Abstract
Photochemical degradation of fluoroquinolones ciprofloxacin, enrofloxacin and norfloxacin in aqueous solution under light conditions relevant to surface waters at neutral and alkaline pH was found to proceed readily with half-lives between 0.9 and 2.7 min. The products of photochemical degradation identified by HPLC-MS included defluorinated, hydroxylated, and decarboxylated structures as well as structures with opened cyclic structures. For all of the studied substances, the reaction pathways were influenced significantly by the pH of the reaction system, with more products formed at alkaline pH than at neutral pH: the ratios of products in neutral and alkaline pH were 16/26, 9/19, 15/23 for ciprofloxacin, enrofloxacin, and norfloxacin, respectively. The structures of photoproducts and pathways of photochemical degradation are proposed. The antibacterial activities of photoproduct mixtures tested on E. coli and S. epidermidis were significantly higher in comparison to parental antibiotics in the case of both ciprofloxacin and enrofloxacin with p-values less than 0.0001 in most cases. The effect of the photoproducts was shown to be dependent on the pH value of the original antibiotic solutions before photodegradation: for ciprofloxacin, antibacterial activity against E. coli was more notably pronounced with regard to neutral pH photoproducts, while a less significant, or in one case not significant, effect of pH was observed against S. epidermidis; for norfloxacin, antibacterial activity against both E. coli and S. epidermidis was especially high with regard to alkaline pH photoproducts.
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Sincere thanks go to Christopher Steer for his diligent proof-reading of this paper.
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The authors gratefully acknowledge the financial support of the research provided by the Faculty of Science, University of South Bohemia. Partial financial support was received from the Grant Agency of the Czech Academy of Science — grant number 31-19-15678S.
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Š. Klementová organised and supervised the research and was a major contributor in writing the manuscript.
M. Poncarová performed photochemical experiments and analysed LC-MS data.
H. Langhansová and J. Lieskovská carried out the testing of antibacterial activity.
D. Kahoun supervised the LC-MS measurements.
P. Fojtíková participated in the HPLC analyses.
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Klementová, Š., Poncarová, M., Langhansová, H. et al. Photodegradation of fluoroquinolones in aqueous solution under light conditions relevant to surface waters, toxicity assessment of photoproduct mixtures. Environ Sci Pollut Res 29, 13941–13962 (2022). https://doi.org/10.1007/s11356-021-16182-6
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DOI: https://doi.org/10.1007/s11356-021-16182-6