title: Development of a liquid chromatography-electrospray chemical ionization tandem mass spectrometry analytical method for analysis of eleven hydroxylated polybrominated diphenyl ethers.
abstract: Recently, hydroxylated polybrominated diphenyl ethers (OH-PBDEs) have emerged as environmentally relevant pollutants due to recent reports of their natural production and metabolism. Recent mechanistic studies in human and rats have shown that some OH-PBDEs are more potent than parent compounds (PBDEs) and may contribute substantially to neurodevelopmental disorders by direct neurotoxicity, or indirectly through altered thyroid disruption. However, analytical methodologies for determination of OH-PBDEs are currently limited. In this study a robust liquid chromatography-electrospray tandem triple quadrupole-linear ion trap mass spectrometer (LC-ESI-QqLIT-MS-MS) in negative mode method was developed for the determination of eleven OH-tri- to OH-hexa-PBDEs. Two different columns were tested and compared for chromatographic separation: a C18 BetaBasic and a Purospher STAR RP 18, working at pH 8 and 10, respectively. Mobile phase (acetonitrile:water) was optimized by changing the pH of the aqueous phase and the concentration of the organic modifier (methanol). The MS-MS parameters (declustering potential (DP), collision energy (CE) and cell exit potential (CXP)) were optimized. Selected reaction monitoring (SRM) was used in order to increase sensitivity. Two SRM transitions ([M-H](-)>[Br](-)) were selected for each OH-PBDE, one for quantification and the second one for confirmation. Under the optimized conditions, the instrumental limits of detection were between 0.17 and 0.72injectedpg. The method provided good linearity (r>0.99 for a concentration range of 0.30-100ng/mL), accuracy and precision (%Dev and %RSD≤20% for intra- and inter-assays).
authors.affiliation: Water and Soil Quality Research Group, Department of Environmental Chemistry, IDAEA, CSIC, Jordi Girona 18-26, 08034 Barcelona, Spain.
authors.forename: Maria Luisa
authors.initials: ML
authors.lastname: Feo
authors.forename: Enrique
authors.initials: E
authors.lastname: Barón
authors.forename: Diana S
authors.initials: DS
authors.lastname: Aga
authors.forename: Ethel
authors.initials: E
authors.lastname: Eljarrat
authors.forename: Damià
authors.initials: D
authors.lastname: Barceló
mesh_terms: D000097:Acetonitriles / Q000737:chemistry; D001189:Aryl Hydrocarbon Hydroxylases / Q000378:metabolism; D002853:Chromatography, Liquid / Q000379:methods*; D065702:Cytochrome P-450 CYP2B6; D004785:Environmental Pollutants / Q000032:analysis*; D055768:Halogenated Diphenyl Ethers / Q000032:analysis* / Q000737:chemistry / Q000378:metabolism; D006801:Humans; D057230:Limit of Detection; D015203:Reproducibility of Results; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods
chemical_list: D000097:Acetonitriles; D004785:Environmental Pollutants; D055768:Halogenated Diphenyl Ethers; C511295:2,2',4,4'-tetrabromodiphenyl ether; D001189:Aryl Hydrocarbon Hydroxylases; C585599:CYP2B6 protein, human; D065702:Cytochrome P-450 CYP2B6; C032159:acetonitrile
keywords: Endocrine disruptor; Flame retardants; OH-PBDE; Polybrominated diphenyl ethers; Triple quadrupole-linear ion trap