不同共代谢基质对四氯乙烯的厌氧生物降解研究

用驯化好的厌氧污泥对葡萄糖、乳酸盐和醋酸盐作为电子供体时四氯乙烯（PCE）的降解进行研究.实验结果表明,PCE是通过还原脱氯发生生物降解的.实验的回归结果表明,反应均符合一级动力学反应速率,常数的大小依次为k乳酸＞k葡萄糖＞k醋酸.表明乳酸盐作为电子供体时PCE的降解速率较快,说明在实验条件下乳酸盐是最合适的电子供体.并且在整个实验过程中由共代谢基质提供的电子供体不是PCE降解的限制因素.     

不同共代谢基质下四氯乙烯厌氧生物降解研究

分别用葡萄糖、乳酸盐和醋酸盐作为驯化好的厌氧污泥的共代谢基质 ,对四氯乙烯 ( PCE)的降解进行研究。结果表明 ,PCE是通过还原脱氯发生生物降解的。实验的回归结果表明 ,反应均符合一级动力学方程 ;反应速率常数的大小依次为 k乳酸盐 >k葡萄糖 >k醋酸盐 ;以乳酸盐作为共代谢基质时 ,PCE的降解速率较快 ,在实验条件下乳酸盐是最合适的共代谢基质     

共代谢基质强化微生物修复四氯乙烯污染地下水

针对微生物修复地下水中四氯乙烯(tetrachloroethylene,PCE)周期长的问题,通过添加共代谢基质强化微生物修复技术以提高修复速率。以某污水处理厂的厌氧活性污泥为菌种来源,采用振荡培养法进行PCE高效降解菌群的驯化和筛选,对微生物降解PCE的温度、初始pH和PCE初始浓度3种影响因素进行了条件优化;使用甲醇、乙醇、葡萄糖、酵母浸膏以及乳酸钠作为共代谢基质,研究了不同共代谢基质条件下微生物群落对PCE的降解规律,并建立了反应动力学模型。结果表明:在种水平上,梭状芽孢杆菌Clostridium sp. FCB45是优势菌种;PCE初始浓度为1 mg·L-1,pH在中性,温度为30℃,共代谢基质为酵母浸膏时,微生物群落的降解效果最好,PCE降解率可高达96.75%,降解速率常数最高可达0.327 d-1;添加共代谢基质强化的微生物降解过程全部符合一级反应动力学模型。添加共代谢基质的微生物实验结果表明,添加共代谢基质可以有效缩短微生物修复周期,对污染地下水的原位生物修复具有一定的参考价值。     

高锰酸钾降解地下水中PCE的研究

以氯代有机污染物中常见的PCE为目标污染物，以自制高锰酸钾溶液为氧化剂，采用批实验方法，探讨了高锰酸钾降解PCE的反应动力学、影响因素以及反应机理。反应结果表明，高锰酸钾降解PCE的反应符合一级动力学方程，反应活化能E为57.119 kJ/mol，在30℃条件下，反应速率常数为0.0076 min^-1，半衰期为91.20 min。在pH在3～10，离子强度在0～0.1030 mol/L之间变化时，反应速率不受明显影响。     

零价铁修复受三氯乙烯污染地下水的实验研究

通过批实验和柱实验研究了三氯乙烯（TCE）初始浓度、四氯乙烯(PCE)等对零价铁去除三氯乙烯的影响，并建立了三氯乙烯降解的反应动力学方程。结果表明：（1）零价铁对TCE具有较好的降解效果，反应符合准一级反应动力学方程，表观反应速率常数随TCE浓度的增加而减小；（2）在铁粉充足的条件下，TCE初始浓度对降解效果影响不显著，且TCE去除率皆可达到90%以上；（3）PCE的存在抑制了TCE的脱氯反应。PCE和TCE共存时，TCE的最大去除率仅为64.2%；TCE脱氯反应的表观反应速率明显降低，反应半衰期由TCE单独存在时的6.8～9.7 h增大到66 h～346.5 h。     

三氯乙烯好氧生物降解的初步研究

工业溶剂三氯乙烯 (TCE)是地下水污染物中发现的最普遍的氯代化合物。本研究的目的是评价以葡萄糖为初始基质时好氧条件下TCE生物降解的可行性 ,以及以TCE为单一基质时的生物降解情况。微生物培养是在好氧条件下以驯化好的活性污泥作为接种体。实验结果表明 ,在 2 5℃时 ,葡萄糖可以在好氧条件下作为共代谢基质使TCE发生生物降解 ,其一级反应速率常数为 0 32 12d-1,半衰期为 2 16d ;TCE可以作为单一基质发生好氧生物转化 ,其一级反应速率常数为 0 2 6 2 4d-1,半衰期为 2 6 4d ;降解过程中无二氯乙烯 (DCE)和氯乙烯 (VC)等中间产物的形成 ;表明葡萄糖共代谢降解TCE的速率大于TCE作为单一基质的降解速率。     

Ni/Fe双金属降解四氯化碳和四氯乙烯的对比试验

以四氯化碳(CT)和四氯乙烯(PCE)为目标污染物,以批试验方法研究Ni/Fe双金属对CT和PCE的还原性脱氯.结果表明:Ni/Fe双金属可有效去除水中的CT和PCE;Ni/Fe双金属对CT和PCE的降解反应均符合准一级反应动力学方程;在相似的反应条件下,Ni/Fe双金属对CT和PCE脱氯的反应速率常数(kobs)之比为1.48和1.67,说明Ni/Fe双金属对CT的脱氯速率要快于对PCE的脱氯速率;Ni/Fe双金属可对PCE完全脱氯,但对CT脱氯过程中产生少量三氯甲烷(TCM).     

催化铁内电解法处理硝基苯废水的机理与动力学研究

对催化铁内电解法处理硝基苯废水降解动力学特性进行了研究。结果表明,降解过程符合准一级动力学规律。进水浓度、pH值和反应温度强烈影响硝基苯的降解速率。在实验pH值范围内,反应速率常数依次为:强酸性>弱碱性>弱酸性>中性;循环伏安扫描图显示了硝基苯可以在铜电极上直接得电子还原,该反应在强酸和弱碱性条件下效果较好。反应速率常数随进水浓度的增大而减小。提高反应温度可改善处理效果,在30~45℃范围内,提高温度对处理效果的改善并不显著;当温度升高到45℃以上时,升温可以显著改善处理效果。     

三氯乙烯好氧生物降解的初步研究

工业溶剂三氯乙烯(TCE)是地下水污染物中发现的最普遍的氯代化合物。本研究的目的是评价以葡萄糖为初始基质时好氧条件下TCE生物降解的可行性，以及以TCE为单一基质时的生物降解情况。微生物培养是在好氧条件下以驯化好的活性污泥作为接种体。实验结果表明，在25℃时，葡萄糖可以在好氧条件下作为共代谢基质使TCE发生生物降解，其一级反应速率常数为0．3212d^-1，半衰期为2．16d；TCE可以作为单一基质发生好氧生物转化，其一级反应速率常数为0．2624d^-1，半衰期为2．64d；降解过程中无二氯乙烯(DCE)和氯乙烯(VC)等中间产物的形成；表明葡萄糖共代谢降解TCE的速率大于TCE作为单一基质的降解速率。     

厨余发酵液与乙酸钠、葡萄糖脱氮性能的比较

通过与乙酸钠、葡萄糖对比,利用批式实验方法对厨余发酵液作为反硝化碳源的脱氮性能进行了研究.在不同COD/N条件下,对3种碳源的反硝化NOx--N去除率进行了比较,研究发现,当COD/N =6.5时,厨余发酵液可以满足反硝化对电子供体的要求,其反硝化潜能PD=0.146 g NOx--N /g COD.然后,在COD/N =5.0条件下,利用动力学方程对反硝化过程进行分段模拟,发现厨余发酵液组在Ss降解阶段的比反硝化速率为7.44 mg NOx--N/(g VSS·h),其整个反硝化阶段的比反硝化速率是乙酸钠组的0.77倍,是葡萄糖组的2.1倍,结果表明,厨余发酵液可以作为快速降解碳源用于反硝化脱氮.     

Comparison between acetate and hydrogen as electron donors and implications for the reductive dehalogenation of PCE and TCE

Bioremediation by reductive dehalogenation of groundwater contaminated with tetrachloroethene (PCE) or trichloroethene (TCE) is generally carried out through the addition of a fermentable electron donor such as lactate, benzoate, carbohydrates or vegetable oil. These fermentable donors are converted by fermenting organisms into acetate and hydrogen, either of which might be used by dehalogenating microorganisms. Comparisons were made between H2 and acetate on the rate and extent of reductive dehalogenation of PCE. PCE dehalogenation with H2 alone was complete to ethene, but with acetate alone it generally proceeded only about half as fast and only to cis-1,2-dichloroethene (cDCE). Additionally, acetate was not used as an electron donor in the presence of H2. These findings suggest the fermentable electron donor requirement for PCE dehalogenation to ethene can be reduced up to 50% by separating PCE dehalogenation into two stages, the first of which uses acetate for the conversion of PCE to cDCE, and the second uses H2 for the conversion of cDCE to ethene. This can be implemented with a recycle system in which the fermentable substrate is added down-gradient, where the hydrogen being produced by fermentation effects cDCE conversion into ethene. The acetate produced is recycled up-gradient to achieve PCE conversion into cDCE. With the lower electron donor usage required, potential problems of aquifer clogging, excess methane production, and high groundwater chemical oxygen demand (COD) can be greatly reduced.     

Effects of biomass accumulation on microbially enhanced dissolution of a PCE pool: a numerical simulation

Recent studies have shown that dechlorinating bacteria can accelerate the dissolution rate of dense, nonaqueous phase liquids (DNAPLs) containing tetrachloroethene (PCE). We present an advection-dispersion-reaction model for a two-dimensional domain, with groundwater flowing over a pool of free-product PCE. PCE is converted to cis-1,2-dichloroethene (cDCE) and toxicity due to PCE or cDCE is neglected. We adopt previously published correlations relating biomass concentrations and hydraulic conductivity, accounting for biofilm growth and plug-like growth. The system of coupled equations is solved numerically. The high biotransformation rate of PCE increases the concentration gradient of PCE at the water-DNAPL interface, enhancing dissolution. The higher the electron donor (ED) concentration, the larger the dissolution enhancement. Based on the values of maximum specific rate we used, when the electron donor is unlimited, the active biomass accumulates adjacent to the water-NAPL interface and microbial reactions can significantly enhance the pool dissolution. The resulting steady-state dissolution rate can be approximated by a half-order solution when zero-order kinetics are suitable for representing the microbial reaction. However, bioclogging may significantly reduce local hydraulic conductivity; thus, it decreases the flow near the water-DNAPL interface, decreasing dissolution. When the ED is the limiting factor, active biomass accumulates away from the interface. This creates a no-flow zone between the active biomass and the interface. The enlargement of the no-flow zone, due to the donor limitation, diminishes the concentration gradient and the flushing around the water-DNAPL interface. Such adverse impacts may significantly decrease the enhancement predicted by models that do not consider the effects of bioclogging.     

Dechlorination of PCE in the presence of Fe0 enhanced by a mixed culture containing two Dehalococcoides strains

A mixed culture capable of supplying its energy requirements by the oxidation of zero-valent iron (Fe0) and concomitant reduction of chlorinated ethenes was established. The culture contained Dehalococcoides species as determined by polymerase chain reaction (PCR) with genus specific primers. The use of a newly designed ARDRA procedure and subsequent sequencing revealed the presence of two Dehalococcoides strains, one closely related to Dehalococcoides ethenogenes strain 195, a bacterium respiring with chlorinated ethenes, and one closely related to strain CBDB1 a chlorobenzene and dioxin dehalogenating anaerobe. The mixed culture was used to study dechlorination of tetrachloroethene (PCE) to ethene in the presence of Fe0. Whereas abiotic transformation of PCE by Fe0 led to incomplete dechlorination, the mixed culture mediated fast and complete dechlorination of PCE to ethene with Fe0 as electron donor. Compared to cultures with hydrogen added as electron donor, cultures with Fe0 as electron donor showed the same or higher rates of PCE dechlorination. Growth of the Dehalococcoides strains in the mixed culture is linked to the presence of Fe0 as electron donor and PCE as electron acceptor demonstrating that Dehalococcoides spp. play a pivotal role in the dechlorination of chlorinated ethenes in Fe0 systems.     

Comparison of bioaugmentation and biostimulation for the enhancement of dense nonaqueous phase liquid source zone bioremediation.

Two 11.7-m(3) experimental controlled release systems (ECRS), packed with sandy model aquifer material and amended with tetrachloroethene (PCE) dense nonaqueous phase liquid (DNAPL) source zone, were operated in parallel with identical flow regimes and electron donor amendments. Hydrogen Releasing Compound (Regenesis Bioremediation Products, Inc., San Clemente, California), and later dissolved lactate, served as electron donors to promote dechlorination. One ECRS was bioaugmented with an anaerobic dechlorinating consortium directly into the source zone, and the other served as a control (biostimulated only) to determine the benefits of bioaugmentation. The presence of halorespiring bacteria in the aquifer matrix before bioaugmentation, shown by nested polymerase chain reaction with phylogenetic primers, suggests that dechlorinating catabolic potential may be somewhat widespread. Results obtained corroborate that source zone reductive dechlorination of PCE is possible at near field scale and that a system bioaugmented with a competent halorespiring consortium can enhance DNAPL dissolution and dechlorination processes at significantly greater rates than in a system that is biostimulated only.     

Development of a biobarrier for the remediation of PCE-contaminated aquifer

The industrial solvent tetrachloroethylene (PCE) is among the most ubiquitous chlorinated compounds found in groundwater contamination. The objective of this study was to develop a biobarrier system, which includes a peat layer to enhance the anaerobic reductive dechlorination of PCE in situ. Peat was used to supply primary substrate (electron donor) continuously. A laboratory-scale column experiment was conducted to evaluate the feasibility of this proposed system or PCE removal. This experiment was performed using a series of continuous-flow glass columns including a soil column, a peat column, followed by two consecutive soil columns. Anaerobic acclimated sludges were inoculated in all three soil columns to provide microbial consortia for PCE biodegradation. Simulated PCE-contaminated groundwater with a flow rate of 0.25 l/day was pumped into this system. Effluent samples from each column were analyzed for PCE and its degradation byproducts (trichloroethylene (TCE), cis-dichloroethylene (cis-DCE), vinyl chloride (VC), ethylene (ETH), and ethane). Results show that the decrease in PCE concentrations and production of PCE byproducts were observed over a 65-day operating period. Up to 98% of PCE removal efficiency was obtained in this passive system. Results indicate that the continuously released organics from peat column enhanced PCE biotransformation. Thus, the developed biobarrier treatment scheme has the potential to be developed into a cost-effective in situ PCE-remediation technology, and can be utilized as an interim step to aid in system scale-up.     

Batch reactor kinetic studies on the reductive dechlorination of chlorinated ethylenes by tetrakis-(4-sulfonatophenyl)porphyrin cobalt

Tetrakis-(4-sulfonatophenyl)porphyrin cobalt was identified as a highly-active reductive dechlorination catalyst for chlorinated ethylenes. Through batch reactor kinetic studies, degradation of chlorinated ethylenes proceeded in a step-wise fashion with the sequential replacement of Cl by H. For perchloroethylene (PCE) and trichloroethylene (TCE), the dechlorination products were quantified and the C₂ mass was accounted for. Degradation of the chlorinated ethylenes was found to be first-order in substrate. Dechlorination trials with increasing catalyst concentration showed a linearly increasing pseudo first-order rate constant which yielded rate laws for PCE and TCE degradation that are first-order in catalyst. The dechlorination activity of this catalyst was compared to that of another water-soluble cobalt porphyrin under the same reaction conditions and found to be comparable for PCE and TCE.     

Continuous-flow column study of reductive dehalogenation of PCE upon bioaugmentation with the Evanite enrichment culture

A continuous-flow anaerobic column experiment was conducted to evaluate the reductive dechlorination of tetrachloroethene (PCE) in Hanford aquifer material after bioaugmentation with the Evanite (EV) culture. An influent PCE concentration of 0.09 mM was transformed to vinyl chloride (VC) and ethene (ETH) within a hydraulic residence time of 1.3 days. The experimental breakthrough curves were described by the one-dimensional two-site-nonequilibrium transport model. PCE dechlorination was observed after bioaugmentation and after the lactate concentration was increased from 0.35 to 0.67 mM. At the onset of reductive dehalogenation, cis-dichloroethene (c-DCE) concentrations in the column effluent exceeded the influent PCE concentration indicating enhanced PCE desorption and transformation. When the lactate concentration was increased to 1.34 mM, c-DCE reduction to vinyl chloride (VC) and ethene (ETH) occurred. Spatial rates of PCE and VC transformation were determined in batch-incubated microcosms constructed with aquifer samples obtained from the column. PCE transformation rates were highest in the first 5 cm from the column inlet and decreased towards the column effluent. Dehalococcoides cell numbers dropped from approximately 73.5% of the total Bacterial population in the original inocula, to about 0.5% to 4% throughout the column. The results were consistent with estimates of electron donor utilization, with 4% going towards dehalogenation reactions.     

Kinetics and mechanism of oxidation of tetrachloroethylene with permanganate

The kinetics, reaction pathways and product distribution of oxidation of tetrachloroethylene (PCE) by potassium permanganate (KMnO4) were studied in phosphate-buffered solutions under constant pH, isothermal, completely mixed and zero headspace conditions. Experimental results indicate that the reaction is first-order with respect to both PCE and KMnO4 and has an activation energy of 9.3+/-0.9 kcal/mol. The second-order rate constant at 20 degrees C is 0.035+/-0.004 M(-1) s(-1), and is independent of pH and ionic strength (I) over a range of pH 3-10 and I approximately 0-0.2 M, respectively. The PCE-KMnO4 reaction may proceed through further oxidation and/or hydrolysis reaction pathways, greatly influenced by the acidity of the solution, to yield CO2(g), oxalic acid, formic acid and glycolic acid. Under acidic conditions (e.g., pH 3), the further oxidation pathway will dominate and PCE tends to be directly mineralized into CO2 and chloride. Under neutral (e.g., pH 7) and alkaline conditions (e.g., pH 10), the hydroxylation pathway dominates the reaction and PCE is primarily transformed into oxalic acid prior to complete PCE mineralization. Moreover, all chlorine atoms in PCE are rapidly liberated during the reaction and the rate of chloride production is very close to the rate of PCE degradation.     

Cosolvent effect on the catalytic reductive dechlorination of PCE

Reductive dechlorination of chlorinated organic contaminants is an effective approach to treat this widespread group of environmentally hazardous substances. Metalloporphyrins can be used to catalyze reduction reactions by shuttling electrons from a reducing agent (electron donor) to chlorinated organic contaminants, thus rendering them to non-chlorinated acetylene, ethylene or ethane as major products. Iron, nickel and vanadium oxide tetraphenyl porphyrins (TPPs) were used as models of non-soluble metalloporphyrins that are common in subsurface environments, and hence may inflect on the ability to use natural ones. The effect of cosolvents on metalloporphyrins is demonstrated to switch the reduction of tetrachlorethylene (PCE) from no reaction to complete PCE transformation within 24 h and the production of final non-chlorinated compounds. Variations in product distributions for the different metalloporphyrins indicate that changes in the core metal can influence reaction rates and effective pathways. Furthermore, different cosolvents can generate varied product distributions, again suggesting that different pathways and/or rates are operative in the reduction reactions. Comparison of different cosolvent effects on PCE reduction using vitamin B12--a soluble natural metalloporphyrinogen--as the catalyst shows less pronounced differences between reactions in various cosolvent solutions versus only aqueous solution.