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.     

Sodium borohydride reduction of individual polybrominated diphenyl ethers

Many chemicals in use today lack appropriate documentation on their environmental properties, fate, and effects. To counteract this lack of documentation it is vital to thoroughly investigate a compound’s fate in the environment before it comes into use. The present study is describing a novel method for assessing the reduction potential of polybrominated diphenyl ethers (PBDEs), as a part of a project aimed to create an experimental model for determination of chemical persistence. The reductive transformation of 15 PBDE congeners using sodium borohydride was determined. Pseudo-first-order reaction rate constants of the transformations were determined by monitoring the disappearance of the investigated congeners. The reductions lead primarily to formation of lower brominated PBDEs. Each PBDE congener was tested in a total of ten replicates which showed a relative standard deviation of 31% or less. The decaBDE, BDE-209 was approximately 3 times as prone to reductive transformation as BDE-207. The three nonaBDEs, BDE-206, BDE-207, and BDE-208, showed similar reductive potential. The reactivity of the tested octaBDEs was quite variable, from 5% to 24% of the reactivity of BDE-209 for BDE-196 and BDE-198, respectively. The heptaBDEs studied were in the range of the less reactive octaBDEs, except for BDE-181 which was as high as 13% of the reactivity of BDE-209. The results presented give a method for measuring the propensity of PBDEs, and possibly similar compounds, to undergo reductions. They indicate a potential route to a vital piece of information in the assessment of environmental persistence of chemicals.     

Dietary exposure of juvenile common sole (Solea solea L.) to polybrominated diphenyl ethers (PBDEs): Part 1. Bioaccumulation and elimination kinetics of individual congeners and their debrominated metabolites

The uptake and elimination of six PBDE congeners (BDE-28, -47, -99, -100, -153, -209) were studied in juvenile common sole (Solea solea L.) exposed to spiked contaminated food over a three-month period, then depurated over a five-month period. The results show that all of the studied PBDEs accumulate in fish tissues, including the higher brominated congener BDE-209. Several additional PBDE congeners were identified in the tissues of exposed fish, revealing PBDE transformation, mainly via debromination. The identified congeners originating from PBDE debromination include BDE-49 and BDE-202 and a series of unidentified tetra-, penta-, and hepta- BDEs. Contaminant assimilation efficiencies (AEs) were related to their hydrophobicity (log K_ow) and influenced by PBDE biotransformation. Metabolism via debromination appears to be a major degradation route of PBDEs in juvenile sole in comparison to biotransformation into hydroxylated metabolites.     

Photochemical degradation of six polybrominated diphenyl ether congeners under ultraviolet irradiation in hexane

The photodegradation of six individual PBDE congeners (BDE-28, 47, 99, 100, 153, 183) in hexane was investigated under UV light in the sunlight region, employing a mercury lamp filtered with Pyrex glass. All photodegradation reactions followed the pseudo-first-order kinetics, with the half-lives ranging from 0.26h for BDE-183 to 6.46h for BDE-100. The photochemical reaction rates of PBDEs decreased with decreasing number of bromine substituents in the molecule, also in some cases were influenced by the PBDE substitution pattern. Principal photoproducts detected were less brominated PBDEs, and no PBDE-solvent adducts were found. Consecutive reductive debromination was confirmed as the main mechanism for the photodegradation of PBDEs in hexane. In general, debromination firstly occurred on the more substituted rings, when the numbers of bromine atoms on the two phenyl rings were unequal. For less brominated PBDEs, the photoreactivity of bromines at various positions of phenyl rings decreased in the order: ortho>para; while for higher brominated PBDEs, the difference became not significant.     

Bioaccumulation kinetics of sediment-associated DE-83 in benthic invertebrates (Nereis succinea, polychaete)

Polychaetes (Nereis succinea) were exposed to DE-83 contaminated sediments to investigate the bioaccumulation and bioavailability of nona- and deca-BDEs in sediment. All the major congeners in DE-83 were bioavailable to the lugworms. The uptake coefficients (K_s) of nona- and deca-BDE congeners in lugworms were in the range of 0.18-0.65 (d⁻¹), with the values of BDE-207 and -208 slightly higher than those of BDE-206 and -209. Elimination of nona- and deca-BDE congeners from lugworms was very fast. The estimated half-lives of nona- and deca-BDE congeners in the lugworms were at 0.7 d. The bioavailability of nona- and deca-BDE congeners was very low, with BSAF of 0.017 for BDE-206 and -209 and 0.054 for BDE-207 and -208. These may be due to the large molecular size and high affinity of PBDEs to sediment particles. The contribution of BDE-206 in the profile of nona-BDEs in lugworm tissue decreased with exposure time while those of BDE-207 and -208 increased, which could be the result of the biotransformation of BDE-209 to BDE-207 and -208.     

Polybrominated diphenyl ether exposure to electronics recycling workers--a follow up study

Workers at an electronics recycling plant have previously been shown to have elevated serum levels of polybrominated diphenyl ethers (PBDEs) compared to referents without occupational PBDE exposure. Subsequent structural changes and industrial hygiene measures at the plant were applied to improve the work environment. The present study aims to assess the impact of these work environment changes on the occupational exposure to PBDEs.

Blood were drawn from the workers and analyzed at two different laboratories, and serum concentrations of several PBDE congeners were determined by GC/MS or GC/HRMS. Cross-sectional studies were performed prior to (in 1997; N = 19) and after (in 2000; N = 27) workplace improvements. Longitudinal studies were performed on twelve of the workers that were sampled at both occasions.

Even though the amount of processed goods had doubled in 2000 as compared to 1997, there was a significant decrease in the serum levels of BDE-183 and BDE-209. For BDE-209 the levels observed in year 2000 were even lower than in referents with no occupational exposure. In contrast to the decrease of higher brominated diphenyl ethers, the concentrations of BDE-47 did not significantly change. For BDE-153, the cross-sectional study indicated no change, whereas the longitudinal follow up indicated a significant increase.

This study shows that the industrial hygiene improvements clearly reduced the occupational exposure to BDE-183 and BDE-209 at the plant. Still, the levels of hexa- to nonaBDEs but not BDE-209 were elevated, compared to referents with no occupational exposure.     

Fate of PBDEs during food processing: Assessment of formation of mixed chlorinated/brominated diphenyl ethers and brominated dioxins/furans

The aim of this study was to evaluate effects of food processing on PBDE levels, in particular influence of heat treatment on degradation of PBDEs, including possible formation of chlorinated diphenyl ethers or brominated dioxins/furans as degradation products. It was shown that PBDEs heated in the presence of chlorine (from either organic or inorganic sources) formed mixed chlorinated/brominated diphenyl ethers. However, no PCDEs were formed in the presence of lipids. Lipid medium increased stability of PBDEs exposed to UV irradiation. Profile of congeners formed in result of the debromination reaction was significantly different than profiles observed by some other authors in aliphatic organic solvents. Grilling processes increased concentrations (calculated on the fresh product basis) of the studied compounds by 4–8/22–34% for electric/coal grill, respectively. Depending on the congener and on the applied heat treatment, PBDE mass in pork meat after grilling dropped by 26–53%. No detectable quantities of either brominated dioxins or furans were formed during thermal processing of food containing typical levels of PBDEs.     

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.     

PBDEs in leachates from municipal solid waste dumping sites in tropical Asian countries: phase distribution and debromination

Polybrominated diphenyl ethers (PBDEs) are extensively used as flame retardants in many consumer products, and leachates from landfills have been identified as one of the possible sources of PBDEs in the environment. Meanwhile, the unprecedented economic and population growths of some Asian countries over the last decade have led to significant increases in the amount of waste containing PBDEs in that region. This study investigates the status of PBDEs in leachates from municipal solid waste dumping sites (MSWDS) in tropical Asian countries. A total of 46 PBDE congeners were measured, both in the adsorbed (n?=?24) and dissolved (n?=?16) phases, in leachate samples collected, from 2002 to 2010, from ten MSWDS distributed among the eight countries of Lao PDR, Cambodia, Vietnam, India, Indonesia, Thailand, the Philippines, and Malaysia. PBDEs were predominantly found in the adsorbed phase. Partitioning of PBDEs in the dissolved phase was associated with the presence of dissolved organic matter; the apparent organic carbon-normalized partition coefficients (K′_oc) of the BDE congeners were lower by two to four orders of magnitude than the K _oc predicted from the octanol–water partition coefficients (K _ow). The total PBDE concentrations from mono- to deca-BDEs ranged from 3.7 to 133,000 ng/L, and showed a trend toward higher concentrations in the more populous and industrialized Asian countries. The congener profiles in the leachates basically reflected the composition of PBDE technical mixtures. The occurrence of congeners not contained, or in trace concentrations, in technical products (e.g., BDEs 208, 207, 206, 202, 188, 179, 49, 17/25, 8, 1) was observed in most of the leachate samples, suggesting the debromination of technical mixtures, including BDE-209, in the MSWDS of tropical Asian countries. Moreover, the temporal trend indicated the reduction of BDE-209 over time, with a corresponding increase in and/or emergence of lower brominated PBDE congeners. The results indicated that MSWDS of tropical Asian countries are potential sources of environmental PBDEs, which may be transported to the aquatic environment via dissolution with dissolved organic matter. MSWDS could be amplifiers of PBDE toxicity in the environment, possibly through debromination.     

Bioaccumulation, maternal transfer and elimination of polybrominated diphenyl ethers in wild frogs

To investigate bioaccumulation, maternal transfer and elimination of polybrominated diphenyl ethers (PBDEs) in amphibians, we collected adult frogs (Rana limnocharis) from a rice field in an e-waste recycling site in China. We found that ∑PBDEs in the whole frogs and various tissues (brain, liver, testis and egg) ranged from 17.10 to 141.11 ng g⁻¹ wet weight. Various tissues exhibited a similar PBDE congener profile, which was characterized by intermediate brominated congeners (BDE-99 and BDE-153) as the largest contributors, with less lower brominated congeners (BDE-28 and BDE-47) and higher brominated congeners (BDE-209). The maternal transfer capacity of PBDEs declined with the increase in bromine numbers of PBDE congeners. We suggest that the bromine atom number (the molecular size, to some degree) might be a determining factor for the maternal transport of a PBDE congener rather than K_ow (Octanol-Water partition coefficient), which expresses a compound’s lipophilicity. ∑PBDEs concentrations in frogs decreased over time during a depuration period of 54 days when these wild frogs were brought to the lab from the e-waste recycling site. The half-life of ∑PBDEs was 35 days, with about 14 days for BDE-47, and 36 and 81 days for BDE-99 and BDE-153, respectively. The data shows that the elimination of PBDEs has no essential difference from aquatic and terrestrial species.     

Brominated flame retardants in dust from UK cars--within-vehicle spatial variability, evidence for degradation and exposure implications

Polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and tetrabromobiphenol-A (TBBP-A) were measured in a preliminary study of dust from passenger cabins and trunks of 14 UK cars. Concentrations in cabin dust of HBCDs, TBBP-A, and BDEs 47, 85, 99, 100, 153, 154, 183, 196, 197, 202, 203, 206, 207, 208, and 209 exceeded significantly (p < 0.05) those in trunk dust. Sampling cabin dust thus appears to provide a more accurate indicator of human exposure via car dust ingestion than trunk dust. Elevated cabin concentrations are consistent with greater in-cabin use of BFRs. In five cars, while no significant differences (p > 0.05) in concentrations of HBCDs and most PBDEs were detected in dust sampled from four different seating areas; concentrations of TBBP-A and of PBDEs 154, 206, 207, 208, and 209 were significantly higher (p < 0.05) in dust sampled in the front seats. Possible photodebromination of BDE-209 was indicated by significantly higher (p < 0.05) concentrations of BDE-202 in cabin dust. In-vehicle exposure via dust ingestion to PBDEs, HBCDs and TBBP-A exceeded that via inhalation. Comparison with overall exposure via diet, dust ingestion, and inhalation shows while in-vehicle exposure is a minor contributor to overall exposure to BDE-99, ΣHBCDs, and TBBP-A, it is a significant pathway for BDE-209.     

Debromination of polybrominated diphenyl ether-99 (BDE-99) in carp (Cyprinus carpio) microflora and microsomes

Based on previous findings in dietary studies with carp (Cyprinus carpio), we investigated the mechanism of 2,2',4,4',5-pentabromodiphenyl ether (BDE-99) debromination to 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) using liver and intestinal components. In vitro aerobic and anaerobic experiments tested the ability of carp intestinal microflora to debrominate BDE-99. No debromination of BDE-99 to BDE-47 was observed in microfloral samples; therefore, carp enzymatic pathways were assessed for debromination ability. After sixty-min incubation, intestine and liver microsomes exhibited 83+/-34% and 106+/-18% conversions, respectively, of BDE-99 to BDE-47; with no significant (p>0.05) difference between organ debromination capabilities. Microsomal incubations with BDE-99, enzyme cofactors and competing substrates assessed the potential mechanisms of debromination. The presence of NADPH in the microsomal assay did not significantly (p>0.05) affect BDE-99 debromination, which suggest that cytochrome P450 enzymes are not the main debrominating pathway for BDE-99. Co-incubation of BDE-99 spiked microsomes with reverse thyronine (rT3) significantly (p<0.05) decreased the debromination capacity of intestinal microsomes indicating the potential of catalytic mediation via thyroid hormone deiodinases. The significant findings of this study are that intestinal microflora are not responsible for BDE-99 debromination, however, it is an endogenous process which occurs with approximately equal activity in intestine and liver microsomes and it can be inhibited by rT3.     

Assessment of polybrominated diphenyl ethers in eggs of waterbirds from South China

Concentrations of total polybrominated diphenyl ethers (PBDEs) in Ardeid eggs from Hong Kong, Xiamen and Quanzhou in south China ranged from 140-1000, 30-550 and 140-380ngg(-1), lipid wt., respectively. There were spatial and interspecies variations in the abundance and congeneric profiles of PBDEs. The different congeneric profiles observed among the study sites may be associated with the developmental phases of the cities, as well as a possible consequence of debromination of BDE209. Marked concentrations of higher-brominated diphenyl ethers (BDEs 183, 196, 197, 206, 207 and 209) were detected in the egg samples from all sites, probably indicating uptake of BDE209 by top predators, and that there is widespread occurrence of BDE209 in south China. Comparisons of egg concentrations of BDEs 47, 99, 153 and 209 with tentative critical concentrations for neurobehavioral effects and oxidative stress indicated some potential risks for BDE99 and BDE209 in the Ardeid populations.     

Absorption, disposition and excretion of polybrominated diphenyl ethers (PBDEs) in chicken

Except for fish, no toxicokinetic data on polybrominated diphenyl ethers (PBDEs) is available on relevant animals for the human food chain. In the present work, absorption, elimination through eggs and disposition of PBDEs in laying chickens were studied and compared to dioxin behaviour. Hens were fed with diet containing 3.4 mg/kg feed of PBDEs and 0.95 ng TEQ/kg feed of polychlorodibenzo-p-dioxins (PCDDs) and polychlorodibenzofurans (PCDFs). PBDEs have been demonstrated to show drastically different behaviours from PCDD/Fs and dioxin-like compounds. Excretion of PBDEs increased for two weeks and then decreased to nearly 0%. Sixty-two percent of ingested 2,2',4,4'-tetraBDE (BDE-47) were found in excreta after two weeks, suggesting a reductive debromination of PBDEs in the digestive tract. PBDE level in eggs increased during five weeks and reached 24 microg/g fat. After then, levels decreased to 3 microg/g fat at the end of the trial. PBDE bioconcentration factors estimated for abdominal fat varied from 0.7 for BDE-47 to 2 for BDE-183.     

Exposure to polybrominated diphenyl ethers and tetrabromobisphenol A among computer technicians

This study investigates exposure to polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA), which are used as flame retardants in electronic equipment, in a group of technicians with intense computer work. Thirteen PBDE congeners and TBBPA were quantified in serum from 19 computer technicians. Previously investigated groups of hospital cleaners with no computer experience, and clerks working full-time at computer screens were used for comparison. The computer technicians had serum concentrations of BDE-153, BDE-183 and BDE-209 that were five times higher than those reported among hospital cleaners and computer clerks. The median levels observed among the computer technicians were 4.1, 1.3, and 1.6 pmol/g lipid weight, respectively. In contrast, for BDE-47 there was no difference between the computer technicians and the others. BDE-100, BDE-203, and three structurally unidentified octa-BDEs and three nona-BDEs, were present in almost all samples from the computer technicians. Further, TBBPA was detected in 8 out of 10 samples. The levels of BDE-153, BDE-183, and one of the octa-BDEs were positively correlated with duration of computer work among technicians. On a group level an exposure gradient was observed, from the least exposed cleaners to the clerks, and to the highest exposed group of computer technicians. A dose (duration of computer work)-response relationship among computer technicians was demonstrated for some higher brominated PBDE congeners. Thus, it is evident that PBDEs used in computers and electronics, including the fully brominated BDE-209, contaminate the work environment and accumulate in the workers tissues.     

Sorption-desorption behavior of polybrominated diphenyl ethers in soils

Polybrominated diphenyl ethers (PBDEs) are flame retardants that are commonly found in commercial and household products. These compounds are considered persistent organic pollutants. In this study, we used 4,4′-dibromodiphenyl ether (BDE-15) as a model compound to elucidate the sorption and desorption behavior of PBDEs in soils. The organic carbon-normalized sorption coefficient (K_OC) of BDE-15 was more than three times higher for humin than for bulk soils. However, pronounced desorption hysteresis was obtained mainly for bulk soils. For humin, increasing concentration of sorbed BDE-15 resulted in decreased desorption. Our data illustrate that BDE-15 and probably other PBDEs exhibit high sorption affinity to soils. Moreover, sorption is irreversible and thus PBDEs can potentially accumulate in the topsoil layer. We also suggest that although humin is probably a major sorbent for PBDEs in soils, other humic materials are also responsible for their sequestration.     

Theoretical study on the chemical properties of polybrominated diphenyl ethers

Density functional theory calculations at the B3LYP/6-31+G(d) and B3LYP/aug-cc-pVDZ levels were performed to obtain the equilibrium structures, thermodynamic properties, and electron affinities (EA) of 14 polybrominated diphenyl ether (PBDE) congeners in the gas phase. All congeners except for those of symmetric BDE are found to have two or more conformational isomers. The optimized geometries of the most stable conformational isomers are in agreement with recently published X-ray crystallographic data. The thermodynamic properties of the congeners with a given number of bromine substitutions are strongly dependent on the substitution pattern, whereas the EA values also depend on the number of bromine substitutions. The vertical electron affinities (EA(Ver)) calculated for the selected BDE congeners at the B3LYP/aug-cc-pVDZ level are all positive except for di-BDEs, and are correlated with the initial reductive debromination rate constants obtained recently [Keum, Y.-S., Li, Q.X., 2005. Reductive debromination of polybrominated diphenyl ethers by zerovalent iron. Environ. Sci. Technol. 39, 2280]. All adiabatic electron affinities (EA(Ada)) are positive, and suggest that the BDE congeners act as electron acceptors when reacting with receptors in living cells. The calculated EA(Ada) values differ considerably from those of EA(Ver) because of the large geometrical relaxation from the neutral to the anionic BDE congeners, highlighted by the lengthening of a C-Br bond. The elongated C-Br bond, which occurs at the alpha position, is directly involved in the debromination of n-bromodiphenyl to (n-1)-bromodiphenyl ethers in the reductive debromination experiments.     

Behavior of decabromodiphenyl ether (BDE-209) in soil: effects of rhizosphere and mycorrhizal colonization of ryegrass roots

A rhizobox experiment was conducted to investigate degradation of decabromodiphenyl ether (BDE-209) in the rhizosphere of ryegrass and the influence of root colonization with an arbuscular mycorrhizal (AM) fungus. BDE-209 dissipation in soil varied with its proximity to the roots and was enhanced by AM inoculation. A negative correlation (P < 0.001, R² = 0.66) was found between the residual BDE-209 concentration in soil and soil microbial biomass estimated as the total phospholipid fatty acids, suggesting a contribution of microbial degradation to BDE-209 dissipation. Twelve and twenty-four lower brominated PBDEs were detected in soil and plant samples, respectively, with a higher proportion of di- through hepta-BDE congeners in the plant tissues than in the soils, indicating the occurrence of BDE-209 debromination in the soil-plant system. AM inoculation increased the levels of lower brominated PBDEs in ryegrass. These results provide important information about the behavior of BDE-209 in the soil-plant system.     

Identification and quantification of products formed via photolysis of decabromodiphenyl ether

Background, aim, and scope  Decabromodiphenyl ether (DecaBDE) is used as an additive flame retardant in polymers. It has become a ubiquitous environmental contaminant, particularly abundant in abiotic media, such as sediments, air, and dust, and also present in wildlife and in humans. The main DecaBDE constituent, perbrominated diphenyl ether (BDE-209), is susceptible to transformations as observed in experimental work. This work is aimed at identifying and assessing the relative amounts of products formed after UV irradiation of BDE-209. Materials and methods  BDE-209, dissolved in tetrahydrofuran (THF), methanol, or combinations of methanol/water, was exposed to UV light for 100 or 200 min. Samples were analyzed by gas chromatography/mass spectrometry (electron ionization) for polybrominated diphenyl ethers (PBDEs), dibenzofurans (PBDFs), methoxylated PBDEs, and phenolic PBDE products. Results  The products formed were hexaBDEs to nonaBDEs, monoBDFs to pentaBDFs, and methoxylated tetraBDFs to pentaBDFs. The products found in the fraction containing halogenated phenols were assigned to be pentabromophenol, dihydroxytetrabromobenzene, dihydroxydibromodibenzofuran, dihydroxytribromodibenzofuran, and dihydroxytetrabromodibenzofuran. The PBDEs accounted for approximately 90% of the total amount of substances in each sample and the PBDFs for about 10%. Discussion  BDE-209 is a source of PBDEs primarily present in OctaBDEs but also to some extent in PentaBDEs, both being commercial products now banned within the EU and in several states within the USA. It is notable that OH-PBDFs have not been identified or indicated in any of the photolysis studies performed to date. Formation of OH-PBDFs, however, may occur as pure radical reactions in the atmosphere. Conclusions  Photolysis of decaBDE yields a wide span of products, from nonaBDEs to hydroxylated bromobenzenes. It is evident that irradiation of decaBDE in water and methanol yields OH-PBDFs and MeO-PBDFs, respectively. BDE-202 (2,2′,3,3′,5,5′,6,6′-octabromodiphenyl ether) is identified as a marker of BDE-209 photolysis. Recommendations and perspectives  BDE-209, the main constituent of DecaBDE, is primarily forming debrominated diphenyl ethers with higher persistence which are more bioaccumulative than the starting material when subjected to UV light. Hence, DecaBDE should be considered as a source of these PBDE congeners in the environment. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Multi-year measurements of polybrominated diphenyl ethers (PBDEs) in the Arctic atmosphere

Weekly high-volume air samples have been collected in the Canadian High Arctic (Alert, Nunavut) since 1992. Fifteen polybrominated diphenyl ethers (PBDEs) are quantified in 104 samples over the time period of 2002–2004. To our knowledge, this study reports the first continuous multi-year measurements of PBDEs in Arctic air. Average air concentrations (in pg m⁻³) were 7.7 (0.40–47) and 1.6 (0.091–9.8) for 14 PBDEs (excluding BDE-209) and BDE-209, respectively, over the entire sampling period. BDE-28/33, 47, 99, 100, 153, 154, and 209 accounted for 90% (72–97%, n=104) of the 15 PBDEs. Occurrence of BDE-47, 99, and 209 suggests that PBDEs in Alert air were likely associated with the usage of “penta-BDE” and “deca-BDE” technical mixtures worldwide. Natural logarithm of concentrations for less brominated PBDEs correlated significantly with ambient temperatures in the summertime, suggesting importance of volatilization emissions in a local and/or regional scale. On the other hand, episodically elevated concentrations of the less brominated PBDEs in the wintertime and lack of seasonality for the non-volatile BDE-209 indicate potential inputs of particle-bound PBDEs through long-range transport (LRT), especially during the Arctic haze season. Inter-annual trend data further show that concentrations of the eight PBDEs increased inter-annually in 2002–2004 with doubling times of 2–6 years, which were similar to growth rates found in Arctic biotic samples. The results of this study and previous measurements suggest that potential sources of PBDEs in Arctic air include both volatilization emissions and LRT inputs.