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Improved detection of multiple environmental antibiotics through an optimized sample extraction strategy in liquid chromatography-mass spectrometry analysis

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Abstract

A solid-phase extraction/liquid chromatography/electrospray ionization/multi-stage mass spectrometry (SPE-LC-ESI-MS/MS) method was optimized in this study for sensitive and simultaneous detection of multiple antibiotics in urban surface waters and soils. Among the seven classes of tested antibiotics, extraction efficiencies of macrolides, lincosamide, chloramphenicol, and polyether antibiotics were significantly improved under optimized sample extraction pH. Instead of only using acidic extraction in many existing studies, the results indicated that antibiotics with low pK a values (<7) were extracted more efficiently under acidic conditions and antibiotics with high pK a values (>7) were extracted more efficiently under neutral conditions. The effects of pH were more obvious on polar compounds than those on non-polar compounds. Optimization of extraction pH resulted in significantly improved sample recovery and better detection limits. Compared with reported values in the literature, the average reduction of minimal detection limits obtained in this study was 87.6 % in surface waters (0.06–2.28 ng/L) and 67.1 % in soils (0.01–18.16 ng/g dry wt). This method was subsequently applied to detect antibiotics in environmental samples in a heavily populated urban city, and macrolides, sulfonamides, and lincomycin were frequently detected. Antibiotics with highest detected concentrations were sulfamethazine (82.5 ng/L) in surface waters and erythromycin (6.6 ng/g dry wt) in soils. The optimized sample extraction strategy can be used to improve the detection of a variety of antibiotics in environmental surface waters and soils.

The flowchart illustrating the optimized SPE-LC-ESI-MS/MS method

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Acknowledgments

This work is supported by the Singapore National Research Foundation under its Environment and Water Technologies Strategic Research Programme and administered by the Environment and Water Industry Programme Office (EWI) of the PUB on project 1102-IRIS-12-02. This study is also financially supported by Singapore Ministry of Education research grant (R-302-000-051-133), Singapore-Peking-Oxford Research Enterprise (COY-15-EWI-RCFSA/N197-1), and Purdue University. We thank Singapore Public Utilities Board (PUB) and National Parks Board (NParks) for their kind help on sampling and the National University of Singapore Environmental Research Institute (NERI) and the NERI-Agilent Research Alliance for their technical support.

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Authors and Affiliations

  1. Department of Civil and Environmental Engineering, National University of Singapore, Singapore, 117411, Singapore

    Xinzhu Yi & Barry C. Kelly

  2. Department of Food Science and Agricultural Chemistry, McGill University, Ste-Anne-de-Bellevue, Quebec, H9X 3V9, Canada

    Stéphane Bayen

  3. Department of Civil Engineering, University of Nebraska-Lincoln, Lincoln, NE, 68588-6105, USA

    Xu Li

  4. School of Civil Engineering and Division of Environmental and Ecological Engineering, Purdue University, 550 Stadium Mall Drive, West Lafayette, IN, 47907, USA

    Zhi Zhou

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  1. Xinzhu Yi
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Yi, X., Bayen, S., Kelly, B.C. et al. Improved detection of multiple environmental antibiotics through an optimized sample extraction strategy in liquid chromatography-mass spectrometry analysis. Anal Bioanal Chem 407, 9071–9083 (2015). https://doi.org/10.1007/s00216-015-9074-7

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