Tris(1,3-dichlorpropyl)phosphat – Bestimmung von Bis(1,3-dichlorpropyl)phosphat in Urin mittels LC-APCI-ESI-MS/MS
Biomonitoring-Methode
Petra Krystek1 (Methodenentwicklung)Henry Beeltje1 (Methodenentwicklung)
Marc Machiel George Houtzager1 (Methodenentwicklung)
Eric Martin van den Hoeven1 (Methodenentwicklung)
Laura Kuhlmann2 (Methodenprüfung)
Elisabeth Eckert2 (Methodenprüfung)
Thomas Göen2 (Leitung der Arbeitsgruppe „Analysen in biologischem Material“ der Ständigen Senatskommission zur Prüfung gesundheitsschädlicher Arbeitsstoffe, Deutsche Forschungsgemeinschaft; Methodenprüfung)
Andrea Hartwig3 (Vorsitz der Ständigen Senatskommission zur Prüfung gesundheitsschädlicher Arbeitsstoffe, Deutsche Forschungsgemeinschaft)
MAK Commission4
1 TNO – Location Utrecht, Environmental Monitoring, Sensing and Analysis, P.O. Box 80015, NL-3508 TA Utrecht, Niederlande
2 Friedrich-Alexander-Universität Erlangen-Nürnberg, Institut und Poliklinik für Arbeits-, Sozial- und Umweltmedizin, Henkestraße 9–11, 91054 Erlangen, Deutschland
3 Institut für Angewandte Biowissenschaften, Abteilung Lebensmittelchemie und Toxikologie, Karlsruher Institut für Technologie (KIT), Adenauerring 20a, Geb. 50.41, 76131 Karlsruhe, Deutschland
4 Ständige Senatskommission zur Prüfung gesundheitsschädlicher Arbeitsstoffe, Deutsche Forschungsgemeinschaft, Kennedyallee 40, 53175 Bonn, Deutschland
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.
