Debromination Of BDE-209 Research Articles

Polybrominated Diphenyl Ethers and Alternative Flame Retardants in Air and Precipitation Samples from the Northern Lake Victoria Region, East Africa

High volume air and precipitation samples were collected close to the shore of Lake Victoria at Entebbe, Uganda, between October 2008 and July 2010 inclusive. Polybrominated diphenyl ethers (PBDEs) and alternative flame retardants (AFRs) were analyzed by GC-MS. BDEs 47, 99, and 209 were the predominant PBDEs with mean concentrations (in air) of 9.84, 4.38, 8.27 pg m(-3) and mean fluxes in precipitation of 3.40, 6.23, and 7.82 ng m(-2) sample(-1), respectively. 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), and hexabromocyclododecane (HBCDD), anti- and syn-Dechlorane plus were detected at levels comparable with those of PBDEs. Both PBDEs and AFRs in air generally increased from 2008 to 2010. Elevated PBDE concentrations in air were associated with slow moving low altitude air masses from the region immediately adjacent to the lake, while low concentrations were mostly associated with fast moving westerly and southwesterly air masses. Analysis of the octa- and nona-BDE profiles suggested photolysis and pyrolytic debromination of BDE-209 in the air samples. The highly halogenated and most abundant PBDEs and AFRs in air also predominated in precipitation samples. This is the first study to report flame retardants in high volume air samples and precipitation in Equatorial Africa.

Interaction of polybrominated diphenyl ethers and aerobic granular sludge: biosorption and microbial degradation.

As a new category of persistent organic pollutants, polybrominated diphenyl ethers (PBDEs) have become ubiquitous global environmental contaminants. No literature is available on the aerobic biotransformation of decabromodiphenyl ether (BDE-209). Herein, we investigated the interaction of PBDEs with aerobic granular sludge. The results show that the removal of BDE-209 from wastewater is mainly via biosorption onto aerobic granular sludge. The uptake capacity increased when temperature, contact time, and sludge dosage increased or solution pH dropped. Ionic strength had a negative influence on BDE-209 adsorption. The modified pseudo first-order kinetic model was appropriate to describe the adsorption kinetics. Microbial debromination of BDE-209 did not occur during the first 30 days of operation. Further study found that aerobic microbial degradation of 4,4′-dibromodiphenyl ether happened with the production of lower BDE congeners.

Microcosm study on fate of polybrominated diphenyl ethers (PBDEs) in contaminated mangrove sediment

Polybrominated diphenyl ethers (PBDEs) are toxic and ubiquitous environmental contaminants, but their fate in aquatic environments is not clear. A mangrove microcosm study was employed to investigate the fate of two abundant congeners, BDE-47 and BDE-209, in contaminated sediment. After seven months, more than 90% of the spiked BDE-47 in the mangrove sediment was removed with the formation of lower brominated PBDEs, including BDE-28, -17, -15, -8, -7/4, suggesting that microbial debromination was the main contributor. Debromination of BDE-209 was also observed in the sediment but its dissipation rate was significantly lower than BDE-47. All these congeners were taken up, translocated and accumulated into the tissues of two typical mangrove plants, Kandelia obovata and Avicennia marina. PBDEs, even at very high contamination levels, in the sediment (5000ngg−1) and the debrominated congeners did not pose any adverse effect on the dry weight, augmentation and root/shoot ratio of either mangrove species. This is the first study to reveal that anaerobic microbial debromination and uptake by mangrove plants are the key processes controlling the fate of PBDEs in mangrove sediment.

Reductive debromination of decabromodiphenyl ether by anaerobic microbes from river sediment

Polybrominated diphenyl ethers (PBDEs) are emerging persistent organic pollutants and have consequently drawn much environmental concern. The objective of this study was to evaluate reductive debromination of decabromodiphenyl ether (BDE-209) by anaerobic microbes from river sediment under various conditions. The debromination rates for BDE-209 were enhanced by the addition of brij 30, brij 35, rhamnolipid, surfactin, vitamin B12, zero-valent iron, acetate, lactate, and pyruvate. Zero-valent iron yielded the highest BDE-209 debromination. For the various PBDE congeners, the high-to-low order of debromination rates in sediment was BDE-209 > BDE-99 > BDE-47 > BDE-28 > BDE-15. The intermediate products resulting from the reductive debromination of BDE-209 in sediment were nona-BDE (BDE-207), octa-BDEs (BDE-196, 197), hepta-BDEs (BDE-183, 184, 191), hexa-BDEs (BDE-138, 154), penta-BDEs (BDE-85, 99, 100, 119), tetra-BDEs (BDE-47, 49, 66, 71), tri-BDEs (BDE-17, 28), di-BDEs (BDE-7, 15), and mono-BDE (BDE-3). Our result shows BDE-209 can be debrominated successively to BDE-3 by anaerobic microbes from river sediment. This research offers feasible methods for removal of BDE-209 in river sediment for bioremediation.

Historical occurrences of polybrominated diphenyl ethers and polychlorinated biphenyls in Manila Bay, Philippines, and in the upper Gulf of Thailand

Historical trends of the accumulation of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in a typical tropical Asian environment were investigated using radio-dated sediment cores from Manila Bay, the Philippines and from the upper Gulf of Thailand. Vertical profiles indicated earlier usage of PCBs than of PBDEs which coincided with their industrial production. The increasing concentrations of total PBDEs and PCBs toward the surface suggested an increased consumption of PBDEs; and possible leakage of PCBs from old machineries into the aquatic environment in recent years. Current input of PCBs to the catchment of Manila Bay was supported by the analyses of air samples and plastic resin pellets. The vertical profiles of total PBDEs in the cores (i.e., rapidly increasing concentrations corresponding to the mid-1980s until mid-1990s, followed by a decrease until the early 2000s, and increasing again toward the surface) likely corresponded to the rapid economic growth in Asia in the 1990s, the Asian financial crisis in 1997, and the economic recovery since early 2000s. BDE-209 was predominant especially on the surface layers. BDEs 47 and 99 generally decreased toward the surface, reflecting the phase-out of the technical penta-PBDE products and the regulation by the Stockholm Convention in recent years. Increasing ratios of BDE-202/209, 206/209, 207/209 and decreasing % of BDE-209 down the core layers may provide evidence for the anaerobic debromination of BDE-209 in the sediment cores. Inventories in ng/cm2 of total PCBs were higher than total PBDEs (92 vs. 34 and 47 vs. 11 in the Philippines; 47 vs. 33 in Thailand). However, the doubling times indicated faster accumulation of total PBDEs (6–7years) and BDE-209 (6–7.5years) than of PCBs (8–11years). Furthermore, the temporal increase in BDE-209 was comparable to or faster than those reported in other water bodies around the world.

Bioaccumulation and debromination of BDE-209 in Japanese medaka (Oryzias Latipes) when continuously exposed to environmental relevant concentrations

BDE-209 is the most commonly used commercial polybrominated diphenyl ether, and is of particular concern due to its accumulation and debromination to more toxic congeners in aquatic organisms. In this study, Japanese medaka were continuously exposed to BDE-209 with the exposure concentrations ranging from 1 to 1000 ng/L for 15, 30 and 60 days in a flowing-through exposure device. The results showed that BDE-209 could be accumulated in fish muscle at environmental relevant concentrations and its concentration in the muscle increased with the increase of exposure time and reached to a steady state. Toxicokinetic data showed that the dose-dependent half-life of BDE-209 in the muscle of medaka ranged from 16.5 to 19.4 days. Low brominated congeners could be detected, where tri- to hexa-BDEs were predominant congeners with up to 46% to 93% of total PBDEs and lower brominated BDEs may have slower elimination rates. Concentration level of BDE-155 ranged from several ng/g wet weight (ww) to a maximum of 178 ng/g ww. BDE-154 and BDE-153 as intermediates in fish under continuous exposure were negligible. By comparing with previous work, fish may have a different bioaccumulation capacity and metabolic pattern from other species, either because of species difference or the manner of exposures.

Fate and Ecological Effects of Decabromodiphenyl Ether in a Field Lysimeter

Flame-retardant polybrominated diphenyl ethers (PBDEs) are environmental contaminants. Deca-BDE is increasingly used commercially, but little is known about the long-term fate and impact of its major component, decabromodiphenyl ether (BDE-209), on the soil environment. In this study, we investigated the fate and ecological effect of BDE-209 over 4 years in outdoor lysimeters in a field planted with a rice-wheat rotation. BDE-209 and six lower-brominated PBDEs (BDE-28, -47, -99, -153, -154, and -183) were detected in soil layers of the test lysimeter. We calculated an average BDE-209 migration rate of 1.54 mg·m(-2)·yr(-1). In samples collected in May 2008, November 2008, November 2009, November 2010, and November 2011, 95.5%, 94.3%, 108.1%, 33.8%, and 35.5% of the spiked BDE-209 were recovered, respectively. We predicted the major pathway for debromination of BDE-209 in soil to be: BDE-209→BDE-183→BDE-153/BDE-154→BDE-99→BDE-47→BDE-28. In plants, BDE-209 and seven lower-brominated PBDEs (BDE-28, -47, -99, -100, -153, -154, and -183) were detected. BDE-100 was mainly derived from the debromination of BDE-154 in plants, but sources of other lower-brominated PBDEs were still difficult to determine. In soils containing BDE-209 for 4 years, soil urease activity increased, and soil protease activity slightly decreased. Our results provide important insights for understanding the behavior of BDE-209 in agricultural soils.

In vitro biotransformation of decabromodiphenyl ether (BDE-209) and Dechlorane Plus flame retardants: A case study of ring-billed gull breeding in a pollution hotspot in the St. Lawrence River, Canada

Decabromodiphenyl ether (deca-BDE) mixture (~97% of BDE-209) is now facing usage restrictions worldwide, which is leading to increased utilization of a series of alternative, replacement flame retardant (FR) products. Among these, Dechlorane Plus (DP) is receiving growing attention as this FR is increasingly being detected in wildlife samples, including birds from North America, Europe and Asia. Recent survey conducted in a known FR hotspot in the St. Lawrence River basin near Montreal (QC, Canada) revealed unexpectedly high detection frequencies and concentrations of BDE-209 and DP isomers (syn- and anti-DP) in the liver of breeding ring-billed gulls (Larus delawarensis) (RBGUs). Despite the global distribution of these current-use FRs, there is to our knowledge no study that has addressed the in vitro biotransformation of BDE-209 and DP isomers in birds. This study aimed at understanding the in vitro metabolism of BDE-209 and syn- and anti-DP using liver microsomes of Montreal-breeding RBGUs. Although BDE-15 (positive assay control) was consistently and positively depleted over the 90-min time frame of the in vitro assay, no depletion was observed for BDE-209 and DP isomers. These results suggest that CYP isoenzyme-mediated reductive dehalogenation of BDE-209 and DP is not likely to be a substantial metabolic pathway in RBGUs. However, investigations on deiodinases (expression, activity) should be considered in future studies as these enzymes have been suggested to be involved in the sequential debromination of BDE-209 in fish and human studies. High levels of BDE-209 determined in liver of RBGUs that strongly correlated with those of known or suggested BDE-209 debromination products (hepta- through nona-BDEs) may thus be indicative of concomitant dietary (e.g., fish consumption) and environmental exposure in the greater Montreal area, combined with poor or lack of metabolic capability toward these FRs.

Efficient Oxidative Debromination of Decabromodiphenyl Ether by TiO2-Mediated Photocatalysis in Aqueous Environment

Direct evidence was first demonstrated for the oxidative degradation of decabromodiphenyl ether (BDE209) in aqueous TiO(2) dispersions under UV irradiation (λ > 340 nm). BDE209 was hardly debrominated over TiO(2) in UV-irradiated acetonitrile dispersions, but the addition of water into the dispersions greatly enhanced its photocatalytic oxidative debromination. The debromination efficiency of BDE209 as high as 95.6% was achieved in aqueous TiO(2) dispersions after 12 h of UV irradiation. The photocatalytic oxidation of BDE209 resulted in generation of aromatic ring-opening intermediates such as brominated dienoic acids, which were further degraded by prolonging UV irradiation time. The photocatalytic oxidative debromination of BDE209 was further confirmed by the observation that the BDE209 degradation in water-acetonitrile mixtures with different water contents was positively correlated with the formation of •OH radicals, but not photogenerated electrons. The use of water not only avoided the scavenging of reactive radicals by organic solvent but also enhanced the adsorption of BDE209 on the surface of TiO(2), both of which favor the contact of BDE209 with photogenerated holes and •OH species. The confirmation of efficient oxidative degradation and debromination of BDE209 is very important for finding new ways to remove polybrominated diphenyl ethers from the environment.

Accumulation and debromination of decabromodiphenyl ether (BDE-209) in juvenile fathead minnows (Pimephales promelas) induces thyroid disruption and liver alterations.

Polybrominated diphenyl ether (PBDE) flame retardants are known to affect thyroid hormone (TH) regulation. The TH-regulating deiodinases have been implicated in these impacts; however, PBDE effects on the fish thyroid system are largely unknown. Moreover, the liver as a potential target of PBDE toxicity has not been explored in young fish. This study measured decabromodiphenyl ether (BDE-209) effects on TH regulation by measuring deiodinase activity in juvenile fathead minnows (Pimephales promelas). Dietary accumulations and debromination of BDE-209 were also measured, and the morphology of thyroid and liver tissues was examined. Juvenile fathead minnows (28 days old) received a 28-day dietary treatment of BDE-209 at 9.8 ± 0.16 μg/g of food at 5% of their body weight per day followed by a 14-day depuration period in which they were fed clean food. Chemical analysis revealed that BDE-209 accumulated in tissues and was metabolized to reductive products ranging from penta- to octaBDEs with 2,2',4,4',5,6'-hexabromodiphenyl ether (BDE-154) being the most accumulative metabolite. By day 28 of the exposure, rates of outer and inner ring deiodination (ORD and IRD, respectively) of thyroxine (T4) were each reduced by ∼74% among treatments. Effects on T4-ORD and T4-IRD remained significant even after the 14-day depuration period. Histological examination of treated fish showed significantly increased thyroid follicular epithelial cell heights and vacuolated hepatocyte nuclei. Enlarged biliary passageways may be the cause of the distinctive liver phenotype observed, although further testing is needed. Altogether, these results suggest that juvenile fish may be uniquely susceptible to thyroid disruptors like PBDEs.

Tissue Distribution and Associated Toxicological Effects of Decabrominated Diphenyl Ether in Subchronically Exposed Male Rats

Concerns about decabrominated diphenyl ether (BDE-209) have arisen recently due to its increasing concentrations in the environment. We investigated the tissue concentration, distribution, and the debromination of BDE-209 after oral exposure, using rats as a model. Three groups of male rats were administrated by oral gavage with corn oil containing 0, 10, or 50 mg/kg bw/day of BDE-209 over 90 days. After exposure, BDE-209 and its metabolites levels in the liver, kidney, and adipose of the rats were measured. The mRNA expression levels of cytochrome P450 (CYP) enzymes in liver, serum thyroid hormone levels, and open-field tests were also measured. BDE-209 and several octa- and nona-BDE congeners were detected in the tissues of the dosed rats, indicating that BDE-209 was bioavailable and biotransformative in male rats. BDE-209 and its debrominated congeners had no mRNA level effect on selective genes from the CYP family in the liver or on the spontaneous behavior of adult male rats. Conversely, the level of thyroid hormone, total triiodothyronine (T3) in rats from the dosed treatments increased significantly compared to the control group.

Can biotransformation of BDE-209 in lake trout cause bioaccumulation of more toxic, lower-brominated PBDEs (BDE-47, -99) over the long term?

Much debate exists on the future direction of policy related to the deca-brominated diphenyl ethers (deca-BDE) mixture. This debate, in part, results from the fact that BDE-209 can debrominate to more toxic lower-polybrominated diphenyl ethers (PBDEs). However, such debromination is difficult to study using measured concentrations alone because of the short-term nature of laboratory experiments and the presence of lower-brominated congeners in the environment. Here, a rigorously calibrated, multichemical, dynamic fish model (Bhavsar et al. 2008, Environ. Sci. Technol., 42, 3724-3731) is used to predict the debromination of BDE-209 to more toxic lower-brominated PBDEs over a 15-year life period of piscivorous- and non-piscivorous lake trout (pLT, npLT; Salvelinus namaycush). A sensitivity analysis was performed by changing BDE-209 dietary dose, gut absorption efficiency and half-life for generally conservative scenarios. Estimated BDE-209, -99 and -47 concentrations were compared with human fish consumption guidelines developed using the draft U.S.EPA tolerable daily intakes. The model predicted that bioaccumulation of BDE-209 as well as BDE-47 and -99 due to dietary exposure to deca-BDE over the 15-year period would not be appreciable in pLT (generally unrestricted consumption advisory) and would be moderate in npLT (unrestricted to 2 meals/month advisory) even for worst-case scenarios.

Characterization of polychlorinated biphenyls and brominated flame retardants in sediments from riverine and coastal waters of Surabaya, Indonesia

A total of 33 surficial sediments from riverine and coastal waters from Surabaya, Indonesia were analyzed for PCBs and BFRs. Concentrations of PCBs (62 congeners), PBDEs (14 congeners) and HBCDs (3 isomers) varied from <DL–420, <DL–35 and <DL–5.4ngg−1dw, respectively. Higher concentrations of these compounds were found in riverine than coastal sediments. Their levels and distribution were influenced by proximity to the point sources and TOC. The predominant congeners were CB-153, -28, -138, -149, -180, -33 and BDE-209, -207, -206, -197, -196, -183, -99, -47 for PCBs and PBDEs, respectively, and γ-isomer for HBCDs. Debromination of BDE-209 might be taking place producing lower toxic congeners in sediment. Levels of PCBs in riverine sediments were comparable with some polluted areas worldwide, but PBDEs and HBCDs were lower. Hazard assessment of PCBs indicated possible toxic potential, particularly in areas close to point sources.

Residues of Polybrominated Diphenyl Ethers in Honeys from Different Geographic Regions

Polybrominated diphenyl ethers (PBDEs) are a class of widely used flame-retardants. Fifty honey samples labeled as being from different countries and regions were analyzed for 27 PBDE congeners. The concentrations of the 26 PBDEs, excluding BDE-209, ranged from 300 to 10,550 pg/g while the concentrations of BDE-209 ranged from nondetected to 9,260 pg/g. The honey samples labeled as originating in developed countries generally displayed higher concentrations of the total 27 PBDEs than those labeled as being from developing countries. Concentrations of 26 PBDEs ranged from 2,720 to 10,550 pg/g in honeys originating in developed countries and ranged from 1,030 to 3,470 pg/g in those from developing countries. BDE-209 was a dominant PBDE congener in all honey samples, on average accounting for 16% and 65% of the total 27 PBDEs in honeys from developed and developing countries, respectively. Honeys originating in developing countries, however, showed much higher BDE-209 levels and higher ratios of BDE-209 relative to the other PBDE congeners. In addition, some highly brominated PBDE congeners such as BDE-196, -197, -206, and -207 showed elevated concentrations in honeys from developing countries. The findings were in agreement with the long, heavy historical uses of PBDE products in developed countries and the current, heavy uses of BDE-209 in developing countries. When BDE-209 was fortified in honey and incubated in the dark for four weeks at 25 or 60 degrees C, BDE-153, -183, -206, and -207 were detected as debromination products of BDE-209. Less brominated congeners in honeys may primarily come from the environment. Debromination of BDE-209 is also a source of less brominated congeners in honeys. The detection of PBDEs in honeys suggests that human exposure to PBDEs occurs as a result of honey consumption.

Behavior of Decabromodiphenyl Ether (BDE-209) in the Soil−Plant System: Uptake, Translocation, and Metabolism in Plants and Dissipation in Soil

Deca-bromodiphenyl ether (BDE-209) is the major component of the commercial deca-BDE flame retardant. There is increasing concern over BDE-209 due to its increasing occurrence in the environment and in humans. In this study the behavior of BDE-209 in the soil-plant system was investigated. Accumulation of BDE-209 was observed in the roots and shoots of all the six plant species examined, namely ryegrass, alfalfa, pumpkin, summer squash, maize, and radish. Root uptake of BDE-209 was positively correlated with root lipid content (P < 0.001, R(2) = 0.81). The translocation factor (TF, C(shoot)/C(root)) of BDE-209 was inversely related to its concentration in roots. Nineteen lower brominated (di- to nona-) PBDEs were detected in the soil and plant samples and five hydroxylated congeners were detected in the plant samples, indicating debromination and hydroxylation of BDE-209 in the soil-plant system. Evidence of a relatively higher proportion of penta- through di-BDE congeners in plant tissues than in the soil indicates that there is further debromination of PBDEs within plants or low brominated PBDEs are more readily taken up by plants. A significant negative correlation between the residual BDE-209 concentration in soil and the soil microbial biomass measured as the total phospholipid fatty acids (PLFAs) (P < 0.05, R(2) = 0.74) suggests that microbial metabolism and degradation contribute to BDE-209 dissipation in soil. These results provide important information about the behavior of BDE-209 in the soil-plant system.

Time-Trends and Congener Profiles of PBDEs and PCBs in California Peregrine Falcons (Falco peregrinus)

High levels (microg/g lw) of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were measured in peregrine falcon eggs from California (n = 90 eggs from 52 birds, 38 nest sites, collected 1986-2007, SigmaPBDEs median = 4.53, range = 0.08-53.1). Over the past 22 years, PBDE levels more than tripled each decade in the eggs, whereas PCB levels had no significant changes. PBDE levels were highest in eggs from major California cities ("Big Cities"), whereas PCBs showed no difference across the regions. For PBDEs, Big City eggs had markedly different patterns from Coastal eggs: BDE-209 and the higher brominated PBDEs (hexa-nona) were dominant congeners in Big City eggs, while BDE-47 and -99 were dominant in Coastal eggs. In many of the birds that gave multiple eggs over time ("time series"), PBDE patterns changed over time: the high proportions of BDE-209 and higher brominated PBDEs (short half-lives) in young birds contrasted with increasingly higher proportions of BDE-153 (long half-life) and other lower brominated PBDEs as the birds aged. These data are consistent with metabolic debromination of BDE-209 (t(1/2) = 1-2 weeks) to the lower brominated PBDEs, with accumulation over time of BDE-153 (t(1/2) = 3-4 years). In contrast, PCB patterns showed no differences by locations, and did not change over time. Diet (prey birds) may explain the urban PBDE pattern, as the patterns in urban pigeons and peregrines were similar, with high proportions of BDE-209 and the higher-brominated PBDEs. Also, our prey data (feathers from peregrine nests) showed urban peregrines having a higher proportion (>2 fold) of granivorous/opportunistic birds (e.g., "introduced feral" pigeons, mourning doves, starlings) in their diet than coastal peregrines. In summary, these data indicate that BDE-209 exits consumer products as an environmental contaminant to be taken up by wildlife (particularly in urban locations), and undergoes metabolic debromination to the banned lower-brominated PBDEs. High levels of the higher-brominated PBDE congeners, especially in urban locations, permitted accurate measures of relative proportions of homologues in each of the hexa-nona congener classes. Using the major hexa-nona homologues in each of these classes, we propose a pathway for the stepwise, metabolic debromination of BDE-209.

Unusual hepta‐ and octabrominated diphenyl ethers and nonabrominated diphenyl ether profile in California, USA, peregrine falcons (Falco peregrinus): More evidence for brominated diphenyl ether‐209 debromination

High (maximum of 4.1 ppm lipid weight) levels of BDE-209 and other higher brominated diphenyl ethers (BDEs) found in California, USA, peregrine falcon (Falco peregrinus) eggs (n = 95) provided an opportunity to examine homolog profiles of nona-, octa-, and hepta-BDEs as possible evidence for biological debromination of BDE-209. We found two congeners in eggs, an unidentified hepta-BDE (BDE-heptaUNK) and BDE-202 (octa-BDE) that are not present in commercial mixtures. In addition, BDE-208 (nona-BDE) was present at much higher (10-fold) proportions in eggs than in commercial mixtures. To examine whether these unusual homolog patterns arose from assimilation of environmentally degraded BDE commercial mixtures, we compared nona-hepta-BDE homolog profiles of peregrine falcon eggs with those of weathered BDEs present in various abiotic matrices (sludge, sediment, and dusts). We found the profiles differed significantly: BDE-207 was the major nona-BDE in eggs, whereas BDE-206 was the major nona-BDE in abiotic matrices. Thus, the evidence for the biological debromination of BDE-209 in peregrine falcons is twofold: Eggs have two congeners (BDE-202 and -heptaUNK) that are not reported for any commercial mixtures nor in the abiotic matrices examined thus far, and eggs have higher-brominated BDE homolog patterns that are different from those found in commercial mixtures or environmental matrices.

Electrolytic debromination of PBDEs in DE-83 TM technical decabromodiphenyl ether

Electrochemical debromination of the commercial decabromodiphenyl ether flame retardant DE-83 TM 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.

Reductive Debromination of Polybrominated Diphenyl Ethers in Anaerobic Sediment and a Biomimetic System

Because of the bioaccumulation of penta- and tetrapolybrominated diphenyl ether (PBDE) flame retardants in biota,the environmental biotransformation of decabromodiphenyl ether (BDE-209) is of interest. BDE-209 accounts for more than 80% by mass of PBDE production and is the dominant PBDE in sediments. Most sediments are anaerobic and reports of microbial reductive dehalogenation of hydrophobic persistent organohalogen pollutants are numerous. Reductive debromination of BDE-209 in the environment could provide a significant source of lesser-brominated PBDEs to biota. Moreover, a recent study showed that BDE-209 debrominates in sewage sludge, and another demonstrated that some halorespiring bacteria will debrominate BDE-209. To determine whether reductive debromination of BDE-209 occurs in sediments, parallel experiments were conducted using anaerobic sediment microcosms and a cosolvent-enhanced biomimetic system. In the biomimetic system, reductive debromination occurred at rates corresponding to bromine substitution levels with a BDE-209 half-life of only 18 s compared with a halflife of almost 60 days for 2,2',4,4'-tetrabromodiphenyl ether. In sediment, the measured debromination half-life of BDE-209 was well over a decade and was in good agreement with the predicted value obtained from the biomimetic experiment. Product congeners were predominantly double para-substituted. BDE-209 debrominated in sediment with a corresponding increase in nona-, octa-, hepta-, and hexa-PBDEs. Nine new PBDE congeners appeared in sediment from reductive debromination. Given the very large BDE-209 burden already in sediments globally, it is important to determine whether this transformation is a significant source of lesser-brominated PBDEs to the environment.

Debromination of Decabrominated Diphenyl Ether by Resin-Bound Iron Nanoparticles

Nanoscale zerovalent iron, n-ZVI, was found to be highly effective in reductively debrominating decabromodiphenyl ether (BDE209) at ambient conditions and without the catalysis of noble metals. A method was developed to immobilize n-ZVI particles on a cation-exchange resin. The n-ZVI coated resin was then mixed with BDE209 in a water/ acetone (1:1) solution, and the reaction was allowed to proceed for up to 10 days. The first-order rate constant of BDE209 disappearance was estimated to be 0.28 - 0.04 h(-1). The debromination was found to be stepwise, and less-brominated congeners were produced with increasing reaction time. Dechlorination of decachlorobiphenyl (PCB209) was also investigated, but the reaction rate was much slower than the debromination of BDE209. Identification of the reaction products was highly challenging and was assisted by regression equations between experimental and reference gas chromatographic relative retention times, with confirmation by high-resolution mass spectrometry and reference to quantitative structure retention relationships. For randomly selected PBDE and PCB congeners, the net charges of individual atoms were calculated using the quantum chemical computation to explore the difference in relative vulnerability of halogens at different substitution positions between PBDEs and PCBs.