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Metabolism of a sea lamprey pesticide by fish liver enzymes part B: method development and application in quantification of TFM metabolites formed in vivo

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Abstract

The sea lamprey (Petromyzon marinus) is a destructive invasive species in the Great Lakes. Since the 1960s, tons of the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) has been applied to selected tributaries each year to eliminate or reduce sea lamprey larval populations. Therefore, the environmental impact of TFM needs to be evaluated. However, the metabolism of TFM and its mechanism of selective toxicity in sea lamprey is not yet fully understood. Based upon our previous report on the identification, synthesis, and characterization of TFM metabolites observed in liver incubates from sea lamprey and non-target fishes, we now provide a robust assay for quantifying TFM and its metabolites in fish liver tissue. This method is important for assessing bioaccumulation of TFM in the ecosystems. The compounds purified in our previous report were used to develop and validate a quantitative ultra-high-performance liquid chromatography–tandem mass spectrometry (UHPLC-MS/MS) assay for TFM and TFM metabolites formed in vivo. Several sample preparation techniques were compared, and a protein precipitation method was selected. The unavailability of stable isotopic internal standards was overcome by using a matrix matching method. After a thorough validation, this method was applied to determine the concentrations of TFM and its metabolites in fish liver tissues from animals exposed to TFM, and in the comparison between dead animals and survivors. Seven of eight expected metabolites were observed, some for the first time in vivo. Our results indicate that in vivo nitroreduction, glucuronidation, sulfation, and glutathione conjugation are involved in TFM metabolism in sea lamprey.

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Acknowledgements

This research was supported by the Great Lakes Fishery Commission. A.D.J. was supported by the USDA National Institute of Food and Agriculture Hatch project MICL-02143. The authors also thank Andrew Paul Buchinger (local angler) and Professor Kim Scribner (MSU Dept. of Fisheries & Wildlife) for the gifts of fresh blue gill livers and fresh lake sturgeon livers, respectively.

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Authors and Affiliations

  1. Department of Fisheries and Wildlife, Michigan State University, 480 Wilson Rd., East Lansing, MI, 48824, USA

    Ugo Bussy, Yu-Wen Chung-Davidson, Tyler Buchinger, Ke Li & Weiming Li

  2. RTSF Mass Spectrometry and Metabolomics Core, Michigan State University, Biochemistry Building, 603 Wilson Rd., East Lansing, MI, 48824, USA

    Scott A. Smith & A. Daniel Jones

  3. Department of Biochemistry and Molecular Biology, Michigan State University, Biochemistry Building, 603 Wilson Rd., East Lansing, MI, 48824, USA

    A. Daniel Jones

  4. Department of Chemistry, Michigan State University, 578 S Shaw Lane, East Lansing, MI, 48824, USA

    A. Daniel Jones

  5. Department of Physiology, Michigan State University, 567 Wilson Rd., East Lansing, MI, 48824, USA

    Weiming Li

Authors
  1. Ugo Bussy
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  2. Yu-Wen Chung-Davidson
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  3. Tyler Buchinger
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  4. Ke Li
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  5. Scott A. Smith
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  6. A. Daniel Jones
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  7. Weiming Li
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Corresponding author

Correspondence to Weiming Li.

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We declare no conflict of interests. Animal tissues used in analyses were collected by staff of USGS Lake Huron Biological Station, Millersburg, MI 49759, USA. Experimental protocols involving the handling of fishes were carried out in accordance with United States federal guidelines for care and use of animals and were approved by the American Fisheries Society through the “Use of Fishes in Research Committee, 2014”.

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Bussy, U., Chung-Davidson, YW., Buchinger, T. et al. Metabolism of a sea lamprey pesticide by fish liver enzymes part B: method development and application in quantification of TFM metabolites formed in vivo. Anal Bioanal Chem 410, 1763–1774 (2018). https://doi.org/10.1007/s00216-017-0831-7

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  • DOI: https://doi.org/10.1007/s00216-017-0831-7

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