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Aqueous multivariate phototransformation kinetics of dissociated tetracycline: implications for the photochemical fate in surface waters

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Abstract

Antibiotics are ubiquitous pollutants in aquatic systems and can exist as different dissociated species depending on the water pH. New knowledge of their multivariate photochemical behavior (i.e., the photobehavior of different ionized forms) is needed to improve our understanding on the fate and possible remediation of these pharmaceuticals in surface and waste waters. In this study, the photochemical degradation of aqueous tetracycline (TC) and its dissociated forms (TCH20, TCH−, and TC2−) was investigated. Simulated sunlight experiments and matrix calculations indicated that the three dissociated species had dissimilar photolytic kinetics and photooxidation reactivities. TC2− photodegraded the fastest due to apparent photolysis with a kinetic constant of 0.938 ± 0.021 min−1, followed by TCH− (0.020 ± 0.005 min−1) and TCH20 (0.012 ± 0.001 min−1), whereas TCH− was found to be the most highly reactive toward •OH (105.78 ± 3.40 M−1 s−1), and TC2− reacted the fastest with 1O2 (344.96 ± 45.07 M−1 s−1). Water with relatively high pH (e.g., ~ 8–9) favors the dissociated forms of TCH− and TC2− which are most susceptible to photochemical loss processes compared to neutral TC. The calculated corresponding environmental half-lives (t1/2,E) in sunlit surface waters ranged from 0.05 h for pH = 9 in midsummer to 3.68 h for pH = 6 in midwinter at 45° N latitude. The process was dominated by apparent photolysis (especially in summer, 62–91%), followed by 1O2 and •OH oxidation. Adjusting the pH to slightly alkaline conditions prior to UV or solar UV light treatment may be an effective way of enhancing the photochemical removal of TC from contaminated water.

Aqueous multiple photochemical behavior of dissociated tetracycline (TCH20, TCH−, and TC2−) is first comprehensively reported on revealing the phototransformation kinetics and implications for the fate in surface waters.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21577029 and 41476084), China Scholarship Council (CSC) Scholarship (201704180014 and 201704180009), the Key Laboratory for Ecological Environment in Coastal Areas (201602), and the Marine Science Foundation (2012501) of SOA, China.

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Author notes

  1. Linke Ge and Qianqian Dong contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian, 116023, China

    Linke Ge, Jun Li, Peng Zhang & Ziwei Yao

  2. Lancaster Environment Centre, Lancaster University, Lancaster, LA1 4YQ, UK

    Linke Ge, Crispin Halsall & Peng Zhang

  3. School of Environmental Science and Technology, Dalian Maritime University, Dalian, 116023, China

    Qianqian Dong & Degao Wang

  4. Department of Environmental Science and Analytical Chemistry, Stockholm University, 10691, Stockholm, Sweden

    Chang-Er L. Chen

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  1. Linke Ge
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  2. Qianqian Dong
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  4. Chang-Er L. Chen
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Correspondence to Peng Zhang.

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Responsible editor: Philippe Garrigues

Highlights

➢ Distinct photochemistry of dissociated tetracycline (TCH20, TCH−, and TC2−) was reported

➢ TC2− underwent apparent photolysis the fastest, followed by TCH− and TCH20

➢ TCH− was the most highly reactive toward •OH, while TC2− reacted the fastest with 1O2

➢ Environmental fate was assessed based on pH-dependent dissociation and photobehavior

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Ge, L., Dong, Q., Halsall, C. et al. Aqueous multivariate phototransformation kinetics of dissociated tetracycline: implications for the photochemical fate in surface waters. Environ Sci Pollut Res 25, 15726–15732 (2018). https://doi.org/10.1007/s11356-018-1765-0

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