Tris(1,3-dichloropropyl) phosphate – Determination of bis(1,3-dichloropropyl) phosphate in urine by LC-APCI-ESI-MS/MS
Biomonitoring Method – Translation of the German version from 2024
Petra Krystek1 (Method development)Henry Beeltje1 (Method development)
Marc Machiel George Houtzager1 (Method development)
Eric Martin van den Hoeven1 (Method development)
Laura Kuhlmann2 (External verification)
Elisabeth Eckert2 (External verification)
Thomas Göen2 (Head of the working group “Analyses in Biological Materials” of the Permanent Senate Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area, Deutsche Forschungsgemeinschaft; External verification)
Andrea Hartwig3 (Chair of the Permanent Senate Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area, Deutsche Forschungsgemeinschaft)
MAK Commission4
1 TNO – Location Utrecht, Environmental Monitoring, Sensing and Analysis, P.O. Box 80015, NL-3508 TA Utrecht, The Netherlands
2 Friedrich-Alexander-Universität Erlangen-Nürnberg, Institute and Outpatient Clinic of Occupational, Social, and Environmental Medicine, Henkestraße 9–11, 91054 Erlangen, Germany
3 Institute of Applied Biosciences, Department of Food Chemistry and Toxicology, Karlsruhe Institute of Technology (KIT), Adenauerring 20a, Building 50.41, 76131 Karlsruhe, Germany
4 Permanent Senate Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area, Deutsche Forschungsgemeinschaft, Kennedyallee 40, 53175 Bonn, Germany
Abstract
The working group “Analyses in Biological Materials” of the German Senate Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area (MAK Commission) developed and verified this biomonitoring method for the determination of urinary concentrations of bis(1,3-dichloropropyl) phosphate (BDCPP), which is the major metabolite of tris(1,3-dichloropropyl) phosphate (TDCPP). TDCPP is one of the most commonly used organophosphate flame retardants in cars, residential furniture, and products containing polyurethane foam, and has been detected in dust from private houses, office buildings, and car interiors, suggesting that a majority of the general population is exposed to TDCPP. The aim of this work was to establish a reliable, selective, and sensitive method for the detection of BDCPP in urine. The urine samples are spiked with the internal standard d10-BDCPP and slightly acidified. Cleanup by mixed-mode anion-exchange solid-phase extraction is applied, and BDCPP is detected by liquid chromatography with simultaneous atmospheric pressure chemical ionisation and electrospray ionisation-tandem mass spectrometry. Calibration is carried out in ultra-pure water ∶ MeOH (4 ∶ 1, v/v). Good precision data with standard deviations below 7%, as well as good accuracy data with mean relative recoveries in the range of 93.6–101%, show that the method provides reliable and accurate analytical results. The method is both selective and sensitive, and the limit of quantitation of 0.2 ng BDCPP/l urine is sufficient to determine occupational exposure as well as higher background exposure levels to TDCPP in the general population.
