Dissolution of residual non-aqueous phase liquids in porous media: pore-scale mechanisms and mass transfer rates

Experiments designed to elucidate the pore-scale mechanisms of the dissolution of a residual non-aqueous phase liquid (NAPL), trapped in the form of ganglia within a porous medium, are discussed. These experiments were conducted using transparent glass micromodels with controlled pore geometry, so that the evolution of the size and shape of individual NAPL ganglia and, hence, the pore-scale mass transfer rates and mass transfer coefficients could be determined by image analysis. The micromodel design permitted reasonably accurate control of the pore water velocity, so that the mass transfer coefficients could be correlated in terms of a local (pore-scale) Peclet number. A simple mathematical model, incorporating convection and diffusion in a slit geometry was developed and used successfully to predict the observed mass transfer rates. For the case of non-wetting NAPL ganglia, water flow through the corners in the pore walls was seen to control the rate of NAPL dissolution, as recently postulated by Dillard and Blunt [Water Resour. Res. 36 (2000) 439–454]. Break-up of doublet non-wetting phase ganglia into singlet ganglia by snap-off in pore throats was also observed, confirming the interplay between capillarity and mass transfer. Additionally, the effect of wettability on dissolution mass transfer was demonstrated. Under conditions of preferential NAPL wettability, mass transfer from NAPL films covering the solid surfaces was seen to control the dissolution process. Supply of NAPL from the trapped ganglia to these films by capillary flow along pore corners was observed to result in a sequence of pore drainage events that increase the interfacial area for mass transfer. These observations provide new experimental evidence for the role of capillarity, wettability and corner flow on NAPL ganglia dissolution.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

An analytical solution to multi-component NAPL dissolution equations

This note presents a novel method for determining the changing composition of a multi-component NAPL body dissolving into moving groundwater, and the consequent changes in the aqueous phase solute concentrations in the surrounding pore water. A canonical system of coupled non-linear governing equations is derived which is suitable for representation of both pooled and residual configurations, and this is solved. Whereas previous authors have handled such problems numerically, it is shown that these governing equations succumb to analytical solution. By a suitable substitution, the equations become decoupled, and the problem collapses to a single first-order equation. The final result is expressed implicitly, with time as a function of the number of moles of the least soluble component, m₁. The number of moles of each other component is expressed explicitly in terms of m₁. It is shown that the time-m₁ relationship has a well behaved inverse. An example is given in which the analytic solution is verified against traditional finite difference analysis, and its computational efficiency is shown.     

Petroleum NAPL Depletion Estimates and Selection of Marker Constituents from Compositional Analysis

Spills and releases of hydrocarbons may result in zones of nonaqueous phase liquids (NAPL) within soils and groundwater. The NAPL will change, or “weather” over time due to a range of physical, chemical, and biological processes. Hydrocarbon constituents in environmental samples collected from NAPL-impacted groundwater wells, sediments, or soils vary in composition over time due to weathering. The changing composition can be used to estimate mass depletion rates and trends for the bulk NAPL and for individual constituent chemicals relative to marker constituents which are less susceptible to weathering. Methods for the selection of marker constituents and for quantitatively and conservatively estimating NAPL depletion rates and trends over time are shown. Estimates are included for two sites with different NAPL mixtures present (crude oil and gasoline/diesel-range product), for which depletion of half the initial total NAPL is estimated at 13.6 ± 2.9 years and 7.3 ± 1.8 years respectively, and with no active NAPL remediation at either site. Similar methods for oil or NAPL depletion estimates have often relied on a prior-identified suite of presumed-conserved marker constituents. The method presented here includes steps which identify the best set of analyzed candidate marker constituents in a NAPL mixture. This can confirm prior-selected markers but is particularly useful for NAPL mixtures in which no prior-identified marker constituents are present.     

Analytical Model for Removal of a Uniformly Distributed Single-Component NAPL Under Nonequilibrium Conditions

In this paper a simple analytical model is presented for the one-dimensional transport equation describing the removal of a uniformly distributed, single-component NAPL under nonequilibrium conditions. Both advective and dispersive transport are included in the model. The model describes two distinct stages: a solution for the time the amount of NAPL declines but the length of the NAPL-containing region remains constant, and a solution from the moment the front, behind which all NAPL is depleted, starts to move. The model is valid for both dissolution (i.e., by water) or volatilization (i.e., by air). Dissolution (or volatilization) is considered a firstorder rate process with a constant mass-transfer rate coefficient. As expected, the model approaches the solution for equilibrium conditions if the mass-transfer coefficient tends to infinity. Even though the model is based on some rigorous assumptions, the simplicity of the model makes it useful for obtaining an initial mass-transfer rate coefficient from experimental data, which can be used to estimate the time required to dissolve all NAPL, as shown for two data sets taken from the literature.     

Numerical simulation of gas venting for NAPL site remediation

A control volume, finite element method is used to discretize the three phase, three component equations for simulation of gas venting. The discrete equations are solved using full Newton iteration. Any combinations of phases can exist, and variable substitution is used to take into account phase appearance and disappearance. Some example computations are presented for two dimensional axisymmetric geometry. Several different scenarios for gas venting are examined. High rate air injection can be effective at removing NAPL both in the unsaturated and saturated zones. The numerical techniques can handle problems having node pore volume gas throughputs (in a timestep) of the order of 10⁶, which greatly exceeds the maximum stable explicit timestep size.     

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.     

A multiphase flow and multispecies reactive transport model for DNAPL-involved Compound Specific Isotope Analysis

This study presents a multiphase flow and multispecies reactive transport model for the simultaneous simulation of NAPL and groundwater flow, dissolution, and reactive transport with isotope fractionation, which can be used for better interpretation of NAPL-involved Compound Specific Isotope Analysis in 3D heterogeneous hydrogeologic systems. The model was verified for NAPL-aqueous phase equilibrium partitioning, aqueous phase multi-chain and multi-component reactive transport, and aqueous phase multi-component transport with isotope fractionation. Several illustrative examples are presented to investigate the effect of DNAPL spill rates, degradation rate constants, and enrichment factors on the temporal and spatial distribution of the isotope signatures of chlorinated aliphatic hydrocarbon groundwater plumes. The results clearly indicate that isotope signatures can be significantly different when considering multiphase flow within the source zone. A series of simulations indicate that degradation and isotope enrichment compete with dissolution to determine the isotope signatures in the source zone: isotope ratios remain the same as those of the source if dissolution dominates the reaction, while heavy isotopes are enriched in reactants along groundwater plume flow paths when degradation becomes dominant. It is also shown that NAPL composition can change from that of the injected source due to the partitioning of components between the aqueous and NAPL phases even when degradation is not allowed in NAPL phase. The three-dimensional simulation is presented to mechanistically illustrate the complexities in determining and interpreting the isotopic signatures with evolving DNAPL source architecture.     

Remediation of NAPL source zones: lessons learned from field studies at Hill and Dover AFB

Innovative remediation studies were conducted between 1994 and 2004 at sites contaminated by nonaqueous phase liquids (NAPLs) at Hill and Dover AFB, and included technologies that mobilize, solubilize, and volatilize NAPL: air sparging (AS), surfactant flushing, cosolvent flooding, and flushing with a complexing-sugar solution. The experiments proved that aggressive remedial efforts tailored to the contaminant can remove more than 90% of the NAPL-phase contaminant mass. Site-characterization methods were tested as part of these field efforts, including partitioning tracer tests, biotracer tests, and mass-flux measurements. A significant reduction in the groundwater contaminant mass flux was achieved despite incomplete removal of the source. The effectiveness of soil, groundwater, and tracer based characterization methods may be site and technology specific. Employing multiple methods can improve characterization. The studies elucidated the importance of small-scale heterogeneities on remediation effectiveness, and fomented research on enhanced-delivery methods. Most contaminant removal occurs in hydraulically accessible zones, and complete removal is limited by contaminant mass stored in inaccessible zones. These studies illustrated the importance of understanding the fluid dynamics and interfacial behavior of injected fluids on remediation design and implementation. The importance of understanding the dynamics of NAPL-mixture dissolution and removal was highlighted. The results from these studies helped researchers better understand what processes and scales are most important to include in mathematical models used for design and data analysis. Finally, the work at these sites emphasized the importance and feasibility of recycling and reusing chemical agents, and enabled the implementation and success of follow-on full-scale efforts.