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Analysis of the flame retardant metabolites bis(1,3-dichloro-2-propyl) phosphate (BDCPP) and diphenyl phosphate (DPP) in urine using liquid chromatography–tandem mass spectrometry

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Abstract

Organophosphate triesters tris(1,3-dichloro-2-propyl) phosphate (TDCPP) and triphenyl phosphate are widely used flame retardants (FRs) present in many products common to human environments, yet understanding of human exposure and health effects of these compounds is limited. Monitoring urinary metabolites as biomarkers of exposure can be a valuable aid for improving this understanding; however, no previously published method exists for the analysis of the primary TDCPP metabolite, bis(1,3-dichloro-2-propyl) phosphate (BDCPP), in human urine. Here, we present a method to extract the metabolites BDCPP and diphenyl phosphate (DPP) in human urine using mixed-mode anion exchange solid phase extraction and mass-labeled internal standards with analysis by atmospheric pressure chemical ionization liquid chromatography tandem mass spectrometry. The method detection limit was 8 pg mL−1 urine for BDCPP and 204 pg mL−1 for DPP. Recoveries of analytes spiked into urine ranged from 82 ± 10% to 91 ± 4% for BDCPP and from 72 ± 12% to 76 ± 8% for DPP. Analysis of a small number of urine samples (n = 9) randomly collected from non-occupationally exposed adults revealed the presence of both BDCPP and DPP in all samples. Non-normalized urinary concentrations ranged from 46–1,662 pg BDCPP mL−1 to 287–7,443 pg DPP mL−1, with geometric means of 147 pg BDCPP mL−1 and 1,074 pg DPP mL−1. Levels of DPP were higher than those of BDCPP in 89% of samples. The presented method is simple and sufficiently sensitive to detect these FR metabolites in humans and may be applied to future studies to increase our understanding of exposure to and potential health effects from FRs.

The flame retardant TDCPP is metabolized to BDCPP and detected in human urine.

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Acknowledgments

The authors thank Alex Konstantinov and Wellington Labs, Inc. for synthesis and donation of BDCPP, and Dr. Vladimir N. Belov at Max Planck Institute for Biophysical Chemistry, Göttingen, Germany, for synthesis of d10-BDCPP and d10-DPP. The authors also acknowledge funding support from NIEHS (grants RO1ES016099 and RO1ES015829). Alexander van Nuijs and Adrian Covaci are financially supported by Ph.D. and postdoctoral fellowships, respectively, from the Research Scientific Foundation-Flanders (FWO).

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Authors and Affiliations

  1. Nicholas School of the Environment, Duke University, Durham, NC, 27708, USA

    E. M. Cooper & H. M. Stapleton

  2. Toxicological Center, University of Antwerp, 2610, Wilrijk, Belgium

    A. Covaci & A. L. N. van Nuijs

  3. School of Public Health, Boston University, Boston, MA, 02118, USA

    T. F. Webster

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  1. E. M. Cooper
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  2. A. Covaci
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  3. A. L. N. van Nuijs
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  4. T. F. Webster
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  5. H. M. Stapleton
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Correspondence to H. M. Stapleton.

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Cooper, E.M., Covaci, A., van Nuijs, A.L.N. et al. Analysis of the flame retardant metabolites bis(1,3-dichloro-2-propyl) phosphate (BDCPP) and diphenyl phosphate (DPP) in urine using liquid chromatography–tandem mass spectrometry. Anal Bioanal Chem 401, 2123–2132 (2011). https://doi.org/10.1007/s00216-011-5294-7

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  • DOI: https://doi.org/10.1007/s00216-011-5294-7

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