ showed more As uptake in the presence of Fe but also more Fe desorption during flushout with As-free solutions such that net As uptake was similar to, or less than that of, the Fe-free experiment. Fits to bulk Fe X-ray absorption near-edge spectroscopy (XANES) spectra showed no change between unreacted and reacted sediments. Manganese XANES revealed small increases in absorption in the spectral region associated with Mn(II) after reaction, indicating sediment Mn reduction. However, XANES spectra showed that Mn is not present as Mn(IV)O2(s) but is probably substituted into other sediment minerals as a mixture of Mn(II,III). Quantitative analyses of As XANES spectra, which indicated mixtures of As(III) and As(V) after reaction with As(III) solutions, were used to estimate a fraction of As(V) in excess of native As(V) in the sediment (0.2 mmol kg(-1)) that corresponds to sorbed As(III) oxidized to As(V). The spectroscopic and solution data indicate that the aquifer sediments have a limited abiotic capacity to oxidize As(III), which did not exceed 30% of the total amount of As sorbed and was estimated in the range of 0.025-0.4 mmol kg-(-1) sediment. In the presence of dissolved Fe2+, the precipitation of Fe(III) hydrous oxide phases will be an effective mechanism for As scavenging only if there exists sufficient dissolved oxygen in groundwater to oxidize Fe. Once the aqueous oxidative capacity is exhausted, dissolved Fe2+ may compete with As(III) for the limited abiotic oxidation supplied by sediment Mn-bearing phases.