Insights into the Oxidation of Organic Cocontaminants during Cr(VI) Reduction by Sulfite: The Overlooked Significance of Cr(V)

Literature works reported that organic cocontaminants could be degraded during Cr(VI), a contaminant, reduction by sulfite (Cr(VI)/sulfite process). However, the role of Cr(V) and Cr(IV) intermediates in the Cr(VI)/sulfite process has been overlooked. In this study, we confirmed the generation of Cr(V) and proposed a new mechanism for the decomposition of coexisting organic contaminants during Cr(VI)/sulfite reactions occurring in oxygenated solutions at pH_ini 4.0 with the molar ratio of sulfite to Cr(VI) of 10.0. UV-visible and electron paramagnetic resonance (EPR) spectra indicate that Cr(V) was the predominant Cr intermediates in oxygenated solutions, while Cr(IV) accumulated in deoxygenated solutions. The contribution of Cr(V) to the degradation of organic contaminants was verified by the EPR spectra collected at 2 K and using methyl phenyl sulfoxide as a probe compound. Both Cr(V) and SO₄ ^•- contributed to the decomposition of organic contaminants in oxygenated solutions, with the relative contributions from each species being strongly dependent on properties of the target organic cocontaminants. The key mechanisms responsible for Cr(V) accumulation were supported by DFT calculations, and the degradation kinetics of organic cocontaminants was simulated with the program Kintecus 6.51. This work advances the fundamental understanding of the oxidative transformation of coexisting organic contaminants in this process.