PCE Saturation Research Articles

Influence of distribution characteristics of residual DNAPL on mass transfer in porous media under ethanol co-solvent flushing

The remediation of residual dense non-aqueous phase liquid (DNAPL) enhanced by co-solvents or surfactants has been investigated in many studies. Nevertheless, the influences of the residual DNAPL distribution characteristics in a porous medium, and the concentrations of the co-solvents or surfactants on the mass transfer rate of DNAPL remain relatively unexplored. For this reason, existing empirical models neglect the effects of the heterogeneity in the distribution of residual DNAPL, and the compositions of flushing floods on the DNAPL mass transfer rate. In this work, a two-dimensional micro-model is used to quantify the lumped mass transfer rate coefficients of PCE. Results show that increasing the injection rate and the ethanol concentration of flushing floods improves the mass transfer rate of PCE. Moreover, this micro-model allows for accurate quantification of variations in morphological characteristics of PCE blobs. The relative standard deviation σ of residual PCE saturation, as an indicator of morphological characteristics of PCE blobs, varies with decreasing saturation. Standard saturation S0 is used to represent the heterogeneity of residual PCE distribution. The more heterogeneous the PCE distribution, the larger the S0, and the slower the mass transfer rate. According to the variation of relative standard deviation σ with saturation, the PCE dissolution process can be divided into three stages, where the strong convection, weak convection, and diffusion within a limited distance are the primary controlling mechanisms for PCE mass transfer, respectively. Based on our study, a new empirical model, considering the distribution characteristics of residual PCE and the ethanol concentrations, is proposed to predict the PCE mass transfer process dominated by different mass transfer mechanisms in different dissolution stages.

A numerical model to simulate the NAPL source zone remediation by injecting zero-valent iron nanoparticles

A continuum-scale numerical model is developed to simulate the flow, mass-transfer, and reactive processes taking place during the injection of zero-valent iron nanoparticles (nZVI) in a water-saturated porous medium, containing a chlorinated non-aqueous phase liquid (NAPL) at its residual saturation (source zone). Firstly, the transport of the nanoparticles (NP) is modelled by coupling the nanoparticles transport with their deposition in a porous medium. A systematic sensitivity analysis is done to examine the individual effect of each parameter on the spatial and temporal evolution of nanoparticle concentration along the column length. The parameters quantifying the kinetics of attachment/detachment between the nanoparticles and the porous medium (sand grains) are estimated via inverse modeling. Secondly, the kinetics of the reaction of nZVI with dissolved tetrachloroethylene (PCE) is based on the numerical predictions of the statistical shrinking-core model that couples the mass-transfer with the reactive processes taking place at a nanoparticle scale. The continuum NP transport model is then extended to include the reactive flows by combining the dynamics of PCE ganglia dissolution and nZVI reactions with mass balances for the residual PCE saturation, the dissolved PCE concentration, and the nZVI concentration in the aqueous phase. Sensitivity analyses are performed on the NP transport-NAPL remediation model with a view to clarify the effects of dimensionless parameters (dimensionless flow velocity, Damköhler numbers) on the fate of nZVI and trapped PCE ganglia. Finally, the residual PCE remediation efficiency is numerically predicted as a function of the injected NP mass. This efficiency is compared with the respective experimental results of a PCE source zone remediation test performed in a sand column, by using as adjustable parameters the kinetic coefficients of the nanoparticles deposition on sand grains. The remediation efficiency of the PCE source zone is maximized when the injected nZVI maintains its reactivity throughout its flow in the porous medium. To design an efficient NAPL source zone remediation strategy, the parameters must be set to values which will ensure that the nZVI is kept to a higher than zero concentration throughout the length of the porous medium.

Removal of tetrachloroethylene from homogeneous and heterogeneous porous media: Combined effects of surfactant solubilization and oxidant degradation

High efficiency and cost-effective remediation technologies are needed to remove tetrachloroethylene (PCE) from the source zones in soil and groundwater systems. This work evaluated the ability of a biodegradable surfactant (Tween 80) coupled with an effective oxidant (Fe2+ (activation agent)–citrate (chelating agent) activated persulfate (PS, oxidant)) to remove PCE from porous media. Batch experiments were used to optimize the oxidant by testing the effects of PS, citrate, and Fe2+ concentrations on the PCE degradation. The optimal molar ratio of PS/citrate/Fe2+/PCE was 15:15:5:1 for PCE degradation in presence of the surfactant. Four sandbox experiments were performed to compare the effectiveness of the surfactant and the combination of the surfactant with the optimized oxidant in the removal of PCE from homogeneous and heterogeneous porous media. PCE saturation distributions in the sandboxes were quantified using a light transmission system. In addition, the PCE, PS, and Cl− concentrations in the effluents were also monitored during the experiments. While the Tween 80 solution removed about 52% and 67% of PCE from the homogeneous and heterogeneous porous media; the combination solution was more effective with removal rates of 80% and 84%, respectively. The enhanced PCE removal was due to the combined effects of the surfactant solubilization and PS oxidation: (1) Tween 80-enhanced solubilization resulted in an enlarged effective contact and reaction between PCE and PS; and (2) PS degraded the PCE from the soluble phase and thus facilitated its dissolution from the source zone, resulting in more efficient use of Tween 80. Findings from this work indicate that the combination of surfactant and oxidant can provide an effective way for the remediation of PCE in soils and groundwater.

Use of geostatistical models in DNAPL source zone architecture and dissolution profiles assessment in spatially variable aquifer

Following the accidental subsurface release of dense nonaqueous phase liquids (DNAPLs), spatial variability of physical and chemical soil/contaminant properties can exert a controlling influence on infiltration pathways and organic entrapment. DNAPL spreading, fingering, and pooling typically result in source zones characterized by irregular contaminated regions with complex boundaries. Spatial variability in aquifer properties also influences subsequent DNAPL dissolution and aqueous transport dynamics. An increasing number of studies have investigated the effects of subsurface heterogeneity on the fate of DNAPL; however, previous work was limited to the examination of the behavior of single-component DNAPL in systems with simple and well-defined aqueous and solid surface chemistry. From a DNAPL remediation point of view, such an idealized assumption will bring a large discrepancy between the designs based on the model simulation and the reality. The research undertaken in this study seeks to stochastically explore the influence of spatially variable porous media on DNAPL entrapment and dissolution profiles in the saturated groundwater aquifer. A 3D, multicomponent, multiphase, compositional model, UTCHEM, was used to simulate natural gradient water flooding processes in spatially variable soils. Porosity was assumed to be uniform or simulated using sequential Gaussian simulation (SGS) and sequential indicator simulation (SIS). Soil permeability was treated as a spatially random variable and modeled independently of porosity, and a geostatistical method was used to generate random distributions of soil permeability using SGS and SIS (derived from measured grain size distribution curves). Equally possible 3D ensembles of aquifer realizations with spatially variable permeability accounting of physical heterogeneity could be generated. Tetrachloroethene (PCE) was selected as a DNAPL representative as it was frequently discovered at many contaminated groundwater sites worldwide, including Thailand. The randomly generated permeability fields were incorporated into UTCHEM to simulate DNAPL source zone architecture under 96-L hypothetical PCE spill in heterogeneous media and stochastic analysis was conducted based on the simulated results. Simulations revealed considerable variations in the predicted PCE source zone architecture with a similar degree of heterogeneity, and complex initial PCE source zone distribution profoundly affected PCE recovery time in heterogeneous media when subject to natural gradient water flush. The necessary time to lower PCE concentrations below Thai groundwater quality standard ranged from 39 years to more than 55 years, suggesting that spatial variability of subsurface formation significantly affected the dissolution behavior of entrapped PCE. The temporal distributions of PCE saturation were significantly altered owing to natural gradient water flush. Therefore, soil heterogeneity is a critical factor to design strategies for characterization and remediation of DNAPL contaminated sites. The systematic and comprehensive design algorithm developed and described herein perhaps serves as a template for application at other DNAPL sites in Thailand.

COUPLING INFLUENCES OF AQUIFER SPATIAL VARIABILITY AND WASTE COMPOSITIONS ON DISTRIBUTION AND RECOVERY OF DNAPL IN STATISTICALLY HOMOGENEOUS NONUNIFORM POROUS MEDIA

PCE and TCE saturation distributions are generated with stochastic models to incorporate spatially varying aquifer properties. The influence of aquifer property correlation on fluid migration and entrapment is explored in cross-sectional 2D numerical two-phase saturated flow models extracted from 3D geostatistical realizations generated from well-published aquifer data in a nonuniform sandy aquifer. An effort to model a mixture of DNAPL is exercised by employing five compounds DNAPL; a 6:1:1:1:1 by volume ratio of PCE, toluene, 2-chlorotoluene, 1-bromohexane, and 1-bromoheptane. Comparisons of PCE, TCE, and DNAPL mixture suggest that the choices involving chemical waste compositions greatly influenced the saturation and distribution of DNAPL (i.e., pathways and organic spreading). The organic wastes released into the system can escape to the other 2D cross sections as the waste mixtures are more mobile compared to pure phase. Coupled application of stochastic model of aquifer spatial variability as well as chemical waste compositions can significantly influence predicted DNAPL infiltration depth, entrapment, and recovery. The resultant distribution profiles of DNAPL mass within the source zone also have implications for DNAPL recovery and subsequent downstream mass fluxes in remediation operations.

A modified light transmission visualization method for DNAPL saturation measurements in 2-D models

In this research, a light transmission visualization (LTV) method was used to quantify dense non-aqueous phase liquids (DNAPL) saturation in two-dimensional (2-D), two fluid phase systems. The method is an expansion of earlier LTV methods and takes into account both absorption and refraction light theories. Based on this method, DNAPL and water saturations can rapidly be obtained point wise across sand-packed 2-D flow chambers without the need to develop a calibration curve. A single point calibration step is, however, needed when dyed DNAPL is used to account for the change in the transmission factor at the dyed DNAPL–water interface. The method was applied to measure, for the first time, undyed DNAPL saturation in small 2-D chambers. Known amounts of DNAPL, modeled by tetrachloroethylene (PCE), were added to the chamber and these amounts were compared to results obtained by this LTV method. Strong correlation existed between results obtained based on this method and the known PCE amounts with an R 2 value of 0.993. Similar experiments conducted using dyed PCE showed a stronger correlation between results obtained by this LTV method and the known amounts of dyed PCE added to the chamber with an R 2 value of 0.999. The method was also used to measure dyed PCE saturation in a large 2-D model following sparging experiments. Results obtained from image analyses following each sparging event were compared to results obtained by two independent techniques, namely gas chromatography–mass spectrometry (GC/MS) analyses and carbon column extraction. There was a good agreement between the results obtained by this LTV method and those obtained by the two independent techniques when experiments were carried out under stable light source conditions and errors in mass balance were minor. The method presented here can be expanded to measure fluid contents in three fluid phase systems and provide a non-destructive, non-intrusive tool to investigate changes in DNAPL architecture and flow characteristics in laboratory experiments.

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.

Dip-angle influence on areal DNAPL recovery by co-solvent flooding with and without pre-flooding

A two-dimensional (2D) laboratory model was used to study effects of gravity on areal recovery of a representative dense non-aqueous phase liquid (DNAPL) contaminant by an alcohol pre-flood and co-solvent flood in dipping aquifers. Recent studies have demonstrated that injection of alcohol and co-solvent solutions can be used to reduce in-situ the density of DNAPL globules and displace the contaminant from the source zone. However, contact with aqueous alcohol reduces interfacial tension and causes DNAPL swelling, thus facilitating risk of uncontrolled downward DNAPL migration. The 2D laboratory model was operated with constant background gradient flow and a DNAPL spill was simulated using tetrachloroethene (PCE). The spill was dispersed to a trapped, immobile PCE saturation by a water flood. Areal PCE recovery was studied using a double-triangle well pattern to simulate a remediation scheme consisting of an alcohol pre-flood using aqueous isobutanol (∼ 10% vol.) followed by a co-solvent flood using a solution of ethylene glycol (65%) and 1-propanol (35%). Experiments were conducted with the 2D model oriented in the horizontal plane and compared to experiments at the 15° and 30° dip-angle orientations. Injection was applied either in the downward or upward direction of flow. Experimental results were compared to theoretical predictions for flood front stability and used to evaluate effects of gravity on areal PCE recovery. Sensitivity experiments were performed to evaluate effects of the alcohol pre-flood on PCE areal recovery. For experiments conducted with the alcohol pre-flood and the 2D model oriented in the horizontal plane, results indicate that 89–93% of source zone PCE was recovered. With injection oriented downward, results indicate that areal PCE recovery was 70–77% for a 15° dip angle and 57–59% for a 30° dip angle. With injection oriented upward, results indicate that areal PCE recovery was 57–60% at the 30° dip angle, which was similar to PCE recovery for injection in the downward flow direction. Lower areal PCE recovery at greater dip angles in either direction of flow was attributed to DNAPL swelling and migration, flood front instabilities and bypassing of the displaced fluid past the extraction wells during the alcohol pre-flood. Additional results demonstrate that the use of an alcohol pre-flood can be beneficial in improving DNAPL recovery in the horizontal orientation, but pre-flooding may reduce areal recovery efficiency in dip-angle orientations. This study also demonstrates the use of theoretical perturbation (fingering) analysis in predicting NAPL recovery efficiency for flooding processes in remediating aquifers with dip angles.

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.

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.

Dissolution of residual tetrachloroethylene in fractional wettability porous media: correlation development and application

This work explores the dissolution behavior of residual tetrachloroethylene (PCE) in chemically heterogeneous soils. A numerical solute transport simulator, that incorporates rate-limited dissolution and desorption using linear driving force expressions, was developed and applied to analyze soil column dissolution data and to conduct numerical dissolution experiments. Published mass transfer coefficients were unable to accurately predict the observed dissolution of entrapped PCE in fractional wettability porous media (media containing both water- and PCE-wet solid surfaces). A two-parameter power function expression for the lumped mass transfer coefficient was developed and successfully fit to these data. Correlations were then developed for the fitted mass transfer model parameters as a function of wettability and grain size distribution characteristics. The power function model, in conjunction with the parameter correlations, yielded reasonable predictions for long-term dissolution behavior in the more PCE-wetting media. Poorer predictions for the more water-wet materials were attributed to an increased sensitivity of effluent concentration behavior to temporal changes in PCE saturation in these systems. Many of the effluent concentration curves exhibited low and persistent concentration tailing after recovery of the separate phase PCE. This tailing behavior could be adequately modeled by incorporation of rate-limited desorption. Results from numerical experiments indicate that both the magnitude and spatial distribution of wettability can significantly influence PCE dissolution behavior and remediation time.

Mobilization of residual tetrachloroethylene during alcohol flushing of clay-containing porous media

Mobilization of residual DNAPL in a contaminated aquifer may be problematic for the application of enhanced dissolution remediation techniques such as alcohol or surfactant flushing. The objective of this study was to investigate the effects of clay fines on residual saturation, permeability and the onset of mobilization of PCE during alcohol flushing. Column experiments were conducted with soils containing 0%, 2%, 5%, 10%, and 20% clay that was completely mixed within a well-sorted Ottawa sand. Column characterization included pressure-saturation relationships, pore-size distribution, permeability, and residual saturation. The columns were flushed with isopropyl alcohol (IPA) in concentration increments to determine when mobilization of PCE occurred. Trapping numbers were calculated. Results showed that increasing amounts of clay resulted in decreased hydraulic conductivity, increased residual PCE saturation and a larger pore size distribution. Residual PCE was found to begin to mobilize in the clay-mixed media at a range of trapping numbers below those reported in the literature for homogeneous well-sorted sand. This suggests that the potential to mobilize the residual PCE is greater in the mixed media. This may be explained by the formation of multi-pore branched ganglia in the clay-containing media as opposed to singlet formation in a well-sorted media. The multi-pore ganglia may mobilize more readily than singlets due to the added force of head acting on the PCE interface where the trapping is occurring. Using a narrow range of trapping numbers determined in homogeneous media to predict mobilization may not be appropriate in mixed media because mobilization was noted at a variety of trapping numbers. However, relationships between the trapping number at mobilization and various soil parameters such as the amount of clay, residual DNAPL saturation, and pore size distribution, indicate that these, coupled with the trapping number, may aid in our ability to predict mobilization.

Synchrotron radiation measurement of multiphase fluid saturations in porous media: Experimental technique and error analysis

Multiphase flow in porous media is an important research topic. In situ, nondestructive experimental methods for studying multiphase flow are important for improving our understanding and the theory. Rapid changes in fluid saturation, characteristic of immiscible displacement, are difficult to measure accurately using gamma rays due to practical restrictions on source strength. Our objective is to describe a synchrotron radiation technique for rapid, nondestructive saturation measurements of multiple fluids in porous media, and to present a precision and accuracy analysis of the technique. Synchrotron radiation provides a high intensity, inherently collimated photon beam of tunable energy which can yield accurate measurements of fluid saturation in just one second. Measurements were obtained with precision of ±0.01 or better for tetrachloroethylene (PCE) in a 2.5 cm thick glass-bead porous medium using a counting time of 1 s. The normal distribution was shown to provide acceptable confidence limits for PCE saturation changes. Sources of error include heat load on the monochromator, periodic movement of the source beam, and errors in stepping-motor positioning system. Hypodermic needles pushed into the medium to inject PCE changed porosity in a region approximately ±1 mm of the injection point. Improved mass balance between the known and measured PCE injection volumes was obtained when appropriate corrections were applied to calibration values near the injection point.