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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.)

The toxicity of microplastics (MPs) to aquatic animals is closely related to the presence and release kinetics of contained additives, as most plastic products contain various additives. However, the relationship between the occurrence and release of additives from MPs, and their individual or combined toxicity remains unclear. In this study, the nanoscale distribution and release of tetrabromobisphenol A (TBBPA, a common flame retardant with endocrine-disrupting effect) in polystyrene (PS) MPs, and the long-term (60 days) toxicity of TBBPA and MPs containing TBBPA (at doses of 0 %, 1 %, 10 %, w/w) to Xenopus tropicalis tadpoles were investigated. Exposure to 10 μg/L TBBPA alone was the most toxics, while the encapsulation of TBBPA in MPs significantly delayed its lethal toxicity to tadpoles by inhibiting the rapid and extensive release of TBBPA. PS MPs alone and MPs containing 10 % TBBPA exhibited delayed survival toxicity compared to TBBPA alone, whereas PS MPs containing 1 % TBBPA did not show this effect but inhibited growth. These findings suggest that chronic toxicity assessments should be based on long-term (months or even years) exposure experiments due to the encapsulation-controlled slow release of toxic additives., 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.)

Surface particulates collected from the workshop floors of three major e-waste recycling sites (Taizhou, Qingyuan, and Guiyu) in China were analyzed for tetrabromobisphenol A/S (TBBPA/S) and their derivatives to investigate the environmental pollution caused by e-waste recycling activities. Mean concentrations of total TBBPA/S analogs in surface particulates were 31,471-116,059 ng/g dry weight (dw). TBBPA, TBBPA-BGE, and TBBPA-BDBPE were the most frequently detected in particulates with average concentration ranges of 17,929-78,406, 5601-15,842, and 5929-21,383 ng/g dw, respectively. Meanwhile, TBBPA, TBBPA-BGE, and TBBPA-BDBPE were the most abundant TBBPA/S analogs, accounting for around 96% of the total. The composition profiles of TBBPA/S analogs differed significantly among three e-waste sites. Similarly, principal component analysis uncovered different pollution patterns among different sites. The discrepancy in the profiles of TBBPA/S analogs largely relied on the e-waste types recycled in different areas. E-waste recycling led to the release of TBBPA/S analogs, and TBBPA/S analogs produced differentiation during migration from source (surface particulates) to nearby soil. More researches are necessary to find a definite relationship between pollution status and e-waste types and study differentiation behavior of TBBPA/S analogs in migration and diffusion from source to environmental medium., 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 Inc. All rights reserved.)

Tetrabromobisphenol A bis (2- hydroxyethyl) ether (TBBPA-DHEE), as one of the main derivatives of Tetrabromobisphenol A, been attracted attention for its health risks. In this study, the neurotoxicity, mechanism, and susceptivity of TBBPA-DHEE exposure to sexually developing male rats were systematically studied. Neurobehavioral research showed that TBBPA-DHEE exposure could significantly affect the behavior, learning,and memory abilities of male-developing rats, and aggravate their depression. TBBPA-DHEE exposure could inhibit the secretion of neurotransmitters. Transcriptomics studies show that TBBPA-DHEE can significantly affect gene expression, and a total of 334 differentially expressed genes are enriched. GO function enrichment analysis shows that TBBPA-DHEE exposure can significantly affect the expression of genes related to synapses and cell components. KEGG function enrichment analysis shows that TBBPA-DHEE exposure can significantly affect the expression of signal pathways related to nerves, nerve development, and signal transduction. Susceptibility analysis showed that female rats were more susceptible to TBBPA-DHEE exposure than male rats. Therefore, TBBPA-DHEE exposure has neurodevelopmental toxicity to male developmental rats, and female developmental rats are more susceptible than male developmental rats. Its possible molecular mechanism is that TBBPA-DHEE may inhibit the secretion of neurotransmitters and affect signal pathways related to neurodevelopment and signal transduction., 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. Published by Elsevier Ltd.)

The large usage of Tetrabromobisphenol A (TBBPA) in consumer products leads to ubiquitous distribution globally, however, studies on the occurrence of their debromination compounds were rather scarce. Also, though many studies illustrate the effectiveness of hair analysis to assess human exposure to organic pollutants, evidence on the associations with health implications is still fairly limited. Herein, 598 participants from across China were employed to investigate chronic, low-level exposure to TBBPA and debromination products by hair analysis. The geomean concentrations of TBBPA, 2,2',6-tribromobisphenol A (Tri-BBPA), 2,2'- and 2,6-dibromobisphenol A (Di-BBPA), and 2-monobromobisphenol A (Mo-BBPA) were 1.07, 0.145, 0.135, and 0.894 ng/g, respectively, indicating nonnegligible health risks of debromination products. Hair analyte levels correlated with population age and population density among sampling regions. Sexual- and spatial-variations were observed with higher concentrations in females and in E-waste recycling sites. Logistic regression models showed that TBBPA exposure (adjusted odds ratio (OR): 1.02, 95 % confidential interval (CI): 1.01-1.05) was positively associated with risk of metabolic syndrome by adjusting for various covariates. These findings imply usefulness of hair as an alternative biomonitoring tool to assess human exposure to TBBPA and relative health effects, which highlights public concerns on co-exposure to these chemicals., 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. Published by Elsevier B.V.)

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.)

Tetrabromobisphenol A (TBBPA) and its derivatives are regarded as new contaminants, raising much attention on their environmental occurrence and fates. However, the sensitive detection of TBBPA and its main derivatives is still a great challenge. This study investigated a sensitive method for simultaneous detection of TBBPA and its ten derivatives using high-performance liquid chromatography coupled with triple quadrupole mass spectrometry (HPLC-MS/MS) with atmospheric pressure chemical ionization (APCI) source. The method exhibited much better performance than previously reported methods. Furthermore, it was successfully applied in determining complicated environmental samples, including sewage sludge, river water and vegetable samples with concentration range from undetected (n.d.) to 25.8 ng g -1 dry weight (dw). For sewage sludge, river water and vegetable samples, the spiking recoveries of TBBPA and its derivatives ranged from 69.6 ± 7.0% to 86.1 ± 12.9%, 69.5 ± 13.9% to 87.5 ± 6.6%, and 68.2 ± 5.6% to 80.2 ± 8.3%, respectively; the accuracy ranged from 94.9 ± 4.6% to 113 ± 5%, 91.9 ± 10.9% to 112 ± 7%, and 92.1 ± 5.1% to 106 ± 6%, and the method quantitative limits ranged from 0.00801 to 0.224 ng g -1 dw, 0.0104-0.253 ng L -1 , and 0.00524-0.152 ng g -1 dw, respectively. Moreover, the present manuscript describes for the first time the simultaneous detection of TBBPA and ten derivatives from various environmental samples, providing fundamental work for further research on their environmental occurrences, behaviors and fates., 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 B.V. All rights reserved.)

The uptake, translocation, and transformation of 2,2',4,4'-tetra brominated diphenyl ether (BDE-47) in wheat ( Triticum aestivum L.) were comprehensively investigated by hydroponic experiments using compound-specific stable isotope analysis (CSIA) and transcriptome analysis. The results indicated that BDE-47 was quickly adsorbed on epidermis of wheat roots and then absorbed in roots via water and anion channels as well as an active process dependent on energy. A small fraction of BDE-47 in roots was subjected to translocation acropetally, and an increase of δ 13 C values in shoots than roots implied that BDE-47 in roots had to cross at least one lipid bilayer to enter the vascular bundle via transporters. In addition, accompanied by the decreasing concentrations, δ 13 C values of BDE-47 showed the increasing trend with time in shoots, indicating occurrence of BDE-47 transformation. OH-PBDEs were detected as transformation products, and the hydroxyl group preferentially substituted at the ortho-positions of BDE-47. Based on transcriptome analysis, genes encoding polybrominated diphenyl ether (PBDE)-metabolizing enzymes, including cytochrome P450 enzymes, nitrate reductases, and glutathione S -transferases, were significantly upregulated after exposure to BDE-47 in shoots, further evidencing BDE-47 transformation. This study first reported the stable carbon isotope fractionation of PBDEs during translocation and transformation in plants, and application of CSIA and transcriptome analysis allowed systematically characterize the environmental behaviors of pollutants in plants.

Polychlorinated Biphenyls (PCBs) and Polybrominated Diphenyl Ethers (PBDEs) are extensively present in humans and may disturb glucose metabolism during pregnancy. However, previous reports on the associations between PCBs/PBDEs levels and gestational diabetes mellitus (GDM) have been inconsistent. We performed a nested case-control study to measure the serum levels of 6 PCB and 7 PBDE congeners in early pregnancy, and to assess their associations with GDM risk and blood glucose levels. Totally, 208 serum samples (104 GDM cases and 104 controls) were included based on a prospective cohort which was carried out in Jiangsu province, China, from 2020 to 2022. The results showed that PCB-153 was the major PCB congener, whereas PBDE-47 was the predominant PBDE congener. The continuous concentrations of PCB-153, PBDE-28, and total PCB were significantly related to an increased risk of GDM, with adjusted ORs (95%CI) of 1.25 (1.04-1.50), 1.19 (1.02-1.39), and 1.37 (1.05-1.79), respectively. Potential dose-response relationships were also observed between serum levels of PCB-153 (P = 0.011), PBDE-28 (P = 0.028), total PCB (P = 0.048), and total PCB/PBDE (P = 0.010) and GDM risk. Moreover, PCB-153, PBDE-28 and total PCB levels were positively related to 1-h OGTT blood glucose (adjusted β PCB-153 : 0.14, 95%CI: 0.00-0.28; adjusted β PBDE-28 : 0.20, 95%CI: 0.08-0.32; adjusted β total PCB : 0.30, 95%CI: 0.09-0.50), whereas none of the PCBs/PBDEs were statistically related to fasting blood glucose and 2-h OGTT blood glucose (all P > 0.05). Further meta-analysis also supported the association of PCBs exposure with GDM risk. Our study provides further evidence that PCBs/PBDEs exposure may increase GDM risk during pregnancy., 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 transformation products and mechanism of tetrabromobisphenol A (TBBPA) derivatives are still largely unknown compared with TBBPA. In this paper, sediment, soil and water samples (15 sites, 45 samples) collected in a river flowing through brominated flame retardant manufacturing zone were analyzed to determine TBBPA derivatives, byproducts, and transformation products. TBBPA derivatives and byproducts were detected with concentrations ranging from none detection to 1.1 × 10 4  ng/g dw and with detection frequencies of 0-100 % in all samples. The concentrations of TBBPA derivatives such as TBBPA bis(2,3-dibromopropyl) ether (TBBPA-BDBPE) and TBBPA bis(allyl ether) in sediment and soil samples were higher than that of TBBPA. In addition, the occurrence of various unknown bromobisphenol A allyl ether analogs in the samples was further confirmed by using 11 synthesized analogs, which might be produced during the waste treatment process of the factories. The possible transformation pathways of TBBPA-BDBPE were revealed for the first time by using UV/base/persulfate (PS) as designed photooxidation waste treatment system in the laboratory. Ether bond cleavage, debromination, and β-scission contributed to the transformation of TBBPA-BDBPE and the occurrence of transformation products in the environment. The concentrations of the transformation products of TBBPA-BDBPE ranged from none detection to 3.4 × 10 2  ng/g dw. These data provide new insights into the fate of TBBPA derivatives in environmental compartments., 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 B.V. 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.)

Background: High-brominated flame retardants (BFRs) can be released into the environment from consumer products, such as electric and electronic equipment, and enter the human body by different pathways. Because of their toxicity and the regulations, it is very relevant to know their levels and trends in human samples. However, chromatographic serum analysis of some of these compounds represents nowadays a challenge in the general population., Objective: To optimize and validate an instrumental method based on gas chromatography coupled to mass spectrometry, which, together with a simple sample preparation procedure, allows the analysis of decabromodiphenyl ether (BDE-209), decabromodiphenyl ethane (DBDPE), and tetrabromobisphenol A-bis(2,3-dibromopropyl ether) (TBBPA-DBPE) in human serum samples from the general population., Method: To minimize the high degradation during instrumental analysis, GC parameters such as injection volumes, carrier flow rates, and column lengths were assessed and optimized. This instrumental approach in combination with solid-phase extraction (SPE) followed by multilayer silica gel column purification allowed satisfactory analysis using only 1 mL of serum., Results: The performance of the complete method was evaluated at three spiking levels, 0.01, 0.05, and 0.2 ng/mL. Recoveries in the range 87-108% were obtained whereas the relative standard deviation in interday measurements, were, in general, lower than 19%. Limits of detection were in the range of 0.0045-0.0070 ng/mL. The optimized procedure was successfully applied to the determination of the investigated pollutants in real human samples of general population., Conclusions: The proposed method could contribute to the inclusion of these environmental pollutants in human biomonitoring (HBM) studies, increasing the knowledge of levels and trends in the general population., Highlights: GC-MS parameters optimization to minimize instrumental analytes degradation. Successful application to human serum samples from the general population. Tetrabromobisphenol A bis(2,3-dibromopropyl ether) human serum levels are reported for the first time., (© The Author(s) 2023. Published by Oxford University Press on behalf of AOAC INTERNATIONAL. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

This study evaluates the adequacy of a USEPA Method 1613 alternative analytical method for analysis of persistent organic pollutants (POPs) in soil from the immediate vicinity of industrialized areas in the eThekwini municipal area in South Africa. The objective of this study is in line with the Stockholm Convention Article 11 on research, development, and monitoring. Furthermore, it became imperative to find an alternative analytical procedure to USEPA Method 1613 that could cater to studies conducted in Africa where recent reviews have indicated that most African countries lack the technical and instrumental capacity for performing analysis of dioxin-like compounds according to USEPA Method 1613, which entails the use of high-resolution chromatography and high-resolution mass spectrometry instrumentation. The study aimed to ascertain the utility of an alternative two-dimensional gas chromatography-time of flight mass spectrometry method for analysis of trace-level priority POPs in soil, along with a fast single quadrupole gas chromatography-mass spectrometry method. The analytical methods were applied to the analysis of POPs on soil samples from industrial areas with oil refineries and a pulp and paper manufacturing company, while other samples were collected near the electricity substations and a landfill site. Analytical results showed BDE 209 as the dominant contaminating polybrominated diphenyl ether (concentration ranges from 0.006 to 5.71 ng g -1 ). Polybrominated biphenyls (PBBs) 9, 10, and 49 were the dominant PBBs detected in 78% of the sites tested, although their concentrations were below the limit of quantification (LOQ). Polychlorinated dibenzo-p-dioxins and furans and dioxin-like polychlorinated biphenyls detected could not be quantified above their respective LOQs, indicating that the Durban area has low priority pollutant contamination levels compared to other regions around the world. The methods developed are a starting point that will inform considerations for routine evaluation and management of soil contamination, which plays a vital role in environmental management. Integr Environ Assess Manag 2023;19:749-762. © 2022 SETAC., (© 2022 SETAC.)

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.

Persistent organic pollutants, including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and other brominated flame retardants, were detected in the liver, muscle, and ovary tissues of the Indonesian coelacanth (Latimeria menadoensis) incidentally caught around Gangga Island, North Sulawesi Province, Indonesia, on November 5, 2014. Concentrations of total PCBs (209 congeners, 300-2600 ng g -1 lipid weight) in all tissues showed higher than those of PBDEs (41 congeners, 3.9-6.3 ng g -1 lw) and BTBPE (1.1-3.6 ng g -1 lw). The tissue-specific PCB and PBDE profiles were likely due to differences in the lipid composition. Toxic equivalent (TEQ) values of dioxin-like PCBs in coelacanth tissues were lower than the benchmark values for early-life fish. However, compared with the data reported for deep-sea fishes in the Pacific and Indian Oceans, the relatively high concentrations of PCBs detected in this study raise concerns regarding Indonesian coelacanth conservation and habitat conditions., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Human serum albumin (HSA) was used as a model protein to explore the effects of brominated flame retardant (BFR) binding and the corona formation on polystyrene nanoplastics (PNs). Under physiological conditions, HSA helped to disperse PNs but promoted the formation of aggregates in the presence of tetrabromobisphenol A (TBBPA, Δ D h = 135 nm) and S (TBBPS, Δ D h = 256 nm) at pH 7. At pH 4, these aggregates became larger with fewer electrostatic repulsion effects (Δ D h = 920 and 691 nm for TBBPA and TBBPS, respectively). However, such promotion effects as well as BFR binding are different due to structural differences of tetrabromobisphenol A and S. Environmental kosmotropes efficiently stabilized the structure of HSA and inhibited BFR binding, while the chaotropes favored bioconjugated aggregate formation. Such effects were also verified in natural seawater. The newly gained knowledge may help us anticipate the behavior and fate of plastic particles and small molecular pollutants in both physiological and natural aqueous systems.

Tetrabromobisphenol A (TBBPA) is a known endocrine disruptor employed in a range of consumer products and has been predominantly found in different environments through industrial processes and in human samples. In this review, we aimed to summarize published scientific evidence on human biomonitoring, toxic effects and mode of action of TBBPA in humans. Interestingly, an overview of various pretreatment methods, emerging detection methods, and treatment methods was elucidated. Studies on exposure routes in humans, a combination of detection methods, adsorbent-based treatments and degradation of TBBPA are in the preliminary phase and have several limitations. Therefore, in-depth studies on these subjects should be considered to enhance the accurate body load of non-invasive matrix, external exposure levels, optimal design of combined detection techniques, and degrading technology of TBBPA. Overall, this review will improve the scientific comprehension of TBBPA in humans as well as the environment, and the breakthrough for treating waste products containing TBBPA.

TBBPA bis(2-hydroxyethyl) ether (TBBPA-DHEE), one of the main derivatives of TBBPA, has been widely detected in environmental samples and been discovered to be potential neurotoxic. In this study, the juvenile zebrafish were selected as the research subject to explore the neurotoxicity and its mechanism of low-dose TBBPA-DHEE exposure, and to reveal the neurotoxicity susceptibility in different sexes. Behavioral studies revealed that TBBPA-DHEE could significantly reduce the swimming velocity, maximum acceleration and cumulative duration of high-speed mobility, significantly increasing the cumulative duration of low-speed mobility and average social distance. It significantly reduced the contents of ATP, glutamate and Ca 2+ in the whole brain. The histopathological study demonstrated that TBBPA-DHEE could cause brain tissue damage in female and male juvenile zebrafish. The comprehensive data analysis indicated that female zebrafish were more susceptible to TBBPA-DHEE exposure than male zebrafish. Transcriptomic analysis showed that TBBPA-DHEE could significantly affect the expressions of behavioral and development-related genes. Furthermore, female and male juvenile zebrafish have different molecular mechanisms of neurotoxicity. For female juvenile zebrafish, the potential mechanism of neurotoxicity could be that it interfered with the feedback regulation of nerves by affecting the related genes expressions in the signaling pathways such as Ca 2+ signaling, Wnt signaling and synapses. For male juvenile zebrafish, the potential mechanism of neurotoxicity may be through affecting the expression of related genes in hormones and neuro-related genes. This research could reveal the potential neurotoxicity of TBBPA-DHEE to aquatic organisms, which will be helpful to reveal the health effects of the emerging environmental pollutants., 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 © 2022. Published by Elsevier Inc.)

Endocrine-disrupting chemicals (EDCs) are now ubiquitously distributed in the environment. Tetrabromobisphenol A bis(2-hydroxyethyl) ether (TBBPA-DHEE) pollution in environment media poses a significant threat to humans and aquatic organisms as a result of its potential neurotoxicity and endocrine-disrupting effect. The endocrine-disrupting effects of TBBPA-DHEE on aquatic organisms, however, have received limited attention. In this study, the neurotoxicity and reproductive endocrine-disruptive effect of TBBPA-DHEE was evaluated by observing the neurobehavioral changes, vitellogenin (VTG), testosterone, 17β-estradiol and gene expression levels in adult male and female zebrafish exposed to TBBPA-DHEE (0.05, 0.2 and 0.3 mg/L) for 100 days. Furthermore, transcriptomic analysis was conducted to unravel other potential neuroendocrine-disrupting mechanism. Our result showed TBBPA-DHEE significantly (p < 0.05) altered the locomotor behavior and motor coordination abilities in both sexes. Steroid hormone and VTG levels were also altered indicating the neuroendocrine-disrupting effect of TBBPA-DHEE on the hypothalamic-pituitary-gonadal-axis. A total of 1568 genes were upregulated and 542 genes downregulated in males, whereas, 1265 upregulated and 535 downregulated genes were observed in females. The KEGG enrichment analysis showed that cell cycle and p55 signaling pathways were significantly enriched due to TBBPA-DHEE exposure. These pathways and its component genes are potential target of EDCs. The significant upregulation of genes in these pathways could partly explain the neuroendocrine disrupting effect of TBBPA-DHEE. The observed toxic effects of TBBPA-DHEE observed in this study is confirmation of the endocrine-disrupting toxicity of this chemical which would be valuable in biosafety evaluation and biomonitoring of TBBPA-DHEE for public health purposes., 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 © 2022 Elsevier Inc. All rights reserved.)

Aquatic worms are considered a suitable group to evaluate the effects of contaminants on the environment, although one of the main challenges is to use the species of local occurrence. Recently, Pristina longiseta was suggested to be used in acute bioassays. In this context, this study aimed to establish a chronic exposure for ecotoxicological bioassays using the cosmopolitan species of occurrence in Brazilian freshwater P. longiseta. Firstly, we tested three exposure times (4, 7, and 10 days) under the presence or absence of aeration for reproduction outputs. After determining the best configuration (7 days without aeration), we assessed the effects of the chronic exposures using the standardized reference substance potassium chloride (KCl), the antibiotic sulfamethoxazole (SMX), the flame retardant tetrabromobisphenol A (TBBPA), and the sugarcane vinasse. Our results showed suitability for applying the chronic exposure using P. longiseta and indicated the sensitivity of the offspring to KCl (EC50-7d = 0.51 g/L). Sulfamethoxazole and TBBPA caused a significant decrease in the offspring of P. longiseta (EC50-7d = 59.9 µg/L and < 62.5 µg/L, respectively). Sugarcane vinasse showed high toxicity for the species, and 4.26% of vinasse was calculated as EC50-7d. Therefore, the described protocol was successfully applied as an ecotoxicological bioassay to evaluate the effects of environmental contaminants on the reproduction rate of the freshwater worm P. longiseta., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Studies exploring the association of tetrabromobisphenol A (TBBPA) with breast cancer and related mechanisms are limited. To investigate the relationship between TBBPA levels in breast adipose and breast cancer, we carried out case-control research. As well as further examine the mediating role of adipose metabolites between TBBPA and breast cancer using the metabolomics approach. In this study, the concentration of TBBPA was determined utilizing ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) after a solid phase extraction (SPE) pretreatment. High-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) was employed to analyze adipose metabolomics. Evaluation of metabolites linked to TBBPA exposure and breast cancer was performed utilizing mediation analysis. With an estimated OR (95%CI) of 1.153 (1.023, 1.299), TBBPA was firmly linked with breast cancer. We also used propensity score matching analysis and sensitivity analysis to reduce the effect of confounding factors on the results. Metabolomics of adipose suggested significant perturbation in the linoleic acid metabolism pathway. In addition, for PC (16:0/16:0) as phospholipids, a mediation effect on the associations of TBBPA exposure with breast cancer risks was observed (estimated mediation percentage: 56.58%). Understanding the relationship between TBBPA exposure and the risk of breast cancer may be facilitated by the findings, which point to potential mediation metabolites., 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 © 2022 Elsevier Ltd. All rights reserved.)

Tetrabromobisphenol A bis (2-hydroxyethyl ether) (TBBPA-DHEE) is a derivative of Tetrabromobisphenol A (TBBPA) used as an intermediate flame retardant in engineering polymers. The mechanism of neurodevelopmental toxicity of TBBPA-DHEE remains unclear due to limited toxicological data. We performed behavioral and transcriptomic analyses to assess the neurodevelopmental effects of TBBPA-DHEE on developing zebrafish and potential toxicity mechanisms. Our result shows that exposure to TBBPA-DHEE significantly increased mortality, deformity rate, and reduction in hatch rate, hatchability, and body length relative to the DMSO control. The behavior analysis indicates that TBBPA-DHEE significantly reduced the spontaneous movement of larva compared to the control. The TSH and GH levels were significantly reduced in all the exposure groups in a concentration-dependent manner relative to the DMSO control. TBBPA-DHEE exhibited a significant reduction in locomotor activity across all the exposure groups in the light/dark locomotion test. The transcriptomic analysis result shows that 579 genes were differentially expressed. KEGG analysis shows the enrichment of complement cascade, JAK-STAT signaling pathway, cytokine-cytokine interaction, and phototransduction pathway resulting in a change in mRNA expression of their genes. These observed changes in developmental endpoints, hormonal level, and alteration in mRNA expression of component genes involved in neurodevelopmental pathways could be part of the possible mechanism of the observed toxic effects of TBBPA-DHEE exposure on zebrafish. This study could reveal the possible neurodevelopmental toxicity of TBBPA-DHEE to aquatic species, which could help uncover the health implications of emerging environmental contaminants., 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 © 2022 Elsevier Inc. All rights reserved.)

Background: Tetrabromobisphenol A (TBBPA) is the most commonly used brominated flame retardant (BFR) in the industry. TBBPA has been determined in environmental samples, food, tap water, dust as well as outdoor and indoor air and in the human body. Studies have also shown the toxic potential of this substance. In search of a better and less toxic BFR, tetrabromobisphenol S (TBBPS) has been developed in order to replace TBBPA in the industry. There is a lack of data on the toxic effects of TBBPS, while no study has explored apoptotic mechanism of action of TBBPA and TBBPS in human leukocytes., Methods: The cells were separated from leucocyte-platelet buffy coat and were incubated with studied compounds in concentrations ranging from 0.01 to 50 µg/mL for 24 h. In order to explore the apoptotic mechanism of action of tested BFRs, phosphatidylserine externalization at cellular membrane (the number of apoptotic cells), cytosolic calcium ion and transmembrane mitochondrial potential levels, caspase-8, -9 and -3 activation, as well as PARP-1 cleavage, DNA fragmentation and chromatin condensation in PBMCs were determined., Results: TBBPA and TBBPS triggered apoptosis in human PBMCs as they changed all tested parameters in the incubated cells. It was also observed that the mitochondrial pathway was mainly involved in the apoptotic action of studied compounds., Conclusions: It was found that TBBPS, and more strongly TBBPA, triggered apoptosis in human PBMCs. Generally, the mitochondrial pathway was involved in the apoptotic action of tested compounds; nevertheless, TBBPS more strongly than TBBPA caused intrinsic pathway activation.

The northeastern Pacific northern and southern resident killer whale (Orcinus orca) populations are listed as threatened and endangered in Canada, respectively, with persistent, bioaccumulative contaminants, such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), posing threats to their recovery. Concentrations of PCBs and PBDEs in subtidal surface sediments collected from 97 sites along the British Columbia (BC) coast were used to identify their distribution and profiles, and to assess killer whale habitat quality. Victoria Harbour (VH3 (site ID: 1) ) sediments exhibited the highest PCB and PBDE concentrations. For PCBs, PCB-138 was found at the highest concentration, followed by PCB-153, PCB-110, PCB-149, PCB-101, and PCB-118. For PBDEs, individual congeners were ranked as follows: BDE-209 > BDE-207 > BDE-206 > BDE-208 > BDE-47 > BDE-99. Principal component analyses (PCA) illustrated the variations in contaminant profiles, with PC1 for PCBs and PBDEs correlated with the octanol-water partition coefficient (log K OW , p < 0.003). Based on the PCA, sediment particle size, total organic carbon (TOC), and water depth at collection were other factors associated with the distribution of PBDEs, while PCB profiles were associated with TOC. Total PCB and PBDE concentrations at 100% and 34% of the sites, respectively, exceeded the recently adopted British Columbia's Ministry of Environment and Climate Change Strategy Working Sediment Quality Guidelines (PCBs 3.7 pg/g dry wt and PBDEs 1000 pg/g dry wt), considered protective of killer whales. Our findings suggest that the legacy of banned PCBs and PBDEs has the potential to constrain the recovery of killer whales as a result of their mobilization from sediments and consequent uptake by marine food webs. Environ Toxicol Chem 2022;41:2139-2151. © 2022 SETAC., (© 2022 SETAC.)

Tetrabromobisphenol A bis(2-hydroxyetyl) ether (TBBPA-DHEE) is among the main derivatives of Tetrabromobisphenol A (TBBPA). Result from previous study showed that TBBPA-DHEE can cause neurotoxicity in rat. In this study, zebrafish larvae were used for evaluation of TBBPA-DHEE-induced developmental toxicity, apoptosis, oxidative stress and the potential molecular mechanisms of action. Our result showed that TBBPA-DHEE exposure caused a significant concentration-dependent developmental toxicity endpoints like death rate, malformation rate, growth rate. TBBPA-DHEE altered locomotor and enzymes activities of larvae and caused apoptosis within the brain indicating the potential TBBPA-DHEE-induced cardiac, brain impairment in the zebrafish larvae. Our transcriptomic analysis shows that 691 genes were differentially expressed (DEGs) (539 upregulated, 152 downregulated). The KEGG and GO enrichment pathway analysis shows that the DEGs were involved in development, immunity, enzyme activity. Our study provides novel evidence on the neurodevelopmental toxicity and toxicity mechanism of TBBPA-DHEE which are vital for assessment of the environmental toxicity and risk assessment of the chemical., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDDs) have attracted extensive attention due to their strong persistence and toxicity. However, little has been known about their pollution status in fishing ports, which are typical sinks of land-sourced pollutants. In this study, we investigated the occurrence, distribution and ecological risk of TBBPA and HBCDDs in sediments from fishing ports along the coast of South China. The concentrations of TBBPA and ΣHBCDD (sum of α-, β-, and γ-HBCDD) in the fishing-port sediments were in the ranges of 0.02-21.5 ng/g dw and 1.06-14.1 ng/g dw, respectively. γ-HBCDD was the predominant diastereoisomer in most fishing-port sediments. The enantiomeric analysis indicated a preferential enrichment of (-)-enantiomers for α-, β-, and γ-HBCDD. The geographical location of fishing ports is a significant determinant of distribution for TBBPA and HBBCDs. The concentrations of TBBPA and HBCDDs in fishing-port sediments were strongly associated with local population density, but weakly correlated with total organic carbon content of the sediment. The mass inventories of TBBPA and ΣHBCDD were estimated to be 77.0 ng/cm 2 and 141 ng/cm 2 , respectively. The ecological risk assessment demonstrated that TBBPA and HBCDDs in fishing-port sediments exhibited low risks to marine organisms. This study contributes to the understanding pollution situation of fishing ports, and provides a reference for environmental safety assessment and environmental pollution control., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Tetrabromobisphenol A (TBBPA) and its debromination (∑BBPA) and O-methylation (∑MeO-TBBPA) products were widely detected in matched sediments, fish, and whelks samples collected from a typical electronic waste (e-waste) dismantling site in Southern China, with concentrations ranging from 19.8 to 1.52 × 10 4 , 8.05 to 1.84 × 10 3 , and 0.08 to 11.9 ng/g dry weight in sediments, and 6.96 to 1.97 × 10 5 , 3.84 to 7.07 × 10 3 , and 3.42 to 472 ng/g lipid in biotas, for TBBPA, ∑BBPA, and ∑MeO-TBBPA, respectively. Significantly higher concentrations of these targets were found in samples collected close to the e-waste site, indicating their potential e-waste sources. Tri-BBPA was the most abundant debromination products in sediments, whereas diMeO-TBBPA was the dominant O-methylation product in biotas. Relatively higher levels of diMeO-TBBPA found in liver and kidneys, suggesting these chemicals might be mainly derived from the in vivo biotransformation. Furthermore, significantly higher biota-sediment accumulation factor values were found for diMeO-TBBPA than these of TBBPA, indicating that O-methylation would increases their accumulation in aquatic organisms. Our study provides insights into the accumulation and biotransformation of TBBPA in aquatic systems. Further studies should pay attention to the occurrence as well as potential health risks of these transformation products., 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 © 2022 Elsevier B.V. All rights reserved.)

As a widely used brominated flame retardants (BFRs), tetrabromobisphenol A (TBBPA) has been detected in various environmental matrices and is known to cause negative effects on both the environment and human health. In this study, a combined method was developed for the abatement of TBBPA contaminated soil based on successive steps of solvent extraction (SE) and catalytic hydrodebromination (HDB) over Pd/C. The results showed that TBBPA could be efficiently extracted from the TBBPA contaminated soil with polar solvents. Subsequently, TBBPA could be completely hydrodebrominated over Pd/C in ethanol, via multistep ultimately yielding bisphenol A. Moreover, NaOH, NH 3 H 2 O, and Et 3 N were more favorable to promote the HDB of 4-TBBPA over Pd/C, and 100% bromide atom removal ratio of TBBPA was achieved within 40 min when [NaOH] 0 /[organic-Br] 0 was more than 1.10 in ethanol. However, the catalytic activity of Pd/C decreased with the repeated use in ethanol. To study the mechanism for this phenomenon, fresh and used catalysts were analyzed by characterization techniques including scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray spectrometer (EDS). It was found that the deactivation of Pd/C catalyst caused by the gradual accumulation of NaBr could be recovered by washing with water. On the basis of these studies, an effective and practical system for the combined method of SE and catalytic HDB over Pd/C was developed to dispose BFRs contaminated soils., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Polybrominated biphenyls (PBBs) can bioaccumulate in nature and are toxic to humans. Long-time exposure to PBBs in pregnant women can lead to the birth of an infant with abnormal conditions. Hence, in this study, we used molecular docking, molecular dynamics, Taguchi experimental design, and fractional factorial experimental design to identify the developmental toxicity characteristics of 10 typical developmental toxic pollutants such as PBBs to which humans are frequently exposed. Furthermore, the correlation and sensitivity analyses of molecular developmental toxicity and structural parameters were performed. The molecular key structural parameters of the pollutants affecting human development were screened. Moreover, the supplementary food factors that could alleviate the developmental toxicity of pollutants were screened to develop supplementary food schemes to prevent or alleviate human developmental toxicity in the special population (e.g., pregnant women, infants) exposed to the pollutants. The results showed that the developmental toxicity was controlled by the main effects of the 10 pollutants. Among the 10 pollutants with developmental toxicity, the most significant pollutant with the main effects was PBB-153 (37.06%). In addition, the correlation and sensitivity analyses of the molecular developmental toxicity of the pollutants and structural parameters showed that the total energy value and infrared C-H vibration frequency of the pollutants were significantly correlated with human developmental toxicity. Accordingly, 15 supplementary food cofactors were selected for the Taguchi experiment design, among which the top seven cofactors were designed by fractional factorial analysis. The most significant cofactor that alleviated the developmental toxicity of PBB-153 exposure was the combination of carotene and docosahexaenoic acid (DHA), with an improvement of 17.28%. The combination of carotene and DHA significantly alleviated the effects of toxicity caused by most of the other pollutants, indicating that the selected supplementary food has certain universality. In this study, we developed a method to identify the characteristics of the developmental toxicity of pollutant exposure and developmental toxicity alleviation. Our study provided theoretical support for the regulation strategy of developmental toxicity caused by pollutants such as PBBs., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

BFRs (brominated flame retardants) are a class of compounds that are added to or applied to polymeric materials to avoid or reduce the spread of fire. Tetrabromobisphenol A (TBBPA) is one of the known BFR used many in industries today. Due to its wide application as an additive flame retardant in commodities, TBBPA has become a common indoor contaminant. Recent researches have raised concerns about the possible hazardous effect of exposure to TBBPA and its derivatives in humans and wildlife. This review gives a thorough assessment of the literature on TBBPA and its derivatives, as well as environmental levels and human exposure. Several analytical techniques/methods have been developed for sensitive and accurate analysis of TBBPA and its derivatives in different compartments. These chemicals have been detected in practically every environmental compartment globally, making them a ubiquitous pollutant. TBBPA may be subject to adsorption, biological degradation or photolysis, photolysis after being released into the environment. Treatment of TBBPA-containing waste, as well as manufacturing and usage regulations, can limit the release of these chemicals to the environment and the health hazards associated with its exposure. Several methods have been successfully employed for the treatment of TBBPA including but not limited to adsorption, ozonation, oxidation and anaerobic degradation. Previous studies have shown that TBBPA and its derivative cause a lot of toxic effects. Diet and dust ingestion and have been identified as the main routes of TBBPA exposure in the general population, according to human exposure studies. Toddlers are more vulnerable than adults to be exposed to indoor dust through inadvertent ingestion. Furthermore, TBBP-A exposure can occur during pregnancy and through breast milk. This review will go a long way in closing up the knowledge gap on the silent and over ignored deadly effects of TBBPA and its derivatives and their attendant consequences., (Copyright © 2021 Elsevier Inc. All rights reserved.)

The widespread use of halogenated flame retardants in recent years has led to the accumulation of TBBPA in water, which may cause potential harm to living organisms. The phototransformation of the flame retardant TBBPA in alkaline saline water under simulated sunlight irradiation was investigated. The effects of abiotic factors such as the initial concentration of TBBPA, chloride ion concentration, solution pH, inorganic anions and cations, dissolved organic matter (DOM) were studied. The results showed that the phototransformation rate of TBBPA accelerated with the decrease of the initial concentration of TBBPA, the increase of chloride ion concentration and solution pH. The scavenging experiments showed that •OH, 1 O 2 , O 2 • - and 3 TBBPA* all participated in the phototransformation of TBBPA. The presence of NO 3 - , CO 3 2- , SO 4 2- , Mg 2+ , Ca 2+ , Fe 3+ and fulvic acid (FA) all inhibited the phototransformation of TBBPA in the present study. The phototransformation products of TBBPA were detected by liquid chromatography-mass spectrometry (LC-MS), and the phototransformation pathways were proposed. This is the first report on the photo-induced generation of halogen exchange products from TBBPA in saline solutions, which will contribute to a better understanding of the environmental behavior and risks of BFRs in water., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

To improve the efficacy of organic pollutant removal using sulfate radicals, we designed MIP@C-Fe-Nx, a molecularly imprinted material capable of targeting the degradation of tetrabromobisphenol A (TBBPA), which can be used as both adsorbent and catalyst to recognize and degrade Tetrabromobisphenol A (TBBPA) accurately, and the final removal rate of TBBPA can reach 104.6 mg·g -1 . Based on the synergistic effects of MIP@C-Fe-Nx on the excellent organic pollutant recognition and catalytic performance, low concentrations of TBBPA can be pre-targeted, concentrated, and fixed on the surface of MIP, and degraded simultaneously in-situ by·OH and SO 4 •- which are produced by activating PS with C-Fe-Nx. Recognition experiments demonstrated that MIPs had perfect performance in recognizing and adsorbing TBBPA and debromination intermediates. The DFT calculations and HPLC-MS analysis indicated that MIP@C-Fe-Nx had a targeted recognition and accumulation for TBBPA and debromination intermediates, for example, dibromobisphenol A, monobromobisphenol A, and bisphenol A, thus avoid the formation of toxic intermediates causing secondary contamination., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Ferrous sulfide (FeS) and humic acid (HA) are typical black substances in black bloom water. Based on the strong reduction ability of FeS and the photosensitivity of HA, the transformation of toxic organic pollutants by the combination of FeS and HA (HA-FeS) is not clear. In order to explore this issue, the stability of HA-FeS was analyzed by measuring the hydrodynamic diameter and zeta potential of HA-FeS, and then the removal mechanism and possible degradation pathway of tetrabromobisphenol A (TBBPA) by HA-FeS under continuous illumination were discussed. The results showed that the hydrodynamic diameter of FeS was reduced and the stability of FeS was improved, and it was easily suspended after FeS combined with the HA in the water. The combination of HA and FeS promoted the removal of TBBPA in water, no matter it was in the presence or absence of light. Besides, compared with the absence of light, the removal efficiency of TBBPA was improved by HA-FeS with continuous light. There were two reasons for the increase in the removal efficiency of TBBPA by HA-FeS. On the one hand, Fe 2+ and S 2- of HA-FeS had more stable chemical valence and obtained better reducibility under continuous light than that in the dark. On the other hand, light induced the release of active species (O 2 - , 1 O 2 , and OH) in the HA-FeS composite colloid and further promoted the degradation of organic pollutants. Therefore, the black substances (FeS) of black blooms may play a beneficial role in the removal of pollutants under sunlight., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The present study evaluated the binding potencies (equilibrium dissociation constant: K D ) of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) with the constitutive androstane receptor (CAR)&#95;ligand binding domain (LBD) of the Baikal seal (bsCAR&#95;LBD) and mouse (mCAR&#95;LBD) using a surface plasmon resonance (SPR) biosensor. The binding affinities of individual congeners with mCAR&#95;LBD tended to be higher than those with bsCAR&#95;LBD but the differences were within the same order of magnitude. Notably, PBDE congeners showed higher binding affinities for both CAR&#95;LBDs than PCB congeners. In silico docking simulations demonstrated that PBDEs had more non-covalent interactions with specific amino acid residues in both CAR&#95;LBDs than PCBs, supporting the results of their binding affinities. Binding affinity comparisons among congeners revealed the structural requirements for higher binding; mono or di ortho-, tri meta-, and di para‑chlorine substitutions for PCBs, and di or tri ortho-, mono meta-, and di para‑bromine substitutions for PBDEs. The binding potencies of these congeners unlikely accounted for their previously reported CAR-mediated transactivation potencies, implying that their transactivation is regulated in a ligand-dependent, but a distinct manner from ligand binding. Risk assessment analysis showed that the K D values of individual PCB and PBDE congeners were 1-4 orders of magnitude higher than their respective hepatic concentrations in wild Baikal seal population., 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 © 2021 Elsevier B.V. All rights reserved.)

Degradation of tetrabromobisphenol A (TBBPA), an emerging micropollutant, by photo/Fe 3+ /sulfite process was investigated under different operational conditions and water matrices. 91% of TBBPA was efficiently degraded within 30 min in the Fe 3+ /sulfite system under sunlight irradiation when the initial pH was 6.0, which is much higher than that of TBBPA without irradiation (52%). The acceleration of radical generation and direct photolysis by photo irradiation were responsible for the enhanced TBBPA degradation. Although this process showed better performance on TBBPA degradation in weak acid conditions, the high removal efficiency was also achieved at near-neutral pH. HO, SO 4 - and direct photolysis contributed to TBBPA degradation. Direct photolysis and SO 4 - presented the dominant contribution. The degradation rate increased with elevating the Fe 3+ dose (10-40 μM), but slightly decreased when the Fe 3+ dose was further raised to 100 μM. Similarly, the degradation efficiency initially increased with increasing the sulfite dose (100-400 μM), but decreased when the sulfite concentration reached 1000 μM. Dissolved oxygen played a crucial role in TBBPA degradation, the presence of water matrices such as humic acid (0.8-4.0 mg/L), bicarbonate (0.5-10 mM) and chloride (0.5-10 mM) retarded TBBPA degradation. This study proposed a new efficient strategy to enhance TBBPA degradation in the Fe 3+ /sulfite process., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Halogenated natural products (HNPs) were identified from organic extracts of the marine sponge Hyrtios proteus from The Bahamas using gas chromatography with electron capture negative ion mass spectrometry and non-targeted gas chromatography with electron ionization mass spectrometry. The HNPs found have similar properties to anthropogenic persistent organic pollutants (POPs). Two ortho-methoxy brominated diphenyl ethers (MeO-BDEs) 2'-MeO-BDE 68 and 6-MeO-BDE 47 were the most abundant compounds. Fourteen other MeO-BDEs were detected along with several polybrominated dibenzo-p-dioxins (PBDDs) (1,3,7-triBDD, 1,3,6,8-tetraBDD and 1,3,7,9-tetraBDD) and MeO-PBDDs. Further analysis of a higher trophic level octopus (Octopus maya) from the same FAO fishing area showed that the major HNPs detected in Hyrtios proteus were also predominant. Moreover, HNPs were more than 30-fold higher in abundance than the major POPs in the octopus, i.e., polychlorinated biphenyls. Hence, Caribbean marine organisms, including those potentially used for food, harbor relatively high concentrations of HNPs., (Copyright © 2021 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.)

The gradual emissions of tetrabromobisphenol A (TBBPA) from the primitive recycling of E-waste create human health threats, which urgently require to develop an efficient, rapid yet simple detection method. The present study conducts a highly sensitive molecularly imprinted photoelectrochemical sensor (MIPES) containing molecularly imprinted (MI)-TiO 2 , Au, and reduced graphene oxide for the trace detection of TBBPA in indoor dust and surface water from an E-waste recycling area. The photocurrent response is used to evaluate the sensing performance of the MIPES toward TBBPA detection. The working potential for amperometry is 0.48 V. The wavelength range for photoelectrochemical detection is 320-780 nm. The sensor shows a detection range of 1.68 to 100 nM with a low limit of detection of 0.51 nM (LOD = 3 s b /S) and a limit of quantification of 1.68 nM (LOQ = 3.3 LOD). In addition, the MIPES sensor exhibits rapid, excellent reproducibility, selectivity, and long-term stability toward TBBPA detection. The relative standard deviation of three measurements for real samples is less than 7.0%, and the recovery range is 90.0-115%. The surface of molecular imprinting contributes to the high charge separation and sensing photocurrent response of TBBPA, which is confirmed by single-particle photoluminescence spectroscopy. The present study provides a new facile sensor with highly sensitive yet rapid response to detect environmental pollutants in E-waste by using the MIPES., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

The effects of polybrominated biphenyls (PBBs) on human health have previously attracted much attention, but recent studies of PBBs have been focused on BB-153 and a few other congeners. PBB concentrations in serum samples from residents of an area containing an electronic waste dismantling site were determined in this study. The total PBB concentrations (i.e., the sums of the concentrations of the 35 PBB congeners) were 229-1360 ng/g lipid. The BB-153 concentrations were markedly higher in the samples from people living in the electronic waste dismantling area than in samples from people living in a nearby control area. BB-153 was found in all of the samples from the study exposure area but the concentrations were relatively low (0.07-4.70 ng/g lipid). High BB-1 concentrations were found for the first time in serum from people living in both the electronic waste dismantling and control areas. The BB-1 concentrations were 211-1280 ng/g lipid. The retention times of the 35 PBB standards and PCBs (polychlorinated biphenyls) with similar structures were used to predict the retention times of unidentified PBB congeners to allow the PBB distributions in the serum samples to be identified. A total of 26 previously unidentified PBB congeners were identified in the human serum samples. BB-5, BB-35, BB-79, and BB-109 were found in >50% of the samples. The PBB patterns in the serum samples were different from the patterns previously found in serum after a PBB contamination incident in 1973, so the health risks currently posed by PBBs are worth studying., (Copyright © 2021. Published by Elsevier Ltd.)

Concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were measured in 23 seafood species widely consumed by the Korean population in the periods of 2005-2007, 2010-2011, and 2015-2017. The Σ 82 PCB (sum of 82 PCB congeners) and Σ 19 PBDE (sum of 19 PBDE congeners) concentrations in the seafood samples of 2015-2017 were 0.06-6.69 ng/g wet weight and 0.01-1.60 ng/g wet weight, respectively. The Σ 82 PCB and Σ 19 PBDE concentrations in the samples were significantly correlated. Elevated PCB and PBDE concentrations were found in fatty fish, such as herring, mackerel, and tuna. The current human intakes of PCBs and PBDEs were much lower than the tolerable daily intake or lowest observed adverse effect level. The levels and human dietary intakes of PCBs and PBDEs in the 2015-2017 survey showed decreases of 17-73% and 57-86%, respectively, compared with those in 2005-2007 and 2010-2011 surveys. This indicates that global bans on PCBs and PBDEs have been effective, and their levels and human exposure to them have been gradually declining., (© 2021. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Tetrabromobisphenol A (TBBPA), halogenated carbazole (HCZ), and their analogs are the emerging pollutants invading the marine environment. So far, a few methods have been reported for the simultaneous analysis of these pollutants due to their large polarity difference. In this study, an effective extraction and cleanup strategy was developed for the simultaneous determination of 19 TBBPA and HCZ congeners in seafood. The 19 analytes could be directly analyzed through high performance liquid chromatography after ultrasonic extraction (methanol, duplicate ethyl acetate-acetone (1:1, v/v)) and gel permeation chromatography cleanup. The acceptable spike-recoveries were within 65.7-118.3%; the precision was intra-/inter-day RSDs: 0.0-6.7%/0.0-8.5%; and the matrix effects were between -14.1% and 12.4%. The detection limits and quantification limits were 0.002-0.014 and 0.020-0.200 µg g -1 dw, respectively. Additionally, this method successfully analyzed the seafood samples and the concentrations of these analytes were in range of nd-5.4 µg g -1 dw., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Tetrabromobisphenol A (TBBPA) is a kind of brominated flame retardant that is usually added to products to reduce their flame retardancy. However, its extensive use has resulted in their residues being found in the environment, which is very harmful. Herein, an indirect competitive immunosensor has been established for TBBPA detection based on the signal amplification system. Pd nanospheres in situ reduced on the surface of MnO 2 nanosheet hybrid (MnO 2 /Pd) was used as the label for the secondary antibody through the Pd-N bond, and gold-toluidine blue composite was loaded onto MWCNTs (MWCNTs/Au-TB), which functioned as the platform for the immunosensor. The spherical structure of Pd had abundant catalytic active sites, which enhanced the catalytic activity of MnO 2 /Pd as the label, hence amplifying the signal response. Besides, MWCNTs/Au-TB improved electron transfer and produced a strong signaling pathway for immobilizing antigens through the Au-NH 2 bond, which can specifically recognize primary antibodies to improve sensitivity. The immunosensor had a linear concentration range of 0-81 ng/mL, a low detection limit of 0.17 ng/mL (S/N = 3), with good stability, selectivity, and reproducibility based on the above advantages. Additionally, the acceptable accuracy and recoveries (recoveries, 92-124%; CV, 3.3-8.8%) in the real water sample analysis indicated that this strategy is promising for emerging pollutant analysis.

Tetrabromobisphenol-A and Tetrabromobisphenol-S (TBBPA/S) and their derivatives have attracted widespread attention owing to their environmental risks and adverse effects on human health. In this study, we developed an analytical method based on ultra-high performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry (UPLC-MS/MS) for the simultaneous determination of TBBPA/S and their eight derivatives in soil samples. After ultrasonic extraction, TBBPA/S and their derivatives were purified using an LC-Si cartridge with 1 mL acetone and 30 mL dichloromethane/n-hexane (1/1, v/v) as the eluent. In the multiple reaction monitoring (MRM) mode, TBBPA and TBBPS were quantified with electrospray ionization (ESI), whereas their derivatives were quantified with atmospheric pressure chemical ionization (APCI). The proposed method was verified with blank spiking and matrix spiking experiments. All target compounds were recovered at the range of 78-124% and the average recoveries of surrogate standard 13 C 12 -labeled TBBPA were 103% and 99% in spiked blank and soil samples, respectively. The method quantitative limits (MQLs) of TBBPA/S and their derivatives in soil samples ranged from 0.22 to 8.8 pg/g dw. These results indicated that an effective method was provided for the analysis of TBBPA/S and their derivatives in abiotic matrices., 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 © 2021. Published by Elsevier B.V.)

Soil contamination with tetrabromobisphenol A (TBBPA) has been an environmental concern for many years, but in situ studies of the fate and potential risk of TBBPA are lacking. In this study, we investigated the dissipation, metabolism, strong alkali-hydrolytic (SAH-TBBPA), and vertical movement of TBBPA in the field with and without rice-wheat rotation and reed growth for 1225 days. After 342 days of incubation, 21.3% of the TBBPA remained in the surface soil accompanied by obvious leaching to deeper soil layers in the first 92 days. By day 1225, TBBPA was nearly absent from the surface soil layer. A very low amount of SAH-TBBPA (2.31-3.43 mg/kg) was detected during the first 342 days of incubation. In the surface soil, five metabolites were identified that represented four interconnected pathways: oxidative skeletal cleavage, O -methylation, type II ipso -substitution, and reductive debromination. Both rice-wheat rotation and monocultural reed growth accelerated TBBPA removal in the field by stimulating the anaerobic debromination and aerobic O -methylation, especially the oxidative skeletal cleavage of TBBPA in the rhizosphere soil. Though far from comprehensive, our study investigated the natural attenuation and metabolism of TBBPA in situ and the influence by crops to estimate the environmental risk of TBBPA in a field scale.

A new kind of NiFe 2 O 4 -based magnetic covalent organic framework nanocomposites (NiFe 2 O 4 @COFs) was fabricated through facile synthesis approach under room temperature. The NiFe 2 O 4 @COFs exhibited higher adsorption capacity for brominated flame retardants than carbon nanotube material based on hydrophobic interactions, π-π stacking interaction, and van der Waals forces. In addition, the adsorption isotherm and the kinetic model were more suitable for Langmuir and pseudo-second-order model, respectively. NiFe 2 O 4 -based magnetic covalent organic framework nanocomposites combined with HPLC-UV (absorption wavelength: 214 nm) technology has excellent adsorption performance, which exhibited low detection limits (0.03-1.9 μg L -1 ), wide linear range (0.11-1000 μg L -1 ), good recoveries (91.5-102%) with a relative standard deviation of less than 2.9%. Finally, the prepared magnetic material was successfully used asadsorbents of magnetic solid-phase extraction and applied to the determination of five BFRs from the real water samples. The adsorption and removal of BFRs by NiFe 2 O 4 @COFs from water samples.

A fluorescent probe has been developed for tetra bromo bisphenol A (TBBPA) detection based on molecularly imprinted polymers (MIPs) combined with wrinkled silica nanoparticles (WSNs) and CdTe quantum dot (QD) hybrid particles. The WSNs with large pore sizes were employed as a structural support platform for QD embedding, and MIPs were synthesized on the surface of QD-embedded WSNs. The synthetic procedure was characterized using transmission electron microscopy, Brunauer-Emmett-Teller measurements, X-ray photoelectron spectrometry, Fourier transform infrared spectroscopy, and zeta potential analysis. The MIP-capped wrinkled silica-QD hybrid particles (WSNs-QDs-MIPs) possessed an adsorption capacity of 96.5 mg g -1 with an imprinting factor of 7.9 towards TBBPA. Under the optimum incubation conditions, the fluorescence intensity (λ ex  = 340 nm, λ em  = 605 nm) was quenched in proportion to added TBBPA in the range 0.025 to 5 μM with a limit of detection of 5.4 nM. The developed probe was successfully applied to the detection of TBBPA in plastic electronic waste samples and the results of this method agreed with those obtained using high-performance liquid chromatography. This method presented a satisfactory selectivity, stability, and reproducibility indicating its potential as a promising probe for TBBPA detection.

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.

The concentrations, distributions, and biomagnification of polybrominated diphenyl ethers (PBDEs) in environmental and biological media in a terrestrial grass ecosystem were studied, The total PBDE concentrations in grasses were 4.00 × 10 -2 to 4.28 ng·g -1 . The total PBDE concentration in weasel muscle (23.2 ng·g -1  l.w.) was the highest concentrations of all animal tissue samples, and the total PBDE concentration in hair from local herdsmen (22.2 ng·g -1  l.w.) was second highest. Less-brominated PBDEs were found to be more strongly biomagnified than more-brominated PBDEs in the grassland food web. PBDEs were found to be much more strongly biomagnified in the food chains of homothermic animals than heterothermic animals. More-brominated PBDEs were not markedly biomagnified in the grassland food web. For example, BDE-153 was not biomagnified in the grassland wildlife food chain but was clearly biomagnified through the sheep, cattle, or horse hair to human hair route. The biomagnification factors and log K ow s negatively correlated for the toad-snake, lizard-snake, and mouse-weasel food chains. The ability of PBDE congeners to become enriched generally decreased as the log K ow increased, and this decrease occurred 100-1000 times more strongly for homothermic animals than heterothermic animals., 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 B.V. All rights reserved.)

Light driven degradation is very promising for pollutants remediation. In the present work, photochemical reaction of tetrabromobisphenol A (TBBPA) under LED white light (λ > 400 nm) irradiation system was investigated to figure out the TBBPA photochemical degradation pathways and isotope fractionation patterns associated with transformation mechanisms. Results indicated that photochemical degradation of TBBPA would happen only with addition to humic acid in air bubbling but not in N 2 bubbling. For photochemical reaction of TBBPA, singlet oxygen ( 1 O 2 ) was found to be important reactive oxygen species for the photochemical degradation of TBBPA. 2,6-Dibromo-4-(propan-2-ylidene)cyclohexa-2,5-dienone and two isopropyl phenol derivatives were identified as the photochemical degradation intermediates by 1 O 2 . 2,6-Dibromo-4-(1-methoxy-ethyl)-phenol was determined as an intermediate via oxidative skeletal rearrangement, reduction and O-methylation. Hydrolysis product hydroxyl-tribromobisphenol A was also observed in the reductive debromination process. In addition, to deeply explore the mechanism, carbon and bromine isotope analysis were performed using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) and gas chromatography-multicollector inductively coupled plasma mass spectrometry (GC/MC/ICPMS) during the photochemical degradation of TBBPA. The results showed that photochemical degradation could not result in statistically significant isotope fractionation, indicated that the bond cleavage of C-C and C-Br were not the rate controlling process. Stable isotope of carbon being not fractionated will be useful for distinguishing the pathways of TBBPA and tracing TBBPA fate in water systems. This work sheds light on photochemical degradation mechanisms of brominated organic contaminants., 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.)