Decabromodiphenylether and hexabromocyclododecane in wild birds from the United Kingdom, Sweden and The Netherlands: Screening and time trends.

The brominated flame retardant decabromodiphenylether (DBDE) was analysed in wild birds to identify the most suitable species for monitoring time trends in DBDE contamination. This information was later used for the design of a 10-year trend study on DBDE in the European Union. DBDE was measured in muscle tissue, liver, and eggs from 10 terrestrial and four aquatic bird species. DBDE was detected in 47% of the terrestrial bird samples (nine species) and in 9% of the aquatic bird samples (six species). Peregrine falcon and sparrowhawk specimens were selected as most suitable species to determine temporal trends of DBDE. For sparrowhawks, no significant change in DBDE concentrations between 1973 and 2001 was found, although in later years more DBDE concentrations were above the detection limit. Peak DBDE levels measured in peregrines in 1995, were followed by a decline in concentrations until 2001. The same species were used for a trend study on hexabromocylcododecane (HBCD). Twenty-four percent of peregrine falcon eggs and 12% of sparrowhawk muscle samples demonstrated measurable HBCD residues. Three diastereomers of HBCD were analysed and the α-diastereomer was the predominant one in most samples. No clear time trends were observed for HBCD in either species. This study demonstrated that these DBDE and HBCD are bioavailable to birds of Northern Europe, although bioaccumulation seems to occur to a limited extent.

Levels and trends of HBCD and BDEs in the European and Asian environments, with some information for other BFRs.

In this paper, we review recent data for brominated flame retardants (particularly BDEs, HBCD and TBBP-A) in samples from the European and Asian environments, including recent temporal trend studies. Research is active and we cite over 100 studies published during 2005-2007. Environmental compartments studied comprise the atmosphere, indoor and outdoor air, sewage sludges, soils and sediments and a variety of biological samples and food chains. Findings include that the lack of reference materials for use in analytical quality control and method validation identified earlier has been addressed, and certified concentrations are now available for a number of BDE congeners in six pre-existing and one new reference materials. BDE209 was certified in three samples of indoor dust. The analysis of BDE209 remains problematic, but suitable methods for its determination are available and need to be applied. The contamination of indoor environments with BFRs has been recognised as representing a significant uptake pathway, particularly via dust. Additional data for TBBP-A are needed from areas, where it is produced and used, primarily Asia, as the worst-case scenario. As a reactive flame retardant it is less likely to leach from finished products. Also, issues regarding the importance of e-waste recycling as a source of BFRs to the local populations and the local environment require urgent study, certainly in China and possibly elsewhere. Generally, trends show a levelling in concentrations of BDEs and increases in concentrations of HBCD wherever determined and BDE209 in Asia.

A significant downturn in levels of hexabromocyclododecane in the blubber of harbor porpoises (Phocoena phocoena) stranded or bycaught in the UK: an update to 2006.

In an earlier paper, we reported data indicating a sharp increase in hexabromocyclododecane concentrations in the blubber of 85 harbor porpoises from the UK, from about 2001 onward. That time trend was evaluated using data from 1994-2003, generated on a diastereoisomer basis using LC-MS. In this paper we report additional data for 138 animals collected during 2003-2006. SigmaHBCD concentrations ranged from <10 to 11,500 microg kg(-1) wet weight (up to 12,800 microg kg(-1) lipid weight) and TBBP-A was not detected in any samples. The maximum SigmaHBCD concentration observed in this study was about half that seen in the earlier study (21,400 microg kg(-1) lipid weight) and, in both studies, the highest concentration was for an animal stranded or bycaught in 2003. Investigation of time trends confirmed a statistically significant increase between 2000 and 2001 (p < 0.01) and a statistically significant decrease between 2003 and 2004 (p < 0.05). Neither trend was confounded by age, sex, nutritional status, or location. Possible contributory factors to the observed decrease include the closure in 2003 of an HBCD manufacturing plant in NE England which had considerable emissions up to 2003, and two voluntary schemes intended to reduce emissions of HBCD to the environment from industry which, however, did not formally begin until 2006.

Bioaccumulation and enantiomeric profiling of organochlorine pesticides and persistent organic pollutants in the killer whale (Orcinus orca) from British and Irish waters.

Concentrations and enantiomeric profiles for a range of organochlorine compounds are reported in blubber samples from a number of individual killer whales (Orcinus orca) from British and Irish waters. Elevated contaminant levels and enriched isotopic ratios were determined in one individual whale sampled in the Scottish Western Isles compared to the others suggesting marine mammal based dietary influences. The potential application of isotopic ratios to model contaminant uptake, enantioselective enrichment and accumulation is demonstrated. Data are presented which provide information on enantioselective enrichment factors (EFs) for o,p'-DDT, alpha-HCH and toxaphene congeners CHB26 and CHB 50. This dataset further improves the current database on reported levels of a number of contaminants and provides additional background information on potential metabolic processes in killer whales from British and Irish waters.

The risk of infection from polychlorinated biphenyl exposure in the harbor porpoise (Phocoena phocoena): a case-control approach.

The objective of this study was to determine whether the risk of mortality from infectious disease in harbor porpoise in U.K. waters increased with high exposure to polychlorinated biphenyls (PCBs), using a case-control study design. This is the first time that data from a long-term marine mammal strandings scheme have been used to estimate any increase in risk. The exposure odds ratio (OR) from a logistic regression model with infectious disease deaths as cases and physical trauma deaths as controls, after controlling for the effect of confounding factors, was 1.048 [95% confidence interval (CI), 1.02-1.07]. To further adjust for the difference in energetic status between cases and controls and account for the negative relationship between PCBs (sum of 25 chlorobiphenyl congeners) and blubber mass, we also "standardized" the blubber PCBs to an optimal blubber mass. This lowered the OR to 1.02 (95% CI, 1.00-1.03). Thus, for each 1 mg/kg increase in blubber PCBs, the average increase in risk of infectious disease mortality was 2%. A doubling of risk occurred at approximately 45 mg/kg lipid. In this study, we have endeavored to avoid selection bias by using controls that died of physical trauma as representative of the exposure prevalence in the population that gave rise to the cases. In addition, we controlled for the effect of variation in energetic status among the cases and controls. However, as with case-control studies in human and veterinary epidemiology, unforeseen misclassification errors may result in biased risk estimates in either direction.

Levels of the flame retardants hexabromocyclododecane and tetrabromobisphenol A in the blubber of harbor porpoises (Phocoena phocoena) stranded or bycaught in the U.K., with evidence for an increase in HBCD concentrations in recent years.

Within the U.K. Marine Mammals Stranding Program, analysis of brominated flame retardants began in 1999. Initially, the focus of attention was the brominated diphenyl ethers. Since the withdrawal of the pentamix and octamix polybrominated diphenyl ether (PBDE) formulations from the EU market prior to August 2004, two other high-volume products, hexabromocyclododecane (HBCO) and tetrabromobisphenol A (TBBP-A), have been included. We report the concentrations of these compounds in the blubber of harbor porpoises (Phocoena phocoena) stranded or dying due to physical trauma in the U.K. during the period 1994-2003. Analysis was undertaken using LC/MS method on a diastereoisomer basis. Eighty-five samples were analyzed for HBCD, and 68 of these for TBBP-A. alpha-HBCD dominated over the other isomers and was detected in all samples analyzed at concentrations ranging from 10 to 19 200 microg kg(-1) wet weight. The maximum concentration was about double that reported in earlier U.K. studies. TBBP-A was detected in only 18 samples and at much lower concentrations, from 6 to 35 microg kg(-1) wet weight. Investigation of possible time trends indicated a sharp increase in HBCD concentrations from about 2001 onward, which was not confounded by age (length), sex, nutritional status, or location. This may be a result of changing patterns of use of HBCD following limitations on the production and use of two PBDE formulations within the EU and will feed ongoing risk assessment activities.

Levels and trends of brominated flame retardants in the European environment.

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 summation operatorBDE 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.

Relationships between polychlorinated biphenyls and health status in harbor porpoises (Phocoena phocoena) stranded in the United Kingdom.

To investigate possible relationships between polychlorinated biphenyl (PCB) exposure and infectious disease mortality in harbor porpoises (Phocoena phocoena) in United Kingdom waters, summed blubber concentrations of 25 chlorobiphenyl congeners (sigma25CB) in healthy harbor porpoises that died of acute physical trauma (mainly by-catch; n = 175) were compared with sigma25CB values in animals that died of infectious disease (n = 82). The infectious disease group had significantly greater sigma25CB values (mean, 27.6 mg/kg lipid) than the physical trauma group (mean, 13.6 mg/kg lipid; p < 0.001). This association occurred independently of other potentially confounding variables, including age, sex, two indices of nutritional status, season, region, and year found. Total blubber PCB levels (as Aroclor 1254) were also calculated, enabling direct comparison with a proposed threshold for adverse health effects (including immunosuppression) in marine mammals of 17 mg/kg lipid. In porpoises with total PCB levels greater than 17 mg/kg lipid (n = 154), total PCB levels were significantly higher in the infectious disease group compared to the physical trauma group (p < 0.001). This association was no longer significant in porpoises with total PCB levels of less than 17 mg/kg lipid (n = 103; p > 0.55). These findings are consistent with a causal (immunotoxic) relationship between PCB exposure and infectious disease mortality, and they provide a framework for future quantitative risk-assessment analyses of porpoise populations of known size and PCB exposure.

Distribution and fate of HBCD and TBBPA brominated flame retardants in North Sea estuaries and aquatic food webs.

Tetrabromobisphenol A (TBBPA) and hexabromocyclododecane diastereoisomers (alpha-, beta/-, and gamma-HBCD) were investigated in effluents from sewage treatment works, landfill leachates, sediments, and food web organisms of the North Sea basin. Residues were quantified by liquid chromatography-mass spectrometry. Both flame retardants were enriched in sewage sludges, where a maximum total (sigma) HBCD concentration of 9.1 mg/kg (dry weight; d.w.) was found; TBBPA was at levels of 102 microg/kg. Landfill leachates from The Netherlands showed up to 36 mg (sigmaHBCD)/ kg (d.w.). gamma-HBCD dominated isomeric profiles in sediments, and concentrations were elevated near to a site of HBCD manufacture. alpha-HBCD was the primary congener detected in marine mammals; however, very few samples exhibited TBBPA. sigmaHBCD ranged from 2.1 to 6.8 mg/kg (lipid weight; l.w.) in liver and blubber of harbor porpoises (Phocoena phocoena) and seals (Phoca vitulina). TBBPA levels in cormorant (Phalacrocorax carbo) livers were up to 1 order of magnitude lower compared to sigmaHBCD. HBCD in eels (Anguilla anguilla) from the Scheldt basin (Belgium) reflected the spatial distribution of concentrations in local sediments. This study shows evidence of HBCD bioaccumulation at the trophic level and biomagnification in the ascending aquatic food chain, and these findings justify risk assessment studies at the ecosystem level.

Levels and trends of polybrominated diphenylethers and other brominated flame retardants in wildlife.

In this paper, we review the available data for polybrominated diphenylethers (PBDEs) and other flame retardants in wildlife, with the exception of fishes from Europe and North America which are covered in more detail elsewhere. More data are available for PBDEs than for other compounds, and these show that some of these compounds have become widely distributed in the environment, being found in samples from Europe, Australia, Azerbaijan, North America and the Arctic. Most available data relate to birds and their eggs and marine mammals, but the results of two food web studies are also included. The detection of PBDEs in pelagic marine mammals which feed in deep offshore waters, including baleen whales, indicate that these compounds have found their way into deep-water, oceanic food webs as well as the coastal/shallow sea examples described in detail. In the North Sea study, the most marked increase in lipid-normalised concentrations of six BDE congeners occurred during transfer from predatory fish to marine mammals. In the St. Lawrence Estuary study, marked differences in the ratios observed between species suggested that some fish species may be able to metabolise BDE99.A number of time trend studies have also been conducted, notably in guillemot eggs from Sweden (1969-2000), beluga whales from the Canadian Arctic (1982-1997 and 1989-2001) and from the St. Lawrence Estuary (1988-1999), and ringed seals from the Canadian Arctic (1981-2000). In the temperate latitudes, from these and other studies (e.g. in dated sediment cores), PBDE concentrations began to rise earlier than in those from high latitudes, in line with data for production and use. These trends have now slowed in many cases. Declines could be expected in Europe for many congeners following the cessation of manufacture and use of the penta-mix formulation in the EU, though these are not yet apparent in environmental samples. In Arctic biota, however, the rapidly rising concentrations seen currently in Canada could be expected to continue for some time, reflecting continued production and use of the penta-mix formulation in North America (>95% of the world total) and the impact of long-range atmospheric transport.

Levels of polybrominated diphenyl ether (PBDE) flame retardants in animals representing different trophic levels of the North Sea food Web.

The levels of individual PBDE congeners were investigated in the invertebrate species whelk (Buccinum undatum), seastar (Asterias rubens), and hermit crab (Pagurus bernhardus), the gadoid fish species whiting (Merlangius merlangus) and cod (Gadus morhua), and the marine mammal species harbor seal (Phoca vitulina) and harbor porpoise (Phocoena phocoena). These species are all important representatives of different trophic levels of the North Sea food web. All six major PBDE congeners detected (BDEs 28, 47, 99, 100, 153, and 154) are most prevalent in the commercial Penta-BDE formulation. There is no evidence for the occurrence of the Octa-BDE formulation in the North Sea food web, since its dominant congener, BDE183, was never detected. BDE209, the main congener (> 97%) in the Deca-BDE formulation, was detected only in a minority of the samples and always in concentrations around the limit of detection. Since BDE209 is often the major BDE congener in sediments from the area, the main reason for its low concentrations in biota from the North Sea seems to be a relatively low bioaccumulation potential. This can either be due to a low uptake rate of the very large molecule or a relatively rapid excretion after biotransformation. Since all invertebrates investigated are sentinel species, they are highly representative for the area of capture. The highest lipid-normalized concentrations of PBDEs in the invertebrates occurred near the mouth of the river Tees at the East coast of the UK. The geographical distribution of the PBDEs can be explained by the residual currents in the area. The direction of these currents differs between the summer and the winter season as a result of the presence or absence of vertical summer stratification of the deeper waters north of the Dogger Bank. Summer stratification results in the development of a density-driven bottom water current formed after the onset of vertical stratification of the water column in May leaving the UK coast near Flamborough Head toward the Dogger Bank. In winter, the residual currents run in a more southerly direction and follow the UK coastline. The distribution pattern of the PCBs and p,p'-DDE in the invertebrates was entirely different from that of the PBDEs, which could be expected, since the use of these organochlorines in western Europe peaked in the 1960s and 1970s but has been forbidden more than two decades ago, whereas the production and use of the penta-BDE formulation is of a more recent origin. The higher trophic levels of the North Sea food web were represented by the predatory gadoid fish species whiting and cod and the marine mammal species harbor seal and harbor porpoise. The lipid-normalized levels of the six major PBDE congeners in fish were similar to the levels in the invertebrates, but a biomagnification step in concentrations of generally more than an order of magnitude occurred from gadoid fish to marine mammals. Based on the limited number of samples, no differences could be observed between harbor seal and harbor porpoise. In summary, the results in three species of sentinel invertebrates from a network of stations covering a major part of the North Sea basin showed that the estuary of the river Tees at the UK East coast is a major source for tri- to hexa-PBDEs. Throughout the food-chain, the most marked increase in (lipid-normalized) levels of all six PBDE congeners occurred from predatory (gadoid) fish to marine mammals, agreeing with the transition from gill-breathing to lung-breathing animals. This has serious consequences for the route of elimination of POPs, since their elimination from the blood into the ambient seawater via the gill-membrane is no longer possible.