Analytical and Bioanalytical Chemistry

, Volume 410, Issue 6, pp 1749–1761 | Cite as

Metabolism of a sea lamprey pesticide by fish liver enzymes part A: identification and synthesis of TFM metabolites

  • Ugo Bussy
  • Yu-Wen Chung-Davidson
  • Tyler Buchinger
  • Ke Li
  • Scott A. Smith
  • A. Daniel Jones
  • Weiming Li
Research Paper

Abstract

The sea lamprey (Petromyzon marinus) is a destructive invasive species in the Great Lakes that contributed to the collapse of native fish populations in the mid-1900s. 3-Trifluoromethyl-4-nitrophenol (TFM) is a selective pesticide that has been applied to sea lamprey infested tributaries of the Great Lakes to kill larvae since the 1960s and has reduced the populations by as much as 90%. However, the metabolism of TFM by sea lamprey and non-target species is not fully illuminated. Elucidation of TFM metabolism is critical for understanding its mode of action and possible environmental impact. Here, we describe the screening, identification, synthesis and structural characterization of TFM metabolites in livers from sea lamprey and three non-target species that differ in their ability to survive TFM exposure. We identified glucuronidation, sulfation, N-acetylation, glutathione conjugation, and aromatic nitro group reduction as potential detoxification mechanisms. Seven metabolites were synthesized for use as markers of TFM metabolism in fish. Quantitative 1H NMR was used to assay synthesized metabolite stock solutions that were then used as standard material to develop a quantitative LC-MS/MS method for TFM metabolites.

Keywords

TFM Nitroreduction Pesticide Biomarker synthesis Quantitative analysis LC-MS 

Notes

Acknowledgements

This research was supported by the Great Lakes Fishery Commission. The authors thank Dr. Daniel Holmes from Michigan State University NMR core facility for his technical support. The authors also thank Andrew Paul Buchinger and Professor Kim Scribner for the gifts of fresh blue gill liver and fresh lake sturgeon liver. A.D.J. was supported by the USDA National Institute of Food and Agriculture and Hatch project MICL-02143.

Compliance with ethical standards

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”.

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

216_2017_830_MOESM1_ESM.pdf (37 kb)
ESM 1 (PDF 29 kb)

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2017

Authors and Affiliations

  • Ugo Bussy
    • 1
  • Yu-Wen Chung-Davidson
    • 1
  • Tyler Buchinger
    • 1
  • Ke Li
    • 1
  • Scott A. Smith
    • 2
  • A. Daniel Jones
    • 2
    • 3
    • 4
  • Weiming Li
    • 1
    • 5
  1. 1.Department of Fisheries and WildlifeMichigan State UniversityEast LansingUSA
  2. 2.RTSF Mass Spectrometry and Metabolomics CoreMichigan State UniversityEast LansingUSA
  3. 3.Department of Biochemistry and Molecular BiologyMichigan State UniversityEast LansingUSA
  4. 4.Department of ChemistryMichigan State UniversityEast LansingUSA
  5. 5.Department of PhysiologyMichigan State UniversityEast LansingUSA

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