Kinetics and reaction mechanism of photochemical degradation of diclofenac by UV-activated peroxymonosulfate

Diclofenac (DCF) is a common non-steroidal anti-inflammatory drug, which is frequently detected in different environmental media such as surface water, groundwater, domestic sewage, and sediment. In this study, UV-activated peroxymonosulfate (PMS) was used to degrade DCF by generating active radicals (i.e., SO(4)˙(−) and HO˙) with strong oxidizing properties. The effects of PMS dosage, pH, initial DCF concentration and common water constituents on the removal of DCF as well as its degradation mechanism in UV/PMS system were investigated. Compared to UV alone and PMS alone systems, DCF was removed more efficiently in the UV/PMS system at pH 7.0 due to the contribution of SO(4)˙(−) and HO˙, and its degradation followed the pseudo-first order kinetic model. As the dosage of PMS or solution pH increased, the degradation efficiency of DCF was gradually enhanced. The highest DCF degradation was obtained at pH 11.0 in this study, because the molar absorption coefficient of PMS increased with increasing pH at 254 nm resulting in generation of more reactive radicals at high pH. Removal efficiency of DCF was decreased significantly with the increase in its initial concentration due to the insufficient concentration of radicals. The presence of HCO(3)(−) and NO(3)(−) could promote the degradation of DCF because of the role of carbonate radicals and extra HO˙ formed, respectively, while NOM inhibited DCF degradation due to its competition with DCF for reactive radicals. No obvious influence on DCF degradation was observed in the UV/PMS system with the addition of Cl(−) and SO(4)(2−). The degradation of DCF by UV/PMS in real waters was slightly suppressed compared with its removal in ultrapure water. Seven transformation products were detected using UPLC-QTOF/MS, and the potential degradation mechanism of DCF was thus proposed showing six reaction pathways including hydroxylation, decarboxylation, dechlorination–cyclization, formylation, dehydrogenation and dechlorination–hydrogenation.