High-sensitivity method for determination of tetrabromobisphenol-S and tetrabromobisphenol-A derivative flame retardants in great lakes herring gull eggs by liquid chromatography-atmospheric pressure photoionization-tandem mass spectrometry.
Tetrabromobisphenol-A-bis(2,3-dibromopylether) (TBBP-A-dbpe), tetrabromobisphenol-A-bis(allyl ether) (TBBP-A-ae), and tetrabromobisphenol-S-bis(2,3-dibromopropyl ether) (TBBP-S-dbpe) are derivatives of tetrabromobisphenol-A (TBBP-A), and are all used as brominated flame retardants (BFRs). Using high-performance liquid chromatography-quadrupole-time-of-flight-mass spectrometry with atmospheric pressure photoionization (APPI) in the negative mode (LC-APPI(-)-Q-TOF-MS) and the novel use of pure acetone as dopant and LC mobile phase, full scan mass spectra showed that for these BFRs the dominant isotopic ion cluster was [M + O₂](-), and with other lesser abundant [M + O₂ - HBr](-), and [M - H](-) fragment ions. Subsequently, highly sensitive quantification of TBBP-A-dbpe, TBBP-A-ae, and TBBP-S-dbpe was accomplished via LC-triple quadrupole mass spectrometry with APPI(-) (LC-APPI(-)-MS/MS) via multiple ion monitoring based on the [M + O₂](-) > [Br](-) transition. Low to sub ng/g (wet weight (w.w.)) method limits of detection (LODs) were achieved, i.e., 0.07, 0.03, and 1.28 ng/g w.w. for TBBP-A-dbpe, TBBP-A-ae, and TBBP-S-dbpe, respectively. A variety of herring gull eggs were screened for these BFRs. The eggs were collected during 2008-2009 from several colony sites in the eastern Laurentian Great Lakes (Ontario) and in the St. Lawrence River (Québec). All egg samples had TBBP-S-dbpe concentrations below the LOD, and TBBP-A-ae and TBBP-A-dbpe were quantifiable in 67%-83% of the samples at concentrations up to 0.56 ng/g wet weight. Thus, TBBP-A-ae and TBBP-A-dbpe are present in herring gull eggs from these populations, bioaccumulate in the herring gull food chain, and are transferred from gull to egg.
Ecotoxicology and Wildlife Health Division, Wildlife and Landscape Science Directorate, Science and Technology Branch, Environment Canada, National Wildlife Research Centre, Carleton University, Ottawa, ON, K1A 0H3, Canada. robert.letcher@ec.gc.ca
Robert J
RJ
Letcher
Shaogang
S
Chu
D000818:Animals; D001969:Bromobenzenes / Q000737:chemistry / Q000378:metabolism*; D046091:Charadriiformes; D002853:Chromatography, Liquid; D004531:Eggs / Q000032:analysis*; D004784:Environmental Monitoring / Q000379:methods; D004785:Environmental Pollutants / Q000737:chemistry / Q000378:metabolism; D005411:Flame Retardants / Q000378:metabolism*; D006114:Great Lakes Region; D011075:Polybrominated Biphenyls / Q000737:chemistry / Q000378:metabolism*; D013450:Sulfones / Q000737:chemistry / Q000378:metabolism*; D053719:Tandem Mass Spectrometry
D001969:Bromobenzenes; D004785:Environmental Pollutants; D005411:Flame Retardants; D011075:Polybrominated Biphenyls; D013450:Sulfones; C555802:tetrabromobisphenol-S-bis(2,3-dibromopropyl ether); C020806:tetrabromobisphenol A