Long‐Term Impacts on Groundwater and Reductive Dechlorination Following Bioremediation in a Highly Characterized Trichloroethene DNAPL Source Area

High‐resolution soil and groundwater monitoring was performed to assess the long‐term impacts of bioremediation using bioaugmentation with a dechlorinating microbial consortium (and sodium lactate as the electron donor) in a well‐characterized trichloroethene (TCE) dense nonaqueous phase liquid (DNAPL) source area. Monitoring was performed up to 3.7 years following active bioremediation using a high‐density monitoring network that included several discrete interval multi‐level sampling wells. Results showed that despite the absence of lactate, lactate fermentation transformation products, or hydrogen, biogeochemical conditions remained favorable for the reductive dechlorination of chlorinated ethenes. In locations where soil data showed that TCE DNAPL sources persisted, local contaminant rebound was observed in groundwater, whereas no rebound or continuous decreases in chlorinated ethenes were observed in locations where DNAPL sources were treated. While ethene levels measured 3.7 years after active treatment suggested relatively low (2 to 30%) dechlorination of the parent TCE and daughter products, carbon stable isotope analysis showed that the extent of complete dechlorination was much greater than indicated by ethene generation and that the estimated first‐order rate constant describing the complete dechlorination of TCE at 3.7 years following active bioremediation was approximately 3.6 y–1. Overall, results of this study suggest that biological processes may persist to treat TCE for years after cessation of active bioremediation, thereby serving as an important component of remedial treatment design and long‐term attenuation.     

Biological reduction of chlorinated solvents: Batch-scale geochemical modeling

Simulation of biodegradation of chlorinated solvents in dense non-aqueous phase liquid (DNAPL) source zones requires a model that accounts for the complexity of processes involved and that is consistent with available laboratory studies. This paper describes such a comprehensive modeling framework that includes microbially mediated degradation processes, microbial population growth and decay, geochemical reactions, as well as interphase mass transfer processes such as DNAPL dissolution, gas formation and mineral precipitation/dissolution. All these processes can be in equilibrium or kinetically controlled. A batch modeling example was presented where the degradation of trichloroethene (TCE) and its byproducts and concomitant reactions (e.g., electron donor fermentation, sulfate reduction, pH buffering by calcite dissolution) were simulated. Local and global sensitivity analysis techniques were applied to delineate the dominant model parameters and processes. Sensitivity analysis indicated that accurate values for parameters related to dichloroethene (DCE) and vinyl chloride (VC) degradation (i.e., DCE and VC maximum utilization rates, yield due to DCE utilization, decay rate for DCE/VC dechlorinators) are important for prediction of the overall dechlorination time. These parameters influence the maximum growth rate of the DCE and VC dechlorinating microorganisms and, thus, the time required for a small initial population to reach a sufficient concentration to significantly affect the overall rate of dechlorination. Self-inhibition of chlorinated ethenes at high concentrations and natural buffering provided by the sediment were also shown to significantly influence the dechlorination time. Furthermore, the analysis indicated that the rates of the competing, nonchlorinated electron-accepting processes relative to the dechlorination kinetics also affect the overall dechlorination time. Results demonstrated that the model developed is a flexible research tool that is able to provide valuable insight into the fundamental processes and their complex interactions during bioremediation of chlorinated ethenes in DNAPL source zones.     

Experimental Study of the Effects of DNAPL Distribution on Mass Rebound

The release of stored dissolved contaminants from low permeability zones contributes to plume persistence beyond the time when dense nonaqueous phase liquid (DNAPL) has completely dissolved. This is fundamental to successfully meeting acceptable low concentrations in groundwater that are driven by site‐specific cleanup goals. The study goals were to assess the role of DNAPL entrapment morphology on mass storage and plume longevity. As controlled field studies are not feasible, two‐dimensional (2D) test tanks were used to quantify the significance of mass loading processes from source dissolution and stored mass rebound. A simple two‐layer soil domain representing a high permeable formation sand overlying a zone of lower permeability sand was used in the tests. DNAPL mass depletion through dissolution was monitored via X‐ray photon attenuation, and effluent samples were used to monitor the plume. These data enabled analysis of the DNAPL distribution, the dissolved plume, and the dissolved phase distribution within the low permeability layer. Tests in an intermediate tank showed that mass storage contributes substantially to plume longevity. Detectable effluent concentrations persisted long after DNAPL depletion. The small tank results indicated that the DNAPL morphology influenced the flow field and caused distinctive transport mechanisms contributing to mass storage. Zones of high DNAPL saturation at the interface between the low and high permeability layers exhibited flow bypassing and diffusion dominated transport into the low permeability layer. In the absence of a highly saturated DNAPL zone near the soil interface the contaminant penetrated deeper into the low permeability layer caused by a combination of advection and diffusion.     

Pulsed Air Sparging in Aquifers Contaminated with Dense Nonaqueous Phase Liquids

Air sparging was evaluated for remediation of tetrachloroethylene (PCE) present as dense nonaqueous phase liquid (DNAPL) in aquifers. A two-dimensional laboratory tank with a transparent front wall allowed for visual observation of DNAPL mobilization. A DNAPL zone 50 cm high was created, with a PCE pool accumulating on an aquitard. Detailed process control and analysis yielded accurate mass balances and insight into the mass-transfer limitations during air sparging. Initial PCE recovery rates were high, corresponding to fast removal of residual DNAPL within the zone influenced directly by air channels. The vadose zone DNAPL was removed within a few days, and the recovery in the extracted soil vapors decreased to low values. Increasing the sparge rate and pulsing the air injection led to improved mass recovery, as the pulsing induced water circulation and increased the DNAPL dissolution rate. Dissolved PCE concentrations both within and outside the zone of air channels were affected by the pulsing. Inside the sparge zone, aqueous concentrations decreased rapidly, matching the declining effluent PCE flux. Outside the sparge zone, PCE concentrations increased because highly contaminated water was pushed away from the air injection point. This overall circulation of water may lead to limited spreading of the contaminant, but accelerated the time-weighted average mass removal by 40% to 600%, depending on the aggressiveness of the pulsing. For field applications, pulsing with a daily or diurnal cycling time may increase the average mass removal rate, thus reducing the treatment time and saving in the order of 40% to 80% of the energy cost used to run the blowers. However, air sparging will always fail to remove DNAPL pools located below the sparge point because the air will rise upward from the top of a screen, unless very localized geological layers force the air to migrate horizontally. Unrecognized presence of DNAPL at chlorinated solvent sites residual and pools could potentially hamper success of air sparging cleanups, since the presence of small DNAPL pools, ganglia or droplets can greatly extend the treatment time.     

Investigation and Remediation of a 1,2–Dichloroethane Spill Part I: Short and Long-Term Remediation Strategies

Release of an estimated 150,000 gallons (568,000 L).of 1.2–dichloroethane (EDC) from a buried pipeline into a ditch and surrounding soil resulted in shallow subsurface contamination of a Gulf Coast site. Short-term remediation included removal of EDC DNAPI. (dense nonaqueous phase liquid) by dredging and vacuuming the ditch, and by dredging the river where the ditch discharged. EDC saturation in shallow impacted sediments located beneath the ditch was at or below residual saturation and these sediments were therefore left in place. The ditch was lined, backfilled, and capped. Long-term remediation includes EDC DNAPL recovery and hydraulic containment from the shallow zone with long-term monitoring of the shallow, intermediate, and deep (200 foot) aquifers. Ground water, DNAPL., and dissolved phase models were used to guide field investigations and the selection of an effective remedial action strategy. The DNAPL. modeling was conducted for a two-dimensional vertical cross section of the site, and included the three aquifers separated by two aquitards with microfractures. These aquitards were modeled using a dual porosity approach. Matrix and fracture properties of the aquitards used for DNAPL modeling were determined from small-scale laboratory properties. These properties were consistent with effective hydraulic conductivity determined from ground water flow modeling. A sensitivity analysis demonstrated that the vertical migration of EDC was attenuated by dissolution of EDC into the matrix of the upper aquitard. When the organic/water entry pressure of the aquitard matrix, or the solubility of EDC were decreased to unrealislically low values. EDC DNAPL. accumulated in the aquifer below the upper aquitard.
EDC DNALM, did not reach the regional (deepest) aquifer in any of the cases modeled. The limited extent of vertical EDC migration predicted is supported by ground water monitoring conducted over the four years since the spill.     

Performance of Full‐Scale Enhanced Reductive Dechlorination in Clay Till

At a low permeability clay till site contaminated with chlorinated ethenes (Gl. Kongevej, Denmark), enhanced reductive dechlorination (ERD) was applied by direct push injection of molasses and dechlorinating bacteria. The performance was investigated by long‐term groundwater monitoring, and after 4 years of remediation, the development of degradation in the clay till matrix was investigated by high‐resolution subsampling of intact cores. The formation of degradation products, the presence of specific degraders Dehalococcoides spp. with the vinyl chloride (VC) reductase gene vcrA, and the isotope fractionation of trichloroethene, cis‐dichloroethene (cis‐DCE), and VC showed that degradation of chlorinated ethenes occurred in the clay till matrix as well as in sand lenses, sand stringers, and fractures. Bioactive sections of up to 1.8 m had developed in the clay till matrix, but sections, where degradation was restricted to narrow zones around sand lenses and stringers, were also observed. After 4 years of remediation, an average mass reduction of 24% was estimated. Comparison of the results with model simulation scenarios indicate that a mass reduction of 85% can be obtained within approximately 50 years without further increase in the narrow reaction zones if no donor limitations occur at the site. Long‐term monitoring of the concentration of chlorinated ethenes in the underlying chalk aquifer revealed that the aquifer was affected by the more mobile degradation products cis‐DCE and VC generated during the remediation by ERD.     

Oxygen and Ethene Biostimulation for a Persistent Dilute Vinyl Chloride Plume

Contamination of groundwater with chlorinated ethenes is common and represents a threat to drinking water sources. Standard anaerobic bioremediation methods for the highly chlorinated ethenes PCE and TCE are not always effective in promoting complete degradation. In these cases, the target contaminants are degraded to the daughter products DCE and/or vinyl chloride. This creates an additional health risk, as vinyl chloride is even more toxic and carcinogenic than its precursors. New treatment modalities are needed to deal with this widespread environmental problem. We describe successful bioremediation of a large, migrating, dilute vinyl chloride plume in Massachusetts with an aerobic biostimulation treatment approach utilizing both oxygen and ethene. Initial microcosm studies showed that adding ethene under aerobic conditions stimulated the rapid degradation of VC in site groundwater. Deployment of a full‐scale treatment system resulted in plume migration cutoff and nearly complete elimination of above‐standard VC concentrations.     

Demonstration of Enhanced Bioremediation in a TCE Source Area at Launch Complex 34, Cape Canaveral Air Force Station

The ability of bioremediation to treat a source area containing trichloroethene (TCE) present as dense nonaqueous phase liquid (DNAPL) was assessed through a laboratory study and a pilot test at Launch Complex 34, Cape Canaveral Air Force Center. The results of microcosm testing indicate that the indigenous microbial community was capable of dechlorinating TCE to ethene if amended with electron donor; however, bioaugmentation with a dechlorinating culture (KB-1; SiREM, Guelph, Ontario, Canada) significantly increased the rate of ethene formation. In microcosms, the activity of the dechlorinating organisms in KB-1 was not inhibited at initial TCE concentrations as high as 2 mM. The initially high TCE concentration in ground water (1.2 mM or 155 mg/L) did not inhibit reductive dechlorination, and at the end of the study, the average concentration of ethene (2.4 mM or 67 mg/L) was in stoichiometric excess of this initial TCE concentration. The production of ethene in stoichiometric excess in comparison to the initial TCE concentration indicates that the bioremediation treatment enhanced the removal of TCE mass (either sorbed to soil or present as DNAPL). Detailed soil sampling indicated that the bioremediation treatment removed greater than 98.5% of the initial TCE mass. Confirmatory ground water samples collected 22 months after the bioremediation treatment indicated that chloroethene concentrations had continued to decline in the absence of further electron donor addition. The results of this study confirm that dechlorination to ethene can proceed at the high TCE concentrations often encountered in source areas and that bioremediation was capable of removing significant TCE mass from the test plot, suggesting that enhanced bioremediation is a potentially viable remediation technology for TCE source areas. Dehalococcoides abundance increased by 2 orders of magnitude following biostimulation and bioaugmentation.     

Field Demonstration of the Horizontal Treatment Well (HRX Well®) for Passive In Situ Remediation

The horizontal reactive media treatment well (HRX Well®) uses directionally drilled horizontal wells filled with a treatment media to induce flow-focusing behavior created by the well-to-aquifer permeability contrast to passively capture proportionally large volumes of groundwater. Groundwater is treated in situ as it flows through the HRX Well and downgradient portions of the aquifer are cleaned via elution as these zones are flushed with clean water discharging from the HRX Well. The HRX Well concept is particularly well suited for sites where long-term mass discharge control is a primary performance objective. This concept is appropriate for recalcitrant and difficult-to-treat constituents, including chlorinated solvents, per- and polyfluoroalkyl substances (PFAS), 1,4-dioxane, and metals. A full-scale HRX Well was installed and operated to treat trichloroethene (TCE) with zero valent iron (ZVI). The model-predicted enhanced flow through the HRX Well (compared to the flow in and equivalent cross-sectional area orthogonal to flow in the natural formation before HRX Well installation) and treatment zone width was consistent with flows and widths estimated independently by point velocity probe (PVP) testing, HRX Well tracer testing, and observed treatment in downgradient monitoring wells. The actual average capture zone width was estimated to be between 45 and 69 feet. Total TCE mass discharge reduction was maintained through the duration of the performance monitoring period and exceeded 99.99% (%). Decreases in TCE concentrations were observed at all four downgradient monitoring wells within the treatment zone (ranging from 50 to 74% at day 436), and the first arrival of treated water was consistent with model predictions. The field demonstration confirmed the HRX Well technology is best suited for long-term mass discharge control, can be installed under active infrastructure, requires limited ongoing operation and maintenance, and has low life cycle energy and water requirements.     

Phytoscreening for Vinyl Chloride in Groundwater Discharging to a Stream

This study applies an optimized phytoscreening method to locate a chlorinated ethene plume discharging into a stream. To evaluate the conditions most suitable for successful phytoscreening, trees along the stream bank were monitored through different seasons with different environmental conditions and hence different uptake/loss scenarios. Vinyl chloride (VC) as well as cis‐dichloroethylene (cis‐DCE), trichloroethylene (TCE), and tetrachloroethylene (PCE) were detected in the trees, documenting that phytoscreening is a viable method to locate chlorinated ethene plumes, including VC, discharging to streams. The results reveal, that phytoscreening for VC is more sensitive to environmental conditions affecting transpiration than for the other chlorinated ethenes detected. Conditions leading to higher groundwater uptake by transpiration than contaminant loss by diffusion from the tree trunks are optimal (e.g., low relative humidity, plentiful hours of sunshine and an intermediate air temperature). Additionally, low precipitation prior to the sampling event is beneficial, as uptake of infiltrating precipitation dilutes the concentration in the trees. All chlorinated ethenes were sensitive to dilution by clean precipitation and in some months, this resulted in no detection of contaminants in the trees at all. Under optimal environmental conditions the tree cores allowed detection of chlorinated solvents and their metabolites in the underlying groundwater. Whereas, for less ideal conditions there was a risk of no detection of the more volatile VC. This study is promising for the future applicability of phytoscreening to locate shallow groundwater contamination with the degradation products of chlorinated solvents.     

Attenuation of a Mixed Chromium and Chlorinated Etjeme Ground Wate Plume in Estuarine Influenced Glaciated Sediments

The natural attenuation behavior of a ground water contaminant plume containing chromium and chlorinated ethenes in glaciated sediments was assessed using traditional and nontraditional methods. The mixed waste is transported through and attenuated within an estuarine influenced ground water aquifer of spatially varying redox character and organic carbon content. Contaminant fate and speciation were assessed as a function of geochemical conditions. Total, speciation-based, and sequential chemical extraction analyses were performed to determine contaminant partitioning and the redox capacity of the aquifer. Chromium speciation and partitioning were correlated with the reductive capacity and redox conditions of the aquifer sediments spatially distributed within the aquifer. Reductive dechlorination and partitioning of chlorinated ethenes were correlated with the organic carbon content and redox conditions of the aquifer sediments. The data showed that sharp redox gradients existed within the aquifer. Active reduction and retardation of both chromium and chlorinated ethenes was exhibited. The aqueous hexavalent chromium concentrations decreased to near nondetect levels in the vicinity of the receptor, whereas degradation products of higher-order chlorinated ethenes increased as a fraction of the total chlorinated ethene concentrations along the length of the plume. The potential for competition for reducing power under specific cases within the aquifer was suggested by the data, highlighting the need to include contaminant interactions in natural attenuation assessments.     

Modeling metabolic reductive dechlorination in dense non-aqueous phase liquid source-zones

Recent laboratory experimental evidence has suggested that bioremediation may be an attractive management strategy for dense non-aqueous phase liquid (DNAPL) source-zones. In particular, metabolic reductive dechlorination has been shown to reduce aqueous phase chlorinated ethene contaminant concentrations and enhance DNAPL dissolution, reducing source longevity. Transitioning this technology from the laboratory to the field will be facilitated by tools capable of simulating bioenhanced dissolution. This work presents a mathematical model for metabolic reductive dechlorination in a macroscale two-phase (aqueous-organic) environment. The model is implemented through adaptation of an existing multi-phase compositional simulator, which has been modified to incorporate eight chemical components and four microbial populations: a fermentative population, two dechlorinating populations, and a competitor population (e.g., methanogens). Monod kinetics, modified to incorporate electron donor thresholds, electron acceptor competition, and competitor inhibition, are used to simulate microbial growth and component degradation. The developed model is numerically verified and demonstrated through comparisons with published column-scale dechlorination data. Dechlorination kinetics, electron donor concentrations, and DNAPL saturation and distribution are all found to affect the extent of dissolution enhancement, with enhancements ranging from 1.0 to ∼1.9. Comparison of simulation results with those from a simplified analytic modeling approach suggest that the analytical model may tend to over-predict dissolution enhancement and fail to account for the transient nature of dissolution enhancement, leading to significant (70%) under-prediction of source longevity.     

Assessing the Transport of Pharmaceutical Compounds in a Layered Aquifer Discharging to a Stream

A groundwater plume containing high concentrations of pharmaceutical compounds, mainly sulfonamides, barbiturates, and ethyl urethane, in addition to chlorinated ethenes and benzene was investigated. The contamination originating from a former pharmaceutical industry discharges into a multilayered aquifer system and a downgradient stream. In this study, geological and hydrogeological data were integrated into a numerical flow model to examine identified trends using statistical approaches, including principal component analysis and hierarchal cluster analysis. A joint interpretation of the groundwater flow paths and contaminant concentrations in the different compartments (i.e., groundwater and hyporheic zone) provided insight on the transport processes of the different contaminant plumes to the stream. The analysis of historical groundwater concentrations of pharmaceutical compounds at the site suggested these compounds are slowly degrading. The pharmaceutical compounds migrate in both a deep semiconfined aquifer, as well as in the shallow unconfined aquifer, and enter the stream along a 2-km stretch. This contrasted with the chlorinated ethenes, which mainly discharge to the stream as a focused plume from the unconfined aquifer. The integrated approach developed here, combining groundwater flow modeling and statistical analyses of the contaminant concentration data collected in groundwater and the hyporheic zone, lead to an improved understanding of the observed distribution of contaminants in the unconfined and semiconfined aquifers, and thus to their discharge to the stream. This approach is particularly relevant for large and long-lasting contaminant sources and plumes, such as abandoned landfills and industrial production sites, where field investigations may be very expensive.     

Integrity of Clay Till Aquitards to DNAPL Migration: Assessment Using Current and Emerging Characterization Tools

Field investigations were carried out to determine the occurrence of tetrachloroethene (PCE) dense nonaqueous phase liquid (DNAPL), the source zone architecture and the aquitard integrity at a 30‐ to 50‐year old DNAPL release site. The DNAPL source zone is located in the clay till unit overlying a limestone aquifer. The DNAPL source zone architecture was investigated through a multiple‐lines‐of‐evidence approach using various characterization tools; the most favorable combination of tools for the DNAPL characterization was geophysical investigations, membrane interface probe, core subsampling with quantification of chlorinated solvents, hydrophobic dye test with Sudan IV, and Flexible Liner Underground Technologies (FLUTe) NAPL liners with activated carbon felt (FACT). While the occurrence of DNAPL was best determined by quantification of chlorinated solvents in soil samples supported by the hydrophobic dye tests (Sudan IV and NAPL FLUTe), the conceptual understanding of source zone architecture was greatly assisted by the indirect continuous characterization tools. Although mobile or high residual DNAPL (S _t > 1%) only occurred in 11% of the source zone samples (intact cores), they comprised 86% of the total PCE mass. The dataset, and associated data analysis, supported vertical migration of DNAPL through fractures in the upper part of the clay till, horizontal migration along high permeability features around the redox boundary in the clay till, and to some extent vertical migration through the fractures in the reduced part of the clay till aquitard to the underlying limestone aquifer. The aquitard integrity to DNAPL migration was found to be compromised at a thickness of reduced clay till of less than 2 m.     

Transition probability/Markov chain analyses of DNAPL source zones and plumes

At sites where a dense nonaqueous phase liquid (DNAPL) was spilled or released into the subsurface, estimates of the mass of DNAPL contained in the subsurface from core or monitoring well data, either in the nonaqueous or aqueous phase, can be highly uncertain because of the erratic distribution of the DNAPL due to geologic heterogeneity. In this paper, a multiphase compositional model is applied to simulate, in detail, the DNAPL saturations and aqueous-phase plume migration in a highly characterized, heterogeneous glaciofluvial aquifer, the permeability and porosity data of which were collected by researchers at the University of Tübingen, Germany. The DNAPL saturation distribution and the aqueous-phase contaminant mole fractions are then reconstructed by sampling the data from the forward simulation results using two alternate approaches, each with different degrees of sampling conditioning. To reconstruct the DNAPL source zone architecture, the aqueous-phase plume configuration, and the contaminant mass in each phase, one method employs the novel transition probability/Markov chain approach (TP/MC), while the other involves a traditional variogram analysis of the sampled data followed by ordinary kriging. The TP/MC method is typically used for facies and/or hydraulic conductivity reconstruction, but here we explore the applicability of the TP/MC method for the reconstruction of DNAPL source zones and aqueous-phase plumes. The reconstructed geometry of the DNAPL source zone, the dissolved contaminant plume, and the estimated mass in each phase are compared using the two different geostatistical modeling approaches and for various degrees of data sampling from the results of the forward simulation. It is demonstrated that the TP/MC modeling technique is robust and accurate and is a preferable alternative compared to ordinary kriging for the reconstruction of DNAPL saturation patterns and dissolved-phase contaminant plumes.     

Numerical examination of the factors controlling DNAPL migration through a single fracture

The migration of five dense nonaqueous phase liquids (DNAPLs) through a single fracture in a clay aquitard was numerically simulated with the use of a compositional simulator. The effects of fracture aperture, fracture dip, matrix porosity, and matrix organic carbon content on the migration of chlorobenzene, 1,2-dichloroethylene, trichloroethylene, tetra-chloroethylene, and 1,2-dibromoethane were examined. Boundary conditions were chosen such that DNAPL entry into the system was allowed to vary according to the stresses applied. The aperture is the most important factor of those studied controlling the migration rate of DNAPL through a single fracture embedded in a clay matrix. Loss of mass to the matrix through diffusion does not significantly retard the migration rate of the DNAPL, particularly in larger aperture fractures (e.g., 50 microm). With time, the ratio of diffusive loss to the matrix to DNAPL flux into the fracture approaches an asymptotic value lower than unity. The implication is that matrix diffusion cannot arrest the migration of DNAPL in a single fracture. The complex relationships between density, viscosity, and solubility that, to some extent, govern the migration of DNAPL through these systems prevent accurate predictions without the use of numerical models. The contamination potential of the migrating DNAPL is significantly increased through the transfer of mass to the matrix. The occurrence of opposite concentration gradients within the matrix can cause dissolved phase contamination to exist in the system for more than 1000 years after the DNAPL has been completely removed from the fracture.     

DNAPL Characterization Methods and Approaches, Part 1: Performance Comparisons

Contamination from the use of chlorinated solvents, often classified as dense nonaqueous phase liquids (DNAPLs) when in an undissolved state, represents an environmental challenge with global implications. Mass-transfer limitations due to rate-limited dissolution can lead to long-term aquifer persistence for even small volumetric fractions. The identification of DNAPL source zones located beneath the water table is critical to ultimately achieve site remediation and aquifer restoration. This paper provides a comparison of the advantages and disadvantages of many of the methods being used for detecting and delineating DNAPL contaminant source zones. The objective is to determine which options are best to pursue based on site characteristics, method performance, and method costs. DNAPL characterization methods are grouped into approaches, which include site preparation, characterization, and data-processing activities necessary to design an effective remediation system. We compare the different approaches based on the level of chemical and hydrogeologic resolution, and the need for additional data requirements. Our findings can be used to assist with selection of appropriate site remediation management options.     

Comparison of Line-Drive and Push-Pull Flushing Schemes

The performance of cyclodextrin (CD)‐enhanced push‐pull (PP) and line‐drive (LD) approaches to remediation of a site contaminated with a multicomponent dense nonaqueous phase liquid (DNAPL) present in a surficial sandy aquifer was evaluated in this field study. The treatment techniques were compared to each other and to the projected performance of a conventional water‐flushing system. Performance was assessed based on contaminant mass removed per unit volume of extraction solution and per unit time of operation. As expected, the CD‐enhanced LD and PP approaches to remediation were more efficient than conventional flushing with water. Between the two techniques, the PP approach performed 1.5 to 2 times better than the LD approach, particularly for higher DNAPL saturation of the source zone. This result suggests that forcing the flushing solution directly into and through the DNAPL source zone minimized flow bypassing and consequently resulted in a more efficient transfer of contaminant mass between the DNAPL phase and the flushing solution. Nonuniform treatment zone contaminant concentrations and changes in contaminant composition influenced the treatment performances, but these effects were small and still permitted the comparison of successive tests. Although CD was used as the solubility‐enhancing flushing agent in this study, it is likely that the results can be transferred to other chemically enhanced flushing technologies that use, for example, surfactants or alcohols.     

Investigation and Remediation of a 1,2-Dichloroethane Spill Part II: Documentation of Natural Attenuation

A release of 1,2-dichloroethane. also known as ethylene dichloride (EDC), resulted in shallow subsurface freephase contamination of a Gulf Coast site in the southern United States. The site stratigraphy consists primarily of a low permeability, surficial peat. silt, and clay zone underlain by fractured clay; a confined 12 in deep sand ground water flow zone; a confined 21 m deep fine sand zone of limited ground water flow, followed by a deep aquitard. The Gumbo clay and sandy clay aquitard below the release area overlies and protects the 61 m deep Upper Chicot Aquifer, which is a confined regional aquifer. An ongoing recovery and hydraulic containment program from the primary impacted and laterally and vertically restricted shallow 40-foot sand zone has effectively recovered dense nonaqueous phase liquid (DNAPL) and contained dissolved phase EDC.
Natural attenuation of EDC was demonstrated through (1) a laboratory microcosm study substantiating the ability of the native microbial population in the deeper aquifer lo degrade EDC under anaerobic environmental conditions found at the site. (2) field investigations showing reductions in EDC concentrations over time in many of the wells on site, and (3) an evaluation of the ground water for EDC and its degradation products and oilier geo-chemical parameters such as dissolved oxygen, redox potential, and pH. Degradation products of EDC found in the field investigations included 2-chloroeihanol, ethanol. ethene, and ethane. Dissolved EDC concentrations in selected wells between the first recorded samples and the fourth quarter of 1997 ranged from greater than 4% to 99% reductions. First-order exponential decay half-lives ranged from 0.21 to 4.2 years for wells showing decreases in FDC concentrations over time. Elevated methane concentrations indicated carbon dioxide to be the major terminal electron acceptor.     

The influence of dimensionality on simulations of mass recovery from nonuniform dense non-aqueous phase liquid (DNAPL) source zones

The influence of model dimensionality on predictions of mass recovery from dense non-aqueous phase liquid (DNAPL) source zones in nonuniform permeability fields was investigated using a modified version of the modular three-dimensional transport simulator (MT3DMS). Thirty-two initial two- (2D) and three-dimensional (3D) tetrachloroethene–DNAPL source zone architectures, taken from a recent modeling study, were used as initial conditions for this analysis. Commonly employed source zone metrics were analyzed to determine differences between 2D and 3D predictions: (i) down-gradient flux-averaged contaminant concentration, (ii) reductions in contaminant mass flux through a down-gradient boundary, (iii) source zone ganglia-to-pool (GTP) ratio, and (iv) time required to achieve a remediation objective. 3D flux-averaged contaminant concentrations were approximately 3.5 times lower than concentrations simulated in 2D. This difference was attributed to dilution of the contaminant concentrations down gradient of the source zone. Contaminant flux reduction predictions for a given mass recovery were generally 5% higher in 3D simulations than in 2D simulations. The GTP ratio declined over time as mass was recovered in both 2D and 3D simulations. Although the source longevity (i.e., time required to achieve 99.99% mass recovery) differed between individual 2D and 3D realizations, the mean source longevity for the 2D and 3D simulation ensembles was within 2%. 2D simulations tended to over-predict the time required to achieve lower mass recovery levels (e.g. 50% mass recovery) due to a smaller contaminated area exposed to uncontaminated water. These findings suggest that ensemble averages of 2D numerical simulations of DNAPL migration, entrapment, dissolution, and mass recovery in statistically homogenous, nonuniform media may provide reasonable approximations to average behavior obtained using simulations conducted in fully three-dimensional domains.