Inhibitory effects of antioxidant moieties in humic substances on phototransformation of chlortetracycline mediated by the algae extracellular organic matter

In algae rich waters, sunlight-driven transformation of antibiotics could be accelerated via sensitization by algae extracellular organic matter (EOM), and this photosensitization process will be affected by coexisting humic substances. In this study, we explored the effect and mechanism of humic substances on photodegradation of chlortetracycline (CTC) mediated by EOM. We found that humic substances exhibited a marked inhibitory effect on the EOM-mediated photodegradation of CTC. Given that humic substances exhibited little effects on the EOM-mediated formation of triplet state species, the quenching effect of humic substances on reactive species was excluded. The inhibitory effect of humic substances was mainly attributed to the back reduction of CTC oxidation intermediates by the antioxidant moieties in humic substances. The ozone oxidation treatment for humic substances was applied to destroy antioxidant moieties. After ozonation, the inhibitory effects of humic substances were greatly decreased, confirming the dominant role of antioxidant moieties in humic substances, which inhibited CTC photodegradation mediated by EOM via reducing oxidation intermediates of CTC. This back reduction was further verified to be exergonic via reactive Gibbs free energy, indicating the back reduction by humic substances of CTC oxidation intermediates could occur spontaneously. The present study will be helpful for predicting the fate and risk of CTC in algae rich water environments, and is of great significance for the study of phototransformation of other antibiotics.