Abiotic reductive dechlorination of chlorinated ethylenes by iron-bearing phyllosilicates

Abiotic reductive dechlorination of chlorinated ethylenes (tetrachloroethylene (PCE), trichloroethylene (TCE), cis-dichloroethylene (c-DCE), and vinylchloride (VC)) by iron-bearing phyllosilicates (biotite, vermiculite, and montmorillonite) was characterized to obtain better understanding of the behavior of these contaminants in systems undergoing remediation by natural attenuation and redox manipulation. Batch experiments were conducted to evaluate dechlorination kinetics and some experiments were conducted with addition of Fe(II) to simulate impact of microbial iron reduction. A modified Langmuir-Hinshelwood kinetic model adequately described reductive dechlorination kinetics of target organics by the iron-bearing phyllosilicates. The rate constants stayed between 0.08 (+/-10.4%) and 0.401 (+/-8.1%) day(-1) and the specific initial reductive capacity of iron-bearing phyllosilicates for chlorinated ethylenes stayed between 0.177 (+/-6.1%) and 1.06 (+/-7.1%) microM g(-1). The rate constants for the reductive dechlorination of TCE at reactive biotite surface increased as pH (5.5-8.5) and concentration of sorbed Fe(II) (0-0.15 mM g(-1)) increased. The appropriateness of the model is supported by the fact that the rate constants were independent of solid concentration (0.0085-0.17 g g(-1)) and initial TCE concentration (0.15-0.60 mM). Biotite had the greatest rate constant among the phyllosilicates both with and without Fe(II) addition. The rate constants were increased by a factor of 1.4-2.5 by Fe(II) addition. Between 1.8% and 36% of chlorinated ethylenes removed were partitioned to the phyllosilicates. Chloride was produced as a product of degradation and no chlorinated intermediates were observed throughout the experiment.     

Dechlorination of chlorinated hydrocarbons by bimetallic Ni/Fe immobilized on polyethylene glycol-grafted microfiltration membranes under anoxic conditions

In this study, the dechlorination of chlorinated hydrocarbons including trichloroethylene (TCE), tetrachloroethylene (PCE) and carbon tetrachloride (CT) by bimetallic Ni/Fe nanoparticles immobilized on four different membranes was investigated under anoxic conditions. Effects of several parameters including the nature of membrane, initial concentration, pH value, and reaction temperature on the dechlorination efficiency were examined. The scanning electron microscopic images showed that the Ni/Fe nanoparticles were successfully immobilized inside the four membranes using polyethylene glycol as the cross-linker. The agglomeration of Ni/Fe were observed in poly(vinylidene fluoride), Millex GS and mixed cellulose ester membranes, while a relatively uniform distribution of Ni/Fe was found in nylon-66 membrane because of its hydrophilic nature. The immobilized Ni/Fe nanoparticles exhibited good reactivity towards the dechlorination of chlorinated hydrocarbons, and the pseudo-first-order rate constant for TCE dechlorination by Ni/Fe in nylon-66 were 3.7-11.7 times higher than those in other membranes. In addition, the dechlorination efficiency of chlorinated hydrocarbons followed the order TCE > PCE > CT. Ethane was the only end product for TCE and PCE dechlorination, while dichloromethane and methane were found to be the major products for CT dechlorination, clearly indicating the involvement of reactive hydrogen species in dechlorination. In addition, the initial rate constant for TCE dechlorination increased upon increasing initial TCE concentrations and the activation energy for TCE dechlorination by immobilized Ni/Fe was 34.9 kJ mol⁻¹, showing that the dechlorination of TCE by membrane-supported Ni/Fe nanoparticles is a surface-mediated reaction.     

Abiotic reductive dechlorination of chlorinated ethylenes by soil

Abiotic reductive dechlorination of chlorinated ethylenes by soil in anaerobic environments was characterized to improve knowledge of the behavior of chlorinated ethylenes in natural systems, including systems modified to promote attenuation of contaminants. Target organics in the soil suspension reached sorption equilibrium in 2 days and the sorption isotherm of target organics was properly described by the linear sorption model. A modified Langmuir-Hinshelwood model was developed to describe the kinetics of reductive dechlorination of target organics by soil. The rate constants for the reductive dechlorination of chlorinated ethylenes at the reactive surfaces of reduced soils were found in the range between 0.055 (+/- 8.9%) and 2.60 (+/- 3.2%) day(-1). The main transformation products in reduced soil suspensions were C2 hydrocarbons. No chlorinated intermediates were observed at concentrations above detection limits. Five cycles of reduction of the soil followed by oxidation of the soil with trichloroethylene (TCE) did not affect the removal of TCE. The removal was affected by the reductants used and increased in the order: Fe(II) < dithionite < Fe(II) + dithionite.     

Comparison of an assay for Dehalococcoides DNA and a microcosm study in predicting reductive dechlorination of chlorinated ethenes in the field

The study aims to compare the detection of 16S rRNA gene of Dehalococcoides species and the microcosm study for biotransformation in predicting reductive dechlorination of chlorinated ethenes in ground water at hazardous waste sites. A total of 72 ground water samples were collected from 12 PCE or TCE contaminated sites in the United States. The samples were analyzed and used to construct microcosms in the laboratory. The results showed that the presence of Dehalococcoides DNA was well associated with dechlorination to ethene in the field. Nearly half of the wells where Dehalococcoides DNA was detected had ethene as a dechlorination end product. In comparison, for ground water samples of 16 wells where ethene was detected, ethene was produced in 11 of the corresponding microcosms. For most microcosms, during two years of incubation, dechlorination was less extensive than that observed in the field.     

Comparison of PCE and TCE disappearance in heated volatile organic analysis vials and flame-sealed ampules

The rates of hydrolysis reported for tetrachloroethylene (PCE) and trichloroethylene (TCE) at elevated temperatures range over two orders-of-magnitude, where some of the variability may be due to the presence of a gas phase. Recent studies suggest that volatile organic analysis (VOA) vials provide a low-cost and readily available zero headspace system for measuring aqueous-phase hydrolysis rates. This work involved measuring rates of PCE and TCE disappearance and the corresponding appearance of dechlorination products in water-filled VOA vials and flame-sealed ampules incubated at 21 and 55 °C for up to 95.5 days. While PCE and TCE concentrations readily decreased in the VOA vials to yield first-order half lives of 11.2 days for PCE and 21.1 days for TCE at 55 °C, concentrations of anticipated dechlorination products, including chloride, remained constant or were not detected. The rate of PCE disappearance was 34 times faster in VOA vials at 55 °C compared to values obtained with flame-sealed ampules containing PCE-contaminated water. In addition, the concentration of TCE increased slightly in flame-sealed ampules incubated at 55 °C, while a decrease in TCE levels was observed in the VOA vials. The observed losses of PCE and TCE in the VOA vials were attributed to diffusion and sorption in the septa, rather than to dechlorination. These findings demonstrate that VOA vials are not suitable for measuring rates of volatile organic compound hydrolysis at elevated temperatures.     

Assessing chlorinated ethene degradation in a large scale contaminant plume by dual carbon-chlorine isotope analysis and quantitative PCR

The fate of chlorinated ethenes in a large contaminant plume originating from a tetrachloroethene (PCE) source in a sandy aquifer in Denmark was investigated using novel methods including compound-specific carbon and chlorine isotope analysis and quantitative real-time polymerase chain reaction (qPCR) methods targeting Dehaloccocoides sp. and vcrA genes. Redox conditions were characterized as well based on concentrations of dissolved redox sensitive compounds and sulfur isotopes in SO(4)(2-). In the first 400 m downgradient of the source, the plume was confined to the upper 20 m of the aquifer. Further downgradient it widened in vertical direction due to diverging groundwater flow reaching a depth of up to 50 m. As the plume dipped downward and moved away from the source, O(2) and NO(3)(-) decreased to below detection levels, while dissolved Fe(2+) and SO(4)(2-) increased above detectable concentrations, likely due to pyrite oxidation as confirmed by the depleted sulfur isotope signature of SO(4)(2-). In the same zone, PCE and trichloroethene (TCE) disappeared and cis-1,2-dichloroethene (cDCE) became the dominant chlorinated ethene. PCE and TCE were likely transformed by reductive dechlorination rather than abiotic reduction by pyrite as indicated by the formation of cDCE and stable carbon isotope data. TCE and cDCE showed carbon isotope trends typical for reductive dechlorination with an initial depletion of (13)C in the daughter products followed by an enrichment of (13)C as degradation proceeded. At 1000 m downgradient of the source, cDCE was the dominant chlorinated ethene and had reached the source δ(13)C value confirming that cDCE was not affected by abiotic or biotic degradation. Further downgradient (up to 1900 m), cDCE became enriched in (13)C by up to 8 ‰ demonstrating its further transformation while vinylchloride (VC) concentrations remained low (<1 μg/L) and ethene was not observed. The correlated shift of carbon and chlorine isotope ratios of cDCE by 8 and 3.9 ‰, respectively, the detection of Dehaloccocides sp genes, and strongly reducing conditions in this zone provide strong evidence for reductive dechlorination of cDCE. The significant enrichment of (13)C in VC indicates that VC was transformed further, although the mechanism could not be determined. The transformation of cDCE was the rate limiting step as no accumulation of VC occurred. In summary, the study demonstrates that carbon-chlorine isotope analysis and qPCR combined with traditional approaches can be used to gain detailed insight into the processes that control the fate of chlorinated ethenes in large scale plumes.     

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。     

Aerobic biodegradation of dichloroethenes by indigenous bacteria isolated from contaminated sites in Africa

The widespread use of tetrachloroethene (PCE) and trichloroethene (TCE) as dry cleaning solvents and degreasing agents for military and industrial applications has resulted in significant environmental contamination worldwide. Anaerobic biotransformation of PCE and TCE through reductive dechlorination frequently lead to the accumulation of dichloroethenes (DCEs), thus limiting the use of reductive dechlorination for the biotransformation of the compounds. In this study, seven bacteria indigenous to contaminated sites in Africa were characterized for DCE degradation under aerobic conditions. The specific growth rate constants of the bacterial isolates ranged between 0.346-0.552d(-1) and 0.461-0.667d(-1) in cis-DCE and trans-DCE, respectively. Gas chromatographic analysis revealed that up to 75% of the compounds were degraded within seven days with the degradation rate constants ranging between 0.167 and 0.198d(-1). The two compounds were also observed to be significantly degraded, simultaneously, rather than sequentially, when present as a mixture. Phylogenetic analysis of the 16S rRNA gene sequences of the bacterial isolates revealed their identity as well as their relation to other environmentally-important bacteria. The observed biodegradation of DCEs may contribute to PCE and TCE removal at the aerobic fringe of groundwater plumes undergoing reductive dechlorination in contaminated sites.     

Variability in microbial carbon isotope fractionation of tetra- and trichloroethene upon reductive dechlorination

The variability of stable carbon isotope fractionation upon reductive dechlorination of tetra- and trichloroethene by several microbial strains was investigated to examine the uncertainties related to the in situ application of compound specific isotope analysis (CSIA) of chlorinated ethenes. Carbon isotope fractionation was investigated with a set of microorganisms representative for the currently known diversity of dehalorespirers: Dehalococcoides ethenogenes strain 195, Desulfitobacterium sp. strain Viet1, Desulfuromonas michiganensis and Geobacter lovleyi sp. strain SZ and compared to the previous reports using Sulfurospirillum spp. and Desulfitobacterium sp. strain PCE-S. Carbon isotope fractionation of tetrachloroethene (PCE) and trichlorethene (TCE) was highly variable ranging from the absence of significant fractionation to carbon isotope fractionation (epsilonC) of 16.7 and 3.5-18.9 for PCE and TCE, respectively. Fractionation of both compounds by D. ethenogenes strain 195 (PCE: epsilonC=6.0; TCE: epsilonC=13.7) was similar to the literature data for mixed cultures containing Dehalococcoides spp. D. michiganensis (PCE: no significant fractionation; TCE: epsilonC=3.5) and G. lovleyi sp. strain SZ (PCE no significant fractionation; TCE: epsilonC=8.5) generated the lowest fractionation of all studied strains. Desulfitobacterium sp. strain Viet1 (PCE: epsilonC=16.7) gave the highest enrichment factor for PCE.     

Competing TCE and cis-DCE degradation kinetics by zero-valent iron-experimental results and numerical simulation

The successful dechlorination of mixtures of chlorinated hydrocarbons with zero-valent metals requires information concerning the kinetics of simultaneous degradation of different contaminants. This includes intraspecies competitive effects (loading of the reactive iron surface by a single contaminant) as well as interspecies competition of several contaminants for the reactive sites available. In columns packed with zero-valent iron, the degradation behaviour of trichloroethylene (TCE), cis-dichloroethylene (DCE) and mixtures of both was measured in order to investigate interspecies competition. Although a decreasing rate of dechlorination is to be expected, when several degradable substances compete for the reactive sites on the iron surface, TCE degradation is nearly unaffected by the presence of cis-DCE. In contrast, cis-DCE degradation rates decrease significantly when TCE is added. A new modelling approach is developed in order to identify and quantify the observed competitive effects. The numerical model TBC (Transport, Biochemistry and Chemistry, Sch?fer et al., 1998a) is used to describe adsorption, desorption and dechlorination in a mechanistic way. Adsorption and degradation of a contaminant based on a limited number of reactive sites leads to a combined zero- and first-order degradation kinetics for high and low concentrations, respectively. The adsorption of several contaminants with different sorption parameters to a limited reactive surface causes interspecies competition. The reaction scheme and the parameters required are successfully transferred from Arnold and Roberts (2000b) to the model TBC. The degradation behaviour of the mixed contamination observed in the column experiments can be related to the adsorption properties of TCE and cis-DCE. By predicting the degradation of the single substances TCE and cis-DCE as well as mixtures of both, the calibrated model is used to investigate the effects of interspecies competition on the design of permeable reactive iron barriers. Even if TCE is present in only small concentrations (>3% of molar cis-DCE concentration) it is the contaminant limiting the residence time and the required thickness of the iron barrier.     

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.     

用于四氯乙烯降解的厌氧污泥的培养与驯化研究

由于四氯乙烯 (PCE)的大量使用和不合理的处置使其成为常见的污染物之一。PCE在好氧条件下不发生生物降解 ,只在厌氧条件下通过还原脱氯发生生物降解。本研究主要是对从不同处理厂获得的厌氧污泥进行培养 ,选出合适的厌氧污泥 ,进行降解PCE的厌氧污泥的驯化 ,为以后进行降解PCE的动力学研究和优势菌种的筛选做准备。同时 ,在实验中检测到了三氯乙烯 (TCE) ,表明PCE是通过还原脱氯发生生物降解的。     

Anaerobic transformations and bioremediation of chlorinated solvents

Chlorinated aliphatic compounds, notably the chlorinated solvents, are common contaminants in soil and groundwater at hazardous waste sites. While these compounds are often recalcitrant, under favorable conditions they can be transformed and degraded through microbially mediated processes. There is great interest in understanding the transformations that are observed at contaminated sites and in manipulating these systems to achieve remediation. An important class of transformations occurs in anaerobic environments. Many of the transformations are reductive, and many yield useful energy to specific anaerobic bacteria. They include reductive dechlorination, dehydrochlorination and dichloroelemination. Of these, reductive dechlorination is often a growth-supporting reaction, while the others may be abiological or catalyzed by biological molecules. The reactions may result in chlorinated products, but there are often reaction sequences leading to completely dechlorinated products. The behavior of carbon tetrachloride (CT), 1,1,2,2-tetrachloroethane (TeCA) and the chloroethenes, perchloroethylene (PCE) and trichloroethylene (TCE), illustrate the range of anaerobic transformations that are possible, as well as the limited transformation that often is seen in the environment. CT undergoes reductive and substitutive reactions that are catalyzed by biological molecules but do not support bacterial growth. The anaerobic degradation of TeCA, which is a major contaminant at a site near Tacoma, WA, USA, provides examples of each type of transformation, and the products formed are consistent with the chlorinated compounds that are found in groundwater extraction wells. A laboratory study, using anaerobic sludge that had been fed chlorinated compounds, a cell-free extract from the sludge, and killed controls, showed that TeCA was transformed to four products and that these were further transformed, suggesting that it might be possible to degrade TeCA to innocuous products. Reductive dechlorination of PCE and TCE has been studied in many laboratories. Studies with mixed anaerobic consortia and with several dehalogenating bacteria, including strain 195 (. Isolation of a bacterium that reductively dechlorinates tetrachloroethane to ethane. Science 276, 1568-1571) that transforms PCE to ethene, have demonstrated that reductive dechlorination supports growth of the novel bacteria that carry out the reactions. Hydrogen has been shown to be an electron donor for the bacterial dehalogenation reactions, and kinetic and thermodynamic considerations indicate that dehalogenators can compete in some, but not all, anaerobic environments, pointing to applications of in situ bioremediation and to its limitations. Selected field studies of anaerobic transformations help delineate the applications of this type of bioremediation.     

Self-inhibition can limit biologically enhanced TCE dissolution from a TCE DNAPL

Biodegradation of trichloroethene (TCE) near a Dense Non Aqueous Phase Liquid (DNAPL) can enhance the dissolution rate of the DNAPL by increasing the concentration gradient at the DNAPL-water interface. Two-dimensional flow-through sand boxes containing a TCE DNAPL and inoculated with a TCE dechlorinating consortium were set up to measure this bio-enhanced dissolution under anaerobic conditions. The total mass of TCE and daughter products in the effluent of the biotic boxes was 3-6 fold larger than in the effluent of the abiotic box. However, the mass of daughter products only accounted for 19-55% of the total mass of chlorinated compounds in the effluent, suggesting that bio-enhanced dissolution factors were maximally 1.3-2.2. The enhanced dissolution most likely primarily resulted from variable DNAPL distribution rather than biodegradation. Specific dechlorination rates previously determined in a stirred liquid medium were used in a reactive transport model to identify the rate limiting factors. The model adequately simulated the overall TCE degradation when predicted resident microbial numbers approached observed values and indicated an enhancement factor for TCE dissolution of 1.01. The model shows that dechlorination of TCE in the 2D box was limited due to the short residence time and the self-inhibition of the TCE degradation. A parameter sensitivity analysis predicts that the bio-enhanced dissolution factor for this TCE source zone can only exceed a value of 2 if the TCE self-inhibition is drastically reduced (when a TCE tolerant dehalogenating community is present) or if the DNAPL is located in a low-permeable layer with a small Darcy velocity.     

Self-inhibition can limit biologically enhanced TCE dissolution from a TCE DNAPL

Biodegradation of trichloroethene (TCE) near a Dense Non Aqueous Phase Liquid (DNAPL) can enhance the dissolution rate of the DNAPL by increasing the concentration gradient at the DNAPL-water interface. Two-dimensional flow-through sand boxes containing a TCE DNAPL and inoculated with a TCE dechlorinating consortium were set up to measure this bio-enhanced dissolution under anaerobic conditions. The total mass of TCE and daughter products in the effluent of the biotic boxes was 3–6 fold larger than in the effluent of the abiotic box. However, the mass of daughter products only accounted for 19–55% of the total mass of chlorinated compounds in the effluent, suggesting that bio-enhanced dissolution factors were maximally 1.3–2.2. The enhanced dissolution most likely primarily resulted from variable DNAPL distribution rather than biodegradation. Specific dechlorination rates previously determined in a stirred liquid medium were used in a reactive transport model to identify the rate limiting factors. The model adequately simulated the overall TCE degradation when predicted resident microbial numbers approached observed values and indicated an enhancement factor for TCE dissolution of 1.01. The model shows that dechlorination of TCE in the 2D box was limited due to the short residence time and the self-inhibition of the TCE degradation. A parameter sensitivity analysis predicts that the bio-enhanced dissolution factor for this TCE source zone can only exceed a value of 2 if the TCE self-inhibition is drastically reduced (when a TCE tolerant dehalogenating community is present) or if the DNAPL is located in a low-permeable layer with a small Darcy velocity.     

Photocatalytic oxidation of gaseous chlorinated organics over titanium dioxide

The photocatalytic oxidation of high levels of volatile chlorinated organic compounds in gas phase has been studied using a specially designed photoreactor. The influence of light intensity, initial water vapour concentration, temperature, inlet contaminant concentration and flow rate on destruction efficiency has been investigated. The performance of the titanium catalyst was strongly affected by the presence of water in the air stream. Experiments have been most successfully conducted at room temperature, low initial contaminant concentrations, low flow rates and high light intensities. Several by-products have been detected performing photocatalytic degradation of trichloroethylene (TCE) and tetrachloroethylene (PCE). No catalyst deactivation was observed.     

Selective redox degradation of chlorinated aliphatic compounds by Fenton reaction in pyrite suspension

Selective redox degradation of chlorinated aliphatics by Fenton reaction in pyrite suspension was investigated in a closed system. Carbon tetrachloride (CT) was used as a representative target of perchlorinated alkanes and trichloroethylene (TCE) was used as one of highly chlorinated alkenes. Degradation of CT in Fenton reaction was significantly enhanced by pyrite used as an iron source instead of soluble Fe. Pyrite Fenton showed 93% of CT removal in 140 min, while Fenton reaction with soluble Fe(II) showed 52% and that with Fe(III) 15%. Addition of 2-propanol to the pyrite Fenton system significantly inhibited degradation of TCE (99% to 44% of TCE removal), while degradation of CT was slightly improved by the 2-propanol addition (80-91% of CT removal). The result suggests that, unlike oxidative degradation of TCE by hydroxyl radical in pyrite Fenton system, an oxidation by the hydroxyl radical is not a main degradation mechanism for the degradation of CT in pyrite Fenton system but a reductive dechlorination by superoxide can rather be the one for the CT degradation. The degradation kinetics of CT in the pyrite Fenton system was decelerated (0.13-0.03 min⁻¹), as initial suspension pH decreased from 3 to 2. The formation of superoxide during the CT degradation in the pyrite Fenton system was observed by electron spin resonance spectroscopy. The formation at initial pH 3 was greater than that at initial pH 2, which supported that superoxide was a main reductant for degradation of CT in the pyrite Fenton system.     

Dechlorination and organohalide-respiring bacteria dynamics in sediment samples of the Yangtze Three Gorges Reservoir

Several groups of bacteria such as Dehalococcoides spp., Dehalobacter spp., Desulfomonile spp., Desulfuromonas spp., or Desulfitobacterium spp. are able to dehalogenate chlorinated pollutants such as chloroethenes, chlorobenzenes, or polychlorinated biphenyls under anaerobic conditions. In order to assess the dechlorination potential in Yangtze sediment samples, the presence and activity of the reductively dechlorinating bacteria were studied in anaerobic batch tests. Eighteen sediment samples were taken in the Three Gorges Reservoir catchment area of the Yangtze River, including the tributaries Jialing River, Daning River, and Xiangxi River. Polymerase chain reaction analysis indicated the presence of dechlorinating bacteria in most samples, with varying dechlorinating microbial community compositions at different sampling locations. Subsequently, anaerobic reductive dechlorination of tetrachloroethene (PCE) was tested after the addition of electron donors. Most cultures dechlorinated PCE completely to ethene via cis-dichloroethene (cis-DCE) or trans-dichloroethene. Dehalogenating activity corresponded to increasing numbers of Dehalobacter spp., Desulfomonile spp., Desulfitobacterium spp., or Dehalococcoides spp. If no bacteria of the genus Dehalococcoides spp. were present in the sediment, reductive dechlorination stopped at cis-DCE. Our results demonstrate the presence of viable dechlorinating bacteria in Yangtze samples, indicating their relevance for pollutant turnover.     

Surfactant-enhanced oxidation of trichloroethylene by permanganate--proof of concept

Oxidative dechlorination of chlorinated solvents by permanganate is an emerging technology for remediation of groundwater contaminated with dissolved chlorinated contaminants. In this study, the enhancement of trichloroethylene (TCE) degradation by permanganate in aqueous solution in the presence of surfactant was evaluated through a continuous stir batch reactor system with the presence of permanganate as the limiting reagent and free phase TCE. The TCE degradation was determined by continuous monitoring the amount of chloride produced, which was then reverted to the rate of permanganate consumption. It was found that the chloride production, an indication of TCE degradation, followed a pseudo-first-order reaction kinetics with respect to KMnO(4) in the presence of free phase TCE. When no surfactants were present, the observed pseudo-first-order rate constant (k(obs)) was 0.08-0.19 min(-1) and the half-life (t(1/2)) was 4-9 min for MnO(4)(-). When the surfactant concentration was less than its critical micelle concentration (CMC), the k(obs) values increased to 0.42-0.46 min(-1) and the t(1/2) reduced to 1.5-1.7 min for MnO(4)(-). As the surfactant concentration was greater than the CMC, the k(obs) values increased to 0.56-0.58 min(-1) and the t(1/2) reduced to 1.2-1.3 min. The preliminary results showed that combination of permanganate with a proper type of surfactant can speed up contaminant removal.     

Quantifying chlorinated ethene degradation during reductive dechlorination at Kelly AFB using stable carbon isotopes

Stable isotope analysis of chlorinated ethene contaminants was carried out during a bioaugmentation pilot test at Kelly Air Force Base (AFB) in San Antonio Texas. In this pilot test, cis-1,2-dichloroethene (cDCE) was the primary volatile organic compound. A mixed microbial enrichment culture, KB-1, shown in laboratory experiments to reduce chlorinated ethenes to non-toxic ethene, was added to the pilot test area. Following bioaugmentation with KB-1, perchloroethene (PCE), trichloroethene (TCE) and cDCE concentrations declined, while vinyl chloride (VC) concentrations increased and subsequently decreased as ethene became the dominant transformation product. Shifts in carbon isotopic values up to 2.7 per thousand, 6.4 per thousand, 10.9 per thousand and 10.6 per thousand were observed for PCE, TCE, cDCE and VC, respectively, after bioaugmentation, consistent with the effects of biodegradation. While a rising trend of VC concentrations and the first appearance of ethene were indicative of biodegradation by 72 days post-bioaugmentation, the most compelling evidence of biodegradation was the substantial carbon isotope enrichment (2.0 per thousand to 5.0 per thousand) in ?13C(cDCE). Fractionation factors obtained in previous laboratory studies were used with isotope field measurements to estimate first-order cDCE degradation rate constants of 0.12 h(-1) and 0.17 h(-1) at 115 days post-bioaugmentation. These isotope-derived rate constants were clearly lower than, but within a factor of 2-4 of the previously published rate constant calculated in a parallel study at Kelly AFB using chlorinated ethene concentrations. Stable carbon isotopes can provide not only a sensitive means for early identification of the effects of biodegradation, but an additional means to quantify the rates of biodegradation in the field.