Reductive dechlorination and biodegradation of 2,4,6-trichlorophenol using sequential permeable reactive barriers: laboratory studies

The reductive dechlorination and biodegradation of 2,4,6-trichlorophenol (2,4,6-TCP) was investigated in a laboratory-scale sequential barrier system consisting of a chemical and biological reactive barrier. Palladium coated iron (Pd/Fe) was used as a reactive barrier medium for the chemical degradation of 2,4,6-TCP, and a sand column seeded with anaerobic microbes was used as a biobarrier following the chemical reactive barrier in this study. Only phenol was detected in the effluent from the Pd/Fe column reactor, indicating that the complete dechlorination of 2,4,6-TCP was achieved. The residence time of 30.2-21.2h was required for the complete dechlorination of 2,4,6-TCP of 100 mg l(-1) in the column reactor. The surface area-normalized rate constant (k(SA)) is 3.84 (+/-0.48)x10(-5)lm(-2)h(-1). The reaction rate in the column tests was one order of magnitude slower than that in the batch test. In the operation of the biobarrier, about 100 microM of phenol was completely removed with a residence time of 7-8d. Consequently, the dechlorination prior to biodegradation turns out to increase the overall treatability. Moreover, the sequential permeable reactive barriers, consisting of iron barrier and biobarrier, could be recommended for groundwater contaminated with toxic organic compounds such as chlorophenols.     

pH值对“Fe^0．厌氧微生物”体系去除2，4，6-三氯酚过程的影响

考察了pH值对“Fe^0一厌氧微生物”体系降解2，4，6，一三氯酚（2，4，6．TCP）效果的影响，结果表明：pH值是影响“Fe^0-厌氧微生物”体系降解2，4，6-TCP效果的重要参数，初始pH值直接影响微生物活性和铁腐蚀，进而影响过程pH值变化，反过来又影响铁腐蚀和微生物活性，pH7．0～9．0的中性偏碱范围较适于厌氧微生物生长。Fe^0与微生物对目标污染物的降解具有协同促进作用，其协同促进机制表现在3方面：Fe^0与微生物对体系过程pH值具有互补调节作用，可将体系的pH值调节值适于微生物生长的中性范围；Fe^0腐蚀产生的Fe2＋和H2可为微生物代谢提供电子对和营养物质，从而促进生物还原脱氯的进行；Fe^0的腐蚀过程直接对氯代有机物还原脱氯，而微生物又可促进Fe^0腐蚀。     

Microbial dechlorination of 2,4,6-trichlorophenol in anaerobic sewage sludge

The dechlorination of 2,4,6-trichlorophenol (TCP) in municipal sewage sludge with a chlorophenol (CP)-adapted consortium was investigated. Results show that dechlorination rates differed according to the source of the sludge samples used in the batch experiments. No significant differences in 2,4,6-TCP dechlorination were observed following treatment with inoculum at densities ranging from 10% to 50% (V/V), but a significant delay was noted at 5% (V/V) density. Overall, results show that the higher the 2,4,6-TCP concentration, the slower the dechlorination rate. The addition of acetate, lactate, pyruvate, vitamin B12 or manganese dioxide did not results in a significant change in 2,4,6-TCP dechlorination. Data collected from a bioreactor experiment revealed that pH 7.0 and a total solid concentration of 10 g/L were optimal for dechlorination. Dechlorination rates decreased significantly at higher agitation speeds. 2,4,6-TCP dechlorination was enhanced under methanogenic conditions, but it was inhibited under denitrifying and sulfate-reducing conditions.     

pH值对"Fe0-厌氧微生物"体系去除2,4,6-三氯酚过程的影响

考察了pH值对"Fe0-厌氧微生物"体系降解2,4,6,-三氯酚(2,4,6-TCP)效果的影响,结果表明:pH值是影响"Fe0-厌氧微生物"体系降解2,4,6-TCP效果的重要参数,初始pH值直接影响微生物活性和铁腐蚀,进而影响过程pH值变化,反过来又影响铁腐蚀和微生物活性,pH 7.0～9.0的中性偏碱范围较适于厌氧微生物生长。Fe0与微生物对目标污染物的降解具有协同促进作用,其协同促进机制表现在3方面:Fe0与微生物对体系过程pH值具有互补调节作用,可将体系的pH值调节值适于微生物生长的中性范围;Fe0腐蚀产生的Fe2+和H2可为微生物代谢提供电子对和营养物质,从而促进生物还原脱氯的进行;Fe0的腐蚀过程直接对氯代有机物还原脱氯,而微生物又可促进Fe0腐蚀。     

Kinetics of phenol degradation in an anaerobic fixed-biofilm process.

A mathematical model was developed to describe phenol degradation in an anaerobic fixed-biofilm process. The model incorporates the mechanisms of diffusive mass transport and Monod kinetics. The model was solved using a combination of the orthogonal collocation method and Gear's method. A pilot-scale column reactor was used to verify the model. Batch kinetic tests were conducted independently to determine the biokinetic parameters used in the model, while shear loss and initial thickness of biofilm were assumed so that the model simulated the substrate concentration results well. The removal efficiency for phenol was approximately 98.5% at a steady-state condition. The model accurately described the effluent substrate concentrations and the sequence of biodegradation in the reactor. The model simulations are in agreement with the experimental results. The approaches presented in this paper could be used to design fullscale anaerobic fixed-biofilm reactor systems for the biodegradation of phenolic substrates.     

Biodegradation of 2,4,6-trichlorophenol and associated hydraulic conductivity reduction in sand-bed columns

The aim of this research was to investigate the long-term hydraulic conductivity changes in sand-bed columns exposed to 2,4,6-trichlorophenol (TCP). Continuous flow laboratory studies were conducted using sand-bed columns (15 cm i.d.; 200 cm length) at 20+/-1 degrees C during 365 d. The influence of (i) initial loads of 2,4,6-TCP (15, 30, 45 and 60 mg kg(-1) of 2,4,6-TCP), and (ii) recirculating water velocity (0.09, 0.56 and 1.18 cm min(-1)) on the biodegradation of 2,4,6-TCP and hydraulic conductivity changes in the sand-bed columns were investigated. The experimental results indicated that biodegradation of 2,4,6-TCP followed pseudo-first-order kinetics in the range of k(1)=0.01-1.64 d(-1), and it was influenced by initial load (p<0.01) and recirculating water velocity (p<0.01). Indigenous microbial biomass growth and changes resulted in a spatial (180 cm) and temporal (365 d) reduction of hydraulic conductivity in the sand-bed columns by up to two orders of magnitude during biodegradation of 2,4,6-TCP. The fastest hydraulic conductivity reductions were observed in the sand-bed column operated at the highest recirculating water velocity and highest cumulative load of 2,4,6-TCP following 365 d of continuous treatment (p<0.05).     

Modeling of vapor intrusion from hydrocarbon-contaminated sources accounting for aerobic and anaerobic biodegradation

A one-dimensional steady state vapor intrusion model including both anaerobic and oxygen-limited aerobic biodegradation was developed. The aerobic and anaerobic layer thickness are calculated by stoichiometrically coupling the reactive transport of vapors with oxygen transport and consumption. The model accounts for the different oxygen demand in the subsurface required to sustain the aerobic biodegradation of the compound(s) of concern and for the baseline soil oxygen respiration. In the case of anaerobic reaction under methanogenic conditions, the model accounts for the generation of methane which leads to a further oxygen demand, due to methane oxidation, in the aerobic zone. The model was solved analytically and applied, using representative parameter ranges and values, to identify under which site conditions the attenuation of hydrocarbons migrating into indoor environments is likely to be significant. Simulations were performed assuming a soil contaminated by toluene only, by a BTEX mixture, by Fresh Gasoline and by Weathered Gasoline. The obtained results have shown that for several site conditions oxygen concentration below the building is sufficient to sustain aerobic biodegradation. For these scenarios the aerobic biodegradation is the primary mechanism of attenuation, i.e. anaerobic contribution is negligible and a model accounting just for aerobic biodegradation can be used. On the contrary, in all cases where oxygen is not sufficient to sustain aerobic biodegradation alone (e.g. highly contaminated sources), anaerobic biodegradation can significantly contribute to the overall attenuation depending on the site specific conditions.     

Microbial degradation of phenols: a review

The microbial degradation of phenols has been reviewed including the phenol-degrading microbes, factors affecting degradability, and the use of biotechnology with emphasis on degradation mechanisms and their kinetics. The mechanism of microbial degradation depends on aerobic and anaerobic conditions. Under aerobic conditions, degradation of phenol was shown to be initiated by oxygenation into catechols as intermediates followed by a ring cleavage at either the ortho or meta position, depending on the type of strain. Anaerobic biodegradation of phenol occurs by carboxylation followed by dehydroxylation (reducing reaction) and dearomatisation. It was also clear that the parameters used in the Haldane model are not constants but vary, hence it may never be possible to describe the kinetic properties of a microbial cell with a single set of constants.     

Mutagenicity of anaerobic fenitrothion metabolites after aerobic biodegradation

Previous studies have revealed that the mutagenicity of fenitrothion increases during anaerobic biodegradation, suggesting that this insecticide's mutagenicity could effectively increase after it pollutes anaerobic environments such as lake sediments. To investigate possible changes to the mutagenicity of fenitrothion under aerobic conditions after it had already been increased by anaerobic biodegradation, batch incubation cultures were maintained under aerobic conditions. The mutagenicity, which had increased during anaerobic biodegradation, decreased under aerobic conditions with aerobic or facultative bacteria, but did not disappear completely in 22 days. In contrast, it did not change under aerobic conditions without bacteria or under continued anaerobic conditions. These observations suggest that the mutagenicity of anaerobically metabolized fenitrothion would not necessarily decrease after it arrives in an aerobic environment: this would depend on the presence of suitable bacteria. Therefore, fenitrothion-derived mutagenic compounds may pollute the water environment, including our drinking water sources, after accidental pollution of aerobic waters. Although amino-fenitrothion generated during anaerobic biodegradation of fenitrothion was the principal mutagen, non-trivial contributions of other, unidentified metabolites to the mutagenicity were also observed.     

厌氧—好氧反应系统处理含酚废水的研究

利用好氧污泥转厌氧驯化方法在厌氧复合床内接种培养，处理浓度为1000mg／L左右的含酚废水。研究结果表明，在水力停留时间1d，酚容积负荷1．06kg／（m3·d）的条件下，厌氧复合床内培养出颗粒污泥，处理效果明显提高，本酚去除率达98．7％，COD去除率达98．3％。此时后接一个好氧接触氧化柱，最终出水中检不出酚。     

Carbon/electron source dependence of polychlorinated biphenyl dechlorination pathways for anaerobic granules

The effect of acclimating anaerobic granules from commercial bioreactors with different carbon/electron sources on their ability to reductively dechlorinate a tri-(2,3,4-CB) and heptachlorobiphenyl (2,2',3,3',4,5,6-CB) was studied. The anaerobic granules were first grown in upflow anaerobic sludge blanket (UASB) reactors fed with two different mixtures of carbon/electron sources, i.e., propionate/butyrate/methanol and formate/methanol. Differences in dechlorination patterns for 2,2',3,3',4,5,6-CB were observed in batch experiments inoculated with granules from these two sets of UASB reactors. Variation of the carbon/electron source, during the dechlorination process, had no effect on the dechlorination pathway, but the extents and rates of dechlorination were highest for ethanol and formate and lowest for pyruvate fed batches. Pre-acclimation of different anaerobic sludges to polychlorinated biphenyls (PCBs) shortened the lag period, but did not influence the PCB dechlorination pathway. This is the first time that similar acclimation conditions for several anaerobic microbial communities prior to inoculation were reported to yield similar substrate specificities for the reductive dechlorination of specific PCB congeners. This research demonstrates a successful strategy for the development of biocatalysts to serve as the inoculum of partially decontaminated sites in order to provide microorganisms with specificities complementary to those of naturally occurring dechlorinators.     

Evaluation of TCDD biodegradability under different redox conditions

Polychlorinated dibenzo-p-dioxins have been generated as unwanted by-products in many industrial processes. Although their widespread distribution in different environmental compartments has been recognized, little is known about their fate in the ultimate environment sinks. The highly stable dioxin isomer 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) has been called the most toxic compound known to man. In this laboratory microcosm study, TCDD bioavailability was evaluated under five reduction/oxidation (redox) conditions including aerobic biodegradation, aerobic cometabolism, methanogenesis, iron reduction, and reductive dechlorination. Activated sludge and aquifer sediments from a TCDD and a pentachlorophenol (PCP) contaminated site were used as the inocula. Acetate, sludge cake, and cane molasses were used as the primary substrates (carbon sources) in cometabolism and reductive dechlorination microcosms. After a 90-day incubation period, microcosms constructed under reductive dechlorination conditions were the only treatment showing promising remediation results. The highest TCDD degradation rate [up to 86% of TCDD removal (with an initial concentration of 96 microg/kg of soil)] was observed in the microcosms with anaerobic activated sludge as the microbial inocula and sludge cakes as the primary substrates. Except for reductive dechlorination microcosms, no significant TCDD removal was observed in the microcosms prepared under other conditions. Thus, application of an effective primary substrate to enhance the reductive dechlorination process is a feasible method for TCDD bioremediation. Bioremediation expense can be significantly reduced by the supplement of some less expensive alternative substrates (e.g., sludge cakes, cane molasses). Results would be useful in designing a scale-up in situ or on-site bioremediation system such as bioslurry reactor for field application.     

Heat transfer analysis of cylindrical anaerobic reactors with different sizes: a heat transfer model

The temperature is the essential factor that influences the efficiency of anaerobic reactors. During the operation of the anaerobic reactor, the fluctuations of ambient temperature can cause a change in the internal temperature of the reactor. Therefore, insulation and heating measures are often used to maintain anaerobic reactor’s internal temperature. In this paper, a simplified heat transfer model was developed to study heat transfer between cylindrical anaerobic reactors and their surroundings. Three cylindrical reactors of different sizes were studied, and the internal relations between ambient temperature, thickness of insulation, and temperature fluctuations of the reactors were obtained at different reactor sizes. The model was calibrated by a sensitivity analysis, and the calibrated model was well able to predict reactor temperature. The Nash-Sutcliffe model efficiency coefficient was used to assess the predictive power of heat transfer models. The Nash coefficients of the three reactors were 0.76, 0.60, and 0.45, respectively. The model can provide reference for the thermal insulation design of cylindrical anaerobic reactors.     

Fate of mutagenicity produced during anaerobic biodegradation of the herbicide chlornitrofen (CNP)

The mutagenicity of chlornitrofen (CNP)-containing solutions has been reported to increase during anaerobic biodegradation. In the present study, the fate of this increased mutagenicity under subsequent aerobic and anaerobic incubation conditions was investigated using two Salmonella tester strains, YG 1024 (a frameshift-detecting strain) and YG 1029 (a base-pair-substitution-detecting strain). Mutagenicity for both YG 1024 and YG 1029 strains increased during nine-day anaerobic biodegradation. During subsequent anaerobic incubation, the increased mutagenicity decreased gradually for YG 1029 but did not change significantly for YG 1024. By contrast, the increased mutagenicity decreased rapidly after the conversion to aerobic incubation for both YG 1024 and YG 1029 strains. The rapid decrease in mutagenicity during aerobic incubation was due to decreases, not only in an identified mutagenic metabolite (CNP-amino) but also in unidentified mutagenic metabolites.     

氯苯类化合物的生物降解

氯苯类生物降解机制可分为三类:氧化脱氯、还原脱氯和共代谢.氯苯类的氯化脱氯机制基本遵循一个相似的降解途径,即首先在双氯化酶攻击下形成二醇,此二醇脱氢形成氯代邻二酚.邻二酚开环产物是相应的氯化粘康酸,脱氯过程发生在此粘康酸内酯化过程中和内酯开环后;还原脱氯需要多种微生物共同参与,脱氯途径很不一样,这与不同微生物种群和不同的环境条件有关;共代谢作用降低了氯苯类化合物的生物毒性,使其更易为别的微生物同化.     

Fate of Mutagenicity Produced During Anaerobic Biodegradation of the Herbicide Chlornitrofen (CNP)

The mutagenicity of chlornitrofen (CNP)-containing solutions has been reported to increase during anaerobic biodegradation. In the present study, the fate of this increased mutagenicity under subsequent aerobic and anaerobic incubation conditions was investigated using two Salmonella tester strains, YG1024 (a frameshift-detecting strain) and YG1029 (a base-pair-substitution-detecting strain). Mutagenicity for both YG1024 and YG1029 strains increased during nine-day anaerobic biodegradation. During subsequent anaerobic incubation, the increased mutagenicity decreased gradually for YG1029 but did not change significantly for YG1024. By contrast, the increased mutagenicity decreased rapidly after the conversion to aerobic incubation for both YG1024 and YG1029 strains. The rapid decrease in mutagenicity during aerobic incubation was due to decreases, not only in an identified mutagenic metabolite (CNP-amino) but also in unidentified mutagenic metabolites.     

Effect of alkalinity on the performance of a simulated landfill bioreactor digesting organic solid wastes

This study investigated the effects of alkalinity on the anaerobic treatment of the organic solid wastes collected from the kitchen of Engineering Faculty in Dokuz Eylul University, Izmir, Turkey and the leachate characteristics treated in three simulated landfill anaerobic bioreactors. All of the reactors were operated with leachate recirculation. One reactor was operated without alkalinity addition. The second reactor was operated by the addition of 3 g l-1 d-1 of NaHCO3 alkalinity to the leachate and the third reactor was operated by the addition of 6 g l-1 d-1 NaHCO3 alkalinity to the leachate. After 65 d of anaerobic incubation, it was observed that the chemical oxygen demand (COD), volatile fatty acids (VFA) concentrations, and biochemical oxygen demand to chemical oxygen demand (BOD5/COD) ratios in the leachate samples produced from the alkalinity added reactors were lower than the control reactor while the pH values were higher than the control reactor. The COD values were measured as 18900, 3800 and 2900 mg l-1 while the VFA concentrations were 6900, 1400 and 1290 mg l-1, respectively, in the leachate samples of the control, and reactors containing 3 g l-1 NaHCO3 and 6 g l-1 NaHCO3 after 65 d of anaerobic incubation. The total nitrogen (TN), total phosphorus (TP) and ammonium nitrogen (NH4-N) concentrations in organic solid waste (OSW) significantly reduced in the reactor containing 6 g l-1 NaHCO3 by d 65. The values of pH were 6.54, 7.19 and 7.31, after 65 d of anaerobic incubation, respectively, in the aforementioned reactors results in neutral environmental conditions in alkalinity added reactors. Methane percentage of the control, reactors containing 3 g l-1 NaHCO3 and 6 g l-1 NaHCO3 were 37%, 64% and 65%, respectively, after 65 d of incubation. BOD5/COD ratios of 0.27 and 0.25 were achieved in the 3 and 6 g l-1 NaHCO3 containing reactors, indicating a better OSW stabilization. Alkalinity addition reduced the waste quantity, the organic content of the solid waste and the biodegradation time.     

苯酚的厌氧生物处理

采用不断增加苯酚浓度而降低葡萄糖浓度的方法可驯化厌氧污泥中的微生物，使厌氧污泥最终以苯酚为唯一碳源生长，可显著提高厌氧污泥降解苯酚的能力；对苯酚间歇厌氧降解过程进行了分析。苯酚浓度在0～1.680 mg/L范围内，其厌氧降解过程符合一级动力学。Aiba模型、Haldane模型和Teisser 模型均可很好地描述处于对数期时厌氧污泥的比生长速率与初始底物浓度之间的关系，其中以Teisser 模型模拟的效果最好。将驯化污泥接种于UASB中可实现对含酚废水处理的连续运行，最大的有机负荷达2 g COD/（L·d），稳定运行时苯酚的去除率可维持在96%以上。     

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: groundwater biogeochemistry

Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/ aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally atteuated by a combination of active anaerobic and aerobic biotransformation processes.     

Comparative granule characteristics and biokinetics of sucrose-fed and phenol-fed UASB reactors

Two upflow anaerobic sludge bed (UASB) reactors were fed with a non-inhibitory substrate sucrose and an inhibitory substrate phenol, respectively, to compare granule characteristics and biokinetics. The average size of biomass granules in the sucrose-fed UASB reactor was slightly larger than that of the phenol-fed reactor. The average microbial density was significantly higher in the phenol-fed reactor. The intrinsic biokinetics of sucrose-acidogenesis and phenol-acidogenesis followed Monod and Haldane kinetics, respectively. By comparing half-saturation constants for sucrose and phenol (Ks1,s; Ks1,p), the affinity of phenol to the granule should be much higher. The mass fraction of methanogens (f) in the sucrose-fed reactor decreased with increasing volumetric loading rate (VLR) because of the accumulation of volatile fatty acids (VFAs); the f of the phenol-fed reactor decreased with increasing VLR because acidogenesis was the rate-limiting step. The mass transfer resistance in overall substrate removal in the sucrose-fed reactor was greater than that in the phenol-fed reactor.