title: Validation of a novel and rapid method for the simultaneous determination of some phenolic organohalogens in human serum by GC-MS.
abstract: Over the last decades, more and more studies focused on the impact of endocrine disruptors on the environment and human health. Among them, phenolic organohalogens (POHs) are a particular concern because of their structural resemblance with natural hormones. There are different methods that are known to quantify these compounds in human serum, however, the current extraction techniques are long, fastidious and using harmfull chemicals such as diazomethane and sulfuric acid. Consequently, we developed an alternative, sensitive and faster method to simultaneously quantify pentachlorophenol (PCP), tetrabromobisphenol A (TBBPA), 4 bromophenols, 7 hydroxypolychlorinated biphenyls (OH-PCBs) and 3 hydroxy-polybrominated diphenyl ether (OH-PBDEs) in human serum sample. The clean-up and the enrichment of the sample were performed in a single extraction step using strong anion-exchange solid phase cartridge. After a rapid liquid-liquid extraction step to remove acidic traces, the extract was derivatized using trimethylsilyldiazomethane (TMSD) and finally analyzed by a gas-chromatograph coupled with an electron negative capture chemical ionization source combined with a triple quadrupole mass spectrometer (GC-ENCI-MS) operating in single ion monitoring. The whole procedure was validated according to the total error approach. The inter and intra assay precision were demonstrated to be lower than 20% and the relative bias to be lower than 15% in the dosing range of concentrations. The limit of quantification (LOQ) ranged from 2pgmL-1and 5pgmL-1, except for the PCP (44.6pgmL-1) and for the 2,4,6-tribromophenol (49.6pgmL-1). Finally, the method was successfully applied to measure the POH background contamination in serum samples collected from 20 Belgian blood donors recruited in CHU Mont-Godinne (Namur, Belgium) aged between 21 and 69 years old.
authors.affiliation: Laboratory of Clinical, Forensic and Environmental Toxicology, University of Liege (ULg), CHU (B35), 4000 Liege, Belgium; Center for Interdisciplinary Research on Medicines (C.I.R.M.), University of Liege (ULg), CHU (B35), 4000 Liege, Belgium. Electronic address: pdufour@ulg.ac.be.
authors.forename: Patrice
authors.initials: P
authors.lastname: Dufour
authors.affiliation: Laboratory of Clinical, Forensic and Environmental Toxicology, University of Liege (ULg), CHU (B35), 4000 Liege, Belgium; Center for Interdisciplinary Research on Medicines (C.I.R.M.), University of Liege (ULg), CHU (B35), 4000 Liege, Belgium.
authors.forename: Catherine
authors.initials: C
authors.lastname: Pirard
authors.affiliation: Laboratory of Clinical, Forensic and Environmental Toxicology, University of Liege (ULg), CHU (B35), 4000 Liege, Belgium; Center for Interdisciplinary Research on Medicines (C.I.R.M.), University of Liege (ULg), CHU (B35), 4000 Liege, Belgium.
authors.forename: Corinne
authors.initials: C
authors.lastname: Charlier
mesh_terms: D003978:Diazomethane / Q000031:analogs & derivatives / Q000737:chemistry; D052244:Endocrine Disruptors / Q000097:blood*; D004785:Environmental Pollutants / Q000097:blood; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D055768:Halogenated Diphenyl Ethers / Q000097:blood*; D006801:Humans; D057230:Limit of Detection; D010416:Pentachlorophenol / Q000097:blood*; D010636:Phenols / Q000097:blood*; D011075:Polybrominated Biphenyls / Q000097:blood*; D011078:Polychlorinated Biphenyls / Q000097:blood*; D052616:Solid Phase Extraction / Q000379:methods; D014297:Trimethylsilyl Compounds / Q000737:chemistry
chemical_list: D052244:Endocrine Disruptors; D004785:Environmental Pollutants; D055768:Halogenated Diphenyl Ethers; D010636:Phenols; D011075:Polybrominated Biphenyls; D014297:Trimethylsilyl Compounds; D003978:Diazomethane; D010416:Pentachlorophenol; D011078:Polychlorinated Biphenyls; C020806:tetrabromobisphenol A; C032037:4-bromophenol; C060070:trimethylsilyldiazomethane
keywords: GC-ENCI-MS; Phenolic organohalogens; Serum; Trimethylsilyldiazomethane