The diverse roles of bromide in the degradation of tinidazole during UV-LED/chlorine process at different wavelengths: Kinetics, radical contribution, and degradation pathway

Abstract

Bromide (Br–) is widely present in aquatic environment and plays important roles in pollutant degradation during advanced oxidation processes. This work systematically investigated the effect of Br– on the degradation of tinidazole (TNZ) during ultraviolet light-emitting diode (UV-LED)/chlorine process at different wavelengths (265 and 365 nm). The observed pseudo-first-order constant (k') for the TNZ degradation during UV-LED (365 nm)/chlorine process in the presence of 0.4 mM Br– (0.1125 min−1) was 1.56 times that during UV-LED (365 nm)/chlorine process in the absence of Br–. However, the k' value during UV-LED (265 nm)/chlorine process was reduced by 49.=7 % in the presence of 0.4 mM Br–. At 0–0.4 mM Br−, elevated levels of hydroxyl radicals (HO·) and active bromine species promoted TNZ degradation during UV-LED (365 nm)/chlorine/Br– process, whereas reduced HO· concentration was the main reason for the inhibition of TNZ degradation during UV-LED (265 nm)/chlorine/Br– process. With increasing solution pH from 5.8 to 7.8, the k' value of both processes decreased in the presence of Br–. Meanwhile, the k' value increased with increasing chlorine dosage and decreased with increasing initial TNZ concentration during both processes in the presence of Br–. The presence of Cl− and HCO3– presented negligible effects on the degradation of TNZ. According to the density functional theory calculation and detected intermediates, the degradation pathway of TNZ during both processes in the presence of Br– was proposed. The toxicity evaluation demonstrated that some of the degradation products of TNZ presented lower predicted toxicity values than TNZ. Overall, this work provides a thorough insight into the role of Br– in TNZ degradation during UV-LED/chlorine process at different wavelengths.