Polybrominated Dibenzo-p-dioxins And Dibenzofurans Research Articles

A clean-up method for determination of multi-classes of persistent organic pollutants in sediment and biota samples with an aliquot sample

In the present study, we developed a novel method to simultaneously detect eight classes of persistent organic pollutants (POPs), including polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), polychlorinated naphthalenes (PCNs), organochlorine pesticides (OCPs), short-chain chlorinated paraffins (SCCPs) and Dechlorane Plus (DP), in sediment and fish tissue samples. The samples were extracted by accelerated solvent extraction (ASE) system, and the extracts were purified and fractionated into fraction1 and fraction2 with multi-layer silica gel column, followed by further fractionation using a basic alumina column (fraction1) and a Florisil column (fraction2), respectively. Finally, fractions were analyzed with different chromatographic columns and different detectors according to the properties of a chemical compound. The limit of detection for eight classes of POPs ranged from 1 to 30 pg/gdw in fish tissue samples, and from 1 to 33 pg/gdw in sediment samples, except for SCCPs (from 5.6 to 7.6 ng/g in fish tissue samples, and from 1.2 to 8.3 ng/gdw in sediment samples). The recoveries of eight classes of POPs spiked in fish tissue and sediment samples ranged from 43% to 120%, and from 45% to 115%, respectively. The relative standard deviation (RSD) was less than 25%. The accuracy of method was satisfactorily demonstrated by analysis of standard reference materials NIST SRM 1649b and WMF-01. In addition, the newly developed method was successfully applied for analysis of sediment and fish samples collected from the Baiyangdian Lake.

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.

Characteristics of PM2.5-bound PCDD/Fs, PCBs, PBDD/Fs and PBDEs from a Diesel Generator Using Waste Cooking Oil-based Biodiesel Blends

This study investigates fine particulate matter (PM2.5) bound persistent organic pollutants (POPs) emitted from a diesel generator fueled with three waste cooking oil-based biodiesel (WCO-biodiesel) blends (W0 (pure diesel), W20 (WCO-biodiesel/diesel = 20%/80% (v/v)), and W40). These POPs are polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyl (PCBs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) and polybrominated diphenyl ethers (PBDEs). Experimental results indicate that the mass concentrations of PM2.5-bound PCDD/Fs, PCBs, PBDD/Fs and PBDEs in the engine exhaust are 2.15–3.65, 16.7–35.4, 25.8–46.5 and 303–440 pg Nm–3, respectively, at 1.5–3.0 kW loads for using W0, while the corresponding toxic equivalent (TEQ) concentrations of the above PM2.5-bound pollutants are 0.282–0.527, 0.038–0.051 and 0.064–0.093 pg WHO2005-TEQ Nm–3, respectively (excluding PBDEs, which still have no toxic equivalency factors (TEFs) for TEQ calculation). Using W20 and W40 reduced the mass and TEQ emission concentrations of PM2.5-bound PCDD/Fs, PCBs, PBDD/Fs and PBDEs in comparison with W0. The reductions of mass concentrations in exhausted PM2.5 were in the order PBDEs >> PBDD/Fs > PCBs > PCDD/Fs, while the decrease in toxic concentration followed the order PCDD/Fs > PBDD/Fs > PCBs. Thus, adding WCO-biodiesel to the fuel mixture in generator engines lowers the adverse effects of PM2.5 emissions on the environment and human health.

Formation and degradation of polybrominated dibenzofurans (PBDFs) in the UV photolysis of polybrominated diphenyl ethers (PBDEs) in various solutions

A major environmental concern associated with polybrominated diphenyl ethers (PBDEs) is the potential for their oxidative transformation into the toxic polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs). However, the process that PBDEs are converted into PBDFs by UV light is not well understood. Here, we report on the photolysis of ten lower PBDE congeners (≤tetra) and diphenyl ether (DE) in various solutions to explore the effect of the brominated positions of PBDEs on their transformation to PBDFs. The results suggest that the ortho-bromine substitution is the prerequisite for converting PBDEs into PBDFs in these solutions by UV light. Without an ortho-bromine substituent, PBDE congeners did not generate PBDFs, but sequentially debrominated into DE, which converted into dibenzofuran (DF). The amount of PBDFs that accumulated during the photolysis of PBDEs with one ortho-bromine substituent was much greater than the amount that from the photolysis of PBDEs that with two ortho-bromine substituents. Quantum chemistry data suggests a mechanism of the formation of PBDFs from ortho-brominated PBDEs that involves the formation of ortho-carbon radicals, followed by either an addition of a hydrogen atom extracted from a solvent molecule to form lower PBDEs, or an intramolecular reaction to form PBDFs.

Persistent Organic Pollutant Reductions from a Diesel Engine Generator Fueled with Waste Cooking Oil-based Biodiesel Blended with Butanol and Acetone

ABSTRACTThis investigation focuses on the effects on emissions of persistent organic pollutants (POPs) (polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) and polybrominated diphenyl ethers (PBDEs)) from a diesel engine fuelled by 20 vol% waste cooking oil-based biodiesel (W20) blended with various fractions of dehydrate/hydrous butanol (B/B′) and acetone (A/A′). The emission concentrations of the POPs were in the order PBDE ≫ PBDD/F > PCB > PCDD/F, regardless of the blending fuel or engine load. The POP with highest concentration was PBDE, being 2–3 times that of the others. Conversely, the magnitude of emitted toxicity followed the order PCDD/F > PCB ≈ PBDD/F, while PCDD/F emissions had about 10 times the toxicity concentrations of PCBs and PBDD/Fs. Among the dioxin compounds, the emissions of PCDDs represented 46–73% (average 57%) and 50–72% (average 59%) of total PCDD/F mass and toxicity concentrations, respectively, and were which and were thus significantly higher than those of PCDFs. The non-ortho-PCB contributed almost all toxicity (~100%) of 14 dioxin-like-PCBs, even though its contribution in mass was only 9–32% (average 16%) among the congeners. Similarly, PBDFs accounted for ~100% of toxicity of PBDD/Fs. Additionally, deca-BDEs contributed to most of the mass emissions of PBDEs (47.0–90.5%, 82.4% in average), while nona-BDEs and tri- to octa-BDEs only contributed 10% and 8%, respectively. The reductions of the absolute mass concentrations of POPs from W20 were in the order PBDEs >> PBDD/Fs > PCDD/Fs ≈ PCBs for all multi-component diesel blends. The reduction fractions of POPs were in the order PCDD/F > PCB ≈ PBDD/F > PBDE, and those of TEQ were PCDD/F > PCB > PBDD/F. Thus, the addition of butanol and acetone, whether pure or hydrous, could further lower the POP emissions from W20.

Persistent organic pollutants in the Antarctic coastal environment and their bioaccumulation in penguins

Persistent organic pollutants (POPs), including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), polybrominated biphenyls (PBBs), and polybrominated diphenyl ethers (PBDEs), have been identified in penguins, lichens, soils, and ornithogenic soils in the Antarctic coastal environment in this study. To the best of our knowledge, no previous study has reported PBDD/F and PBB data from Antarctica. The POP mass contents in penguins were in the following order: PCBs >> PBDEs >> PCDD/Fs; PCBs were the dominant pollutants (6310–144,000 pg/g-lipid), with World Health Organization toxic equivalency values being 2–14 times higher than those of PCDD/Fs. Long-range atmospheric transport is the most primary route by which POPs travel to Antarctica; however, local sources, such as research activities and penguin colonies, also influence POP distribution in the local Antarctic environment. In penguins, the biomagnification factor (BMF) of PCBs was 61.3–3760, considerably higher than that for other POPs. According to BMF data in Adélie penguins, hydrophobic PBDE congeners were more biomagnified at log Kow > 6, and levels decreased at log Kow > 7.5 because larger molecular sizes inhibited transfer across cell membranes.

Thermochemical Formation of Polybrominated Dibenzo-p-Dioxins and Dibenzofurans Mediated by Secondary Copper Smelter Fly Ash, and Implications for Emission Reduction.

Heterogeneous reactions mediated by fly ash are important to polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) formation. However, the formation of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) through heterogeneous reactions is not yet well understood. Experiments were performed to investigate the thermochemical formation of PBDD/Fs at 150-450 °C through heterogeneous reactions on fly ash from a secondary copper smelter. The maximum PBDD/F concentration was 325 times higher than the initial PBDD/F concentration in the fly ash. The PBDD/F concentration after the experiment at 150 °C was five times higher than the initial concentration. PBDD/Fs have not previously been found to form at such a low temperature. Secondary-copper-smelter fly ash clearly promoted PBDD/F formation, and this conclusion was supported by the low activation energies that were found in Arrhenius's law calculations. Thermochemical formation of PBDD/Fs mediated by fly ash deposited in industrial facilities could explain "memory effects" that have been found for PCDD/Fs and similar compounds released from industrial facilities. Abundant polybrominated diphenyl ethers (PBDEs) that were formed through fly ash-mediated reactions could be important precursors for PBDD/Fs also formed through fly ash-mediated reactions. The amounts of PBDEs that formed through fly ash-mediated reactions suggested that secondary copper smelters could be important sources of reformed PBDEs.

Comprehensive evaluation of dioxins and dioxin-like compounds in surface soils and river sediments from e-waste-processing sites in a village in northern Vietnam: Heading towards the environmentally sound management of e-waste

The management of electronic waste (e-waste), which can be a source of both useful materials and toxic substances, depending on the processing method, is important for promoting material cycling. In this study, we used the dioxin-responsive chemical-activated luciferase gene expression (DR-CALUX) assay combined with gas chromatography–high-resolution mass spectrometry to evaluate the levels of dioxin-like compounds in surface soils and river sediments collected in and around an e-waste-processing village in northern Vietnam. The WHO-TEQs (Toxic equivalents) of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), coplanar polychlorinated biphenyls (Co-PCBs), and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in soils collected in January 2012 ranged from 0.29 to 310 pg/g (median 2.9 pg/g, n = 32), and the WHO-TEQs in sediments ranged from 0.96 to 58 pg/g (median 4.4 pg/g, n = 8). Dioxin-like activities (CALUX-TEQs [2,3,7,8-TCDD equivalent]) in soils collected in January 2012, 2013, and 2014 ranged from <30 to 4300 pg/g (median <30 pg/g, n = 96), and the activities in sediments ranged from <30 to 4000 pg/g (median 33 pg/g, n = 24). Dioxin-like compounds accumulated in samples collected around e-waste-processing areas such as open-burning sites and e-waste-processing workshops, and the compounds may be transported from their sources to surrounding areas over the course of several years. Some of the CALUX-TEQs, but not WHO-TEQs, values were higher than the maximum acceptable WHO-TEQs promulgated by various authorities, indicating that all dioxin-like compounds should be evaluated in samples collected from e-waste-processing areas. Our findings suggest that open burning and open storage of e-waste should be prohibited and that wastewater treatment should be implemented at each workshop to reduce contamination by dioxin-like compounds from e-waste.

Occurrence of chlorinated and brominated dioxins/furans, PCBs, and brominated flame retardants in blood of German adults.

Persistent organic pollutants are widespread in the environment, and are associated with a particular health and ecological concern. The human body burden of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDDs/Fs), polychlorinated biphenyls (PCBs), polybrominated diphenylether (PBDEs), and hexabromocyclododecanes (HBCDs) was determined. Blood samples were collected in Germany, originating from 42 randomly selected subjects between 20 and 68 years old. The median (95th percentile) concentrations, expressed as WHO2005-TEQ for PCDD/PCDFs and dioxin-like PCBs, were 6.2 (19.1) pg/g l.w. and 4.1 (8.8) pg/g l.w., respectively. PBDDs/Fs were found with a median of 2.8 pgTEQ/g l.w. and a 95th percentile of 8.7 pgTEQ/g l.w. (using similar interim TEF values as for PCDDs/Fs) On a median basis, the contribution of PCDD/Fs, dioxin-like PCBs, and PBDDs/Fs to total TEQ were 47%, 31%, and 21%, respectively. The sum of the 6 non-dioxin-like PCBs exhibited a median of 267ng/g l.w. and a 95th percentile of 834ng/g l.w. The median value for the sum of six tetra- to hepta-PBDE congeners was 1.7ng/g l.w. (95th percentile: 4.9ng/g l.w.). BDE 209 was the most abundant congener with a median of 1.8ng/g l.w. HBCDs were only found in some samples, and concentrations ranged between the limit of detection (5ng/g l.w.) and the limit of quantification (16ng/g l.w.). Results for PBDEs and HBCDs are comparable to other European studies. Our study demonstrated that the body burden of PCDD/Fs and PCBs declined continously since the last three decades, but exposure may exceed precautionary guideline levels.

Characterization of polybrominated dibenzo-p-dioxins and dibenzo-furans (PBDDs/Fs) in environmental matrices from an intensive electronic waste recycling site, South China

Information on environmental distribution and human exposures of polybrominated dibenzo-p-dioxins and dibenzo-furans (PBDDs/Fs) are little reported. In the present study, workshop dust, soil and sediment samples from Longtang and Shijiao, the intensive e-waste recycling sites within Qingyuan City, southern China, were collected and analyzed following the standard method. PBDD/F concentrations (sum of eight 2378-substituted PBDD/F congeners) in different environmental matrices were in the range of 122–4667 ng kg−1 dry wt (dw) for workshop dust, 19.6–3793 ng kg−1 dw for the top soils, and 527 ng kg−1 dw for the surface sediment, which were substantially higher than those of reference sites. The long-distance transport of PBDDs/Fs also impacted the adjacent areas. Contribution of the most two toxic congeners (2,3,7,8-TBDD and 1,2,3,7,8-PeBDD) to the total toxic equivalent quantity (TEQ) increased significantly from “source” (dust) to “sink” (sediment). Dismantling and open burning were the two procedures contributing relatively higher level PBDDs/Fs to the atmosphere, while acid leaching would contaminate soils and waters directly. The estimated daily intakes of eight PBDD/F congeners via soil/dust ingestion and dermal absorption for local residents were higher than those contributed by seventeen PCDD/F congeners in the same set of samples. Children and e-waste processing workers were the most affected groups by the low-tech recycling activities there.

Formation and emission of brominated dioxins and furans during secondary aluminum smelting processes

Secondary aluminum smelting (SAl) processes have previously been found to be important sources of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs). It is crucial that the key factors that influence the formation and emission of PBDD/Fs are identified to allow techniques for decreasing PBDD/F emissions during SAl processes to be developed. In this study, stack gas samples were collected from four typical secondary aluminum smelters that used different raw materials, and the samples were analyzed to allow differences between PBDD/F emissions from different SAl plants to be assessed. The composition of the raw materials was found to be one of the key factors influencing the amounts of PBDD/Fs emitted. The PBDD/F emission factors (per tonne of aluminum produced) for the plants using 100% (Plant1), 80% (Plant2), and 50% (Plant3) dirty aluminum scrap in the raw material feed were 180, 86, and 14 μg t(-1), respectively. The amounts of PBDD/Fs emitted at different stages of the smelting process (feeding-fusion, refining, and casting) were compared, and the feeding-fusion stage was found to be the main stage in which PBDD/Fs were formed and emitted. Effective aluminum scrap pretreatments could significantly decrease PBDD/F emissions. Much higher polybrominated dibenzofuran concentrations than polybrominated dibenzo-p-dioxin concentrations were found throughout the SAl process. The more-brominated congeners (including octabromodibenzo-p-dioxin, octabromodibenzofuran, heptabromodibenzo-p-dioxins, and heptabromodibenzofurans) were the dominant contributors to the total PBDD/F concentrations. The results could help in the development of techniques and strategies for controlling PBDD/F emissions during metallurgical processes.

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in e-waste plastic in Nigeria.

Plastics from cathode ray tube (CRT) casings were sampled in Nigeria and analysed for their polybrominated dibenzo-p-dioxin and dibenzofuran (PBDD/F) content. PBDD/Fs, consisting mainly of PBDFs, were detected in BFR containing plastic with a median (mean) concentration of 18,000 ng/g (41,000 ng/g). The PBDD/Fs levels were highest in samples containing PBDEs, but the levels of PBDFs were two orders of magnitude higher than the levels reported in the technical PBDE mixtures and where frequently exceeding 1000 μg/g of PBDE content. These higher levels are likely to arise from additional transformation of PBDEs during production, use, recycling, or storage, but the processes responsible were not identified in this study. PBDD/Fs in CRT casings containing1,2-bistribromophenoxyethane (TBPE) were dominated by tetrabrominated dibenzo-p-dioxin (TBDDs) with concentrations around 10 μg/g of the TBPE content. The PBDD/Fs in CRT casings containing tetrabromobisphenol A (TBBPA) were found at concentrations around 0.1 μg/g of TBBPA levels. Casings treated with TBPE or TBBPA often contained PBDEs (and PBDF) as impurities-probably originating from recycled e-waste plastics. It was estimated that the 237,000 t of CRT casings stockpiled in Nigeria contain between 2 and 8 t of PBDD/Fs. The total PBDD/F contamination in polymers arising from total historic PBDE production/use is estimated in the order of 1000 t. TEQ values of CRT samples frequently exceeded the Basel Convention's provisional low POPs content of 15 ng TEQ/g. Due to the significant risks to health associated with PBDD/Fs, more detailed studies on the exposure routes from PBDD/Fs in stockpiles are needed.

Comparison of the contributions of polychlorinated dibenzo-p-dioxins and dibenzofurans and other unintentionally produced persistent organic pollutants to the total toxic equivalents in air of steel plant areas

The concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and the “dioxin-like” (dl) compounds polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), polybrominated dibenzo-p-dioxins (PBDDs), and dibenzofurans (PBDFs), were determined in the air samples collected from six steel plants. The toxic equivalent (TEQ) concentrations of the PCDDs, PCDFs, dl-PCBs, dl-PCNs, PBDDs, and PBDFs in the air were 0.01–0.19pgWHO-TEQNm−3, 0.01–0.69pgWHO-TEQNm−3, 0.001–0.089pgWHO-TEQNm−3, 0.002–0.011pgTEQNm−3, 0.004–0.02pgTEQNm−3, and 0.02–0.12pgTEQNm−3, respectively. The PCNs were the most abundant compounds (by mass concentration), contributing about 87% of the total mass concentrations of the analytes that were found in the air of the steel plant areas. The PCDFs contributed about 47% of the total TEQs, following by the PBDFs (28%) and the PCDDs (18%). The dioxin-like compounds together contributed up to 40% of the total TEQs, so their contributions to the toxic effects that could be caused by exposure to the air of the steel plant areas were significant. The congener profiles in the air were similar to the congener profiles that were found in stack gas emissions, indicating that the steelmaking plants were possible sources of the PCDDs, PCDFs, and dioxin-like compounds that were found in the air of the steel plant areas.

Atmospheric Emission of Polybrominated Dibenzo-p-dioxins and Dibenzofurans from Converter Steelmaking Processes

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) and polybrominated diphenyl ethers (PBDEs) were characterized and quantified in stack gas from secondary ventilation systems from five different steelmaking plants. The concentrations of 2,3,7,8-substituted PBDD/Fs (2,3,7,8-PBDD/Fs) and PBDEs were 0.036–0.19 ng/Nm3 (0.32–4.33 pg toxic equivalency (TEQ)/Nm3) and 3.11–40.0 ng/Nm3, respectively, in the stack gas. These concentrations were lower than those in other metallurgical processes, such as electric arc furnaces and iron ore sintering processes. The concentrations of PBDEs were 26–94 times higher than those of PBDD/Fs in the stack gas. The PBDD/F and PBDE emission factors in the stack gas from the steelmaking converter processes (per tonne of steel produced) were 0.048–0.59 µg/t (0.66–20.8 ng TEQ/t) and 6.36–76.6 µg/t, respectively. These data are helpful for establishing an emission inventory of PBDD/Fs from the converter steelmaking industry in China.

Emissions of PBDD/Fs, PCDD/Fs and PBDEs from flame-retarded high-impact polystyrene under thermal stress

The emissions of polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) and their chlorinated analogues (PCDD/Fs) during the thermal treatment of a high impact polystyrene (HIPS) TV casing were investigated. The halogenated compounds were analyzed in the original material and in the gases emitted during its treatment at temperatures between 50°C and 250°C. DecaBDE was the primary PBDE in the TV casing, which also contained high levels of PBDFs (ppm range). At the lower treatment temperatures, non-modified PBDEs evaporated from the samples. Conversely, at 200°C or above, debromination reactions led to the formation of additional tri- through nonaBDE. The formation of new PBDD/Fs was also detected in the gas phase when the plastic was heated to 200°C or 250°C, with higher yields of furans than dioxins. This appreciably increased the toxic equivalent (TEQ) levels of the gas phase relative to those seen in the untreated sample. In all cases, the levels and TEQ contributions from PCDD/Fs were negligible compared to those for brominated analogues.

Contribution of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) to the toxic equivalency of dioxin-like compounds in archived biosolids from the U.S. EPA's 2001 national sewage sludge survey.

The World Health Organization recently proposed the inclusion of brominated congeners in addition to chlorinated congeners when computing the toxic equivalency (TEQ) of dioxin-like compounds (DLCs) in assessments of human health risks. In the present study, 12 polybrominated dibenzo-p-dioxins and furans (PBDD/Fs) were analyzed by gas chromatography/high resolution mass spectrometry in the composited, archived biosolids that were collected in 32 U.S. states and the District of Columbia from 94 wastewater treatment plants by the United States Environmental Protection Agency in its 2001 national sewage sludge survey. Two PBDDs and five PBDFs were detected in the biosolids composites at varying frequencies (40–100%) with a total mean concentration of 10,000 ng/kg dry weight (range: 630–42,800), of which 1,2,3,4,6,7,8-hepta-BDF constituted about 95% by mass. Relative to commercial polybrominated diphenyl ether (PBDE) formulations, the ratio of PBDD/Fs to PBDEs in biosolids was 55-times higher (∼0.002% vs ∼0.11%), which indicates potential PBDE transformation or possibly additional sources of PBDD/Fs in the environment. The TEQ contribution of PBDD/Fs was estimated at 162 ng/kg 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) (range: 15–672), which is equivalent to 75% (range: 12–96%) of the total TEQ in biosolids. The TEQ of DLCs released annually to U.S. soils as a result of the land application of biosolids was estimated at 720 g (range: 530–1600 g). Among all known DLCs determined in biosolids, brominated analogs contributed 370% more TEQ than did chlorinated congeners, which indicates the need to include brominated DLCs in the exposure and risk assessment of land-applied biosolids.

Brominated Dioxins: Little-Known New Health Hazards - A Review

Abstract This article reviews the present state of the science concerning the polybrominated dibenzo-p-dioxins (PBDDs) and dibenzofurans (PBDFs). Everywhere in the world people are exposed to anthropogenic origin chemicals. Some of them are long-lived organic compounds, which persist over the years in the environment. Persistent organic pollutants, such as organohalogen compounds, accumulate in environmental and biological compartments and have adverse effects on the health of humans and animals. Little is known about the brominated and mixed chloro/bromo dioxin and furans. Existing literature suggests that brominated dioxins and furans have similar toxicity profiles to their chlorinated analogues. The exposure data are extremely limited, showing a major data gap in estimating the potential environmental and health risk of these chemicals. The rapid increase in the use of brominated flame retardants (the main source of these pollutants) has raised the level of concern over environmental and health damage from brominated dioxins and furans. It is likely that human as well as wildlife exposure to these contaminants will increase with their greater use. The findings reported here present strong evidence of the PBDDs and PBDFs as an emerging new class of contaminants.

De novo synthesis of brominated dioxins and furans.

On the basis of laboratory experiments with model mixtures (active carbon+CuBr2 at different loads), this work studies the formation of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) by de novo synthesis. For the different samples, the temperature of the maximum carbon oxidation rate was determined by thermogravimetric analysis, and a kinetic model was proposed for the degradation of the materials in an oxidizing atmosphere (synthetic air). The effect of the addition of different amounts of CuBr2 was studied, finding that its presence accelerates the degradation of the carbonaceous structure in the presence of oxygen. The thermal degradation of the samples in air is satisfactorily described by a first-order single-reaction model. In addition, combustion runs of one of the mixtures (consisting of activated carbon+50 wt % CuBr2, pyrolyzed at 700 °C) were performed in a quartz horizontal laboratory furnace. The analysis of the emissions and the solid residue proved the formation of brominated dioxins and furans at 300, 400, and 500 °C, with a maximum yield at 300 °C (91.7 ng/g of total PBDD/Fs) and a higher bromination degree with increasing temperature.

Relative Potency for Altered Humoral Immunity Induced by Polybrominated and Polychlorinated Dioxins/Furans in Female B6C3F1/N Mice

The use of brominated flame retardants and incineration of bromine-containing materials has lead to an increase in polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in the environment. Measurable amounts of PBDD/Fs have been detected in soil, seafood, and human breast milk and serum. Studies indicate that the relative potencies of some PBDD/Fs based on enzyme induction are equivalent to those of some polychlorinated dibenzo-p-dioxins and dibenzofurans. To assess the humoral immunity relative potencies of PBDD/Fs and compare them to their chlorinated analogs, female B6C3F1/N mice received a single oral exposure to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), 2,3,7,8-tetrabromodibenzofuran (TBDF), 2,3,7,8-tetrachlorodibenzofuran (TCDF), 1,2,3,7,8-pentabromodibenzofuran (1PeBDF), 1,2,3,7,8-pentachlorodibenzofuran (1PeCDF), 2,3,4,7,8-pentabromodibenzofuran (4PeBDF), 2,3,4,7,8-pentachlorodibenzofuran (4PeCDF), 2,3-dibromo-7,8-dichlorodibenzo-p-dioxin (DBDCDD), or 2,3,7-tribromodibenzo-p-dioxin (TriBDD). Inhibition of the immunoglobulin M (IgM) antibody forming cell response was measured 4 days following immunization with sheep red blood cells. The data were fit to a Hill model to estimate the ED50 for inhibition. Expression of xenobiotic metabolizing enzyme (XME) and thyroxine transport protein (Ttr) genes in liver was measured by PCR to assess aryl hydrocarbon-mediated responses. TCDD, TBDF, TCDF, 1PeBDF, 4PeBDF, 4PeCDF, and DBDCDD suppressed the IgM antibody response and Ttr gene expression, and upregulated phase I XME genes. 1PeCDF suppressed the IgM antibody response but only upregulated phase I XME genes; TriBDD had no effect on antibody response. The rank order of potency (ED50) for these chemicals was TCDD>TBDF>4PeBDF>TCDF/4PeCDF/1PeBDF>1PeCDF. Whereas TCDD was the most potent compound tested, the brominated analogs were more potent than their chlorinated analogs, suggesting that these compounds should be considered in toxic equivalency factor evaluation and risk assessment.