Accumulation of dechlorination daughter products: A valid metric of chloroethene biodegradation

In situ reductive dechlorination of perchloroethene (PCE) and trichloroethene (TCE) generates characteristic chlorinated (cis‐dichloroethene [cis‐DCE] and vinyl chloride [VC]) and nonchlorinated (ethene and ethane) products. The accumulation of these daughter products is commonly used as a metric for ongoing biodegradation at field sites. However, this interpretation assumes that reductive dechlorination is the only chloroethene degradation process of any significance in situ and that the characteristic daughter products of chloroethene reductive dechlorination persist in the environment. Laboratory microcosms, prepared with aquifer and surface‐water sediments from hydrologically diverse sites throughout the United States and amended with [1,2‐¹⁴C] TCE, [1,2‐¹⁴C] DCE, [1,2‐¹⁴C] DCA, or [1,2‐¹⁴C] VC, demonstrated widely variable patterns of intermediate and final product accumulation. In predominantly methanogenic sediment treatments, accumulation of ¹⁴C‐DCE, ¹⁴C‐VC, ¹⁴C‐ethene, and ¹⁴C‐ethane predominated. Treatments characterized by significant Fe(III) and/or Mn(IV) reduction, on the other hand, demonstrated substantial, and in some cases exclusive, accumulation of ¹⁴CO₂ and ¹⁴CH₄. These results suggest that relying on the accumulation of cis‐DCE, VC, ethene, and ethane may substantially underestimate overall chloroethene biodegradation at many sites. © 2007 Wiley Periodicals, Inc. *

1 This article is a U.S. government work and, as such, is in the public domain in the United States of America.

     

Enhanced bioremediation using whey powder for a trichloroethene plume in a high‐sulfate,fractured granitic aquifer

An in situ bioremediation (ISB) pilot study, using whey powder as an electron donor, is being performed at Site 19, Edwards Air Force Base, California, to treat groundwater contaminated with trichloroethene (TCE) via anaerobic reductive dechlorination. Challenging site features include a fractured granitic aquifer, complex geochemistry, and limited biological capacity for reductive dechlorination. ISB was conducted in two phases with Phase I including one‐and‐a‐half years of biostimulation only using whey powder and Phase II including biostimulation with buffered whey powder and bioaugmentation. Results of Phase I demonstrated effective distribution of whey during injections resulting in depletion of high concentrations of sulfate and methanogenesis, but acid production due to whey fermentation and limited buffering capacity of the aquifer resulted in undesirable impacts to pH. In addition, cis‐1,2‐dichloroethene (cis‐1,2‐DCE) stall was observed, which correlated to the unsuccessful growth of native Dehalococcoides populations. Therefore, Phase II included the successful buffering of whey powder using bicarbonate, which mitigated negative pH effects. In addition, bioaugmentation resulted in successful transport of Dehalococcoides populations to greater than 50 feet away from the injection point four months after inoculation. A concomitant depletion of accumulated cis‐1,2‐DCE was observed at all wells affected by bioaugmented Dehalococcoides. © 2008 Wiley Periodicals, Inc.     

Integrated approach to PCE‐impacted site characterization,site management,and enhanced bioremediation

Tetrachloroethene (PCE)‐ and trichloroethene (TCE)‐impacted sites pose significant challenges even when site characterization activities indicate that biodegradation has occurred naturally. Although site‐specific, regulatory, and economic factors play roles in the remedy‐selection process, the application of molecular biological tools to the bioremediation field has streamlined the assessment of remedial alternatives and allowed for detailed evaluation of the chosen remedial technology. The case study described here was performed at a PCE‐impacted site at which reductive dechlorination of PCE and TCE had led to accumulation of cis‐dichlorethene (cis‐DCE) with concentrations ranging from approximately 10 to 100 mg/L. Bio‐Trap® samplers and quantitative polymerase chain reaction (qPCR) enumeration of Dehalococcoides spp. were used to evaluate three remedial options: monitored natural attenuation, biostimulation with HRC®, and biostimulation with HRC‐S®. Dehalococcoides populations in HRC‐S‐amended Bio‐Traps deployed in impacted wells were on the order of 10³ to 10⁴ cells/bead but were below detection limits in most unamended and HRC‐amended Bio‐Traps. Thus the in situ Bio‐Trap study identified biostimulation with HRC‐S as the recommended approach, which was further evaluated with a pilot study. After the pilot HRC‐S injection, Dehalococcoides populations increased to 10⁶ to 10⁷ cells/bead, and concentrations of cis‐DCE and vinyl chloride decreased with concurrent ethene production. Based on these results, a full‐scale HRC‐S injection was designed and implemented at the site. As with the pilot study, full‐scale HRC‐S injection promoted growth of Dehalococcoides spp. and stimulated reductive dechlorination of the daughter products cis‐DCE and vinyl chloride. © 2008 Wiley Periodicals, Inc.     

The in situ treatment of TCE and PFAS in groundwater within a silty sand aquifer

Chlorinated ethenes such as trichloroethene (TCE), cis‐1,2‐dichloroethene (cis‐1,2‐DCE), and vinyl chloride along with per‐ and polyfluoroalkyl substances (PFAS) have been identified as chemicals of concern in groundwater; with many of the compounds being confirmed as being carcinogens or suspected carcinogens. While there are a variety of demonstrated in‐situ technologies for the treatment of chlorinated ethenes, there are limited technologies available to treat PFAS in groundwater. At a former industrial site shallow groundwater was impacted with TCE, cis‐1,2‐DCE, and vinyl chloride at concentrations up to 985, 258, and 54 µg/L, respectively. The groundwater also contained maximum concentrations of the following PFAS: 12,800 ng/L of perfluoropentanoic acid, 3,240 ng/L of perfluorohexanoic acid, 795 ng/L of perfluorobutanoic acid, 950 ng/L of perfluorooctanoic acid, and 2,140 ng/L of perfluorooctanesulfonic acid. Using a combination of adsorption, biotic, and abiotic degradation in situ remedial approaches, the chemicals of concern were targeted for removal from the groundwater with adsorption being utilized for PFAS whereas adsorption, chemical reduction, and anaerobic biodegradation were used for the chlorinated ethenes. Sampling of the groundwater over a 24‐month period indicated that the detected PFAS were treated to either their detection, or below the analytical detection limit over the monitoring period. Postinjection results for TCE, cis‐1,2‐DCE, and vinyl chloride indicated that the concentrations of the three compounds decreased by an order of magnitude within 4 months of injection, with TCE decreasing to below the analytical detection limit over the 24‐month monitoring period. Cis‐1,2‐DCE, and vinyl chloride concentrations decreased by over 99% within 8 months of injections, remaining at or below these concentrations during the 24‐month monitoring period. Analyses of Dehalococcoides, ethene, and acetylene over time suggest that microbiological and reductive dechlorination were occurring in conjunction with adsorption to attenuate the chlorinated ethenes and PFAS within the aquifer. Analysis of soil cores collected pre‐ and post‐injection, indicated that the distribution of the colloidal activated carbon was influenced by small scale heterogeneities within the aquifer. However, all aquifer samples collected within the targeted injection zone contained total organic carbon at concentrations at least one order of magnitude greater than the preinjection total organic carbon concentrations.     

Performance evaluation of an in situ source area combined remedy for the remediation of commingled chlorinated ethanes and ethenes

The chlorinated volatile organic compounds (CVOCs), tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1‐trichloroethane (1,1,1‐TCA), often found as commingled contaminants of concern (COCs) in groundwater, can degrade via a variety of biotic and abiotic reductive pathways. In situ remediation of a groundwater contaminant source area containing commingled 1,1,1‐TCA, PCE, and TCE was conducted using a combined remedy/treatment train approach. The first step was to create geochemically reducing conditions in the source area to degrade the CVOCs to lesser chlorinated CVOCs (i.e., 1,1‐dichloroethane [1,1‐DCA], 1,1‐dichlorethene [1,1‐DCE], cis‐1,2‐dichoroethene [cis‐1,2‐DCE], and vinyl chloride [VC]) via enhanced reductive dechlorination (ERD). Carbon substrates were injected to create microbial‐induced geochemically reducing conditions. An abiotic reductant (zero‐valent iron [ZVI]) was also used to further degrade the CVOCs, minimizing the generation of 1,1‐DCE and VC, and co‐precipitate temporarily mobilized metals. An in situ aerobic zone was created downgradient of the treatment zone through the injection of oxygen. Remaining CVOC degradation products and temporarily mobilized metals (e.g., iron and manganese) resulting from the geochemically reducing conditions were then allowed to migrate through the aerobic zone. Within the aerobic zone, the lesser chlorinated CVOCs were oxidized and the solubilized metals were precipitated out of solution. The injection of a combination of carbon substrates and ZVI into the groundwater system at the site studied herein resulted in the generation of a geochemically reducing subsurface treatment zone that has lasted for more than 4.5 years. Mass concentrations of total CVOCs were degraded within the treatment zone, with near complete transformation of chlorinated ethenes and a more than 90 percent reduction of CVOC mass concentrations. Production of VC and 1,1‐DCE has been minimized through the combined effects of abiotic and biological processes. CVOC concentrations have declined over time and temporarily mobilized metals are precipitating out of the dissolved phase. Precipitation of the dissolved metals was mitigated using the in situ oxygenation system, also resulting in a return to aerobic conditions in downgradient groundwater. Chloroethane (CA) is the dominant CVOC degradation product within the treatment zone and downgradient of the treatment zone, and it is expected to continue to aerobically degrade over time. CA did not accumulate within and near the aerobic oxygenation zone. The expectations for the remediation system are: (1) the concentrations of CVOCs (primarily in the form of CA) will continue to degrade; (2) total organic carbon concentrations will continue to decline to pre‐remediation levels; and, (3) the groundwater geochemistry will experience an overall trend of transitioning from reducing back to pre‐remediation mildly oxidizing conditions within and downgradient of the treatment zone.     

Enhanced anaerobic bioremediation of a TCE source at the Tarheel Army Missile Plant using EOS

EOS, or emulsified oil substrate, was used to stimulate anaerobic biodegradation of trichloroethene (TCE) and tetrachloroethene (PCE) at a former Army‐owned manufacturing facility located in the Piedmont area of North Carolina. Previous use of chlorinated solvents at the facility resulted in soil and groundwater impacts. Ten years of active remediation utilizing soil vacuum extraction and air sparging (SVE/AS) were largely ineffective in reducing the TCE/PCE plume. In 2002, the Army authorized preparation of an amended Remedial Action Plan (RAP) to evaluate in situ bioremediation methods to remediate TCE in groundwater. The RAP evaluated eight groundwater remediation technologies and recommended EOS as the preferred bioremediation alternative for the site. Eight wells were drilled within the 100 × 100 feet area believed to be the primary source area for the TCE plume. In a first injection phase, dilute EOS emulsion was injected into half of the wells. Distribution of the carbon substrate through the treatment zone was enhanced by pumping the four wells that were not injected and recirculating the extracted water through the injection wells. The process was repeated in a second phase that reversed the injection/extraction well pairs. Overall, 18,480 pounds of EOS were injected and 163,000 gallons of water were recirculated through the source area. Anaerobic groundwater conditions were observed shortly after injection with a corresponding decrease in both PCE and TCE concentrations. Dissolved oxygen, oxidation‐reduction potential, and sulfate concentrations also decreased after injection, while TCE‐degradation products, ferrous iron, and methane concentrations increased. The reduction in TCE allowed the Army to meet the groundwater remediation goals for the site. Approximately 18 months after injection, eight wells were innoculated with a commercially prepared dechlorinating culture (KB‐1) in an attempt to address lingering cis‐1,2‐dichloroethene (cis‐DCE) and vinyl chloride (VC) that continued to be observed in some wells. Dehalococcoides populations increased slightly post‐bioaugmentation. Both cis‐DCE and VC continue to slowly decrease. © 2007 Wiley Periodicals, Inc.     

Borehole‐scale testing of matrix diffusion for contaminated‐rock aquifers

A new method was developed to assess the effect of matrix diffusion on contaminant transport and remediation of groundwater in fractured rock. This method utilizes monitoring wells constructed of open boreholes in the fractured rock to conduct backward diffusion experiments on chlorinated volatile organic compounds (CVOCs) in groundwater. The experiments are performed on relatively unfractured zones (called test zones) of the open boreholes over short intervals (approximately 1 meter) by physical isolation using straddle packers. The test zones were identified with a combination of borehole geophysical logging and chemical profiling of CVOCs with passive samplers in the open boreholes. To confirm the test zones are within inactive flow zones, they are subjected to a series of hydraulic tests. Afterward, the test zones are air sparged with argon to volatilize the CVOCs from aqueous to air phase. Backward diffusion is then measured by periodic passive‐sampling of water in the test zone to identify rebound. The passive (nonhydraulically stressed) sampling negates the need to extract water and potentially dewater the test zone. The authors also monitor active flowing zones of the borehole to assess trends in concentrations in other parts of the fractured rock by purge and passive sampling methods. The testing was performed at the former Pease Air Force Base (PAFB) in Portsmouth, New Hampshire. Bedrock at the former PAFB consists of fractured metasedimentary rocks where the authors investigated back diffusion of cis‐1,2‐dichloroethylene (cis‐1,2‐DCE), a CVOC. Postsparging concentrations of cis‐1,2‐DCE showed initial rebounding followed by declines, excluding an episodic spike in concentrations from a groundwater recharge event. The authors theorize that there are three processes that controlled concentration responses in the test zones postsparging. First, the limited back diffusion of CVOCs from a halo or thin zone of rock around the borehole contributes to the initial rebounding. Second, aerobic degradation of cis‐1,2‐DCE occurred causing declines in concentrations in the test zone. Third, microflow from microfractures contributed to the episodic spike in concentrations following the groundwater recharge event. In active flow zones, the latter two processes are not measurable due to equilibration from groundwater transport between the borehole and active flowing fractures.     

Remedial options for chlorinated volatile organics in a partially anaerobic aquifer

A laboratory study was conducted for the selection of appropriate remedial technologies for a partially anaerobic aquifer contaminated with chlorinated volatile organics (VOCs). Evaluation of in situ bioremediation demonstrated that the addition of electron donors to anaerobic microcosms enhanced biological reductive dechlorination of tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1‐trichloroethane (1,1,1‐TCA) with half‐lives of 20, 22, and 41 days, respectively. Nearly complete reductions of PCE, TCE, 1,1,1‐TCA, and the derivative cis‐dichloroethene were accompanied by a corresponding increase in chloride concentrations. Accumulation of vinyl chloride, ethene, and ethane was not observed; however, elevated levels of ¹⁴CO₂ (from ¹⁴C‐TCE spiked) were recovered, indicating the occurrence of anaerobic oxidation. In contrast, very little degradation of 1,2‐dichloropropane (1,2‐DCP) and 1,1‐dichlorethane (1,1‐DCA) was observed in the anaerobic microcosms, but nutrient addition enhanced their degradation in the aerobic biotic microcosms. The aerobic degradation half‐lives for 1,2‐DCP and 1,1‐DCA were 63 and 56 days, respectively. Evaluation of in situ chemical oxidation (ISCO) demonstrated that chelate‐modified Fenton's reagent was effective in degrading aqueous‐phase PCE, TCE, 1,1,1‐TCA, 1,2‐DCP, etc.; however, this approach had minimal effects on solid‐phase contaminants. The observed oxidant demand was 16 g‐H₂O₂/L‐groundwater. The oxidation reaction rates were not highly sensitive to the molar ratio of H₂O₂:Fe²⁺:citrate. A ratio of 60:1:1 resulted in slightly faster removal of chemicals of concern (COCs) than those of 12:1:1 and 300:1:1. This treatment resulted in increases in dissolved metals (Ca, Cr, Mg, K, and Mn) and a minor increase of vinyl chloride. Treatment with zero‐valent iron (ZVI) resulted in complete dechlorination of PCE, and TCE to ethene and ethane. ZVI treatment reduced 1,1,1‐TCA only to 1,1‐DCA and chloroethane (CA) but had little effect on reducing the levels of 1,2‐DCP, 1,1‐DCA, and CA. The longevity test showed that one gram of 325‐mesh iron powder was exhausted in reaction with > 22 mL of groundwater. The short life of ZVI may be a barrier to implementation. The ZVI surface reaction rates (k_sa) were 1.2 × 10^?2 Lm^?2h^?1, 2 × 10^?3 Lm^?2h^?1, and 1.2 × 10^?3 Lm^?2h^?1 for 1,1,1‐TCA, TCE, and PCE, respectively. Based upon the results of this study, in situ bioremediation appeared to be more suitable than ISCO and ZVI for effectively treating the groundwater contamination at the site. © 2004 Wiley Periodicals, Inc.     

Pilot‐scale evaluation using bioaugmentation to enhance PCE dissolution at dover AFB national test site

An Interstate Technology and Regulatory Council (ITRC) forum was recently held that focused on six case studies in which bioremediation of dense nonaqueous‐phase liquids (DNAPLs) was performed; the objective was to demonstrate that there is credible evidence for bioremediation as a viable environmental remediation technology. The first two case studies from the forum have been previously published; this third case study involves a pilot‐scale demonstration that investigated the effects of biological activity on enhancing dissolution of an emplaced tetrachloroethene (PCE) DNAPL source. It used a controlled‐release test cell with PCE as the primary DNAPL in a porous media groundwater system. Both laboratory tests and a field‐scale pilot test demonstrated that bioaugmentation can stimulate complete dechlorination to a nontoxic end product and that the mass flux from a source zone increases when biological dehalorespiration activity is enhanced through nutrient (electron donor) addition and bioaugmentation. All project goals were met. Important achievements include demonstrating the ability to degrade a PCE DNAPL source to ethene and obtaining significant information on the impacts to the microbial populations and corresponding isotope enrichments during biodegradation of a source area. © 2007 Wiley Periodicals, Inc.     

Chemical and Biological Reduction of PCE by Pneumatic Fracturing and Injection of ZVI in Saprolite

This article presents a case study of the source‐area treatment of tetrachloroethene (PCE) in a low‐permeability formation using zero‐valent iron (ZVI). Evidence of the stimulation of biological reduction processes within the treatment zone occurred. Pneumatic fracturing and injection of microscale ZVI slurry in the overburden and weathered bedrock zones was performed at a commercial brownfields redevelopment site in Maryland. A 20,000‐square‐foot source area impacted with PCE at concentrations greater than 15,000 µg/L was treated at depths ranging from 10 to 70 feet bgs. An average ZVI dosage of 0.0024 iron‐to‐soil mass ratio within the overburden zone led to a 75 percent decrease in PCE mass in less than one year. For the weathered bedrock zone, an average 0.0045 iron‐to‐soil mass ratio resulted in a 92 percent decrease in PCE mass during the same period. The reducing environment and hydrogen generated by the ZVI may have stimulated Dehalobacter populations, as evidenced by concentrations up to 10⁴ cells per milliliter measured within the treatment area despite a groundwater pH as high as 9. The biological reductive dechlorination of the chlorinated ethenes explains the temporary increase in trichloroethene and cis‐1,2‐dichloroethene concentrations. © 2013 Wiley Periodicals, Inc.     

Stimulation of aerobic degradation of chlorinated ethenes in soil by microbial inoculation

Degradation of chlorinated ethenes under aerobic conditions has been reported using a cometabolic pathway. A site in Illinois had shallow contamination and sandy soils, which in combination created aerobic conditions. The aerobic conditions prevented the degradation of chlorinated ethenes by reductive dechlorination. Biodegradation of chloroethenes under aerobic conditions does not occur naturally at all sites; however, it can be enhanced if microorganisms capable of cometabolic degradation are introduced into the soil. In this study, trichloroethene (TCE) removal in the soil was enhanced by the injection of a commercially available microbial inoculum (CL‐OUT® inoculum, CL‐Solutions, Cincinnati, OH) and nutrients and was compared to chlorinated ethene removal in soil that had received nutrients only and soil that had received activated sludge and nutrients. Trichloroethene removal was measured after one week, seven weeks, and eleven weeks. After one week, no significant TCE removal had occurred in any of the test microcosms. After seven weeks, a slight decrease in TCE levels accompanied by an increase in cis‐1,2‐dichloroethene (cis‐1,2‐DCE) was seen in the microcosms that had received CL‐OUT®. After 11 weeks, a marked decrease in TCE levels was observed in the microcosms that had received CL‐OUT®. No significant TCE decrease was observed in any of the other microcosms. These data suggest that organisms capable of aerobic TCE degradation were not present at the site; however, the addition of an inoculum containing such organisms enabled aerobic degradation to occur. © 2008 Wiley Periodicals, Inc.     

Successful application of monitored natural attenuation in a surficial aquifer

Groundwater investigations conducted since 1988 at a Tennessee Department of Environment and Conservation (TDEC) Voluntary Oversight and Assistance Program (VOAP) site located in Millington, Tennessee, have defined the lateral and vertical extent of site chemicals of concern (COCs) consisting of tetrachloroethene (PCE), trichloroethene (TCE), and associated degradation products. Results of a groundwater remedial investigation determined that aquifer conditions were favorable for anaerobic degradation of COCs through reductive dechlorination. A subsequent groundwater feasibility study determined that monitored natural attenuation (MNA) coupled with long‐term groundwater monitoring was the most effective and suitable remedial option for the site. A Record of Decision was issued by the TDEC VOAP approving MNA and long‐term groundwater monitoring as the remedial option for the site, a first for such a site in Tennessee involving chlorinated organics. A groundwater fate and transport model (the 1998 model) developed during the RI was used as the basis for the MNA remedy. Analytical data from 1998 to 2008 indicate COCs in former high‐concentration areas continue to degrade at rates consistent with or ahead of the 1998 model predictions. Evidence of reductive dechlorination is also supported by the continued presence of breakdown products—specifically, vinyl chloride and ethene (terminal endpoint of PCE breakdown through reductive dechlorination). The continued detection of breakdown products along the flow‐path wells also confirms the effectiveness of the MNA remedy at the site. Current analytical data indicate that COC plumes beneath the site are not migrating and are actually retracting. © 2010 Wiley Periodicals, Inc.     

Modified Fenton's processes for effective in‐situ chemical oxidation—Laboratory and field evaluation

Fenton's reagent in its conventional form, although effective for contaminant treatment, is impractical from an in‐situ field application perspective due to low pH requirements (i.e., pH 3‐4), and limited reagent mobility when introduced into the subsurface. Modified Fenton's processes that use chelated‐iron catalysts and stabilized hydrogen peroxide have been developed with the goal of promoting effective in‐situ field application under native pH conditions (i.e., pH 5‐7), while extending the longevity of hydrogen peroxide. Laboratory experiments conducted in soil columns packed with organic soil to compare modified Fenton's catalysts with conventional catalysts (acidified iron [II]) indicated superior mobility and sorption characteristics for modified Fenton's catalysts. Furthermore, the acidic pH of a conventional catalyst was buffered to the native soil range, leading to increased iron precipitation/adsorption following permeation through the soil column. The chelates present within the modified Fenton's catalyst showed greater affinity toward iron compared with the native soil and, hence, minimized iron loss through adsorption during the permeation process even at pH 5‐7. Field effectiveness of the modified Fenton's process was demonstrated at a former dry‐cleaning facility located in northeast Florida. Preliminary laboratory‐scale experiments were conducted on soil‐slurry and groundwater samples to test the process efficacy for remediation of chlorinated solvents. Based on successful experimental results that indicated a 94 percent (soil slurry) to 99 percent (groundwater) reduction of cis‐1,2‐DCE, PCE, and TCE, a field‐scale treatment program was initiated utilizing a plurality of dual‐zone direct push injection points installed in a grid fashion throughout the site. Results of treatment indicated a 72 percent reduction in total chlorinated contamination detected in the site groundwater following the first injection event; the reduction increased to 90 percent following the second injection event. © 2002 Wiley Periodicals Inc.     

Field‐scale evaluation of a biobarrier for the treatment of a trichloroethene plume

In the 1960s, trichloroethene (TCE) was used at what is now designated as Installation Restoration Program Site 32 Cluster at Vandenberg Air Force Base to flush missile engines prior to launch and perhaps for other degreasing activities, resulting in releases of TCE to groundwater. The TCE plume extends approximately 1 kilometer from the previous launch facilities beyond the southwestern end of the site. To limit further migration of TCE and chlorinated degradation by‐products, an in situ, permeable, reactive bioremediation barrier (biobarrier) was designed as a cost‐effective treatment technology to address the TCE plume emanating from the source area. The biobarrier treatment would involve injecting carbon‐based substrate and microbes to achieve reductive dechlorination of volatile organic compounds, such as TCE. Under reducing conditions and in the presence of certain dechlorinating microorganisms, TCE degrades to nontoxic ethene in groundwater. To support the design of the full‐scale biobarrier, a pilot test was conducted to evaluate site conditions and collect pertinent design data. The pilot test results indicated possible substrate delivery difficulties and a smaller radius of influence than had been estimated, which would be used to determine the final biobarrier well spacing. Based on these results, the full‐scale biobarrier design was modified. In January 2010, the biobarrier was implemented at the toe of the source area by adding a fermentable substrate and a dechlorinating microbial culture to the subsurface via an injection well array that spanned the width of the TCE plume. After the injections, the groundwater pH in the injection wells continued to decrease to a level that could be detrimental to the population of Dehalococcoides in the SDC‐9^TM culture. In addition, 7 months postinjection, the injection wells could not be sampled due to fouling. Cleaning was required to restore their functions. Bioassay and polymerase chain reaction analyses were conducted, as well as titration tests, to assess the need for biobarrier amendments in response to the fouling issues and low pH. Additionally, slug tests were performed on three wells to evaluate possible localized differences in hydraulic conductivity within the biobarrier. Based on the test results, the biobarrier was amended with sodium carbonate and inoculated a second time with SDC‐9^TM. The aquifer pH was restored, and reductive dechlorination resumed in the treatment zone, evidenced by the reduction in TCE and the increase in degradation products, including ethene. © 2011 Wiley Periodicals, Inc.     

Chlorinated Solvent Treatment Wetland

A first‐of‐its‐kind wetland restoration project was completed in October 2000 to treat trichloroethene‐(TCE‐)impacted groundwater from a former manufacturing facility prior to discharge into a highly valued recreational surface water body in the upper Midwest. This article summarizes the design, construction, operation, and effectiveness of the restored wetland. The groundwater‐surface water discharge zone at the site was restored as a wetland to improve the natural degradation of TCE and subsequent degradation by‐products. For the past 11 years, the treatment wetland performance was evaluated by monitoring the wetland vegetation, wetland hydraulics, and water chemistry. Water quality data have been used to assess the wetland geochemistry, TCE and TCE‐degradation by‐product concentrations within the wetland, and the surface water quality immediately downgradient of the wetland. The treatment wetland has been performing according to design, with TCE and TCE‐degradation by‐products not exceeding surface water criteria. The monitoring results show that TCE and TCE‐degradation by‐products are entering the treatment wetland via natural hydraulic gradients and that the geochemistry of the wetland supports both reductive dechlorination (anaerobic degradation) and cometabolic degradation (aerobic degradation) of TCE and TCE‐degradation by‐products: cis‐ and trans‐1,2‐dichloroethene and vinyl chloride. © 2013 Wiley Periodicals, Inc.     

Remediation of a Former Dry Cleaner Using Nanoscale Zero Valent Iron

Nanoscale zero valent iron (nZVI) was evaluated in a laboratory treatability study and subsequently injected as an interim measure to treat source area groundwater impacts beneath a former dry cleaner located in Chapel Hill, North Carolina (the site). Dry cleaning operations resulted in releases of tetrachloroethene (PCE) that impacted site soil at concentrations up to 2,700 mg/kg and shallow groundwater at concentrations up to 41 mg/L. To achieve a design loading rate of 0.001 kg of iron per kilogram of aquifer material, approximately 725 kg of NanoFe? (PARS Environmental) was injected over a two‐week period into a saprolite and partially weather rock aquifer. Strong reducing conditions were established with oxidation–reduction potential (ORP) values below –728 mV. pH levels remained greater than 8 standard units for a period of 12 months. Injections resulted in near elimination of PCE within one month. cis‐1,2‐Dichloroethene accumulated at high concentrations (greater than 65 mg/L) for 12 months. MAROS software (Version 2.2; AFCEE, 2006 ) was used to calculate mass reduction of PCE and total ethenes at 96 percent and 58 percent, respectively, compared to baseline conditions. Detections of acetylene confirmed the presence of the beta‐elimination pathway. Detections of ethene confirmed complete dechlorination of PCE. Based on hydrogen gas generation, iron reactivity lasted 15 months. © 2013 Wiley Periodicals, Inc.     

Assessment and monitoring tools for aerobic bioremediation of vinyl chloride in groundwater

Direct aerobic biodegradation of vinyl chloride (VC) offers a remedial solution for persistent vinyl chloride plumes that are not amenable to the anaerobic process of reductive dechlorination because of either prevailing geochemical conditions or the absence of active Dehalococcoides ethenogenes. However, tools are needed to evaluate and optimize aerobic VC bioremediation. This article describes the development and testing of two techniques—a microbiological tool and a molecular tool—for this purpose. Both methods are based on detection of bacteria that can use vinyl chloride and ethene as growth substrates in the presence of oxygen. The microbiological tool is an activity assay that indicates whether bacteria capable of degrading ethene under aerobic conditions are present in a groundwater sample. This activity assay gave positive results in the area of active VC degradation of an aerobic VC bioremediation test site. A rapid semiquantitative genetic assay was also developed. This molecular tool, based on polymerase chain reaction (PCR) detection of a gene involved in the metabolism of both ethene and VC, revealed the presence of potential VC degraders in an enrichment culture and site groundwater. These tools could provide a basis for judging the potential of aerobic VC degradation by ethenotrophs at other sites in addition to offering a mechanism for treatment monitoring and system optimization. © 2009 Wiley Periodicals, Inc.     

Field Evidence of Dissolution and Degradation Rates Enhancement During ISCR and ENA Treatments of Chlorinated Solvents

This article presents field tests comparing two methods of treatment of chlorinated solvents undertaken at the same site. The site is an automobile factory where two chlorinated solvents (CS) plumes were identified. At the first source, in situ chemical reduction (ISCR) was applied, while at the second one, enhanced natural attenuation (ENA) was used. A set of specific multilevel sampling wells were installed approximately 20 m downgradient of the sources to estimate the efficiency of the treatments. The presence of a low‐permeability layer (source 1) or a thick oil lens (source 2) in the top part of the aquifer prevented the CS from reaching the bottom of the aquifer. These layers led to difficulties treating the contamination. At the ISCR and ENA treatment zones, the concentrations of tetrachloroethene (PCE) and trichloroethene (TCE) did not change significantly, while the concentration of metabolites (cis‐1,2‐DCE, vinyl chloride, and ethene) significantly increased 50 to 150 days after treatment. Due to high concentration of CS in the source zone, a mass balance calculation, including chlorine, was possible. It showed that around 1 to 2 percent of the injected products were used to reduce the CS. A detailed analysis and 1D analytical modeling of CS concentrations showed that the treatment led to a large (two to three times) increase in dissolution of the organic phase. This explains why, despite an efficient treatment, the PCE and TCE concentrations remained virtually unchanged. Degradation rates also increased due to the treatment. Due to some differences in the source‐zone chemistry, it was not possible to differentiate between the ISCR and ENA efficiencies. © 2013 Wiley Periodicals, Inc.     

Rapid Cleanup of Chlorinated Solvent Source Zones: Synergies Between Chemical and Biological Degradation

A chlorinated volatile organic compound (cVOC) source area approximately 25 by 100 ft in a heavily industrialized urban area was characterized with groundwater tetrachloroethene (PCE) concentrations up to 9,180 μg/L. This is approximately 6 percent of PCE's aqueous solubility, indicative of the presence of residual dense, nonaqueous phase liquid. The resulting dissolved‐phase plume migrated off‐site. Biotic and abiotic dechlorination using a combination of a food‐grade organic carbon‐based electron donor and zero‐valent iron suspended in a food‐grade emulsifying agent reduced the source area PCE concentrations by 98 percent within 27 weeks, with minimal downgradient migration of daughter products dichloroethene and vinyl chloride. Combining biological dechlorination with iron‐based chemical dechlorination is synergistic, enhancing treatment aggressiveness, balancing pH, and optimizing degradation of both DNAPL and dissolved‐phase cVOCs. © 2013 Wiley Periodicals, Inc.     

Bioremediation of a former dry cleaner using potassium lactate

Chlorinated solvents were released to the surficial groundwater underneath a former dry cleaning building, resulting in a groundwater plume consisting of high concentrations of trichloroethene (TCE) and cis‐1,2‐dichloroethene (cis‐1,2‐DCE) and low concentrations of tetrachloroethene (PCE) and vinyl chloride. The initial remedial action included chemical oxidation via injection of 14,400 gallons of Fenton's Reagent in March 2002, and an additional 14,760 gallons in April 2002. A sharp reduction of contaminant concentrations in groundwater was observed the following month; however, rebound of contaminant concentrations was evident as early as October 2002. A source area of PCE‐impacted soils was excavated in June 2004. Following the excavation, Golder Associates Inc. (2007) implemented a biostimulation plan by injecting 55 gallons of potassium lactate (PURASAL® HiPure P) in September 2005, and again in February 2006. Comparing the preinjection and postinjection site conditions, the potassium lactate treatments were successful in accomplishing a 40 to 70 percent reduction in mass within four months following the second injection. Elevated vinyl chloride concentrations have persisted through both injection events; however, significant vinyl chloride reduction has been observed in one well with the highest total organic carbon (TOC) concentrations following each injection. © 2008 Wiley Periodicals, Inc.