Polybrominated diphenyl ethers and their hydroxylated/methoxylated analogs: environmental sources, metabolic relationships, and relative toxicities

Brominated compounds are ubiquitous in the aquatic environment. The polybrominated diphenyl ether (PBDE) flame retardants are anthropogenic compounds of concern. Studies suggest that PBDEs can be biotransformed to hydroxylated brominated diphenyl ethers (OH-BDE). However, the rate of OH-BDE formation observed has been extremely small. OH-BDEs have also been identified as natural compounds produced by some marine invertebrates. Another class of compounds, the methoxylated BDEs (MeO-BDEs), has also been identified as natural compounds in the marine environment. Both the OH-BDEs and MeO-BDEs bioaccumulate in higher marine organisms. Recent studies have demonstrated that MeO-BDEs can be biotransformed to OH-BDEs and this generates greater amounts of OH-BDEs than could be generated from PBDEs. Consequently, MeO-BDEs likely represent the primary source of metabolically derived OH-BDEs. Given that for some endpoints OH-BDEs often exhibit greater toxicity compared to PBDEs, it is prudent to consider OH-BDEs as chemicals of concern, despite their seemingly "natural" origins.     

Brominated flame retardants and organochlorine contaminants in winter flounder, harp and hooded seals, and North Atlantic right whales from the Northwest Atlantic Ocean

Various brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs) and current-use, non-PBDE BFRs, as well as organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs), were measured in winter flounder, harp and hooded seals, and North Atlantic right whales from the Eastern United States and Canada. The concentrations of PBDEs in winter flounder and right whales were similar in magnitude to the levels of PCBs, which was unlike the pattern observed in seals. In these marine mammals, the levels of PBDEs were orders of magnitude lower than the levels of OCs and PCBs detected. Evidence existed for the accumulation of methoxylated (MeO)-PBDEs of natural origin in seals and right whales. Current-use, non-PBDE BFRs (including hexabromocyclododecane, pentabromoethylbenzene, hexabromobenzene, and pentabromotoluene) were detected in winter flounder and marine mammals. Future research should focus on monitoring PBDEs, current-use, non-PBDE BFRs, and MeO-BDEs of natural origin in marine organisms from Massachusetts and Cape Cod Bays.     

PBDEs, methoxylated PBDEs and HBCDs in Japanese common squid (Todarodes pacificus) from Korean offshore waters

Little information is available on the levels of brominated compounds found in biota from the Korean Peninsula. In this study, Japanese common squids (Todarodes pacificus) were analyzed for 38 polybrominated diphenyl ethers, two methoxylated polybrominated diphenyl ethers and three stereoisomers of hexabromocyclododecane (α, β, and γ-HBCD) from the east and western coasts of the Korean Peninsula. Among 38 PBDEs, 10 PBDEs were detected and their total concentrations ranged from 21 to 292 ng/g lipid wt with a mean concentration of 108 ng/g lipid wt, while two MeO-BDEs and three isomers of HBCDs were detected in all samples. BDE47 showed the highest residual level, followed by BDE99, 154, 153, 28/33. Concentrations of PBDEs and MeO-BDEs were not significantly different between the both sides of the Korean Peninsula; however, HBCD concentrations were higher levels in the East/Japan Sea than the Yellow Sea, indicating that HBCD sources possibly exist in Japan.     

Flame retardants (PBDEs) in marine turtles, dugongs and seafood from Queensland, Australia

Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in numerous products. These compounds have been found to enter the marine environment where they have the potential to bioaccumulate in biota. Limited information is currently available concerning the levels of PBDEs in Australian marine wildlife. This study presents baseline information on PBDE levels in a variety of marine species from Queensland, Australia and considers the influence of species-specific factors on contaminant levels and tissue distribution in marine turtles. Overall, the PBDE levels measured in this study are relatively low compared to marine biota from the northern hemisphere, indicating low level input into the marine system of Queensland. This is in general agreement with global estimates which suggest low PBDE usage in Australia. Previous studies, however, have found relatively high PBDE levels in Australian human milk and sera. This discrepancy in contamination trends between terrestrial and marine biota suggests that future transport of PBDEs may occur to the marine system in Australia.     

Flame retardants (PBDEs) in marine turtles,dugongs and seafood from Queensland,Australia

Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in numerous products. These compounds have been found to enter the marine environment where they have the potential to bioaccumulate in biota. Limited information is currently available concerning the levels of PBDEs in Australian marine wildlife. This study presents baseline information on PBDE levels in a variety of marine species from Queensland, Australia and considers the influence of species-specific factors on contaminant levels and tissue distribution in marine turtles. Overall, the PBDE levels measured in this study are relatively low compared to marine biota from the northern hemisphere, indicating low level input into the marine system of Queensland. This is in general agreement with global estimates which suggest low PBDE usage in Australia. Previous studies, however, have found relatively high PBDE levels in Australian human milk and sera. This discrepancy in contamination trends between terrestrial and marine biota suggests that future transport of PBDEs may occur to the marine system in Australia.     

Endocrine effects of methoxylated brominated diphenyl ethers in three in vitro models

Methoxylated brominated diphenyl ethers (MeO-BDEs) in aquatic environments have been found to be primarily of natural origin in the marine environment and not from biotransformation of synthetic PBDEs. Two of the eight MeO-PBDEs (2′-MeO-BDE-68 and 6-MeO-BDE-47) that were detected in anchovy from the Yangtze River Delta, were natural products from marine organisms. So 2′-MeO-BDE-68 and 6-MeO-BDE-47 were chosen to study the potential to modulate androgen, estrogen, or thyroid hormone receptor- (AR, ER, ThR) mediated responses by use of reporter gene assays. 2′-MeO-BDE-68 was antiandrogenic at 50 μM, estrogenic at 10 μM and antiestrogenic at 10 and 50 μM (IC₅₀ = 4.88 μM). 2′-MeO-BDE-68 enhanced luciferase expression by 5 nM T3 at 50 μM. 6-MeO-BDE-47 exhibited potent antiandrogenicity at 1 μM and greater (IC₅₀ = 41.8 μM) and possessed estrogenic activity at 10 μM and antiestrogenic activity at 10 and 50 μM (IC₅₀ = 6.02 μM).     

Preliminary health risk assessment for polybrominated diphenyl ethers and polybrominated dibenzo-p-dioxins/furans in seafood from Guangzhou and Zhoushan, China

Dietary intake is one of the important routes of human exposure to brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs). The use of PBDEs may also result in exposure to polybrominated dibenzo-p-dioxins and dibenzofurans (PBDDs/DFs), as these compounds are impurities in technical mixtures of BFRs and can also be formed unintentionally by the same processes that generate chlorinated dioxins. This study determined the concentrations of polybrominated compounds in common seafood in Guangzhou and Zhoushan, and assessed the health risks of these chemicals via consumption of contaminated seafood. Seafood samples (fish, bivalves, shrimp, crab, and cephalopods) purchased from local markets in 2003 and 2004 were analyzed for PBDEs and PBDDs/DFs. The highest concentration of total PBDEs (46.3 ng g(-1) lipid wt.) was detected in fish from Guangzhou, in which BDEs 47 and 209 were the two predominant congeners. The total daily intakes of PBDEs, PBDDs, and PBDFs were, 946, 6.39, and 6.54 pg kg(-1) body weight (bw) in Guangzhou, and 489, 4.99, and 7.65 pg kg(-1) bw in Zhoushan, respectively. The hazard ratios for PBDDs and PBDFs were both greater than unity, indicating that these compounds may pose some health risks to the local population.     

Preliminary health risk assessment for polybrominated diphenyl ethers and polybrominated dibenzo-p-dioxins/furans in seafood from Guangzhou and Zhoushan, China

Dietary intake is one of the important routes of human exposure to brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs). The use of PBDEs may also result in exposure to polybrominated dibenzo-p-dioxins and dibenzofurans (PBDDs/DFs), as these compounds are impurities in technical mixtures of BFRs and can also be formed unintentionally by the same processes that generate chlorinated dioxins. This study determined the concentrations of polybrominated compounds in common seafood in Guangzhou and Zhoushan, and assessed the health risks of these chemicals via consumption of contaminated seafood. Seafood samples (fish, bivalves, shrimp, crab, and cephalopods) purchased from local markets in 2003 and 2004 were analyzed for PBDEs and PBDDs/DFs. The highest concentration of total PBDEs (46.3 ng g⁻¹ lipid wt.) was detected in fish from Guangzhou, in which BDEs 47 and 209 were the two predominant congeners. The total daily intakes of PBDEs, PBDDs, and PBDFs were, 946, 6.39, and 6.54 pg kg⁻¹ body weight (bw) in Guangzhou, and 489, 4.99, and 7.65 pg kg⁻¹ bw in Zhoushan, respectively. The hazard ratios for PBDDs and PBDFs were both greater than unity, indicating that these compounds may pose some health risks to the local population.     

Determination of HBCD, PBDEs and MeO-BDEs in California sea lions (Zalophus californianus) stranded between 1993 and 2003

Blubber samples from male California sea lions (Zalphophus californianus) stranded between 1993 and 2003 were analyzed for 27 polybrominated diphenyl ether (PBDE) congeners, three isomers of hexabromocyclododecane (HBCD) and 14 methoxylated polybrominated diphenyl ether (MeO-BDE) congeners. Total PBDEs ranged from 450 ng/g to 4740 ng/g wet mass and total HBCD ranged from < 0.3 ng/g to 12 ng/g wet mass. The concentration of HBCD increased from 0.7 ng/g to12.0 ng/g wet mass in sea lion blubber between 1993 and 2003. However, no significant temporal trend was observed for any of the other brominated compounds over this 10 year period. Only one of the 14 MeO-BDE congeners was detected in the blubber samples, 6-methoxy-2,2',4,4'-tetrabromodiphenyl ether (6-MeO-BDE 47), and concentrations ranged from < 0.2 ng/g to 12 ng/g wet mass. A bromo-, chloro-heterocyclic compound, 1,1'-dimethyl-tetrabromo-dichloro-2,2'-bipyrrole (DBP-Br4Cl2), previously reported in marine species along the Pacific coast, was also identified in the sea lion blubber. DBP-Br4Cl2 ranged from 44 ng/g wet mass to 660 ng/g wet mass and was present at concentrations rivaling the dominant PBDE congener, BDE 47 (2,2',4,4'-tetrabromodiphenyl ether). Concentrations of DBP-Br4Cl2 were positively correlated with 6-MeO-BDE 47 (r = 0.7; p < 0.05). Both of these compounds have been identified in marine algae and sponges, and studies suggest they are both produced from natural sources. This study demonstrates that brominated compounds from both anthropogenic and biogenic sources can accumulate to similar levels in marine mammals. In addition, HBCD concentrations appear to be increasing in California sea lion populations, whereas PBDE concentrations, between 1993 and 2003, were highly variable.     

An Asian quandary: where have all of the PBDEs gone?

Polybrominated diphenyl ethers (PBDEs) are widely used fire retardant compounds which, like polychlorinated biphenyls (PCBs), have become ubiquitous in environmental media. Time trend analyses of PBDE levels in sediments and biota generally show an increasing trend. The lower (tetra- and penta-) PBDEs accumulate and predominate in biota, whilst the higher congeners (deca-) are prevalent in aquatic environments and sediments. PBDEs also biomagnify, with highest concentrations of the lower brominated congeners being seen in top predators including birds, marine mammals and humans. Toxicological studies of PBDEs have been limited, although effects mediated via the thyroid gland may be extremely important. Disturbingly, PBDEs may be sequestering in certain Asian environments to a higher degree than in other parts of the world, due to the unregulated disposal of computers and electronic equipment. However, this potential problem remains poorly investigated, to date.     

Organohalogen contaminants in finless porpoises (Neophocaena phocaenoides) from Korean coastal waters: Contamination status, maternal transfer and ecotoxicological implications

Information on the occurrence of organochlorine compounds (OCs) and polybrominated diphenyl ethers (PBDEs) in marine mammals from Korea is scarce. In this study, OCs and PBDEs were determined in the blubber of 52 finless porpoises (Neophocaena phocaenoides) from Korean coastal waters. The highest contamination was found for DDTs, followed by PCBs, PBDEs, HCHs, CHLs and HCB. Concentrations of OCs in finless porpoises were lower than those reported worldwide, but PBDE contamination was comparable to other studies, due to ongoing use of PBDE products in Korea. Significant gender-specific differences were found for concentrations and accumulation profiles of OCs and PBDEs, due to maternal transfer and lactation of mature females. The BDEs 49 and 66 comprised 4-16% of total PBDEs in finless porpoises, which seems to be associated with debromination of higher BDEs. The DDT levels in Korean finless porpoises have almost reached the levels associated with immunosuppression in marine mammals.     

Chlorinated compounds and polybrominated diphenyl ethers (PBDEs) in mussels (Mytilus galloprovincialis) collected from Apulia Region coasts

This project was carried out to assess the levels and spatial distribution of organochlorine compounds in the coastal marine environment, using mussels as bioindicators to evaluate the coastal water quality. Levels of polychlorobiphenils (PCB), chlorinated pesticides (DDT isomers, HCH isomers, Aldrin, Dieldrin, alfa-Endosulfan, Hexachlorobenzene, Pentachlorobenzene) and polybrominated diphenyl ethers (PBDEs) were determined in tissues from mussels (Mytilus galloprovincialis) collected along the Apulia Region coasts (Mediterranean Sea). Results indicate that contamination by organochlorine compounds is higher in mussels sampled in the Ionian Sea than in those from the Adriatic Sea, with PCB levels up to seven times higher in mussels from Ionian than from the Adriatic Sea. Although PCB levels were above the maximum values indicated by both European Community (EC) and National regulation in several sample sites, the PCB concentrations were particularly high in some stations, suggesting that these locations require a much specific attention. Conversely, results on the mussel contamination by PBDEs highlight their ubiquitous environmental distribution, and underline the need to establish the maximum level for these compounds in foodstuff, according to European Regulations.     

Polybrominated diphenyl ethers (PBDEs) in sediments and mussel tissues from Hong Kong marine waters

Sediments and green-lipped mussels, Perna viridis, were used to investigate concentrations of polybrominated diphenyl ethers (PBDEs) in Hong Kong's marine environment. PBDEs have been used extensively over the past two decades as flame retardants in polymer additives for a variety of plastics, computers, furniture, building materials, and fabrics. Many measurements of PBDEs in various environmental matrices have been reported from Belgium, Holland, Japan, Europe and North America, but few measurements are available for the southeast Asian region and Hong Kong. PBDE congeners (n=15) were measured in 13 sediments and nine mussel samples, taken from Hong Kong marine waters. The Sigma15PBDEs in sediments ranged between 1.7 and 53.6 ng g(-1) dry wt, with the highest concentrations located around the most heavily populated areas of Victoria Harbour and Sai Kung, while the lowest concentrations of Sigma15PBDEs were found at more remote locations of Sha Tau Kok, Wong Chuk Bay, Castle Peak Bay, and Gold Coast. Sigma15PBDEs ranged from 27.0 to 83.7 ng g(-1) dry wt of mussel tissues. Although not identical, most of the congeners in sediments were found in mussel tissues, with BDE-47, BDE-99, BDE-153 and BDE-183 being the most prominent in both matrices. On the basis of a literature survey, the concentrations of PBDEs reported in Hong Kong sediments and mussel tissues are amongst the highest in the world.     

Preliminary health risk assessment for polybrominated diphenyl ethers and polybrominated dibenzo-p-dioxins/furans in seafood from Guangzhou and Zhoushan,China

Dietary intake is one of the important routes of human exposure to brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs). The use of PBDEs may also result in exposure to polybrominated dibenzo-p-dioxins and dibenzofurans (PBDDs/DFs), as these compounds are impurities in technical mixtures of BFRs and can also be formed unintentionally by the same processes that generate chlorinated dioxins. This study determined the concentrations of polybrominated compounds in common seafood in Guangzhou and Zhoushan, and assessed the health risks of these chemicals via consumption of contaminated seafood. Seafood samples (fish, bivalves, shrimp, crab, and cephalopods) purchased from local markets in 2003 and 2004 were analyzed for PBDEs and PBDDs/DFs. The highest concentration of total PBDEs (46.3 ng g⁻¹ lipid wt.) was detected in fish from Guangzhou, in which BDEs 47 and 209 were the two predominant congeners. The total daily intakes of PBDEs, PBDDs, and PBDFs were, 946, 6.39, and 6.54 pg kg⁻¹ body weight (bw) in Guangzhou, and 489, 4.99, and 7.65 pg kg⁻¹ bw in Zhoushan, respectively. The hazard ratios for PBDDs and PBDFs were both greater than unity, indicating that these compounds may pose some health risks to the local population.     

Polybrominated diphenyl ethers (PBDEs) in marine foodstuffs in Australia: residue levels and contamination status of PBDEs

Edible marine products (n=24) collected from the fish markets in Adelaide, Australia, were analysed for the presence of polybrominated diphenyl ethers (PBDEs). The total concentration of 11 PBDE congeners found in the marine products ranged from 1.01 to 45 ng/g fresh weight. Among the samples analysed, imported silver fish and prawns from Vietnam and Thailand respectively, recorded the highest ∑PBDEs concentrations (45.10 and 43.29 ng/g fresh weight) as against 13.08 and 12.57 ng/g fresh weight in Australian king prawns and Gar fish. BDE-209 was the most dominant congener in the marine products followed by BDE-47, 99 and 100. The calculated average daily intakes of ∑PBDEs per day for an adult male and female (19 or more years old) were 1026.8 and 1188.4 ng/kg per day, respectively. This study clearly shows that the dietary exposure to marine foods can contribute to PBDEs accumulation in human body.     

Large and growing environmental reservoirs of Deca-BDE present an emerging health risk for fish and marine mammals

Polybrominated diphenyl ethers (PBDEs) have been the subject of intense scientific and regulatory scrutiny during recent years. Of the three commercial forms (Penta, Octa and Deca) of PBDEs that have been widely used as flame retardants in textiles, furniture upholstery, plastics, and electronics, only Deca-BDE remains on the general market in North America, while a recent ruling of the European Court spells an impending end to its use in Europe. We review here highlights of aquatic research documenting the rapid emergence of PBDEs as a high priority environmental concern in Canada. PBDEs are being introduced in large quantities to the aquatic environment through sewage discharge and atmospheric deposition. In certain environmental compartments, the single congener BDE-209, the main ingredient in the Deca-BDE formulation, has surpassed the legacy PCBs and DDT as the top contaminant by concentration. Limited biomagnification of BDE-209 in aquatic food webs reflects its high log K_ow and preferential partitioning into the particle phase. As a result, large environmental reservoirs of BDE-209 are being created in sediments, and these may present a long-term threat to biota: BDE-209 breaks down into more persistent, more bioaccumulative, more toxic, and more mobile PBDE congeners in the environment.     

Temporal trends of brominated flame retardants in coastal waters of Japan and South China: Retrospective monitoring study using archived samples from es-Bank,Ehime University,Japan

The present paper is a summary of studies conducted at the Center for Marine Environmental Studies, Ehime University, on temporal trends of brominated flame retardants (BFRs) in coastal waters of Japan and South China. Archived marine mammal fat tissues and dated sediment cores were used to evaluate temporal trends of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in relation to their usage in the region. The results indicate that environmental concentrations of these BFRs in Japan and South China increased significantly during the last several decades. Temporal trends in the contaminant concentrations were consistent with historical consumption of the corresponding BFRs. PBDE levels in marine mammals and sediments from Japan, after showing peak concentrations in the 1990s, appear to be leveling off in recent years, in accordance with the discontinued usage of Tetra- and Octa-BDEs in Japan from the 1990s. The change in concentration levels was also accompanied by changes in PBDE congener profiles, i.e. shift towards increased proportion of higher brominated BDEs. Furthermore, in recent years HBCD concentrations in marine mammals from Japan appear to exceed those of PBDEs, presumably reflecting increasing usage of HBCDs over PBDEs. In finless porpoises from the South China Sea, PBDE levels were much higher than HBCD concentrations both in the past and recent years, implying consumption of HBCDs was not as high as that of PBDEs in China. In dated sediment cores from Tokyo Bay, concentrations increased exponentially with doubling times of 4.6–7.9 years, 6.1–12 years and 7.1–12 years for BDE-209, ΣPBDEs and HBCDs, respectively.     

PCB, PCDD/F and PBDE levels and profiles in crustaceans from the coastal waters of Brittany and Normandy (France)

Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analysed in the muscle of various edible marine crustaceans (spider crab, edible crab, velvet swimming crab and Norway lobster) from the Brittany and Normandy coasts (France). The highest concentrations were measured in species collected from Antifer (Seine Bay). PCB and PBDE patterns in crustacean muscles were similar and independent of the geographical area with the predominance of the high chlorinated PCBs (CB153, 138, 118 and 180), and of a few PBDE congeners (BDE47, BDE99, BDE100 and BDE28). Oppositely, dioxin contamination differed with site. The major component in crustaceans from the Seine Bay was 2378-TCDF, whereas specimens from cleaner areas had higher relative concentrations of OCDD. Finally, the comparison of the spider crab contaminant profiles to those measured in mussel and sea bass highlighted two different trends: decapod crustaceans possess relatively strong capacity to metabolise PCBs and PBDEs; however these species might be used as bioindicators for dioxin pollution monitoring in the marine coastal environment.     

Genotoxicity and development effects of brominated flame retardant PBDEs and UV-exposed PBDEs on grass shrimp (Palaemonetes pugio) embryo

To understand how polybrominated diphenyl ethers (PBDEs) affect the hatching sensitivity of grass shrimp embryos in different developmental stages, the hatching rates of embryos were measured after PBDE exposure on the early- and late-stage embryo of grass shrimp. PBDEs had no clear influence on the hatching rate. Also, to investigate on the reproductive and genetic toxicities of UV-exposed PBDEs, the hatching rate and DNA damage of stage 7 embryos were also measured. PBDEs had no significant impact on the hatching rate and DNA damage of grass shrimp in most experimental conditions regardless of embryo developmental stage or UV exposure, but in the case of UV-exposed BDE-47, the hatching rate was decreased, suggesting a potential reproductive toxicity. This research is meaningful because it is the first study to propose that PBDEs can cause reproductive toxicity in marine organism, after flowing into the ocean and undergoing photochemical reactions stimulated by UV.     

Specific profiles of polybrominated diphenylethers (PBDEs) and polychlorinated biphenyls (PCBs) in fish and tucuxi dolphins from the estuary of Paraíba do Sul River, Southeastern Brazil

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) are ubiquitous pollutants in the environment and subject of several studies due to their adverse effects as endocrine disruptors. Despite the concern over widespread distribution of PBDEs even in sparsely populated regions of the world, few studies have reported their occurrence in Brazil. In this study, PBDEs and PCBs levels were measured in selected fish species and dolphins from Paraiba do Sul River, Brazil. BDE 47 and 85 were the predominant congeners. Low chlorinated congeners showed the highest concentrations in fish; however dolphins presented the highest proportion of PCBs 153, followed by 138 and 180. The daily intake of PBDEs and PCBs was estimated for the population of this region. PCB daily intake through consumption of croaker was above the limits set by the Brazilian Ministry of Agriculture, raising great concern over the existence of a source of PCB contamination in Brazil.