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Possibilities and Limitations of Isocratic Fast Liquid Chromatography-Tandem Mass Spectrometry Analysis of Pesticide Residues in Fruits and Vegetables

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Abstract

Currently, state-of-the-art analytical methods for multiclass, multiresidue monitoring of pesticides in foods use ultrahigh performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) for analysis of LC-amenable analytes. UHPLC-MS/MS for > 100 pesticides typically takes 10 min per injection using gradient elution in the reversed-phase mode, plus typically 3–5 min for re-equilibration between injections. Isocratic mobile-phase conditions eliminate need for the re-equilibration, and can greatly speed analysis time. In this study, fast isocratic LC-MS/MS was evaluated using a C18 analytical column of 3 cm × 4.6 mm i.d. with 3 µm particles and a mobile phase consisting of 10 mM ammonium formate at pH 3 in 47.5/47.5/5 (v/v/v) acetonitrile/methanol/water. Flow rate was 0.4 mL/min and injection volume was 50 µL. Sample preparation entailed a formate-buffered QuEChERS method for fruit and vegetable samples, typically yielding extract of 1.27 g/mL sample equivalent in 94/6 acetonitrile/water without additional cleanup. The analysis time was 2.6 min covering 88 diverse pesticide analytes each with three ion transitions (dwell times of 5 ms and 5 ms interscan delays). Validation experiments involving fortification of water, pear, tomato, cucumber, eggplant, and cilantro at 10 and 100 ng/g (n = 10 for each matrix and level) showed that the method achieved acceptable quantification with 70–120% recoveries and ≤ 25% RSD for 32–62 (36–70%) of the analytes depending on the matrix. Using regulatory identification criteria, only 6 false positives occurred above 10 ng/g among 4400 analyte/matrix/sample combinations, but false negatives varied depending on the pesticide/matrix pair, with results improving significantly for analytes with retention times > 1.3 min. This study demonstrated the feasibility and limits of isocratic LC-MS/MS for rapid screening of common commodities monitored for pesticide residues.

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Acknowledgements

The author thanks Robyn Moten for technical assistance in the laboratory and Gary Strahan for NMR analysis of the extracts to determine water content.

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Mention of brand or firm names does not constitute an endorsement by the U.S. Department of Agriculture above others of a similar nature not mentioned.

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  1. US Department of Agriculture, Agricultural Research Service, Eastern Regional Research Center, 600 East Mermaid Lane, Wyndmoor, PA, 19038, USA

    Steven J. Lehotay

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Correspondence to Steven J. Lehotay.

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Published in Chromatographia’s 50th Anniversary Commemorative Issue.

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Lehotay, S.J. Possibilities and Limitations of Isocratic Fast Liquid Chromatography-Tandem Mass Spectrometry Analysis of Pesticide Residues in Fruits and Vegetables. Chromatographia 82, 235–250 (2019). https://doi.org/10.1007/s10337-018-3595-0

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  • DOI: https://doi.org/10.1007/s10337-018-3595-0

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