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Determination of pharmaceuticals and antiseptics in water by solid-phase extraction and gas chromatography/mass spectrometry: analysis via pentafluorobenzylation and stable isotope dilution

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Abstract

A sensitive yet robust analytical method is presented for the simultaneous determination of 12 human pharmaceuticals (valproic acid, phenytoin, ibuprofen, gabapentin, acetaminophen, gemfibrozil, naproxen, ketoprofen, secobarbital, phenobarbital, 5-fluorouracil, and diclofenac) and 6 antiseptics (biosol, biphenylol, p-chloro-m-cresol, p-chloro-m-xylenol, chlorophene, and triclosan). The method employs solid-phase extraction (SPE) followed by a novel pentafluorobenzylation using a mixture of acetontrile/water (1/1, v/v). The method is simple to perform (derivatization can be completed in a single test tube) and eliminates the need for any solvent/SPE cartridge drying or blow-down. It affords excellent resolution, high sensitivity and reproducibility, and freedom from interference even for matrices as complex as untreated sewage. The method was applied to the analysis of sewage samples using 15 isotopically labeled surrogates, which resulted in the detection of 10 of the 12 pharmaceuticals and all of the antiseptics sought. Ten of 15 surrogates were synthesized from pure analytes by a simple H-D exchange reaction employing D2O and D2SO4. Measured recoveries were sensitive to matrix effects and varied substantially among analytes, indicative of the limitations associated with using a single surrogate standard.

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Acknowledgments

We thank Padma T. Venkatraman and Michael Blumenfeld for their initial work on pentafluorobenzylation. Funding for this research was provided by agreement number R82900401-0 from the US Environmental Protection Agency, Science to Achieve Results (STAR) program. Although the research described in the article has been funded wholly by the EPA’s STAR program, it has not been subjected to any EPA review and therefore does not necessarily reflect the views of the Agency, and no official endorsement should be inferred.

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Author notes

  1. Jim T. Yu

    Present address: Department of Environmental and Civil Engineering, Southern Methodist University, Dallas, TX, 75205, USA

  2. Kevin J. Bisceglia

    Present address: Chemistry Department, Bard High School Early College, New York, NY, 10002, USA

Authors and Affiliations

  1. Department of Geography and Environmental Engineering, Johns Hopkins University, Baltimore, MD, 21218-2686, USA

    Jim T. Yu, Kevin J. Bisceglia, Edward J. Bouwer & A. Lynn Roberts

  2. Research Center Weihenstephan for Brewing and Food Quality, Technische Universität München, 80333, München, Germany

    Mehmet Coelhan

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  1. Jim T. Yu
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  5. Mehmet Coelhan
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Correspondence to Mehmet Coelhan.

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Yu, J.T., Bisceglia, K.J., Bouwer, E.J. et al. Determination of pharmaceuticals and antiseptics in water by solid-phase extraction and gas chromatography/mass spectrometry: analysis via pentafluorobenzylation and stable isotope dilution. Anal Bioanal Chem 403, 583–591 (2012). https://doi.org/10.1007/s00216-012-5846-5

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  • DOI: https://doi.org/10.1007/s00216-012-5846-5

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