Transformation of diazepam in water during UV/chlorine and simulated sunlight/chlorine advanced oxidation processes

Psychoactive drug diazepam is one of benzodiazepines widely used in human medicine. It has been found to be relatively resistant to chlorination and photolysis. Here we investigated the transformation mechanism of diazepam in aqueous solution through UV/chlorine and simulated sunlight/chlorine treatments. The results showed that the UV/chlorine and sunlight/chlorine processes significantly increased the degradation of diazepam in water. These observed degradations can be elucidated by in-situ generation of reactive species including hydroxyl radical (HO), reactive chlorine species (RCS) and ozone (O₃) during photolysis of chlorine. In the UV/chlorine treatment, the degradation efficiency of diazepam for HO, chlorine, UV and RCS reaction at 90 min was calculated to be 62.1%, 3.8%, 11.9% and 12.3%, respectively. In the simulated sunlight/chlorine treatment, the calculated degradation of 53.1%, 8.1% and 11.2% was attributed to HO, chlorine and RCS reaction, with negligible loss by O₃ reaction and sunlight irradiation. In the UV/chlorine and sunlight/chlorine treatments, a total of 70 transformation products was detected using a high-resolution TripleTOF mass system. Six transformation pathways have been tentatively proposed for the diazepam, which includes hydroxylation, chlorination, hydrolyzation, N-demethylation, loss of phenyl group, benzodiazepine ring rearrangement and contraction. Most of the obtained transformation products were less toxic to aquatic organisms including fish, daphnia and green algae than diazepam itself according to the toxicity prediction tool, and did not cause significant changes in toxicity to luminescent bacteria.