Effect of NAPL film stability on the dissolution of residual wetting NAPL in porous media: A pore-scale modeling study

Wettability profoundly affects not only the initial distribution of residual NAPL contaminants in natural soils, but also their subsequent dissolution in a flowing aqueous phase. Under conditions of preferential NAPL wettability, the residual NAPL phase is found within the smaller pores and in the form of continuous corner filaments and thick films on pore walls. Such films expose a much greater interfacial area for mass transfer than would be exposed by the same amount of non-wetting NAPL. Importantly, capillary and hydraulic continuity of NAPL filaments and thick films is essential for sustaining NAPL–water counterflow during the course of NAPL dissolution in flowing groundwater—a mechanism which maintains and even increases the interfacial area for mass transfer. Continued dissolution results in gradual thinning of the NAPL films, which may become unstable and rupture causing disconnection of the residual NAPL in the form of clusters. Using a pore network simulator, we demonstrate that NAPL film instability drastically modifies the microscopic configuration of residual NAPL, and hence the local hydrodynamic conditions and interfacial area for mass transfer, with concomitant effects on macroscopically observable quantities, such as the aqueous effluent concentration and the fractional NAPL recovery with time. These results strongly suggest that the disjoining pressure of NAPL films may exert an important, and hitherto unaccounted, control on the dissolution behaviour of a residual NAPL phase in oil wet systems.     

Pore-scale simulation of entrapped non-aqueous phase liquid dissolution

We investigated the dissolution of non-aqueous phase liquids (NAPLs) in a three-dimensional random sphere-pack medium using a pore-scale modeling approach to advance fundamental understanding and connect rigorously to microscale processes. Residual NAPL distributions were generated using a morphological approach and the entrapped non-wetting phase was quantitatively characterized by calculating volume, orientation, interfacial area, and shape of isolated NAPL regions. With a detailed aqueous-phase flow field obtained by a multiple-relaxation time lattice Boltzmann approach, we solved the advective–diffusive equation in the pore space using a high-resolution, adaptive-stencil finite-volume scheme and an operator-splitting algorithm. We show good agreement between the mass transfer rates predicted in the computational approach and previously published experimental observations. The pore-scale simulations presented in this work provide the first three-dimensional comparison to the considerable experimental work that has been performed to derive constitutive relations to quantify mass transfer from a residual NAPL to a flowing aqueous phase.     

Micro-scale experimental investigation of the effect of flow rate on trapping in sandstone and carbonate rock samples

We present the results of a pore-scale experimental study of residual trapping in consolidated sandstone and carbonate rock samples under confining stress. We investigate how the changes in wetting phase flow rate impacts pore-scale distribution of fluids during imbibition in natural, water-wet porous media. We systematically study pore-scale trapping of the nonwetting phase as well as size and distribution of its disconnected globules. Seven sets of drainage-imbibition experiments were performed with brine and oil as the wetting and nonwetting phases, respectively. We utilized a two-phase miniature core-flooding apparatus integrated with an X-ray microtomography system to examine pore-scale fluid distributions in small Bentheimer sandstone (D = 4.9 mm and L = 13 mm) and Gambier limestone (D = 4.4 mm and L = 75 mm) core samples. The results show that with increase in capillary number, the residual oil saturation at the end of the imbibition reduces from 0.46 to 0.20 in Bemtheimer sandstone and from 0.46 to 0.28 in Gambier limestone. We use pore-scale displacement mechanisms, in-situ wettability characteristics, and pore size distribution information to explain the observed capillary desaturation trends. The reduction was believed to be caused by alteration of the order in which pore-scale displacements took place during imbibition. Furthermore, increase in capillary number produced significantly different pore-scale fluid distributions during imbibition. We explored the pore fluid occupancies and studied size and distribution of the trapped oil clusters during different imbibition experiments. The results clearly show that as the capillary number increases, imbibition produces smaller trapped oil globules. In other words, the volume of individual trapped oil globules decreased at higher brine flow rates. Finally, we observed that the pore space in the limestone sample was considerably altered through matrix dissolution at extremely high brine flow rates. This increased the sample porosity from 44% to 62% and permeability from 7.3 D to 80 D. Imbibition in the altered pore space produced lower residual oil saturation (from 0.28 to 0.22) and significantly different distribution of trapped oil globules.     

The influence of wettability on NAPL dissolution fingering

Laboratory experiments and numerical simulations in homogeneous porous media were used to investigate the influence of porous medium wettability on the formation and growth of preferential dissolution pathways, dissolution fingers, during nonaqueous phase liquid (NAPL) dissolution. As the porous medium became increasingly NAPL-wet, dissolution fingers grew wider and slower. This result was observed in physical experiments with 0% and 100% NAPL-wet conditions and confirmed with numerical simulations at these and intermediate wettabilities. A previously derived expression for an upscaled mass transfer rate coefficient that accounts for the growth of dissolution fingers was used to quantify the effect of fingering on overall NAPL removal rates. For the test cases evaluated, NAPL dissolution fingering controlled the overall rate of NAPL dissolution after the dissolution front moved 4 cm in 0% NAPL-wet conditions and 18 cm in 100% NAPL-wet conditions. Thus, even in completely NAPL-wet media dissolution fingering may control the overall rate of NAPL dissolution after relatively short travel distances. The importance of NAPL dissolution fingering in heterogeneous systems with spatially varying NAPL saturations, though, remains an important question for future work.     

Dependence of lumped mass transfer coefficient on scale and reactions kinetics for biologically enhanced NAPL dissolution

Residual dense non-aqueous liquids (NAPLs) in aquifers constitute a great challenge for groundwater cleanup. Active engineered treatment of regions that contain residual NAPLs is often required to shorten the long-term impact of NAPLs on groundwater quality. Enhanced residual NAPL cleanup can be achieved by promoting biodegradation of NAPL components in the aqueous phase, thereby increasing contaminant fluxes from the NAPL phase. Reaction-enhanced NAPL dissolution is often mathematically simulated under the assumption that lumped mass transfer coefficients, used to describe the dissolution behavior of the NAPL phase, are independent of the reactions. However, this assumption is not warranted because reactions occurring near the water–NAPL interface can reduce characteristic mass transfer lengths, which tend to enhance mass transfer over the no-reaction case.In this study, we mathematically investigated the connections between lumped mass transfer coefficients and reaction kinetics over an idealized residual NAPL domain. Since mass transfer is frequently a scale-dependent process, we also examined the influence of system extent on mass transfer coefficients. For our idealized domain with an assumed first-order decay reaction, the results show that lumped mass transfer coefficients depend on reaction kinetics and system scale. The mass transfer coefficient derived from the non-reactive case cannot properly represent the mass transfer process under the reactive conditions. When the advection time scale is long in comparison to the transverse dispersion time scale in the system, a fast reaction can increase significantly the lumped mass transfer coefficient. The mass transfer coefficient used for simulation was also found to be affected by the nature of the numerical scheme used.     

Impact of NAPL architecture on interphase mass transfer: A pore network study

Interphase mass transfer in porous media is commonly modeled using Sherwood number expressions that are developed in terms of fluid and porous medium properties averaged over some representative elementary volume (REV). In this work the influence of sub-grid scale properties on interphase mass transfer was investigated using a two-dimensional pore network model. The focus was on assessing the impact of (i) NAPL saturation, (ii) interfacial area (iii) NAPL spatial distribution at the pore scale, (iv) grain size heterogeneity, (v) REV or domain size and (vi) pore scale heterogeneity of the porous media on interphase mass transfer. Variability of both the mass transfer coefficient that explicitly accounts for the interfacial area and the mass transfer coefficient that lumps the interfacial area was examined. It was shown that pore scale NAPL distribution and its orientation relative to the flow direction have significant impact on flow bypassing and the interphase mass transfer coefficient. This results in a complex non-linear relationship between interfacial area and the REV-based interphase mass transfer rate. Hence, explicitly accounting for the interfacial area does not eliminate the uncertainty of the mass transfer coefficient. It was also shown that, even for explicitly defined flow patterns, changing the domain size over which the mass transfer process is defined influences the extent of NAPL bypassing and dilution and, consequently, the interphase mass transfer. It was also demonstrated that the spatial variability of pore scale parameters such as pore throat diameters may result in different rates of interphase mass transfer even for the same pore size distribution index.     

Effective macroscopic transport parameters between parallel plates with constant concentration boundaries

A macroscopic transport model is developed, following the Taylor shear dispersion analysis procedure, for a 2D laminar shear flow between parallel plates possessing a constant specified concentration. This idealized geometry models flow with contaminant dissolution at pore-scale in a contaminant source zone and flow in a rock fracture with dissolving walls. We upscale a macroscopic transient transport model with effective transport coefficients of mean velocity, macroscopic dispersion, and first-order mass transfer rate. To validate the macroscopic model the mean concentration, covariance, and wall concentration gradient are compared to the results of numerical simulations of the advection–diffusion equation and the Graetz solution. Results indicate that in the presence of local-scale variations and constant concentration boundaries, the upscaled mean velocity and macrodispersion coefficient differ from those of the Taylor–Aris dispersion, and the mass transfer flux described by the first-order mass transfer model is larger than the diffusive mass flux from the constant wall. In addition, the upscaled first-order mass transfer coefficient in the macroscopic model depends only on the plate gap and diffusion coefficient. Therefore, the upscaled first-order mass transfer coefficient is independent of the mean velocity and travel distance, leading to a constant pore-scale Sherwood number of 12. By contrast, the effective Sherwood number determined by the diffusive mass flux is a function of the Peclet number for small Peclet number, and approaches a constant of 10.3 for large Peclet number.     

Non-equilibrium alcohol flooding model for immiscible phase remediation: 2. Model development and application

A non-equilibrium, two-phase, three-component compositional model for the simulation of alcohol flooding has been developed and tested. Inter-phase mass transfer algorithms allow for transfer of all three components at high concentrations and high mass flux rates using a two-film model. The model has been used to simulate alcohol floods where the alcohol has an affinity for either the water-rich phase, or the organic-rich phase. Calibration, using experimental effluent data from an alcohol flood which used a 2-propanol (IPA)-water-tetrachlorethene (PCE) ternary system, indicates that inter-phase mass transfer parameters can be non-unique. Sensitivity studies, completed using the non-equilibrium model for the IPA-water-PCE system, indicate that experimentally derived organic-rich phase composition data should lead to better estimates of the non-wetting phase film thickness. For alcohol flooding experiments where the primary mechanism of non-aqueous phase liquid (NAPL) removal is enhanced dissolution, near-equilibrium conditions may be achieved with NAPL recovery similar for conditions of near-equilibrium and equilibrium. However, for systems where remobilization is the primary mechanism of NAPL recovery, it is expected that although local conditions may approach equilibrium, the resulting NAPL recovery can be significantly lower than would be attained if equilibrium conditions persisted.     

Experimental Investigation of Surfactant-Enhanced Dissolution of Residual NAPL in Saturated Soil

Nonaqueous phase liquid (NAPL) is a long-term source of ground water contamination as the pollutant slowly partitions into the air and water phases. The objective of this work was to study the efficacy of aqueous surfactant solution to enhance the dissolution of a residual NAPL below the capillary fringe, hence reducing the time needed for aquifer restoration. An analytical technique was developed to measure the concentration of NAPL in a nonionic surfactant. Soil column experiments simulated conditions in the saturated soil where a NAPL may become trapped as a discontinuous immobile phase. Experimental results indicate that dissolution was a rate-limited process, approaching equilibrium concentrations after 24 hours. The relative permeability of the aqueous phase initially decreased as surfactant was injected, but increased over time as the saturation of residual NAPL was reduced through mass transfer into the surfactant-enhanced aqueous phase. These findings suggest that enhancing the aqueous phase with a nonionic surfactant may significantly enhance the in situ recovery or residual NAPL.     

Direct numerical simulations of interface dynamics to link capillary pressure and total surface energy

The flow of two immiscible fluids through a porous medium depends on the complex interplay between gravity, capillarity, and viscous forces. The interaction between these forces and the geometry of the medium gives rise to a variety of complex flow regimes that are difficult to describe using continuum models. Although a number of pore-scale models have been employed, a careful investigation of the macroscopic effects of pore-scale processes requires methods based on conservation principles in order to reduce the number of modeling assumptions. In this work we perform direct numerical simulations of drainage by solving Navier–Stokes equations in the pore space and employing the Volume Of Fluid (VOF) method to track the evolution of the fluid–fluid interface. After demonstrating that the method is able to deal with large viscosity contrasts and model the transition from stable flow to viscous fingering, we focus on the macroscopic capillary pressure and we compare different definitions of this quantity under quasi-static and dynamic conditions. We show that the difference between the intrinsic phase-average pressures, which is commonly used as definition of Darcy-scale capillary pressure, is subject to several limitations and it is not accurate in presence of viscous effects or trapping. In contrast, a definition based on the variation of the total surface energy provides an accurate estimate of the macroscopic capillary pressure. This definition, which links the capillary pressure to its physical origin, allows a better separation of viscous effects and does not depend on the presence of trapped fluid clusters.     

A practical model for mobile, residual, and entrapped NAPL in water-wet porous media

Flow of nonvolatile nonaqueous phase liquid (NAPL) and aqueous phases that account for mobile, entrapped, and residual NAPL in variably saturated water-wet porous media is modeled and compared against results from detailed laboratory experiments. Residual saturation formation in the vadose zone is a process that is often ignored in multifluid flow simulators, which might cause an overestimation of the volume of NAPL that reaches the ground water. Mobile NAPL is defined as being continuous in the pore space and flows under a pressure gradient or gravitational body force. Entrapped NAPL is defined as being occluded by the aqueous phase, occurring as immobile ganglia surrounded by aqueous phase in the pore space and formed when NAPL is replaced by the aqueous phase. Residual NAPL is defined as immobile, nonwater entrapped NAPL that does not drain from the pore spaces and is conceptualized as being either continuous or discontinuous. Free NAPL comprises mobile and residual NAPL. The numerical model is formulated on mass conservation equations for oil and water, transported via NAPL and aqueous phases through variably saturated porous media. To account for phase transitions, a primary variable switching scheme is implemented for the oil-mass conservation equation over three phase conditions: (1) aqueous or aqueous-gas with dissolved oil, (2) aqueous or aqueous-gas with entrapped NAPL, and (3) aqueous or aqueous gas with free NAPL. Two laboratory-scale column experiments are modeled to verify the numerical model. Comparisons between the numerical simulations and experiments demonstrate the necessity to include the residual NAPL formation process in multifluid flow simulators.     

Effect of NAPL exposure on the wettability and two‐phase flow in a single rock fracture

Surface‐wetting properties are an important cause of changing the groundwater and two‐phase fluid flows. Various factors affecting the surface wettability were investigated in a parallel‐walled glass fracture with non‐aqueous phase liquid (NAPL) (gasoline, diesel, trichloroethylene, and creosote) wetted surfaces. First, the effect of the duration of NAPL exposure on wettability change was considered at pre‐wet fracture surfaces using the various NAPL species, and the result showed that the surface became hydrophobic after the exposure time of NAPL exceeded 2000 min. Second, the initial wetting state of the surface affected the timing when the wettability change begins as well as the extent of the wettability change in an NAPL‐wetted rock fractures. Under the dry condition, the wettability change was completed within a very short time of exposure to NAPL (~5 min), and then it finally reached the intermediate and weakly NAPL wetting (contact angle of 118°). Under the pre‐wet condition, a relatively long time of exposure (~5000 min) was needed to observe the obvious change of the surface wettability, which was changed up to strongly NAPL wetting (contact angle of 142°). Third, the wettability changed by NAPL exposure was stable and maintained for a long time, regardless of water flushing rate and temperature. Finally, the wettability change by the exposure of NAPL on parallel fracture surfaces was evaluated at various groundwater flow velocities. Result showed that groundwater flow velocity has an important impact upon measured contact angle. Although fracture surfaces were exposed to NAPL at the low groundwater flow velocity, the wettability was not changed from hydrophilic to hydrophobic when the contact time between NAPL and mineral surfaces was not sufficient owing to the pulse‐type movement of NAPL. This implies that the variation of exposure pattern due to groundwater flow on the wettability change can be an important factor affecting the wettability change of fracture surface and migration behaviour at natural fractured rock aquifers in case of NAPL spill. Copyright © 2015 John Wiley & Sons, Ltd.     

Direct numerical simulation of pore-scale flow in a bead pack: Comparison with magnetic resonance imaging observations

A significant body of current research is aimed at developing methods for numerical simulation of flow and transport in porous media that explicitly resolve complex pore and solid geometries, and at utilizing such models to study the relationships between fundamental pore-scale processes and macroscopic manifestations at larger (i.e., Darcy) scales. A number of different numerical methods for pore-scale simulation have been developed, and have been extensively tested and validated for simplified geometries. However, validation of pore-scale simulations of fluid velocity for complex, three-dimensional (3D) pore geometries that are representative of natural porous media is challenging due to our limited ability to measure pore-scale velocity in such systems. Recent advances in magnetic resonance imaging (MRI) offer the opportunity to measure not only the pore geometry, but also local fluid velocities under steady-state flow conditions in 3D and with high spatial resolution. In this paper, we present a 3D velocity field measured at sub-pore resolution (tens of micrometers) over a centimeter-scale 3D domain using MRI methods. We have utilized the measured pore geometry to perform 3D simulations of Navier–Stokes flow over the same domain using direct numerical simulation techniques. We present a comparison of the numerical simulation results with the measured velocity field. It is shown that the numerical results match the observed velocity patterns well overall except for a variance and small systematic scaling which can be attributed to the known experimental uncertainty in the MRI measurements. The comparisons presented here provide strong validation of the pore-scale simulation methods and new insights for interpretation of uncertainty in MRI measurements of pore-scale velocity. This study also provides a potential benchmark for future comparison of other pore-scale simulation methods. © 2012 Elsevier Science. All rights reserved.     

Interphase mass transfer between fluids in subsurface formations: A review

This paper presents a review of the state-of-the-art on interphase mass transfer between immiscible fluids in porous media with focus on the factors that have significant influence on this process. In total close to 300 papers were reviewed focusing to a large extent on the literature relating to NAPL contamination of the subsurface. The large body of work available on this topic was organized according to the length scale of the conducted studies, namely the pore, meso and field scales. The interrelation of interphase mass transfer at these different scales is highlighted. To gain further insight into interphase mass transfer, published studies were discussed and evaluated in terms of the governing flow configurations defined in terms of the wettability and mobility of the different phases. Such organization of the existing literature enables the identification of the interfacial domains that would have significant impact on interphase mass transfer. Available modeling approaches at the various length scales are discussed with regard to current knowledge on the physics of this process. Future research directions are also suggested.     

Pore Water Characteristics Following a Release of Neat Ethanol onto Pre-existing NAPL

Neat ethanol (75.7 L) was released into the upper capillary zone in a continuous-flow, sand-packed aquifer tank (8.2 m³) with an average seepage velocity of 0.75 m/day. This model aquifer system contained a residual nonaqueous phase liquid (NAPL) that extended from the capillary zone to 10 cm below the water table. Maximum aqueous concentrations of ethanol were 20% v/v in the capillary zone and 0.08% in the saturated zone at 25 and 30 cm downgradient from the emplaced NAPL source, respectively. A bench-scale release experiment was also conducted for a similar size spill (scaled to the plan area). The concentrations of ethanol in ground water for both the bench- and pilot-scale experiments were consistent with advective–dispersive limited mass transfer from the capillary to the saturated zone. Concentrations of monoaromatic hydrocarbons and isooctane increased in the pore water of the capillary zone as a result of both redistribution of residual NAPL (confirmed by visualization) and enhanced hydrocarbon dissolution due to the cosolvent effect exerted by ethanol. In the tank experiment, higher hydrocarbon concentrations in ground water were also attributed to decreased hydrocarbon biodegradation activity caused by preferential microbial utilization of ethanol and the resulting depletion of oxygen. These results infer that spills of highly concentrated ethanol will be largely confined to the capillary zone due to its buoyancy, and ethanol concentrations in near-source zone ground water will be controlled by mass transfer limitations and hydrologic conditions. Furthermore, highly concentrated ethanol releases onto pre-existing NAPL will likely exacerbate impacts to ground water, due to NAPL mobilization and dissolution, and decreased bioattenuation of hydrocarbons.     

Effect of NAPL Source Morphology on Mass Transfer in the Vadose Zone

The generation of vapor‐phase contaminant plumes within the vadose zone is of interest for contaminated site management. Therefore, it is important to understand vapor sources such as non‐aqueous‐phase liquids (NAPLs) and processes that govern their volatilization. The distribution of NAPL, gas, and water phases within a source zone is expected to influence the rate of volatilization. However, the effect of this distribution morphology on volatilization has not been thoroughly quantified. Because field quantification of NAPL volatilization is often infeasible, a controlled laboratory experiment was conducted in a two‐dimensional tank (28 cm × 15.5 cm × 2.5 cm) with water‐wet sandy media and an emplaced trichloroethylene (TCE) source. The source was emplaced in two configurations to represent morphologies encountered in field settings: (1) NAPL pools directly exposed to the air phase and (2) NAPLs trapped in water‐saturated zones that were occluded from the air phase. Airflow was passed through the tank and effluent concentrations of TCE were quantified. Models were used to analyze results, which indicated that mass transfer from directly exposed NAPL was fast and controlled by advective‐dispersive‐diffusive transport in the gas phase. However, sources occluded by pore water showed strong rate limitations and slower effective mass transfer. This difference is explained by diffusional resistance within the aqueous phase. Results demonstrate that vapor generation rates from a NAPL source will be influenced by the soil water content distribution within the source. The implications of the NAPL morphology on volatilization in the context of a dynamic water table or climate are discussed.     

Influence of mass transfer resistance on detection of nonaqueous phase liquids with partitioning tracer tests

Partitioning interwell tracer tests (PITTs) are a relatively new technique for measuring the amount of nonaqueous phase liquid (NAPL) within saturated porous media. In this work we examined the influence of mass transfer limitations on the accuracy of measured NAPL from PITTs. Two mathematical models were used along with laboratory column experiments to explore the influence of tracer partition coefficient, tracer detection limit, and injected tracer mass on NAPL measurements. When dimensionless mass transfer coefficients were small, NAPL measurement errors decreased with decreasing tracer partition coefficient, decreasing tracer detection limit, and increasing injected tracer mass. Extrapolating breakthrough curves exponentially reduced but did not eliminate systematic errors in NAPL measurement. Although transport in a single stream tube was used in the mathematical models and laboratory experiments, the results from this simplified domain were supported by data taken from a three-dimensional computational experiment, where the NAPL resided as large pool. Based on these results, we suggest guidelines for interpreting tracer breakthrough data to ascertain the importance of mass transfer limitations on NAPL measurements.     

Intercomparison of 3D pore-scale flow and solute transport simulation methods

Multiple numerical approaches have been developed to simulate porous media fluid flow and solute transport at the pore scale. These include 1) methods that explicitly model the three-dimensional geometry of pore spaces and 2) methods that conceptualize the pore space as a topologically consistent set of stylized pore bodies and pore throats. In previous work we validated a model of the first type, using computational fluid dynamics (CFD) codes employing a standard finite volume method (FVM), against magnetic resonance velocimetry (MRV) measurements of pore-scale velocities. Here we expand that validation to include additional models of the first type based on the lattice Boltzmann method (LBM) and smoothed particle hydrodynamics (SPH), as well as a model of the second type, a pore-network model (PNM). The PNM approach used in the current study was recently improved and demonstrated to accurately simulate solute transport in a two-dimensional experiment. While the PNM approach is computationally much less demanding than direct numerical simulation methods, the effect of conceptualizing complex three-dimensional pore geometries on solute transport in the manner of PNMs has not been fully determined. We apply all four approaches (FVM-based CFD, LBM, SPH and PNM) to simulate pore-scale velocity distributions and (for capable codes) nonreactive solute transport, and intercompare the model results. Comparisons are drawn both in terms of macroscopic variables (e.g., permeability, solute breakthrough curves) and microscopic variables (e.g., local velocities and concentrations). Generally good agreement was achieved among the various approaches, but some differences were observed depending on the model context. The intercomparison work was challenging because of variable capabilities of the codes, and inspired some code enhancements to allow consistent comparison of flow and transport simulations across the full suite of methods. This study provides support for confidence in a variety of pore-scale modeling methods and motivates further development and application of pore-scale simulation methods.     

Pore-scale characteristics of multiphase flow in porous media: A comparison of air–water and oil–water experiments

Studies of NAPL dissolution in porous media have demonstrated that measurement of saturation alone is insufficient to describe the rate of dissolution. Quantification of the NAPL–water interfacial area provides a measure of the expected area available for mass transfer and will likely be a primary determinant of NAPL removal efficiency. To measure the interfacial area, we have used a synchrotron-based CMT technique to obtain high-resolution 3D images of flow in a Soltrol–water–glass bead system. The interfacial area is found to increase as the wetting phase saturation decreases, reach a maximum, and then decrease as the wetting phase saturation goes to zero. These results are compared to previous findings for an air–water–glass bead study; The Soltrol–water interfacial areas were found to peak at similar saturations as those measured for the air–water system (20–35% saturation range), however, the peak values were in some cases almost twice as high for the oil-water system. We believe that the observed differences between the air–water and oil–water systems to a large degree can be explained by the differences in interfacial tensions for the two systems.