Mechanistic insight into the degradation of ciprofloxacin in water by hydroxyl radicals

Ciprofloxacin (CIP), an effective antibacterial drug, is widely used to treat bacterial infections in humans and animals. However, drug pollution from residues and the development of resistant genes may pose serious ecological risks. Among the known methods of CIP degradation, advanced oxidation technology initiated by hydroxyl radicals exhibits great potential. However, an in-depth study of the degradation mechanism is difficult because of the limitations of the testing methods. In this study, CIP oxidation by hydroxyl radicals was evaluated using density functional theory (DFT), and the thermodynamics, kinetics, and toxicity were investigated. The results show that CIP oxidation occurs mainly through the piperazine ring, benzene ring, and CC. High reactivity is achieved in the initial reactions, where only five reactions are not thermodynamically spontaneous. Reactions involving direct hydrogen abstraction by oxygen in this system are superior to the indirect reactions. Some theoretically predicted products, such as P6 and P11, are consistent with those reported in previous experiments, indicating that the theoretical study can provide supplementary information about the oxidation paths. The branching ratios for the hydrogen atom abstraction and addition reactions were 37. 45% and 62.55%, respectively. Finally, this reaction system is completely nontoxic based on toxicity assessment. [Display omitted] •Theoretical calculation of ciprofloxacin degradation by hydroxyl radicals.•Great improvement and supplement to experimental research.•Highest oxidation priority of piperazine compared with other sites.•The direct hydrogen atom abstraction of oxygen is superior to the indirect way.