Surfactant enhanced recovery of tetrachloroethylene from a porous medium containing low permeability lenses. 1. Experimental studies

A matrix of batch, column and two-dimensional (2-D) box experiments was conducted to investigate the coupled effects of rate-limited solubilization and layering on the entrapment and subsequent recovery of a representative dense NAPL, tetrachloroethylene (PCE), during surfactant flushing. Batch experiments were performed to determine the equilibrium solubilization capacity of the surfactant, polyoxyethylene (20) sorbitan monooleate (Tween 80), and to measure fluid viscosity, density and interfacial tension. Results of one-dimensional column studies indicated that micellar solubilization of residual PCE was rate-limited at Darcy velocities ranging from 0.8 to 8.2 cm/h and during periods of flow interruption. Effluent concentration data were used to develop effective mass transfer coefficient (Ke) expressions that were dependent upon the Darcy velocity and duration of flow interruption. To simulate subsurface heterogeneity, 2-D boxes were packed with layers of F-70 Ottawa sand and Wurtsmith aquifer material within 20-30 mesh Ottawa sand. A 4% Tween 80 solution was then flushed through PCE-contaminated boxes at several flow velocities, with periods of flow interruption. Effluent concentration data and visual observations indicated that both rate-limited solubilization and pooling of PCE above the fine layers reduced PCE recovery to levels below those anticipated from batch and column measurements. These experimental results demonstrate the potential impact of both mass transfer limitations and subsurface layering on the recovery of PCE during surfactant enhanced aquifer remediation.     

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.     

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

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

Field demonstration of surfactant-enhanced solubilization of DNAPL at Dover Air Force Base, Delaware

This study reports on a surfactant-based flood for tetrachloroethylene (PCE) removal from a control test cell at the Dover National Test Site. The surfactant formulation (sodium dihexyl sulfosuccinate (Aerosol-MA or AMA), isopropanol and calcium chloride) was able to achieve a high concentration of PCE in swollen micelles (supersolubilization) without vertical PCE migration. The hydraulic system included eight screened wells that were operated in both vertical circulation and line drive configurations. After 10 pore volumes of flushing, the overall PCE removal was 68% (65% of which corresponded to the surfactant flooding alone). In addition, the residual PCE saturation was reduced from 0.7% to 0.2%, and the concentration of PCE in the groundwater was reduced from 37-190 mg/L before the flushing to 7.3 mg/L after flooding. Recycling the surfactant solution reduced the required surfactant mass (and thus cost, and waste) by 90%. Close to 80% of the total PCE removal was obtained during the first five pore volumes which were operated in an upward vertical circulation flow scheme. No free oil phase was observed during the test. Further analysis of multilevel sampler data suggests that most of the trapped oil remaining in the cell was likely localized in secluded regions of the aquifer, which helps explain the lower PCE groundwater concentration after remedial activities. In summary, this field study demonstrated the feasibility of surfactant-enhanced remediation to reduce the mass in the source zone and significantly reduce the PCE aqueous concentration and therefore the risk associated with the contaminant plume.     

Conditions for effective removal of pyrene from an artificially contaminated soil using Pseudomonas aeruginosa 57SJ rhamnolipids

The efficacy of a new rhamnolipid biosurfactants mixture to enhance the removal of pyrene from a soil artificially contaminated was investigated. The molar solubilization ratio (MSR) and the partition coefficient between the micelles and water (log K(m)) were found to be 7.5 x 10(-3) and 5.7, respectively. From soil column studies, the pyrene removal increased linearly with the concentration of the injected biosurfactants solution above the effective critical micellar concentration (0.4 g L(-1)). Flushing with a 5.0 g L(-1) biosurfactants solution increased the pyrene concentration in the effluent by 178 times. At high biosurfactants' concentrations (2.5 and 5.0 g L(-1)), the cumulative pyrene recovery reached 70%. This pyrene remobilization takes place independently of the soil organic carbon solubilization. This study provides a combination of batch and column experiments in order to find the conditions for effective soil remediation using a new rhamnolipids mixture.     

Influence of surfactants on solubilization and fungal degradation of fluorene

Eighteen fungal strains were tested in toxicity assays with surfactants in order to select surfactants and strains tolerant to surfactants for degradation assays. Two nonionic surfactants were used, an alkylphenol ethoxylate, Triton X-100, a sorbitan ester, Tween 80 and an anionic surfactant, sodium dodecyl sulfate. Solubilization and biodegradation tests were conducted in liquid medium batch; fluorene was quantified by HPLC. Results showed the enhancement of fluorene solubilization by the three surfactants, good tolerance of nonionic surfactants by the fungal strains and the enhancement of the biodegradation of fluorene by Doratomyces stemonitis (46-62%) and Penicillium chrysogenum (28-61%) in the presence of Tween 80 (0.324 mM) after 2 days.     

Influence of residual surfactants on DNAPL characterization using partitioning tracers

The partitioning tracer technique is among the DNAPL source-zone characterization methods being evaluated, while surfactant in-situ flushing is receiving attention as an innovative technology for enhanced source-zone cleanup. Here, we examine in batch and column experiments the magnitude of artifacts introduced in estimating DNAPL content when residual surfactants are present. The batch equilibrium tests, using residual surfactants ranging from 0.05 to 0.5 wt.%, showed that as the surfactant concentrations increased, the tracer partition coefficients decreased linearly for sodium hexadecyl diphenyl oxide disulfonate (DowFax 8390), increased linearly for polyoxyethylene (10) oleyl ether (Brij 97), and decreased slightly or exhibited no observable trend for sodium dihexyl sulfosuccinate (AMA 80). Results from column tests using clean sand with residual DowFax 8390 and Tetrachloroethylene (PCE) were consistent with those of batch tests. In the presence of DowFax 8390 (less than 0.5 wt.%), the PCE saturations were underestimated by up to 20%. Adsorbed surfactants on a loamy sand with positively charged oxides showed false indications of PCE saturation based on partitioning tracers in the absence of PCE. Using no surfactant (background soil) gave a false PCE saturation of 0.0004, while soil contacted by AMA 80, Brij 97, and DowFax 8390 gave false PCE saturations of 0.0024, 0.043, and 0.23, respectively.     

Locally-calibrated light transmission visualization methods to quantify nonaqueous phase liquid mass in porous media

Five locally-calibrated light transmission visualization (LTV) methods were tested to quantify nonaqueous phase liquid (NAPL) mass and mass reduction in porous media. Tetrachloroethylene (PCE) was released into a two-dimensional laboratory flow chamber packed with water-saturated sand which was then flushed with a surfactant solution (2% Tween 80) until all of the PCE had been dissolved. In all the LTV methods employed here, the water phase was dyed, rather than the more common approach of dyeing the NAPL phase, such that the light adsorption characteristics of NAPL did not change as dissolution progressed. Also, none of the methods used here required the use of external calibration chambers. The five visualization approaches evaluated included three methods developed from previously published models, a binary method, and a novel multiple wavelength method that has the advantage of not requiring any assumptions about the intra-pore interface structure between the various phases (sand/water/NAPL). The new multiple wavelength method is also expected to be applicable to any translucent porous media containing two immiscible fluids (e.g., water-air, water-NAPL). Results from the sand-water-PCE system evaluated here showed that the model that assumes wetting media of uniform pore size (Model C of Niemet and Selker, 2001) and the multiple wavelength model with no interface structure assumptions were able to accurately quantify PCE mass reduction during surfactant flushing. The average mass recoveries from these two imaging methods were greater than 95% for domain-average NAPL saturations of approximately 2.6x10(-2), and were approximately 90% during seven cycles of surfactant flushing that sequentially reduced the average NAPL saturation to 7.5x10(-4).     

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。     

Laboratory-scale in situ chemical oxidation of a perchloroethylene pool using permanganate

In situ chemical oxidation (ISCO) is an emerging technology for the destruction of some chlorinated solvents present in subsurface environments. A laboratory investigation using a physical model was designed to assess the effectiveness of using permanganate as an oxidant to reduce the mass of a perchloroethylene (PCE) pool. The physical model was filled with silica sand overlying a silica flour base, simulating a two-dimensional saturated sand zone overlying a capillary barrier. PCE was introduced into the model so that it rested on top of the silica flour base, forming a dense nonaqueous phase liquid pool. The experimental methodology involved flushing the model with a permanganate solution for 146 days. During this period, measurements of chloride were used to assess the extent of pool oxidation. Before and after the oxidant flush, the quasi-steady state dissolution from the PCE pool was evaluated. Additionally, tracer studies were completed to assess changes in the flow field due to the oxidation process. At the termination of the experiment nine soil cores extracted from the model were used to detect the presence of MnO2 deposits and to quantify the mass of PCE remaining in the system. Excavation of the remaining material in the model revealed that the MnO2 distribution throughout the model was consistent with that observed in the cores. The oxidant flush was concluded before all of the pure phase PCE had been completely oxidized; however, approximately 45% of the PCE mass was removed, resulting in a fourfold decrease in the quasi-steady state aqueous phase mass loading of PCE from the pool. Measurements of chloride during the oxidant flush and of PCE in the soil cores suggested that the oxidation reaction occurred primarily at the upgradient edge of the PCE pool. MnO2 deposits within the model aquifer decreased the velocity of water directly above the pool, and the overall mass transfer from the remaining PCE pool. The results of this experimental study indicate that ISCO using permanganate is capable of removing substantial mass from a DNAPL pool; however, the performance of ISCO as a pool removal technology will be limited by the formation and precipitation of hydrous MnO2 that occurs during the oxidation process.     

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

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

Different behaviours in the solubilization of polycyclic aromatic hydrocarbons in water induced by mixed surfactant solutions

Water solubility of polycyclic aromatic hydrocarbons (PAHs), viz, naphthalene and phenanthrene, in micellar solutions at 25 °C was investigated, using two series of different binary mixtures of anionic and nonionic surfactants. Tween 80 and Brij-35 were used as nonionic surfactants whereas fatty acids or amphiphilic cyclodextrins (Mod-β-CD) synthesized in our laboratory were used as anionic ones. Solubilization capacity has been quantified in terms of the molar solubilization ratio and the micelle-water partition coefficient, using UV-visible spectrophotometry. Anionic surfactants exhibited less solubilization capacity than nonionics. The mixtures between Tween 80 and Mod-β-CD did not show synergism to increase the solubilization of PAHs. On the other hand, the mixtures formed by Tween 80 and fatty acids at all mole fractions studied produced higher enhancements of the solubility of naphthalene than the individual surfactants. The critical micellar concentration of the mixtures of Tween 80/sodium laurate was determined by surface tension measurements and spectrofluorimetry using pyrene as probe. The system is characterized by a negative interaction parameter (β) indicating attractive interactions between both surfactants in the range of the compositions studied.     

Humic acid enhanced remediation of an emplaced diesel source in groundwater. 1. Laboratory-based pilot scale test

The enhanced solubility of petroleum-derived compounds in humic acid solutions is the basis for a new groundwater remediation technology. In this unique pilot-scale test, a stationary contaminant source consisting of diesel fuel was placed below the water table in a model sand aquifer (1.2 x 5.5 x 1.8-m deep) and flushed with water at a flow rate of 2 cm/h over 5 years. At 51 days, laboratory grade humic acid was added to the water and maintained at a level of approximately 0.8 g/l. The addition of humic acid had only a small impact on the aqueous transport of the BTEX components, which were rapidly dissolved from the diesel, but had a large effect on the flushing of PAHs, including methylated naphthalenes (MNs). Binding to aqueous humic acid enhanced the solubilization of MNs two- to tenfold. During aqueous transport, biodegradation of the BTEX and PAHs occurred, limiting the lateral and longitudinal extent of the diesel contaminant plume in the model aquifer. It appears that through enhanced solubilization, the overall biodegradation rate of the MNs was increased. As the various MNs were depleted from the diesel source, the MN plume shrank and then disappeared.     

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

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

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.     

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   

The principle and effect of transfer agent for the removal of PCE during in situ chemical oxidation

Viscosity remedial technology, which uses a water-soluble polymer mixed with remedial fluids, has been introduced in recent years to improve the removal efficacy of perchloroethylene/tetrachloroethylene (PCE) by improving oxidant coverage (i.e. sweep efficiency). Xanthan gum and hydrolysed polyacrylamide (HPAM) are relatively stable with time and temperature and possess salt and oxidation resistance, indicating that they may be good flooding agents (the former is better than the latter in this work). In this work, we quantified the polymer directly improved oxidation of PCE during transport by using a two-dimensional flow tank. Using a low pore volume (≤3.0), the removal rate of the PCE increased with the polymer concentration before stabilizing at approximately 93.00 and 88.30% for xanthan and HPAM, respectively. In this work, over 80% of PCE was removed via less than 3.0 PV of the SDS solution, whereas complete removal (100%) was achieved with less than 3.0 PV of SDS foam. Furthermore, the new experimental discoveries demonstrate that xanthan is better than HPAM and SDS foam is a better remediation agent than the SDS solution for removing PCE.

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Graphical abstract (Reaction device, A - inlet device (pump 1#), B - 2D tank, C - outflow device (pump 2#), D - data recording and processing device, E - microscopic expression, E (a) - KMnO₄ flushing, E (b) - polymer solution flushing).

     

Humic acid enhanced remediation of an emplaced diesel source in groundwater. 2. Numerical model development and application

A pilot scale experiment for humic acid-enhanced remediation of diesel fuel, described in Part 1 of this series, is numerically simulated in three dimensions. Groundwater flow, enhanced solubilization of the diesel source, and reactive transport of the dissolved contaminants and humic acid carrier are solved with a finite element Galerkin approach. The model (BIONAPL) is calibrated by comparing observed and simulated concentrations of seven diesel fuel components (BTEX and methyl-, dimethyl- and trimethylnaphthalene) over a 1500-day monitoring period. Data from supporting bench scale tests were used to estimate contaminant-carrier binding coefficients and to simulate two-site sorption of the carrier to the aquifer sand. The model accurately reproduced the humic acid-induced 10-fold increase in apparent solubility of trimethylnaphthalene. Solubility increases on the order of 2-5 were simulated for methylnaphthalene and dimethylnaphthalene, respectively. Under the experimental and simulated conditions, the residual 500-ml diesel source was almost completely dissolved and degraded within 5 years. Without humic acid flushing, the simulations show complete source dissolution would take about six times longer.     

Injection of innocuous oils to create reactive barriers for bioremediation: laboratory studies

In situ groundwater remediation may be achieved using stationary permeable barriers created by the injection of a substrate, such as innocuous vegetable oil, into the contaminated aquifer. The oil provides the electron donor stimulating microorganisms to degrade or sequester many contaminants. At present, little is known about the best procedures to use when injecting oil into an aquifer. In this investigation, laboratory column and sand tank studies were used as model systems to explore the effect of different injection parameters on the distribution of oil emulsions into water-saturated sand. The parameters investigated included injection pressures of 70, 1400 and 18,000 KPa; injection times of 15, 30, 60 or 120 s; and the influence of an emulsifier, polyoxyethylenesorbitan monooleate (Tween 80), upon the distribution of the injected oil. The longest injection patterns were achieved at 18,000 KPa. A pattern that was 46+/-1.8 cm long was produced with an 18,000 KPa injection for 60 s. Increasing the injection time to 120 s increased the length of the pattern by only 6.5%. Tween 80 at concentrations of 0.05% increased the width of the injection patterns but did not increase the length of the pattern. A multi-ported injection probe might be used to create in situ permeable barriers approximately 1 m wide.     

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.