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Quantification of DEET and neonicotinoid pesticide biomarkers in human urine by online solid-phase extraction high-performance liquid chromatography-tandem mass spectrometry

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Abstract

Neonicotinoid insecticides are widely used replacements for organophosphate and carbamate insecticides, but the extent of human exposure is largely unknown. On the other hand, based on urinary concentrations of DEET metabolites, human exposure to N,N-diethyl-m-toluamide (DEET) appears to be widespread. We developed a fast online solid-phase extraction high-performance liquid chromatography-isotope dilution tandem mass spectrometry (HPLC-MS/MS) method to measure in 200 μL of human urine the concentrations of six neonicotinoid biomarkers (acetamiprid, N-desmethyl-acetamiprid, clothianidin, imidacloprid, 5-hydroxy-imidacloprid, thiacloprid), and two DEET biomarkers (3-diethyl-carbamoyl benzoic acid, 3-ethyl-carbamoyl benzoic acid). Limits of detection ranged from 0.01 to 0.1 μg/L, depending on the biomarker. Accuracy ranged from 91 to 116% and precision ranged from 3.7 to 10 %RSD. The presented method can be used to increase our understanding of exposure to neonicotinoid insecticides and DEET, and to evaluate the potential health effects from such exposures.

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Acknowledgements

We thank Charlie Chambers for technical assistance and Dr. Peter Kuklenyik for the diagram in the supplemental information.

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Authors and Affiliations

  1. Division of Laboratory Sciences, National Center for Environmental Health, Centers for Disease Control and Prevention, 4770 Buford Hwy, MS F17, Atlanta, GA, 30341, USA

    Samuel E. Baker, Amanda Bishop Serafim, Pilar Morales-Agudelo, Meghan Vidal, Antonia M. Calafat & Maria Ospina

  2. Battelle Memorial Institute, 2987 Clairmont Rd, Suite 450, Atlanta, GA, 30329, USA

    Pilar Morales-Agudelo & Meghan Vidal

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  1. Samuel E. Baker
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  2. Amanda Bishop Serafim
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Correspondence to Maria Ospina.

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Baker, S.E., Serafim, A.B., Morales-Agudelo, P. et al. Quantification of DEET and neonicotinoid pesticide biomarkers in human urine by online solid-phase extraction high-performance liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem 411, 669–678 (2019). https://doi.org/10.1007/s00216-018-1481-0

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