Complete Debromination Research Articles

Catalytic generation of adsorbed atomic H for degradation of 2,2′,4,4′-tetrabromodiphenyl ether by mechanochemically prepared Ni-doped oxalated zero-valent iron

In the homologous series of polybrominated diphenyl ethers (PBDEs), the debromination of low-brominated diphenyl ethers with higher toxicity remains a challenge. Nano zero-valent iron (nZVI) has been extensively studied for the debromination of PBDEs, but its inherent direct electron transfer mechanism is less efficient for low-brominated diphenyl ethers, and there are issues with high preparation costs. In this work, we synthesize Ni-doped oxalated submicron ZVI (FeOXbm/Ni) using a low-cost ball-milling method. FeOXbm/Ni exhibits a debromination rate constant of 0.48 day−1 for 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) in tetrahydrofuran (THF)/water. The debromination rate of FeOXbm/Ni for BDE-47 in water is even faster (0.98 day−1), with the yield of the complete debromination product, diphenyl ether, reaching 76.71%. In real groundwater, FeOXbm/Ni also shows high reactivity toward BDE-47, with a rate constant of 0.33 day−1. Kinetic experiments, quenching experiments, and degradation pathway indicate that the attack of atomic hydrogen on C-Br bonds is the primary degradation mechanism. Electrochemical analysis further show that Ni0 sites could cleave hydrogen into absorbed atomic hydrogen (H∗ABS) and adsorbed atomic hydrogen (H∗ADS), with H∗ADS playing the main role. These findings contribute valuable insights into advancing the large-scale application of ZVI and offer promising strategies for thorough remediation of PBDEs pollution.

Revolutionary ZVI-Entrapped Sol-Gel Silica Matrices: Efficient Catalytic Reduction of High-Concentration Halo-Organic Compounds-Addressing Bromoacetic Acid Contamination in Industrial Wastewaters.

The de-halogenation of highly concentrated halo-organic compounds using Zero Valent Iron entrapped in silica matrices as a catalyst was investigated. This study aimed to evaluate the effectiveness of the Zero Valent Iron-entrapped organically modified silica matrices in transforming highly concentrated hazardous halogenated compounds into environmentally benign materials in the presence of BH4-. The Zero Valent Iron-entrapped silica gel matrices were synthesized using the sol-gel method. The de-halogenation products were analyzed using high-performance liquid chromatography. The results suggest that the Zero Valent Iron-entrapped silica matrices are effective catalysts in the de-halogenation reaction of halo-organics by BH4- with 100% efficiency. The current work also highlights the complete de-bromination of harmful wastewater generated by the bromoacetic acid manufacturing industry using Zero Valent Iron-entrapped silica matrices. Therefore, Zero Valent Iron-entrapped silica matrices can be considered potential candidates for the catalytic removal of highly concentrated halo-organic compounds from contaminated water. This technology can play a crucial role in reducing the environmental impact of hazardous substances.

The degradation of tetrabromobisphenol A by metal-free graphene oxide in the dark

Brominated flame retardants (BFRs) such as tetrabromobisphenol A (TBBPA) were widely detected in the environment. The ease of synthesis of graphene-based materials (GBMs) makes it an excellent metal-free carbon-based catalyst for the reductive debromination of TBBPA. Here we explore the complete debromination of TBBPA from the aqueous environment in the dark using metal-free graphene oxide (GO) and reduced GO (rGO). More importantly, radical scavenger experiments reveal the formation of superoxide radicals and singlet oxygen from the surface of GBMs leading to the debromination of TBBPA. GO shows an enhanced catalytic activity due to enriched O-functional groups on the surface than rGO, as observed by cyclic voltammetry and electrochemical impedance spectroscopy. In addition, the TBBPA degradation pathway was proposed with BPA as the end product and by-products were identified by mass spectroscopy. The complete TBBPA degradation was observed within 240 mins of reaction time (kobs = 8.6×10−3 min−1), which was significantly more efficient than the catalytic activity of other metal-based catalysts. Our study thus provides a new insight into the debromination mechanisms of TBBPA which would exhibit potential for future efficient catalyst development.

Completely recyclable and reusable automatic phase-separable catalytic system for the reductive debromination of polybrominated diphenyl ethers

An automatic phase-separable catalytic system was developed for the reductive debromination of polybrominated diphenyl ethers (PBDEs) using thiol-modified Pd nanoparticles (thiol-Pd NPs) as the catalyst, H2 as the reducing agent, and n-butanol (oil phase) and water (water phase) as solvents. This system achieved efficient and complete debromination of various PBDEs with 1–10 bromine atoms and other bromo-organic pollutants at concentrations ranging from 15 to 1500 mg L−1. Typically, this system achieved a debromination efficiency of 100 % within 15 min for all the tested bromo-organic pollutants. Importantly, the debromination reaction was conducted in a microemulsion state under stirring; upon stopping the stirring, the microemulsion automatically separated into an upper oil phase, a down water phase, and a thiol-Pd NP self-assembled membrane phase at the oil/water interface. These three phases could be easily separated from each other, allowing for their reuse across multiple debromination cycles with good reusability. The thiol modifier enhanced the stability and reusability of Pd NPs and improved the adsorption of PBDEs, facilitating their reaction with atomic hydrogen (the dominant reactive species). This method successfully eliminated PBDEs in soils by integrating with a pre-extraction process.

Magnetically separable Pd-iron-oxides composites as highly efficient and recyclable catalysts for ultra-rapid degradation and debromination of polybrominated diphenyl ethers

When precious nano-metals are used as environmental catalysts, it is important to tune the particle sizes and the reusability of the nano-metals for achieving their highly efficient catalytic performance at a low cost. In the present work, magnetic iron oxides (FeOx-Y) nanoparticles were pre-prepared as supports of nano-metals, where Y represented the mole percentage of Fe(III) in the total iron (Y ≥ 50 %). FeOx-Y (support), PdCl42− (Pd source) and NaBH4 (reducing agent) were added into the organic pollutant solution containing 2,2′,4,4′-tetrabromodiphenyl ether (BDE47). After the NaBH4 was added, the followed reaction realized not only the rapid in-situ preparation of a Pd-loaded FeOx-Y composite catalyst (Pd-FeOx-Y), but also the ultra-fast and complete debromination of BDE47 within 30 s. Comparing the case without adding FeOx-Y, the debromination efficiency of BDE47 was much promoted in the presence of FeOx-Y. The support-induced enhancing effect on the catalytic ability of Pd nanoparticles was improved by increasing the Fe(III) content in the support, being attributed to the much more hydroxyl groups on the support surface. Considering both the catalytic and recovery abilities of Pd-FeOx-Y, Pd-FeOx-75 was the optimal choice because it could be magnetically recovered and re-used for multiple cycles with high catalytic activities. The presently developed “catalyst preparation-pollutant degradation” one-pot system could be applied to conduct complete debromination of all the PBDEs.

Computational study of mechanistic pathway and effect of zero valent metals on reductive debromination of some polybrominated biphenyls

Complete debromination of three polybrominated biphenyls (PBBs), namely 2,2′,3,3′,4,4′-hexabromobiphenyl (PBB-128), 2,2′,3,3′,4,5- hexabromobiphenyl (PBB-129) and 2,2′,3,3′,4,5′- hexabromobiphenyl (PBB-130) aided by zero valent magnesium (Mg0) andzinc (Zn0) in the presence of methanol was studied computationally using dispersion corrected ωB97XD functional with cc-pVTZ basis set. All possible debromination pathways were explored for each parent PBB and the most energetically favoured pathway was identified. Mono-debromination of each PBB afforded a two-step mechanism, viz, formation of a highly charged covalent intermediate that involves a phenyl-metal-bromine connectivity and protonation by methanol molecule.Total activation energy for the step-wise removal of one bromine substituent increased along the debromination pathway. Using substituent positions, favourable sequence of stepwise debromination was found to follow the order 3 or 3′2 or 2′ 4 or 4′, while Mg0catalyzed the debromination reaction better than Zn0. The order of ease of debromination was found to be PBB-128PBB-130PBB-129.

Micro surface modification of Zn/Cu-foam electrode for debromination of tetrabromobisphenol A

Copper nanoparticles (Cu NPs) modified zinc electrode (Cu-Zn/Cu-foam) is successfully prepared via cathodic electrodeposition followed by a galvanic-exchange procedure and characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), Tafel curve and galvanostatic electrolysis. With the reconstruction of Zn through the formation of Cu NPs on the surface, the corrosion current and active surface area are increased, and the activity on the electrochemical reduction of tetrabromobisphenol A (TBBPA) is activated. The TBBPA (10 mmol/L) is almost degraded within 1 h, and the yield of the complete debromination product bisphenol A (BPA) reaches 92 % in 3 h. Furthermore, the surface of used Cu-Zn/Cu-foam electrode become more uniform and CuZn5 is formed, which enabled the stable electro-catalytic activity on the electro-reduction of TBBPA even after ten cycles. Then the degradation mechanism is proposed. The micro galvanic reconstruction of Zn offers a promising strategy for the removal of TBBPA in aquatic environment.

Mechanochemical debromination of waste printed circuit boards with marble sludge in a planetary ball milling process.

An effective management of waste printed circuit board (WCB) recycling presents significant advantages of an economic, social, and environmental nature. This is particularly the case when a suitable valorisation is made of the non-metallic parts of the WCBs, well known for their "hidden" toxicological risks. Such benefits motivate research on techniques that could contribute to mitigating their adverse socio-environmental impacts. In this work, waste printed circuit boards (WCBs) containing tetrabromobisphenol A (TBBPA) as a brominated flame retardant (BFR) underwent debromination using a mechanochemical treatment (MCT) and marble sludge, another recoverable waste, as well as pure CaO as additives. All runs in this work were performed at an intermediate rotation speed of 450rpm, using additive/WCB mass ratios (Rm) of 4:1 and 8:1, ball to powder ratios (BPR) of 20:1 and 50:1, treatment times from 2.5h to 10h, two WCB sizes (powder and 0.84mm) and marble sludge, from original to precalcined conditioning. Stainless steel jars and balls were used to verify the effect of each parameter on the system and to seek an optimum process. Complete debromination of 0.84mm WCBs was achieved at 450rpm, using a Rm of 8:1, a BPR of 50:1, a residence time of 10h (more than 95% in only 5h), and a precalcined marble sludge as additive. The results revealed that when using a Rm of 4:1 instead of 8:1, more waste could be effectively treated, per batch with a lesser need for additives, at the expense of a slightly lower level of debromination efficiency. In the same way, an appropriate apparent ball diameter (with respect to the volume of the used jar) should be carefully studied in relation to WCB size in order to achieve a beneficial total amount of energy transfer during milling.

Diversity of organohalide respiring bacteria and reductive dehalogenases that detoxify polybrominated diphenyl ethers in E-waste recycling sites.

Widespread polybrominated diphenyl ethers (PBDEs) contamination poses risks to human health and ecosystems. Bioremediation is widely considered to be a less ecologically disruptive strategy for remediation of organohalide contamination, but bioremediation of PBDE-contaminated sites is limited by a lack of knowledge about PBDE-dehalogenating microbial populations. Here we report anaerobic PBDE debromination in microcosms established from geographically distinct e-waste recycling sites. Complete debromination of a penta-BDE mixture to diphenyl ether was detected in 16 of 24 investigated microcosms; further enrichment of these 16 microcosms implicated microbial populations belonging to the bacterial genera Dehalococcoides, Dehalogenimonas, and Dehalobacter in PBDE debromination. Debrominating microcosms tended to contain either both Dehalogenimonas and Dehalobacter or Dehalococcoides alone. Separately, complete debromination of a penta-BDE mixture was also observed by axenic cultures of Dehalococcoides mccartyi strains CG1, CG4, and 11a5, suggesting that this phenotype may be fairly common amongst Dehalococcoides. PBDE debromination in these isolates was mediated by four reductive dehalogenases not previously known to debrominate PBDEs. Debromination of an octa-BDE mixture was less prevalent and less complete in microcosms. The PBDE reductive dehalogenase homologous genes in Dehalococcoides genomes represent plausible molecular markers to predict PBDE debromination in microbial communities via their prevalence and transcriptions analysis.

Organohalide respiration potential in marine sediments from Aarhus Bay.

Organohalide respiration (OHR), catalysed by reductive dehalogenases (RDases), plays an important role in halogen cycling. Natural organohalides and putative RDase-encoding genes have been reported in Aarhus Bay sediments, however, OHR has not been experimentally verified. Here we show that sediments of Aarhus Bay can dehalogenate a range of organohalides, and different organohalides differentially affected microbial community compositions. PCE-dechlorinating cultures were further examined by 16S rRNA gene-targeted quantitative PCR and amplicon sequencing. Known organohalide-respiring bacteria (OHRB) including Dehalococcoides, Dehalobacter and Desulfitobacterium decreased in abundance during transfers and serial dilutions, suggesting the importance of yet uncharacterized OHRB in these cultures. Switching from PCE to 2,6-DBP led to its complete debromination to phenol in cultures with and without sulfate. 2,6-DBP debrominating cultures differed in microbial composition from PCE-dechlorinating cultures. Desulfobacterota genera recently verified to include OHRB, including Desulfovibrio and Desulfuromusa, were enriched in all microcosms, whereas Halodesulfovibrio was only enriched in cultures without sulfate. Hydrogen and methane were detected in cultures without sulfate. Hydrogen likely served as electron donor for OHR and methanogenesis. This study shows that OHR can occur in marine environments mediated by yet unknown OHRB, suggesting their role in natural halogen cycling.

On-Surface Debromination of C6Br6: C6 Ring versus C6 Chain

Carbon allotropes comprising sp-hybridized carbon atoms have been investigated for decades for their molecular structure. One of the unsolved mysteries is whether they should take a linear or cyclic configuration in condensed phases due to the lack of atomistic characterizations. Herein, we designed a molecule with a C6 skeleton as a model system to address this issue, which was achieved by eliminating Br atoms from hexabromobenzene (C6Br6) molecule on the Ag(111) substrate via thermal treatment. It is found that the C6 ring intermediate resulting from complete debromination is energetically unstable at room temperature based on theoretical calculations. It subsequently transforms into the C6 polyynic chain via a ring-opening process and ultimately polymerizes into the organometallic polyyne, whose triyne structural unit is revealed by bond-resolved noncontact atomic force microscopy. Theoretical calculations demonstrated an energetically favorable pathway in which the ring-opening process occurs after complete debromination of C6Br6. Our study provides a platform for the synthesis of elusive carbon-rich materials.

Highly efficient catalytic debromination of tetrabromodiphenyl ether with hydrazine as reducing agent: The role of the interaction between the catalyst and the reducing agent

It is still urgently needed to clarify how the reductive dehalogenation is accelerated by the interaction between the catalyst and the reducing agent. In the present work, both Pd and Cu were observed to induce the debromination of 2,2′,4,4′-tetrabromodiphenyl ether (BDE47) with hydrazine hydrate (N2H4·H2O) as reducing agent. In the case of Pd system, all the added BDE47 was debrominated to bromine-free products within 20 min. However, much different debromination behaviors of BDE47 were observed when Cu was used as the catalyst: in the initial stage the debromination efficiency of BDE47 could reach up to 55.3% within 0.5 min; nevertheless the complete debromination could not be achieved by prolonging reaction time. With the aid of DFT calculations, the above-mentioned great differences were attributed to the affinity of Pd to both H and N atoms, and strong Cu–N coordination existed between Cu and the adsorbed hydrazine molecules. The dissociation energy for the cleavage of N–H and N-N bonds of N2H4·H2O adsorbed on Cu was very low, and hence the debromination of BDE47 was ultra-fast due to the spontaneously cleavage of N–H bond but it was inhibited at the later stage by the generated ammonium species (poisoning effect to the Cu catalyst) due to N-N bond cleavage. In contrast, the dissociation energy for the cleavage of N–H bond on the surface of Pd was higher and no ammonium was detected. These guarantee the continuously fast and complete debromination of BDE47 and its intermediates. These new insights to the catalytic mechanism through the interaction between the catalyst and the reducing agent will help to construct an efficient system to remove halogenated organic pollutants.

Rapid debromination of tetrabromobisphenol A by Cu/Fe bimetallic nanoparticles in water, its mechanisms, and genotoxicity after treatments

Tetrabromobisphenol A (TBBPA), a widely used brominated flame retardants, has been detected in various environmental matrices and is known to cause various adverse effects on human bodies. This study examined the feasibility and effectiveness of remediating TBBPA using Cu/Fe bimetallic nanoparticles (Cu/Fe BNPs) at various environmental and operational conditions. In general, TBBPA removal rate and debromination efficiency increased with higher Cu doping, higher Cu/Fe BNPs loading, higher temperature, and lower pH. At optimal conditions, TBBPA was completed removed at a rate constant > 0.2 min−1 where over 90% TBBPA was transformed to BPA within 30 min. The activation energy was found to be 35.6 kJ/mol, indicating that TBBPA was predominantly removed via surface-controlled reactions. Under pH 3–7 and ≥ 25 °C, debromination was the dominant removal mechanism compared to adsorption. The complete debromination pathway and the time-evolution of intermediates byproducts at different pHs were also presented. Cu/Fe BNPs can be reused for more than 6 times with performance constancy. Genotoxic tests showed that the treated solution did not find a significant hazardous potential. The byproducts can be further degraded by additional H2O2 through Fenton reaction. These results demonstrated the efficacy of Cu/Fe BNPs for treating TBBPA and its potential for degrading other halogenated organic compounds.

Offshore Marine Sediment Microbiota Respire Structurally Distinct Organohalide Pollutants.

Marine sediments are a major sink of organohalide pollutants, but the potential for offshore marine microbiota to transform these pollutants remains underexplored. Here, we report dehalogenation of diverse organohalide pollutants by offshore marine microbiota. Dechlorination of polychlorinated biphenyls (PCBs) was observed in four marine sediment microcosms, which was positively correlated with in situ PCB contamination. Three distinct enrichment cultures were enriched from these PCB-dechlorinating microcosms using tetrachloroethene (PCE) as the sole organohalide. All enrichment cultures also dehalogenated polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA), and 2,4,6-trichlorophenol (2,4,6-TCP). Particularly, two enrichments completely debrominated penta-BDEs, the first observation of complete debromination of penta-BDEs in marine cultures. Multiple Dehalococcoides and uncultivated Dehalococcoidia were identified in the initial sediment microcosms, but only Dehalococcoides was dominant in all enrichments. Transcription of a gene encoding a PcbA5-like reductive dehalogenase (RDase) was observed during dehalogenation of different organohalides in each enrichment culture. When induced by a single organohalide substrate, the PcbA5-like RDase dehalogenated all tested organohalides (PCE, PCBs, PBDEs, TBBPA, and 2,4,6-TCP) in in vitro tests, suggesting its involvement in dehalogenation of structurally distinct organohalides. Our results demonstrate the versatile dehalogenation capacity of marine Dehalococcoidia and contribute to a better understanding of the fate of these pollutants in marine systems.

Mechanochemical destruction and mineralization of solid-phase hexabromocyclododecane assisted by microscale zero-valent aluminum

Hexabromocyclododecane (HBCD) has been listed in Annex A of the Stockholm Convention as a persistent and bio-accumulative chemical. While HBCD is often present in the solid form for its low solubility, cost-effective technologies have been lacking for the degradation of solid-phase HBCD. In this work, mechanochemical (MC) destruction of high-energy ball milling was employed for direct destruction of solid-phase HBCD, where a strong reducer, microscale zero-valent aluminum (mZVAl), was used as the co-milling agent. The new mZVAl-assisted MC process achieved complete debromination and mineralization of HBCD within 3 h milling. The optimal operating parameters were determined, including the milling atmosphere, the milling speed, the mZVAl-to-HBCD molar ratio, and the ball-to-mZVAl mass ratio. Fourier transform infrared spectrometry and Raman analyses revealed that the organic structures of HBCD were destroyed and organic bromine was completely converted into inorganic bromide, accompanied by the generation of amorphous and graphite carbon. Analysis of the milled samples by GC–MS demonstrated the absence of obvious organic matter after MC treatment, also indicating the complete degradation and conversion of HBCD to inorganic compounds. Further X-ray photoelectron spectroscopic analysis indicates that the fresh surface of mZVAl was generated upon the MC treatment, and Al(0) served as a strong reducing agent (e-donor) for reductive debromination and destruction of the carbon skeleton. The mZVAl-assisted MC milling appears promising as a non-combustion approach for effective destruction and carbonization/mineralization of solid-phase HBCD or potentially other persistent organic pollutants.

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.

Cu-Catalyzed Hydrodehalogenation of Brominated Aromatic Pollutants in Aqueous Solution

The catalytic effect of copper in Devarda’s Al-Cu-Zn alloy (Dev. alloy) and sole metallic copper, copper salts and copper oxides in the coaction of NaBH4 within the hydrodehalogenation (HDH) of polybrominated phenols, such as the herbicide Bromoxynil in alkaline aqueous solution has been investigated. Namely, the hydrodebromination (HDB) activity of Dev. alloy/NaOH system has been compared to heterogeneous Cu-based catalysts using NaBH4 as a reductant. Differences in the solid-state structures of used Cu-based heterogeneous catalysts after the mentioned HDB process have been studied using the powder XRD and SEM techniques. It was found that some of the used copper-based catalysts are reusable and reasonably effective even at room temperature. Efficiency of the most promising copper-based reduction systems (Dev. alloy/NaOH and Cu-based catalysts/NaBH4) have been successfully tested within the HDB of industrially important brominated flame retardant tetrabromobisphenol A (TBBPA). Dev. alloy/NaOH and Cu-based catalyst generated in-situ within the CuSO4/NaBH4 produced were recognized as the most active HDB agents for complete debromination of both BRX and TBBPA.

Peculiar and full debromination of tetrabromodiphenyl ether on Pd/TiO2: A competing route through hydro-debromination and coupling-debromination

The use of palladium deposited TiO2 (Pd/TiO2) as catalysts yielded complete debromination of 2,2′,4,4′-tetrabromodiphenyl ether (BDE47) in isopropanol solution containing NaOH at 40 °C within 60 min. The final organic products were diphenyl ether and dibenzofuran. It was disclosed that two competing reduction paths (hydro-debromination and coupling-debromination) occurred over Pd nanoparticles. The hydro-debromination was dependent on the participation of active H atom species generated by catalytic transfer hydrogenation on metallic Pd. The coupling-debromination proceeded via the oxidative addition of Pd(0) to Br2C12H8OBr2′, leading to an transition state of Br2PdIIC12H8OBr2′, the reductive dissociation of which resulted in the elimination of Br− ions, producing a new transition state Pd0C12H8OBr2′−. A further oxidative addition of Pd0C12H8OBr2′− generated Br2′PdIIC12H8O−, and its final reductive elimination provided dibenzofuran, leading to the regeneration of Pd(0). The integration of the catalytic coupling and hydrogenation reaction on Pd nanoparticles greatly accelerated the removal of the halogenated organic pollutants.

Degradation of hexabromocyclododecane (HBCD) by nanoscale zero-valent aluminum (nZVAl).

Hexabromocyclododecane (HBCD) has been listed in Annex A of the Stockholm Convention on Persistent Organic Pollutants (POPs) in 2013, but till now there is a lack of efficient methods for its degradation. In this study, nanoscale zero-valent aluminum (nZVAl), an excellent reductant with a very low redox potential of E0(Al3+/Al0)=-1.662V and strong electron transfer ability, was used to reductively degrade HBCD. Nearly 100% HBCD was degraded within 8h reaction at 25°C in ethanol/water (v/v, 50/50) solution without pH adjustment. And about 67% cyclododecatriene (CDT) was obtained, which is the complete debromination product. What's more, the yield of Br- could achieve nearly 100% after optimizing conditions. The reaction was strongly promoted by increasing the dosages of nZVAl or decreasing the initial concentration of HBCD. The temperature had the most significant influence and the degradation was completed in 40min with elevating the reaction temperature to 45°C. The reaction mechanism was further revealed through the characterization of nZVAl particles before and after the reaction by SEM-EDS, TEM, HRTEM, XRD, and XPS. It was found that, after corrosion of the oxide film on the surface of nZVAl, metallic aluminum inside was exposed. The reactive sites were provided and electrons released were transferred from nZVAl to HBCD, causing HBCD degraded to dibromocyclododecadiene (DBCD) and then CDT by reductive debromination. These findings imply that nZVAl can degrade HBCD efficiently with no extra energy input and this offers a new idea for better treatment of HBCD.

Microwave-induced degradation as a novel treatment for destruction of decabromodiphenyl ether sorbed on porous minerals

• Highly hydrophobic BDE-209 sorbed efficiently on the porous minerals evaluated. • Microwave irradiation caused rapid degradation of BDE-209 sorbed on porous minerals. • Surface cations in mineral micropores greatly impacted degradation of sorbed BDE-209. • Full debromination of sorbed BDE-209 occurred under continuous microwave irradiation. • The treatment is promising for full destruction of BDE-209 and other PBDE congeners. Decabromodiphenyl ether (deca-BDE or BDE-209) is a major brominated flame retardant released from plastics in thermal processing of e-waste, and there is a significant need for developing effective technologies for its destruction. This study reports a novel treatment for complete debromination and destruction of BDE-209 by adsorbing it onto porous minerals followed by microwave irradiation. Being highly hydrophobic, BDE-209 could be sorbed efficiently by porous mineral sorbents, with the density and type of surface cations of the sorbents apparently playing little role. Microwave irradiation caused rapid degradation of the BDE-209 sorbed on the porous minerals, and the fastest degradation occurred on the microporous minerals, with the density and type of surface cations present in the mineral micropores had significant impact on the degradation rate. Evolution of the degradation intermediates during the course of microwave irradiation indicates that the sorbed BDE-209 underwent pyrolytic decomposition, involving a series of reactions, including cleavage of the ether bond, debromination, hydroxylation, ring cleavage, and oxidation. Microwave-induced degradation could cause full mineralization of the sorbed BDE-209 without producing lower brominated congeners, which is supported by the results of density functional theory (DFT) calculations and infrared spectra. Together, these findings demonstrate that microporous mineral sorption coupled with microwave irradiation could be a rapid and efficient technology for destruction of BDE-209 and other polybrominated diphenyl ethers (PBDEs).