Transport and fate of nonaqueous phase liquid (NAPL) in variably saturated porous media with evolving scales of heterogeneity

 A stochastic simulation is performed to study multiphase flow and contaminant transport in fractal porous media with evolving scales of heterogeneity. Numerical simulations of residual NAPL mass transfer and subsequent transport of dissolved and/or volatilized NAPL mass in variably saturated media are carried out in conjunction with Monte Carlo techniques. The impact of fractal dimension, plume scale and anisotropy (stratification) of fractal media on relative dispersivities is investigated and discussed. The results indicate the significance of evolving scale of porous media heterogeneity to the NAPL transport in the subsurface. In general, the fractal porous media enhance the dispersivities of NAPL mass plume transport in both the water phase and the gas phase while the influence on the water phase is more significant. The porous media with larger fractal dimension have larger relative dispersivities. The aqueous horizontal dispersivity exhibits a most significant increase against the plume scale.     

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.     

A novel experimental procedure to investigate the biodegradation of NAPL under unsaturated conditions

Soils need to be thoroughly investigated regarding their potential for the natural attenuation of non-aqueous phase liquids (NAPL). Laboratory investigations truly representative of degradation processes in field conditions are difficult to implement for porous media partially saturated with water, NAPL and air. We propose an innovative protocol to investigate degradation processes under steady-state vadose zone conditions. Experiments are carried out in glass columns filled with a sand and, as bacteria source, a soil from a diesel-fuel-polluted site. Water and NAPL (n-hexadecane diluted in heptamethylnonane (HMN)) are added to the porous medium in a two-step procedure using ceramic membranes placed at the bottom of the column. This procedure results, for appropriate experimental conditions, in a uniform distribution of the two fluids (water and NAPL) throughout the column. In a biodegradation experiment non-biodegradable HMN is used to provide NAPL mass, while keeping biodegradable n-hexadecane small enough to monitor its rapid degradation. Biodegradation is followed as a function of time by measuring oxygen consumption, using a respirometer. Degradative activity is controlled by diffusive transfers in the porous network, of oxygen from the gas phase to the water phase and of n-hexadecane from the NAPL phase to the water phase.     

DyeLIF™: A New Direct‐Push Laser‐Induced Fluorescence Sensor System for Chlorinated Solvent DNAPL and Other Non‐Naturally Fluorescing NAPLs

DyeLIF? is a new version of laser‐induced fluorescence (LIF) for high‐resolution three‐dimensional subsurface mapping of nonaqueous phase liquids (NAPLs) in the subsurface. DyeLIF eliminates the requirement that the NAPL contains native fluorophores (such as those that occur in compounds like polynuclear aromatic hydrocarbons [PAHs]) and can therefore be used to detect chlorinated solvents and other nonfluorescing NAPLs that had previously been undetectable with conventional LIF tools. With DyeLIF, an aqueous solution of water and nontoxic hydrophobic dye is continuously injected ahead of the sapphire detection window while the LIF probe is being advanced in the subsurface. If soil containing NAPL is penetrated, the injected dye solvates into the NAPL within a few milliseconds, creating strong fluorescence that is transmitted via fiber‐optic filaments to aboveground optical sensors. A detailed field evaluation of the novel DyeLIF technology was performed at a contaminated industrial site in Lowell, Massachusetts, USA where chlorinated solvent dense nonaqueous phase liquid (DNAPL) persists below the water table in sandy sediments. Continuously cored boreholes were drilled adjacent to 5 of 30 DyeLIF probes that were advanced at that site. The cores were subsampled in high resolution to generate discrete‐depth soil samples as splits at the same depths where DNAPL was detected in the colocated DyeLIF probes. The cores were analyzed above ground using (1) colorimetric screening using hydrophobic dye tests, (2) laboratory extraction and quantitative chemical analysis, (3) “Benchtop” DyeLIF, and (4) volumetric moisture content. Correlation between DyeLIF and aboveground analyses of the soil cores was excellent: 98% agreement with positive DNAPL detections in samples where DNAPL pore saturations were >0.7% (based on quantitative soil analyses) and the ex situ tests. DyeLIF produced the equivalent of one aboveground colorimetric dye test every 0.2 inch (0.5 cm) of probing. With average daily probing of 395 linear feet (120.4 m), this was the equivalent of 12,039 discrete‐depth colorimetric dye tests/day. Because DyeLIF is an in situ measurement, there are no issues with soil core recovery like there would be for conventional ex situ colorimetric dye tests and 100% characterization of the probed intervals is achieved. Tracking the injection rate and pressure of the dye solution provides simultaneous data regarding relative soil permeability, similar to other direct push (DP) hydraulic profiling tools. Conventional LIF is considered the premier DP tool to identify and map NAPL containing PAHs in the subsurface or confirm its absence. While chlorinated solvent DNAPLs at some field sites contain impurities (e.g., solvated greases or oils) that make them detectable with conventional LIF techniques, at other sites, the DNAPL cannot be detected with conventional LIF. At such sites, the injection of a hydrophobic dye ahead of the sapphire window with the DyeLIF system now makes the LIF technology applicable to the many types of NAPLs that were previously invisible using conventional LIF techniques.     

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.     

Unifying NAPL Drawdown and Transmissivity Testing in Unconfined,Confined, Perched,and Fractured Settings using the Z-Factor and MH Principles

Light nonaqueous phase liquid (LNAPL) flow in in fractured rock is governed by the same physics as porous media, but LNAPL discharge to a well from fractured rock is subject to the unique geometry of the fractures within the rock and the degree of interconnectivity between the factures. Previous conceptualization and definition of drawdown of nonaqueous phase liquids (NAPL) has employed a single drawdown value to represent the entire vertical interval of mobile NAPL. Application of the single drawdown model may result in erroneous calculation of NAPL transmissivity in fractured rock settings. This work illustrates how drawdown in multiphase systems can be variable over the vertical interval of mobile NAPL. In settings with discrete fracture networks, it is clear that consistently applying a single drawdown value will not accurately represent the pressure gradients. This work presents the multiphase head (MH) model, which is proposed as a comprehensive methodology for evaluating NAPL drawdown in fractured rock, and unconsolidated porous media. The MH model utilizes fluid statics and physical principles to accurately represent pressure differences in the formation and convert those into NAPL drawdown for discrete elevations. This first principles approach to describing how drawdown varies with NAPL-production zone elevations and fluid levels, resulting in a more accurate representation of discharge vs. fluid elevation behavior. Application of the MH model to various scenarios has identified that dissimilar scenarios can represent similar behavior during recovery from a NAPL removal event or baildown test. The resulting understanding improves the selection of representative portions of baildown test data to use in NAPL transmissivity analysis. Proper conceptualization of drawdown in bedrock identifies an alternate analysis method, the Z-factor, to estimate NAPL transmissivity. The resulting drawdown calculations and transmissivity analysis method result in a comprehensive approach to calculating NAPL transmissivity in both bedrock and unconsolidated porous media.     

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.     

Cyclodextrin-Enhanced Solubilization of Organic Contaminants with Implications for Aquifer Remediation

Reagents that enhance the aqueous solubility of non-aqueous phase organic liquid (NAPL) contaminants are under investigation for use in enhanced subsurface remediation technologies. Cyclodextrin, a glucose-based molecule, is such a reagent. In this paper, laboratory experiments and numerical model simulations are used to evaluate and understand the potential remediation performance of cyclodextrin. Physical properties of cyclodextrin solutions such as density, viscosity, and NAPL-aqueous inter-facial tension are measured. Our analysis indicates that no serious obstacles exist related to fluid properties that would prevent the use of cyclodextrin solutions for subsurface NAPL remediation. Cyclodextrin-enhanced solubilization for a large suite of typical ground water contaminants is measured in the laboratory, and the results are related to the physicochemical properties of the organic compounds. The most-hydrophobic contaminants experience a larger relative solubility enhancement than the less-hydrophobic contaminants but have lower aqueous-phase apparent solubilities. Numerical model simulations of enhanced-solubilization flushing of NAPL-contaminated soil demonstrate that the more-hydrophilic compounds exhibit the greatest mass-removal rates due to their greater apparent solubilities, and thus are initially more effectively removed from soil by enhanced-solubilization-flushing reagents. However, the relatively more hydrophobic contaminants exhibit a greater improvement in contaminant mass-removal (compared with water flushing) than that exhibited for the relatively hydrophilic contaminants.     

DNAPL to LNAPL Transitions During Horizontal Cosolvent Flooding

Cosolvent flooding is a technology with the potential to remove nonaqueous phase liquid (NAPL) sources from the subsurface. It can be used to initiate separate phase mobilization, which allows removal of NAPL within very few pore volumes. Mobilization may result in a sinking DNAPL bank during horizontal flooding of NAPLs denser than water. Reversal of phase density difference between aqueous and DNAPL phases could potentially avoid this downward migration of mobilized DNAPLs. We achieved phase density difference reversal and made DNAPLs float using two components in the cosolvent flooding solution. A low-density cosolvent partitions preferentially into the DNAPL and swells it, which causes a reduction in density of the DNAPL and reversal of the density difference between the NAPL and aqueous phases. A highdensity additive that remains in the aqueous phase allows the cosolvent flooding solution overall to have a density greater than that of water and permits control of the flooding instability. This study focused on tert-butanol as the swelling cosolvent and tetrachloroethylene as the contaminant. In batch tests with sucrose and glycerol as dense additives, phase density difference reversal occurred. To investigate the applicability of phase density difference reversal as a remediation technology, horizontal column and sandbox experiments were performed. These experiments demonstrated the occurrence of phase density difference reversal and effective remediation in horizontal cosolvent floods.     

Effects of In Situ Remediation Using Oxidants or Surfactants on Subsurface Organic Matter and Sorption of Trichloroethene

In situ remediation technologies have the potential to alter subsurface properties such as natural organic matter (NOM) content or character, which could affect the organic carbon‐water partitioning behavior of chlorinated organic solvents, including dense nonaqueous phase liquids (DNAPLs). Laboratory experiments were completed to determine the nature and extent of changes in the partitioning behavior of trichloroethene (TCE) caused by in situ chemical oxidation or in situ surfactant flushing. Sandy porous media were obtained from the subsurface at a site in Orlando, Florida. Experiments were run using soil slurries in zero‐headspace reactors (ZHRs) following a factorial design to study the effects of porous media properties (sand vs. loamy sand with different total organic carbon [TOC] contents), TCE concentration (DNAPL presence or absence), and remediation agent type (potassium permanganate vs. activated sodium persulfate, Dowfax 8390 vs. Tween 80). Results revealed that the fraction of organic carbon (f_oc) of porous media after treatment by oxidants or surfactants was higher or lower relative to that in the untreated media controls. Isotherm experiments were run using the treated and control media to measure the distribution coefficient (K_d) of TCE. Organic carbon‐water partitioning coefficient values (K_oc) calculated from the experimental data revealed that K_oc values for TCE in the porous media were altered via treatment using oxidants and surfactants. This alteration can affect the validity of estimates of contaminant mass remaining after remediation. Thus, potential changes in partitioning behavior should be considered to help avoid decision errors when judging the effectiveness of an in situ remediation technology.     

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.     

Partition coefficients for alcohol tracers between nonaqueous-phase liquids and water from UNIFAC-solubility method

In this work, we have applied a group-contribution activity-coefficient model, UNIFAC, and the solubility of alcohols in water to estimate partition coefficients for alcohol tracers between water and nonaqueous-phase liquids (NAPLs). The effects of temperature and mutual solubility between NAPL and aqueous phases on the estimation of partition coefficients were also investigated. By comparing the estimated results with experimental partition coefficients for 30 alcohol tracers between 10 NAPLs and water, we found that: i) the UNIFAC-solubility method, in which the UNIFAC model in its infinite-dilution form is applied to the NAPL phase and the solubility of tracers in water is used for estimation of the activity coefficient in the aqueous phase, works better than the UNIFAC model; ii) a linear relation between the logarithm of partition coefficients and the logarithm of tracer solubility in water is observed for those tracers having a similar chemical structure (i.e. the same number of branched methyl groups). This can serve as a useful tool for quick selection of the tracers that exhibit the desired partition coefficients; iii) the effect of mutual solubility between NAPL and aqueous phases can be neglected because such miscibility is very small, usually of the order of 10⁻³ mole/mole unit; and iv) temperature variation between 15° and 25°C does not significantly affect partition coefficients.     

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.     

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.     

Visualization experiments of biodegradation in porous media and calculation of the biodegradation rate

Biodegradation in porous media is studied with carefully controlled and well-characterized experiments in model porous media constructed of etched glass. Porous media of this type allow visual observation of the phenomena that take place at pore scale. An aqueous solution of five organic pollutants (toluene, phenol, o-cresol, naphthalene and 1,2,3-trimethylbenzene) was used as a model NAPL (representing creosote). The bacteria used were Pseudomonas fluorescens, which are indigenous (even predominant) in many contaminated soils. The maximum aqueous concentrations of the specific organic substances, below which biodegradation becomes possible, were determined as a function of temperature from toxicity experiments. Visualization experiments were made under various flow velocities and organic loadings to study the morphology and thickness of the biofilm as a function of the pore size and the distance from the entrance, and the efficiency of biodegradation. The efficiency of biodegradation decreased as the aqueous concentration of NAPL at the inlet increased and/or as the flow velocity increased. The thickness of biofilm decreased as the distance from the inlet increased and/or the pore diameter decreased. A quasi-steady-state theoretical model of biodegradation was used to calculate the values of the mesoscopic biochemical rates and to predict the profile of NAPL concentration in the porous medium and the thickness of biofilm in pores. The agreement between experimental data and model predictions is quite satisfactory.     

Multiple Well-Shutdown Tests and Site-Scale Flow Simulation in Fractured Rocks

A new method was developed for conducting aquifer tests in fractured-rock flow systems that have a pump-and-treat (P&T) operation for containing and removing groundwater contaminants. The method involves temporary shutdown of individual pumps in wells of the P&T system. Conducting aquifer tests in this manner has several advantages, including (1) no additional contaminated water is withdrawn, and (2) hydraulic containment of contaminants remains largely intact because pumping continues at most wells. The well-shutdown test method was applied at the former Naval Air Warfare Center (NAWC), West Trenton, New Jersey, where a P&T operation is designed to contain and remove trichloroethene and its daughter products in the dipping fractured sedimentary rocks underlying the site. The detailed site-scale subsurface geologic stratigraphy, a three-dimensional MODFLOW model, and inverse methods in UCODE_2005 were used to analyze the shutdown tests. In the model, a deterministic method was used for representing the highly heterogeneous hydraulic conductivity distribution and simulations were conducted using an equivalent porous media method. This approach was very successful for simulating the shutdown tests, contrary to a common perception that flow in fractured rocks must be simulated using a stochastic or discrete fracture representation of heterogeneity. Use of inverse methods to simultaneously calibrate the model to the multiple shutdown tests was integral to the effectiveness of the approach.     

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.     

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.     

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.     

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.