Field, laboratory, and modeling study of reactive transport of groundwater arsenic in a coastal aquifer.

A field, laboratory, and modeling study of As in groundwater discharging to Waquoit Bay, MA, shed light on coupled control of chemistry and hydrology on reactive transport of As in a coastal aquifer. Dissolved Fe(III) and As(III) in a reducing groundwater plume bracketed by an upper and a lower redox interface are oxidized as water flows toward the bay. This results in precipitation of Fe(III) oxides, along with oxidation and adsorption of As to sediment at the redox interfaces where concentrations of sedimentary HCl-leachable Fe (80-90% Fe(III)) are 734 +/- 232 mg kg(-1) and sedimentary phosphate-extractable As (90-100% As(VI) are 316 +/- 111 microg kg(-1) and are linearly correlated. Batch adsorption of As(III) onto orange, brown, and gray sediments follows Langmuir isotherms and can be fitted by a surface complexation model (SCM) assuming a diffuse layer for ferrihydrite. The sorption capacity and distribution coefficient for As increase with decreasing sediment Fe(II)/Fe. To allow accumulation of the amount of sediment As, similar hydrogeochemical conditions would have been operating for thousands of years at Waquoit Bay. The SCM simulated the observed dissolved As concentration better than a parametric approach based on Kd. Site-specific isotherms should be established for Kd- or SCM-based models.