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. 2019 Aug;411(20):5013-5021. doi: 10.1007/s00216-019-01925-9. Epub 2019 Jun 20.

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. Graphical abstract.

Keywords: 3-Phenoxybenzoic acid; 6-Chloronicotinic acid; Cohorts; Exposure; Metabolites; Neonicotinoids; Pesticides; Pyrethroids.

MeSH terms

  • Biomarkers / urine
  • Cohort Studies
  • Environmental Exposure*
  • Environmental Monitoring / methods
  • Gas Chromatography-Mass Spectrometry / methods*
  • Humans
  • Limit of Detection
  • Neonicotinoids / standards
  • Neonicotinoids / urine*
  • Pesticides / standards
  • Pesticides / urine*
  • Pyrethrins / standards
  • Pyrethrins / urine*
  • Reference Standards

Substances

  • Biomarkers
  • Neonicotinoids
  • Pesticides
  • Pyrethrins