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Cohort-friendly protocol for the determination of two urinary biomarkers of exposure to pyrethroids and neonicotinoids using gas chromatography-triple quadrupole mass spectrometry

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Abstract

Neonicotinoids (NEOs) and synthetic pyrethroids (PYRs) are active ingredients of commercial pesticides and/or insecticides with extensive indoor and outdoor applications, worldwide. Improved exposure metrics are warranted for NEOs and PYRs, if we are to better understand their human health effects. A cohort-friendly protocol for determining non-specific biomarkers of exposure to NEOs and PYRs, e.g. 6-chloronicotinic acid (6-CN) and 3-phenoxybenzoic acid (3-PBA), respectively, in human urine voids was proposed. A series of optimization experiments were conducted to validate the bioanalytical protocol using gas chromatography coupled with triple quadrupole mass spectrometry (GC-QqQ-MS/MS) in MRM mode. The method reached low detection limits for both analytes (0.075 μg L−1 for 6-CN and 0.050 μg L−1 for 3-PBA) in a short preparation and analysis time. The method used small initial urine sample volume (2 mL), short extraction time (≈ 240 min for the batches of 32 samples) and instrumental analysis time (≈ 14 min) for both pesticide metabolites in a single run. This protocol could facilitate the assessment of population exposure metrics for these pesticides and their inclusion in health risk assessment.

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Fig. 1
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Fig. 3

Abbreviations

2-PBA:

2-Phenoxybenzoic acid

3-PBA:

3-Phenoxybenzoic acid

6-CN:

6-Chloronicotinic acid

FMU:

First morning void urine

GC-QqQ-MS/MS:

Gas chromatography coupled with triple quadrupole mass spectrometry

MRM:

Multi-reaction monitoring

NEOs:

Neonicotinoids

PYRs:

Pyrethroids

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Acknowledgements

The authors wish to thank the European Commission and the LIFE+ programme for funding the ORGANIKO LIFE+ project awarded to KC Makris. We thank Dr. Kalliopi Fotopoulou for preparing Fig. 1

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Authors and Affiliations

  1. Cyprus International Institute for Environmental and Public Health, Water and Health Laboratory, Cyprus University of Technology, Irenes 95, 3041, Limassol, Cyprus

    Pantelis Charisiadis, Thibaut Delplancke & Konstantinos C. Makris

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  1. Pantelis Charisiadis
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  2. Thibaut Delplancke
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Correspondence to Konstantinos C. Makris.

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It has been conducted following strict bioethics guidelines and it was approved by the Cyprus National Bioethics Committee (ΕΕΒΚ/ΕΠ/2016/25).

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Charisiadis, P., Delplancke, T. & Makris, K.C. Cohort-friendly protocol for the determination of two urinary biomarkers of exposure to pyrethroids and neonicotinoids using gas chromatography-triple quadrupole mass spectrometry. Anal Bioanal Chem 411, 5013–5021 (2019). https://doi.org/10.1007/s00216-019-01925-9

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