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1.
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.  相似文献   

2.
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 a previous work, a theoretical model was developed to predict the optimum injection ratio of air to steam that would eliminate accumulation of DNAPL ahead of the temperature front and thus minimize the potential for downward migration. In this work, the theoretical model is summarized, and an experiment is presented in order to evaluate the optimum injection ratio prediction. In the experiment, a two-dimensional water saturated sand pack is contaminated with a known mass of TCE (DNAPL). The system is then remediated by co-injecting air and steam at the predicted optimum injection ratio, calculated based on the average contaminant soil concentration in the sand pack. Results for the co-injection of air and steam are compared to results for the injection of pure steam or pure air. Injection at the predicted optimum injection ratio for a volumetric average NAPL saturation, reduced accumulation of the contaminant ahead of the condensation front by over 90%, as compared to steam injection alone. This indicates that the optimum injection ratio prediction is a valuable tool for limiting the spreading of DNAPL during steam-enhanced extraction. Injection at the optimum injection ratio resulted in earlier recovery of contaminant than for steam injection alone. Co-injection of steam and air is also shown to result in much higher recovery rates than air injection alone.  相似文献   

3.
Numerical simulation of steam injection into a water-saturated porous medium may be hindered by unphysical behavior causing the model to slow down. We show how spurious water flow may arise on the boundary between a steam zone and a saturated zone, giving rise to dramatic pressure drops. This is caused by the discretization of the temperature gradient coupled with the direct relation between pressure and temperature in the steam zone. The problem may be a severe limitation to numerical modeling. A solution is presented where the spurious water flow is blocked and this widely enhances the performance of the model. This new method is applied to a previously reported example exhibiting numerical problems. Furthermore, it is applied to the simulation of 2-D sandbox experiments where LNAPL is remediated from a smearing zone by steam injection. These experiments would have been difficult to analyze numerically without the adjustment to prevent spurious flow.  相似文献   

4.
A soil core, obtained from a contaminated field site, contaminated with a mixture of volatile and semivolatile organic compounds (VOC and SVOC) was subjected to air and steam flushing. Removal rates of volatile and semivolatile organic compounds were monitored during flushing. Air flushing removed a significant portion of the VOC present in the soil, but a significant decline in removal rate occurred due to decreasing VOC concentrations in the soil gas phase. Application of steam flushing after air flushing produced a significant increase in contaminant removal rate for the first 4 to 5 pore volumes of steam condensate. Subsequently, contaminant concentrations decreased slowly with additional pore volumes of steam flushing. The passage of a steam volume corresponding to 11 pore volumes of steam condensate reduced the total VOC concentration in the soil gas (at 20 degrees C) by a factor of 20 to 0.07 mg/l. The corresponding total SVOC concentration in the condensate declined from 11 to 3 mg/l. Declines in contaminant removal rates during both air and steam flushing indicated rate-limited removal consistent with the persistence of a residual organic phase, rate-limited desorption, or channeling. Pressure gradients were much higher for steam flushing than for air flushing. The magnitude of the pressure gradients encountered during steam flushing for this soil indicates that, in addition to rate-limited contaminant removal, the soil permeability (2.1 x 10(-9) cm2) would be a limiting factor in the effectiveness of steam flushing.  相似文献   

5.
Natural remobilization of multicomponent DNAPL pools due to dissolution   总被引:1,自引:0,他引:1  
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.  相似文献   

6.
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.  相似文献   

7.
Even in the absence of mobilization of dense nonaqueous phase liquid (DNAPL), the microemulsion that forms when the surfactant solubilizes a dense contaminant such as trichloroethylene will be more dense than water and tends to migrate downward. This paper addresses the issue of migration with a new concept: surfactant enhanced aquifer remediation at neutral buoyancy. Laboratory results of surfactant remediation in two-dimensional model aquifers show that downward migration of microemulsion containing solubilized dense contaminants can be reduced to an acceptable level, even in the absence of capillary barriers in the aquifer. One model experiment was designed to exhibit a small degree of vertical migration and full capture of the microemulsion at the extraction well. The second experiment was designed to demonstrate the effect of large buoyancy forces that lead to excessive downward migration of the microemulsion. Density measurements of aqueous solutions containing sodium dihexyl sulfosuccinate surfactant, isopropanol, trichloroethylene, and sodium chloride are presented. A companion paper presents the results of the flow and transport calculations needed for this approach to surfactant flooding.  相似文献   

8.
To explore the viability of Steam Enhanced Remediation (SER) in fractured rock a small-scale steam injection and water/vapour extraction pilot study was conducted at the former Loring Air Force Base in northern Maine, USA. A detailed well testing program was undertaken to assist in the design of the injection and extraction well array, and to assess the possibility of off-site heat and contaminant migration. A structurally complex limestone having low matrix porosity and a sparse distribution of fractures underlies the study site. To characterize the groundwater and steam flow pathways, single-well slug tests and more than 100 pulse interference tests were conducted. The results of the well testing indicate that the study site is dominated by steeply dipping bedding plane fractures that are interconnected only between some wells in the injection/extraction array. The SER system was designed to take advantage of interconnected fractures located at depth in the eastern end of the site. An array of 29 wells located in an area of 60 by 40 m was used for steam injection and water/vapour extraction. The migration of heat was monitored in several wells using thermistor arrays having a 1.5 m vertical spacing. Temperature measurements obtained during and after the 3 month steam injection period showed that heat migration generally occurred along those fracture features identified by the pulse interference testing. Based on these results, it is concluded that the pulse interference tests were valuable in assisting with the design of the injection/extraction well geometry and in predicting the migration pathways of the hot water associated with the steam injection. The pulse interference test method should also prove useful in support of any other remedial method dependant on the fracture network for delivery of remedial fluid or extraction of contaminants.  相似文献   

9.
Surfactant-enhanced aquifer remediation (SEAR) involves the injection of surfactant solutions into aquifers contaminated with nonaqueous phase liquids (NAPL). Batch and column experiments were used to assess the effect of surfactant formulation on the rate of NAPL solubilization. The experimental variables were surfactant type, surfactant concentration, electrolyte concentration, and cosolvent concentration. Model equations were proposed and solved to describe solubilization under the conditions of each type of experiment. Using these models, a solubilization rate constant, kappa(b), and an overall mass transfer rate coefficient, kappa, were estimated from the batch and column experiments, respectively. The solubilization rate constant was consistently sensitive to surfactant type, surfactant concentration, and electrolyte concentration. The estimated solubilization rate constants varied over two orders of magnitude. The results of the column experiments also were sensitive to the surfactant formulation. Variations in the fitted mass transfer rate coefficient parameter, beta(0), were related to variations in the surfactant formulations. A comparison between the results of the batch and column experiments yields an apparent relationship between beta(0) and kappa(b). This relationship suggests that the mass transfer rate coefficient is directly related to the formulation of the surfactant solution.  相似文献   

10.
Because of their low solubility, waste chemicals in the form of nonaqueous phase liquids (NAPLs) that are entrapped in subsurface formations act as long-term sources of groundwater contamination. In the design of remediation schemes that use surfactants, it is necessary to estimate the mass transfer rate coefficients under multi-dimensional flow fields that exit at field sites. In this study, we investigate mass transfer under a two-dimensional flow field to obtain an understanding of the basic mechanisms of surfactant-enhanced dissolution and to quantify the mass transfer rates. Enhanced dissolution experiments in a two-dimensional test cell were conducted to measure rates of mass depletion from entrapped NAPLs to a flowing aqueous phase containing a surfactant. In situ measurement of transient saturation changes using a gamma attenuation system revealed dissolution patterns that are affected by the dimensionality of the groundwater flow field. Numerical modeling of local flow fields that changed with time, due to depletion of NAPL sources, enabled the examination of the basic mechanisms of NAPL dissolution in complex groundwater systems. Through nonlinear regression analysis, mass transfer rates were correlated to porous media properties, NAPL saturation and aqueous phase velocity. Results from the experiments and numerical analyses were used to identify deficiencies in existing methods of analysis that uses assumptions of one-dimensional flow, homogeneity of aquifer properties, local equilibrium and idealized transient mass transfer.  相似文献   

11.
A variety of column experiments have been completed for the purpose of selecting and evaluating suitable surfactants for remediation of nonaqueous phase liquids (NAPLs). The various NAPLs tested in the laboratory experiments were tetrachloroethylene (PCE), trichloroethylene (TCE), jet fuel (JP4) and a dense nonaqueous phase liquid from a site at Hill Air Force Base, UT. Both Ottawa sand and Hill field soil were used in these experiments. Surfactant candidates were first screened using phase behavior experiments and only the best ones were selected for the subsequent column experiments. Surfactants which showed high contaminant solubilization, fast coalescence times, and the absence of liquid crystal phases and gels during the phase behavior experiments were tested in soil column experiments. The primary objective of the soil column experiments was to identify surfactants that recovered at least 99% of the contaminant. The secondary objective was to identify surfactants that show low adsorption and little or no loss of hydraulic conductivity during the column experiments. Results demonstrated that up to 99.9% of the contaminants were removed as a result of surfactant flooding of the soil columns. The addition of xanthan gum polymer to the surfactant solution was shown to increase remediation efficiency as a lower volume of surfactant was required for recovering a given volume of NAPL. Based on these experimental results, guidelines for designing highly efficient and robust surfactant floods have been developed and applied to a field demonstration.  相似文献   

12.
A feasibility study of polychlorinated biphenyl (PCB) removal from contaminated soils using microwave-generated steam (MGS) was performed. Initial experimental results show that MGS effectively removed PCBs from contaminated soil with an overall removal efficiency of greater than 98% at a steam-to-soil mass ratio of 3:1. Removal efficiency was found to be dependent upon the amount of steam employed, expressed as a mass ratio of steam applied to soil mass. Evaporation was identified as a major mechanism in removing PCBs from the soil. Rapid expansion and evaporation of pore water by microwave dielectric heating accelerated evaporation rates of PCB molecules. Increased solubility of PCBs into the heated aqueous phase is also hypothesized. Together these effects increase mass-transfer rates, thus enhancing removal of PCBs from the soil.  相似文献   

13.
A novel method to remediate dense nonaqueous phase liquid (DNAPL) source zones that incorporates in situ density conversion of DNAPL via alcohol partitioning followed by displacement with a low interfacial tension (IFT) surfactant flood has been developed. Previous studies demonstrated the ability of the density-modified displacement (DMD) method to recover chlorobenzene (CB) and trichloroethene (TCE) from heterogeneous porous media without downward migration of the dissolved plume or free product. However, the extent of alcohol (n-butanol) partitioning required for in situ density conversion of high-density NAPLs, such as tetrachloroethene (PCE), could limit the utility of the DMD method. Hence, the objective of this study was to compare the efficacy of two n-butanol delivery approaches: an aqueous solution of 6% (wt) n-butanol and a surfactant-stabilized macroemulsion containing 15% (vol) n-butanol in water, to achieve density reduction of PCE-NAPL in two-dimensional (2-D) aquifer cells. Results of liquid-liquid equilibrium studies indicated that density conversion of PCE relative to water occurred at an n-butanol mole fraction of 0.56, equivalent to approximately 5 ml n-butanol per 1 ml of PCE when in equilibrium with an aqueous solution. In 2-D aquifer cell studies, density conversion of PCE was realized using both n-butanol preflood solutions, with effluent NAPL samples exhibiting density reductions ranging from 0.51 to 0.70 g/ml. Although the overall PCE mass recoveries were similar (91% and 93%) regardless of the n-butanol delivery method, the surfactant-stabilized macroemulsion preflood removed approximately 50% of the PCE mass. In addition, only 1.2 pore volumes of the macroemulsion solution were required to achieve in situ density conversion of PCE, compared to 6.4 pore volumes of the 6% (wt) n-butanol solution. These findings demonstrate that use of the DMD method with a surfactant-stabilized macroemulsion containing n-butanol holds promise as an effective source zone remediation technology, allowing for efficient recovery of PCE-DNAPL while mitigating downward migration of the dissolved plume and free product.  相似文献   

14.
A particular problem with the release of dense nonaqueous phase liquids (DNAPLs) into the environment is identifying where the DNAPL is and if it is still moving. This question is particularly important at sites where thousands of cubic meters of DNAPLs were disposed of. To date, results from laboratory models have not been scaled to predict analogous migration at the larger length and time scales appropriate for sites where large volumes of DNAPLs were released. Modified inspectional analysis is a technique for developing scaling relationships through nondimensionalizing the governing equations. It was applied in this study to scale observations of DNAPL migration in a laboratory model to four hypothetical scenarios in the field where large volumes of DNAPL were released. One scenario was compared to a large DNAPL spill site. The length and time scales of DNAPL movement predicted from our analysis are consistent with those predicted from a numerical model of this site. To our knowledge, this is the first application of modified inspectional analysis for release of DNAPLs in a laboratory model. This methodology may prove useful for scaling results from other laboratory investigations of DNAPL migration to field-scale systems.  相似文献   

15.
Subsurface heterogeneity at sites contaminated with nonaqueous phase liquids (NAPLs) reduces the effectiveness of traditional remediation measures. One cause may be the increased proportion of NAPL that is hydraulically isolated due to capillary trapping in heterogeneously-wetted materials. This study examines the wettability of ten materials, ranging from minerals, such as calcite and dolomite, to carbonaceous materials, such shale and coal, in air and water, NAPL and air, and NAPL and water systems. The wettability differed depending on which phase the solid material was initially immersed in: the less crystalline solids, if initially contacted by water were water-wet, but if initially contacted by NAPL were NAPL-wet. This difference, termed here wettability hysteresis, was observed for a suite of halogenated NAPLs and was independent of equilibration time. The degree of wettability hysteresis was greatest in the NAPL and water systems, with the magnitude of the difference increasing with the carbonaceous materials. Since the degree of capillary trapping in subsurface materials is related to wettability, the phenomenon of wettability hysteresis suggests that system history is a factor that may increase the heterogeneity of NAPL source zones.  相似文献   

16.
The formation of residual, discontinuous nonaqueous phase liquids (NAPLs) in the vadose zone is a process that is not well understood. To obtain data that can be used to study the development of a residual NAPL saturation in the vadose zone and to test current corresponding models, detailed transient experiments were conducted in intermediate-scale columns and flow cell. The column experiments were conducted to determine residual carbon tetrachloride (CCl(4)) saturations of two sands and to evaluate the effect of CCl(4) vapors on the water distribution. In the intermediate-scale flow cell experiment, a rectangular zone of the fine-grained sand was packed in an otherwise medium-grained matrix. A limited amount of CCl(4) was injected from a small source and allowed to redistribute until a pseudo steady state situation had developed. A dual-energy gamma radiation system was used to determine fluid saturations at numerous locations. The experiments clearly demonstrated the formation of residual CCl(4) saturations in both sands. Simulations with an established multifluid flow simulator show the shortcomings of current relative permeability-saturation-capillary pressure (k-S-P) models. The results indicate that nonspreading behavior of NAPLs should be implemented in simulators to account for the formation of residual saturations.  相似文献   

17.
A pilot scale field trial was conducted to evaluate the recovery of volatile, light non-aqueous phase liquids (LNAPLs) using a novel remediation method termed supersaturated water injection (SWI). SWI uses a patented technology to efficiently dissolve high concentrations of CO2 into water at elevated pressures. This water is injected into the subsurface resulting in the nucleation of CO2 bubbles at and away from the injection point. The nucleating bubbles coalesce, rise and volatilize residual LNAPL ganglia. In this study, an LNAPL composed of 103 kg of volatile pentane and hexane, and 30 kg of non-volatile Soltrol was emplaced below the water table at residual saturation. The SWI technology removed 78% of the pentane and 50% of the less volatile hexane. Contaminant mass was still being removed when the system was shut down for practical reasons. The mass removed is comparable to that expected for air sparging but a much smaller volume of gas was injected using the SWI system.  相似文献   

18.
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.  相似文献   

19.
Between September 5 and October 5,1989 a field demonstration of the NovaTerra, Inc. Detoxifier [formerly called Toxic Treatment (USA)] was performed by the U.S. EPA under the Superfund Innovative Technology Evaluation (SITE) program. The NovaTerra Detoxifier process injects steam and hot air directly into the ground to vaporize and strip volatile and semivolatile organics. Two augers loosen and homogenize the soil during the stripping process. The steam, hot air and organics are carried to the soil surface and collected for treatment.

The field demonstration was performed at the GATX Annex Terminal located at the Port of Los Angeles, San Pedro, California. Approximately 17 percent of the 5.2 acre site is contaminated with chlorinated solvents, plasticizers, coatings, adhesives and paint additives, and other miscellaneous chemicals from aboveground storage tanks and transfer operations to railroad cars.

The objectives of this SITE Demonstration were to determine the in situ soil concentrations before and after treatment, quantify process stream emissions (fugitive and sidestreams), determine process operating conditions, and determine if vertical migration of contaminants is occurring. Results from the SITE demonstration showed that a substantial amount of the VOCs were removed, about half the SVOCs were removed, there was very little fugitive air emissions from the operation, and what little downward migration occured (if any) was inconsequential.  相似文献   

20.
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.  相似文献   

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