Arsenic release from arsenopyrite oxidative dissolution in the presence of citrate under UV irradiation

Abstract

Arsenopyrite oxidative dissolution is one of the most important sources of arsenic (As) pollution in the soils and waters around sulfide mining areas. Sunlight and low-molecular-weight organic acids in the environment affect the redox behavior of sulfide minerals. In this work, the As release from arsenopyrite was studied in the presence of citrate under UV irradiation, and the effects of dissolved oxygen and citrate concentrations and pH on As release rate were also investigated. The results indicated that As release from the oxidative dissolution of arsenopyrite is affected by the complexation between citrate and dissolved iron ions. Under dark conditions in air atmosphere, dissolved oxygen, Fe(III)-citrate and the active intermediate product O2− facilitated the release of As at pH 7.0, and the As release rate increased first and then decreased with increasing pH from 5.0 to 9.0. Under UV irradiation in air atmosphere at pH 7.0, the reactive oxygen species (ROS) including O2− and OH generated by Fe(III)-citrate through the photo-Fenton reaction accelerated the As release and oxidation. However, Fe(III)-citrate photolysis led to the rapid flocculation and precipitation of dissolved iron ions, inhibiting the further oxidation of arsenopyrite. With increasing pH from 5.0 to 9.0, the As release rate gradually decreased under UV irradiation. Increases in the concentrations of citrate and dissolved oxygen promoted the formation of Fe(III)-citrate and ROS in the reaction system under both UV irradiation and dark conditions. The present work expands our understanding of the geochemical behavior of As in near-neutral pH environment.