Effects of humic electron mediators on reductive dechlorination of polychlorinated biphenyl by consortia enriched from terrestrial and marine environments.

Humic electron mediators can facilitate the reductive dehalogenation of organohalogenated compounds by accelerating electron transfer. To investigate the effect of humic electron mediators on the microbial anaerobic reductive dechlorination of Polychlorinated biphenyls (PCBs), three types of humic electron mediators, humin (HM), humic acid (HA), and anthraquinone-2,6-disulfonic acid (AQDS, HA analogs), were added to PCB dechlorination cultures enriched from different sources in terrestrial and marine environments (T and M cultures). The results showed that meta- and para-site dechlorination occurred in the M culture, while only meta-site dechlorination occurred in the T culture. The dechlorination process N and the dechlorination process H or H' are presented in both cultures. HM enhanced PCB dechlorination metabolic activity in both cultures mainly by promoting meta-site dechlorination. HA showed a weak promoting effect on the M culture by promoting para-chlorine removal but inhibited the dechlorination metabolism of the terrestrial-origin culture, inhibiting meta-chlorine removal. AQDS showed inhibitory effects on both cultures by inhibiting the microbial removal of meta-chlorine. High-throughput sequencing and qPCR results suggest that HM is not a carbon source for the potential dechlorinating metabolism of Dehalococcoides but may promote reductive dechlorination by changing the community structure, and AQDS may inhibit anaerobic reductive dechlorination of PCBs by inhibiting the growth of Dehalococcoides. This study provides insights into the mechanism of enhancing PCB microbial dechlorination mediated by humic substances and plays a significant role in extending the application prospects of PCBs bioremediation technology.

Biochar-enhanced anaerobic mixed culture for biodegradation of 1,2-dichloroethane: Microbial community, mechanisms, and techno-economics.

While anaerobic digestion (AD) has been employed for the degradation of chlorinated aliphatic hydrocarbons, the associated digester performance might suffer from volatile fatty acids accumulation, insufficient substrate-microbes interaction, and lower biogas yields. To overcome these limitations, this study is the first to augment the hydrocarbon-degrading microbial capacities by adding agricultural waste-based biochar to the digestion medium. 1,2-dichloroethane (1,2-DCA) was selected as the target pollutant because it is discharged in large quantities from oil refining, petrochemical, and chemical industries, causing serious environmental and human health concerns. A multi-chamber anaerobic reactor (MAR) was operated at a 1,2-DCA loading rate of 1.13 g/L/d, glucose dosage (as an electron donor) range of 200-700 mg/L, and hydraulic retention time of 11.2 h, giving dechlorination = 32.2 ± 6.9% and biogas yield = 210 ± 30 mL/g CODremoved. These values increased after biochar supplementation (100 mg/g volatile solids, VS, as an inoculum carrier) up to 60.2 ± 11.5% and 290 ± 40 mL/g CODremoved, respectively, owing to the enhancement of dehydrogenase enzyme activities. Burkholderiales (15.3%), Clostridiales (2.3%), Bacteroidales (3.5%), Xanthomonadales (3.3%), and Rhodobacterales (6.1%) involved in 1,2-DCA degradation were dominant in the reactor supplemented with biochar. It's suggested that biochar played a major role in facilitating the direct interspecies electron transfer (DIET) between syntrophic bacteria and methanogens, where chloride, ethylene glycol, and acetate derived from 1,2-DCA dechlorination could be further used to promote methanogenesis and methane production. The synergetic effect of adsorption and dechlorination towards 1,2-DCA removal was validated at various biochar dosages (50-120 mg/g) and 1,2-DCA concentrations (50-1000 mg/L). The techno-economic results showed that the cost of treating 1,2-DCA-laden discharge (100 m3/d) by the MAR module could be 0.83 USD/m3 with a payback period of 6.24 years (NPV = 2840 USD and IRR = 10%), retrieving profits from pollution reduction (9542 USD/yr), biogas selling (10418 USD/yr), and carbon credit (10294 USD/yr).

A review of hydrogen chloride removal from calcium- and sodium-based sorbents.

With the steady progress of ultra-low emissions in various industries, the management of unconventional pollutants is gradually attracting attention. A such unconventional pollutant that negatively affects many different processes and pieces of equipment is hydrogen chloride (HCl). Although it has strong advantages and potential in the treatment of industrial waste gas and synthesis gas, the process technology of removing HCl by calcium- and sodium-based alkaline powder has not yet been thoroughly studied. The impact of reaction factors on the dechlorination of calcium- and sodium-based sorbents is reviewed, including temperature, particle size, and water form. The most recent developments in sodium- and calcium-based sorbents for capturing hydrogen chloride were presented, and the dechlorination capabilities of various sorbents were contrasted. In the low-temperature range, sodium-based sorbents had a stronger dechlorination impact than calcium-based sorbents. Surface chemical reactions and product layer diffusion between solid sorbents and gases are crucial mechanisms. Meanwhile, the effect of the competitive behavior of SO2 and CO2 with HCl on the dechlorination performance has been taken into account. The mechanism and necessity of selective hydrogen chloride removal are also provided and discussed, and future research directions are pointed out to provide the theoretical basis and technical reference for future industrial practical applications.

Cathode potential regulates the microbiome assembly and function in electrostimulated bio- dechlorination system.

Mechanism of microbiome assembly and function driven by cathode potential in electro-stimulated microbial reductive dechlorination system remain poorly understood. Here, core microbiome structure, interaction, function and assembly regulating by cathode potential were investigated in a 2,4,6-trichlorophenol bio-dechlorination system. The highest dechlorination rate (24.30 µM/d) was observed under - 0.36 V with phenol as a major end metabolite, while, lower (-0.56 V) or higher (0.04 V or -0.16 V) potentials resulted in 1.3-3.8 times decreased of dechlorination kinetic constant. The lower the cathode potential, the higher the generated CH4, revealing cathode participated in hydrogenotrophic methanogenesis. Taxonomic and functional structure of core microbiome significantly shifted within groups of - 0.36 V and - 0.56 V, with dechlorinators (Desulfitobacterium, Dehalobacter), fermenters (norank_f_Propionibacteriaceae, Dysgonomonas) and methanogen (Methanosarcina) highly enriched, and the more positive interactions between functional genera were found. The lowest number of nodes and links and the highest positive correlations were observed among constructed sub-networks classified by function, revealing simplified and strengthened cooperation of functional genera driven by group of - 0.36 V. Cathode potential plays one important driver controlling core microbiome assembly, and the low potentials drove the assembly of major dechlorinating, methanogenic and electro-active genera to be more deterministic, while, the major fermenting genera were mostly governed by stochastic processes.

Visible-Light-Induced Vicinal Dichlorination of Alkenes through LMCT Excitation of CuCl2.

This work demonstrates photoredox vicinal dichlorination of alkenes, based on the homolysis of CuCl2 in response to irradiation with visible light. This catalysis proceeds via a ligand to metal charge transfer process and provides an exciting opportunity for the synthesis of 1,2-dichloride compounds using an inexpensive, low-molecular-weight chlorine source. This new process exhibits a wide substrate scope, excellent functional group tolerance, extraordinarily mild conditions and does not require external ligands. Mechanistic studies show that the ready formation of chlorine atom radicals is responsible for the facile formation of C-Cl bonds in this synthetic process.

Reducing the Impact of Perfusion Medical Waste on the Environment.

The U.S. healthcare system generates more than five billion pounds of waste each year. Waste disposal has become a serious environmental problem facing healthcare institutions. The operating room is the second largest source of hospital waste, and no current standards exist regarding perfusion waste reuse or recycling. A typical perfusion circuit produces approximately 15 pounds of plastic that ends up incinerated once used. Contaminated perfusion circuits consisting primarily of polyvinyl chloride (PVC) and polycarbonate are difficult to sterilize, reuse, or recycle. A literature review of Internet-based and peer-reviewed publications was conducted to identify all resources that describe sterilizing, dechlorinating, reusing, and recycling of medical-grade disposable products. There are several chemical methods available to re-harvest PVC after it has been properly decontaminated and melted down. Dichlorination by near-critical methanol shows promise in the recovery of additives such as plasticizers, stabilizers, and lubricants. The reinjection of PVC may have ecological and economic advantages. Dechlorinated PVC also creates a less toxic by-product when incinerated. Although this process is not recycling, it lessens the impact of poisonous chlorine gas release into the atmosphere. Sterilizing, dechlorinating, and recycling the perfusion circuit may be a promising avenue for reducing the ecological impact of perfusion waste. Although an economically sensitive mode of reusing, reducing, and recycling a circuit does not currently exist, this presentation will explore the perfusion waste dilemma and present potential solutions in hopes of promoting future reuse and recycling opportunities.

Diversity of bacteria and archaea in the groundwater contaminated by chlorinated solvents undergoing natural attenuation.

Chlorinated solvents (CS)-contaminated groundwater poses serious risks to the environment and public health. Microorganisms play a vital role in efficient remediation of CS. In this study, the microbial community (bacterial and archaeal) composition of three CS-contaminated groundwater wells located at an abandoned chemical factory which covers three orders of magnitude in concentration (0.02-16.15 mg/L) were investigated via 16S rRNA gene high-throughput sequencing. The results indicated that Proteobacteria and Thaumarchaeota were the most abundant bacterial and archaeal groups at the phylum level in groundwater, respectively. The major bacterial genera (Flavobacterium sp., Mycobacterium sp. and unclassified Parcubacteria taxa, etc.) and archaeal genera (Thaumarchaeota Group C3, Miscellaneous Crenarchaeotic Group and Miscellaneous Euryarchaeotic Group, etc.) might be involved in the dechlorination processes. In addition, Pearson's correlation analyses showed that alpha diversity of the bacterial community was not significantly correlated with CS concentration, while alpha diversity of archaeal community greatly decreased with the increased contamination of CS. Moreover, partial Mantel test indicated that oxidation-reduction potential, dissolved oxygen, temperature and methane concentration were major drivers of bacterial and archaeal community composition, whereas CS concentration had no significant impact, indicating that both indigenous bacterial and archaeal community compositions are capable of withstanding elevated CS contamination. This study improves our understanding of how the natural microbial community responds to high CS-contaminated groundwater.

Enzyme-electrolytic degradation of dichloromethane: Efficiency, kinetics and mechanism.

Enzymatic electrolysis cell (EEC) has advantages over microbial electrolysis cell (MEC) due to the needless of microbe inoculation and high-efficiency of enzymatic reaction. In this study, an EEC was first applied to achieve the effective degradation of halogenated organic pollutants and dichloromethane (CH2Cl2) was utilized as a model pollutant. The results indicate that the degradation efficiency of CH2Cl2 after 2 hr reaction in the EEC was almost 100%, which was significantly higher than that with enzyme (51.1%) or current (19.0%). The current induced the continuous regeneration of reduced glutathione (GSH), thus CH2Cl2 was degraded under the catalysis of GSH-dependent dehalogenase through stepwise dechlorination, and successively formed monochloromethane (CH3Cl) and methane (CH4). The kinetic result shows that with a current of 15 mA, the maximum specific degradation rate of CH2Cl2 (3.77 × 10-3hr-1) was increased by 5.7 times. The optimum condition for CH2Cl2 dechlorination was also obtained with pH, current and temperature of 7.0, 15 mA and 35°C, respectively. Importantly, this study helps to understand the behavior of enzymes and the fate of halogenated organic pollutants with EEC, providing a possible treatment technology for halogenated organic pollutants.

Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes.

The enantioselective dichlorination of alkenes is a continuing challenge in organic synthesis owing to the limitations of selective and independent antarafacial delivery of both electrophilic chlorenium and nucleophilic chloride to an olefin. Development of a general method for the enantioselective dichlorination of isolated alkenes would allow access to a wide variety of polyhalogenated natural products. Accordingly, the enantioselective suprafacial dichlorination of alkenes catalyzed by electrophilic organoselenium reagents has been developed to address these limitations. The evaluation of twenty-three diselenides as precatalysts for enantioselective dichlorination is described, with a maximum e.r. of 76:24 Additionally, mechanistic studies suggest an unexpected Dynamic Kinetic Asymmetric Transformation (DyKAT) process may be operative.

Organocatalytic, Enantioselective Dichlorination of Unfunctionalized Alkenes.

The use of a new class of unsymmetrical cinchona-alkaloid-based, phthalazine-bridged organocatalysts enabled the highly enantioselective dichlorination of unfunctionalized alkenes. In combination with the electrophilic chlorinating agent 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) and triethylsilyl chloride (TES-Cl) as the source of nucleophilic chloride, 1-aryl-2-alkyl alkenes were dichlorinated with enantioselectivities of up to 94:6 er. Initial mechanistic investigations suggest that no free chlorine is formed, and by replacement of the chloride by fluoride, enantioselective chlorofluorinations of alkenes are possible.

Adsorptive and Reductive Removal of Chlorophenol from Wastewater by Biomass-Derived Mesoporous Carbon-Supported Sulfide Nanoscale Zerovalent Iron.

Chlorinated compounds in a water environment pose serious threats to humanity. A nanoscale zerovalent iron (nZVI) has desirable properties for water dichlorination, but its reactivity is still limited by agglomeration and oxidation. In this study, the mesoporous carbon (MC) derived from biomass waste was prepared for immobilizing nZVI, and the nZVI@MC was further modified by sulfur (S-nZVI@MC) to relieve surface oxidation. The synergistic effect between nZVI and surface modification, the reaction conditions and the removal mechanism were investigated systematically. The characterization results showed nZVI was successfully loaded on the surface of MC, and the aggregation of nZVI was prevented. Moreover, sulfidation modification resulted in the formation of FeS on the surface of nZVI, which effectively alleviated surface oxidation of nZVI and promoted the electron transfer. Batch experiments demonstrated S-nZVI@MC had greatly enhanced reactivity towards 2,4,6-trichlorphenol (TCP) as compared to MC and nZVI, and the removal rate could reach 100%, which was mainly attributed to the significant synergistic effect of MC immobilization and sulfidation modification. Furthermore, the TCP removal process was well described by a Langmuir adsorption model and pseudo-second-order model. The possible mechanism for enhanced removal of TCP is the fast adsorption onto S-nZVI@MC and effective reduction by S-nZVI. Therefore, with excellent reducing activity and antioxidation, S-nZVI@MC has the potential as a pollutant treatment.

Phosphorus Pentachloride Promoted gem-Dichlorination of 2'- and 3'-Deoxynucleosides.

Halogen substitution at various positions of canonical nucleosides has generated a number of bioactive structural variants. Herein, the synthesis of two unique series of sugar modified nucleosides bearing a gem-dichloro group is presented. The synthetic plan entails the controlled addition of phosphorus pentachloride to suitably protected 2'- or 3'-ketodeoxynucleoside intermediates as the key step, facilitating the rapid construction of such functionalized molecules. Under the same reaction conditions, the highest chemoselectivity was observed for the formation of 2',2'-dichloro-2',3'-dideoxynucleosides, while a competing 2',3'-elimination process occurred in the case of the 3',3'-dichloro counterparts.

Reaction mechanism of organoselenium-catalyzed syn-dichlorination of alkenes: a DFT study.

A new method for the syn-dichlorination of alkenes at room temperature has been proposed by Denmark et al. The method uses diselenide (PhSeSePh) as the precatalyst, benzyltriethylammonium chloride (BnEt3NCl) as the source of chlorine, and an N-fluoropyridinium salt as the oxidant to recover the catalyst. This approach has achieved exquisite diastereocontrol on a number of alkene substrates. In this paper, we report the results of DFT calculations we performed to study the mechanism of this reaction. We were able to identify a reasonable reaction path, including the intermediate and transition-state structures. The results also indicate that PhSeCl3, rather than PhSeCl, is the active catalyst.

An unusual triphenylphosphine oxide catalyzed stereoselective 1,3-dichlorination of unsaturated ketoesters.

An unusual Ph3PO-catalyzed stereoselective 1,3-dicholorination of an unsaturated ketoester has been developed. The novel activation mode involved in this cascade reaction can promote consecutively elusive transformations. The products were obtained with good yields and excellent stereoselectivities. This reaction makes important complementation to the limitations associated with the field of dichlorination.