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。     

Enhanced desorption of phenanthrene from contaminated soil using anionic/nonionic mixed surfactant

A new approach using an anionic/nonionic mixed surfactant, sodium dodecyl sulphate (SDS) with Triton X-100 (TX100), was utilized for the desorption of phenanthrene from an artificial contaminated natural soil in an aim to improve the efficiency of surfactant remediation technology. The experimental results showed that the presence of SDS not only reduced the sorption of TX100 onto the natural soil, but also enhanced the solubilization of TX100 for phenanthrene, both of which resulted in the distribution of phenanthrene in soil-water systems decreasing with increasing mole fraction of SDS in surfactant solutions. These results can be attributed to the formation of mixed micelles in surfactant solution and the corresponding decrease in the critical micelle concentration of TX100 in mixed solution. The batch desorption experiments showed that the desorption percentage of phenanthrene from the contaminated soil with mixed solution was greater than that with single TX100 solution and appeared to be positively related to the mole fraction of SDS in surfactant solution. Thus, the anionic/nonionic mixed surfactants are more effective for the desorption of phenanthrene from the contaminated soil than a single nonionic surfactant.     

Solubilization and biodegradation of phenanthrene in mixed anionic-nonionic surfactant solutions

The effects of mixed anionic-nonionic surfactants, sodium dodecyl sulfate (SDS) mixed with Tween80 (TW80), Triton X-100 (TX100) and Brij35 respectively on the solubility enhancement and biodegradation of phenanthrene in the aqueous phase were investigated. The efficiency of solubilization and biodegradation of phenanthrene in single-, and mixed-surfactant solutions were also compared. The critical micellar concentrations (CMCs) of mixed surfactants were sharply lower than that of sole SDS. The degree of solubility enhancements by the mixed surfactants followed the order of SDS-TW80>SDS-Brij35>SDS-TX100. Synergistic solubilization was observed in the mixed surfactant solutions, in which the molar ratios of SDS to nonionic surfactant were 1:0, 9:1, 7:3, 5:5, 3:7, 1:9 and 0:1 while the total concentration of surfactants was kept at 5.0 and 10.0 mM, respectively. SDS-Brij35 exhibited more significant degree of synergistic solubility enhancement for phenanthrene. The mixed surfactants exhibited no inhibitory effect on biodegradation of phenanthrene. Substantial amounts of the solubilized phenanthrene by mixed surfactants were completely degraded by phenanthrene-degrading microorganisms within 96 h. The results suggested that anionic-nonionic surfactants would improve the performance of remediation of PAH-contaminated soils.     

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.     

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.     

Synergistic solubilization of polycyclic aromatic hydrocarbons by mixed anionic-nonionic surfactants

Water solubility enhancements of naphthalene (Naph), acenaphthylene (Acen), anthracene (An), phenanthrene (Phen) and pyrene (Py) by micellar solutions of single and mixed anionic-nonionic surfactants were measured and compared. Effects of typical inorganic ions, such as NH(4)(+), Na(+) and Mg(2+) coexisted with the organic pollutants (in soils) on water solubilities of polycyclic aromatic hydrocarbons (PAHs) in the presence of single and mixed surfactants were also investigated. Solubilities of PAHs in water are greatly enhanced in a linear fashion by each of Triton X-100 (TX100), Triton X-305 (TX305), Brij 35, and sodium dodecyl sulfate (SDS). Solubility enhancement efficiencies of surfactants above the critical micelle concentration (CMC) follow the order of TX100>Brij 35>TX305>SDS. PAHs are solubilized synergistically in mixed anionic-nonionic surfactant solutions, especially at low surfactant concentrations. The synergistic power of the mixed surfactants is SDS-TX305>SDS-Brij 35>SDS-TX100. Synergistic effect of a given mixed-surfactant solution on different PAHs also appears to be linearly related to the solute logK(ow). The noted synergism for the mixed surfactants is attributed to the formation of mixed micelles, the lower CMC of the mixed-surfactant solutions, and the increase of the solute's molar solubilization ratio or micellar partition coefficients (K(mc)) because of the lower polarity of the mixed micelles. Suitable quantity of inorganic cations can enhance the solubilization capacities of anionic-nonionic mixed surfactants, the effect being Mg(2+)>NH(4)(+)>Na(+). The water solubility of pyrene was slightly increased by anthracene and significantly increased by 1,2,3-TCB in the presence of SDS-Brij 35. Mixed surfactants may improve the performance of surfactant-enhanced remediation of soils and sediments by decreasing the applied surfactant level and thus the remediation cost.     

Effect of nonionic surfactant partitioning on the dissolution kinetics of residual perchloroethylene in a model porous medium

At concentrations above the critical micelle concentration, surfactants can significantly enhance the solubilization of residual nonaqueous phase liquids (NAPL) and, for this reason, are the focus of research on surfactant-enhanced aquifer remediation (SEAR). As a consequence of their amphiphilic nature, surfactants may also partition to various extents between the organic and aqueous phases, thereby affecting SEAR performance. We report here on the observation and analysis of the effect of surfactant partitioning on the dissolution kinetics of residual perchloroethylene (PCE) by aqueous solutions (1000 mg/L) of the non-ionic surfactant Triton X-100 in a model porous medium. For this fluid system, batch equilibration experiments showed that the surfactant partitions strongly into the NAPL (NAPL-water partition coefficient equal to 12.5). Dynamic interfacial tension (IFT) measurements were employed to study surfactant diffusion and interfacial adsorption. The dynamic IFT measurements were consistent with partitioning of the surfactant between the two liquid phases. PCE dissolution experiments, conducted in a transparent glass micromodel using an aqueous surfactant solution, were contrasted to experiments using clean water. Surfactant partitioning was observed to delay significantly the onset of micellar solubilization of PCE, an observation reproduced by a numerical model. This effect is attributed to the reduction of surfactant concentration in the immediate vicinity of the NAPL-water interface, which accompanies transport of the surfactant into the NAPL. Accordingly, it is suggested that both the rate and the extent of diffusion of the surfactant into the NAPL affect the onset of and the driving force for micellar solubilization. While many surfactants do not readily partition in NAPL, this possibility must be considered when selecting non-ionic surfactants for the enhanced solubilization of residual chlorinated solvents in porous media.     

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.     

蓖麻油衍生微乳液对菲的增溶和洗脱作用及其对菲污染土壤的修复机理

比较研究了蓖麻油硫酸盐(SCOS)与普通表面活性剂Triton X-100(TX100)、Tween 80(TW80)、Brij35、十二烷基苯磺酸钠(SDBS)和十二烷基硫酸钠(SDS)等对菲的增溶和洗脱作用.结果表明,菲表观溶解度与SCOS的浓度呈单一线性关系,SCOS微乳液对菲的增溶比SR=0.0314为最大,菲在微乳相和水相之间的分配系数logKem=4.44,大于菲在胶束相和水相之间的分配系数(logKmc).1:10土-水体系下,SCOS微乳液对菲污染土壤的清洗速率最快,清洗效率最高.SCOS有望成为土壤有机污染淋洗修复的增效试剂.     

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.     

Influence of surfactant sorption on the removal of phenanthrene from contaminated soils

Laboratory column flushing experiments were conducted to remove phenanthrene from contaminated soils by Triton X-100 (TX100) with an aim to investigating the effect of surfactant sorption on the performance of surfactant-enhanced remediation process. The effluent concentration of phenanthrene from soil columns showed strong dependence on the sorption breakthrough curves of TX100. The removal of phenanthrene from contaminated soils was enhanced only when the sorption breakthrough of TX100 occurred and the influent concentration of TX100 was greater than the critical enhanced flushing concentration (CEFC). The sorption of surfactant onto soils and the subsequent partitioning of contaminants into soil-sorbed surfactant had a significant effect on the solute equilibrium distribution coefficient (KD) and thus the flushing efficiency for phenanthrene. A model was developed to predict KD and CEFC values for simulating the performance of surfactant-enhanced flushing for contaminated soils. These results are of practical interest in developing effective and safe surfactant-enhanced remediation technologies.     

Anionic surfactant remediation of soil columns contaminated by nonaqueous phase liquids

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.     

Changes in contaminant mass discharge from DNAPL source mass depletion: evaluation at two field sites

Changes in contaminant fluxes resulting from aggressive remediation of dense nonaqueous phase liquid (DNAPL) source zone were investigated at two sites, one at Hill Air Force Base (AFB), Utah, and the other at Ft. Lewis Military Reservation, Washington. Passive Flux Meters (PFM) and a variation of the Integral Pumping Test (IPT) were used to measure fluxes in ten wells installed along a transect down-gradient of the trichloroethylene (TCE) source zone, and perpendicular to the mean groundwater flow direction. At both sites, groundwater and contaminant fluxes were measured before and after the source-zone treatment. The measured contaminant fluxes (J; ML(-2)T(-1)) were integrated across the well transect to estimate contaminant mass discharge (M(D); MT(-1)) from the source zone. Estimated M(D) before source treatment, based on both PFM and IPT methods, were approximately 76 g/day for TCE at the Hill AFB site; and approximately 640 g/day for TCE, and approximately 206 g/day for cis-dichloroethylene (DCE) at the Ft. Lewis site. TCE flux measurements made 1 year after source treatment at the Hill AFB site decreased to approximately 5 g/day. On the other hand, increased fluxes of DCE, a degradation byproduct of TCE, in tests subsequent to remediation at the Hill AFB site suggest enhanced microbial degradation after surfactant flooding. At the Ft. Lewis site, TCE mass discharge rates subsequent to remediation decreased to approximately 3 g/day for TCE and approximately 3 g/day for DCE approximately 1.8 years after remediation. At both field sites, PFM and IPT approaches provided comparable results for contaminant mass discharge rates, and show significant reductions (>90%) in TCE mass discharge as a result of DNAPL mass depletion from the source zone.     

Selection of surfactant in remediation of DDT-contaminated soil by comparison of surfactant effectiveness

With an aim to select the most appropriate surfactant for remediation of DDT-contaminated soil, the performance of nonionic surfactants Tween80, TX-100, and Brij35 and one anionic surfactant sodium dodecyl benzene sulfonate (SDBS) in enhancement of DDT water solubility and desorption of DDT from contaminated soil and their adsorption onto soil and ecotoxicities were investigated in this study. Tween80 had the highest solubilizing and soil-washing ability for DDT among the four experimental surfactants. The adsorption loss of surfactants onto soil followed the order of TX-100 > Tween80 > Brij35 > SDBS. The ecotoxicity of Tween80 to ryegrass (Lolium perenne L.) was lowest. The overall performance considering about the above four aspects suggested that Tween80 should be selected for the remediation of DDT-contaminated soil, because Tween80 had the greatest solubilizing and soil-washing ability for DDT, less adsorption loss onto soil, and the lowest ecotoxicity in this experiment.     

Distribution of polycyclic aromatic hydrocarbons in soil-water system containing a nonionic surfactant

The effect of a nonionic surfactant, Triton X-100 (TX100), on the distribution of four representative polycyclic aromatic hydrocarbons (PAHs), phenanthrene, fluorene, acenaphthene and naphthalene, in soil-water system was studied on a natural soil. The apparent soil-water distribution coefficient with surfactant (Kd*) for these compounds increased when TX100 equilibrium concentration from zero to around the critical micelle concentration (CMC), followed by a decrease in Kd* at TX100 equilibrium concentration greater than CMC. This is a direct result of surfactant sorption onto soil followed by PAHs partitioning to the sorbed surfactant. The values of carbon-normalized solute distribution coefficient (Kss) with the sorbed TX100 are greater than the corresponding partition coefficients with soil organic matter (Koc), which indicates the soil-sorbed nonionic surfactant is more effective per unit mass as a partitioning medium than the native soil organic matter for PAHs. When Kd* = Kd the corresponding initial concentration of surfactant was defined as critical washing concentration (CWC). Depending on the surfactant initial concentration below or above the CWC, the addition of nonionic surfactant can enhance the retardation of soil for PAHs or promote the removal of PAHs from soil, respectively. The values of Kd* and CWC can be predicted by a model, which correlates them with the compounds' octanol-water partition coefficients (Kow), soil property and the amount of soil-sorbed surfactant.     

The effects of surfactant formulation on nonequilibrium NAPL solubilization

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.     

Benzene removal from waste water using aqueous surfactant two-phase extraction with cationic and anionic surfactant mixtures

A novel separation technique known as an aqueous surfactant two-phase (ASTP) extraction is a promising method to remove organic contaminants from wastewater. When cationic and anionic surfactants are mixed at certain surfactant concentrations and compositions, the solution separates into two immiscible aqueous phases. One is the surfactant-rich and the other is the surfactant-dilute phase. The organic contaminants will solubilize into the surfactant aggregates and concentrate in the small volume surfactant-rich phase. The other phase contains only small amount of surfactants and contaminants as the treated water. Most ASTP studies have used nonionic surfactants above the cloud point. Mixtures of anionic and cationic surfactants can also exhibit aqueous-aqueous phase separation and can be used in the ASTP extraction process. The phase behavior and performance of ASTP extraction using cationic surfactant dodecyltrimethylammonium bromide (DTAB) and anionic surfactant alkyldiphenyloxide di-sulfonate (DPDS) to extract benzene from wastewater was investigated in batch experiments. It was found that phase separation only occurs over a narrow range of molar ratios of DTAB:DPDS from 1.6:1 to 2.4:1. In this study, a 2:1 molar ratio of DTAB:DPDS at which there is no net charge in the surfactant aggregates show the highest extraction efficiency and lowest critical micelle concentration value with greatest synergism (highest negative values of the micellar interaction parameter). At a total surfactant concentration of 50mM, the benzene partition ratio is 48 and 72% of the benzene is extracted into the surfactant-rich phase solution in a single stage extraction, which is superior performance compared to ASTP extraction using nonionic surfactants.     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

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.     

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.