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1.
The transformability of trihalomethanes, carbon tetrachloride, 1,1,1-trichloroethane, 1,2-dibromoethane, tetrachloroethylene, hexachloroethane, and dibromochloropropane was studied under conditions of denitrification, sulfate respiration, and methanogenesis. These compounds at concentrations commonly found in groundwater were continuously administered to anoxic biofilm columns that resembled groundwater environments. Acetate was the primary substrate to support microbial growth. All of the compounds studied were transformed under methanogenesis. Bromoform, bromodichloromethane, carbon tetrachloride, and hexachloroethane were transformed even under the less reducing conditions of denitrification. Some of the compounds were partially mineralized to CO2. However, reductive dehalogenation appeared to be the predominant mechanism for removal. Characterization of the available electron acceptors in the subsurface is important for assessing organic micropollutant biotransformation. Reaction rates observed in the laboratory biofilms indicate that biotransformation could be responsible for significant removals of these halogenated compounds in the subsurface.  相似文献   

2.
This study investigated the anaerobic degradation of five polycyclic aromatic hydrocarbons (PAHs) from Erren River sediment in southern Taiwan. The degradation rates of PAH were in the order: acenaphthene > fluorene > phenanthrene > anthracene > pyrene. The degradation rate was enhanced when the five compounds were present simultaneously in river sediment. Comparison of the PAH degradation rates under three reducing conditions showed the following order: sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The addition of electron donors (acetate, lactate and pyruvate) enhanced PAH degradation under methanogenic and sulfate-reducing conditions. However, the addition of acetate, lactate or pyruvate inhibited PAH degradation under nitrate-reducing conditions. The addition of heavy metals, nonylphenol and phthalate esters (PAEs) inhibited PAH degradation. Our results show that sulfate-reducing bacteria, methanogen and eubacteria are involved in the degradation of PAH; sulfate-reducing bacteria constitute a major microbial component in PAH degradation. Of the microorganism strains isolated from the sediment samples, we found that strain ER9 expressed the greatest biodegrading ability.  相似文献   

3.
Bill M  Schüth C  Barth JA  Kalin RM 《Chemosphere》2001,44(5):1281-1286
Dehalogenation of trichloroethene (TCE) in the aqueous phase, either on palladium catalysts with hydrogen as the reductant or on metallic iron, was associated with strong changes in delta13C. In general, the delta13C of product phases were more negative than those of the parent compound and were enriched with time and fraction of TCE remaining. For dehalogenation with iron, the delta13C of TCE and products varied from -42/1000 to +5/1000. For the palladium experiments, the final product, ethane, reached the initial delta13C of TCE at completion of the dehalogenation reaction. During dehalogenation, the carbon isotope fractionation between TCE and product phases was not constant. The variation in delta13C of TCE and products offers a new monitoring tool that operates independently of the initial concentration of pollutants for abiotic degradation processes of TCE in the subsurface, and may be useful for evaluation of remediation efficiency.  相似文献   

4.
This study investigated the anaerobic degradation of five polycyclic aromatic hydrocarbons (PAHs) from Erren River sediment in southern Taiwan. The degradation rates of PAH were in the order: acenaphthene > fluorene > phenanthrene > anthracene > pyrene. The degradation rate was enhanced when the five compounds were present simultaneously in river sediment. Comparison of the PAH degradation rates under three reducing conditions showed the following order: sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The addition of electron donors (acetate, lactate and pyruvate) enhanced PAH degradation under methanogenic and sulfate-reducing conditions. However, the addition of acetate, lactate or pyruvate inhibited PAH degradation under nitrate-reducing conditions. The addition of heavy metals, nonylphenol and phthalate esters (PAEs) inhibited PAH degradation. Our results show that sulfate-reducing bacteria, methanogen and eubacteria are involved in the degradation of PAH; sulfate-reducing bacteria constitute a major microbial component in PAH degradation. Of the microorganism strains isolated from the sediment samples, we found that strain ER9 expressed the greatest biodegrading ability.  相似文献   

5.
回顾了硝基芳香化合物和偶氮化合物在厌氧条件下的生物脱毒、转化和矿化作用的研究成果。这些研究表明 ,由于硝基和偶氮基具有强烈的吸电子性 ,好氧条件下很难降解。但是 ,硝基和偶氮基芳香化合物在产甲烷菌群作用下较易还原脱毒 ,转化为相应的芳香胺类 ,其毒性要小几个数量级 ,因而有些毒性很高的芳香化合物废水可利用厌氧反应器处理 ,而且反应过程中发现一些芳香胺类化合物可被完全矿化 ,表明一些含氮芳香化合物可作为厌氧菌的碳源和能源 ,在厌氧条件下被完全生物降解。  相似文献   

6.
Investigation of a groundwater plume containing up to 24 g l(-1) phenolic compounds suggested that over a period of nearly 50 years, little degradation had occurred despite the presence of a microbial community and electron acceptors within the core of the plume. In order to study the effect of contaminant concentration on degradation behaviour, laboratory microcosm experiments were performed under aerobic and anaerobic conditions at four different concentrations obtained by diluting contaminated with uncontaminated groundwater. The microcosms contained groundwater with total phenols at ca. 200, 250, 660 and 5000 mg l(-1), and aquifer sediment that had been acclimatised within the plume for several months. The microcosms were operated for a period of 390-400 days along with sterile controls to ascertain whether degradation was microbially mediated or abiotic. Under aerobic conditions, degradation only occurred at concentrations up to 660 mg l(-1) total phenols. At phenol concentrations below 250 mg l(-1) a benzoquinone intermediate, thought to originate from the degradation of 2,5-dimethylphenol, was isolated and identified. This suggested an unusual degradative pathway for this compound; its aerobic degradation more commonly proceeding via catecholic intermediates. Under anaerobic conditions, degradation only occurred in the most dilute microcosm (total phenols 195 mg l(-1)) with a loss of p-cresol accompanied by a nonstoichiometric decrease in nitrate and sulphate. By inference, iron(III) from the sediment may also have been used as a terminal electron acceptor, in which case the amount of biologically available iron released was calculated as 1.07 mg Fe(III)/g of sediment. The study shows that natural attenuation is likely to be stimulated by dilution of the plume.  相似文献   

7.
This review is predicated upon the need for a detailed process-level understanding of factors influencing the reduction of anthropogenic organic chemicals in natural aquatic systems. In particular, abiotic reductions of anthropogenic organic chemicals are reviewed. The most important reductive reaction is alkyl dehalogenation (replacement of chloride with hydrogen) which occurs in organisms, sediments, sewage sludge, and reduced iron porphyrin model systems. An abiotic mechanism involving a free radical intermediate has been proposed. The abstraction of vicinal dihalides (also termed dehalogenation) is another reduction that may have an abiotic component in natural systems. Reductive dehalogenation of aryl halides has recently been reported and further study of this reaction is needed. Several other degradation reactions of organohalides that occur in anaerobic environments are mentioned, the most important of which is dehydrohalogenation. The reduction of nitro groups to amines has also been thoroughly studied. The reactions can occur abiotically, and are affected by the redox conditions of the experimental system. However, a relationship between nitro-reduction rate and measured redox potential has not been clearly established. Reductive dealkylation of the N- and O-heteroatom of hydrocarbon pollutants has been observed but not investigated in detail. Azo compounds can be reduced to their hydrazo derivatives and a thorough study of this reaction indicates that it can be caused by extracellular electron transfer agents. Quinone-hydroquinone couples are important reactive groups in humic materials and similar structures in resazurin and indigo carmine make them useful as models for environmental redox conditions. The interconversion of sulfones, sulfoxides, and sulfides is a redox process and is implicated in the degradation of several pesticides though the reactions need more study. Two reductive heterocyclic cleavage reactions are also mentioned. Finally, several difficulties (both semantic and experimental) that recur in the studies reviewed are discussed. The subtle effects of various sterilization techniques on extracellular biochemicals and complex chemical reducing agents in sediment have stifled attempts to separate abiotic from biological degradation reactions. The characterization of redox conditions in a natural system is still problematic since measured redox potential is not adequate. Suggestions for future research toward a process-level understanding of abiotic chemical reductions are made.  相似文献   

8.
Disappearance rate constants are reported for the reductive transformation of 17 halogenated aliphatic hydrocarbons in anaerobic sediment-water samples. Statistical experimental design in combination with multivariate chemical characterization of their chemical properties was used to select the compounds. Degradation followed pseudo first-order kinetics through at least two half-lives for 15 of the 17 compounds. Of all the compounds investigated, 1,2,3-trichloropropane and dichloromethane were unique in that they were dehalogenated according to zero-order kinetics. Reductive dehalogenation was the sole transformation reaction taking place.  相似文献   

9.
Simulation of biodegradation reactions within a reactive transport framework requires information on mechanisms of terminal electron acceptor processes (TEAPs). In initial modeling efforts, TEAPs were approximated as occurring sequentially, with the highest energy-yielding electron acceptors (e.g. oxygen) consumed before those that yield less energy (e.g., sulfate). Within this framework in a steady state plume, sequential electron acceptor utilization would theoretically produce methane at an organic-rich source and Fe(II) further downgradient, resulting in a limited zone of Fe(II) and methane overlap. However, contaminant plumes often display much more extensive zones of overlapping Fe(II) and methane. The extensive overlap could be caused by several abiotic and biotic processes including vertical mixing of byproducts in long-screened monitoring wells, adsorption of Fe(II) onto aquifer solids, or microscale heterogeneity in Fe(III) concentrations. Alternatively, the overlap could be due to simultaneous utilization of terminal electron acceptors. Because biodegradation rates are controlled by TEAPs, evaluating the mechanisms of electron acceptor utilization is critical for improving prediction of contaminant mass losses due to biodegradation. Using BioRedox-MT3DMS, a three-dimensional, multi-species reactive transport code, we simulated the current configurations of a BTEX plume and TEAP zones at a petroleum-contaminated field site in Wisconsin. Simulation results suggest that BTEX mass loss due to biodegradation is greatest under oxygen-reducing conditions, with smaller but similar contributions to mass loss from biodegradation under Fe(III)-reducing, sulfate-reducing, and methanogenic conditions. Results of sensitivity calculations document that BTEX losses due to biodegradation are most sensitive to the age of the plume, while the shape of the BTEX plume is most sensitive to effective porosity and rate constants for biodegradation under Fe(III)-reducing and methanogenic conditions. Using this transport model, we had limited success in simulating overlap of redox products using reasonable ranges of parameters within a strictly sequential electron acceptor utilization framework. Simulation results indicate that overlap of redox products cannot be accurately simulated using the constructed model, suggesting either that Fe(III) reduction and methanogenesis are occurring simultaneously in the source area, or that heterogeneities in Fe(III) concentration and/or mineral type cause the observed overlap. Additional field, experimental, and modeling studies will be needed to address these questions.  相似文献   

10.
Arbeli Z  Ronen Z  Díaz-Báez MC 《Chemosphere》2006,64(9):1472-1478
This study was aimed at improving our understanding of the physiology of the microorganisms that reductively dehalogenate tetrabromobisphenol-A (TBBPA). Activity was followed in contaminated sediments from a polluted streambed as well as from fracture filling material underlying the stream. Reductive dehalogenation was observed in surface sediments but not in fracture filling samples from a depth of 3m. Likewise, anaerobic microbial activity, represented by sulphate reduction, was much higher in the surface sediment. In the culture enriched from the surface sediment, optimal microbial debromination of TBBPA took place at a salinity of 2% and 3% NaCl, temperature of 30 degrees Celsius, and pH of 7-8. Ethanol, pyruvate and the combination of hydrogen with acetate were the most suitable electron donors and carbon sources for this culture. Alternative electron acceptors like Fe(3+), SO(4)(2-), SO(3)(2-), NO(3)(-) and 2,4,6-tribromophenol inhibited TBBPA debromination. The debrominating bacteria were heat sensitive (80 degrees Celsius, for 10min) but were not inhibited by bromoethanesulphonate or molybdate. This study allowed optimisation of our culturing conditions, but was also important for understanding the factors which influence TBBPA debromination in situ.  相似文献   

11.
The effect of several sulphur compounds: sodium sulphate, sodium sulphide, ferrous sulphide,pyrite and an organosulphonic acid on the kinetics of the iron (Fe °) induced degradation of carbon tetrachloride was examined under aerobic conditions. It was observed that all of the sulphur compounds investigated significantly accelerated the reaction. The mechanisms of the processes studied as well as their possible influence on the efficiency of the iron-induced dehalogenation of pollutants, both in situ and in above-ground treatment are discussed.  相似文献   

12.
Continued input of airplane de-icing/anti-icing fluids (ADAF) to runway adjacent soils may result in the depletion of soil-borne terminal electron acceptors. We studied the transport and transformation of propylene glycol (PG), the major constituent of many ADAF, in topsoil and subsoil samples using saturated column experiments at 4 degrees C and 20 degrees C. The export of soil-borne DOC was generally high, non-exhaustive and rate limited. Retardation of added PG was negligible. Rapid PG degradation was observed only in topsoil materials high in organic matter at 20 degrees C. At 4 degrees C, no significant degradation was observed. Thus, under unfavorable, i.e., wet and cold conditions typical for winter de-icing operations, PG and its metabolites will be relocated to deeper soil horizons or even to the groundwater. In subsoil materials, PG degradation was very slow and incomplete. We found that subsoil degradation depended on the import of active microorganisms originating from the organic-rich topsoil material. The degradation efficiency is strongly influenced by the flow velocity, i.e., the residence time of PG in the soil column. Poorly crystalline iron(III) and manganese(IV) (hydr)oxides are used during microbial respiration acting as terminal electron acceptors. This results in the formation and effective relocation of reduced and mobile Fe and Mn species. Long-term application of ADAF to runway adjacent soil as well as the lasting consumption of Fe and Mn will tend to decrease the soil redox potential. Without proper counteractive measures, this will eventually favor the development of methanogenic conditions.  相似文献   

13.
We present an approach for characterizing in situ microbial degradation using the 13C/12C isotope fractionation of contaminants as an indicator of biodegradation. The 13C/12C isotope fractionation of aromatic hydrocarbons was studied in anoxic laboratory soil percolation columns with toluene or o-xylene as the sole carbon and electron source, and sulfate as electron acceptor. After approximately 2 months' of incubation, the soil microbial community degraded 32 mg toluene l(-1) and 44 mg o-xylene l(-1) to less than 0.05 mg l(-1), generating a stable concentration gradient in the column. The 13C/12C isotope ratio in the residual non-degraded fraction of toluene and o-xylene increased significantly, corresponding to isotope fractionation factors (alphaC) of 1.0015 and 1.0011, respectively. When the extent of biodegradation in the soil column was calculated based on the measured isotope ratios (R(t)) and an isotope fractionation factor (alphaC=1.0017) obtained from a sulfate-reducing batch culture the theoretical residual substrate concentrations (C(t)) matched the measured toluene concentrations in the column. This indicated that a calculation of biodegradation based on isotope fractionation could work in systems like soil columns. In a field study, a polluted, anoxic aquifer was analyzed for BTEX and PAH contaminants. These compounds were found to exhibit a significant concentration gradient along an 800-m groundwater flow path downstream of the source of contamination. A distinct increase in the carbon isotope ratio (delta13C) was observed for the residual non-degraded toluene (7.2 per thousand ), o-xylene (8.1 per thousand ) and naphthalene fractions (1.2 per thousand ). Based on the isotope values and the laboratory-derived isotope fractionation factors for toluene and o-xylene, the extent to which the residual substrate fraction in the monitoring wells had been degraded by microorganisms was calculated. The results revealed significant biodegradation along the groundwater flow path. In the wells at the end of the plume, the bioavailable toluene and o-xylene fractions had been almost completely reduced by in situ microbial degradation. Although indane and indene showed decreasing concentrations downstream of the groundwater flow path, suggesting microbial degradation, their carbon isotope ratios remained constant. As the physical properties of these compounds are similar to those of BTEX compounds, the constant isotope values of indane and indene indicated that microbial degradation did not lead to isotope fractionation of all aromatic hydrocarbons. In addition, physical interaction with the aquifer material during the groundwater passage did not significantly alter the carbon isotope composition of aromatic hydrocarbons.  相似文献   

14.
The biodegradation of phenols (5, 60, 600 mg l−1) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer. The aqueous phase was sampled and analyzed for phenols and selected redox sensitive parameters on a regular basis. An experiment with sandstone material from specific depth intervals from a vertical profile across the ammonium plume was also conducted. The miniature microcosms used in this experiment were sacrificed for sampling for phenols and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms.The redox conditions in the anaerobic microcosms were mixed nitrate and Fe(III) reducing. Nitrate and Fe(III) were apparently the dominant electron acceptors at high and low nitrate concentrations, respectively. When biomass growth is taken into account, nitrate and Fe(III) reduction constituted sufficient electron acceptor capacity for the mineralization of the phenols observed to be degraded even at an initial phenols concentration of 60 mg l−1 (high) in an unamended microcosm, whereas nitrate reduction alone is unlikely to have provided sufficient electron acceptor capacity for the observed degradation of the phenols in the unamended microcosm.For microcosm systems, with solid aquifer materials, dissolution of organic substances from the solid material may occur. A quantitative determination of the speciation (mineral types and quantity) of electron acceptors associated with the solids, at levels relevant for degradation of specific organic compounds in aquifers, cannot always be obtained. Hence, complete mass balances of electron acceptor consumption for specific organic compounds degradation are difficult to confine. For aquifer materials with low initial Fe(II) content, Fe(II) determinations on solids and in aqueous phase samples may provide valuable information on Fe(III) reduction. However, in microcosms with natural sediments and where electron acceptors are associated with the sediments, complete mass-balances for substrates and electron acceptors are not likely to be obtained.  相似文献   

15.
16.
Shibata A  Toyota K  Miyake K  Katayama A 《Chemosphere》2007,68(11):2096-2103
Anaerobic degradation of phenol, p-cresol, 4-n-propylphenol (n-PP), 4-i-propylphenol (i-PP), 4-n-butylphenol (n-BP) and 4-sec-butylphenol (sec-BP) was observed in a paddy soil supplemented with nitrate. We detected the metabolites 4′-hydroxypropiophenone (HPP) from n-PP, 4-i-propenylphenol from i-PP, and 4-(1-butenyl)phenol and 4′-hydroxybutyrophenone (HBP) from n-BP. Compared with the original soils, Betaproteobacteria became predominant in the microcosm during the degradation of phenol and p-cresol whereas no remarkable change was observed in the community degrading propylphenols and butylphenols. The microcosm, however, did not degrade 4-t-butylphenol (t-BP), 4-t-octylphenol (t-OP) and 4-n-octylphenol (n-OP). Paddy soil supplemented with sulfate or iron (III) as electron acceptors did not degrade phenol and 4-alkylphenols with the exception of the degradation of p-cresol in sulfate-reducing conditions. It was demonstrated for the first time that anaerobic microbial degradation of alkylphenols, in a paddy soil supplemented with nitrate as an electron acceptor, occurred via oxidation of the alpha carbon in the alkyl chain.  相似文献   

17.
The fate of fuel oxygenates such as methyl tert-butyl ether (MTBE) in the subsurface is governed by their degradability under various redox conditions. The key intermediate in degradation of MTBE and ethyl tert-butyl ether (ETBE) is tert-butyl alcohol (TBA) which was often found as accumulating intermediate or dead-end product in lab studies using microcosms or isolated cell suspensions. This review discusses in detail the thermodynamics of the degradation processes utilizing various terminal electron acceptors, and the aerobic degradation pathways of MTBE and TBA. It summarizes the present knowledge on MTBE and TBA degradation gained from either microcosm or pure culture studies and emphasizes the potential of compound-specific isotope analysis (CSIA) for identification and quantification of degradation processes of slowly biodegradable pollutants such as MTBE and TBA. Microcosm studies demonstrated that MTBE and TBA may be biodegradable under oxic and nearly all anoxic conditions, although results of various studies are often contradictory, which suggests that site-specific conditions are important parameters. So far, TBA degradation has not been shown under methanogenic conditions and it is currently widely accepted that TBA is a recalcitrant dead-end product of MTBE under these conditions. Reliable in situ degradation rates for MTBE and TBA under various geochemical conditions are not yet available. Furthermore, degradation pathways under anoxic conditions have not yet been elucidated. All pure cultures capable of MTBE or TBA degradation isolated so far use oxygen as terminal electron acceptor. In general, compared with hydrocarbons present in gasoline, fuel oxygenates biodegrade much slower, if at all. The presence of MTBE and related compounds in groundwater therefore frequently limits the use of in situ biodegradation as remediation option at gasoline-contaminated sites. Though degradation of MTBE and TBA in field studies has been reported under oxic conditions, there is hardly any evidence of substantial degradation in the absence of oxygen. The increasing availability of field data from CSIA will foster our understanding and may even allow the quantification of degradation of these recalcitrant compounds. Such information will help to elucidate the crucial factors of site-specific biogeochemical conditions that govern the capability of intrinsic oxygenate degradation.  相似文献   

18.
同分异构体喹啉和异喹啉的缺氧降解性能比较   总被引:3,自引:0,他引:3  
研究了同分异构体的含氮杂环化合物喹啉和异喹啉在缺氧条件下的降解情况,发现两者表现出不同的缺氧降解特性。喹啉可以在缺氧条件下得到有效降解,其缺氧降解的最佳碳氮比为8。在最佳碳氮比条件下,喹啉的缺氧降解过程符合一级动力学规律,在其降解过程中首先以硝酸盐为电子受体,当硝酸盐氮浓度为零时,亚硝酸盐氮浓度达到最高,此后喹啉的降解主要以亚硝酸盐为电子受体,并和亚硝酸盐氮同时达到最低浓度。异喹啉对硝酸盐的利用甚微,其降解主要表现为厌氧降解特征,降解过程符合零级动力学规律。  相似文献   

19.
Zhuang L  Gui L  Gillham RW 《Chemosphere》2012,89(7):810-816
This study examined the role of denitrifying and sulfate-reducing bacteria in biodegradation of pentaerythritol tetranitrate (PETN). Microbial inocula were obtained from a PETN-contaminated soil. PETN degradation was evaluated using nitrate and/or sulfate as electron acceptors and acetate as a carbon source. Results showed that under different electron acceptor conditions tested, PETN was sequentially reduced to pentaerythritol via the intermediary formation of tri-, di- and mononitrate pentaerythritol (PETriN, PEDN and PEMN). The addition of nitrate enhanced the degradation rate of PETN by stimulating greater microbial activity and growth of nitrite reducing bacteria that were responsible for degrading PETN. However, a high concentration of nitrite (350 mg L−1) accumulated from nitrate reduction, consequently caused self-inhibition and temporarily delayed PETN biodegradation. In contrast, PETN degraded at very similar rates in the presence and absence of sulfate, while PETN inhibited sulfate reduction. It is apparent that denitrifying bacteria possessing nitrite reductase were capable of using PETN and its intermediates as terminal electron acceptors in a preferential utilization sequence of PETN, PETriN, PEDN and PEMN, while sulfate-reducing bacteria were not involved in PETN biodegradation. This study demonstrated that under anaerobic conditions and with sufficient carbon source, PETN can be effectively biotransformed by indigenous denitrifying bacteria, providing a viable means of treatment for PETN-containing wastewaters and PETN-contaminated soils.  相似文献   

20.
The alteration of physico-chemical properties of sediment organic matter (SOM) incubated under current-harvesting conditions as well as no-current producing conditions over 120 days using sediment microbial fuel cell systems was examined. The SOM was microbially oxidized under anaerobic conditions with an electrode serving as a terminal electron acceptor. It was found that SOM around the electrochemically-active electrodes became more humified, aromatic, and polydispersed, and had a higher average molecular weight, along with its partial degradation and electricity generation compared to that for the original sediment. These changes in SOM properties were analogous to those commonly observed in the early stages of the SOM diagenetic process (i.e. humification). Such a humification-like process was evidently more stimulated when electrical current was produced than no-current condition. These new findings associated with microbially-catalyzed electricity generation may present a potential for the energy-efficient remediation, monitoring, and/or management of the geo-environment.  相似文献   

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