Unveiling the enhancement mechanisms of algogenic extracellular organic matters on chlortetracycline photodegradation: Constitutive relationships of compound components and reactive oxygen species generation

Algogenic extracellular organic matters (EOMs) have been found to play a crucial role in the photodegradation of antibiotics. However, the specific molecular structure compositions of EOMs have not been fully characterized, and the intrinsic association between the structure and the production of ROS remains unclear. In this study, EOMs from Chlorella Vulgaris were characterized using FT-ICR-MS. Based on the FT-ICR-MS results, nine representative model compounds (MCs, i.e., benzene, naphthalene, anthracene, phenanthrene, glucose, l-glutamic, triglyceride, tannic and lignin) were applied to investigate the physicochemical properties of EOMs and the ROS changes induced by the photoreaction of chlortetracycline (CTC). With the help of quenching assays, nine MCs were classified into prone-ROS and non-prone-ROS fractions. Prone-ROS compounds generate O2− upon electron transfer to 3O2, which then produces ·OH after disproportionation to generate hydrogen peroxide. The formation of 1O2 is attributed to energy transfer from prone-ROS to 3O2. Density functional theory revealed that prone-ROS exhibited higher reactivity compared to non-prone-ROS, this finding is as well supported by the result of steady-state photolysis measurement. Our study gives a new insight into photochemical fate of CTC in aquatic environments, providing theoretical basis for assessing antibiotics' ecological risk accurately. [Display omitted] •Nine MCs exhibited a promotion effect on the EOM-mediated photodegradation of CTC.•Prone-ROS had higher reactivity on the EOM-mediated formation of 3EOM*.•Back reduction by antioxidant of 3EOM* inhibited CTC photodegradation.•CTC photodegradation is complex process of ROS, electron transfer and energy transfer.•EOM mediated CTC photodegradation was exergonic based on Gibbs free energy.