Efficient reductive recovery of arsenic from acidic wastewater by a UV/dithionite process

The removal of arsenic (As(III)) from acidic wastewater using neutralization or sulfide precipitation generates substantial arsenic-containing hazardous solid waste, posing significant environmental challenges. This study proposed an advanced ultraviolet (UV)/dithionite reduction method to recover As(III) in the form of valuable elemental arsenic (As(0)) from acidic wastewater, thereby avoiding hazardous waste production. The results showed that more than 99.9 % of As(III) was reduced to As(0) with the residual concentration of arsenic below 25.0 μg L^-1 within several minutes when the dithionite/As(III) molar ratio exceeded 1.5:1 and the pH was below 4.0. The content of As(0) in precipitate reached 99.70 wt%, achieving the purity requirements for commercial As(0) products. Mechanistic investigations revealed that SO₂^·‒ and H· radicals generated by dithionite photolysis under UV irradiation are responsible for reducing As(III) to As(0). Dissolved O₂, Fe(III), Fe(II), Mn(II), dissolved organic matter (DOM), and turbidity slightly inhibited As(III) reduction via free radicals scavenging or light blocking effect, whereas other coexisting ions, such as Mg(II), Zn(II), Cd(II), Ni(II), F(-I), and Cl(-I), had limited influence on As(III) reduction. Moreover, the cost of treating real arsenic-containing (250.3 mg L^-1) acidic wastewater was estimated to be as low as $0.668 m^-3, demonstrating the practical applicability of this method. This work provides a novel method for the reductive recovery of As(III) from acidic wastewater.