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A liquid chromatography-mass spectrometry method for the enantioselective multiresidue determination of nine chiral agrochemicals in urine using an enrichment procedure based on graphitized carbon black

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Abstract

Many agrochemicals are chiral molecules, and most of them are marketed as racemates or diastereomeric mixtures. Stereoisomers that are not the active enantiomer have little or no pesticidal activity and can exert serious toxic effects towards non-target organisms. Thus, investigating the possible exposure to different isomers of chiral pesticides is an urgent need. The present work was aimed at developing a new enantioselective high-performance liquid chromatography-mass spectrometry method for the simultaneous determination of nine chiral pesticides in urine. Two solid-phase extraction (SPE) procedures, based on different carbon-based sorbents (graphitized carbon black (GCB) and buckypaper (BP)), were developed and compared. By using GCB, all analytes were recovered with yields ranging from 60 to 97%, while BP allowed recoveries greater than 54% for all pesticides except those with acid characteristics. Baseline separation was achieved for the enantiomers of all target agrochemicals on a Lux Cellulose-2 column within 24 min under reversed-phase mode. The developed method was then validated according to the FDA guidelines for bioanalytical methods. Besides recovery, the other evaluated parameters were precision (7–15%), limits of detection (0.26–2.21 µg/L), lower limits of quantitation (0.43–3.68 µg/L), linear dynamic range, and sensitivity. Finally, the validated method was applied to verify the occurrence of the pesticide enantiomers in urine samples from occupationally exposed workers.

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Funding

This work was supported by INAIL (Istituto Nazionale per l’Assicurazione contro gli Infortuni sul Lavoro, i.e. the National Institute for Insurance against Accidents at Work) in the frame of its scientific research programs 2019–2022 [BRIC 2019 funding of the project “One Health model for studying a scenario of exposure to plant protection products: effects on human health and food quality”] and 2022–2026 [BRIC 2022 funding the project “Innovative analytical techniques and omic approach for the exposure analysis to pesticides] and by Sapienza University of Rome (Start-up research project protocol number AR1221814C70F4A4).

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Authors and Affiliations

  1. Department of Chemistry, Sapienza University, Rome, Italy

    Elena Lucci, Lorenzo Antonelli, Anita Scipioni, Paolo Lupattelli & Alessandra Gentili

  2. INAIL-DiMEILA, Chemical Risk Laboratory, Monte Porzio Catone Research Centre, Rome, Italy

    Monica Gherardi

  3. Department of Science and Technology for Humans and the Environment, University Campus Bio-Medico of Rome, Rome, Italy

    Chiara Fanali

  4. School in Nanoscience and Advanced Technologies, University of Verona, Verona, Italy

    Salvatore Fanali

  5. Institute of Physical and Analytical Chemistry, School of Exact and Natural Sciences, Tbilisi State University, Tbilisi, Georgia

    Bezhan Chankvetadze

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  1. Elena Lucci
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Correspondence to Alessandra Gentili.

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Source of biological material

Sixty-three urine samples were collected from occupationally exposed workers after their work shifts. The samples, collected in 50 mL centrifuge tubes, were stored at − 18 °C till their analysis. All participants provided informed consent, and both the study and the sampling protocol were approved by the Ethics Committee of the University of Rome “Università Campus Bio-Medico di Roma” (Prot. 83/20 OSS ComEt CBM).

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Lucci, E., Antonelli, L., Gherardi, M. et al. A liquid chromatography-mass spectrometry method for the enantioselective multiresidue determination of nine chiral agrochemicals in urine using an enrichment procedure based on graphitized carbon black. Anal Bioanal Chem 416, 1127–1137 (2024). https://doi.org/10.1007/s00216-023-05098-4

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