Environmental Science and Pollution Research

, Volume 25, Issue 30, pp 30609–30616 | Cite as

DFT/TDDFT insights into effects of dissociation and metal complexation on photochemical behavior of enrofloxacin in water

  • Se WangEmail author
  • Zhuang WangEmail author
  • Ce Hao
  • Willie J. G. M. Peijnenburg
Research Article


Elucidation of the mechanisms underlying the effects of different dissociated forms and metal ion complexation on the photochemical behavior of antibiotics in aqueous media is a key problem and requires further research. We examined the mechanism of the direct photolysis of enrofloxacin (ENRO) in different dissociated forms in water and the impact of metal ions (Mg2+) on the photolysis of ENRO using density functional theory and time-dependent density functional theory. The results showed that different dissociated forms of ENRO exhibited diverse maximum electronic absorbance wavelengths (ENRO3+ (264 nm) < ENRO (278 nm) < ENRO0 (280 nm) < ENRO2+ (282 nm) < ENRO+ (306 nm)). The calculations of the reaction pathways and activation energies (Ea) in the photolysis of ENRO0/ENRO+/ENRO showed that defluorination was the main reaction pathway. The removal of cyclopropane was the main reaction pathway for the direct photolysis of ENRO2+/ENRO3+. Furthermore, the presence of Mg2+ was observed to change the order of the maximum electronic absorbance wavelengths and increases the intensities of the ENRO absorbance peaks. Calculations of the photolysis reaction pathways showed that the presence of Mg2+ increased the Ea for the most direct photolysis pathways of ENRO, while its presence decreased the Ea for several partial direct photolysis pathways such as the pathway in which the piperazine ring moiety of ENRO0/ENRO3+ is damaged and the pathway in which cyclopropane is released from ENRO3+. The findings on the photolysis behavior of ENRO in water system have provided useful information on the risk assessment of antibiotics.


Enrofloxacin Dissociated species Photochemical behavior DFT Combined pollution 



This research was supported by the National Natural Science Foundation of China (41601519) and the Natural Science Foundation of Jiangsu Province (BK20150891). Se Wang would like to thank the Chinese Scholarship Council (CSC) for financial support (201708320051).

Supplementary material

11356_2018_3032_MOESM1_ESM.doc (35.6 mb)
ESM 1 (DOC 36504 kb)


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Environmental Science and Engineering, Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution ControlNanjing University of Information Science and TechnologyNanjingPeople’s Republic of China
  2. 2.Institute of Environmental Sciences (CML)Leiden UniversityLeidenThe Netherlands
  3. 3.State Key Laboratory of Fine ChemicalsDalian University of TechnologyDalianPeople’s Republic of China
  4. 4.National Institute of Public Health and the EnvironmentCenter for the Safety of Substances and ProductsBilthovenThe Netherlands

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