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.
Letcher
Robert J
RJ
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
Chu
Shaogang
S
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