Influence of metal ions on glyphosate detection by FMOC-Cl
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Glyphosate (GLP, N-(phosphonomethyl)glycine) is the most important broadband herbicide in the world, but discussions are controversial regarding its environmental behaviour and distribution. Residue analyses in a variety of environmental samples are commonly conducted by HPLC–MS where GLP needs to be derivatised with 9-fluoromethoxycarnonyl chloride (FMOC-Cl). Since this derivatisation reaction was suspected to be inhibited by metal ions in the sample matrix, the present study provides a comprehensive experimental study of the effect of metal ions (Al3+, Ca2+, Cd2+, Co2+, Cu2+, Fe2+, Fe3+, Mg2+, Mn2+, Zn2+) on derivatisation and GLP recovery. Results show that some metals (Cd2+, Co2+, Cu2+, Mn2+ and Zn2+) decreased the GLP recovery down to 19 to 59%. Complementary, quantum chemical modelling of 1:1 GLP–metal complexes as well as their reactivity with respect to FMOC-Cl was performed. Here, a decrease in reactivity of FMOC-Cl towards GLP–metal complexes is observed; i.e. the reaction is non-spontaneous in contrast to the free GLP case. The present results are in accord with previous studies and provide an explanation that full GLP recovery in different matrices was never reached. Remedy strategies to compensate for the inhibition effect are explored such as pH adjustment to acidic or alkaline conditions or addition of ethylenediaminetetraacetic acid (EDTA). In general, our results question the use of internal isotopic labelled standards (ILS) since this presupposes the presence of the analyte and the ILS in the same (free) form.
KeywordsGlyphosate (GLP) FMOC-Cl Complex formation Derivatisation EDTA
The modelling part of this work has been performed within the InnoSoilPhos-project (http://www.innosoilphos.de/default.aspx), funded by the German Federal Ministry of Education and Research (BMBF) in the frame of the BonaRes-program (No. 031A558). Peter Gros acknowledges a PhDgrant from the state of Mecklenburg-Western Pommerania. This research was conducted within the scope of the Leibniz ScienceCampus Phosphorus Research Rostock.
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
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