Nonaqueous Phase Liquid Dissolution Research Articles

Convergence of DNAPL Source Strength Functions with Site Age

Dissolution of dense nonaqueous phase liquid (DNAPL) source zones can be accurately predicted based on appropriate characterization of the source zone architecture, which controls the rate of mass discharge or source strength function. However, the architecture changes temporally as the source zone mass is depleted by dissolution. To generalize comparisons between contaminated sites with different porewater velocities or contaminant solubilities, site age is defined in terms of the fraction of contaminant mass that has been eluted from the source zone by aqueous dissolution. Here changes in DNAPL architecture during dissolution of a source zone were measured by light transmission visualization in laboratory flow chambers. Architectures measured at ages corresponding to initial conditions, 20, 50, and 90% mass removal were used in an equilibrium streamtube (EST) model to accurately predict subsequent dissolution. It is shown both experimentally and theoretically that as DNAPL contaminated sites age, fractional reductions in contaminant discharge and mass converge to become equal, regardless of the initial architecture. This behavior is a consequence of convergence from log-normal to exponential behavior. Analysis of errors in dissolution predictions suggests that the age of many contaminated sites is likely sufficient that architecture and source strength function characterization may not be necessary as it can be assumed with reasonable accuracy that future dissolution will follow an exponential decay model.

Variations in expression of carbon isotope fractionation of chlorinated ethenes during biologically enhanced PCE dissolution close to a source zone

The stable carbon isotope values of tetrachloroethene (PCE) and its degradation products were monitored during studies of biologically enhanced dissolution of PCE dense nonaqueous phase liquid (DNAPL) to determine the effect of PCE dissolution on observed isotope values. The degradation of PCE was monitored in a 2-dimensional model aquifer and in a pilot test cell (PTC) at Dover Air Force Base, both with emplaced PCE DNAPL sources. Within the plume down gradient from the source, the isotopic fractionation of dissolved PCE and its degradation products were consistent with those observed in biodegradation laboratory studies. However, close to the source zone significant shifts in the isotope values of dissolved PCE were not observed in either the model aquifer or PTC due to the constant input of newly dissolved, non fractionated PCE, and the small isotopic fractionation associated with PCE reductive dechlorination by the mixed microbial culture used. Therefore the identification of reductive dechlorination in the presence of PCE DNAPL was based upon the appearance of daughter products and the isotope values of those daughter products. An isotope model was developed to simulate isotope values of PCE during the dissolution and degradation of PCE adjacent to a DNAPL source zone. With the exception of very high degradation rate constants (>1/day) stable carbon isotope values of PCE estimated by the model remained within error of the isotope value of the PCE DNAPL, consistent with measured isotope values in the model aquifer and in the PTC.

Enhanced Dissolution of Trichloroethene: Effect of Carbohydrate Addition and Fermentation Processes

Remediation of source areas is challenging because lingering contaminants are often present as nonaqueous phase liquid (NAPL) and sorbed mass, and therefore difficult to remove via biodegradation or other commonly used remedial methods. Experimental results indicate that enhanced dissolution of a model NAPL, trichloroethene (TCE), can occur through the addition and/or subsequent fermentation of a dilute molasses solution. Enhanced mass transfer occurs by two mechanisms, depending upon whether the molasses solution is fresh or has fermented. The addition of fresh molasses worked to increase TCE solubility (>200%), thereby increasing mass transfer from the NAPL phase. Mixing TCE NAPL with a fermented molasses solution, however, increased TCE mass flux via the formation of a NAPL/aqueous phase emulsion. In addition, fermented liquid may have also decreased the soil partitioning coefficient (Kd) of TCE, indicating that enhanced transfer of sorbed mass to the aqueous phase could also occur in the presence of fermented molasses. These results provide guidance on how remedial systems may be optimized to increase NAPL and sorbed-mass dissolution and are therefore important, particularly when bioremediation is used to polish residual source zones.

Interphase mass transfer in variable aperture fractures: Controlling parameters and proposed constitutive relationships

Interphase mass transfer in variable aperture fractures occurs in many problems where two immiscible fluids are present, such as dissolution of dense nonaqueous phase liquids into groundwater, dissolution of CO2 in deep saline aquifers, and evaporation of trapped water by flowing gas during natural gas production. Typically, one fluid is entrapped by capillary forces and resides in immobilized regions whose distribution and geometry are controlled by the relative influence of capillary, gravitational, and viscous forces within the fracture. For the case of fractures bounded by a low porosity/permeability matrix, interphase mass transfer occurs predominantly owing to diffusive/advective transport from the entrapped phase interface into the phase flowing through the fracture. We explore the relative influence of the initial entrapped phase geometry and mean flowing phase velocities on the dissolution of the entrapped phase. Our systematic simulations use a percolation‐based model of phase invasion and depth‐averaged models of flow, transport, and mass transfer. The invasion model provides a physically based distribution of entrapped phase within the fracture and the mass transfer model implicitly calculates interphase mass transfer from discrete regions of entrapped phase without the need for empirical mass transfer relationships. Results demonstrate behavior across a wide range of initial entrapped phase distributions, with entrapped phase saturations ranging from zero to near the percolation threshold. Interfacial area evolves with a near‐linear dependence on entrapped phase saturation during dissolution in each simulation, and fracture‐scale intrinsic mass transfer rate coefficients exhibit a nonlinear dependence on Peclet number and a negligible dependence on entrapped phase saturation. These observations provide a basis for the development of constitutive relationships that quantify interphase mass transfer in variable aperture fractures as a function of entrapped phase saturation and flow rate; coarse‐grid dissolution simulations using these constitutive relationships demonstrate good agreement with results from the high‐resolution mechanistic simulations.

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

AbstractNeat 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.

Spatial and Temporal Distributions of Geobacter lovleyi and Dehalococcoides spp. during Bioenhanced PCE-NAPL Dissolution

The spatial and temporal distributions of multiple reductively dechlorinating bacteria were simultaneously assessed in a one-dimensional sand column containing a tetrachloroethene (PCE) nonaqueous phase liquid (NAPL) source and associated plume zones. The column was uniformly inoculated with a PCE-to-ethene dechlorinating microbial consortium that contained Dehalococcoides spp., Dehalobacter spp., and Geobacter lovleyi strain SZ. Geobacter and Dehalococcoides populations grew and colonized the column material, including the mixed-NAPL (0.25 mol/mol PCE in hexadecane) source zone. In contrast, Dehalobacter cells did not colonize the porous column material, and planktonic Dehalobacter cell titers remained below the detection limit of ca. 2.6 x 10(2) cells/mL throughout the experiment. Significant PCE dechlorination was observed and resulted in bioenhanced NAPL dissolution up to 21-fold (maximum) and 5.2-fold (cumulative) relative to abiotic dissolution. cis-1,2-Dichloroethene (cis-DCE) wasthe primary dechlorination product although vinyl chloride (VC) was also formed throughout the experiment. Ethene production occurred after significant depletion of PCE from the NAPL and when cis-DCE concentrations dropped below 6 microM. Data obtained after increasing the column residence time from 1.1 to 2.8 days and introducing a VC pulse to the column indicated that both the residence time and cis-DCE inhibition limited significant VC and ethene production. Although both Geobacter and Dehalococcoides cells were present and active in the mixed-NAPL source zone and plume region, Geobacter cell numbers were typically more than 1 order of magnitude higher than Dehalococcoides cell numbers, which is consistent with the production of predominantly cis-DCE. Analysis of both liquid- and solid-phase samples indicated that Geobacter cells grew and remained attached to the porous medium within the source zone but were largely planktonic in the plume region. In contrast Dehalococcoides cell were attached throughoutthecolumn,and Dehalococcoides cell titers increased by 1 to 2 orders of magnitude over the length of the column, correlating to increases in VC concentrations. The results from this study highlight that bioenhanced dissolution is governed by a complex interplay between resident dechlorinators, contaminant concentrations, and other aquifer-specific characteristics (e.g., hydrology).

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.

Predicting dense nonaqueous phase liquid dissolution using a simplified source depletion model parameterized with partitioning tracers

Simulations of nonpartitioning and partitioning tracer tests were used to parameterize the equilibrium stream tube model (ESM) that predicts the dissolution dynamics of dense nonaqueous phase liquids (DNAPLs) as a function of the Lagrangian properties of DNAPL source zones. Lagrangian, or stream‐tube‐based, approaches characterize source zones with as few as two trajectory‐integrated parameters, in contrast to the potentially thousands of parameters required to describe the point‐by‐point variability in permeability and DNAPL in traditional Eulerian modeling approaches. The spill and subsequent dissolution of DNAPLs were simulated in two‐dimensional domains having different hydrologic characteristics (variance of the log conductivity field = 0.2, 1, and 3) using the multiphase flow and transport simulator UTCHEM. Nonpartitioning and partitioning tracers were used to characterize the Lagrangian properties (travel time and trajectory‐integrated DNAPL content statistics) of DNAPL source zones, which were in turn shown to be sufficient for accurate prediction of source dissolution behavior using the ESM throughout the relatively broad range of hydraulic conductivity variances tested here. The results were found to be relatively insensitive to travel time variability, suggesting that dissolution could be accurately predicted even if the travel time variance was only coarsely estimated. Estimation of the ESM parameters was also demonstrated using an approximate technique based on Eulerian data in the absence of tracer data; however, determining the minimum amount of such data required remains for future work. Finally, the stream tube model was shown to be a more unique predictor of dissolution behavior than approaches based on the ganglia‐to‐pool model for source zone characterization.

Evaluation of simplified mass transfer models to simulate the impacts of source zone architecture on nonaqueous phase liquid dissolution in heterogeneous porous media

Nonaqueous phase liquid (NAPL) dissolution was studied in three-dimensional (3D) heterogeneous experimental aquifers (25.5 cm × 9 cm × 8.5 cm) with two different longitudinal correlation lengths (2.1 cm and 1.1 cm) and initial spill volumes (22.5 ml and 10.5 ml). Spatial and temporal distributions of NAPL during dissolution were measured using magnetic resonance imaging (MRI). At high NAPL spill volume, average effluent concentrations initially increased during dissolution, as NAPL pools transitioned to NAPL ganglia, and then decreased as the total NAPL–water interfacial area decreased over time. Experimental results were used to test six dissolution models: (i and ii) a one-dimensional (1D) model using either specific NAPL–water interfacial area values estimated from MR images at each time step (i.e., 1D quasi-steady state model), or an empirical mass transfer ( Sh′) correlation (i.e., 1D transient model), (iii and iv) a multiple analytical source superposition technique (MASST) using either the NAPL distribution determined from MR images at each time step (i.e., MASST steady state model), or the NAPL distribution determined from mass balance calculations (i.e., MASST transient model), (v) an equilibrium streamtube model, and (vi) a 3D grid-scale pool dissolution model (PDM) with a dispersive mass flux term. The 1D quasi-steady state model and 3D PDM captured effluent concentration values most closely, including some concentration fluctuations due to changes in the extent of flow reduction. The 1D transient, MASST steady state and transient, and streamtube models all showed a monotonic decrease in effluent concentration values over time, and the streamtube model was the most computationally efficient. Changes during dissolution of the effective NAPL–water interfacial area estimated from imaging data are similar to changes in effluent concentration values. The 1D steady state model incorporates estimates of the effective NAPL–water interfacial area directly at each time point; the 3D PDM does so indirectly through mass balance and a relative permeability function, which causes reduced water flow through high saturation NAPL regions. Hence, when model accuracy is required, the results indicate that a surrogate of this effective interfacial area is required. Approaches to include this surrogate in the MASST and streamtube models are recommended.

Microbial activity and distribution during enhanced contaminant dissolution from a NAPL source zone

Laboratory experiments were conducted to assess microbial reductive dechlorination in one-dimensional sand columns containing a 10 cm long source zone of uniformly distributed residual tetrachloroethene (PCE) nonaqueous phase liquid (NAPL), a 10 cm long transition zone directly down-gradient of the source zone containing some nonuniformly distributed NAPL ganglia, and a 40 cm long plume region down-gradient of the transition zone. The activity and distribution of S ulfurospirillum multivorans, a PCE-to-1,2- cis-dichloroethene ( cis-DCE) dechlorinating bacterium, was evaluated in columns containing either a mixed-NAPL (0.25 mol/mol PCE in hexadecane) or pure PCE-NAPL. Significant dechlorination of PCE to cis-DCE was observed in the mixed-NAPL column, resulting in 53% PCE-NAPL mass recovery in the effluent with PCE-NAPL dissolution enhanced by up to 13.6-fold (maximum) and 4.6-fold (cumulative) relative to abiotic dissolution. Quantitative real-time PCR targeting pceA, the PCE reductive dehalogenase gene of S. multivorans, revealed that S. multivorans cells were present in the NAPL source zone, and increased in numbers (i.e., grew) throughout the source and transition zones. In contrast, minimal reductive dechlorination and microbial growth were observed in the column containing pure PCE-NAPL, where aqueous-phase PCE concentrations reached saturation. These results demonstrate that microbial growth within NAPL source zones is possible, provided that contaminant concentrations remain below levels toxic to the dechlorinating organisms, and that microbial growth can result in significant bioenhanced NAPL dissolution.

Modelling dissolution of multi-component non-aqueous phase liquids using Pareto distributions

A distributed-site non-aqueous phase liquid (NAPL) dissolution model that can capture the physical process of dissolution is presented. The model uses a Pareto distribution of effective interfacial area and a correlation for the mass transfer. Model parameters are obtained using a formal constrained non-linear optimisation technique. The model is applied on effluent data from two soil column experiments. The results of the Pareto distributed site model, with only two parameters to fit, were compared to two-site and multi-site models as well as the beta distributed-site model. The Pareto distributed-site model produces equal or smaller error estimates than the other models.

The influence of precipitate formation on the chemical oxidation of TCE DNAPL with potassium permanganate

A three-dimensional two-phase flow model is coupled to a non-linear reactive transport model to study the efficacy of potassium permanganate treatment on dense, non-aqueous phase liquid (DNAPL) source removal in porous media. A linear relationship between the soil permeability ( k) and concentration of manganese dioxide precipitate ([MnO 2(s)]), k = k o + S rind [MnO 2(s)], is utilized to simulate nodal permeability reductions due to precipitate formation. Using published experimental column studies, an S rind = −5.5 × 10 −16 m 2 L/mg was determined for trichloroethylene (TCE) DNAPL. This S rind was then applied to treatment simulations on three-dimensional TCE DNAPL source zones comprising either DNAPL at residual saturations, or DNAPL at pooled saturations. DNAPL dissolution without oxidation treatment, simulated using equilibrium and the Nambi and Powers [Nambi I, Powers S. Mass transfer correlations for non-aqueous phase liquid dissolution from regions with high initial saturations. Water Resour Res 2003;39(2):1–11, SBH 4] mass transfer expression, required 31 and 36 years, respectively, to eliminate the residual source zone. For equilibrium dissolution with continuous treatment and no precipitate influence ( S rind = 0 m 2 L/mg), the residual source zone was removed after 11 years. However, when considering the precipitate influence (i.e., S rind = −5.5 × 10 −16 m 2 L/mg), 21 years of treatment were necessary to remove the DNAPL. When considering pulse treatments of 1 and 2 years duration followed by only dissolution, approximately 36 and 38 years, respectively, were required before the source zone was depleted, suggesting that there is no benefit to pulse treatment. Similar trends were observed when allowing 10 years of dissolution prior to treatment initiation. The treatment behaviour of the pooled TCE source, while slightly more efficient than the residual saturation source, was similar. Based on simulation findings, the precipitate (rind) formation significantly influences DNAPL treatment with permanganate; the most significant reductions in efficacy were observed for single pulse treatments (of 1 and 2 years), which exhibited times to source depletion similar to the case of dissolution without treatment.

Concentration Rebound Following In Situ Chemical Oxidation in Fractured Clay

A two-dimensional, transient-flow, and transport numerical model was developed to simulate in situ chemical oxidation (ISCO) of trichloroethylene and tetrachloroethylene by potassium permanganate in fractured clay. This computer model incorporates dense, nonaqueous phase liquid dissolution, reactive aquifer material, multispecies matrix diffusion, and kinetic formulations for the oxidation reactions. A sensitivity analysis for two types of parameters, hydrogeological and engineering, including matrix porosity, matrix organic carbon, fracture aperture, potassium permanganate dosage, and hydraulic gradient, was conducted. Remediation metrics investigated were the relative rebound concentrations arising from back diffusion and percent mass destroyed. No well-defined correlation was found between the magnitude of rebound concentrations during postremedy monitoring and the amount of contaminant mass destroyed during the application. Results indicate that all investigated parameters affect ISCO remediation in some form. Results indicate that when advective transport through the fracture is dominant relative to diffusive transport into the clay matrix (large System Peclet Number), permanganate is more likely to be flushed out of the system and treatment is not optimal. If the System Peclet Number is too small, indicating that diffusion into the matrix is dominant relative to advection through the fracture, permanganate does not traverse the entire fracture, leading to postremediation concentration rebound. Optimal application of ISCO requires balancing advective transport through the fracture with diffusive transport into the clay matrix.

Nonaqueous‐Phase Liquid Infiltration and Immobilization in Heterogeneous Media: 2. Application to Stochastically Heterogeneous Formations

We performed a series of well‐controlled laboratory experiments investigating the infiltration and subsequent immobilization of nonaqueous‐phase liquid (NAPL) in saturated heterogeneous media. A system of two distinct aquifer zones separated by a dipping interface was considered. Heterogeneity was represented by a spatially correlated random field with known geostatistical parameters in one zone in combination with a homogenous packing of the other zone. The effects of heterogeneity on NAPL flow and entrapment in each of the two zones were investigated. The time‐varying NAPL saturations were continuously monitored in space and the final static entrapment–saturation distribution was accurately measured. The immobilized‐NAPL distribution contributes to plume generation from source zones. The results show that capillary barriers produced by the small‐scale heterogeneity strongly influenced the migration paths and the final distribution of NAPL both in space and across different saturation ranges. The NAPL was immobilized both by snap‐off to discontinuous blobs and ganglia and by capillary barriers at textural interfaces. Heterogeneity generally increased entrapment, because spatial variations in capillary properties caused NAPL to be entrapped at higher saturations. Heterogeneity in the finer formation provided points of entry into this formation where the NAPL subsequently could spread as the pressure built up. The NAPL was immobilized at high saturations because high displacement pressures in the fine materials inhibited flow at low saturations. The accessibility for water flow through NAPL occurrences and thereby also the dissolution of NAPL is limited by (i) high entrapped NAPL saturations that decrease the aqueous‐phase relative permeability and (ii) the location of NAPL inside a formation with low average permeability.

Characterization of NAPL Source Zone Architecture and Dissolution Kinetics in Heterogeneous Porous Media Using Magnetic Resonance Imaging

A direct visualization method using magnetic resonance imaging (MRI) was developed to characterize sand grain size distribution, nonaqueous phase liquid (NAPL) source zone architecture, and aqueous flowpaths in a three-dimensional (3-D) flowcell (26.5 cm x 10.5 cm x 10.5 cm) packed with a heterogeneous distribution of five different sand fractions. All images were acquired at a resolution of 0.1875 cm x 0.1875 cm x 0.225 cm. A 1H image of pore water resolved the heterogeneous permeability field; grain size differences as small as 0.1 mm could be distinguished. A time series of 1H images of water doped with the paramagnetic tracer MnCl2 were acquired and used to obtain voxel-scale breakthrough curves. Water preferentially flowed through coarse sands before NAPL release. After NAPL release, the flow bypassed NAPLzones, and bypassing was more evident for high NAPL saturation zones. A time series of 19F images of NAPL were acquired and used to determine voxel-scale NAPL saturation (Sn) during dissolution. Results show that 93% of NAPL mass was in the coarsest sand, most NAPL was trapped as pools and not as residual ganglia, NAPL saturation increased with depth, and the NAPL dissolution front moved vertically from the top to the bottom of the flowcell during the first 170 pore volumes of waterflushed. NAPL component effluent concentrations initially increased due to the development of flow in zones with decreasing NAPL saturation. Flowpath images suggest that this occurs as NAPL transitions from pools (Sn > 0.15) to residual ganglia. The results highlight the importance of flow bypassing and provide the opportunity to develop more accurate NAPL dissolution models.

Upscaling of mass transfer rate coefficient for the numerical simulation of dense nonaqueous phase liquid dissolution in heterogeneous aquifers

Mass transfer from entrapped dense nonaqueous phase liquids (DNAPLs) in heterogeneous aquifers takes place in natural, three‐dimensional groundwater flow fields. However, mass transfer processes are characterized in the laboratory in columns or flow cells under conditions of one‐dimensional or two‐dimensional water flow. Dissolution data generated in these test systems are used to determine empirical parameters of correlations that relate a dimensionless form of a mass transfer coefficient (Sherwood number) to other dimensionless groups that capture the basic processes contributing to mass transfer (e.g., Reynolds and Schmidt numbers). These phenomologically based empirical correlations, which are referred to as Gilland‐Sherwood models, are not directly applicable in predicting the dissolution of DNAPLs in the field as they do not capture the effects of aquifer heterogeneity and DNAPL entrapment morphology (referred to as DNAPL entrapment architecture). Numerical simulation of DNAPL dissolution requires the discretization of the problem domain into computational grid blocks and assignment of an effective mass transfer coefficient to each of these blocks containing DNAPL. A methodology for upscaling is needed to determine the grid‐scale effective mass transfer coefficient from the laboratory‐determined empirical correlations. It is our hypothesis that the upscaled effective mass transfer coefficient needs to contain information on the field‐scale heterogeneity and DNAPL entrapment architecture. This hypothesis was tested through a Monte‐Carlo‐based numerical experiment using a laboratory‐validated dissolution model with the goal of developing and testing an upscaling method. The developed upscaling method involves the use of geostatistical parameters that capture the aquifer heterogeneity and the DNAPL entrapment architecture. These parameters were determined to be the variance of log hydraulic conductivity, correlation lengths, and the normalized second moments of DNAPL mass distribution in the entrapment zone. Monte Carlo numerical simulation experiments combined with inverse modeling were used in this theoretical development and to determine parameters of the proposed upscaled Gilland‐Sherwood mass transfer correlation. Through these numerical modeling studies, the upscaled mass transfer correlation was successfully verified. Sensitivity analyses indicate that the normalized second moment, which describes the spreading of DNAPL mass in the vertical directions, was the most sensitive parameter in simulating the mass transfer at large scales.

Modelling of iron cycling and its impact on the electron balance at a petroleum hydrocarbon contaminated site in Hnevice, Czech Republic

Over a period of several decades multiple leaks of large volumes from storage facilities located near Hnevice (Czech Republic) have caused the underlying Quaternary aquifer to be severely contaminated with nonaqueous phase liquid (NAPL) petroleum hydrocarbons. Beginning in the late 1980's the NAPL plume started to shrink as a consequence of NAPL dissolution exceeding replenishment and due to active remediation. The subsurface was classified geochemically into four different zones, (i) a contaminant-free zone never occupied by NAPL or dissolved contaminants, (ii) a re-oxidation zone formerly occupied by NAPL, (iii) a zone currently occupied by NAPL, and (iv) a lower fringe zone between the overlying NAPL and the deeper underlying contaminant-free zone. The study investigated the spatial and temporal variability of the redox zonation at the Hnevice site and quantified the influence of iron-cycling on the overall electron balance. As a first step inverse geochemical modelling was carried out to identify possible reaction models and mass transfer processes. In a subsequent step, two-dimensional (forward) multi-component reactive transport modelling was performed to evaluate and quantify the major processes that control the geochemical evolution at the site. The study explains the observed enrichment of the lower fringe zone with ferrihydrite as a result of the re-oxidation of ferrous iron. It suggests that once the NAPL zone started to shrink the dissolution of previously formed siderite and FeS by oxygen and nitrate consumed a significant part of the oxidation capacity for a considerable time period and therefore limited the penetration of electron acceptors into the NAPL contaminated zone.

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.

Determination of NAPL−Water Interfacial Areas in Well-Characterized Porous Media

The nonaqueous-phase liquid (NAPL)-water interfacial area is an important parameter which influences the rate of NAPL dissolution in porous media. The aim of this study was to generate a set of baseline data for specific interfacial area for a two-phase-entrapped NAPL-water system in well-characterized porous media and subsequently use these data to evaluate two current theoretical models. The first model tested distributes entrapped NAPL over the pore classes based on Land's algorithm and assumes the resulting blobs to be spherical. The other model is thermodynamically based, assuming that reversible work done on the system results in an increase in interfacial area, such that the area between drainage and imbibition retention curves can be related to the interfacial area. Interfacial tracer tests (IFTT) were used to measure specific entrapped NAPL (hexadecane)-water interfacial areas in columns packed with four grades (12/20, 20/30, 30/40, 40/50) of silica sand. By use of the anionic surfactant dihexylsulfosuccinate (Aerosol MA80), IFTT gave specific interfacial areas between 58 cm(-1) for the finest sand and 16 cm(-1) for the coarsest, compared to values of between 33 and 7 cm(-1) for the first model and between 19 and 5 cm(-1) for the thermodynamic model. Results from the literature suggest that nonspherical blobs shapes occur relatively frequently; hence it is reasonable to suggest that the assumption of spherical NAPL blobs may explain the underprediction by the first model. The thermodynamic model underestimates the interfacial area because it assumes that entrapment occurs only within the largest pores. A modified version of the latter model, allowing entrapment across all pore classes, yielded values between 58 and 13 cm(-1). Of the models tested the modified thermodynamic model best predicts the interfacial area.

Étude expérimentale de la dispersion active d'un polluant hydrocarboné en milieu poreux hétérogène

This study deals with Non Aqueous Phase Liquid (NAPL) dissolution in subsurface water in order to predict the pollutant plume development and to optimize remediation processes. An experimental study of NAPL dissolution in porous media is presented. Local water saturation and effluent pollutant concentration measurements are presented for several kinds of porous media. Experimental results show clearly the influence of microscopic and/or macroscopic heterogeneities of the porous media and the distribution of the pollutant on the active dispersion of the NAPL. The NAPL dissolution occurs in several steps which highlights the existence of non-local equilibrium related to the heterogeneity of the porous media. To cite this article: A. Yra et al., C. R. Mecanique 334 (2006).