1. Publishing
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    3. Overview
    4. MAK Collection
    5. The MAK Collection for Occupational Health and Safety
    6. Article
    7. Volume 8 (2023)
    8. Issue 2
    9. Glyphosat – Bestimmung von Glyphosat und AMPA in Urin mittels GC-MS/MS
Cover: The MAK Collection for Occupational Health and Safety

The MAK Collection for Occupational Health and Safety

German Research Foundation – Permanent Senate Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area
(MAK Commission)

ISSN 2509-2383



Glyphosat – Bestimmung von Glyphosat und AMPA in Urin mittels GC-MS/MS

Biomonitoring-Methode

Hans-Wolfgang Hoppe1 (Methodenentwicklung)
Ute Fest1 (Methodenentwicklung)
Elisabeth Eckert2 (Methodenprüfung)
Johannes Müller2 (Methodenprüfung)
  Thomas Göen2 (Leitung der Arbeitsgruppe „Analysen in biologischem Material“ der Ständigen Senatskommission zur Prüfung gesundheitsschädlicher Arbeitsstoffe, Deutsche ForschungsgemeinschaftMethodenprüfung; )
  Andrea Hartwig3 (Vorsitz der Ständigen Senatskommission zur Prüfung gesundheitsschädlicher Arbeitsstoffe, Deutsche Forschungsgemeinschaft)
  MAK Commission4

1 MVZ Medizinisches Labor Bremen GmbH, Haferwende 12, 28357 Bremen, Deutschland
2 Friedrich-Alexander-Universität Erlangen-Nürnberg, Institut und Poliklinik für Arbeits-, Sozial- und Umweltmedizin, Henkestraße 9–11, 91054 Erlangen, Deutschland
3 Institut für Angewandte Biowissenschaften, Abteilung Lebensmittelchemie und Toxikologie, Karlsruher Institut für Technologie (KIT), Adenauerring 20a, Geb. 50.41, 76131 Karlsruhe, Deutschland
4 Ständige Senatskommission zur Prüfung gesundheitsschädlicher Arbeitsstoffe, Deutsche Forschungsgemeinschaft, Kennedyallee 40, 53175 Bonn, Deutschland

Abstract

The working group “Analyses in Biological Materials” of the Permanent Senate Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area developed and verified the presented biomonitoring method. Glyphosate (N‑phosphonomethylglycine) is a synthetic phosphonic acid derivative which has been used as a broad-spectrum herbicide since 1974. Its only known metabolite is aminomethylphosphonic acid (AMPA). Exposure in occupational settings is predominantly due to inhalation and dermal contact with glyphosate. The general population is exposed to glyphosate and AMPA via both dietary (plant and animal products) and environmental (soils, surface water, and groundwater) exposure.

The aim of this work was to develop a selective method for the determination of glyphosate and AMPA in urine. The method has been comprehensively validated, and the reliability data have been confirmed by replication and verification of the procedure in a second, independent laboratory. The analytes are directly derivatised in the dried urine sample with trifluoroacetic anhydride and trifluoroethanol without an initial extraction step. Calibration is performed using aqueous calibration standards processed analogously to the samples. As internal standards, glyphosate‑d2 and 13C,15N‑AMPA are added to the urine samples and calibration standards. The derivatives are measured after capillary gas-chromatographic separation with tandem mass-spectrometric detection (GC‑MS/MS) using negative chemical ionisation (NCI).

The good precision and accuracy data show that the method provides reliable and accurate analytical results. The method is both selective and sensitive, and the quantitation limit of 0.1 μg/l urine for glyphosate and AMPA is sufficient to determine occupational exposure as well as higher background levels in the general population.

Keywords

glyphosate, AMPA, biomonitoring, urine, GC-MS/MS