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。     

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.     

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

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

Effects of initial saturation on properties modification and displacement of tetrachloroethene with aqueous isobutanol

Packed column experiments were conducted to study effects of initial saturation of tetrachloroethene (PCE) in the range of 1.0-14% pore volume (PV) on mobilization and downward migration of the non-aqueous phase liquid (NAPL) product upon contact with aqueous isobutanol ( approximately 10 vol.%). This study focused on the consequences of swelling beyond residual saturation. Columns were packed with mixtures of neat PCE, water and glass beads and waterflooded to establish a desired homogeneous residual saturation, and then flooded with aqueous isobutanol under controlled hydraulic conditions. Results showed a critical saturation of approximately 8% PV for these packed column experimental conditions. At low initial PCE saturations (<8% PV), experimental results showed reduced risk of NAPL-product migration upon contact with aqueous isobutanol. At higher initial PCE saturations (>8% PV), results showed NAPL-product mobilization and downward migration which was attributed to interfacial tension (IFT) reduction, swelling of the NAPL-product, and reduced density modification. Packed column results were compared with good agreement to theoretical predictions of NAPL-product mobilization using the total trapping number, N(T). In addition to the packed column study, preliminary batch experiments were conducted to study the effects of PCE volumetric fraction in the range of 0.5-20% on density, viscosity, and IFT modification as a function of time following contact with aqueous isobutanol ( approximately 10 vol.%). Modified NAPL-product fluid properties approached equilibrium within approximately 2 h of contact for density and viscosity. IFT reduction occurred immediately as expected. Measured fluid properties were compared with good agreement to theoretical equilibrium predictions based on UNIQUAC. Overall, this study demonstrates the importance of initial DNAPL saturation, and the associated risk of downward NAPL-product migration, in applying alcohol flooding for remediation of DNAPL contaminated ground water sites.     

Solubilization of DNAPLs by mixed surfactant: reduction in partitioning losses of nonionic surfactant

Efforts to remediate the dense nonaqueous phase liquids (DNAPLs) by mobilizing them face with risks of driving the contaminants deeper into aquifer zones. This spurs research for modifying the approach for in situ remediation. In this paper, a novel solubilization of DNAPLs by mixed nonionic and anionic surfactant, Triton X-100 (TX100) and sodium dodecylbenzene sulfonate (SDBS), was presented and compared with those by single ones. Given 1:40 phase ratio of DNAPL:water (v/v) and the total surfactant concentration from 0.2 to 10gl(-1), mixed TX100-SDBS at the total mass ratios of 3:1, 1:1 and 1:3 exhibited significant solubilization for the DNAPLs, trichloroethene (TCE), chlorobenzene (CB) and 1,2-dichlorobenzene (1,2-DCB). The solubilization extent by mixed TX100-SDBS was much larger than by single TX100 and even larger than by single SDBS at the ratios of 1:1 and 1:3, respectively. TX100 partitioning into the organic phase dictated the solubilization extent. The TX100 losses into TCE, CB and 1,2-DCB phases were more than 99%, 97% and 97% when single TX100 was used. With SDBS alone, no SDBS partitioned into DNAPLs was observed and in mixed systems, SDBS decreased greatly the partition loss of TX100 into DNAPLs. The extent of TX100 partition decreased with increasing the amount of SDBS. The mechanism for reduction of TX100 partition was discussed. TX100 and SDBS formed mixed micelles in the solution phase. The inability of SDBS to partition into DNAPLs and the mutual affinity of SDBS and TX100 in the mixed micelle controlled the partitioning of TX100 into DNAPL phase. The work presented here demonstrates that mixed nonionic-anionic surfactants would be preferred over single surfactants for solubilization remediation of DNAPLs, which could avoid risks of driving the contaminants deeper into aquifers and decrease the surfactant loss and remediation cost.     

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.     

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.     

Using polymer solutions to enhance recovery of mobile coal tar and creosote DNAPLs

Direct pumping and enhanced recovery of coal tar and creosote dense, non-aqueous phase liquids (DNAPLs) from the subsurface have had mixed results because these DNAPLs are viscous fluids that can potentially alter aquifer wettability. To improve the inefficiencies associated with waterflooding, the research presented here considered the use of a polymer solution that can be added to the injected flood solution to increase the viscosity and decrease the velocity of the flooding solution. Results from one-dimensional, vertically oriented laboratory column experiments that evaluate the recovery of coal-derived DNAPL with both water and polymer flooding solutions are presented. The final DNAPL saturation remaining in the column was assessed in water and oil-wet systems for three viscous DNAPLs. Adding polymer to increase the aqueous solution viscosity did not have a significant impact in water-wet systems. A final DNAPL saturation of approximately 19% was achieved for both water and polymer floods. In contrast, the addition of polymer significantly improved recovery in oil-wet systems. The final saturation was over 40% in oil-wet systems after waterflooding, but approximately 19% with a polymer flushing solution. Although the final saturation produced with polymer flooding was similar between the oil- and water-wet systems, differences in the relative permeability and distribution of DNAPL in the porous matrix caused the DNAPL recovery to be much slower in the oil-wet system.     

Improving the extraction of tetrachloroethylene from soil columns using surfactant gradient systems

In this work, we extend the recently developed gradient approach for surfactant-enhanced remediation of dense non-aqueous phase liquid (DNAPL)-impacted sites. The goal of the gradient approach is to maximize the DNAPL solubilization capacity in swollen micelles (Type I aqueous microemulsions) while at the same time minimizing the potential for DNAPL mobilization. In this work, we introduce a modified version of the capillary/trapping curve that we refer to as the gradient curve to help interpret and/or design the gradient approach. The gradient curve presents the residual DNAPL saturation as a function of interfacial tension and microemulsion viscosity. This approach demonstrates that keeping a low viscosity of the microemulsion phase is not only important for keeping a low head loss during surfactant flooding but also to prevent oil mobilization. Eight microemulsion systems were evaluated in this research; these systems were evaluated based on their tetrachloroethylene (PCE) solubilization capacity, interfacial tension (IFT), viscosity, density, and coalescence kinetics. Two of these systems were chosen for evaluation in site-specific column tests using an increasing electrolyte gradient to produce a decreasing IFT/increasing solubilization gradient system. The column studies were conducted with media from Dover Air Force Base in Dover, DE. Both solubilized and mobilized DNAPL were quantified. During the column studies, we observed that substantial PCE was mobilized when the residual level of PCE in the column was significantly higher than the steady-state residual saturation level being approach (as predicted from the gradient curve). Four column studies were performed, three of which were used to asses the validity of the gradient curve in predicting the residual saturation after each gradient step. From these tests we observed that starting IFTs of less than 1 mN/m all produced the same mobilization potential. In the last column, we used an additional gradient step with an initial IFT above 1 mN/m to dramatically reduce the amount of PCE mobilize. Based on the good agreement between column results and projections based on the gradient curve, we propose this as a preferred method for designing gradient surfactant flushing systems.     

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.     

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.     

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.     

Refinement of the density-modified displacement method for efficient treatment of tetrachloroethene source zones

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.     

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   

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

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

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.     

Aquifer washing by micellar solutions: 1: Optimization of alcohol–surfactant–solvent solutions

Phase diagrams were used for the formulation of alcohol–surfactant–solvent and to identify the DNAPL (Dense Non Aqueous Phase Liquid) extraction zones. Four potential extraction zones of Mercier DNAPL, a mixture of heavy aliphatics, aromatics and chlorinated hydrocarbons, were identified but only one microemulsion zone showed satisfactory DNAPL recovery in sand columns. More than 90 sand column experiments were performed and demonstrate that: (1) neither surfactant in water, alcohol–surfactant solutions, nor pure solvent can effectively recover Mercier DNAPL and that only alcohol–surfactant–solvent solutions are efficient; (2) adding salts to alcohol–surfactant or to alcohol–surfactant–solvent solutions does not have a beneficial effect on DNAPL recovery; (3) washing solution formulations are site specific and must be modified if the surface properties of the solids (mineralogy) change locally, or if the interfacial behavior of liquids (type of oil) changes; (4) high solvent concentrations in washing solutions increase DNAPL extraction but also increase their cost and decrease their density dramatically; (5) maximum DNAPL recovery is observed with alcohol–surfactant–solvent formulations which correspond to the maximum solubilization in Zone C of the phase diagram; (6) replacing part of surfactant SAS by the alcohol n-butanol increases washing solution efficiency and decreases the density and the cost of solutions; (7) replacing part of n-butanol by the nonionic surfactant HOES decreases DNAPL recovery and increases the cost of solutions; (8) toluene is a better solvent than D-limonene because it increases DNAPL recovery and decreases the cost of solutions; (9) optimal alcohol–surfactant–solvent solutions contain a mixture of solvents in a mass ratio of toluene to D-limonene of one or two. Injection of 1.5 pore volumes of the optimal washing solution of n-butanol–SAS–toluene–D-limonene in water can recover up to 95% of Mercier DNAPL in sand columns. In the first pore volume of the washing solution recovered in the sand column effluent, the DNAPL is in a water-in-oil microemulsion lighter than the excess aqueous phase (Winsor Type II system), which indicates that part of the DNAPL was mobilized. In the next pore volumes, DNAPL is dissolved in a oil-in-water microemulsion phase and is mobilized in an excess oil phase lighter than the microemulsion (Winsor Type I system). The main drawback of this oil extraction process is the high concentration of ingredients necessary for DNAPL dissolution, which makes the process expensive. Because mobilization of oil seems to occur at the washing solution front, an injection strategy must be developed if there is no impermeable limit at the aquifer base. DNAPL recovery in the field could be less than observed in sand columns because of a smaller sweep efficiency related to field sand heterogeneities. The role of each component in the extraction processes in sand column as well as the Winsor system type have to be better defined for modeling purposes. Injection strategies must be developed to recover ingredients of the washing solution that can remain in the soil at the end of the washing process. ©1997 Elsevier Science B.V.     

A new concept: the use of neutrally-buoyant microemulsions for DNAPL remediation

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.     

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.