Efficient removal of Cr(VI) at alkaline pHs by sulfite/iodide/UV: Mechanism and modeling

Efficient removal of toxic hexavalent chromium (Cr(VI)) under alkaline conditions is still a challenge due to the relatively low reactivity of CrO₄^2-. This study proposed a new sulfite/iodide/UV process to remove Cr(VI). The removal of Cr(VI) followed pseudo-zero-order kinetics at alkaline pHs, and was enhanced by sulfite and iodide with synergy. Compared with sulfite/UV, iodide in sulfite/iodide/UV showed about 40 times higher concentration-normalized enhancement for Cr(VI) removal, and reduced the requirement of sulfite ([S(IV)]₀/[Cr(VI)]₀ of about 2.1:1) by more than 90%. The Cr(VI) removal was accelerated by decreasing pH and by increasing temperature, and was slightly influenced by dissolved oxygen, carbonate, and humic acid. The process was still effective in real surface water and industrial wastewater. Mechanism and pathways of Cr(VI) removal were revealed by quenching experiments, competition kinetic analysis, product identification and quantification, and mass and electron balance. Both e_aq^- and SO₃^•- were responsible for Cr(VI) removal, making contributions of about 75% and 25%, respectively. When e_aq^- mainly reacted with Cr(VI), SO₃^•- participated in reduction of Cr(V) and Cr(IV) intermediates, with Cr(III), S₂O₆^2-, and SO₄^2- as the final products. A model was developed to predict removal kinetics of Cr(VI), and well interpreted the roles of S(IV) and iodide in the process. This study sheds light on mechanism of Cr(VI) removal at alkaline pHs by kinetic modeling, and thus advances the applicability of this promising process for water decontamination.