Development of a UHPLC-MS/MS method to enhance the detection of Glyphosate, AMPA and Glufosinate at sub-microgram / L levels in water samples

Glyphosate is the best-selling herbicide worldwide. The toxicity on ecosystems and the possible effects on human health have long been at the centre of a complex controversy concerning the authorisation for its use. The peculiar chemical-physical properties of glyphosate, AMPA and glufosinate make their determi-nation at trace levels in the water a real analytical challenge. All three compounds can be derivatised to less polar ones and FMOC-Cl (9-fluorenylmethyl chloroformate) is the most common pre-column derivati-sation reagent used for this analysis. It can be successfully combined with Ultra-High-Performance Liquid Chromatography with Mass Spectrometry (UHPLC-MS/MS) to determine all three analytes in one method as part of water monitoring programs. The developed method aims to determine glyphosate with AMPA and glufosinate at sub-micrograms/L levels in groundwater, surface and water by UHPLC-MS/MS after derivatisation with FMOC-Cl. The novelty of this method is its high simplicity, robustness and sensitivity allowing the identification and quantification of the compounds at the detection limits required by the European regulations (0.1 mu g /L). No pre-concentration or purification steps (by using Solid Phase Extrac-tion cartridges) are necessary for our method saving time and consumables costs. The method demon-strated an excellent linear relationship (R 2 >= 0.999) in the concentration range from 0.025 to 10 mu g /L for glyphosate and AMPA and 0.025 to 5 mu g /L for glufosinate. The method Limit Of Quantification (LOQ) is 0.025 mu g/L, the lowest among all previously published studies, and it was demonstrated according to the European SANTE guidelines.(c) 2022 The Author(s). Published by Elsevier B.V.This is an open access article under the CC BY-NC-ND license ( http://creativecommons.org/licenses/by-nc-nd/4.0/ )

Automated summary

This study developed a simple, robust, and sensitive method for the determination of glyphosate, AMPA, and glufosinate in groundwater, surface water, and water using UHPLC-MS/MS as part of water monitoring programs. The method achieved the detection limits required by European regulations and demonstrated excellent linearity and low quantification limits.