Thermal formation of polybrominated dibenzofurans and dioxins from decabromodiphenyl ether flame retardant: Influence of antimony(III) oxide and the polymer matrix

While pure decabromodiphenyl ether forms highly brominated PBDF in combustion at 700°C in yields of ca. 7000 ppm the yield is significantly increased up to 16 percent in the polymeric matrix and the presence of antimony(III) oxide. Combustion of the ternary mixture results in a decrease of the temperature maximum to 500°C; the ratio of isomers is changed to lower brominated PBDF with the tetrabromo compounds as most abundant products.     

Electrolytic debromination of PBDEs in DE-83 technical decabromodiphenyl ether

Electrochemical debromination of the commercial decabromodiphenyl ether flame retardant DE-83 in partly aqueous tetrahydrofuran (THF) solution gave lower brominated congeners by sequential loss of bromine atoms. Hydrodebromination was most facile for the most heavily brominated congeners. It involves initial electron transfer and proton transfer from water, rather than hydrogen atom abstraction from THF, as shown by experiments with deuterated water. The product distribution from electrolysis involves preferential loss of bromine meta- and para- to the ether linkage, comparable with the products of metabolism of BDE-209 in various organisms. Significantly, the environmentally relevant congeners BDE-47, BDE-99, and BDE-154 were not major products of debromination of BDE-209 by the electron transfer mechanism.     

Determination of polybrominated diphenyl ethers and PBDD/Fs during the recycling of high impact polystyrene containing decabromodiphenyl ether and antimony oxide

A high impact polystyrene (HIPS) plastic, flame retarded with decabromodiphenyl ether (DecaBDE) and antimony trioxide (Sb2O3) has been repeatedly processed and the amount of debromination of the flame retardant and possible formation of PBDD/F was monitored. No indications of debromination were found. The reprocessed (recycled) plastic was found to comply with the German Chemicals Banning Ordinance. The concentrations of relevant PBDD/F congeners were at least one order of magnitude below the regulated limit values for PBDD/F (1 ppb for the sum of four congeners, 5 ppb for the sum of all eight regulated congeners).     

Study of the transference rules for bromine in waste printed circuit boards during microwave-induced pyrolysis

The production of waste printed circuit boards (WPCBs) has drawn increasing global concern, especially because the high bromine (Br) content (5-15%) places obstacles in the way of simple disposal techniques. Microwave-induced pyrolysis of WPCBs provides a promising way to dispose of these hazardous and resource-filled wastes. The transference rules for Br during microwave-induced pyrolysis have been investigated experimentally. It was found that the microwave energy could be used more efficiently to accelerate the heating rate and improve the final pyrolysis temperature by adding some activated carbon (AC) as microwave absorbents. The high temperature and rapid pyrolysis process promoted the yields of gaseous products and the decomposition of brominated compounds into hydrogen bromide and then benefited the capture of Br and the debromination of byproducts. The application of a calcium carbonate (CaCO3) layer overhead led to over 95% debromination of the liquid products and over 50% capture of the total Br. It can be concluded that the presented method is suitable for the control of Br transference in the recycling of WPCBs. This method can also be extended to the disposal of the electronic scraps.     

The individual and cumulative effect of brominated flame retardant and polyvinylchloride (PVC) on thermal degradation of acrylonitrile-butadiene-styrene (ABS) copolymer

Acrylonitrile-butadiene-styrene (ABS) copolymers without and with a polybrominated epoxy type flame retardant were thermally degraded at 450 degrees C alone (10 g) and mixed with polyvinylchloride (PVC) (8 g/2 g). Gaseous and liquid products of degradation were analysed by various gas chromatographic methods (GC with TCD, FID, AED, MSD) in order to determine the individual and cumulative effect of bromine and chlorine on the quality and quantity of degradation compounds. It was found that nitrogen, chlorine, bromine and oxygen are present as organic compounds in liquid products, their quantity depends on the pyrolysed polymer or polymer mixture. Bromophenol and dibromophenols were the main brominated compounds that come from the flame retardant. 1-Chloroethylbenzene was the main chlorine compound observed in liquid products. It was also determined that interactions appear at high temperatures during decomposition between the flame retardant, PVC and the ABS copolymer.     

Alkaline hydrothermal treatment of brominated high impact polystyrene (HIPS-Br) for bromine and bromine-free plastic recovery

A method to recover both Br and Br-free plastic from brominated flame retardant high impact polystyrene (HIPS-Br) was proposed. HIPS-Br containing 15% Br was treated in autoclave at 280 degrees C using water or KOH solution of various amounts and concentrations. Hydrothermal treatment (30 ml water) leads to 90% debromination of 1g HIPS-Br but plastic is strongly degraded and could not be recovered. Alkaline hydrothermal treatment (45 ml or 60 ml KOH 1M) showed similar debromination for up to 12 g HIPS-Br and plastic was recovered as pellets with molecular weight distribution close to that of the initial material. Debromination occurs at melt plastic/KOH solution interface when liquid/vapour equilibrium is attained inside autoclave (280 degrees C and 7 MPa in our experimental conditions) and depends on the plastic amount/KOH volume ratio. The antimony oxide synergist from HIPS-Br remains in recovered plastic during treatment. A pictorial imagination of the proposed debromination process is presented.     

Pyrolysis of tetrabromobisphenol-A containing paper laminated printed circuit boards

Tetrabromobisphenol-A (TBBA) is the most common brominated fire retardant. In this study, a TBBA containing paper laminated printed circuit board (PCB) prepared from novolac was pyrolysed by both TGA and in a quartz glass reactor between 40 and 1,000 degrees C. The products were online detected by MS. It was found that the PCB degraded in three steps. Step one (<270 degrees C) consisted of the evolution of water and CO(2) from the paper laminate. In the second step, between 270 and 370 degrees C, the fire retardant decomposed, releasing HBr and brominated aromatics. In the third step, at temperatures above 370 degrees C, the phenol resin decomposed and char was formed. Compared to pure TBBA, which mainly produces brominated phenols, the brominated products enclosed in the char released HBr during the last degradation step as well as during the second step. Most of the bromine left the resin in the form of HBr, with about 14% of the bromine being fixed in brominated aromatics and less than 2% remaining in the residue.     

Physicochemical properties of selected polybrominated diphenyl ethers and extension of the UNIFAC model to brominated aromatic compounds

The aqueous solubilities (S(w)) at various temperatures from 283 K to 308 K and 1-octanol/water partition coefficients (K(ow)) for four polybrominated diphenyl ethers (PBDEs: 4,4'-dibromodiphenyl ether (BDE-15), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153)) were measured by the generator column method. The S(w) and K(ow) data revealed the effect of bromine substitution and basic structure on S(w) and K(ow). To estimate the infinite dilution activity coefficients (gamma(i)(w,infinity)) of the PBDEs in water from the S(w) data, enthalpies of fusion and melting points for those compounds were measured with a differential scanning calorimeter. Henry's Law constants (H(w)) of the PBDEs were derived from the determined gamma(i)(w,infinity) and literature vapor pressure data. Some physicochemical characteristics of PBDEs were also suggested by comparing the present property data with that of polychlorinated dibenzo-p-dioxins, brominated phenols and brominated benzenes in past studies. Furthermore, in order to represent different phase equilibria including solubility and partition equilibrium for other brominated aromatic compounds using the UNIFAC model, a pair of UNIFAC group interaction parameters between the bromine and water group were determined from the S(w) and K(ow) data of PBDEs and brominated benzenes. The ability of the determined parameters to represent both properties of brominated aromatics was evaluated.     

PVC-induced chlorine-bromine exchange in the pyrolysis of polybrominated diphenyl ethers, -biphenyls, -dibenzodioxins and dibenzofurans

Extensive chlorine-for-bromine exchange occurs when 1,2,3,4-tetrabromodibenzodioxin (TBrDD), polybromodibenzodioxin/furan mixtures (PBrDD/F), and technical brominated diphenyl ethers and -biphenyls are pyrolyzed at 800°C in the presence of PVC. Tetra-ClDD, BrCl₃DD, Br₂Cl₂DD, and Br₃ClDD could be detected from the pyrolysis of 1,2,3,4-TBrDD. A number of chloro/bromodibenzodioxins and furans as well as chlorinated dibenzodioxins and furans are formed in the residues of the PBrDD/F mixtures. Only chlorinated and chlorinated/brominated diphenyl ethers and no dioxins and furans occured during the pyrolysis of brominated diphenyl ethers in the presence of PVC. Through the exchange of bromine with chlorine, chlorinated and chlorinated/brominated biphenyls could be detected from the pyrolysates of hexabromobiphenyl.     

润滑油废白土的热解处理

以润滑油废白土为原料,利用电热解法,研究了热解终温、加热速率和CaO添加量对热解产物的影响。实验结果表明:热解终温对热解产物的影响最为显著。随着热解终温的升高,不凝气产量和产油率均迅速增加。当热解终温达到600℃时,其增加的速率逐渐缓慢增大。当控制热解终温为800℃、加热速率为16℃/min、CaO添加量为0.5%时,富氢气体产量为189.2 L/kg,气体中主要成分为H2和CH4,其含量分别为27.97%和41.64%;热解残渣含油率和重金属溶出物均低于标准规定值,热解油产率为10.98%,回收率为38.94%,其主要成分为汽油、柴油和重油3部分组成,分别含19.13%、31.35%和49.52%。     

Combustion of flame retardants

2,4,6-Tribromoaniline (TBA) is used in the preparation of various dyes, polymers, and, in combination with antimony trioxide, as a flame retardant in the textile and plastic industry. Pyrolysis studies of TBA done previously in our laboratory indicated the presence of some potentially toxic nitrogen analogs of dioxins. Combustion of TBA was further studied using a flame to simulate the conditions of an incinerator; it was observed that, along with the formation of phenazines, small but significant amounts of brominated benzidines and carbazoles were also formed.     

Methods for synthesis of nonabromodiphenyl ethers and a chloro-nonabromodiphenyl ether

Polybrominated diphenyl ethers (PBDEs) have been used extensively as brominated flame retardants (BFRs) in textiles, upholstery and electronics. They are ubiquitous contaminants in wildlife and humans. A low concentration of nonabrominated diphenyl ethers (nonaBDEs) is present in commercial DecaBDE and they are also abiotic and biotic debromination products of decabromodiphenyl ether (BDE-209). The objective of the present work was to develop methods for synthesis of the three nonaBDEs, 2,2',3,3',4,4',5,5',6-nonabromodiphenyl ether (BDE-206), 2,2',3,3',4,4',5,6,6'-nonabromodiphenyl ether (BDE-207) and 2,2',3,3',4,5,5',6,6'-nonabromodiphenyl ether (BDE-208), with the intention of making them available as authentic standards for analytical, toxicological and stability studies, as well as studies regarding physical-chemical properties. Two methods were developed, one based on perbromination of phenoxyanilines and the other via reductive debromination of BDE-209 by sodium borohydride followed by chromatographic separation of the three nonaBDE isomers formed. An additional nonabrominated compound, 4'-chloro-2,2',3,3',4,5,5',6,6'-nonabromodiphenyl ether (Cl-BDE-208), was also synthesized in the present work. Cl-BDE-208, prepared by the perbromination of 4-chlorodiphenyl ether, may be used as an internal standard in analysis of highly brominated diphenyl ethers. BDE-206, BDE-207, BDE-208 and Cl-BDE-208 were characterized by 1H NMR, 13C NMR, electron ionization mass spectra and by their melting points. The structures of all three nonaBDEs have been characterized previously by X-ray crystallography.     

Effect of Tween 80 and beta-cyclodextrin on degradation of decabromodiphenyl ether (BDE-209) by White rot fungi

The environmental safety of decabromodiphenyl ether (BDE-209), a widely used flame retardant, has been the topic of controversial discussions during the past several years. Degradation of BDE-209 into lower brominated diphenyl ether congeners, exhibiting a higher bioaccumulation potential, has been a critical issue. White rot fungi are known to degrade a wide variety of recalcitrant pollutants. In this work, white rot fungi were used to degrade BDE-209 in liquid culture medium, and the effects of Tween 80 and beta-cyclodextrin on BDE-209 degradation by white rot fungi were evaluated. On the basis of these results, it appears that BDE-209 could be degraded by white rot fungi, and Tween 80 and beta-cyclodextrin can both increase the biodegradation. The best result in Tween 80 experiments was obtained at a Tween 80 concentration of 500mgl(-1) within 10d, which showed 96.5% (w/w) BDE-209 transformed. Tween 80 at a high concentration will restrain the fungal growth and the degradation of BDE-209. However, beta-cyclodextrin had positive effects both on the BDE-209 degradation and the fungal growth.     

Synergistic degradation of deca-BDE by an enrichment culture and zero-valent iron

Debromination of decabromodiphenyl ether (deca-BDE) by microbe and by zero-valent iron (ZVI) has been reported previously. However, no study has indicated the presence of microorganisms and their effect on ZVI-mediated reduction of deca-BDE. Synergistic degradation of deca-BDE by an enrichment culture and ZVI was studied. It was found that synergistic effects enhanced the debromination of deca-BDE as well as promoting the reduction of lower brominated products. ZVI stimulated microbial debromination by serving as an electron donor. Correlation analysis also confirmed that ZVI was capable of enhancing microbial population in the debromination of deca-BDE. Conversely, the enrichment culture produced acid which maintained pH stability and stimulated the oxidation of ZVI. The enrichment culture supplied its energy requirements by the oxidation of ZVI and concomitant reduction of deca-BDE, but incapable of growth and reduction of BDE-209 without ZVI and vice versa. Compared to the initial culture, the microbial community of the enrichment culture became dominated by several bacterial genera based on the results of 16S rRNA-gene pyrosequencing.     

Polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) and monobromo-polychlorinated dibenzo-p-dioxins/dibenzofurans (MoBPXDD/Fs) in the atmosphere and bulk deposition in Kyoto, Japan

Polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) and monobromo-polychlorinated dibenzo-p-dioxins/dibenzofurans (MoBPXDD/Fs) in atmosphere, bulk atmospheric deposition and soil in Kyoto, which is an urban city in Japan, were measured. Decabromodiphenyl ether (D(10)BDE, BDE-209) was detected in relatively high concentrations compared to other PBDE congeners in most samples. Similar results, in which D(10)BDE was predominantly detected, were reported in other studies in Japan. However, these homologue profiles differ from those of studies conducted in North America. The partitioning of semivolatile organic compounds between atmospheric gas phase and particulate-associated phase is an important factor in their environmental behavior. In this study, atmospheric particulate phase fraction (f(P)) of the brominated compounds increased with increasing bromine number, and f(P) was higher in samples collected in winter than in those collected in summer. Moreover, f(P) of PBDFs and MoBPXDFs was higher than that of PCDFs with the same halogen number. These results agree well with expectations from the vapor pressure of the brominated compounds and PCDD/Fs. Among the brominated compounds in the atmosphere, the level of MoBPXDD/Fs correlates positively with that of PCDD/Fs. This relationship has been previously observed in waste incineration samples. These results suggest that one of the sources of MoBPXDD/Fs in the atmosphere is incineration byproduct. The level of PBDD/Fs seems to correlate positively with that of PBDEs. This relationship suggest that the PBDD/Fs in the atmosphere relate to PBDEs, which is an impurity of PBDE products, or formed by the manufacture or combustion of plastics containing PBDEs.     

A spectroscopic study of the bromination of the endocrine disruptor ethynylestradiol

Bromination of ethynylestradiol (EE2) was studied using fluorescence and conventional and stopped-flow absorbance spectroscopy. EE2 transformations in the presence of bromine were determined to proceed through sequential reactions. The first step is very rapid and results in the formation of a brominated cyclohexadienone that is susceptible to reduction but in oxidative conditions it undergoes a transformation into monobromo-EE2 in a first-order OH- -accelerated reaction. The transformation from monobromo-EE2 to dibromo-EE2 follows a similar mechanism. The rates of reactions of bromine-substituted EE2 species are orders of magnitude lower than that of the parent compound indicating that these species can persist in conditions typical for water treatment operations.     

Surface catalyzed halogenation-dehalogenation reactions of aromatic bromine compounds adsorbed on fly ash

Brominated aromatic compounds like brominated benzenes, diphenylethers and dibenzodioxins adsorbed on the surface of fly ash from a municipal waste incininerator give mixed brominated/chlorinated und completely chlorinated aromatic compounds. These consecutive halogenation-dehalogenation reactions proceed by a nucleophilic mechanism, which is favoured by a high concentration of chloride on the fly ash. Results of kinetic and stereoselective behavior of these reactions will be discussed. The relevance of these results for PCDD/PCDF formation from bromine precursors in municipal waste incinerators will be discussed.     

Bromination of 2-methoxydiphenyl ether to an average of tetrabrominated 2-methoxydiphenyl ethers

Brominated 2-phenoxyanisoles (2-methoxydiphenyl ethers, 2-MeO-BDEs) are a class of halogenated natural products, produced by algae and sponges. Especially two tetrabrominated isomers, i.e. 2′-MeO-BDE 68 (BC-2) and 6-MeO-BDE 47 (BC-3), have also been frequently determined in environmental and food samples. In addition, 2-MeO-BDEs are under discussion as metabolites of polybrominated diphenyl ethers (PBDEs). In this study, we synthesized the backbone 2-methoxydiphenyl ether and brominated it to an average degree of four bromine substituents. The reaction mixture only contained one major product (∼90%) along with three further MeO-BDEs and ∼5% hydroxylated BDEs. In all likelihood, the HO-BDEs were formed in a side reaction by cleavage of the methoxy group. The major MeO-BDE was identified as 6′-methoxy-2,3′,4,4′-tetrabromodiphenyl ether (6′-MeO-BDE-66). The HO-BDEs were separated by KOH/n-hexane partitioning, and the resulting 2-MeO-BDEs were fractionated by means of high-speed counter-current chromatography (HSCCC). Due to the excellent enrichment facilities of HSCCC, some 15 MeO-BDEs, mainly present at traces only, could be detected in 26 fractions, and eight of them could be characterized by nuclear magnetic resonance spectroscopy (NMR). Only two of the compounds - 2′-MeO-BDE 68 and 6-MeO-BDE 123 - had been characterized as natural products while the prominent halogenated natural product 6-MeO-BDE 47 was not detected at all in the reaction product. The “non-natural” 2-MeO-BDEs may be useful internal standards in trace analysis.     

Non-polar halogenated natural products bioaccumulated in marine samples. II. Brominated and mixed halogenated compounds

Several identified and potential natural brominated bioaccumulative compounds were studied in this work. 4,6-dibromo-2-(2('),4(')-dibromo)phenoxyanisole (BC-2) previously detected in Australian marine mammals and isolated from sponges, was synthesized. Two byproducts (a tetrabromo isomer and a tribromo congener) were investigated as well. The byproducts of the synthesis were not identified in the environmental samples investigated. Previously described natural brominated compounds (BC-1, BC-2, BC-3, BC-10, BC-11, MHC-1) and anthropogenic brominated diphenyl ethers (BDE-47, BDE-99, BDE-100, BDE-154) were detected in a sample of human milk. The sample was from a woman from the Faeroe Islands who frequently consumed fish as well as whale blubber and meat. The most abundant compound originated from the natural tetrabromo phenoxyanisole BC-3 which may have a 3:1 distribution of bromine on the two phenyl units. This sample also accumulated a dibromochloroanisole, as well as a previously unknown mixed halogenated compound (MHC-X) and an unknown, most likely aromatic brominated compound. Co-elutions on a DB-5 column were found for BDE-99 and BC-11 as well as BDE-154 and the unknown brominated compound. This suggests that quantification of these two compounds has to be carried out carefully.Two samples of lower trophic level, namely Baltic cod liver and Mexican mussel tissue, were investigated as well. The cod liver samples contained BDE congeners but also abundant signals for the natural 2,3,3('),4,4('),5,5(')-heptachloro-1(')-methyl-1,2(')-bipyrrole Q1 and tribromoanisole (TBA). The mussel sample contained Q1, TBA, another halogenated anisole, BC-1, BC-2, and BC-3, as well as additional, potential natural brominated compounds in the elution range of tribromophenoxyanisoles.