Novel Brominated Flame Retardants Research Articles

Comparative evaluation and QSAR modeling of developmental neurotoxicity of novel brominated flame retardants in zebrafish

The novel brominated flame retardants (NBFRs) have received wide concerns due to their ubiquitous occurrence in the environment and their potential risks to ecosystems and human health. However, the toxicity data of NBFRs are still lacking, especially their toxicity comparison data, and toxicity predictions for untested NBFRs are extremely limited. In this study, eight commonly used NBFRs and decabromodiphenyl ether (BDE209) were selected to compare their toxicity at concentrations between 0.03 and 3.69 μM, by exposing zebrafish embryos until 120 h post-fertilization (hpf) and evaluating 18 toxicity indicators including basic development indicators and a series of behavioral indicators. The toxicity potency of the tested compounds ranked by the total number of significantly affected endpoints were pentabromobenzene (PBB) ≈ 2,4,6-tribromophenol (TBP) > BDE209 ≈ bis(2-ethylhexyl) tetrabromophthalate (TBPH) > pentabromotoluene (PBT) ≈ 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB) > 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) > hexabromobenzene (HBB) > decabromodiphenyl ethane (DBDPE). Almost all the tested compounds affected the locomotor behavior of zebrafish larvae, suggesting that the refined behavioral indicators were sensitive endpoints. Furthermore, the quantitative structure-activity relationship (QSAR) model we developed suggested that molecular surface area (MSA) might be the critical factor for determining the developmental neurotoxicity of NBFRs to zebrafish larvae, except for congeners with larger molecules (e.g. DBDPE, BTBPE). These findings would contribute to elucidating the toxicity differences among various NBFRs and provide important references for their toxicity prediction.

Temporal and spatial distribution of novel brominated flame retardants in atmosphere of the Beijing-Tianjin-Hebei region, China

The occurrence and spatio-temporal distribution of atmospheric novel brominated flame retardants (NBFRs) were studied across five sampling sites in the Beijing-Tianjin-Hebei (BTH) region over a whole year. By collecting samples (gas and particle) with a high-volume active air sampler (HV-AAS), nine NBFRs were analyzed and the sum concentrations ranged from 1.65 to 344 pg/m3, with the highest value found in the urban sampling site in Shijiazhuang City. Decabromodiphenylethane (DBDPE) was the predominant congener, which accounted for 60% of ∑9NBFRs on average, while it was 90% of ∑9NBFRs in the rural site and significantly higher than those observed in the urban sites (one-way ANOVA, p < 0.05). The levels of particle-bound NBFRs were significantly correlated with the variation of total suspended particulates (TSP) and temperature (p < 0.01), indicating their evident impact on the spatio-temporal distribution of NBFRs. Moreover, a significantly positive correlation was observed between the concentrations of 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB) and bis (2-ethyl-1-hexyl) tetrabromophthalate (BEH-TEBP) (p < 0.01). Monocyclic brominated flame retardants (including PBBz, PBT, PBEB, HBB and TBP-DBPE) were correlated with each other (p < 0.01) in both gas and particle phase, suggesting their co-occurrence and the similar source in the environment. The gas-particle partitioning behavior was well predicted by the Li-Jia Empirical Model, and the results indicated that the target NBFRs did not reach the equilibrium state in air. This is one of very few studies revealed the spatio-temporal distribution of atmospheric NBFRs in the BTH region.

Dermal exposure assessment of formal e-waste dismantlers to flame retardants and plasticizers using passive sampling methodologies

The recycling of e-waste can lead to the release of organic chemicals when materials containing additives are subjected to dismantling and grinding. In this context, the exposure of workers from a Catalonian e-waste facility to flame retardants and plasticizers (including organophosphate esters (OPEs), polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs) and dechloranes) was assessed using T-shirts and wristbands as passive samplers. The study area includes an area exclusively dedicated to cathodic ray-tube (CRT) TVs dismantling, and a grinding area where the rest of e-waste is ground. All the families of compounds were detected in both T-shirts and wristbands, with the highest concentration levels corresponding to OPEs, followed by PBDEs, NBFRs, and dechloranes. The CRT area presented higher concentration levels than the grinding area. The compounds with higher concentrations in T-shirts were 2-ethylhexyl diphenyl phosphate (EHDPP), diphenyl cresyl phosphate (DCP) and triphenyl phosphate (TPHP), and the total concentration of all groups ranged between 293 and 8324 ng/dm2-h (hour). In the case of the wristbands, the most abundant compounds were DCP, TPHP, and BDE-209, with total concentrations between 188 and 2248 ng/dm2-h. The two sampling methods appear to be complementary, as T-shirts collect coarser particles, while wristbands also capture volatile compounds. Based on normalized surface and time concentrations, the estimated daily intake (EDI) through dermal contact was calculated and carcinogenic and non-carcinogenic risks (CR and non-CR) associated with this activity assessed. The results show median CR 29 and 16 times below the threshold in CRT and grinding areas respectively. The non-CR medians were 2 and 3 times below the threshold, although in the CRT area one exceptional value surpassed the threshold, suggesting that risk can exist for some workers in the facility.

Enhancing degradation of novel brominated flame retardants by sulfate modified C3N4: Synergistic effect of photocatalytic oxidation and reduction processes

Novel brominated flame retardants (NBFRs) pose serious risks to aquatic organisms and human health due to their persistence and toxicity. Herein, sulfate ions (SO42-) decorated C3N4 (SO42-@CN) photocatalyst material was synthesized for the rapid degradation of NBFRs by a synergistic effect of photocatalytic oxidation and reduction reactions. Compared with bare C3N4, the SO42-@CN exhibited efficient photocatalytic NBFRs removal performance. The degradation rates constant of hexabromobenzene and pentabromotoluene by SO42-@CN were 0.177 and 0.0906 min-1, respectively, which were 2.9 and 6.7 times higher than that by C3N4. It was confirmed that SO42-@CN could generate more active substances (such as sulfate radicals, and hydroxyl radicals) and promote the oxidation of NBFRs. Meanwhile, SO42- accelerated the separation of photogenerated electron-holes by promoting the formation of hydrogenated structures, allowing more photogenerated electrons to participate in the debromination reduction process. This work provides a new insight for the practical application of visible light driven photocatalytic technology in NBFRs residues degradation.

The effect of anthropogenic activities on the behavior of novel brominated flame retardants in surface soil of Northern China urbanized zone

Novel brominated flame retardants (NBFRs) have emerged as an alternative to traditional brominated flame retardants (BFRs) and may pose risks to the environment and human health. However, the distribution pattern of NBFRs in urbanized zones and their association with multiple socioeconomic variables have not been adequately explored. Herein, seven NBFRs were investigated in surface soil samples from Tianjin, China, a typical urbanized area. The ∑7NBFRs ranged from n.d. to 101 ng/g, dry weight (dw) (mean: 12.6 ± 17.6 ng/g dw), which exhibited a relatively elevated level compared to NBFRs in soils from other regions worldwide. Decabromodiphenylethane (DBDPE) was the main contaminant, and its concentration ranged from 0.378 to 99 ng/g, dry weight (dw) (mean: 11.4 ± 17.0 ng/g dw), accounting for 81 % of the ∑7NBFRs. Notably, NBFRs exhibited peak concentrations within residential zones, significantly surpassing those recorded in the remaining four regions (green, farmland, water environment and other) (p < 0.05). Furthermore, the concentration of NBFRs in the soil of the Binhai New District within Tianjin was the highest, significantly exceeding that of other administrative areas, which was closely related to the intensive industrial activities in this region. The above results indicate that human activities are a key factor affecting the concentration of NBFRs in the soil. Moreover, a variety of statistical methods were employed to investigate the correlation between socioeconomic variables and the distribution of NBFRs. The concentration of NBFRs showed a significant correlation with population density and the gross domestic product (GDP) (p < 0.05), and the incorporation of administrative regional planning into structural equation models demonstrated an indirect influence on the spatial distribution of NBFRs concentration, mediated by its impact on population density. These results emphasize the association between NBFRs contamination and the degree of urbanization, thereby providing valuable insights for assessing the exposure risk of NBFRs among urban residents.

Occurrence and distribution of legacy and novel brominated flame retardants in river and sediments in southwest China: A seasonal investigation

Brominated flame retardants (BFRs) and their substitutes are prevalent in the environment, especially near industrial point sources. In non-point source pollution areas, it is crucial to investigate the seasonal pollution characteristics to identify the pollution sources. In this study, compositional profiles, seasonal variations, and ecological risks of legacy BFRs and novel BFRs (NBFRs) in the water and sediment from the Tuojiang River located in southwest China were investigated. The results indicated that ΣBFRs ranged from not detected (n.d.) to 42.0 ng/L in water and from 0.13 to 17.6 ng/g in sediment, while ΣNBFRs ranged from n.d. to 15.8 ng/L in water, and from 0.25 to 6.82 ng/g in sediment. A significant seasonal variation was observed in water and sediments with high proportions of legacy BFRs (median percentage of 68.8% and 51.3% in water and sediment) in the dry season, while NBFRs (median percentage of 53.2% and 71.6% in water and sediment) exhibited predominance in the wet season. This highlighted the importance of surface runoff and atmospheric deposition as important sources of NBFRs in aquatic environments. Moreover, there were high ratios of decabromodiphenyl ethane (DBDPE) and BDE-209 (average: 1.38 and 2.76 in dry and wet season) in sediments adjacent to the residual areas, indicating a consumption shift from legacy BFRs to NBFRs in China. It was observed that legacy BFRs showed higher ecological risks compared to NBFRs in both water and sediment environments, with BDE-209 posing low to medium risks to sediment organisms. This study provides better understanding of contamination characteristics and sources of legacy BFRs and NBFRs in non-point source pollution areas.

Estimating Octanol-Water Partition Coefficients of Novel Brominated Flame Retardants by Reversed-Phase High-Performance Liquid Chromatography and Computational Models.

Legacy brominated flame retardants, including polybrominated diphenyl ethers (PBDEs), have been classified as persistent organic pollutants and replaced with novel brominated flame retardants (NBFRs). The octanol-water partition coefficients (log KOW) of NBFRs have been computationally estimated, but the log KOW values provided by these methods can differ by 1 to 3 orders of magnitude. Given the importance of this parameter in fate and toxicity models, we indirectly measured the log KOW values of eight NBFRs by their capacity factor (k') on a reversed-phase high-performance liquid chromatography (HPLC) C18 column by isocratic elution and compared these measured values with those estimated by nine computational models. Log KOW values were obtained for the NBFRs 1,2-bis(2,4,6-tribromophenoxy) ethane, pentabromobenzene, pentabromoethylbenzene, pentabromotoluene, 2-ethylhexyl 2,3,4,5-tetrabromobenzoate, allyl 2,4,6-tribromophenylether, 2,3-dibromopropyl-2,4,6-tribromophenyl ether, and bis(2-ethylhexyl) tetrabromophthalate. A training set of phthalates, polychlorinated biphenyls, PBDEs, and halogenated benzenes were chosen to obtain the log k'-log KOW calibration for the NBFRs. The computational models KowWIN, XLogP3, EAS-E Suite, COSMOtherm, DirectML, and Abraham polyparameter linear free energy relationships all predicted the log KOW values of the calibration compounds to within 1 order of magnitude without significant bias. The median of these models predicted log KOW values for the calibration compounds that were close to those known in the literature with root mean square error (RMSE) = 0.224 and for the NBFRs that were close to those measured by HPLC (RMSE = 0.334). Environ Toxicol Chem 2024;43:2105-2114. © 2024 SETAC.

Contamination characteristics and dietary intake risk of brominated flame retardants in fishes around a typical e-waste dismantling site in Southern China

Polybrominated diphenyl ethers (PBDEs) and their substitutes, novel brominated flame retardants (NBFRs), are ubiquitously present in the aquatic environment of electronic waste (e-waste) dismantling region, leading to their inevitable absorption and accumulation by aquatic organisms, which can be transferred to human via directly aquatic product consumption or through food chain, thereby posing potential health risks. This study focused on fish samples from Guiyu and its surrounding areas, and found the total PBDEs concentrations were 24–7400 ng/g lw (mean: 1800 ng/g lw) and the total NBFRs concentrations were 14 to 2300 ng/g lw (mean: 310 ng/g lw).Significant positive correlations were found among PBDE congeners, among different NBFRs, and between NBFRs and commercial PBDEs that they replace. ΣPBDEs and ΣNBFRs in the intestine were 620–350,000 and 91–81,000 ng/g lw (mean: 83000 and 12,000 ng/g lw, respectively), significantly exceeding those in the gills, where ΣPBDEs and ΣNBFRs were 14–37,000 and 39–45,000 ng/g lw (mean: 9200 and 2400 ng/g lw, respectively). The ΣPBDEs and ΣNBFRs showed no non-carcinogenic risks to the target population through dietary intake. Despite the significantly higher daily intake of decabromodiphenyl ethane (DBDPE) compared to decabromodiphenyl ether (BDE209), the non-carcinogenic risk associated with BDE209 remained higher than that of DBDPE. Our findings can assist researchers in understanding the presence of BFRs in aquatic organisms, inhabiting e-waste dismantling areas, and in evaluating the associated health risks posed to humans through dietary exposure.

The emerging and legacy persistent organic contaminants in corals of the South China Sea

Seawater warming, ocean acidification and chemical pollution are the main threats to coral growth and even survival. The legacy persistent organic contaminants (POCs), such as polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), and the emerging contaminants, including polybrominated diphenyl ethers (PBDEs), dechlorane plus (DPs) and novel brominated flame retardants (NBFRs) were studied in corals from Luhuitou fringing reef in Sanya Bay and Yongle atoll in Xisha Islands, the South China Sea (SCS). Total average concentrations of ∑16PAHs, ∑23OCPs, ∑34PCBs, ∑8PBDEs, ∑2DPs and ∑5NBFRs in 20 coral species (43 samples) from the SCS were 40.7 ± 34.6, 5.20 ± 5.10, 0.197 ± 0.159, 3.30 ± 3.70, 0.041 ± 0.042 and 36.4 ± 112 ng g−1 dw, respectively. PAHs and NBFRs were the most abundant compounds and they are likely to be dangerous pollutants for future coral growth. Compared to those found in other coral reef regions, these pollutants concentrations in corals were at low to median levels. Except for PBDEs, POCs in massive Porites were significantly higher than those in branch Acropora and Pocillopora (p < 0.01), as large, closely packed corals may be beneficial for retaining more pollutant. The current study contributes valuable data on POCs, particularly for halogenated flame retardants (HFRs, including PBDEs, DPs and NBFRs), in corals from the SCS, and will improve our knowledge of the occurrence and fate of these pollutants in coral reef ecosystems.

Bioaccumulation and Trophodynamics of Novel Brominated Flame Retardants (NBFRs) in Marine Food Webs from the Arctic and Antarctic Regions.

The pervasive contamination of novel brominated flame retardants (NBFRs) in remote polar ecosystems has attracted great attention in recent research. However, understanding regarding the trophic transfer behavior of NBFRs in the Arctic and Antarctic marine food webs is limited. In this study, we examined the occurrence and trophodynamics of NBFRs in polar benthic marine sediment and food webs collected from areas around the Chinese Arctic Yellow River Station (n = 57) and Antarctic Great Wall Station (n = 94). ∑7NBFR concentrations were in the range of 1.27-7.47 ng/g lipid weight (lw) and 0.09-1.56 ng/g lw in the Arctic and Antarctic marine biota, respectively, among which decabromodiphenyl ethane (DBDPE) was the predominant compound in all sample types. The biota-sediment bioaccumulation factors (g total organic carbon/g lipid) of NBFRs in the Arctic (0.85-3.40) were 4-fold higher than those in the Antarctica (0.13-0.61). Trophic magnification factors (TMFs) and their 95% confidence interval (95% CI) of individual NBFRs ranged from 0.43 (95% CI: 0.32, 0.60) to 1.32 (0.92, 1.89) and from 0.34 (0.24, 0.49) to 0.92 (0.56, 1.51) in the Arctic and Antarctic marine food webs, respectively. The TMFs of most congeners were significantly lower than 1, indicating a trophic dilution potential. This is one of the very few investigations on the trophic transfer of NBFRs in remote Arctic and Antarctic marine ecosystems, which provides a basis for exploring the ecological risks of NBFRs in polar regions.

Uptake and translocation of brominated flame retardants in tomato plants (Solanum lycopersicum L.): Results from a standard soil-based biotest

The uptake and translocation of four polybrominated diphenyl ethers (PBDEs) and four novel brominated flame retardants (NBFRs) in tomato plants (Solanum lycopersicum L.) were investigated via the RHIZOtest, a standard soil-based biotest, optimized for organic compounds. Tomato plants were exposed to soil samples spiked with 0 (i.e. control), 5.00 or 50.00 ng g−1dw of each compound. Compared of those of the control, exposure to increasing spiking concentrations resulted in average reductions of 13% and 26% (w/w) in tomato plant biomass. Higher concentrations of NBFRs were analyzed both in roots, ranging from 0.23 to 8.01 ng g−1dw for PBDEs and from 1.25 to 18.51 ng g−1dw for NBFRs, and in shoots, ranging from 0.09 to 5.58 ng g−1dw and from 0.47 to 7.78 ng g−1dw for PBDEs and NBFRs, respectively. This corresponded to an average soil uptake of 5% for PBDEs and 9% for NBFRs at the lower soil-spiking level, and 3% for PBDEs and 6% for NBFRs at the higher soil spiking level. Consequently, among both initial spiking levels, the soil-root concentration factor (RCF) values were lower on average for PBDEs (0.13 ± 0.05 g dw soil g−1dw roots) than for NBFRs (0.33 ± 0.16 g dw soil g−1dw roots). Conversely, nondifferent values of the root-shoot transfer factor (TF) were calculated for both PBDEs (0.54 ± 0.13 g dw roots g−1dw shoots) and NBFRs (0.49 ± 0.24 g dw roots g−1dw shoots). The differences and similarities reported in the RCF and TF between and within the two groups of compounds can be explained by their properties. The calculated RCF and TF values of the PBDEs exhibited a decreasing trend as the number of bromine atoms increased. Additionally, a robust negative linear correlation was observed between RCF values and the respective logKow values for the PBDEs, at both soil-spiking levels. The root uptake of NBFRs exhibited a negative correlation with their hydrophobicity; however, this was not observed in the context of root-to-shoot transfer. The presence of a second aromatic ring appears to be the key factor influencing the observed variations in NBFRs, with biphenyl NBFRs (BTBPE and DBDPE) characterized by lower uptake and reduced translocation potential than monophenyl PBEB and HBB. Understanding the transfer of these compounds to crops, especially near plastic recycling waste sites, is crucial for understanding the risks of their potential inclusion in the human food chain.

Novel and legacy brominated flame retardants in human breast milk and house dust from Denmark

A suite of novel brominated flame retardants (NBFRs), hexabromocyclododecanes (HBCDDs), polybrominated diphenyl ethers (PBDEs) and dechlorane plus were measured in matched samples of house dust (n = 47) and human breast milk (n = 40) from Denmark sampled in 2007, i.e., shortly after PBDE restrictions were implemented in Europe providing a valuable reference point. The most abundant BFR in breast milk was BDE-153 with a median concentration of 0.79 ng/g lipid followed by BDE-47 (median: 0.61 ng/g lipid) and BDE-209 (median: 0.53 ng/g lipid). Levels of bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP) were comparable (median: 0.78 ng/g lipid); however, they were based on fewer samples. α-HBCDD was the most abundant HBCDD in breast milk (median: 0.24 ng/g lipid) and detected in all samples. The house dust samples were dominated by BDE-209 (median: 432 ng/g) and γ-HBCDD (median: 177 ng/g); among the NBFRs, the highest levels were found for decabromodiphenyl ethane (DBDPE) (median: 86.2 ng/g) and BEH-TEBP (median: 26.7 ng/g). BDE-28, 47 and 153 were significantly correlated between breast milk and serum (rs = 0.73-0.81, P &lt; 0.0001); however, this was not the case for any of the NBFRs. Intake estimates for a 3-month-old infant indicated that for most of the flame retardants, breast milk was by far the dominant route of exposure, whereas dust only contributed substantially for BDE-209, γ-HBCDD, and to some extent α-HBCDD. This study is the first to report on human exposure to NBFRs in Denmark and shows that internal exposure levels of NBFRs were similar to those of most PBDEs already at the time of PBDE restrictions.

Debromination of novel brominated flame retardants using Zn-based additives: A viable thermochemical approach in the mitigation of toxic effects during e-waste recycling

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 (ZnFe2O4). 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.

Impact of Legislation on Brominated Flame Retardant Concentrations in UK Indoor and Outdoor Environments: Evidence for Declining Indoor Emissions of Some Legacy BFRs.

Concentrations of polybrominated diphenyl ethers, hexabromocyclododecane (HBCDD), and novel brominated flame retardants (NBFRs) were measured in indoor dust, indoor air, and outdoor air in Birmingham, UK. Concentrations of ΣBFRs ranged from 490 to 89,000 ng/g, 46-14,000 pg/m3, and 22-11,000 pg/m3, respectively, in UK indoor dust, indoor air, and outdoor air. BDE-209 and decabromodiphenyl ethane (DBDPE) were the main contributors. The maximum concentration of DBDPE (10,000 pg/m3) in outdoor air is the highest reported anywhere to date. In contrast with previous studies of outdoor air in Birmingham, we observed significant correlations between concentrations of tri- to hepta-BDEs and HBCDD and temperature. This may suggest that primary emissions from ongoing use of these BFRs have diminished and that secondary emissions (e.g., evaporation from soil) are now a potentially major source of these BFRs in outdoor air. Conversely, the lack of significant correlations between temperature and concentrations of BDE-209 and DBDPE may indicate that ongoing primary emissions from indoor sources remain important for these BFRs. Further research to clarify the relative importance of primary and secondary sources of BFRs to outdoor air is required. Comparison with earlier studies in Birmingham reveals significant (p < 0.05) declines in concentrations of legacy BFRs, but significant increases for NBFRs over the past decade. While there appear minimal health burdens from BFR exposure for UK adults, dust ingestion of BDE-209 may pose a significant risk for UK toddlers.

Novel ultrasound assisted extraction and d-SPE clean-up for the analysis of multiple legacy and emerging organic contaminants in edible fish

Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), phthalate esters (PAEs) are pervasive environmental pollutants, posing threats to both ecosystems and human health. Although several analytical methods were developed for these compounds, they are not performed simultaneously. This study addresses the need for a sustainable, novel, analytical approach capable of simultaneously determining these diverse chemical classes in edible fish muscles. Employing ultrasound extraction coupled with dispersive solid-phase extraction (d-SPE) as a cleanup procedure, the method was compared to conventional techniques, revealing significant improvements. Analytical parameters were thoroughly assessed, and the innovative method demonstrated notable advantages, reducing extraction and purification times by approximately 74–80 % and solvent consumption by around 94–97 %. Applied to Mediterranean Sea fish samples, the results underscore the method's potential as a viable, sustainable alternative to traditional approaches, promising enhanced efficiency and reduced environmental impact.

Historical Occurrence and Composition of Novel Brominated Flame Retardants and Dechlorane Plus in Sediments from an Electronic Waste Recycling Site in South China.

Novel brominated flame retardants (NBFRs) and dechlorane plus (DP) have been widely used as alternatives to traditional BFRs. However, little is known about the temporal trends of NBFR and DP pollution in e-waste recycling sites. In the current study, three composite sediment cores were collected from an e-waste-polluted pond located in a typical e-waste recycling site in South China to investigate the historical occurrence and composition of NBFRs and DP. The NBFRs and DP were detected in all layers of the sediment cores with concentration ranges of 5.71~180,895 and 4.95~109,847 ng/g dw, respectively. Except for 2,3,5,6-tetrabromo-p-xylene (pTBX) and 2,3,4,5,6-pentabromoethylbenzene (PBEB), all the NBFR compounds and DP showed a clear increasing trend from the bottom to top layers. These results implied the long-term and severe contamination of NBFRs and DP. Decabromodiphenyl ethane (DBDPE) was the most abundant NBFR with the contribution proportions of 58 ± 15%, 73 ± 15%, and 71 ± 18% in three sediment cores, followed by 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE) and pentabromobenzene (HBB). The ratios of BTBPE/Octa-BDEs and DBDPE/Deca-BDEs varied from 0.12 to 60 and from 0.03 to 0.49, respectively, which had no clear increase trends with a decrease in sediment depth. As for DP, the fanti values (the concentration ratios of anti-DP to the sum of anti-DP and syn-DP) in sediment cores ranged from 0.41 to 0.83, almost falling in the range of those in DP technical products, suggesting that DP degradation did not occur in sediment cores. The environmental burdens of DBDPE, BTBPE, HBB, PBT, PBEB, pTBX, and DP were estimated to be 34.0, 5.67, 10.1, 0.02, 0.02, 0.01, and 34.8 kg, respectively. This work provides the first insight into the historical contamination status of NBFRs and DP in the sediments of an e-waste recycling site.

Computational Risk Assessment of Persistence, Bioaccumulation, and Toxicity of Novel Flame-Retardant Chemicals.

Novel brominated flame retardants (NBFRs) have emerged as chemicals of environmental concern, as they have been widely used as an alternative to polybrominated diphenyl ethers (PBDEs). Considering the similar structural features of NBFRs and PBDEs necessitates a comprehensive investigation to understand the physicochemical relationships of these compounds and their ability to alter biological functions. In this study, we investigated the persistent nature of NBFRs in terms of thyroid-disrupting potential by understanding the structure-stability aspects using density functional theory (DFT)-based reactivity parameters and interactions via molecular docking and molecular dynamics (MD) simulations. The results indicate that the DFT-based stability descriptor (chemical hardness) is associated with the persistent nature of NBFRs. The computed molecular interaction profile revealed prominent interactions between thyroid receptor-β (TR-β) and NBFRs. Stable trajectory and interactions with TR-β were obtained with ATE, p-TBX, PBT, PBEB, and TBBPA-DBPE during 100 ns of MD simulation. The results of these studies have suggested that the presence of a higher number of halogenated atoms increases the stability vis-à-vis the persistence and endocrine disruption potential of NBFRs.

The transport and distribution of novel brominated flame retardants (NBFRs) and organophosphate esters (OPEs) in soils and moss along mountain valleys in the Himalayas

Although the Himalayas act as a natural barrier, studies have demonstrated that certain traditional persistent organic pollutants (POPs) can be transported into the Tibetan Plateau (TP) through the mountain valleys. Herein, we selected five mountain valleys in the Himalayas to investigate novel flame retardants (NFRs), as representative novel POPs, their concentration, distribution, transport behavior, potential sources and ecological risk. The results revealed that total concentrations of 7 novel brominated flame retardants (NBFRs) ranged from 4.89 to 2853 pg/g dry weight (dw) in soil and from not detected (ND) to 4232 pg/g dw in moss. Additionally, total concentrations of 10 organophosphate esters (OPEs) ranged from ND to 84798 pg/g dw in soil. Among the NFRs, decabromodiphenylethane (DBDPE) and tri-phenyl phosphate (TPhP) were the predominant compounds. NBFRs and OPEs concentrations were slightly higher than those in the polar regions. The correlation between different compounds and altitude varies in different areas, indicating that the NFRs distribution in the mountain valleys result from a combination of long-range transport and local sources. The ecological risk assessment using risk quotient (RQs) revealed that TPhP and tris (2-chloroisopropyl) phosphate (TCIPP) exhibited medium or high risks at some sites. This study sheds light on the transport pathways and environmental behaviors of the NFRs in the valleys and highlights the need for increased attention to the ecological risks posed by OPEs in the TP.

Bioaccumulation of novel brominated flame retardants in crucian carp (Carassius auratus): Implications for electronic waste recycling area monitoring

Bioaccumulation factor (BAF) of pollutants is an important parameter for evaluating their bioaccumulation potential and an important indicator for evaluating their environmental risks. However, little study exits on the BAF of novel brominated flame retardants (NBFRs). The present study determined 17 NBFRs in 24 water samples in dissolved phase and 93 crucian carp samples collected from an electronic waste recycling site in northern China, in order to examine their contamination, distribution and bioaccumulation. The results showed that the targeted NBFRs were widely detectable in the dissolved phase and crucian carps. In dissolved phase, allyl 2,4,6-tribromophenyl ether (ATE) had the highest detectable rate (100%) and concentration (mean: 1.3 ± 0.62 ng/L), but in crucian carp, hexachlorocyclopentenyl-dibromocyclooctane (HCDBCO) was the one with the highest detectable rate (89%) and concentration (mean: 16 ± 9.2 ng/g wet weight (ww)) among all 17 NBFRs. The discharge and water solubility of NBFRs determined their concentration in the dissolved phase, while the concentration of NBFRs in crucian carp was the results of their discharge and food exposure. The estimated BAFs exceeded 5000 L/kg for petabromoethylbenzene (PBEB), pentabromotoluene (PBT), HCDBCO, pentabromobenzyl acrylate (PBBA), 1,2,3,4,5-pentabromobenzene (PBBZ), 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), hexabromobenzene (HBBZ), and α-1,2,5,6-tetrabromocyclooctane (α-TBCO), suggesting that these compounds were above the hazard standard of bioaccumulation. Although the BAFs of 2,3,5,6-tetrabromo-p-xylene (p-TBX), 1,2-bis(2,4,6-tribromophenoxy)-ethane (BTBPE), α-/β-tetrabromoethylcyclohexane (α-/β-TBECH) and ATE were less than 5000, the potential of bioaccumulation cannot be ignored. The log BAF of tested NBFRs showed a pattern of first increasing and then decreasing with the increase of log KOW, the water solubility of NBFRs, the exposure to fish, the uptake and depuration of fish were the key factor to this pattern. To our knowledge, the BAF values of the most of NBFRs calculated in this study were not reported in the published work previously.

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

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