Residence time effects on arsenate surface speciation at the aluminum oxide-water interface

Bioavailability of metals/metalloids is often rate limited by contact time (i.e., residence time) in soils and sediments, resulting in irreversible reactions. The fate and transport of the contaminants must be predicted/modeled not only on short-term (<48 h) adsorption/desorption studies but also on long-term (months-years) reactions. However, there is very little information on the long-term effects of metal/metalloid partitioning reactions in soils and soil components. In this study, residence time effects (3 days–1 yr) on As(V) adsorption/desorption reactions and on As(V) surface speciation at the aluminum oxide-water interface were investigated using batch adsorption/desorption experiments coupled with time-resolved Extended X-ray Absorption Fine Structure spectroscopy (EXAFS). Biphasic As(V) adsorption kinetics were observed at pH 4.5 and 7.8, and whereas the reaction at pH 4.5 was nearly completed after 3 days, slow adsorption continued at pH 7.8 after 1 year. The longer the residence time (3 days–1 yr), the greater the decrease in As(V) desorption at both pHs, suggesting nonsingular reactions. EXAFS analyses on aged As(V) reacted aluminum oxide at both pHs showed that As-Al interatomic distances were 3.11 − 3.14 Å (±0.13 Å) in all of the aged samples (3 days to 1 yr) at pH 4.5 and 7.8, suggesting that predominantly bidentate binuclear bonding environments were present. As a point of interest, X-ray Absorption Near Edge Structure spectroscopy (XANES) features suggested some changes in the local chemical structure of adsorbed As(V) with aging. The surface transformations such as (i) a rearrangement of surface complexes and/or (ii) a conversion of surface complexes into aluminum arsenate-like precipitates might be important chemical factors responsible for the decrease in As(V) reversibility with aging.