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Development of a sensitive direct injection LC-MS/MS method for the detection of glyphosate and aminomethylphosphonic acid (AMPA) in hard waters

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Abstract

Glyphosate is currently the most widely used herbicide in the world; however, the zwitterionic and highly polar properties of glyphosate make current pesticide analysis methods unsuitable for its trace analysis in natural waters. Additionally, current glyphosate analysis methods do not account for waters of varying hardness, which is vital as glyphosate can complex with cationic species such as Ca2+ and Mg2+ in the environment. We detail here a robust LC-MS/MS method for the quantitation of glyphosate and its primary transformation product aminomethylphosphonic acid (AMPA) in environmental waters of varying water hardness. Chromatographic separation was achieved with a reversed-phase and weak anion-exchange mixed-mode column. We found that the addition of EDTA into hard water samples increases the response of both glyphosate and AMPA in the mass spectrometer. Limits of detection of 0.23 and 0.30 μg L−1 for glyphosate and AMPA in EDTA-amended hard water were achieved, respectively. We have demonstrated that the accuracy of the method was consistent over a wide range of water hardness levels up to a maximum of ~340 mg mL−1 CaCO3 hardness. We validated the method using matrix fortification of uncontaminated environmental samples from US river water. We then demonstrated that the method was successful at quantifying glyphosate and AMPA across surface and drinking water samples of varying water hardness from North Carolina and Sri Lanka. Measured concentrations of glyphosate and AMPA ranged from 1.6 to 13 μg L−1 and 0.50 to 2.5 μg L−1, respectively. This study represents a significant increase in sensitivity for LC-MS/MS analysis of glyphosate in hard water systems.

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Funding support was provided from the National Institutes of Health through the Duke University Superfund Research Center (P42 ES010356) and the Duke Environmental Analysis Laboratory (U2C ES030851).

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  1. Department of Civil and Environmental Engineering, Duke University, 121 Hudson Hall, Box 90287, Durham, NC, 27708-0287, USA

    Jake C. Ulrich & P. Lee Ferguson

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Ulrich, J.C., Ferguson, P.L. Development of a sensitive direct injection LC-MS/MS method for the detection of glyphosate and aminomethylphosphonic acid (AMPA) in hard waters. Anal Bioanal Chem 413, 3763–3774 (2021). https://doi.org/10.1007/s00216-021-03324-5

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