The removal of arsenic (As(V) and As(III)) from strongly acidic wastewater using traditional neutralization or sulfuration precipitation methods produces a large amount of arsenic-containing hazardous wastes, which poses a potential threat to the environment. In this study, an ultraviolet/formic acid (UV/HCOOH) process was proposed to reductively remove and recover arsenic from strongly acidic wastewater in the form of valuable elemental arsenic (As(0)) products to avoid the generation of hazardous wastes. We found that more than 99% of As(V) and As(III) in wastewater was reduced to highly pure solid As(0) (>99.5 wt %) by HCOOH under UV irradiation. As(V) can be efficiently reduced to As(IV) (H2AsO3 or H4AsO4) by hydrogen radicals (H•) generated from the photolysis of HCOOH through dehydroxylation or hydrogenation. Then, As(IV) is reduced to As(III) by H• or through its disproportionation. The reduction of As(V) to H4AsO4 by H• and the disproportionation of H4AsO4 are the main reaction processes. Subsequently, As(III) is reduced to As(0) not only by H• through stepwise dehydroxylation but also through the disproportionation of intermediate arsenic species As(II) and As(I). With additional density functional theory calculations, this study provides a theoretical foundation for the reductive removal of arsenic from acidic wastewater.
Keywords: DFT calculations; UV/HCOOH process; advanced reduction process; elemental arsenic; free radicals.