Effects of NAPL Contaminants on the Permeability of a Soil‐Bentonite Slurry Wall Material

Soilbentonite slurry walls are designed to inhibit the subsurface movement of contaminants from hazardous waste sites. Although it is generally accepted that high concentrations of organic compounds will adversely affect soilbentonite slurry walls and clay liners, previous research investigating the effects of NAPLs on the conductivity of clay wall materials has been inconclusive. In this study the effects of various organics (benzene, aniline, trichloroethylene, ethylene dichloride, methylene chloride) on the effective conductivity of a typical soilbentonite slurry wall material were studied under two effective stress conditions, 200 and 52kPa. The hydraulic conductivity for the soilbentonite material permeated with water averaged 1.52×10^-8cms^-1. Compared to water, there was little change in conductivity when the sample was permeated with a solution containing a NAPL compound at its solubility limit, except for aniline. However, there was a one to two order of magnitude decrease in conductivity when the sample was permeated with a pure NAPL for all NAPLs tested. When the soilbentonite material was permeated with a water/NAPL/water/NAPL sequence, the conductivity decreased one to two orders of magnitude when a NAPL was introduced following water; however, when water was reintroduced after the NAPL, the conductivity increased to the initial hydraulic conductivity. The conductivity again decreased one to two orders of magnitude when the NAPL was reintroduced. This trend occurred for all NAPLs tested, and the fluid properties of the NAPL compounds alone did not account for the decrease in conductivity compared to water.     

Simulation of immiscible multiphase flow in porous media: A focus on the capillary fringe of oil-contaminated aquifers

This paper deals with the analysis of some aspects of the vertical and lateral migration of oil spills in the unsaturated and the capillary zone of a phreatic aquifer. Our motivation stems from the fact that such contamination represents a severe danger for ground-water resources all over the world and from the present acute problem of jet-fuel contamination in some location of Israel. In the present study, we shall focus our efforts on the analysis of the upper layers of the aquifer which are often subjected to the most significant oil contamination. Neglecting coupled processes effects such as dilution, adsorption and volatilization, also adopting Richard's assumption, a three-phase flow model is introduced with capillary heads of the water and the oil as variables. The resulting model which is coupled and strongly non-linear is solved using a vertical two-dimensional Finite-Element procedure together with a quasi-Newton optimization algorithm. Applying that scheme, various scenarios of oil migration in the unsaturated and the capillary zone were simulated. Some migration characteristics prediced by the numerical simulations are discussed. In particular, the dynamics of the water and oil phases during the migration process is discussed.     

Analytical Modeling of Nonaqueous Phase Liquid Dissolution with Green's Functions

Equilibrium and bicontinuum nonequilibrium formulations of the advection–dispersion equation (ADE) have been widely used to describe subsurface solute transport. The Green's Function Method (GFM) is particularly attractive to solve the ADE because of its flexibility to deal with arbitrary initial and boundary conditions, and its relative simplicity to formulate solutions for multidimensional problems. The Green's functions that are presented can be used for a wide range of problems involving equilibrium and nonequilibrium transport in semiinfinite and infinite media. The GFM is applied to analytically model multidimensional transport from persistent solute sources typical of nonaqueous phase liquids (NAPLs). Specific solutions are derived for transport from a rectangular source (parallel to the flow direction) of persistent contamination using first, second, or thirdtype boundary or source input conditions. Away from the source, the first and thirdtype condition cannot be expected to represent the exact surface condition. The secondtype condition has the disadvantage that the diffusive flux from the source needs to be specified a priori. Near the source, the thirdtype condition appears most suitable to model NAPL dissolution into the medium. The solute flux from the pool, and hence the concentration in the medium, depends strongly on the mass transfer coefficient. For all conditions, the concentration profiles indicate that nonequilibrium conditions tend to reduce the maximum solute concentration and the total amount of solute that enters the porous medium from the source. On the other hand, during nonequilibrium transport the solute may spread over a larger area of the medium compared to equilibrium transport.     

Pore-Scale Analysis of NAPL Blob Dissolution and Mobilization in Porous Media

A pore-scale analysis of nonaqueous phase liquid (NAPL) blob dissolution and mobilization in porous media was presented. Dissolution kinetics of residual NAPLs in an otherwise water-saturated porous medium was investigated by conducting micromodel experiments. Changes in residual NAPL volume were measured from recorded video images to calculate the mass transfer coefficient, K and the lumped mass transfer rate coefficient, k. The morphological characteristics of the blobs such as specific and intrinsic area were found to be independent of water flow rate except at NAPL saturations below 2%. Dissolution process was also investigated by separating the mass transfer into zones of mobile and immobile water. The fractions of total residual NAPL perimeters in contact with mobile water and immobile water were measured and their relationship to the mass transfer coefficient was discussed. In general, residual NAPLs are removed by dissolution and mobilization. Although these two mechanisms were studied individually by others, their simultaneous occurrence was not considered. Therefore, in this study, mobilization of dissolving NAPL blobs was investigated by an analysis of the forces acting on a trapped NAPL blob. A dimensional analysis was performed to quantify the residual blob mobilization in terms of dimensionless Capillary number (Ca _I). If Ca _I is equal to or greater than the trapping number defined as , then blob mobilization is expected.     

Non-aqueous phase liquid drop formation within a water saturated fracture

This work focuses on the mechanisms of non-aqueous phase liquid (NAPL) drop formation within a single fracture fed from a NAPL reservoir by way of a circular orifice, such as a pore. The fracture is assumed to be fully saturated, the relative wettability of the system is assumed water-wet, and the water velocity profile within the fracture is described by a Poiseuille flow. The size of the NAPL drops is investigated for various water flow velocities and NAPL entrance diameters. A force balancing method was used to determine the radii of detached drops. The drop sizes calculated from the model developed here are shown to be in agreement with available experimental drop size data. It is shown that at low Reynolds numbers the buoyancy force is the dominant force acting on the drop during the formation process and at high Reynolds numbers the viscous forces dominate. A simplified expression relating the geometry of the fractured system to the drop radii is developed from the model equations, and it is shown to predict drop radii that match well with both the model simulations and the available experimental data.     

Practical application of 1H benchtop NMR spectroscopy for the characterization of a nonaqueous phase liquid from a contaminated environment

Nonaqueous phase liquids (NAPLs) located at the surface of the water table and/or below the water table are often a significant source for groundwater contamination near current or former commercial/industrial facilities. Due to the complex and long history of many industrial sites, these NAPLs often contain a complex mixture of contaminants and as such can be difficult to fully characterize using conventional analytical methods. Remediation and risk assessment activities at sites containing NAPLs may, subsequently, be hindered as the contamination profile may not be fully understood. This paper demonstrates the application of bench-scale ¹H nuclear magnetic resonance (NMR) spectroscopy as a practical tool to assist with the characterization of complex NAPLs. Here, a NAPL collected from a contaminated site situated near a former chemical manufacturing facility was analyzed using a combination of one-dimensional (1D) ¹H NMR spectroscopy and two-dimensional (2D) ¹H J-resolved spectroscopy (JRES). It is shown that 1D NMR experiments are useful in the rapid identification of the classes of compounds present, whereas 2D JRES NMR experiments are useful in identifying specific compounds. The use of benchtop NMR spectroscopy as a simple and cost effective tool to assist in the analysis of contaminated sites may help improve the practical characterization of many heavily contaminated sites and facilitate improved risk assessments and remedial strategies.     

Effect of ultrasound on oil removal from soils

The soil-flushing method enhanced by ultrasonic waves is a new technique that potentially can become an effective method for in situ remediation of the ground contaminated by NAPL hydrocarbons. This study investigated the effectiveness of ultrasound enhancement in the soil-flushing method for a range of conditions involving soil type, soil density, flushing rate, and sonication power. The study was conducted in the laboratory using specially designed and fabricated equipment. The test results indicated that the rate of contaminant extraction increased considerably with increasing sonication power up to the level where cavitation occurred. The effectiveness of sonication-enhanced soil-flushing can be expressed as a function of (D(10))(2)*i, in which D(10) is the effective grain size, and i is the hydraulic gradient.     

A Physically Based Model of Dissolution of Nonaqueous Phase Liquids in the Saturated Zone

The design of remediation strategies for nonaqueous phase liquid (NAPL) contaminants involves predicting the rate of NAPL dissolution. A physically based model of an idealized pore geometry was developed to predict nonaqueous phase liquid dissolution rate coefficients. A bundle of parallel pores in series model is used to represent NAPL dissolution as a function of three processes: pore diffusion, corner diffusion, and mixing and multiple contact. The dissolution rate coefficient is expressed in terms of the modified Sherwood number (Sh) and is a function of Peclet (Pe) number. The model captures the complex behavior of Sh versus Pe data for both water-wet (Powers, 1992) and NAPL-wet (Parker et al., 1991) media. For water-wet media, the observed behavior can be broken down into four distinct regions. Each region represents a different physical process controlling NAPL dissolution: the low-Pe region is controlled by pore diffusion; the low- to moderate-Pe region is a transition zone; the moderate-Pe region is controlled by mixing and multiple contact; and the high-Pe region is controlled by corner diffusion. For the high-Pe conditions typical of most column experiments, the model involves only one fitting parameter. For NAPL-wet media, NAPL dissolution is governed exclusively by corner diffusion, and the model again involves only one fitting parameter.     

The use of radon (Rn-222) and volatile organic compounds in monitoring soil gas to localize NAPL contamination at a gas station in Rio Claro,São Paulo State,Brazil

This study focuses on the presence of radon (²²²Rn) and volatile organic compounds (VOCs) in soil gases at a gas station located in the city of Rio Claro, São Paulo, Brazil, where a fossil fuel leak occurred. The spatial distribution results show a correlation between ²²²Rn and VOCs, consistent with the fact that radon gas has a greater chemical affinity with organic phases than with water. This finding demonstrates that the presence of a residual hydrocarbon phase in an aquifer can retain radon, leading to a reduced radon content in the soil gas. The data in this study confirm the results of previous investigations, in which the method used in this study provided a preliminary fingerprint of a contaminated area. Furthermore, the data analysis time is brief, and only simple equipment is required.     

Micromodel Observation of the Role of Oil Layers in Three-Phase Flow

We have studied the flow of a non-aqueous phase liquid (NAPL, or oil), water and air at the pore scale using a micromodel. The pore space pattern from a photomicrograph of a two-dimensional section through a Berea sandstone was etched onto a silicon wafer. The sizes of the pores in the micromodel are in the range 3–30,m and are the same as observed in the rock from which the image was taken. We conducted three-phase displacement experiments at low capillary numbers (in the order of 10^-7) to observe the presence of predicted displacement mechanisms at the pore scale. We observed stable oil layers between the wetting phase (water) and the non-wetting phase (gas) for the water–decane–air system, which has a negative equilibrium spreading coefficient, as well as four different types of double displacements where one fluid displaces another that displaces a third. Double imbibition and double drainage are readily observed, but the existence of an oil layer surrounding the gas phase makes the other double displacement combinations very unlikely.