Entrapment and dissolution of DNAPLs in heterogeneous porous media

Two-dimensional multiphase flow and transport simulators were refined and used to numerically investigate the entrapment and dissolution behavior of tetrachloroethylene (PCE) in heterogeneous porous media containing spatial variations in wettability. Measured hydraulic properties, residual saturations, and dissolution parameters were employed in these simulations. Entrapment was quantified using experimentally verified hydraulic property and residual saturation models that account for hysteresis and wettability variations. The nonequilibrium dissolution of PCE was modeled using independent estimates of the film mass transfer coefficient and interfacial area for entrapped and continuous (PCE pools or films) saturations. Flow simulations demonstrate that the spatial distribution of PCE is highly dependent on subsurface wettability characteristics that create differences in PCE retention mechanisms and the presence of subsurface capillary barriers. For a given soil texture, the maximum and minimum PCE infiltration depth was obtained when the sand had intermediate (an organic-wet mass fraction of 25%) and strong (water- or organic-wet) wettability conditions, respectively. In heterogeneous systems, subsurface wettability variations were also found to enhance or diminish the performance of soil texture-induced capillary barriers. The dissolution behavior of PCE was found to depend on the soil wettability and the spatial PCE distribution. Shorter dissolution times tended to occur when PCE was distributed over large regions due to an increased access of flowing water to the PCE. In heterogeneous systems, capillary barriers that produced high PCE saturations tended to exhibit longer dissolution times.     

Influence of surfactant-facilitated interfacial tension reduction on chlorinated solvent migration in porous media: observations and numerical simulation

The ability of a multiphase flow model to capture the migration behavior of chlorinated solvents under conditions of surfactant-facilitated interfacial tension (IFT) reduction is assessed through comparison of model predictions with observations from controlled laboratory experiments. Tetrachloroethene (PCE) was released in two-dimensional saturated systems, packed with sandy media that incorporated rectangular lenses of capillary contrast. Spatially uniform interfacial tension conditions were created in the tanks by pre-flushing the porous medium with either Milli Q water or an aqueous surfactant solution. Experimental observations showed that surfactant-facilitated IFT reductions substantially lowered capillary resistance to the vertical downward migration of PCE and enabled PCE to enter finer grained, less permeable lenses that were not penetrated in the absence of surfactant. An immiscible flow model was used to simulate the conditions of the laboratory experiments. Under higher IFT conditions (47.5 and 5 dyn/cm), the model could successfully predict the general migration behavior of the organic liquid. Model predictions, however, exhibited poorer agreement with observed migration pathways under low IFT conditions (0.5 dyn/cm). In all cases, the predicted PCE distributions were influenced by selection of the parametric model for capillary retention and relative permeability. Simulated migration rates were more consistent with observed behavior when the Brooks-Corey/Burdine model was employed. For low interfacial tensions, improved predictions of migration pathways were obtained through grid refinement and incorporation of small-scale packing variability. Simulations highlight the substantial sensitivity of model predictions to the capillary pressure-scaling factor, grid resolution, and small-scale porosity variations at interfaces of permeability contrast under reduced IFT conditions.     

Infiltration and redistribution of perchloroethylene in partially saturated, stratified porous media

Contamination of the subsurface by nonaqueous phase liquids (NAPLs) is a widespread problem. To investigate the behavior of a nonspreading, dense NAPL (DNAPL) in the vadose zone, we conducted perchloroethylene (PCE) infiltration experiments in nominally 1- and 2-dimensional (D), stratified porous media. In addition, the usefulness and limitations of a multifluid flow simulator to describe PCE infiltration and redistribution under the experimental conditions were tested. The physical simulations were conducted in a column (1-D) and a flow container (2-D) which were packed with two distinct layers of coarse-grained sand and a fine-grained sand layer in between. Volumetric water and PCE contents were determined with a fully automated dual-energy gamma radiation system. While migrating through the drier parts of the coarse-grained sand layers, PCE appeared to wet the water–air interface rather than displacing any water. In the wetter parts of the porous medium, PCE displaced water and behaved as a true nonwetting fluid. PCE showed a limited response to gradients in capillary pressure and rather high values for the volumetric PCE content were measured in the fine-grained sand layers. This was attributed to the nonspreading nature of PCE. The multifluid flow simulator appeared to predict the initial PCE movement in the vadose zone reasonably well. However, the model was not capable of predicting the final amounts of PCE retained in either the unsaturated or saturated part of the flow domain, mainly because the simulator does not consider the nonspreading flow behavior of NAPLs.     

Microbial physiology-based model of ethanol metabolism in subsurface sediments

Dense non-aqueous phase liquids (DNAPLs) present in the subsurface may contain surface active compounds that impact DNAPL migration and distribution. While a number of studies have revealed the role surface active compounds play in altering the wettability of quartz sand, few have considered the implications for other minerals common to contaminated sites. This study extends understanding of DNAPL/surfactant wettability to iron oxide surfaces. Specifically, quartz and iron oxide-coated sands in a tetrachloroethene (PCE)/water system containing the organic base (an organic molecule that acts as a base) dodecylamine (DDA) were compared at a variety of scales. Wettability of the minerals' surfaces, and the impact of wettability on capillary resistance to DNAPL entry, were assessed as a function of pH through: (i) advancing and receding contact angles, (ii) primary drainage capillary pressure-saturation experiments, and (iii) small, two-dimensional, flow cell experiments. The work revealed that, at neutral pH and under identical boundary capillary pressures, DNAPL invaded quartz sand but not iron oxide-coated sand; however, at low pH, DNAPL invaded both sands equally. These differences were demonstrated to be due to wettability alterations associated with the strength of attractive forces between DDA and the mineral surface, dictated by the isolectric point of the minerals and system pH. Observed differences in DNAPL invasion behavior were consistent with measured intrinsic contact angles and P(c)-S relationships, the latter requiring scaling by the operative contact angle inside the porous medium for a meaningful comparison. This study suggests that the distribution of minerals (and, more specifically, their isoelectric points), as well as the aqueous phase pH at a given site, may have a significant impact on the DNAPL source zone architecture.     

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.     

The significance of heterogeneity on mass flux from DNAPL source zones: an experimental investigation

Understanding the process of mass transfer from source zones of aquifers contaminated with organic chemicals in the form of dense non-aqueous phase liquids (DNAPL) is of importance in site management and remediation. A series of intermediate-scale tank experiments was conducted to examine the influence of aquifer heterogeneity on DNAPL mass transfer contributing to dissolved mass emission from source zone into groundwater under natural flow before and after remediation. A Tetrachloroethylene (PCE) spill was performed into six source zone models of increasing heterogeneity, and both the spatial distribution of the dissolution behavior and the net effluent mass flux were examined. Experimentally created initial PCE entrapment architecture resulting from the PCE migration was largely influenced by the coarser sand lenses and the PCE occupied between 30 and 60% of the model aquifer depth. The presence of DNAPL had no apparent effect on the bulk hydraulic conductivity of the porous media. Up to 71% of PCE mass in each of the tested source zone was removed during a series of surfactant flushes, with associated induced PCE mobilization responsible for increasing vertical DNAPL distributions. Effluent mass flux due to water dissolution was also found to increase progressively due to the increase in NAPL-water contact area even though the PCE mass was reduced. Doubling of local groundwater flow velocities showed negligible rate-limited effects at the scale of these experiments. Thus, mass transfer behavior was directly controlled by the morphology of DNAPL within each source zone. Effluent mass flux values were normalized by the up-gradient DNAPL distributions. For the suite of aquifer heterogeneities and all remedial stages, normalized flux values fell within a narrow band with mean of 0.39 and showed insensitivity to average source zone saturations.     

Effects of ethanol addition on micellar solubilization and plume migration during surfactant enhanced recovery of tetrachloroethene

Alcohol addition has been suggested for use in combination with surfactant flushing to enhance solubilization kinetics and permit density control of dense non-aqueous phase liquid (DNAPL)-laden surfactant plumes. This study examined the effects of adding ethanol (EtOH) to a 4% Tween 80 (polyoxyethylene (20) sorbitan monooleate) solution used to flush tetrachloroethene (PCE)-contaminated porous media. The influence of EtOH concentration, subsurface layering and scale on flushing solution delivery and PCE recovery was investigated through a combination of experimental and mathematical modeling studies. Results of batch experiments demonstrated that the addition of 2.5%, 5% and 10% (wt.) EtOH incrementally increased the PCE solubilization capacity and viscosity of the surfactant solution, while reducing solution density from 1.002 to 0.986 g/cm3. Effluent concentration data obtained from one-dimensional (1-D) column experiments were used to characterize rate-limited micellar solubilization of residual PCE, which was strongly dependent upon flow velocity and weakly dependent upon EtOH concentration. Two-dimensional (2-D) box studies illustrated that minor differences (0.008 g/cm3) between flushing and resident solution density can strongly influence surfactant front propagation. A two-dimensional multiphase simulator, MISER, was used to model the influence of EtOH composition on the aqueous flow field and PCE mass recovery. The ability of the numerical simulator to predict effluent concentrations and front propagation was demonstrated for both 1-D columns and 2-D boxes flushed with EtOH-amended Tween 80 solutions. Results of this study quantify the potential influence of alcohol addition on surfactant solution properties and solubilization capacity, and demonstrate the importance of considering small density variations in remedial design.     

Multiphase flow and transport through fractured heterogeneous porous media

The migration of Dense, Non-Aqueous Phase Liquid (DNAPL) and dissolved phase contamination through a fractured heterogeneous porous medium has been investigated through the use of a multiphase compositional model. The sensitivity of the timescales of migration and the distribution of contaminant in the subsurface to the mean permeability, the variance of the permeability, and the degree of fracturing of the domain were examined. It was found that increasing the mean permeability of the domain allowed the DNAPL to penetrate deeper into the subsurface, while decreasing the mean permeability caused the DNAPL to pool at shallower depths. The presence of fractures within the system was found to control the infiltration only in the most fractured domain. Moment analysis of the nonwetting phase showed that large-scale movement had ceased after approximately 9 years (maximum duration of the source-on condition was approximately 4.5 years). This tended to be due to a redistribution of the DNAPL towards a residual configuration, as was evidenced by the gradual trending of average nonwetting phase saturations within the domain to a static value. The dissolved phase plume was found to migrate at essentially the same rate as the nonwetting phase, due to the reduced relative permeability of lenses containing DNAPL, and due to diffusive losses of mass to the matrix of fractured clay and silty-clay lenses. Some exceptions to this were found when the DNAPL could not overcome the displacement pressure of a lens, and could not by-pass the lens due to the lack of available driving force after the source had been shut off.     

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.     

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.     

Surfactant enhanced recovery of tetrachloroethylene from a porous medium containing low permeability lenses. 2. Numerical simulation

A numerical model of surfactant enhanced solubilization was developed and applied to the simulation of nonaqueous phase liquid recovery in two-dimensional heterogeneous laboratory sand tank systems. Model parameters were derived from independent, small-scale, batch and column experiments. These parameters included viscosity, density, solubilization capacity, surfactant sorption, interfacial tension, permeability, capillary retention functions, and interphase mass transfer correlations. Model predictive capability was assessed for the evaluation of the micellar solubilization of tetrachloroethylene (PCE) in the two-dimensional systems. Predicted effluent concentrations and mass recovery agreed reasonably well with measured values. Accurate prediction of enhanced solubilization behavior in the sand tanks was found to require the incorporation of pore-scale, system-dependent, interphase mass transfer limitations, including an explicit representation of specific interfacial contact area. Predicted effluent concentrations and mass recovery were also found to depend strongly upon the initial NAPL entrapment configuration. Numerical results collectively indicate that enhanced solubilization processes in heterogeneous, laboratory sand tank systems can be successfully simulated using independently measured soil parameters and column-measured mass transfer coefficients, provided that permeability and NAPL distributions are accurately known. This implies that the accuracy of model predictions at the field scale will be constrained by our ability to quantify soil heterogeneity and NAPL distribution.     

Removal of DNAPL contamination from the saturated zone by the combined effect of vertical upward flushing and density reduction

A common aspect of innovative remediation techniques is that they tend to reduce the interfacial tension between the aqueous and non-aqueous phase liquids, resulting in mobilization of the organic contaminant. This complicates the remediation of aquifers, contaminated with Dense Non-Aqueous Phase Liquids (DNAPLs), as they are likely to migrate downwards, deeper into the aquifer and into finer layers. A possible solution is the use of swelling alcohols, which tend to reduce the density difference between the aqueous phase and the DNAPL. To avoid premature mobilization upon the initial contact between the DNAPL and the alcohol, several researchers have proposed the use of vertical upward flow of the alcohol. In this paper, we present an equation, which describes the upward mobilization of both continuous and discontinuous DNAPLs and so the important parameters governing the upward controlled mobilization of the DNAPL. The need and required magnitude of this specific discharge was investigated by conducting four column experiments in which the initial density of the DNAPL and the permeability was varied. It was shown that the required flow velocities increase with the permeability of the porous medium and the initial density difference between the aqueous phase and the DNAPL. Whenever the specific discharge falls below the critical value, the DNAPL moves downward. A second set of column experiments looked at the impact of permeability of porous medium on the solubilization and mobilization of DNAPL during alcohol flooding. Columns, packed with coarse or fine sand, containing a residual trichloroethylene (TCE) or perchloroethylene (PCE) saturation were flushed with the alcohol mixture at a fixed specific discharge rate. The induced pressure gradients in the aqueous phase, which were higher in the fine sand, resulted for this porous medium in extensive mobilization of the DNAPL against the direction of the buoyancy force. The density of the first NAPL coming out of the top of the fine sand was close to that of the pure DNAPL. In the coarser sand, the pressure gradients were sufficient to prevent downward migration of the DNAPL, but upward mobilization was minimal. The predominant removal mechanism in this case was the much slower solubilization.     

Prediction of two-phase capillary pressure-saturation relationships in fractional wettability systems

Capillary pressure/saturation data are often difficult and time consuming to measure, particularly for non-water-wetting porous media. Few capillary pressure/saturation predictive models, however, have been developed or verified for the range of wettability conditions that may be encountered in the natural subsurface. This work presents a new two-phase capillary pressure/saturation model for application to the prediction of primary drainage and imbibition relations in fractional wettability media. This new model is based upon an extension of Leverett scaling theory. Analysis of a series of DNAPL/water experiments, conducted for a number of water/intermediate and water/organic fractional wettability systems, reveals that previous models fail to predict observed behavior. The new Leverett–Cassie model, however, is demonstrated to provide good representations of these data, as well as those from two earlier fractional wettability studies. The Leverett–Cassie model holds promise for field application, based upon its foundation in fundamental scaling principles, its requirement for relatively few and physically based input parameters, and its applicability to a broad range of wetting conditions.     

Effectiveness of nanoscale zero-valent iron for treatment of a PCE-DNAPL source zone

Nanoscale zero-valent iron (nZVI) has received considerable attention as a potential in situ remediation technology for treating chlorinated solvent source zones. Experimental and mathematical modeling studies were conducted to investigate the performance of nZVI in the transformation of tetrachloroethene (PCE) entrapped as a dense nonaqueous phase liquid (DNAPL). Injection of a 60 g/L suspension of nZVI into a column containing 20-30 mesh Ottawa sand and PCE-DNAPL at a residual saturation of 5.5% resulted in a uniform distribution of nZVI and minimal displacement of PCE. Subsequent flushing with 267 pore volumes of water containing 3mM CaCl(2) at a Darcy velocity of 0.75 m/day resulted in steady-state effluent concentrations of PCE near the solubility limit (ca. 200mg/L) and production of dissolved-phase ethene (10-30 mg/L). Over the duration of the experiment, approximately 30% of the initial PCE-DNAPL mass reacted to form ethene, 50% was eluted as dissolved-phase PCE, and 20% remained in the column as PCE-DNAPL. To further explore the implications of the nZVI column results, a multiphase transport model was developed that incorporated rate-limited PCE-DNAPL dissolution and reactions with nZVI. Using a fitted pseudo first-order transformation rate coefficient of 1.421/h, the model accurately captured observed trends in effluent concentrations of PCE and ethene and overall mass balance. A model sensitivity study reveals a strong dependence of treatment effectiveness on system characteristics. The sensitivity analysis suggests that an increase in the extent of PCE transformation is facilitated by decreasing flow rate, emplacement of nZVI down-gradient of the DNAPL source zone, and decreasing length of the DNAPL source zone. These findings indicate that, although emplacement of high concentrations of nZVI within a PCE-DNAPL source zone can result in substantial transformation of the parent compound, careful attention to design parameters (e.g. flow rate, location and amount nZVI delivered) will be required to achieve complete conversion to benign reaction products.     

Multiphase flow and transport in fractured clay/sand sequences.

A numerical model (Queen's University Multi-Phase Flow Simulator, QUMPFS) was used to assess the rate of trichloroethylene (TCE) dense, non-aqueous phase liquid (DNAPL) migration through fractured clay, with special attention focused on the influence of interbedded sand lenses. The presence of these sand lenses was found to increase the time required for the non-wetting phase to migrate through the full 30 m vertical extent of the clay sequence from a few days to several years. Applied vertical hydraulic gradients were found to be moderately influential in systems consisting solely of fractured clays, yet one of the dominant factors controlling speed of vertical migration when sand lenses were present. Larger displacement pressure of the sands relative to that of the fractures leads to slower DNAPL migration rates, due to the delays that occur during build-up of capillary pressures. Dissolution of DNAPL and subsequent matrix diffusion of the aqueous phase has little effect on the rate of DNAPL migration through systems consisting of fractured clay only, yet slows the rate of migration in systems containing sand lenses. In all cases examined, the rate of DNAPL loading to the lower aquifer far exceeded the rate of aqueous phase mass loading. It was also found that DNAPL reaches the lower aquifer at approximately the same time as the aqueous phase plumes even for systems experiencing downward groundwater flow due to the attenuation of the aqueous phase through matrix diffusion.     

Dip-angle influence on areal DNAPL recovery by co-solvent flooding with and without pre-flooding

A two-dimensional (2D) laboratory model was used to study effects of gravity on areal recovery of a representative dense non-aqueous phase liquid (DNAPL) contaminant by an alcohol pre-flood and co-solvent flood in dipping aquifers. Recent studies have demonstrated that injection of alcohol and co-solvent solutions can be used to reduce in-situ the density of DNAPL globules and displace the contaminant from the source zone. However, contact with aqueous alcohol reduces interfacial tension and causes DNAPL swelling, thus facilitating risk of uncontrolled downward DNAPL migration. The 2D laboratory model was operated with constant background gradient flow and a DNAPL spill was simulated using tetrachloroethene (PCE). The spill was dispersed to a trapped, immobile PCE saturation by a water flood. Areal PCE recovery was studied using a double-triangle well pattern to simulate a remediation scheme consisting of an alcohol pre-flood using aqueous isobutanol ( approximately 10% vol.) followed by a co-solvent flood using a solution of ethylene glycol (65%) and 1-propanol (35%). Experiments were conducted with the 2D model oriented in the horizontal plane and compared to experiments at the 15 degrees and 30 degrees dip-angle orientations. Injection was applied either in the downward or upward direction of flow. Experimental results were compared to theoretical predictions for flood front stability and used to evaluate effects of gravity on areal PCE recovery. Sensitivity experiments were performed to evaluate effects of the alcohol pre-flood on PCE areal recovery. For experiments conducted with the alcohol pre-flood and the 2D model oriented in the horizontal plane, results indicate that 89-93% of source zone PCE was recovered. With injection oriented downward, results indicate that areal PCE recovery was 70-77% for a 15 degrees dip angle and 57-59% for a 30 degrees dip angle. With injection oriented upward, results indicate that areal PCE recovery was 57-60% at the 30 degrees dip angle, which was similar to PCE recovery for injection in the downward flow direction. Lower areal PCE recovery at greater dip angles in either direction of flow was attributed to DNAPL swelling and migration, flood front instabilities and bypassing of the displaced fluid past the extraction wells during the alcohol pre-flood. Additional results demonstrate that the use of an alcohol pre-flood can be beneficial in improving DNAPL recovery in the horizontal orientation, but pre-flooding may reduce areal recovery efficiency in dip-angle orientations. This study also demonstrates the use of theoretical perturbation (fingering) analysis in predicting NAPL recovery efficiency for flooding processes in remediating aquifers with dip angles.     

Insights into the use of time-lapse GPR data as observations for inverse multiphase flow simulations of DNAPL migration

Perchloroethylene (PCE) saturations determined from GPR surveys were used as observations for inversion of multiphase flow simulations of a PCE injection experiment (Borden 9 m cell), allowing for the estimation of optimal bulk intrinsic permeability values. The resulting fit statistics and analysis of residuals (observed minus simulated PCE saturations) were used to improve the conceptual model. These improvements included adjustment of the elevation of a permeability contrast, use of the van Genuchten versus Brooks-Corey capillary pressure-saturation curve, and a weighting scheme to account for greater measurement error with larger saturation values. A limitation in determining PCE saturations through one-dimensional GPR modeling is non-uniqueness when multiple GPR parameters are unknown (i.e., permittivity, depth, and gain function). Site knowledge, fixing the gain function, and multiphase flow simulations assisted in evaluating non-unique conceptual models of PCE saturation, where depth and layering were reinterpreted to provide alternate conceptual models. Remaining bias in the residuals is attributed to the violation of assumptions in the one-dimensional GPR interpretation (which assumes flat, infinite, horizontal layering) resulting from multidimensional influences that were not included in the conceptual model. While the limitations and errors in using GPR data as observations for inverse multiphase flow simulations are frustrating and difficult to quantify, simulation results indicate that the error and bias in the PCE saturation values are small enough to still provide reasonable optimal permeability values. The effort to improve model fit and reduce residual bias decreases simulation error even for an inversion based on biased observations and provides insight into alternate GPR data interpretations. Thus, this effort is warranted and provides information on bias in the observation data when this bias is otherwise difficult to assess.     

Effective parameters for two-phase flow in a porous medium with periodic heterogeneities

Computational simulations of two-phase flow in porous media are used to investigate the feasibility of replacing a porous medium containing heterogeneities with an equivalent homogeneous medium. Simulations are performed for the case of infiltration of a dense nonaqueous phase liquid (DNAPL) in a water-saturated, heterogeneous porous medium. For two specific porous media, with periodic and rather simple heterogeneity patterns, the existence of a representative elementary volume (REV) is studied. Upscaled intrinsic permeabilities and upscaled nonlinear constitutive relationships for two-phase flow systems are numerically calculated and the effects of heterogeneities are evaluated. Upscaled capillary pressure-saturation curves for drainage are found to be distinctly different from the lower-scale curves for individual regions of heterogeneity. Irreducible water saturation for the homogenized medium is found to be much larger than the corresponding lower-scale values. Numerical simulations for both heterogeneous and homogeneous representations of the considered porous media are carried out. Although the homogenized model simulates the spreading behavior of DNAPL reasonably well, it still fails to match completely the results form the heterogeneous simulations. This seems to be due, in part, to the nonlinearities inherent to multiphase flow systems. Although we have focussed on a periodic heterogeneous medium in this study, our methodology is applicable to other forms of heterogeneous media. In particular, the procedure for identification of a REV, and associated upscaled constitutive relations, can be used for randomly heterogeneous or layered media as well.     

表面活性剂强化抽出处理含水层中DNAPL污染物的去除特征

为明确表面活性剂强化抽出处理含水层中DNAPL污染物过程中表面活性剂的增强修复效果,及DNAPL自身理化性质和介质孔径的影响,利用数码图像分析技术对1,2-二氯乙烷和四氯乙烯2种DNAPL在石英砂填充的二维砂箱中的抽取迁移过程进行了实验模拟研究,并对抽出水样中DNAPL的浓度进行了测试分析。结果表明,实验条件下加入低浓度(0.18%)的十二烷基苯磺酸钠(SDBS)大幅提高了对弱透水层截留的2种DNAPL聚集体的抽出处理效率。1,2-二氯乙烷在该表面活性剂溶液中的表观溶解度远高于四氯乙烯,因此其短时间内的绝对去除率更高。SDBS强化抽出处理DNAPL的作用机理以增溶作用为主,而其增流作用使DNAPL迁移流动后分布面积增大,增加了与表面活性剂溶液接触的面积,对增溶作用起到促进效果。细粒介质中DNAPL迁移后的最大分布面积较大,因此体系中DNAPL的溶解速率较高。在DNAPL聚集体质量与水力梯度固定的条件下,油水界面张力越低,DNAPL的密度越大,DNAPL垂向迁移的风险就越大。本研究为修复工程中如何依据DNAPL种类与场地多孔介质的情况选择表面活性剂提供了参考。     

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.