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In this study, the photochemical degradation of the antibiotic oxytetracycline (OTC) at different pH values was investigated in aqueous solution under visible and solar light irradiation. Particular emphasis was given to the kinetics and mechanism during the photolytic and photocatalytic degradation of OTC. A comparative study of the photolysis of OTC under solar light, with different initial concentrations and in the presence of scavengers of reactive oxygen species (ROS), revealed a self-photosensitization pathway with evidence of singlet oxygen generation at pH 8.5 and 11.0 during OTC photolysis. The three-dimensional fluorescence spectra of OTC at different pH values demonstrate that OTC only exhibits significant emission spectra at pH 8.5 and 11.0. The change of the internal electrostatic force between the electron withdrawing group and the dehydrogenation moiety of OTC as a function of solution pH values was proposed as a critical factor influencing the energy states and observed reaction pathways of OTC under light irradiation. Moreover, the mechanism of photochemical degradation of OTC was investigated with nitrogen and fluorine doped titanium dioxide (NF-TiO 2 ) film at different pH values under visible and solar light in the presence of tert-butyl alcohol (TBA), sodium azide (NaN 3 ), potassium iodine (KI) and catalase as scavengers. Five pathways, including direct photolytic degradation, UV/vis light-induced photocatalytic oxidation and reduction, and visible light-induced self-photosensitized oxidation and reduction, were proposed and verified during the photocatalytic degradation of OTC with NF-TiO 2 film.

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Carbonate radical (CO3(•-)), a selective oxidant, reacts readily with electron-rich compounds through electron transfer and/or hydrogen abstraction. In this study, the role of CO3(•-) in degrading oxytetracycline (OTC) by UV only, UV/H2O2 and UV/persulfate (UV/PS) advanced oxidation processes (AOPs) in the presence of HCO3(-) or CO3(2-) was investigated. For UV only process, the presence of photosensitizers, i.e., nitrate (NO3(-)) and natural organic matter (NOM), had different impacts on OTC degradation, i.e., an enhancing effect by NO3(-) due to the generation of HO(•) and a slight inhibiting effect by NOM possibly due to a light scattering effect. Differently for UV/H2O2 and UV/PS processes, the presence of NO3(-) hardly influenced the destruction of OTC. Generation of CO3(•-) presented a positive role on OTC degradation by UV/NO3(-)/HCO3(-). Such influence was also observed in the two studied AOPs in the presence of both bicarbonate and other natural water constituents. When various natural water samples from different sources were used as reaction matrices, UV only and UV/H2O2 showed an inhibiting effect while UV/PS demonstrated a comparable or even promoting effect in OTC decomposition. After elucidating the potential contribution of UV direct photolysis via excited state OTC* at an elevated reaction pH condition, putative OTC transformation byproducts via CO3(•-) reaction were identified by ultra-high definition accurate-mass quadrupole time-of-flight tandem mass spectrometry (QTOF/MS). Five different reaction pathways were subsequently proposed, including hydroxylation (+16 Da), quinonization (+14 Da), demethylation (-14 Da), decarbonylation (-28 Da) and dehydration (-18 Da). The significant role of UV at high pH and CO3(•-) on OTC removal from contaminated water was therefore demonstrated both kinetically and mechanistically.

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Microcystin-LR (MC-LR), an algal toxin (cyanotoxin) common in sources of drinking water, poses a major human health hazard due to its high toxicity. In this study, UV/chlorine was evaluated as a potentially practical and effective process for the degradation of MC-LR. Via mass spectrometry analysis, fewer chlorinated-MC-LR products were detected with UV/chlorine treatment than with chlorination, and a transformation pathway for MC-LR by UV/chlorine was proposed. Different degrees of rapid degradation of MC-LR were observed with varying pH (6-10.4), oxidant dosage (0.5-3 mg L), natural organic matter (0-7 mg L), and natural water sources. In contrast to the formation of primarily chloroform and dichloroacetic acid in deionized water where MC-LR serves as the only carbon source, additional chlorinated disinfection byproducts were produced when sand filtered natural water was used as a background matrix. The UV/chlorine treated samples also showed quantitatively less cytotoxicity in vitro in HepaRG human liver cell line tests than chlorination treated samples. Following 16 min (96 mJ cm) of UV irradiation combined with 1.5 mg L chlorine treatment, the cell viability of the samples increased from 80% after exposure to 1 mg L MC-LR to 90%, while chlorination treatment evidenced no reduction in cytotoxicity with the same reaction time.

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