Structural characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2,5,6-tetrabromocyclooctane (TBCO)

1,2,5,6-Tetrabromocyclooctane (TBCO) is a commercial brominated flame retardant that is employed mainly as an additive in textiles, paints and plastics. Very little is known about its presence or behavior in the environment or its analysis. TBCO can exist as two diastereomers, the stereochemistries of which have not been previously reported. We have named the first eluting isomer, under HPLC conditions, as alpha-TBCO (α-TBCO) and the later eluting isomer as beta-TBCO (β-TBCO) when using an Acquity UPLC BEH C₁₈ column with methanol/acetonitrile/water as the mobile phase. The structural elucidation of these two isomers was accomplished by ¹H NMR spectroscopy, GC/MS, LC/MS and X-ray structure determinations. α-TBCO is (1R,2R,5S,6S)-1,2,5,6-tetrabromocyclooctane and β-TBCO is rac-(1R,2R,5R,6R)-1,2,5,6-tetrabromocyclooctane. As with some other brominated cycloaliphatic compounds, TBCO is thermally labile and the isomers easily interconvert. A thermal equilibrium mixture of α- and β-TBCO consists of approximately 15% and 85% of these isomers, respectively. Separation of the two diastereomers, with minimal thermal interconversion between them, is achievable by careful selection of GC-capillary column length and injector temperature. LC/MS analyses of TBCO also presents an analytical challenge due to poor resolution of the isomers on chromatographic stationary phases, and weak intensity of molecular ions (or major fragment ions) when using LC-ESI/MS. Only bromide ions were seen in the mass spectra. APCI and APPI also failed to produce the molecular ion with sufficient intensity for identification.     

The individual and cumulative effect of brominated flame retardant and polyvinylchloride (PVC) on thermal degradation of acrylonitrile-butadiene-styrene (ABS) copolymer

Acrylonitrile-butadiene-styrene (ABS) copolymers without and with a polybrominated epoxy type flame retardant were thermally degraded at 450 degrees C alone (10 g) and mixed with polyvinylchloride (PVC) (8 g/2 g). Gaseous and liquid products of degradation were analysed by various gas chromatographic methods (GC with TCD, FID, AED, MSD) in order to determine the individual and cumulative effect of bromine and chlorine on the quality and quantity of degradation compounds. It was found that nitrogen, chlorine, bromine and oxygen are present as organic compounds in liquid products, their quantity depends on the pyrolysed polymer or polymer mixture. Bromophenol and dibromophenols were the main brominated compounds that come from the flame retardant. 1-Chloroethylbenzene was the main chlorine compound observed in liquid products. It was also determined that interactions appear at high temperatures during decomposition between the flame retardant, PVC and the ABS copolymer.     

Comparative toxicity of a brominated flame retardant (tetrabromobisphenol A) on microalgae with single and multi-species bioassays

The potential threat of emerging chemicals to the aquatic flora is a major issue. The purpose of the study was to develop a multispecies microalgae test in order to determine the impact of species interactions on the cytoxicity of an emergent toxic contaminant: the tetrabromobisphenol A (TBBPA). Single and multi-species tests were thus performed to study the effects of this flame retardant on two microalgae (Pseudokirchneriella subcapitata and Nitzschia palea) commonly observed in freshwater. A synthetic medium was designed to allow the growth of both species. The algae were exposed to 1.8, 4.8, 9.2, 12.9 and 16.5 μM of TBBPA for 72 h. After staining with fluorescein diacetate (FDA), viable cells of each alga species were analyzed by flow cytometry based on chlorophyll autofluorescence and intracellular esterase activity. Density and abundance of viable cells were assessed to follow the population growth and the cell viability. In TBBPA treated samples, the growth of the two microalgae was significantly inhibited at the three highest concentrations (9.2, 12.9 and 16.5 μM) in the two tests. At the end of the experiment (t = 72 h), the cell viability was also significantly smaller at these concentrations. The decreases of growth rate and viable cell abundance in TBBPA treated populations of N. palea were significantly higher in multi-species test in comparison with the single-species test. No significant differences were noticed between the two tests for P. subcapitata populations exposed to TBBPA.     

Effect of brominated flame retardant on the pyrolysis products of polymers originating in WEEE

Environmental Science and Pollution Research - Chemical recycling is an environmentally friendly method, which is often used for the recycling of plastics included in waste electric and electronic...     

Correction to: Effect of brominated flame retardant on the pyrolysis products of polymers originating in WEEE

Environmental Science and Pollution Research - A Correction to this paper has been published: https://doi.org/10.1007/s11356-021-15862-7     

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.     

Volatilization of 1,2-dibromo-3-chloropropane (DBCP) from soils.

The volatilization of DBCP from soils, as affected by the soil characteristics and application techniques, was studied in a laboratory experiment. The volatilization rate of DBCP applied in water was higher from sandy and silty loam soils than from clay soil. Water added after DBCP application acted as a soil cover, decreasing the volatilization rate. The results obtained with DBCP application in hexane to air-dry soils, indicate that adsorption could be an important factor in reducing the volatilization losses. Diffusion coefficients were calculated from the volatilization parameters, by using a simplified relationship between volatilization losses and diffusion through soil.     

Review of historical aquatic toxicity and bioconcentration data for the brominated flame retardant tetrabromobisphenol A (TBBPA): effects to fish,invertebrates, algae,and microbial communities

This paper summarizes the historical and recent research on the aquatic toxicology and bioconcentration potential of tetrabromobisphenol A (TBBPA), a major flame retardant in electronics. Historical studies on TBBPA are presented in detail, and are compared with more recent research. The historical studies have not been published to date, though they were pivotal in regulatory assessments by the European Union, Canada, and the USA. These assessments have enabled the use of TBBPA as a flame retardant in electronic applications, to the present. The studies were conducted under a Test Rule by the US Environmental Protection Agency in 1987, and were sponsored by member companies of the North American Flame Retardants Alliance (NAFRA) through the American Chemistry Council. The studies were conducted under Good Laboratory Practice procedures, and include 6 acute toxicity tests of TBBPA with fish, invertebrates, algae, and microbes, eight chronic tests, and three bioconcentration studies with fish and invertebrates. Methods and empirical data for each study are detailed in an electronic supplement. Results of the NAFRA studies are compared with recent findings on TBBPA toxicity. Molluscan shell growth may be uniquely sensitive to TBBPA, more sensitive than chronic fish or crustacean toxicity endpoints. Several of the NAFRA studies and several independent studies have reported toxicities exceeding the empirical water solubility limits of TBBPA (in the range of 2.0 mg/L depending on pH). The validity of these results is discussed.     

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.     

Polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants in air and seawater of the European Arctic

The spatial distribution of polybrominated diphenyl ethers (PBDEs) and several alternative non-PBDE, non-regulated brominated flame retardants (BFRs) in air and seawater and the air-seawater exchange was investigated in East Greenland Sea using high-volume air and water samples. Total PBDE concentrations (Ó₁₀PBDEs) ranged from 0.09 to 1.8 pg m⁻³ in the atmosphere and from 0.03 to 0.64 pg L⁻¹ in seawater. Two alternative BFRs, Hexabromobenzene (HBB) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), showed similar concentrations and spatial trends as PBDEs. The air-seawater gas exchange was dominated by deposition with fluxes up to −492 and −1044 pg m⁻² day⁻¹ for BDE-47 and DPTE, respectively. This study shows the first occurrence of HBB, DPTE and other alternative flame retardants (e.g., pentabromotoluene (PBT)) in the Arctic atmosphere and seawater indicating that they have a similar long-range atmospheric transport potential (LRAT) as the banned PBDEs.     

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.     

Multivariate data analysis of organochlorines and brominated flame retardants in Baltic Sea guillemot (Uria aalge) egg and muscle

Concentrations of organochlorines (OCs) and brominated flame-retardants (BFRs) were determined in guillemot (Uria aalge) eggs from the island of Stora Karls? in the Baltic Sea where 10 eggs/year were collected in the years 2000, 2001 and 2002. The dominating contaminant in egg was p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) with a geometric mean (GM) concentration of 18200 ng/g lipid weight (lw). The GM concentration in egg of hexabromocyclododecane (HBCD) of 140 ng/glw, was significantly higher than that of polybrominated diphenyl ether (summation operatorPBDE) of 77 ng/glw. For the evaluation of the data multivariate data analysis techniques namely principal components analysis (PCA), partial least squares regression (PLS), soft independent modelling of class analogy (SIMCA classification), and PLS discriminant analysis (PLS-DA), were used. We investigated whether the eggs' biological characteristics co-varied with egg concentrations of OCs and BFRs, and found e.g., significant negative correlations between egg weight and concentrations of HCB and p,p'-DDE. A PLS model with analyzed BFRs as the Y matrix and OCs as the X matrix could, with varying accuracy, calculate the concentrations of BFRs in the individual egg from their concentrations of OCs (e.g., R(2)Y of 0.89 for BDE47, and of 0.50 for HBCD). Lastly, we compared the contaminant concentrations in the eggs to those in previously analyzed pectoral muscles from adult guillemots from Stora Karls?, from the year 2000. A PLS-DA model, showed that some of the contaminants (e.g., HBCD and CB28) had significantly higher concentrations in egg than in muscle, although 7 of the 14 contaminants showed no difference in concentrations between the two matrices.     

Trends of brominated diphenyl ethers in fresh and archived Great Lakes fish (1979-2005)

While few environmental measurements of brominated diphenyl ethers (BDEs) were completed prior to the mid-1990s, analysis of appropriately archived samples might enable the determination of contaminant trends back to the introduction of these chemicals. In this paper, we first investigate the stability of BDEs in archived frozen and extracted fish samples, and then characterize trends of these chemicals in rainbow smelt (Osmerus mordax) and lake trout (Salvelinus namaycush) in each of the Great Lakes between 1979 and 2005. We focus on the four most common congeners (BDE-47, 100, 99 and 153) and use a change-point analysis to detect shifts in trends. Analyses of archived fish samples yielded precise BDE concentration measurements with only small losses (0.8% per year in frozen fish tissues, 2.2% per year in refrigerated extracts). Trends in fish from all Great Lakes showed large increases in BDE concentrations that started in the early to mid-1980s with fairly consistent doubling times (generally 2-4 years except in Lake Erie smelt where levels increased very slowly), though concentrations and trends show differences by congener, fish species and lake. The most recent data show that accumulation rates are slowing, and concentrations of penta- and hexa-congeners in trout from Lakes Ontario and Michigan and smelt from Lake Ontario started to decrease in the mid-1990s. Trends in smelt and trout are evolving somewhat differently, and trout concentrations in the five lakes are now ranked as Michigan>Superior=Ontario>Huron=Erie, and smelt concentrations as Michigan>Ontario>Huron>Superior>Erie. The analysis of properly archived samples permits the reconstruction of historical trends, congener distributions, biomagnification and other information that can aid the understanding and management of these contaminants.     

Thermal formation of polybrominated dibenzofurans and dioxins from decabromodiphenyl ether flame retardant: Influence of antimony(III) oxide and the polymer matrix

While pure decabromodiphenyl ether forms highly brominated PBDF in combustion at 700°C in yields of ca. 7000 ppm the yield is significantly increased up to 16 percent in the polymeric matrix and the presence of antimony(III) oxide. Combustion of the ternary mixture results in a decrease of the temperature maximum to 500°C; the ratio of isomers is changed to lower brominated PBDF with the tetrabromo compounds as most abundant products.     

Biotransformation of the flame retardant tetrabromo-bisphenol A by human and rat sub-cellular liver fractions

The comparative in vitro metabolism of the flame retardant tetrabromo-bisphenol A was studied in rat and human using a [(14)C]-radio-labelled molecule. Tetrabromo-bisphenol A is metabolised into the corresponding glucuronide (liver S9 fractions) and several other metabolites produced by cytochrome P450 dependent pathways (liver microsomes and liver S9 fractions). No major qualitative differences were observed between rat and human, regardless of the selected concentration, within the 20-200 microM range. Tetrabromo-bisphenol A undergoes an oxidative cleavage near the central carbon of the molecule, that leads to the production of hydroxylated dibromo-phenol, hydroxylated dibromo-isopropyl-phenol and glutathione conjugated dibromo-isopropyl-phenol. The main metabolites of tetrabromo-bisphenol A are two molecules of lower polarity than the parent compound, characterised as a hexa-brominated compound with three aromatic rings and a hepta-brominated dimer-like compound, respectively. Both structures, as well as the lower molecular weight metabolites resulting from the breakdown of the molecule, suggest the occurrence of chemically reactive intermediates formed following a first step oxidation of tetrabromo-bisphenol A.     

溴系阻燃剂生产厂周边土壤中多溴联苯醚的污染特征与源解析

采集了山东潍坊某溴系阻燃剂生产厂周边表层土壤样品,分析了土壤中14种多溴联苯醚(PBDEs)的含量、组成和分布特征,并进行了来源解析和致癌风险评价.结果表明,道路土壤中14种PBDEs总质量浓度(∑14PBDEs)为1513.56～6303.74 ng/g,平均值为3515.43 ng/g,农田土壤中∑14 PBDEs...     

Spatial distribution and accumulation of brominated flame retardants, polychlorinated biphenyls and organochlorine pesticides in blue mussels (Mytilus edulis) from coastal waters of Korea

Blue mussels (Mytilus edulis) from 20 locations along the coastal waters of Korea were analyzed to elucidate the characteristic distribution and contamination status of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), polychlorinated biphenyls (PCBs) and organochlorine pesticides. To our knowledge, this is the first study to report on the contamination status of HBCDs from Korea. PBDEs and HBCDs were found in mussels at levels ranging from 6.6 to 440 and from 6.0 to 500 ng/g lipid wt., respectively. Concentrations of PBDEs in mussels from Korea were higher or comparable to available data in mussels from other countries. Among the organochlorine compounds (OCs) analyzed, levels of PCBs and DDTs were the highest followed by CHLs, HCHs and hexachlorobenzene. For all the compounds, higher concentrations were found in mussels from southeastern coast of Korea. The present study shows the importance of mussels as bioindicators for monitoring contaminants in coastal waters.     

Monobromo and higher brominated congeners of the marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1)

The marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) is widely distributed in the environment. In this study, we screened samples which have previously been found to contain remarkably high residues of Q1 (blubber of marine mammals from Australia, samples from Antarctica, human milk from the Faroe Island) for the additional presence of mixed chlorinated and brominated congeners. Using GC/ECNI-MS, all samples tested were positive and many contained four out of five possible bromohexachloro congeners (BrCl6-MBPs), five out of 14 possible dibromopentachloro congeners (Br2Cl5-MBPs), five of 21 possible tribromotetrachloro-congeners (Br3Cl4-MBPs), as well as several higher brominated congeners. About 20 heptahalo congeners of Q1 are described for the first time in the scientific literature. Isomers eluted within about one minute, respectively. Hence it is possible, that the peak clusters identified may be composed of more, co-eluting congeners. Similarities in the GC/ECNI-MS mass spectra with polychlorinated biphenyls (PCBs) were addressed. We also suggest an acronym system similar to that in use for polychlorinated biphenyls that may simplify the use of this substance class in scientific papers. In the samples from Australia, BrCl6-MBPs and Br2Cl5-MBPs amounted for 7-27.5% and 0.4-4.2% of Q1, respectively whereas Br3Cl4-MBPs and higher brominated MBPs were found in the range of <1% of Q1 or less.     

Evaluation of spatial distribution and accumulation of novel brominated flame retardants,HBCD and PBDEs in an Italian subalpine lake using zebra mussel (Dreissena polymorpha)

Because of the reduction in the use of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD), novel brominated flame retardants (NBFRs), including 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB), and pentabromoethylbenzene (PBEB), started to be marketed as alternatives to the banned formulations. In this study, the spatial distribution and accumulation of NBFRs, PBDEs, and HBCD in the biota have been investigated in the littoral compartment of a large and deep subalpine lake (Lake Maggiore, Northern Italy), using zebra mussel Dreissena polymorpha and roach (Rutilus rutilus) as bioindicators. To our knowledge, this is the first study reporting the contamination of NBFRs in the freshwater invertebrate D. polymorpha. Contamination of zebra mussel due to PBEB, HBB, and BTBPE was low, ranging from 0.9 to 2.9 ng/g lipid weight, from 1.1 to 2.9 ng/g l.w., and from 3.5 to 9.5 ng/g l.w., respectively. PBEB and BTBPE in roach were always below the detection limit, while the contamination of HBB ranged from < limits of detection (LOD) to 1.74 ng/g l.w., indicating a weak contamination. DBDPE was < LOD in all the considered biological samples. Finally, HBCD was detected in all organic tissues with mean concentrations up to 74.4 ng/g l.w. PBDE results, supported by principal component analysis elaboration, suggested a possible contamination due to the congeners composing the penta- and deca-BDE technical formulations, which are present in the Lake Maggiore basin. The biomagnification factor values showed that tetra- and penta-BDE biomagnified, while octa-, nona-, and deca-BDE were still bioavailable and detectable in the fish muscles, but they do not biomagnified. Considering the other BFRs, only HBCD showed a moderate biomagnification potential.