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.     

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.     

Controlled release, blind test of DNAPL remediation by ethanol flushing

A dense nonaqueous phase liquid (DNAPL) source zone was established within a sheet-pile isolated cell through a controlled release of perchloroethylene (PCE) to evaluate DNAPL remediation by in-situ cosolvent flushing. Ethanol was used as the cosolvent, and the main remedial mechanism was enhanced dissolution based on the phase behavior of the water-ethanol-PCE system. Based on the knowledge of the actual PCE volume introduced into the cell, it was estimated that 83 L of PCE were present at the start of the test. Over a 40-day period, 64% of the PCE was removed by flushing the cell with an alcohol solution of approximately 70% ethanol and 30% water. High removal efficiencies at the end of the test indicated that more PCE could have been removed had it been possible to continue the demonstration. The ethanol solution extracted from the cell was recycled during the test using activated carbon and air stripping treatment. Both of these treatment processes were successful in removing PCE for recycling purposes, with minimal impact on the ethanol content in the treated fluids. Results from pre- and post-flushing partitioning tracer tests overestimated the treatment performance. However, both of these tracer tests missed significant amounts of the PCE present, likely due to inaccessibility of the PCE. The tracer results suggest that some PCE was inaccessible to the ethanol solution which led to the inefficient PCE removal rates observed. The flux-averaged aqueous PCE concentrations measured in the post-flushing tracer test were reduced by a factor of 3 to 4 in the extraction wells that showed the highest PCE removal compared to those concentrations in the pre-flushing tracer test.     

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.     

PCE dissolution and simultaneous dechlorination by nanoscale zero-valent iron particles in a DNAPL source zone

While the capability of nanoscale zero-valent iron (NZVI) to dechlorinate organic compounds in aqueous solutions has been demonstrated, the ability of NZVI to remove dense non-aqueous phase liquid (DNAPL) from source zones under flow-through conditions similar to a field scale application has not yet been thoroughly investigated. To gain insight on simultaneous DNAPL dissolution and NZVI-mediated dechlorination reactions after direct placement of NZVI into a DNAPL source zone, a combined experimental and modeling study was performed. First, a DNAPL tetrachloroethene (PCE) source zone with emplaced NZVI was built inside a small custom-made flow cell and the effluent PCE and dechlorination byproducts were monitored over time. Second, a model for rate-limited DNAPL dissolution and NZVI-mediated dechlorination of PCE to its three main reaction byproducts with a possibility for partitioning of these byproducts back into the DNAPL was formulated. The coupled processes occurring in the flow cell were simulated and analyzed using a detailed three-dimensional numerical model. It was found that subsurface emplacement of NZVI did not markedly accelerate DNAPL dissolution or the DNAPL mass-depletion rate, when NZVI at a particle concentration of 10g/L was directly emplaced in the DNAPL source zone. To react with NZVI the DNAPL PCE must first dissolve into the groundwater and the rate of dissolution controls the longevity of the DNAPL source. The modeling study further indicated that faster reacting particles would decrease aqueous contaminant concentrations but there is a limit to how much the mass removal rate can be increased by increasing the dechlorination reaction rate. To ensure reduction of aqueous contaminant concentrations, remediation of DNAPL contaminants with NZVI should include emplacement in a capture zone down-gradient of the DNAPL source.     

Cosolvent-enhanced chemical oxidation of perchloroethylene by potassium permanganate

A laboratory study was conducted to examine cosolvent-enhanced in-situ chemical oxidation (ISCO) of perchloroethylene (PCE) using potassium permanganate (KMnO4). The conceptual basis for this new technique is to enhance permanganate oxidation of dense non-aqueous phase liquids (DNAPLs) with the addition of a cosolvent, thereby increasing DNAPL solubility while avoiding mobilization. Among 17 cosolvent candidates screened, tertiary butyl alcohol (TBA) and acetone were the most stable in the presence of KMnO4, both of which increased PCE aqueous solubility significantly, and therefore are suitable to be used as cosolvent in this study. Batch experiments indicated that the second-order rate constant for PCE oxidation by potassium permanganate was 0.043+/-0.002 M(-1) s(-1) in the purely aqueous (no cosolvent) solution. In the presence of 20% cosolvent (volume fraction=fc=0.2), the rate constant decreased to 0.036+/-0.003 M(-1) s(-1) with TBA and to 0.031+/-0.002 M(-1) s(-1) with acetone. However, in the presence of free-phase PCE, chloride ion concentration from PCE oxidation in acetone/water solutions (fc=0.2) was about twice that in aqueous solutions, indicating that the increase in PCE solubility more than compensated for the decrease in reaction rate constant, such that the oxidation efficiency of PCE was increased with cosolvent. A complete chlorine mass balance was observed in the aqueous system, whereas approximately 70% was obtained in TBA/water or acetone/water (fc=0.2). In soil columns containing residual DNAPL and subjected to isocratic flushing with step-wise increases in f(c) cosolvent, TBA at fc=0.2 resulted in PCE mobilization, whereas acetone at fc相似文献   

Characterization of DNAPL from the U.S. DOE Savannah River Site

The composition of chlorinated hydrocarbon DNAPLs (dense non-aqueous phase liquids) from field sites can be substantially different than the material originally purchased for use as a solvent. Waste management practices at the U.S. Department of Energy's (DOE) Savannah River Site (SRS) included co-disposal of a wide range of organic and inorganic wastes. In 1991, a clear, orange-colored DNAPL was found in two wells near the SRS M-area settling basin. Waste effluent from the fuel and target fabrication facilities that were discharged to this settling basin included acids, caustics, metals and chlorinated solvents. The characterization of the SRS DNAPL suggests that numerous constituents partitioned into the DNAPL during its use as a solvent, co-disposal and ultimate migration through the subsurface. Trace constituents in the DNAPL include metals, from processing operations or co-disposal practices and subsurface minerals, high molecular weight hydrocarbons and alkyl esters, and acids. This complex mixture results in DNAPL-water interfacial properties that are substantially different than would be expected from a simple mixture of PCE and TCE. Under conditions when there is a high DNAPL to water volume ratio, a semi-rigid film accumulates on water droplets suspended in the DNAPL. It is concluded that the array of precipitated metal species comprising this film contributes to the interfacial tension that is over an order of magnitude lower than expected for a "clean" PCE/TCE mixture.     

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.     

Cosolvent effects of alcohols on the Henry's law constant and aqueous solubility of tetrachloroethylene (PCE)

The effects of selected cosolvents ethyl alcohol (EtOH), isopropyl alcohol (IPA), and tertbutyl alcohol (TBA) on the Henry's law constant (H) of tetrachloroethylene (PCE) in aqueous solutions were investigated using the static headspace method. Alcohols in solution at a concentration around 20% and above acted as cosolvents increasing the aqueous solubility of PCE, which resulted in lower H values for PCE as compared to the value of H in deionized water. TBA, the most hydrophobic of the three alcohols, exhibited the strongest cosolvent effects, while EtOH had the weakest effects. A ln-linear relationship was observed between H and the volumetric fraction of alcohol added. Investigation of the solubilization of PCE in alcohol solutions confirmed the cosolvent trend observed for the three alcohols. A ln-ln relationship was observed between H and the enhanced solubility of PCE at a particular alcohol concentration. It was also observed that the value of H is a function of the enhanced solubility regardless of the type of cosolvent used. The results from this research further define the behavior of PCE in alcohol flooding solutions used in the remediation of PCE contaminated media.     

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.     

Infiltration of PCE in a system containing spatial wettability variations

A two-dimensional infiltration experiment was conducted to investigate and quantify the effect of spatial wettability variations on DNAPL migration and entrapment in saturated sands. Experimental observations of tetrachloroethylene (PCE) infiltration showed that organic-wet sand lenses acted as very effective capillary barriers, retaining PCE and inhibiting its downward migration. A multiphase numerical simulator was used to model this sand box experiment. The simulator incorporates wettability-modified van Genuchten and Brooks-Corey capillary pressure/saturation relationships as well as Burdine and Mualem relative permeability relationships. PCE mass distributions, estimated by image analysis of digital photographs taken during the infiltration event, were compared to simulation results. Although both relative permeability models were qualitatively able to predict the PCE retention in the organic-wet layers, simulations with the Mualem model failed to capture the observed rate of PCE migration. A traditional multiphase simulator, incorporating water-wet capillary retention relations, failed to predict both PCE pathways and retention behavior. This study illustrates the potential influence of subsurface wettability variations on DNAPL migration and entrapment and supports the use of modified capillary relations in conjunction with the Burdine model in multiphase flow simulators.     

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.     

Design of aquifer remediation systems: (1) describing hydraulic structure and NAPL architecture using tracers

Aquifer heterogeneity (structure) and NAPL distribution (architecture) are described based on tracer data. An inverse modelling approach that estimates the hydraulic structure and NAPL architecture based on a Lagrangian stochastic model where the hydraulic structure is described by one or more populations of lognormally distributed travel times and the NAPL architecture is selected from eight possible assumed distributions. Optimization of the model parameters for each tested realization is based on the minimization of the sum of the square residuals between the log of measured tracer data and model predictions for the same temporal observation. For a given NAPL architecture the error is reduced with each added population. Model selection was based on a fitness which penalized models for increasing complexity. The technique is demonstrated under a range of hydrologic and contaminant settings using data from three small field-scale tracer tests: the first implementation at an LNAPL site using a line-drive flow pattern, the second at a DNAPL site with an inverted five-spot flow pattern, and the third at the same DNAPL site using a vertical circulation flow pattern. The Lagrangian model was capable of accurately duplicating experimentally derived tracer breakthrough curves, with a correlation coefficient of 0.97 or better. Furthermore, the model estimate of the NAPL volume is similar to the estimates based on moment analysis of field data.     

Design of aquifer remediation systems: (1) Describing hydraulic structure and NAPL architecture using tracers

Aquifer heterogeneity (structure) and NAPL distribution (architecture) are described based on tracer data. An inverse modelling approach that estimates the hydraulic structure and NAPL architecture based on a Lagrangian stochastic model where the hydraulic structure is described by one or more populations of lognormally distributed travel times and the NAPL architecture is selected from eight possible assumed distributions. Optimization of the model parameters for each tested realization is based on the minimization of the sum of the square residuals between the log of measured tracer data and model predictions for the same temporal observation. For a given NAPL architecture the error is reduced with each added population. Model selection was based on a fitness which penalized models for increasing complexity. The technique is demonstrated under a range of hydrologic and contaminant settings using data from three small field-scale tracer tests: the first implementation at an LNAPL site using a line-drive flow pattern, the second at a DNAPL site with an inverted five-spot flow pattern, and the third at the same DNAPL site using a vertical circulation flow pattern. The Lagrangian model was capable of accurately duplicating experimentally derived tracer breakthrough curves, with a correlation coefficient of 0.97 or better. Furthermore, the model estimate of the NAPL volume is similar to the estimates based on moment analysis of field data.     

Manipulation of density and viscosity for the optimization of DNAPL recovery by alcohol flooding

Laboratory experiments demonstrate that in situ recovery of pooled tetrachloroethene (PCE) from porous media may be accomplished more efficiently using multiple-step alcohol floods than with single alcohol floods. To optimize flooding efficiency while maintaining a low risk of downward DNAPL mobilization, a three-step flooding process is developed employing an isobutanol preflood, a composite alcohol mainflood, and a polymer solution postflood. The density and viscosity of these solutions are manipulated to prevent the onset and propagation of viscous and gravitational fingers, while maintaining phase behavior critical for efficient miscible NAPL displacement. An aqueous partitioning preflood solution of 10% by volume (10% v) isobutanol reduces the NAPL density in situ to approximately 1.00 g/ml by swelling the NAPL prior to miscible displacement induced by the mainflood. The composite alcohol mainflood, containing 65% v ethylene glycol and 35% v 1-propanol maintains miscibility while achieving neutral buoyancy and near stable displacement of the NAPL. Aqueous solutions of xanthan gum polymer efficiently displace the mainflood, reducing viscous fingering associated with waterfloods. Two-dimensional experiments using the multiple-step technique achieve 99.8% DNAPL mass recovery using a total of 0.45 pore volumes of alcohol, illustrating greater recovery efficiency than previous alcohol flooding formulations under comparable conditions.     

A theoretical model of air and steam co-injection to prevent the downward migration of DNAPLs during steam-enhanced extraction

When steam is injected into soil containing a dense volatile non-aqueous phase liquid contaminant the DNAPL vaporized within the heated soil region condenses and accumulates ahead of the steam condensation front. If enough DNAPL accumulates, gravitational forces can overcome trapping forces allowing the liquid contaminant to flow downward. By injecting air with steam, a portion of the DNAPL vapor remains suspended in equilibrium with the air, decreasing liquid contaminant accumulation ahead of the steam condensation front, and thus reducing the possibility of downward migration. In this work, a one-dimensional theoretical model is developed to predict the injection ratio of air to steam that will prevent the accumulation of volatile DNAPLs. The contaminated region is modeled as a one-dimensional homogeneous porous medium with an initially uniform distribution of a single component contaminant. Mass and energy balances are combined to determine the injection ratio of air to steam that eliminates accumulation of the contaminant ahead of the steam condensation front, and hence reduces the possibility of downward migration. The minimum injection ratio that eliminates accumulation is defined as the optimum injection ratio. Example calculations are presented for three DNAPLs, carbon tetrachloride (CCl4), trichloroethylene (TCE), and perchloroethylene (PCE). The optimum injection ratio of air to steam is shown to depend on the initial saturation and the volatility of the liquid contaminant. Numerical simulation results are presented to validate the model, and to illustrate downward migration for ratios less than optimum. Optimum injection ratios determined from numerical simulations are shown to be in good agreement with the theoretical 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.     

Field study of TCE diffusion profiles below DNAPL to assess aquitard integrity

An area where a free-product accumulation of trichloroethylene (TCE) dense non-aqueous phase liquid (DNAPL) occurs at the bottom of a 10-m-thick surficial sand aquifer was studied to determine the integrity of the underlying, 20-m-thick, clayey silt aquitard formed of glaciolacustrine sediment. TCE concentration-versus-depth profiles determined from aquitard cores collected at five locations indicated penetration of detectable TCE 2.5 to 3.0 m into the aquitard. Two of the profiles show persistent DNAPL at the aquitard interface, while two others indicate that DNAPL, present initially, was completely dissolved away producing concentration declines at the aquitard interface. The fifth profile suggests shallow DNAPL penetration (<0.5 m) into the aquitard, however, this penetration, which was likely caused by cross-contamination during core collection or cone penetrometry (CPT) of the aquitard interface, did not increase the maximum depth of TCE penetration. Combining the field profiles with one-dimensional model simulations, downward migration of the aqueous TCE front, defined as the EPA MCL of 5 microg/l, which was below the analytical detection limit, was projected to a distance between 4 and 5 m below the top of the aquitard. Using a single set of estimated aquitard parameter values, simulations of aqueous TCE migration into the aquitard provided a good fit to four of the field profiles with a migration time of 35 to 45 years, consistent with the history of TCE use at the site. These simulations indicate aqueous TCE migration is diffusion-dominated with only small advective influence by the downward groundwater velocity of 2 to 3 cm/year or less in the aquitard due to pumping of the underlying aquifer to supply water to the facility in the past 50 years. The applicability of the parameter values was confirmed by in situ diffusion experiments of 1-year duration, in which stainless steel cylinders containing DNAPL were inserted into the aquitard. The diffusion-dominated nature of the profiles indicates that the aquitard provides long-term protection of the underlying aquifer from contamination from this DNAPL zone. Simulations of long-term migration of the TCE solute front indicate breakthrough to the lower aquifer at 1200 years for the no advection scenario and at 500 years if the strong downward hydraulic gradient persists. However, even after breakthrough, the mass flux through the aquitard to the underlying aquifer remains relatively low, and when considered in terms of potential impacts to pumping wells, concentrations are not expected to increase significantly above present-day MCLs. The use of contaminant profiles of different time and distance scales, in addition to hydraulic data, dramatically improves the ability to assess aquitard integrity, and provides improved transport parameter values for estimating contaminant arrival times and fluxes. The apparent lack of deep preferential pathways for TCE migration, such as open fractures, is probably due to the softness of the silty aquitard deposit and minimal physical or chemical weathering of the aquitard provides long-term protection of the underlying aquifer from contamination from this DNAPL zone. Simulations of long-term migration of the TCE solute front indicate breakthrough to the lower aquifer at 1200 years for the no advection scenario and at 500 years if the strong downward hydraulic gradient persists. However, even after the breakthrough, the mass flux through the aquitard to the underlying aquifer remains relatively low, and when considered in terms of potential impacts to pumping wells , concentrations are not expected to increase significantly above present-day MCLs. The use of contaminant profiles of different time and distance scales, in addition to hydraulic data, dramatically improves the ability to assess aquitard integrity, and provides improved transport parameter values for estimating contaminant arrival times and fluxes. The apparent lack of deep preferential pathways for TCE migration, such as open fractures, is probably due to the softness of the silty aquitard deposit and minimal physical or chemical weathering of the aquitard.     

Controlled release,blind tests of DNAPL characterization using partitioning tracers

The partitioning tracer technique for dense nonaqueous phase liquid (DNAPL) characterization was evaluated in an isolated test cell, in which controlled releases of perchloroethylene (PCE) had occurred. Four partitioning tracer tests were conducted, two using an inverted, double five-spot pumping pattern, and two using vertical circulation wells. Two of the four tests were conducted prior to remedial activities, and two were conducted after. Each test was conducted as a "blind test" where researchers conducting the partitioning tracer tests had no knowledge of the volume, method of release, nor resulting spatial distribution of DNAPL. Multiple partitioning tracers were used in each test, and the DNAPL volume estimates varied significantly within each test based on the different partitioning tracers. The tracers with large partitioning coefficients generally predicted a smaller volume of PCE than that expected based on the actual release volume. However, these predictions were made for low DNAPL saturations (average saturation was approximately 0.003), under conditions near the limits of the method's application. Furthermore, there were several factors that may have hindered prediction accuracy, including tracer degradation and remedial fluid interference.     

Variations in expression of carbon isotope fractionation of chlorinated ethenes during biologically enhanced PCE dissolution close to a source zone

The stable carbon isotope values of tetrachloroethene (PCE) and its degradation products were monitored during studies of biologically enhanced dissolution of PCE dense nonaqueous phase liquid (DNAPL) to determine the effect of PCE dissolution on observed isotope values. The degradation of PCE was monitored in a 2-dimensional model aquifer and in a pilot test cell (PTC) at Dover Air Force Base, both with emplaced PCE DNAPL sources. Within the plume down gradient from the source, the isotopic fractionation of dissolved PCE and its degradation products were consistent with those observed in biodegradation laboratory studies. However, close to the source zone significant shifts in the isotope values of dissolved PCE were not observed in either the model aquifer or PTC due to the constant input of newly dissolved, non fractionated PCE, and the small isotopic fractionation associated with PCE reductive dechlorination by the mixed microbial culture used. Therefore the identification of reductive dechlorination in the presence of PCE DNAPL was based upon the appearance of daughter products and the isotope values of those daughter products. An isotope model was developed to simulate isotope values of PCE during the dissolution and degradation of PCE adjacent to a DNAPL source zone. With the exception of very high degradation rate constants (>1/day) stable carbon isotope values of PCE estimated by the model remained within error of the isotope value of the PCE DNAPL, consistent with measured isotope values in the model aquifer and in the PTC.