Pulsed Air Sparging in Aquifers Contaminated with Dense Nonaqueous Phase Liquids

Air sparging was evaluated for remediation of tetrachloroethylene (PCE) present as dense nonaqueous phase liquid (DNAPL) in aquifers. A two-dimensional laboratory tank with a transparent front wall allowed for visual observation of DNAPL mobilization. A DNAPL zone 50 cm high was created, with a PCE pool accumulating on an aquitard. Detailed process control and analysis yielded accurate mass balances and insight into the mass-transfer limitations during air sparging. Initial PCE recovery rates were high, corresponding to fast removal of residual DNAPL within the zone influenced directly by air channels. The vadose zone DNAPL was removed within a few days, and the recovery in the extracted soil vapors decreased to low values. Increasing the sparge rate and pulsing the air injection led to improved mass recovery, as the pulsing induced water circulation and increased the DNAPL dissolution rate. Dissolved PCE concentrations both within and outside the zone of air channels were affected by the pulsing. Inside the sparge zone, aqueous concentrations decreased rapidly, matching the declining effluent PCE flux. Outside the sparge zone, PCE concentrations increased because highly contaminated water was pushed away from the air injection point. This overall circulation of water may lead to limited spreading of the contaminant, but accelerated the time-weighted average mass removal by 40% to 600%, depending on the aggressiveness of the pulsing. For field applications, pulsing with a daily or diurnal cycling time may increase the average mass removal rate, thus reducing the treatment time and saving in the order of 40% to 80% of the energy cost used to run the blowers. However, air sparging will always fail to remove DNAPL pools located below the sparge point because the air will rise upward from the top of a screen, unless very localized geological layers force the air to migrate horizontally. Unrecognized presence of DNAPL at chlorinated solvent sites residual and pools could potentially hamper success of air sparging cleanups, since the presence of small DNAPL pools, ganglia or droplets can greatly extend the treatment time.     

A Comparison of Field Techniques for Confirming Dense Nonaqueous Phase Liquids

Dense nonaqueous phase liquids (DNAPLs) are immiscible fluids with a specific gravity greater than, water. When present, DNAPLs present a serious and long-term source of continued ground water and soil contamination (Pankow and Cherry 1996). Accurate characterization and delineation of DNAPL in the subsurface is critical for evaluating restoration potential and for remedy design at a site. However, obtaining accurate and definitive direct evidence of DNAPL is difficult. A field study was recently performed comparing several approaches to DNAPL characterization at a site where anecdotal and limited direct evidence of DNAPL exists. The techniques evaluated included a three-dimensional high-resolution seismic survey, field screening of soil cores with a flame ionization detector (FID)/organic vapor analyzer (OVA), hydrophobic (Sudan IV) dye-impregnated reactive FLUTe® (Flexible Liner Underground Technologies) liner material in combination with Rotasonic drill cores, centrifuged soil with Sudan IV dye, ultraviolet light (UV) fluorescence, a Geoprobe® Membrane Interface Probe (MIP®), and phase equilibrium partitioning evaluations based on laboratory analysis of soil samples. Sonic drilling provided reliable continuous cores from which minor soil structures could be evaluated and screened with an OVA, The screening provided reliable preliminary data for identifying likely DNAPL zones and for selecting samples for further analyses. The FLUTe liner material provided the primary direct evidence of the presence of DNAPL and reliable information on the thickness and nature of its occurrence (i.e., pooled or ganglia). The MIP system provided good information regarding the subsurface lithology and rapid identification and delineation of probable DNAPL areas. The three-dimensional seismic survey was of minimal benefit to this study, and the centrifuging of samples with Sudan IV dye and the use of UV fluorescence provided no benefit. Results of phase equilibrium partitioning concentration calculations for soil samples (to infer the presence of DNAPL) were in good agreement with the site screening data. Additionally, screening data compared well with previous ground water data and supported using 1% of the pure phase solubility limit of Freon 113 (2 mg/L) as an initial means to define the DNAPL study area. Based on the results of this study, the preferred approach for identifying and delineating DNAPL in the subsurface is to initially evaluate ground water data and define an area where dissolved concentrations of the target analyte(s) approach 1% of the pure phase solubility limit. Within this study area, the MIP device is used to more specifically identify areas and lithologic zones where DNAPL may have accumulated. Core samples (either Rotasonic or Geoprobe) are then collected from zones where MIP readings are indicative of the presence of DNAPL. Soil samples from the free-product portions of the core(s) are then submitted to a laboratory for positive analyte identification. Soil analyses are then combined with site-specific geotechnical information (i.e., fraction organic carbon, soil bulk density, and porosity) and equilibrium partitioning algorithms used to estimate concentrations of organic contaminants in soil samples that would be indicative of free product. Used in combination, the soil analysis and the MIP records appear to provide accurate DNAPL identification and delineation.     

Specification of Matrix Cleanup Goals in Fractured Porous Media

Semianalytical transient solutions have been developed to evaluate what level of fractured porous media (e.g., bedrock or clay) matrix cleanup must be achieved in order to achieve compliance of fracture pore water concentrations within a specified time at specified locations of interest. The developed mathematical solutions account for forward and backward diffusion in a fractured porous medium where the initial condition comprises a spatially uniform, nonzero matrix concentration throughout the domain. Illustrative simulations incorporating the properties of mudstone fractured bedrock demonstrate that the time required to reach a desired fracture pore water concentration is a function of the distance between the point of compliance and the upgradient face of the domain where clean groundwater is inflowing. Shorter distances correspond to reduced times required to reach compliance, implying that shorter treatment zones will respond more favorably to remediation than longer treatment zones in which back‐diffusion dominates the fracture pore water response. For a specified matrix cleanup goal, compliance of fracture pore water concentrations will be reached sooner for decreased fracture spacing, increased fracture aperture, higher matrix fraction organic carbon, lower matrix porosity, shorter aqueous phase decay half‐life, and a higher hydraulic gradient. The parameters dominating the response of the system can be measured using standard field and laboratory techniques.     

Magnetic Resonance Imaging of Nonaqueous Phase Liquid Distribution in Unconsolidated Soils Using Discriminatory Freezing

Organic contaminants present as nonaqueous phase liquids (NAPLs) in the subsurface often pose a long-term risk to human health and the environment. Investigating the distribution of NAPLs in porous media remains a major challenge in risk assessment and management of contaminated sites. Conventional soil coring and monitoring wells have been widely used over past decades as the primary means of subsurface investigation to determine NAPL extent. Known limitations of conventional approaches have led us to explore an alternative or a complementary technique to provide high-quality information of NAPL source zone architecture. This work advances an imaging tool for a variety of organic NAPL contaminants in unconsolidated soils through magnetic resonance imaging (MRI) of frozen cores. Using trichloroethylene (TCE) and o-xylene as model species, we illustrate that discriminatory freezing of water, while keeping the NAPL in a liquid state, enables high-resolution qualitative delineation of NAPL distribution within porous media. This novel approach may help improve site conceptual models and consequentially lead to highly tailored, more efficient remedial measures.     

Experiment and Simulation of Non-Reactive Solute Transport in Porous Media

To more accurately predict the migration behavior of pollutants in porous media, we conduct laboratory scale experiments and model simulation. Aniline (AN) is used in one-dimensional soil column experiments designed under various media and hydrodynamic conditions. The advection-dispersion equation (ADE) and the continuous-time random walk (CTRW) were used to simulate the breakthrough curves (BTCs) of the solute transport. The results show that the media and hydrodynamic conditions are two important factors affecting solute transport and are related to the degree of non-Fickian transport. The simulation results show that CTRW can more effectively describe the non-Fickian phenomenon in the solute transport process than ADE. The sensitive parameter in the CTRW simulation process is , which can reflect the degree of non-Fickian diffusion in the solute transport. Understanding the relationship of with velocity and media particle size is conducive to improving the reactive solute transport model. The results of this study provide a theoretical basis for better prediction of pollutant transport in groundwater.     

Simulation of Tidal Effects on Contaminant Transport in Porous Media

A one-dimensional numerical model is developed with oscillating velocities and dispersions to simulate the migration process of a contaminant plume within tidally influenced aquifers. Model simulations demonstrate that a major effect the tidal fluctuation has on the migration process of a contaminant plume is the exit concentration discharging to the tidal estuary. Tidal fluctuation causes the exit concentration levels to be significantly diluted by the surface-water body of the estuary. Sensitivity analyses demonstrate that tidal fluctuation hastens the rate of plume migration near the bank of the estuary because of the relatively high advective and dispersive fluxes induced by tides. However, tides affect the migration process only over a short distance from the tidal-water interface (about 40 ft for the parameters used in this study). If the contaminant plume is located far beyond the interface, tidal fluctuations will not affect the rate of plume migration until an existing regional ground-water flow velocity brings the plume to the tidally active zone. With or without tides, the rate of contaminant migration increases with higher regional hydraulic gradient. Furthermore, the effects of tidal fluctuations on the transport process become insignificant with higher regional hydraulic gradients.     

Electrokinetic Migration of Nitrate Through Heterogeneous Granular Porous Media

This study investigates and quantifies the influence of physical heterogeneity in granular porous media, represented by materials with different hydraulic conductivity, on the migration of nitrate, used as an amendment to enhance bioremediation, under an electric field. Laboratory experiments were conducted in a bench‐scale test cell under a low applied direct current using glass bead and clay mixes and synthetic groundwater to represent ideal conditions. The experiments included bromide tracer tests in homogeneous settings to deduce controls on electrokinetic transport of inorganic solutes in the different materials, and comparison of nitrate migration under homogeneous and heterogeneous scenarios. The results indicate that physical heterogeneity of subsurface materials, represented by a contrast between a higher‐hydraulic conductivity and lower‐hydraulic conductivity material normal to the direction of the applied electric field exerts the following controls on nitrate migration: (1) a spatial change in nitrate migration rate due to changes in effective ionic mobility and subsequent accumulation of nitrate at the interface between these materials; and (2) a spatial change in the voltage gradient distribution across the hydraulic conductivity contrast, due to the inverse relationship with effective ionic mobility. These factors will contribute to higher mass transport of nitrate through low hydraulic conductivity zones in heterogeneous porous media, relative to homogeneous host materials. Overall electrokinetic migration of amendments such as nitrate can be increased in heterogeneous granular porous media to enhance the in situ bioremediation of organic contaminants present in low hydraulic conductivity zones.