Benzophenone-4 (BP-4) is one of the UV filters widely used in personal care products (PCPs). BP-4 has been identified as an emergent contaminant detected in influent and effluent of wastewater treatment plants (WWTPs) at high concentrations showing that conventional treatment is unable to remove it, subsequently, the presence of BP-4 in surface water is inevitable. In this study, we focus on the degradation of this compound by chlorine, and we report the efficiency of its removal from water by applying two advanced oxidation processes UV/TiO2 and UV/H2O2 aiming to achieve a superior mineralization result. The study was performed in purified water (pH = 6.5, temperature = 25 °C) with an initial concentration of BP-4 similar to that detected in WWTPs (10 mg/L). The results showed that 76% of BP-4 was degraded after 80 min of reaction with chlorine leading to the formation of one by-product persistent in the solution. The oxidation by UV/TiO2 and UV/H2O2 led to a total removal of BP-4 and their generated by-products after 50 and 10 min of reactions, respectively. The kinetic study showed that BP-4 degradation by UV/H2O2 and UV/TiO2 followed pseudo-first-order reaction kinetics and the apparent rate constants (kapp) were determined to be 0.48 min-1 and 0.08 min-1, respectively. The degradation of BP-4 by chlorine followed first-order reaction kinetics with kapp = 0.02 min-1. The identification of by-product structures was performed using liquid chromatography with electrospray ionization and tandem mass spectrometry (MS/MS. The fragmentation of BP-4 and by-product ions at different collision energies allowed to propose the pathways of degradation and to predict the toxicity using a silico toxicity program which confirmed a higher toxicity of all generated by-products.
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