Equilibrium nonaqueous phase liquid pool geometry in coarse soils with discrete textural interfaces

This paper presents a model for the geometry of nonaqueous phase liquid (NAPL) pools and mounds in homogeneous soils and soils with discrete textural interfaces. It is shown that the concepts of capillary pressure-saturation curve hysteresis and entry pressures are integral to the complete conceptualization of pool and mound geometry. Unless hysteresis is included in the analysis, light NAPL (LNAPL) in homogeneous soils cannot exist in pools at all, and dense NAPL (DNAPL) will not mound on horizontal textural interfaces unless lateral confining boundaries are present. The proposed model also implies that remobilization of DNAPL pools will occur at lower hydraulic gradients than those predicted with previous models. Comparing predicted and experimental DNAPL and LNAPL pool thicknesses and the location of an LNAPL lens with respect to the top of the capillary fringe validate the model.     

Natural remobilization of multicomponent DNAPL pools due to dissolution

Mixtures of dense nonaqueous phase liquids (DNAPLs) trapped in the subsurface can act as long-term sources of contamination by dissolving into flowing groundwater. If the components have different solubilities then dissolution will alter the composition of the remaining DNAPL. We theorized that a multicomponent DNAPL pool may become mobile due to the natural dissolution process. In this study, we focused on two scenarios: (1) a DNAPL losing light component(s), with the potential for downward migration; and (2) a DNAPL losing dense component(s), with the potential for upward migration following transformation into a less dense than water nonaqueous phase liquid (LNAPL). We considered three binary mixtures of common groundwater contaminants: benzene and tetrachloroethylene (PCE), PCE and dichloromethane (DCM), and DCM and toluene. A number of physical properties that control the retention and transport of DNAPL in porous media were measured for the mixtures, namely: density, interfacial tension, effective solubility, and viscosity. All properties except density exhibited nonlinear relationships with changing molar ratio of the DNAPL. To illustrate the potential for natural remobilization, we modelled the following two primary mechanisms: the reduction in pool height as mass is lost by dissolution, and the changes in fluid properties with changing molar ratio of the DNAPL. The first mechanism always reduces the capillary pressure in the pool, while the second mechanism may increase the capillary pressure or alter the direction of the driving force. The difference between the rate of change of each determines whether the potential for remobilization increases or decreases. Static conditions and horizontal layering were assumed along with a one-dimensional, compositional modelling approach. Our results indicated that for initial benzene/PCE ratios greater than 25:75, the change in density was sufficiently faster than the decline in pool height to promote DNAPL breakthrough into the adjacent porous medium. In contrast, there was no potential for natural remobilization of a PCE-DCM mixture, primarily because the densities of the components are not sufficiently different. Dissolution of a DCM-toluene mixture decreased the density, reducing the tendency for downward displacement. However, the ultimate transformation from a DNAPL to an LNAPL may induce upward displacement. These results suggest that at sites with DNAPL pools containing a mix of components of sufficiently different densities and relative solubilities, natural remobilization may be an active mechanism, with implications for site evaluation and remediation.     

Commentary: assessment of past infiltration fluxes through Yucca Mountain on the basis of the secondary mineral record-is it a viable methodology?

Two papers recently published in the Journal of Contaminant Hydrology by Marshall et al. [Marshall, B.D., Neymark, L.A., Peterman, Z.E., 2003. Estimation of past seepage volumes from calcite distribution in the Topopah Spring Tuff, Yucca Mountain, Nevada. J. Contam. Hydrol. 62-63, 237-247] and Xu et al. [Xu, T., Sonnenthal, E., Bodvarsson, G., 2003. A reaction-transport model for calcite precipitation and evaluation of infiltration fluxes in unsaturated fractured rock. J. Contam. Hydrol. 64, 113-127] attempt to assess past volumes of seepage and infiltration fluxes through the vadose zone of Yucca Mountain, Nevada, on the basis of the modeling of the spatial distribution of secondary calcite. In this commentary, we argue that the employed methodology is not viable. In addition, the thermal boundary conditions used in simulations do not correspond to the temperatures of the mineral forming fluids established on the basis of the fluid inclusion studies.     

Numerical simulations of radon as an in situ partitioning tracer for quantifying NAPL contamination using push-pull tests

Presented here is a reanalysis of results previously presented by [Davis, B.M., Istok, J.D., Semprini, L., 2002. Push-pull partitioning tracer tests using radon-222 to quantify non-aqueous phase liquid contamination. J. Contam. Hydrol. 58, 129-146] of push-pull tests using radon as a naturally occurring partitioning tracer for evaluating NAPL contamination. In a push-pull test where radon-free water and bromide are injected, the presence of NAPL is manifested in greater dispersion of the radon breakthrough curve (BTC) relative to the bromide BTC during the extraction phase as a result of radon partitioning into the NAPL. Laboratory push-pull tests in a dense or DNAPL-contaminated physical aquifer model (PAM) indicated that the previously used modeling approach resulted in an overestimation of the DNAPL (trichloroethene) saturation (S(n)). The numerical simulations presented here investigated the influence of (1) initial radon concentrations, which vary as a function of S(n), and (2) heterogeneity in S(n) distribution within the radius of influence of the push-pull test. The simulations showed that these factors influence radon BTCs and resulting estimates of S(n). A revised method of interpreting radon BTCs is presented here, which takes into account initial radon concentrations and uses non-normalized radon BTCs. This revised method produces greater radon BTC sensitivity at small values of S(n) and was used to re-analyze the results from the PAM push-pull tests reported by Davis et al. The re-analysis resulted in a more accurate estimate of S(n) (1.8%) compared with the previously estimated value (7.4%). The revised method was then applied to results from a push-pull test conducted in a light or LNAPL-contaminated aquifer at a field site, resulting in a more accurate estimate of S(n) (4.1%) compared with a previously estimated value (13.6%). The revised method improves upon the efficacy of the radon push-pull test to estimate NAPL saturations. A limitation of the revised method is that 'background' radon concentrations from a non-contaminated well in the NAPL-contaminated aquifer are needed to accurately estimate NAPL saturation. The method has potential as a means of monitoring the progress of NAPL remediation.     

Mobilization of small DNAPL pools formed by capillary entrapment

We performed an experimental study to quantify the critical conditions for the mobilization of small pools of dense nonaqueous phase liquids (DNAPLs) that may form at capillary-heterogeneity boundaries. A series of experiments were conducted in columns packed with uniform sands arranged to create capillary heterogeneities. DNAPL pools readily formed in these packings and were more easily mobilized than trapped DNAPL ganglia. A model was developed to describe the critical conditions for DNAPL pool mobilization. Pool mobilization was expected when a dimensionless pool trapping number N(T)p> 1 while mobilization was observed in our experiments when N(T)p>0.76+/-0.16 (+/- 95% confidence interval). The difference between the model prediction and the experimental observations was attributed to experimental error. Using this model for DNAPL pool mobilization, a simple numerical experiment was conducted to illustrate use of the model and to explore the effect of scale on the critical conditions for pool mobilization. With an increase in system scale flow bypassing around the DNAPL pool increased and the system-averaged conditions for the onset of mobilization changed: a greater system-average Darcy flux or lower interfacial tensions were required for DNAPL pool mobilization. This result illustrates the importance of system scale on mobilization of DNAPL pools in systems with capillary heterogeneities.     

Assessing impacts of partial mass depletion in DNAPL source zones: II. Coupling source strength functions to plume evolution

Analytical solutions, describing the time-dependent DNAPL source-zone mass and contaminant discharge rate, derived previously in Part I [Falta, R.W., Rao, P.S., Basu, N., this issue. Assessing the impacts of partial mass depletion in DNAPL source zones: I. Analytical modeling of source strength functions and plume response. J. Contam. Hydrol.] are used as a flux-boundary condition in a semi-analytical contaminant transport model. These analytical solutions assume a power relationship between the flow-averaged source concentration, and the source DNAPL mass; the empirical exponent (gamma) is a function of the flow field heterogeneity, DNAPL architecture, and the correlation between them. The DNAPL source strength terms can account for partial source remediation, either at time zero, or at some later time after the DNAPL release. The transport model considers advection, retardation, three-dimensional dispersion, and sequential first-order decay/production of several species. A separate solution is used to compute the time-dependent mass of each contaminant in the plume. A series of examples using different values of gamma shows how the benefits of partial DNAPL source remediation can vary with site conditions. In general, when gamma>1, relatively large short-term reductions in the plume concentrations and mass occur, but the source longevity is not strongly affected. Conversely, when gamma<1, the short-term reductions in the plume concentrations and mass are smaller, but the source longevity can be greatly reduced. In either case, the source remediation effort is much more effective if it is undertaken at an early time, before much contaminant mass has entered the plume. If the remediation effort is significantly delayed, the leading parts of the plume are not affected by the source remediation, and additional control or remediation of the plume itself is required.     

Multiphase flow and transport caused by spontaneous gas phase growth in the presence of dense non-aqueous phase liquid

Disconnected bubbles or ganglia of trapped gas may occur below the top of the capillary fringe through a number of mechanisms. In the presence of dense non-aqueous phase liquid (DNAPL), the disconnected gas phase experiences mass transfer of dissolved gases, including volatile components from the DNAPL. The properties of the gas phase interface can also change. This work shows for the first time that when seed gas bubbles exist spontaneous gas phase growth can be expected to occur and can significantly affect water-gas-DNAPL distributions, fluid flow, and mass transfer. Source zone behaviour was observed in three different experiments performed in a 2-dimensional flow cell. In each case, a DNAPL pool was created in a zone of larger glass beads over smaller glass beads, which served as a capillary barrier. In one experiment effluent water samples were analyzed to determine the vertical concentration profile of the plume above the pool. The experiments effectively demonstrated a) a cycle of spontaneous gas phase expansion and vertical advective mobilization of gas bubbles and ganglia above the DNAPL source zone, b) DNAPL redistribution caused by gas phase growth and mobilization, and c) that these processes can significantly affect mass transport from a NAPL source zone.     

Bench-scale visualization of DNAPL remediation processes in analog heterogeneous aquifers: surfactant floods and in situ oxidation using permanganate

We have conducted well-controlled DNAPL remediation experiments within a 2-D, glass-walled, sand-filled chamber using surfactants (Aerosol MA and Tween 80) to increase solubility and an oxidant (permanganate) to chemically degrade the DNAPL. Initial conditions for each remediation experiment were created by injecting DNAPL as a point source at the top of the chamber and allowing the DNAPL to migrate downward through a water-filled, heterogeneous, sand-pack designed to be evocative of a fluvial depositional environment. This migration process resulted in the DNAPL residing as a series of descending pools. Lateral advection across the chamber was used to introduce the remedial fluids. Photographs and digital image analysis illustrate interactions between the introduced fluids and the DNAPL. In the surfactant experiments, we found that DNAPL configured in a series of pools was easily mobilized. Extreme reductions in DNAPL/water interfacial tension occurred when using the Aerosol MA surfactant, resulting in mobilization into low permeability regions and thus confounding the remediation process. More modest reductions in interfacial tension occurred when using the Tween 80 surfactant resulting in modest mobilization. In this experiment, capillary forces remained sufficient to exclude DNAPL migration into low permeability regions allowing the excellent solubilizing properties of the surfactant to recover almost 90% of the DNAPL within 8.6 pore volumes. Injection of a potassium permanganate solution resulted in precipitation of MnO2, a reaction product, creating a low-permeability rind surrounding the DNAPL pools. Formation of this rind hindered contact between the permanganate and the DNAPL, limiting the effectiveness of the remediation. From these experiments, we see the value of performing visualization experiments to evaluate the performance of proposed techniques for DNAPL remediation.     

Determining effective interfacial tension and predicting finger spacing for DNAPL penetration into water-saturated porous media

The difficulty in determining the effective interfacial tension limits the prediction of the wavelength of fingering of immiscible fluids in porous media. A method to estimate the effective interfacial tension using fractal concepts was presented by Chang et al. [Water Resour. Res. 30 (1994) 125]. We modified the method in that the macroscopic interface length was used instead of the system width. Methods to determine the macroscopic and the microscopic interface length are given. Lab experiments of dense nonaqueous phase liquid (DNAPL) penetrating into water-saturated glass beads were carried out in a two-dimensional (2-D) transparent chamber. The displacement processes were recorded using a 35-mm camera or a video camera, which was directly connected to and controlled by a computer. Unlike the method of Chang et al. (1994), the modified method used here gives a constant value of the effective interfacial tension over time. The predicted wavelengths of fingering are relatively close to those observed except for the fine beads.     

Prediction of mass-transfer coefficient for solute transport in porous media

Several previously reported laboratory studies related to transport of solutes through packed columns were utilized to develop predictive relationships for mass-transfer rate coefficient. The data were classified into two groups: those obtained under rate-limited mass transfer between mobile and immobile water regions (physical nonequilibrium conditions), and those derived from rate-limited mass transfer between instantaneous and slow sorption sites (sorption nonequilibrium conditions). The mass-transfer coefficient in all these studies was obtained by fitting breakthrough data to a transport model employing a first-order rate limitations with a "constant" mass-transfer coefficient, independent of flow conditions. This study demonstrated that the mass-transfer coefficient in these models is dependent on system parameters including pore-water velocity, length-scale, retardation coefficient, and particle or aggregate size. Predictive relationships were developed, through regression analysis, relating mass-transfer coefficient to residence time. The developed relationships adequately estimated previously reported field mass-transfer values. Successful simulations of field desorption data reported by Bahr [J. Contam. Hydrol. 4 (1989) 205] further demonstrate the potential applicability of the developed relationships.     

Prediction and minimization of vertical migration of DNAPLS using surfactant enhanced aquifer remediation at neutral buoyancy

Surfactant enhanced aquifer remediation (SEAR) had previously been thought to require a capillary barrier below the contaminated zone to prevent the vertical migration of a microemulsion containing solubilized DNAPL. This paper shows the vertical migration of the dense microemulsion is described and predicted by the value of three dimensionless scaling groups. Embedded within these scaling groups are four design parameters. The value of these parameters can be manipulated in order to reduce the amount of vertical migration anticipated for a given remediation design. Plots have been constructed that illustrate the relationship between vertical migration and the value of the scaling groups; such plots can be used to predict vertical migration and to determine appropriate screen intervals of extraction wells to ensure full capture of the contaminants. This predictive capability has been verified in laboratory experiments. Predicted migration of the microemulsion agreed within about 2% of that observed. Development of the scaling groups is presented, remediation design implications are discussed, and laboratory verification is shown. Additional discussion of the laboratory work is given in a companion paper [Kostarelos, K., Pope, G.A., Rouse, B.A., Shook, G.M., 1998. A new concept: the use of neutrally-buoyant microemulsions for DNAPL remediation, J. Contam. Hydro., this edition].     

A proposed model to include a residual NAPL saturation in a hysteretic capillary pressure-saturation relationship

A residual non-aqueous phase liquid (NAPL) present in the vadose zone can act as a contaminant source for many years as the compounds of concern partition to infiltrating groundwater and air contained in the soil voids. Current pressure-saturation-relative permeability relationships do not include a residual NAPL saturation term in their formulation. This paper presents the results of series of two- and three-phase pressure cell experiments conducted to evaluate the residual NAPL saturation and its impact on the pressure-saturation relationship. A model was proposed to incorporate a residual NAPL saturation term into an existing hysteretic three-phase parametric model developed by Parker and Lenhard [Water Resour. Res. 23(12) (1987) 2187], Lenhard and Parker [Water Resour. Res. 23(12) (1987) 2197] and Lenhard [J. Contam. Hydrol. 9 (1992) 243]. The experimental results indicated that the magnitude of the residual NAPL saturation was a function of the maximum total liquid saturation reached and the water saturation. The proposed model to incorporate a residual NAPL saturation term is similar in form to the entrapment model proposed by Parker and Lenhard, which was based on an expression presented by Land [Soc. Pet. Eng. J. (June 1968) 149].     

Modelling the migration of contaminants through variably saturated dual-porosity, dual-permeability chalk

In the Hesbaye region in Belgium, tracer tests performed in variably saturated fissured chalk rocks presented very contrasting results in terms of transit times, according to artificially controlled water recharge conditions prevailing during the experiments. Under intense recharge conditions, tracers migrated across the partially or fully saturated fissure network, at high velocity in accordance with the high hydraulic conductivity and low effective porosity (fracture porosity). At the same time, a portion of the tracer was temporarily retarded in the almost immobile water located in the matrix. Under natural infiltration conditions, the fissure network remained inactive. Tracers migrated downward through the matrix, at low velocity in relation with the low hydraulic conductivity and the large porosity of the matrix. Based on these observations, Brouyère et al. (2004a) [Brouyère, S., Dassargues, A., Hallet, V., 2004a. Migration of contaminants through the unsaturated zone overlying the Hesbaye chalky aquifer in Belgium: a field investigation, J. Contam. Hydrol., 72 (1-4), 135-164, doi: 10.1016/j.conhyd.2003.10.009] proposed a conceptual model in order to explain the migration of solutes in variably saturated, dual-porosity, dual-permeability chalk. Here, mathematical and numerical modelling of tracer and contaminant migration in variably saturated fissured chalk is presented, considering the aforementioned conceptual model. A new mathematical formulation is proposed to represent the unsaturated properties of the fissured chalk in a more dynamic and appropriate way. At the same time, the rock water content is partitioned between mobile and immobile water phases, as a function of the water saturation of the chalk rock. The groundwater flow and contaminant transport in the variably saturated chalk is solved using the control volume finite element method. Modelling the field tracer experiments performed in the variably saturated chalk shows the adequacy and usefulness of the new conceptual, mathematical and numerical model.     

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.     

Analytical solutions for reactive transport under an infiltration-redistribution cycle

Transport of reactive solute in unsaturated soils under an infiltration-redistribution cycle is investigated. The study is based on the model of vertical flow and transport in the unsaturated zone proposed by Indelman et al. [J. Contam. Hydrol. 32 (1998) 77], and generalizes it by accounting for linear nonequilibrium kinetics. An exact analytical solution is derived for an irreversible desorption reaction. The transport of solute obeying linear kinetics is modeled by assuming equilibrium during the redistribution stage. The model which accounts for nonequilibrium during the infiltration and assumes equilibrium at the redistribution stage is termed partial equilibrium infiltration-redistribution model (PEIRM). It allows to derive approximate closed form solutions for transport in one-dimensional homogeneous soils. These solutions are further applied to computing the field-scale concentration by adopting the Dagan and Bresler [Soil Sci. Soc. Am. J. 43 (1979) 461] column model. The effect of soil heterogeneity on the solute spread is investigated by modeling the hydraulic saturated conductivity as a random function of horizontal coordinates. The quality of the PEIRM is illustrated by calculating the critical values of the Damk?hler number which provide the achievable accuracy in estimating the solute mass in the mobile phase. The distinguishing feature of transport during the infiltration-redistribution cycle as compared to that of infiltration only is the finite depth of solute penetration. For irreversible desorption, the maximum solute penetration W/theta(r) is determined by the amount of applied water W and the residual water content theta(r). For sorption-desorption kinetics, the maximum depth of penetration z(r)(e, infinity ) also depends on the ratio between the rate of application and the column-saturated conductivity. It is shown that z(r)(e, infinity ) is bounded between the depths W/(theta(r)+K(d)) and W/theta(r) corresponding to the maximum solute penetration for equilibrium transport and for irreversible desorption, respectively. This feature of solute penetration explains the unusual phenomena of plume contraction after an initial period of spreading [Lessoff, S.C., Indelman, P., Dagan, G., 2002. Solute transport in infiltration-redistribution cycles in heterogeneous soils. In Raats, P.A.C., Smiles, D.,Warrick, A.W. (Eds), Environmental Mechanics: Water, Mass and Energy Transport in the Biosphere. American Geophysical Union, pp. 133-144]. Unlike transport under equilibrium conditions, when the solute is completely concentrated at the front, the solute under nonequilibrium conditions is spread out behind the front. Heterogeneity leads to additional spreading of the plume.     

Design of aquifer remediation systems: (2) estimating site-specific performance and benefits of partial source removal

A Lagrangian stochastic model is proposed as a tool that can be utilized in forecasting remedial performance and estimating the benefits (in terms of flux and mass reduction) derived from a source zone remedial effort. The stochastic functional relationships that describe the hydraulic "structure" and non-aqueous phase liquid (NAPL) "architecture" have been described in a companion paper (Enfield, C.G., Wood, A.L., Espinoza, F.P., Brooks, M.C., Annable, M., Rao, P.S.C., this issue. Design of aquifer remediation systems: (1) describing hydraulic structure and NAPL architecture using tracers. J. Contam. Hydrol.). The previously defined functions were used along with the properties of the remedial fluids to describe remedial performance. There are two objectives for this paper. First, is to show that a simple analytic element model can be used to give a reasonable estimate of system performance. This is accomplished by comparing forecast performance to observed performance. The second objective is to display the model output in terms of change in mass flux and mass removal as a function of pore volumes of remedial fluid injected. The modelling results suggest that short term benefits are obtained and related to mass reduction at the sites where the model was tested.     

The velocity of DNAPL fingering in water-saturated porous media: laboratory experiments and a mobile-immobile-zone model.

Dense nonaqueous phase liquids (DNAPLs) are immiscible with water and can give rise to highly fingered fluid distributions when infiltrating through water-saturated porous media. In this paper, a conceptual mobile-immobile-zone (MIZ) model is presented to describe the structure of a DNAPL finger in water-saturated porous media and the velocity of finger propagation. A finger is composed of a finger body and a tip. The finger body has a mobile core and an immobile sheath. All the DNAPL within the tip of a finger is mobile. Lab experiments utilizing image analyses of a DNAPL (PCE) penetrating into water-saturated homogeneous glass beads were carried out in a two-dimensional transparent chamber. The results show that the fingers elongated almost linearly with time. The fingers did not grow laterally after the tip of the finger had passed. The average finger diameters were between 3.9 and 5.4 mm for PCE propagation in water-saturated glass bead porous media with mean particle diameters from 0.32 to 1.36 mm. The estimated mobile core diameters were 51-60% of the average finger diameters.     

The velocity of DNAPL fingering in water-saturated porous media: laboratory experiments and a mobile–immobile–zone model

Dense nonaqueous phase liquids (DNAPLs) are immiscible with water and can give rise to highly fingered fluid distributions when infiltrating through water-saturated porous media. In this paper, a conceptual mobile–immobile–zone (MIZ) model is presented to describe the structure of a DNAPL finger in water-saturated porous media and the velocity of finger propagation. A finger is composed of a finger body and a tip. The finger body has a mobile core and an immobile sheath. All the DNAPL within the tip of a finger is mobile. Lab experiments utilizing image analyses of a DNAPL (PCE) penetrating into water-saturated homogeneous glass beads were carried out in a two-dimensional transparent chamber. The results show that the fingers elongated almost linearly with time. The fingers did not grow laterally after the tip of the finger had passed. The average finger diameters were between 3.9 and 5.4 mm for PCE propagation in water-saturated glass bead porous media with mean particle diameters from 0.32 to 1.36 mm. The estimated mobile core diameters were 51–60% of the average finger diameters.     

Influence of rate-limited sorption on the cleanup of layered soils by vapor extraction

The conditions under which rate-limited sorption is important for cleanup of layered soils by vapor extraction are investigated. The investigation includes two steps: (a) the cleanup time is estimated for a number of scenario cases by means of a numerical model and (b) the numerical results are approximated using analytical solutions derived for simplified models. In this way, equations are derived, which give insight into the influence of different parameters characterizing the properties of the soil, the geometry of the formation, the mass transfer mechanisms in it, and the distribution of the contaminant mass in the different phases (gas phase, water phase and solid phase). The numerical model used is based on the advection-dispersion differential equations for Darcian isothermal airflow, local equilibrium contaminant mass transfer between gas phase and soil water and first-order kinetics for mass transfer between soil water and solid phase. The numerical results are approximated combining an analytical solution to estimate cleanup time in layered formations for local equilibrium sorption, which has been presented in a previous work (J. Contam. Hydrol., 36 (1999) 105). with an analytical solution based on the well-mixed reservoir model under consideration of rate-limited sorption. The analytical approximation of the cleanup time is in reasonable agreement with the numerical results and allows its estimation with small computational effort.     

Mobilization and entry of DNAPL pools into finer sand media by cosolvents: two-dimensional chamber studies

Two-dimensional chamber studies were conducted to determine qualitative and quantitative performance of cosolvents targeted at pooled dense non-aqueous phase liquid (DNAPL) (perchlorethylene, PCE) residing above a fine-grain capillary barrier. Downward mobilization of DNAPL, up gradient along an overriding cosolvent front, was observed. This produced significant pooling above a fine-grain layer that in some cases lead to entry into the capillary barrier beneath. Entry pressure calculations using physical and hydrogeologic parameters provided an excellent prediction of breakthrough of DNAPL into the capillary barrier. Calculations predict approximately 0.5 m of DNAPL would be necessary to enter a Beit Netofa clay, under extreme cosolvent flooding conditions (100% ethanol). Gradient injection of cosolvent did not appear to provide any benefit suggesting a rapid decrease in interfacial tension (IFT) compared to the rate of DNAPL solubilization. Use of a partitioning alcohol (tertiary butyl alcohol, TBA) resulted in DNAPL swelling and reduced entry into the capillary barrier. However, the trapping of flushing solution, containing PCE, could potentially lead to longer remediation times.