Sulfate-accelerated photochemical oxidation of arsenopyrite in acidic systems under oxic conditions: Formation and function of schwertmannite.

The weathering of arsenopyrite is closely related to the generation of acid mine drainage (AMD) and arsenic (As) pollution. Solar radiation can accelerate arsenopyrite oxidation, but little is known about the further effect of SO42- on the photochemical process. Here, the photooxidation of arsenopyrite was investigated in the presence of SO42- in simulated AMD environments, and the effects of SO42- concentration, pH and dissolved oxygen on arsenopyrite oxidation were studied as well. SO42- could accelerate the photooxidation of arsenopyrite and As(III) through complexation between nascent schwertmannite and As(III). Fe(II) released from arsenopyrite was oxidized to form schwertmannite in the presence of SO42-, and the photooxidation of arsenopyrite occurred through the ligand-to-metal charge-transfer process in schwertmannite-As(III) complex along with the formation of reactive oxygen species in the presence of O2. The photooxidation rate of arsenopyrite first rose and then fell with increasing SO42- concentration. In the pH range of 2.0-4.0, the photooxidation rate of arsenopyrite progressively increased in the presence of SO42-. This study reveals how SO42- promotes the photooxidation of arsenopyrite and As release in the AMD environment, and improves the understanding of the transformation and migration of As in mining areas.