Abstract  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.

Abstract  In this paper, we review those data which have recently become available for brominated flame retardants (particularly the brominated diphenyl ethers (BDEs) and hexabromocyclododecane (HBCD)) in samples from the European environment. Environmental compartments studied comprise the atmosphere, sediments and soils, sewage sludges, and a variety of biological samples and food chains. This is currently a very active research area, and we cite over 70 studies reported in the literature during 2003–04. Findings include that the input of BDEs (especially BDE209) to the Baltic Sea by atmospheric deposition now exceeds that of PCBs by a factor of almost 40 times. Sewage sludge samples from both industrial and background locations show concentrations of BDEs, HBCD and tetrabromobisphenol-A (TBBP-A) that are of a similar order, indicating that the major source is from diffuse leaching from products into wastewater streams from users, households and industries generally. Point-sources from industries using BFRs (e.g. the textile industry) also generate local hot-spots. Sediment core studies identified the presence of two of the three PBDE formulations. The penta-mix formulation was clearly present from the beginning of the 1970s, but the deca-mix only appeared in the late 1970s. BDE183, BDE209 and HBCD were detected in peregrine falcons from Sweden and other birds feeding on terrestrial food chains. BDEs are found widely distributed in fish, including those from high mountain lakes in Europe, as a consequence of long-range atmospheric transport and deposition. A temporal trend study in archived freeze-dried mussels from the Seine estuary, France, indicated an exponential increase in BDE concentrations during the period 1982–1993, which levelled off in 1999 and 2001 and then began to decline after 2002. HBCD was detected in liver and blubber samples from harbour seals and harbour porpoises from the Wadden and North Seas, though very few animals yielded positive values for TBBP-A. There are difficulties in comparing data on ∑BDE from studies in which different suites of BDE congeners have been determined, and we suggest a common suite which will allow the study of all three commercial PBDE formulations.