Are free radicals actually responsible for enhanced oxidation of contaminants by Cr(VI) in the presence of bisulfite?

Recently, the technology for the remediation of Cr(VI) pollutant via bisulfite has been found to be effective for fast elimination of co-contaminants especially in acidic solution, where free radicals (i.e., sulfate and/or hydroxyl radicals) are proposed to act as dominant oxidants. Here, it was demonstrated that high-valent Cr intermediate played a primary role in the Cr(VI)/bisulfite system through applying methyl phenyl sulfoxide (PMSO) as a probe. PMSO was effectively transformed in the Cr(VI)/bisulfite system with appreciable generation of methyl phenyl sulfone (PMSO) product, while PMSO was oxidized by free radicals to hydroxylated and/or polymeric products rather than PMSO. The involvement of high-valent Cr species was further supported by the formation of O-labeled PMSO in O labeling experiments, where the incorporation of O from solvent water HO into PMSO was likely resulted from competitive oxygen exchange of Cr-oxo species with water. The relative contribution of high valent Cr species versus free radicals was evaluated based on the yield of PMSO, which was dependent on the solution chemistry such as [Cr(VI)]:[bisulfite] ratio and dissolved oxygen. This work advances the understanding of chromium chemistry involved in the Cr(VI)/bisulfite system. These findings have important implications on the application of this "waste control by waste" technology for environmental decontamination.