Hydroxylated transformation products obtained after UV irradiation of the current-use brominated flame retardants hexabromobenzene, pentabromotoluene, and pentabromoethylbenzene.

Hexabromobenzene (HBB), pentabromotoluene (PBT), and pentabromoethylbenzene (PBEB) are current-use brominated flame retardants (cuBFRs) which have been repeatedly detected in environmental samples. Since information on hydroxylated transformation products (OH-TPs) was scarcely available, the three polybrominated compounds were UV irradiated for 10 min in benzotrifluoride. Fractionation on silica gel enabled the separate collection and identification of OH-TPs. For more insights, aliquots of the separated OH-TPs were UV irradiated for another 50 min (60 min total UV irradiation time). The present investigation of polar UV irradiation products of HBB, PBT, and PBEB was successful in each case. Altogether, eight bromophenols were detected in the case of HBB (three Br3-, four Br4-, and one Br5-isomer), and nine OH-TPs were observed in the case of PBT/PBEB (six Br3- and three Br4-congeners). In either case, Br➔OH exchange was more relevant than H➔OH exchange. Also, such exchange was most relevant in meta- and ortho-positions. As a further point, and in agreement with other studies, the transformation rate decreased with decreasing degree of bromination. UV irradiation of HBB additionally resulted in the formation of tri- and tetrabrominated dihydroxylated compounds (brominated diphenols) that were subsequently identified. These dihydroxylated transformation products were found to be more stable than OH-TPs.

Toxicity of decabromodiphenyl ethane on lettuce: Evaluation through growth, oxidative defense, microstructure, and metabolism.

Decabromodiphenyl ethane (DBDPE) as the most widely used novel brominated flame retardants (NBFRs), has become a ubiquitous emerging pollutant in the environment. However, its toxic effects on vegetable growth during agricultural production have not been reported. In this study, we investigated the response mechanisms of hydroponic lettuce to DBDPE accumulation, antioxidant stress, cell structure damage, and metabolic pathways after exposure to DBDPE. The concentration of DBDPE in the root of lettuce was significantly higher than that in the aboveground part. DBDPE induced oxidative stress on lettuce, which stimulated the defense of the antioxidative system of lettuce cells, and the cell structure produced slight plasma-wall separation. In terms of metabolism, metabolic pathway disorders were caused, which are mainly manifested as inhibiting amino acid biosynthesis and metabolism-related pathways, interfering with the biosyntheses of amino acids, organic acids, fatty acids, carbohydrates, and other substances, and ultimately manifested as decreased total chlorophyll content and root activity. In turn, metabolic regulation alleviated antioxidant stress. The mechanisms of the antioxidative reaction of lettuce to DBDPE were elucidated by IBR, PLS-PM analysis, and molecular docking. Our results provide a theoretical basis and research necessity for the evaluation of emerging pollutants in agricultural production and the safety of vegetables.

Emission and environmental distribution of decabromodiphenyl ethane (DBDPE) in China from 2006 to 2026: Retrospection, forecasting, and implications for assessment and management.

Decabromodiphenyl ethane (DBDPE) is the main alternative to decabromodiphenyl ether (deca-BDE) in commercial use. However, there is increasing evidence show that DBDPE is a potential persistent organic pollutant, and it has been found ubiquitously in environmental media across China in recent years. Monitoring studies have not been able to determine the overall levels and temporal trends of DBDPE contamination in China, and have been unable to explain how emission patterns can affect their environmental distribution. Therefore, this study estimated the temporal variance of DBDPE emissions and environmental concentrations in five regions of China from 2006 to 2026 using the PROduction-To-EXposure (PROTEX) mass balance model. The results showed that Guangdong Province was the greatest DBDPE pollution hotspot in China due to emissions from plastics manufacturing and e-waste disposal; there was also severe pollution in Shandong Province, where almost all the DBDPE in China is produced. The DBDPE concentrations in indoor and outdoor environments increased substantially in all regions during 2006-2021. Furthermore, in Guangdong Province and Shandong Province, the ratio of indoor/outdoor air concentrations was greater than or close to 1, indicative of significant outdoor emission sources of DBDPE. In contrast, the ratios for the Beijing-Tianjin-Hebei region, East China, and Southwest China were below 1 due to the indoor use of electronic equipment containing DBDPE. The temporal trends of these ratios indicated that DBDPE contamination has gradually spread from high-concentration environments with strong emission sources to low-concentration environments. The outcomes of this study have important implications for the risk assessment of DBDPE use in China and can be used to establish contamination-mitigation actions.

Histopathological and transcriptomic analyses reveal the reproductive endocrine-disrupting effects of decabromodiphenyl ethane (DBDPE) in mussel Mytilus galloprovincialis.

The novel brominated flame retardant DBDPE has become a widespread environmental contaminant and could affect reproductive endocrine system in vertebrates. However, information about reproductive endocrine-disrupting effects of DBDPE on invertebrates is totally unknown. In this study, mussels Mytilus galloprovincialis were exposed to 1, 10, 50, 200 and 500 µg/L DBDPE for 30 days. Histopathological and transcriptomic analyses were performed to assess the reproductive endocrine-disrupting effects of DBDPE in mussels and the potential mechanisms. DBDPE promoted the gametogenesis in mussels of both sexes according to histological observation, gender-specific gene expression (VERL and VCL) and histological morphometric parameter analysis. Transcriptomic analysis demonstrated that DBDPE suppressed the genes related to cholesterol homeostasis and transport in both sexes via different LRPs- and ABCs-mediated pathways. DBDPE also disturbed nongenomic signaling pathway including signaling cascades (GPR157-IP3-Ca2+) in males and secondary messengers (cGMP) in females, and subsequently altered the expression levels of reproductive genes (VMO1, ZAN, Banf1 and Hook1). Additionally, dysregulation of energy metabolism in male mussels induced by DBDPE might interfere with the reproductive endocrine system. Overall, this is the first report that DBDPE evoked reproductive endocrine-disruptions in marine mussels. These findings will provide important references for ecological risk assessment of DBDPE pollution in marine environment.

Reduced mitochondrial DNA copy number in occupational workers from brominated flame retardants manufacturing plants.

Decabrominated diphenyl ether (BDE-209) and its substitute decabromodiphenyl ethane (DBDPE) are two flame retardants that have similar structure and are widely used in various industrial products. The accumulation and potential toxicity of them to human health have already aroused attention, and some research showed that they may affect mitochondrial function. Therefore, this study focused on the population with high exposure to brominated flame retardants (BFRs) and the related changes in mtDNA copy number (mtDNAcn) in whole blood. 334 blood samples were collected from three groups of people in Shandong Province, including 42 BDE-209 occupational exposure workers from the BDE-209 manufacturing plant, 131 DBDPE occupational exposure workers from the DBDPE manufacturing plant, and 161 non-BFRs occupational exposure residents from the BFRs contaminated area. We measured the levels of BDE-209, DBDPE in serum sample, and the mtDNAcn in whole blood sample and analyzed these data by multiple linear regression. The average concentrations of BDE-209, DBDPE and ∑(BDE-209 + DBDPE) in BDE-209 occupational workers were 3510, 639 and 4600 ng/g lw, respectively; the average concentrations of BDE-209, DBDPE and ∑(BDE-209 + DBDPE) in DBDPE occupational workers were 229, 4040 and 4470 ng/g lw, respectively; the average concentrations of BDE-209, DBDPE and ∑(BDE-209 + DBDPE) in non-BFRs occupational exposure residents were 66.3, 45.7 and 137 ng/g lw, respectively. The relative mtDNAcn was 0.823 in BDE-209 occupational workers, 0.845 in DBDPE occupational workers and 0.989 in non-BFRs occupational exposure residents. A 10-fold increase in BDE-209, DBDPE concentrations was separately associated with a 0.068 and 0.063 decrease in mtDNAcn. Therefore, our study implied that BFRs may affect mitochondrial function. As increasing BFRs exposure has emerged in recent years, the relationship between BFRs exposure and mitochondrial function needs further study.

Decabromodiphenyl Ether versus Decabromodiphenyl Ethane: Source, Fate, and Influencing Factors in a Coastal Sea Nearing Source Region.

Both decabromodiphenyl ether (BDE 209) and decabromodiphenyl ethane (DBDPE) are still produced in large quantities in China, especially in the Shandong Province closed to the Bohai Sea (BS). This study conducted a comprehensive investigation of the distribution and budget of brominated flame retardants (BFRs) in the BS. BDE 209 was the predominant BFR in most of the investigated rivers flowing into the BS, although DBDPE exceeded BDE 209 in certain rivers as a result of the replacement of BDE 209 with DBDPE in North China. The spatial distributions of BFRs in the rivers were controlled by the proximity of the BFR manufacturing base and the extent of urbanization. BFRs' spatial distribution in the BS was influenced by a combination of land-based pollution sources, environmental parameters (e.g., suspended particulate matter, particulate organic carbon, and particulate black carbon), and hydrodynamic conditions. The spatial variation trend of BDE 209/DBDPE ratios in various environmental media provided useful information. Vertically, the BDE 209/DBDPE ratio decreased from the seawater surface layer to the sediment, indicating their differential transport in the BS. A multi-box mass balance model and analysis of BDE 209 showed that degradation was the primary sink of BFRs in seawater (∼68%) and surface sediment (∼72%) in the BS.

Different Hepatic Concentrations of Bromobenzene, 1,2-Dibromobenzene, and 1,4-Dibromobenzene in Humanized-Liver Mice Predicted Using Simplified Physiologically Based Pharmacokinetic Models as Putative Markers of Toxicological Potential.

Bromobenzene is an industrial solvent that elicits toxicity predominantly in the liver. In this study, the hepatic concentrations of bromobenzene and its related compounds 1,2-dibromobenzene and 1,4-dibromobenzene in humanized-liver mice were predicted after single oral administrations by simplified physiologically based pharmacokinetic (PBPK) models that had been set up on experimental plasma concentrations after single oral doses of 100 mg/kg to rats and 100-250 mg/kg to control mice and humanized-liver mice. The output values by simplified PBPK models were consistent with measured blood substrate concentrations in rats, control mice, and humanized-liver mice with suitable input parameter values derived from in silico prediction and the literature or estimated by fitting the measured plasma substrate concentrations. The predicted time-dependent hepatic concentrations after virtual administrations in humanized-liver mice were partly confirmed with single measured hepatic concentrations of bromobenzene and 1,4-dibromobenzene 2 h after oral doses of 150-250 mg/kg to humanized-liver mice. Moreover, leaked human albumin mRNA, a marker of the extent of human hepatic injuries, in humanized-liver mouse plasma was detected after oral administration of bromobenzene, 1,2-dibromobenzene, and 1,4-dibromobenzene. These results suggest that dosimetry approaches for determining tissue and/or blood exposures of hepatic toxicants bromobenzene, 1,2-dibromobenzene, and 1,4-dibromobenzene in humanized-liver mice were useful after virtual oral doses using simplified PBPK models. Using simplified PBPK models and plasma data from humanized-liver mice has potential to predict and evaluate the hepatic toxicity of bromobenzenes and related compounds in humanized-liver mice and in humans.

Brominated flame retardants in home dust and its contribution to brominated flame retardants bioaccumulation in children hair.

Brominated flame retardants (BFRs) in house dust have raised significant concern around the world. However, few studies have reported the correlation between BFR concentrations in house dust and children's hair samples. In this study, BFR concentrations in house dust and children's hair were measured. Chemical analysis showed that the total concentrations of polybrominated diphenyl ethers (PBDEs) in house dust ranged from 334 to 4444 ng g-1, with a median of 442 ng g-1, and the concentrations in children's hair ranged from 352 to 655 ng g-1, with a median of 530 ng g-1. In addition, two alternative flame retardants, pentabromoethylbenzene (PBEB) and hexabromobenzene, were frequently detected in house dust and human hair. BDE209 was the most abundant PBDE congener detected in both house dust and children's hair. A significant correlation was found between the integrated PCA score of BFR concentrations in house dust and in children's hair (r2 = 0.31, P < 0.05), indicating the great contribution of house dust to the bodily burden of PBDEs in children. Risk assessment indicated that children's exposure to PBDEs via non-dietary intake of house dust should be recognized as an important exposure pathway.

Spatial distribution and hazard of halogenated flame retardants and polychlorinated biphenyls to common kingfisher (Alcedo atthis) from a region of South China affected by electronic waste recycling.

Numerous studies have reported bioaccumulation of halogenated flame retardants (HFRs) and polychlorinated biphenyls (PCBs) in wildlife from electronic waste (e-waste) recycling sites. However, the concentrations and hazards of HFRs and PCBs in wildlife from non-e-waste sites which were not involved in any known e-waste recycling activities in the e-waste-impacted region are still unclear. Polybrominated diphenyl ethers (PBDEs), alternative HFRs (AHFRs; including dechlorane plus, decabromodiphenyl ethane, and 1,2-bis(2,4,6-tribromophenoxy) ethane), and PCBs were quantified in common kingfishers (Alcedo atthis) from a region affected by e-waste recycling in South China, and potential adverse effects were evaluated. Concentrations of ∑PBDEs and ∑PCBs in kingfishers ranged from 2.1 × 103-1.3 × 105 ng/g lipid mass (lm) and 2.1 × 103-1.5 × 106 ng/g lm, respectively. At e-waste recycling sites, these concentrations were 100- to 1000-fold greater than those in kingfishers from non-e-waste areas, where concentrations of ∑PBDEs and ∑PCBs were 16-1.2 × 103 and 39-3.0 × 103 ng/g lm, respectively. Concentrations of ∑AHFRs in kingfishers from e-waste sites and non-e-waste sites ranged from 8.5 to 3.6 × 102 and 0.8-2.9 × 102 ng/g lm, respectively. The greatest concentrations of PCBs in kingfishers were measured from the e-waste sites. Additionally, kingfishers from four non-e-waste sites in the vicinity of e-waste sites had greater PCB concentrations compared to the other six non-e-waste sites. Concentrations of AHFRs were negatively and significantly correlated with distance from an e-waste site, which indicated that AHFRs from non-e-waste sites might be influenced by point sources. Further, a significant (r2 = 0.53, p = 0.02) positive correlation between human population density and concentrations of ∑PBDEs in kingfishers from non-e-waste sites was observed. Concentrations of either PBDEs or PCBs from e-waste sites might pose severe, adverse reproductive effects to kingfishers, while the potential for adverse effects of PBDEs and PCBs to kingfishers from most non-e-waste sites seemed minimal.

Polybrominated diphenyl ethers and alternative halogenated flame retardants in mollusks from the Chinese Bohai Sea: Levels and interspecific differences.

Polybrominated diphenyl ethers (PBDEs) and alternative halogenated flame retardants (AHFRs) were measured in eleven mollusk species collected from the Chinese Bohai Sea. PBDEs and AHFRs were detected in all species, and their average total concentrations were in the range of 22.5-355 and 10.0-84.3 ng/g lipid weight, respectively. Decabromodiphenyl ether (BDE-209) and decabromodiphenylethane (DBDPE) were the dominant halogenated flame retardants (HFRs), contributing 22.5% to 73.6% and 3.1% to 38.3% of the total HFRs, respectively. The levels of PBDEs and AHFRs were moderate to high from a global perspective. Interspecific differences in the accumulation of PBDEs and AHFRs were characterized by heat map and cluster analysis. Composition profile differences were also observed, with higher proportions of AHFRs in gastropods than in bivalves. These species-specific differences in concentrations and profiles in mollusks were attributed to different species traits, including feeding habit, trophic level, and metabolic potential.

Halogenated flame retardants in the sediments of the Chinese Yellow Sea and East China Sea.

With the phasing out of traditional polybrominated diphenyl ethers (PBDEs), significant volumes of alternative brominated flame retardants (aBFRs) are being used and released into the environment compartment, especially in coastal regions. The levels and distribution of PBDEs, aBFRs, and dechlorane plus (DPs) were investigated in the surface sediments of the Yellow Sea (YS) and East China Sea (ECS) to examine the distribution and sources of these hydrophobic contaminants. The level and distribution of pollutants in the sediments of YS and ECS show obvious regional differences. As a major replacement for decabromodiphenyl ether (BDE 209), decabromodiphenyl ethane (DBDPE) was the dominant compound observed in the surface sediments, with a concentration one order of magnitude higher than that of BDE 209. High concentrations were found in the depositional zones of the YS, indicating that these contaminants may originate from land-based pollution sources (likely from the Laizhou Bay manufacturing base) near the Bohai Sea. The pollutants can be carried by the coastal current together with the sediment from the Yellow River, transported through the Bohai Strait and deposited in the mud zone of Northern and Southern YS. Low levels of halogenated flame retardants (HFRs) were found in the estuary of the Yangtze River and ECS, indicating that Yangtze River contributes less HFRs to the region. Riverine discharge, atmospheric deposition, surface runoff, ocean current system, and mud area deposition effects may be significant factors influencing the distributions of HFRs.

Stocks, flows and emissions of DBDPE in China and its international distribution through products and waste.

Decabromodiphenyl ethane (DBDPE) is an alternative to the commercial decabromodiphenyl ether (deca-BDE) mixture but has potentially similar persistence, bioaccumulation potential and toxicity. While it is widely used as a flame retardant in electrical and electronic equipment (EEE) in China, DBDPE could be distributed globally on a large scale with the international trade of EEE emanating from China. Here, we performed a dynamic substance flow analysis to estimate the time-dependent mass flows, stocks and emissions of DBDPE in China, and the global spread of DBDPE originating in China through the international trade of EEE and e-waste. Our analysis indicates that, between 2006 and 2016, ∼230 thousand tonnes (kt) of DBDPE were produced in China; production, use and disposal activities led to the release of 196 tonnes of DBDPE to the environment. By the end of 2016, ∼152 kt of the DBDPE produced resided in in-use products across China. During the period 2000-2016, ∼39 kt of DBDPE were exported from China in EEE products, most of which (>50%) ended up in North America. Based on projected trends of China's DBDPE production, use and EEE exports, we predict that, by 2026, ∼74 and ∼14 kt of DBDPE originating in China will reside in in-use and waste stocks, respectively, in regions other than mainland China, which will act as long-term emission sources of DBDPE worldwide. This study discusses the considerable impact of DBDPE originating in China and distributed globally through the international trade of EEE; this is projected to occur on a large scale in the near future, which necessitates countermeasures.

Levels, distributions, and ecological risk assessments of polybrominated diphenyl ethers and alternative flame retardants in river sediments from Vaal River, South Africa.

Sediments are known to be the ultimate sink for most pollutants in the aquatic environment. In this study, the concentrations of both legacy polybrominated diphenyl ethers (PBDEs) and alternative halogenated flame retardants (AHFRs) were measured in sediments samples from the Vaal River catchment. The concentrations of Σ7BDE-congeners ranged from 20 to 78 ng g-1 dry weight (dw) with BDE-209, -99, and -153 as the dominant congeners. The concentrations observed ranged from 9.4-56, 4-32, and 1-10.6 ng g-1 for BDE-209, -99, and -153, respectively. The concentrations of AHFRs, mainly contributed by decabromodiphenyl ethane (DBDPE) at approximately 95% of total AHFRs, ranged from 64 to 359 ng g-1 dw while the concentration of polybrominated biphenyls (PBBs), mainly PBB-209, ranged from 3.3-7.1 ng g-1 dw. The ratios of AHFRs to PBDEs observed in this study were 0.76, 1.17, and 7.3 for 2-ethyl-1-hexyl-2,3,4,5-tetrabromobenzoate and bis-(2-ethylhexyl)-tetrabromophthalate (EH-TBB & BEH-TEBP)/penta-BDE; 1,2-bis-(2,4,6-tribromophenoxy) ethane (BTBPE)/octa-BDE; and DBDPE/BDE209, respectively. These results indicate dominance of some AHFRs compared to PBDEs. Our results indicates that BDE-99 poses high risk (RQ > 1) while BDE-209 posed medium risk (0.1 < RQ < 1). Though the concentration of DBDPE was several orders of magnitude higher than BDE209, its ecological risk was found to be negligible (RQ < 0.01). Thus, more attention is required to regulate the input (especially the e-waste recycling sites) of brominated flame retardants into the environment.

Temporal trends of decabromodiphenyl ether and emerging brominated flame retardants in dust, air and window surfaces of newly built low-energy preschools.

The envelope of low-energy buildings is generally constructed with significant amounts of plastics, sealants and insulation materials that are known to contain various chemical additives to improve specific functionalities. A commonly used group of additives are flame retardants to prevent the spread of fire. In this study, decabromodiphenyl ether (BDE-209) and fourteen emerging brominated flame retardants (BFRs) were analyzed in indoor dust, air and on the window surface of newly built low-energy preschools to study their occurrence and distribution. BDE-209 and decabromodiphenyl ethane (DBDPE) were frequently detected in the indoor dust (BDE-209: <4.1-1200 ng/g, DBDPE: <2.2-420 ng/g) and on window surfaces (BDE-209: <1000-20 000 pg/m2 , DBDPE: <34-5900 pg/m2 ) while the other thirteen BFRs were found in low levels (dust: <0.0020-5.2 ng/g, window surface: 0.0078-35 pg/m2 ). In addition, the detection frequencies of BFRs in the indoor air were low in all preschools. Interestingly, the dust levels of BDE-209 and DBDPE were found to be lower in the environmentally certified low-energy preschools, which could be attributed to stricter requirements on the chemical content in building materials and products. However, an increase of some BFR levels in dust was observed which could imply continuous emissions or introduction of new sources.

Measurement of legacy and emerging flame retardants in indoor dust from a rural village (Kopawa) in Nepal: Implication for source apportionment and health risk assessment.

Under the Stockholm Convention, signatory countries are obliged to direct source inventories, find current sources, and provide ecological monitoring evidence to guarantee that the encompassing levels of persistent organic pollutants (POPs) are declining. However, such monitoring of different types of POPs are to a great degree constrained in most developing countries including Nepal and are primarily confined to suspected source area/ densely populated regions. In this study, 9 polybrominated diphenyl ethers (PBDEs), 2 dechlorane plus (DPs), 6 novel brominated flame retardants (NBFRs) and 8 organophosphate ester flame retardants (OPFRs) were investigated in indoor dust from a rural area (Kopawa) in Nepal in order to evaluate their occurrence/level, profile, spatial distribution and their sources. Additionally, health risk exposure was estimated to anticipate the possible health risk to the local population. The results showed that OPFRs was the most abundant FR measured in the dust. The concentration of ∑8OPFRs was about 2, 3 and 4 orders of magnitude higher than the ∑6NBFRs, ∑9PBDEs, and ∑2DPs, respectively. Tris (methylphenyl) phosphate (TMPP) and Tris (2-ethylhexyl) phosphate (TEHP) were the most abundant OPFRs analyzed in the dust; while decabromodiphenyl ethane (DBDPE) exceeded among NBFRs. Likewise, 2,2',3,3',4,4',5,5',6,6'-decabromodiphenylether (BDE-209) was the most identified chemical among PBDEs. The total organic carbon (TOC) content in dust was significantly and positively connected with octa-BDEs (Rho = 0.615, p < 0.01), BTBPE (Rho = 0.733, p < 0.01), TPHP (Rho = 0.621, p < 0.01), TEHP (Rho = 0.560, p < 0.01) and TMPPs (Rho = 0.550, p < 0.01), while black carbon (BC) was either weakly related or not related, suggesting little or no impact of BC in the distribution of FRs. Principal component analysis indicated the contribution from commercial penta-, octa- and deca-BDEs formulation, the adhesive substance, food packaging and paints, and degradation of BDE-209 as the essential sources of FRs. Health risk exposure estimates showed that dermal absorption via dust as the primary route of FRs intake. The estimated daily exposure of PBDEs, NBFRs and OPFRs were 2-10 orders of magnitude lower than their corresponding reference dose (RfD), suggesting insignificant risk. However, other routes such as inhalation and dietary intake might still be significant in the case of Kopawa which should be tested in future.

Novel brominated flame retardant (NBFR) concentrations and spatial distributions in global fishmeal.

Novel brominated flame retardants (NBFRs), which are lipophilic compounds that have been widely applied after the phasing-out of legacy BFRs, can bioaccumulate through the food chain. However, information on NBFRs in animal feeds, the beginning of farm-to-fork pathway, is very limited. Fishmeal is one of the most widely applied feedstuff worldwide. The present study identified eleven NBFRs from ninety-two globally collected fishmeal samples with levels in the range of 0.13-822 (mean: 15.1 ±â€¯85.5) ng/g lipid weight (lw). Hexabromobenzene (HBB) and pentabromotoluene (PBT) were the most prevalent contributors (detection frequencies: 95.7% and 73.9%, respectively), and decabromodiphenylethane (DBDPE) was the weightiest contributor (accounted for 67.1% of the ΣNBFRs, mean: 12.1 ±â€¯84.8 ng/g lw). From a geographical view, the highest NBFR level was found in Chinese fishmeal. The NBFRs fell within an order of magnitude in South America, Southeast Asia, Europe and United States. DBDPE was predominant in the fishmeal collected from China, South America and United States, but it was not detected in European fishmeal. The NBFR levels are significantly lower compared to the polybrominated diphenyl ethers (PBDEs) (p < 0.01), indicating that the distribution of NBFRs was not as wide as PBDEs in fishmeal. DBDPE was significantly correlated with BDE209 (r = 0.557, p < 0.01), which implies that the two chemicals might have similar sources. Quantitative structure-activity relationship (QSAR)results imply that the NBFRs might have similar persistence and biomagnification potential as legacy lipophilic POPs.

New brominated flame retardants and dechlorane plus in the Arctic: Local sources and bioaccumulation potential in marine benthos.

The aim of the present study was to investigate the presence and bioaccumulation of new flame retardants (nBFRs), polybrominated diphenyl ethers (PBDEs) and dechlorane plus (DDC-CO) in the marine environment close to an Arctic community. Passive sampling of air and water and grab sampling of sediment and amphipods was used to obtain samples to study long-range transport versus local contributions for regulated and emerging flame retardants in Longyearbyen, Svalbard. BDE-47 and -99, α- and ß-tetrabromoethylcyclohexane (DBE-DBCH), syn- and anti-dechlorane plus (DDC-CO) were detected in all investigated matrices and the DDC-COss at higher concentrations in the air than reported from other remote Arctic areas. Water concentrations of ΣDDC-COSs were low (3 pg/L) and comparable to recent Arctic studies. ΣnBFR was 37 pg/L in the water samples while ΣPBDE was 3 pg/L. In biota, ΣDDC-COSs dominated (218 pg/g ww) followed by ΣnBFR (95 pg/g ww) and ΣPBDEs (45 pg/g ww). When compared with other areas and their relative distribution patterns, contributions from local sources of the analysed compounds cannot be ruled out. This should be taken into account when assessing long-range transport of nBFRs and DDC-COs to the Arctic. High concentrations of PBDEs in the sediment indicate that they might originate from a small, local source, while the results for some of the more volatile compounds such as hexabromobenzene (HBBz) suggest long-range transport to be more important than local sources. We recommend that local sources of flame retardants in remote areas receive more attention in the future.

Legacy and alternative brominated flame retardants in outdoor dust and pine needles in mainland China: Spatial trends, dust-plant partitioning and human exposure.

Concentrations of 26 brominated flame retardants (BFRs), including 19 polybrominated diphenyl ethers congeners (PBDEs), 3 isomers of hexabromocyclododecanes (HBCDs), and 4 alternative BFRs (alt-BFRs; hexabromobenzene, pentabromotoluene, 1,2-bis(2,4,6-tribromphenoxy)ethane, and decabromodiphenylethane) were determined in outdoor settled dust and pine needles collected across mainland China. BFRs were extensively found in the two matrices, with mean total concentrations at 4090 and 314 ng/g dry weight (dw), in dust and pine needles, respectively. The total BFRs concentrations in dust significantly varied among three mixed-land-use categories, with mean concentrations of 74.3, 1284, and 25,525 ng/g dw in rural, urban, and point source areas, respectively. For PBDE congeners, dust samples contained predominantly BDE-209 (69.2% of the total BFRs), whereas lower brominated PBDEs such as BDE-28 (19.7%), -47 (11.0%), and -99 (12.2%) accounted for higher proportions in pine needles. Spatial distribution of BFRs showed distinct geographical signatures with the highest levels found in South Central China. Application of McLachlan's framework to our data suggested that the uptake of BFRs in pine needles was controlled primarily by kinetically limited gaseous deposition and by particle-bound deposition. Assessment on human exposure to BFRs through outdoor dust ingestion revealed a low risk for Chinese adults and toddlers.

Emerging brominated flame retardants and dechlorane-related compounds in European eels (Anguilla anguilla) from Latvian lakes.

Fifteen halogenated flame retardants (HFRs) including seven emerging brominated flame retardants (EBFRs) and eight dechlorane-related compounds (DRCs) were analyzed in eels (Anguilla anguilla) sampled from five Latvian lakes. Out of the seven EBFRs, hexabromocyclododecane (HBCD) and decabromodiphenyl ethane (DBDPE) were found in eels in quantifiable concentrations, up to 6.58 and 33.0 ng g-1 lipid weight (l.w.), respectively. The mean total concentration of DRCs (∑DRC) in the samples was 0.62 ng g-1 l.w. and the geographical distribution of DRC contamination was nearly uniform among the selected lakes. Dechlorane 602 (Dec 602) was the predominant component, whereas the composition of mixture containing syn- and anti-Dechlorane Plus (DP) stereoisomers showed a pronounced enrichment of the anti-DP isomer and was close to the composition of OxyChem® DP commercial product. The determined concentrations of HFRs were lower than in other studies of aquatic biota from Europe and Asia, and the obtained results reflect the acceptable environmental status of Latvian lakes with regard to the total content of HBCD (∑HBCD), considering the environmental quality standards (EQS) stated in the Directive 2013/39/EU. The highest ∑HBCD levels were observed in eels from lakes corresponding to the industrialization of those areas, while the results of principal component analysis (PCA) showed that the concentration of HBCD depended on the particular sampling lake, reflecting non-uniform contamination of the Latvian environment with this EBFR.

Evaluation of carbon isotope fractionation during anaerobic reductive dehalogenation of chlorinated and brominated benzenes.

Compound specific stable isotope analysis (CSIA) has been established as a useful tool to evaluate in situ biodegradation. Here, CSIA was used to determine microbial dehalogenation of chloro- and bromobenzenes in microcosms derived from Hackensack River sediments. Gas chromatography-isotope ratio mass spectrometry (GC-IRMS) was used to measure carbon isotope fractionation during reductive dehalogenation of hexachlorobenzene (HCB), pentachlorobenzene (PeCB), 1,2,3,5-tetrachlorobenzene (TeCB), 1,2,3,5-tetrabromobenzene (TeBB), and 1,3,5-tribromobenzene (TriBB). Strong evidence of isotope fractionation coupled to dehalogenation was not observed in the substrate, possibly due to the low solubilities of the highly halogenated benzene substrates and a dilution of the isotope signal. Nonetheless, we could measure a depletion of the δ13C value in the dichlorobenzene product during dechlorination of HCB, the sequential depletion and enrichment of δ13C value for trichlorobenzene in TeCB dechlorinating cultures, and the enrichment of δ13C during debromination of TriBB. This indicates that a measurable isotope fractionation occurred during reductive dehalogenation of highly halogenated chloro- and bromobenzenes in aquatic sediments. Thus, although more quantitative measurements will be needed, the data suggests that CSIA may have application for monitoring in situ microbial reductive dehalogenation of highly halogenated benzenes.