Structure characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane

1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) is used primarily as an additive flame retardant. 1H NMR spectroscopy and an X-ray structure determination have revealed that a technical mixture consists largely of two (of the four possible) diastereomers, 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), in a mole ratio of approximately 1:1. The two other possible isomers, gamma- and delta-TBECH, were not detected in a technical mixture. The TBECH isomers are thermally sensitive and can easily interconvert at temperatures of 125 degrees C. A thermal equilibrium mixture of alpha-, beta-, gamma- and delta-TBECH consists of approximately 33%, 33%, 17% and 17% of these isomers, respectively. Separation of all four TBECH diastereomers, with minimal thermal interconversion of the isomers, was achieved by careful selection of GC-capillary column length and injector temperature. Although technical TBECH does not contain the gamma- and delta-isomers, they may still be relevant environmental contaminants since manufacturing processes utilize thermal processes which may induce their formation.     

Distribution and transportability of hexabromocyclododecane (HBCD) in the Asia-Pacific region using skipjack tuna as a bioindicator

The geographical distribution of hexabromocyclododecane (HBCD) was investigated through analysis of muscle tissue of skipjack tuna (Katsuwonus pelamis) collected from offshore waters of Asia-Pacific region (Japan, Taiwan, Philippines, Indonesia, Seychelles, Brazil, Japan Sea, East China Sea, South China Sea, Indian Ocean and North Pacific Ocean). HBCD was detected in almost all samples analyzed (<0.1 to 45 ng/g lipid weight basis), indicating widespread presence of this compound in the marine environment. Elevated concentrations of HBCD were found in skipjack tuna from areas around Japan, which have the larger modern industrial/urban societies, and implicated these areas as primary regional sources. All three individual HBCD isomers (alpha-, gamma- and beta-HBCD) were detected in almost all samples; the percentage contribution of the alpha-isomer to total HBCD increased with increasing latitude. The estimated empirical 1/2 distance for alpha-HBCD was 8500 km, which is one of the highest atmospheric transportability among various halogenated persistent organic pollutants (POPs).     

Structural characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2,5,6-tetrabromocyclooctane (TBCO)

1,2,5,6-Tetrabromocyclooctane (TBCO) is a commercial brominated flame retardant that is employed mainly as an additive in textiles, paints and plastics. Very little is known about its presence or behavior in the environment or its analysis. TBCO can exist as two diastereomers, the stereochemistries of which have not been previously reported. We have named the first eluting isomer, under HPLC conditions, as alpha-TBCO (α-TBCO) and the later eluting isomer as beta-TBCO (β-TBCO) when using an Acquity UPLC BEH C₁₈ column with methanol/acetonitrile/water as the mobile phase. The structural elucidation of these two isomers was accomplished by ¹H NMR spectroscopy, GC/MS, LC/MS and X-ray structure determinations. α-TBCO is (1R,2R,5S,6S)-1,2,5,6-tetrabromocyclooctane and β-TBCO is rac-(1R,2R,5R,6R)-1,2,5,6-tetrabromocyclooctane. As with some other brominated cycloaliphatic compounds, TBCO is thermally labile and the isomers easily interconvert. A thermal equilibrium mixture of α- and β-TBCO consists of approximately 15% and 85% of these isomers, respectively. Separation of the two diastereomers, with minimal thermal interconversion between them, is achievable by careful selection of GC-capillary column length and injector temperature. LC/MS analyses of TBCO also presents an analytical challenge due to poor resolution of the isomers on chromatographic stationary phases, and weak intensity of molecular ions (or major fragment ions) when using LC-ESI/MS. Only bromide ions were seen in the mass spectra. APCI and APPI also failed to produce the molecular ion with sufficient intensity for identification.     

Synthesis of the two minor isomers, delta- and epsilon-1,2,5,6,9,10-hexabromocyclododecane, present in commercial hexabromocyclododecane

Hexabromocyclododecane (HBCD) is prepared commercially by bromination of cis,trans,trans-cyclododecatriene (ctt-CDT) and widely used as a flame retardant, particularly in polystyrene foams. Commercial HBCD consists largely of three diastereomers, alpha-, beta-, and gamma-HBCD, the structures of which have been known for many years. Recently, the presence in the mixture of small amounts of two minor diastereomers, delta- and epsilon-HBCD, has been reported. Bearing in mind the manner in which commercial HBCD is generated, it was anticipated that these components are probably formed by bromination of trans,trans,trans-cyclododecatriene (ttt-CDT), a common contaminant in commercial ctt-CDT. Indeed, when a sample of ttt-CDT was brominated it gave two products, the NMR spectra and LC/MS and GC/MS behaviour of which confirmed that they are identical to the minor components, delta- and epsilon-HBCD, present in commercial HBCD.     

Distribution of hexabromocyclododecane in Detroit River suspended sediments

The distribution of hexabromocyclododecane (HBCD) isomers (alpha, beta and gamma) was determined in Detroit River suspended sediments using liquid chromatography tandem mass spectrometry (LC/MS/MS). Individual isomers of HBCD were measured at concentrations ranging from <0.025 to 1.9 ng/g (dry wt.) for the alpha-isomer, <0.025 to 0.28 ng/g for the beta-isomer, and <0.025 to 2.3 ng/g for the gamma-isomer. Concentrations of total HBCD ranged from <0.075 to 3.7 ng/g. Roughly two-thirds of HBCD profiles in suspended sediments were dominated by the gamma-isomer, and were similar to profiles of commercial technical mixtures. Profiles in the remaining samples were dominated by the alpha-isomer. The beta-isomer was consistently detected at substantially lower levels than the other isomers; this isomer is a minor constituent in the commercial technical mixtures. Seasonal sampling showed significant shifts in the relative ratios of the HBCD isomers. The spatial distribution of HBCD in the Detroit River was similar to other persistent organic pollutants (e.g., PCBs), and showed a strong association with urban/industrial activities in the watershed. However, the highest HBCD concentrations (2.6-3.7 ng/g) were associated with areas of contemporary industrial activity, and were much lower than maximum concentrations of PCBs (2.2 microg/g) found in areas of the Detroit River associated with historical industrial activity.