Reductive dechlorination pathways for substituted benzenes: a correlation with electronic properties

Electronic properties were correlated with observed reductive dechlorination pathways by unacclimated consortia for chlorinated phenols, dihydroxybenzenes, benzoic acids, and anilines. Molecular structures and properties were calculated using the semi-empirical Modified Neglect of Differential Overlap method at the Cornell Supercomputing Facility. Observed preferential positions for reductive dechlorination by unacclimated consortia correlate well with the largest negative value for the carbon-chlorine bond charge. Of 16 dechlorination pathways observed for unacclimated bacteria, the most negative carbon-chlorine bond charge correlated with 15 pathways.This correlation between the observed dechlorination position and the parent compound's electronic properties is consistent with the observed reductive dechlorination of chlorophenols and chlorinated dihydroxybenzenes at the ortho position, and the meta dechlorination of chlorobenzoic acids. Net carbonchlorine bond charges also correlate with the preferred dechlorination position for two of three known chloroaniline pathways, suggesting preferential removal of chlorines from the ortho position of chloroanilines.Abbreviations CA chloroaniline - CBz chlorobenzoic acid - CC chlorocatechol - CP chlorophenol - DCA dichloroaniline - DCBz dichlorobenzoic acid - DCC dichlorocatechol - DCH dichlorohydroquinone - DCP dichlorophenol - DCR dichlororesorcinol - PCP pentachlorophenol - TCA trichloroaniline - TCBz trichlorobenzoic acid - TCC trichlorocatechol - TCH trichlorohydroquinone - TCP trichlorophenol - TCR trichlororesorcinol - TeCA tetrachloroaniline - TeCBz tetrachlorobenzoic acid - TeCC tetrachlorocatechol - TeCH tetrachlorohydroquinone - TeCP tetrachlorophenol - TeCR tetrachlororesorcinol     

Anaerobic degradation and dehalogenation of chlorosalicylates and salicylate under four reducing conditions

The anaerobic biodegradability and transformationof the mono-and dichlorinated salicylates(2-hydroxybenzoates) was examined under denitrifying,Fe (III) reducing, sulfate reducing andmethanogenic conditions. 3,6-Dichlorosalicylateand 6-chlorosalicylate are anaerobic microbialmetabolites of dicamba, a widely used herbicide.Anaerobic microcosms were established withdicamba treated soil from Wyoming, and golfcourse drainage stream sediments from NewJersey, which were each spiked with salicylate,3,6-dichlorosalicylate or one of the fourmonochlorosalicylate isomers. Salicylatewas degraded under denitrifying, sulfidogenic andmethanogenic conditions. In methanogenicenrichments 5-chlorosalicylate and 3-chlorosalicylatewere reductively dehalogenated to salicylatewhich was then utilized. Dehalogenation ofmonochlorinated salicylates to salicylate wasalso observed in denitrifying chlorosalicylatedegrading cultures. The study revealed thatthe position of the chlorine substituent as well as thepredominant electron accepting process affectthe rate and extent of chlorosalicylate degradationin anoxic environments.     

Sulphate-reducing bacteria,palladium and the reductive dehalogenation of chlorinated aromatic compounds

The surfaces of cells of Desulfovibrio desulfuricans,Desulfovibrio vulgaris and a new strain, Desulfovibrio sp. `Oz-7' were used to manufacturea novel bioinorganic catalyst via the reduction of Pd(II) to Pd(0) at the cell surface usinghydrogen as the electron donor. The ability of the palladium coated (palladised) cells to reductivelydehalogenate chlorophenol and polychlorinated biphenyl species was demonstrated. Dried, palladisedcells of D. desulfuricans, D. vulgaris and Desulfovibrio sp. `Oz-7'were more effective bioinorganic catalysts than Pd(II) reduced chemically under H₂ orcommercially available finely divided Pd(0). Differences were observed in the catalyticactivity of the preparations when compared with each other. Negligible chloride release occurredfrom chlorophenol and polychlorinated biphenyls using biomass alone.     

Biological decomposition of dichloromethane from a chemical process effluent

The application of specialized microorganisms to treat dichloromethane (DM) containing process effluents was studied. An aerobic fluidized bed reactor with a working volume of 801 filled with sand particles as carriers for the bacteria was used. Oxygen was introduced into the recycle stream by an injector device. DM was monitored semi-continuously. A processor controlled the feed volume according to the DM effluent concentration. Mineralization rates of 12 kg DM/m_bioreactor³ · d were reached within about three weeks using synthetic wastewater containing 2000 mg/l DM as single carbon compound. DM from process water of a pharmaceutical plant was reduced from about 2000 mg/l in the feed to below 1 mg/l in the effluent at volumetric loading rates of 3 to 4 kg DM/m_bioreactor³ · d. Degradation of wastewater components like acetone and isopropanol were favoured, thus making the process less attractive for waste streams containing high amounts of DOC other than of DM. DM concentrations of up to 1000 mg/l were tolerated by the immobilized microorganisms and did not influence their DM degradation capacity. The ability to mineralize DM was lost when no DM was fed to the reactor for 10 days.     

填埋场氯代烃生物降解过程的机制转化与调控研究及展望

明晰氯代烃在复杂污染体系中的生物转化机制对强化污染物原位生物修复有重要意义。填埋场属典型复合污染场地,本文对不同地区填埋场填埋气中氯代烃种类、含量和其在覆盖层中的降解情况进行统计分析,发现填埋气中主要包括氯代烷烃和氯代烯烃两大类污染物,其浓度分别为0.20–32.45μg/m~3和0.50–32.45μg/m~3;覆盖土对氯代烃降解速率随着氯原子取代的增多而降低。基于覆盖层中微生物种类多、生长底物复杂多样和不同梯度氧气含量差异等特点,总结得出氯代烃在覆盖土中的降解途径主要是好氧共代谢、直接氧化和厌氧还原脱氯;并基于不同工况特点构建了氯代烃在填埋场覆盖层底部扩散至大气界面过程的生物转化机制模型。最后就复杂环境体系中氯代烃类污染物的去除进行了展望。     

地下水脱卤过程中的微生物种间代谢互作：提高原位氯代烯烃厌氧脱氯效能的有效途径

有机卤呼吸细菌(organohalide-respiring bacteria, OHRB)在氯代烯烃污染地下水的原位生物修复中扮演着关键性的角色,提高其丰度及活性对氯代烯烃的完全去除具有重要意义。在实际环境中,有机卤呼吸细菌往往与多种微生物共存,微生物种间代谢互作现象十分普遍,有机污染物的完全无害化往往需要通过微生物菌群的协同代谢作用来实现。因此,本文围绕微生物种间代谢互作进行综述,对目前获得的脱氯微生物菌种资源及脱氯机理进行了回顾,重点阐述了专性OHRB、非专性OHRB和非OHRB的种间代谢互作行为及机制,并提出以种间代谢互作为指导进行合成微生物群落的构建来有效提高氯代烯烃厌氧生物降解效率,为实现环境氯代烯烃类有机污染物的快速、彻底无害化提供理论指导。     

Anaerobic Microbial Reductive Dehalogenation of Chlorinated Ethenes

The current knowledge on microbial reductive dechlorination of chlorinated ethenes (CEs) and its application are discussed. Physiological studies on CEs dechlorinating microorganisms indicate that a distinction can be made between cometabolic dechlorination and halorespiration. Whereas cometabolic dechlorination is a coincidental and nonspecific side reaction, catalyzed by several methanogenic and acetogenic bacteria, halorespiration is a specific enzymatic reaction from which metabolic energy can be gained. In contrast to the well-studied biological dechlorination of PCE to cis-DCE, little is known about the biology of the further dechlorination from cis-DCE to ethene. Bacteria performing the latter reaction have not yet been isolated. Microbial reductive dechlorination can be applied to the in situ bioremediation of CEs contaminated sites. From laboratory and field studies, it has become clear that the dechlorination of tetrachloroethene (PCE) to cis-clichloroethene (cis-DCE) occurs rapidly and can be stimulated relatively easily. However, complete reduction to ethene appears to be a slower process that is more difficult to achieve.     

一株脱卤单胞菌属有机卤呼吸细菌的分离纯化与基础特征

[目的]分离鉴定新型有机卤呼吸细菌,拓展有机氯污染物降解菌种资源.[方法]在限制性培养基中,基于特定脱卤微生物的能量代谢特点以及对抗生素的抗性特征,应用绝迹稀释法从脱氯富集培养物中分离纯化新型有机卤呼吸细菌.通过添加酵母提取物和聚合酶链反应-限制性片段长度多态性等方法鉴定菌株纯度.通过考察细胞形态、16SrRNA系统发...     

厌氧微生物菌群XH-1对2,4,6-三氯苯酚的降解特性

有机污染物2,4,6-三氯苯酚(2,4,6-TCP)普遍存在于地下水和河流底泥等厌氧环境中。为了探究厌氧微生物菌群XH-1对2,4,6-TCP的降解能力,本研究以2,4,6-TCP为底物,接种XH-1建立微宇宙培养体系,并以中间产物4-氯苯酚(4-CP)和苯酚为底物分别进行分段富集培养,利用高效液相色谱分析底物的降解转化,同时基于16S rRNA基因高通量测序分析微生物群落结构变化。结果表明: 2,4,6-TCP(122 μmol·L^-1)以0.15 μmol·d^-1的速率在80 d内被完全降解转化,降解中间产物分别为2,4-二氯苯酚(2,4-DCP)、4-氯苯酚和苯酚,所有中间产物最终在325 d被完全降解。高通量测序结果表明,脱卤杆菌和脱卤球菌可能驱动2,4,6-TCP还原脱氯,其中,脱卤球菌可能在4-CP的脱氯转化中发挥重要作用,并与丁酸互营菌和产甲烷菌联合作用彻底降解2,4,6-TCP。     

Characterization of a Microbial Consortium Capable of Rapid and Simultaneous Dechlorination of 1,1,2,2-Tetrachloroethane and Chlorinated Ethane and Ethene Intermediates

Mixed cultures capable of dechlorinating chlorinated ethanes and ethenes were enriched from contaminated wetland sediment at Aberdeen Proving Ground (APG) Maryland. The “West Branch Consortium” (WBC-2) was capable of degrading 1,1,2,2-tetrachloroethane (TeCA), trichloroethene (TCE), cis and trans 1,2-dichloroethene (DCE), 1,1,2-trichloroethane (TCA), 1,2-dichloroethane, and vinyl chloride to nonchlorinated end products ethene and ethane. WBC-2 dechlorinated TeCA, TCA, and cisDCE rapidly and simultaneously. A Clostridium sp. phylogenetically closely related to an uncultured member of a TCE-degrading consortium was numerically dominant in the WBC-2 clone library after 11 months of enrichment in culture. Clostridiales, including Acetobacteria, comprised 65% of the bacterial clones in WBC-2, with Bacteroides (14%), and epsilon Proteobacteria (14%) also numerically important. Methanogens identified in the consortium were members of the class Methanomicrobia, which includes acetoclastic methanogens. Dehalococcoides did not become dominant in the culture, although it was present at about 1% in the microbial population. The WBC-2 consortium provides opportunities for the in situ bioremediation of sites contaminated with mixtures of chlorinated ethenes and ethanes.     

共代谢条件下光合细菌对2-氯苯酚的生物降解

光合细菌PSB-1D不能利用2-氯苯酚(2-CP)作为唯一的碳源和能源.选用苹果酸、丙酸钠、乙酸钠、柠檬酸钠、苯酚、葡萄糖和可溶性淀粉等7种不同碳源作为光合细菌PSB-1D降解2-CP的共代谢基质,考察了在黑暗好氧培养条件下,不同共代谢基质对PSB-1D生长及降解2-CP效果的影响.结果表明:葡萄糖能够很好地促进PSB-1D的大量繁殖,提高降解效果,缩短降解周期,为最佳共代谢基质.对葡萄糖的投加浓度进行了优化,当葡萄糖的投加浓度为3 g·L-1时,菌株PSB-1D培养168 h后的菌体生长浓度△D560为1.749,2-CP的半衰期为3.9 d,降解速率常数为0.00864 h-1.采用SDS-PAGE对微生物全细胞蛋白质进行分析发现,在共代谢过程中当菌株PSB-1D利用葡萄糖作为底物提供能源和碳源时,可诱导产生2-CP特异性降解酶.     

Dechlorination of 2,3,5,6-tetrachlorobiphenyl by a phototrophic enrichment culture

A phototrophic enrichment culture, using acetate as carbon source, reductively dechlorinated 2,3,5,6-tetrachlorobiphenyl. ortho chlorines were removed preferentially over meta chlorines. Tri- and dichlorobiphenyls were the major products. During 14 months incubation, chlorine was removed from 58% of the target molecules; 19% of the total chlorines were removed. Dechlorination did not occur in a control culture incubated in the dark.     

Role of electron-donating cosubstrates in the anaerobic biotransformation of chlorophenoxyacetates to chlorophenols by a bacterial consortium enriched on phenoxyacetate

A bacterial consortium that anaerobically mineralized phenoxyacetate, with transient production of phenol as an intermediate, was obtained from a methanogenic aquifer site near the Norman, OK municipal landfill. This consortium was able to convert the eight halogenated chlorophenoxyacetates tested to the corresponding chlorophenols. The chlorophenols were not subsequently metabolized. The addition of reduced substrates increased the rate of degradation of all chlorophenoxyacetates, with 78% of mono- and di-chlorinated substrates being transformed to chlorophenols in butyrate-amended cultures, compared to less than 37% transformed in unsupplemented cultures. Butyrate increased the transformation of 2,4,5-trichlorophenoxyacetate from 10% to 20%. An experiment evaluating the effects of several compounds on the side-chain cleavage reaction of 3-chlorophenoxyacetate showed that addition of compounds with readily act as hydrogen donors (butyrate, crotonate, ethanol, propionate, and hydrogen) resulted in 2 to 5 times the amount of 3-chlorophenoxyacetate transformed compared to controls with no amendment, formate had a slight stimulatory effect, and acetate and methanol had no effect. Butyrate addition also increased the rate of phenoxyacetate degradation, resulting in transient phenol accumulation not observed in butyrate-unamended controls. These results support the hypothesis that the side-chain cleavage of phenoxyacetate is a reductive process that is stimulated by the oxidation of reduced cosubstrates.     

Role of sulfate in microbial transformations of environmental contaminants: Chlorinated aromatic compounds

Despite recent progress made in describing microbial transformations that occur under anaerobic conditions, our understanding of the role sulfate‐reducing bacteria may play in the remediation of environmental contaminants is still very limited. The objective of this mini‐review is to summarize what is currently known of the metabolism of chlorinated aromatic compounds in the presence of sulfate. Sulfidogenic processes are discussed with respect to the thermodynamics of haloaromatic oxidation and to their potential use in the in situ bioremediation of hazardous organic wastes. A comprehensive listing is made of anaerobic transformations that involve both halogenated and nonhalogenated monoaromatic substrates by denitrifiers, dissimilatory iron‐reducing bacteria, and methanogenic consortia. In contrast to other anaerobic processes, studies involving sulfate‐mediated metabolism of hazardous organic compounds have been neglected; however, the recent success in defining methanogenic transformations, in particular, has enhanced expectations of defining an analogous role for sulfate‐reducing microbial communities in low redox environments that have become contaminated with hazardous substances.     

Aerobic biodegradation of trichloroethylene using a consortium of five bacterial strains

Degradation with an aerobic consortium was used to evaluate the bioremediation trichloroethylene (TCE) as a model substrate. After one week, 228-1186 mg TCE l(-1) was degraded at rates of 20-50 microg TCE l(-1) h(-1). The introduction of 10 mg toluene l(-1) enhanced the degradation rates for TCE when greater than 600 mg l(-1). Using isolated enzymes, a TCE degradation intermediate(s) appears inhibitory to the oxygenase enzymes thereby diminishing the overall degradation.     

Microbial Reductive Dechlorination of Weathered and Exogenous Co-planar Polychlorinated Biphenyls (PCBs) in an Anaerobic Sediment of Venice Lagoon

The occurrence of reductive dechlorination processes towards pre-existing PCBs and five exogenous coplanar PCBs were investigated in a contaminated sediment of Porto Marghera (Venice Lagoon, Italy) suspended, under strictly anaerobic conditions, in water collected from the same site. PCB dechlorination started after five months of incubation, when sulfate initially occurring in the microcosms was completely depleted and methanogenesis was in progress. It was ascribed to sulfate-reducing bacteria. Several pre-existing hexa-, penta- and tetra-chlorinated biphenyls were slowly bioconverted into tri- and di-, ortho-substituted PCBs from the 5th to the 16th month of experiment. Spiked coplanar PCBs, i.e., 3,3′,4,4′-tetrachlorobiphenyl, 3,3′,4,4′,5- and 2,3′,4,4′,5-pentachlorobiphenyls, 3,3′,4,4′,5,5′- and 2,3,3′,4,4′,5-hexachlorobiphenyls, were extensively transformed (by about 90%) into lower chlorinated congeners, such as 3,3′,5,5′-/2,3′,4,4′-tetrachlorobiphenyl, 3,3′,5-, 2,4,4′-, 2,3′,4- and 2,3′,5-trichlorobiphenyl, 3,4-/3,4′- and 3,3′-dichlorobiphenyl and 2-chlorobiphenyl. The reductive dechlorination of spiked PCBs did not influence significantly the biotransformation rate and extent of pre-existing PCBs.     

Degradation of chlorinated guaiacols in anaerobic acetate enrichment conditions

Chlorinated guaiacols (4,5,6-trichloro-, 4,5-dichloro-, and 4-chloro-guaiacol) at 0.2 mM were completely degraded by anaerobic digester sludge within 4 d, but complete removal of TeCG could not be attained. The removal rates of chlorinated guaiacols by adsorption and biodegradation were in the following order: 4,5-dichloroguaiacol > 4-chloroguaiacol = 4,5,6-trichloroguaiacol > tetrachloroguaiacol. The most rapid initial TeCG degradation occurred in the glucose-supplemented cultures. However, the degradation rate of 4,5,6-TriCG was not increased significantly by supplementary glucose.     

Reductive dechlorination of 1,2-dichloroethane and chloroethane by cell suspensions of methanogenic bacteria

Concentrated cell suspensions of methanogenic bacteria reductively dechlorinated 1,2-dichloroethane via two reaction-mechanisms: a dihalo-elimination yielding ethylene and two hydrogenolysis reactions yielding chloroethane and ethane, consecutively. The transformation of chloroethane to ethane was inhibited by 1,2-dichloroethane. Stimulation of methanogenesis caused an increase in the amount of dechlorination products formed, whereas the opposite was found when methane formation was inhibited. Cells of Methanosarcina barkeri grown on H₂/CO₂ converted 1,2-dichloroethane and chloroethane at higher rates than acetate or methanol grown cells.Abbreviations BrES 2-bromoethanesulfonic acid - CA chloroethane - 1,2-DCA 1,2-dichloroethane - F₄₃₀ Ni(II)tetrahydro-(12, 13)-corphin with an uroporphinoid (III) ligand skeleton     

光合细菌对芳香族化合物厌氧降解的研究进展

许多被有毒性的芳香族化合物污染的环境实际上是缺氧的 ,因此芳香族化合物的厌氧降解逐渐引起人们的兴趣。芳香族化合物的厌氧还原降解机制从根本上不同于好氧条件下的氧化降解机制 ,而光合细菌一直以来是研究芳香族化合物厌氧降解的模式菌株。因此 ,从生理学、酶学及分子生物学角度出发概括了对光合细菌厌氧降解芳香族化合物的研究动态。