A Design Tool for Solar Thermal Remediation Using Borehole Heat Exchangers.

Low temperature heating of the subsurface (increases of about 5-20 °C) can substantially increase rates of biotic and abiotic destruction of dissolved contaminants such as chlorinated solvents. Low-temperature heating can be sustainably and cost-effectively achieved using solar thermal collectors coupled with closed-loop borehole heat exchangers. This technology has been implemented at several sites in the United States and abroad with favorable results. The design of a solar thermal remediation system requires a quantitative understanding of heat transfer from the array of borehole heat exchangers. We present an easy-to-use design tool that is based on a transient three-dimensional analytical heat transfer solution and is programmed in Visual Basic in Excel. This tool can be used to quickly explore the effect of design variables on the forecast temperature field. Typical design variables would include the site-specific average and monthly solar insolation data, solar collector configuration, borehole heat exchanger geometry and spacing, and the effects of environmental variables such as groundwater velocity, background subsurface temperature, and thermal conductivity. The design tool has been verified by comparisons with the TOUGH2 multiphase heat transfer code for a three-dimensional multi-heater system with seasonally variable thermal power rates. The code has been validated by comparisons to observed temperatures measured at a solar thermal field remediation application at a site in Colorado.

Impact of matrix diffusion on the migration of groundwater plumes for Perfluoroalkyl acids (PFAAs) and other non-degradable compounds.

Groundwater fate and transport modeling results demonstrate that matrix diffusion plays a role in attenuating the expansion of groundwater plumes of "non-degrading" or highly recalcitrant compounds. This is especially significant for systems where preferred destructive attenuation processes, such as biological and abiotic degradation, are weak or ineffective for plume control. Under these conditions, models of nondestructive physical attenuation processes, traditionally dispersion or sorption, do not demonstrate sufficient plume control unless matrix diffusion is considered. Matrix diffusion has been shown to be a notable emergent impact of geological heterogeneity, typically associated with back diffusion and extending remediation timeframes through concentration tailing of the trailing edge of a plume. However, less attention has been placed on evaluating how matrix diffusion can serve as an attenuation mechanism for the leading edge of a plume of non-degrading compounds like perfluoroalkyl acids (PFAAs), including perfluorooctane sulfonate (PFOS). In this study, the REMChlor-MD model was parametrically applied to a generic unconsolidated and heterogeneous geologic site with a constant PFOS source and no degradation of PFOS in the downgradient edge of the plume. Low levels of mechanical dispersion and retardation were used in the model for three different geologic heterogeneity cases ranging from no matrix diffusion (e.g., sand only) to considerable matrix diffusion using low permeability ("low-k") layers/lenses and/or aquitards. Our analysis shows that, in theory, many non-degrading plumes may expand for significant time periods before dispersion alone would eventually stabilize the plume; however, matrix diffusion can significantly slow the rate and degree of this migration. For one 100-year travel time scenario, consideration of matrix diffusion results in a simulated PFOS plume length that is over 80% shorter than the plume length simulated without matrix diffusion. Although many non-degrading plumes may continue to slowly expand over time, matrix diffusion resulted in lower concentrations and smaller plume footprints. Modeling multiple hydrogeologic settings showed that the effect of matrix diffusion is more significant in transmissive zones containing multiple low-k lenses/layers than transmissive zones underlain and overlain by low-k aquitards. This study found that at sites with significant matrix diffusion, groundwater plumes will be shorter, will expand more slowly, and may be amenable to a physical, retention-based, Monitored Natural Attenuation (MNA) paradigm. In this case, a small "Plume Assimilative Capacity Zone" in front of the existing plume could be reserved for slow, de minimus, future expansion of a non-degrading plume. If potential receptors are protected in this scenario, then this approach is similar to allowances for expanding plumes under some existing environmental regulatory programs. Accounting for matrix diffusion may support new strategic approaches and alternative paradigms for remediation even for sites and conditions with "non-degrading" constituents such as PFAAs, metals/metalloids, and radionuclides.

Chlorinated Ethene Degradation Rate Coefficients Simulated with Intact Sandstone Core Microcosms.

Abiotic transformation of trichloroethene (TCE) in fractured porous rock such as sandstone is challenging to characterize and quantify. The objective of this study was to estimate the pseudo first-order abiotic reaction rate coefficients in diffusion-dominated intact core microcosms. The microcosms imitated clean flow through a fracture next to a contaminated rock matrix by exchanging uncontaminated groundwater, unamended or lactate-amended, in a chamber above a TCE-infused sandstone core. Rate coefficients were assessed using a numerical model of the microcosms that were calibrated to monitoring data. Average initial rate coefficients for complete dechlorination of TCE to acetylene, ethene, and ethane were estimated as 0.019 y-1 in unamended microcosms and 0.024 y-1 in lactate-amended microcosms. Moderately higher values (0.026 y-1 for unamended and 0.035 y-1 for lactate-amended) were obtained based on 13C enrichment data. Abiotic transformation rate coefficients based on gas formation were decreased in unamended microcosms after ∼25 days, to an average of 0.0008 y-1. This was presumably due to depletion of reductive capacity (average values of 0.12 ± 0.10 µeeq/g iron and 18 ± 15 µeeq/g extractable iron). Model-derived rate coefficients and reductive capacities for the intact core microcosms aligned well with results from a previous microcosm study using crushed sandstone from the same site.

Simulation of in situ biodegradation of 1,4-dioxane under metabolic and cometabolic conditions.

Bioaugmentation is an option for aerobic remediation of groundwater contaminated with 1,4-dioxane. One approach uses microbes that cometabolize 1,4-dioxane following growth on a primary substrate (e.g., propane), whereas another uses microbes (e.g., Pseudonocardia dioxivorans CB1190) capable of using 1,4-dioxane as a sole substrate. The relative merits of these approaches are difficult to distinguish based on field data alone, and theoretical analyses of these processes have yet to be published. The objective of this study was to compare these remediation options using a transport model that incorporates advection, dispersion and biodegradation reactions described by multi-substrate Monod kinetics and co-inhibition effects. The transport model was coupled to an approximate steady-state air sparging simulation used to estimate gas (propane and oxygen) distribution at the field scale. The model was calibrated with field data for 1,4-dioxane and propane concentrations from a previously reported pilot study. The two remediation approaches were evaluated under different conditions that vary the initial concentration of 1,4-dioxane and the loading rates of oxygen, propane, and biomass. The metrics used to evaluate the remediation success were the time to reach an average 1,4-dioxane concentration of 1 µg L-1 and the percent of 1,4-dioxane biodegraded after 10 years of simulation. Results indicate that the initial concentration of 1,4-dioxane strongly influences which remediation approach is more effective. When initial concentrations were <10 mg L-1, propane-driven cometabolism led to faster remediation; whereas metabolic biodegradation was faster when initial concentrations were 10 mg L-1 or higher. Below 0.25 mg L-1, the viability of metabolic biodegradation improved, although cometabolism by propanotrophs still required less time to reach 1 µg L-1. Biomass injection rates had a strong effect on the rate of metabolism but not cometabolism because continuous input of primary substrate supported growth of propanotrophs. The performance of both cultures was negatively affected by a decrease in oxygen injection rate. The endogenous decay coefficient and the dispersion rate for biomass had a significant impact on cometabolic and metabolic biodegradation of 1,4-dioxane. The maximum specific rate for cometabolism of 1,4-dioxane, the dispersion rate for 1,4-dioxane, and effective porosity also had significant effects on the time to achieve remediation with propanotrophs.

Semi-analytical method for matrix diffusion in heterogeneous and fractured systems with parent-daughter reactions.

A semi-analytical/numerical method for modeling matrix diffusion in heterogeneous and fractured groundwater systems is developed. This is a significant extension of the Falta and Wang (2017) method that only applied to diffusion in an aquitard of infinite thickness. The current solution allows for the low permeability matrix to be embedded within a numerical gridblock, having finite average thickness, a specified volume fraction and a specified interfacial area with the high permeability domain. The new formulation also allows for coupled parent-daughter decay reactions with multiple species that each have independent retardation factors, decay rates, and yield coefficients in both the high and low permeability parts of the system. The method uses a fitting function to approximate the transient concentration profile in the low permeability part of each gridblock so that the matrix diffusion flux into the high permeability part of the gridblock can be computed as a concentration dependent source-sink term. This approach is efficient because the only unknowns in each gridblock are the concentrations in the high permeability domain, so there is practically no increase in computational effort compared to a conventional transport simulation. The method is shown to compare favorably with an analytical solution for matrix diffusion in fractured media with parallel fractures, with an analytical solution for matrix diffusion with parent-daughter decay reactions, with laboratory experiments of matrix diffusion in a layered system, with a laboratory experiment involving lens shaped inclusions, and with fine grid numerical simulations of transport in highly heterogeneous systems.

A semi-analytical method for simulating matrix diffusion in numerical transport models.

A semi-analytical approximation for transient matrix diffusion is developed for use in numerical contaminant transport simulators. This method is an adaptation and extension of the heat conduction method of Vinsome and Westerveld (1980) used to simulate heat losses during thermally enhanced oil recovery. The semi-analytical method is used in place of discretization of the low permeability materials, and it represents the concentration profile in the low permeability materials with a fitting function that is adjusted in each element at each time-step. The resulting matrix diffusion fluxes are added to the numerical model as linear concentration-dependent source/sink terms. Since only the high permeability zones need to be discretized, the numerical formulation is extremely efficient compared to traditional approaches that require discretization of both the high and low permeability zones. The semi-analytical method compares favorably with the analytical solution for transient one-dimensional diffusion with first order decay, with a two-layer aquifer/aquitard solution, with the solution for transport in a fracture with matrix diffusion and decay, and with a fully numerical solution for transport in a thin sand zone bounded by clay with variable decay rates.

Numerical Analysis of Thermal Remediation in 3D Field-Scale Fractured Geologic Media.

Thermal methods are promising for remediating fractured geologic media contaminated with volatile organic compounds, and the success of this process depends on the coupled heat transfer, multiphase flow, and thermodynamics. This study analyzed field-scale removal of trichloroethylene (TCE) and heat transfer behavior in boiling fractured geologic media using the multiple interacting continua method. This method can resolve local gradients in the matrix and is less computationally demanding than alternative methods like discrete fracture-matrix models. A 2D axisymmetric model was used to simulate a single element of symmetry in a repeated pattern of extraction wells inside a large heated zone and evaluate effects of parameter sensitivity on contaminant recovery. The results showed that the removal of TCE increased with matrix permeability, and the removal rate was more sensitive to matrix permeability than any other parameter. Increasing fracture density promoted TCE removal, especially when the matrix permeability was low (e.g., <10(-17) m(2)). A 3D model was used to simulate an entire treatment zone and the surrounding groundwater in fractured material, with the interaction between them being considered. Boiling was initiated in the center of the upper part of the heated region and expanded toward the boundaries. This boiling process resulted in a large increase in the TCE removal rate and spread of TCE to the vadose zone and the peripheries of the heated zone. The incorporation of extraction wells helped control the contaminant from migrating to far regions. After 22 d, more than 99.3% of TCE mass was recovered in the simulation.

Experimental method for characterizing CVOC removal from fractured clays during boiling.

Conventional remediation methods that rely on contact with contaminants can be ineffective in fractured media, but thermal methods of remediation involving CVOC stripping at boiling temperature show promise. However, limited experimental data are available to characterize thermal remediation because of challenges associated with high temperature. This research reports an experimental method using uniformly contaminated clay packed into two types of experimental cells, a rigid-wall stainless steel tube and a flexible-wall Teflon tube in a pressurized chamber. Both tubes are 5 cm in diameter and approximately 25 cm long. This laboratory apparatus was developed as a 1D physical model for contaminant transport in a cylindrical matrix towards a fracture, which is represented by one end of the cylinder and serves as the outlet of vapor and contaminant. The clay was contaminated with dissolved 1,2-dichloroethane (DCA) and bromide, and the columns were heated to more than 100 °C and then the top end was depressurized to atmospheric pressure to induce boiling. The outflow was condensed and analyzed for contaminant mass. The flexible-wall cell was confined to 100 kPa (gage), allowing equilibrium boiling temperatures of approximately 120 °C to be maintained. The clay was sampled before and after heating and extracted to determine the DCA distribution along the length of the column. During a typical test in the rigid-wall cell, internal temperatures and pressures along the column during heating reached the saturated vapor pressure curve. DCA concentrations in the recovered condensate were up to 12 times of the initial pore concentration in the clay. Less than 5% of non-volatile bromide was recovered. Significant removal of DCA and water occurred along the entire length of the clay column. This suggests that boiling was occurring in the clay matrix.

Kinetics of 1,2-dichloroethane and 1,2-dibromoethane biodegradation in anaerobic enrichment cultures.

1,2-Dichloroethane (1,2-DCA) and 1,2-dibromoethane (ethylene dibromide [EDB]) contaminate groundwater at many hazardous waste sites. The objectives of this study were to measure yields, maximum specific growth rates (µ), and half-saturation coefficients (K(S)) in enrichment cultures that use 1,2-DCA and EDB as terminal electron acceptors and lactate as the electron donor and to evaluate if the presence of EDB has an effect on the kinetics of 1,2-DCA dehalogenation and vice versa. Biodegradation was evaluated at the high concentrations found at some industrial sites (>10 mg/liter) and at lower concentrations found at former leaded-gasoline sites (1.9 to 3.7 mg/liter). At higher concentrations, the Dehalococcoides yield was 1 order of magnitude higher when bacteria were grown with 1,2-DCA than when they were grown with EDB, while µ's were similar for the two compounds, ranging from 0.19 to 0.52 day(-1) with 1,2-DCA to 0.28 to 0.36 day(-1) for EDB. K(S) was larger for 1,2-DCA (15 to 25 mg/liter) than for EDB (1.8 to 3.7 mg/liter). In treatments that received both compounds, EDB was always consumed first and adversely impacted the kinetics of 1,2-DCA utilization. Furthermore, 1,2-DCA dechlorination was interrupted by the addition of EDB at a concentration 100 times lower than that of the remaining 1,2-DCA; use of 1,2-DCA did not resume until the EDB level decreased close to its maximum contaminant level (MCL). In lower-concentration experiments, the preferential consumption of EDB over 1,2-DCA was confirmed; both compounds were eventually dehalogenated to their respective MCLs (5 µg/liter for 1,2-DCA, 0.05 µg/liter for EDB). The enrichment culture grown with 1,2-DCA has the advantage of a more rapid transition to 1,2-DCA after EDB is consumed.

Numerical analysis of contaminant removal from fractured rock during boiling.

A multiphase heat transfer numerical model is used to simulate a laboratory experiment of contaminant removal at boiling temperatures from a rock core representing the matrix adjacent to a fracture. The simulated temperature, condensate production, contaminant and bromide concentrations are similar to experimental data. A key observation from the experiment and simulation is that boiling out approximately 1/2 pore volume (50 mL) of water results in the removal of essentially 100% of the dissolved volatile contaminant (1,2-DCA). A field-scale simulation using the multiple interacting continua (MINC) discretization approach is conducted to illustrate possible applications of thermal remediation of fractured geologic media, assuming uniform heating. The results show that after 28% of the pore water (including both steam vapor and liquid water) was extracted, and essentially all the 1,2-DCA mass (more than 99%) was removed.

Henry's law constants of chlorinated solvents at elevated temperatures.

Henry's law constants for 12 chlorinated volatile organic compounds (CVOCs) were measured as a function of temperature ranging from 8 to 93°C, using the modified equilibrium partitioning in closed system (EPICS) method. The chlorinated compounds include tetrachloroethylene, trichloroethylene, cis-1,2-dichloroethylene, vinyl chloride, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, chloroethane, carbon tetrachloride, chloroform, dichloromethane, and chloromethane. The variation in Henry's constants for these compounds as a function of temperature ranged from around 3-fold (chloroethane) to 30-fold (1,2-dichloroethane). Aqueous solubilities of the pure compounds were measured over the temperature range of 8-75°C. The temperature dependence of Henry's constant was predicted using the ratio of pure vapor pressure to aqueous solubility, both of which are functions of temperature. The calculated Henry's constants are in a reasonable agreement with the measured results. With the improved data on Henry's law constants at high temperatures measured in this study, it will be possible to more accurately model subsurface remediation processes that operate near the boiling point of water.

Remediation of NAPL source zones: lessons learned from field studies at Hill and Dover AFB.

Innovative remediation studies were conducted between 1994 and 2004 at sites contaminated by nonaqueous phase liquids (NAPLs) at Hill and Dover AFB, and included technologies that mobilize, solubilize, and volatilize NAPL: air sparging (AS), surfactant flushing, cosolvent flooding, and flushing with a complexing-sugar solution. The experiments proved that aggressive remedial efforts tailored to the contaminant can remove more than 90% of the NAPL-phase contaminant mass. Site-characterization methods were tested as part of these field efforts, including partitioning tracer tests, biotracer tests, and mass-flux measurements. A significant reduction in the groundwater contaminant mass flux was achieved despite incomplete removal of the source. The effectiveness of soil, groundwater, and tracer based characterization methods may be site and technology specific. Employing multiple methods can improve characterization. The studies elucidated the importance of small-scale heterogeneities on remediation effectiveness, and fomented research on enhanced-delivery methods. Most contaminant removal occurs in hydraulically accessible zones, and complete removal is limited by contaminant mass stored in inaccessible zones. These studies illustrated the importance of understanding the fluid dynamics and interfacial behavior of injected fluids on remediation design and implementation. The importance of understanding the dynamics of NAPL-mixture dissolution and removal was highlighted. The results from these studies helped researchers better understand what processes and scales are most important to include in mathematical models used for design and data analysis. Finally, the work at these sites emphasized the importance and feasibility of recycling and reusing chemical agents, and enabled the implementation and success of follow-on full-scale efforts.

Experimental demonstration of contaminant removal from fractured rock by boiling.

This study was conducted to experimentally demonstrate removal of a chlorinated volatile organic compound from fractured rock by boiling. A Berea sandstone core was contaminated by injecting water containing dissolved 1,2-DCA (253 mg/L) and sodium bromide (144 mg/L). During heating, the core was sealed except for one end, which was open to the atmosphere to simulate an open fracture. A temperature gradient toward the outlet was observed when boiling occurred in the core. This indicates that steam was generated and a pressure gradient developed toward the outlet, pushing steam vapor and liquid water toward the outlet. As boiling occurred, the concentration of 1,2-DCA in the condensed effluent peaked up to 6.1 times higher than the injected concentration. When 38% of the pore volume of condensate was produced, essentially 100% of the 1,2-DCA was recovered. Nonvolatile bromide concentration in the condensate was used as an indicator of the produced steam quality (vapor mass fraction) because it can only be removed as a solute, and not as a vapor. A higher produced steam quality corresponds to more concentrated 1,2-DCA removal from the core, demonstrating that the chlorinated volatile compound is primarily removed by partitioning into vapor phase flow. This study has experimentally demonstrated that boiling is an effective mechanism for CVOC removal from the rock matrix.

Numerical modeling of thermal conductive heating in fractured bedrock.

Numerical modeling was employed to study the performance of thermal conductive heating (TCH) in fractured shale under a variety of hydrogeological conditions. Model results show that groundwater flow in fractures does not significantly affect the minimum treatment zone temperature, except near the beginning of heating or when groundwater influx is high. However, fracture and rock matrix properties can significantly influence the time necessary to remove all liquid water (i.e., reach superheated steam conditions) in the treatment area. Low matrix permeability, high matrix porosity, and wide fracture spacing can contribute to boiling point elevation in the rock matrix. Consequently, knowledge of these properties is important for the estimation of treatment times. Because of the variability in boiling point throughout a fractured rock treatment zone and the absence of a well-defined constant temperature boiling plateau in the rock matrix, it may be difficult to monitor the progress of thermal treatment using temperature measurements alone.

Simulation of the effect of remediation on EDB and 1,2-DCA plumes at sites contaminated by leaded gasoline.

An analytical model is used to simulate the effects of partial source removal and plume remediation on ethylene dibromide (EDB) and 1,2-dichloroethane (1,2-DCA) plumes at contaminated underground storage tank (UST) sites. The risk posed by EDB, 1,2-DCA, and commingled gasoline hydrocarbons varies throughout the plume over time. Dissolution from the light nonaqueous phase liquid (LNAPL) determines the concentration of each contaminant near the source, but biological decay in the plume has a greater influence as distance downgradient from the source increases. For this reason, compounds that exceed regulatory standards near the source may not in downgradient plume zones. At UST sites, partial removal of a residual LNAPL source mass may serve as a stand alone remedial technique if dissolved concentrations in the source zone are within several orders of magnitude of the applicable government or remedial standards. This may be the case with 1,2-DCA; however, EDB is likely to be found at concentrations that are orders of magnitude higher than its low Maximum Contaminant Level (MCL) of 0.05 microg/L (micrograms per liter). For sites with significant EDB contamination, even when plume remediation is combined with source depletion, significant timeframes may be required to mitigate the impact of this compound. Benzene and MTBE are commonly the focus of remedial efforts at UST sites, but simulations presented here suggest that EDB, and to a lesser extent 1,2-DCA, could be the critical contaminants to consider in the remediation design process at many sites.

Anaerobic biodegradation of ethylene dibromide and 1,2-dichloroethane in the presence of fuel hydrocarbons.

Field evidence from underground storage tank sites where leaded gasoline leaked indicates the lead scavengers 1,2-dibromoethane (ethylene dibromide, or EDB) and 1,2-dichloroethane (1,2-DCA) may be present in groundwater at levels that pose unacceptable risk. These compounds are seldom tested for at UST sites. Although dehalogenation of EDB and 1,2-DCA is well established, the effect of fuel hydrocarbons on their biodegradability under anaerobic conditions is poorly understood. Microcosms (2 L glass bottles) were prepared with soil and groundwater from a UST site in Clemson, South Carolina, using samples collected from the source (containing residual fuel) and less contaminated downgradient areas. Anaerobic biodegradation of EDB occurred in microcosms simulating natural attenuation, but was more extensive and predictable in treatments biostimulated with lactate. In the downgradient biostimulated microcosms, EDB decreased below its maximum contaminant level (MCL) (0.05 microg/L) at a first order rate of 9.4 +/- 0.2 yr(-1). The pathway for EDB dehalogenation proceeded mainly by dihaloelimination to ethene in the source microcosms, while sequential hydrogenolysis to bromoethane and ethane was predominant in the downgradient treatments. Biodegradation of EDB in the source microcosms was confirmed by carbon specific isotope analysis, with a delta13C enrichment factor of -5.6 per thousand. The highest levels of EDB removal occurred in microcosms that produced the highest amounts of methane. Extensive biodegradation of benzene, ethylbenzene, toluene and ortho-xylene was also observed in the source and downgradient area microcosms. In contrast, biodegradation of 1,2-DCA proceeded at a considerably slower rate than EDB, with no response to lactate additions. The slower biodegradation rates for 1,2-DCA agree with field observations and indicate that even if EDB is removed to below its MCL, 1,2-DCA may persist.

Methodology for comparing source and plume remediation alternatives.

It is often difficult at contaminated sites to decide whether remediation effort should be focused on the contaminant source, the dissolved plume, or on both zones. The decision process at these sites is hampered by a lack of quantitative tools for comparing remediation alternatives. A new screening-level mass balance approach is developed for simulating the transient effects of simultaneous ground water source and plume remediation. The contaminant source model is based on a power function relationship between source mass and source discharge, and it can consider partial source remediation at any time after the initial release. The source model serves as a time-dependent mass flux boundary condition to a new analytical plume model, where flow is assumed to be one dimensional, with three-dimensional dispersion. The plume model simulates first-order sequential decay and production of several species, and the decay rates and parent/daughter yield coefficients are variable functions of time and distance. This new method allows for flexible simulation of natural attenuation or remediation efforts that enhance plume degradation. The plume remediation effort may be temporary or delayed in time, limited in space, and it may have different chemical effects on different contaminant species in the decay chain.

Temporal evolution of DNAPL source and contaminant flux distribution: impacts of source mass depletion.

We investigated, using model simulations, the changes occurring in the distribution of dense non-aqueous phase liquid (DNAPL) mass (Sn) within the source zone during depletion through dissolution, and the resulting changes in the contaminant flux distribution (J) at the source control plane (CP). Two numerical codes (ISCO3D and T2VOC) were used to simulate selected scenarios of DNAPL dissolution and transport in three-dimensional, heterogeneous, spatially correlated, random permeability fields with emplaced sources. Data from the model simulations were interpreted based on population statistics (mean, standard deviation, coefficient of variation) and spatial statistics (centroid, second moments, variograms). The mean and standard deviation of the Sn and J distributions decreased with source mass depletion by dissolution. The decrease in mean and standard deviation was proportional for the J distribution resulting in a constant coefficient of variation (CV), while for the Sn distribution, the mean decreased faster than the standard deviation. The spatial distributions exhibited similar behavior as the population distribution, i.e., the CP flux distribution was more stable (defined by temporally constant second moments and range of variograms) than the Sn distribution. These observations appeared to be independent of the heterogeneity of the permeability (k) field (variance of the log permeability field=1 and 2.45), correlation structure (positive vs. negative correlation between the k and Sn domains) and the DNAPL dissolution model (equilibrium vs. rate-limited), for the cases studied. Analysis of data from a flux monitoring field study (Hill Air Force Base, Utah) at a DNAPL source CP before and after source remediation also revealed temporal invariance of the contaminant flux distribution. These modeling and field observations suggest that the temporal evolution of the contaminant flux distribution can be estimated if the initial distribution is known. However, the findings are preliminary and broader implications to sampling strategies for remediation performance assessment need to be evaluated in additional modeling and experimental studies.

Modeling field-scale cosolvent flooding for DNAPL source zone remediation.

A three-dimensional, compositional, multiphase flow simulator was used to model a field-scale test of DNAPL removal by cosolvent flooding. The DNAPL at this site was tetrachloroethylene (PCE), and the flooding solution was an ethanol/water mixture, with up to 95% ethanol. The numerical model, UTCHEM accounts for the equilibrium phase behavior and multiphase flow of a ternary ethanol-PCE-water system. Simulations of enhanced cosolvent flooding using a kinetic interphase mass transfer approach show that when a very high concentration of alcohol is injected, the DNAPL/water/alcohol mixture forms a single phase and local mass transfer limitations become irrelevant. The field simulations were carried out in three steps. At the first level, a simple uncalibrated layered model is developed. This model is capable of roughly reproducing the production well concentrations of alcohol, but not of PCE. A more refined (but uncalibrated) permeability model is able to accurately simulate the breakthrough concentrations of injected alcohol from the production wells, but is unable to accurately predict the PCE removal. The final model uses a calibration of the initial PCE distribution to get good matches with the PCE effluent curves from the extraction wells. It is evident that the effectiveness of DNAPL source zone remediation is mainly affected by characteristics of the spatial heterogeneity of porous media and the variable (and unknown) DNAPL distribution. The inherent uncertainty in the DNAPL distribution at real field sites means that some form of calibration of the initial contaminant distribution will almost always be required to match contaminant effluent breakthrough curves.