Low‐Capacity Well Pairs for Treating Contaminated Groundwater in Homogeneous and Heterogeneous Aquifers

Groundwater remediation alternatives were simulated for homogeneous and heterogeneous aquifers with a numerical mass transport model. Low‐energy alternatives involved an injection–extraction well pair positioned along a downgradient linear transect. This transect was located 5 m from the contaminant plume and oriented perpendicular to the regional hydraulic gradient. Through numerous trials, for one homogeneous and three heterogeneous settings, the model identified an optimal spacing and minimum pumping rate for a well pair: (1) centered on the downgradient tip of the plume (best centered), and (2) anywhere along the downgradient transect (best overall). Results suggest that low‐energy well pairs are an effective means for containing and removing some contaminant plumes, and best‐performing configurations are generally not centered on the downgradient tip of the initial contaminant plume. ©2015 Wiley Periodicals, Inc.     

Remediating Contaminated Groundwater With Low‐Capacity Injection and Nonpumped Wells

This modeling study evaluated the capability of low‐capacity wells injecting clean water and nonpumped wells equipped with filter media for containing and removing a contaminant plume in groundwater. Outcomes were compared for configurations of: (1) nonpumped wells, (2) nonpumped wells and injection wells (injecting less than 1 m³/d), and (3) no wells (baseline scenario). Results suggest that hybrid configurations featuring both types of wells can be an effective, low‐cost strategy for containing and remediating contaminated groundwater. Strategically positioned injection wells funnel contaminant plumes toward nonpumped wells, thus requiring fewer nonpumped wells to contain and remove a contaminant plume. © 2013 Wiley Periodicals, Inc.     

Seven‐year performance evaluation of a permeable reactive barrier

In June and July 2001, the Massachusetts Department of Environmental Protection (MassDEP) installed a permeable reactive barrier (PRB) to treat a groundwater plume of chlorinated solvents migrating from an electronics manufacturer in Needham, Massachusetts, toward the Town of Wellesley's Rosemary Valley wellfield. The primary contaminant of concern at the site is trichloroethene (TCE), which at the time had a maximum average concentration of approximately 300 micrograms per liter directly upgradient of the PRB. The PRB is composed of a mix of granular zero‐valent iron (ZVI) filings and sand with a pure‐iron thickness design along its length between 0.5 and 1.7 feet. The PRB was designed to intercept the entire overburden plume; a previous study had indicated that the contaminant flux in the bedrock was negligible. Groundwater samples have been collected from monitoring wells upgradient and downgradient of the PRB on a quarterly basis since installation of the PRB. Inorganic parameters, such as oxidation/reduction potential, dissolved oxygen, and pH, are also measured to determine stabilization during the sampling process. Review of the analytical data indicates that the PRB is significantly reducing TCE concentrations along its length. However, in two discrete locations, TCE concentrations show little decrease in the downgradient monitoring wells, particularly in the deep overburden. Data available for review include the organic and inorganic analytical data, slug test results from nearby bedrock and overburden wells, and upgradient and downgradient groundwater‐level information. These data aid in refining the conceptual site model for the PRB, evaluating its performance, and provide clues as to the reasons for the PRB's underperformance in certain locations. © 2008 Wiley Periodicals, Inc.     

Modeling of water quality downgradient of a mulch biowall

Groundwater treatment biowalls may be located close to a surface water body to prevent contaminant discharge from a groundwater plume into the surface water. Groundwater contaminants passing through the biowall are treated within the biowall or immediately downgradient of the biowall. Biowalls designed and constructed for the treatment of chlorinated solvents typically contain either a solid and/or liquid source of organic carbon to promote contaminant degradation by enhanced anaerobic reductive dechlorination. Common solid organic materials in biowalls include wood mulch or similar waste plant material, and common liquid organic materials are vegetable oil (possibly emulsified) or other long‐chain fatty acids. Such biowalls then develop anaerobic conditions in the constructed biowall volume, and potentially downgradient, as dissolved oxygen originally present in the aquifer is consumed. This groundwater condition can lead to the appearance of sulfide if groundwater influent to the biowall contains moderate to high sulfate concentrations. Other researchers have presented evidence for groundwater conditions downgradient of a biowall or a permeable reactive barrier (PRB) that are altered in relation to groundwater quality, besides the desired effect of contaminant degradation or removal by precipitation. The objective of this work was to investigate with modeling the changes in downgradient groundwater species chemistry as a result of a constructed biowall. This was accomplished with a chemical species model to predict levels of sulfate and sulfide present in groundwater in close downgradient proximity to the biowall. The results indicate that downgradient chemical changes could impact a surface water body to which groundwater discharges. The model described could be enhanced by incorporating additional design variables that should be considered in biowall feasibility assessments.     

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.     

Re‐evaluation of treatment approach for a site contaminated with Freon‐113 and 1,1,1‐trichloroethane

This study demonstrates a remedial approach for completing the remediation of an aquifer contaminated with 1,1,2‐trichlorotrifluoroethane (Freon‐113) and 1,1,1‐trichloroethane (TCA). In 1987, approximately 13,000 pounds of Freon‐113 were spilled from a tank at an industrial facility located in the state of New York. The groundwater remediation program consisted of an extraction system coupled with airstripping followed by natural attenuation of residual contaminants. In the first phase, five recovery wells and an airstripping tower were operational from April 1993 to August 1999. During this time period over 10,000 pounds of CFC‐13 and 200 pounds of TCA were removed from the groundwater and the contaminant concentrations decreased by several orders of magnitude. However, the efficiency of the remediation system to recover residual Freon and/or TCA reduced significantly. This was evidenced by: (1) low levels (< 10 ppb) of Freon and TCA captured in the extraction wells and (2) a slight increase of Freon and/or TCA in off‐site monitoring wells. A detailed study was conducted to evaluate the alternative for the second‐phase remediation. Results of a two‐year groundwater monitoring program indicated the contaminant plume to be stable with no significant increase or decrease in contaminant concentrations. Monitored geochemical parameters suggest that biodegradation does not influence the fate and transport of these contaminants, but other mechanisms of natural attenuation (primarily sorption and dilution) appear to control the fate and transport of these contaminants. The contaminants appear to be bound to the soil matrix (silty and clay units) with limited desorption as indicated by the solid phase analyses of contaminant concentrations. Results of fate and transport modeling indicated that contaminant concentrations would not exceed the action levels in the wells that showed a slight increase in contaminant concentrations and in the downgradient wells (sentinel) during the modeled timeframe of 30 years. This feasibility study for natural attenuation led to the termination of the extraction system and a transaction of the property, resulting in a significant financial benefit for the original site owner. © 2003 Wiley Periodicals, Inc.     

Chloroethene dechlorination in acidic groundwater: Implications for combining fenton's treatment with natural attenuation

A sulfuric acid leak in 1988 at a chloroethene‐contaminated groundwater site at the Naval Air Station Pensacola has resulted in a long‐term record of the behavior of chloroethene contaminants at low pH and a unique opportunity to assess the potential impact of source area treatment technologies, which involve acidification of the groundwater environment (e.g., Fenton's‐based in situ chemical oxidation), on downgradient natural attenuation processes. The greater than 75 percent decrease in trichloroethene (TCE) concentrations and the shift in contaminant composition toward predominantly reduced daughter products (dichloroethene [DCE] and vinyl chloride [VC]) that were observed along a 30‐m groundwater flow path characterized by highly acidic conditions (pH = 3.5 ± 0.4) demonstrated that chloroethene reductive dechlorination can continue to be efficient under persistent acidic conditions. The detection of Dehalococcoides‐type bacteria within the sulfuric acid/chloroethene co‐contaminant plume was consistent with biotic chloroethene reductive dechlorination. Microcosm studies conducted with ¹⁴C‐TCE and ¹⁴C‐VC confirmed biotic reductive dechlorination in sediment collected from within the sulfuric acid/chloroethene co‐contaminant plume. Microcosms prepared with sediment from two other locations within the acid plume, however, demonstrated only a limited mineralization to ¹⁴CO₂ and ¹⁴CO, which was attributed to abiotic degradation because no significant differences were observed between experimental and autoclaved control treatments. These results indicated that biotic and abiotic mechanisms contributed to chloroethene attenuation in the acid plume at NAS Pensacola and that remediation techniques involving acidification of the groundwater environment (e.g., Fenton's‐based source area treatment) do not necessarily preclude efficient chloroethene degradation. © 2007 Wiley Periodicals, Inc.     

Combined MODFLOW‐FRACTRAN Application to Assess Chlorinated Solvent Transport and Remediation in Fractured Sedimentary Rock

Detailed field investigations and numerical modeling were conducted to evaluate transport and fate of chlorinated solvent contamination in a fractured sedimentary bedrock aquifer (sandstone/siltstone/mudstone) at a Superfund site in central New Jersey. Field investigations provided information on the fractured rock system hydrogeology, including hydraulic gradients, bulk hydraulic conductivity, fracture network, and rock matrix, and on depth discrete contaminant distribution in fractures (via groundwater sampling) and matrix (via detailed subsampling of continuous cores). The numerical modeling endeavor involved application of both an equivalent porous media (EPM) model for flow and a discrete fracture network (DFN) model for transport. This combination of complementary models, informed by appropriate field data, allowed a quantitative representation of the conceptual site model (CSM) to assess relative importance of various processes, and to examine efficacy of remedial alternatives. Modeling progressed in two stages: first a large‐scale (20 km x 25 km domain) 3‐D EPM flow model (MODFLOW) was used to evaluate the bulk groundwater flow system and contaminant transport pathways under historic and current aquifer stress conditions and current stresses. Then, results of the flow model informed a 2‐D DFN transport model (FRACTRAN) to evaluate transport along a 1,000‐m flowpath from the source represented as a 2‐D vertical cross‐section. The combined model results were used to interpret and estimate the current and potential future extent of rock matrix and aqueous‐phase contaminant conditions and evaluate remedial strategies. Results of this study show strong effects of matrix diffusion and other processes on attenuating the plume such that future impacts on downgradient well fields under the hydraulic stresses modeled should be negligible. Results also showed futility of source remediation efforts in the fractured rock, and supported a technical impracticability (TI) waiver for the site. © 2013 Wiley Periodicals, Inc.     

In situ soil stabilization for source control of a lithium and bromate groundwater plume

Historic mineral ore processing operations at the former Cyprus Foote Mineral Site located in East Whiteland Township, Pennsylvania, have resulted in the creation of an approximately 10,000‐foot‐long off‐site groundwater plume impacted with lithium and bromate. The plume emanating from the site is impacting the groundwater quality of downgradient private residences. As an early part of the remedial implementation, the private residences were provided with public water connections while the source control efforts were being designed and implemented. Bromate and lithium have recently emerged as groundwater contaminants subjected to increased regulatory scrutiny. This is evidenced in a recently lowered Federal Maximum Contaminant Level (MCL) for bromate of 0.010 milligrams per liter and a Medium‐Specific Concentration (MSC) of 0.005 mg/L for lithium recently proposed by the Pennsylvania Department of Environmental Protection (PADEP) for all groundwater within the Commonwealth. Elevated concentrations for bromate and lithium were detected above the Proposed Remediation Goals (PRGs) for the site, MCLs, and MSCs at a distance of 7,300 feet and 9,200 feet from the source area, respectively. To reduce the contaminant concentrations within the groundwater plume, which will ultimately result in a regressing plume, and to enable the Brownfield redevelopment of this Superfund site, auger‐based, in situ soil stabilization (ISS) with depths of up to 75 feet below ground surface (bgs) was selected as the remedy. The remedial implementation required the temporary removal and relocation of over 100,000 cubic yards of overburden to expose the lithium‐bearing tailings prior to treatment. Using customized 90‐foot‐long, 9‐foot‐diameter augers attached to cranes and drilling platforms, ancillary support excavators, and approximately 21,000 tons of reagent; 2,019 ISS columns were advanced to depths ranging from 10 to 74 feet bgs. This resulted in the creation of an in situ low‐permeablity 117,045‐yd³ “quasi‐monolith,” which encompasses a lateral extent of approximately three acres. The integration of a comprehensive ISS design with a comprehensive long‐term groundwater‐monitoring plan ensured the success of the ISS implementation and will enable a continued evaluation of the off‐site groundwater quality. © 2009 Wiley Periodicals, Inc.     

Construction of a permeable reactive barrier in a residential neighborhood

In June 2001, the Massachusetts Department of Environmental Protection (DEP) installed a permeable reactive barrier (PRB) within a roadway in Needham, Massachusetts, to treat a plume of chlorinated solvents migrating toward two public water‐supply wells located in the adjacent town of Wellesley, Massachusetts. The solvents originated from an electronics manufacturer located approximately 2,300 feet upgradient of the roadway and 5,200 feet upgradient of the public supply wells. Chlorinated solvents, primarily trichloroethene (TCE), had migrated past the roadway to within 300 feet of the public supply wells. Two contaminant transport models prepared by the DEP's design contractor and the EPA indicated that the plume would reach the well field if no response actions were taken. To mitigate the future impact to the municipal well field, the DEP decided to install a PRB composed of zero‐valent granular iron across the path of the plume along Central Avenue in Needham. Though several dozen PRBs have been installed at sites worldwide and the technology is no longer considered innovative, the application of the technology in a roadway that receives 17,000 vehicles per day within a residential neighborhood is unique and presented difficulties not typically associated with PRB installations. The Needham PRB was also one of the first zero‐valent iron PRBs installed using the slurry trench method to treat chlorinated compounds. © 2002 Wiley Periodicals, Inc.     

Innovative applications of subgrade biogeochemical reactors: Three case studies

Subgrade biogeochemical reactors (SBGRs) are an in situ remediation technology shown to be effective in treating contaminant source areas and groundwater hot spots, while being sustainable and economical. This technology has been applied for over a decade to treat chlorinated volatile organic compound source areas where groundwater is shallow (e.g., less than approximately 30 feet below ground surface [ft bgs]). However, this article provides three case studies describing innovative SBGR configurations recently developed and tested that are outside of this norm, which enable use of this technology under more challenging site conditions or for treatment of alternative contaminant classes. The first SBGR case study addresses a site with groundwater deeper than 30 ft bgs and limited space for construction, where an SBGR column configuration reduced the maximum trichloroethene (TCE) groundwater concentration from 9,900 micrograms per liter (μg/L) to <1 μg/L (nondetect) within approximately 15 months. The second SBGR is a recirculating trench configuration that is supporting remediation of a 5.7‐acre TCE plume, which has significant surface footprint constraints due to the presence of endangered species habitat. The third SBGR was constructed with a new amendment mixture and reduced groundwater contaminant concentrations in a petroleum hydrocarbon source area by over 97% within approximately 1 year. Additionally, a summary is provided for new SBGR configurations that are planned for treatment of additional classes of contaminants (e.g., hexavalent chromium, 1,4‐dioxane, dissolved explosives constituents, etc.). A discussion is also provided describing research being conducted to further understand and optimize treatment mechanisms within SBGRs, including a recently developed sampling approach called the aquifer matrix probe.     

Natural attenuation with varying degrees of aquifer heterogeneity: Implications for groundwater monitoring

This study evaluated the effect of heterogeneity in hydraulic conductivity on the tendency for contaminant plumes to attenuate via dilution, hydrodynamic dispersion, and molecular diffusion in simulated aquifers. Simulations included one homogeneous and four increasingly heterogeneous hydraulic conductivity fields. A numerical mass transport model generated an initial contaminant plume for each case; all initial plumes had the same mass. Next, the model simulated plume migrations through the simulated aquifers. Results suggest that highly heterogeneous settings are potentially effective at plume attenuation. Low‐velocity zones in heterogeneous settings delay plume travel, enabling more time for natural processes to lower contaminant concentrations in groundwater. © 2012 Wiley Periodicals, Inc.     

Designing funnel‐and‐gate groundwater remediation systems near property corners

Numerical models were used to simulate alternative funnel‐and‐gate groundwater remediation structures near property corners in hypothetical homogeneous and heterogeneous unconfined aquifers. Each structure comprised a highly permeable central gate (hydraulic conductivity = 25 m/d) and soil‐bentonite slurry walls (hydraulic conductivity = 0.00009 m/d). Gates were perpendicular to regional groundwater flow and approximately 5 m from a contaminant plume's leading tip. Funnel segments collinear to the central gate reached property boundaries; additional funnel segments followed property boundaries in the most hydraulically upgradient direction. Structures were 1 m thick and anchored into the base of the aquifer. Two structures were simulated for each aquifer: one with a 3.0‐m‐long central gate and funnels on either side; and a second with a 1.5‐m‐long central gate, funnels on either side, and 0.75‐m‐long end gates. Funnels were lengthened in successive simulations, until a structure contained a contaminant plume. Results suggest that, for the same total gate length, one‐gate structures may facilitate more rapid remediation, up to 44 percent less time in trials conducted in this study, than multiple‐gate structures constructed near property corners. However, in order to effectively contain a plume, one‐gate structures were up to 46 percent larger than multiple‐gate structures. © 2011 Wiley Periodicals, Inc.     

The Use of Natural Systems to Remediate Groundwater: Department of Energy Experience at the Savannah River Site

Natural remediation is moving toward the forefront as engineers clean groundwater at the Savannah River Site (SRS), a major Department of Energy (DOE) installation near Aiken, South Carolina. This article reviews two successful, innovative remediation methods currently being deployed: biosparging to treat chlorinated solvents and phytoremediation to address tritium in groundwater. The biosparging system reintroduces oxygen into the groundwater and injects nutrient compounds for in‐situ remediation. The system has greatly reduced the concentrations of trichloroethylene (TCE) and vinyl chloride in wells downgradient from a sanitary landfill (SLF). Phytoremediation is an emerging technology that promises effective and inexpensive cleanup of certain hazardous wastes. Using natural processes, plants can break down, trap and hold, or transpire contaminants. This article discusses the use of phytoremediation to reduce the discharge of tritium to an on‐site stream at SRS. © 2002 Wiley Periodicals Inc. *     

Performance assessment of hanging funnel‐and‐gate structures designed by reverse particle tracking for capturing polluted groundwater

The objective of this study was to evaluate the capability of partially penetrating (hanging) funnel‐and‐gate structures, designed using reverse flow trajectories, for capturing plumes of contaminated groundwater. Linear capture structures, comprised of two slurry cutoff walls on either side of a permeable gate, were positioned perpendicular to regional groundwater flow in a hypothetical unconfined aquifer. A four‐step approach was used for each of two simulated settings: (1) a numerical mass transport model generated a contaminant plume originating from a source area; (2) a particle‐tracking model projected groundwater flow paths upstream from a treatment gate; (3) the structure was widened and deepened until bounding path lines contained the plume; and (4) mass transport simulation tested the ability of the structure to capture the plume. Results of this study suggest that designing funnel‐and‐gate structures using reverse particle tracking may result in too small a structure to capture a contaminant plume. This practice generally ignores effects of hydrodynamic dispersion, which may enlarge plumes such that contaminants move beneath or around a capture structure. This bypassing effect may be considerable even for low values of dispersivity. Particle‐tracking approaches may also underestimate the amount of time required to reduce contaminant concentrations to acceptable levels. © 2007 Wiley Periodicals, Inc.     

In-Situ Fenton-Like Oxidation of Volatile Organics: Laboratory,Pilot, and Full-Scale Demonstrations

Laboratory, pilot, and full-scale experiments were used to evaluate and optimize the ISOTEC^SM remedial process at a warehousing facility in Union, New Jersey. Based on modified Fenton's oxidative chemistry, the ISOTEC^SM process uses a proprietary catalytic agent that delays formation of reactive hydroxyl radicals. This allows adequate dispersion of the hydroxyl radicals, which is an oxidizing agent, throughout a contaminant plume. Ground-water at the site was contaminated with high levels of gasoline and waste oil constituents, principally BTEX and MTBE. Bench scale microcosm studies were used to evaluate the appropriate site-specific stoichiometric relationships between catalyst, stabilizers, and oxidizers; the effect of contaminant type and concentration; and the pH optima. Based on results of the laboratory studies, a pilot-scale study was performed at the site. One injection point for catalyst, stabilizers, and oxidant was installed in the contaminated zone at the site, with one hydraulically connected downgradient well used for monitoring. A single treatment of the reagents in the optimal stoichiometry determined from the laboratory study was injected in-situ over a period of three days. A 98.5 percent reduction in volatile organics was observed in the area treated, with the radial extent of treatment estimated to be approximately 20 feet, based on the presence of hydroxyl radicals detected in hydraulically connected areas and at the surface. The full-scale process employed six injection points and three treatment cycles over a three-month period. Subsequent to treatment, contaminant levels were either nondetectable or were reduced to below applicable New Jersey groundwater standards, with regulatory closure on the site achieved in less than one year.     

Insufficient source area remediation results in the rebound of TCE breakdown products in groundwater

In the early 1990s, a soil removal action was completed at a former disposal pit site located in southern Michigan. This action removed waste oil, cutting oil, and chlorinated solvents from the unsaturated zone. To contain groundwater contaminant migration at the site, a groundwater pump‐and‐treat system comprised of two extraction wells operating at a combined flow of 50 gallons per minute, carbon treatment, and a permitted effluent discharge was designed, installed, and operated for over 10 years. Groundwater monitoring for natural attenuation parameters and contaminant attenuation modeling demonstrated natural attenuation of the contaminant plume was adequate to attain site closure. As a result of incomplete contaminant source removal, a rebound of contaminants above the levels established in the remedial action plan (RAP) has occurred in the years following system shutdown and site closure. Groundwater concentrations have raised concerns regarding potential indoor air quality at adjacent residential properties constructed in the past 9 to 10 years. The only remedial option available in the original RAP is to resume groundwater pump‐and‐treat. To remediate the source area, an alternate remediation strategy using an ozone sparge system was developed. The ozone sparge remediation strategy addresses the residual saturated zone contaminants beneath the former disposal pit and reestablishes site closure requirements without resumption of the pump‐and‐treat system. A pilot study was completed successfully; and the final system design was subsequently approved by the Michigan Department of Environmental Quality. The system was installed and began operations in July 2010. As of the January 2011 monitoring event, the system has shown dramatic improvement in site contaminant concentrations. The system will continue to operate until monitoring results indicate that complete treatment has been obtained. The site will have achieved the RAP objectives when the system has been shut down and meets groundwater residential criteria for four consecutive quarters. © 2011 Wiley Periodicals, Inc.     

Implications of MTBE for Intrinsic Remediation of Underground Fuel Tank Sites

MTBE in groundwater has been shown to travel over 1,000 feet downgradient from its source in several comprehensive field studies conducted across North America. The biodegradability of MTBE is examined by summarizing all the significant literature on the subject and by detailing the findings of recent field investigations of MTBE transport. In Orange County, California, the persistence of MTBE is analyzed and statistical representations of source variability are presented. Regional and far field transport of MTBE in groundwater sourced from underground gasoline storage tanks are summarized in comprehensive tables of frequency and plume length. Estimates of source mass and duration allow for comparison of associated plume size. The conclusion reached after reviewing all the available literature on MTBE is that its biodegradability seems slight and the size of the plumes are surprisingly large. Intrinsic or natural attenuation remedies for MTBE merit close scrutiny.     

Matrix Diffusion Modeling Applied to Long‐Term Pump‐and‐Treat Data: 1. Method Development

Despite the installation in the 1980s and 1990s of hydraulic containment systems around known source zones (four slurry walls and ten pump‐and‐treat systems), trichloroethene (TCE) plumes persist in the three uppermost groundwater‐bearing units at the Middlefield‐Ellis‐Whisman (MEW) Superfund Study Area in Mountain View, California. In analyzing TCE data from 15 recovery wells, the observed TCE mass discharge decreased less than an order of magnitude over a 10‐year period despite the removal of an average of 11 pore volumes of affected groundwater. Two groundwater models were applied to long‐term groundwater pump‐and‐treat data from 15 recovery wells to determine if matrix diffusion could explain the long‐term persistence of a TCE plume. The first model assumed that TCE concentrations in the plume are controlled only by advection, dispersion, and retardation (ADR model). The second model used a one‐dimensional diffusion equation in contact with two low‐permeability zones (i.e., upper and lower aquitard) to estimate the potential effects of matrix diffusion of TCE into and out of low‐permeability media in the plume. In all 15 wells, the matrix diffusion model fit the data much better than the ADR model (normalized root mean square error of 0.17 vs. 0.29; r² of 0.99 vs. 0.19), indicating that matrix diffusion is a likely contributing factor to the persistence of the TCE plume in the non‐source‐capture zones of the MEW Study Area's groundwater‐extraction wells. © 2013 Wiley Periodicals, Inc.     

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.