Identilication of the novel cycloaliphatic brominated flame retardant 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane in Canadian Arctic beluga (Delphinapterus leucas).
1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) is used primarily as an additive flame retardant. Technical grade TBECH consists of near equimolar amounts of two (of a possible four) diastereoisomers: rac-(1R,2R)-1,2-dibromo-(4S)-4-((1S)-1,2-dibromoethyl)cyclohexane ((alpha-TBECH) and rac-(1R,2R)-1,2-dibromo-(4S)-4-((1R)-1,2-dibromoethyl)cyclohexane (beta-TBECH). The two other possible isomers, gamma- and delta-TBECH, appear in the technical mixture when heated at temperatures above 120 degrees C. Careful selection of GC-capillary column length was critical in resolution of the two main diastereoisomers. Column lengths of 60 or 30 m (0.25 microm film thickness) resulted in incomplete separation of the alpha- and beta-isomers, while on a 10 m column, the isomers were baseline separated. The gamma- and delta-isomers could not be resolved on any column length in this study. Increased injector port temperature induced thermal conversion of the alpha- and beta-isomers to gamma- and delta-TBECH. Electron impact ionization (EI) was used to provide specificity because no characteristic ions in the electron capture negative ionization (ECNI) mass spectrum of TBECH were evident. In EI, the dominant ions in the mass spectrum corresponded to a concomitant loss of HBr and Br from the molecular ion; the biggest peak in this ion cluster (m/z 266.9208) was used for quantitation and the second biggest peak (m/z 264.9227) was used for confirmation. Beluga (Delphinapterus leucas) blubber extracts of animals from the Canadian Arctic (n=29) were analyzed using low resolution (LR) MS and high resolution (HR) MS run at a resolving power of 10,000. beta-TBECH was the only isomer observed in the samples and was detected in 17 samples. The LRMS technique appeared to overestimate beta-TBECH concentrations compared to HRMS, suggesting a small interference arose at the nominal mass monitored. This potential interference also led to some false positive and negative values (n=7) based on the expected ion ratio of the quantitation and confirmation ions. Observed concentrations of the beta-isomer as measured by HRMS ranged from 1.1 to 9.3 ng/g (lipid weight).
Tomy
Gregg T
GT
Department of Fisheries and Oceans, Arctic Aquatic Research Division, Winnipeg, MB, R3T 2N6 Canada. tomyg@dfo-mpo.gc.ca
Pleskach
Kerri
K
Arsenault
Gilles
G
Potter
Dave
D
McCrindle
Robert
R
Marvin
Chris H
CH
Sverko
Ed
E
Tittlemier
Sheryl
S
D000273:Adipose Tissue / Q000378:metabolism; D000818:Animals; D050643:Beluga Whale / Q000378:metabolism*; D003510:Cyclohexanes / Q000378:metabolism*; D004784:Environmental Monitoring; D005260:Female; D005411:Flame Retardants / Q000378:metabolism*; D008401:Gas Chromatography-Mass Spectrometry; D008297:Male; D014874:Water Pollutants, Chemical / Q000378:metabolism*
D003510:Cyclohexanes; D005411:Flame Retardants; D014874:Water Pollutants, Chemical; C517232:1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane