Removal of methylisothiazolinone biocide from wastewater by VUV/UV advanced oxidation process: Kinetics, mechanisms...

Methylisothiazolinone (MIT) is frequently used as antimicrobial in household and industrial products, and poses ecological and health risks to aquatic organisms and humans. In this study, vacuum ultraviolet (VUV)/ultraviolet (UV) irradiation was found highly efficient for removal of MIT. The rate constant of MIT degradation (k_obs) under VUV/UV irradiation was 3.75 μEinstein^-1 cm², which was around 12.5 times higher than that under UV irradiation. The •OH concentration during the VUV/UV process was 1.0 × 10^-12 M. The contributions of UV photolysis and •OH oxidation to MIT degradation under VUV/UV irradiation were 7.3% and 92.7%, respectively. The optimum solution pH (6.0-7.1) gave k_obs 33%-39% higher than those at pH 3.9 and 9.3. CO₃^2-/HCO₃^- inhibited MIT degradation and the k_obs decreased by 74% when the concentration of CO₃^2-/HCO₃^- was increased to 1 mM. The order of MIT removal efficiency under VUV/UV irradiation was ultrapure water > secondary effluent > reverse osmosis (RO) concentrate, because of the light screening and •OH quenching effect of actual wastewater. In RO concentrate, the rate constant of MIT degradation under VUV/UV irradiation was 22% higher than that obtained under UV irradiation. The reduction of TOC, UV₂₅₄, and total fluorescence regional integration of the RO concentrate during VUV/UV process were 7.2%, 34.9%, and 52.3%, respectively. Twelve main transformation products of MIT were identified after VUV/UV degradation. The main degradation mechanisms of MIT were sulfur atom oxidation and hydroxyl addition. Quantitative structure-activity relationship analysis showed that VUV/UV degradation was an efficient method to remove the toxicity of MIT.