An overview of policies for managing polybrominated diphenyl ethers (PBDEs) in the Great Lakes basin

The Great Lakes are an important environmental and economic resource for Canada and the United States. The ecological integrity of the Great Lakes, however, is becoming increasingly threatened by a number of persistent, bio-accumulative and harmful chemicals that enter the Great Lakes ecosystem through fluvial and atmospheric deposition. Polybrominated diphenyl ethers (PBDEs), a class of brominated flame retardant, are among such chemicals, whose concentration in the Great Lakes has greatly increased in recent years. Despite growing concern over the possible health and environmental effects of these compounds, only four of the eight Great Lakes states have enacted regulations to ban/restrict the use of PBDE while the two Canadian Great Lakes provinces are yet to endorse any regulation. Of the three main commercial PBDE mixtures (pentaBDE, octaBDE and decaBDE), penta- and octaBDE are no longer manufactured or imported into the United States and Canada. DecaBDE, however, still finds use in a variety of products. In the present paper, the authors review the current regulations and policies for managing PBDEs in the Great Lakes jurisdictions and briefly review commercially available non-bromine chemical alternatives to PBDE. As these alternatives are comparatively more expensive than PBDE, future adoption of more eco-friendly flame retardants by the polymer industry will likely depend on stricter legislation regulating the use of PBDE and/or an increased public demand for PBDE-free products.     

Polybrominated diphenyl ether flame retardants in the North American environment

North America consumes over half of the world's production of polybrominated diphenyl ether (PBDE) flame retardants. About 98% of global demand for the Penta-BDE mixture, the constituents of which are the most bioaccumulative and environmentally widespread, resides here. However, research on the environmental distribution of PBDEs in North America has lagged behind that in Northern Europe. Examination of available governmentally maintained release data suggests that Deca-BDE use in the US substantially exceeds that in Canada. Penta-BDE use probably follows a similar pattern. PBDE demand in Mexico is uncertain, but is assumed to be comparatively modest. Recent research examining air, water, sediment, sewage sludge and aquatic biota suggests that Penta-BDE constituents are present in geographically disparate locations in the US and Canada. The less brominated congeners have been observed in areas distant from their known use or production, e.g. the Arctic. PBDEs have been detected in low concentrations in North American air, water and sediment, but much higher levels in aquatic biota. Increased burdens as a function of position in the food web have been noted. PBDE concentrations in US and Canadian sewage sludges appear to be at least 10-fold greater than European levels and may be a useful barometer of release. In general, PBDE concentrations in environmental media reported in North America are comparable or exceed those observed elsewhere in the world. In contrast to Europe, environmental burdens are increasing over time here, consistent with the greater consumption of the commercial mixtures. However, data remain relatively scarce. Deca-BDE in the North American environment appears largely restricted to points of release, e.g. urban areas and those where PBDE-containing sewage sludges have been applied. This lack of redistribution is likely due to its extremely low volatility and water solubility. Penta-BDE and Deca-BDE products are used in different applications and this may also be a factor controlling their environmental release.     

A review on human exposure to brominated flame retardants--particularly polybrominated diphenyl ethers

Brominated flame retardants (BFRs) have been and are still heavily used as additive or reactive chemicals in polymers and textiles. Only a few of the BFRs have been assessed in human subjects with a major data set on internal exposures to polybrominated diphenyl ethers (PBDEs). Increasing PBDE levels have been observed in mothers' milk from Sweden as well as in blood from Germany and Norway. The levels are in general lower than PCB levels. However, the PBDE concentrations found in the North Americans are considerably higher compared to European subjects. The PBDEs are dominated by 2,2',4,4'-tetrabromodiphenyl ether (BDE-47). Decabromodiphenyl ether (BDE-209) is reported both in the general population and in occupationally exposed persons showing the bioavailability of this high molecular weight compound. While the lower and medium brominated diphenyl ethers are persistent, BDE-209 has a fairly short half-life of approximately 2 weeks. Tetrabromobisphenol A (TBBPA) is readily eliminated in humans showing a half-life of about 2 days. Still, TBBPA is accumulated in humans but a continuous exposure to this BFR is required to maintain a certain level in the human subject. TBBPA has not been detected in the general population but in people exposed at work. The current review addresses human exposure routes and levels of BFRs.     

Toxic effects of brominated flame retardants in man and in wildlife

Brominated flame retardants (BFRs) are ubiquitous industrial chemicals, and many of them are produced in large volumes. Due to this fact, several BFRs are found in quantifiable levels in wildlife, as well as in humans. However, we are still lacking information on the effects of BFR in wildlife and, especially, in man. This review summarises the biological effects of polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA) and derivates, hexabromocyclododecane (HBCD) and polybrominated biphenyls (PBBs), however excluding other aspects such as environmental levels. These BFR groups were selected because of a large volume production (PBDEs, TBBPA and derivates), and availability of some toxicity data in spite of much lower production volumes (HBCD and PBBs). In addition, the increase in levels of PBDEs in human (breast milk) and wildlife samples during later time made it especially interesting to include this BFR group. PBDES: The commercial PBDE products predominantly consist of so-called penta-, octa- and decabromodiphenyl ether products. Each product consists of a rather narrow range of congeners and is named after the dominating congener as regards the bromination pattern. Generally, the PentaBDEs seem to cause adverse effects at the comparably lowest dose, whereas much higher doses were needed for effects of the DecaBDEs. The critical effects of PentaBDEs are those on neurobehavioural development (from 0.6 mg/kg body weight) and, at somewhat higher dose, thyroid hormone levels in rats and mice, of OctaBDEs on fetal toxicity/teratogenicity in rats and rabbits (from 2 mg/kg body weight), and of DecaBDEs on thyroid, liver and kidney morphology in adult animals (from 80 mg/kg body weight). Carcinogenicity studies, only performed for DecaBDEs, show some effects at very high levels, and IARC (1990) evaluates DecaBDEs not classifiable as to its carcinogenicity to humans. TBBPA: The toxicity of TBBPA in the experimental in vivo studies is suggested to be low. In most reported studies, only doses in g/kg body weight were effective, but at least one study suggested renal effects at around 250 mg/kg body weight. Although difficult to include and interpret in a quantitative risk assessment, the in vitro effects on immunological and thyroid hormones, as well as binding to erythrocytes should be noted. Before a solid standpoint could be reached on TBBPA toxicity additional studies must be performed. This statement is even more valid regarding the TBBPA derivates, where there is an almost complete lack of toxicity data. HBCD: Also in the case of HBCD, relevant toxicity studies are lacking. Based on the present animal studies, a critical effect is seen in the liver and on thyroid hormones (LOAEL 100 mg/kg body weight/day). However, in a recent short paper behavioural effects in mice pups were observed already at 0.9 mg/kg body weight, and behavioural effects may be a sensitive endpoint for HBCD, as well as for other BFRs. PBBS: Due to the Michigan accident in 1973-1974, many toxicity studies on PBBs are available. The critical experimental effects are those on reproduction and carcinogenicity, and a NOAEL of 0.15 mg/kg body weight/day could be suggested based on the cancer effects. In man no unequivocal effects have been observed, although in some studies neurological and musculoskeletal symptoms were suggested. Based on the carcinogenic effects in animals, a human TDI of 0.15 microg/kg body weight has been presented.To conclude, the toxicity data are almost entirely based on experimental models. There are differences among the BFR groups, as well as within these groups, both regarding type of toxic effect and at what dose it appears. As BFRs will continue to appear both in industrial applications and, even if the production has ceased, in our environment, there is a continued need for effects studies on BFRs.     

Environmental release and behavior of brominated flame retardants

Recently, environmental problems relating to brominated flame retardants (BFRs) have become a matter of greater concern than ever before, because of the recent marked increase in levels of polybrominated diphenyl ethers (PBDEs) found in human milk in Sweden and North America. The question that arises is whether environmental levels of PBDEs and other BFRs will continue to increase, causing toxic effects to humans. In an attempt to elucidate the current state of the science of BFRs, we review the consumer demand for BFRs (mainly in Japan), the characteristics of waste flame-retarded products, sources of emission, environmental behavior, routes of exposure of humans, temporal trends, and thermal-breakdown products of BFRs. At present, flame-retarded consumer products manufactured 10-20 years ago, when PBDEs were frequently used, are being dumped. The possible major sources of emission of BFRs into the environment are effluent and flue gases from BFR factories and other facilities processing BFRs. With respect to the environmental behavior of BFRs, the lower brominated compounds are, on the whole, predicted to be more volatile, more water soluble, and more bioaccumulative than the higher brominated compounds. The most probable route for exposure of the general human population to PBDEs, especially the lower brominated congeners, is through the diet. The release of BFRs from consumer products treated with these compounds could also lead to human exposure. Temporal trends in PBDE levels in the environment and in humans worldwide seem to vary considerably, depending on the regions or country, with possible reflections of the historic and current use of PBDEs. The environment and the general human population are also exposed to the thermal-breakdown products of PBDEs, such as polybrominated and mixed brominated/chlorinated dibenzo-p-dioxins and dibenzofurans (PBDDs/DFs and mixed PXDDs/DFs).     

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

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

Novel brominated flame retardants: a review of their analysis, environmental fate and behaviour

This review summarises current knowledge about production volumes, physico-chemical properties, analysis, environmental occurrence, fate and behaviour and human exposure to the "novel" brominated flame retardants (NBFRs). We define the term NBFRs as relating to BFRs which are new to the market or newly/recently observed in the environment. Restrictions and bans on the use of some polybrominated diphenyl ether (PBDE) formulations, in many jurisdictions, have created a market for the use of NBFRs. To date, most data on NBFRs have arisen as additional information generated by research designed principally to study more "traditional" BFRs, such as PBDEs. This has led to a wide variety of analytical approaches for sample extraction, extract purification and instrumental analysis of NBFRs. An overview of environmental occurrence in abiotic matrices, aquatic biota, terrestrial biota and birds is presented. Evidence concerning the metabolism and absorption of different NBFRs is reviewed. Human exposure to NBFRs via different exposure pathways is discussed, and research gaps related to analysis, environmental sources, fate, and behaviour and human exposure are identified.     

Metabolism in the toxicokinetics and fate of brominated flame retardants--a review

Several classes of brominated flame retardants (BFRs), namely polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCCD), bis(2,4,6-tribromophenoxy)ethane (BTBPE), and tris(2,3-dibromopropyl)phosphate (Tris), have been identified as environmental contaminants. PBDEs, TBBPA, and HBCCD are of particular concern due to increasing environmental concentrations and their ubiquitous presence in the tissues of humans and wildlife from Europe, Japan, and North America. Regardless, the toxicokinetics, in particular metabolism, of BFRs has received little attention. The present review summarizes the current state of knowledge of BFR metabolism, which is an important factor in determining the bioaccumulation, fate, toxicokinetics, and potential toxicity of BFRs in exposed organisms. Of the minimal metabolism research done, BFRs have been shown to be susceptible to several metabolic processes including oxidative debromination, reductive debromination, oxidative CYP enzyme-mediated biotransformation, and/or Phase II conjugation (glucuronidation and sulfation).However, substantially more research on metabolism is necessary to fully assess BFR fate, uptake and elimination kinetics, metabolic pathways, inter-species differences, the influence of congener structure, and the potential health risks to exposed organisms.     

An overview of commercially used brominated flame retardants,their applications,their use patterns in different countries/regions and possible modes of release

Brominated flame retardants (BFRs) are used in a variety of consumer products and several of those are produced in large quantities. These compounds have been detected in environmental samples, which can be attributed to the anthropogenic uses of these compounds. Brominated flame retardants are produced via direct bromination of organic molecules or via addition of bromine to alkenes; hence, an overview of the production and usage of bromine over the past three decades is covered. Production, application, and environmental occurrence of high production brominated flame retardants including Tetrabromobisphenol A, polybrominated biphenyls, Penta-, Octa-, Deca-brominated diphenyl ether (oxide) formulation and hexabromocyclododecane are discussed.     

Pesticide levels and environmental risk in aquatic environments in China — A review

China is one of the largest producers and consumers of pesticides in the world today. Along with the widespread use of pesticides and industrialization, there is a growing concern for water quality. The present review aims to provide an overview of studies on pesticides in aquatic environments in China. The levels in the water, sediment and biota were scored according to a detailed environmental classification system based on ecotoxicological effect, which is therefore a useful tool for assessing the risk these compounds pose to the aquatic ecosystem. Our review reveals that the most studied areas in China are the most populated and the most developed economically and that the most frequently studied pesticides are DDT and HCH. We show maps of where studies have been conducted and show the ecotoxicological risk the pesticides pose in each of the matrices. Our review pinpoints the need for biota samples to assess the risk. A large fraction of the results from the studies are given an environmental classification of “very bad” based on levels in biota. In general, the risk is higher for DDT than HCH. A few food web studies have also been conducted, and we encourage further study of this important information from this region.The review reveals that many of the most important agricultural provinces (e.g., Henan, Hubei and Hunan) with the largest pesticide use have been the subject of few studies on the environmental levels of pesticides. We consider this to be a major knowledge gap for understanding the status of pesticide contamination and related risk in China. Furthermore, there is also a lack of studies in remote Chinese environments, which is also an important knowledge gap. The compounds analyzed and reported in the studies represent a serious bias because a great deal of attention is given to DDT and HCH, whereas the organophosphate insecticides dominating current use are less frequently investigated. For the future, we point to the need for an organized monitoring plan designed according to the knowledge gaps in terms of geographical distribution, compounds included, and risks.     

Determinants of brominated flame retardants in breast milk from a large scale Norwegian study

Brominated flame retardants (BFRs), particularly polybrominated diphenyl ethers (PBDEs), are widely present in human populations. In order to investigate human exposure pathways and associations with socioeconomic and lifestyle factors, 393 breast milk samples from mothers living in various regions throughout Norway were analyzed. Up to ten PBDE congeners were measured in all the samples, hexabromocyclododecane (HBCD) and BDE-209 in subsets of 310 and 46, respectively. The median concentrations of the sum of the seven most prominent PBDEs (BDE-28, 47, 99, 100, 153, 154 and 183), BDE-209 and HBCD were 2.1, 0.32 and 0.86 ng/g lipids, respectively. These concentrations are comparable to the levels generally observed in human populations in Europe. The frequency distributions were quite skewed with long tails towards higher concentrations. Maternal age, parity, education, having a cohabitant employed as electrician, and ventilation were factors significantly associated with some of the BFRs, although these factors only explained a small amount of the variability (R² 0.04–0.16). The mothers' diet was not found to influence the breast milk PBDE and HBCD levels. Our results show that sources other than the diet are important for the variability seen in breast milk BFR concentrations and that exposure from the indoor atmosphere should be emphasized in future studies.     

Brominated flame retardants and polychlorinated biphenyls in fish from the river Scheldt, Belgium

Levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and polychlorinated biphenyls (PCBs) were measured in several fish species originating from the river Scheldt (Belgium). Five sampling locations were chosen in a highly industrialized area along the river, while two ponds in the vicinity of the river served as reference sites. The present study is a follow-up of a survey performed in 2000 which reported extremely high levels of PBDEs and HBCDs in eel (Anguilla anguilla) collected from the same region (Oudenaarde, Flanders). The sum of tri- to hepta-BDE congeners (2270+/-2260 ng/g lipid weight (lw), range 660-11500 ng/g lw) and total HBCDs (4500+/-3000 ng/g lw, range 390-12100 ng/g lw) were one order of magnitude higher than levels usually reported from freshwater systems, indicating the presence of point sources. In most samples, levels of total HBCDs were higher than those of PBDEs, probably due to the high density of factories using HBCD as an additive brominated flame retardant (BFR). The high values of HBCDs were confirmed by both gas- and liquid-chromatography-mass spectrometry. Although BFR levels were between the highest ever reported in freshwater ecosystems, PCBs could be detected at even higher concentrations (16000+/-14300 ng/g lw, range 3900-66600 ng/g lw), being among the highest levels recorded in Belgium. The inter-sampling site variation of PBDEs, HBCDs and PCBs was comparable. All locations presented similar PBDE congener profiles, with BDE 47 being the dominant congener, followed by BDE 100, BDE 99 and BDE 49, probably originating from the former use of the penta-BDE technical mixture. In order to estimate the impact of these point sources on human exposure, we further focussed on eels which showed a considerable decrease in the PBDE and HBCD levels between 2000 and 2006. Due to the wide span in concentrations between the different sampling locations, a variable contribution to the total human exposure through local eel consumption was estimated. The calculated daily intake ranged from 3 ng to 330 ng PBDEs/day for normal eel consumers, but was as high as 9800 ng PBDEs/day for anglers, which may be considered at risk.     

Polybrominated diphenyl ether in the East Asian environment: a critical review

Polybrominated diphenyl ethers (PBDEs) have been extensively used as flame retardants in consumer goods. Sufficient evidence shows that PBDEs have been rapidly accumulating in the environment worldwide. In Asia, deca-bromodiphenyl ether has been produced and used in large quantities, while penta-BDE has largely ceased in the mid-1990s. This paper summarizes and critically reviews the status of PBDE pollution in East Asia, with emphases on the comparisons with Europe and North America and the interpretation of the differences. In general, the concentrations of PBDEs in atmosphere, sludge, human and biological samples of East Asia are comparable to or lower than those in Europe and North America. However, in the sediments of waters near densely populated and heavily industrialized areas, PBDE levels are among the highest ever reported in the literature. In Japan and China, concentrations of PBDEs in sediment cores showed an increasing trend for the past 20-30 years. Also, PBDEs levels in human breast milk in Japan increased about 10-fold in the past 20 years. The presence of PBDEs in fur seal has increased about 150-fold in 1994 than that in 1972. Regional and inter-continental transport cannot be confirmed due to insufficient information. However, the detection of a number of PBDE congeners in a pristine lake on the Qinghai-Tibet Plateau may be an evidence of their long-range transport.     

Decabromodiphenyl ether (deca-BDE) commercial mixture components, and other PBDEs, in airborne particles at a UK site

The occurrence of the major components of the decabromodiphenyl ether (deca-BDE) flame retardant and other PBDEs was investigated in daily air particulate samples from 17th April to 20th May 2004 at a semi-rural site in north-west England. BDE-209 was found at between <0.49 and 100 pg m(-3) (median 13 pg m(-3)), and other higher-brominated PBDE congeners were also found, particularly the nona-BDEs (e.g. BDE-207: <0.042-79 pg m(-3), median 2.5 pg m(-3)). Deca- and nona-BDEs dominated the median particulate sample congener profile: 60% BDE-209, 16% BDE-207, 6% BDE-208 and 4% BDE-206. Nona-BDEs were greatly enriched, relative to BDE-209, compared to the deca-BDE commercial mixture, which may suggest degradation of BDE-209 between source and sampling site, or release from older deca-BDE commercial mixtures, which may have contained higher proportions of nona-BDEs. The highest PBDE concentrations occurred when air-masses passed over urban and industrial areas to the SSW-SW, though small local influences may also be seen. PBDE concentrations appear to have been influenced mainly by particle levels: 1-3 microm diameter particles for BDE-153, and 3-10 microm particles for BDEs with 7-10 Br atoms. BDE-153 may either be released from combustion sources, or re-condense onto small particles after emission, whereas BDE-209 and nona-BDEs appear to be associated with larger dust particles from industrial or domestic sources.     

Are brominated flame retardants endocrine disruptors?

Brominated flame retardants (BFRs) are a group of compounds that have received much attention recently due to their similarity with "old" classes of organohalogenated compounds such as polychlorinated biphenyls (PCBs), in terms of their fate, stability in the environment and accumulation in humans and wildlife. Toxic effects, including teratogenicity, carcinogenicity and neurotoxicity, have been observed for some BFR congeners, in particular the brominated diphenyl ethers (BDEs). This concise review focuses on the potency of BFRs and to disrupt endocrine systems, and attempts to answer the question whether or not BFRs are endocrine disruptors. Evidence is provided on the disruption of the thyroid hormone system by BFRs, with particular emphasis on the BDEs, as most recent data is available on this class of flame retardants. Similar to the hydroxylated PCBs, in vitro mechanistic studies as well as animal experiments have demonstrated the effects of BDEs on thyroid hormone transport and metabolism. An overview of possible effects of BFRs on the estrogen system is also provided. Research gaps are outlined, as well as ongoing and future studies in the European community aimed at contributing to comprehensive risk assessments based on the endocrine-disrupting effects of BFRs.     

Effects of pre and postnatal exposure to low levels of polybromodiphenyl ethers on neurodevelopment and thyroid hormone levels at 4 years of age

There are at present very few studies of the effects of polybromodiphenyl ethers (PBDEs), used as flame retardants in consumer products, on neurodevelopment or thyroid hormone levels in humans. The present study aims to examine the association between pre and postnatal PBDE concentrations and neurodevelopment and thyroid hormone levels in children at age 4years and isolate the effects of PBDEs from those of PCBs, DDT, DDE and HCB. A prospective birth cohort in Menorca (Spain) enrolled 482 pregnant mothers between 1997 and 1998. At 4years, children were assessed for motor and cognitive function (McCarthy Scales of Children's Abilities), attention-deficit, hyperactivity and impulsivity (ADHD-DSM-IV) and social competence (California Preschool Social Competence Scale). PBDE concentrations were measured in cord blood (N=88) and in serum of 4years olds (N=244). Among all congeners analyzed only PBDE 47 was quantified in a reasonable number of samples (LOQ=0.002ng/ml). Exposure to PBDE 47 was analyzed as a dichotomous variable: concentrations above the LOQ (exposed) and concentrations below (referents). Scores for cognitive and motor functions were always lower in children pre and postnatally exposed to PBDE47 than in referents, but none of these associations was statistically significant (β coefficient (95%CI) of the total cognition score: -2.7 (-7.0, 1.6) for postnatal exposure, and -1.4 (-9.2, 6.5) for prenatal exposure). Postnatal exposure to PBDE 47 was statistically significantly related to an increased risk of symptoms on the attention deficit subscale of ADHD symptoms (RR (95%CI)=1.8 (1.0, 3.2)) but not to hyperactivity symptoms. A statistically significant higher risk of poor social competence symptoms was observed as a consequence of postnatal PBDE 47 exposure (RR (95%CI)=2.6 (1.2, 5.9)). Adjustment for other organochlorine compounds did not influence the results. Levels of thyroid hormones were not associated to PBDE exposure. This study highlights the importance of assessing the effects of PBDE exposure not just prenatally but also during the early years of life. In the light of current evidence a precautionary approach towards PBDE exposure of both mothers and children seems warranted.     

Photochemistry of a major commercial polybrominated diphenyl ether flame retardant congener: 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE153)

The photochemistry of a major commercial polybrominated diphenyl ether (PBDE) flame retardant congener, 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE153), was investigated in acetonitrile, distilled water, and seawater. After a short irradiation period in acetonitrile at 302 nm, the major photoproducts of BDE153 included 2,2',4,4',5-(BDE99), 2,2',4,5,5'-(BDE101), and 2,4,4',5,5'-(BDE118) substituted penta-BDEs as primary photohydrodebromination products, 2,2',4,4'-(BDE47), 3,3',4,4'-(BDE77), 2,3',4,4'-(BDE66), and 2,2',4,5'-(BDE49) substituted tetra-BDEs as secondary photohydrodebromination products, a suite of non-2,3,7,8-substituted mono- through penta-brominated dibenzofurans, and three tetrabrominated 2-hydroxybiphenyl congeners. By comparison, irradiation in distilled water and seawater gave increased relative photohydrodebromination contributions and no evidence for the formation of brominated dibenzofurans or 2-hydroxybiphenyls. In all solvent systems, subsequent degradation of primary and secondary photoproducts under continuing irradiation led to a steadily decreasing reaction mass balance. The results suggest a short photochemical half-life for BDE153 in aquatic systems, with rapid photohydrodebromination to some of the most prevalent penta- and tetra-brominated diphenyl ether congeners typically observed in environmental matrices.     

Several current-use, non-PBDE brominated flame retardants are highly bioaccumulative: evidence from field determined bioaccumulation factors

With the phaseout of brominated flame retardants (BFRs) polybrominated diphenyl ethers (PBDEs), some non-PBDE BFRs have prompted to be alternatives to the discontinued PBDEs. To assess the bioaccumulation potential of these chemicals, field bioaccumulation factors (BAFs) for several non-PBDE BFRs including hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), pentabromotoluene (PBT), pentabromoethylbenzene (PBEB), and hexabromobenzene (HBB), were determined in the aquatic species from a natural pond in an electronic waste recycling site in South China. The log BAFs ranged 2.58-6.01, 3.24-5.58, 3.44-5.98, 2.85-5.98, 3.32-6.08, 2.04-4.77, 2.72-4.09 and 3.31-5.54 for α-HBCD, β-HBCD, γ-HBCD, ∑HBCDs, BTBPE, PBT, PBEB, and HBB, respectively. The log BAF values for HBCD isomers, BTBPE, and HBB were greater than 3.7 (corresponding BAF value 5000) in most of the investigated species, demonstrating their highly bioaccumulative properties. α-, β-, and γ-HBCDs, BTBPE, and HBB appeared comparable or had even greater BAFs compared to PBDE congeners with similar K(OW), suggesting that these BFRs may have a potentially high environmental risk. The BAFs for the given BFR compound were largely variable between species, due to the species-specific feeding ecology, trophic level, and metabolic capacity for these pollutants. Positive linear relationships between log BAF and log K(OW) (r2 = 0.59, p = 0.04), and molecular weight (r2 = 0.54, p = 0.06) of non-PBDE BFRs were observed in the species with low trophic level (Chinese mysterysnail), suggesting that the chemical's physicochemical properties also played key roles in the bioaccumulation processes.     

Dietary PBDE intake: a market-basket study in Belgium

A food market-basket, representative for the general Belgian population, containing various meat, fish and dairy food products, was assembled and analysed for its polybrominated diphenyl ether (PBDE) content. Additionally, fast food samples were also investigated. Based on the measured PBDE levels, an average daily dietary intake estimate of PBDEs was calculated. Of all foods analysed, fish had the highest average sum of PBDE levels (BDEs 28, 47, 99, 100, 153, 154, and 183; 460 pg/g ww), followed by dairy products and eggs (260 pg/g ww), fast food (86 pg/g ww) and meat products (70 pg/g ww). One fresh salmon filet had the highest total concentration of PBDEs (2360 pg/g ww), whereas levels in steak and chicken breast were the lowest of all foods analysed. BDE 209 was never found above LOQ in any food. PBDE intake calculations were based on the average daily food consumption in Belgium and were estimated between 23 and 48 ng/day of total PBDEs (lower and upper bound). This value is in accordance with what was previously reported for diets from geographical distinct areas, such as Canada, Finland, Spain, Sweden and the UK. Although it is only a minor constituent of the Belgian diet, fish is the major contributor to the total daily PBDE-intake (around 40%) due to the high PBDE levels in this type of food. Although low contaminated, meat products account for around 30% of the total dietary intake of PBDEs. Dairy products and eggs contribute to a lesser degree (less than 30%).