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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 Wang
  • Zhuang Wang
  • Ce Hao
  • Willie J. G. M. Peijnenburg
Research Article

Abstract

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.

Keywords

Enrofloxacin Dissociated species Photochemical behavior DFT Combined pollution 

Notes

Funding

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)

References

  1. Ahmad I, Bano R, Musharraf SG, Sheraz MA, Ahmed S, Tahir H, ul Arfeen Q, Bhatti MS, Shad Z, Hussain SF (2015) Photodegradation of norfloxacin in aqueous and organic solvents: A kinetic study. J Photoch Photobio A 302:1–10CrossRefGoogle Scholar
  2. Babić S, Periša M, Škorić I (2013) Photolytic degradation of norfloxacin, enrofloxacin and ciprofloxacin in various aqueous media. Chemosphere 91:1635–1642CrossRefGoogle Scholar
  3. Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652CrossRefGoogle Scholar
  4. Burke K, Werschnik J, Gross EKU (2005) Time-dependent density functional theory: past, present, and future. J Chem Phys 123:062206CrossRefGoogle Scholar
  5. Chu C, Stamatelatos D, McNeill K (2017) Aquatic indirect photochemical transformations of natural peptidic thiols: impact of thiol properties, solution pH, solution salinity and metal ions. Environ Sci Process Impacts 19:1518–1527CrossRefGoogle Scholar
  6. Cuprys A, Pulicharla R, Lecka J, Brar SK, Drogui P, Surampalli RY (2018) Ciprofloxacin-metal complexes -stability and toxicity tests in the presence of humic substances. Chemosphere 202:549–559CrossRefGoogle Scholar
  7. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H.P., Izmaylov, A.F., Bloino, J., Zheng, G., Sonnenberg, J.L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J.A., Peralta Jr., J.E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Rega, N., Millam, J.M., Klene, M., Knox, J.E., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Martin, R.L., Morokuma, K., Zakrzewski, V.G., Voth, G.A., Salvador, P., Dannenberg, J.J., Dapprich, S., Daniels, A.D., Farkas, O., Foresman, J.B., Ortiz, J.V., Cioslowski, J., Fox, D.J., 2009, Gaussian 09 Package, Gaussian, Inc., Wallingford CTGoogle Scholar
  8. Fukui K (1981) The path of chemical reactions - the IRC approach. Accounts Chem. Res. 14:363–368CrossRefGoogle Scholar
  9. Ge L, Chen J, Wei X, Zhang S, Qiao X, Cai X, Xie Q (2010) Aquatic photochemistry of fluoroquinolone antibiotics: kinetics, pathways, and multivariate effects of main water constituents. Environ Sci Technol 44:2400–2405CrossRefGoogle Scholar
  10. Guo H, Ke T, Gao N, Liu Y, Cheng X (2017) Enhanced degradation of aqueous norfloxacin and enrofloxacin by UV-activated persulfate: kinetics, pathways and deactivation. Chem Eng J 316:471–480CrossRefGoogle Scholar
  11. Hafuka A, Yoshikawa H, Yamada K, Kato T, Takahashi M, Okabe S, Satoh H (2014) Application of fluorescence spectroscopy using a novel fluoroionophore for quantification of zinc in urban runoff. Water Res 54:12–20CrossRefGoogle Scholar
  12. Hong KY, de Albuquerque CDL, Poppi RJ, Brolo AG (2017) Determination of aqueous antibiotic solutions using SERS nanogratings. Anal Chim Acta 982:148–155CrossRefGoogle Scholar
  13. Jiang X, Wang Z, Zhang Y, Wang F, Zhu M, Yao J (2016) The mutual influence of speciation and combination of cu and Pb on the photodegradation of dimethyl o-phthalate. Chemosphere 165:80–86CrossRefGoogle Scholar
  14. Knapp CW, Cardoza LA, Hawes JN, Wellington EMH, Larive CK, Graham DW (2005) Fate and effects of enrofloxacin in aquatic systems under different light conditions. Environ. Sci. Technol. 39:9140–9146CrossRefGoogle Scholar
  15. Kohn W, Becke AD, Parr RG (1996) Density functional theory of electronic structure. J Chem Phys 100:12974–12980CrossRefGoogle Scholar
  16. Kovacevic G, Sabljic A (2013) Mechanisms and reaction-path dynamics of hydroxyl radical reactions with aromatic hydrocarbons: the case of chlorobenzene. Chemosphere 92:851–856CrossRefGoogle Scholar
  17. Kümmerer K (2009a) Antibiotics in the aquatic environment – a review – part I. Chemosphere 75:417–434CrossRefGoogle Scholar
  18. Kümmerer K (2009b) Antibiotics in the aquatic environment – a review – part II. Chemosphere 75:417–434CrossRefGoogle Scholar
  19. Li Y, Niu J, Wang W (2011) Photolysis of Enrofloxacin in aqueous systems under simulated sunlight irradiation: kinetics, mechanism and toxicity of photolysis products. Chemosphere 85:892–897CrossRefGoogle Scholar
  20. Li Y, Niu J, Shang E, Zheng M, Luan T (2014) Effects of nitrate and humic acid on enrofloxacin photolysis in an aqueous system under three light conditions: kinetics and mechanism. Environ Chem 11:333–340CrossRefGoogle Scholar
  21. Qiang Z, Adams C (2004) Potentiometric determination of acid dissociation constants (pKa) for human and veterinary antibiotics. Water Res 38:2874–2890CrossRefGoogle Scholar
  22. Shah, S., Hao, C., 2017. Quantum chemical investigation on photodegradation mechanisms of sulfamethoxypyridazine with dissolved inorganic matter and hydroxyl radical. J. Environ. Sci-China 85–92CrossRefGoogle Scholar
  23. Shah S, Zhang H, Song X, Hao C (2015) Quantum chemical study of the photolysis mechanisms of sulfachloropyridazine and the influence of selected divalent metal ions. Chemosphere 138:765–769CrossRefGoogle Scholar
  24. Sortino S, Condorelli G, De Guidi G, Giuffrida S (1998) Molecular mechanism of photosensitization-XI. Membrane damage and DNA cleavage photoinduced by enoxacin. Photochem Photobiol 68:652–659CrossRefGoogle Scholar
  25. Sturini M, Speltini A, Maraschi F, Pretali L, Profumo A, Fasani E, Albini A, Migliavacca R, Nucleo E (2012a) Photodegradation of fluoroquinolones in surface water and antimicrobial activity of the photoproducts. Water Res 46:5575–5582CrossRefGoogle Scholar
  26. Sturini M, Speltini A, Maraschi F, Profumo A, Pretali L, Irastorza EA, Fasani E, Albini A (2012b) Photolytic and photocatalytic degradation of fluoroquinolones in untreated river water under natural sunlight. Appl. Catal. B-Environ. 119-120:32–39CrossRefGoogle Scholar
  27. Sturini M, Speltini A, Maraschi F, Profumo A, Tarantino S, Gualtieri AF, Zema M (2016) Removal of fluoroquinolone contaminants from environmental waters on sepiolite and its photo-induced regeneration. Chemosphere 150:686–693CrossRefGoogle Scholar
  28. Tomasi J, Mennucci B, Cammi R (2005) Quantum mechanical continuum solvation models. Chem Rev 105:2999–3093CrossRefGoogle Scholar
  29. Wammer KH, Korte AR, Lundeen RA, Sundberg JE, McNeill K, Arnold WA (2013) Direct photochemistry of three fluoroquinolone antibacterials: Norfloxacin, ofloxacin, and enrofloxacin. Water Res 47:439–448CrossRefGoogle Scholar
  30. Wang S, Wang Z (2017) Elucidating direct photolysis mechanisms of different dissociation species of norfloxacin in water and Mg2+ effects by quantum chemical calculations. Molecules 22:1949CrossRefGoogle Scholar
  31. Wang S, Song X, Hao C, Gao Z, Chen J, Qiu J (2014) Elucidating photodehalogenation mechanisms of polychlorinated and polybrominated dibenzo-p-dioxins and dibenzofurans and Mg2+ effects by quantum chemical calculations. Comput Theor Chem 1042:49–56CrossRefGoogle Scholar
  32. Wang S, Song X, Hao C, Gao Z, Chen J, Qiu J (2015) Elucidating triplet-sensitized photolysis mechanisms of sulfadiazine and metal ions effects by quantum chemical calculations. Chemosphere 122:62–69CrossRefGoogle Scholar
  33. Wei X, Chen J, Xie Q, Zhang S, Ge L, Qiao X (2013) Distinct photolytic mechanisms and products for different dissociation species of ciprofloxacin. Environ. Sci. Technol. 47:4284–4290CrossRefGoogle Scholar
  34. Wen X, Niu C, Zhang L, Liang C, Zeng G (2018) A novel Ag2O/CeO2 heterojunction photocatalysts for photocatalytic degradation of enrofloxacin: possible degradation pathways, mineralization activity and an in depth mechanism insight. Appl Catal B-Environ 221:701–714CrossRefGoogle Scholar
  35. Werner JJ, Arnold WA, Mcneill K (2006) Water hardness as a photochemical parameter: tetracycline photolysis as a function of calcium concentration, magnesium concentration, and pH. Environ. Sci. Technol. 40:7236–7241CrossRefGoogle Scholar
  36. Wu M, Que C, Tang L, Xu H, Xiang J, Wang J, Shi W, Xu G (2016) Distribution, fate, and risk assessment of antibiotics in five wastewater treatment plants in shanghai, China. Environ Sci Pollut Res 23:18055–18063CrossRefGoogle Scholar
  37. Zhang Y, Cai X, Lang X, Qiao X, Li X, Chen J (2012) Insights into aquatic toxicities of the antibiotics oxytetracycline and ciprofloxacin in the presence of metal: complexation versus mixture. Environ Pollut 166:48–56CrossRefGoogle Scholar
  38. Zhang Z, Liu J, Feng T, Yao Y, Gao L, Jiang G (2013) Time-resolved fluoroimmunoassay as an advantageous analytical method for assessing the total concentration and environmental risk of fluoroquinolones in surface waters. Environ. Sci. Technol. 47:454–462CrossRefGoogle Scholar
  39. Zhang YN, Zhou Y, Qu J, Chen J, Zhao J, Lu Y, Li C, Xie Q, Peijnenburg WJGM (2018) Unveiling the important roles of coexisting contaminants on photochemical transformations of pharmaceuticals: fibrate drugs as a case study. J Hazard Mater 358:216–221CrossRefGoogle Scholar
  40. Zhao G-J, Han K-L (2009) Excited state electronic structures and photochemistry of heterocyclic annulated perylene (HAP) materials tuned by heteroatoms: S, se, N, O, C, Si, and B. J Phys Chem A 113:4788–4794CrossRefGoogle Scholar
  41. Zhao G-J, Han K-L (2010) pH-controlled twisted intramolecular charge transfer (TICT) excited state via changing the charge transfer direction. Phys Chem Chem Phys 12:8914–8918CrossRefGoogle Scholar
  42. Zhao G-J, Han K-L (2012) Hydrogen bonding in the electronic excited state. Accounts Chem Res 45:404–413CrossRefGoogle Scholar
  43. Zhao W, Guo Y, Lu S, Yan P, Sui Q (2016) Recent advances in pharmaceuticals and personal care products in the surface water and sediments in China. Front Environ Sci Eng 10:2CrossRefGoogle Scholar
  44. Ziarrusta H, Val N, Dominguez H, Mijangos L, Prieto A, Usobiaga A, Etxebarria N, Zuloaga O, Olivares M (2017) Determination of fluoroquinolones in fish tissues, biological fluids, and environmental waters by liquid chromatography tandem mass spectrometry. Anal Bioanal Chem 409:6359–6370CrossRefGoogle Scholar
  45. Zuccato E, Castiglioni S, Bagnati R, Melis M, Fanelli R (2010) Source, occurrence and fate of antibiotics in the Italian aquatic environment. J Hazard Mater 179:1042–1048CrossRefGoogle Scholar

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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