Mechanism of norfloxacin transformation by horseradish peroxidase and various redox mediated by humic acid and microplastics

The catalysis of HRP coupling with redox mediator was a feasible technology for the transformation of antibiotics. This work screened three effective redox mediators syringaldehyde (SYR), acetosyringone (AS) and p-coumaric acid (PCA) for the norfloxacin (NOR) transformation in HRP/redox mediator system. Then, compared their transformation characteristics under varying conditions. The molecular docking results indicated HRP catalytic mediator was spontaneous, and the absolute value order of free energy between three redox mediators and HRP was consistent with the order of NOR removal in experiment. The presence of humic acid (HA) and polystyrene (PS) microplastics could block the removal of NOR, and the inhibition effect was proportional to the level of HA and PS particles. Seven and six possible intermediate products were identified by using SYR/AS and PCA as redox mediators, respectively, and potential NOR transformation pathways were proposed. SYR and AS treatment had the same transformation products and pathways due to their similar structure, including defluorination, oxidation, cross-coupled with mediator, demethylation and dehydrogenation. While for the PCA group, NOR not only performed the above action (except defluorination), but also underwent decarbonylation. These findings may expand our knowledge of the conversion and fate of fluoroquinolones through HRP coupled with redox mediator in the environment.