Removal Of Polybrominated Diphenyl Ethers Research Articles

Occurrence and Ecotoxicological Impacts of Polybrominated Diphenyl Ethers (PBDEs) in Electronic Waste (E-Waste) in Africa: Options for Sustainable and Eco-Friendly Management Strategies

Polybrominated diphenyl ethers (PBDEs) are persistent contaminants used as flame retardants in electronic products. PBDEs are contaminants of concern due to leaching and recalcitrance conferred by the stable and hydrophobic bromide residues. The near absence of legislatures and conscious initiatives to tackle the challenges of PBDEs in Africa has allowed for the indiscriminate use and consequent environmental degradation. Presently, the incidence, ecotoxicity, and remediation of PBDEs in Africa are poorly elucidated. Here, we present a position on the level of contamination, ecotoxicity, and management strategies for PBDEs with regard to Africa. Our review shows that Africa is inundated with PBDEs from the proliferation of e-waste due to factors like the increasing growth in the IT sector worsened by the procurement of second-hand gadgets. An evaluation of the fate of PBDEs in the African environment reveals that the environment is adequately contaminated, although reported in only a few countries like Nigeria and Ghana. Ultrasound-assisted extraction, microwave-assisted extraction, and Soxhlet extraction coupled with specific chromatographic techniques are used in the detection and quantification of PBDEs. Enormous exposure pathways in humans were highlighted with health implications. In terms of the removal of PBDEs, we found a gap in efforts in this direction, as not much success has been reported in Africa. However, we outline eco-friendly methods used elsewhere, including microbial degradation, zerovalent iron, supercritical fluid, and reduce, reuse, recycle, and recovery methods. The need for Africa to make and implement legislatures against PBDEs holds the key to reduced effect on the continent.

Quantifying the removal of polybrominated diphenyl ethers (PBDEs) in physical, chemical, and biological sludge treatment systems

Polybrominated diphenyl ethers (PBDE) are priority contaminants historically used as flame retardants. PBDEs are known to occur in wastewater biosolids posing potential concerns with the beneficial land application of the biosolids. This study evaluated the removal of 21 congeners in nine full-scale sludge treatment systems including pelletization (P), alkaline stabilization (AS), and aerobic (AE) and anaerobic (AN) digestion. It is the first study to conduct a mass balance analysis of a broad spectrum of PBDEs during physical, chemical, and biological sludge treatment. The PBDE congener pattern in raw sludge and biosolids samples was consistent with commercial formulations. The fully brominated congener BDE-209 dominated biosolids from all sites with an average concentration of 620 ng/g dry weight (dw), followed by BDE-99 (173 ng/g dw) and BDE-47 (162 ng/g dw). Mass balance analysis on the P and AS processes showed no change in PBDE mass flows with treatment. However, aerobic and anaerobic digestion processes reported significant levels of removal and formation of individual congeners, though the results were not consistent between facilities. One aerobic digestion process (AE2) reported an overall average removal of 48%, whereas the other (AE1) reported very high levels of accumulation of tri- and tetraBDE congeners. Similarly, there were significant variations in PBDE behavior across the five anaerobic digestion plants studied. The plant with the longest solids retention time (SRT) (AN1) reported a moderate removal (50%) of overall PBDE loading and lower congeners, whereas other plants (AN2-AN5) showed significant low (−19%) to high (−166%) levels of formation of lower congeners. The results suggest that reduced SRTs result in formation of lower congeners while extended SRTs can lead to moderate removal of some PBDEs. Conventional sludge treatment result in low to moderate PBDE removal and advanced thermal conversion technologies may be needed to improve the contaminant removal during sludge treatment.

Occurrence and removal of legacy plasticizers and flame retardants through a drinking water treatment plant

The occurrence of thirty-four flame retardants and plasticizers throughout treatment steps in a drinking water treatment plant (DWTP) was analyzed to assess removal efficiencies of filtration, ultraviolet (UV) treatment, and chlorination. Legacy compounds and replacements were included to compare their presence and persistence. Twenty-four-hour composite sampling, offset to account for retention time, was performed at a direct filtration DWTP in Montreal, Canada over a three-day period. Polybrominated diphenyl ethers (PBDEs), considered legacy flame retardants, were infrequently detected or at concentrations <1 ng/L. When overall removal efficiencies could be calculated, the removal of ∑7PBDEs was 49 and 94 % for days 2 and 3, respectively. No removal could be calculated on day 1 as PBDEs were only detected in finished drinking water. Higher brominated PBDEs BDE-183 and BDE-154 were only detected in raw water. Organophosphate esters (OPEs), considered replacement flame retardants, were frequently detected in all water samples. The total average concentration of ∑15OPes was 501 ng/L in raw water and 162 ng/L in drinking water, with an average removal efficiency of 67 %. OPEs were mainly removed during filtration, with TCIPP, TDCIPP, and TPHP showing statistically significant removal of 76, 84, and 95 %, respectively. The total average concentration of ∑8plasticizers was 2938 ng/L in raw water and 116 ng/L in drinking water. All plasticizers, except for metabolite MEHP, had significant removal from filtration, and the overall removal of plasticizers ranged from 20 % for DEP to 99 % for DEHP. Drinking water treatment decreases the concentration of these contaminants in drinking water but was less effective in removing flame retardants than plasticizers, as indicated by their higher number of PBDEs detected and higher concentrations of OPEs measured. To our knowledge, it is the first report of the removal of PBDEs, OPE metabolites and plasticizer replacements (DEHA, DIDA, DINCH, DINP) during drinking water treatment.

Insight into the application of magnetic molecularly imprinted polymers in soil-washing effluent: Selective removal of 4,4′-dibromodiphenyl ether, high adaptivity of material and efficient recovery of eluent

Soil washing techniques can effectively remove soil polybrominated diphenyl ethers (PBDEs), but further removal of PBDEs from washing effluent is disrupted by environmental factors and coexisting organic matter. Hence, this work prepared novel magnetic molecularly imprinted polymers (MMIPs) to selectively remove PBDEs in soil washing effluent and recycling surfactants, with Fe3O4 nanoparticles as the magnetic core, methacrylic acid (MAA) as the functional monomer, and ethylene glycol dimethacrylate (EGDMA) as the cross-linker. Later, the prepared MMIPs were applied to adsorb 4,4′-dibromodiphenyl ether (BDE-15) in Triton X-100 soil-washing effluent and characterized by scanning electron microscopy (SEM), infrared spectrometry (FT-IR), nitrogen adsorption and desorption experiments. According to our observations, BDE-15 equilibrium adsorptions on dummy-template magnetic molecularly imprinted adsorbent (D-MMIP, 4-bromo-4′-hydroxyl biphenyl as template) and part-template magnetic molecularly imprinted adsorbent (P-MMIP, toluene as template) were reached within 40 min, and their equilibrium adsorption capacities were 164.54 μmol/g and 145.55 μmol/g, respectively, with imprinted factor α > 2.03, selectivity factor β > 2.14, and selectivity S > 18.05. MMIPs exhibited good adaptability to pH, temperature, and cosolvent. Our Triton X-100 recovery rate reached as high as 99.9%, and MMIPs maintained a more than 95% adsorption capacity after being recycled five times. Our results offer a novel approach to selectively remove PBDEs in soil-washing effluent, with efficient recovery of surfactants and adsorbents in soil-washing effluent.

Degradation efficiency and mechanism of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) by thermally activated persulfate system

Polybrominated diphenyl ethers (PBDEs) as a typical brominated flame retardant (BFR) have attracted worldwide attention due to the high environmental risk and resistance to conventional remediation processes. In this study, thermally activated persulfate (TAP) process was applied to degrade 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47), which is the most toxic and representative PBDEs in e-waste dismantling sites. Impact factors such as PDS dosage, heating temperature, and initial pH were evaluated. Results showed that BDE-47 can be 100% degraded within 180 min under the condition of PDS:BDE-47 = 1000:1, 60 °C, and pH = 7. Quenching experiments combined with EPR analysis further proved the important role of SO4·− in oxidating BDE-47. According to high-resolution mass spectrometry (HRMS) analysis, only one oxidation product of low toxicity was detected during the oxidation process. Theoretical calculations further revealed that the oxidation process mainly involved radical attack at C–Br bond, cleavage of C–Br bond, and fission of ether bond, and HSO4· may also play an important role in BDE-47 degradation in TAP system. In addition, TAP system exhibited universality as all selected PBDE congeners can be degraded, and the degradation rate of PBDEs was greatly affected by the number of substituted Br atoms in a negative trend. Overall, these findings indicate that TAP can be applied as an effective method for removal of PBDEs, and we provide a new insight for the practical application of TAP technology in BDE-47 degradation from experimental and theoretical aspects.

Comparative evaluation and prioritization of key influences on biodegradation of 2,2′,4,4′-tetrabrominated diphenyl ether by bacterial isolate B. xenovorans LB400

Polybrominated diphenyl ethers (PBDEs) are a class of persistent organic pollutants being widely distributed and harmful to human health and wildlife, and the development of sustainable rehabilitation strategies including microbial degradation is of great concern. Although the increasing number of bacteria, especially the broad-spectrum and potent aerobes have been isolated for the efficient removal of PBDEs, the external influences and the corresponding influential mechanism on biodegradation are not fully understood yet. Given the wide-spectrum biodegradability of aerobic bacterial isolate, B. xenovorans LB400 for PBDEs, the dual impacts of many pivotal factors including pH, temperature, presence of dissolved organic matter (DOM) and cadmium ion etc. were comprehensively revealed on biodegradation of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47). Due to the structural resemblance and stimulation of specific enzyme activity in bacteria, the biphenyl as substrates showed the greater capacity than non-aromatic compounds in improving biodegradation. The individual adaptation to neutrality and cultivation at about 30 °C was beneficial for biodegradation since the bacterial cellular viability and enzyme activity was mostly preserved. Although it was possibly good for the induction of hormesis and favorable to enhance the permeability or bioavailability of pollutant, the exceeding increase of Cd2+ or DOM may not give the profitable increase of biodegradation yet for the detrimental effect. For biodegradation, the mechanistic relationship that took account of the integrative correlation with the influential factors was artfully developed using partial least square (PLS) regression technique. Relative to the most significant influence of culture time and initial concentration of BDE-47, the larger relevance of other factors primarily marked as pH and DOM was consecutively shown after the quantitative prioritization. This may not only help understand the influential mechanism but provide a prioritizing regulation strategy for biodegradation of BDE-47. The PLS-derived relationship was validated with the certain predictability in biodegradation, and could be used as an alternative to accelerate a priori evaluation of suitability or improve the feasibility of such bacteria in remediation of PBDEs in the environment.

Congener-specificity, dioxygenation dependency and association with enzyme binding for biodegradation of polybrominated diphenyl ethers by typical aerobic bacteria: Experimental and theoretical studies

Polybrominated diphenyl ethers (PBDEs) are a group of organic pollutants that have attracted much concerns of scientific community over the ubiquitous distribution, chemical persistence and toxicological risks in the environment. Though a great number of aerobic bacteria have been isolated for the rapid removal of PBDEs, the knowledge about biodegradation characteristics and mechanism is less provided yet. Herein, the congener-specificity of aerobic biodegradation of PBDEs by typical bacteria, i.e. B. xenovorans LB400 was identified with the different biodegradation kinetics, of which the changes were largely hinged on the bromination pattern. The more bromination isomerically at ortho-sites other than meta-sites or the single bromination at one of aromatic rings might always exert the positive effect. The biodegradation of PBDEs should be thermodynamically constrained to some extent because the calculated Gibbs free energy changes of initial dioxygenation by quantum chemical method increased with the increase of bromination. Within the transition state theory, the high correlativity between the apparent biodegradation rates and Gibbs free energy changes implied the predominance and rate-limiting character of initial dioxygenation, while the regioselectivity of dioxygenation at the ortho/meta-sites was also manifested for the more negative charge population. The molecular binding with the active domain of dioxygenase BphA1 in aerobe was firstly investigated using docking approach. As significantly illustrated with the positive relationship, the higher binding affinity with BphA1 should probably signify the more rapid biodegradation. Besides the edge-on π-π stacking of PBDEs with F227 or Y277 and π-cation formulation with histidines (H233, H239) in BphA1, the reticular hydrophobic contacts appeared as the major force to underpin the high binding affinity and rapid biodegradation of PBDEs. Overall, the experimental and theoretical results would not only help understand the aerobic biodegradation mechanism, but facilitate enhancing applicability or strategy development of engineering bacteria for bioremediation of PBDEs in the environment.

Efficient removal of polybrominated diphenyl ethers from soil washing effluent by dummy molecular imprinted adsorbents: Selectivity and mechanisms

Surfactant enhanced elution is an effective method for removing hydrophobic organic pollutants from soils. The key to the development of leaching technology is selective removal of targeted pollutants in soil washing effluent and recycling of surfactant solutions. In this study, a molecular imprinting technique was applied to selectively sorb polybrominated diphenyl ethers (PBDEs) in soil washing effluent. The novel molecular imprinted polymers (MIPs) using different template molecules were synthesized by precipitation polymerization. Adsorption behaviors and mechanisms of MIPs were studied through experiments and theoretical calculations. The results show that 4-bromo-4′-hydroxybiphenyl and toluene can be effective imprinting molecule for MIPs synthesis. The maximal adsorption capacity of selected dummy molecular imprinted polymer (D1-MIP) was 1032.36 µmol/g, and that of part molecular imprinted polymer (P-MIP) was 981.13 µmol/g. Their imprinting factors in 5 PBDEs adsorption ranged from 2.13 to 5.88, the recovery percentage of Triton X-100 can reach 99.09%, confirming the feasibility of reusing surfactant. Various PBDEs could be removed by MIPs, and Quantitative Structure Property Relationship analysis revealed that PBDEs’ molecular volume, planarity, polarity, and hydrophobicity have major influences on their adsorption performance. DFT calculation revealed that Van der Waals force and hydrogen bonding played important roles during selective adsorption. These results can provide effective theoretical guidance for surfactant enhanced soil elution in practical engineering applications.

Removal of polybrominated diphenyl ethers in high impact polystyrene (HIPS) from waste TV sets.

Most studies have shown that improper disposal of e-waste can accelerate the release of high concentrations of polybrominated diphenyl ethers (PBDEs), and this situation causes environmental pollution and human health risks. The recycling technology of waste electronic plastics based on solvent processes can reduce environmental pollution and health risks from PBDEs. In this study, high impact polystyrene (HIPS) from waste TV sets was taken as the research object, and d-limonene and n-propanol were used as solvent and precipitant, respectively. We studied the relationship between the precipitation conditions and the size of precipitate particles, and the effect laws of precipitation conditions on the removal percentage of PBDEs were discussed. Transferring behavior of PBDEs during precipitation was investigated, and the parameters suitable for removing PBDEs from HIPS solution were confirmed. Results showed that lower HIPS concentration in d-limonene, lower precipitation temperature, higher mass ratio of n-propanol to HIPS solution, and greater stirring speed were conducive to form smaller and more uniform precipitate particles. All conditions (concentration, temperature, mass ratio, and stirring rate) that could increase the solubility of PBDEs in the mixed solvent of limonene and n-propanol or decrease the swelling degree of HIPS precipitate particles, or reduce the size of particles could improve the removal percentage of PBDEs. The investigated results indicated that insoluble PBDEs (e.g., decabromodiphenyl ether) transferred into the HIPS precipitate mainly through the generated crystals and then precipitated together with the HIPS particles, and soluble PBDEs (e.g., octabromodiphenyl ether) migrated into the precipitate by the solution entrained. The precipitate particles, which measured approximately 1.0mm (on average), were obtained when the solution containing 10% of HIPS from waste TV shell was precipitated by adding n-propanol equivalent totwice the mass of the solution at 40°C and 3000 r/min stirring speed. The total concentration of PBDEs in the precipitate particles (dried) was reduced to 2369mg/kg, and 88.06% of the PBDEs in the original plastic solution was successfully removed by this process.

Enhanced reductive debromination of decabromodiphenyl ether by organic-attapulgite supported Fe/Pd nanoparticles: Synergetic effect and mechanism

Effective removal of polybrominated diphenyl ethers (PBDEs) from the environment is essential for the ecosystem and human health. Reductive debromination of PBDEs by nanoscale zerovalent iron (nZVI) has become an important technology. However, the agglomeration and low persistence catalytic activity of nZVI particles have become urgent problems to be improved. Herein, we report the first application of a new organo-attapulgite (OA) supported Fe/Pd nanoparticles (OA-Fe/Pd) composite for decabromodiphenyl ether (BDE209) removal. BDE209 was efficiently removed using OA-Fe/Pd with a reaction rate that was 9.97 times greater than that of the nZVI due to the synergetic effect of support material OA and Pd loading. OA could prevent nZVI particles from agglomeration and adsorb BDE209 molecules to its surface. Pd could supply atomic hydrogen and also prevent the oxidation of nZVI particles. The degradation of BDE209 by OA-Fe/Pd was affected by many factors and followed pseudo first-order kinetics. The degradation of BDE209 by OA-Fe/Pd underwent a stepwise debromination manner with the H-transfer dominant mechanism. BDE209 (25 mg∙L-1) could be degraded to penta-BDEs to diphenyl ether (DE) by 3.0 g∙L-1 OA-Fe/Pd within 240 min under neutral condition. This study provides some inspiration for improving the removal efficiency of PBDEs with nZVI-based materials.

Identification of Reductive Dehalogenases That Mediate Complete Debromination of Penta- and Tetrabrominated Diphenyl Ethers in Dehalococcoides spp.

Polybrominated diphenyl ethers (PBDEs) are persistent, highly toxic, and widely distributed environmental pollutants. The microbial populations and functional reductive dehalogenases (RDases) responsible for PBDE debromination in anoxic systems remain poorly understood, which confounds bioremediation of PBDE-contaminated sites. Here, we report a PBDE-debrominating enrichment culture dominated by a previously undescribed Dehalococcoides mccartyi population. A D. mccartyi strain, designated TZ50, whose genome contains 25 putative RDase-encoding genes, was isolated from the debrominating enrichment culture. Strain TZ50 dehalogenated a mixture of pentabrominated diphenyl ether (penta-BDE) and tetra-BDE congeners (total BDEs, 1.48 μM) to diphenyl ether within 2 weeks (0.58 μM Br-/day) via ortho- and meta-bromine elimination; strain TZ50 also dechlorinated tetrachloroethene (PCE) to vinyl chloride and ethene (260.2 μM Cl-/day). Results of native PAGE, proteomic profiling, and in vitro enzymatic activity assays implicated the involvement of three RDases in PBDE and PCE dehalogenation. TZ50_0172 (PteATZ50) and TZ50_1083 (TceATZ50) were responsible for the debromination of penta- and tetra-BDEs to di-BDE. TZ50_0172 and TZ50_1083 were also implicated in the dechlorination of PCE to trichloroethene (TCE) and of TCE to vinyl chloride/ethene, respectively. The other expressed RDase, TZ50_0090 (designated BdeA), was associated with the debromination of di-BDE to diphenyl ether, but its role in PCE dechlorination was unclear. Comparatively few RDases are known to be involved in PBDE debromination, and the identification of PteATZ50, TceATZ50, and BdeA provides additional information for evaluating debromination potential at contaminated sites. Moreover, the ability of PteATZ50 and TceATZ50 to dehalogenate both PBDEs and PCE makes strain TZ50 a suitable candidate for the remediation of cocontaminated sites. IMPORTANCE The ubiquity, toxicity, and persistence of polybrominated diphenyl ethers (PBDEs) in the environment have drawn significant public and scientific interest to the need for the remediation of PBDE-contaminated ecosystems. However, the low bioavailability of PBDEs in environmental compartments typically limits bioremediation of PBDEs and has long impeded the study of anaerobic microbial PBDE removal. In the current study, a novel Dehalococcoides mccartyi strain, dubbed strain TZ50, that expresses RDases that mediate organohalide respiration of both PBDEs and chloroethenes was isolated and characterized. Strain TZ50 could potentially be used to remediate multiple cooccurring organohalides in contaminated systems.

Current progress in degradation and removal methods of polybrominated diphenyl ethers from water and soil: A review

The widespread of polybrominated diphenyl ethers (PBDEs) in the environment has caused rising concerns, and it is an urgent endeavor to find a proper way for PBDEs remediation. Various techniques such as adsorption, hydrothermal and thermal treatment, photolysis, photocatalytic degradation, reductive debromination, advanced oxidation processes (AOPs) and biological degradation have been developed for PBDEs decontamination. A comprehensive review of different PBDEs remediation techniques is urgently needed. This work focused on the environmental source and occurrence of PBDEs, their removal and degradation methods from water and soil, and prospects for PBDEs remediation techniques. According to the up-to-date literature obtained from Web of Science, it could be concluded that (i) photocatalysis and photocatalytic degradation is the most widely reported method for PBDEs remediation, (ii) BDE-47 and BDE-209 are the most investigated PBDE congeners, (iii) considering the recalcitrance nature of PBDEs and more toxic intermediates could be generated because of incomplete degradation, the combination of different techniques is the most potential solution for PBDEs removal, (iv) further researches about the development of novel and effective PBDEs remediation techniques are still needed. This review provides the latest knowledge on PBDEs remediation techniques, as well as future research needs according to the up-to-date literature.

Bromination effect of polybrominated diphenyl ethers on the graphyne surface on enhanced adsorption characteristics using density functional theory study

Among various techniques for treating polybrominated diphenyl ethers (PBDEs), adsorption and removal methods using carbon materials are widely applied to remove and decompose organic pollutants with high efficiency. Of many carbon allotropes, theoretically developed graphyne has numerous promising applicabilities for its strong carbon chemical bond, large conjugate system, good chemical stability, and excellent electrical conductivity. To evaluate the PBDE removal capability of graphyne as an adsorbent, we investigated the adsorption properties of ten PBDE species on graphyne using the density functional theory calculation. Furthermore, we analyzed the correlation between the hydrophobicity and adsorption characteristics of PBDEs and found that the adsorption energy increased with the hydrophobicity and the bromination number, indicating a linear relationship for only seven samples. In BDE154, BDE183, and BDE209, however, this linearity was not clearly found because when the bromine groups of the PBDE structures were located at 6,6′, two phenyl rings repelled each other to limit adsorption. From a water solvation model, graphyne also indicated a high adsorption capacity of PBDEs. It is worth noting that graphyne is considered to be a suitable material for PBDE adsorption, and the adsorption reaction may vary depending on the structural characteristics and hydrophobicity of the PBDEs.

A novel management strategy for removal and degradation of polybrominated diphenyl ethers (PBDEs) in waste printed circuit boards

Waste printed circuit boards (PCBs) contain a high level of brominated flame retardants (BFRs), among which polybrominated biphenyl ethers (PBDEs) are the most widely used additive BFRs. PBDEs are considered to be a type of persistent organic pollutants (POPs). The efficient removal/degradation of PBDEs in waste PCBs is an urgent problem in electronic waste treatment, but the degradation of PBDEs is a great challenge due to their extreme stability and persistence in nature. In this study, a novel management strategy was developed for removal and degradation of PBDEs in waste PCBs by using a simple subcritical methanol (SubCM) process. The results showed that reaction temperature, residence time, solid-to-liquid ratio, and additive NaOH are key factors influencing the removal of PBDEs from waste PCBs. Under optimal conditions (200 °C, 60 min, 1:20 g/mL), the removal efficiency of ∑8PBDEs from waste PCBs could reach 91.3% and 98.8% for the proposed process of SubCM and SubCM + NaOH, respectively. When the temperature is below 200 °C, highly brominated PBDEs congeners in waste PCBs were degraded into 2,'3,4′,6-Tetrabromodiphenyl ether (BDE71) and 2,4,4′-Tribromodiphenyl ether (BDE28) after SubCM treatment. 4-Bromophenyl ether (BDE4) and diphenyl ether were generated by the further debromination of BDE71 and BDE28 with the increase of treatment temperature. The debromination temperature of PBDEs congeners in SubCM could be markedly lowered by adding 4 g/L of NaOH. The complete debromination of PBDEs congeners in waste PCBs could be achieved at 300 °C and 250 °C for the developed process of SubCM and SubCM + NaOH, respectively.

Do pyrene and Kandelia obovata improve removal of BDE-209 in mangrove soils?

Combined pollution caused by polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) in mangrove wetlands is serious, with their remediation to be been paid more and more attention. However, little is known about the combined impact of PAHs and mangrove species on removal of PBDEs in contaminated soils. In this study, BDE-209 and pyrene were selected and a 9 months experiment was conducted to explore how BDE-209 removal in contaminated soil varied with pyrene addition and Kandelia obovata planting, and to clarify corresponding microbial responses. Results showed that BDE-209 removals in soil induced by pyrene addition or K. obovata planting were significant and stable after 6 months, with the lowest levels of BDE-209 in combined pyrene addition with K. obovata planting. Unexpected, root uptake of BDE-209 in K. obovata was limited for BDE-209 removal in soil, which was verified by lower total amount of BDE-209 bioaccumulated in K. obovata's root. In soil without K. obovata planting, BDE-209 removal caused by pyrene addition coexisted with changed bacterial abundance at phylum Planctomycetes and Chloroflexi, class Planctomycetacia, and genus Blastopirellula. K. obovata-induced removal of BDE-209 in soil may be related to bacterial enrichment in phylum Proteobacteria, class Gammaproteobacteria and genus Ilumatobacter, Gaiella. Thus, in BDE-209 contaminated soil, microbial community responses induced by pyrene addition and K. obovata planting were different at phylum, class and genus levels. This is the first study demonstrating that pyrene addition and K. obovata planting could improve BDE-209 removal, and differently affected the corresponding responses of microbial communities.

Effect of light on the transformation of BDE-47 by living and autoclaved cultures of Microcystis flos-aquae and Chlorella vulgaris

Polybrominated diphenyl ethers (PBDEs) are ubiquitous and toxic contaminants found in high concentrations in watercourses, and are not well removed by conventional wastewater treatment facilities. This study aimed to evaluate the removal and transformation of BDE-47, one of the environmentally predominant PBDE congener, by a green alga (Chlorella vulgaris) and a cyanobacterium (Microcystis flos-aquae) under different light conditions. Living and autoclaved cultures were exposed to BDE-47 at a concentration of 10 μg L−1 for 7 days. Both species removed >90% of BDE-47 very shortly after spiking. Light intensity affected the transformation of BDE-47 in living cultures of both species, since 5 to 11 times more debromination products were measured at a light intensity of 100 μmol photons m−2 s−1 than at 20 μmol photons m−2 s−1. Living cultures of M. flos-aquae transformed BDE-47 at a rate of 0.22 day−1 while no transformation was observed in the respective autoclaved cultures. On the contrary, both living and autoclaved cultures of C. vulgaris had similar BDE-47 transformation rates of 0.05–0.06 day−1. Debromination of BDE-47 was a predominant transformation pathway in cultures of C. vulgaris, with two times higher BDE-28 concentrations measured than in M. flos-aquae, while hydroxylation was more dominant with the cyanobacterium. Most BDE-47 and its debromination product BDE-28 were found on the cell surface of both species. These results reveal that different transformation mechanisms were involved in C. vulgaris and M. flos-aquae cultures and confirm the importance of species selection for the removal of PBDEs from contaminated environments.

Efficient photocatalytic debromination of 2,2ʹ,4,4ʹ-tetrabromodiphenyl ether by Ag-loaded CdS particles under visible light

Highly active and visible light-driven Ag-loaded CdS photocatalysts were prepared via a hydrothermal synthesis and photodeposition method. The removal and debromination of 2,2ʹ,4,4ʹ-tetrabromodiphenyl ether was achieved efficiently using this Ag-loaded CdS under visible light, with a removal efficiency of 100% and a debromination ratio of 44.3% being achieved within 30 min. Both the reaction solvent and the water content were found to have a strong influence on the removal efficiency and the debromination ratio. In addition, the stepwise debromination preference was ortho ≫ para, thereby indicating that the main debromination pathway was electron reduction. The stability and efficiency of these Ag-loaded CdS photocatalysts for the removal of BDE47 were satisfactory, and so our results confirmed the development of a promising visible light-driven catalyst for the removal of polybrominated diphenyl ethers.

Spatial distribution and diversity of organohalide-respiring bacteria and their relationships with polybrominated diphenyl ether concentration in Taihu Lake sediments.

It is acknowledged that organohalide-respiring bacteria (OHRB) can degrade polybrominated diphenyl ethers (PBDEs); however, very little is known about the distribution of OHRB or their response to PBDE contamination in natural sediments. We collected sediments from 28 sampling sites in Taihu Lake, China, and investigated the spatial distribution and diversity of OHRB, and the relationships between the PBDE contamination levels and the PBDE removal potential. The abundances of five typical OHRB genera, namely Dehalobacter, Dehalococcoides, Dehalogenimonas, Desulfitobacterium, and Geobacter, ranged from 0.34×104 to 19.4×107 gene copies g-1 dry sediment, and varied significantly among different areas of Taihu Lake. OHRB were more abundant in sediments from Meiliang and Zhushan Bay, where the PBDE concentrations were higher, and the phylotype diversity of the OHRB belonging to the family Dehalococcoidaceae was lower, than reported for other areas. While the sulfate concentrations explained much of the spatial distribution of OHRB, PBDE concentrations were also a strong influence on the abundance and diversity of OHRB in the sediments. For Dehalococcoides, Dehalogenimonas and Geobacter, the abundance of each genus was positively related to its own potential to remove PBDEs. The dominant OHRB genus, Dehalogenimonas, may contribute most to in situ bioremediation of PBDEs in Taihu Lake.

Removal rate and releases of polybrominated diphenyl ethers in two wastewater treatment plants, Korea

Wastewater treatment plants (WWTPs) play an important role in minimizing the release of many pollutants into the environment. Nineteen congeners in two WWTPs in Korea were determined to investigate the occurrence and fate of polybrominated diphenyl ethers (PBDEs) during wastewater treatment processes. The concentration of total PBDEs was 69.6 and 183 ng/L in influent, which declined to 1.59 and 2.34 ng/L in the final effluent, respectively (Tongyeong and Jinhae WWTPs). PBDEs were found to exist mostly in the particulate phase of wastewater, which rendered sedimentation efficient for the removal of PBDEs. BDE-209 was the predominant congener in the influent and sludge. Most of the PBDEs entering the WWTPs presumably ended up in the sludge, with < 2% being discharged with the final effluent. According to the mass loading estimation, every day 2.55–9.29 g PBDEs entered the two WWTPs, 2.8–10.4 g were disposed to landfill sites in sludge form and 0.06–0.12 g were discharged to the surrounding water through final effluent, respectively. Preliminary results indicated that the ecological risk to organisms in soil exposed to PBDEs through the usage of sludge application to agricultural land was relatively low. To our knowledge, this study is the first to report on the removal efficiency of PBDEs in a WWTP in Korea.

Toward integrated detection and graphene-based removal of contaminants in a lab-on-a-chip platform

A novel, miniaturized microfluidic platform was developed for the simultaneous detection and removal of polybrominated diphenyl ethers (PBDEs). The platform consists of a polydimethylsiloxane (PDMS) microfluidic chip for an immunoreaction step, a PDMS chip with an integrated screen-printed electrode (SPCE) for detection, and a PDMS-reduced graphene oxide (rGO) chip for physical adsorption and subsequent removal of PBDE residues. The detection was based on competitive immunoassay-linked binding between PBDE and PBDE modified with horseradish peroxidase (HRP-PBDE) followed by the monitoring of enzymatic oxidation of o-aminophenol (o-AP) using square wave anodic stripping voltammetry (SW-ASV). PBDE was detected with good sensitivity and a limit of detection similar to that obtained with a commercial colorimetric test (0.018 ppb), but with the advantage of using lower reagent volumes and a reduced analysis time. The use of microfluidic chips also provides improved linearity and a better reproducibility in comparison to those obtained with batch-based measurements using screen-printed electrodes. In order to design a detection system suitable for toxic compounds such as PBDEs, a reduced graphene oxide–PDMS composite was developed and optimized to obtain increased adsorption (based on both the hydrophobicity and π–π stacking between rGO and PBDE molecules) compared to those of non-modified PDMS. To the best of our knowledge, this is the first demonstration of electrochemical detection of flame retardants and a novel application of the rGO-PDMS composite in a biosensing system. This system can be easily applied to detect any analyte using the appropriate immunoassay and it supports operation in complex matrices such as seawater.