Identification of biotransformation products of macrolide and fluoroquinolone antimicrobials in membrane bioreactor treatment by ultrahigh-performance liquid chromatography/quadrupole time-of-flight mass spectrometry
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Ultrahigh-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry was applied for the identification of transformation products (TPs) of fluoroquinolone (norfloxacin and ciprofloxacin) and macrolide (azithromycin, erythromycin, and roxitromycin) antimicrobials in wastewater effluents from a Zenon hollow-fiber membrane bioreactor (MBR). The detected TPs were thoroughly characterized using the accurate mass feature for the determination of the tentative molecular formulae and MS-MS experiments for the structural elucidation of unknowns. Several novel TPs, which have not been previously reported in the literature, were identified. The TPs of azithromycin and roxithromycin, identified in MBR effluent, were conjugate compounds, which were formed by phosphorylation of desosamine moiety. Transformation of fluoroquinolones yielded two types of products: conjugates, formed by succinylation of the piperazine ring, and smaller metabolites, formed by an oxidative break-up of piperazine moiety to form the 7-[(2-carboxymethyl)amino] group. A semi-quantitative assessment of these TPs suggested that they might have contributed significantly to the overall balance of antimicrobial residues in MBR effluents and thus to the overall removal efficiency. Determination of TPs during a period of 2 months indicated a conspicuous dynamics, which warrants further research to identify microorganisms involved and treatment conditions leading to their formation.
KeywordsAntimicrobials Fluoroquinolone Macrolide Transformation products Membrane bioreactor Liquid chromatography–mass spectrometry
This work was financially supported by the Ministry of Science, Education and Sports of the Republic of Croatia through the project on organic contaminants as molecular markers of the anthropogenic impact on the environment (Project No: 098-0982934-2712). Technical assistance of Nenad Muhin is also gratefully acknowledged.
- 1.Kümmerer K (2008) Pharmaceuticals in the environment: sources, fate, effects and risks, 3 rdth edn. Springer, HeidelbergGoogle Scholar
- 13.Wetzstein HG, Stadler M, Tichy H-V, Dalhoff A, Karl W (1999) Appl Environ Microbiol 65:1556–1563Google Scholar
- 20.Senta I, Matosic M, Korajlija Jakopovic H, Terzic S, Mijatovic I, Ahel M (Submitted to J Hazard Mater) Removal of antimicrobials using advanced wastewater treatment.Google Scholar
- 21.Senta I (2009) Occurrence and behavior of sulfonamides, fluoroquinolones, macrolides and trimethoprim in wastewater and natural water, PhD thesis, Zagreb.Google Scholar
- 24.Zhang Y, Jiang H, Go EP, Desaire H (2006) J Am Mass Spectrom 17: 1282-.Google Scholar
- 29.Noguchi N, Emura A, Matsuyama H, O’Hara K, Sasatsu M, Kono M (1995) Antimicrobial Agents Chemother 39:2359–2363Google Scholar