Polybrominated Dibenzo-p-dioxins And Dibenzofurans Research Articles

Emission, distribution and formation characteristics of polybrominated dibenzo-p-dioxins and dibenzofurans during co-disposal of hexabromocyclododecane-containing waste in cement kiln

Hexabromocyclododecane (HBCD)-containing waste was co-disposed in a cement kiln to evaluate its destruction removal efficiency (DRE) and its impact on polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) formation. The DRE of HBCD exceeded 99.9999 %. The residual HBCD after disposal was mainly found in kiln head ash and clinker. Stack gas at kiln head and tail exhibited average PBDD/Fs emission levels (sum of 13 2,3,7,8-PBDD/Fs congeners) of 0.36 and 0.42 ng m−3, respectively, with octa-BDD predominating. However, in the kiln tail ash, hexaBDF and hepta-BDF were secondarily generated, leading to an increase in PBDFs concentration. Notably, most HBCD underwent debromination and ring-opening in the calciner, with released bromine absorbed and removed by CaO. Its decomposition products such as polycyclic aromatic hydrocarbons, biphenyls and their derivatives served as carbon sources for PBDD/Fs synthesis. However, co-disposal of HBCD did not significantly raise PBDD/Fs emissions but altered their homolog distribution from PBDDs to PBDFs. Emission factors of HBCD and PBDD/Fs were the highest in the clinker at 6.55 × 102 and 0.55 × 102 μg t−1, respectively. Therefore, attention was needed for the potential secondary release of pollutants during the transportation and utilization of clinker. These findings enhanced understanding of the distribution and formation pathways of PBDD/Fs during cement kiln co-processing, providing insights for their source control.

Pyrolysis of 1,2-bis(2,4,6-tribromophenoxy)ethane: Theoretical and experimental research

1,2-Bis(2,4,6-tribromophenoxy)ethane (BTBPE), as a novel brominated flame retardant, is widely applied to various plastic products to improve flame resistance. In this paper, we have carried out theoretical and experimental studies on the pyrolysis of BTBPE. The density functional theory (DFT) method at M06/cc-pVDZ theoretical level was used to calculate thermodynamic and kinetic parameters, and the pyrolysis mechanisms of BTBPE were in detail analyzed based on theoretical calculation data and relevant experimental findings. In unimolecular pyrolysis reaction, concerted reaction mechanism with a four-membered ring transition state at low temperatures leads to high yields of 2,4,6-tribromophenol and vinyl 2,4,6-tribromophenol ether, and free radical reaction at high temperatures generates 2,4,6-tribromophenoxy and 2,4,6-tribromophenoxy-ethyl by direct breakage of the CO bond. The 2,4,6-tribromophenoxy radical can further catalyze BTBPE decomposition to form 2,4,6-tribromophenol and vinyl 2,4,6-tribromophenol ether. Reactions of the BTBPE molecule with H radicals mainly proceed via debromination, which results in the production of HBr and low-brominated congeners. The 2,4,6-tribromophenol and 2,4,6-tribromophenoxy undergo a CO coupling reaction to eliminate OH, which is the principal pathway for the generation of polybrominated diphenyl ethers (PBDEs). The formation of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) involves the self-condensation of 2,4,6-tribromophenoxys, debromination, rearrangement, and cyclization. The energy barrier of the reaction path forming PBDD is lower than that of the reaction path forming PBDFs. Therefore, the yield of brominated dibenzo-p-dioxin is higher than that of brominated dibenzofuran. The experimental results of pyrolysis are in good agreement with our theoretical research.

Influence of bromination arrangement and level on the formation of polybrominated dibenzo-p-dioxins and dibenzofurans from pyrolysis and combustion of polybrominated diphenyl ethers: Mechanisms and kinetics

Controlling the emission of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) presents a huge challenge in the thermo-chemical conversion of halogenated waste. It is crucial to understand the formation of PBDD/Fs to effectively control their emissions. This paper utilizes density functional theory calculations to comprehensively explore the mechanisms and kinetics of PBDD/Fs formation using 65 polybrominated diphenyl ethers (PBDEs) with varying bromination arrangements and levels. The study uncovers two new pathways for the formation of PBDFs from PBDEs, i.e., two-step H2 elimination and ether-ketone isomerization at ortho-C(H) sites. These pathways are applicable to PBDEs with specific bromination arrangements. In the case of some PBDEs, their initial energy barriers are comparable to the generally accepted direct HBr elimination. It is found that low-brominated PBDEs have a higher risk of forming PBDD/Fs, while high-brominated PBDEs are more likely to break ether bonds and generate polybromobenzenes. The study also investigates the effects of polymer materials and metals on the formation of PBDD/Fs from PBDEs to explain the high yield of PBDD/Fs in the co-treatment of PBDEs with polymers and metals. The involvement of polymers and metals significantly reduces the energy barriers for the formation of PBDD/F precursors, namely ortho-phenyl-type radicals, accelerating the formation of PBDD/Fs. This study markedly advances the present understanding of the transformation of PBDEs into PBDD/Fs and provides theoretical guidance for reducing pollutant emissions in the thermal treatment and cleaner conversion of PBDE-containing waste.

Global survey of dioxin- and thyroid hormone-like activities in consumer products and toys

BackgroundChildren and consumers are exposed to increasingly complex mixtures of known and as-yet-unknown toxic chemicals from toys and products. However traditional chemical analysis methods only evaluate a small number of chemicals at a time thereby restricting consumer awareness of the full range of potentially harmful chemicals in products. MethodsWe used high-throughput effect-based non-animal methods to investigate exposures to complex chemical mixtures of several kinds of brominated flame retardants (BFRs) for their dioxin- and thyroid hormone-like activities in various kinds of consumer products and toys from 26 different countries, on four continents (Africa, America, Asia and Europe) in combination with chemical analysis of various polybrominated flame retardants (BFRs) and their impurities (such as polyhalogenated PCDD/Fs and PBDD/Fs). ResultsWe found high levels of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in toys and now, for the first time, also in consumer products that are manufactured from black plastics containing certain brominated flame retardants (BFRs). The presence of PBDD/PBDFs as well as other BFRs in various black plastic materials from additional countries as well as additional kinds of consumer products as confirmed by effect-based in vitro reporter gene DR CALUX and TTR-TRβ CALUX assays as well as congener-specific chemical analysis. We compared total Toxicity Equivalent (TEQ) levels of PBDD/F-TEQs analysed by chemical analysis to by CALUX bioassay measured Biological equivalence (BEQ) concentrations (for further info see at ISO 23196, ISO, 2022). In the case of TBBPA, both chemical and TTR-TRβ CALUX analysis measure direct the amount of TBBPA. Finally, the daily ingestion of 2,3,7,8-TCDD equivalents from PBDD/Fs-contaminated plastic toys by child mouthing habits have been related to our earlier study (Budin et al., 2020). ConclusionsInteraction of children with such contaminated plastics may significantly contribute to the daily uptake of dioxin- and thyroid hormone transport disrupting-like compounds. Effect-based bioassays for dioxin- and thyroid hormone-like activities are relevant to pick-out such complex mixtures of known and yet unknown (and therefore not regulated) substances for safer and more sustainable plastics. Low POPs Content Levels and other mechanisms set under the Basel and Stockholm Conventions are set far too high to prevent a significant flow of BFRs and PBDD/Fs into consumer products.

Investigation on formation mechanisms of PBDD/Fs from 2,6-dibromophenol pyrolysis using density functional theory (DFT) method

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) are the potential persistent organic pollutants in the environment. A comprehensive understanding of the formation and evolution mechanisms of PBDD/Fs contributes to better control their emissions. In this paper, the formation mechanisms of PBDD/Fs from 2,6-dibromophenol pyrolysis were investigated, and the kinetic and thermodynamic parameters in all formation pathways were calculated through using density functional theory (DFT) method B3P86 with the 6-311 + G(d,p) basis set. The calculation results show that the 2-bromophenoxy radical is a major decomposition product in initial pyrolysis of 2,6-dibromophenol, and dimerization of bromophenoxy radicals occurs mainly through O-C coupling or C-C coupling. O-C coupling results in the formation of PBDD precursors, and C-C coupling results in the formation of PBDF precursors. The formation of PBDD/Fs proceeds mainly via H-abstraction or H-transfer, cyclization, and debromination or dehydroxylation. The energy barriers of rate-determining steps in the formation of PBDDs are lower than those of PBDFs, so the formations of brominated dibenzo-p-dioxins are superior to the formations of brominated dibenzofurans.

Variation in the formation characteristics of PBDD/F, brominated PAH, and PBDE congeners along the secondary copper smelting processes

Simultaneous determination of 58 congeners of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), brominated polycyclic aromatic hydrocarbons (Br-PAHs), and polybrominated diphenyl ethers (PBDEs) from multiple stages of industrial-scale secondary copper smelting plants was conducted with the aim of understanding their variations and control. In addition to the historical manufacture of PBDEs as brominated flame retardants, this study confirmed that PBDEs can be unintentionally produced and released from the secondary copper industry. The average mass emission factors of PBDD/Fs, PBDEs, and Br-PAHs from different sources were 10.0, 5.21 × 103, and 7.24 × 103 μg t−1, respectively. Therefore, the emission of brominated persistent organic pollutants (POPs) in the secondary copper industry should be of concern. The concentration of brominated POPs increased from the gas cooling stage to stack outlet due to the possible “memory effect” and the regenerated POPs were mainly low-brominated homologs. A comparison of brominated POPs with corresponding chlorinated analogs in the same process indicated that the formation pathway of Br-PAHs was consistent with that of chlorinated PAHs. However, unlike chlorinated dioxins and furans, PBDD/Fs can also be formed from PBDEs as precursors, leading to obvious increases in highly brominated furans. Therefore, inhibiting the unintentional formation of PBDEs is important for controlling brominated POPs emissions.

Occurrence and formation pathways analysis of PBDD/Fs from 2,4,6-tribromophenol under thermal reaction conditions

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) are highly toxic and persistent compounds that provoke a wave of publicity. Bromophenols are important precursors for forming PBDD/Fs, and their reaction path has always been a research hotspot. In this study, the formation characteristic of PBDD/Fs from 2,4,6-TBP were studied. The yields of 2,3,7,8-substituted PBDD/Fs and 2,4,6,8-TBDF for the different thermal products ranged from 0.067 to 10.3 ng/g and 0.207–9.68 ng/g, respectively. The effects of adding Cu, Fe, and Sb2O3 were investigated and found to be more inclined to accelerate the formation of ortho-substituted PBDD/Fs than 2,3,7,8-PBDD/Fs. The formation pathways of 2,3,7,8-substituted PBDD/Fs and 2,4,6,8-TBDF were also proposed. 2,4,6,8-TBDF is generated in the C-C coupling reactions of some radical intermediates from the debromination of 2,4,6-TBP. The 2,3,7,8-PBDD/Fs are produced through more complex debromination, bromine substitution, and bromine rearrangement reactions. In addition, various catalytic effects on PBDD/F formation pathways were found, and the catalytic effect of Cu by the Ullmann reaction was the highest, while bromophenol oxidation by Fe was the highest. These results proved that both 2,3,7,8-substituted and non-2,3,7,8-substituted PBDD/Fs would be generated from 2,4,6-TBP, and the effects of the catalyst on the Br substituted position of 2,3,7,8-substituted PBDD/Fs were much lower than the Br-substituted position on bromophenol.

Control of extreme brominated persistent organic pollutant emissions from start-ups of waste-to-energy incinerators

Unlike chlorinated persistent organic pollutants (Cl-POPs), few studies have investigated the emissions of brominated POPs (Br-POPs), including polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), polybrominated biphenyls (PBBs), and polybrominated diphenyl ethers (PBDEs), from start-up processes of municipal solid waste incinerators (MSWIs). Presently, there are no studies published on Br-POP control during this period. This study found that start-up processes could contribute to at least 27%, 55%, and 2% PBDD/F, PBB, and PBDE emissions of an entire year of MSWI operations. High PBDD/F and PBDE emission rates were observed at the beginning of the start-up, indicating that control measures should be conducted before or at the beginning of the start-ups. PBBs behaved like Cl-POPs with high emission rates observed at the POP-formation temperature window (250–450 °C). Unlike Cl-POPs, inhibiting adsorptive memory effects by cleaning the accumulated ash was the most effective control strategy for PBDD/F and PBDE emissions, accounting for 72.8% and 51.3% of total reductions, respectively. Contrarily, inhibiting Br-POP formation by cleaning the accumulated ash and shortening the residence time of the flue gas in 250–450 °C contributed to the highest PBB reduction (67.5%). Overall, the control strategies reduced PBDD/F and PBB emissions by >97% and PBDEs by 61%. This study shows that PBDD/Fs and PBDEs behave differently from their chlorinated equivalents and require different control strategies. In conclusion, the control strategies proposed can reduce Br-POP emissions during start-up successfully, and they require no modifications to existing control devices.

Brominated and chlorinated contaminants in food (PCDD/Fs, PCBs, PBDD/Fs PBDEs): Simultaneous determination and occurrence in Italian produce

Validated methodology for the simultaneous determination of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) and polybrominated diphenyl ethers (PBDEs) in foods of animal origin is presented. Method performance indicators were equivalent or better than those required for the control of EU regulated (EU, 2017/644) PCDD/F and PCB congeners in these foods, and for risk assessment through dietary intake. The method uses a high (>90%) proportion of 13Carbon-labelled surrogates for internal standardisation combined with high resolution mass spectrometry that allow accurate quantitation, and this was confirmed by multiple successful participations in proficiency testing for PCDD/Fs, PCBs and PBDEs in food. The same validation and method performance requirements as used for PCDD/Fs were followed for PBDD/Fs. The analysis of a range of food samples (eggs, milk, fish, shellfish, pork, beef and poultry), showed the occurrence of all four classes of contaminants at varying concentration ranges. In general, PCBs were the most prominent contaminant, both, in terms of dioxin-like toxicity, as well as in the occurrence of non-dioxin-like congeners, an observation that concurs with those made in other studies on Italian foods. The levels of PCDD/F and PCB occurrence are consistent with a gradual decline in contamination as reported by some other similar studies. Although all the determined contaminants were detected in the sampled foods, there was poor correlation between the occurrences of the brominated and chlorinated contaminants, and between PBDEs and PBDD/Fs, but better associations were observed between the occurrences of the chlorinated contaminants.

Liver-specific decrease in Tff3 gene expression in infant mice perinatally exposed to 2,3,7,8-tetrabromodibenzofuran or 2,3,7,8-tetrachlorodibenzo-p-dioxin.

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/DFs) are byproducts of brominated flame retardants and can cause adverse health effects. Although exposure to polychlorinated (PC) DD/DFs induces toxic effects, including liver injury and neurobehavioral disorder, little is known about toxicities associated with PBDD/DF exposure. Thus, we examined effects of perinatal exposure to brominated congener on the infant mouse. Gene expression in several organs, such as the liver and brain, was analyzed in mouse offspring born to dams administered 2,3,7,8-tetrabromodibenzofuran (TBDF; 9 or 45 μg/kg body weight) or 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD; 3 μg/kg body weight) on gestational day 12.5. An increase in liver size was observed in TBDF- or TCDD-exposed offspring in infancy. Gene microarray analysis revealed that 163 and 36 genes were markedly upregulated and downregulated, respectively, in the liver of TBDF-exposed mice compared with those in vehicle-treated mice on postnatal day (PND) 5. Significant increases in Cyp1a1, Cyp1a2, Fmo3, and Pnliprp1 and decreases in Tff3, Ocstamp, Kcnk16, and Lgals2 mRNA levels in TBDF-exposed offspring on PNDs 5 and 12 were confirmed by quantitative PCR. In particular, a significant reduction in Tff3 mRNA in the liver, but not in the brain, small intestine, colon, and kidney, was observed in offspring perinatally exposed to TBDF or TCDD. Ultrasonic calls of TBDF- or TCDD-exposed offspring on PNDs 3-5 were impaired. Taken together, perinatal exposure to polyhalogenated dioxin/furan congeners disrupts gene expression patterns in the liver and ultrasonic calling during infancy. These results suggest that liver injury may contribute to neurobehavioral disorder.

Insights into the metabolic mechanism of PBDEs catalyzed by cytochrome P450 enzyme 3A4: A QM/MM study

Elucidating the metabolic mechanism and the derivatives of polybrominated diphenyl ethers (PBDEs) is significant to risk assessment. This study delineated the metabolic mechanism of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) catalyzed by P450 enzymes using a combination of molecular dynamic (MD), quantum mechanics/molecular mechanics (QM/MM) and density functional theory (DFT). The calculation results reveal that the electrophilic addition is the main pathway for the biotransformation of BDE-47 catalyzed by P450 enzymes. 6-hydroxy-2,2′,4,4′-tetrabromodiphenyl ether (6-OH-BDE-47) is a more kinetically preferable product than 5-hydroxy-2,2′,4,4′-tetrabromodiphenyl ether (5-OH-BDE-47). Electrophilic addition reaction can lead to the formation of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs). The ecotoxicity assessment indicates that the final products of BDE-47 are still toxic to aquatic organisms, but the solubility increase of the hydroxylated products can accelerate their excretion from the body. We expect that the established metabolic mechanism and the derivatives will be used to predict the biotransformation of other PBDE congeners catalyzed by P450 enzymes in human livers.

Occurrence, Human Exposure, and Risk Assessment of Polybrominated Dibenzo-p-Dioxins and Dibenzofurans, Polychlorinated Naphthalenes, and Metals in Atmosphere Around Industrial Parks in Jiangsu, China.

Air samples were collected around industrial parks in Jiangsu, China, to allow the concentrations, profiles, and risk assessment of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), polychlorinated naphthalenes (PCNs), and metals to be investigated. The concentrations of ΣPBDD/Fs and ΣPCNs were 1324.26-2080.98fg/m3 (11.35-42.57fg I-TEQ/m3) and 10,404.9-29,322.9fg/m3 (1.32-7.19fg I-TEQ/ m3), respectively. The highest concentration of ΣPBDD/Fs and ΣPCNs were observed at site C. PBDD/Fs were mainly dominated by PBDFs. The main contributor to the ΣPBDD/Fs in all samples was 1,2,3,4,6,7,8-HpBDF, which accounted for 25.75%-39.4%. For PCNs, the predominating homologues were tetra-, tri- and penta-CNs, which contributed 30.7%-43.3%, 24.7%-31.0%, and 10.6%-21.6%, respectively. As for metals, the pollution of As, Mn, Cr, and Ni in most samples exceeded National Ambient Air Quality Standards of China. Assessing the risk of inhalation exposure showed that there were potential carcinogenic risks to local residents.

Dissolution of brominated epoxy resin for environment friendly recovery of copper as cupric oxide nanoparticles from waste printed circuit boards using ammonium chloride roasting

This work focuses on development of an environment benign approach for separation of brominated epoxy resin (BER) and recovery of copper (Cu) as copper oxide (CuO) from end-of-life waste printed circuit boards (PCBs). The typical Cu concentration in PCBs varies in the range of 60 kg/t – 270 kg/t of Cu, which is much higher than its respective mineral ores. In the present work, dimethylformamide (DMF) was used for dissolution of BER followed by roasting with ammonium chloride (NH4Cl) for recovery of Cu. Separation of BER provides better metallic surface exposer and mitigates the possibility of formation of toxic polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) during the roasting process. More than 97% of BER was separated from the PCBs using DMF as solvent at 140 °C. The investigation revealed that at reaction conditions, dry HCl vapour formed due to decomposition of NH4Cl, reacts with Cu in presence of air to form CuCl2. The solid residue obtained after roasting was subsequently treated with water for extraction of CuCl2. More than 93% Cu was extracted when the delaminate PCBs (DPCBs) was roasted at optimum conditions of temperature: 275 °C, NH4Cl dose: 300%, and time: 180 min. From the leached solution, Cu was precipitated using ammonia solution as precipitating agent, which subsequently calcined at 500 °C to obtain 98% pure CuO nanoparticles (NPs).

Characterizing the emissions of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) from electric arc furnaces during steel-making

The amount of steel produced using electric arc furnaces (EAFs) has been increasing in recent years. In this study, stack gases from EAFs in steelmaking plants were analyzed to determine if they are also dominant sources of polybrominated dibenzo-p-dioxin and dibenzofuran (PBDD/F) emissions in China. Isotope dilution high-resolution gas chromatography high-resolution mass spectrometry for qualitative and quantitative analysis of PBDD/F congeners revealed that the mean PBDD/F mass concentrations were 271.1–9467.8 pg Nm−3 for the preheating stages (PS) of three EAF plants and that the corresponding toxic equivalents (TEQs) were 10.8–971.2 pg TEQ Nm−3. The PBDD/F mass concentration from the smelting stage (SS) at plant E3 was 261.9 pg Nm−3 (4.5 pg TEQ Nm−3). The PBDD/F emission factors (EF) during the preheating stage for the three plants were 0.0356–1.51 μg TEQ t−1, and the EF was 0.0359 μg TEQ t−1 during the E3 smelting stage. PBDD/Fs were found to contribute 2.39–67.85% to the total mass and 2.84–57.68% to the total dioxin TEQ. These wide fluctuations were caused by differences in the composition of feeding materials and the working temperature of bag filters. Overall, the results indicate that PBDD/F emissions from EAF steelmaking should receive increased attention. The PBDD/F congener patterns among the three EAF plants were variable, possibly because of differences in raw materials. The results presented herein will facilitate assessment of the contribution of EAFs to total PBDD/F emissions in China and investigations of PBDD/F emissions at different stages of steelmaking processes using EAFs.

Exposure and health risk assessment of secondary contaminants closely related to brominated flame retardants (BFRs): Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in human milk in shanghai

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), as the secondary environmental pollutants of the widely used brominated flame retardants (BFRs), possess the similar physicochemical and toxic properties as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). However, studies on human body exposure to them are extremely limited. In this study, forty human milk samples collected in Shanghai were measured for 13 PBDD/F congeners using gas chromatography-high resolution mass spectrometry (GC-HRMS), to investigate their exposure level and characteristics, potential source and corresponding health risks to breastfed infants. The results showed no PBDDs but three PBDF congeners including 2,3,7,8-TBDF, 1,2,3,4,6,7,8-HpBDF and OBDF (mean concentration (detection rates) are 3.2 pg/g (72.5%), 9.5 pg/g (100%) and 28 pg/g (67.5%), respectively) were detected. The average toxic equivalent quantity (TEQ, 0.42 pg/g lw) presented the highest concentration level compared to other regions reported. The contribution of PBDFs to the total TEQ of PBDD/Fs and PCDD/Fs is 6.8%. The correlation between PBDD/Fs and age or dietary habits was not observed, which normally existed in their chlorinated analogues-PCDD/Fs. Significant correlations were observed between PBDFs and highly brominated polybrominated diphenyl ethers (PBDEs) (especially for BDE 183 and BDE 209). The correlation between PCDD/Fs and PBDFs was not observed except 2,3,7,8-TBDF. The high PBDFs exposure in Shanghai may originate from the emission of PBDEs and/or non-PBDE BFRs in environment, according to the consistency of the environmental data previously reported. The average estimated dietary intakes (EDI) for breastfed infants is 2.0 pg TEQ/kg·bw/day (0.13–13 pg TEQ/kg·bw/day), within the range of the tolerable daily intake (TDI) for TCDD (1–4 pg TEQ/kg·bw/day) suggested by the World Health Organization (WHO). However, given the high toxicity of PBDD/Fs, the potential health risks of these pollutants for breastfed infants should be of concern.

Behavioral impairments in infant and adult mouse offspring exposed to 2,3,7,8-tetrabromodibenzofuran in utero and via lactation

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/DFs) have been unintentionally produced and emitted from the lifecycle of products containing brominated flame retardants, such as polybrominated diphenyl ether, which is suspected to cause developmental neurotoxicity (DNT). Although it is plausible that PBDD/DFs can also induce DNT, information regarding their neurotoxic potential is currently limited. Hence, in the present study, we examined the effects of in utero and lactational exposure to brominated dibenzofurans on infant and adult offspring behavior to understand the mechanism of PBDD/DFs toxicity and detect effective behavioral endpoints in DNT assessment. We analyzed the behavior of mouse offspring born to dams administered 2,3,7,8-tetrabromodibenzofuran (2,3,7,8-TeBDF; dose of 0, 9, or 45 μg/kg) or 2,3,8-tribromodibenzofuran (2,3,8-TrBDF; dose of 0, 75.6, or 378 μg/kg) on gestational day 12.5. In mouse offspring born to dams exposed to 2,3,7,8-TeBDF, the exploratory behavior in a novel environment in adulthood and ultrasonic vocalization (USV) during infancy were significantly reduced. Additionally, AhR-target genes, such as Cyp1a1, were induced in the liver of 2,3,7,8-TeBDF-exposed offspring in a dose-dependent manner. Conversely, no significant changes in the infant and adult behaviors and expression level of AhR-target genes were observed in the 2,3,8-TrBDF-exposed offspring. These results suggest that 2,3,7,8-TeBDF can induce DNT and that the analysis of exploratory behavior in a novel environment and USV may be useful endpoints to assess DNT of dioxin-related substances.

The formation pathways of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) from pyrolysis of polybrominated diphenyl ethers (PBDEs): Effects of bromination arrangement and level

This study presents comprehensive formation pathways of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) from the pyrolysis of polybrominated diphenyl ethers (PBDEs). A total of 23 PBDE congeners, from mono- to hepta- brominated, were selected to conduct the pyrolysis experiments. The results suggest that n-PBDEs (where n means the number of bromine substituents) can transform into n/(n-1) PBDFs and (n-1)/(n-2) PBDDs as long as they meet certain structural requirement. One single PBDE congener can only transform (if possible) specific PBDF or PBDD based on their specific brominated arrangement by direct/oxygen bridge connecting the two ortho-carbon atoms. Among all selected BDEs, we found that only 2,2′,4,4′,5,5′-hexaBDE (BDE-153) can transform into 2,3,7,8-tetraBDD, which is most toxic congener among these group of compounds. When the degree of bromination increased, the yield of polybromobenzene increased, while that of the PBDD/Fs decreased, suggesting that the higher PBDEs favors to break the ether bond to form polybromobenzene, while the lower PBDEs favor transformation into PBDD/Fs. We proposed that the results in this study greatly improved our understanding on the transformation of PBDD/Fs from PBDEs in the pyrolysis process.

Polybrominated dibenzo-p-dioxins (PBDDs) and – dibenzofurans (PBDFs) in cod (Gadus morhua) liver-derived products from 1972 to 2017

Literature data on the occurrence and prevalence of polybrominated dibenzo-p-dioxins (PBDDs) and polybrominated dibenzofurans (PBDFs) in foods including seafood are scarce. In this study, a number of cod-derived products including medicinal grade cod liver oils sourced from Northern Atlantic waters (Iceland, Norway) and the Baltic Sea (Poland) during 1972–2001 and canned cod liver sourced from the Baltic Sea in 2017, showed detectable levels of PBDFs: such as 2,3,8-TrBDF at 0.57 to 5.249 pg g−1 fat and 1,2,3,4,6,7,8-HpBDF at <0.018 to 0.302 pg g−1 fat. PBDDs were not detected in the cod liver oils. Canned cod liver products showed low levels of 2,3,7,8-TeBDD in the range <0.017 to 0.022 pg g−1 whole weight and 1,2,3,7,8-PeBDD at <0.03 to 0.039 pg g−1 whole weight. These concentrations were computed to yield upper bound toxic equivalences (TEQs) of 0.14 to 0.17 pg g−1 for the oils and 0.12 to 0.25 pg g−1 for the canned products (0.08 pg g−1 ww for both products). The resulting supplementary and dietary intakes are low (0.02 to 0.11 pg kg−1 bm day−1 for the oils and 0.07 to 0.17 pg kg−1 bm week−1 for the canned livers) in comparison to the recently expressed tolerable weekly intake of 2 pg kg−1 bm week−1. However, the intakes are underestimates, as due to a lack of analytical standards not all PBDD/F TEQ contributing congeners could be included. The PBDD/F TEQ contributes to the cumulative toxicity arising from other contaminants such as chlorinated dioxins and polychlorinated biphenyls.

Brominated dioxins and furans in a cement kiln co-processing municipal solid waste

A field study and theoretical calculations were performed to clarify the levels, profiles, and distributions of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in a cement kiln co-processing solid waste, with a focus on the PBDF formation mechanism. The raw materials contributed greatly to input of PBDD/Fs into the cement kiln. The PBDD/F concentrations in the raw materials were much higher than those in particle samples from different process stages in the cement kiln. The PBDD/F concentrations in the clinkers were 1.40% of the concentrations in the raw materials, which indicated that the high destruction efficiencies for PBDD/Fs by cement kiln. PBDD/F distribution patterns in particle samples collected from different process stages indicated the cement kiln backend was a major site for PBDD/F formation. PBDFs with high levels of halogenation, such as heptabrominated furans (HpBDF), were the dominant contributors to the total PBDD/F concentrations and accounted for 42%–73% of the total PBDD/F concentrations in the particle samples. Our results showed that co-processing of municipal solid waste in a cement kiln may influence the congener profile of PBDD/Fs, especially for the higher halogenated PBDD fraction. In addition, there were significant correlations between the decabromodiphenyl ether and heptabrominated furan concentrations, which is an indicator of transformation from polybrominated diphenyl ethers to PBDD/Fs. Theoretical calculations were performed and demonstrated that elimination of HBr and Br2 from polybrominated diphenyl ethers were the dominant formation pathways for PBDD/Fs. These pathways differed from that for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs).

Release and Transformation of BTBPE During the Thermal Treatment of Flame Retardant ABS Plastics.

Thermal scenarios inevitably occur during the lifecycle of engineering plastics laden with brominated flame retardants (BFRs). However, little information on the fate of embedded BFRs during the thermal processes is available. In this study, we measured the release and transformation of a typical BFR, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), during the thermal treatment of acrylonitrile butadiene styrene (ABS) plastics. The possible thermal scenarios were simulated by varying the heating temperature and atmosphere. The maximum release rate of BTBPE was observed at 350 °C. A release kinetic model was developed to explore the mechanism of BTBPE release while heating ABS. Material-phase diffusion was found to be the rate-determining step during release. According to the developed release model, it was estimated that 0.04-0.17% of embedded BTBPE could be released to air during the industrial processing of ABS plastics. When the heating temperature was ≥350 °C, approximately 15-56% of embedded BTBPE decomposed to bromophenols (BPs) and 1,3,5-tribromo-2-(vinyloxy) benzene (TBVOB), and the decomposition followed a first-order kinetics at 350 °C. Polybrominated dibenzo- p-dioxins and dibenzofurans (PBDD/Fs) were also significantly formed at ≥350 °C from BPs and TBVOB via a precursor mechanism. A higher temperature (≥450 °C) was favorable for the formation of PBDFs.