Occurrence and geochemical behavior of arsenic in a coastal aquifer–aquitard system of the Pearl River Delta, China

Elevated concentrations of arsenic, up to 161 μg/L, have been identified in groundwater samples from the confined basal aquifer underlying the aquitard of the Pearl River Delta (PRD). Both aquatic arsenic in pore water and solid arsenic in the sediments in the basal aquifer and aquitard were identified. Arsenic speciation of groundwater in the basal aquifer was elucidated on a pH-Eh diagram. In the PRD, arsenic is enriched in groundwater having both low and high salinity, and arsenic enriched groundwater is devoid of dissolved oxygen, has negative Eh values, is slightly alkaline, and has abnormally high concentrations of ammonium and dissolved organic carbon, but low concentrations of nitrate and nitrite. Results of geochemical and hydrochemical analyses and sequential extraction analysis suggest that reductive dissolution of iron oxyhydroxide could be one of the important processes that mobilized solid arsenic. We speculate that mineralization of sedimentary organic matter could also contribute to aquatic arsenic. Scanning electron microscope analysis confirms that abundant authigenic pyrite is present in the sediments. Sulphate derived from paleo-seawater served as the important sulfur source for authigenic pyrite formation. Co-precipitation of arsenic with authigenic pyrite significantly controlled concentrations of aquatic arsenic in the coastal aquifer–aquitard system.

► Coastal aquifer and aquitard are treated as an integrate system. ► Both aquatic arsenic and solid arsenic are observed. ► Aquatic arsenic is derived from reductive dissolution of iron oxyhydroxide. ► Aquatic arsenic can also derived from mineralization of sedimentary organic matter. ► Co-precipitation of arsenic with authigenic pyrite is significant in such a system.