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.

Pilot-scale demonstration of surfactant-enhanced PCE solubilization at the Bachman Road site. 2. System operation and evaluation.

A pilot-scale demonstration of surfactant-enhanced aquifer remediation (SEAR) was conducted during the summer of 2000 at the Bachman Road site in Oscoda, MI. Part two of this two-part paper describes results from partitioning and nonpartitioning tracer tests, SEAR operations, and post-treatment monitoring. For this field test, 68 400 L of an aqueous solution of 6% (wt) Tween 80 were injected to recover tetrachloroethene-nonaqueous phase liquid (PCE-DNAPL) from a shallow, unconfined aquifer. Results of a nonreactive tracer test, conducted prior to introducing the surfactant solution, demonstrate target zone sweep and hydraulic control, confirming design-phase model predictions. Partitioning tracer test results suggest PCE-DNAPL saturations of up to 0.74% within the pilot-scale treatment zone, consistent with soil core data collected during site characterization. Analyses of effluent samples taken from the extraction well during SEAR operations indicate that a total of 19 L of PCE and 95% of the injected surfactant were recovered. Post-treatment monitoring indicated that PCE concentrations at many locations within the treated zone were reduced by as much as 2 orders of magnitude from pre-SEAR levels and had not rebounded 450 days after SEAR operations ceased. Pilot-scale costs ($365 900) compare favorably with design-phase cost estimates, with approximately 10% of total costs attributable to the intense sampling density and frequency. Results of this pilot-scale test indicate that careful design and implementation of SEAR can result in effective DNAPL mass removal and a substantial reduction in aqueous concentrations within the treated source zone under favorable geologic conditions

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.

Entrapment and dissolution of DNAPLs in heterogeneous porous media.

Two-dimensional multiphase flow and transport simulators were refined and used to numerically investigate the entrapment and dissolution behavior of tetrachloroethylene (PCE) in heterogeneous porous media containing spatial variations in wettability. Measured hydraulic properties, residual saturations, and dissolution parameters were employed in these simulations. Entrapment was quantified using experimentally verified hydraulic property and residual saturation models that account for hysteresis and wettability variations. The nonequilibrium dissolution of PCE was modeled using independent estimates of the film mass transfer coefficient and interfacial area for entrapped and continuous (PCE pools or films) saturations. Flow simulations demonstrate that the spatial distribution of PCE is highly dependent on subsurface wettability characteristics that create differences in PCE retention mechanisms and the presence of subsurface capillary barriers. For a given soil texture, the maximum and minimum PCE infiltration depth was obtained when the sand had intermediate (an organic-wet mass fraction of 25%) and strong (water- or organic-wet) wettability conditions, respectively. In heterogeneous systems, subsurface wettability variations were also found to enhance or diminish the performance of soil texture-induced capillary barriers. The dissolution behavior of PCE was found to depend on the soil wettability and the spatial PCE distribution. Shorter dissolution times tended to occur when PCE was distributed over large regions due to an increased access of flowing water to the PCE. In heterogeneous systems, capillary barriers that produced high PCE saturations tended to exhibit longer dissolution times.

Influence of surfactant-facilitated interfacial tension reduction on chlorinated solvent migration in porous media: observations and numerical simulation.

The ability of a multiphase flow model to capture the migration behavior of chlorinated solvents under conditions of surfactant-facilitated interfacial tension (IFT) reduction is assessed through comparison of model predictions with observations from controlled laboratory experiments. Tetrachloroethene (PCE) was released in two-dimensional saturated systems, packed with sandy media that incorporated rectangular lenses of capillary contrast. Spatially uniform interfacial tension conditions were created in the tanks by pre-flushing the porous medium with either Milli Q water or an aqueous surfactant solution. Experimental observations showed that surfactant-facilitated IFT reductions substantially lowered capillary resistance to the vertical downward migration of PCE and enabled PCE to enter finer grained, less permeable lenses that were not penetrated in the absence of surfactant. An immiscible flow model was used to simulate the conditions of the laboratory experiments. Under higher IFT conditions (47.5 and 5 dyn/cm), the model could successfully predict the general migration behavior of the organic liquid. Model predictions, however, exhibited poorer agreement with observed migration pathways under low IFT conditions (0.5 dyn/cm). In all cases, the predicted PCE distributions were influenced by selection of the parametric model for capillary retention and relative permeability. Simulated migration rates were more consistent with observed behavior when the Brooks-Corey/Burdine model was employed. For low interfacial tensions, improved predictions of migration pathways were obtained through grid refinement and incorporation of small-scale packing variability. Simulations highlight the substantial sensitivity of model predictions to the capillary pressure-scaling factor, grid resolution, and small-scale porosity variations at interfaces of permeability contrast under reduced IFT conditions.