Trace Co(II) triggers peracetic acid activation in phosphate buffer: New insights into the oxidative species responsible for ciprofloxacin removal

Peracetic acid (PAA) emerges as a promising disinfectant and oxidant applied worldwide, and its application has been broadened for advanced oxidation processes (AOPs) in wastewater treatment. Current studies on transition metal-activated AOPs utilized relatively high concentrations of catalysts, leading to potential secondary pollution concerns. This study boosts the understanding of reaction mechanism in PAA activation system under a low-level concentration. Herein, trace levels of Co(II) (1 μM) and practical dosages of PAA (50–250 μM) were employed, achieving noticeable ciprofloxacin (CIP) degradation efficiencies (75.8–99.0%) within 20 min. Two orders of magnitude of the CIP’s antibacterial activity significantly decreased after Co(II)/PAA AOP treatment, which suggested the effective ecological risk control capability of the reaction system. The degradation performed well in various water matrices and the primary reactive species is proposed to be CoHPO4-OO(O)CCH3 complexes with scavenging tests and electron paramagnetic resonance tests. The degradation pathway of fluoroquinolones including piperazine ring-opening (dealkylation and oxidation), defluorination, and decarboxylation, were systematically elucidated. This study boosts a comprehensive and novel understanding of PAA-based AOP for CIP degradation. [Display omitted] •Efficient CIP degradation was achieved using PAA activated by trace Co(II).•The CoHPO4-(O)OOCH3 complexes was speculated as the major reactive species in the presence of phosphate buffer.•Fluoroquinolones degradation includes piperazine ring-opening, defluorination, and decarboxylation.•CIP antibacterial activity was eliminated by two orders of magnitude via Co(II)/PAA system.