Fluid and porous media property effects on dense nonaqueous phase liquid migration and contaminant mass flux

The effects of fluid and porous media properties on dense nonaqueous phase liquid (DNAPL) migration and associated contaminant mass flux generation were evaluated. Relationships between DNAPL mass and solute mass flux were generated by measuring steady-state mass flux following stepwise injection of perchloroethylene (PCE) into flow chambers packed with homogeneous porous media. The effects of fluid properties including density and interfacial tension (IFT), and media properties including grain size and wettability were evaluated by varying the density contrast and interfacial tension properties between PCE and water, and by varying the porous media mean grain diameter and wettability characteristics. Contaminant mass flux was found to increase as grain size decreased, suggesting enhanced lateral and vertical DNAPL spreading with higher fluid entry pressure. Mass flux showed a slight increase as the DNAPL approached neutral buoyancy, likely due to enhanced vertical spreading above the injection point. DNAPL spatial distribution and contaminant mass flux were only minimally affected by IFT and by intermediate-level wettability changes, but were dramatically affected by wettability reversal. The relationship between DNAPL loading and flux generation became more linear as grain size decreased and density contrast between fluids decreased. These results imply that capillary flow characteristics of the porous media and fluid properties will control mass flux generation from source zones.     

Field evaluation of the solvent extraction residual biotreatment technology

The Solvent Extraction Residual Biotreatment (SERB) technology was evaluated at a former dry cleaner site in Jacksonville, FL, where an area of tetrachloroethylene (PCE) contamination was identified. The SERB technology is a treatmenttrain approach for complete site restoration, which combines an active in situ dense nonaqueous-phase liquid (DNAPL) removal technology, cosolvent extraction, with a passive enhanced in situ bioremediation technology, reductive dechlorination. During the in situ cosolvent extraction test, approximately 34 kL of 95% ethanol/5% water (v:v) was flushed through the contaminated zone, which removed approximately 60% of the estimated PCE mass. Approximately 2.72 kL of ethanol was left in the subsurface, which provided electron donorfor enhancement of biological processes in the source zone and downgradient areas. Quarterly groundwater monitoring for over 3 yr showed decreasing concentrations of PCE in the source zone from initial values of 4-350 microM to less than 150 microM during the last sampling event. Initially there was little to no daughter product formation in the source zone, but after 3 yr, measured concentrations were 242 microM for cis-dichloroethylene (cis-DCE), 13 microM for vinyl chloride, and 0.43 microM for ethene. In conjunction with the production of dissolved methane and hydrogen and the removal of sulfate, these measurements indicate that in situ biotransformations were enhanced in areas exposed to the residual ethanol. First-order rate constants calculated from concentration data for individual wells ranged from -0.63 to -2.14 yr(-1) for PCE removal and from 0.88 to 2.39 yr(-1) for cis-DCE formation. First-order rate constants based on the change in total mass estimated from contour plots of the groundwater concentration data were 0.75 yr(-1) for cis-DCE, -0.50 yr(-1) for PCE, and -0.33 yr(-1) for ethanol. Although these attenuation rate constants include additional processes, such as sorption, dispersion, and advection, they provide an indication of the overall system dynamics. Evaluation of the groundwater data from the former dry cleaner site showed that cosolvent flushing systems can be designed and utilized to aid in the enhancement of biodegradation processes at DNAPL sites.     

Reactive tracer tests to predict dense nonaqueous phase liquid dissolution dynamics in laboratory flow chambers

Reactive tracer tests were conducted to evaluate the relationship between contaminant mass reduction, Rm, and flux reduction, Rj, in laboratory experiments with porous media contaminated with a dense nonaqueous phase liquid (DNAPL). The reduction in groundwater contaminant flux resulting from partial mass removal was obtained from continuous and pulsed cosolvent and surfactant flushing dissolution tests in laboratory flow chambers packed with heterogeneous porous media. Using the streamtubes concept a Lagrangian analytical solution was applied to study the contaminant dissolution. The analytical solution was independently parametrized using nonreactive and reactive tracertests and the predicted dissolution was compared to the observed data. Analytical solution parameters related to aquifer hydrodynamic heterogeneities were determined from a nonreactive tracer, while those related to DNAPL spatial distribution heterogeneity were obtained from a reactive tracer. Reactive travel time variance, derived from this combination of tracers, was used to predict the relationship between Rm and Rj. Predictions based on the tracer tests closely matched measured dissolution data, suggesting that tracers can be used to characterize the DNAPL spatial distribution heterogeneity controlling the dissolution behavior. Experimental results demonstrated that increased reactive travel time variance led to greater flux reduction for a given partial mass removal.     

Experimental and numerical validation of the total trapping number for prediction of DNAPL mobilization

The total trapping number (N(T)), quantifying the balance of gravitational, viscous, and capillaryforces acting on an entrapped dense nonaqueous phase liquid (DNAPL) droplet was originally developed as a criterion to predict the onset and extent of residual DNAPL mobilization in porous media. The ability of this approach to predict mobilization behavior, however, has not been rigorously validated in multidimensional systems. In this work, experimental observations of residual tetrachloroethene (PCE) mobilization in rectangular columns are compared to predictions obtained using a multiphase compositional finite-element simulator that was modified to incorporate the dependence of entrapped residual,flow, and transport parameters on the total trapping number. Consistent with calculated NT values (1.21 x 10(-3)-1.10 x 10(-2)), residual PCE-DNAPL was mobilized immediately upon contact with a low-interfacial tension (IFT) surfactant solution and rapidly migrated downward to form a bank of mobile DNAPL. The numerical model accurately captured the onset and extent of PCE-DNAPL mobilization, the angle and migration of the DNAPL bank, the swept path of the surfactant solution, and cumulative PCE recovery. These findings demonstrate the utility of the total trapping number for prediction of DNAPL mobilization behavior during low-IFT flushing.     

Changes in interfacial tension of chlorinated solvents following flow through U.K. soils and shallow aquifer material

The interfacial tension (IFT) that arises at the interface between water and an immiscible organic liquid is a key parameter affecting the transport and subsequent fate of the organic liquid in water-saturated porous media. In this paper, data are presented that show how contact between a range of soil types and chlorinated hydrocarbon solvent (CHS) dense nonaqueous phase liquids (DNAPLs) can affect DNAPL/water IFT values. The soils examined are indicative of U.K. soil types and shallow aquifer materials. The solvents investigated were tetrachloroethylene (PCE) and trichloroethylene (TCE). Lab grade, recovered field DNAPL and industrial waste chlorinated solvent mixtures were used. The data from batch and column experiments invariably revealed that water/DNAPL IFT values change following contact with unsaturated soils. In the majority of cases, the IFT values increase following soil exposure. However, after contact with an organic-rich soil, the IFT of the lab grade solvents decreased. The experimental evidence suggests that these reductions are linked to the removal of organic material from the soil and its subsequent incorporation into the solvent IFT increases in the case of lab solvents are shown to be linked to the removal of stabilizers (added by the manufacturers to obviate degradation) that are removed by adsorption to soil mineral surfaces. Similarly, it is conjectured that adsorption of surface-active compounds from the industrial waste samples to soil surfaces is responsible for increases in the IFT in these samples. Finally, it was observed that invading CHSs are capable of dissolving and subsequently mobilizing in-situ soil contaminants. GC/MS analysis revealed these mobilized soil contaminants to be polyaromatic hydrocarbons and phthalate esters.     

Reductions in contaminant mass discharge following partial mass removal from DNAPL source zones

Although in situ remediation technologies have been used to aggressively treat dense nonaqueous phase liquid (DNAPL) source zones, complete contaminant removal or destruction is rarely achieved. To evaluate the effects of partial source zone mass removal on dissolved-phase contaminant flux, four experiments were conducted in a two-dimensional aquifer cell that contained a tetrachloroethene (PCE) source zone and down-gradient plume region. Initial source zone PCE saturation distributions, quantified using a light transmission system, were expressed in terms of a ganglia-to-pool ratio (GTP), which ranged from 0.16 (13.8% ganglia) to 1.6 (61.5% ganglia). The cells were flushed sequentially with a 4% (wt.) Tween 80 surfactant solution to achieve incremental PCE mass removal, followed by water flooding until steady-state mass discharge and plume concentrations were established. In all cases, the GTP ratio decreased with increasing mass removal, consistent with the observed preferential dissolution of PCE ganglia and persistence of high-saturation pools. In the ganglia-dominated system (GTP = 1.6), greater than 70% mass removal was required before measurable reductions in plume concentrations and mass discharge were observed. For pool-dominated source zones (GTP < 0.3), substantial reductions (>50%) in mass discharge were realized after only 50% mass removal.     

Surfactant-enhanced air sparging in saturated sand

Air sparging as a subsurface remedial technique can be enhanced bythe addition of a surfactant. The effect of reduced surface tension of water on the extent of air intrusion and air saturation during air sparging in porous media was investigated. A sand column and a two-dimensional sand box were used for the experiments. The surface tension was controlled using an anionic surfactant, sodium dodecyl benzene sulfonate, and the concentration used was below the critical micelle concentration. Using the sand column, the air saturation was measured at different surface tensions and at different airflow rates. Initially water-saturated, the air saturation achieved in the column by air sparging at a surface tension of 3.42 x 10(-2) N/m was up to 5 times larger than that of water with no surfactant. Atthe same time, the rate at which the air saturation increased as a function of airflow rate was greater at reduced surface tensions. For box experiments with homogeneous sand, reduction of the surface tension caused a dramatic increase in the sparging area up to 5.2 times of that generated using water with no surfactant. A sand box experiment containing a vertical channel produced preferential flow of the air phase injected at the bottom of the channel when the surfactant was not applied. However, reducing the surface tension was found to promote airflow through the preferential channel and the finer sand surrounding the channel. These observations support the use of low concentration surfactants to improve air sparging swept zones.     

Biological enhancement of tetrachloroethene dissolution and associated microbial community changes

A bench-scale study was performed to evaluate the enhancement of tetrachloroethene (PCE) dissolution from a dense nonaqueous phase liquid (DNAPL) source zone due to reductive dechlorination. The study was conducted in a pair of two-dimensional bench-scale aquifer systems using soil and groundwater from Dover Air Force Base, DE. After establishment of PCE source zones in each aquifer system, one was biostimulated (addition of electron donor) while the other was biostimulated and then bioaugmented with the KB1 dechlorinating culture. Biostimulation resulted in the growth of iron-reducing bacteria (Geobacter) in both systems as a result of the high iron content of the Dover soil. After prolonged electron donor addition methanogenesis dominated, but no dechlorination was observed. Following bioaugmentation of one system, dechlorination to ethene was achieved, coincident with growth of introduced Dehalococcoides and other microbes in the vicinity and downgradient of the PCE DNAPL (detected using DGGE and qPCR). Dechlorination was not detected in the nonbioaugmented system over the course of the study, indicating that the native microbial community, although containing a member of the Dehalococcoides group, was not able to dechlorinate PCE. Over 890 days, 65% of the initial emplaced PCE was removed in the bioaugmented, dechlorinating system, in comparison to 39% removal by dissolution from the nondechlorinating system. The maximum total ethenes concentration (3 mM) in the bioaugmented system occurred approximately 100 days after bioaugmentation, indicating that there was at least a 3-fold enhancement of PCE dissolution atthis time. Removal rates decreased substantially beyond this time, particularly during the last 200 days of the study, when the maximum concentrations of total ethenes were only about 0.5 mM. However, PCE removal rates in the dechlorinating system remained more than twice the removal rates of the nondechlorinating system. The reductions in removal rates over time are attributed to both a shrinking DNAPL source area, and reduced flow through the DNAPL source area due to bioclogging and pore blockage from methane gas generation.     

Dehalorespiration model that incorporates the self-inhibition and biomass inactivation effects of high tetrachloroethene concentrations

In the vicinity of dense nonaqueous phase liquid (DNAPL) contaminant source zones, aqueous concentrations of tetrachloroethene (PCE) in groundwater may approach saturation levels. In this study, the ability of two PCE-respiring strains (Desulfuromonas michiganensis and Desulfitobacterium strain PCE1) to dechlorinate high concentrations of PCE was experimentally evaluated and depended on the initial biomass concentration. This suggests high PCE concentrations permanently inactivated a fraction of biomass, which, if sufficiently large, prevented dechlorination from proceeding. The toxic effects of PCE were incorporated into a model of dehalorespirer growth by adapting the transformation capacity concept previously applied to describe biomass inactivation by products of cometabolic TCE oxidation. The inactivation growth model was coupled to the Andrews substrate utilization model, which accounts for the self-inhibitory effects of PCE on dechlorination rates, and fit to the experimental data. The importance of incorporating biomass inactivation and self-inhibition effects when modeling reductive dechlorination of high PCE concentrations was demonstrated by comparing the goodness-of-fit of the Andrews biomass inactivation and three alternate models that do capture these factors. The new dehalorespiration model should improve our ability to predict contaminant removal in DNAPL source zones and determine the inoculum size needed to successfully implement bioaugmentation of DNAPL source zones.     

Investigation of the wetting behavior of coal tar in three phase systems and its modification by poloxamine block copolymeric surfactants

The removal of dense nonaqueous phase liquid mixtures (DNAPLs) from rocks and subsurface soils is an ongoing remedial challenge. Very often the wetting preferences of the system are not altered by exposure to the DNAPL. However, there are systems where the wetting properties of the solid phase have been altered from strongly water wetting by exposure to the DNAPL. In these cases some technique is necessary for reducing the work of adhesion between the DNAPL and the mineral surface. The focus of this report is the problems posed by coal tar in unconsolidated sands. It is shown that coal tar can alter the wetting properties of quartz, the principal component of sands, and is thus capable of adhering to the surface. In this investigation the ability of several members of the poloxamine family of polymeric surfactants to aid in the removal of coal tar from sand was evaluated. The poloxamines are tetrafunctional block copolymeric surfactants, which contain four poly(ethylene oxide)-block-poly(propylene oxide) chains joined to a central ethylenediamine moiety via the nitrogen atoms. Contact angle measurements of coal tar on a quartz surface immersed in aqueous surfactant solution and the interfacial tension between coal tar and aqueous surfactant solution have been measured. Coal tar/water interfacial tensions are reduced to values in the region of 2 mN m(-1) at surfactant concentrations of approximately 0.1 w/v %. Poloxamine surfactant impact on the static contact angle is more complex. In some cases the polymeric surfactants alter the wetting behavior from strongly water wetting to weakly water wetting. However, other poloxamines appear to have little if any impact on the contact angle, which remains strongly water wetting. The foregoing measurements have then been used to calculate the work of adhesion of the coal tar to quartz and the results qualitatively compared with the concentration of surfactant solution required to visually demonstrate the complete de-adhesion of coal tar to the quartz. It is shown that at surfactant concentrations below the critical micelle concentration (cmc) of the surfactant, the work of adhesion can be reduced sufficiently to ensure complete removal of coal tar from both quartz and sand.     

A laboratory study of surfactant flushing of DNAPL in the presence of macroemulsion

Computed tomography (CT) monitored experiments are conducted in a three-dimensional water-saturated sandpack to evaluate the performance of a biodegradable surfactant (Glucopon-425N) in recovering a residually trapped dense nonaqueous phase liquid (DNAPL) tetrachloroethylene (PCE) from two sandpacks. Effects of flow rate, surfactant concentration, and pore size on the remediation process are evaluated. Axial variation in porosity of a sandpack has significant effect on the residual distribution of DNAPL in the sandpack and its subsequent recovery. DNAPL is recovered in two stages in general: mobilization followed by macroemulsion-solubilization. Mobilized DNAPL is recovered as a free-phase for all the experiments in the 30-mesh sandpack and only limited mobilization was observed in the 50-mesh sandpack. The dominant mechanism of recovery is macroemulsion flow (accounts for 46-86% of solubilized-emulsified PCE) in both the sands which leads to much higher PCE effluent concentration than the solubility limit as determined in batch solubilization studies. The effluent PCE concentration in the later stage depends on surfactant concentration but not on surfactant flow rate or pore size.     

Transport and deposition of polymer-modified Fe0 nanoparticles in 2-D heterogeneous porous media: effects of particle concentration, Fe0 content, and coatings

Concentrated suspensions of polymer-modified Fe(0) nanoparticles (NZVI) are injected into heterogeneous porous media for groundwater remediation. This study evaluated the effect of porous media heterogeneity and the dispersion properties including particle concentration, Fe(0) content, and adsorbed polymer mass and layer thickness which are expected to affect the delivery and emplacement of NZVI in heterogeneous porous media in a two-dimensional (2-D) cell. Heterogeneity in hydraulic conductivity had a significant impact on the deposition of NZVI. Polymer modified NZVI followed preferential flow paths and deposited in the regions where fluid shear is insufficient to prevent NZVI agglomeration and deposition. NZVI transported in heterogeneous porous media better at low particle concentration (0.3 g/L) than at high particle concentrations (3 and 6 g/L) due to greater particle agglomeration at high concentration. High Fe(0) content decreased transport during injection due to agglomeration promoted by magnetic attraction. NZVI with a flat adsorbed polymeric layer (thickness ～30 nm) could not be transported effectively due to pore clogging and deposition near the inlet, while NZVI with a more extended adsorbed layer thickness (i.e., ～70 nm) were mobile in porous media. This study indicates the importance of characterizing porous media heterogeneity and NZVI dispersion properties as part of the design of a robust delivery strategy for NZVI in the subsurface.     

Solubility and sorption by soils of 8:2 fluorotelomer alcohol in water and cosolvent systems

The solubility and sorption by five soils of 8:2 fluorotelomer alcohol (FTOH) were measured from water and cosolvent/ water solutions. Aqueous solubility and soil-water distribution coefficients (Kd,w, L kg(-1)) were extrapolated from cosolvent data using a log-linear cosolvency model and compared to direct aqueous measurements. Liquid chromatography tandem mass spectrometry with electrospray ionization was employed to analyze the 8:2 FTOH in solutions and soil extracts. The cosolvent-extrapolated water solubility is 0.224 mg L(-1), in good agreement with the measured value of 0.194 mg L(-1). All sorption isotherms were generally linear regardless of cosolvent composition or soil organic carbon (OC) content. Kd,w values extrapolated from cosolvent data were similar but consistently higher than those measured in aqueous solutions. The latter was hypothesized to be due to dissolved OC (DOC) in the aqueous slurries. An average log KDOC of 5.30 was estimated and supported by DOC and Kd,w measurements at two soil-water ratios. Sorption appeared to be driven by hydrophobic partitioning with a log KOC value of 4.13 +/- 0.16. Irreversible sorption was also observed and appeared to be related to OC content, with the extraction efficiency reduced from 85% to 45% with increasing contact time from 3 to 72 h for the highest OC soil.     

Dissolution-induced contact angle modification in dense nonaqueous phase liquid/water systems

The contact angle between DNAPL, water, and aquifer material interfaces influences the spatial distribution of DNAPLs as they infiltrate into the aquifer, and may ultimately influence their remediation. The objective of this work was to evaluate the effects of dissolution on contact angle. Just as physically retracting a sessile drop reduces its contact angle with a surface, it was speculated that dissolution could cause contact angles to be reduced. Long-term dissolution experiments were conducted over the course of days to weeks, examining the dissolution of sessile drops of two DNAPLs, trichloroethylene (TCE) and tetrachloroethylene (PCE), in water and low concentration surfactant solutions, on glass surfaces. Experiments found that dissolution led to a continuous decrease of contact angle measured through the DNAPL drop, in most cases to near 0 degrees, far lower than angles achievable through measurements of receding contact angles for the same systems. Pinning of drop contact diameter was observed in most experiments. A model developed on the basis of the Bashforth-Adams equation to predict the effect of dissolution on contact angle for drops with a pinned contact diameter showed very good agreement with experimental observations.     

Physicochemical basis for cosolvent modulation of β-lactoglobulin functionality: Interfacial tension study

The impact of neutral cosolvents on the thermal stability of globular proteins in aqueous solutions depends on the nature of the cosolvent, e.g., sorbitol causes a pronounced increase in the thermal denaturation temperature (T_m) of β-lactoglobulin (β-lg), whereas glycerol does not. When a protein unfolds there is a change in the exposed surface area and in the type of molecular interactions that occur at the protein–solvent–cosolvent interface. These changes contribute to the free energy change associated with protein denaturation and depend on cosolvent type. In this study we measured the equilibrium interfacial tensions of aqueous glycerol (0–70% w/w) and sorbitol (0–55% w/w) solutions as a function of temperature to provide insights into the role of the interfacial energy on the thermal stability of β-lg. There was a slight increase in interfacial tension with increasing sorbitol concentration, indicating its preferential exclusion from the oil–water interface. On the other hand, there was an appreciable decrease in interfacial tension with increasing glycerol concentration, indicating its preferential accumulation at the oil–water interface. These changes were largely independent of the measurement temperature (30–80 °C). Our results suggest that sorbitol increases the T_m of β-lg mainly through a steric exclusion effect, whereas glycerol has little effect on T_m because the steric exclusion effect is counter-balanced by a differential interaction effect.     

Comparison between donor substrates for biologically enhanced tetrachloroethene DNAPL dissolution

Tetrachloroethene (PCE) dense nonaqueous-phase liquid (DNAPL) can act as a persistent groundwater contamination source for decades. Biologically enhanced dissolution of pure PCE DNAPL has potential for reducing DNAPL longevity as indicated previously (Environ. Sci. Technol. 2000, 34, 2979). Reported here are expanded studies to evaluate donor substrates that offer different remediation strategies for bioenhanced DNAPL dissolution, including pentanol (soluble substrate, fed continuously), calcium oleate (insoluble substrate, placed in column initially by alternate pumping of sodium oleate and calcium chloride), and olive oil (mixed with PCE and placed in column initially). Compared with a no-substrate column control, the DNAPL dissolution rate was enhanced about three times when directly coupled with biological transformation. The major degradation product formed was cDCE, but significant amounts of VC and ethene were also found with some columns. Extensive methanogenesis, which reduced PCE transformation, occurred in both the pentanol-fed and oleate-amended columns, but not in the olive-oil-amended column, suggesting that methanogens managed to colonize column niches where PCE DNAPL was not present. Detrimental methane production in the pentanol-fed column was nearly eliminated by presaturating the feed solution with PCE. These results suggest potential DNAPL remediation strategies to enhance dehalogenation while controlling competitive methanogenic utilization of donor substrates.     

Applicability of colloid filtration theory in size-distributed, reduced porosity, granular media in the absence of energy barriers

The vast majority of colloid transport experiments use granular porous media with narrow size distribution to facilitate comparison with colloid filtration theory, which represents porous media with a single collector size. In this work we examine retention of colloids ranging in size from 0.21 to 9.1 μm in diameter, in columns packed with uniform and size-distributed borosilicate glass bead porous media with porosity ranging from 0.38 to 0.28. Conditions were favorable to attachment (absent a significant energy barrier). The goal was to determine the applicability of colloid filtration theory to colloid retention in these media. We also directly observed deposition at the pore scale in packed flow cells. The pore domain was characterized via high resolution computerized X-ray micro tomography (HRXMT). The flow field was examined using Lattice-Boltzmann flow simulation methods (LBM). The influence of preferential flow paths on colloid retention in the lowest porosity media was accounted for by correcting the fluid velocity. Straining in pore throats too small to pass was not a significant contributor to colloid retention despite colloid-to-collector size ratios up to 0.05. Mechanistic simulations via the Ma-Pedel-Fife-Johnson correlation equation (MPFJ) for colloid filtration predicted the experimentally observed trends in deposition with porosity when a number-based mean grain size was used.     

Biologically enhanced mass transfer of tetrachloroethene from DNAPL in source zones: experimental evaluation and influence of pool morphology

High-saturation pools of dense nonaqueous phase liquid (DNAPL) are long-term sources of groundwater contamination at many hazardous-waste sites. DNAPL pools consist of a high saturation zone with slow dissolution overlaid by a transition zone with lower saturations and more rapid dissolution. Effects of biological activity on pool dissolution must be understood to evaluate and implement bioremediation strategies. Bioenhanced dissolution of tetrachloroethene (PCE) in transition zones of high-saturation pools was investigated in a custom-designed 5-cm flow cell. Experiments were conducted to characterize mass transfer following DNAPL emplacement, with and without an active microbial culture capable of reductive dehalogenation. For average pool saturations < or = 0.55, mass transfer during biodegradation was enhanced by factors of 4-13, due primarily to high mass flux of PCE degradation products. However, at an average pool saturation of 0.74, mass transfer was enhanced by factors less than 1.5. Mass transfer was significantly greater from pools with an observable transition zone than without. Advective flow through multiphase transition zones enhanced dissolution and biological activity. These laboratory-scale experimental results suggest that biotechnologies may be effective remediation strategies for depletion of source zones within pool transition zones.     

Residual alcohol influence on NAPL saturation estimates based on partitioning tracers

The influence of residual cosolvent on the partitioning tracer technique for estimating a nonaqueous phase liquid (NAPL) saturation in porous media was investigated. Batch equilibrium and column miscible displacement tests were used to evaluate the influence of residual alcohol cosolvents in the aqueous phase on partitioning and transport of alcohol tracers through sandy soil columns containing tetrachloroethylene (PCE). As the volume fraction of cosolvent alcohol (f(c)) increased ( f(c) < or = 0.1; 10 vol %), partition coefficients (K(nc)) for the alcohol tracers linearly decreased for residual cosolvent ethanol, linearly increased for residual cosolvent tert-butyl alcohol, and did not exhibit an evident change for residual cosolvent 2-propanol. These observations are consistent with measured changes in solubility (S(c)) of the alcohol tracers over the same range (f(c) < or = 0.1) of these residual cosolvent alcohols. Column miscible displacement tests using ethanol as a residual cosolvent ( f(c) < or = 0.1) exhibited earlier partitioning tracer breakthrough leading to an underestimation of NAPL saturation (S(n)) when constant, cosolvent-free partitioning coefficients were assumed. The underestimation magnitude increased with higher initial residual cosolvent alcohol in the columns. The S(n) underestimates were not significant but were 1-10% lower than the actual S(n) (0.18). The estimated partition coefficients based on column tests with residual cosolvent (K(col)) were consistently less than those based on batch tests. Column tests with low (0.5%) and high (15%) S(n) revealed that the residual cosolvent alcohol effect was different depending on the amount of NAPL in the column. Using ethanol for a cosolvent (10%) and 2,4-dimethyl-3-pentanol as a partitioning tracer, the S(n) values were underestimated by about 17% and 5%, respectively, in the low and high NAPL saturation columns.     

Pilot-scale demonstration of surfactant-enhanced PCE solubilization at the Bachman Road site. 1. Site characterization and test design

A pilot-scale demonstration of surfactant-enhanced aquifer remediation (SEAR) was conducted to recover dense nonaqueous phase liquid (DNAPL) tetrachloroethene (PCE) from a sandy glacial outwash aquifer underlying a former dry cleaning facility at the Bachman Road site in Oscoda, MI. Part one of this two-part paper describes site characterization efforts and a comprehensive approach to SEAR test design, effectively integrating laboratory and modeling studies. Aquifer coring and drive point sampling suggested the presence of PCE-DNAPL in a zone beneath an occupied building. A narrow PCE plume emanating from the vicinity of this building discharges into Lake Huron. The shallow unconfined aquifer, characterized by relatively homogeneous fine-medium sand deposits, an underlying clay layer, and the absence of significant PCE transformation products, was judged suitable for the demonstration of SEAR. Tween 80 was selected for application based upon its favorable solubilization performance in batch and two-dimensional sand tank treatability studies, biodegradation potential, and regulatory acceptance. Three-dimensional flow and transport models were employed to develop a robust design for surfactant delivery and recovery. Physical and fiscal constraints led to an unusual hydraulic design, in which surfactant was flushed across the regional groundwater gradient, facilitating the delivery of concentrations of Tween 80 exceeding 1% (wt) throughout the treatment zone. The potential influence of small-scale heterogeneity on PCE-DNAPL distribution and SEAR performance was assessed through numerical simulations incorporating geostatistical permeability fields based upon available core data. For the examined conditions simulated PCE recoveries ranged from 94to 99%. The effluent treatment system design consisted of low-profile air strippers coupled with carbon adsorption to trap off-gas PCE and discharge of treated aqueous effluent to a local wastewater treatment plant. The systematic and comprehensive design methodology described herein may serve as a template for application at other DNAPL sites.