Polybrominated Dibenzo-p-dioxins Research Articles

Naturally occurring organobromine compounds (OBCs) including polybrominated dibenzo-p-dioxins in the marine sponge Hyrtios proteus from The Bahamas

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

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.

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.

In silico toxicity evaluation of dioxins using structure-activity relationship (SAR) and two-dimensional quantitative structure-activity relationship (2D-QSAR).

Prediction of pEC50 values of dioxins binding with the aryl hydrocarbon receptor (AhR) is of great significance for exploring how dioxins induce toxicity in human body and evaluating their environmental behaviors and risks. To reveal the factors that influence the toxicity of dioxins, provide more accurate mathematical models for predicting the pEC50 values of dioxins, and supplement the toxicity database of persistent organic pollutants, qualitative structure-activity relationship (SAR) and two-dimensional quantitative structure-activity relationship (2D-QSAR) were used in this study. The research objects in this study were 60 organic compounds with pEC50 values and 162 compounds without pEC50 values, which included polychlorinated dibenzofurans (PCDFs), polychlorinated dibenzo-p-dioxins (PCDDs), and polybrominated dibenzo-p-dioxins (PBDDs). The qualitative structure-activity relationship (SAR) was performed first and concluded that halogen substitutions at any of the 2, 3, 7, and 8 sites increased the pEC50 value of the compound. Moreover, two-dimensional quantitative structure-activity relationship (2D-QSAR) models were established by employing multiple linear regression (MLR) method and artificial neural network (ANN) algorithm to investigate the factors affecting the pEC50 values of dioxins molecules. MLR was used to establish the well-understood linear model and ANN was used to establish a more accurate non-linear model. Both models have good fitting, robustness, and predictive ability. Importantly, the ability of dioxins binding to AhR is mainly determined by molecular descriptors including E1m, SM09_AEA (dm), RDF065u, F05 [Cl-Cl], and Neoplastic-80. In addition, the pEC50 values of the 162 dioxins without toxicity data were predicted by MLR and ANN models, respectively.

Facile synthesis of bromo- and mixed bromo/chloro dibenzo-p-dioxins and [14C]-labeled 1,3,7,8-tetrabromodibenzo-p-dioxin

Polybrominated dibenzo-p-dioxins (PBDDs) and mixed bromo/chloro dibenzo-p-dioxins (PXDDs) are persistent organic pollutants that can possess the same toxicity as their fully chlorinated analogs (PCDDs) and have been identified in the same matrices. Herein a general synthetic methodology is described to produce multiple congeners of PBDDs and PXDDs with varying degrees of halogenation and substitution patterns for use as analytical and/or internal standards, and for absorption, disposition, metabolism, and excretion (ADME) studies. The syntheses of PBDDs and PXDDs were accomplished by condensing a common precursor, 4,5-dibromo catechol, with variable precursors, i.e., polychlorinated 1-chloro-2-nitrobenzenes or polybrominated 1-fluoro-2-nitrobenzenes, to introduce a desired number of halogens and specific substitution patterns. Initial attempts to synthesize PBDDs and PXDDs were performed in potassium carbonate with DMSO at 145–150 °C. PXDDs syntheses resulted in formation of the desired products at >90% purity but attempts at higher brominated PBDDs syntheses resulted in dehalogenated by-products. To preclude by-product formation, additional syntheses for some PBDDs were conducted by refluxing the precursors in acetonitrile, which resulted in pure products at higher yield. Six PXDDs ranging from four to six halogens were synthesized (20–84% yield), of which three contained the halogen substitution pattern of 2,3,7,8. Five PBDDs ranging from four to six bromines were produced in 23–83% yield, three of which were toxic. Using the initial DMSO method, [14C]-1,3,7,8-tetrabromodibenzo-p-dioxin (0.26 μCi/μmol; 11% overall yield) was synthesized from commercially available [14C]-phenol to allow an ADME study to be conducted.

Computational investigation of the atmospheric oxidation reactions of polybrominated dibenzo-p-dioxins initiated by OH radicals

Density functional theory (DFT) method was used to study OH-initiated atmospheric oxidative reactions of some polybrominated dibenzo-p-dioxins (PBDDs). B3LYP functional and 6–311++G (2df,p) basis set were applied to optimize molecular structures of all stationary points involved in the investigated reactions. The rate constants for key elementary reactions were estimated by means of transition state theory. The computational results demonstrate that all addition reactions of PBDDs with OH radicals can occur spontaneously at standard conditions, however, the OH addition reactions are very slow due to low atmospheric concentration of OH radicals. Addition reactions occurring at γ-C position dominate in OH addition of all PBDDs. With the number of bromine atoms substituting at α-sites increases, the overall rate coefficients of OH addition decrease. The succeeding addition reactions of PBDD-OH adducts with O2 take place hardly both thermodynamically and kinetically. Abstraction reaction of H atoms by O2 is a governing route for PBDD-α(β)-adducts without bromine atoms at the same site, while the fused-ring CO bond fission is a main reaction channel for PBDD-γ-adducts, which will produce substituted phenoxy radicals.

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.

Brominated dioxins/furans and hydroxylated polybrominated diphenyl ethers: Occurrences in commercial 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and 2,4,6-tribromophenol, and formation during synthesis of BTBPE

Polybrominated dibenzo-p-dioxins (PBDDs) and hydroxylated polybrominated diphenyl ethers (OH-PBDEs) can be formed from bromophenols (BPs) by thermal degradation, biosynthesis or phototransformation. However, it is unknown whether PBDDs and OH-PBDEs can be formed during the chemical production processes that utilize BPs as raw materials. 2,4,6-tribromophenol (2,4,6-TBP) is an important raw material for the synthesis of 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), a novel brominated flame retardant. In this study, PBDDs, polybrominated dibenzofurans (PBDFs) and OH-PBDEs have been identified and quantified in commercially available BTBPE and 2,4,6-TBP. Furthermore, their formation as unintentional by-products during the laboratory synthesis of BTBPE from 2,4,6-TBP and 1,2-dibromoethane in the presence of sodium carbonate has also been investigated. 2,3,7,8-substituted PBDDs and PBDFs (2,3,7,8-PBDD/Fs) were undetectable in commercial samples of BTBPE and present in low levels (nanogram per gram) in 2,4,6-TBP. Two tetrabrominated dibenzo-p-dioxins (TeBDDs), namely 1,3,6,8- and 1,3,7,9-TeBDD, and three hydroxylated pentabrominated diphenyl ethers (OH-pentaBDEs), namely 4′-OH-BDE121, 2′-OH-BDE121, and 6′-OH-BDE100, were identified or tentatively identified, and quantitatively estimated to be at concentrations in the range of undetectable to several thousands of nanograms per gram in commercial BTBPE and 2,4,6-TBP. TeBDDs and OH-pentaBDEs were formed as by-products from 2,4,6-TBP during BTBPE synthesis. Further studies need to be conducted in order to determine whether PBDD/Fs and OH-PBDEs are also formed during the industrial synthesis of other chemical compounds that utilize BPs as raw materials or intermediates.

Characterization and inventory of PBDD/F emissions from deca-BDE, polyethylene (PE) and metal blends during the pyrolysis process

The thermal treatment of waste electrical and electronic equipment (WEEE) is regarded as the largest potential contributor to the environmental release of polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs). Herein, the pyrolysis of decabromodiphenyl ether (deca-BDE), polyethylene (PE) and metal blends was conducted to investigate the emission characteristics of PBDD/Fs at different thermal treatment conditions. The total yield of polybrominated dibenzo-p-dioxins (PBDDs) was less than that of polybrominated dibenzofurans (PBDFs) during the pyrolysis of the PE matrix and metal blends. 2,3,7,8-TBDF and 1,2,3,7,8-PBDF were the dominant congeners emitted from the pyrolysis. Temperature, presence of oxygen and type of added metal were the critical influencing factors for the PBDD/F formation rates and speciation in the pyrolysis process.

Theoretical Investigation on Mechanistic and Kinetic Transformation of 2,2',4,4',5-Pentabromodiphenyl Ether.

This study investigates the decomposition of 2,2',4,4',5-pentabrominated diphenyl ether (BDE99), a commonly detected pollutant in the environment. Debromination channels yielding tetrabrominated diphenyl ethers and hydrogen abstracting aromatic bromine atom formations play significant roles in the reaction of BDE99 + H, in which the former absolutely predominates bimolecular reactions. Polybrominated dibenzo-p-dioxins (PBDDs) and polybrominated dibenzofurans (PBDFs) can be produced during BDE99 pyrolysis, especially for PBDFs under inert conditions. The expected dominant pathways in a closed system are debromination products and PBDF formations. The bimolecular reaction with hydroxyl radical mainly leads to hydroxylated BDE99s rather than hydroxylated tetrabrominated diphenyl ethers. PBDDs are then generated from ortho-hydroxylated PBDEs. HO2 radical reactions rarely proceed. The total rate constants for the BDE99 reaction with hydrogen atoms and hydroxyl radicals exhibit positive dependence on temperature with values of 1.86 × 10(-14) and 5.24 × 10(-14) cm(3) molecule(-1) s(-1) at 298.15 K, respectively.

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.

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.

Occurrence of Brominated Persistent Organic Pollutants (PBDD/DFs, PXDD/DFs, and PBDEs) in Baltic Wild Salmon (Salmo salar) and Correlation with PCDD/DFs and PCBs

The contamination profiles of polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), diphenyl ethers (PBDEs), and mixed monobromo/chloro dibenzo-p-dioxins (PXDDs) and dibenzofurans (PXDFs) were determined in the tissue of Baltic wild salmon and compared with those of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs). Out of the analyzed PXDD/DFs, only the 3-B-2,7,8-triCDF was detected (in the concentration range of 0.039-0.075 pg g(-1) fresh weight (f.w.)). The toxic equivalents (TEQs) for analyzed PBDD/DFs (0.074-0.142 pg TEQ g(-1) f.w.) were found to contribute on average 2.1% to the total PCDD/DF-PBDD/DF-TEQ. The total concentrations of 27 PBDE congeners were in the range of 1.3-5.6 ng g(-1) f.w., with an average of 3.3 ng g(-1) f.w. The levels of PCDD/DFs and PCBs were found to be in the range of 4.53-14.6 pg WHO(2005)-PCDD/DF-PCB-TEQ g(-1) f.w., and concentrations of these compounds in most of the analyzed samples were above the maximum levels specified in Commission Regulation (EU) No. 1259/2011. Good correlation was observed between WHO(2005)-PCDD/DF-TEQ and WHO(2005)-PCB-TEQ (r(2) = 0.98), and these parameters were well correlated with the total sum of PBDE concentrations (r(2) = 0.91 and r(2) = 0.94, respectively). The results suggest that the consumption of Baltic wild salmon has no crucial impact on the average POP intake for typical Latvians.

OH-Initiated Oxidation Mechanisms and Kinetics of 2,4,4′-Tribrominated Diphenyl Ether

2,4,4'-Tribromodiphenyl ether (BDE-28) was selected as a typical congener of polybrominated diphenyl ethers (PBDEs) to examine its fate both in the atmosphere and in water solution. All the calculations were obtained at the ground state. The mechanism result shows that the oxidations between BDE-28 and OH radicals are highly feasible especially at the less-brominated phenyl ring. Hydroxylated dibrominated diphenyl ethers (OH-PBDEs) are formed through direct bromine-substitution reactions (P1∼P3) or secondary reactions of OH-adducts (P4∼P8). Polybrominated dibenzo-p-dioxins (PBDDs) resulting from o-OH-PBDEs are favored products compared with polybrominated dibenzofurans (PBDFs) generated by bromophenols and their radicals. The complete degradation of OH adducts in the presence of O2/NO, which generates unsaturated ketones and aldehydes, is less feasible compared with the H-abstraction pathways by O2. Aqueous solution reduces the feasibility between BDE-28 and the OH radical. The rate constant of BDE-28 and the OH radical is determined to be 1.79 × 10(-12) cm(3) molecule(-1) s(-1) with an atmospheric lifetime of 6.7 days.

Polybrominated Dibenzo-p-Dioxins, Dibenzofurans, and Biphenyls: Inclusion in the Toxicity Equivalency Factor Concept for Dioxin-Like Compounds

In 2011, a joint World Health Organization (WHO) and United Nations Environment Programme (UNEP) expert consultation took place, during which the possible inclusion of brominated analogues of the dioxin-like compounds in the WHO Toxicity Equivalency Factor (TEF) scheme was evaluated. The expert panel concluded that polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), and some dioxin-like biphenyls (dl-PBBs) may contribute significantly in daily human background exposure to the total dioxin toxic equivalencies (TEQs). These compounds are also commonly found in the aquatic environment. Available data for fish toxicity were evaluated for possible inclusion in the WHO-UNEP TEF scheme (van den Berg et al., 1998). Because of the limited database, it was decided not to derive specific WHO-UNEP TEFs for fish, but for ecotoxicological risk assessment, the use of specific relative effect potencies (REPs) from fish embryo assays is recommended. Based on the limited mammalian REP database for these brominated compounds, it was concluded that sufficient differentiation from the present TEF values of the chlorinated analogues (van den Berg et al., 2006) was not possible. However, the REPs for PBDDs, PBDFs, and non-ortho dl-PBBs in mammals closely follow those of the chlorinated analogues, at least within one order of magnitude. Therefore, the use of similar interim TEF values for brominated and chlorinated congeners for human risk assessment is recommended, pending more detailed information in the future.

Powerful GC-TOF-MS Techniques for Screening, Identification and Quantification of Halogenated Natural Products

Comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC×GC TOFMS) and gas chromatography/high-resolution time-of-flight mass spectrometry (GC-HRT) were used to detect and identify halogenated natural products (HNPs) in tissue homogenate, in this case brominated analytes present in a marine snail. Two classes of brominated anthropogenic compounds, polybrominated diphenyl ethers (PBDEs) and brominated dibenzofurans, were analyzed for comparison. Following conventional preparation, the sample was analyzed using GC×GC-TOF-MS. Isotope ratio scripts were used to compile a list of putatively brominated analytes from amongst the thousands of features resolved in the two-dimensional chromatogram. The structured nature of the chromatogram was exploited to propose identifications for several classes of brominated compounds, and include additional candidates that fell marginally outside the script tolerances. The sample was subsequently analyzed by GC-HRT. The high-resolution mass spectral data confirmed many formula assignments, facilitated confident assignment of an alternate formula when an original proposal did not hold, and enabled unknown identification. Identified HNPs include hydroxylated and methoxylated PBDE analogs, polybrominated dibenzo-p-dioxins (PBDDs) and hydroxyl-PBDDs, permitting the environmental occurrence and fate of such compounds to be studied.

Photochemical Formation of Polybrominated Dibenzo-p-dioxins from Environmentally Abundant Hydroxylated Polybrominated Diphenyl Ethers

High levels of polybrominated dibenzo-p-dioxins (PBDDs) have been found in Baltic Sea biota, where the toxic load owing to, for example, polychlorinated dibenzo-p-dioxins and other organic pollutants is already high. The levels and geographic pattern of PBDDs suggest biogenic rather than anthropogenic origin, and both biotic and abiotic formation pathways have been proposed. Photochemical formation from hydroxylated polybrominated diphenyl ethers (OH-PBDE) is a proposed pathway for PBDDs in marine environments. Ultraviolet radiation-initiated transformations of OH-BDEs 47, 68, 85, 90, 99, and 123, which all are abundant in the environment, were investigated. It was shown that the most abundant PBDDs in the environment (1,3,7-triBDD and 1,3,8-triBDD) can be formed from the most abundant OH-BDEs (OH-BDE 47 and OH-BDE 68) at high rates and with percentage yields. In fact, most of the PBDDs that have been identified in the Baltic Sea environment were formed with high yield from the six studied OH-PBDE, through initial cyclization and subsequent debromination reactions. The high formation yields point to this route as an important source of PBDDs in biota. However, congeners showing relatively high retention in fish, specifically 1,3,6,8- and 1,3,7,9-tetraBDD, were not formed. These are likely formed by enzymatic coupling of brominated phenols.

Formation of Environmentally Relevant Brominated Dioxins from 2,4,6,-Tribromophenol via Bromoperoxidase-Catalyzed Dimerization

Polybrominated dibenzo-p-dioxins (PBDD) are emerging environmental pollutants with structural similarities to the highly characterized toxicants polychlorinated dibenzo-p-dioxins. The geographical and temporal variations of PBDD in biota samples from the Baltic Sea do not display features that are normally related to anthropogenic sources such as incineration, and therefore the natural formation of PBDDs has been suggested. This study of the bromoperoxidase mediated oxidative coupling of 2,4,6-tribromophenol (an abundant substance that is naturally formed in marine systems) identified the formation of ppb-level yields of 1,3,6,8-tetrabromodibenzo-p-dioxin (1,3,6,8-TeBDD) through direct condensation. Additional TeBDDs (1,3,7,9-TeBDD, 1,2,4,7-TeBDD, and/or 1,2,4,8-TeBDD) and tri-BDDs (1,3,7-TrBDD and 1,3,8-TrBDD) were frequently formed but at lower yields. The formation of these TeBDDs probably proceeds via bromine shifts or Smiles rearrangements, whereas the TrBDDs may result from subsequent debromination processes. Because all of the congeners formed by oxidative coupling and subsequent reactions are also found in Baltic Sea biota, the results support the theory that PBDDs are formed from natural precursors.

Retention and maternal transfer of environmentally relevant polybrominated dibenzo‐p‐dioxins and dibenzofurans, polychlorinated dibenzo‐p‐dioxins and dibenzofurans, and polychlorinated biphenyls in zebrafish (Danio rerio) after dietary exposure

High levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), mono- and non-ortho-polychlorinated biphenyls (PCBs), and polybrominated dibenzo-p-dioxins (PBDDs) are found in fish from coastal areas in the Baltic Sea, which may cause ecotoxicological effects. To increase our understanding of the persistency of the emerging pollutants polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), fish feed was spiked with 21 PBDD/Fs, 17 PCDD/Fs, and 30 PCBs and fed to zebrafish (Danio rerio). Concentrations in fish and eggs were examined during a 6- or 12-week uptake period, and a 6-week elimination period. Steady-state was reached for 2-, 3-, 7-, and/or 8-substituted tri- and tetra-BDD/Fs; 2,3,7,8-tetra-BDD (2,3,7,8-TeBDD) was the most strongly retained. Steady-state was not reached for tetra- to hexa-CDDs. Non-2,3,7,8 congeners showed little or no retention. Most PCBs had high retention and did not reach steady state. Half-lives decreased in the order PCBs > PCDD/Fs > PBDD/Fs. Concentrations of 2,3,7,8-substituted penta- to octa-CDD/Fs decreased with their degree of chlorination, suggesting that the rate-limiting factor for uptake is low bioavailability. Maternal transfer was observed for all retained compounds, with most transfer factors <1, indicating that transfer rates are affected by the poor water solubility of the compounds. The limited retention of the major PBDD congeners found in Baltic Sea fish suggests that they are exposed to high or very high concentrations via either food or water.

Brominated phenols, anisoles, and dioxins present in blue mussels from the Swedish coastline.

Naturally occurring hydroxylated polybrominated diphenyl ethers (OH-PBDEs), their methoxylated counterparts (MeO-PBDEs), and polybrominated dibenzo-p-dioxins (PBDDs), together with their potential precursors polybrominated phenols (PBPs) and polybrominated anisoles (PBAs), were analyzed in blue mussels (Mytilus edulis) gathered along the east coast (bordering the Baltic Sea) and west coast of Sweden (bordering the North Sea). Brown algae (Dictyosiphon foenicolaceus) and cyanobacteria (Nodularia spumigena) from the Baltic Sea, considered to be among the primary producers of these compounds, were also analyzed for comparison. The samples were liquid-liquid extracted, separated into a phenolic and a neutral fraction, and subsequently analyzed by gas chromatography-mass spectrometry (GS-MS). The levels of OH-PBDEs, MeO-PBDEs and PBDDs were significantly higher in Baltic Sea mussels than in those from the west coast, whereas the levels of PBPs and PBAs displayed the opposite pattern. The blue mussels from the Baltic Sea contained high levels of all analyzed substances, much higher than the levels of, e.g., polybrominated diphenyl ethers. In addition, the GC-MS chromatogram of the phenolic fraction of the west coast samples was dominated by four unknown peak clusters, three of which were tentatively identified as dihydroxy-PBDEs and the other as a hydroxylated-methyl-tetraBDE. Clearly, all of the compounds analyzed are natural products, both in the Baltic and the North Sea. However, the geographical differences in composition may indicate different origin, e.g., due to differences in the occurrence and/or abundance of various algae species along these two coasts or possibly a more extensive dilution on the west coast.