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Halogenated organic compounds are persistent pollutants that pose a serious threat to human health and the safety of ecosystems. Cobamides are essential cofactors for reductive dehalogenases (RDase) in organohalide-respiring bacteria (OHRB), which catalyze the dehalogenation process. This review systematically summarizes the impact of cobamides on organohalide respiration. The catalytic processes of cobamide in dehalogenation processes are also discussed. Additionally, we examine OHRB, which cannot synthesize cobamide and must obtain it from the environment through a salvage pathway; the co-culture with cobamide producer is more beneficial and possible. This review aims to help readers better understand the importance and function of cobamides in reductive dehalogenation. The presented information can aid in the development of bioremediation strategies.
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Plastics are invading nearly all ecosystems on earth, acting as emerging repositories for toxic organic pollutants and thereby imposing substantial threats to ecological integrity. The colonization of plastics by microorganisms, forming the plastisphere, has garnered attention due to its potential influence on biogeochemical cycles. However, the capability of plastisphere microorganisms to attenuate organohalide pollutants remains to be evaluated. This study revealed that the plastisphere, collected from coastal ecosystems, harbors unique microbiomes, while the natural accumulation of organohalide pollutants on plastics may favor the proliferation of organohalide-respiring bacteria (OHRB). Laboratory tests further elucidated the high potential of plastisphere microbiota to reductively dehalogenate a variety of organohalide pollutants. Notably, over 70% tested plastisphere completely debrominated tetrabromobisphenol A (TBBPA) and polybrominated diphenyl ethers (PBDEs) to nonhalogenated products, whereas polychlorinated biphenyls (PCBs) were converted to lower congeners under anaerobic conditions. Dehalococcoides, Dehalogenimonas, and novel Dehalococcoidia populations might contribute to the observed dehalogenation based on their growth during incubation and positive correlations with the quantity of halogens removed. Intriguingly, large fractions of these OHRB populations were identified in a lack of the currently known TBBPA/PBDEs/PCBs reductive dehalogenase (RDase) genes, suggesting the presence of novel RDase genes. Microbial community analyses identified organohalides as a crucial factor in determining the composition, diversity, interaction, and assembly of microbes derived from the plastisphere. Collectively, this study underscores the overlooked roles of the plastisphere in the natural attenuation of persistent organohalide pollutants and sheds light on the unignorable impacts of organohalide compounds on the microbial ecology of the plastisphere.
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Microbiota , Plásticos , Poluentes Orgânicos Persistentes/metabolismo , Bactérias/metabolismo , Éteres Difenil Halogenados/metabolismo , Biodegradação AmbientalRESUMO
Dehalogenating bacteria are still deficient when targeted to deal with chlorinated hydrocarbons (CHCs) contamination: e.g., slow metabolic rates, limited substrate range, formation of toxic intermediates. To enhance its dechlorination capacity, biochar and its composites with appropriate surface activity and biocompatibility are selected for coupled dechlorination. Because of its special surface physical and chemical properties, it promotes biofilm formation by dehalogenating bacteria on its surface and improves the living environment for dehalogenating bacteria. Next, biochar and its composites provide active sites for the removal of CHCs through adsorption, activation and catalysis. These sites can be specific metal centers, functional groups or structural defects. Under microbial mediation, these sites can undergo activation and catalytic cycles, thereby increasing dechlorination efficiency. However, there is a lack of systematic understanding of the mechanisms of dechlorination in biogenic and abiogenic systems based on biochar. Therefore, this article comprehensively summarizes the recent research progress of biochar and its composites as a "Taiwan balm" for the degradation of CHCs in terms of adsorption, catalysis, improvement of microbial community structure and promotion of degradation and metabolism of CHCs. The removal efficiency, influencing factors and reaction mechanism of the degraded CHCs were also discussed. The following conclusions were drawn, in the pure biochar system, the CHCs are fixed to its surface by adsorption through chemical bonds on its surface; the biochar composite material relies on persistent free radicals and electron shuttle mechanisms to react with CHCs, disrupting their molecular structure and reducing them; biochar-coupled microorganisms reduce CHCs primarily by forming an "electron shuttle bridge" between biological and non-biological organisms. Finally, the experimental directions to be carried out in the future are suggested to explore the optimal solution to improve the treatment efficiency of CHCs in water.
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Zero-valent iron (ZVI) applied to the remediation of contaminated groundwater (GW) in situ, especially using engineered permeable reactive barriers (PRBs), has been proven to be an effective reactive material. However, many of ZVI brands do not represent tailored reagents specifically regarding destroying pollutants in GW. Thus, their reactivity towards certain contaminants in GW may vary significantly in a wide range even with different production batches of the same ZVI brand. This issue has rarely been known and consequently not addressed to a higher extend so far. Therefore, this study implemented extensive, long-term column experiments followed by short-term batch experiments for chlorinated volatile organic compounds (cVOCs) degradation for developing a semi-empirical test methodology to thoroughly resolve this pivotal issue by achieving an improved quality assurance guidance regarding proper field-scale emplacement of different ZVI brands and their production batches. The results showed that during column experiments perchloroethylene (PCE) led to a significant degradation up to a certain period but sulfate-reducing microorganisms enhanced the dehalogenation and led approximately to 100 % PCE removal. However, the efficacy varied for different ZVI brands, i.e., Gotthart Maier (GM) and Sponge Iron (Responge®). Furthermore, it could be shown that it might even vary among different production batches of the same ZVI brand. It was also observed that evolution of sulfate-reducing microorganisms may improve the efficacy of PCE degradation vastly that occur at different intensities with different ZVI brands and their respective production batches over time. Further, comparing comprehensive long-term column (kobs = 0.0488 1/h) and short-term batch experiments (kobs = 0.07794 1/h) as well as refined kinetic analyses (kobs = 0.0424 1/h) clearly prove that an appropriate guidance protocol for successful full-scale in situ remediation is required for properly select the right ZVI brand and production batch before it is loaded to a PRB in the field.
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Recuperação e Remediação Ambiental , Água Subterrânea , Ferro , Poluentes Químicos da Água , Água Subterrânea/química , Ferro/química , Recuperação e Remediação Ambiental/métodos , Compostos Orgânicos VoláteisRESUMO
The aim of this study was to obtain new halolactones with a gem-dimethyl group in the cyclohexane ring (at the C-3 or C-5 carbon) and a methyl group in the lactone ring and then subject them to biotransformations using filamentous fungi. Halolactones in the form of mixtures of two diasteroisomers were subjected to screening biotransformations, which showed that only compounds with a gem-dimethyl group located at the C-5 carbon were transformed. Strains from the genus Fusarium carried out hydrolytic dehalogenation, while strains from the genus Absidia carried out hydroxylation of the C-7 carbon. Both substrates and biotransformation products were then tested for antimicrobial activity against multidrug-resistant strains of both bacteria and yeast-like fungi. The highest antifungal activity against C. dubliniensis and C. albicans strains was obtained for compound 5b, while antimicrobial activity against S. aureus MRSA was obtained for compound 4a.
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Antibacterianos , Biotransformação , Lactonas , Testes de Sensibilidade Microbiana , Lactonas/química , Lactonas/farmacologia , Lactonas/metabolismo , Antibacterianos/farmacologia , Antibacterianos/química , Fusarium/efeitos dos fármacos , Antifúngicos/farmacologia , Antifúngicos/química , Absidia/metabolismo , Estrutura Molecular , Candida albicans/efeitos dos fármacos , Staphylococcus aureus Resistente à Meticilina/efeitos dos fármacosRESUMO
Evaluating the role of antimicrobials biotransformation in the regulation of metabolic functions and antimicrobial resistance evolution in wastewater biotreatment systems is crucial to ensuring water security. However, the associated mechanisms remain poorly understood. Here, we investigate triclocarban (TCC, one of the typical antimicrobials) biotransformation mechanisms and the dynamic evolution of systemic function disturbance and antimicrobial resistance risk in a complex anaerobic hydrolytic acidification (HA)-anoxic (ANO)/oxic (O) process. We mined key functional genes involved in the TCC upstream (reductive dechlorination and amide bonds hydrolysis) and downstream (chloroanilines catabolism) biotransformation pathways by metagenomic sequencing. Acute and chronic stress of TCC inhibit the production of volatile fatty acids (VFAs), NH4+ assimilation, and nitrification. The biotransformation of TCC via a single pathway cannot effectively relieve the inhibition of metabolic functions (e.g., carbon and nitrogen transformation and cycling) and enrichment of antimicrobial resistance genes (ARGs). Importantly, the coexistence of TCC reductive dechlorination and hydrolysis pathways and subsequent ring-opening catabolism play a critical role for stabilization of systemic metabolic functions and partial control of antimicrobial resistance risk. This study provides new insights into the mechanisms linking TCC biotransformation to the dynamic evolution of systemic functions and risks, and highlights critical regulatory information for enhanced control of TCC risks in complex biotreatment systems.
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Biotransformação , Carbanilidas , Águas Residuárias , Eliminação de Resíduos Líquidos , Resistência Microbiana a Medicamentos/genética , Poluentes Químicos da Água/metabolismoRESUMO
Sewage sludge adsorbs a large amount of harmful organic pollutants, particularly the persistent and hydrophobic polyhalogenated compounds (PHCs). PHCs have been subjected to biological and chemical oxidation treatments during wastewater treatment processes; however, the species and concentrations of their transformation products (TPs) in sludge remain unknown, and the transformation pathways are unclear. In this study, 234 TPs of PHCs, including 77 TPs of chlorinated paraffins (CPs-TPs), 102 TPs of organochlorine pesticides (OCPs-TPs), 45 TPs of dechlorane plus (DPs-TPs), and 10 TPs of brominated flame retardants (BFRs-TPs), were identified in sludge through Ph4PCl-enhanced ionization coupled with ultra-performance liquid chromatography-Orbitrap-mass spectrometry. Based on the chemical structures of the identified TPs, we identified three major transformation pathways: dehalogenation-hydroxylation, carbon chain decomposition, and desulfurization. Approximately 97 TPs were newly discovered through the pathways. Carbon chain decomposition products of OCPs and DPs were detected for the first time at relatively high abundances. More hydroxylation products of DPs and hexabromocyclododecane (HBCD) and multi-dehalogenation products of heptachlor, toxaphene, DPs and HBCDs were detected at relative intensities higher than those of the known TPs. The oxidation treatment of sludge achieved up to 13 %-94 % of PHCs to be removed, with dehalogenation-hydroxylation as the main transformation pathway. Advanced treatment technologies are needed for degradation of both PHCs and their TPs.
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Esgotos , Esgotos/química , Poluentes Químicos da Água/química , Hidrocarbonetos Clorados/química , Retardadores de Chama , Praguicidas/químicaRESUMO
CONTEXT: Organic halides stand as invaluable reagents with diverse applications in synthetic chemistry and various industrial processes. Despite their utility, concerns arise due to their inherent toxicity. Addressing these apprehensions, hydro-dehalogenation has emerged as a promising strategy involving the replacement of halogen atoms with hydrogen atoms to transform toxic organic halides into hydrocarbons. This study delves into the computational exploration of hydro-dehalogenation reactions of benzyl halide, mediated by frustrated Lewis pairs (FLPs), using density functional theory (DFT). The reactions entail the formation of FLP1 or FLP2 in the presence of TMP or lutidine with B(C6F5)3, respectively. This is followed by heterolytic cleavage of dihydrogen and subsequent reaction with benzyl halides. Non-covalent interaction analysis underscores the significance of π-π stacking and CH-π interactions in stabilizing transition states. Additionally, the activation strain model (ASM) dissects activation energies, revealing the substantial impact of strain energy on reaction barriers. Energy decomposition analysis (EDA) offers insights into the contributions of electrostatic, orbital, and dispersion energies to the overall attractive interaction energy. The investigation extends to hydro-dehalogenation reactions of ethyl halides, uncovering distinct mechanisms and activation barriers. This comprehensive analysis illuminates the intricacies of hydro-dehalogenation reactions, providing valuable insights into their mechanisms and paving the way for future studies in this field. METHODS: Geometry optimizations were carried out at the M06-2X/def2-SVP level of theory, which was performed using the Gaussian 16 program. Solvent-corrected single-point energies were also calculated using the polarizable continuum model (PCM) at the PCM(chloroform)-M06-2X/def2-TZVP//M06-2X/def2-SVP level of theory. The Gibbs free energy correction was determined from computations performed at the M06-2X/def2-SVP level of theory. Principal interacting orbital (PIO) analysis was conducted using the NBO 6.0 software. The nature of bonding in the respective transition state (TS) structures was analyzed using atoms-in-molecules (AIM) analyses. Additionally, the presence of non-covalent interactions (NCI) was exemplified using Multiwfn software.
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Biological regulation often depends on reversible reactions such as phosphorylation, acylation, methylation, and glycosylation, but rarely halogenation. A notable exception is the iodination and deiodination of thyroid hormones. Here, we report detection of bromotyrosine and its subsequent debromination during Drosophila spermatogenesis. Bromotyrosine is not evident when Drosophila express a native flavin-dependent dehalogenase that is homologous to the enzyme responsible for iodide salvage from iodotyrosine in mammals. Deletion or suppression of the dehalogenase-encoding condet (cdt) gene in Drosophila allows bromotyrosine to accumulate with no detectable chloro- or iodotyrosine. The presence of bromotyrosine in the cdt mutant males disrupts sperm individualization and results in decreased fertility. Transgenic expression of the cdt gene in late-staged germ cells rescues this defect and enhances tolerance of male flies to bromotyrosine. These results are consistent with reversible halogenation affecting Drosophila spermatogenesis in a process that had previously eluded metabolomic, proteomic, and genomic analyses.
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Proteínas de Drosophila , Fertilidade , Espermatogênese , Tirosina , Animais , Masculino , Proteínas de Drosophila/metabolismo , Proteínas de Drosophila/genética , Tirosina/metabolismo , Tirosina/análogos & derivados , Drosophila melanogaster/metabolismo , Drosophila melanogaster/genética , Drosophila/genética , Drosophila/metabolismo , Animais Geneticamente Modificados , Hidrolases/metabolismo , Hidrolases/genéticaRESUMO
Tetrabromobisphenol A (TBBPA), a common brominated flame retardant and a notorious pollutant in anaerobic environments, resists aerobic degradation but can undergo reductive dehalogenation to produce bisphenol A (BPA), an endocrine disruptor. Conversely, BPA is resistant to anaerobic biodegradation but susceptible to aerobic degradation. Microbial degradation of TBBPA via anoxic/oxic processes is scarcely documented. We established an anaerobic microcosm for TBBPA dehalogenation to BPA facilitated by humin. Dehalobacter species increased with a growth yield of 1.5 × 108 cells per µmol Br- released, suggesting their role in TBBPA dehalogenation. We innovatively achieved complete and sustainable biodegradation of TBBPA in sand/soil columns columns, synergizing TBBPA reductive dehalogenation by anaerobic functional microbiota and BPA aerobic oxidation by Sphingomonas sp. strain TTNP3. Over 42 days, 95.11 % of the injected TBBPA in three batches was debrominated to BPA. Following injection of strain TTNP3 cells, 85.57 % of BPA was aerobically degraded. Aerobic BPA degradation column experiments also indicated that aeration and cell colonization significantly increased degradation rates. This treatment strategy provides valuable technical insights for complete TBBPA biodegradation and analogous contaminants.
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Biodegradação Ambiental , Retardadores de Chama , Oxirredução , Fenóis , Bifenil Polibromatos , Bifenil Polibromatos/metabolismo , Bifenil Polibromatos/química , Anaerobiose , Aerobiose , Fenóis/metabolismo , Retardadores de Chama/metabolismo , Compostos Benzidrílicos/metabolismo , Sphingomonas/metabolismo , Halogenação , Poluentes do Solo/metabolismoRESUMO
Developing the films of N-containing unsubstituted poly(p-phenylene) (PPP) films for diverse applications is significant and highly desirable because the replacement of sp2 C atoms with sp2 N atoms will bring novel properties to the as-prepared polymers. In this research, an electrochemical-dehalogenation polymerization strategy is employed to construct two N-containing PPP films under constant potentials, where 2,5-diiodopyridine (DIPy) and 2,5-dibromopyrazine (DBPz) are used as starting agents. The corresponding polymers are named CityU-23 (for polypyridine) and CityU-24 (for polypyrazine). Moreover, it is found that both polymers can form films in situ on different conductive substrates (i.e., silicon, gold, ITO, and nickel), satisfying potential device fabrication. Furthermore, the as-obtained thin films of CityU-23 and CityU-24 exhibit good performance of alkaline hydrogen evolution reaction with the overpotential of 212.8 and 180.7 mV and the Tafel slope of 157.0 and 122.4 mV dec-1, respectively.
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The sequencing electroreduction-electrooxidation process has emerged as a promising approach for the degradation of the chloronitrobenzenes (CNBs) due to its elimination of electro-withdrawing groups in the reduction process, facilitating further removal in the subsequent oxidation process. Herein, we developed a cathode consisting of atom Pd on a Ti plate, which enabled the electro-generation of atomic hydrogen (H*) and the efficient electrocatalytic activation of H2O2 to hydroxyl radical (â¢OH). Cyclic voltammetry (CV) curves and electron spin resonance (ESR) spectra verified the existence of H* and â¢OH. The electroreduction-electrooxidation system achieved 94.7% of 20 mg L-1 2,4-DCNB removal with a relatively low H2O2 addition (5 mM). Moreover, the inhibition rate of Photobacterium phosphoreum in the effluent decreased from 95% to 52% after the sequencing electroreduction-electrooxidation processes. It was further revealed that the H* dominated the electroreduction process and triggered the electrooxidation process. Our work sheds light on the effective removal of electron-withdrawing groups substituted aromatic contaminants from water and wastewater.
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Hidrogênio , Nitrobenzenos , Oxirredução , Águas Residuárias , Poluentes Químicos da Água , Águas Residuárias/química , Poluentes Químicos da Água/química , Nitrobenzenos/química , Hidrogênio/química , Técnicas Eletroquímicas/métodos , Eliminação de Resíduos Líquidos/métodosRESUMO
We report a family of donor-acceptor thermally activated delayed fluorescent (TADF) compounds based on derivatives of DMAC-TRZ, that are strongly photoreducing. Both Eox and thus E*ox could be tuned via substitution of the DMAC donor with a Hammett series of p-substituted phenyl moieties while Ered remained effectively constant. These compounds were assessed in the photoinduced dehalogenation of aryl halides, and analogues bearing electron withdrawing groups were found to produce the highest yields. Substrates of up to Ered=-2.72â V could be dehalogenated at low PC loading (1â mol %) and under air, conditions much milder than previously reported for this reaction. Spectroscopic and chemical studies demonstrate that all PCs, including literature reference PCs, photodegrade, and that it is these photodegradation products that are responsible for the reactivity.
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A supramolecular assembly was constructed based on the tetraphenylethylene derivatives (TPEs) and nor-seco-cucurbit[10]uril (ns-Q[10]). Upon introduction of the dye Rhodamine B (RB) into the TPEs@ns-Q[10] assembly, an energy transfer process can occur from the TPEs@ns-Q[10] assembly to RB. Moreover, after the addition of Nile Red (NiR), a two-step sequential energy transfer process from the TPEs@ns-Q[10] assembly to RB and then to NiR can occur. Additionally, the dye Eosin Y (ESY) was introduced into the TPEs@ns-Q[10] assembly and an energy transfer process can take place from the TPEs@ns-Q[10] assembly to ESY. To utilize the harvested energy from the TPEs@ns-Q[10]-RB-NiR and TPEs@ns-Q[10]-ESY system, we applied the TPEs@ns-Q[10] assembly-based light-harvesting systems (LHSs) as a catalyst for the advancement of the photocatalytic dehalogenation reaction in aqueous solution. When promoted with 0.5 mol % catalyst, the reaction yield reached 78 and 68%, demonstrating the promising potential of TPEs@ns-Q[10] assembly-based LHSs in the promotion of the photocatalytic dehalogenation reaction.
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BACKGROUND: Macroalgae, especially reds (Rhodophyta Division) and browns (Phaeophyta Division), are known for producing various halogenated compounds. Yet, the reasons underlying their production and the fate of these metabolites remain largely unknown. Some theories suggest their potential antimicrobial activity and involvement in interactions between macroalgae and prokaryotes. However, detailed investigations are currently missing on how the genetic information of prokaryotic communities associated with macroalgae may influence the fate of organohalogenated molecules. RESULTS: To address this challenge, we created a specialized dataset containing 161 enzymes, each with a complete enzyme commission number, known to be involved in halogen metabolism. This dataset served as a reference to annotate the corresponding genes encoded in both the metagenomic contigs and 98 metagenome-assembled genomes (MAGs) obtained from the microbiome of 2 red (Sphaerococcus coronopifolius and Asparagopsis taxiformis) and 1 brown (Halopteris scoparia) macroalgae. We detected many dehalogenation-related genes, particularly those with hydrolytic functions, suggesting their potential involvement in the degradation of a wide spectrum of halocarbons and haloaromatic molecules, including anthropogenic compounds. We uncovered an array of degradative gene functions within MAGs, spanning various bacterial orders such as Rhodobacterales, Rhizobiales, Caulobacterales, Geminicoccales, Sphingomonadales, Granulosicoccales, Microtrichales, and Pseudomonadales. Less abundant than degradative functions, we also uncovered genes associated with the biosynthesis of halogenated antimicrobial compounds and metabolites. CONCLUSION: The functional data provided here contribute to understanding the still largely unexplored role of unknown prokaryotes. These findings support the hypothesis that macroalgae function as holobionts, where the metabolism of halogenated compounds might play a role in symbiogenesis and act as a possible defense mechanism against environmental chemical stressors. Furthermore, bacterial groups, previously never connected with organohalogen metabolism, e.g., Caulobacterales, Geminicoccales, Granulosicoccales, and Microtrichales, functionally characterized through MAGs reconstruction, revealed a biotechnologically relevant gene content, useful in synthetic biology, and bioprospecting applications. Video Abstract.
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Anti-Infecciosos , Microbiota , Rodófitas , Alga Marinha , Rodófitas/genética , Rodófitas/metabolismo , Microbiota/genética , Bactérias/genética , Bactérias/metabolismo , Alga Marinha/genética , Alga Marinha/metabolismo , Metagenoma , Halogênios/metabolismoRESUMO
Zero-valent iron (ZVI) reduction represents a promising methodology for water remediation, but its broad application is limited by two critical challenges (i.e., aggregation and passivation). Here, we report a hybrid strategy of photochemical-promoted ZVI reduction with high efficiency and reduction capacity for removing coexisting refractory pollutants in water. A composite material with Pd/Fe bimetallic nanoparticles supported onto semiconducting metal oxide (Pd/Fe@WO3-GO) was prepared and subsequently used as the model catalyst. By using the developed strategy with visible light as light source, this catalyst showed a remarkable catalytic performance for simultaneously eliminating 4-chlorophenol (4-CP) and Cr(VI), with dehalogenation rate as high as 0.43 min-1, outperforming the reported ZVI-based catalysts. A synergistic interaction of photocatalysis and ZVI reduction occurred in this strategy, where the interfacial electron transfer on particles surface were greatly strengthened with light irradiation. The activation was attributed to the dual functions of semiconducting material as support to disperse Pd/Fe nanoparticles and as (photoexcited) electron donor to directly trigger reduction reactions and/or indirectly inhibit the formation of oxides passivation layer. Both direct electron transfer and H*-mediated indirect electron transfer mechanisms were confirmed to participate in the reduction of pollutants, while the later was quantitatively demonstrated as the predominant reaction route. Importantly, this strategy showed a wide pH applicability, long-term durability and excellent catalytic performance in different real-water systems. This work provides new insights into ZVI reduction and advances its applications for the removal of combined organic and inorganic pollutants. The developed photochemical-promoted ZVI reduction strategy holds a great potential for practical applications.
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Anthropogenic organohalide pollutants pose a severe threat to public health and ecosystems. In situ bioremediation using organohalide respiring bacteria (OHRB) offers an environmentally friendly and cost-efficient strategy for decontaminating organohalide-polluted sites. The genomic structures of many OHRB suggest that dehalogenation traits can be horizontally transferred among microbial populations, but their occurrence among anaerobic OHRB has not yet been demonstrated experimentally. This study isolates and characterizes a novel tetrachloroethene (PCE)-dechlorinating Sulfurospirillum sp. strain SP, distinguishing itself among anaerobic OHRB by showcasing a mechanism essential for horizontal dissemination of reductive dehalogenation capabilities within microbial populations. Its genetic characterization identifies a unique plasmid (pSULSP), harboring reductive dehalogenase and de novo corrinoid biosynthesis operons, functions critical to organohalide respiration, flanked by mobile elements. The active mobility of these elements was demonstrated through genetic analyses of spontaneously emerging nondehalogenating variants of strain SP. More importantly, bioaugmentation of nondehalogenating microcosms with pSULSP DNA triggered anaerobic PCE dechlorination in taxonomically diverse bacterial populations. Our results directly support the hypothesis that exposure to anthropogenic organohalide pollutants can drive the emergence of dehalogenating microbial populations via horizontal gene transfer and demonstrate a mechanism by which genetic bioaugmentation for remediation of organohalide pollutants could be achieved in anaerobic environments.
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Chloroflexi , Poluentes Ambientais , Ecossistema , Bactérias/genética , Respiração , Família Multigênica , Biodegradação AmbientalRESUMO
The electrocatalytic hydrodehalogenation (EHDH) process mediated by atomic hydrogen (H*) is recognized as an efficient method for degrading halogenated organic pollutants (HOPs). However, a significant challenge is the excessive energy consumption resulting from the recombination of H* to H2 production in the EHDH process. In this study, a promising strategy was proposed to generate piezo-induced atomic H*, without external energy input or chemical consumption, for the degradation and dehalogenation of HOPs. Specifically, sub-5 nm Ni nanoparticles were subtly dotted on an N-doped carbon layer coating on BaTiO3 cube, and the resulted hybrid nanocomposite (Ni-NC@BTO) can effectively break C-X (X = Cl and F) bonds under ultrasonic vibration or mechanical stirring, demonstrating high piezoelectric driven dehalogenation efficiencies toward various HOPs. Mechanistic studies revealed that the dotted Ni nanoparticles can efficiently capture H* to form Ni-H* (Habs) and drive the dehalogenation process to lower the toxicity of intermediates. COMSOL simulations confirmed a "chimney effect" on the interface of Ni nanoparticle, which facilitated the accumulation of H+ and enhanced electron transfer for H* formation by improving the surface charge of the piezocatalyst and strengthening the interfacial electric field. Our work introduces an environmentally friendly dehalogenation method for HOPs using the piezoelectric process independent of the external energy input and chemical consumption.
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Poluentes Ambientais , Hidrogênio/metabolismo , Halogênios/químicaRESUMO
Polybrominated diphenyl ethers (PBDEs) are persistent pollutants that may undergo microbial-mediated debromination in anoxic environments, where diverse anaerobic microbes such as methanogenic archaea co-exist. However, current understanding of the relations between PBDE pollution and methanogenic process is far from complete. To address this knowledge gap, a series of anaerobic soil microcosms were established. BDE-47 (2, 2', 4, 4'-tetrabromodiphenyl ether) was selected as a model pollutant, and electron donors were supplied to stimulate the activity of anaerobes. Debromination and methane production were monitored during the 12 weeks incubation, while obligate organohalide-respiring bacteria (OHRBs), methanogenic, and the total bacterial communities were examined at week 7 and 12. The results demonstrated slow debromination of BDE-47 in all microcosms, with considerable growth of Dehalococcoides and Dehalogenimonas over the incubation observed in most BDE-47 spiked treatments. In addition, the accumulation of intermediate metabolites positively correlated with the abundance of Dehalogenimonas at week 7, suggesting potential role of these OHRBs in debromination. Methanosarcinaceae were identified as the primary methanogenic archaea, and their abundance were correlated with the production of debrominated metabolites at week 7. Furthermore, it was observed for the first time that BDE-47 considerably enhanced methane production and increased the abundance of mcrA genes, highlighting the potential effects of PBDE pollution on climate change. This might be related to the inhibition of reductive N- and S-transforming microbes, as revealed by the quantitative microbial element cycling (QMEC) analysis. Overall, our findings shed light on the intricate interactions between PBDE and methanogenic processes, and contribute to a better understanding of the environmental fate and ecological implication of PBDE under anaerobic settings.
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Poluentes Ambientais , Éteres Difenil Halogenados , Éteres Difenil Halogenados/metabolismo , Anaerobiose , Éter/metabolismo , Bactérias/metabolismo , Etil-Éteres/metabolismo , Archaea/metabolismo , Poluentes Ambientais/metabolismo , Metano/metabolismoRESUMO
The production of added-value chemicals via pyrolysis of plastic wastes, such as those from electrical and electronic equipment (WEEE), needs addressing their usual contamination with halogens (mainly Br and Cl). This work compares the conversion via pyrolysis and hydropyrolysis of a real WEEE plastic, having a complex composition, in two different reactor configurations: down-flow (DF) and up-flow (UF). Likewise, the effects of incorporating a Pd/Al2O3 catalyst and using two different pressures (1 and 6 bar) have been assessed. With the DF mode, pyrolysis at 1 bar leads to an oil yield above 80 wt% and a total halogen content of about 600 ppm (vs 1600 ppm in the water-washed WEEE plastic). Under DF catalytic hydropyrolysis at 6 bar, this high oil yield is maintained while its dehalogenation degree is improved (142 ppm). Operating with the up-flow configuration, under 6 bar and H2 presence, leads to some reduction in the oil yield (about 70 wt%) but significantly decreases the oil halogen content (55 ppm Cl and total elimination of Br). These results have been related to the slower pyrolysis and longer residence time in the thermal zone of the UF configuration, which favours the halogen-trapping effect of the char fraction, and the pressure-enhanced hydrodehalogenation activity of the catalyst. This study highlights the environmental benefits of the proposed process, emphasizing the lower halogen content in the resulting oils and promoting a more sustainable approach to plastic waste valorisation.