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.     

Hydraulic displacement of dense nonaqueous phase liquids for source zone stabilization

Hydraulic displacement is a mass removal technology suitable for stabilization of a dense, nonaqueous phase liquid (DNAPL) source zone, where stabilization is defined as reducing DNAPL saturations and reducing the risk of future pool mobilization. High resolution three-dimensional multiphase flow simulations incorporating a spatially correlated, heterogeneous porous medium illustrate that hydraulic displacement results in an increase in the amount of residual DNAPL present, which in turn results in increased solute concentrations in groundwater, an increase in the rate of DNAPL dissolution, and an increase in the solute mass flux. A higher percentage of DNAPL recovery is associated with higher initial DNAPL release volumes, lower density DNAPLs, more heterogeneous porous media, and increased drawdown of groundwater at extraction wells. The fact that higher rates of recovery are associated with more heterogeneous porous media stems from the fact that larger contrasts in permeability provide for a higher proportion of capillary barriers upon which DNAPL pooling and lateral migration can occur. Across all scenarios evaluated in this study, the ganglia-to-pool (GTP) ratio generally increased from approximately 0.1 to between approximately 0.3 and 0.7 depending on the type of DNAPL, the degree of heterogeneity, and the imposed hydraulic gradient. The volume of DNAPL recovered as a result of implementing hydraulic displacement ranged from between 9.4% and 45.2% of the initial release volume, with the largest percentage recovery associated with 1,1,1 trichloroethane, the least dense of the three DNAPLs considered.     

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.     

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.     

Evaluation of an upscaled model for DNAPL dissolution kinetics in heterogeneous aquifers

Estimates of contaminant fluxes from DNAPL sources as a function of time and DNAPL mass reduction are important to assess the long-term sustainability and costs of monitored natural attenuation and to determine the benefits of partial source removal. We investigate the accuracy of the upscaled mass transfer function (MTF) proposed by Parker and Park [Parker JC, Park E. Modeling field-scale dense nonaqueous phase liquid dissolution kinetics in heterogeneous aquifers. WRR 2004;40:W05109] to describe field-scale dissolved phase fluxes from DNAPL sources for a range of scenarios generated using high-resolution 3-D numerical simulations of DNAPL infiltration and long-term dissolved phase transport. The results indicate the upscaled MTF is capable of accurately describing field-scale DNAPL dissolution rates as a function of time. For finger-dominated source regions, an empirical mass depletion exponent in the MTF takes on values greater than one which results in predicted mass flux rates that decrease continuously with diminishing DNAPL mass over time. Lens-dominated regions exhibit depletion exponents less than one, which results in more step-function like mass flux versus time behavior. Mass fluxes from DNAPL sources exhibiting both lens- and finger-dominated subregions were less accurately described by the simple MTF, but were well described by a dual-continuum model of the same form for each subregion. The practicality of calibrating a dual-continuum model will likely depend on the feasibility of obtaining spatially resolved field measurements of contaminant fluxes or concentrations associated with the subregions using multilevel sampling or some other means.     

DNAPL accumulation in wells and DNAPL recovery from wells: Model development and application to a laboratory study

Dense nonaqueous phase liquid (DNAPL) accumulation and recovery from wells cannot be accurately modeled through typical pressure or flux boundary conditions due to gravity segregation of water and DNAPL in the wellbore, the effects of wellbore storage, and variations of wellbore inflow and outflow rates with depth, particularly in heterogeneous formations. A discrete wellbore formulation is presented for numerical modeling of DNAPL accumulation in observation wells and DNAPL removal from recovery wells. The formulation includes fluid segregation, changing water and DNAPL levels in the well and the corresponding changes in fluid storage in the wellbore. The method was added to a three-dimensional finite difference model (CompSim) for three phase (water, gas, DNAPL) flow. The model predictions are compared to three-dimensional pilot scale experiments of DNAPL (benzyl alcohol) infiltration, redistribution, recovery, and water flushing. Model predictions match experimental results well, indicating the appropriateness of the model formulation. Characterization of mixing in the extraction well is important for predicting removal of highly soluble organic compounds like benzyl alcohol. A sensitivity analysis shows that the incorporation of hysteresis is critical for accurate prediction. Among the multiphase flow and transport parameters required for modeling, results are most sensitive to soil intrinsic permeability.     

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.     

Comparison of alternative upscaled model formulations for simulating DNAPL source dissolution and biodecay

This paper compares the performance of analytical and numerical approaches for modeling DNAPL dissolution with biodecay. A solution derived from a 1-D advective transport formulation (“Parker” model) is shown to agree very closely with high resolution numerical solutions. A simple lumped source mass balance solution in which with decay is assumed proportional to DNAPL mass (“Falta1” model) over- or underpredicts aqueous phase biodecay depending on the magnitude of the exponential factor governing the relationship between dissolution rate and DNAPL mass. A modification of the Falta model that assumes decay proportional to the source exit concentration is capable of accurately simulating source behavior with strong aqueous phase biodecay if model parameters are appropriately selected or calibrated (“Falta2” model). However, parameters in the lumped models exhibit complex interdependencies that cannot be quantified without consideration of transport processes within the source zone. Combining the Falta2 solution with relationships derived from the Parker model was found to resolve these limitations and track the numerical model results. A method is presented to generalize the analytical solutions to enable simulation of partial mass removal with changes in source parameters over time due to various remedial actions. The algorithm is verified by comparison with numerical simulation results. An example application is presented that demonstrates the interactions of partial mass removal, enhanced biodecay, enhanced mass transfer and source zone flow reduction applied at various time periods on contaminant flux reduction. Increasing errors that arise in numerical solutions with coarse discretization and high decay rates are shown to be controlled by using an adjusted decay coefficient derived from the Parker analytical solution.     

Three-Dimensional Simulation of Volatile Organic Compound Mass Flux from the Vadose Zone to Groundwater

Low-permeability layers of the vadose zone containing volatile organic compounds (VOCs) may persist as source zones for long time periods and may provide contamination to groundwater. At sites with low recharge rates, where vapor migration is the dominant transport process, the impact of vadose zone sources on groundwater may be difficult to assess. Typical assessment methods include one-dimensional numerical and analytical techniques. The one-dimensional approaches only consider groundwater coupling options through boundary conditions at the water table and may yield artificially high mass flux results when transport is assumed to occur by gas-phase diffusion between a source and an interface with a zero concentration boundary condition. Improvements in mass flux assessments for VOCs originating from vadose zone sources may be obtained by coupling vadose zone gas transport and dissolved contaminant transport in the saturated zone and by incorporating the inherent three-dimensional nature of gas-phase transport, including the potential of density-driven advection. This paper describes a series of three-dimensional simulations using data from the U.S. Department of Energy's Hanford site, where carbon tetrachloride is present in a low-permeability zone about 30 m above the groundwater. Results show that, for most cases, only a relatively small amount of the contaminant emanating from the source zone partitions into the groundwater and that density-driven advection is only important when relatively high source concentrations are considered.     

Characterization of Crystalline Bedrock Contaminated by Dense Nonaqueous Liquid

A systematic hydrogeologic site characterization has been completed in a fractured rock flow system, with the objective of identifying contaminant migration and fate pathways from a historical release of 1,1,1-trichloroethane (TCA). The study integrated hydrogeologic analysis techniques such as borehole geophysical logging, pumping test analysis, and hydrochemical facies analysis to study the impact of a dense nonaqueous phase liquid (DNAPL) in a sparsely fractured crystalline bedrock. The assessment methodology can be divided into two parts: (1) characterization of the source area, where DNAPL is acting as a residual source of TCA, and (2) characterization of the downgradient plume. Reduction in DNAPL mass in the source area has resulted in significant and sustained reductions in downgradient concentrations, suggesting that remediation of fractured crystalline bedrock contaminated with DNAPL is possible and not "technically infeasible."     

Predicting DNAPL entrapment and recovery: the influence of hydraulic property correlation

The influence of aquifer property correlation on multiphase fluid migration, entrapment and recovery was explored by incorporating correlated and uncorrelated porosity, permeability, and capillary pressure-saturation (P_c-Sat) parameter fields in a cross-sectional numerical multiphase flow model. Comparison of two-dimensional entrapped organic saturation distributions for a simulated tetrachloroethylene (PCE) spill in ensembles of aquifer realizations suggests that the degree of spatial correlation in P_c-Sat parameters exerts a controlling influence on dense nonaqueous phase liquid (DNAPL) spreading and redistribution in saturated aquifers. The predicted evolution of DNAPL source zones and resultant remediation efficiency under surfactant enhanced aquifer remediation (SEAR) also appear to be strongly influenced by the spatial correlation of aquifer parameters and multiphase flow constitutive relationships. Results for a limited number of realizations selected from each ensemble showed that removal of 60% to 99% of entrapped PCE could reduce dissolved contaminant concentration and mass flux by approximately two orders of magnitude under natural gradient conditions. Aqueous phase contaminant mass flux did not vary uniformly as a function of % DNAPL removed, however, and notable differences in behavior were observed for models incorporating correlated versus uncorrelated P_c-Sat and permeability fields. Although these results must be confirmed through analysis of additional realizations, it is likely that similar or larger differences between correlated and uncorrelated system behavior will be observed in aquifers with greater spatially variability than that of the nonuniform, homogeneous sand aquifer studied here. Funding for this research was provided by the United States Environmental Protection Agency, Great Lakes and Mid-Atlantic Center for Hazardous Substance Research under Grant No. R-825540, the Michigan Department of Environmental Quality under Contract No. Y80011, and the Strategic Environmental Research and Development Program under Project No. CU-1293. The content of this publication does not necessarily represent the views of these agencies and has not been subject to agency review.     

Modeling unstable alcohol flooding of DNAPL-contaminated columns

Alcohol flooding, consisting of injection of a mixture of alcohol and water, is one source removal technology for dense non-aqueous phase liquids (DNAPLs) currently under investigation. An existing compositional multiphase flow simulator (UTCHEM) was adapted to accurately represent the equilibrium phase behavior of ternary and quaternary alcohol/DNAPL systems. Simulator predictions were compared to laboratory column experiments and the results are presented here. It was found that several experiments involved unstable displacements of the NAPL bank by the alcohol flood or of the alcohol flood by the following water flood. Unstable displacement led to additional mixing compared to ideal displacement. This mixing was approximated by a large dispersion in one-dimensional simulations and or by including permeability heterogeneities on a very small scale in three-dimensional simulations. Three-dimensional simulations provided the best match. Simulations of unstable displacements require either high-resolution grids, or need to consider the mixing of fluids in a different manner to capture the resulting effects on NAPL recovery.     

Impact of seasonal variations in hydrological stresses and spatial variations in geologic conditions on a TCE plume at an industrial complex in Wonju,Korea

Spatial and temporal variations in a trichloroethylene (TCE) plume at an industrial complex in Wonju, Korea, were examined based on hydrogeological data and seven rounds of groundwater quality data collected over a year. The site has considerable vertical heterogeneities; the top layer of soil is covered by impermeable paving material at several locations, followed by a series of reclaimed or residual soil layers, and with weathered rocks to the crystalline biotite granite at the bottom. Areal heterogeneity in the surface conditions plays an important role in controlling groundwater recharge. The heterogeneity structure is influenced by complex surface conditions paved with asphalt and concrete. Owing to the presence of limited recharge area and concentrated summer precipitation events, the effects of seasonal variations on groundwater hydraulics tend to diminish with distance from the recharge area. This result was established by analysing the influence of the contrasting surface recharge conditions between the near‐source zone and the far zone, and the seasonally concentrated precipitation on the transport patterns of a TCE plume. In addition, variations in the plume's downstream contaminant flux levels were also analysed along a transect line near the source zone. The results show that the general tendency of the TCE plume contaminant concentration and mass discharges were reproducible if we account for seasonal recharge variations and the associated changes in the groundwater level. During recharge events, the TCE concentration variations appear to be influenced by leaching of the residual dense non‐aqueous‐phase liquid (DNAPL) TCE trapped in the unsaturated zone. This result shows that seasonal variations in contaminant plume near the source zone is inevitable at this site, and that these variations indicate the presence of residual DNAPL at or above the water table, at least in some isolated locations. Copyright © 2011 John Wiley & Sons, Ltd.     

Bioremediation Management Reduces Mass Discharge at a Chlorinated DNAPL Site

Adaptive site management and aggressive bioremediation in the source zone of a complex chlorinated dense nonaqueous phase liquid (DNAPL) site reduced total chlorinated hydrocarbon mass discharge by nearly 80%. Successful anaerobic bioremediation of chlorinated hydrocarbons can be impaired by inadequate concentrations of electron donors, competing electron acceptors, specific inhibitors such as chloroform, and potentially by high contaminant concentrations associated with residual DNAPL. At the study site, the fractured bedrock aquifer was impacted by a mixture of chlorinated solvents and associated daughter products. Concentrations of 1,1,2,2‐tetrachloroethane (1,1,2,2‐TeCA), 1,1,2‐trichloroethane (1,1,2‐TCA), and 1,2‐dichloroethane (1,2‐DCA) were on the order of 100 to 1000 mg/L. Chloroform was present as a co‐contaminant and background sulfate concentrations were approximately 400 mg/L. Following propylene glycol injections, concentrations of organohalide‐respiring bacteria including Dehalococcoides and Dehalogenimonas spp. increased by two to three orders of magnitude across most of the source area. Statistical analysis indicated that reaching volatile fatty acid concentrations greater than 1000 mg/L and depleting sulfate to concentrations less than 50 mg/L were required to achieve a Dehalococcoides concentration greater than the 10⁴ cells/mL recommended for generally effective reductive dechlorination. In a limited area, chloroform concentrations greater than 5 mg/L inhibited growth of Dehalococcoides populations despite the availability of electron donor and otherwise appropriate geochemical conditions. After implementing a groundwater recirculation system targeting the inhibited area, chloroform concentrations decreased permitting significant increases in concentrations of Dehalococcoides and vinyl chloride reductase gene copies.     

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.     

A multiphase flow and multispecies reactive transport model for DNAPL-involved Compound Specific Isotope Analysis

This study presents a multiphase flow and multispecies reactive transport model for the simultaneous simulation of NAPL and groundwater flow, dissolution, and reactive transport with isotope fractionation, which can be used for better interpretation of NAPL-involved Compound Specific Isotope Analysis in 3D heterogeneous hydrogeologic systems. The model was verified for NAPL-aqueous phase equilibrium partitioning, aqueous phase multi-chain and multi-component reactive transport, and aqueous phase multi-component transport with isotope fractionation. Several illustrative examples are presented to investigate the effect of DNAPL spill rates, degradation rate constants, and enrichment factors on the temporal and spatial distribution of the isotope signatures of chlorinated aliphatic hydrocarbon groundwater plumes. The results clearly indicate that isotope signatures can be significantly different when considering multiphase flow within the source zone. A series of simulations indicate that degradation and isotope enrichment compete with dissolution to determine the isotope signatures in the source zone: isotope ratios remain the same as those of the source if dissolution dominates the reaction, while heavy isotopes are enriched in reactants along groundwater plume flow paths when degradation becomes dominant. It is also shown that NAPL composition can change from that of the injected source due to the partitioning of components between the aqueous and NAPL phases even when degradation is not allowed in NAPL phase. The three-dimensional simulation is presented to mechanistically illustrate the complexities in determining and interpreting the isotopic signatures with evolving DNAPL source architecture.     

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.     

Dissolution of nonaqueous phase liquid pools in anisotropic aquifers

A two-dimensional numerical transport model is developed to determine the effect of aquifer anisotropy and heterogeneity on mass transfer from a dense nonaqueous phase liquid (DNAPL) pool. The appropriate steady state groundwater flow equation is solved implicitly whereas the equation describing the transport of a sorbing contaminant in a confined aquifer is solved by the alternating direction implicit method. Statistical anisotropy in the aquifer is introduced by two-dimensional, random log-normal hydraulic conductivity field realizations with different directional correlation lengths. Model simulations indicate that DNAPL pool dissolution is enhanced by increasing the mean log-transformed hydraulic conductivity, groundwater flow velocity, and/or anisotropy ratio. The variance of the log-transformed hydraulic conductivity distribution is shown to be inversely proportional to the average mass transfer coefficient.     

Bioaugmentation in a Well‐Characterized Fractured Rock DNAPL Source Area

A field demonstration was performed at Edwards Air Force Base to assess bioaugmentation for treatment of a well‐characterized tetrachloroethene (PCE) dense nonaqueous phase liquid (DNAPL) source area in fractured rock. Groundwater recirculation was employed to deliver remedial amendments, including bacteria, to facilitate reductive dechlorination and enhance DNAPL dissolution. An active treatment period of 9 months was followed by a 10‐month posttreatment rebound evaluation. Dechlorination daughter products were observed in both the shallow and deep fracture zones following treatment. In the shallow fracture zone, the calculated DNAPL mass removed was approximately equal to the DNAPL mass estimated using partitioning tracer testing, and no rebound in chlorinated ethenes or ethene was observed during the posttreatment period. A maximum DNAPL dissolution enhancement factor of 5 was observed in the shallow fracture zone. In the deep fracture zone, only approximately 45% of the DNAPL mass—as estimated via partitioning tracer testing—was removed and rebound in the total molar chlorinated ethenes + ethene was observed. The difference in behavior between the shallow and deep fracture zones was attributed to DNAPL architecture and the fracture flow field.     

The influence of precipitate formation on the chemical oxidation of TCE DNAPL with potassium permanganate

A three-dimensional two-phase flow model is coupled to a non-linear reactive transport model to study the efficacy of potassium permanganate treatment on dense, non-aqueous phase liquid (DNAPL) source removal in porous media. A linear relationship between the soil permeability (k) and concentration of manganese dioxide precipitate ([MnO_2(s)]), k = k_o + S_rind [MnO_2(s)], is utilized to simulate nodal permeability reductions due to precipitate formation. Using published experimental column studies, an S_rind = −5.5 × 10⁻¹⁶ m² L/mg was determined for trichloroethylene (TCE) DNAPL. This S_rind was then applied to treatment simulations on three-dimensional TCE DNAPL source zones comprising either DNAPL at residual saturations, or DNAPL at pooled saturations.