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.     

Occurrence and levels of polybrominated diphenyl ethers (PBDEs) in recent sediments and marine organisms from Xiamen offshore areas, China

Surface sediments and porewater from 12 sites within Xiamen offshore areas and organisms from a heavily contaminated site Yuandang Lagoon were sampled and analyzed for eight polybrominated diphenyl ethers (PBDEs) congeners (-28, -47, -99, -100, -153, -154, -183 and -209). The total concentrations of eight PBDEs (∑₈PBDEs) and BDE-209 in sediments ranged from 0.27 to 76.54 ng/g with an average of 16.31 ng/g and from 0.10 to 70.11 ng/g with an average of 14.94 ng/g, respectively. Concentrations of ∑₈PBDEs in porewater ranged from 2.5 to 34.1 ng/L, with a mean value of 15.3 ng/L. In this study, the partition coefficients (log ) of PBDE congeners (without -209) were significantly correlated with their octanol-water partition coefficients (log K_OW) (r² = 0.74, P < 0.01). ∑₈PBDE concentrations ranged from 0.33 to 1.26 ng/g (lipid weight) in marine organisms, and PBDE congener patterns were significantly different between fish and clam, crab.     

Occurrence of persistent organic pollutants in marine fish from the Natuna Island,South China Sea

Five marine fish species were collected from the Natuna Island, South China Sea to investigate the occurrence of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs). Concentrations of PBDEs, PCBs, and DDTs in marine fish ranged from 2.85 to 7.82, 14.3 to 48.1, and 7.99 to 40.3 ng/g lipid weight, respectively. Higher concentrations of PBDEs, PCBs, and DDTs were observed in Snakefish (Trachinocephalus myops), which might be attributed to their different feeding and living habits. PCBs were the predominant POPs in all marine fish, followed by DDTs and PBDEs. BDE 47 and PCB 153 were the predominant congener of PBDEs and PCBs, respectively. Compositional distribution of DDTs indicated the possible presence of fresh input sources around the Natuna Island. The ratios of o,p′-DDT/p,p′-DDT being less than 1 in fish samples suggested that DDT contributions from dicofol seemed considerably low. New input sources of DDT in South China Sea are worth further research.     

Bioaccumulation and trophic transfer of polybrominated diphenyl ethers (PBDEs) in a marine food web from Liaodong Bay,North China

The concentrations of 21 polybrominated diphenyl ethers (PBDEs) congeners were analyzed in organisms within a marine food web collected from the Liaodong Bay, North China. The total concentrations of PBDEs in all samples ranged from 0.87 to 91.4 ng g⁻¹ lipid weight (lw). BDE-47 was the predominant congener and had a concentration ranging from 0.30 to 36.1 ng g⁻¹ lw. The trophic magnification factors (TMF) of the PBDEs were calculated using the trophic levels obtained from the stable nitrogen isotope ratios. The TMF value of ∑PBDEs was 3.50 for the entire food web and 2.21 for the food web excluding seabirds. Four concentration ratios, BDE-99/BDE-100, BDE-99/BDE-47, BDE-153/BDE-154 and BDE-183/BDE-154, decreased linearly with the increase of the trophic levels in the invertebrates and the fishes (p < 0.01). The results suggested that the PBDEs were steadily metabolized in the trophic transfer process along the food chain.     

Temporal trend, spatial distribution, and terrestrial sources of PBDEs and PCBs in Masan Bay, Korea

Congener specific determination of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) was carried out in 21 surface sediment samples and a sediment core from Masan Bay, Korea. Among the 40 PBDE congeners targeted only 29 were detectable. PBDE congener profile within sediments was dominated by BDE-209 followed by BDEs-99, -47, -153 and -183, sequentially. In surface sediments, the average ΣPBDEs levels approached that of average ΣPCBs values. However, trends observed in the sediment core suggest that this pattern will alter over time and result in higher surface sediment PBDE concentrations than PCBs in future. Various diffuse and point sources for PBDEs and PCBs were identified in this location. Shipping and other industrial activities were associated with PCB contamination while domestic and industrial waste discharges corresponded with PBDE contamination. The average concentration for PBDEs and PCBs in surface sediments were 5.7, 7.2 ng/g dry weight, respectively.     

Polybrominated diphenyl ether congeners in the young-of-the-year bluefish,Pomatomus saltatrix,from several nursery habitats along the US Atlantic coastline

Spatial trends of polybrominated diphenyl ether (PBDE) congeners were examined by using high resolution gas chromatography – low resolution electron impact mass spectrometry (GC-EIMS) in 414 samples of young-of-the-year (YOY) bluefish (Pomatomus saltatrix) collected from a total of 29 nursery habitats along the US Atlantic coastline from Massachusetts to Florida. Of the 26 target PBDE congeners, BDE-47 (4 Br), BDE-100 (5 Br), BDE-49 (4 Br), BDE-99 (5 Br), and BDE-154 (6 Br) were the five most frequently detected congeners in the order of decreasing importance. The sum of the concentrations of five major PBDE congeners, referred to as ΣPBDEs, varied between estuaries and also among samples from a given estuary. ΣPBDEs were lowest in YOY bluefish from Vineyard Sound, Nantucket Sound, Great Bay, Delaware Bay, Lynnhaven Bay, Cape Lookout, and Crescent Beach, with maximum ΣPBDE concentrations below 10 ng/g wet weight. ΣPBDEs in three bluefish samples from Stamford Harbor were detected at relatively high to unusually high concentrations of 69.1, 205, and 561 ng/g wet weight. ΣPBDE values for other Stamford Harbor bluefish were generally low. Highest PBDE concentrations were detected in the vicinity of industrial and urban locations within the New York – New Jersey metropolitan complex. Among them, bluefish from Newark Bay were generally the most contaminated with an average ΣPBDE value of 56.6 ± 30.8 ng/g wet weight. ΣPBDEs in bluefish from Newark Bay were numerically greater than ΣPBDEs in bluefish from all locations, however these differences were not statistically significant. Modest to good correlations between ΣPBDEs and lipids were observed for YOY bluefish from Buzzards Bay, Upper New Bedford Harbor, Lower New Bedford Harbor, Outer New Bedford Harbor, Providence Harbor, Housatonic River, Norwalk Harbor, Little Neck Bay, Newark Bay, Sandy Hook Bay, Great Bay, Delaware Bay, Patuxent River and Crescent Beach. Poor correlations between ΣPBDE and lipids were observed for bluefish from other estuaries. ΣPBDEs were not always correlated with fish length or weight. ΣPBDEs in YOY bluefish along the US Atlantic coastline modestly paralleled ΣPBDEs in mussels and oysters, from not exact but geographically loosely similar locations, reported in the NOAA Mussel Watch Program. A number of researchers who used the high resolution mass spectrometry reported additional PBDE congeners. Although PBDE congeners we report do appear to be the prominent congeners in these studies, it is likely that the comparisons will be skewed in certain instances.     

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.     

Polybrominated diphenyl ethers and polychlorinated biphenyls in sediments of southwest Taiwan: regional characteristics and potential sources

Very little information is available on the contamination of coastal sediments of Taiwan by PBDEs and PCBs. In this study, we determined the concentrations of 19 PBDE and 209 PCB congeners in 57 surface sediment samples to identify the possible sources of PBDEs and PCBs. The total PBDE and PCB concentrations ranged from below detection limit to 7.73 ng/g and 0.88-7.13 ng/g, respectively; these values are within the ranges observed for most coastal sediments worldwide. The PBDE congeners were dominated by BDE-209 (50.7-99.7%), with minor contributions from penta- and octa-BDEs. The signatures of PCB congeners suggested that PCB residues in Kaohsiung coast may be the legacy of past use or the result of ongoing inputs from the maintenance, repair and salvage of old ships. Principal component analysis of the congener-specific composition of PBDEs and PCBs revealed distinct regional patterns that are related to the use of commercial products.     

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.     

PCBs, PBDEs and organochlorine pesticides in crabs Hepatus pudibundus and Callinectes danae from Santos Bay, State of São Paulo, Brazil

The occurrence of persistent organic pollutants (POPs) as polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDE) in crabs Hepatus pudibundus and Callinectesdanae was assessed from two different places inside of the Santos Bay and Moela Island near one of the most economically important metropolitan areas in Southern Brazil. Among POPs analyzed, ∑PCBs (222-923 ng g(-1)lipid weight) and ∑DDTs (154-410 ng g(-1)lw) exhibited the highest concentrations in the crabs. ∑HCHs ranged from 10.3 to 30.9 ng g(-1)lw and were found in all individuals. Other OCPs found in lower concentration was Mirex (7.6-41.6 ng g(-1)lw) and HCB (5.83-16.9 ng g(-1)lw). ∑PBDEs (24.1 ng g(-1)lw) were only found in one male individual from the species C. danae collected near to the submarine sewage of Santos. Male crabs showed higher POP concentrations than female crabs for those two species.     

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.     

Polybrominated diphenyl ethers (PBDEs) and organochlorines in small cetaceans from Hong Kong waters: levels, profiles and distribution

Polybrominated diphenyl ethers (PBDEs) and organochlorine compounds (OCs) were determined in the blubber, liver and kidney of Indo-Pacific humpback dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides) stranded in Hong Kong coastal waters during 1995–2001. Among the organohalogen compounds analyzed, DDTs were the most dominant contaminants with concentrations ranging from 9.9 to 470 μg/g lipid wt. PBDEs in Hong Kong cetaceans, which are reported for the first time, were detected in all the samples with values ranging from 0.23 to 6.0 μg/g lipid wt., with a predominance of BDE-47. Results from this study suggest PBDEs should be classified as priority pollutants in Asia. Higher concentrations were found in humpback dolphins than in finless porpoises, and this was attributed mainly to differences in habitat. Elevated residues of PCBs and DDTs in some cetaceans suggest these species may be at risk.     

Persistent halogenated compounds in two typical marine aquaculture zones of South China

Samples of two seawater farmed fish (crimson snapper (Lutjanus erythopterus) and snubnose pompano (Trachinotus blochii)), water, air, sediment, fish feed, macroalgae and phytoplankton were collected from two estuarine bays (Daya Bay and Hailing Bay) in South China. The concentrations of persistent halogenated compounds (PHCs) including polybrominated diphenyl ethers (PBDEs), organochlorine pesticides and polychlorinated biphenyls (PCBs) varied widely with the different sample matrices under investigation. The compositional patterns in fish, fish feed, macroalgae and phytoplankton, as well as the good correlations between the abundances of p,p'-DDT and BDE-209 and their metabolites (i.e., p,p'-DDD and p,p'-DDE for p,p'-DDT and BDE-47 for BDE-209) in fish indicated the occurrence of DDT and PBDE biotransformation in fish body. Finally, the marine aquaculture environment in South China is somewhat biologically impaired by DDT-contaminated water, sediment and fish feed, and there may be some cancer risk associated with fish consumption for humans, especially for urban residents.     

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.     

Polybrominated diphenyl ethers do not affect metamorphosis but alter the proteome of the invasive slipper limpet Crepidula onyx

Man-made polybrominated diphenyl ethers (PBDEs) used as flame retardants in various consumer products may be harmful to marine organisms. Larvae of some marine invertebrates, especially invasive species, can develop resistance to PBDEs through altered protein expression patterns or proteome plasticity. This is the first report of a proteomics approach to study BDE-47 induced molecular changes in the invasive limpet Crepidula onyx. Larvae of C. onyx were cultured for 5 days (hatching to metamorphosis) in the presence of BDE-47 (1 μg L⁻¹). Using a 2-DE proteomics approach with triple quadrupole and high-resolution TOF-MS, we showed that BDE-47 altered the proteome structure but not the growth or metamorphosis of C. onyx larvae. We found eight significant differentially expressed proteins in response to BDE-47, deemed the protein expression signature, consisting of cytoskeletal, stress tolerance, metabolism and energy production related proteins. Our data suggest C. onyx larvae have adequate proteome plasticity to tolerate BDE-47 toxicity.     

Differential biomagnification of PCB, PBDE, Hg and Radiocesium in the food web of the European hake from the NW Mediterranean

Consumption of marine organisms represents one of the main exposure sources of contaminants for human populations. To obtain a global view of the contamination in commercial fish in the NW Mediterranean Sea, we analysed four types of priority contaminants (PCBs, PBDEs, Hg and (137)Cs) in the European hake, Merluccius merluccius, from the Gulf of Lions in relation with organism's trophic level (δ(15)N). All contaminants presented a significant increase in concentration in hake muscle with trophic level. However, obvious differences between contaminants were evidenced. Biomagnification factors (BMF and FWMF) along the hake food web were higher for Hg and CB-153 than for BDE-47 and (137)Cs, and increase in contaminant concentration with trophic level occurred at different rates depending on contaminants. Such differences of biomagnification patterns can be related to physico-chemical properties of the different contaminants.     

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.     

Persistent halogenated compounds in two typical marine aquaculture zones of South China

Samples of two seawater farmed fish (crimson snapper (Lutjanus erythopterus) and snubnose pompano (Trachinotus blochii)), water, air, sediment, fish feed, macroalgae and phytoplankton were collected from two estuarine bays (Daya Bay and Hailing Bay) in South China. The concentrations of persistent halogenated compounds (PHCs) including polybrominated diphenyl ethers (PBDEs), organochlorine pesticides and polychlorinated biphenyls (PCBs) varied widely with the different sample matrices under investigation. The compositional patterns in fish, fish feed, macroalgae and phytoplankton, as well as the good correlations between the abundances of p,p′-DDT and BDE-209 and their metabolites (i.e., p,p′-DDD and p,p′-DDE for p,p′-DDT and BDE-47 for BDE-209) in fish indicated the occurrence of DDT and PBDE biotransformation in fish body. Finally, the marine aquaculture environment in South China is somewhat biologically impaired by DDT-contaminated water, sediment and fish feed, and there may be some cancer risk associated with fish consumption for humans, especially for urban residents.     

A whole life cycle assessment on effects of waterborne PBDEs on gene expression profile along the brain-pituitary-gonad axis and in the liver of zebrafish

Polybrominated diphenyl ethers (PBDEs) are now found ubiquitously in the aquatic environment and biota, and there is a growing concern that PBDEs may disrupt endocrine systems, leading to reproductive impairments of aquatic animals. In our study, zebrafish (Danio rerio) were exposed to the 5 ng/L, 1 μg/L and 50 μg/L of DE-71 for the duration of the whole life cycle (120 days, from eggs to adults). The expression of selected genes along the brain-pituitary-gonadal (BPG) axis and liver, and the levels of plasma sex hormones were examined. In male fish, up-regulation of GnRH in brain, FSHβ and LHβ in pituitary, FSH-receptor, LH-receptor, and CYP19a in testis was clearly evident, while down-regulation of CYP11a and 3β-HSD was found in testis. In female fish, a 2.4-fold up-regulation of 3β-HSD was found in ovary upon exposure to 50 μg/L of DE-71. GnRH in brain, FSHβ and LHβ in pituitary were also up-regulated, while ERβ, TH and TPH in brain and GnRH-receptor in pituitary were significantly down-regulated. Hepatic ERα, AR and VTG in males were all down-regulated, while hepatic ERα and AR in female were up-regulated. Serum estradiol (E2) was reduced in both male and female upon exposure to DE-71, while significant increases in serum testosterone (T) and 11-keto-testosterone (11-KT) were only found in male but not female fish. The ratio of T/E2 as well as the ratio of 11-KT/E2 in male fish increased in a dose-dependent manner upon exposure to DE-71. Our overall results showed that whole life exposure of DE-71 altered the expression of regulatory genes and receptors at all three levels of the BPG axis in zebrafish, and the responses are sex dependent. The observed disruption of GnRH and GtHs can be further related to the subsequent disruption in both levels and balance sex steroid hormones.