Superfast degradation of micropollutants in water by reactive species generated from the reaction between chlorine dioxide and sulfite

Chlorine dioxide (ClO₂) is used as an oxidant or disinfectant in (waste)water treatment, whereas sulfite is a prevalent reducing agent to quench the excess ClO₂. This study demonstrated that seven micropollutants with structural diversity could be rapidly degraded in the reaction between ClO₂ and sulfite under environmentally relevant conditions in synthetic and real drinking water. For example, carbamazepine, which is recalcitrant to standalone ClO₂ or sulfite, was degraded by 55%-80% in 10 s in the ClO₂/sulfite process at 30-µM ClO₂ and 30-µM sulfite concentrations within a pH range of 6.0-11.0. Results from experiments and a kinetic model supported that chlorine monoxide (ClO^·) and sulfate radicals (SO₄^·-) were generated in the ClO₂/sulfite process, while hydroxyl radical generation was insignificant. Apart from radicals, dichlorine trioxide (Cl₂O₃) was generated and largely contributed to micropollutant degradation, supported by experimental results using stopped-flow spectrometry and quantum chemical calculations. The impacts of pH, sulfite dosage, and water matrix components (chloride, bicarbonate, and natural organic matter) on micropollutant abatement in the ClO₂/sulfite process were evaluated and discussed. When treating the real potable water, the concentrations of organic (five regulated disinfection byproducts) and inorganic byproducts (chlorite and chlorate) formed in the ClO₂/sulfite process were all below the drinking water standards. This study disclosed fundamental knowledge advancements relevant to the reaction mechanisms between ClO₂ and sulfite, and highlighed a novel process to abate micropollutants in water and wastewater.