TY - JOUR

T1 - Aqueous multivariate phototransformation kinetics of dissociated tetracycline

T2 - implications for the photochemical fate in surface waters

AU - Ge, Linke

AU - Dong, Qianqian

AU - Halsall, Crispin James

AU - Chen, Chang-Er

AU - Li, Jun

AU - Wang, Degao

AU - Zhang, Peng

AU - Yao, Ziwei

N1 - The final publication is available at Springer via http://dx.doi.org/10.1007/S11356-018-1756-0

PY - 2018/6

Y1 - 2018/6

N2 - 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 photooxidationreactivities. 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−1s−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 inmidsummer 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 UVor solar UV light treatment may be an effective way of enhancing the photochemical removal of TC from contaminated water.

AB - 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 photooxidationreactivities. 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−1s−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 inmidsummer 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 UVor solar UV light treatment may be an effective way of enhancing the photochemical removal of TC from contaminated water.

KW - Tetracycline

KW - Dissociation

KW - Apparent photolysis

KW - Hydroxyl radical

KW - Singlet oxygen

KW - Environmental half-lives

U2 - 10.1007/s11356-018-1765-0

DO - 10.1007/s11356-018-1765-0

M3 - Journal article

VL - 25

SP - 15726

EP - 15732

JO - Environmental Science and Pollution Research

JF - Environmental Science and Pollution Research

SN - 0944-1344

IS - 16

ER -