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Assessing the presence of enrofloxacin and ciprofloxacin in piggery wastewater and their adsorption behaviour onto solid materials, with a newly developed chromatographic method

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Abstract

Veterinary antibiotics could enter the environment after the application of manure or farm wastewater on soil as fertilizer. In this study, a UPLC-MS/MS analytical method was developed and validated for the simultaneous determination of enrofloxacin (ENR) and ciprofloxacin (CIP) at environmental relevant concentrations in piggery wastewater, piggery wastewater solids, agricultural soil and ground water with good performance characteristics. The method recovery for ENR and CIP was 94.2 and 89.9% in the filtered piggery wastewater, 81.3 and 82% in the wastewater solid material, 78.1 and 76.8% in the soil and 95.6 and 97.3% in the ground water. The Limit of Detection (LOD) and Limit of Quantification (LOQ) for ENR were 21 and 64 ng L−1 and for CIP was 18 and 54 ng L−1, respectively. The method was implemented to monitor ENR and CIP in the wastewater of a piggery facility in Cyprus which applied anaerobic treatment before the final disposal of the reclaimed water. The highest antibiotic concentrations were measured in the wastewater samples collected from the nursery, where ENR is continuously used, with average concentration 31.4 μg L−1 for ENR and 16.0 μg L−1 for CIP. After the anaerobic digester, the two antibiotics were found only on the solid matter of the treated wastewater with an average concentration of 1.7 μg kg−1 for ENR and 1.0 μg kg−1 for CIP. The antibiotics adsorption at pH = 7 on clay soil, quartz sand and on solid matter isolated from the piggery wastewater was found to be higher than 95% for all solid materials. The concentration of the antibiotics in soil samples taken from a field where reclaimed piggery wastewater was applied for 10 years and in samples of groundwater from a nearby well was found for all samples below the LOD.

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References

  • Alder AC, McArdell CS, Golet EM, Kohler HPE, Molnar E, Pham Thi NA, Siegrist H, Suter MJF, Giger W (2004) Environmental exposure of antibiotics in wastewaters, sewage sludges and surface waters in Switzerland. In: Kummerer K (ed) Pharmaceuticals in the environment: sources, fate, effects and risks, 2nd edn. Springer-Verlag, Berlin, pp 55–66

    Chapter  Google Scholar 

  • Choma IM (2003) TLC separation of fluoroquinolones: searching for better selectivity. J Liq Chromatogr Relat Technol 26:2673–2685

    Article  CAS  Google Scholar 

  • Clesceri LS, Greenberg AE, Eaton AD (1999) Standard methods for the examination of water and wastewater, 20th edn. American Public Health Association, American Water Works Association and Water Environment Federation, Washington DC 2671 p

    Google Scholar 

  • Conkle JL, Lattao C, White JR, Cook RL (2010) Competitive sorption and desorption behavior for three fluoroquinolone antibiotics in a wastewater treatment wetland soil. Chemosphere 80:1353–1359

    Article  CAS  Google Scholar 

  • Figueroa-Diva RA, Vasudevan D, MacKay AA (2010) Trends in soil sorption coefficients within common antimicrobial families. Chemosphere 79:786–793

    Article  CAS  Google Scholar 

  • Fink L, Dror I, Berkowitz B (2012) Enrofloxacin oxidative degradation facilitated by metal oxide nanoparticles. Chemosphere 86:144–149

    Article  CAS  Google Scholar 

  • Frade VMF, Dias M, Teixeira ACSC, Palma M (2014) Environmental contamination by fluoroquinolones—review. Braz J Pharm Sci 50:41–54

    Article  CAS  Google Scholar 

  • Golet EM, Strehler A, Alder AC, Giger W (2002a) Determination of fluoroquinolone antibacterial agents in sewage sludge and sludge-treated soil using accelerated solvent extraction followed by solid-phase extraction. Anal Chem 74:5455–5462

    Article  CAS  Google Scholar 

  • Golet EM, Strehler A, Alder AC, Giger W (2002b) Environmental exposure and risk assessment of fluoroquinolone antibacterial agents in wastewater and river water of the Glatt Valley watershed, Switzerland. Environ Sci Technol 36:3645–3651

    Article  CAS  Google Scholar 

  • Golet EM, Xifra I, Siegrist H, Alder AC, Giger W (2003) Environmental exposure assessment of fluoroquinolone antibacterial agents from sewage to soil. Environ Sci Technol 37:3243–3249

    Article  CAS  Google Scholar 

  • Knapp CW, Cardoza LA, Hawes JN, Wellington EMH, Larive CH, Graham DW (2005) Fate and effects of enrofloxacin in aquatic systems under different light conditions. Environ Sci Technol 39:9140–9146

    Article  CAS  Google Scholar 

  • Lillenberg M, Yurchenko S, Kipper K, Herodes K, Pihl V, Lõhmus R, Ivask M, Kuu A, Kutti S, Litvin SV, Nei L (2010) Presence of fluoroquinolones and sulphonamides in urban sewage sludge and their degradation as a result of composting. Int J Environ Sci Technol 7:307–312

    Article  CAS  Google Scholar 

  • Lützhøft HCH, Vaes WHJ, Freidig AP, Halling-Sørensen B, Hermens JLM (2000) Influence of pH and other modifying factors on the distribution behavior of 4- quinolones to solid phases and humic acids studied by “negligible-depletion” SPME-HPLC. Environ Sci Technol 34:4989–4994

    Article  Google Scholar 

  • Morales-Muñoz S, Luque-Garcia JL, Luque de Castro MD (2004) Continuous microwave-assisted extraction coupled with derivatization and fluorometric monitoring for the determination of fluoroquinolone antibacterial agents from soil samples. J Chromatogr A 1059:25–31. http://www.sciencedirect.com/science/article/pii/S002196730401742X

  • Nowara A, Burhenne J, Spiteller M (1997) Binding of fluoroquinolone carboxylic acid derivatives to clay minerals. J Agric Food Chem 45:1459–1463

    Article  CAS  Google Scholar 

  • OECD (2000) Guidelines for the Testing of Chemicals, Section 1: Physical-Chemical properties - Test No. 106: adsorption-desorption using a batch equilibrium method. Available on line: http://www.oecdilibrary.org/docserver/download/9710601e.pdf?expires=1502348502&id=id&accname=guest&checksum=73C723F8D39126F1305FDB1689FCF9A9

  • Petrovic M, Hernando MD, Diaz-Cruz MS, Barcelo D (2005) Liquid chromatography–tandem mass spectrometry for the analysis of pharmaceutical residues in environmental samples: a review. J Chromatogr A 1067:1–14

    Article  CAS  Google Scholar 

  • Picò Y, Andreu V (2007) Fluoroquinolones in soil—risks and challenges. Anal Bioanal Chem 387:1287–1299

    Article  Google Scholar 

  • Speltini A, Sturini M, Maraschi F, Profumo A, Albini A (2011) Analytical methods for the determination of fluoroquinolones in solid environmental matrices. Trends Anal Chem 30:1337–1350

    Article  CAS  Google Scholar 

  • Sturini M, Speltini A, Maraschi F, Rivagli E, Profumo A (2010) Solvent-free microwave- assisted extraction of fluoroquinolones from soil and liquid chromatography-fluorescence determination. J Chromatogr A 1217:7316–7322

    Article  CAS  Google Scholar 

  • Tong L, Ping L, Wang Y, Zhu K (2009) Analysis of veterinary antibiotic residues in swine wastewater and environmental water samples using optimized SPE-LC/MS/MS. Chemosphere 74:1090–1097

    Article  CAS  Google Scholar 

  • Turiel E, Bordin G, Rodriguez AR (2006) Study of the evolution and degradation products of ciprofloxacin and oxolinic acid in river water samples by HPLC–UV/MS/MS–MS. J Environ Monit 7:189–195

    Article  Google Scholar 

  • Van Doorslaer X, Dewulf J, Van Langenhove H, Demeestere K (2014) Fluoroquinolone antibiotics: an emerging class of environmental micropollutants. Sci Total Environ 500-1:250–269

    Article  Google Scholar 

  • Wammer K, Korte A, Lundeen R, Sundberg J, McNeill K, Arnold W (2013) Direct photochemistry of three fluoroquinolone antibacterials: norfloxacin, ofloxacin, and enrofloxacin. Water Res 47:439–448

    Article  CAS  Google Scholar 

  • Yan W, Hu S, Jing C (2012) Enrofloxacin sorption on smectite clays: effects of pH, cations, and humic acid. J Colloid Interface Sci 372:141–147

    Article  CAS  Google Scholar 

  • Zhou X, Chen CH, Yue L, Sun Y, Ding H, Liu Y (2008) Excretion of enrofloxacin in pigs and its effect on ecological environment. Environ Toxicol Pharmacol 26:272–277

    Article  CAS  Google Scholar 

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Acknowledgments

The authors are grateful to the owners and the staff of the CAFO for all their support and assistance during the samplings and for the data on the function of the unit and the wastewater collection and treatment system which were kindly provided as well as the data on the administered doses of enrofloxacin.

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Authors and Affiliations

  1. Civil and Environmental Engineering Department, University of Cyprus, P.O. Box 20537, 1678, Nicosia, Cyprus

    Andreas Parpounas & Despo Fatta-Kassinos

  2. Nireas, International Water Research Center, University of Cyprus, P.O. Box 20537, 1678, Nicosia, Cyprus

    Andreas Parpounas, Vassilis Litskas, Evroula Hapeshi, Costas Michael & Despo Fatta-Kassinos

Authors
  1. Andreas Parpounas
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  2. Vassilis Litskas
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  3. Evroula Hapeshi
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  4. Costas Michael
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  5. Despo Fatta-Kassinos
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Correspondence to Costas Michael or Despo Fatta-Kassinos.

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Responsible editor: Roland Kallenborn

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Parpounas, A., Litskas, V., Hapeshi, E. et al. Assessing the presence of enrofloxacin and ciprofloxacin in piggery wastewater and their adsorption behaviour onto solid materials, with a newly developed chromatographic method. Environ Sci Pollut Res 24, 23371–23381 (2017). https://doi.org/10.1007/s11356-017-9849-9

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  • DOI: https://doi.org/10.1007/s11356-017-9849-9

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