title: Halogenated phenolic compound determination in plasma and serum by solid phase extraction, dansylation derivatization and liquid chromatography-positive electrospray ionization-tandem quadrupole mass spectrometry.
abstract: A robust, sensitive and accurate method was developed for the simultaneous determination in plasma and serum of suite a halogenated phenolic compounds (HPCs) for which several are known to persist in the environment and analytically pure standards are available. Namely, 14 congeners of hydroxylated polybrominated diphenyl ethers (OH-PBDEs), six congeners of hydroxylated polychlorinated biphenyls (OH-PCBs), pentachlorophenol, pentabromophenol and the flame retardant tetrabromobisphenol A (TBBPA). Solid phase extraction (SPE) enriched the target compounds and cleaned up the samples as a result of efficient adsorption on a strong anion-exchange solid phase SPE cartridge (Oasis MAX). After final clean-up the HPCs were derivatized with dansyl chloride and analyzed by liquid chromatography-tandem mass spectrometry with electrospray ionization in positive mode (ESI(+)). Chromatographic separation was achieved on a Luna PFP(2) column (2mm×100mm, 3μm particle size) with mobile phases of water and acetonitrile (both containing 0.1% formic acid). The addition of the dansyl moiety to the HPCs greatly improved analyte sensitivity as the electrospray ionization efficiency was enhanced. Instrument limits of detection (ILODs) for LC-ESI(+)-MS/MS analysis of the HPCs were in the range of 0.01-0.07ng/mL and the method limits of quantification (MLOQs) were in the range of 0.02-0.15ng/g. Recovery efficiencies of the suite of HPCs ranged from 64% to 118% with relative standard deviations from 2% to 12% from fortified bovine serum samples. The method was successfully applied for HPC determination in representative polar bear and snapping turtle plasma samples.
authors.affiliation: Ecotoxicology and Wildlife Health Division, Science and Technology Branch, Environment Canada, National Wildlife Research Centre, Carleton University, Ottawa, ON K1A 0H3, Canada.
authors.forename: Shaogang
authors.initials: S
authors.lastname: Chu
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Letcher
mesh_terms: D002853:Chromatography, Liquid / Q000379:methods*; D003619:Dansyl Compounds / Q000737:chemistry*; D006219:Halogens / Q000097:blood*; D057230:Limit of Detection; D010636:Phenols / Q000097:blood*; D011786:Quality Control; D015203:Reproducibility of Results; D052616:Solid Phase Extraction / Q000379:methods*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods*
chemical_list: D003619:Dansyl Compounds; D006219:Halogens; D010636:Phenols
keywords: Dansylation and SPE; Halogenated phenolic compounds; LC–ESI(+)–MS/MS; Plasma