Determination of glyphosate, glufosinate and their major metabolites in urine by the UPLC-MS/MS method applicable to biomonitoring and epidemiological studies

Abstract

The preoccupation concerning glyphosate (GLYP) has rapidly grown over recent years, and the availability of genetically modified crops that are resistant to GLYP or glufosinate (GLUF) has increased the use of these herbicides. The debate surrounding the carcinogenicity of GLYP has raised interest and the desire to gain information on the level of exposure of the population. GLYP and aminomethylphosphonic acid (AMPA) are commonly simultaneously analysed. GLUF is sometimes also monitored, but its major metabolite, 3-[hydroxy(methyl)phosphinoyl]propionic acid (3MPPA), is rarely present in the method. Using a pentafluorobenzyl derivative to extract the analytes from human urine, we present a method that contains four important analytes to monitor human exposure to GLYP and GLUF. The use of the flash freeze technique speeds up the extraction process and requires less organic solvent than conventional liquid-liquid extraction. The limits of detection in the low μg/L range enable the use of this method for epidemiological studies. The results obtained for 35 volunteers from the Quebec City area are presented with the results from multiple interlaboratory comparisons (G-EQUAS, HBM4EU and OSEQAS). This methodology is currently being used in the Maternal-Infant Research on Environmental Chemicals (MIREC-ENDO) study and in the Canadian Health Measures Survey (CHMS).

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Acknowledgements

The authors wish to acknowledge the contributions of Anny-France Hudon, Claudine Roussy, Nathalie Morissette and Marie-Pier Ouellet, who collaborated with us to develop and improve this analytical method.

Funding

Financial support was provided by an internal budget dedicated to development and research.

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Correspondence to Jean-François Bienvenu.

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Ethics approval

This study involves the use of human urine samples collected from multiple volunteer donors, including laboratory staff and members of their family. According to the rules and regulations concerning ethical review in Québec, particularly those specified in the Civil Code (http://legisquebec.gouv.qc.ca/fr/ShowDoc/cs/CCQ-1991) and in subsequent IRB practice, appropriate regulation was followed for the current project because it was considered as evaluation and therefore, no IRB was required.

Consent to participate

We obtained the consent of all participants (or parental consent in case of minors) to use the urine samples for method development and validation, and they may also be used for research and publications. Participants were protected by the removal of any personal identifiers that may have linked the participant to the donation. The samples were coded to maintain the anonymity of the participants and disconnect the identity of each participant from the data generated from their urine sample. Furthermore, all the staff members of the CTQ are required to sign a confidentiality agreement upon hiring.

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Bienvenu, JF., Bélanger, P., Gaudreau, É. et al. Determination of glyphosate, glufosinate and their major metabolites in urine by the UPLC-MS/MS method applicable to biomonitoring and epidemiological studies. Anal Bioanal Chem (2021). https://doi.org/10.1007/s00216-021-03194-x

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Keywords

  • Glyphosate
  • Glufosinate
  • PFBBr
  • Urine
  • Flash freeze