Halogenated aromatic pollutants in routine animal-derived food of south China: Occurrence, sources, and dietary intake risks.

Halogenated aromatic pollutants (HAPs) including polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs), and polybrominated diphenyl ethers (PBDEs) exhibit diverse toxicities and bio-accumulation in animals, thereby imposing risks on human via animal-derived food (ADF) consumption. Here we examined these HAPs in routine ADFs from South China and observed that PBDEs and PCBs showed statistically higher concentrations than PCDD/Fs and PBDD/Fs. PCDD/Fs and PCBs in these ADFs were mainly from the polluted feed and habitat of animals, except PCDD/Fs in egg, which additionally underwent selective biotransformation/progeny transfer after the maternal intake of PCDD/F-polluted stuff. PBDEs and PBDD/Fs were mostly derived from the extensive use of deca-BDE and their polluted environments. Significant interspecific differences were mainly observed for DL-PCBs and partly for PBDD/Fs and PBDEs, which might be caused by their distinct transferability/biodegradability in animals and the different living habit and habitat of animals. The dietary intake doses (DIDs) of these HAPs via ADF consumption were all highest for toddlers, then teenagers and adults. Milk, egg, and fish contributed most to the DIDs and risks for toddlers and teenagers, which results of several cities exceeded the recommended thresholds and illustrated noteworthy risks. Pork, fish, and egg were the top three risk contributors for adults, which carcinogenic and non-carcinogenic risks were both acceptable. Notably, PBDD/Fs showed the lowest concentrations but highest contributions to the total risks of these HAPs, thereby meriting continuous attention.

Evaluation of hexabromocyclododecane (HBCD), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) and polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) outflows during the destruction of HBCD wastes in a hazardous waste incinerator.

This paper presents an evaluation of hexabromocyclododecane (HBCD), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) and polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) outflows during the destruction of HBCD waste stockpiles in IZAYDAS Hazardous Waste Incinerator (HWI) in Kocaeli, Türkiye. HBCD wastes containing 100 % pure HBCD were in 25 kg packages with 63 % Br content were co-incinerated in a 3-day test burn with average feed rate of 26 kg/h. HBCD, PBDD/Fs and PCDD/Fs were measured in the outlet streams to quantify the amount of unintended POPs releases associated with the processing of HBCD waste and to observe the POP removal performance of air pollution control equipment (APCE) of the incinerator. Total mass outflow rate of HBCDs is calculated as 2.6 g/day, corresponding to destruction efficiency of 99.9996 %. Total toxicity of the brominated dioxins was measured as 0.00044 ng TEQ/Nm3 on average, while highly brominated congeners are dominant. PCDD/F concentrations in the outflow streams during HBCD test burns are produced similar congener distributions with those given in the previous studies, with the dominance of 7,8-chlorinated congeners. Mass flows in the outlet streams indicated that the efficiency of ESP and wet scrubbers for the removal of PCDD/Fs and HBCDs. Flue gas concentrations of PCDD/Fs, HBCDs and PBDD/Fs obtained in HBCD burn test indicated that burning HBCD wastes cause no significant emissions as operational parameters and total halogen content in the menu are kept within the incinerator limits.

Theoretical study on pyrolysis mechanism of decabromodiphenyl ether (BDE-209) using DFT method.

Decabromodiphenyl ether (BDE-209), as a brominated flame retardant (BFR), is widely applied to various consumer products due to its superior performance and affordable pricing to improve the flame resistance of materials. To better comprehend the pyrolysis behavior of BDE-209 and the evolution process of main pyrolysis products, the thermal degradation mechanism of BDE-209 was studied using density functional theory (DFT) method at the theoretical level of M06/cc-pVDZ, and thermodynamic parameters were calculated in this paper. Unimolecular degradation was dominated by cleavage of the ether linkage, which results in a high yield of hexabromobenzene, and fission of the ortho-position C-Br bond is the main competitive reaction channel. In the system of BDE-209 + H, the pyrolysis reaction is majorly characterized by debromination, leading to the formation of considerable HBr and low-brominated diphenyl ethers. Additionally, the hydrogen-derived splitting of the ether bond acts as a mainly competitive channel, which is the source of polybromophenols and polybromobenzenes. The formation of polybrominated dibenzofuran (PBDF) derives from the cyclization reaction of ortho-phenyl-type radicals, which are readily generated through the ortho-position Br atom abstraction by H radical. The formation of polybrominated dibenzo-p-dioxin (PBDD) involves the ortho-C-O coupling reaction of polybromophenoxy radicals, debromination reaction, and cyclization reaction. And the total yield of PBDD/Fs was significantly increased when H was involved. Results presented in this work will provide the helpful information for the treatment and reuse of BDE-209-containing waste plastics through using pyrolysis technology.

PCDD/Fs and PBDD/Fs in sediments from the river encompassing Guiyu, a typical e-waste recycling zone of China.

Severe pollution of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and their brominated analogues (PBDD/Fs) was frequently reported for the waters located near unregulated e-waste recycling areas. However, the migrations of these high-level dioxins via waterways and their potential threats to the lower reaches were seldom investigated. In this study, we analyzed PCDD/Fs and PBDD/Fs in 27 surficial sediments collected from the Lian River encompassing the Guiyu, China e-waste recycling zone, and investigated their distributions, sources, migration behaviors and risks. Both PCDD/Fs and PBDD/Fs in these sediments exhibited a spatial trend of Guiyu > Guiyu downriver > Guiyu upriver, illustrating that the Guiyu e-waste recycling activities were the uppermost dioxin contributors in this watershed. Sediments from different Guiyu villages demonstrated big gaps in PCDD/F concentrations and congener compositions, and the reason was attributed to the diverse e-waste recycling activities practiced in these villages. Sediments near the e-waste open-burning areas demonstrated extremely high PCDD/F concentrations and unique PCDD/F profiles featured by low-chlorinated PCDFs (tetra- to hexa-), which is quite different from the OCDD-dominant PCDD/F profile found in most of the Lian River sediments. The geographical distributions of PCDD/F concentrations and profiles illustrate that the substantial amount of PCDD/Fs in Guiyu sediments were mainly retained in local and vicinal water bodies. The principal component analysis (PCA) results further confirm that the high-level PCDD/Fs in Guiyu sediments exhibited quite limited translocations downstream and therefore exerted little influences on the lower reaches. Pentachlorophenol use in history, ceramic industry and vehicle exhaust were diagnosed as the major PCDD/F sources for most sediments of the Lian River. Total toxicity equivalent quantities (TEQs) of 70% of the Lian River sediments surpassed the high-risk limit specified for mammalian life by the U.S.EPA (25 pg TEQ g-1), and most of these sediments were from Guiyu and its near downstream, which merit continuous attention and necessary remediation measures.

Low-temperature oxidation of monobromobenzene: Bromine transformation and yields of phenolic species.

Brominated benzenes and phenols constitute direct precursors in the formation of bromine-bearing pollutants; most notably PBDD/Fs and other dioxin-type compounds. Elucidating accurate mechanisms and constructing robust kinetic models for the oxidative transformation of bromobenzenes and bromophenols into notorious Br-toxicants entail a comprehensive understanding of their initial oxidation steps. However, pertinent mechanistic studies, based on quantum chemical calculations, have only focused on secondary condensation reactions into PBDD/Fs and PBDEs. Literature provide kinetic parameters for these significant reactions, nonetheless, without attempting to compile the acquired Arrhenius coefficients into kinetic models. To fill in this gap, this study sets out to illustrate primary chemical phenomena underpinning the low-temperature combustion of a monobromobenzene molecule (MBZ) based on a detail chemical kinetic model. The main aim is to map out temperature-dependent profiles for major intermediates and products. The constructed kinetic model encompasses several sub-mechanisms (i.e, HBr and benzene oxidation, bromination of phenoxy radicals, and initial reaction of oxygen molecules with MBZ). In light of germane experimental observations, the formulated kinetic model herein offers an insight into bromine speciation, conversion profile of MBZ, and formation of higher brominated congeners of benzene and phenol. For instance, the model satisfactorily accounts for the yields of dibromophenols from oxidation of a 2-bromophenol (2-MBP) molecule, in reference to analogous experimental measurements. From an environmental perspective, the model reflects the accumulation of appreciable loads of 2-bromophenoxy radicals at intermediate temperatures (i.e., a bromine-containing environmental persistent free radical, EPFR) from combustion of MBZ and 2-MBP molecules. Acquired mechanistic/kinetic parameters shall be useful in comprehending the complex bromine transformation chemistry in real scenarios, most notably those prevailing in thermal recycling of brominated flame retardants (BFRs).

Environmental characteristics and formations of polybrominated dibenzo-p-dioxins and dibenzofurans.

Polybrominated dibenzo-p-dioxins and furans (PBDD/Fs) are emerging persistent organic pollutants (POPs) that have similar or higher toxicities than the notorious dioxins. Toxicities, formation mechanisms, and environmental fates of PBDD/Fs are lacking because accurate quantification, especially of higher brominated congeners, is challenging. PBDD/F analysis is difficult because of photolysis and thermal degradation and interference from polybrominated diphenyl ethers. Here, literatures on PBDD/F analysis and environmental occurrences are reviewed to improve our understanding of PBDD/F environmental pollution and human exposure levels. Although PBDD/Fs behave similarly to dioxins, different congener profiles between PBDD/Fs and dioxins in the environment indicates their different sources and formation mechanisms. Herein, potential sources and formation mechanisms of PBDD/Fs were critically discussed, and current knowledge gaps and future directions for PBDD/F research are highlighted. An understanding of PBDD/F formation pathways will allow for development of synergistic control strategies for PBDD/Fs, dioxins, and other dioxin-like POPs.

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 1324.26-2080.98 fg/m3 (11.35-42.57 fg I-TEQ/m3) and 10,404.9-29,322.9 fg/m3 (1.32-7.19 fg 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.

Bromination of Carbon and Formation of PBDD/Fs by Copper Bromide in Oxidative Thermal Process.

Brominated aromatic compounds are unintentionally generated during various thermal processes, including municipal solid waste incineration, electric-waste open burning, and secondary copper smelting. Copper (Cu) plays an important role in the formation of brominated aromatic compounds. In the present study, the thermochemical behaviors of Cu and Br in model samples, including copper bromide (CuBr2) and activated carbon, were studied using in situ X-ray absorption near-edge structure (XANES) and thermogravimetry. Quantification of polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) was also conducted by gas chromatograph-high resolution mass spectrometer. Three key reactions were identified: (i) the reduction of CuBr2 to CuBr (room temperature to 300 °C), (ii) the generation of Br bonded with aromatic carbon (150-350 °C), and (iii) the oxidation of copper (>350 °C). Maximum amounts of PBDD/Fs were found in residual solid phase after heating at 300 °C. The analytical results indicated the direct bromination of aromatic carbon by the debromination of copper bromides (I, II) and that CuBr and CuO acted as catalysts in the oxidation of the carbon matrix. The bromination mechanisms revealed in this study are essential to the de novo formation of PBDD/Fs and other brominated aromatic compounds.

Induction of AhR transactivation by PBDD/Fs and PCDD/Fs using a novel human-relevant, high-throughput DRhuman CALUX reporter gene assay.

Polychlorinated dioxins and dibenzofurans (PCDD/Fs) are highly toxic contaminants that are strictly regulated and monitored in the environment and food to reduce human exposure. Recently, the increasing occurrence of polybrominated dioxins and dibenzofurans (PBDD/Fs) in the environment is raising concerns about the impact on human health by the combined exposure to chlorinated and brominated analogues of dioxins. Toxicological properties of PBDD/Fs relative to PCDD/Fs have not been firmly established, and brominated dioxins are not included in routine monitoring programs. In this study, we set out to determine human-relevant congener-specific potency values for a range of brominated and chlorinated dioxin congeners, based on their aryl hydrocarbon receptor (AhR)-mediated mode of toxic action. Transactivation of the AhR was measured using dioxin-responsive (DR) CALUX reporter gene assays. Because of known species-differences in dioxin-mediated toxicity, we developed and used a HepG2 human liver cell-based DR human CALUX assay that is a variant of the rodent-based DR CALUX. The assay was found to be highly inducible and stable, with low variations between independent measurements. Using both DR CALUX assays in an automated high-throughput mode we found that overall PBDD/Fs were as potent as PCDD/Fs in inducing AhR transactivation, but congener-specific differences were observed. We also observed species-specific differences in sensitivity and potency when comparing DR human REP values to those obtained in the rat-based DR CALUX. Finally, we observed significant differences between WHO-TEF values and DR human REP values, suggesting that actual WHO-TEF values may underestimate the hazards associated with exposure of humans to dioxins.

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.

Temporal trends in radiometrically dated sediment cores from English lakes show polybrominated diphenyl ethers correlate with brominated but not mixed bromo/chloro dioxins and furans.

This paper reports concentrations between ~1950 and present, of polybrominated diphenyl ethers (PBDEs) and polybrominated dibenzo-p-dioxins and furans (PBDD/Fs), in radiometrically-dated sediment cores from three English lakes. Mixed bromo/chloro dibenzo-p-dioxins and furans (PXDD/Fs) were measured in two of the same lakes. Concentrations of PXDD/Fs decreased over time to the present. To our knowledge, this is the first report of temporal trends of PXDD/Fs in the environment. In contrast, concentrations of PBDEs increased towards the present and were significantly correlated (R = 0.88-0.98; p < 0.05) with concentrations of PBDFs in all three lakes. These observations suggest that the sources of PXDD/Fs are not related to PBDEs and differ from those of PBDFs. We also report for the first time the presence of octabromodibenzofuran (OBDF) in the two most recent core slices at one lake. The source of OBDF in these samples is unclear. While OBDF has been reported previously as a significant contaminant of some commercial formulations of Deca-BDE, it is also present in Octa-BDE products and in emissions from a variety of combustion activities. Overall, while the positive correlation between PBDEs and PBDFs suggests increased use of PBDEs has contributed substantially to environmental contamination with PBDFs; examination of PBDF homologue patterns implies emissions from combustion activities are likely also important.

Formation of polybrominated dibenzofurans (PBDFs) and polybrominated diphenyl ethers (PBDEs) from oxidation of brominated flame retardants (BFRs).

Brominated aromatic rings constitute main structural entities in virtually all commercially deployed brominated flame retardants (BFRs). Oxidative decomposition of BFRs liberates appreciable quantities of bromobenzenes (BBzs). This contribution reports experimental measurements for the generation of notorious polybrominated dibenzofurans (PBDFs) and polybrominated diphenyl ethers (PBDEs) from oxidation of monobromobenzene (MBBz). In the light of developed product profiles, we map out reaction pathways and report kinetic parameters for PBDFs and PBDEs formation from coupling reactions of MBBz molecule and its derived ortho-bromophenoxy (o-BPhxy) radical using quantum chemical calculations. The identification and quantitation of product species involve the use of gas chromatograph - triple quadrupole mass spectrometer (GC-QQQMS) operating in the multiple reaction monitoring (MRM) mode. Bimolecular reactions of MBBz and o-BPhxy result in the generation of twelve pre-PBDF intermediates, of which four can also serve as building blocks for the synthesis of PBDEs. These four intermediates are denoted as pre-PBDE/pre-PBDF, with the remaining eight symbolised as pre-PBDF. The resonance-stabilised structure of the o-BPhxy radical accumulates more spin density character on its phenoxy O atom (30.9 %) in reference to ortho-C and para-C sites. Thus, the formation of the pre-PBDE/pre-PBDF structures via O/o-C couplings advances faster as it requires lower activation enthalpies (79.2 - 84.9 kJ mol-1) than the pre-PBDF moieties, which arise via pairing reactions involving o-C(H or Br)/o-C(H or Br) sites (97.2 - 180.2 kJ mol-1). Kinetic analysis indicates that, the O/o-C pre-PBDE/pre-PBDF adducts self-eject the out-of-plane H atoms to produce PBDEs, rather than undergo a three-step mechanism forming PBDFs. However, experimental measurements demonstrate PBDEs appearing in lower yields as compared to those of PBDFs; presumably due to H- and Br-induced conversion of the PBDEs into PBDFs following a simple ring-closure reaction. High reaction temperatures facilitate loss of ortho Br atom from PBDEs, followed by cyclisation step to generate PBDFs. PBDFs are observed in a narrow temperature range of 700-850 °C, whereas PBDEs form between 550-850 °C. Since formation mechanisms of PBDFs and polybrominated dibenzo-p-dioxins (PBDDs) are typically only sensitive to the bromination at ortho positions, the results reported herein apply also to higher brominated isomers of BBzs.

Detection of high PBDD/Fs levels and dioxin-like activity in toys using a combination of GC-HRMS, rat-based and human-based DR CALUX® reporter gene assays.

Brominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) are increasingly reported at significant levels in various matrices, including consumer goods that are manufactured from plastics containing certain brominated flame retardants. PBDD/Fs are known ligands for the aryl hydrocarbon receptor (AhR) but are not yet considered in the hazard assessment of dioxin mixtures. The aim of the present study was to determine if PBDD/Fs levels present in plastic constituents of toys could pose a threat to children's health. PBDD/Fs, unlike their chlorinated counterparts (PCDD/Fs), have not been officially assigned toxic equivalence factors (TEFs) by the WHO therefore, we determined their relative potency towards AhR activation in both human and rodent cell-based DR CALUX® bioassays. This allowed us to compare GC-HRMS PBDD/F congener levels, converted to total Toxic Equivalents (TEQ) by using the PCDD/F TEFs, to CALUX Bioanalytical Equivalents (BEQ) levels present in contaminated plastic constituents from children's toys. Finally, an estimate was made of the daily ingestion of TEQs from PBDD/Fs-contaminated plastic toys by child mouthing habits. It is observed that the daily ingestion of PBDD/Fs from contaminated plastic toys may significantly contribute to the total dioxin daily intake of young children.

Pathways and influential factors study on the formation of PBDD/Fs during co-processing BDE-209 in cement kiln simulation system.

The thermal processes of cement kilns are sources of polybrominated dibenzofurans and dioxins (PBDD/Fs); however, when co-processing decabromodiphenyl ether (BDE-209) soil in cement kilns, very few reports have investigated the mechanism of PBDD/Fs formation from BDE-209. Therefore, the pathways and factors that influence the formation of PBDD/Fs were investigated using Box-Behnken design (BBD) of the response surface methodology (RSM) at lab-scale. The PBDEs, HBr/Br2 and PBDD/Fs emissions in flue gas from the simulated thermal process were analyzed using gas chromatography/mass spectroscopy (GC/MS), high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS), and ion chromatography (IC). Density functional theory (DFT) was also used to further discuss the formation of PBDD/Fs. The major products of BDE-209 thermal decomposition in flue gas were 97.1% HBr/Br2 (a.v. 26.6%/70.6%) > 2.7% PBDEs >0.2% PBDD/Fs. Formation of precursors were the main pathways for PBDD/Fs, and those precursors were dominated by higher-brominated PBDEs (heptã deca-BDEs); debromination of BDE-209 was also a crucial pathway for the formation of PBDD/Fs throughout the thermal process. Interestingly, it was easier to form HpBDD/Fs from OBDD/Fs than from PBDEs. The O2 percentage and interaction factors of O2 percentage, temperature, and CaCO3 percentage have the largest influence on PBDD/Fs emissions and formation.

The formation of PBDFs from the ortho-disubstituted phenol precursors: A comprehensive theoretical study on the PBDD/Fs formation from 2,4,6-tribromophenol.

Bromophenols are known as direct precursors of the notorious polybrominated dibenzo-p-dioxin/dibenzofurans (PBDD/Fs). There is a long-held viewpoint that only the more toxic dioxin-type products could be formed from the ortho-disubstituted phenols, totally contrary to the experimental observations that both PBDDs and PBDFs are generated. To tackle the issue, the gaseous formation mechanism of PBDD/Fs from 2,4,6-tribromophenol (TBP), a typical ortho-disubstituted phenol, was investigated in this study. Firstly, the reactions between TBP and the active H radical produce three key radical species including the bromophenoxyl radical, the substituted phenyl radical and phenoxyl diradical. The self- and cross-combinations of these radical species and TBP yield not only the dioxin-type products 1,3,6,8-TeBDD and 1,3,7,9-TeBDD, but also the brominated dibenzofurans 1,3,6,8-TeBDF and 2,4,6,8-TeBDF. Notably, the reactions involving the phenyl C sites in the substituted phenyl and phenoxyl diradicals are demonstrated to be both thermodynamically and kinetically more favorable than those involving the bromophenoxyl radical and the TBP molecule. Most importantly, the findings of the present work are of great importance as it provides feasible pathways to form less toxic dibenzofuran-type products from the ortho-disubstituted phenols. These results will improve the understanding of the PBDD/Fs formation mechanism from phenol precursors.

Emission characteristics of polychlorinated, polybrominated and mixed polybrominated/chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs, PBDD/Fs, and PBCDD/Fs) from waste incineration and metallurgical processes in China.

Typical thermal processes are common sources of polychlorinated, polybrominated and mixed polybrominated/chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs, PBDD/Fs, and PBCDD/Fs); however, very few reports have investigated their coemission. To clarify the emission characteristics of these DD/Fs, two municipal waste incinerators (MWIs), three hazardous waste incinerators (HWIs), one cement kiln coprocessing municipal waste incinerator (CMWI), one secondary copper smelter (SCu), and one iron and steel sintering smelter (ISS) in China were investigated. In total, 17 congeners of PCDD/Fs, 14 congeners of PBDD/Fs, and 12 congeners of PBCDDs in stack flue gases from these thermal processes were analyzed using a high-resolution gas chromatograph/high-resolution mass spectrometer (HRGC/HRMS) in this study. PCDD/Fs, PBDD/Fs and PBCDD/Fs were detectable in all samples, with total concentrations of 911-5.15 × 103 pg/Nm3 (80.2-414 pg TEQ/Nm3). The concentrations of each DD/F were similar within the same type of facility and varied among different types of facilities. The contributions of PBDD/Fs and PBCDD/Fs to the total concentrations exceeded that of PCDD/Fs in some cases, such as in HWIs and SCu. In general, the ∑Cl4-7 CDFs and ∑Cl7-8 CDDs, 1,2,3,4,6,7,8-HpBDF, and 1-B-2,3,7,8-TeCDD and 2-B-1,3,7,8-TeCDD were the dominant congeners in the PCDD/F, PBDD/F, and PBCDD/F mass concentrations, respectively. Several other congeners present at low mass concentrations, such as 1,2,3,4,7,8-HxBDF, have potential as major contributors to the TEQs due to their high toxic equivalency factors. These results reveal the necessity of synergistically inhibiting the occurrences of PCDD/Fs, PBDD/Fs, and PBCDD/Fs from these sources and provide valuable information for use in the source identification of these pollutants in the environment.

Poultry eggs as a source of PCDD/Fs, PCBs, PBDEs and PBDD/Fs.

Regardless of the country or region of the world, poultry eggs are one of the most important components of the human diet. Nutritional value is derived from them, but chicken eggs can be contaminated with POPs. The aim of the study was to compare the impact of different types of chicken husbandry system on bioaccumulation of selected POPs. The HRGC/HRMS method was used for determination of 58 congeners of chlorinated and brominated halogenated aromatic hydrocarbons. The influence of the farm rearing system on concentration and congener profile was seen for most groups of tested contaminants, of which the eggs were a source. Human exposure to dioxins and dioxin-like compounds as a result of consumption of contaminated eggs should be a subject of concern. The occurrence of PCDD/Fs, PCBs, PBDEs, and PBDD/Fs in commonly consumed foodstuffs such as eggs supports the need for further research on environmental pollutants and for determination of exposure as the result of their occurrence in different food categories.

Emissions, environmental levels, sources, formation pathways, and analysis of polybrominated dibenzo-p-dioxins and dibenzofurans: a review.

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) were labeled potential persistent organic pollutants by the Stockholm Convention and have structures and toxicities similar to those of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), which has caused considerable concern. This article reviews the current available literature on the status, sources, formation pathways, and analysis of PBDD/Fs. PBDD/Fs are widely generated in industrial thermal processes, such as those for brominated flame retardant (BFR) products, e-waste dismantling, metal smelting processes, and waste incineration. PBDD/Fs can form via the following routes: precursor formation, de novo formation, biosynthesis, and natural formation. The levels of PBDD/Fs in the environment and in organisms and humans have increased due to extensive consumption and the increasing inventory of BFRs; thus, the risk of human exposure to PBDD/Fs is expected to be high.

Characterization of PBDD/F emissions from simulated polystyrene insulation foam via lab-scale programmed thermal treatment testing.

Accidental fires and open combustion are regarded as major potential contributors to the environmental release of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs). The characterization of PBDD/Fs emitted from thermal treatment of simulated polystyrene (PS) foam is reported in this study. PS, hexabromocyclododecane (HBCDD) and metals (or metallic compounds) composed the test samples, which imitated real extruded (XPS) and expanded (EPS) polystyrene thermal insulation foams. Test samples were subjected to thermal treatments under different experimental conditions. This study shows that the temperature, metal (metallic compound) content, and type of atmosphere are the key factors in the formation of congeners and PBDD/Fs during thermal processes. The total yield of polybrominated dibenzofurans (PBDFs) was greater than that of the polybrominated dibenzo-p-dioxins (PBDDs) during the test, and 1,2,3,7,8-PeBDF and 2,3,7,8-TBDF were the predominant congeners emitted during the thermal treatment experiments.

Formation of 1,3,8-tribromodibenzo-p-dioxin and 2,4,6,8-tetrabromodibenzofuran in the oxidation of synthetic hydroxylated polybrominated diphenyl ethers by iron and manganese oxides under dry conditions.

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are ubiquitous and highly toxic emerging endocrine disruptors found in surface and subsurface soils and clay deposits. Seriously, they could be easily transformed to the more toxic dioxins (PBDD/Fs) in photochemical processes and incineration, but the spontaneous formation of PBDD/Fs has rarely been reported. This study focused on the formation of 1,3,8-tribromodibenzo-p-dioxin (1,3,8-TrBDD) and 2,4,6,8-tetrabromodibenzofuran (2,4,6,8-TeBDF) from 2'-OH-BDE-68 and 2,2'-diOH-BB-80 under the oxidization of iron and manganese oxides (goethite and MnOx). Approximately 0.09 µmol/kg (2.33%) and 0.17 µmol/kg (4.15%) were transformed to 1,3,8-TrBDD and 2,4,6,8-TeBDF by goethite in 8 days and a higher conversion 0.15 µmol/kg (3.77%) and 0.23 µmol/kg (5.74%) were observed for MnOx in 4 days. However, the formation of PBDD/Fs, probably proceeding via Smiles rearrangements and bromine elimination processes, was greatly inhibited by the presence of water. Transformation of OH-PBDEs by goethite and MnOx was accompanied by release of Fe and Mn ions and the possible pathways for the formation of reaction products were proposed. In view of the ubiquity of OH-PBDEs and metal oxides in the environment, oxidation of OH-PBDEs mediated by goethite and MnOx is likely an abiotic route for the formation of PBDD/Fs.