Aquatic photolysis of high-risk chemicals of emerging concern from secondary effluent mediated by sunlight irradiation for ecological safety and the enhanced methods.

Natural sunlight can reduce the chemicals of emerging concern (CECs) and biological effects from the discharged domestic wastewater. But the aquatic photolysis and biotoxic variations of specific CECs detected in secondary effluent (SE) were not clear. In this study, 29 CECs were detected in the SE, and 13 medium- and high-risk CECs were identified as target chemicals based on their ecological risk assessment. To comprehensively explore the photolysis properties of the identified target chemicals, the direct and self-sensitized photodegradation of the target chemicals, even the indirect photodegradation in the mixture, were investigated and compared with these photodegradation in the SE. Of the 13 target chemicals, only five chemicals (including dichlorvos (DDVP), mefenamic acid (MEF), diphenhydramine hydrochloride (DPH), chlorpyrifos (CPF), and imidacloprid (IMI)) underwent direct and self-sensitized photodegradation processes. The removal of DDVP, MEF, and DPH was attributed to self-sensitized photodegradation, which was mainly mediated by •OH; CPF and IMI primarily relied on direct photodegradation. Synergistic and/or antagonistic actions that occurred in the mixture improved/decreased the rate constants of five photodegradable target chemicals. Meanwhile, the biotoxicities (acute toxicity and genotoxicity) of the target chemicals (including individual chemicals and the mixture) were significantly reduced, which can explain the reduction of biotoxicities from SE. For the two refractory high-risk chemicals, atrazine (ATZ) and carbendazim (MBC), algae-derived intracellular dissolved organic matter (IOM) on ATZ, and IOM and extracellular dissolved organic matter (EOM) on MBC had slightly promotion for their photodegradation; while peroxysulfate, and peroxymonosulfate served as sensitizers were activated by natural sunlight and effectively improved their photodegradation rate, and then reduced their biotoxicities. These findings will promote the development of CECs treatment technologies based on sunlight irradiation.