Tetrabromobisphenol A Research Articles

Biotransformation of Tetrabromobisphenol A and Its Analogs by Selected Gut Bacteria Strains: Implications for Human Health.

Knowledge of the biotransformation of tetrabromobisphenol A (TBBPA) and its related contaminants by human gut microbiota (GM) remains unexplored. Here, TBBPA and its four analogs were incubated with mixed GM strains, and nine rhamnosylated or debrominated transformation products (TPs) were discovered. Remarkably, rhamnosylation was identified as a common and unique microbial transformation pathway for these contaminants, and six of the seven rhamnosylated TPs were reported for the first time. Additionally, a kinetic transformation study also showed a rapid and strong bioaccumulation of TBBPA and TPs by Clostridium manihotivorum. Genomic analysis and phylogenetic studies identified C1.1_02053 as the gene encoding the C. manihotivorum working rhamnosyltransferase (CmRT), showing elevated gene expression with higher TBBPA exposure. Molecular docking identified five critical amino acid residues in CmRT that catalyze TBBPA rhamnosylation, and molecular dynamics simulations further confirmed the stability of the CmRT-TBBPA complex. Dynamic metabolomics analysis showed microbial growth-dependent disturbing effects in C. manihotivorum upon TBBPA exposure, and key metabolic pathways related to rhamnosyltransferase showed changes closely related to the transformation process. These findings provide insights into the unique transformation of environmental contaminants by the GM and highlight the disturbing effects of exogenous chemicals on the GM, as well as the potential impacts on overall human health.

Assessing plasmatic transport inhibitors of thyroid hormone in mammals in the Xenopus Eleutheroembryonic Thyroid Assay (XETA).

The Xenopus Eleutheroembryonic Thyroid Assay (XETA, OECD TG 248) was established as an alternative to the Amphibian Metamorphosis Assay (AMA, OECD TG 231) for the analysis of (anti-)thyroid activity of chemicals. The XETA is a New Approach Method (NAM) since the embryonic life stages used in the assay are not yet feeding independently, which renders the assay to be considered a non-animal test under many national laws. Physiologically, the used embryos are not fully developed yet, and thus there are limitations to the XETA for detecting certain mechanisms along the hypothalamic-pituitary-thyroid (HPT) axis. However, the plasmatic transport inhibition of thyroid hormone should physiologically be detectable in the XETA but has not yet been sufficiently investigated. Here, we tested three substances that are known, amongst others, to inhibit thyroid hormone transport by competitive binding to transthyretin in mammalian studies, namely pentachlorophenol (PCP), tetrabromo bisphenol A (TBBPA), and mefenamic acid. Following the test guideline, X. laevis eleutheroembryos of Nieuwkoop-Faber stage 45 were exposed for 72h at 21°C in 6-well plates to different concentrations of the test substances. For PCP and TBBPA, the XETA showed a decrease in fluorescence intensity, which would be expected for thyroid hormone transport inhibition amongst other, similar modes of action, while for the lower potency substance mefenamic acid, a trend was visible, but no statistically significant inhibition was detected. Overall, the results indicate that in the XETA, the plasmatic transport inhibition of thyroid hormone should be detectable alongside other inhibitory modes of action on the HPT axis.

Catalytic pyrolysis mechanism of tetrabromobisphenol A by calcium oxide: A density functional theory study

In this paper, the mechanisms of catalytic pyrolysis of tetrabromobisphenol A (TBBPA) by calcium oxide (CaO) were studied through density functional theory methods. The results indicate that the phenolic hydroxyl group of TBBPA is the preferred site for CaO to extract protons, and the generated anion further transforms into 2,6-dibromophenol via demethylation and hydrogen transfer reactions. The reaction activity of CaO with hydrogen bromide is relatively high, with an energy barrier of 133.2 kJ/mol. CaO produces calcium ions, which combine with bromine ions to form calcium bromide to achieve the purpose of fixing bromine. In addition, the participation of calcium ions results in the OH bond being easier to crack, which further lowers the reaction energy barrier of keto-enol tautomerism reactions H2O produced during catalytic pyrolysis also has an obvious catalytic effect, and the energy barrier of the keto-enol tautomerism reaction decreased from 309.1 kJ/mol to 150.6 kJ/mol with the participation of H2O.

Histone Methylation-Mediated Reproductive Toxicity to Consumer Product Chemicals in Caenorhabditis elegans: An Epigenetic Adverse Outcome Pathway (AOP).

The significance of histone methylation in epigenetic inheritance underscores its relevance to disease and the chronic effects of environmental chemicals. However, limited evidence of the causal relationships between chemically induced epigenetic changes and organismal-level effects hinders the application of epigenetic markers in ecotoxicological assessments. This study explored the contribution of repressive histone marks to reproductive toxicity induced by chemicals in consumer products in Caenorhabditis elegans, applying the adverse outcome pathway (AOP) framework. Triclosan (TCS) and tetrabromobisphenol A (TBBPA) exposures caused reproductive toxicity and altered histone methyltransferase (HMT) and histone demethylase (HDM) activities, increasing the level of trimethylation of H3K9 and H3K27. Notably, treatment with an H3K27-specific HMT inhibitor alleviated reproductive defects and the transcriptional response of genes related to vitellogenin, xenobiotic metabolism, and oxidative stress. Comparison of points of departure (PODs) based on calculated benchmark concentrations (BMCs) revealed the sensitivity of histone-modifying enzyme activities to these chemicals. Our findings suggest that the 'disturbance of HMT and HDM' can serve as the molecular initiating event (MIE) leading to reproductive toxicity in the epigenetic AOP for TCS and TBBPA. The study extended the biological applicability of these enzymes by identifying model species with analogous protein sequences and functions. This combined approach enhances the essentiality, empirical support, and taxonomic domain of applicability (tDOA), which are crucial considerations for ecotoxicological AOPs. Given the widespread use and environmental distribution of chemicals in consumer products, this study proposes histone-modifying enzyme activity as an effective screening tool for reproductive toxicants and emphasizes the integration of epigenetic mechanisms into a prospective ERA.

Tetrabromobisphenol A biotransformation in aged soil: Mechanism analysis induced by root exudates during rhizoremediation of Helianthus annus

Rhizoremediation, recognized as a progressive strategy for the removal of organic pollutants in soil, prominently focused on the influence of root exudates-induced alterations within the rhizosphere on the bioavailability and transformation of pollutants. However, the influence of root exudates on the ultimate fate of tetrabromobisphenol A (TBBPA) in soil remains unclear. The current study embarked on a comprehensive examination of the biotransformation process and underlying mechanisms of TBBPA driven by root exudates of Helianthus annus in rhizospheric soil. The pot experiment underscored the constructive impact of root exudates on enhancing the TBBPA dissipation efficiency within lab-controlled, with the increments of 18.77 %∼38.64 %. The core bacterial players responsible for TBBPA biotransformation were identified, with the prominent genus being Saccharibacteria_genera_incertae_sedis, unclassified_Sphingomonadaceae, and Parcubacteria_genera_incertae_sedis. In rhizospheric soil, a comprehensive analysis disclosed the presence of 20 different biotransformation products of TBBPA. Notably, root exudates were found to predominantly drive the reductive debromination pathway. This study provided for the first concrete evidence that root exudates can promote the desorption of TBBPA from soils. The current study aimed to decipher the molecular mechanisms in biotransformation process of TBBPA mediated by root exudates, and also provided reference for the environmental behavior of organic pollutants induced by root exudates.

Developmental exposures to common environmental pollutants result in long-term Reprogramming of hypothalamic-pituitary axis in mice

Humans are exposed to a range of endocrine disrupting chemicals (EDCs). Many studies demonstrate that exposures to EDCs during critical windows of development can permanently affect endocrine health outcomes. Most experimental studies address changes in secretion of hormones produced by gonads, thyroid gland and adrenals, and little is known about the ability of EDCs to produce long-term changes in the hypothalamic-pituitary (HP) control axes. Here, we examined the long-term effects of three common EDCs on male mouse HP gene expression, following developmental exposures. Pregnant mice were exposed to 0.2 mg/ml solutions of bisphenol S (BPS), 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47), or 3,3′,5,5′-tetrabromobisphenol A (TBBPA) from pregnancy day 8 through lactation day 21 (weaning day). Male offspring were left untreated until postnatal day 140, where pituitaries and hypothalami were collected. Pituitaries were assed for gene expression via RNA sequencing, while specific genes were assessed for expression in hypothalami via RT-qPCR. Differential expression, as well as gene enrichment and pathway analysis, indicated that all three chemicals induced long-term changes, (mostly suppression) in pituitary genes involved in its endocrine function. BPS and BDE-47 produced effects overlapping significantly at the level of effected genes and pathways. All three chemicals altered pathways of gonad and liver HP axes, while BPS altered HP-adrenal and BDE-47 altered HP-thyroid pathways specifically. All three chemicals reduced expression of immune genes in the pituitaries. Targeted gene expression in the hypothalamus indicates down regulation of hypothalamic endocrine control genes by BPS and BDE-47 groups, concordant with changes in the pituitary, suggesting that these chemicals suppress overall HP endocrine function. Interestingly, all three chemicals altered pituitary genes of GPCR-mediated intracellular signaling molecules, key signalers common to many pituitary responses to hormones. The results of this study show that developmental exposures to common EDCs have long-term impacts on hormonal feedback control at the hypothalamic-pituitary level.

Olfactory toxicity of tetrabromobisphenol A to the goldfish Carassius auratus

Tetrabromobisphenol A (TBBPA) is one of the most extensively used brominated flame retardants and its increasing use in consumer products has raised concerns about its ecotoxicity. Given the ubiquity of TBBPA in aquatic environments, it is inevitable that these chemicals will enter the olfactory chambers of fish via water currents. Nevertheless, the olfactory toxicity of TBBPA to aquatic organisms and the underlying toxic mechanisms have yet to be elucidated. Therefore, we investigated the olfactory toxicity of TBBPA in the goldfish Carassius auratus, a model organism widely used in sensory biology. Results showed that exposure to TBBPA resulted in abnormal olfactory-mediated behaviors and diminished electro-olfactogram (EOG) responses, indicating reduced olfactory acuity. To uncover the underlying mechanisms of action, we examined the structural integrity of the olfactory epithelium (OE), expression levels of olfactory G protein-coupled receptors (GPCRs), enzymatic activities of ion transporters, and fluctuations in neurotransmitters. Additionally, comparative transcriptomic analysis was employed to investigate the molecular mechanisms further. Our study demonstrates for the first time that TBBPA at environmentally relevant levels can adversely affect the olfactory sensitivity of aquatic organisms by interfering with the transmission of aqueous stimuli to olfactory receptors, impeding the binding of odorants to their receptors, disrupting the olfactory signal transduction pathway, and ultimately affecting the generation of action potentials.

Bromine-containing copolymer polycarbonate for simultaneous thermal stability, transparency, and thin-wall flame-retardant polycarbonate

The incorporation of traditional low molecule bromine flame retardants can enhance the flame retardancy of polycarbonate (PC), yet their poor compatibility with PC impairs its transparency and mechanical properties. Here, brominated polycarbonate (B50PC) was synthesized by interfacial polycondensation method using bisphenol A, tetrabromobisphenol A, and triphosgene. The number average molecular weight (Mn) of B50PC reached 14,600, and compared to the low molecule bromine flame retardant tetrabromobisphenol A (TBBPA), its initial decomposition temperature increased by 38.7 % under air atmosphere. The PC composites containing 5 wt% B50PC achieved the V-0 rating in the UL-94 test, with LOI increased by 10.3 %. At the same time, the peak heat release rate (PHRR) was decreased by 28.6 % and the ignition time (TTI) was delayed by 21.3 %. Compared with that of samples with TBBPA, the composite with the same amount of B50PC maintained the original elongation at break of PC and the transmittance remained at 84.9 %. In summary, the composites with B50PC maintains outstanding transparency and mechanical properties while enhancing the flame retardancy. This work has developed a high molecular bromine flame retardant that combines flame retardancy and transparency, offering a strategy for expanding the application of PC in the electronics, construction, and aerospace sectors.

Enhanced removal of tetrabromobisphenolA (TBBPA) from e-waste by Fe–S nanoparticles and Fe–S/CuS nanocomposite with response surface methodology (RSM)

TetrabromobisphenolA is a well-known member of the brominated flame retardant group and is widely used as a highly effective fire-retardant additive in electronic and electrical equipment. TBBPA is commonly found in various environmental sources and can be harmful to human health. This study presents a simple approach to preparing a magnetic nanocomposite, offering a straightforward method that results in consistent quality and low resource consumption. The nanocomposite has a high surface-to-volume ratio for the removal of tetrabromobisphenolA. Various characterization techniques, including XRD, FTIR, EDX, FESEM, VSM, TEM, and BET analyses were used to characterize the Fe–S nanoparticles and Fe–S/CuS. The results showed that Fe–S/CuS nanocomposite successfully removed over 97% of the initial TBBPA (15 mg L−1) under optimized conditions determined by RSM, such as a contact time of 15 min, pH of 7, Fe–S/CuS nanocomposite dosage of 0.69 g L−1, and salt concentration of 0.10%. The RSM analysis provided a second-order polynomial model with a confidence level of 93% (F = 29.58; p < 0.0001) to predict the TBBPA removal efficiency at various concentrations. In the adsorption kinetic studies, the second-order kinetic model provided the best fit for the experimental data. Additionally, Fe–S/CuS nanocomposite shows great potential for practical applications and environmental remediation efforts, making it a valuable asset for real-sample use in environmental settings.

Plastisphere Microbiomes Respiring Persistent Organohalide Pollutants.

Plastics are invading nearly all ecosystems on earth, acting as emerging repositories for toxic organic pollutants and thereby imposing substantial threats to ecological integrity. The colonization of plastics by microorganisms, forming the plastisphere, has garnered attention due to its potential influence on biogeochemical cycles. However, the capability of plastisphere microorganisms to attenuate organohalide pollutants remains to be evaluated. This study revealed that the plastisphere, collected from coastal ecosystems, harbors unique microbiomes, while the natural accumulation of organohalide pollutants on plastics may favor the proliferation of organohalide-respiring bacteria (OHRB). Laboratory tests further elucidated the high potential of plastisphere microbiota to reductively dehalogenate a variety of organohalide pollutants. Notably, over 70% tested plastisphere completely debrominated tetrabromobisphenol A (TBBPA) and polybrominated diphenyl ethers (PBDEs) to nonhalogenated products, whereas polychlorinated biphenyls (PCBs) were converted to lower congeners under anaerobic conditions. Dehalococcoides, Dehalogenimonas, and novel Dehalococcoidia populations might contribute to the observed dehalogenation based on their growth during incubation and positive correlations with the quantity of halogens removed. Intriguingly, large fractions of these OHRB populations were identified in a lack of the currently known TBBPA/PBDEs/PCBs reductive dehalogenase (RDase) genes, suggesting the presence of novel RDase genes. Microbial community analyses identified organohalides as a crucial factor in determining the composition, diversity, interaction, and assembly of microbes derived from the plastisphere. Collectively, this study underscores the overlooked roles of the plastisphere in the natural attenuation of persistent organohalide pollutants and sheds light on the unignorable impacts of organohalide compounds on the microbial ecology of the plastisphere.

The degradation of tetrabromobisphenol A by metal-free graphene oxide in the dark

Brominated flame retardants (BFRs) such as tetrabromobisphenol A (TBBPA) were widely detected in the environment. The ease of synthesis of graphene-based materials (GBMs) makes it an excellent metal-free carbon-based catalyst for the reductive debromination of TBBPA. Here we explore the complete debromination of TBBPA from the aqueous environment in the dark using metal-free graphene oxide (GO) and reduced GO (rGO). More importantly, radical scavenger experiments reveal the formation of superoxide radicals and singlet oxygen from the surface of GBMs leading to the debromination of TBBPA. GO shows an enhanced catalytic activity due to enriched O-functional groups on the surface than rGO, as observed by cyclic voltammetry and electrochemical impedance spectroscopy. In addition, the TBBPA degradation pathway was proposed with BPA as the end product and by-products were identified by mass spectroscopy. The complete TBBPA degradation was observed within 240 mins of reaction time (kobs = 8.6×10−3 min−1), which was significantly more efficient than the catalytic activity of other metal-based catalysts. Our study thus provides a new insight into the debromination mechanisms of TBBPA which would exhibit potential for future efficient catalyst development.

Brominated Flame Retardants (BFRs) in China Over the Past Half-Century: Stocks, Flows, Fates, and Ecological Risks.

China is a significant producer and consumer of various brominated flame retardants (BFRs), raising environmental concerns due to their widespread presence and potential threats to ecosystems and organisms. This study adopts a life cycle perspective, combining material flow analysis, multimedia environmental modeling, and ecological risk assessment to systematically analyze the substance metabolism and ecological risks of six BFR types in China from 1970 to 2021. The findings reveal that China's cumulative BFR consumption reached 3.3 Mt, with the electronics sector being the predominant contributor at 52.1%. Consequently, 1.5 kt of BFRs were released into the environment, with 24.9%, 31.5%, and 43.6% being discharged into the air, water, and soil, respectively. Notably, the proportion of novel BFRs in emissions has steadily increased over the years, exemplified by the increase in decabromodiphenyl ethane (DBDPE) from 21.3% in 2010 to 30.1% in 2021. Geographically, BFR concentrations are higher in the eastern and southwestern regions compared to those in the northwest. Presently, certain BFRs like tetrabromobisphenol A (TBBPA) and DBDPE exhibit moderate to high ecological risks, primarily concentrated in the Shandong and Sichuan provinces. A combination of efficient recycling, emission control, and substitution with novel flame-retardant can minimize the exposure of BFRs to the environment and organisms.

Highly sensitive response to the toxicity of environmental chemicals in transparent casper zebrafish

The response sensitivity to toxic substances is the most concerned performance of animal model in chemical risk assessment. Casper (mitfaw2/w2;mpv17a9/a9), a transparent zebrafish mutant, is a useful in vivo model for toxicological assessment. However, the ability of casper to respond to the toxicity of exogenous chemicals is unknown. In this study, zebrafish embryos were exposed to five environmental chemicals, chlorpyrifos, lindane, α-endosulfan, bisphenol A, tetrabromobisphenol A (TBBPA), and an antiepileptic drug valproic acid. The half-lethal concentration (LC50) values of these chemicals in casper embryos were 62–87 % of that in the wild-type. After TBBPA exposure, the occurrence of developmental defects in the posterior blood island of casper embryos was increased by 67–77 % in relative to the wild-type, and the half-maximal effective concentration (EC50) in casper was 73 % of that in the wild-type. Moreover, the casper genetic background significantly increased the hyperlocomotion caused by chlorpyrifos and lindane exposure compared with the wild-type. These results demonstrated that casper had greater susceptibility to toxicity than wild-type zebrafish in acute toxicity, developmental toxicity and neurobehavioral toxicity assessments. Our data will inform future toxicological studies in casper and accelerate the development of efficient approaches and strategies for toxicity assessment via the use of casper.

Enhanced electrochemical oxidation and machine learning-assisted sensing of tetrabromobisphenol A using activated carbon facilitated CoWO4 heterostructures

The escalating levels of environmental pollution, particularly from commercially used products, highlight the imperative of efficient sensor technologies to facilitate timely and effective remediation strategies. Herein, a simple method is proposed to enhance the electrochemical performance of CoWO4 structures by coupling them with activated carbon (AC) for direct tetrabromobisphenol A (TBPA) oxidation. The systematic comparison shows that incorporation of AC with CoWO4 not only improves the overall effective surface area (ESA) of the catalyst by 1.8-fold but also improves the cyclic voltammetry (CV) based irreversible oxidation current by 2.0-fold owing to improved conductivity and surface characteristics. Differential pulse voltammetry (DPV) based optimization of the sensory characteristics confirmed robust electrocatalytic TBPA oxidation within a 0.1 to 1.0 µM concentration range, achieving a 0.024 µM detection limit within PBS (0.1 M) (pH 5.0). Moreover, density functional theory (DFT) analysis confirms the non-covalent interaction favorability between TBPA and CoWO4 surface, validating TBPA’s easy adsorption onto the catalytic surface and, thus, facilitated electron mobility between the molecule and the catalyst during the surface oxidation process. The DPV sensing interpreted using machine learning (ML) algorithms confirmed the detection accuracy of the developed sensor. Among the adopted models, artificial neural networks (ANN) achieved the highest R2 score (0.9659) and the lowest values across Mean Squared Error (MSE), Mean Absolute Error (MAE), and Root Mean Squared Error (RMSE) error matrices confirming its suitability in deciphering DPV correlations.Integrating ANN with DPV based electrocatalytic oxidation sensing underscores machine learning’s potential in analyzing complex electrochemical signatures, thus advancing intelligent sensing for precise environmental monitoring.

Screening (ant)agonistic activities of xenobiotics on the retinoic acid receptor alpha (RARα) using in vitro and in silico analysis

Retinoic acid receptors (RARs) are known as crucial endocrine receptors that could mediate a broad diversity of biological processes. However, the data on endocrine disrupting effects of emerging chemicals by targeting RAR (ant)agonism are far from sufficient. Herein, we investigated the RARα agonistic or antagonistic activities for 75 emerging chemicals of concern, and explored their interactions with this receptor. A recombinant two-hybrid yeast assay was used to examine the RARα activities of the test chemicals, wherein 7 showed effects of RARα agonism and 54 exerted potentials of RARα antagonism. The representative chemicals with RARα agonistic activities, i.e. 4-hydroxylphenol (4-HP) and bisphenol AF (BPAF), significantly increased the mRNA levels of CRABP2 and CYP26A1, while 4 select chemicals with RARα antagonistic potentials, including bisphenol A (BPA), tetrabromobisphenol A (TBBPA), 4-tert-octylphenol (4-t-OP), and 4-n-nonylphenol (4-n-NP), conversely decreased the transcriptional levels of the test genes. The in silico molecular docking analysis using 3 different approaches further confirmed the substantial binding between the chemicals with RARα activities and this nuclear receptor protein. This work highlights the promising strategy for screening endocrine-disrupting effects of emerging chemicals of concern by targeting RARα (ant)agonism.

Visible light-induced photocatalytic degradation of tetrabromobisphenol A on platinized tungsten oxide

In this study, we investigated the degradation of the flame retardant tetrabromobisphenol A (TBBPA) using platinized tungsten oxide (Pt/WO3), synthesized via a simple photodeposition method, under visible light. The results of degradation experiments show a significant enhancement in TBBPA degradation upon surface platinization of WO3, with the degradation rate increasing by 13.4 times compared to bare WO3. The presence of Pt on the WO3 surface stores conduction band electrons, which facilitates the two-electron reduction of oxygen and enhances the production of valence band holes (hVB+) and hydroxyl radicals (●OH). Both hVB+ and ●OH are significantly involved in the degradation of TBBPA in the visible light-irradiated Pt/WO3 system. This was verified through fluorescence spectroscopy employing coumarin as a chemical probe and oxidizing species-quenching experiments. The analysis of degradation products and their toxicity assessment demonstrate that the toxicity of TBBPA-contaminated water is significantly reduced after Pt/WO3 photocatalysis. The degradation rate of TBBPA increased with increasing Pt/WO3 dosage, reached an optimum at a Pt content of 0.5 wt%, but decreased with increasing TBBPA concentration. The decrease in degradation efficiency of Pt/WO3 was minor, both in the presence of various anions and after repeated use. This study proposes that Pt/WO3 is a viable photocatalyst for the degradation of TBBPA in water under visible light.

Update of the scientific opinion on tetrabromobisphenol A (TBBPA) and its derivatives in food.

The European Commission asked EFSA to update its 2011 risk assessment on tetrabromobisphenol A (TBBPA) and five derivatives in food. Neurotoxicity and carcinogenicity were considered as the critical effects of TBBPA in rodent studies. The available evidence indicates that the carcinogenicity of TBBPA occurs via non-genotoxic mechanisms. Taking into account the new data, the CONTAM Panel considered it appropriate to set a tolerable daily intake (TDI). Based on decreased interest in social interaction in male mice, a lowest observed adverse effect level (LOAEL) of 0.2 mg/kg body weight (bw) per day was identified and selected as the reference point for the risk characterisation. Applying the default uncertainty factor of 100 for inter- and intraspecies variability, and a factor of 3 to extrapolate from the LOAEL to NOAEL, a TDI for TBBPA of 0.7 μg/kg bw per day was established. Around 2100 analytical results for TBBPA in food were used to estimate dietary exposure for the European population. The most important contributors to the chronic dietary LB exposure to TBBPA were fish and seafood, meat and meat products and milk and dairy products. The exposure estimates to TBBPA were all below the TDI, including those estimated for breastfed and formula-fed infants. Accounting for the uncertainties affecting the assessment, the CONTAM Panel concluded with 90%-95% certainty that the current dietary exposure to TBBPA does not raise a health concern for any of the population groups considered. There were insufficient data on the toxicity of any of the TBBPA derivatives to derive reference points, or to allow a comparison with TBBPA that would support assignment to an assessment group for the purposes of combined risk assessment.

Efficient removal of tetrabromobisphenol A in the Mn1Fe0.5Al0.5-LDO@BC/peroxymonosulfate water purification system

Tetrabromobisphenol A (TBBPA) brominated flame retardants in water posed threat to the ecological system due to its persistence and biomagnification. In this work, an efficient water purification system based on sulfate radical-based advanced oxidation processes (SR-AOPs) with Mn1Fe0.5Al0.5-LDO@BC as the core was constructed by adjusting the key preparation parameters, optimizing catalyst performance and exploring operating conditions. Under the optimal conditions of Mn1Fe0.5Al0.5-LDO@BC/PMS system (calcination temperature of 600 oC, 0.1 g/L Mn1Fe0.5Al0.5-LDO@BC, 0.15 mM PMS, pH value of 7–), 15 mg/L TBBPA was almost completely degraded within 30 min. Mn1Fe0.5Al0.5-LDO@BC/PMS water purification system exhibited resistance to inorganic anions and humic acid. In addition, Mn1Fe0.5Al0.5-LDO@BC reflected better cycle stability and ecological environmental protection. Electron paramagnetic resonance (EPR) and quenching experiments verified the existence of a large number of dominant active species in the water purification system, especially the contribution of O2•– and 1O2 to the degradation of TBBPA. Finally, the catalytic mechanism and possible degradation pathway of TBBPA were elucidated, and the toxicity of the intermediates was predicted. This work provided novel insights into the efficient purification of TBBPA brominated flame retardants in wastewater.

Ultrasonic preparation of fluorinated functionalised magnetic covalent organic frameworks for adsorption and removal of tetrabromobisphenol A

Tetrabromobisphenol A (TBBPA) was a widely used brominated flame retardant, and had attracted widespread attention from researchers due to its potential adverse effects on ecosystems and human health. Therefore, to eliminate the negative effects of TBBPA, methods for the adsorption and removal of TBBPA are urgently needed. In this work, the fluorine-functionalised magnetic covalent organic frameworks (Fe3O4@TFAPT-TFPA@COF) were first prepared through a simple and rapid ultrasound method to efficiently adsorpt and remove TBBPA. Firstly, a pre-modification strategy was used to modify fluorine functional groups onto amine monomers via superacid catalyzed trimerization. Then, amine and aldehyde monomers undergo Schiff base reaction smoothly to form a COF layer coated on the surface of Fe3O4 nanoparticles. The characterisation results indicated that the prepared Fe3O4@TFAPT-TFPA@COF had a high surface area, porosity, crystallinity and abundant F-containing binding sites. Additionally, the adsorption process of prepared Fe3O4@TFAPT-TFPA@COF complied with pseudo-second-order kinetics and the Langmuir adsorption model. It had a large adsorption capacity (107.5 mg g−1), could effectively remove tetrabromobisphenol A within 4 minutes and had excellent regeneration ability within eighth repetitions. Finally, tetrabromobisphenol A was efficiently removed by a small separation column loaded with Fe3O4@TFAPT-TFPA@COF, achieving levels below the detection limit (< 0.05 mg L−1) and providing practical application value for the real-time removal of TBBPA. The main mechanisms promoting the excellent adsorption performance of TBBPA were through halogen bonds, electrostatic interactions, π-π stacking, and hydrogen bonding interactions, providing potential reference value for the adsorption ability and mechanism of TBBPA in other applications.

Non-flammable polymer electrolyte with fast ion conductivity for high-safety Li batteries

The safety and ionic conductivity of solid polymer electrolytes have hindered their large-scale application. Tetrabromobisphenol A (TBBA) is regarded as an efficient flame retardant for polymers. However, the -OH group of TBBA is active during electrochemical process and results in the sacrifice of capacity in battery cycling. Herein, a new organic filler, TBBA-dichlorobutane (TD) is generated by replacing the H of -OH in TBBA using the 1,4-dichlorobutane through copolymerization modification. The electrochemical stability of TD has been improved, which facilitates the generation of the solid electrolyte interphase (SEI) layer of LiBr, improving interface ionic conductivity. Meanwhile, the addition of TD significantly reduces the crystallinity of polyacrylonitrile (PAN), improving the ionic conductivity of the electrolyte. Furthermore, the electrochemical mechanism has been characterized by in-situ Raman and Fourier transform infrared (FT-IR) spectra, revealing the high stability and fast ion transfer ability of electrolytes. From the theoretical calculation (density functional theory (DFT), COMSOL, and molecular dynamics (MD)), the priority combination between lithium-ion and the bromine in PAN-TD (P-TD), as well as uniform lithium-ion flux, can be certified. Therefore, the LiFePO4//Li battery exhibits a specific capacity of 157 mA h g−1 at 0.5 C and maintains 154 mA h g−1 after 100 cycles. At the same time, the safety properties have been improved by the formation of the carbon layer and the capture of free radicals through bromine, exhibiting an oxygen index as high as 29 %.