Effects of source zone heterogeneity on surfactant-enhanced NAPL dissolution and resulting remediation end-points

The effectiveness of removal of nonaqueous phase liquids (NAPLs) from the entrapment source zone of the subsurface has been limited by soil heterogeneity and the inability to locate all entrapped sources. The goal of this study was to demonstrate the uncertainty of degree of source removal associated with aquifer heterogeneity. In this demonstration, source zone NAPL removal using surfactant-enhanced dissolution was considered. Model components that simulate the processes of natural dissolution in aqueous phase and surfactant-enhanced dissolution were incorporated into an existing code of contaminant transport. The dissolution modules of the simulator used previously developed Gilland-Sherwood type phenomenological models of NAPL dissolution to estimate mass transfer coefficients that are upscaleable to multidimensional flow conditions found at field sites. The model was used to simulate the mass removal from 10 NAPL entrapment zone configurations based on previously conducted two-dimensional tank experiments. These entrapment zones represent the NAPL distribution in spatially correlated random fields of aquifer hydraulic conductivity. The numerical simulations representing two-dimensional conditions show that effectiveness of mass removal depends on the aquifer heterogeneity that controls the NAPL entrapment and delivery of the surfactant to the locations of entrapped NAPLs. Flow bypassing resulting from heterogeneity and the reduction of relative permeability due to NAPL entrapment reduces the delivery efficiency of the surfactant, thus prolonging the remediation time to achieve desired end-point NAPL saturations and downstream dissolved concentrations. In some extreme cases, the injected surfactant completely bypassed the NAPL source zones. It was also found that mass depletion rates for different NAPL source configurations vary significantly. The study shows that heterogeneity result in uncertainties in the mass removal and achievable end-points that are directly related to dissolved contaminant plume development downstream of the NAPL entrapment zone.     

Parameters that control the cleanup of fractured permeable aquifers

This study develops a modeling approach for simulating and evaluating entrapped light nonaqueous-phase liquid (light NAPL-LNAPL) dissolution and transport of the solute in a fractured permeable aquifer (FPA). The term FPA refers to an aquifer made of porous blocks of high permeability that embed fractures. The fracture network is part of the domain characterized by high permeability and negligible storage. Previous studies show that sandstone aquifers often represent FPAs. The basic model developed in this study is a two-dimensional (2-D) model of permeable blocks that embed oblique equidistant fractures with constant aperture and orientation. According to this model, two major parameters govern NAPL dissolution and transport of the solute. These parameters are: 1) the dimensionless interphase mass transfer coefficient, K(f0), and 2) the mobility number, N(M0). These parameters represent measures of heterogeneity affecting flow, NAPL dissolution, and transport of the solute in the domain. The parameter K(f0) refers to the rate at which organic mass is transferred from the NAPL into the water phase. The parameter N(M0) represents the ratio of flow through the porous blocks to flow through the fracture network in regions free of entrapped NAPL. It also provides a measure of groundwater flow bypassing regions contaminated by entrapped NAPL. In regions contaminated by entrapped NAPL our simulations have often indicated very low permeability of the porous blocks, enabling a significant increase of the fracture flow at the expense of the permeable block flow. Two types of constitutive relationships also affect the rate of FPA cleanup: 1) the relationship between the saturation of the entrapped NAPL and the permeability of the porous blocks, and 2) the relationships representing effects of the entrapped NAPL saturation and the permeable block flow velocity on rates of interphase mass transfer. This study provides basic tools for evaluating the characteristics of pump-and-treat cleanup of FPAs by referring to sets of parameters and constitutive relationships typical of FPAs. The numerical simulations carried out in this study show that at high initial saturation of the entrapped NAPL, during initial stages of the FPA cleanup the contaminant concentration increases, but later it decreases. This phenomenon originates from significant groundwater bypassing the NAPL entrapped in the permeable blocks via the fracture network.     

Hot water flushing for immiscible displacement of a viscous NAPL

Thermal remediation techniques, such as hot water flooding, are emerging technologies that have been proposed for the removal of nonaqueous phase liquids (NAPLs) from the subsurface. In this study a combined laboratory and modeling investigation was conducted to determine if hot water flooding techniques would improve NAPL mass removal compared to ambient temperature water flushing. Two experiments were conducted in a bench scale two-dimensional sandbox (55 cmx45 cmx1.3 cm) and NAPL saturations were quantified using a light transmission apparatus. In these immiscible displacement experiments the aqueous phase, at 22 degrees C and 50 degrees C, displaced a zone with initial NAPL saturations on the order of 85%. The interfacial tension and viscosity of the selected light NAPL, Voltesso 35, are strongly temperature-dependent. Experimental results suggest that hot water flooding reduced the size of the high NAPL saturation zone, in comparison to the cold water flood, and yielded greater NAPL mass recovery (75% NAPL removal vs. 64%). Hot water flooding did not, however, result in lower residual NAPL saturations. A numerical simulator was modified to include simultaneous flow of water and organic phases, energy transport, temperature and pressure. Model predictions of mass removal and NAPL saturation profiles compared well with observed behavior. A sensitivity analysis indicates that the utility of hot water flooding improves with the increasing temperature dependence of NAPL hydraulic properties.     

Investigation of the Contamination of Fractured Formations by Non-Newtonian Oil Pollutants

In many practical applications, non-aqueous phase liquid (NAPL) pollutants exhibiting a clearly non-Newtonian rheological behavior (e.g. crude oil, suspensions of engine oils, asphalt, creosote, etc.) may migrate through fractured formations and contaminate aquifers. The present work is the first step toward the development of non-Darcian models concerning the non-linear NAPL flow in single fractures, and detemiination of the coupled effects of non-Newtonian NAPL rheology and flow rate on the transient immiscible displacement of an aqueous phase by a NAPL. Initially, a protocol is developed for the preparation and rheological characterization of synthetic non-Newtonian NAPLs, which are based on waxy oils. Then, an artificial transparent glass-etched single fracture of controlled morphology is fabricated and used for the measurement of the non-linear pressure gradient--superficial velocity relationship for the flow of NAPL of varying rheology. Pore network simulations and effective medium approximation (EMA) are used for the interpretation of the experimental results and derivation of an analytic non-Darcian one-phase flow model. Visualization experiments of the immiscible displacement of an aqueous phase by Newtonian and non-Newtonian NAPLs are performed on the artificial fracture under controlled values of the viscosity ratio and capillary number (ratio of viscous to capillary forces). Comparative study of the Newtonian and non-Newtonian NAPL flow patterns allows us to evaluate the interactive effects of NAPL rheology, flow rates and fracture morphology on the spatial and temporal distribution of such liquid pollutants within single fractures     

Radon as a naturally occurring tracer for the assessment of residual NAPL contamination of aquifers

The noble gas radon has a strong affinity to non-aqueous phase-liquids (NAPLs). That property makes it applicable as naturally occurring partitioning tracer for assessing residual NAPL contamination of aquifers. In a NAPL contaminated aquifer, radon dissolved in the groundwater partitions preferably into the NAPL. The magnitude of the resulting radon deficit in the groundwater depends on the NAPL-specific radon partition coefficient and on the NAPL saturation of the pore space. Hence, if the partition coefficient is known, the NAPL saturation is attainable by determination of the radon deficit. After a concise discussion of theoretical aspects regarding radon partitioning into NAPL, related experimental data and results of a field investigation are presented. Aim of the laboratory experiments was the determination of radon partition coefficients of multi-component NAPLs of environmental concern. The on-site activities were carried out in order to confirm the applicability of the "radon method" under field conditions.     

Investigation of the Contamination of Fractured Formations by Non-Newtonian Oil Pollutants

In many practical applications, non-aqueous phase liquid (NAPL) pollutants exhibiting a clearly non-Newtonian rheological behavior (e.g. crude oil, suspensions of engine oils, asphalt, creosote, etc.) may migrate through fractured formations and contaminate aquifers. The present work is the first step toward the development of non-Darcian models concerning the non-linear NAPL flow in single fractures, and determination of the coupled effects of non-Newtonian NAPL rheology and flow rate on the transient immiscible displacement of an aqueous phase by a NAPL. Initially, a protocol is developed for the preparation and rheological characterization of synthetic non-Newtonian NAPLs, which are based on waxy oils. Then, an artificial transparent glass-etched single fracture of controlled morphology is fabricated and used for the measurement of the non-linear pressure gradient—superficial velocity relationship for the flow of NAPL of varying rheology. Pore network simulations and effective medium approximation (EMA) are used for the interpretation of the experimental results and derivation of an analytic non-Darcian one-phase flow model. Visualization experiments of the immiscible displacement of an aqueous phase by Newtonian and non-Newtonian NAPLs are performed on the artificial fracture under controlled values of the viscosity ratio and capillary number (ratio of viscous to capillary forces). Comparative study of the Newtonian and non-Newtonian NAPL flow patterns allows us to evaluate the interactive effects of NAPL rheology, flow rates and fracture morphology on the spatial and temporal distribution of such liquid pollutants within single fractures.     

Multispectral image analysis method to determine dynamic fluid saturation distribution in two-dimensional three-fluid phase flow laboratory experiments

The need for measuring dynamic fluid saturation distribution in multi-dimensional three-fluid phase flow experiments is hampered by lack of appropriate techniques to monitor full field transient flow phenomena. There is no conventional technique able to measure dynamic three-fluid phase saturation at several array points of the flow field at the same time. A multispectral image analysis technique was developed to determine dynamic NAPL, water and air saturation distribution in two-dimensional three-fluid phase laboratory experiments. Using a digital near-infrared camera, images of sand samples with various degrees of NAPL, water and air saturation were taken, under constant lighting conditions and within three narrow spectral bands of the visible and near-infrared spectrum. It was shown that the optical density defined for the reflected luminous intensity was a linear function of the NAPL and the water saturation for each spectral band and for any two and three-fluid phase systems. This allowed the definition of dimensionless lump reflection coefficients for the NAPL and the water phase within each spectral band. Consequently, at any given time, two images taken within two different spectral bands provided two linear equations which could be solved for the water and the NAPL saturation. The method was applied to two-dimensional three-phase flow experiments, which were conducted to investigate the migration and the distribution of LNAPL in the vadose zone. The method was used to obtain continuous, quantitative and dynamic full field mapping of the NAPL saturation as well as the variation of the water and the air saturation during NAPL flow. The method provides a non-destructive and non-intrusive tool for studying multiphase flow for which rapid changes in fluid saturation in the entire flow domain is difficult to measure using conventional techniques.     

Mass flux from a non-aqueous phase liquid pool considering spontaneous expansion of a discontinuous gas phase

The partitioning of non-aqueous phase liquid (NAPL) compounds to a discontinuous gas phase results in the repeated spontaneous expansion, snap-off, and vertical mobilization of the gas phase. This mechanism has the potential to significantly affect the mass transfer processes that control the dissolution of NAPL pools by increasing the vertical transport of NAPL mass and increasing the total mass transfer rate from the surface of the pool. The extent to which this mechanism affects mass transfer from a NAPL pool depends on the rate of expansion and the mass of NAPL compound in the gas phase. This study used well-controlled bench-scale experiments under no-flow conditions to quantify for the first time the expansion of a discontinuous gas phase in the presence of NAPL. Air bubbles placed in glass vials containing NAPL increased significantly in volume, from a radius of 1.0 mm to 2.0 mm over 215 days in the presence of tetrachloroethene (PCE), and from a radius of 1.2 mm to 2.3 mm over 22 days in the presence of trans-1,2-dichloroethene (tDCE). A one-dimensional mass transfer model, fit to the experimental data, showed that this expansion could result in a mass flux from the NAPL pool that was similar in magnitude to the mass flux expected for the dissolution of a NAPL pool in a two-fluid (NAPL and water) system. Conditions favouring the significant effect of a discontinuous gas phase on mass transfer were identified as groundwater velocities less than ~0.01 m/day, and a gas phase that covers greater than ~10% of the pool surface area and is located within ~0.01 m of the pool surface. Under these conditions the mass transfer via a discontinuous gas phase is expected to affect, for example, efforts to locate NAPL source zones using aqueous concentration data, and predict the lifetime and risk associated with NAPL source zones in a way that is not currently included in the common conceptual models used to assess NAPL-contaminated sites.     

Characterization of pore scale NAPL morphology in homogeneous sands as a function of grain size and NAPL dissolution

In this study, we investigate pore scale morphology of nonaqueous phase liquids (NAPLs) trapped in different pore sizes using tracer techniques. Specific interfacial area and saturation of NAPL trapped in homogeneous sands were measured using the interfacial and partitioning tracer techniques. The observed NAPL-water interfacial areas increased in a log-linear fashion with decreasing sand grain size, but showed no clear trend with residual NAPL saturation formed in the various grain sizes. The measured values were used to calculate the NAPL morphology index, which characterizes the spatial NAPL distribution within the pore space. The NAPL morphology indices, increased exponentially with decreasing grain size, indicating that the NAPL becomes smaller, but more blobs. For a fixed grain size, the specific interfacial area and saturation of the NAPL were measured following changes caused by dissolution using alcohol. The observed interfacial areas showed a decrease linearly as a function of the NAPL saturation.     

Evaluation of simplified mass transfer models to simulate the impacts of source zone architecture on nonaqueous phase liquid dissolution in heterogeneous porous media

Nonaqueous phase liquid (NAPL) dissolution was studied in three-dimensional (3D) heterogeneous experimental aquifers (25.5 cm x 9 cm x 8.5 cm) with two different longitudinal correlation lengths (2.1 cm and 1.1 cm) and initial spill volumes (22.5 ml and 10.5 ml). Spatial and temporal distributions of NAPL during dissolution were measured using magnetic resonance imaging (MRI). At high NAPL spill volume, average effluent concentrations initially increased during dissolution, as NAPL pools transitioned to NAPL ganglia, and then decreased as the total NAPL-water interfacial area decreased over time. Experimental results were used to test six dissolution models: (i and ii) a one-dimensional (1D) model using either specific NAPL-water interfacial area values estimated from MR images at each time step (i.e., 1D quasi-steady state model), or an empirical mass transfer (Sh') correlation (i.e., 1D transient model), (iii and iv) a multiple analytical source superposition technique (MASST) using either the NAPL distribution determined from MR images at each time step (i.e., MASST steady state model), or the NAPL distribution determined from mass balance calculations (i.e., MASST transient model), (v) an equilibrium streamtube model, and (vi) a 3D grid-scale pool dissolution model (PDM) with a dispersive mass flux term. The 1D quasi-steady state model and 3D PDM captured effluent concentration values most closely, including some concentration fluctuations due to changes in the extent of flow reduction. The 1D transient, MASST steady state and transient, and streamtube models all showed a monotonic decrease in effluent concentration values over time, and the streamtube model was the most computationally efficient. Changes during dissolution of the effective NAPL-water interfacial area estimated from imaging data are similar to changes in effluent concentration values. The 1D steady state model incorporates estimates of the effective NAPL-water interfacial area directly at each time point; the 3D PDM does so indirectly through mass balance and a relative permeability function, which causes reduced water flow through high saturation NAPL regions. Hence, when model accuracy is required, the results indicate that a surrogate of this effective interfacial area is required. Approaches to include this surrogate in the MASST and streamtube models are recommended.     

Impact of nonaqueous phase liquid (NAPL) source zone architecture on mass removal mechanisms in strongly layered heterogeneous porous media during soil vapor extraction

An existing multiphase flow simulator was modified in order to determine the effects of four mechanisms on NAPL mass removal in a strongly layered heterogeneous vadose zone during soil vapor extraction (SVE): a) NAPL flow, b) diffusion and dispersion from low permeability zones, c) slow desorption from sediment grains, and d) rate-limited dissolution of trapped NAPL. The impacts of water and NAPL saturation distribution, NAPL-type (i.e., free, residual, or trapped) distribution, and spatial heterogeneity of the permeability field on these mechanisms were evaluated. Two different initial source zone architectures (one with and one without trapped NAPL) were considered and these architectures were used to evaluate seven different SVE scenarios. For all runs, slow diffusion from low permeability zones that gas flow bypassed was a dominant factor for diminished SVE effectiveness at later times. This effect was more significant at high water saturation due to the decrease of gas-phase relative permeability. Transverse dispersion contributed to fast NAPL mass removal from the low permeability layer in both source zone architectures, but longitudinal dispersion did not affect overall mass removal time. Both slow desorption from sediment grains and rate-limited mass transfer from trapped NAPL only marginally affected removal times. However, mass transfer from trapped NAPL did affect mass removal at later time, as well as the NAPL distribution. NAPL flow from low to high permeability zones contributed to faster mass removal from the low permeability layer, and this effect increased when water infiltration was eliminated. These simulations indicate that if trapped NAPL exists in heterogeneous porous media, mass transfer can be improved by delivering gas directly to zones with trapped NAPL and by lowering the water content, which increases the gas relative permeability and changes trapped NAPL to free NAPL.     

The effect of multicomponent diffusion on NAPL dissolution from spherical ternary mixtures

This paper investigates the dissolution characteristics of ternary nonaqueous phase liquid (NAPL) mixtures with the goal of comparing the relative contributions of multicomponent (intra-NAPL) diffusion, film transfer and thermodynamic nonideality. These contributions are compared at the pore scale and intermediate scale (several centimeters downstream from the source). Trichloroethene (TCE), tetrachloroethene (PCE) and 1,1,1-trichloroethane (TCA) were selected to model a reasonably ideal mixture; TCE, PCE and octanol were selected as a relevant nonideal mixture. A multicomponent diffusion-based dissolution model incorporating hydrodynamic theory was formulated to estimate intra-NAPL concentration gradients and associated aqueous interfacial concentrations for ideally shaped (spherical) NAPL blobs. Pore scale dissolution times for this model were compared to those generated using the conventional well-mixed NAPL dissolution model, applying the same film transfer boundary condition in both cases. Activity coefficients (spatially and temporally variable for the diffusion model, temporally variable for the well-mixed model) were estimated using UNIFAC. NAPL interfacial concentration histories generated using the pore scale models were used as input in a three-dimensional groundwater transport model (MT3DMS) to compare downstream concentration distributions. For the relatively large NAPL bodies simulated (r=0.6 cm), intra-NAPL diffusion effects were found to be significant at the pore scale and were strongly impacted by the mixture's thermodynamic ideality. At the intermediate scale, and for the conditions tested, modest differences in the simulations suggested that intra-NAPL diffusion effects would be negligible compared to those associated with mixture composition uncertainty, dissolution rate processes related to NAPL-induced permeability effects and hydrodynamic issues associated with flow field heterogeneity.     

Intermediate-scale 2D experimental investigation of in situ chemical oxidation using potassium permanganate for remediation of complex DNAPL source zones

In situ chemical oxidation is a technology that has been applied to speed up remediation of a contaminant source zone by inducing increased mass transfer from DNAPL sources into the aqueous phase for subsequent destruction. The DNAPL source zone can consist of one or more individual sources that may be present as an interconnected pool of high saturation, as a region of disconnected ganglia at residual saturation, or as combinations of these two morphologies. Potassium permanganate (KMnO(4)) is a commonly employed oxidant that has been shown to rapidly destroy DNAPL compounds like PCE and TCE following second-order kinetics in an aqueous system. During the oxidation of a target DNAPL compound, or naturally occurring reduced species in the subsurface, manganese oxide (MnO(2)) solids are produced. Research has shown that these manganese oxide solids may result in permeability reductions in the porous media thus reducing the ability for oxidant to be transported to individual DNAPL sources. It can also occur at the DNAPL-water interface, decreasing contact of the oxidant with the DNAPL. Additionally, MnO(2) formation at the DNAPL-water interface, and/or flow-bypassing as a result of permeability reductions around the source, may alter the mass transfer from the DNAPL into the aqueous phase, potentially diminishing the magnitude of any DNAPL mass depletion rate increase induced by oxidation. An experiment was performed in a two-dimensional (2D) sand-filled tank that included several discrete DNAPL source zones. Spatial and temporal monitoring of aqueous PCE, chloride, and permanganate concentrations was used to relate changes in mass depletion of, and mass flux, from DNAPL residual and pool source zones to chemical oxidation performance and MnO(2) formation. During the experiment, permeability changes were monitored throughout the 2D tank and these were related to MnO(2) deposition as measured through post-oxidation soil coring. Under the conditions of this experiment, MnO(2) formation was found to reduce permeability in and around DNAPL source zones resulting in changes to the overall flow pattern, with the effects depending on source zone configuration. A pool with little or no residual around it, in a relatively homogeneous flow field, appeared to benefit from resulting MnO(2) pore-blocking that substantially reduced mass transfer from the pool even though there was relatively little PCE mass removed from the pool. In contrast, a pool with residual around it (in a more typical heterogeneous flow field) appeared to undergo increased mass transfer as MnO(2) reduced permeability, altering the water flow and increasing the mixing at the DNAPL-water interface. Further, the magnitude of increased PCE mass depletion during oxidation appeared to depend on the PCE source configuration (pool versus ganglia) and decreased as MnO(2) was formed and deposited at the DNAPL-water interface. Overall, the oxidation of PCE mass appeared to be rate-limited by the mass transfer from the DNAPL to aqueous phase.     

Effect of scale and dimensionality on the surfactant-enhanced solubilization of a residual DNAPL contamination

The mass transfer rate from residual dense non-aqueous phase liquids (DNAPLs) to the mobile aqueous phase is an important parameter for the efficiency of surfactant-enhanced remediation through solubilization of this type of contamination. The mass transfer kinetics are highly dependent on the dimensionality of the system. In this study, irregularly shaped residual TCE saturations in two-dimensional saturated flow fields were flushed with a 2% polyoxyethylene sorbitan (20) monooleate (POESMO) solution until complete removal had been achieved. A numerical model was developed and used for the simulation of the various surfactant-flushing experiments with different initial saturation patterns and flow rates. Through optimization against in situ concentration and saturation data, a phenomenological power-law model for the relationship between the mass transfer rate from the DNAPL to the mobile aqueous phase on the one hand and the residual DNAPL saturation and the flow velocity on the other hand was derived. The obtained mass transfer rate parameters provide a reasonable fit to the experimental data, predicting the cleanup time and the general saturation and concentration pattern quite well but failing to predict the concentration curves at every individual sampling port. The obtained mass transfer rate model gives smaller values for the predicted mass transfer rate but shows a comparable dependence on water flow and saturation as in earlier published one-dimensional column experiments with identical characteristics for porous medium, DNAPL and surfactant. Mass transfer rate predictions were about one order of magnitude lower in the 2-D flow cell experiment than in 1-D column experiments. These results give an indication for the importance of dimensionality during surfactant remediation.     

Simple screening models of NAPL dissolution in the subsurface

Three simple screening models of nonaqueous phase liquid (NAPL) dissolution in the subsurface are proposed based on the NAPL mass conservation and the assumption of proportionality between the residual NAPL source zone concentration and the remaining residual NAPL mass. The purpose of the proposed models is to predict the solute concentration in the zone of the residual NAPL as a result of dissolution. The predicted source zone concentration decrease is used to simulate and account for the decrease of dissolution rate with time. The proposed simple NAPL dissolution models enable the pseudo-equilibrium formulation to be used and therefore the numerical simulations for field application problems can be simplified compared to the non-equilibrium counterpart. With proper choice of empirical parameters, the proposed simple screening models can work as well as more complex dissolution rate correlation models, such as that of Imhoff et al. [Water Resour. Res. 30 (1994) 307-320]. It is found that the proposed models are very good for quantifying non-equilibrium dissolution, which is characterized by tailing of breakthrough curves. The models are especially useful for situations of small residual NAPL saturation, which are typical for many field applications.     

DNAPL source depletion: linking architecture and flux response

The relationship between dense non-aqueous phase liquid (DNAPL) mass reduction and contaminant mass flux was investigated experimentally in four model source zones. The flow cell design for the experiments featured a segmented extraction well that allowed for analysis of spatially resolved flux information. This flux information was coupled with image analysis of the NAPL spatial distribution to investigate the relationship between flux and the up-gradient NAPL architecture. Results indicate that in the systems studied, the relationship between DNAPL mass reduction and contaminant mass flux was primarily controlled by the NAPL architecture. A specific definition of NAPL architecture was employed where the source zone is resolved into a collection of streamtubes with spatial variability in NAPL saturation along each streamtube integrated and transformed into an effective NAPL content for each streamtube. The distribution of NAPL contents among the streamtubes (NAPL architecture) controlled dissolution dynamics. Two simplified models, a streamtube model and an effective Damkohler number model, were investigated for their ability to simulate dissolution dynamics.     

Effect of soil layering on NAPL removal behavior in soil-heated vapor extraction

Soil heating has been proposed as a method to enhance the vapor extraction of NAPLs from contaminated soils. Three-dimensional fluid flow and heat transfer simulations have been performed for soil-heated vapor extraction to determine the transient system performance for a hypothetical configuration. Soil layering has been considered in evaluation of the initial non-aqueous phase liquid (NAPL) distribution and in evaporation and transport to the vapor extraction location. Results from this layered model are compared with results for a homogeneous system with an initially uniform NAPL, indicating the influence of layering, the initial NAPL distribution, the type of NAPL, and the possibility of enhanced vapor diffusion. Not only is the NAPL removal time reduced significantly with the addition of heat, but the uncertainty in the removal time owing to a number of difficult to characterize in situ factors, such as layering and the initial NAPL distribution, is much less than for standard soil vapor extraction without heating, owing to the rise in temperature and increase in NAPL vapor pressure with time.     

Two-dimensional laboratory simulation of LNAPL infiltration and redistribution in the vadose zone

A quantitative two-dimensional laboratory experiment was conducted to investigate the immiscible flow of a light non-aqueous phase liquid (LNAPL) in the vadose zone. An image analysis technique was used to determine the two-dimensional saturation distribution of LNAPL, water and air during LNAPL infiltration and redistribution. Vertical water saturation variations were also continuously monitored with miniature resistivity probes. LNAPL and water pressures were measured using hydrophobic and hydrophilic tensiometers. This study is limited to homogeneous geological conditions, but the unique experimental methods developed will be used to examine more complex systems. The pressure measurements and the quantification of the saturation distribution of all the fluids in the entire flow domain under transient conditions provide quantitative data essential for testing the predictive capability of numerical models. The data are used to examine the adequacy of the constitutive pressure-saturation relations that are used in multiphase flow models. The results indicate that refinement of these commonly used hydraulic relations is needed for accurate model prediction. It is noted in particular that, in three-fluid phase systems, models should account for the existence of a residual NAPL saturation occurring after NAPL drainage. This is of notable importance because residual NAPL can act as a non negligible persistent source of contamination.     

Reaction-enhanced mass transfer and transport from non-aqueous phase liquid source zones

The objective of the following research is to theoretically quantify the enhancement of interphase mass transfer of dissolved non-aqueous phase liquid (NAPL) compounds from the non-aqueous phase to the aqueous phase and the enhancement of dispersive mass transport from a NAPL zone due to destruction of dissolved NAPL compounds. For relatively slow reaction rates, such as for permanganate and perchloroethene (PCE), local-scale mass transfer enhancement is expected to be small. Dispersive mass transport with reaction from a horizontal NAPL zone can be quantified using equations derived for a mathematically equivalent falling film reactor system. In contrast to local-scale interphase mass transfer, dispersive mass transport from NAPL zones may be significantly increased by reaction. Enhancement factors due to destruction of the NAPL compound(s) are mainly dependent on NAPL solubility and oxidant concentration and to a lesser extent on reaction rate, stoichiometry, and transverse dispersion coefficients. Higher NAPL solubility and/or lower oxidant concentration reduces the maximum expected enhancement factor. Reaction enhancement factors for mass transport from NAPL zones are expected to be in the range of 5-50 for permanganate and chlorinated solvents. Theoretical results suggest that assuming instantaneous reaction rates may be appropriate for dispersive mass transport from NAPL zones.