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

• Published in: Analytical and bioanalytical chemistry Vol. 401; no. 7; pp. 2123 - 2132
• Main Authors: Cooper, E. M., Covaci, A., van Nuijs, A. L. N., Webster, T. F., Stapleton, H. M.
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer-Verlag 01.10.2011; Springer
• Subjects: Adult; Analytical Chemistry; Applied sciences; Biochemistry; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Chromatographic methods and physical methods associated with chromatography; Chromatography, Liquid; Exact sciences and technology; Flame retardants; Flame Retardants - analysis; Flame Retardants - metabolism; Food Science; Global environmental pollution; Health; Human; Humans; Laboratory Medicine; Mass spectrometry; Metabolites; Monitoring/Environmental Analysis; Organophosphorus Compounds - urine; Original Paper; Other chromatographic methods; Phosphates; Pollution; Spectrometric and optical methods; Tandem Mass Spectrometry; Urine; Urine; Flame retardant; Method; Metabolite; Phosphates; Solid phase extraction; Atmospheric pressure; Internal standard; Biological marker; Product; Chemical enrichment; Anion exchange; Sample preparation; Detection limit; Adult; Monitoring; Human; Sample; Use; Ultratrace compound; Liquid chromatography; Exposure; Concentration; Chemical ionization; Mass spectrometry MS/MS; Environment; Small sample
• ISSN: 1618-2642; 1618-2650
• DOI: 10.1007/s00216-011-5294-7

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