Environmental factors in debromination activity of polybrominated diphenyl ethers by hepatic microsomes of freshwater fish

Although the debromination of polybrominated diphenyl ethers (PBDEs) in fish species has been studied, environmental factors, such as chemical contamination and habitat temperature, have not been well understood. This study compared debromination of BDE209 by hepatic microsomes of wild and cultured fish. PBDE concentrations in muscle tissue were lower in cultured fish than in wild fish. Debromination activity was high in wild common carp, followed by cultured common carp, moderate in cultured ayu sweetfish, and low in two cultured fish (rainbow trout and cherry salmon) and wild Japanese sea bass. Although common carps have been known as the species which have higher debromination ability, there were differences between wild and cultured common carps. First, wild common carp debrominated much more BDE209 than cultured common carp. Second was debromination of BDE209 lasted 96 h in wild carp but only 24 h in cultured carp. Wild carp were collected from warm wastewater effluent with consistently high concentrations of micropollutants. Cultured carp were collected from colder clean waters. Therefore, environmental factors in debromination include contamination or ambient temperature. To investigate the effects of habitat environment on debromination of PBDEs, we collected wild carp in summer and winter at two different locations with similar PBDE contamination levels. Carp collected from the natural river in winter had the highest BDE99 debromination activity. Although the results indicated seasonal difference of debromination of BDE209, we could not confirm whether habitat temperature or physiological cycle of carp affected to debromination ability. Thus, further investigation such as in vivo experiment is required.

     

Exposure to polybrominated diphenyl ethers associated with consumption of marine and freshwater fish in Hong Kong

Concentrations of polybrominated diphenyl ethers (PBDEs) in market fish have not previously been reported in Hong Kong. Axial and ventral muscles from 10 each common species of freshwater and marine fish purchased from markets in Hong Kong were analyzed for 22 PBDEs. Among the 10 freshwater fish species, spotted snakehead (Channa maculate) contained the highest level of PBDEs in ventral muscle (130 ng g(-1) wet wt.). For marine fish, bigeye (Priacanthus macracanthus) showed significantly higher levels of PBDEs (60.7 ng g(-1)wet wt. in ventral tissue) than all other marine species. The levels of PBDEs in fish samples ranged from 0.53 to 130 ng g(-1)wetwt. The tetrabrominated congener BDE-47 and pentabrominated BDE-99 were the predominant congeners, which accounted for 27% and 30%, respectively, of the total PBDEs. Daily PBDE intake was calculated according to the different fish consumption rate for Hong Kong consumers, and the results ranged from 222 to 1198 ng day(-1) for marine fish and 403-2170 ng day(-1) for freshwater fish. The daily PBDE intake from fish reported here were higher than those reported from the United States (8.94-15.7 ng day(-1)) and Europe (14-23.1 ng day(-1)).     

Brominated-chlorinated diphenyl ethers formed by thermolysis of polybrominated diphenyl ethers at low temperatures

Polybrominated diphenyl ethers (PBDEs) are a group of brominated flame retardants (BFRs) used mainly as additives in different kinds of plastic material. Various PBDEs are found in all environmental compartments as well as in tissue and blood serum of animals and humans due to their persistence and tendency to bioaccumulate. Emission of PBDEs into the environment can occur during recycling of PBDE-containing plastic material or during their uncontrolled or insufficient combustion as e.g. in accidental fires or landfill fires. Under these circumstances, PBDEs can also function as precursor molecules for the formation of polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). In this study, we qualitatively investigated the reaction of two PBDE congeners, 2,2′,4,4′-tetrabromo diphenyl ether (BDE 47) and 2,2′,4,4′,5,5′-hexabromo diphenyl ether (BDE 153), as well as hexabromobenzene (HBB), a flame retardant used in the past, when exposed to temperatures between 250 °C and 500 °C. The formed reaction products were analysed by high resolution gas chromatography–low resolution mass spectrometry (HRGC-LRMS). Among others brominated–chlorinated diphenyl ethers were formed by chlorodebromination of the PBDEs. In addition, thermolysis of BDE 47 and BDE 153 in the presence of tetrachloromethane as model substance for an organic chlorine source was studied. Thermal treatment of HBB resulted in the formation of brominated–chlorinated benzenes.     

Occurrence, bioaccumulation and potential sources of polybrominated diphenyl ethers in typical freshwater cultured fish ponds of South China

To determine the potential input sources of polybrominated diphenyl ethers (PBDEs) to fish farming environments in South China, samples of seven various environmental matrices were collected from October 2006-September 2007. Tri- to deca-BDEs were detected in all samples analyzed, with mean concentrations (±standard deviations) at 5.7 ± 3.6 ng/L in pond water, 15 ± 11 ng/g dry wt. in pond sediment, 12 ± 3.8 ng/g dry wt. in bank soil, 21 ± 20 ng/g lipid wt. in fish, and 93 ± 62 ng/g lipid wt. in fish feeds. In addition, BDE-209 was the major constituent in all samples except fish and BDE-47 was predominant in fish samples. Relatively high abundances of BDE-49 were detected in all the samples compared to those in the penta-BDE technical products. Several bioaccumulation factors were evaluated. Finally, statistical analyses suggested that fish feed, as well as pond water at a lesser degree, may have been the major source of PBDEs in freshwater farmed fish.     

Sorption-desorption behavior of polybrominated diphenyl ethers in soils

Polybrominated diphenyl ethers (PBDEs) are flame retardants that are commonly found in commercial and household products. These compounds are considered persistent organic pollutants. In this study, we used 4,4′-dibromodiphenyl ether (BDE-15) as a model compound to elucidate the sorption and desorption behavior of PBDEs in soils. The organic carbon-normalized sorption coefficient (K_OC) of BDE-15 was more than three times higher for humin than for bulk soils. However, pronounced desorption hysteresis was obtained mainly for bulk soils. For humin, increasing concentration of sorbed BDE-15 resulted in decreased desorption. Our data illustrate that BDE-15 and probably other PBDEs exhibit high sorption affinity to soils. Moreover, sorption is irreversible and thus PBDEs can potentially accumulate in the topsoil layer. We also suggest that although humin is probably a major sorbent for PBDEs in soils, other humic materials are also responsible for their sequestration.     

State of polybrominated diphenyl ethers in China: an overview

Polybrominated diphenyl ethers (PBDEs), extensively used as flame retardants, are ubiquitous environmental contaminants that are found in both abiotic and biotic environmental samples. Sufficient evidence shows that PBDEs have been rapidly accumulating in the environment of China, especially in the Southeast regions. This paper summarizes and critically reviews the published scientific data on PBDEs in China, including the levels of PBDEs in the air, soil, water, sediment, the terrestrial and marine organisms, and human samples in China. The data preliminarily reveal the state of PBDEs in China.     

Kinetics and pathways for the debromination of polybrominated diphenyl ethers by bimetallic and nanoscale zerovalent iron: effects of particle properties and catalyst

Polybrominated diphenyl ethers (PBDEs) are recognized as a new class of widely-distributed and persistent contaminants for which effective treatment and remediation technologies are needed. In this study, two kinds of commercially available nanoscale Fe⁰ slurries (Nanofer N25 and N25S), a freeze-dried laboratory-synthesized Fe⁰ nanoparticle (nZVI), and their palladized forms were used to investigate the effect of particle properties and catalyst on PBDE debromination kinetics and pathways. Nanofers and their palladized forms were found to debrominate PBDEs effectively. The laboratory-synthesized Fe⁰ nanoparticles also debrominated PBDEs, but were slower due to deactivation by the freeze-drying and stabilization processes in the laboratory synthesis. An organic modifier, polyacrylic acid (PAA), bound on N25S slowed PBDE debromination by a factor of three to four compared to N25. The activity of palladized nZVI (nZVI/Pd) was optimized at 0.3 Pd/Fe wt% in our system. N25 could debrominate selected environmentally-abundant PBDEs, including BDE 209, 183, 153, 99, and 47, to end products di-BDEs, mono-BDEs and diphenyl ether (DE) in one week, while nZVI/Pd (0.3 Pd/Fe wt%) mainly resulted in DE as a final product. Step-wise major PBDE debromination pathways by unamended and palladized Fe⁰ are described and compared. Surface precursor complex formation is an important limiting factor for palladized Fe⁰ reduction as demonstrated by PBDE pathways where steric hindrance and rapid sequential debromination of adjacent bromines play an important role.     

Reductive debromination of nonabrominated diphenyl ethers by sodium borohydride and identification of octabrominated diphenyl ether products

A method was developed to study reductive transformation of highly brominated diphenyl ethers (BDEs). The method development is a part of a broader project where it will be used to determine the susceptibility of environmental pollutants to reductive conditions, in an attempt to create a scheme for determination of chemical’s persistence. This paper focuses on identification of octabrominated diphenyl ether transformation products from reductive debromination of the three nonabrominated diphenyl congeners (nonaBDE), BDE-206, -207 and -208. Sodium borohydride was used to explore the reductive debromination of the nonaBDEs. The transformation products were collected at two time-points and identified products were quantified by GC-MS. The reduction of the nonaBDEs lead primarily to debrominated products, mainly octaBDEs. The three nonabrominated DEs gave isomer-related transformation product patterns. BDE-207 and BDE-208 showed a propensity for ortho-debromination in the initial reaction step, while no discrimination between initial debromination positions was seen for BDE-206. All three nonabrominated DEs displayed a preferred initial debromination on the fully brominated DE ring.     

Determination of polybrominated diphenyl ethers (PBDEs) in fish samples from rivers and estuaries in Taiwan

Polybrominated diphenyl ethers (PBDEs) have been used extensively over the past two decades as flame retardants in many types of polymers, and have been found to be a class of contaminants of concern. Measurements of PBDEs in various environmental matrices from Sweden, Holland, Japan, North America, and elsewhere have been reported. We report data of PBDEs in fish samples taken from six rivers and three estuaries in Taiwan. Seven PBDE congeners were observed in all sixty samples. BDE-47 was found to be the dominant congener in all waters, and BDE-154 contributed more than BDE-99 and BDE-100. Nonetheless, BDE-154 and BDE-183 were the predominant congeners in some species studied. These results are somewhat different from those from other countries, where the pattern is typically BDE-47 > 99 >100 >154, 153, and is postulated to be due to the extensive use of octa-BDE rather than penta-BDE in Taiwan. The average concentration distribution across all samples of the sum of PBDE congeners ranged from 30.6 ng/g lipid to 281 ng/g lipid. The concentrations of PBDEs in fishes reported here are higher than those reported from European countries, but lower than those from the United States.     

Concentrations of polybrominated diphenyl ethers in blood serum from New Zealand

Polybrominated diphenyl ethers (PBDEs) were measured in samples of human blood serum taken from 23 donors in Wellington, New Zealand. Concentrations expressed as the sum of congeners 47, 99, 100, 153, 154, and 183 (SigmaPBDE) were - at an average of 7.17 ng SigmaPBDE g (lipid)(-1) - within the range reported for human tissues in Europe, but lower than in Australia and North America. The most likely source of this contamination is considered to be the release of PBDEs from imported consumer goods. The congener pattern observed is in line with that reported for human tissues outside North America, but shows a lower contribution of PBDE 47 to SigmaPBDE than observed in North Americans. No significant (p>0.1) differences between concentrations in males and females were detected, and no relationship between donor age and SigmaPBDE concentration was observed. One donor displayed concentrations that were significantly elevated (i.e. > average +2 standard deviations) above those in others in this study.     

House dust as a source of human exposure to polybrominated diphenyl ethers in Kuwait

This study reports concentrations of polybrominated diphenyl ethers (PBDEs) in dust samples collected from 17 homes in Kuwait. PBDEs were measured in all homes investigated with mean summation operatorPBDEs concentration ranging from 1 to 393 ng g(-1), with a geometric mean of 76 ng g(-1). The dominant congener in all samples was BDE 209 constituting ca. 85% of the summationPBDEs followed by BDE 99 (5%), BDE 47 (4.5%), and BDE 183 (2%). The congener mixture in dust is dominated by those in deca and penta formulations. Using the measured concentrations and estimates of dust ingestion rates for children and adults, estimated human non-dietary exposure based on mean PBDE levels were 14.8 and 1.5 ng day(-1) for children and adults, respectively. The 10-fold difference in exposure estimates between children and adults in this study supports previous reports that children are at greater risk from pollutants that accumulate indoors. The ubiquitous distribution of these chemicals as noted in this study highlights the fact that we are continuously exposed to low doses of chemicals in the indoor environment.     

Disruption of thyroid hormone binding to sea bream recombinant transthyretin by ioxinyl and polybrominated diphenyl ethers

A number of chemicals released into the environment share structural similarity to the thyroid hormones (THs), thyroxine (T(4)) and triiodothyronine (T(3)) and it is thought that they may interfere with the thyroid axis and behave as endocrine disruptors (EDs). One of the ways by which such environmental contaminants may disrupt the TH axis is by binding to TH transporter proteins. Transthyretin (TTR) is one of the thyroid hormone binding proteins responsible for TH transport in the blood. TTR forms a stable tetramer that binds both T(4) and T(3) and in fish it is principally synthesized in the liver but is also produced by the brain and intestine. In the present study, we investigate the ability of some chemicals arising from pharmaceutical, industrial or agricultural production and classified as EDs, to compete with [I(125)]-T(3) for sea bream recombinant TTR (sbrTTR). Ioxinyl, a common herbicide and several polybrominated diphenyl ethers were strong inhibitors of [I(125)]-T(3) binding to TTR and some showed even greater affinity than the natural ligand T(3). The TTR competitive binding assay developed offers a quick and effective tool for preliminary risk assessment of chemicals which may disrupt the thyroid axis in teleost fish inhabiting vulnerable aquatic environments.     

Assessment of polybrominated diphenyl ethers in eggs of waterbirds from South China

Concentrations of total polybrominated diphenyl ethers (PBDEs) in Ardeid eggs from Hong Kong, Xiamen and Quanzhou in south China ranged from 140-1000, 30-550 and 140-380ngg(-1), lipid wt., respectively. There were spatial and interspecies variations in the abundance and congeneric profiles of PBDEs. The different congeneric profiles observed among the study sites may be associated with the developmental phases of the cities, as well as a possible consequence of debromination of BDE209. Marked concentrations of higher-brominated diphenyl ethers (BDEs 183, 196, 197, 206, 207 and 209) were detected in the egg samples from all sites, probably indicating uptake of BDE209 by top predators, and that there is widespread occurrence of BDE209 in south China. Comparisons of egg concentrations of BDEs 47, 99, 153 and 209 with tentative critical concentrations for neurobehavioral effects and oxidative stress indicated some potential risks for BDE99 and BDE209 in the Ardeid populations.     

GC/MS analysis of polybrominated diphenyl ethers in fish collected from the Inland Sea of Seto, Japan

Development of an analytical method for polybrominated diphenyl ethers (PBDEs) in fish and their concentration in Japanese marine fish were investigated. Fish homogenate was extracted with diethyl ether/hexane (1 + 3). The extract was cleaned up by automated gel permeation chromatography (GPC) and then by mini-column chromatography, which consisted of three layers of silica gel and sulfuric acid-impregnated silica gel. The PBDE fraction was concentrated and injected into a GC/MS with negative chemical ionization (NCl). Recoveries of the 15 individual PBDEs (BDE-15, 28, 37, 47, 66, 71, 75, 77, 85, 99, 100, 119, 153, 154, and 209) each at a fortification level of 4 ng/g lipid were in the range of 88-128% and the relative standard deviations (RSD) were 0.43-7.6% (n = 4). Seven species of marine fish (conger eel, flounder, gray mullet, horse mackerel, red sea bream, sea bass, and yellowtail) were collected from the Inland Sea of Seto, and were analyzed with the developed method. Seven PBDEs (BDE-28, 47, 66, 99, 100, 153, and 154) were detected in all the samples. The most abundant PBDE congener was BDE-47 found in all the samples. Relatively high levels of PBDEs were found in the gray mullets and yellowtails.     

Bioaccumulation of polybrominated diphenyl ethers in harbor seals from the northwest Atlantic

Polybrominated diphenyl ethers (PBDEs) were analyzed in blubber of harbor seals (Phoca vitulina concolor) collected between 1991 and 2005 along the northwest Atlantic. ∑PBDE concentrations (mono- to hexa-BDEs) detected in blubber samples (n = 42) ranged from 80 to 25 720 ng g⁻¹ lw, (overall mean 2403 ± 5406 ng g⁻¹ lw). By age, mean ∑PBDE concentrations were: 3645 ± 7388, 2945 ± 5995, 1385 ± 1265, and 326 ± 193 ng g⁻¹ lw in pups, yearlings, adult males, and adult females, respectively. Unlike the trend for PCBs, no decreasing gradient from urban to rural/remote areas was observed for PBDEs in these samples, likely reflecting inputs from local sources. No significant temporal trend was observed for PBDEs in harbor seals between 1991 and 2005, although congener profiles shifted over time. Tetra-BDE-47 was the dominant congener, followed by BDEs-99, -100, -153, -154, and -155 in varying order, suggesting exposure to the penta-BDE product. In adult males, the hexa-BDEs contributed more to the total (22%) than BDEs-99 and -100 (14%), and concentrations of BDE-155 were elevated compared with -154. Higher BDEs were detected in a subset of seals (n = 12) including hepta-BDE-183, the marker for the octa-BDE mixture, and octa-BDE-197, along with several unidentified hepta- and octa- congeners. BDE-209 was detected in seal blubber at concentrations ranging from 1.1 to 8 ng g⁻¹ lw, indicating that deca-BDE is bioavailable in this marine food web. This is the first study to document the accumulation of BDE-209 at measurable levels in wild harbor seals. While the PBDE patterns in blubber indicate exposure to all three BDE commercial mixtures, the data also suggest that BDE-209 debromination by seal prey fish may contribute to the loading of lower brominated congeners (hexa- to octa-BDEs) in these seals.     

Bioaccumulation of polybrominated diphenyl ethers in harbor seals from the northwest Atlantic

Polybrominated diphenyl ethers (PBDEs) were analyzed in blubber of harbor seals (Phoca vitulina concolor) collected between 1991 and 2005 along the northwest Atlantic. ∑PBDE concentrations (mono- to hexa-BDEs) detected in blubber samples (n = 42) ranged from 80 to 25 720 ng g⁻¹ lw, (overall mean 2403 ± 5406 ng g⁻¹ lw). By age, mean ∑PBDE concentrations were: 3645 ± 7388, 2945 ± 5995, 1385 ± 1265, and 326 ± 193 ng g⁻¹ lw in pups, yearlings, adult males, and adult females, respectively. Unlike the trend for PCBs, no decreasing gradient from urban to rural/remote areas was observed for PBDEs in these samples, likely reflecting inputs from local sources. No significant temporal trend was observed for PBDEs in harbor seals between 1991 and 2005, although congener profiles shifted over time. Tetra-BDE-47 was the dominant congener, followed by BDEs-99, -100, -153, -154, and -155 in varying order, suggesting exposure to the penta-BDE product. In adult males, the hexa-BDEs contributed more to the total (22%) than BDEs-99 and -100 (14%), and concentrations of BDE-155 were elevated compared with -154. Higher BDEs were detected in a subset of seals (n = 12) including hepta-BDE-183, the marker for the octa-BDE mixture, and octa-BDE-197, along with several unidentified hepta- and octa- congeners. BDE-209 was detected in seal blubber at concentrations ranging from 1.1 to 8 ng g⁻¹ lw, indicating that deca-BDE is bioavailable in this marine food web. This is the first study to document the accumulation of BDE-209 at measurable levels in wild harbor seals. While the PBDE patterns in blubber indicate exposure to all three BDE commercial mixtures, the data also suggest that BDE-209 debromination by seal prey fish may contribute to the loading of lower brominated congeners (hexa- to octa-BDEs) in these seals.     

超声波辅助萃取—气质联用色谱法测定活性污泥中的多溴联苯醚

建立了活性污泥中多溴联苯醚(PBDEs)的分析方法。活性污泥经超声波辅助萃取,用酸性硅胶、铜粉及复合硅胶柱纯化后,采用气质联用色谱(GC/MS)对7种PBDEs单体进行测定,内标法定量。结果表明,该方法具有很好的精密性和准确性,方法检测限为17～121 pg/g,加标回收率为84.5%～109.0%,相对标准偏差(RSD)为0.5%～2.8%,回收率指示物3,3’,4,4’-四溴联苯醚(BDE-77)的回收率平均值为89.2%,RSD为0.8%,能够满足活性污泥中PBDEs的测定要求。采用所建立的方法对杭州和台州的活性污泥样品进行了测定,结果显示,台州样品中PBDEs含量高于杭州样品,但两者都低于相关文献所报道的北美及欧洲国家活性污泥中PBDEs的含量。     

Environmental pollutants in the Swedish marine ecosystem, with special emphasis on polybrominated diphenyl ethers (PBDE)

Levels of polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDT) and perfluorinated organic compounds (PFCs) were analysed in whole herring (Clupea harengus) and sprat (Sprattus sprattus), eggs from common eider (Somateria mollissima) and eggs and livers from herring gull (Larus argentatus) from the Swedish west coast. The contaminant values obtained were compared with published values from the Arctic marine ecosystem. Tetra- and penta-brominated PBDEs were detected at low levels in herring, sprat and common eider (ΣPBDE 0.3-2.0 ng g⁻¹ ww), while the levels were higher in the herring gull samples (ΣPBDE 1.3-29.9 ng g⁻¹ ww). Hexa-decaBDEs were also found in samples from herring gulls. Eggs from herring gulls from the sub-Arctic contained four times more PBDE than the Swedish herring gulls eggs. Fish samples from the Arctic had two times higher levels of PBDEs and DDTs than similar samples from Sweden. The higher levels of contaminants in fish and seabirds from the Arctic reflect differences in transport processes, feeding ecology (reflected by trophic levels) and metabolism. PBDEs contributed to <10% of the total contaminant load in all investigated samples. The relative contribution of DDTs was higher in fish and bird samples from the Arctic when compared to Swedish samples, e.g. 65% in glaucous gull livers compared to 10% in herring gull livers. This study shows that even though the Swedish west coast is more urban than the Arctic, higher pollutants levels are found in seabird species from the Arctic.     

Levels and distribution of polybrominated diphenyl ethers (PBDEs) in the freshwater environment surrounding a PBDE manufacturing plant in China

Polybrominated diphenyl ethers (PBDEs) were determined in muscle, liver and eggs of freshwater fishes and surface sediments from the Nongkang River in Jinhu, Jiangsu Province, China. The present study is the first to report PBDE concentrations in the freshwater environment surrounding a PBDE manufacturing plant in China. The concentrations of 13 PBDE congeners in muscle, liver and eggs of freshwater fishes ranged from <LOD to 130, <LOD to 252 and <LOD to 33.3 ng/g lipid wt, respectively, while the concentrations of 13 PBDE congeners in surface sediments from sewage outfall, upstream and downstream of the river were 52, 9.2, 7.1 ng/g organic carbon wt, respectively. Contamination by PBDEs in this area was not serious when compared with other regions of the world. A relatively high proportion of BDE-183 was found, consistent with the octa-BDE technical mixtures from the manufacturing plant by the side of the river.