Hydraulic displacement of dense nonaqueous phase liquids for source zone stabilization

Hydraulic displacement is a mass removal technology suitable for stabilization of a dense, nonaqueous phase liquid (DNAPL) source zone, where stabilization is defined as reducing DNAPL saturations and reducing the risk of future pool mobilization. High resolution three-dimensional multiphase flow simulations incorporating a spatially correlated, heterogeneous porous medium illustrate that hydraulic displacement results in an increase in the amount of residual DNAPL present, which in turn results in increased solute concentrations in groundwater, an increase in the rate of DNAPL dissolution, and an increase in the solute mass flux. A higher percentage of DNAPL recovery is associated with higher initial DNAPL release volumes, lower density DNAPLs, more heterogeneous porous media, and increased drawdown of groundwater at extraction wells. The fact that higher rates of recovery are associated with more heterogeneous porous media stems from the fact that larger contrasts in permeability provide for a higher proportion of capillary barriers upon which DNAPL pooling and lateral migration can occur. Across all scenarios evaluated in this study, the ganglia-to-pool (GTP) ratio generally increased from approximately 0.1 to between approximately 0.3 and 0.7 depending on the type of DNAPL, the degree of heterogeneity, and the imposed hydraulic gradient. The volume of DNAPL recovered as a result of implementing hydraulic displacement ranged from between 9.4% and 45.2% of the initial release volume, with the largest percentage recovery associated with 1,1,1 trichloroethane, the least dense of the three DNAPLs considered.     

Predicting DNAPL entrapment and recovery: the influence of hydraulic property correlation

The influence of aquifer property correlation on multiphase fluid migration, entrapment and recovery was explored by incorporating correlated and uncorrelated porosity, permeability, and capillary pressure-saturation (P_c-Sat) parameter fields in a cross-sectional numerical multiphase flow model. Comparison of two-dimensional entrapped organic saturation distributions for a simulated tetrachloroethylene (PCE) spill in ensembles of aquifer realizations suggests that the degree of spatial correlation in P_c-Sat parameters exerts a controlling influence on dense nonaqueous phase liquid (DNAPL) spreading and redistribution in saturated aquifers. The predicted evolution of DNAPL source zones and resultant remediation efficiency under surfactant enhanced aquifer remediation (SEAR) also appear to be strongly influenced by the spatial correlation of aquifer parameters and multiphase flow constitutive relationships. Results for a limited number of realizations selected from each ensemble showed that removal of 60% to 99% of entrapped PCE could reduce dissolved contaminant concentration and mass flux by approximately two orders of magnitude under natural gradient conditions. Aqueous phase contaminant mass flux did not vary uniformly as a function of % DNAPL removed, however, and notable differences in behavior were observed for models incorporating correlated versus uncorrelated P_c-Sat and permeability fields. Although these results must be confirmed through analysis of additional realizations, it is likely that similar or larger differences between correlated and uncorrelated system behavior will be observed in aquifers with greater spatially variability than that of the nonuniform, homogeneous sand aquifer studied here. Funding for this research was provided by the United States Environmental Protection Agency, Great Lakes and Mid-Atlantic Center for Hazardous Substance Research under Grant No. R-825540, the Michigan Department of Environmental Quality under Contract No. Y80011, and the Strategic Environmental Research and Development Program under Project No. CU-1293. The content of this publication does not necessarily represent the views of these agencies and has not been subject to agency review.     

Site-Specific Design for Dual Phase Recovery and Stabilization of Pooled DNAPL

Volume reduction and lowering of capillary pressure within a large DNAPL pool are utilized as objectives in the design of a large-scale dual phase recovery system at a chemical manufacturing facility in the United States. By reducing DNAPL pool height through mass removal, capillary pressure is lowered, resulting in a reduced potential for future vertical and horizontal mobilization of the chlorinated solvent DNAPL pool. The DNAPL pool extends over an approximately 200 m by 275 m area in low permeability fill deposits overlying a clay aquitard. A three-dimensional multiphase flow model was employed to arrive at a final design incorporating nine horizontal drains (total length 664 m) and a pulsed pumping system. The numerical model was calibrated to the results of a 42-day field pilot-test involving the removal of approximately 25,000 L of DNAPL from a single, 55 m long horizontal drain. Numerical simulation revealed that gravity drainage, as opposed to hydraulic gradients in the water phase, is the dominant recovery mechanism at this site. This stems from the relatively high density and the viscosity of the DNAPL, and the relatively low permeability of the formation deposits. The use of pulsed pumping is shown to reduce the volume of contaminated ground water recovered from the 9-drain system, without significant reduction of the total volume of DNAPL recovered.     

Transition probability/Markov chain analyses of DNAPL source zones and plumes

At sites where a dense nonaqueous phase liquid (DNAPL) was spilled or released into the subsurface, estimates of the mass of DNAPL contained in the subsurface from core or monitoring well data, either in the nonaqueous or aqueous phase, can be highly uncertain because of the erratic distribution of the DNAPL due to geologic heterogeneity. In this paper, a multiphase compositional model is applied to simulate, in detail, the DNAPL saturations and aqueous-phase plume migration in a highly characterized, heterogeneous glaciofluvial aquifer, the permeability and porosity data of which were collected by researchers at the University of Tübingen, Germany. The DNAPL saturation distribution and the aqueous-phase contaminant mole fractions are then reconstructed by sampling the data from the forward simulation results using two alternate approaches, each with different degrees of sampling conditioning. To reconstruct the DNAPL source zone architecture, the aqueous-phase plume configuration, and the contaminant mass in each phase, one method employs the novel transition probability/Markov chain approach (TP/MC), while the other involves a traditional variogram analysis of the sampled data followed by ordinary kriging. The TP/MC method is typically used for facies and/or hydraulic conductivity reconstruction, but here we explore the applicability of the TP/MC method for the reconstruction of DNAPL source zones and aqueous-phase plumes. The reconstructed geometry of the DNAPL source zone, the dissolved contaminant plume, and the estimated mass in each phase are compared using the two different geostatistical modeling approaches and for various degrees of data sampling from the results of the forward simulation. It is demonstrated that the TP/MC modeling technique is robust and accurate and is a preferable alternative compared to ordinary kriging for the reconstruction of DNAPL saturation patterns and dissolved-phase contaminant plumes.     

Experimental Study of the Effects of DNAPL Distribution on Mass Rebound

The release of stored dissolved contaminants from low permeability zones contributes to plume persistence beyond the time when dense nonaqueous phase liquid (DNAPL) has completely dissolved. This is fundamental to successfully meeting acceptable low concentrations in groundwater that are driven by site‐specific cleanup goals. The study goals were to assess the role of DNAPL entrapment morphology on mass storage and plume longevity. As controlled field studies are not feasible, two‐dimensional (2D) test tanks were used to quantify the significance of mass loading processes from source dissolution and stored mass rebound. A simple two‐layer soil domain representing a high permeable formation sand overlying a zone of lower permeability sand was used in the tests. DNAPL mass depletion through dissolution was monitored via X‐ray photon attenuation, and effluent samples were used to monitor the plume. These data enabled analysis of the DNAPL distribution, the dissolved plume, and the dissolved phase distribution within the low permeability layer. Tests in an intermediate tank showed that mass storage contributes substantially to plume longevity. Detectable effluent concentrations persisted long after DNAPL depletion. The small tank results indicated that the DNAPL morphology influenced the flow field and caused distinctive transport mechanisms contributing to mass storage. Zones of high DNAPL saturation at the interface between the low and high permeability layers exhibited flow bypassing and diffusion dominated transport into the low permeability layer. In the absence of a highly saturated DNAPL zone near the soil interface the contaminant penetrated deeper into the low permeability layer caused by a combination of advection and diffusion.     

Acoustic and electromagnetic properties of soils saturated with salt water and NAPL

Electrical, seismic, and electromagnetic methods can be used for noninvasive determination of subsurface physical and chemical properties. In particular, we consider the evaluation of water salinity and the detection of surface contaminants. Most of the relevant properties are represented by electric conductivity, P-wave velocity, and dielectric permittivity. Hence, it is important to obtain relationships between these measurable physical quantities and soil composition, saturation, and frequency. Conductivity in the geoelectric frequency range is obtained with Pride's model for a porous rock. (The model considers salinity and permeability.) White's model of patchy saturation is used to calculate the P-wave velocity and attenuation. Four cases are considered: light nonaqueous phase liquid (LNAPL) pockets in water, dense nonaqueous phase liquid (DNAPL) pockets in water, LNAPL pockets in air, and DNAPL pockets in air. The size of the pockets (or pools), with respect to the signal wavelength, is modeled by the theory. The electromagnetic properties in the GPR frequency range are obtained by using the Hanai–Bruggeman equation for two solids (sand and clay grains) and two fluids (LNAPL or DNAPL in water or air). The Hanai–Bruggeman exponent (1/3 for spherical particles) is used as a fitting parameter and evaluated for a sand/clay mixture saturated with water.Pride's model predicts increasing conductivity for increasing salinity and decreasing permeability. The best-fit exponent of the Hanai–Bruggeman equation for a sand/clay mixture saturated with water is 0.61, indicating that the shape of the grains has a significant influence on the electromagnetic properties. At radar frequencies, it is possible to distinguish between a water-saturated medium and a NAPL-saturated medium, but LNAPL- and DNAPL-saturated media have very similar electromagnetic properties. The type of contaminant can be better distinguished from the acoustic properties. P-wave velocity increases with frequency, and has dissimilar behaviour for wet and dry soils.     

Recovery of Coal Tar and Creosote from Porous Media: The Influence of Wettability

The recovery of coal tar or creosote, which are dense nonaqueous phase liquids (DNAPLs), from the subsurface has been used as a means of site remediation at several former manufactured-gas plant sites and wood-treating facilities. Surface-active components in these complex DNAPL can have acid/base and surfactant characteristics that can significantly affect the wettability in these systems, with a reversal to DNAPL wetting at low pHs. These changes in wettability as a function of pH were employed to evaluate their significance on waterflooding efficiency in one-dimensional soil columns. The use of pH as a means of controlling wettability resulted in identical density and viscosity properties between the water-and DNAPL-wet conditions. At some of the higher pHs, the interracial tension changed as well as the wettability. Maintaining a constant dimensionless capillary number was used to minimize the effect of this variable. DNAPL saturations remaining in the DNAPL-wet systems after waterflooding ranged from 38% to 47%. Significantly lower final DNAPL saturations were achieved for water-wetting systems (15% to 30%).     

油藏条件下孔隙岩样毛管和电学性质研究

本文系统总结了国内外关于油藏条件下岩石物理基础实验研究的成果、现状及发展方向。油藏条件主要是指油藏实际的温度、压力、毛管及电性平衡、饱和顺序和润湿性质等。实验研究及现场资料均表明，油藏条件和地面实际室条件下饱和流体孔隙岩样毛管及电学性质有很大差惜同藏条件下毛管及电学性质实际研究对准确评价油气储量及促进岩石物理学基础理论发展具有重要意义。     

Identifying the representative flow unit for capillary dominated two-phase flow in porous media using morphology-based pore-scale modeling

In this paper, we extend pore-morphology-based methods proposed by Hazlett (1995) and Hilpert and Miller (2001) to simulate drainage and imbibition in uniformly wetting porous media and add an (optional) entrapment of the (non-)wetting phase. By improving implementation, this method allows us to identify the statistical representative elementary volume and estimate uncertainty by computing fluid flow properties and saturation distributions of hundreds of subsamples within a reasonable time-frame. The method was utilized to study three different porous medium systems and results demonstrate that morphology-based pore-scale modeling is a viable approach to assess the representative elementary volume with respect to capillary dominated two-phase flow. The focus of this paper is the determination of the representative elementary volume for multiphase-flow properties for a digital representation of a rock.     

Investigation and Remediation of a 1,2–Dichloroethane Spill Part I: Short and Long-Term Remediation Strategies

Release of an estimated 150,000 gallons (568,000 L).of 1.2–dichloroethane (EDC) from a buried pipeline into a ditch and surrounding soil resulted in shallow subsurface contamination of a Gulf Coast site. Short-term remediation included removal of EDC DNAPI. (dense nonaqueous phase liquid) by dredging and vacuuming the ditch, and by dredging the river where the ditch discharged. EDC saturation in shallow impacted sediments located beneath the ditch was at or below residual saturation and these sediments were therefore left in place. The ditch was lined, backfilled, and capped. Long-term remediation includes EDC DNAPL recovery and hydraulic containment from the shallow zone with long-term monitoring of the shallow, intermediate, and deep (200 foot) aquifers. Ground water, DNAPL., and dissolved phase models were used to guide field investigations and the selection of an effective remedial action strategy. The DNAPL. modeling was conducted for a two-dimensional vertical cross section of the site, and included the three aquifers separated by two aquitards with microfractures. These aquitards were modeled using a dual porosity approach. Matrix and fracture properties of the aquitards used for DNAPL modeling were determined from small-scale laboratory properties. These properties were consistent with effective hydraulic conductivity determined from ground water flow modeling. A sensitivity analysis demonstrated that the vertical migration of EDC was attenuated by dissolution of EDC into the matrix of the upper aquitard. When the organic/water entry pressure of the aquitard matrix, or the solubility of EDC were decreased to unrealislically low values. EDC DNAPL. accumulated in the aquifer below the upper aquitard.
EDC DNALM, did not reach the regional (deepest) aquifer in any of the cases modeled. The limited extent of vertical EDC migration predicted is supported by ground water monitoring conducted over the four years since the spill.     

DNAPL accumulation in wells and DNAPL recovery from wells: Model development and application to a laboratory study

Dense nonaqueous phase liquid (DNAPL) accumulation and recovery from wells cannot be accurately modeled through typical pressure or flux boundary conditions due to gravity segregation of water and DNAPL in the wellbore, the effects of wellbore storage, and variations of wellbore inflow and outflow rates with depth, particularly in heterogeneous formations. A discrete wellbore formulation is presented for numerical modeling of DNAPL accumulation in observation wells and DNAPL removal from recovery wells. The formulation includes fluid segregation, changing water and DNAPL levels in the well and the corresponding changes in fluid storage in the wellbore. The method was added to a three-dimensional finite difference model (CompSim) for three phase (water, gas, DNAPL) flow. The model predictions are compared to three-dimensional pilot scale experiments of DNAPL (benzyl alcohol) infiltration, redistribution, recovery, and water flushing. Model predictions match experimental results well, indicating the appropriateness of the model formulation. Characterization of mixing in the extraction well is important for predicting removal of highly soluble organic compounds like benzyl alcohol. A sensitivity analysis shows that the incorporation of hysteresis is critical for accurate prediction. Among the multiphase flow and transport parameters required for modeling, results are most sensitive to soil intrinsic permeability.     

Field scale impacts of spatially correlated relative permeability in heterogeneous multiphase systems

Two-dimensional numerical simulations of two-phase (DNAPL-water) flow in spatially correlated random fields demonstrate the influence of nonwetting phase (NWP) relative permeability–saturation (k_r,N–S_W) relationships correlated to porous media intrinsic permeability (k). Both the volume of porous media invaded by the NWP and the length of time during which the NWP is migrating are under predicted if k_r,N–k correlation is not accounted for in the model formulation. Not accounting for the k_r,N–k correlation resulted in under predicting the volume of porous media invaded by up to approximately 10%, which is likely not significant for many practical applications. However, not accounting for the k_r,N–k correlation resulted in under predicting field scale migration times by up to a factor of 4, which is likely significant in that the migration times are on the order of years to several decades for the DNAPL (1,2-DCE) considered in this study. The under prediction of migration times was greater for lower permeability aquifers.     

Remedial Options for Creosote- Contaminated Sites

Free-phase DNAPL recovery operations are becoming increasingly prevalent at creosote-contaminated aquifer sites. This paper illustrates the potential of both classical and innovative recovery methods. The UTCHEM multiphase flow and transport numerical simulator was used to predict the migration of creosote DNAPL during a hypothetical spill event, during a long-term redistribution after the spill, and for a variety of subsequent free-phase DNAPL recovery operations. The physical parameters used for the DNAPL and the aquifer in the model are estimates for a specific creosote DNAPL site. Other simulations were also conducted using physical parameters that are typical of a trichloroethene (TCE) DNAPL. Dramatic differences in DNAPL migration were observed between these simulations.     

The effect of microporosity on transport properties in porous media

Sizeable amounts of connected microporosity with various origins can have a profound effect on important petrophysical properties of a porous medium such as (absolute/relative) permeability and capillary pressure relationships. We construct pore-throat networks that incorporate both intergranular porosity and microporosity. The latter originates from two separate mechanisms: partial dissolution of grains and pore fillings (e.g. clay). We then use the reconstructed network models to estimate the medium flow properties. In this work, we develop unique network construction algorithms and simulate capillary pressure–saturation and relative permeability–saturation curves for cases with inhomogeneous distributions of pores and micropores. Furthermore, we provide a modeling framework for variable amounts of cement and connectivity of the intergranular porosity and quantifying the conditions under which microporosity dominates transport properties. In the extreme case of a disconnected inter-granular network due to cementation a range of saturations within which neither fluid phase is capable of flowing emerges. To our knowledge, this is the first flexible pore scale model, from first principles, to successfully approach this behavior observed in tight reservoirs.     

Grid refinement for modeling multiphase flow in discretely fractured porous media

A study of the effects of grid discretization on the migration of DNAPL within a discrete-fracture network embedded in a porous rock matrix is presented. It is shown that an insufficiently fine discretization of the fracture elements can lead to an overprediction of the volume of DNAPL that continues to migrate vertically at the intersection of a vertical and horizontal fracture. Uniform discretization of elements at the scale of one centimetre (or less) accurately resolved the density and capillary pressure components of the head gradient in the DNAPL. An alternative, non-uniform method of discretization of elements within the discrete-fracture network is presented whereby only fracture elements immediately adjacent to fracture intersections are refined. To further limit the number of elements employed, the porous matrix elements adjacent to the fracture elements are not similarly refined. Results show this alternative method of discretization reduces the numerical error to an acceptable level, while allowing the simulation of field-scale DNAPL contamination problems. The results from two field-scale simulations of a DNAPL-contaminated carbonate bedrock site in Ontario, Canada are presented. These simulations compare different methods of grid discretization, and highlight the importance of grid refinement when simulating DNAPL migration problems in fractured porous media.     

Dissolution of nonaqueous phase liquid pools in anisotropic aquifers

A two-dimensional numerical transport model is developed to determine the effect of aquifer anisotropy and heterogeneity on mass transfer from a dense nonaqueous phase liquid (DNAPL) pool. The appropriate steady state groundwater flow equation is solved implicitly whereas the equation describing the transport of a sorbing contaminant in a confined aquifer is solved by the alternating direction implicit method. Statistical anisotropy in the aquifer is introduced by two-dimensional, random log-normal hydraulic conductivity field realizations with different directional correlation lengths. Model simulations indicate that DNAPL pool dissolution is enhanced by increasing the mean log-transformed hydraulic conductivity, groundwater flow velocity, and/or anisotropy ratio. The variance of the log-transformed hydraulic conductivity distribution is shown to be inversely proportional to the average mass transfer coefficient.     

Hierarchical simulator of biofilm growth and dynamics in granular porous materials

A new simulator is developed for the prediction of the rate and pattern of growth of biofilms in granular porous media. The biofilm is considered as a heterogeneous porous material that exhibits a hierarchy of length scales. An effective-medium model is used to calculate the local hydraulic permeability and diffusion coefficient in the biofilm, as functions of the local geometric and physicochemical properties. The Navier–Stokes equations and the Brinkman equation are solved numerically to determine the velocity and pressure fields within the pore space and the biofilm, respectively. Biofilm fragments become detached if they are exposed to shear stress higher than a critical value. The detached fragments re-enter into the fluid stream and move within the pore space until they exit from the system or become reattached to downstream grain or biofilm surfaces. A Lagrangian-type simulation is used to determine the trajectories of detached fragments. The spatiotemporal distributions of a carbon source, an electron acceptor and a cell-to-cell signaling molecule are determined from the numerical solution of the governing convection–diffusion–reaction equations. The simulator incorporates growth and apoptosis kinetics for the bacterial cells and production and lysis kinetics for the EPS. The specific growth rate of active bacterial cells depends on the local concentrations of nutrients, mechanical stresses, and a quorum sensing mechanism. Growth-induced deformation of the biofilms is implemented with a cellular automaton approach. In this work, the spatiotemporal evolution of biofilms in the pore space of a 2D granular medium is simulated under high flow rate and nutrient-rich conditions. Transient changes in the pore geometry caused by biofilm growth lead to the formation of preferential flowpaths within the granular porous medium. The decrease of permeability caused by clogging of the porous medium is calculated and is found to be in qualitative agreement with published experimental results.     

A physical–chemical model for the static water retention characteristic of unsaturated porous media

Water retention characteristic or water retention curve (WRC) is an important constitutive feature of porous media, and also meanwhile is an indispensable requirement in hydraulic transport modelling. Previous experiments have indicated that the specific surface area of porous media has effects on the WRC. It has also been observed that a linear relationship generally exists between the air–water interface area and the water saturation within unsaturated porous media. However it seems that no detailed study on their internal linkage with the WRC has been reported yet. This paper, at first gives a review of the development of WRC modelling, then it tries to explain the water retention characteristic according to the physical and chemical behaviours of the phases involved in unsaturated porous media. Using the traditional capillary theory, the volume averaging theorem and the advances in physical chemistry of interfacial surfaces, this paper then derives out a formula which represents the water retention characteristic of porous media. This formula demonstrates the internal linkage of the WRC to the specific surface area of porosities. It also shows agreements with the experimental observations mathematically. Based on this formula, a fitting model is proposed for the static WRC of porous media. Finally, this model is tested to fit the WRC measurements of a wide range of porous materials. Comparison with other main models is presented.     

Static and push-pull methods using radon-222 to characterize dense nonaqueous phase liquid saturations

Naturally occurring radon in ground water can potentially be used as an in situ partitioning tracer to characterize dense nonaqueous phase liquid (DNAPL) saturations. The static method involves comparing radon concentrations in water samples from DNAPL-contaminated and noncontaminated portions of an aquifer, while the push-pull method involves the injection (push) and extraction (pull) of a radon-free test solution from a single well. In the presence of DNAPL, radon concentrations during the pull phase are retarded, with retardation manifested in greater dispersion of radon concentrations relative to a conservative tracer. The utility of these methods was investigated in the laboratory using a physical aquifer model (PAM). Static and push-pull tests were performed before and after contamination of the PAM sediment pack with trichloroethene (TCE), and after alcohol cosolvent flushing and pump-and-treat remediation. Numerical simulations were used to estimate the retardation factor for radon in push-pull tests. Radon partitioning was observed in static and push-pull tests conducted after TCE contamination. Calculated TCE saturations ranged up to 1.4% (static test) and 14.1% (push-pull test). Post-remediation tests showed decreases in TCE saturations. The results show that radon is sensitive to changes in DNAPL saturation in space and time. However, the methods are sensitive to DNAPL saturation heterogeneity, test location, sample size, and test design. The influence of these factors on test results, as well as the apparent overestimation of the retardation factor in push-pull tests, warrant further investigation.     

Theoretical estimation of free and entrapped nonwetting–wetting fluid interfacial areas in porous media

Fluid–fluid interfacial areas play important roles in numerous subsurface processes such as dissolution, volatilization, and adsorption. Integral expressions have been derived to estimate both entrapped (discontinuous) and free (continuous) nonwetting fluid–wetting fluid specific interfacial areas in porous media. The expressions, compatible with widely used capillary head-saturation and entrapment models, require information on capillary head-saturation relation parameters, porosity, and fluid-pair interfacial tension. In addition, information on the maximum entrapped nonwetting fluid saturation as well as the main drainage branch reversal point for water and total liquid saturations is necessary to estimate entrapped fluid interfacial areas. Implementation of the interfacial area equations in continuum-based multifluid flow simulators is straightforward since no additional parameters are needed than those required by the simulators to complete the multifluid flow computations. A limited sensitivity analysis, based on experimentally obtained parameter values, showed that imposed variations resulted in logical and consistent changes in predicted specific interfacial areas for both entrapped and free nonwetting fluid–wetting fluid systems. A direct comparison with published experimental work to test the derived expressions was limited to free air–water systems and yielded reasonable results. Such comparisons are often not possible because of the lack of information given on retention parameters, and variables used to determine nonwetting fluid entrapment. This contribution is dedicated to John W. Cary.