Unveil the mechanism of photosensitized fluoroquinolones enhancing chlortetracycline photodegradation under simulated sunlight: Batch experiments and DFT calculation.

Fluoroquinolones (FQs), as the most commonly used antibiotics, are ubiquitous in the aquatic environment. The FQs' self-sensitization process could generate reactive oxygen species (ROS), which could react with other coexisting organic pollutants, impacting their transformation behaviors. However, the FQs' influences and mechanisms on the photochemical transformation of coexisting antibiotics are not yet revealed. In this study, we found ofloxacin (OFL) and norfloxacin (NOR), the two common FQs, can obviously accelerate chlortetracycline (CTC) photodegradation. In the presence of OFL and NOR (i.e., 10 μM), CTC photodegradation rate constants increased by 181.1% and 82.9%, respectively. With the help of electron paramagnetic resonance (EPR) and quenching experiments, this enhancement was attributed to aromatic ketone structure in FQs, which absorbed photons to generate ROS (i.e., OFL*, NOR*,O, and •OH). Notably, OFL* or NOR* was dominantly contributed to the enhanced CTC photodegradation, with the contribution ratios of 79.9% and 77.3% in CTC indirect photodegradation, respectively. Compared to CTC direct photodegradation, some new photodegradation products were detected in FQs solution, suggesting that OFL* or NOR* may oxide CTC through electron transfer. Moreover, the higher triple-excited state energy of OFL and NOR over DFT calculation implied that energy transfer from OFL* or NOR* to CTC was also theoretically feasible. Therefore, the presence of FQs could significantly accelerate the photodegradation of coexisting antibiotics mainly via electron or energy transfer of FQs*. The present study provided a new insight for accurately evaluating environmental behaviors and risks when multiple antibiotics coexist.