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Brominated flame retardants (BFRs) exhibit excellent flame retardant properties and are widely used in various industries. Among the common BFRs, tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCDs) pose substantial ecological and human health risks due to their extensive application and long-range transport. This study established 131 sample collection sites along the coast of the South China Sea (SCS) in Guangdong Province to assess the concentration, distribution, inventory, and ecological risk of TBBPA and HBCDs in surface sediments. The concentrations of TBBPA in SCS sediments ranged from < limit of detection (LOD) to 80 μg/kg dry weight (dw), and those of HBCDs from < LOD to 18 μg/kg dw. The diastereoisomers of HBCDs (α-, β-, and γ-HBCD) in the sediment samples accounted for 36 %, 13 %, and 51 %, respectively. Human activities, particularly those associated with nearby electronic waste disassembly and textile and garment industries, considerably influenced the dispersion of TBBPA and HBCDs. The inventories of TBBPA and HBCDs in Guangdong Province's SCS were estimated to be 3.2 × 10 5  kg and 7.2 × 10 4  kg, respectively. The average risk quotient values ranged from <0.01 to 0.016, indicating a low to negligible environmental risk. This study provides deeper insights into the distribution and scientific significance of HBCDs and TBBPA in SCS sediment samples, elucidates the current state of BFR contamination, and offers recommendations for future research on environmental safety and human health in the region., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Brominated flame retardants (BFRs) are bromine-bearing additives added to the polymeric fraction in various applications to impede fire ignition. The Stockholm Convention and various other legislations abolished legacy BFRs usage and hence, the so-called novel BFRs (NBFRs) were introduced into the market. Recent studies spotlighted their existence in household dust, aquifers and aquatic/aerial species. Co-pyrolysis of BFRs with metal oxides has emerged as a potent chemical recycling approach that produces a bromine-free stream of hydrocarbon. Herein, we investigate the debromination of two prominent two NBFRs; namely tetrabromobisphenol A 2,3-dibromopropyl ether (TD) and tetrabromobisphenol A diallyl ether (TAE) through their co-pyrolysis with zinc oxide (ZnO) and franklinite (ZnFe 2 O 4 ). Most of the zinc content in electrical arc furnace dust (EAFD) exists in the form of these two metal oxides. Conversion of these metal oxides into their respective bromides could also assist in the selective extraction of the valuable zinc content in EAFD. The debromination potential of both oxides was unveiled via a multitude of characterization studies to analyze products (char, gas and condensates). The thermogravimetric analysis suggested a pyrolytic run up to 500 °C and the TAE treatment with ZnO produced only a trivial amount of brominated compounds (relative area, 0.83%). Phenol was the sole common compound in condensable products; potentially formed by the β-scission debromination reaction from the parental molecular skeleton. Inorganic compounds and methane were the major constituents in the gaseous products. The pyrochar analyses confirmed the presence of metal bromides retained in the residue, averting the bromine release into the atmosphere. The ion chromatography analysis portrayed <8% of HBr gas release into the atmosphere upon pyrolysis with ZnO. The ZnO dominance herein envisaged further probes into other spinel ferrites in combating brominated polymers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The brominated flame retardant tetrabromobisphenol A-bis(2,3-dibromo-2-methylpropyl ether) (TBBPA-DBMPE) is a recommended substitute for hexabromocyclododecane (HBCD), a banned persistent organic pollutant, yet its potential toxicities remains largely unexplored. Here, we investigated the effects of a long-term exposure to TBBPA-DBMPE at nominal doses of 50 and 1000 μg/kg/d on lipid homeostasis in CD-1 mice, in comparison with 50 μg/kg/d HBCD as a positive control. Male pups received chemical treatments through maternal administration via drinking water from postnatal day 0-21, followed by direct administration through drinking water after weaning. On the 23rd week after treatment, the oral lipid tolerance test revealed that low-dose TBBPA-DBMPE as well as HBCD affected lipid tolerance, although the fasting serum triglyceride (TG) levels were not altered. When chemical treatment was extended to the 32nd week, TBBPA-DBMPE-treated animals displayed adipocyte hypertrophy in both white adipose tissue (eWAT) and brown adipose tissue (BAT) and hepatic steatosis, which was largely consistent with the effects of HBCD. These findings indicate that like HBCD, TBBPA-DBMPE led to increased lipid load in mice. Interestingly, we also observed intestinal histological changes, coupled with increased expression of lipid absorption-related genes in both HBCD and TBBPA-DBMPE treatments, suggesting increased lipid absorption. This was supported by in vitro findings that both HBCD and TBBPA-DBMPE promoted lipid accumulation in IEC-6 cells under the stress of oleic acid for 6 h, implying that altered lipid absorption by the intestine may partly contributed to increased lipid load in mice. Overall, the effects of 50 μg/kg/d TBBPA-DBMPE in terms of some parameters were comparable with 50 μg/kg/d HBCD, suggesting that TBBPA-DBMPE may not be an ideal substitute of HBCD., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Spatial and temporal trends of tetrabromobisphenol (TBBPA) and hexabromocyclododecane (HBCD) in mangrove sediments from the Pearl River Estuary (PRE) in South China were evaluated. Concentrations of TBBPA and HBCD in mangrove sediments ranged from 0.23 to 13.3 and 0.36 to 54.7 ng g -1 dry weight. The highest TBBPA concentration was seen in Guangzhou mangrove wetland near a dockyard and a ferry terminal where TBBPA is utilized in the coatings for the shipbuilding industry. The rapid development of building might elucidate the higher concentrations of HBCD in Shenzhen mangrove sediments. γ-HBCD and α-HBCD was the two main diastereoisomer of HBCD in mangrove sediments with contributions of 56.1 % and 34.0 %. Sediments from the three PRE mangrove ecosystems were selectively enriched for (-)-γ-HBCD. TBBPA concentrations in mangrove sediments from Guangzhou rose during 2012-2015 and declined from 2015 to 2021. HBCD concentrations in the PRE mangrove sediments exhibited an increasing trend from 2012 to 2021., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The principal objective in the treatment of e-waste is to capture the bromine released from the brominated flame retardants (BFRs) added to the polymeric constituents of printed circuits boards (PCBs) and to produce pure bromine-free hydrocarbons. Metal oxides such as calcium hydroxide (Ca(OH) 2 ) have been shown to exhibit high debromination capacity when added to BFRs in e-waste and capturing the released HBr. Tetrabromobisphenol A (TBBA) is the most commonly utilized model compound as a representative for BFRs. Our coauthors had previously studied the pyrolytic and oxidative decomposition of the TBBA:Ca(OH) 2 mixture at four different heating rates, 5, 10, 15, and 20 °C/min, using a thermogravimetric (TGA) analyzer and reported the mass loss data between room temperature and 800 °C. However, in the current work, we applied different machine learning (ML) and chemometric techniques involving regression models to predict the TGA data at different heating rates. The motivation of this work was to reproduce the TGA data with high accuracy in order to eliminate the physical need of the instrument itself, so that this could save significant experimental time involving sample preparation and subsequently minimizing human errors. The novelty of our work lies in the application of ML techniques to predict the TGA data from e-waste pyrolysis since this has not been conducted previously. The significance of our work lies in the fact that e-waste is ever increasing, and predicting the mass loss curves faster will enable better compositional analysis of the e-waste samples in the industry. Three ML models were employed in our work, namely Linear, random forest (RF), and support vector regression (SVR), out of which the RF method exhibited the highest coefficient of determination ( R 2 ) of 0.999 and least error of prediction as estimated by the root mean squared error (RMSEP) at all 4 heating rates for both pyrolysis and oxidation conditions. An 80:20 split was used for calibration and validation data sets. Furthermore, for showing versatility and robustness of the best-predicting RF model, it was also trained using all the data points in the lower heating rates of 5 and 10 °C/min and predicted on all the data points for the higher heating rates of 15 and 20 °C/min to again obtain a high R 2 of 0.999. The excellent performance of the RF model showed that ML techniques can be used to eliminate the physical use of TGA equipment, thus saving experimental time and potential human errors, and can further be applied in other real-time e-waste recycling scenarios.

Ecotoxicological effects of photolytic degradation mixtures of the two brominated flame retardants PolymericFR and Tetrabromobisphenol A-bis (2,3-dibrom-2-methyl-propyl) Ether (TBBPA-BDBMPE) have been studied in vitro and in vivo. Both substances were experimentally degraded separately by exposure to artificial UV-light and the resulting degradation mixtures from different time points during the UV-exposure were applied in ecotoxicological tests. The in vitro investigation showed no effects of the degraded flame retardants on the estrogenic and androgenic receptors via the CALUX (chemically activated luciferase gene expression) assay. Short-term exposures (up to 96 h) of Lumbriculus variegatus lead to temporary physiological reactions of the annelid. The exposure to degraded PolymericFR lead to an increased activity of Catalase, while the degradation mixture of TBBPA-BDBMPE caused increases of Glutathione-S-transferase and Acetylcholine esterase activities. Following a chronic exposure (28 d) of L. variegatus, no effects on the growth, reproduction, fragmentation and energy storage of the annelid were detected. The results indicate that the experimental degradation of the two flame retardants causes changes in their ecotoxicological potential. This might lead to acute physiological effects on aquatic annelids, which, however, do not affect the animals chronically according to our results., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Esther Smollich reports a relationship with DEUTSCHE ROCKWOOL GmbH & Co. KG that includes: employment. This employment has been taken up after the finalization of the experimental work reported in this article., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Hexabromocyclododecane (HBCD) and Tetrabromobisphenol A (TBBP-A) are brominated flame retardants widely used in variety of industrial and consumer products (e.g., automobiles, electronics, furniture, textiles and plastics) to reduce flammability. HBCD and TBBPA can also contaminate the environment, mainly water, dust, air and soil, from which human exposure occurs. This constant exposure has raised some concerns against human health. These compounds can act as endocrine disruptors, a property that gives them the ability to interfere with hormonal function and quantity, when HBCD and TBBPA bind target tissues in the body. Studies in human and animals suggest a correlation between HBCD and TBBPA exposure and adverse health outcomes, namely thyroid disorders, neurobehavior and development disorders, reproductive health, immunological, oncological and cardiovascular diseases. However, in humans these effects are still poorly understood, once only a few data evaluated the human health effects. Thus, the purpose of this review is to present the toxicity effects of HBCD and TBBPA and how these compounds affect the environment and health, resorting to data and knowledge of 255 published papers from 1979 to 2020., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Soil samples were collected at 61 sites of the national monitoring network for persistent organic pollutants (POPs) in South Korea. The target compounds were brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), hexabromocyclododecanes (HBCDDs), and tetrabromobisphenol A (TBBPA). The mean concentrations of Σ 27 PBDEs, Σ 3 HBCDDs, and TBBPA in soil were 222, 17.2, and 4.4 ng/g, respectively, but PBBs were not detected. Industrial sites had statistically higher BFR concentrations than suburban sites but no significant difference compared with urban sites. The commercial deca-BDE mixtures were the most likely source of PBDE contamination in the soil samples, with the minor influence of commercial penta-BDE and octa-BDE mixtures. The profiles of HBCDDs in most soil samples differed from those in the powder types of technical HBCDD mixtures, indicating that they are affected by the HBCDDs contained in commercial products and the conversion of HBCDD diastereoisomers (γ-HBCDD to α-HBCDD) in the environment. The concentrations of Σ 27 PBDEs, Σ 3 HBCDDs, and TBBPA were significantly correlated with population density, gross domestic product, and the number of companies (p < 0.01), indicating a direct impact of anthropogenic activities. Significant correlations among BFRs were determined (0.63 < r < 0.74, p < 0.01), suggesting that these pollutants had similar sources. Relatively good correlations (0.44 < r < 0.98, p < 0.01) between BDE-209 and other light BDEs (except for BDE-71, -77, -126, -156, and -205) might result from the degradation of heavy BDEs under anaerobic and natural sunlight conditions. To the best of our knowledge, this study provides the most comprehensive soil monitoring data for various BFRs in South Korea. Furthermore, it is the first report on soil contamination by deca-BDE, HBCDDs, and TBBPA in South Korea., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

We investigated the occurrence of chemical pollutants in major e-waste sites in West Africa and usefulness of cytotoxicity and induction of ethoxyresorufin-O-deethylase (EROD) in determining the effects of some detected brominated flame retardants (BFRs) and e-waste soil-derived extracts. Analysis of the e-waste site samples using AAS and GC-MS techniques revealed the presence of a range of toxic metals as well as persistent and toxic organic pollutants, respectively, in the vicinity of the e-waste sites. As expected, the occurrence (%) of all the detected chemical pollutants in experimental soils significantly (P < 0.05) differs from occurrence (%) in control soil. The calculated LC 50 values on RBL-2H3 cells of the detected tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD) were 3.75 μM and 4.2 μM, respectively. Tribromophenol (TBP), dibromobiphenyl (DBB), and decabromodiphenyl ether (DBDE) were remarkably less toxic on RBL-2H3 cells compared with TBBPA and HBCD as they did not reduce RBL-2H3 cell viability below 50% in the tested concentration range (0-20 μM). The study revealed that TBBPA and HBCD could induce significant RBL-2H3 cell death through caspase-dependent apoptosis. The study further shows that the cytotoxicity of some of these BFRs could increase synergistically when in mixtures and potentially activate inflammation through the stimulation of mast cell degranulation. The e-waste soil-derived extracts induced a concentration-dependent increase in EROD activity in the exposed RTG-W1 cells. Ultimately, nonpolar extracts had higher EROD-inducing potency compared with polar extracts and hence suggesting the presence in higher amounts of AhR agonists in nonpolar e-waste soil-derived extracts than polar extracts. Overall, there is urgent need for actions in order to improve the environmental quality of the e-waste sites.

Tetrabromobisphenol A (TBBPA) and Hexabromocyclododecanes (HBCDs) are commonly used as brominated flame retardants in large volumes, and accumulate in plants and animals in the environment, and people are exposed to them when consuming food. As many countries are monitoring them in food, it is necessary to develop a method to analyze them simultaneously for cost efficiency. A method was developed and optimized under different conditions using accelerated solvent extraction to extract the lipids from the samples, acid silica column to clean the samples and liquid chromatography coupled with tandem mass spectrometry to determine TBBPA and HBCDs. The method was validated in different kinds of food. Uncertainty of measurement was calculated by combining all uncertainties of contributors. Intermediate precision (reproducibility) was the most influential contributor to uncertainty. 5 food categories with 115 samples were analyzed with the method, and mackerels containing high level of fat were highly contaminated by TBBPA and HBCDs., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Tetrabromobisphenol A (TBBPA) and Hexabromocyclododecanes (HBCDs) are two of the most used BFRs and they have cumulated in the environment. TBBPA and HBCDs in food were determined and their risks were assessed. The analytical method used was validated in different food categories, and the performance parameters were acceptable based on the criteria of AOAC. Fish and cephalopods were contaminated with TBBPA higher than other foods, and fish contained higher levels of HBCDs than other foods. α-HBCD was the predominant diastereomer in fish and meat and had strong correlations with HBCDs in fish and cephalopods. HBCDs accumulated easier than TBBPA in food. People were exposed to TBBPA from 0.125 ng kg -1 b.w. day -1 to 0.284 ng kg -1 b.w. day -1 and HBCDs from 0.353 ng kg -1 b.w. day -1 to 1.006 ng kg -1 b.w. day -1 via food and air. Food mainly contributed to exposure to TBBPA and HBCDs and vegetables were the main contributors for exposure to TBBPA and HBCDs in food. MOEs for the whole population were over 100, and the risks of exposure to TBBPA and HBCDs from food and the environment were of low concern to public health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) are legacy brominated flame retardants which are still produced and used in China. In this study, 187 surface soils from the Pearl River Delta (PRD) urban conurbation in China were collected, and the effects of urban conurbation development on the concentrations, distributions and human exposure risk of HBCDs and TBBPA were investigated. The concentration ranges of Σ 3 HBCD (sum of α-, β-, and γ-HBCD) and TBBPA in soil were below the limit of quantification (-1 dry weight (dw) and < LOQ to 53.1 ng g -1 dw, respectively. Concentration levels of HBCDs and TBBPA in the PRD were affected both by distributions of land-use type and by the location of the city. Soils from residential areas contained the highest concentrations of Σ 3 HBCD (median: 1.75 ng g -1 dw) and TBBPA (1.92 ng g -1 dw) among all land-use types. In addition, soils from the central PRD had higher Σ 3 HBCD and TBBPA levels (0.46 and 0.90 ng g -1 dw) than those from the surrounding areas (0.17 and 0.07 ng g -1 dw). The concentrations of Σ 3 HBCD and TBBPA were highly correlated with urbanization level, population density, regional GDP and per capita income in all cities studied (p < 0.01), which indicates that the prosperity of the urban conurbation may play an important role in soil contamination of HBCDs and TBBPA in the PRD. Children living in residential areas had the highest estimated daily intakes of Σ 3 HBCD (7.09 pg kg -1 d -1 ) and TBBPA (7.76 pg kg -1 d -1 ), suggesting that people living in residential areas have a relatively higher exposure risk of HBCDs and TBBPA. This is a comprehensive study to report the effects of prosperity indices and land use indicators of an urban conurbation on the occurrence of HBCDs and TBBPA in soil in China., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Levels of hexabromocyclododecane isomers α, β, γ, (HBCDDs) and tetrabromobisphenol A (TBBP-A) were determined in 24 representative samples of different wild fish and seafood species (benthic: N = 16; pelagic: N = 8) and 16 samples of farmed bivalve molluscs from the West Mediterranean Sea (FAO 37, 1.3 sub-area). An LC-MS/MS-based method with limits of quantification (LOQS) in the range of 0.01-0.05 ng g -1 fresh weight (fw) was utilized. While α HBCDD was found in 80% of the 24 wild species samples, β and γ congeners were found in 33% and 25%, respectively. ΣHBCDD content ranged from 0.03 (Aristeus antennatus) to 0.68 (Sardina pilchardus) ng g -1 fw as Upper Bound values across 2.00-4.46 trophic levels. In farmed molluscs, HBCDD congeners were always present and ranged from 0.22-0.52 ng g -1 fw, with the exception of one farm (1.23-2.06 ng g -1 fw), whose values suggest the presence of a regular emission source. TBBP-A levels always fell below the LOQ of 0.05 ng g -1 fw in all samples. The results are in good agreement with results of previous studies from the Mediterranean Sea. The Environmental Quality Standard for human health from fish and seafood local consumption was set at 165 μg g -1 fw. The Margin of Exposure of 490,020 as the ratio between the considered Health Based Guidance Level of 0.79 mg kg -1 body weight and the geo-referenced HBCDD intake (P95 fish and seafood intake; mean ΣHBCDD contamination) indicates no threat to food safety., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Brominated flame retardants (BFRs) such as tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs) are of ecological concern due to their ubiquitous presence and adverse effects. There is a paucity of data on environmental fate of such compounds in mangrove wetlands, which are unique ecosystems in coastal intertidal areas and act as natural sinks for many pollutants. In this study, mangrove plants and sediments were collected from an urban nature reserve in South China to investigate bioaccumulation and translocation of TBBPA and HBCDs. The mean (range) concentrations of TBBPA and ΣHBCD in roots, stems and leaves were 67 (ow were negatively correlated (p = 0.03), indicating passive translocation of HBCDs, driven by water movement during transpiration. Sediment-root bioaccumulation factors and log TFs (stem to leaf) both showed no obvious correlation with log K ow of HBCD diastereoisomers. These results reflected the complex behavior of HBCDs in mangrove plants, which have not been sufficiently captured in laboratory-based studies of plant contaminant accumulation., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Direct immersion solid phase microextraction (DI-SPME) coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS) is of significant research interest because of its low solvent consumption, simple design, and efficient, sensitive, fast performance. In this work, a combination of these two methods (DI-SPME-LC-MS) for the determination of tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD) in water was developed. Important factors, which included temperature, stirring rate, salt concentration, pH value and adsorption time, were evaluated in for the optimization of solid phase microextraction (SPME) method. The method was developed using spiked natural waters in a concentration range of 0.1-10 ng mL -1 , and showed notable linearity with regression coefficients ranging between 0.992 and 0.999. The limits of detection varied from 0.01 to 0.04 ng mL -1 (at S/N = 3) and relative standard deviation (RSD < 11%) were obtained showing that the precision of the method was reliable. Recoveries were in relatively high levels for both analytes and ranged from 88% to 108%. Moreover, in comparison with the performance time of traditional sample pretreatment methods such as solid-phase extraction (SPE), accelerated solvent extraction (ASE), and liquid-liquid extraction (LLE), DI-SPME-LC-MS takes only approximately 35 min to perform. The optimized method was successfully applied for monitoring concentrations of TBBPA and HBCD in water., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA) and polybrominated diphenyl ether (PBDEs) are three legacy brominated flame retardants (BFRs); however, they are still produced and used in China. In this study, these three BFRs were measured in commonly consumed animal-based and plant-based foodstuffs from Beijing, China, and the dietary intakes of these BFRs by adults in Beijing were estimated to assess the related health concerns. The median levels of TBBPA in animal-based foodstuffs ranged from

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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Currently, the HBCDs were listed in Annex A by the Stockholm Convention, and the knowledge on the contamination of TBBPA and HBCDs in soil and road dust in China is still limited, and it is unclear what role is played by dust particle size distribution. In this study, a total of 81 soil and 43 road dust samples were analyzed with TBBPA and ΣHBCDs concentrations ranging from < LOQ to 33.8 ng/g dw (dry weight) and 0.43-15.2 ng/g dw in soil, and from < LOQ to 74.1 ng/g dw and 7.25-14.0 ng/g dw in road dust, respectively. TBBPA and HBCDs exhibited different spatial distribution patterns in soil, where relatively high levels of HBCDs were found in industrial area and commercial area, while high levels of TBBPA were detceted in residential area. However, no distinct variation in spatial distribution of these two compounds was observed in road dust. Different diastereoisomer profiles of HBCDs were also found with γ-HBCD predominating in soil and α-HBCD occupying a large proportion in road dust. The α-/γ-HBCD values in road dust were significantly greater (T-test, P < 0.05) than those in soil, which suggested that γ-HBCD in road dust were likely to transform into α-HBCD compared with soil. The distribution of dust particle size showed that HBCDs levels were increasing with the decreasing in particle sizes, while the TBBPA showed some "accidental" peak values in specific diameter ranges. The estimated daily intakes (EDIs) of TBBPA and HBCDs were assessed through dust ingestion, dermal absorption and inhalation via road dust, and all the exposure estimates were well below the reference dose (RfD), but the toddlers were more vulnerable to TBBPA and HBCDs intakes, which should be paid more attention., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Reliable quantifications of brominated flame retardants (BFRs) not only ensure compliance with laws and regulations on the use of BFRs in commercial products, but also is key for accurate risk assessments of BFRs. Acetone is a common solvent widely used in the analytical procedure of BFRs, but our recent study found that acetone can react with some BFRs. It is highly likely that such reactions can negatively affect the quantifications of BFRs in environmental samples. In this study, the effects of acetone on the extraction yields of three representative BFRs [i.e., decabrominated diphenyl ether (decaBDE), hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA)] were evaluated in the Soxhlet extraction (SE) system. The results showed that acetone-based SE procedure had no measureable effect for the recovery efficiencies of decaBDE but could substantially lower the extraction yields for both TBBPA and HBCD. After 24 h of extraction, the recovery efficiencies of TBBPA and HBCD by SE were 93 and 78% with acetone, 47 and 70% with 3:1 acetone:n-hexane, and 82 and 94% with 1:1 acetone:n-hexane, respectively. After 72 h of extraction, the extraction efficiencies of TBBPA and HBCD decreased to 68 and 55% with acetone, 0 and 5% with 3:1 acetone/n-hexane mixtures, and 0 and 13% with 1:1 acetone/n-hexane mixtures, respectively. The study suggested that the use of acetone alone or acetone-based mixtures should be restricted in the quantitative analysis of HBCD and TBBPA. We further evaluated nine alternative solvents for the extraction of the three BFRs. The result showed that diethyl ether might be reactive with HBCD and may not be considered as the alternative to acetone used solvents for the extraction of HBCD.

This study investigated contamination trends and factors affecting the levels of brominated flame retardants (BFRs), including hexabromocyclododecane (HBCD) diastereomers, tetrabromobisphenol A (TBBP-A), and 2,4,6-tribromophenol (2,4,6-TBP), in breast milk in Japan. Breast milk samples (n = 64) were collected from mothers living in six prefectures in Japan. The mean concentrations were 2.2, 0.19, 0.29, 3.0, and 0.59 ng/g lipid weight for α-HBCD, β-HBCD, γ-HBCD, TBBP-A, and 2,4,6-TBP, respectively. Based on the previous studies, the levels of ΣHBCD in Japanese women's milk appear to be increasing, and the levels of TBBP-A are higher than those in other Asian countries. Although ΣHBCD were not correlated to phenolic BFRs, the concentration of β-HBCD was significantly correlated to the concentrations of TBBP-A (r = 0.440, p < 0.01) and 2,4,6-TBP (r = 0.320, p < 0.01). The concentration of γ-HBCD increased significantly with maternal age (r = 0.378, p < 0.01), but the concentrations of the other analytes were not dependent on age. The concentration of α-HBCD was higher in primiparae than in multiparae (p < 0.05), while TBBP-A was higher in multiparae. No significant correlation was found between the phenolic BFR levels in milk and mothers' age, working place, and drinking/smoking habits. These results suggest that exposure to α- and γ-HBCD diastereomers could be affected by maternal age and parity, respectively, because of their different kinetics and sources. Therefore, these factors should be considered when conducting infant risk assessments., (Copyright © 2018. Published by Elsevier Ltd.)

Brominated flame retardants (BFRs) are a large group of widely used chemicals, which have been produced and used since 1970s. As a consequence of substantial and long-term usage, BFRs have been found to be ubiquitous in humans, wildlife, and abiotic matrices around the world. Although several reports have reviewed BFRs contamination in general, none have focused specifically on foods and human milk, and the corresponding dietary exposure. Foods (including human milk) have long been recognized as a major pathway of BFRs intake for non-occupationally exposed persons. This review summarizes most available BFRs data in foods and human milk from China in recent years, and emphasizes several specific aspects, i.e., contamination levels of legacy and emerging BFRs, dietary exposure assessment and related health concerns, comparison between various BFRs, and temporal changes in BFRs contamination., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The occurrence of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), tetrabromobisphenol A (TBBPA) and other phenolic brominated flame retardants (BFRs) in Irish foodstuffs has been assessed. A total of 53 food samples including eggs, milk, fish, fat and offal were tested. Eighty-one percent of the samples contained at least one measurable PBDE congener. The most abundant and frequently occurring congeners were BDE-47, BDE-49, BDE-99, BDE-100 and BDE-209 with the highest concentrations found in fish, fat and eggs. Summed concentrations for the measured PBDEs ranged from 0.02 μg/kg to 1.37 μg/kg whole weight. At least one HBCD stereoisomer was found in twenty-six percent of the samples with α-HBCD being the most frequently detected. The highest concentrations were found in fat and oily fish samples. TBBPA was only detected in one farmed salmon sample at 0.01 μg/kg. Bromophenol residues were found in fourteen out of the 53 samples, specifically in eggs and fish, with concentrations ranging from 0.28 to 0.98 μg/kg whole weight. These data contribute to the EU-wide EFSA risk assessment on these contaminants that is currently underway., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

An ultra-high performance liquid chromatography - tandem mass spectrometry (UHPLC-MS/MS) method was developed and validated (in-house) for the quantification of selected brominated flame retardants (BFRs), including tetrabromobisphenol A (TBBPA), hexabromocyclododecanes (HBCDs), tetrabromobisphenol S (TBBPS) and bromophenols (BPs), in various food matrices. The sample preparation consisted of extraction of TBBPS with acidified acetonitrile followed by a fast dispersive solid-phase extraction (dSPE) clean-up and extraction of the other BFRs with a mixture of hexane and dichloromethane (1:1, v/v) with subsequent clean-up using acidified silica (44%, w/w). The limits of quantification of the method varied widely for the types of food matrices and the different classes of BFRs from 4 pg g -1 wet weight (ww) to 8 ng g -1 ww. For most of the analytes the apparent recovery was in the range 70-120%, and the method precision (under repeatability conditions) was below 20%. The method was successfully applied in proficiency testing exercises as well as for analysis of various food items. Only 25% of the collected food samples contained BFRs, with 4-bromophenol and α-HBCD as the only detected compounds. The contaminated foodstuffs were fish and eggs with concentrations in the range from 48 to 305 pg g -1 ww.

A national survey of three currently used brominated flame retardants (BFRs), tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD) and decabrominated diphenyl ether (BDE-209) in human milk was conducted in 2011. Human milk from 16 provinces of China were collected, pooled and measured. The estimated daily intake (EDI) via human milk ingestion for nursing infant and the related health risks were evaluated. The median levels of TBBPA, HBCD and BDE-209 were 1.21, 6.83 and 0.556ng/g lipid weight (lw), respectively. Levels of BDE-209 were lower than those of TBBPA, indicating that the production and application of deca-BDE in China has been below that of TBBPA after the restriction of PBDEs. Moreover, contamination levels of TBBPA and HBCD in this survey were higher than those observed in last national survey conducted in 2007, indicating an increase of TBBPA and HBCD in the environment from 2007 to 2011. The mean estimated daily intakes (EDIs) of TBBPA, HBCD and BDE-209 via human milk for 1-6months old infant were 39.2, 51.7 and 3.65ng/kgbw/day, respectively. For risk assessment, margin of exposure (MOE) was calculated by comparing the BMDL 10 (benchmark dose lower confidence limit for a benchmark response of 10%) to the EDI of each BFR. Large MOEs indicates that the estimated dietary exposure to these three BFRs for nursing infant is unlikely to raise significant health concerns. Compared with some currently used novel BFRs which also measured in this survey, higher contamination levels were found in some non-PBDE BFRs, indicating that the consumption pattern of BFRs has shifted from PBDEs to non-PBDE BFRs in China., (Copyright © 2017 Elsevier B.V. All rights reserved.)

TBBPA and HBCDs are the two classes of flame retardants that are still allowed for use by the European Commission. In May 2013, HBCDs were listed as Persistent Organic Pollutants under the Stockholm Convention, and they were banned with an exemption on EPS/XPS for cavity wall insulation. This study describes the development and optimisation of a rapid LC-ESI-MS/MS method using isotopic dilution quantification including a simplified extraction step using a mixture of solvents and sulphuric acid hydrolysis followed by the one-shot analysis of TBBPA and each of the α-, β- and γ-HBCD diastereoisomers. The limits of detection and quantification (LOD and LOQ) were 0.5 and 2.5 ng g -1 (lipid weight, lw) for TBBPA and HBCD diastereoisomers, respectively. The method was applied to analyse 106 samples of individual mature breast milk. TBBPA was quantified in 42% of these samples within a range of -1 lw. HBCD diastereoisomers were quantified in 8%, 3% and 3% of the collected samples for α-, β- and γ-HBCDs, respectively. The α-form was predominant in each quantifiable breast milk sample. The rapid newly developed LC-MS/MS method appears to be suitable for simultaneously analysing and quantifying TBBPA and HBCDs (three isomers) in human breast milk with the aim of establishing BFR multi-contamination profiles of breast milk samples., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The concentrations and spatial distributions of hexabromocyclododecane (HBCDD) and tetrabromobisphenol A (TBBPA) were measured in tree bark from different functional areas of Shanghai. ΣHBCDD (sum of α-, β-, and γ-HBCDD) concentrations ranged from 1.2 × 10 2 to 6.6 × 10 3 ng g -1 lw (median 5.7 × 10 2 ng g -1 lw) and TBBPA concentrations ranged from 48 to 7.2 × 10 4 ng g -1 lw (median 2.8 × 10 2 ng g -1 lw). The concentrations of ΣHBCDD and TBBPA all followed the order of industrial areas > commercial areas > residential areas. The mean percentage of α-HBCDD in bark samples (44%) from Shanghai was higher than that in technical HBCDD products, but comparable with that in air. The concentrations of TBBPA and individual HBCDD diastereoisomers between industrial areas and commercial areas were correlated. Based on the concentrations of HBCDD in the bark, the corresponding atmospheric HBCDD concentrations were estimated. Compared with the published data for HBCDD in urban air, the estimated atmospheric HBCDD concentrations in Shanghai had a relatively high level, and more attention should be paid to the pollution status of HBCDD in Shanghai.

World-wide, the prevalence of brominated flame retardants (BFRs) is well documented for routine analysis of environmental and biological matrices. There is, however, limited information on these compounds in the African environment and insufficient information on the analytical approaches used to obtain data. This paper presents a review on BFR levels in the African environment and the various analytical methodologies specifically applied in Africa for polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls and alternative-BFRs. The analyses include liquid sample preparation using liquid-liquid and solid phase extraction and solid sample preparation involving Soxhlet extraction, with ultrasound-assisted extraction increasingly being applied. Instrumental detection techniques were limited to gas chromatography coupled with electron capture detector and electron impact ionisation with single quadrupole mass spectrometers. Information on congener profile prevalence in indoor dust, soil, aquatic environment (water, sediment, and aquatic organisms), eggs, wastewater treatment plant compartments, landfills (leachate and sediment) and breast milk are presented. Although PBDEs were inconsistently detected, contamination was reported for all investigated matrices in the African environment. The manifestation in remote regions indicates the ubiquitous prevalence and long-range transport of these compounds. Levels in sediment, and breast milk from some African countries were higher than reported for Asia and Europe. Due to limited data or non-detection of alternative-BFRs, it is unclear whether banned formulations were replaced in Africa. Most of the data reported for BFR levels in Africa were obtained in non-African laboratories or in South Africa and formed the basis for our discussion of reported contamination levels and related methodologies., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) are two kinds of brominated flame retardants and widely present in the environment and biota. The levels, spatial distributions and mass inventories of HBCD and TBBPA were investigated in sediments and paddy soils from the Liaohe River Basin in northeast China. The concentrations of ΣHBCD and TBBPA were in the range of not detected (nd) to 4.02ng/g dry weight (dw) and 0.03 to 4.06ng/g dw, respectively. γ-HBCD was dominated in sediments, while the abundance of α-HBCD was relatively high in paddy soils. The spatial distributions of HBCD and TBBPA in surface sediments and paddy soils indicated that the local point-input was their major source. The significant correlation between total organic carbon (TOC) contents and the HBCD levels suggested that TOC content also exerted an influence on the distribution of HBCD in sediments. Meanwhile, it was found that the irrigation with river water was not the major transportation pathway of HBCD and TBBPA in paddy soils. Based on the study, it was estimated that there were about 1.67tons HBCD and 2.20tons TBBPA deposited into sediments of the Liaohe River system every year. The total mass inventories of HBCD and TBBPA in sediments were far higher than that in paddy soils., (Copyright © 2016. Published by Elsevier B.V.)

The concentrations and distribution of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), and tetrabromobisphenol A (TBBPA) were investigated in 28 sediment samples collected from Taihu Lake, Eastern China. The results showed that all three classes of compounds were detected in 28 sediment samples but that PBDEs were the main contaminants in the study area. The total PBDE concentrations ranged from 3.77 to 347 ng/g dry weight (dw) with a mean value of 72.8 ng/g dw, whereas the concentrations ranged from 0.168 to 2.66 and from 0.012 to 1.30 ng/g dw for HBCD and TBBPA, respectively. In all of the sediment samples, BDE-209 was the predominant congener, accounting for 95.9 to 98.6 % of the total PBDEs, which indicated that commercial mixtures of deca-BDEs were the main sources of PBDE contamination. Higher concentrations of PBDEs were found in samples collected from Meiliang Bay and Gonghu Bay near the inflow river, which suggested that inflow runoff might play an important role in the PBDE levels in Taihu Lake sediments.

Brominated flame retardants (BFRs) which were detected extensively in environmental and biota samples worldwide, have raised significant concerns during past decades for their persistence, bioaccumulation and potential toxicity to ecological environment and human health. In this paper, we have compiled and reviewed existing literature on the contamination status of BFRs in abiotic and biotic environments in China, including polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane, tetrabromobisphenol A and new BFRs. Temporal trends were also summarized and evaluated. Based on this review, it has been concluded that (1) high concentrations of PBDEs were generally related to the e-waste disposal processing, while the spatial distribution pattern of other BFRs was not necessarily in accordance with this; (2) extremely high concentrations of BFRs in indoor dust emphasized the importance of indoor contamination to human body burdens, while more work need to be done to confirm its contribution; (3) PBDEs in electronics dismantling workers were higher compared to the general population, indicating the occupational exposure should be of particular concern; (4) more data are now becoming available for BFRs in aquatic and terrestrial organisms not previously studied, while studies that consider the occurrence of BFRs in organisms of different trophic levels are still of urgent need for evaluating the fate of BFRs in the food web; and (5) limited data showed a decreasing trend for PBDEs, while more data on time trends of BFR contamination in various matrices and locations are still needed before the impact of regulation of BFRs can be assessed., (Copyright © 2015. Published by Elsevier Ltd.)

Conflicting evidence exists about whether concentrations of persistent organic chemicals in human milk decrease over the course of lactation. This has implications for the timing of sampling human milk for exposure assessment purposes. We examined this issue by measuring concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), the HBCD degradation products tetrabromocyclododecenes (TBCDs), and tetrabromobisphenol-A (TBBP-A) in human milk collected in 2010-2011 from 10 first-time mothers from Birmingham, UK. To evaluate whether concentrations varied significantly over the first 12 months postpartum, 12 samples were taken-one per month-from each mother, amounting to 120 samples overall. While concentrations of most of our target contaminants displayed no significant variation (p > 0.1) over the duration of our study, significant increases were detected in concentrations of ∑TBCDs (p = 0.029, average increase 1.4%/month) and BDE-153 (p = 0.058, average increase 4.2%/month). When compared to data obtained from a different set of UK mothers from a related but geographically wider catchment area sampled contemporaneously to this study, the ratio of median concentrations of BDE-153 to BDE-99 was markedly lower in the current study (0.46 compared to 1.32). This may reflect unidentified differences in exposure of the participants in the two studies.

Tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs) were analyzed in 12 tissues of prey (mud carp) and predator (northern snakehead) fish from an e-waste area, South China. The TBBPA concentrations in different tissues ranged from 0.03 to 2.85 ng/g wet weight (ww) in mud carp and 0.04 to 1.30 ng/g ww in northern snakehead. The concentrations of HBCDs ranged from 0.07 to 96.9 ng/g ww in mud carp and 0.18 to 240 ng/g ww in northern snakehead. HBCD levels in tissues were correlated with lipid content for both fish species, while this correlation was only found in mud carp for TBBPA. Meanwhile, northern snakehead exhibited higher HBCD levels but lower TBBPA levels than mud carps. These observations are attributed to the more polar and reactive properties of TBBPA than HBCDs. α-HBCD was the predominant diastereoisomer of HBCDs in all tissues of mud carp and northern snakehead, except for chyme of mud carp. All the analyzed tissues in mud carp showed an enrichment of (+)-α-HBCD enantiomer with EF (enantiomeric fraction) values of 0.53-0.62, but that in northern snakehead showed an enrichment of (-)-α-HBCD enantiomer with EF values of 0.35-0.5. Considering the fact that the mud carp is one of the diet items of northern snakehead, the different enantiomer accumulation characteristics of α-HBCD between the two fish species in the present study indicated that prey and predator fish could prefer to biotransform different enantiomers of α-HBCD.

Hexabromocyclododecanes (HBCDs) and tetrabromobisphenol A (TBBPA) are of increasing concern because of their potential environmental persistence, bioaccumulation and toxicity. Tris-(2,3-dibromopropyl)isocyanurate (TBC) is another brominated flame retardant (BFR) which has recently been found in the environment and begun to attract attention. The objective of this study is to determine the concentration of these three BFRs in surface soil samples collected from a heavily industrialized and urbanized region in East China. Levels of ∑HBCDs ranged from below detection limits (0.020 ng g(-1)) to 102.6 ng g(-1) on a dry weight basis (dw) with a median level of 15.8 ng g(-1) dw. For TBBPA, the concentration ranged from below detection limits (0.025 ng g(-1)) to 78.6 ng g(-1) dw with a median level of 9.17 ng g(-1) dw. TBC was found at relatively lower concentrations ranging from below detection limits (0.024 ng g(-1)) to 16.4 ng g(-1) dw with a median level of 0.95 ng g(-1) dw. The concentrations of these three BFRs are significantly positively correlated, indicating a common source. Variable BFRs levels were found in different types of soils, with significantly higher concentrations observed at waste dumping sites and industrial areas. The diastereoisomer profiles of HBCDs in most of the soil samples differed from those of the commercial products. The mass inventories of HBCDs, TBBPA and TBC in this region gave preliminarily estimates of 6.68, 2.67 and 0.85 kg, respectively. Therefore, the ubiquitous contamination of soils by these BFRs may well reflect their widespread usage in the study area.

In the present study, a novel analytical approach for the simultaneous determination of 18 perfluoroalkyl substances (PFASs) and 11 brominated flame retardants (BFRs) including their hydroxylated metabolites and brominated phenols has been developed and validated for breast milk and infant formula. The sample preparation procedure based on extraction using acetonitrile and subsequent purification by dispersive solid-phase extraction (d-SPE) employing C18 sorbent is rapid, simple and high-throughput. Ultra-high performance liquid chromatography (UHPLC) interfaced with a tandem mass spectrometry (MS/MS) was employed for the identification/quantification of these compounds. The method recoveries of target compounds for both matrices ranged from 80% to 117% with relative standard deviations lower than 28% and quantification limits in the range of 3-200 pg/mL for milk and 5-450 pg/g for infant formula. Within the pilot study, the new method was used for the analysis of PFASs and BFRs in 50 human breast milks and six infant formulas. In the breast milk samples the total contents of PFASs and BFRs were in the range of 38-279 and 45-16,200 pg/mL, respectively. The most abundant PFASs detected in all tested breast milk samples were perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS), the latter contaminant was present not only as a linear form but also as a branched isomers. The incidence of BFRs was lower, the only representatives of this group, tetrabromobiphenol A (TBBPA) and α-hexabromocyclododecane (α-HBCD), were detected in less than 30% of breast milk samples. None of the infant formulas contained BFRs, traces of either PFOS, PFOA or PFNA were found in three samples., (© 2013 Elsevier B.V. All rights reserved.)

The occurrence and distribution characteristics of tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD) in water and sediments from Taihu Lake, China, were investigated. The analytes were quantified by reversed-phase liquid chromatography coupled to electrospray ionization mass spectrometry. The TBBPA levels in water ranged from below the limit of detection (LOD) to 1.12 ng/L, whereas levels in sediments were between 0.056 ng/g dry weight and 2.15 ng/g dry weight. Regarding HBCD, concentrations were from below the LOD to 0.37 ng/L for water samples and from 0.046 ng/g dry weight to 2.56 ng/g dry weight for sediments. No correlation was found between sediment total organic carbon content and TBBPA/HBCDs, while significant positive correlations (r2 = 0.63, p < 0.005) were observed between TBBPA concentrations and HBCD concentrations in sediments. The highest TBBPA (2.15 ng/g dry wt) and total HBCD concentration (2.56 ng/g dry wt) was found at sampling site 1 (S1), while total HBCD levels fell dramatically with increasing distance from S1, suggesting that the estuary inputs around Taihu Lake were important sources of TBBPA and HBCDs. Compared with the pollution levels in the other regions of the world, the concentrations of TBBPA and HBCDs in Taihu Lake were at a moderate or low level. Further study on the sources of TBBPA and HBCDs is required for both assessment of their potential risks and better pollution management in Taihu Lake., (© 2013 SETAC.)

Hexabromocyclododecane diastereoisomers (α, β, and γ-HBCD) and tetrabromobisphenol A (TBBPA) were investigated in air conditioning filter dust (designated as particulate phase of indoor air, PPIA) collected from an office building in Shenzhen, China in 2009. Concentrations of ΣHBCD (sum of α-, β-, and γ-HBCD) ranged from 652 to 122, 973 ng/g in PPIA. Generally, γ-HBCD was the most abundant diastereomer. Concentrations of TBBPA ranged from 30 to 59, 140 ng/g in PPIA. According to our results, approximate 61.9 pg/kg body weight/day (pg/kg/d) PM2.5 bound ΣHBCD can be inhaled deep into the lungs and 31.3 pg/kg/d PM10 bound ΣHBCD tends to be deposited in the upper parts of the respiratory system, and those values of TBBPA were 28.7 pg/kg/d and 14.5 pg/kg/d for the lower and upper respiratory tracts, respectively. The average intakes of ΣHBCD via dust inhalation and ingestion were 37.92 pg/kg/d and 2, 079 pg/kg/d for adults, and those data of TBBPA were 17.62 pg/kg/d and 966.2 pg/kg/d, respectively. Our research found that exposure via indoor dust inhalation and ingestion contributed more than dietary pathway. Sensitivity analysis result suggests that the concentration of HBCD and TBBPA is the most significant parameter governing estimated results, and the other parameters, such as body weight and inhalation rate, do not affect the outcome much., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs) were determined in water, sediments, sediment cores, and three fish species from a river running through a highly industrialized area in South China. TBBPA concentrations exceeded those of HBCDs in the sediment and the dissolved phase of water and its levels in fish were at the high end of worldwide figures. 26% of HBCDs and 99% of TBBPA were found in dissolved phase of water. Plecostomus occupying high trophic level exhibited higher HBCD levels and higher abundance of α-HBCD than mud carp and nile tilapia which occupy low trophic level. An enrichment of (+)-α-HBCD in three fish species but (-)-α-HBCD in sediment was observed. As for γ-HBCD, most of sediment exhibited racemic while a species-dependence in fish sample was found. No clear trend was found for vertical distribution of enantiomeric profile for γ-HBCD, suggesting that the enantioselectivity of degradation of γ-HBCD is limited., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Three brominated flame retardants (BFRs), tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD) and polybrominated diphenyl ethers (PBDEs), were measured in 103 human milk samples collected from Beijing in 2011. The donors' personal information, such as dietary habit and socioeconomic and lifestyle factors, was obtained by questionnaires. Ultra-performance liquid chromatography-mass spectrometry (UPLC-MS/MS) analysis indicated that the levels of TBBPA ranged from

Tetrabromobisphenol-A (TBBP-A) and hexabromocyclododecanes (HBCDs) are brominated flame retardants that have been found in human milk and serum throughout the world, but have received comparatively little attention in the United States. The objective of this study is to determine concentrations of these analytes in samples of breast milk collected from first-time mothers in the Greater Boston, Massachusetts area and to explore predictors of exposure. Human milk samples were analyzed by LC-ESI-MS/MS for TBBP-A, HBCDs (the α, β, and γ diastereomers), and HBCD degradation products: pentabromocyclododecanes (PBCDs) and tetrabromocyclododecadienes (TBCDs). HBCD diastereomers were detected in all samples with α-HBCD present in the highest proportion. TBBP-A, PBCDs, and TBCDs were detected in 35%, 42%, and 56% of the analyzed samples, respectively. Self-reported demographic, dietary and behavioral data were examined as predictors of HBCD levels. Levels of HBCD were significantly, positively associated with the number of stereo and video electronics in the home (17% increase/item; 95% Confidence Interval (CI) = 4-31%) and reduced in participants who regularly chose organic foods compared to those who did not (0.51, 95% CI = 0.32-0.82). These results suggest that lifestyle factors are related to body burdens of HBCD and that domestic electronics may be an important source of HBCD exposure in the indoor environment.

Since the EFSA enquired a call for data for TBBPA and HBCD in 2009, the analytical determination of these compounds in food became of regulatory interest. Therefore, a method for the simultaneous determination of TBBPA and the three major HBCD stereoisomers was developed. Conventional techniques like soxhlet, ASE, GPC, sulphuric acid digestion, and acidified silica SPE are generally used in sample pre-treatment while detection is mostly performed by LC-MSMS. A combined analysis of HBCD and TBBPA is problematic due to the hydroxyl groups in the TBBPA molecule. However, using a specific mesh-size sodium sulphate in ASE extraction and an acid silica column combined with a Sep-pack Plus silica cartridge for purification resulted in recoveries between 80% and 110% for all compounds. The accuracy and reproducibility determined using proficiency test samples were 104% and 4% for the sum of the HBCD isomers. Typical limits of detection were 0.01 ng/g product or 0.004 ng on column, while the linear dynamic range is between 0.01 ng and 10 ng on column. Levels of TBBPA and HBCD isomers were determined in eel samples. TBBPA was occasionally detected and only marginally above the quantification limit of 0.05 ng/g, whereas total amounts of HBCD were between 0.2 and 150 ng/g with α-HBCD being the dominant HBCD isomer., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) were measured in surface sediments in the Pearl River Delta, southern China. The concentrations ranged from 0.06 to 304 ng/g dry weight for TBBPA and from 0.03 to 31.6 ng/g for total HBCD. The correlations between the TBBPA and HBCD concentrations were significant in rivers (Dongjiang, Zhujiang, Beijiang, and Dayanhe Rivers) with local input sources but not significant in the Xijiang River and Pearl River Estuary without local sources. HBCD was dominated by γ-HBCD (averaged 52.5-75.0%), whereas α-HBCD contributions were relatively high in sediments from the urban areas. The enantiomeric fractions of γ-HBCD in the sediments (averaged from 0.431 ± 0.035 to 0.479 ± 0.010) differed significantly from that in HBCD technical product except for samples from the e-waste area (Dayanhe River, 0.488 ± 0.091). This suggests that enantioselective biotransformation of HBCD occurs in the aquatic environment in this region., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Brominated flame retardants (BFRs) have been used in a variety of consumer products in the past four decades. The vapor pressures for three widely used BFRs, that is, tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), and octabromodiphenyl ethers (octaBDEs) mixtures, were determined using the Knudsen effusion method and compared with those of decabromodiphenyl ether (BDE209). The values measured extrapolated to 298.15 K are 8.47 × 10⁻⁹, 7.47 × 10⁻¹⁰, and 2.33 × 10⁻⁹  Pa, respectively. The enthalpies of sublimation for these BFRs were estimated using the Clausius-Clapeyron equation and are 143.6 ± 0.4, 153.7 ± 3.1, and 150.8 ± 3.2 kJ/mole, respectively. In addition, the enthalpies of fusion and melting temperatures for these BFRs were also measured in the present study., (Copyright © 2011 SETAC.)

Polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and tetrabromobiphenol-A (TBBP-A) were measured in a preliminary study of dust from passenger cabins and trunks of 14 UK cars. Concentrations in cabin dust of HBCDs, TBBP-A, and BDEs 47, 85, 99, 100, 153, 154, 183, 196, 197, 202, 203, 206, 207, 208, and 209 exceeded significantly (p<0.05) those in trunk dust. Sampling cabin dust thus appears to provide a more accurate indicator of human exposure via car dust ingestion than trunk dust. Elevated cabin concentrations are consistent with greater in-cabin use of BFRs. In five cars, while no significant differences (p>0.05) in concentrations of HBCDs and most PBDEs were detected in dust sampled from four different seating areas; concentrations of TBBP-A and of PBDEs 154, 206, 207, 208, and 209 were significantly higher (p<0.05) in dust sampled in the front seats. Possible photodebromination of BDE-209 was indicated by significantly higher (p<0.05) concentrations of BDE-202 in cabin dust. In-vehicle exposure via dust ingestion to PBDEs, HBCDs and TBBP-A exceeded that via inhalation. Comparison with overall exposure via diet, dust ingestion, and inhalation shows while in-vehicle exposure is a minor contributor to overall exposure to BDE-99, ΣHBCDs, and TBBP-A, it is a significant pathway for BDE-209., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

Tetrabromobisphenol-A (TBBP-A), hexabromocyclododecane (HBCD) and its degradation products were determined in 34 human milk samples from Birmingham, UK. TBBP-A was detected in 36% of samples (average=0.06 ng g(-1) lw), with HBCDs detected in all samples (average ΣHBCDs=5.95 ng g(-1) lw). α-HBCD comprised 62-95% ΣHBCDs while β- and γ-HBCD constituted 2-18% and 3-33% respectively. Enantioselective enrichment of (-)-α-HBCD (average enantiomer fraction=0.29) was observed indicating potential enantioselectivity associated with HBCD absorption, metabolism and/or excretion. The degradation products pentabromocyclododecenes (average=0.04 ng g(-1) lw; n=9) and tetrabromocyclododecadienes (average=0.15 ng g(-1) lw; n=25) were detected for the first time in human tissues. Average exposures of a nursing infant to ΣHBCDs and TBBP-A (35 and 1 ng kg(-1) bw day(-1) respectively) via breast milk exceeded upper-bound dietary intakes of both UK adults and toddlers. Using a simple pharmacokinetic model, intakes of UK adults via inhalation, diet and dust ingestion were converted to predicted body burdens. Predictions compared well with those observed for HBCDs but observed body burdens of TBBP-A exceeded predictions. This may indicate the human half-life of TBBP-A is greater than observed previously, that intakes may be underestimated, or that concentrations reported here reflect recent elevated episodic exposure., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

The fate of tetrabromobisphenol A (TBBPA) and hexabromocyclododecane diastereomers (α-, β-, and γ-HBCD) and uptake by plants (cabbage and radish) was investigated. In a short-term (8 weeks) experiment, sorption to soil matrix resulted in 90% decline in recovery of these compounds in the experimental soil. However, nearly 50% of initial HBCDs recovered in mixed cabbage-radish treatments, which suggested that interspecific plant interactions might enhance the bioavailability of HBCDs. Although both plant species could uptake TBBPA and HBCDs, cabbage showed greater accumulating ability. Up to 3.5-10.0-fold higher HBCD concentrations were observed than TBBPA concentrations in all plant tissues, and the distribution of HBCDs in plant tissues was diastereomer-specific. The predominance of α-HBCD in shoot tissues for both species might be attributed to diastereomer-specific translocation of HBCDs, shift in diastereomer pattern and/or selective metabolization of γ-HBCD within plants. The results showed that strong sorption to soil particles reduced the potential of human exposure to BFRs in the soil. However, plants increased the exposure risk by uptaking these compounds and by enhancing their bioavailability. The results also provide insight into transport mechanisms of TBBPA and HBCD diastereomers in soil-plant systems., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

This paper describes the development of a methodology for the simultaneous determination and quantification of hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA), and related compounds (bisphenol A, monobromobisphenol A, dibromobisphenol A, and tribromobisphenol A) in sludge and sediment samples. The selected method is based on an extraction with dichloromethane: methanol followed by purification via SPE C(18) cartridges. Instrumental determination was carried out by liquid chromatography-quadrupole linear ion trap mass spectrometry (LC-QqLIT-MS), with quantification based on isotopic dilution method. Analyte recoveries were in the range of 39-120% and 88-126% for spiked sewage and sediment, respectively. Repeatability of replicate extractions was better than 13% relative standard deviation. Linearity was checked in the range of 0.05 and 25 injected nanograms. Limits of detection (LODs) and limits of quantification (LOQs) were in the range of 0.6 and 2.7 ng/g and 1.4 and 66 ng/g for sediment and sludge samples, respectively. The developed method was applied to sewage sludge and sediment samples collected along the Ebro River and Cinca River, one of its tributaries (northeast of Spain). TBBPA levels in sewage sludge ranged from not quantified to 1,329 ng/g dw, whereas levels in sediment samples were lower, between not detected and 15 ng/g dw. As regards HBCD, concentrations were between not detected and 375 ng/g for sludge samples and 0.8 and 1850 ng/g for sediments.

Halogenated persistent organic pollutants (chlorobiphenyls (CBs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and tetrabromobisphenol-A (TBBP-A)) and total lipid content were measured in the liver and muscle of three species of deep water fish (black scabbard, roundnose grenadier and black dogfish) collected from the Rockall Trough, to the west of Scotland, in 2006. CB concentrations (SigmaICES (International Council for the Exploration of the Seas)7 CBs) >500 microg kg(-1) lipid weight) were found in 9 of the 31 deep water fish liver samples. Non-ortho CBs were measured in samples with the highest ortho CB concentrations. Non-ortho CBs (CB81, 77, 126 and 169) were not detected in any of the fish muscle samples. In liver, CB81 was not detected in any of the samples while CB169 was detected in all but one sample. The total 'dioxin-like' CB concentration was calculated based on the 5 mono-ortho and 4 non-ortho CBs measured. The non-ortho CB concentration made a very small contribution to the total 'dioxin-like' CB concentrations (<1%). Concentrations for the individual ICES7 CBs in fish liver were above OSPAR Background Assessment Concentrations (BACs) in all three species, except for CB28 and 101 in black dogfish. Toxic Equivalent (TEQs) concentrations calculated for the five mono-ortho and four non-ortho CBs measured, and estimated TEQs calculated using published models in the fish muscle indicated that consumption of deep water fish muscle is unlikely to represent a risk to human health. However, dioxins and furans were not measured and the contribution to the calculated TEQs from these compounds was not taken into account. Calculated and estimated TEQs for some roundnose grenadier liver samples exceeded the 25 pg g(-1) wet weight limit for fish liver and, therefore, there may be a health risk if consumed. PBDEs were detected in both the liver and muscle of the deep water fish, whilst HBCD and TBBP-A were not detected in any of the deep water fish.

Hexabromocyclododecanes (alpha-, beta-, and gamma-HBCDs) and tetrabromobisphenol-A (TBBP-A) were determined in indoor air from homes (n=33; median concentrations sigma HBCDs = 180 pg m(-3); TBBP-A = 15 pg m(-3)), offices (n=25; 170; 11), public microenvironments (n=4; 900; 27) and outdoor air (n=5; 37; 1). HBCDs and TBBP-A were also determined in dust from homes (n=45; median concentrations sigma HBCDs = 1300 ng g(-1); TBBP-A = 62 ng g(-1)), offices (n=28; 760; 36), cars (n=20; 13,000; 2), and public microenvironments (n=4; 2700; 230). While sigma HBCDs in car dust significantly exceeded (p < 0.05) those in homes and offices, TBBP-A in car dust was significantly lower (p < 0.05) than that in homes and offices. No significant differences were observed between sigma HBCDs and TBBP-A in air or dust from homes and offices. Compared to dietary and inhalation exposures, dust ingestion constitutes an important pathway of exposure to HBCDs and TBBP-A for the UK population. Specifically, using average dust ingestion rates and concentrations in dust, dust ingestion constitutes for adults 34% (TBBP-A) and 24% (HBCDs) of overall exposure, and for toddlers 90% (TBBP-A) and 63% (HBCDs). Inhalation appears a minor exposure pathway to both HBCDs and TBBP-A. On average, dust is 33% alpha-, 11% beta-, and 56% gamma-HBCD, while air is 22% alpha-, 11% beta-, and 65% gamma-HBCD.

With the recent ban of pentabromodiphenyl ether (technical PentaBDE) and octabromodiphenyl ether (technical OctaBDE) mixtures in the European Union (EU) and in parts of the United States, decabromodiphenyl ether (technical DecaBDE) remains as the only polybrominated diphenyl ether (PBDE) based flame retardant available, today. The EU risk assessment report for DecaBDE identified a high level of uncertainty associated with the suitability of the current risk assessment approach for secondary poisoning by debromination of DecaBDE to toxic lower brominated diphenylethers. Addressing this still open question, we investigated concentrations and temporal trends of DecaBDE, NonaBDE, and OctaBDE congeners in the sediments of Greifensee, a small lake located in an urban area close to Zürich, Switzerland. PBDE appeared first in sediment layers corresponding to the mid 1970s. While total Tri-HeptaBDE (BDE-28, -47, -99, -100, -153, -154 and -183) concentrations leveled off in the mid 1990s to about 1.6 ng/g dw (dry weight), DecaBDE levels increased steadily to 7.4 ng/g dw in 2001 with a doubling time of 9 years. Hexabromocyclododecanes (HBCD) appeared in Greifensee sediments in the mid 1980s. They are an important class of flame retardants that are being used in increasing amounts, today. As was observed for DecaBDE, HBCD concentrations were continuously increasing to reach 2.5 ng/g dw in 2001. Next to DecaBDE, all 3 NonaBDE congeners (BDE-208, BDE-207, and BDE-206) and at least 7 out of the 12 possible OctaBDE congeners (BDE-202, BDE-201, BDE-197/204, BDE-198/203, BDE-196/200, BDE-205, and BDE-194) were detected in the sediments of Greifensee. Highest concentrations were found in the surface sediments with 7.2, 0.26, 0.14, and 1.6 ng/g dw for Deca-, Nona-, Octa-, and the sum of Tri-HeptaBDE, respectively. While DecaBDE and NonaBDE were found to increase rapidly, the increase of OctaBDE was slower. Congener patterns of Octa- and NonaBDE present in sediments of Greifensee did not change with time. Consequently, there was no evidence for sediment mediated long-term transformation of PBDE within the observed time span of almost 30 years. Despite the high persistence of DecaBDE, environmental debromination occurs, as shown by the detection of a shift in congener patterns of Octa- and NonaBDE in sediments, compared to the respective congener patterns in technical PBDE products. The OctaBDE congener BDE-202 was detected in sediments, representing a transformation product that is not reported in any of the technical PBDE products. Comparison of OctaBDE congener patterns in sediments with OctaBDE congener patterns from known sources reveals that (i) they were distinctively different from the congener patterns in technical PBDE products and (ii) that they were similar to the OctaBDE patterns in house dust and photodegradation products of DecaBDE, suggesting contributions from these sources.

In this paper, the first data on brominated flame retardants (BFRs), in particular polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in eggs of bird species from South Africa are described (N=43). Concentrations of PBDEs were detected in all the studied species and in all the geographic areas. Highest concentrations of PBDEs were measured in bird eggs from the Vaal River, which is situated downstream of the most industrialized area in South Africa. Sum-PBDE concentrations were highest in eggs of one African sacred ibis (396 ng g(-1) lipid weight (lw)), possibly due to foraging on dumping sites. Lowest mean level of sum-PBDEs (2.3 ng g(-1) lw) was measured in cattle egrets (N=11) from Barberspan Sanctuary, a Ramsar site. The PBDE congener pattern showed large differences, reflecting different trophic levels, migratory behavior, distance to the source, and, exposure to different PBDE mixtures, among others. HBCD was detected only in four species, and highest levels were measured in one egg of African sacred ibis (71 ng g(-1) lw). In most species, levels of PBDEs were one to several orders of magnitude lower than levels of DDTs and PCBs. PBDEs correlated strongly with DDTs, PCBs and some other organochlorines (OCs), indicating the same source. The widespread occurrence of PBDEs in the South African avian species showed a strong need for further investigations of PBDEs in the Southern African environment.