Degradation of chloromethylisothiazolinone antimicrobial by Vacuum-Ultraviolet/Ultraviolet irradiation: Reactive species, degradation pathway and toxicity evaluation

Chloromethylisothiazolinone (CMIT) has been extensively used as antimicrobial in cosmetics, detergents, wall paints, and anti-fouling products. To prevent the potential ecological and health risks, the degradation mechanisms and toxicity changes of CMIT by Vacuum-Ultraviolet/Ultraviolet (VUV/UV) irradiation were investigated in this study. VUV/UV irradiation showed better performance on CMIT degradation compared to sole UV photolysis. The removal efficiency of CMIT with photon fluence of 0.6 μEinstein/cm² was 8% and 100% by UV or VUV/UV irradiation, respectively. Radical quenching experiments indicated that 254 nm photolysis, 185 nm photolysis, and •OH oxidation contributed to CMIT degradation during VUV/UV process, with fluence-based apparent rate constants of 0.16, 0.13, and 4.9 μEinstein⁻¹cm², respectively. The formation of H₂O₂ during VUV/UV process increased to 0.7 mg/L at 4.5 min, and the concentration of •OH ranged within 1.0–3.8 × 10⁻¹² M. The degradation of CMIT by VUV/UV irradiation in neutral condition was slightly higher than that in acidic and basic conditions. The removal efficiency of CMIT with reaction time of 2 min decreased from 92.2% to 34.3% when the concentration of HCO₃⁻/CO₃²⁻ increased to 1 mM. The degradation of CMIT by VUV/UV irradiation in secondary effluents was lower than that in ultrapure water because of the •OH scavenging effects, but still 2.9 times higher than that by UV photolysis. Four main degradation mechanisms of CMIT were observed during VUV/UV process, including the oxidation of sulfur, addition of hydroxyl groups on the double-carbon-bond, demethylation on the nitrogen, and substitution of organochlorine atom by hydroxyl group. Based on the quantitative structure activity relationship analysis, most products of CMIT underwent complete detoxification to fish and daphnia. 40% of products still showed acute toxicity to algae, but most of them were less toxic than CMIT.