Citrate-enhanced release of arsenic during pyrite oxidation at circumneutral conditions

The release of arsenic (As) from the oxidation of As-rich pyrite is an important source of the high arsenic in groundwater. As a widespread low-molecular-weight organic acid, citrate plays an important role on the cycling of Fe(II)/Fe(III) through complexation in circumneutral subsurface environments, while the influence of citrate on the release of As from the oxidation of As-rich pyrite is poorly understood. In this study, As was loaded onto pyrite particles under anoxic conditions, and its release was investigated in the presence of 0-1 mM citrate at pH 7.4 under oxic conditions. As-loaded pyrite suspension was prepared by the equilibrium of 2.67 μM As(III) in 10 g/L pyrite under anoxic conditions with the decrease in dissolved As(III) concentration to 1 μM. The suspension was subsequently exposed to air for oxygenation. In the absence of citrate, the oxygenation decreased the partitioning of As in the solution because of the re-adsorption of aqueous As by the in situ generated Fe(III) oxyhydroxides. However, with the increase in citrate concentration from 0.1 to 1 mM, the As partitioned in the solution increased from 0.3 to 2.67 μM. In the presence of 1 mM citrate, the As(III) was almost completely oxidized to As(V) during the oxygenation. The mechanisms of citrate-enhanced release of As were mainly attributed to the ligand exchange of citrate with As for pyrite surface sites, the competitive adsorption of citrate with As on Fe(III) oxyhydroxides and pyrite, and the partitioning of As on the newly formed Fe(III) colloids. This finding presents an overlooked mechanism of the release of pyrite-associated As under oxic and circumneutral conditions.