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.     

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.     

Reductive dechlorination of a chlorinated solvent plume in Houston,Texas

Chlorinated solvents such as tetrachloroethene (perchloroethene, PCE) and trichloroethene (TCE) have been extensively used in various industrial applications for many years. Because neither are typically consumed through their various uses, they are often released to the environment through industrial application or disposal. Once released, PCE and TCE tend to migrate downward into groundwater, where they persist. In the current case study, cheese whey was used as a groundwater amendment to facilitate the reductive dechlorination of a chlorinated solvent plume underlying an auto dealer/repair shop in Harris County, Texas. From September 2010 to January 2014, over 32,000 gallons of cheese whey were injected into the subsurface resulting in a marked reduction in oxidation–reduction potential (ORP) and nitrate concentrations, coupled with an increase in ferrous iron concentrations. Statistical trend analyses indicate the primary contaminants, PCE and TCE, as well as the daughter product cis‐1,2‐dichloroethene (cDCE), all exhibited a positive response, as evidenced by statistically decreasing trends, and/or reversal in concentration trends, subsequent to cheese whey injections. Maximum concentrations of PCE and TCE in key test wells decreased by as much as 98.97 percent and 99.17 percent, respectively. In addition, the bacterial genus Dehalococcoides, capable of complete reduction of PCE to non‐toxic ethene, was found to be more abundant in the treatment area, as compared to background concentrations. Because cheese whey is a by‐product of the cheese making process, the cost of the product is essentially limited to transport. This study demonstrates cheese whey to be an effective groundwater amendment at a cost which is orders of magnitude lower than popular industry alternatives.     

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.     

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.     

Optimal Treatment Zone Moves During Enhanced Reductive Dechlorination in Fractured Bedrock

An enhanced bioremediation pilot test was implemented to study the efficacy of enhancing in situ reductive dechlorination of tetrachloroethene (PCE) in shallow bedrock where some intrinsic degradation to cis‐1,2‐dichloroethene (cis‐1,2‐DCE) was observed without further degradation to vinyl chloride or nontoxic ethene. Limited Dehalococcoides spp. cell concentrations were present within the study area prior to the gravity‐fed injection of an injectate of fermentable carbon substrates in native anaerobic groundwater. Direct connectivity between the injection well screen and performance monitoring well was evidenced and resulted in the degradation of nearly all PCE to cis‐1,2‐DCE, significant decrease in pH, and apparent inhibited Dehalococcoides spp. growth in the study area groundwater in the first six months. After 24 months, nearly all cis‐1,2‐DCE had degraded to nontoxic ethene, pH rebounded to more optimal levels, and abundant growth of Dehalococcoides spp. (6.8E05 cells/mL) and its functional gene expressions responsible for complete dechlorination were evident. The observations indicated initial poor dechlorination within the injection zone did not preclude effective treatment, allowing sufficient monitoring time showed the effective treatment zone (or more‐optimal fringe) first moved outward from the injection zone beyond the monitoring point and then receded back toward the point of injection over a period of two years. ©2015 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.     

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.     

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.     

Optimizing remediation strategies for a former dry‐cleaner site

Residual tetrachloroethene (PCE) contamination at the former Springvilla Dry Cleaners site in Springfield, Oregon, posed a potential risk through the vapor intrusion, direct contact, and off‐site beneficial groundwater uses. The Oregon Department of Environmental Quality utilized the State Dry Cleaner Program funds to help mitigate the risks posed by residual contamination. After delineation activities were complete, the source‐area soils were excavated and treated on‐site with ex situ vapor extraction to reduce disposal costs. Residual source‐area contamination was then chemically oxidized using sodium permanganate. Dissolved‐phase contamination was subsequently addressed with in situ enhanced reductive dechlorination (ERD). ERD achieved treatment goals across more than 4 million gallons of aquifer impacted with PCE concentrations up to 7,800 micrograms per liter prior to remedial activities. The ERD remedy introduced electron donors and nutrient amendments through groundwater recirculation and slug injection across two aquifers over the course of 24 months. Adaptive and mass‐targeted strategies reduced total remedy costs to approximately $18 per ton within the treatment areas. © 2010 Wiley Periodicals, Inc.     

Characterization and pilot‐scale studies for chemical oxidation remediation of fractured shale

The distribution of volatile organic compounds (VOCs) in fractured shale overlain by thin (< 10 feet) overburden at the Watervliet Arsenal near Albany, New York, was initially determined by sampling water from the fracture network using packer systems in boreholes and also using conventional monitoring wells. Furthermore, short‐term pumping and injection tests were conducted and the boreholes were logged using a variety of geophysical and hydrophysical tools. Tetrachloroethene is the dominant VOC in the groundwater, with lesser concentrations of trichloroethene and degradation products (cis‐1,2‐dichloroethene, trans‐1,2‐dichloroethene, and vinyl chloride). The vertical VOC distributions in the rock matrix were obtained from continuous‐cored holes from which small rock samples, collected at many depths between 18 and 150 feet below ground surface, were analyzed. The rock core VOC concentrations were determined by methanol extraction of crushed rock followed by direct methanol injection onto a gas chromatograph and subsequent estimation of rock porewater VOC concentrations. The rock core data support the concept that diffusion‐driven mass transfer has caused nearly all the VOC mass initially present in the fractures to now reside in the rock matrix, which has a porosity three or four orders of magnitude larger than the bulk fracture porosity. The results of the site characterization indicate that an effective site investigation strategy in fractured shale must include characterization of both the fracture and matrix contaminant distribution. These results also indicate that the most favorable remediation technologies for this fractured shale are those that will destroy VOCs in the rock matrix, particularly contaminants in the sorbed phase, and also destroy the VOC mass in the fractures including both dissolved and immiscible phases. The site characterization resulted in the selection of potassium permanganate for an in situ chemical oxidation pilot study. © 2004 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.     

Modeling remediation time using natural attenuation at a dry‐cleaner site

Contaminants from dry‐cleaning sites, primarily tetrachloroethene (PCE), trichloroethene (TCE), cis‐dichloroethene (cis‐DCE), and vinyl chloride (VC), have become a major concern because of the limited funds and regulatory programs to address them. Thus, natural attenuation and its effectiveness for these sites needs to be evaluated as it might provide a less costly alternative to other remediation methods. In this research, data from a site in Texas were analyzed and modeled using the Biochlor analytical model to evaluate remediation times using natural attenuation. It was determined that while biodegradation and source decay were occurring at the site, the resulting attenuation rates were not adequate to achieve cleanup in a reasonable time frame without additional source remediation or control strategies. Cleanup times exceeded 100 years for all constituents at the site boundary and 800 years at the source for PCE, assuming cleanup levels of 0.005 mg/L for PCE and TCE and 0.07 mg/L and 0.002 mg/L for cis‐DCE and VC, respectively. © 2005 Wiley Periodicals, Inc.     

Air Sparging Pilot Testing Including In-Well Temperature Measurement

Air sparging was pilot tested at a site where a groundwater plume containing cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC) and arsenic resulted from landfill operations. In addition to the commonly used methods for estimating air sparging zone of influence (ZOI), in-well temperature was monitored using sensitive thermocouples and data loggers at several monitoring wells of various screened intervals during the test. Following 42 days of pilot testing, the downgradient monitoring well samples were below maximum contaminant levels (MCLs)for all contaminants of concern, VC and dissolved arsenic were below detection limits (0.5 and 10 milligrams per liter [μg/L], respectively) in all of the downgradient monitoring wells. The ZOI monitoring results indicated that at some locations use of mounding data may overestimate the ZOI when the temperature data suggest that no sparged air was entering the well screen. Therefore, monitoring in-well temperature may provide additional useful information for estimating air sparging ZOI and is more indicative of air pathways than other monitoring methods. In addition, the temperature data were valuable for selecting a pulse frequency and duration to optimize groundwater mixing.     

CSIA of TCE and Daughter Products With Multiple Sources,Multiple Attenuation Mechanisms,and Low Ethene

One of the most often asked questions from regulators considering monitored natural attenuation (MNA) for a site is if there are mechanisms in situ that can completely detoxify the contaminant of concern. This article describes a method that uses data derived from compound‐specific isotope analysis (CSIA) to investigate if complete in situ degradation of trichloroethene (TCE) has occurred. MNA was the selected remediation strategy at the former England Air Force Base (fEAFB) in Louisiana. Previously declining concentrations of TCE, 1,2‐cis‐dichloroethene, and vinyl chloride had increased in selected wells, and less ethene was observed than expected on the basis of mass balance. Reductive dechlorination, partial or otherwise, could not explain observed trends, so the question at fEAFB had become: Was there an in situ mechanism for complete TCE detoxification (i.e., complete degradation to innocuous end products) at the site? CSIA was used for investigating this question at fEAFB. A previously developed formalism was adapted to interpret the CSIA data to answer the question. Standard interpretation assuming only reductive dechlorination demonstrated detoxification in 9 of the 15 contaminated wells, whereas the interpretation developed here did so in 14. © 2014 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.     

Enhancing Reductive Dechlorination With Nutrient Addition

Enhanced reductive bioremediation (ERB) of halogenated organics has become widely accepted and implemented to reduce risks to human health and the environment posed by these compounds. The family of chlorinated ethenes (e.g., trichloroethene) is among the most common contaminants treated using ERB techniques. The number of microbial species able to fully dechlorinate ethenes is small, and many times their population numbers are low. As a result, many ERB practitioners have turned to the injection of designer bacteria within treatment zones as a means to accelerate the process. Otherwise, many remediation projects encounter “cis‐stall,'' or the accumulation of the cis‐1,2‐dichloroethene and vinyl chloride intermediates. This article discusses three unique case studies where the addition of a balanced macro‐ and micro‐nutrient source substantially accelerated the chlorinated ethene ERB process, independent of the electron‐donor substrate applied. © 2013 Wiley Periodicals, Inc.     

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.     

Conceptual Site Model Development and Phased Remedy Implementation to Achieve Vapor Screening Goals at a Former Dry Cleaner

Tetrachloroethene (PCE) releases at a former dry cleaner resulted in impacts to soil and shallow groundwater beneath and adjacent to the building. Subsurface impacts led to vapor intrusion with PCE concentrations between 900 and 1,200 micrograms per cubic meter (μg/m³) in indoor air. The migration pathways of impacted soil vapor were evaluated through implementation of a helium tracer test and vapor sampling of an exterior concrete block wall. Results confirmed that the concrete block wall acted as a conduit for vapor intrusion into the building. A combination of remediation efforts focused on mass reduction in the source area as well as mitigation efforts to inhibit vapor migration into the building. Excavation of soils beneath the floor slab and installation of a spray‐applied vapor barrier resulted in PCE concentrations in indoor air decreasing by over 97.9 percent. Operation of an active ventilation system installed under the floor slab and groundwater remediation via injections of nano‐scale zero valent iron (nZVI) further reduced PCE concentrations in indoor air by over 99.8 percent compared to baseline conditions. While significant reductions of PCE concentrations in groundwater were observed within two months after injection, maximum reductions to PCE concentrations in indoor air were not observed for an additional 12 months. © 2014 Wiley Periodicals, Inc.