Photochemical behavior of benzophenone sunscreens induced by nitrate in aquatic environments

Benzophenones (BPs), which are widely used UV filters, have aroused considerable public concern owing to their potential endocrine-disrupting activities. Herein, we systematically investigated their photochemical behavior and fate, which is mediated by nitrate in aquatic environments. The results showed that 10 μM of 3 BPs can be completely degraded within 4 h of simulated sunlight irradiation in a 10 mM nitrate solution at pH 8.0, and 2,4-dihydroxybenzophenone (BP-1) has a 31.6% mineralization rate after 12 h irradiation. Their photolytic rates (k_obs) presented a significant linear correlation with the logarithmic values of the nitrate concentration for 0.1-10 mM (R² > 0.98), and in three actual waters, the rates of BP-1 were also positively related to the intrinsic nitrate concentration. Furthermore, higher transformation rates under alkaline condition were observed, especially for BP-1, with its k_obs at pH 10 being 8.3-fold higher than that at pH 6.0. Moreover, dissolved oxygen (DO) also has an impact on the reaction kinetics to some degree. According to the quenching experiments, we found that three reactive oxygen species (ROS), namely, •OH, •NO, and •NO₂, participated in this photolysis of BPs, and the contribution of •OH accounted for 32.1%. Furthermore, we selected BP-1 as the model molecule to study the transformation pathways and toxicity changes in this system. Four main transformation pathways including hydroxylation, nitrosylation, nitration, and dimerization were proposed, based on liquid chromatography quadrupole time-of-flight mass spectrometry (LC-Q-TOF-MS) analysis and density functional theory (DFT). According to the toxicity test, the formed intermediates were more toxic to Photobacterium phosphoreum than the parent BP-1. Therefore, these results can help reveal primary phototransformation mechanisms and evaluate the potential ecological risks of BPs in aquatic environments.