Rapid photooxidation of As(III) through surface complexation with nascent colloidal ferric hydroxide

Contamination of water and soils with arsenic, especially inorganic arsenic, has been one of the most important topics in the fields of environmental science and technology. The interactions between iron and arsenic play a very significant role in the environmental behavior and effect of arsenic species. However, the mechanism of As(III) oxidation in the presence of iron has remained unclear because of the complicated speciation of iron and arsenic. Photooxidation of As(III) on nascent colloidal ferric hydroxide (CFH) in aqueous solutions at pH 6 was studied to reveal the transformation mechanism of arsenic species. Experiments were done by irradiation using light-emitting diodes with a central wavelength of 394 nm. Results show that photooxidation of As(III) and photoreduction of Fe(III) occurred simultaneously under oxic or anoxic conditions. Photooxidation of As(III) in the presence of nascent CFH occurred through electron transfer from As(III) to Fe(III) induced by absorption of radiation into a ligand-to-metal charge-transfer (LMCT) band. The estimated quantum yield of photooxidation of As(III) at 394 nm was (1.023 ± 0.065) × 10(-2). Sunlight-induced photooxidation of As(III) also occurred, implying that photolysis of the CFH-As(III) surface complex could be an important process in environments wherein nascent CFH exists.