Degradation of iopromide during the UV-LED/chlorine reaction: Effect of wavelength, radical contribution, transformation products, and toxicity.

Three different UV-LED wavelengths (265, 310, and 365 nm) were used in the UV-LED/chlorine reaction to investigate the degradation mechanism of iopromide (IPM) at different wavelengths, a representative iodinated contrast media compound. The degradation rate (k'IPM) increased from pH 6-8 at 265 nm, but, decreased as the pH increased up to 9 at 310 nm and 365 nm. Radical scavenging experiments showed that reactive chlorine species (RCS) are the dominant radical species at all wavelengths, but a higher contribution of OH• was observed at lower pH and longer wavelengths. The contribution of RCS decreased but the contribution of OH• increased as the wavelength increased. Among RCS, the largest contribution was found to be ClO•. Total nine transformation products (TPs) were identified by LC-QTOF-MS during the UV-LED/chlorine reaction at 265 nm. Based on the identified TPs and their time profiles, we proposed a degradation pathway of IPM during UV-LED/chlorine reaction. The Microtox test using V. fischeri showed that no significant increase in toxicity was observed at all wavelengths. The synergistic effect of UV-LED and chlorine was greater at a higher wavelength by the electrical efficiency per order (EEO) calculation.

Propiconazole degradation and its toxicity removal during UV/H2O2 and UV photolysis processes.

Propiconazole (PRO) is a triazole fungicide that is frequently detected in the water. In this study, we investigated the kinetics and degradation mechanism of PRO during the UV photolysis and UV/H2O2 processes. PRO was removed by the pseudo-first-order kinetics in both processes. The removal of PRO was enhanced by increasing H2O2 concentration in the UV/H2O2 process. The highest removal under neutral conditions, and lower removal of PRO were observed in acidic and alkaline pHs in the UV/H2O2 process. The presence of natural water ingredients such as Cl-, NO3-, humic acid acted as radical scavengers, but HCO3- ion acted as both radical promoter and scavenger in the UV/H2O2 process. The transformation products (TPs) of PRO during both processes were identified using LC-QTOF/MS. Four TPs ([M+H]+ = 238, 256, 306, and 324) were identified during UV photolysis, and six TPs ([M+H]+ = 238, 256, 306, 324, 356, and 358) were identified in the UV/H2O2 process. Among the identified TPs, TP with [M+H]+ values of 356 and 358 were newly identified in the UV/H2O2 process. In addition, ionic byproducts, such as Cl-, NO3-, formate (HCOO-), and acetate (CH3COO-), were newly identified, indicating that significant mineralization was achieved in the UV/H2O2 process. Based on the identified TPs and ionic byproducts, the degradation mechanisms of PRO during two processes were proposed. The major reactions in both processes were ring cleavage and cyclization, and hydroxylation by OH radicals. The Microtox test with Vibrio fischeri showed that, while the toxicity of the reaction solution increased first, then gradually decreased during UV photolysis, the UV/H2O2 process initially increased toxicity at 10 min due to the production of TPs, but toxicity was completely removed as the reaction progressed. The results obtained in this study imply that the UV/H2O2 process is an effective treatment for eliminating PRO, its TPs, and the resulting toxicity in water.