Leaching of brominated flame retardants in leachate from landfills in Japan

Leachate samples were taken from seven different landfills and concentrations of brominated flame retardants (BFRs), i.e. polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA), were quantified. Leaching characteristics of BFRs, especially factors affecting leachability, were clarified to obtain basic information regarding the release of BFRs into the environment. The results obtained for observed levels of the sum of PBDE-47, -99 and -100 were n.d.--4000 pg/l for the raw leachate and n.d. for the treated one, respectively, and those of TBBPA were n.d.--620,000 pg/l for the raw leachate and n.d.--11,000 pg/l for the treated one, respectively. Three sites that not only had crushed material from bulk wastes such as waste electric and electronic equipment, but also were under operation or within a year since closure, indicated a higher concentration of BFRs than the other sites. In particular extremely high concentration of PBDEs was observed at a site with a large amount of organics. Considering the leaching characteristics of BFRs, there exists the possibility that leachability of PBDEs is influenced by the presence of dissolved humic matter (DHM) in the leachate. The high removal efficiency for BFRs in the leachate treatment process was also confirmed.     

Novel trends in the thermo-chemical recycling of plastics from WEEE containing brominated flame retardants

Environmental Science and Pollution Research - The amount of plastics from waste electric and electronic equipment (WEEE) has enormously increased nowadays, due to the rapid expansion and...     

Analysis of brominated flame retardants in house dust

The main objective of this study was to create a robust analytical method to analyse the flame retardants decabromodiphenylether (BDE-209), hexabromocyclododecane (HBCD), and tetrabromobisphenol-A (TBBPA) in house dust in order to estimate the degree of contamination of indoor environment. A liquid chromatography method equipped with a UV-detector and electro spray-tandem mass spectrometry was used to achieve this result. Applying an external calibration for BDE-209, an internal calibration for TBBPA, and a standard addition method for HBCD low limits of quantification were obtained. The analytical procedure was carried out under exclusion of UV-light as the target compounds potentially degrade when being exposed to UV-light. Empirical data were obtained in addition to the dust samples to estimate potential influences of apartment characteristics. A weak correlation between the number of electric devices and TBBPA was found.     

Analysis of brominated flame retardants in house dust

The main objective of this study was to create a robust analytical method to analyse the flame retardants decabromodiphenylether (BDE-209), hexabromocyclododecane (HBCD), and tetrabromobisphenol-A (TBBPA) in house dust in order to estimate the degree of contamination of indoor environment. A liquid chromatography method equipped with a UV-detector and electro spray-tandem mass spectrometry was used to achieve this result. Applying an external calibration for BDE-209, an internal calibration for TBBPA, and a standard addition method for HBCD low limits of quantification were obtained. The analytical procedure was carried out under exclusion of UV-light as the target compounds potentially degrade when being exposed to UV-light. Empirical data were obtained in addition to the dust samples to estimate potential influences of apartment characteristics. A weak correlation between the number of electric devices and TBBPA was found.     

An overview of brominated flame retardants in the environment

The presence of brominated flame retardant (BFR) chemicals, and particularly polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD), has become of increasing concern to scientists over the past decade. Environmental studies conducted primarily in Europe, Japan and North America indicate that these chemicals are ubiquitous in sediment and biota. The levels of PBDEs seem to be increasing, and several trends, including in humans, indicate that this increase may be rapid. The occurrence of high concentrations of certain PBDE isomers may be sufficient to elicit adverse effects in some wildlife. There is also concern that levels could cause adverse effects in sensitive human populations such as young children, indigenous peoples, and fish consumers. However, our knowledge about these chemicals, their sources, environmental behavior, and toxicity is limited, making risk assessment difficult. In this paper, the current state of knowledge is reviewed and areas for further research recommended to improve future monitoring and risk assessment efforts.     

Levels and trends of brominated flame retardants in the Arctic

Polybrominated diphenyl ethers (PBDEs) containing two to seven bromines are ubiquitous in Arctic biotic and abiotic samples (from zooplankton to polar bears (Ursus maritimus) and humans; air, soil, sediments). The fully brominated decabromodiphenyl ether (BDE-209), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA) and polybrominated biphenyls (PBBs) are also present in biotic and abiotic samples. Spatial trends of PBDEs and HBCD in top predators are similar to those seen for polychlorinated biphenyls (PCBs) and indicate western Europe and eastern North America as source regions. Concentrations of tetra- to heptaBDEs have increased significantly in North American and Greenlandic Arctic biota and in Greenland freshwater sediments paralleling trends seen further south. For BDE-209, increasing concentrations in Greenlandic peregrine falcons (Falco peregrinus) and in dated lake sediment cores in the Canadian Arctic have been seen during the 1990s. BDE-47, -99, -100 and -153 are observed to biomagnify in Arctic food webs. summation operatorPBDE concentrations in Arctic samples are lower than in similar sample types from more southerly regions and are one or more orders of magnitude lower than summation operatorPCB concentrations except for some levels for air. Air and harbor sediment results for PBDEs indicate that there are local sources near highly populated areas within the Arctic. Findings of PBBs on moss and TBBPA on an air filter, and that both are found in biota at high trophic levels indicates that these compounds may also reach the Arctic by long-range atmospheric transport. Based on the evidence of their presence in the Arctic and indications that most if not all are undergoing long-range transport, these brominated flame retardants (BFRs) have characteristics that qualify them as POPs according to the Stockholm Convention.     

Anaerobic degradation of brominated flame retardants in sewage sludge

Tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), and decabromodiphenyl ether (DecaBDE) are high production volume chemicals used as flame retardants in plastics for products such as electronic equipment, insulation panels, and textiles. The environmental safety of brominated flame retardants, especially their persistence, bioaccumulation, and toxicity is a controversial topic. Here, we studied and compared the degradation of TBBPA, HBCD, and DecaBDE under anaerobic conditions in digested sewage sludge. The half-lives of TBBPA and a technical HBCD mixture were 0.59 and 0.66 d, respectively. The fact that (+/-)-alpha-HBCD exhibited an almost doubled half-life compared to (+/-)-beta-HBCD and (+/-)-gamma-HBCD is an important finding with respect to the discussion on the persistence of individual HBCD stereoisomers and the recent reports on strong relative enrichment of alpha-HBCD in biota. We found no statistically significant enantioselective degradation of alpha-, beta-, or gamma-HBCD. Half-lives of TBBPA and a technical HBCD mixture were not dependent on the presence of additional nutrients or primers. Concentrations of TBBPA and a technical HBCD mixture decreased also in sterile control samples, however, at a rate that was more than a factor of 50 smaller than in incubations under non-sterile conditions. Compared to TBBPA and a technical HBCD mixture, DecaBDE exhibited a much longer half-life of 7 x 10(2)d in the same system. Pseudo-first-order degradation rate constants decreased according to the following sequence: TBBPA congruent with(+/-)-gamma-HBCD congruent with(+/-)-beta-HBCD>(+/-)-alpha-HBCD>DecaBDE. Preliminary investigations suggest that degradation of TBBPA, HBCD, and DecaBDE occurs in full-scale anaerobic digesters, as well.     

Levels and trends of brominated flame retardants in the European environment

In this paper, we review those data which have recently become available for brominated flame retardants (particularly the brominated diphenyl ethers (BDEs) and hexabromocyclododecane (HBCD)) in samples from the European environment. Environmental compartments studied comprise the atmosphere, sediments and soils, sewage sludges, and a variety of biological samples and food chains. This is currently a very active research area, and we cite over 70 studies reported in the literature during 2003-04. Findings include that the input of BDEs (especially BDE209) to the Baltic Sea by atmospheric deposition now exceeds that of PCBs by a factor of almost 40 times. Sewage sludge samples from both industrial and background locations show concentrations of BDEs, HBCD and tetrabromobisphenol-A (TBBP-A) that are of a similar order, indicating that the major source is from diffuse leaching from products into wastewater streams from users, households and industries generally. Point-sources from industries using BFRs (e.g. the textile industry) also generate local hot-spots. Sediment core studies identified the presence of two of the three PBDE formulations. The penta-mix formulation was clearly present from the beginning of the 1970s, but the deca-mix only appeared in the late 1970s. BDE183, BDE209 and HBCD were detected in peregrine falcons from Sweden and other birds feeding on terrestrial food chains. BDEs are found widely distributed in fish, including those from high mountain lakes in Europe, as a consequence of long-range atmospheric transport and deposition. A temporal trend study in archived freeze-dried mussels from the Seine estuary, France, indicated an exponential increase in BDE concentrations during the period 1982-1993, which levelled off in 1999 and 2001 and then began to decline after 2002. HBCD was detected in liver and blubber samples from harbour seals and harbour porpoises from the Wadden and North Seas, though very few animals yielded positive values for TBBP-A. There are difficulties in comparing data on summation operatorBDE from studies in which different suites of BDE congeners have been determined, and we suggest a common suite which will allow the study of all three commercial PBDE formulations.     

Distribution and levels of brominated flame retardants in sewage sludge

One hundred and sixteen sewage sludge samples from 22 municipal wastewater treatment plants in Sweden were analysed for brominated flame retardants. Polybrominated diphenyl ethers (PBDEs) were in the range n.d.-450 ng/g wet weight, tetrabromobisphenol A (TBBPA) varied between n.d. and 220 ng/g wet weight, 2,4,6-tribromophenol was in the range n.d.-0.9 ng/g wet weight and polybrominated biphenyls were not detected (except for a possible analytical interference). There was a significant variation in the samples among plants. Influence from industries and other local sources can therefore be assumed. The correlation pattern indicated contribution from three different types of technical products; composed of either low-brominated PBDEs, decaBDE or TBBPA.     

Transfer of brominated flame retardants from components into dust inside television cabinets

Television (TV) set components are highly flame resistant, with their added brominated compounds such as polybrominated diphenyl ethers (PBDEs). These compounds might be released indoors via dust, which presents a potential exposure pathway for humans in the home environment. In this study, we collected dust from inside TV sets and TV set component samples (parts of housing front cabinets, rear cabinets and circuit boards) of five sets used in Japan. We measured BFRs (i.e., PBDEs, tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs)) and polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/DFs). Analytical results of the TV components showed that the concentrations of PBDEs, TBBPA and PBDFs (48,000mug/g, 19,000mug/g and 9600ng/g as mean values, respectively) were all highest in the rear cabinets. The SigmaPBDD concentrations (460ng/g as a mean value) detected were highest in the circuit board samples. The respective SigmaPBDE and SigmaPBDF concentrations in the dust samples were 67-500mug/g (mean 300mug/g) and 180-650ng/g (mean 410ng/g). Such concentrations were 2-3 orders of magnitude higher than those previously reported for house dust samples, which suggests that the brominated compounds are transferred from TV components into dust. Comparison of congener patterns of the brominated compounds in the dust identified the components as the source of these BFRs.     

New insights into the endocrine disrupting effects of brominated flame retardants

The objective of this review is to provide an overview of recent studies demonstrating the endocrine disrupting (ED) effects of brominated flame retardants (BFRs), while highlighting interesting data presented at the recent international BFR workshop in Amsterdam in April, 2007. A review written in 2002 was used as a starting point and about 60 publications published since 2003 were reviewed. New insights into the in vivo effects of BFRs on thyroid hormone, estrogen and androgen pathways in both mammalian and non-mammalian models are provided, and novel (in vitro) findings on the mechanisms underlying ED effects are highlighted. Special attention is also given to reports on neurotoxicological effects at relatively low doses of BFRs, although an endocrine-related mechanism is disputable. Convincing evidence has been published showing that BFRs and importantly, BFR metabolites, have the potential to disrupt endocrine systems at multiple target sites. While some studies suggest a wide margin of safety between effect concentrations in rodent models and levels encountered in humans and the environment, other studies demonstrate that exposure to low doses relevant for humans and wildlife at critical time points in development can result in profound effects on both endocrine pathways and (neuro)development.     

Combustion of brominated flame retardants and behavior of its byproducts

The substance flow rate of PBDDs/DFs into flue gas and incineration residues from incineration of three types of waste samples containing brominated flame retardants were examined. The samples used consisted of PBDEs (a typical retardant), used TV casing materials (actual waste materials), and waste printed circuit boards. PBDDs/DFs concentrations in the experimental samples of PBDEs/PE, waste TV casing materials and printed circuit boards ranged between 3000 and 130,000 ng/g. These values are very high when compared to other investigations. The increase of chlorine concentration in input sample reduced the ratio of PBDDs/DFs in flue gas and raised the ratio of PCDDs/DFs. With adequate combustion control and flue gas treatment, the amount of PBDDs/DFs released from the incineration of resin containing brominated flame retardants was lower than the input amount. The presence of PBDDs/DFs in incineration residues dominated the total amount of dioxins released. When PBDDs/DFs, PCDDs/DFs and PXDDs/DFs were considered as a total, the total amount released was lower than the total amount input.     

Concentrations and specific loads of brominated flame retardants in sewage sludge

Many substances related to human activities end up in wastewater and accumulate in sewage sludge. The present study focuses on two classes of brominated flame retardants: polybrominated diphenyl ethers (BDE28, BDE47, BDE49, BDE66, BDE85, BDE99, BDE100, BDE119, BDE138, BDE153, BDE154, BDE183, BDE209) and hexabromocyclododecane (HBCD) detected in sewage sludge collected from a monitoring network in Switzerland. Mean concentrations (n=16 wastewater treatment plants) were 310, 149, 95 and 17microg per kg dry matter for decaBDE, HBCD, penta- and octaBDE, respectively. These numbers correspond well with other studies from European countries. DecaBDE, HBCD, penta- and octaBDE showed average specific loads (load per connected inhabitant per year) in sludge of 6.1, 3.3, 2.0 and 0.3mgcap(-1)yr(-1), respectively. This is in line with consumption and storage of the compounds in the environment and the anthroposphere. Discrepancies observed for octaBDE and HBCD can be explained by the release from materials where these compounds are incorporated in and/or their degradation during anaerobic sludge treatment. Loads from different types of monitoring sites showed that brominated flame retardants ending up in sewage sludge originate mainly from surface runoff, industrial and domestic wastewater.     

Analysis of Ah receptor pathway activation by brominated flame retardants

Brominated flame-retardants (BFRs) are used as additives in plastics to decrease the rate of combustion of these materials, leading to greater consumer safety. As the use of plastics has increased, the production and use of flame-retardants has also grown. Many BFRs are persistent and have been detected in environmental samples, raising concerns about the biological/toxicological risk associated with their use. Most BFRs appear to be non-toxic, however there is still some concern that these compounds, or possible contaminants in BFRs mixtures could interact with cellular receptors. In this study we have examined the interaction of decabromodiphenyl ether, Firemaster BP4A (tetrabromobisphenol A), Firemaster PHT4 (tetrabromophthalic anhydride), hexabromobenzene, pentabromotoluene, decabromobiphenyl, Firemaster BP-6 (2,2^′,4,4^′,5,5^′-hexabromobiphenyl) and possible contaminants of BFR mixtures with the Ah receptor. Receptor binding and activation was examined using the Gel Retardation Assay and increased expression of dioxin responsive genes was detected using the reporter gene based CALUX assay. The results demonstrate the ability of BFRs to activate the AhR signal transduction pathway at moderate to high concentrations as assessed using both assays. AhR-dependent activation by BFRs may be due in part to contaminants present in commercial/technical mixtures. This was suggested by our comparative analysis of Firemaster BP-6 versus its primary component 2,2^′,4,4^′,5,5^′-hexabromobiphenyl. Some technical mixtures of brominated flame-retardants contain brominated biphenyls, dioxins or dibenzofurans as contaminants. When tested in the CALUX assay these compounds were found to be equivalent to, or more active than their chlorinated analogues. Relative effective potency values were determined from dose response curves for these brominated HAHs.     

Characterization of polychlorinated biphenyls and brominated flame retardants in surface soils from Surabaya, Indonesia

In this study, soil contamination by PCBs, PBDEs, HBCDs and two novel BFRs such as 1,2-bis-(2,4,6-tribromopenoxy) ethane (BTBPE) and decabromodiphenyl ethane (DBDPE) in various locations such as industrial, urban, rural, dumping site and agricultural areas of Surabaya, Indonesia has been characterized in order to evaluate their contamination status, profiles, potential sources, fate and behavior. Range and median concentrations of PCBs, PBDEs, HBCDs, BTBPE and DBDPE were ND - 9.6 (1.2), 0.069 - 24 (7.4), ND - 1.8 (0.48), ND - 1.7 (0.14) and ND - 7.6 (2.2) ng g⁻¹ dw, respectively. Industrial, urban and dumping areas were inventoried as the main sources of these pollutants. Decreasing gradient levels were observed for these contaminants from industrial district, urban, dumping site, rural and agricultural areas, in that order. Furthermore, organic carbon contents and proximity to the point sources were found as the major controlling factors. Contaminant profiles were characterized by the predominance of hexa-, hepta- and penta-homologues for PCBs; deca-, nona- and octa- for PBDEs and α-isomer for HBCDs. Product mixtures such as Ar1260/KC600 and Ar1254/KC500 for PCBs, deca- and octa-BDEs for PBDEs were the possible common formulations used in study area. To our knowledge, this is a first comprehensive study on characterization of soil contamination by PCBs, PBDEs and HBCDs together with two novel BFRs in a highly industrialized city located in tropical region. This study provides baseline information for establishing national monitoring programs in Indonesia.     

Emissions of organophosphate and brominated flame retardants from selected consumer products and building materials

The emissions of selected flame retardants were measured in 1- and 0.02-m³ emission test chambers and 0.001-m³ emission test cells. Four product groups were of interest: insulating materials, assembly foam, upholstery/mattresses, and electronics equipment. The experiments were performed under constant environmental conditions (23°C, 50% RH) using a fixed sample surface area and controlled air flow rates. Tris (2-chloro-isopropyl)phosphate (TCPP) was observed to be one of the most commonly emitted organophosphate flame retardants in polyurethane foam applications. Depending on the sample type, area-specific emission rates (SER_a) of TCPP varied between 20 ng m⁻² h⁻¹ and 140 μg m⁻² h⁻¹.The emissions from electronic devices were measured at 60°C to simulate operating conditions. Under these conditions, unit specific emission rates (SER_u) of organophosphates were determined to be 10–85 ng unit⁻¹ h⁻¹. Increasing the temperature increased the emission of several flame retardants by up to a factor of 500. The results presented in this paper indicate that emissions of several brominated and organophosphate flame retardants are measurable. Polybrominated diphenylethers exhibited an SER_a of between 0.2 and 6.6 ng m⁻² h⁻¹ and an SER_u of between 0.6 and 14.2 ng unit⁻¹ h⁻¹. Because of sink effects, i.e., sorption to chamber components, the emission test chambers and cells used in this study have limited utility for substances low vapour pressures, especially the highly brominated compounds; hexabromocyclododecane had an SER_a of between 0.1 and 29 ng m⁻² h⁻¹ and decabromodiphenylether was not detectable at all.     

Maternal transfer of brominated flame retardants in zebrafish (Danio rerio)

In many species reproduction and embryonic development have been shown to be sensitive to environmental contaminants. Understanding embryonic exposure to environmental contaminants is thus highly important. In this study concentrations of brominated flame retardants (BFRs) were measured in zebrafish eggs after parental exposure for 42 days via the diet. Zebrafish were exposed to two doses of eleven structurally-diverse BFRs. Eight BFRs were detected in the female zebrafish and maternal transfer to eggs was evident for all eight compounds. The highest concentrations in eggs were observed for hexabromocyclododecane (HBCD) and 2,4,4'-tribromodiphenyl ether (BDE 28), followed by 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE 183) and tetrabromobisphenol A 2,3-dibromopropyl ether (TBBPA DBPE). Five potential BFR metabolites were tentatively identified in female fish and maternal transfer was observed also for these compounds. The lipid adjusted concentrations in eggs were significantly higher than the concentrations in female fish for several of the BFRs. Further, the results showed a generally higher transfer in the lower exposure level and also indicated a dependency on the physico-chemical properties of the compounds.     

Pyrolysis and GC/MS-analysis of brominated flame retardants in on-line operation

Flame retardants such as brominated diphenyl ethers (Bromkal 70-5-DE, FR 300 BA), 2,4,6-tribromophenol, pentabromophenol and hexabromobiphenyl were pyrolyzed at 600°C, 700°C, 800°C and 900°C in absence of oxygen in a SGE pyrojector, and the residues were analyzed by means of GC/MS in on-line operation. The pyrolysis of Bromkal 70-5-DE hereby yielded bromobenzenes (PBBz), bromophenols (PBP) and brominated dibenzofurans (PBDF). PBBz, bromonaphthalenes (PBN) and PBDF could be detected in the FR 300 BA pyrolysate, whereas brominated benzenes and dibenzodioxins formed during the pyrolysis of 2,4,6-tribromophenol. Unlike the pyrolysis of 2,4,6-tribromophenol, pentabromophenol pyrolysis produced mainly bromobenzenes along with traces of bromonaphthalenes, bromodioxins and bromodiphenyl ethers. The pyrogram of hexabromobiphenyl showed bromobenzenes and brominated biphenyls as key pyrolysate components.