Skip to main content
SpringerLink
Log in

Oxidation of ofloxacin by Oxone/Co2+: identification of reaction products and pathways

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

Oxidative degradation of ofloxacin (OFX) by sulfate free radicals (SO4 −•) in the UV/Oxone/Co2+oxidation process was investigated for the first time, with a special focus upon identifying the transformation products as well as understanding the reaction pathways. Thirteen main compounds were identified after the initial transformation of OFX; the detailed structural information of which were characterized by high-performance liquid chromatography–high resolution mass spectrometry and MS fragmentation analysis. The degradation pathways mainly encompassed ring openings at both the piperazinyl substituent and the quinolone moiety, indicating that the usage of SO4 −• aided the oxidative degradation of OFX to undergo more facile routes compared to those in previous reports by using OH•/h+ as the oxidant, where the initial transformation attacks were mainly confined to the piperazine moiety. Moreover, in this study, smart control over the pH conditions of the oxidation system via different modes of Oxone dosage resulted in the selective degradation of the functional sites of OFX molecule, where it was shown that the SO4 −•-driven destruction of the quinolone moiety of OFX molecule favored the neutral pH conditions. This would be beneficial for the reduction of bacterial resistance against quinolones in the aqueous environment.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  • Anipsitakis GP, Dionysiou DD (2003) Degradation of organic contaminants in water with sulfate radicals generated by the conjunction of peroxymonosulfate with cobalt. Environ Sci Technol 37:4790–4797

    Article  CAS  Google Scholar 

  • Anipsitakis GP, Dionysiou DD, Gonzalez M (2006) Cobalt-mediated activation of peroxymonosulfate and sulfate radical attack on phenolic compounds. Implications of chloride ions. Environ Sci Technol 40:1000–1007

    Article  CAS  Google Scholar 

  • Antoniou MG, De la Cruzb AA, Dionysiou DD (2010) Degradation of microcystin-LR using sulfate radicals generated through photolysis, thermolysis and e- transfer mechanisms. Appl Catal B Environ 96:290–298

    Article  CAS  Google Scholar 

  • Calamari D, Zuccato E, Castiglioni S, Bagnati R, Fanelli R (2003) Strategic survey of therapeutic drugs in the rivers Po and Lambro in Northern Italy. Environ Sci Technol 37:1241–1248

    Article  CAS  Google Scholar 

  • Calza P, Medana C, Carbone F (2008) Characterization of intermediate compounds formed upon photoinduced degradation of quinolones by high-performance liquid chromatography/high-resolution multiple-stage mass spectrometry. Rapid Commun Mass Spectrom 22:1533–1552

    Article  CAS  Google Scholar 

  • Chu DTW, Fernandes PB (1989) Structure-activity relationships of the fluoroquinolones. Antimicrob Agents Chemother 33:131–135

    Article  CAS  Google Scholar 

  • De Witte B, Dewulf J, Demeestere K, De Vyvere VV, De Wispelaere P, Van Langenhove H (2008) Ozonation of ciprofloxacin in water: HRMS identification of reaction products and pathways. Environ Sci Technol 42:4889–4895

    Article  Google Scholar 

  • De Witte B, Langenhove HV, Hemelsoet K, Demeestere K, De Wispelaere P, Speybroeck VV, Dewulf J (2009) Levofloxacin ozonation in water: rate determining process parameters and reaction pathway elucidation. Chemosphere 76:683–689

    Article  Google Scholar 

  • Goyne KW, Chorover J, Kubicki JD, Zimmerman AR, Brantley SL (2005) Sorption of the antibiotic ofloxacin to mesoporous and nonporous alumina and silica. J Colloid Interface Sci 283:160–170

    Article  CAS  Google Scholar 

  • Hapeshi E, Achilleos A, Vasquez MI, Michael C, Xekoukoulotakis NP, Mantzavinos D, Kassinos D (2010) Drugs degrading photocatalytically: kinetics and mechanisms of ofloxacin and atenolol removal on titania suspensions. Water Res 44:1737–1746

    Article  CAS  Google Scholar 

  • Hapeshi E, Fotiou I, Fatta-Kassinos D (2013) Sonophotocatalytic treatment of ofloxacin in secondary-treated effluent and elucidation of its transformation products. Chem Eng J 15:96–105

    Article  Google Scholar 

  • Hooper DC (2000) New uses for new and old quinolones and the challenge of resistance. Clin Infect Dis 30:243–245

    Article  CAS  Google Scholar 

  • Jørgensen SE, Halling-Sørensen B (2000) Drugs in the environment. Chemosphere 40:691–699

    Article  Google Scholar 

  • Karl W, Schneider J, Wetzstein HG (2006) Outlines of an “exploding” network of metabolites generated from the fluoroquinolone enrofloxacin by the brown rot fungus Gloeophyllum striatum. Appl Microbiol Biotechnol 71:101–113

    Article  CAS  Google Scholar 

  • Klamerth N, Rizzo L, Malato S, Maldonado MI, Agüera A, Fernández-Alba AR (2010) Degradation of 15 emerging contaminants at μg L−1 initial concentrations by mild solar photo-Fenton in MWTP effluents. Water Res 44:545–554

    Article  CAS  Google Scholar 

  • Kummerer K (2009) Antibiotics in the aquatic environment: A review—Part I. Chemosphere 75:417–434

    Article  Google Scholar 

  • Liang CJ, Su HW (2009) Identification of sulfate and hydroxyl radicals in thermally activated persulfate. Ind Eng Chem Res 48:5558–5562

    Article  CAS  Google Scholar 

  • Liang CL, Guo YY, Chien YC, Wu YJ (2010) Oxidative degradation of MTBE by pyrite-activated persulfate: proposed reaction pathways. Ind Eng Chem Res 49:8858–8864

    Article  CAS  Google Scholar 

  • Michael I, Hapeshi E, Michael C, Fatta-Kassinos D (2010) Solar Fenton and solar TiO2 catalytic treatment of ofloxacin in secondary-treated effluents: evaluation of operational and kinetic parameters. Water Res 44:5450–5462

    Article  CAS  Google Scholar 

  • Minisci F, Citterio A (1983) Electron-transfer processes: peroxydisulfate, a useful and versatile reagent in organic chemistry. Acc Chem Res 16:27–32

    Article  CAS  Google Scholar 

  • Nikolaou A, Meric S, Fatta D (2007) Occurrence patterns of pharmaceuticals in water and wastewater environments. Anal Bioanal Chem 387:1225–1234

    Article  CAS  Google Scholar 

  • Noel GJ (2009) A review of levofloxacin for the treatment of bacterial infections. Clin Med Ther 1:433–458

    CAS  Google Scholar 

  • Oliphant CM, Green GM (2002) Quinolones: a comprehensive review. Am Fam Physician 65:455–464

    Google Scholar 

  • Pérez M, Torrades F, Domènech X, Peral J (2002) Fenton and photo-Fenton oxidation of textile effluents. Water Res 36:2703–2710

    Article  Google Scholar 

  • Peyton GR (1993) The free-radical chemistry of persulfate-based total organic carbon analyzers. Mar Chem 41:91–103

    Article  CAS  Google Scholar 

  • Polacheka H, Holcbergb G, Sapirb G, Tsadkin-Tamira M, Polachekc J, Katzb M, Ben-Zvia Z (2005) Transfer of ciprofloxacin, ofloxacin, and levofloxacin across the perfused human placenta in vitro. Eur J Obstet Gynecol Reprod Biol 122:61–65

    Article  Google Scholar 

  • Radjenović J, Petrović M, Barceló D (2009) Fate and distribution of pharmaceuticals in wastewater and sewage sludge of the conventional activated sludge (CAS) and advanced membrane bioreactor (MBR) treatment. Water Res 43:831–841

    Article  Google Scholar 

  • Renew JE, Huang GH (2004) Simultaneous determination of fluoroquinolones, sulfonamide, and trimethoprim antibiotics in wastewater using tandem solid-phase extraction and liquid chromatography-electrospray mass spectrometry. J Chromatogr A 1042:113–121

    Article  CAS  Google Scholar 

  • Shen LL, Mitscher LA, Sharma PN, O’Donnell TJ, Chu DWT, Cooper CS, Rosen T, Pernett AG (1989) Mechanism of inhibition of DNA gyrase by quinolone antibacterials: a cooperative drug-DNA binding model. Biochemistry 28:3886–3894

    Article  CAS  Google Scholar 

  • Shinh YJ, Putra WN, Huang YH, Tsai JC (2012) Mineralization and deflourization of 2,2,3,3-tetrafluoro-1-propanol (TFP) by UV/persulfate oxidation and sequential adsorption. Chemosphere 89:1262–1266

    Article  Google Scholar 

  • Sun JH, Li XY, Feng JL, Tian XK (2009) Oxone/Co2+ oxidation as an advanced oxidation process: comparison with traditional Fenton oxidation for treatment of landfill leachate. Water Res 43:4363–4369

    Article  CAS  Google Scholar 

  • Sun JH, Song MK, Feng JL, Pi YQ (2012) Highly efficient degradation of Ofloxacin by UV/Oxone/Co2+ oxidation process. Environ Sci Pollut Res 19:536–1543

    Google Scholar 

  • Vasquez MI, Hapeshi E, Fatta-Kassinos D, Kümmerer K (2013) Biodegradation potential of ofloxacin and its resulting transformation products during photolytic and photocatalytic treatment. Environ Sci Pollut Res 20:1302–1309

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The research was supported by the Key Scientific and Technological Project of Henan province (grant no. 102102310244 and 102102310303), Basic and Cutting-Edge Technology Research Project of Henan province, People’s Republic of China (grant no. 102300410098), Innovation Scientists and Technicians Troop Construction Projects of Henan Province, Plan for Scientific Innovation Talent of Henan Province (grant no. 134200510014).

Author information

Author notes

  1. Jingyu Sun

    Present address: Center for Nanochemistry (CNC), College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, People’s Republic of China

Authors and Affiliations

  1. School of Environment, Key Laboratory for Yellow River and Huaihe River Water Environmental and Pollution Control, Ministry of Education, Henan Key Laboratory for Environmental Pollution Control, Henan Normal University, Xinxiang, 453007, People’s Republic of China

    Yunqing Pi, Jinglan Feng, Mengke Song & Jianhui Sun

  2. Department of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, UK

    Jingyu Sun

Authors
  1. Yunqing Pi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jinglan Feng
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jingyu Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mengke Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jianhui Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jianhui Sun.

Additional information

Responsible editor: Leif Kronberg

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOC 331 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Pi, Y., Feng, J., Sun, J. et al. Oxidation of ofloxacin by Oxone/Co2+: identification of reaction products and pathways. Environ Sci Pollut Res 21, 3031–3040 (2014). https://doi.org/10.1007/s11356-013-2220-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-013-2220-x

Keywords

Search

Navigation