Novel Brominated Flame Retardants Research Articles

Impact of brominated flame retardants on lipid metabolism: An in vitro approach

Brominated flame retardants (BFRs) are chemicals employed to lower the flammability of several objects. These endocrine disruptor chemicals are lipophilic and persistent in the environment. Due to these characteristics some have been restricted or banned by the European Union, and replaced by several new chemicals, the novel BFRs (NBFRs). BFRs are widely detected in human samples, such as adipose tissue and some were linked with altered thyroid hormone levels, liver toxicity, diabetes and metabolic syndrome in humans. However, the disturbance in lipid metabolism caused by BFRs with emphases to NBFRs remains poorly understood. In this study, we used a pre-adipocyte (3T3-L1) cell line and a hepatocyte (HepG2) cell line to investigate the possible lipid metabolism disruption caused by four BFRs: hexabromobenzene (HBB), pentabromotoluene (PBT), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) and hexabromocyclododecane (HBCD). For that purpose, proliferation and Oil Red O assays, as well as, medium fatty acids profile evaluation using Gas chromatography and RNA extraction for quantitative RT-PCR assays were performed. We detected a significant reduction in the proliferation of preadipocytes and an increased lipid accumulation during differentiation caused by HBB. This BFR also lead to a significant increased expression of IL-1β and decreased expression of PGC-1α and adiponectin. Nevertheless, PBT, TBB and HBCD show to increase lipid accumulation in hepatocytes. PBT also display a significant increase of PPARγ gene expression. Lipid accumulation in the cells can occur by diverse mechanisms depending on the BFR. These results highlight the importance of endocrine disruptor compounds in obesity etiopathogeny.

Approach to Predicting the Size-Dependent Inhalation Intake of Particulate Novel Brominated Flame Retardants.

The risk of human exposure to particulate novel brominated flame retardants (NBFRs) in the atmosphere has received increasing attention from scientists and the public, but currently, there is no reliable approach to predict the intake of these compounds on the basis of their size distribution. Here, we develop a reliable approach to predict the size-dependent inhalation intake of particulate NBFRs, based on the gas/particle (G/P) partitioning behavior of the NBFRs. We analyzed the concentrations of eight NBFRs in 363 size-segregated particulate samples and 99 paired samples of gaseous and bulk particles. Using these data, we developed an equation to predict the G/P partitioning quotients of NBFRs in particles in different size ranges (KPi) based on particle size. This equation was then successfully applied to predict the size-dependent inhalation intake of particulate NBFRs in combination with an inhalation exposure model. This new approach provides the first demonstration of the effects of the temperature-dependent octanol-air partitioning coefficient (KOA) and total suspended particle concentration (TSP) on the intake of particulate NBFRs by inhalation. In an illustrative case where TSP = 100 μg m-3, inhalation intake of particulate NBFRs exceeded the intake of gaseous NBFRs when log KOA > 11.4.

Maize plant (Zea mays) uptake of organophosphorus and novel brominated flame retardants from hydroponic cultures

The root uptake and root-shoot translocation of seven organophosphorus flame retardants (OPFRs) and four novel brominated flame retardants (NBFRs) were assessed in this investigation using hydroponic grown maize plants (Zea mays). Three initial liquid concentrations for each considered compound were examined (i.e., 0.3 μg L−1, 3 μg L−1, 30 μg L−1). The results indicated that the 30 μg L−1 treatments were phytotoxic, as they resulted in a significant decrease in shoot dry weight. Plant-driven removal of the tested FRs decreased with the increasing initial spiking level and were reportedly higher for the NBFRs (range 42%–10%) than OPFRs (range 19%–7%). All the considered FRs were measured in the roots (range 0.020–6.123 μg g−1 dry weight -DW-) and shoots (range 0.012–1.364 μg g−1 DW) of the tested plants, confirming that there was uptake. Linear relationships were identified between the chemical concentrations in the plant parts and the tested hydroponic concentrations. Root concentration factors were positively correlated with the specific lipophilicity (i.e., logKow) of the tested FRs and were determined to be higher for the NBFRs than the OPFRs. The NBFRs had a higher root uptake rate than the OPFRs, and this trend was more significant with the increasing treatment concentrations. Shoot/root concentration factors were found to be lower than the unity value for 10 of the 11 tested compounds. These results can be related to the specific molecular configurations and the occurrence of different functional groups in the tested compounds. The results will help to improve risk assessment procedures and fine tune our understanding of human receptor responses to the ingestion of maize crops grown on agricultural sites irrigated with water contaminated by FRs.

Novel brominated flame retardants (NBFRs) in soil and moss in Mt. Shergyla, southeast Tibetan Plateau: Occurrence, distribution and influencing factors

Research on the environmental fate and behavior of novel brominated flame retardants (NBFRs) remains limited, especially in the remote alpine regions. In this study, the concentrations and distributions of NBFRs were investigated in soils and mosses collected from two slopes of Shergyla in the southeast of the Tibetan Plateau (TP), to unravel the environmental behaviors of NBFRs in this background area. The total NBFR concentrations (∑7NBFRs) ranged from 34.2 to 879 pg/g dw in soil and from 72.8 to 2505 pg/g dw in moss. ∑7NBFRs in soil samples collected in 2019 were significantly higher than those in 2012 (p < 0.05). Decabromodiphenyl ethane (DBDPE) was the predominant NBFR, accounting for 90% of ∑7NBFRs on average. The ratio of the concentrations in moss and soil showed significantly positive correlations with LogKOA except for DBDPE (p < 0.05), indicating that the role of mosses as accumulators compared to soils are more pronounced for more volatile NBFRs. In addition, the concentrations of NBFRs generally decreased with increasing altitude on the south-facing slope, whereas on the north-facing slope some NBFRs exhibited different trends, suggesting concurrent local and long-range transport sources. Normalization based on total organic carbon/lipid concentrations strengthened the correlation with altitude, implying that the altitude gradient of the mountain slope and forest cover could jointly affect the distribution of NBFRs in the TP. Furthermore, principal components analysis (PCA) with multiple linear regression analysis (MLRA) showed that the average contribution of the mountain cold trapping effect (MCTE) accounted for the major (77%) contribution and forest filter effect (FFE) has only a modest contribution to the deposition of NBFRs in soil.

Current pollution status, spatial features, and health risks of legacy and emerging halogenated flame retardants in agricultural soils across China

Soil is a major reservoir and a secondary source of semi-volatile organic chemicals, while studies on the pollution status of halogenated flame retardants (HFRs) in agricultural soils are limited. In this study, a total of twenty-five chemicals including novel brominated flame retardants (NBFRs), polybrominated diphenyl ethers (PBDEs), and dechlorane plus (DPs) was analyzed in the agricultural soils across China to investigate the occurrence, spatial distribution, potential sources, influencing factors and their associated human health risks. The results showed that BDE-209 (125–130,183 pg/g, dry weight, d.w.) was the most abundant flame retardant of PBDEs, followed by decabromodiphenyl ethane (DBDPE) (9.27–22,864 pg/g, d.w.). Meanwhile, the DPs (anti-DP plus syn-DP) were in the range of ND-1229 pg/g (d.w.), and the range of fanti values (the concentration of anti-DP divided by the sum of the concentrations of two isomers) in this study greatly matched those of commercial products, suggesting the effect of proximity to the source region. The higher levels of HFRs were found in Eastern and Southern regions of China. Spatial distribution implied that e-waste recycling activities and plastic processing have shown more importance in releasing legacy flame retardants (FRs) into the environment than the manufacturing process, while all are important for novel FRs. Correlation analysis between influencing factors and HFRs indicated that the distribution of most pollutants was more affected by anthropogenic source factors than environmental factors. The results of the principal component analysis demonstrated that deca-BDE and its alternative products were the major contributors to the sources of HFRs pollution. Human health risks assessment via oral intake and dermal contact pathways presented that the selected pollutants posed a no-carcinogenic risk to children and adults. It is worth noting that supervision of the disposal process of the NBFRs should be strengthened in the future.

Oxidative stress and endoplasmic reticulum stress contributed to hepatotoxicity of decabromodiphenyl ethane (DBDPE) in L-02 cells

Decabromodiphenyl ethane (DBDPE) is one of the most commonly used novel brominated flame retardants (NBFRs), and its mass production and widespread application have caused health threats to the human being. Existing studies have shown that DBDPE has hepatotoxicity. And we have found that DBDPE could change cytochrome P450 3A (CYP3A) expression levels in rat livers, whereas the mechanism is unclear. In this study, we exposed human normal hepatocyte (L-02) to DBDPE to further study the effect and mechanism of DBDPE on hepatocellular injury and liver metabolic enzyme CYP3A changes in vitro. The results showed that DBDPE caused L-02 cell viability decrease, lactate dehydrogenase (LDH) and transaminase release, ultrastructural damage, and apoptosis. Moreover, DBDPE exposure induced oxidative stress (i.e., increased ROS generation and MDA levels and decreased GSH content, SOD activity, and mitochondrial membrane potential) and endoplasmic reticulum (ER) stress in L-02 cells as evidenced by the elevated PERK and IRE-1α expression levels. These results confirmed that DBDPE is toxic to hepatocytes. Besides, the CYP3A expression level was decreased in DBDPE exposed L-02 cells. However, pretreatment of L-02 cells with antioxidant N-Acetyl-l-cysteine (NAC) and endoplasmic reticulum stress inhibitor 4-PBA inhibited DBDPE-induced oxidative stress, endoplasmic reticulum stress, CYP3A expression decrease, and apoptosis. Therefore, we demonstrated that DBDPE could exert toxic effects and decrease CYP3A expression on L-02 cells by inducing ER stress and oxidative stress.

Characteristics of legacy and novel brominated flame retardants in water and sediment surrounding two e-waste dismantling regions in Taizhou, eastern China

A total of 51 water and 43 sediment samples were collected from the locations surrounding the two e-waste dismantling zones in Taizhou, the Fengjiang resource recycling industrial zone (FJ, shut down in 2017) and the Taizhou resource recycling base (TZ, newly constructed in recent years). The concentrations of polybrominated diphenyl ethers (PBDEs) ranged from 1.7 to 44 ng/L in water and from not detected (nd) to 7100 ng/g in sediment. Novel brominated flame retardants (NBFRs) ranged from 0.29 to 1.6 ng/L in water, and from nd to 5300 ng/g in sediment. The levels of PBDEs and NBFRs in the water were comparable between FJ and TZ, while their concentrations were higher in the sediment from FJ than those from TZ. The levels of BDE-28, BDE-153, pentabromotoluene (PBT), pentabromobenzene (PBB), ∑PBDEs and ∑BFRs in the water from FJ or TZ were found to be significantly negatively associated with the distance from the zone center. However, in the sediments from FJ and TZ, the BFRs levels did not decrease from the center to the outer regions. BDE-209 and decabromodiphenyl ethane (DBDPE) were predominant in the sediments and the ratio of DBDPE/BDE-209 were as high as 5.6 (mean: 0.97). The mass burden of PBDEs, BDE-209, DBDPE, 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), and HBB in the riverine sediments in Luqiao District was 829, 787, 363, 85, and 61 kg, respectively. The ecological risk assessment revealed that BDE-99 posed an unacceptable risk to aquatic life at 86% of the locations. The hazard quotients for penta-BDE, BDE-209, and HBB exceeded one for 30%, 28%, and 2.3% of the sediment samples, respectively.

Investigation on Sex Hormone-Disruption Effects of Two Novel Brominated Flame Retardants (DBDPE and BTBPE) in Male Zebrafish (Danio rerio) and Two Human Cell Lines (H295R and MVLN)

Decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromo-phenoxy) ethane (BTBPE) are novel brominated flame retardants (NBFRs) and have been detected in variety of environment and biota. Although sex endocrine-disrupting potential has been suggested in experimental studies, their adverse effects on sex steroid hormones and underlying mechanisms are largely unclear. The purpose of the present study is to investigate the sex hormone-disrupting effects of two NBFRs using in vivo and in vitro models together. For this, male zebrafish (Danio rerio) along with human adrenocortical carcinoma (H295R) and breast carcinoma (MVLN) cell lines were employed. In male zebrafish, 14-day exposure to DBDPE significantly increased 17β-estradiol (E2) concentrations. Disruption of sex hormone regulation was also suggested after exposure to BTBPE, i.e., the increasing trend of E2 levels, E2/11-ketotestosterone (11-KT) ratio, and estrogen receptor-alpha (erα) and erβ gene expression levels. In H295R cells, an E2/T ratio showed an increasing trend by DBDPE exposure, but transcriptions of major genes in steroidogenesis pathway were not affected. Taken together, our observation implies that two NBFRs could cause the sex hormone disruption potential in male zebrafish and H295R cells but probably not through alteration of steroidogenesis pathway.

Persistent organic pollutant (POPs) concentrations from great-winged petrels nesting in Western Australia

Marine animals that traverse coastal and offshore environments are potentially exposed to multiple sources of pollution. Baseline data of pollutant concentrations of these fauna are needed in remote areas as human populations grow and economic development increases because changes may affect local wildlife in unforeseen ways. Persistent organic pollutant (POPs) concentrations were quantified in an understudied seabird, the great-winged petrel (Pterodroma macroptera), that breeds in southern Western Australia. Organochlorine pesticides, polychlorinated biphenyls (PCBs), and novel brominated flame retardants (NBFRs) were measured in adults. Total POPs concentrations ranged 5.6–46.4 ng g−1 ww. The most frequently detected POPs were the dichlorodiethyltrichloroethane (DDT) metabolite 4,4'DDE, the PCB CB-28, and the BFR polybrominated diphenyl ether BDE-99. These results contribute to the limited POPs data in marine fauna in this remote region, and the Southern Hemisphere, adding to the growing body of evidence that remote regions are affected by global trends of POPs distributions.

Contamination status, emission sources, and human health risk of brominated flame retardants in urban indoor dust from Hanoi, Vietnam: the replacement of legacy polybrominated diphenyl ether mixtures by alternative formulations.

This study investigated the occurrence, distribution of several additive brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and some novel brominated flame retardants (NBFRs) in urban indoor dust collected from ten inner districts of Hanoi, Vietnam to assess the contamination status, emission sources, as well as their associated human exposure through indoor dust ingestion and health risks. Total concentrations of PBDEs and NBFRs in indoor dust samples ranged from 43 to 480 ng g-1 (median 170 ng g-1) and from 56 to 2200 ng g-1 (median 180 ng g-1), respectively. The most abundant PBDE congener in these dust samples was BDE-209 with concentrations ranging from 29 to 360 ng g-1, accounting for 62.6-86.5% of total PBDE levels. Among the NBFRs analyzed, decabromodiphenyl ethane (DBDPE) was the predominant compound with a mean contribution of 98.6% total NBFR amounts. Significant concentrations of DBDPE were detected in all dust samples (median 180 ng g-1, range 54-2200 ng g-1), due to DBDPE as a substitute for deca-BDE. Other NBFRs such as 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), pentabromoethylbenzene (PBEB) and 2,2',4,4',5,5'-hexabromobiphenyl (BB-153) were found at very low levels. Based on the measured BFR concentrations, daily intake doses (IDs) of PBDEs and NBFRs via dust ingestion at exposure scenarios using the median and 95th percentile levels for both adults and children were calculated for risk assessment. The results showed that the daily exposure doses via dust ingestion of all compounds, even in the high-exposure scenarios were also lower than their reference dose (RfD) values. The lifetime cancer risks (LTCR) were much lower than the threshold level (10-6), which indicated the acceptable health risks resulting from indoor BFRs exposure for urban residents in Hanoi.

Probing Legacy and Alternative Flame Retardants in the Air of Chinese Cities

An increasing number of alternative flame retardants (FRs) are being introduced, following the international bans on the use of polybrominated diphenyl ether (PBDE) commercial mixtures. FRs' production capacity has shifted from developed countries to developing countries, with China being the world's largest producer and consumer of FRs. These chemicals are also imported with e-waste to China. Therefore, it is important to understand the current status of regulated brominated FRs, their phase-out in China, and their replacement by alternatives. In this study, a broad suite of legacy and alternative FRs, including eight PBDEs, six novel brominated FRs (NBFRs), two dechlorane plus variants (DPS), and 12 organophosphate FRs (OPFRs) were evaluated in the air of 10 large Chinese cities in 2018. OPFRs are the most prevalent FRs in China, exhibiting a wide range of 1-612 ng/m3, which is several orders of magnitude higher than PBDEs (1-1827 pg/m3) and NBFRs (1-1428 pg/m3). BDE 209 and DBDPE are the most abundant compounds in brominated FRs (>80%). The North China Plain (NCP, excluding Beijing), Guangzhou, and Lanzhou appear to be three hotspots, although with different FR patterns. From 2013/2014 to 2018, levels of PBDEs, NBFRs, and DPs have significantly decreased, while that of OPFRs has increased by 1 order of magnitude. Gas-particle partitioning analysis showed that FRs could have not reached equilibrium, and the steady-state model is better suited for FRs with a higher log KOA (>13). To facilitate a more accurate FR assessment in fine particles, we suggest that, in addition to the conventional volumetric concentration (pg/m3), the mass-normalized concentration (pg/g PM2.5) could also be used.

Temporal trends of novel brominated flame retardants in mollusks from the Chinese Bohai Sea (2011-2018).

Novel brominated flame retardants (NBFRs) have emerged as an alternative to traditional brominated flame retardants (BFRs); however, they may pose risks to the environment and human health. To investigate the occurrence, temporal trends, and human exposure of seven typical NBFRs (∑7 NBFRs), seven species of mollusks (n=329) were collected from coastal cities in the Chinese Bohai Sea area from 2011 to 2018. The ∑7 NBFRs ranged from 1.52 to 154ng/g dry weight (dw) (mean: 14.9±21.21ng/g dw), higher than in other areas worldwide. Decabromodiphenylethane (DBDPE) was the main contaminant, contributing to 33% of the NBFRs. Temporal trends indicate that the DBDPE and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) concentrations in mollusks increased significantly (P<0.05) at rates of about 26% and 5.4%, respectively. This suggests that these NBFRs are continuously released into the environment of the Bohai Sea area. The higher NBFR concentrations in the southern sampling sites relative to the northern sampling sites were consistent with the spatial distribution of the NBFR industry in the Bohai Rim Economic Circle. Chlamys farreri possessed the highest ∑7 NBFR concentrations compared with the other species, while the lowest concentrations were found in Neverita didyma and Rapana venosa, suggesting interspecific differences in bioaccumulation. The estimated daily intake of NBFRs was low, and as the main contaminant, DBDPE was unlikely to pose significant human health risks. Overall, this is the first study to comprehensively assess the occurrence, spatial distribution, and temporal trends of NBFRs in mollusks.

Brominated flame retardants (BFRs) in marine food webs from Bohai Sea, China

In this study, brominated flame retardants (BFRs), including 13 polybrominated diphenyl ethers (PBDEs) and 17 novel brominated flame retardants (NBFRs) are determined in 18 species (including plankton, invertebrate, and fish) from Bohai Sea, China. Trophic transfer of these compounds is also assessed in the marine food web.Significant trophic magnification (p < 0.01) for 11 PBDE congeners (BDE-17, BDE-28, BDE-47, BDE-49, BDE-66, BDE-85, BDE-99, BDE-100, BDE-153, BDE154 and BDE-183) is observed. No significant correlation is observed for BDE-138 (p = 0.06), and significant trophic dilution is observed for BDE-209 (p < 0.0001). In PBDEs, BDE-66 has the highest TMF value of 3.9 (95% confidence interval (CI): 3.2–4.7), followed by BDE-47 (TMF: 3.8, 95% CI: 2.6–5.4) and BDE-28 (3.0, 2.2–4.1). For NBFRs, ATE, TBECH (include α- and β-isomer), PBBZ, TBCO (include α- and β-isomer), PBT, DPTE, HBBZ, PBBA, BTBPE, PBEB and HCDBCO are observed significant trophic magnification (p < 0.01), significant trophic dilution is observed for BATE (p < 0.01), DBDPE (p < 0.001) and OBIND (p < 0.0001), no significant correlation is observed for p-TBX (p = 0.77). In NBFRs, PBT has the highest TMF value of 4.5 (95% CI: 3.1–6.3), followed by PBEB (TMF: 4.0, 95% CI: 2.1–7.6) and HCDBCO (3.9, 3.1–5.0). Regression analysis between KOW and TMF values of BFRs suggest that TMF values have a trend of first rising and then falling against the values of log KOW. Generally, chemicals with higher KOW value have stronger trophic magnification capacity than those with lower ones, but due to the influence of bioavailability, the trophic magnification ability of the superhydrophobic compounds may be inhibited. To our best knowledge, this is the first report of trophic transfer of NBFRs in marine food web and trophic transfer of 9 NBFRs (α-TBECH, p-TBX, BATE, PBBZ, α-TBCO, β-TBCO, DPTE, OBIND, and HCDBCO) in aquatic food web.

A low-volume air sampling method for legacy and novel brominated flame retardants in indoor environment using a newly developed sorbent mixture

Brominated flame retardants (BFRs) are a series of stable and outstanding flame retardants bringing human exposure risks in indoor environment. However, sampling methods now available for BFRs are solvent-consuming and relatively complicated. This study provides a new option of low-volume air sampling device using cartridges with a sorbent mixture for different types of legacy and novel BFRs. In this study, we found that HC-C18 sorbent is most suitable for polybrominated diphenyl ethers (PBDEs) and novel BFRs (NBFRs) enrichment, and that NH2 for hexabromocyclododecanes (HBCDs). The sorbent mixture was optimized using a complex of HC-C18 and NH2 sorbents with elution recovery of 69.4% ± 7.9–117% ± 10%, pumping-through recovery of 84.5% ± 7.9–127% ± 36%, and breakthrough recovery of 70.8% ± 3.4–118% ± 6% for PBDEs, NBFRs, and HBCDs in indoor air. A sequential elution was also achieved using hexane for PBDEs and NBFRs and ethyl acetate for HBCDs. The method was validated with field sampling at nine student dormitory rooms. For legacy BFRs, all the isomers of HBCDs were detected in the air of nine rooms with the median concentrations of 91, 33, and 25 pg/m3 for (±)α-HBCD, (±)β-HBCD, (±)γ-HBCD, respectively, while PBDEs were hardly detected. In contrast, NBFRs were detected at total concentrations of 15–811 pg/m3. Pentabromotoluene (PBT) was the most frequently detected NBFRs with a median concentration of 4 pg/m3, followed by EHTBB at 56 pg/m3 and HBBZ at 21 pg/m3. For the risk assessment, the total hazard index value for air inhalation of BFRs was estimated at 6.1⎓10−4–0.35, which are consistently lower than 1, indicating no immediate health risk, while their long-term effects remain worth concerns.

Occurrence and spatial distribution of legacy and novel brominated flame retardants in seawater and sediment of the South China sea.

The occurrence and spatial distribution of polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) in seawater and surficial sediment samples (N=19 and 45, respectively) from the South China Sea (SCS) in 2018 were investigated, and the correlation between BFRs and site parameters (total organic carbon, depth, etc.) were assessed by principal component analysis. The concentration ranges of ΣPBDEs in seawater and sediments were 0.90-4.40ng/L and 0.52-22.67ng/g dry weight (dw), respectively, while those of ΣNBFRs were 0.49-37.42ng/L and 0.78-82.29ng/g dw, respectively. BDE-209 and decabromodiphenyl ethane were the predominant BFRs, accounting for 38.65% and 36.94% in seawater and 26.71% and 68.42% in sediments, respectively. Notably, tris(2,3-dibromopropyl)isocyanurate and 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, seldomly detected in aquatic matrices worldwide, were detected for the first time in the study area, and their relatively high levels and detection frequencies indicate the ubiquitous application of these NBFRs in the Pearl River Delta. Zhuhai and Jiangmen are the main sources of NBFRs in the SCS. Preliminary risk assessment on NBFRs using hazard quotient indicates low to medium risks to marine organisms at some sites. The occurrence of NBFRs in the SCS highlights the prioritization of more toxicological information on these compounds.

Chlorinated and brominated persistent compounds in hard coral, soft coral, and parrotfish from remote Mascarene islands

Persistent halogenated compounds (PHC) are of concern for human and environmental health. Persistent Organic Pollutants (POPs) are regulated by international treaties, but alternative compounds such as novel brominated flame retardants (NBFRs) and Dechlorane Plus (DP) are not—yet they are increasingly used. There are no data on PHCs in coral reef biota from tropical islands in the western Indian Ocean (WIO). For this assessment, three hard coral genera, two soft coral genera, and ember parrotfish (Scarus rubroviolaceus) were collected from the remote Rodrigues, Agalega, and St. Brandon’s Atoll (Republic of Mauritius) in the Mascarene Basin of the WIO. Five compounds — Pentabromotoluene (PBT), γ-HCH, p,p’-DDE, HCB, and BDE-47— were quantifiable in all samples. Hard coral consistently contained the lowest concentrations of PHCs, except for NBFRs. The presence of BDE-47 suggests long-range aerial transport. We quantified DP, currently a candidate POP, in coral reef biota. PBT was measured in all samples also suggests long-range transport. Because the hard coral, soft coral, and fish had differing concentrations and patterns of PHCs, future surveys should stratify sampling accordingly. Agalega and St. Brandon’s Atoll can be considered as locations to monitor changes in background concentrations of pollutants due to their remoteness.

Slopes and intercepts from log-log correlations of gas/particle quotient and octanol-air partition coefficient (vapor-pressure) for semi-volatile organic compounds: II. Theoretical predictions vs. monitoring

The logarithm of gas/particle (G/P) partition quotient (logKP) has been found to have a linear relationship with logKOA (octanol-air partition coefficient) with slope mo and intercept bo and logPL (subcooled liquid vapor pressure) with slope mp and intercept bp. In the sister paper of the present work, analytical equations to predict the slope mo and intercept bo based on logKOA and predict the slope mp and intercept bp based on logPL are developed using steady state theory. In this work, the equations are evaluated using world-wide monitoring data (262 pairs for mo and bo values and 292 pairs for mp and bp values produced from more than 10,000 monitiring data worldwide) for selected seven groups of semi-volatile organic compounds (SVOCs), including polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-p-dioxins and polychorinated dibenzofurans (PCDD/Fs), polyclorinated biphenyl (PCBs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated naphthalenes (PCNs), organochlorinated pesticides (OCPs), novel brominated flame retardants (NBFRs), and other selected halogenated flame retardants. The slopes and intercepts predicted by the steady state equations reproduce the trends observed in monitoring regression results for the seven SVOC groups, with 44.4% of the variation of monitoring mo values accounted for by logKOA and 48.2% of the variation of monitoring mp values accounted for by logPL. Theoretically, the values of mo can be any value between 0 and 1 dependent on the values of KOA, and are not constrained to 1 as in equilibrium theory. Likewise, the values of mp can be any value between 0 and -1 dependent on the values of PL, and not constrained to −1 predicted by the equilibrium theory. The influence of sampling artifacts on the G/P partitioning of SVOCs has most likely been overemphasized by the equilibrium theory. Thus, the equilibrium approach should be abandoned in favor of the steady state approach for calculating the G/P partition quotients for SVOCs with high KOA values (>1011.38) or low PL values (<10−4.92).

Serum levels of novel brominated flame retardants (NBFRs) in residents of a major BFR-producing region: Occurrence, impact factors and the relationship to thyroid and liver function

Five currently used novel brominated flame retardants (NBFRs) were determined in 172 serum samples collected from nonoccupational residents of a major BFR-producing region. All the 5 NBFRs presented high detection frequencies (DFs, >90%), and decabromodiphenyl ethane (DBDPE), a substitute of decabrominated diphenyl ethers (deca-BDE), was the most abundant NBFR. The levels of DBDPE were from <LOD to 1590 ng/g lw, with a median level of 32.5 ng/g lw. The median levels of other NBFRs were from 0.134 to 2.87 ng/g lw, which were at least 10 times lower than that of DBDPE. Moreover, a comparison to other studies showed that our results were significantly higher than studies conducted in background population. The levels of some NBFRs adjusted by serum lipid showed negative and significant correlation with BMI, whereas the difference disappeared when NBFRs levels were calculated based on serum volume. Certain NBFRs in female showed significantly higher concentrations than those in male. No significant effect of age, smoking habit, education level and children birth (in female) on serum NBFR levels was observed. The relationship between the serum levels of NBFRs and a series of thyroid/liver injury biomarkers was further analyzed to evaluate the health effects of these NBFRs to human being. Results showed that a 10-fold increment in the serum DBDPE level was associated with decreased total triiodothyronine (TT3) level (−0.037 nmol/L) [95% CI: −0.070, −0.003]， whereas serum pentabromoethylbenzene (PBEB) level was associated with increased total triiodothyronine (TT3) level (0.031 nmol/L) [95% CI: 0.001, 0.060]. For liver indicators, a 10-fold increment in the serum level of PBT was associated with decreased Ln aspartate aminotransferase/alanine aminotransferase (AST/ALT) level (−0.068) [95% CI: −0.129, −0.007]. A 10-fold increment in the serum level of BTBPE was associated with increased TBIL level (0.869 μmol/L) [95% CI: 0.175, 1.564], direct bilirubin (DBIL) level (0.231 μmol/L) [95% CI: 0.075, 0.388] and IDBIL level (0.638 μmol/L) [95% CI: 0.091, 1.185]. Our findings indicate that BFR production is posing heavy BFR contamination to surrounding environment and human being, and which might relate to thyroid disruption and liver injury.

Occurrence and mass balance of emerging brominated flame retardants in a municipal wastewater treatment plant

As a class of alternative flame retardants, “novel” brominated flame retardants (NBFRs) have been widely used in clothing, textiles, electronics, building materials, and plastics and are frequently found in environmental samples. Although the use and discharge of NBFRs are increasing all over the world, little information is available about their fates and removal in wastewater treatment plants (WWTPs). This study investigated the occurrence and behavior of 2,4,6-tribromophenyl allyl ether (ATE), 2,3-dibromopropyl tribromophenyl ether (DPTE), tetrabromo-o-chlorotoluene (TBCT), pentabromobenzyl acrylate (PBBA), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (TBPH), and decabromodiphenyl ethane (DBDPE) in a municipal WWTP in Beijing, China. Four of the NBFRs (ATE, BTBPE, TBPH, and DBDPE) were detected in all wastewater and biosolid samples. The dominant compound in both wastewater and biosolid samples was DBDPE, with concentrations in the ranges of 6.4–18 ng/L and 83–288 ng/g dry weight (dw), respectively. A mass flow analysis indicated that the overall removal efficiencies were 31±18% for ATE, 97±1.5% for DPTE, 79±11% for BTBPE, 87±5.3% for TBPH, and 93±3.3% for DBDPE, but the removal efficiency in aqueous phase only ranged from -43 (ATE) to 57% (DBDPE). The low and negative removal efficiencies of ATE were possibly due to the transformation of DPTE during the anaerobic treatment processes. Under the aerobic conditions, BTBPE, TBPH and DBDPE underwent a very slow biodegradation. A total of 68−91% of the initial mass loadings of ATE, BTBPE, TBPH and DBDPE were found in the biosolid samples, suggesting that the four NBFRs were removed mainly via sorption in the WWTP.The biosolid was a huge reservoir of target NBFRs, and effective removal of NBFRs during treatment in the WWTP is critical.

Legacy and emerging flame retardants (FRs) in the urban atmosphere of Pakistan: Diurnal variations, gas-particle partitioning and human health exposure

Atmospheric concentration of legacy (LFRs) and emerging flame retardants (EFRs) including 8 polybrominated diphenyl ethers (PBDEs), 6 novel brominated flame retardants (NBFRs), 2 dechlorane plus isomers (DP), and 8 chlorinated organophosphate flame retardants (OPFRs) were consecutively measured in eight major cities across Pakistan. A total of 96 samples (48 PM2.5 & 48 PUFs) were analyzed and the concentrations of ∑8PBDEs (gaseous+particulate) ranged between 40.8 and 288 pg/m3 with an average value of 172 pg/m3. ∑6NBFRs ranged between 12.0 and 35.0 pg/m3 with an average value of 22.5 pg/m3 while ∑8OPFRs ranged between 12,900–40,800 pg/m3 with an average of 24,700 pg/m3. Among the studied sites, Faisalabad city exhibited the higher concentrations of FRs among all cities which might be a consequence of textile mills and garment manufacturing industries. While analyzing the diurnal patterns, OPFRs depicted higher concentrations during night-time. The estimated risks of all groups of FRs from inhalation of ambient air were negligible for all the cities, according to USEPA guidelines. Nonetheless, our study is the first to report gaseous and particulate concentrations of FRs in air on a diurnal basis across major cities in Pakistan, offering insights into the atmospheric fate of these substances in urban areas in a sub-tropical region.