Persistent organic pollutants in two dolphin species with focus on toxaphene and polybrominated diphenyl ethers

Assessing trends of persistent organic pollutants (POPs) in marine mammals is difficult due to age, gender, and metabolism influences on accumulation. To help elucidate these effects in dolphins, POP concentrations were determined in the Atlantic white-sided dolphin, Lagenorhynchus acutus, a pelagic delphinid inhabiting North Atlantic waters, and in the rough-toothed dolphin, Steno bredanensis, a pelagic delphinid inhabiting tropical and subtropical waters. The specific objectives of this study were to determine baseline POP concentrations in L. acutus and S. bredanensis blubber samples and to examine the effects of age, gender, and metabolism on POP concentrations in dolphin blubber. Focus was aimed at contaminants of emerging concern, specifically, toxaphene and polybrominated diphenyl ethers (PBDEs). Samples collected from L. acutus (n = 47) stranding events in Massachusetts (1993--2000) and S. bredanensis samples (n = 15) were analyzed for PCBs, toxaphene, and other organic pesticides by gas chromatography/mass spectrometry (GC/MS). Age and gender influences were similar between the two species, with adult females having significantly lower POP concentrations as compared to adult males and juveniles. Mean sigma toxaphene concentrations were highest in juvenile L. acutus, 13.0 (6.7) microg/g wet mass (1 SD), and lowest in adult female S. bredanensis, 1.49 (1.4) microg/g wet mass. sigma PBDE (sum of congeners 47, 99, 100, 153, and 154) concentrations were highest in juvenile L. acutus, 2.41 (1.2) microg/g wet mass, and lowest in adult female S. bredanensis, 0.51 (0.6) microg/g wet mass. POP concentrations did not significantly differ between adult males and juveniles, suggesting metabolism of congeners and/or dilution with growth. PBDE concentrations in juvenile white-sided dolphins were not significantly related to collection year, suggesting that there may be a lag period for higher concentrations to be detected in pelagic marine mammals such as L. acutus or that concentrations have already peaked in this species prior to the first collection in 1993.     

Polybrominated diphenyl ethers and polychlorinated biphenyls in a marine foodweb of coastal Florida

Nine species of marine fish, including teleost fishes, sharks, and stingrays, and two species of marine mammals (dolphins) collected from Florida coastal waters were analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) to evaluate biomagnification factors (BMF) of these contaminants in a coastal foodweb. In addition, bottlenose dolphins and bull sharks collected from the Florida coast during the 1990s and the 2000s were analyzed for evaluation of temporal trends in PBDE and PCB levels in coastal ecosystems. Mean concentrations of PBDEs in muscle tissues of teleost fishes ranged from 8.0 ng/g, lipid wt (in silver perch), to 88 ng/g, lipid wt (in hardhead catfish), with an overall mean concentration of 43 +/- 30 ng/g, lipid wt. Mean concentrations of PBDEs in muscle of sharks ranged from 37.8 ng/g, lipid wt, in spiny dogfish to 1630 ng/g, lipid wt, in bull sharks. Mean concentrations of PBDEs in the blubber of bottlenose dolphins and striped dolphins were 1190 +/- 1580 and 660 ng/g, lipid wt, respectively. Tetra-BDE 47 (2,2',4,4'-) was the major congener detected in teleost fishes and dolphin samples, followed by BDE-99, BDE-153, BDE-100, and BDE-154. In contrast, BDE-209 was the most abundant congener in sharks. Concentrations of PBDEs and PCBs in dolphins and sharks were 1-2 orders of magnitude greater than those in lower trophic-level fish species, indicating biomagnification of both of these contaminants in the marine foodweb. Based on the analysis of sharks and dolphins collected over a 10-year period, an exponential increase in the concentrations of PBDEs and PCBs has occurred in these marine predators. The doubling time of PBDE and PCB concentrations was estimated to be 2-3 years for bull sharks and 3-4 years for bottlenose dolphin.     

Levels of hexabromocyclododecane in harbor porpoises and common dolphins from western European seas, with evidence for stereoisomer-specific biotransformation by cytochrome p450

Commercial hexabromocyclododecane (HBCD) is a high-production-volume flame-retardant applied in polystyrene foams. It contains three stereoisomers, of which gamma-HBCD always dominates. Here we report on the levels of HBCD in blubber of harbor porpoise and common dolphin from different European seas. The highest total (sigma)-HBCD levels were measured in harbor porpoises stranded on the Irish and Scottish coasts of the Irish Sea (median concentration 2.9 microg (g of lipid)(-1)) and the northwest coast of Scotland (median concentration 5.1 microg (g of lipid)(-1)). The median levels in other areas were, for the harbor porpoise south coast of Ireland, 1.2 microg (g of lipid)(-1), for the coasts of The Netherlands, Belgium, and France north of Calais (southern North Sea), 1.1 microg (g of lipid)(-1), for the east coast of Scotland (northern North Sea), 0.77 microg (g of lipid)(-1), and, for Galicia (Spain), 0.1 microg (g of lipid)(-1). The median levels for the common dolphin were, for west coast of Ireland, 0.9 microg (g of lipid)(-1), for the French coast of the English Channel between Normandy and Brest, 0.4 microg (g of lipid)(-1), and, for Galicia, 0.2 microg (g of lipid)(-1). A subset of 10 harbor porpoise and 9 common dolphin blubber samples representing all areas were analyzed by LC/MS to determine the diastereomeric composition of their HBCD residues. All samples showed exclusively the peak of alpha-HBCD. To test if biotransformation by the cytochrome P450 system could explain the observed compositional difference with technical HBCD mixtures, a number of in vitro assays with microsomal preparations of liver were carried out. We had to revert to material stored at -80 degrees C from laboratory rats and a fresh harbor seal found dead in the Dutch Wadden Sea, since such liver samples of cetaceans were not in our possession. The in vitro assays showed that beta- and gamma-HBCDs were indeed significantly metabolized when incubated in the presence of NADPH as electron donor, compared to a set of reference samples which were identical except for the addition of NADPH. In contrast, the peak of alpha-HBCD did not decrease significantly in the presence of NADPH. In separate microsomal assays with beta- and gamma-HBCDs, new peaks of brominated compounds (signal at m/z = 79 or 81) with masses of [M + 0] were formed only when NADPH was added. This confirms the process of cytochrome P450 mediated biotransformation. Although rat and harbor seal belong to different families of the mammalia than the cetaceans, we propose that biotransformation by the cytochrome P450 system is also the most likely process to explain the exclusive accumulation of alpha-HBCD in harbor porpoise and common dolphin.     

Hexabromocyclododecane in marine species from the Western Scheldt Estuary: diastereoisomer- and enantiomer-specific accumulation

Hexabromocyclododecane (HBCD) is a widely used brominated flame retardant, which is increasingly reported in the environment. Here, we report on the diastereomeric and, for the first time, on the enantiomeric composition of HBCD in muscle and liver of several fish species caught in the Western Scheldt Estuary (The Netherlands). The total HBCD content (sum of alpha-, beta-, and gamma-diastereoisomers), as well as the distribution of diastereoisomers and enantiomers, varied between the species. The levels of total HBCD (9-1110 ng/g lipid weight) found in fish tissues were higher than those measured in fish from European rivers with no known point sources of HBCD but lower than in fish samples collected near factories producing or using HBCD. The concentrations of total HBCD expressed on a lipid weight basis were higher in liver than in muscle for bib and whiting, while in sole, HBCD had no preferential distribution between the tissues. A similar pattern for liver and muscle distribution was already observed for polybrominated diphenyl ethers (PBDEs) in these species. The alpha-HBCD diastereoisomer was most abundant in all fish samples with a higher contribution to the total HBCD levels in liver compared to muscle for bib and whiting. The gamma-HBCD diastereoisomer accumulated less in liver than in muscle of sole, bib, and whiting. For the first time, enantiomer fractions were determined for HBCD diastereoisomers in liver of three fish species and in muscle of two fish species. A significant enrichment of the (+) alpha-HBCD enantiomer was found in whiting and bib liver samples. A high enantioselectivity has also been seen for the gamma-HBCD diastereoisomer in whiting liver.     

Brominated flame retardants in fish and shellfish - levels and contribution of fish consumption to dietary exposure of Dutch citizens to HBCD

In order to determine the contamination with brominated flame retardants (BFR) in fish regularly consumed by Dutch citizens, 44 samples of freshwater fish, marine fish, and shellfish were analyzed for polybrominated diphenyl ethers (PBDE), tetrabromobisphenol-A (TBBP-A) and its methylated derivative (me-TBBP-A), and hexabromocyclododecane (HBCD), including its alpha-, beta- and gamma-diastereomers. The highest BFR concentrations were found in pike-perch and eel from the highly industrialized and urbanized rivers Rhine and Meuse. The sum concentrations of BDE 28, 47, 99, 100, 153, 154, 183, 209, and brominated biphenyl (BB) 153 and HBCD (selection based on The European Food Safety Authority monitoring recommendation) ranged from below quantification limits to 17 ng/g wet weight (ww) in marine fish and in freshwater fish from 0.6 ng/g ww in pike-perch to 380 ng/g ww in eel. The BDE congener profile in all fish and shellfish samples is dominated by BDE 47, followed by BDE 99, except for eel in which BDE 100 is higher than BDE 99. BDE 209 was detected in two mussel samples, most likely due to BDE 209 contaminated particulate matter in their intestines. Total-HBCD (as determined by GC/electron capture negative ion (ECNI)-MS) was detected in 22 out of the 44 samples in concentrations between 0.20 ng/g in marine fish and 230 ng/g ww in eel. Three HBCD diastereomers were determined by HPLC/ESI-MS/MS. alpha-HBCD was the prevalent congener in most fish samples, followed by gamma-HBCD. beta-HBCD, TBBP-A and me-TBBP-A were only detected in a few samples and at low concentrations. A considerable difference was found between HBCD results obtained from GC/ECNI-MS and HPLC/ESI-MS/MS: the GC/ECNI-MS results were 4.4 times higher, according to regression analysis. There is hardly any data on human dietary exposure to HBCD available. We have estimated the fish-related dietary exposure of HBCD for the average Dutch population. The medium bound intake was estimated at 8.3 ng/day for a 70-kg person (0.12 ng/kg bodyweight/day). For this estimation, we relied mostly on HPLC/ESI-MS/MS data as we argue that these results are more accurate than those obtained by GC/ECNI-MS.     

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.     

Fine-scale spatial variation of persistent organic pollutants in bottlenose dolphins (Tursiops truncatus) in Biscayne Bay, Florida

Bottlenose dolphins (Tursiops truncatus) are long-term residents and apex predators in southeast U.S. estuaries and are vulnerable to bioaccumulation of persistent organic pollutants (POPs). Dart biopsy samples were collected from 45 dolphins in Biscayne Bay (Miami, FL), 34 of which were matched using fin markings to a photo identification catalogue. Blubber samples were analyzed for 73 polychlorinated biphenyl (PCB) congeners, six polybrominated diphenyl ether (PBDE) congeners, and organochlorine pesticides including dichloro-diphenyl-trichloroethane (DDT) and metabolites, chlordanes, and dieldrin. Total PCBs (sigma 73PCBs) were present in the highest concentrations and were 5 times higher in males with sighting histories in the northern, metropolitan area of Biscayne Bay than males with sighting histories in the southern, more rural area [geometric mean: 43.3 (95% confidence interval: 28.0-66.9) vs 8.6 (6.3-11.9) microg/g wet mass, respectively]. All compound classes had higher concentrations in northern animals than southern. The differences in POP concentrations found on this small geographic scale demonstrate that differential habitat use can strongly influence pollutant concentrations and should be considered when interpreting bottlenose dolphin POP data. The PCB concentrations in northern Bay dolphins are high as compared to other studies of estuarine dolphins and may place these animals at risk of reproductive failure and decreased immune function.     

Biomagnification of alpha- and gamma-hexabromocyclododecane isomers in a Lake Ontario food web

The extent of bioaccumulation of hexabromocyclododecane (HBCD) isomers (alpha, beta, and gamma) was determined in the Lake Ontario pelagic food web using liquid chromatography tandem mass spectrometry (LC/MS/MS). Concentrations of the alpha-isomer were consistently higher than that of the gamma-isomer. The beta-isomer was below method detection limits in all samples. Whole body concentrations (ng/g, wet wt) of alpha- and gamma-HBCD were highest in the top predator lake trout samples ranging from 0.4 to 3.8 ng/g for the alpha-isomer and 0.1 to 0.8 ng/g for the gamma-isomer. For the prey fish species, the trends in alpha- and gamma-HBCD levels were slimy sculpin > smelt > alewife. Mean concentrations of total (sigma) HBCD (sum of alpha- and gamma-isomers) in the macrozooplankter Mysis relicta (0.14 +/- 0.02 ng/g wet wt) and in the benthic invertebrate Diporeia hoyi (0.16 +/- 0.02 ng/g, wet wt) were similar and approximately twice as high as in plankton (0.06 +/- 0.02 ng/g, wet wt). A strong positive linear relationship was found between sigmaHBCD concentrations (wet wt) and trophic level based on delta15N suggesting that HBCD biomagnifies in the Lake Ontario food web. The trophic magnification factor (TMF = 6.3) derived from the slope of the sigmaHBCD - trophic level relationship was slightly higher than TMFs for p,p'-DDE (6.1) and sigmaPCBs (5.7) found previously. Biomagnification factors (BMF, calculated as the ratio of lipid corrected concentration in predator/lipid corrected concentration in prey) were variable between feeding relationships and ranged from 0.4 to 10.8 for the alpha-isomer and from 0.2 to 10 for gamma-isomers.     

Biotransformation enzymes and thyroid axis disruption in juvenile rainbow trout (Oncorhynchus mykiss) exposed to hexabromocyclododecane diastereoisomers

Juvenile rainbow trout (Oncorhynchus mykiss) were fed either a reference diet or one of three diets enriched with alpha, beta, or gamma diastereoisomers of hexabromocyclododecane (HBCD, C12H18Br6) for 56 days. This exposure period was followed by 112 days during which all fish were fed the reference diet. Potential effects of HBCD on phase I and II biotransformation enzyme activities and thyroid axis disruption were examined. Disruption of the thyroid axis was most evident in the gamma-HBCD exposed group, as indicated by lower circular FT4 and higher FT3 as well as an increase in thyroid epithelial cell height. However, fish fed the alpha-HBCD enriched diet also exhibited altered glucuronyltransferase activity and thyroid epithelial cell heights and the beta-HBCD group had altered FT4 and FT3 and glucuronyltransferase activity. T4ORD activity was not affected after 14 days, but was significantly lower among all HBCD exposed fish compared to the reference fish after 56 days. Results from these experiments indicate that all isomers have the potential to disrupt thyroid homeostasis.     

Enantioselective bioaccumulation of hexabromocyclododecane and congener-specific accumulation of brominated diphenyl ethers in an eastern Canadian Arctic marine food web

The extent of trophic transfer of the three diastereoisomers of hexabromocyclododecane (HBCD) and seven brominated diphenyl ether (BDE) congeners was examined in components of an Arctic marine food web from eastern Canada. Alpha and gamma-HBCD diastereoisomers were detected in all species and total (sigma) HBCD concentrations ranged from 0.6 +/- 0.2 pg/g (geometric mean +/- 1 x standard error (SE), lipid weight (lw)) in arctic cod to 3.9 +/- 0.9 ng/g (lw) in narwhal. beta-HBCD was below method detection limits in all the samples. Mean sigmaBDE (sum of seven congeners) concentrations ranged from 0.4 +/- 0.2 ng/g (lw) in walrus to 73 +/- 10 ng/g (lw) in zooplankton. The relative trophic status of biota was determined by nitrogen stable isotopes (delta15N), and results indicated clear differences in HBCD isomer and BDE congener profiles with trophic level (TL). Trophic magnification was observed for the alpha-diastereoisomer and BDE-47 as concentrations increased with increasing TL in the food web, whereas there was trophic dilution of gamma-HBCD and BDE-209 through the food web. Only the (-)alpha-enantiomer showed a strong positive relationship between concentration and TL (p < 0.01) with a trophic magnification factor (TMF) value of 2.2. A small but significant increase in the enantiomeric fraction value of the alpha-enantiomers with TL was also observed (r2 = 0.22, p < 0.005), implying that there is an overall preferential enrichment of the (-)alpha-enantiomer relative to the (+)alpha-enantiomer likely due to the greater bioaccumulation potential of the (-)alpha-enantiomer and/or to the greater susceptibility of the (+)alpha-enantiomer to metabolism.     

Concentrations and spatial variations of polybrominated diphenyl ethers and several organochlorine compounds in fishes from the northeastern United States

Fish from four lakes, two small lakes in the northeastern United States and two of the Great Lakes, were analyzed to determine the concentrations and spatial variations of polybrominated diphenyl ethers (PBDE) in this region. Three of the lakes were considered to have background levels of PBDEs; one lake was close to a suspected source. The PBDE concentrations were compared to organochlorine pesticide and PCB concentrations. Age and trophic position did not influence the organohalogen concentrations in the fish collected from the four locations. At the three background locations, the sum of PBDE concentrations ranged from 6.9 +/- 1.4 to 18 +/- 1 ng/g wet weight, or 150 +/- 9 to 300 +/- 80 ng/g lipid, and these values were similar to those of some of the organochlorine pesticides, such as total chlordane, but lower than sum of PCB concentrations. At the lake near the suspected source, the sum of PBDE concentration was 65 +/- 8 ng/g wet weight, or 2,400 +/- 600 ng/g lipid, and it exceeded the sum of PCB concentration. The hexabrominated congeners made up 43% of the total mass of PBDEs at this lake, and 7% at the background locations. Fish to sediment concentration ratios indicated that the tetra- through hexa-substituted congeners have a similar bioavailability, while the deca-substituted congener does not seem to be bioavailable at all.     

Occurrence and bioavailability of polybrominated diphenyl ethers and hexabromocyclododecane in sediment and fish from the Cinca River, a tributary of the Ebro River (Spain)

Fish and sediments from four places along the Spanish River Cinca were analyzed for polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). The samples were collected up- and downstream from Monzón, a heavily industrialized town draining to the river. PBDEs and HBCD were found in sediments at levels ranging from 2 to 42 ng/g dry weight and from not detected (nd) to 514 ng/g dry weight, respectively. Twenty-three fish samples (Barbus graellsi) collected at the same places were also analyzed, showing levels from nd to 446 ng/g wet weight for PBDEs and from nd to 1172 ng/g wet weight for HBCD. The lowest values for both sediment and fish samples were found upstream of the industry. Of 40 congeners (from mono- to deca-BDEs) included in the analytical work, 8 PBDE congeners were detected in river sediments, whereas 17 different PBDEs were found in fish samples. Large fish-to-sediment ratios for these brominated compounds indicate that they are highly bioavailable, with the exception of deca-BDE which was only detected in sediment samples. Concentrations of PBDEs and HBCD were slightly higher in muscle tissues than in liver samples obtained from the same specimen of fish. Moreover, PBDE and HBCD concentrations are correlated with fish length indicating the bioaccumulation of these contaminants.     

Comparison of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in Lake Michigan salmonids

Polybrominated diphenyl ethers (PBDEs) have been used extensively over the past two decades as flame retardants in most types of polymers. Many measurements of PBDEs in various environmental matrices from Sweden, Holland, Japan, and elsewhere have been reported, but few measurements are available for North America. PBDEs in 21 coho and chinook salmon taken from Lake Michigan tributaries in 1996 were measured for this study. The salmon samples were extracted and initially analyzed for polychlorinated biphenyl (PCB) congeners. It was demonstrated for these samples that the same extract fraction contains PBDEs. Six PBDE congeners were observed in all 21 samples, and the rank order of concentration of these congeners was similar to that in commercial mixtures of PBDEs. The average concentration across all samples of the sum of PBDE congeners was 80.1 ng/g of wet weight or 2,440 ng/g of lipid. This is much less than the average sum PCB concentration (1,450 ng/g of wet weight; 43,100 ng/g of lipid). However, the average concentration of the most abundant PBDE congener (IUPAC BDE-49: 52.1 ng/g wet, 1,590 ng/g of lipid) was about one-third of the average concentration of the most abundant PCB congener (IUPAC CB-153: 149 ng/g wet, 4,550 ng/g of lipid). On the basis of an extensive literature survey, the concentrations of PBDEs reported here are among the highest in the world for salmon in open waters. The concentrations of PBDEs and PCBs are both correlated with fish length and mass, but not with lipid content. The concentrations of PBDEs and PCBs are highly correlated in individual fish, implying that PBDEs are as prevalent as PCBs in Lake Michigan.     

Brominated flame retardants in Canadian chicken egg yolks

Chicken eggs categorised as conventional, omega-3 enriched, free range and organic were collected at grading stations in three regions of Canada between 2005 and 2006. Free run eggs, which were only available for collection from two regions, were also sampled during this time frame. Egg yolks from each of these egg types (n = 162) were analysed to determine brominated flame retardant levels, specifically polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). PBDEs were detected in 100% of the 162 samples tested, while HBCD was observed in 85% of the egg yolks. Total PBDE concentrations in egg yolks ranged from 0.018 to 20.9 ng g(-1) lipid (median = 3.03 ng g(-1) lipid), with PBDE 209 identified as being the major contributor to ΣPBDE concentrations. In addition to PBDE 209, PBDE 99, 47, 100, 183 and 153 were important contributors to ΣPBDE concentrations. Total HBCD concentrations ranged from below the limit of detection to a maximum concentration of 71.9 ng g(-1) lipid (median = 0.053 ng g(-1) lipid). The α-isomer was the dominant contributor to ΣHBCD levels in Canadian egg yolks and was the most frequently detected HBCD isomer. ΣPBDE levels exhibited large differences in variability between combinations of region and type. ΣHBCD concentrations were not significantly different among regions, although differences were observed between the different types of egg yolks analysed in the present study.     

Enantiomer-specific accumulation of PCB atropisomers in the bowhead whale (Balaena mysticetus)

Blubber (n = 40) and liver (n = 20) samples from the bowhead whale (Balaena mysticetus) were collected during the 1997-1998 Native (Inuit) subsistence harvests in Barrow, AK. Bowhead tissues and zooplankton were analyzed for polychlorinated biphenyl (PCB) concentrations and the enantiomeric fractions (EFs) of eight chiral PCB congeners (PCB-91, 95, 135, 136, 149, 174, 176, and 183) to quantify the enantiomer-specific accumulation of PCBs in this cetacean. PCB concentrations in bowhead blubber were low (mean +/- 1 SE: 610 +/- 54 ng g(-1) lipid) relative to other cetaceans. The accumulation of several chiral PCBs (PCB-91, 135, 149, 174, 176, and 183) in bowhead blubber was enantiomer-specific relative to bowhead liver and zooplankton, suggesting that biotransformation processes within the bowhead whale are enantioselective. The EFs for PCB-95 and 149 were significantly correlated with body length in male and female whales, while EFs for PCB-91 correlated with length in males only. Despite evidence for enantioselective biotransformation, all three congeners bioaccumulated in the bowhead relative to PCB-153. Results suggest that enantioselective accumulation of PCB-91, 95, and 149 is influenced by PCB concentrations, age, and/or the modification of an uncharacterized stereoselective process (or processes) during sexual maturity.     

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.     

Hexabromocyclododecanes (HBCDs) in the environment and humans: a review

Hexabromocyclododecanes (HBCDs) are brominated aliphatic cyclic hydrocarbons used as flame retardants in thermal insulation building materials, upholstery textiles, and electronics. As a result of their widespread use and their physical and chemical properties, HBCDs are now ubiquitous contaminants in the environment and humans. This review summarizes HBCD concentrations in several environmental compartments and analyzes these data in terms of point sources versus diffuse sources, biomagnification potential, stereoisomer profiles, time trends, and global distribution. Generally, higher concentrations were measured in samples (air, sediment, and fish) collected near point sources (plants producing or processing HBCDs), while lower concentrations were recorded in samples from locations with no obvious sources of HBCDs. High concentrations were measured in top predators, such as marine mammals and birds of prey (up to 9600 and 19 200 ng/g lipid weight, respectively), suggesting a biomagnification potential for HBCDs. Relatively low HBCD concentrations were reported in the few human studies conducted to date (median values varied between 0.35 and 1.1 ng/g lipid weight). HBCD levels in biota are increasing slowly and seem to reflect the local market demand. One important observation is the shiftfrom the high percentage of the gamma-HBCD stereoisomer in the technical products to a dominance of the alpha-HBCD stereoisomer in biological samples. A combination of factors such as variations in solubility, partitioning behavior, uptake, and, possibly, selective metabolism of individual isomers may explain the observed changes in stereoisomer patterns. Recommendations for further work include research on how HBCDs are transferred from products into the environment upon production, use, and disposal. Time trends need to be analyzed more in detail, including HBCD stereoisomers, and more data on terrestrial organisms are needed, especially for humans. Whenever possible, HBCDs should be analyzed as individual stereoisomers in order to address their fate and effects.     

Bottlenose dolphins as indicators of persistent organic pollutants in the western North Atlantic Ocean and northern Gulf of Mexico

Persistent organic pollutants (POPs) including legacy POPs (PCBs, chlordanes, mirex, DDTs, HCB, and dieldrin) and polybrominated diphenyl ether (PBDE) flame retardants were determined in 300 blubber biopsy samples from coastal and near shore/estuarine male bottlenose dolphins (Tursiops truncatus) sampled along the U.S. East and Gulf of Mexico coasts and Bermuda. Samples were from 14 locations including urban and rural estuaries and near a Superfund site (Brunswick, Georgia) contaminated with the PCB formulation Aroclor 1268. All classes of legacy POPs in estuarine stocks varied significantly (p < 0.05) among sampling locations. POP profiles in blubber varied by location with the most characteristic profile observed in bottlenose dolphins sampled near the Brunswick and Sapelo estuaries along the Georgia coast which differed significantly (p < 0.001) from other sites. Here and in Sapelo, PCB congeners from Aroclor 1268 dominated indicating widespread food web contamination by this PCB mixture. PCB 153, which is associated with non-Aroclor 1268 PCB formulations, correlated significantly to human population indicating contamination from a general urban PCB source. Factors influencing regional differences of other POPs were less clear and warrant further study. This work puts into geographical context POP contamination in dolphins to help prioritize efforts examining health effects from POP exposure in bottlenose dolphins.     

Current-use flame retardants in the eggs of herring gulls (Larus argentatus) from the Laurentian Great Lakes

Of the 13, current-use, non-polybrominated diphenyl ether (PBDE) flame retardants (FRs) monitored, hexabromobenzene (HBB), pentabromoethylbenzene (PBEB), pentabromotoluene (PBT), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and alpha- and gamma-isomers of hexabromocyclododecane (HBCD), and the syn- and anti-isomers of the chlorinated Dechlorane Plus (DP) were quantified in egg pools of herring gulls (Larus argentatus) collected in 2004 from six sites in all five of the Laurentian Great Lakes of North America. alpha-HBCD concentrations ranged from 2.1 to 20 ng/g (wet weight (ww)). Other "new" FR levels ranged from 0.004 to 1.4 ng/g ww and were much lower than those of the major BDE congeners that are in technical mixtures (namely BDE-47, -99, -100), where sigma3PBDE ranged from 186 to 498 ng/g ww. Nineteen hepta-BDEs (sigma(hepta) = 4.9-11 ng/g ww), octa-BDEs (alpha(octa) = 2.6-9.1 ng/g ww), and nona-BDEs (sigma(nona) = 0.12-5.6 ng/g ww) were detectible at all six colonies, while BDE-209 was low but quantifiable (< 0.1-0.21 ng/g ww) at two colonies. sigma-DP (syn- and anti-isomers) concentrations in eggs from all sites ranged from 1.5 to 4.5 ng/g ww. Our findings indicate that mother herring gulls are exposed to several, current-use flame retardants via their diet, and in ovo transfer occurred to their eggs. Given the aquatic diet of herring gull, this suggests that there are non-PBDE BFRs present in the gull-associated aquatic food web of the Great Lakes.     

Diastereoisomer- and enantiomer-specific profiles of hexabromocyclododecane in the atmosphere of an urban city in South China

Hexabromocyclododecanes (HBCDs) are ubiquitous contaminants in the environment, but little is known on the occurrence and distribution of HBCDs in the background atmosphere of urban environments. In this study, air samples were collected from four sites in the city of Guangzhou, a typical fast developing metropolitan of South China, for quantifying the concentration levels, diasteroisomer profiles, gas-particle distribution and enantiomeric fractions of HBCDs. The results showed that the measured mean atmospheric HBCD concentrations ranged from 0.69 to 3.09 pg/m3, which were similar to those reported from remote or urban sites of the U.S., but were significantly lower than those of Europe. The analysis on diastereoisomer profiles indicated that alpha-HBCD (59--68%) was the dominant isomer and beta-HBCD was a minor isomer in all air samples, which appeared to be different from commercial products. A large variable percentage of HBCDs (69.1--97.3%) are existed in the particle phase, suggesting that long-range tansport of HBCDs might be occur in some environmental conditions. The results of enantiomeric fractions indicated that beta- and gamma-HBCD were racemic mixtures in the tested air samples and that (--)-alpha-HBCD was slightly enriched in the typical urban site, implying that the HBCDs in these studied sites might be a mixture of emissions from both local sources and soil-air exchange.