Degradation Of BDE-209 Research Articles

Degradation of Polybrominated Aiphenyl Ethers in a UV Advanced Reduction Process with Different Reducing Agents

Polybrominated diphenyl ethers (PBDEs) are toxic and persistent, and their efficient degradation is currently a challenge. In this study, decabromodiphenyl ether (BDE-209) was selected as the target compound and was degraded by a UV photochemical system with different reducing agent. The result showed that the optimal BDE-209 removal in 1 hour by UV/sodium sulphite (Na2SO3) was 86.87%. With the same concentration of BDE-209 and reaction time, the optimal removal rate by UV/sodium borohydride (NaBH4) was 89.25%. Kinetic analysis revealed that the degradation of BDE-209 conformed to the first-order kinetic model. The order of rate constant of different UV photochemical processes is kUV<kUV/Na2SO3<kUV/NaBH4. Debromination rate indicated that reducing agents can promote the removal of bromine during the degradation of BDE-209. As a reducing agent, sodium borohydride showed a better enhanced effect for the removal of bromines.

A photocatalyst of graphene oxide (GO)/Ag3PO4 with excellent photocatalytic activity over decabromodiphenyl ether (BDE-209) under visible light irradiation

A series of graphene oxide (GO)/Ag3PO4 composites were synthesized using ion exchange-chemical precipitation method with different GO content, and the photocatalytic reduction degradation effect on decabromodiphenyl ether (BDE-209) over GO/Ag3PO4 was also studied. The optimized composite exhibited superior photocatalytic activity. When the content of GO was 7%, the degradation efficiency of BDE-209 could reach 97.33% in anoxic water with methanol as electron donors after 8 h of visible light irradiation, being 3 times that over pure Ag3PO4 and the BDE-209 reduction generated 3Br-8Br PBDEs congeners. The photocatalytic degradation of BDE-209 has been further investigated under different reaction conditions, such as photocatalyst dosage and pH of reaction system. According to analysis of the intermediates’s generation, accumulation and distribution, we proposed that the BDE-209 reduction mechanism was the multi-electron reduction process. GO not only trapped electrons to improve the charge separation on Ag3PO4, but also fleetingly transferred the accumulated electrons to BDE-209. This study indicates that GO/Ag3PO4 could be a promising material for environmental treatment of persistent pollutants.

Photolysis of highly brominated flame retardants leads to time-dependent dioxin-responsive mRNA expression in chicken embryonic hepatocytes

Tetradecabromo-1,4-diphenoxybenzene (TeDB-DiPhOBz) and 2,2′,3,3′,4,4′,5,5′,6,6′-decabromodiphenyl ether (BDE-209) are flame retardant chemicals that can undergo photolytic degradation. The present study compared the time-dependent photolyic degradation of TeDB-DiPhOBz and BDE-209, and dioxin-like product formation as a result of (UV) irradiation (I; irradiation time periods of 0, 1, 4, 15 and 40 days). Photo-degraded product fractions of UV-I-TeDB-DiPhOBz (nominal concentration: 1.9 μM) were administered to chicken embryonic hepatocytes (CEH), and significant induction of CYP1A4/5 mRNA expression was observed for fractions collected at the day 15 and 40 time points (fold change of 7.3/3.6 and 9.1/4.7, respectively). For the UV-I-BDE-209 fractions (nominal concentration: 10 μM), significant CYP1A4/5 up-regulation occurred at all time points, and the fraction collected on day 1 induced the greatest fold change of 510/86, followed by 410/68 (day 4) and 110/26 (day 15), respectively. For the UV-I-BDE-209 fraction collected at day 40, significant CEH cytotoxicity was observed. As a result, CYP1A4/5 expression was determined at a nominal concentration of 1 μM instead of 10 μM and CYP1A4/5 fold changes of 11/8.2 (day 40) were observed. Fractions eliciting the greatest CYP1A4/5 mRNA upregulation were further screened for transcriptomic effects using a PCR array comprising 27 dioxin-responsive genes. A total of 6 and 16 of the 27 target genes were up or down-regulated following UV-I-TeDB-DiPhOBz and UV-I-BDE-209 exposure, respectively. Overall, and regardless of the formation rate, these results raise concerns regarding the potential formation of dioxin-like compounds from flame retardants in products and materials such as plastics, and in natural sunlight irradiation situations in the environment (e.g. in landfill sites or electronic waste facilities).

Solid surface-mediated photochemical transformation of decabromodiphenyl ether (BDE-209) in aqueous solution

Polybrominated diphenyl ethers (PBDEs) are brominated flame retardants which have received considerable attention due to their global distribution, bioaccumulation potential, environmental persistence, and possible toxic effects. In this work, the photodegradation of decabromodiphenyl ether (BDE-209) in aqueous system was investigated by preloading it on the surface of various solid matrices. After 6 h of Xe lamp irradiation, almost complete degradation of BDE-209 was observed on silica gel (SG), with much slower degradation occurring in other adsorbents. The degradation of BDE-209 on SG sample followed pseudo-first-order kinetics, and the observed reaction rate constant was decreased by lowering pH, adding humic acid and increasing the initial BDE-209 concentration. In addition to direct photolysis, BDE-209 could be oxidized by hydroxyl radicals generated from SG, as confirmed by the electron paramagnetic resonance (EPR) technology. Product analysis showed that BDE-209 was mainly decomposed into lower brominated PBDEs, polybrominated dibenzofurans (PBDFs), hydroxylated PBDEs (OH-PBDEs), hydroxylated PBDFs (OH-PBDFs), bromophenols and bromide ions. Thus, consecutive debromination, intramolecular elimination of HBr, hydroxyl addition and the cleavage of ether bond were proposed as the degradation pathways. This study may help understanding the photochemical transformation of solid surface adsorbed BDE-209 in natural surface waters, which is important to evaluate the environmental fate of PBDEs.

The key role of biochar in the rapid removal of decabromodiphenyl ether from aqueous solution by biochar-supported Ni/Fe bimetallic nanoparticles

Some problems exist in the current remediation of polybrominated diphenyl ethers (PBDEs) from aqueous solution by using iron-based nanoparticles. Our efforts have contributed to the synthesis of biochar-supported Ni/Fe bimetallic nanoparticle composites (BC@Ni/Fe). Under the optimum operating parameters of BC@Ni/Fe, the morphologic analysis revealed that biochar effectively solved the agglomeration of Ni/Fe nanoparticles and the removal efficiency of BDE209 obtained by BC@Ni/Fe (91.29%) was seven times higher than the sum of biochar (2.55%) and Ni/Fe (11.22%) in 10 min. The degradation products of BDE209 in the solution and absorbed on the BC@Ni/Fe were analyzed with gas chromatography-mass spectroscopy, which indicated that the degradation of BDE209 was mainly a process of stepwise debromination. Meanwhile, compared with Ni/Fe nanoparticles, the adsorption ability of the by-products of BDE209 by BC@Ni/Fe was greater, to a certain extent, which reduced the additional environmental burden. In addition, the concentration of nickle ion leaching from the Ni/Fe nanoparticles was 3.09 mg/L; conversely, the concentration of nickle leaching from BC@Ni/Fe was not detected. This excellent performance in our study indicates a possible means to enhance the reactivity and reduce the secondary risks of Ni/Fe nanoparticles.

Treatment of decabromodiphenyl ether (BDE209) contaminated soil by solubilizer-enhanced electrokinetics coupled with ZVI-PRB.

Decabromodiphenyl ether (BDE209) is a typical soil contaminant released from e-waste recycling sites (EWRSs). Electrokinetics (EK) has been considered as an excellent treatment technology with a promising potential to effectively remove organic pollutants in soil. In this study, the treatment of BDE209-polluted soil by EK was explored. All the EK experiments were conducted under a constant voltage gradient (2Vcm-1) for 14days. Deionized water (DI water), hydroxypropyl-β-cyclodextrin (HPCD), sodium dodecyl sulfate (SDS), and humic acid (HA) were applied as the processing fluid. The experimental results showed that all the solubilizers could effectively promote the mobility and transport of BDE209 in the soil via the electro-osmotic flow (EOF) or electromigration. The removal efficiencies achieved in S1 section were 24, 22, and 26% using HPCD, SDS, and HA as the processing fluid. However, the removal of BDE209 for the entire soil cell was not achieved until zero valence iron (ZVI) was inserted at the center of soil column as a permeable reactive barrier (PRB) or (ZVI-PRB), which enhanced the degradation of BDE209. As ZVI-PRB was installed in EK5 and EK6 experiments, the corresponding average removal efficiencies increased to 16 and 13%, respectively. Additionally, the degradation products of BDE209 analyzed by GC-MS suggested that debromination of BDE209 was the main potential degradation mechanism in the EK treatment in the presence of ZVI-PRB.

Development of Brominated Flame Retardants (BFRs) Analysis with Liquid Chromatography-Tandem Mass Spectrometry (LC/MS/MS) in Sewage Sludge Matrix

LC-MS methods have become a very important method for brominated flame retardants (BFRs) analysis and replaced the traditional GC-MS method. This method enables the combination of excellence LC separation column with the sensitivity and specificity of state-of-the-art mass spectrometers and also suitable for the analysis of thermolabile and polar BFRs. In this study, a LC-MS/MS method has been developed for several classes of BFRs in sewage sludge matrix by combining the optimized LEE extraction and GPC cleanup. The advantages of the method include low detection limits (pg range), and the absence of thermal degradation of BDE-209.

Synergistic effect between Fe and Bi2O3 on enhanced mechanochemical treatment of decabromodiphenyl ether

The present work investigated the mechanochemical (MC) treatment of powdery decabromodiphenyl ether (BDE209) with Bi2O3 and/or Fe powders as co-milling reagents. The simultaneous use of Bi2O3 and Fe with a Bi:Fe:Br molar ratio of 1:1:1 led to a BDE209 degradation of 96.6% within 2h of ball milling at rotation speed of 400rpm, whereas only 66.0% and 24.0% of BDE209 was removed in the MC-Bi2O3 and MC-Fe system, respectively. It was demonstrated that the MC process activated the lattice oxygen (O2−) of Bi2O3 and promoted its reaction with BDE209, whereas Fe initiated the reduction of BDE209. The MC treatment of BDE209 through a single reductive in the MC-Fe system or oxidative process in the MC-Bi2O3 system was not efficient, due to that BDE209 is rather difficultly oxidized and the debrominated intermediates are resistant to reduction. When combining Bi2O3 with Fe, the reductive debromination of BDE209 over Fe and the subsequent oxidation of debrominated products over Bi2O3 were integrated into a concerted process. The rapid reduction of BDE209 over Fe not only released Br− ions, which acted as the dopant to improve the activity of O2− in Bi2O3, but also generated less brominated intermediates, which were more susceptible to the O2−-participating reaction over Bi2O3. Thus, a strong synergistic effect between Bi2O3 and Fe was observed on the MC degradation of BDE209.

Enhanced degradation of BDE209 in spiked soil by ferrous-activated persulfate process with chelating agents.

In order to maintain the quantity of ferrous ions, two eco-friendly chelating agents (CAs), i.e., sodium citrate (Citrate) and sodium gluconate (Glu), have been introduced into a traditional iron activated sodium persulfate (PS) system (Fe2+/PS). The results indicated that the PS/CA/Fe2+ oxidation could be an effective method for BDE209 removal. Effects of the chelating agents, reagents dosage, and pH were evaluated in batch experiments. Glu was observed to be more effective than citrate. In addition, the rate constants (k 1) of BDE209 removal indicated a quadratic curve relationship with initial persulfate concentrations (k 1=-0.019×[PS]02+0.031×[PS]0+0.007, R 2=0.933, [PS]0=0.1-1.0M) and a good linear relationship with initial ferrous contents (k 1=0.109×[Fe2+]0+0.002, R 2=0.943). Furthermore, as a reducing agent, ascorbic acid (H2A) could enhance the degradation rate of BDE209, which might be because H2A accelerated the transformation process from Fe3+- to Fe2+-gluconate complexes.

Effect of solvent on debromination of decabromodiphenyl ether by Ni/Fe nanoparticles and nano zero-valent iron particles.

Nano zero-valent iron (nZVI) and its modified nanomaterials are widely used in the degradation of some halogenated organic pollutants. In this study, we explored the effects of different proportions of tetrahydrofuran (THF) (50, 60, 70, 80, 90, and 100%) on the degradation of decabromodiphenyl ether (BDE209) by Ni/Fe and nZVI nanoparticles with reference to the degradation kinetics, products, and pathway. The results illustrated that the effects of solvent on the degradation of BDE209 were similar when the two kinds of nanomaterials were used, although the Ni/Fe bimetallic nanoparticles exhibited a better catalytic activity compared with the pure nZVI during the degradation of BDE209. The apparent reaction rate constant (k obs) increased with the proportion of the water in the system, enhancing the degradation of BDE209. In terms of degradation products, a high proportion of THF led to an accumulation of higher-brominated BDEs, inhibiting the further debromination of BDE209. The inhibitory effect of the solvent (THF) can be explained that water played a role of hydrogen donor during the reductive degradation of BDE209 in the THF/water system. However, the proportion of THF in the degradation system posed no effect on the BDE209 debromination pathway and debromination location. The difficulty of para-debromination was observed in all of the solvent systems.

Excellently reactive Ni/Fe bimetallic catalyst supported by biochar for the remediation of decabromodiphenyl contaminated soil: Reactivity, mechanism, pathways and reducing secondary risks

Ni/Fe bimetallic nanoparticles were synthesized using biochar as a support (BC@Ni/Fe) and their effectiveness in removing BDE209 from soil was investigated. BET, SEM, TEM, XPS and FTIR were used to characterize the catalyst, and the efficiencies of biochar, Ni/Fe nanoparticles and BC@Ni/Fe for removing BDE209 from soil were compared. The results showed that Ni/Fe bimetallic nanoparticles highly dispersed in the biochar, reducing its agglomeration. Thus, the reaction activity of BC@Ni/Fe was increased. The removal efficiency of BDE209 by BC@Ni/Fe was 30.2% and 69% higher than that by neat Ni/Fe and biochar, respectively. Meanwhile, an enhanced degradation efficiency of PBDEs in soil was realized by monitoring the formation of Br⿿ ions with time in the system. In addition, the degradation products identified by GC⿿MS showed that the reductive degradation of BDE209 proceeded through stepwise or multistage debromination, for which the degradation pathways and removal mechanisms were speculated. Furthermore, BC@Ni/Fe reduced the bioavailability of metals in soil and adsorbed the degradation products of BDE209, representing an improvement over neat Ni/Fe nanoparticles for the remediation of PBDEs-contaminated soil.

Oxidation and mechanism of decabromodiphenyl ether (BDE209) by thermally activated persulfate (TAP) in a soil system

Decabromodiphenyl ether (BDE209) poses a significant threat to human health. Most research so far has focused on BDE209 debromination by the reduction, which will produce more toxic products and further cause more serious environmental problems. In this study, we focused on thermally activated persulfate oxidation of BDE209. Various factors have been investigated, such as initial persulfate (0.05, 0.1, 0.2 and 0.5M) or BDE209 content, temperature, pH and inorganic ion. The results show the of BDE209 removal rate constants (k1) indicated quadratic curve relationship with initial persulfate concentrations (k1=−0.293×[PS]02+0.267×[PS]0+0.046, R2=0.917, [PS]0=0.05–0.5M) and a good linear relationship with initial BDE209 contents (k1=−0.004×[BDE209]0+0.312, R2=0.994). At the test pH range of 3–9, the highest degradation efficiency occurred at pH 5. However, inhibitory effects were observed in the presence of bicarbonate (HCO3−), and chloride (Cl−) exhibited either positive or inhibitive effect on the BDE209 degradation. The addition of an appropriate level of Cl− (e.g., [Cl−]0/[PS]0=0.1/1) could significantly enhance the BDE209 decomposition, while higher contents of Cl− (e.g., [Cl−]0/[PS]0=2/1) resulted in totally inhibitory effect.

Aerobic degradation of BDE-209 by Enterococcus casseliflavus: Isolation, identification and cell changes during degradation process

Decabromodiphenyl ether (BDE-209) is one of the most commonly used brominated flame retardants that have contaminated the environment worldwide. Microbial bioremediation has been considered as an effective technique to remove these sorts of persistent organic pollutants. Enterococcus casseliflavus, a gram-positive bacterium capable of aerobically transforming BDE-209, was isolated by our team from sediments in Guiyu, an e-waste dismantling area in Guangdong Province, China. To promote microbial bioremediation of BDE-209 and elucidate the mechanism behind its aerobic degradation, the effects of BDE-209 on the cell changes of E. casseliflavus were examined in this study. The experimental results demonstrated that the high cell surface hydrophobicity (CSH) of E. casseliflavus made the bacteria absorb hydrophobic BDE-209 more easily. E. casseliflavus responded to BDE-209 stress, resulting in an increase in cell membrane permeability and accumulation of BDE-209 inside the cell. The differential expression of intracellular protein was analyzed through two-dimensional gel electrophoresis (2-DE). More than 50 differentially expressed protein spots were reproducibly detected, including 25 up, and 25 down regulated after a 4 days exposure. Moreover, the apoptotic-like cell changes were observed during E. casseliflavus mediated degradation of BDE-209 by means of flow cytometry.

Biosorption and degradation of decabromodiphenyl ether by Brevibacillus brevis and the influence of decabromodiphenyl ether on cellular metabolic responses.

There is global concern about the effects of decabromodiphenyl ether (BDE209) on environmental and public health. The molecular properties, biosorption, degradation, accumulation, and cellular metabolic effects of BDE209 were investigated in this study to identify the mechanisms involved in the aerobic biodegradation of BDE209. BDE209 is initially absorbed by wall teichoic acid and N-acetylglucosamine side chains in peptidoglycan, and then, BDE209 is transported and debrominated through three pathways, giving tri-, hepta-, octa-, and nona-bromodiphenyl ethers. The C-C bond energies decrease as the number of bromine atoms on the diphenyl decreases. Polybrominated diphenyl ethers (PBDEs) inhibit protein expression or accelerate protein degradation and increase membrane permeability and the release of Cl(-), Na(+), NH4 (+), arabinose, proteins, acetic acid, and oxalic acid. However, PBDEs increase the amounts of K(+), Mg(2+), PO4 (3-), SO4 (2-), and NO3 (-) assimilated. The biosorption, degradation, accumulation, and removal efficiencies when Brevibacillus brevis (1 g L(-1)) was exposed to BDE209 (0.5 mg L(-1)) for 7 days were 7.4, 69.5, 16.3, and 94.6 %, respectively.

Aerobic debromination of BDE-209 by Rhodococcus sp. coupled with zerovalent iron/activated carbon.

In this study, an aerobic strain identified as Rhodococcus sp. was isolated from the sediment of a typical electronic waste disassemble site, Taizhou, China. This strain could use BDE-209 as the sole carbon and energy source and degrade 65.1% of BDE-209 (initial concentration being 50 mg/L) within 144 h. To explore the BDE-209 degradation properties of this strain with the co-existed electronic donor, zerovalent iron/activated carbon (ZVI/AC) was introduced to build a microbial-chemical coupling system, which was found to promote the degradation of BDE-209 slightly (74.7% in 144 h). Moreover, the debromination products in both of the batch experiments were determined with GC/MS, which showed that lower brominated PBDE congeners were produced almost in order of the number of bromine ions, ranged from nona- to di-BDEs. In addition, the possible debromination pathways of BDE-209 for each system were proposed respectively, which confirmed the microbial activity of BDE-209 debromination. Since some of the lower-brominated BDE congeners are much toxic than BDE-209, these microbial activities might bring potential hazards to the environment with BDE-209 contamination. It is the first time to investigate the transformation of BDE-209 with microbial-chemical coupling system, which is universal in the nature, thus suggesting that the ecological safety of environment exposed to PBDEs should be focused in the future.

Green mechanochemical oxidative decomposition of powdery decabromodiphenyl ether with persulfate

A method was developed for efficiently degrading powdery decabromodiphenyl ether (BDE209) by using mechanochemical (MC) activation of persulfate (PS). Characteristic Raman spectra of BDE209 corresponding to CBr and CO bonds were decreased in intensity and finally disappeared as the MC reaction proceeded. The BDE209 removal was influenced by the molar ratio of PS to BDE209, the mass ratio of milling ball to reaction mixtures, the ball size, and the ball rotation speed. Under optimal conditions, the new method could achieve a complete degradation, debromination and mineralization of BDE209 within 3h of milling. However, the degradation removal (or debromination efficiency) was decreased to only 51.7% (15.6%) and 67.8% (31.5%) for the use of CaO and peroxymonosulfate, respectively. The analyses of products demonstrated that once the degradation was initiated, BDE209 molecules were deeply debrominated and fully mineralized in the MC-PS system. The strong oxidizing ability of this system was due to the reactive sulfate radicals generated from the MC-enhanced activation of PS, which was confirmed with electron spin resonance spectroscopy. Because no toxic low brominated polybrominated diphenyl ethers were accumulated as byproducts, the proposed MC oxidative degradation method will have promising applications in the treatment of solid BDE209 at high concentrations.

Removal of decabromodiphenyl ether (BDE-209) by sepiolite-supported nanoscale zerovalent iron

Nanoscale zerovalent iron (nZVI) synthesized using sepiolite as a supporter was used to investigate the removal kinetics and mechanisms of decabromodiphenyl ether (BDE-209). BDE-209 was rapidly removed by the prepared sepiolite-supported nZVI with a reaction rate that was 5 times greater than that of the conventionally prepared nZVI because of its high surface area and reactivity. The degradation of BDE-209 occurred in a stepwise debromination manner, which followed pseudo-first-order kinetics. The removal efficiency of BDE-209 increased with increasing dosage of sepiolite-supported nZVI particles and decreasing pH, and the efficiency decreased with increasing initial BDE-209 concentrations. The presence of tetrahydrofuran (THF) as a cosolvent at certain volume fractions in water influenced the degradation rate of sepiolite-supported nZVI. Debromination pathways of BDE-209 with sepiolite-supported nZVI were proposed based on the identified reaction intermediates, which ranged from nona- to mono-brominated diphenylethers (BDEs) under acidic conditions and nonato penta-BDEs under alkaline conditions. Adsorption on sepiolite-supported nZVI particles also played a role in the removal of BDE-209. Our findings indicate that the particles have potential applications in removing environmental pollutants, such as halogenated organic contaminants.

Removing polybrominated diphenyl ethers in pure water using Fe/Pd bimetallic nanoparticles

Polybrominated diphenyl ethers (PBDEs) have been widely used as fire-retardants. Due to their high production volume, widespread usage, and environmental persistence, PBDEs have become ubiquitous contaminants in various environments.Nanoscale zero-valent iron (ZVI) is an effective reductant for many halogenated organic compounds. To enhance the degradation efficiency, ZVI/Palladium bimetallic nanoparticles (nZVI/Pd) were synthesized in this study to degrade decabromodiphenyl ether (BDE209) in water. Approximately 90% of BDE209 was rapidly removed by nZVI/Pd within 80 min, whereas about 25% of BDE209 was removed by nZVI. Degradation of BDE209 by nZVI/Pd fits pseudo-first-order kinetics. An increase in pH led to sharply decrease the rate of BDE209 degradation. The degradation rate constant in the treatment with initial pH at 9.0 was more than 6.8 × higher than that under pH 5.0. The degradation intermediates of BDE209 by nZVI/Pd were identified and the degradation pathways were hypothesized. Results from this study suggest that nZVI/Pd may be an effective tool for treating polybrominated diphenyl ethers (PBDEs) in water.

A preliminary assessment of polychlorinated biphenyls and polybrominated diphenyl ethers in deep-sea sediments from the Indian Ocean

Ten surface sediments were collected from the open Indian Ocean at depths below 4000m in 2011, for the analysis of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). The concentrations of Σ32 PCBs, Σ7 PBDEs, and BDE-209 were 120–514, 49–152, and 7–133pg/g, respectively. These concentrations are close to the lowest values recorded in the global marine environment. The PCBs had a relatively uniform composition, and were dominated by low chlorinated congeners. The concentrations of di-, tri-, and tetra-PCBs were strongly correlated with the total organic carbon (TOC), suggesting the dissolved PCBs were derived from the atmosphere via diffusive air–water exchange, and absorbed by phytoplankton. A high proportion of BDE209 was only detected in the sediment of the low fan of the Ganga River. There were weak correlations between low brominated BDEs and TOC, implying the degradation of BDE209 is a possible source of lower-brominated BDEs in deep-sea sediments.

Microbial communities associated with anaerobic degradation of polybrominated diphenyl ethers in river sediment.

Polybrominated diphenyl ethers (PBDEs) are extensively used as a class of flame retardants and have become ubiquitous environmental pollutants. We aimed to uncover the changes in microbial community with PBDE anaerobic degradation with and without zero-valent iron in sediment from the Erren River, considered one of the most heavily contaminated rivers in Taiwan. PBDE anaerobic degradation in sediment was analyzed by gas chromatography with an electron capture detector. Microbial community composition was analyzed by a pyrosequencing-based metagenomic approach. The anaerobic degradation rate of BDE-209 was higher than BDE-28 in sediment; the addition of zero-valent iron enhanced the degradation rates of both. In total, 19 known bacterial genera (4 major genera: Clostridium, Lysinibacillus, Rummeliibacillus, and Brevundimonas) were considered PBDE degradation-associated bacteria (sequence frequency negatively correlated with PBDE remaining percentage) as were four known archaea genera (Methanobacterium, Methanosarcina, Methanocorpusculum, and Halalkalicoccus; sequence frequency positively correlated with PBDE remaining percentage). The composition of bacteria and that of archaea affected the anaerobic degradation of BDE-28 and BDE-209. The addition of zero-valent iron further decreased the archaea content to undetectable levels.