Infiltration of PCE in a system containing spatial wettability variations

A two-dimensional infiltration experiment was conducted to investigate and quantify the effect of spatial wettability variations on DNAPL migration and entrapment in saturated sands. Experimental observations of tetrachloroethylene (PCE) infiltration showed that organic-wet sand lenses acted as very effective capillary barriers, retaining PCE and inhibiting its downward migration. A multiphase numerical simulator was used to model this sand box experiment. The simulator incorporates wettability-modified van Genuchten and Brooks-Corey capillary pressure/saturation relationships as well as Burdine and Mualem relative permeability relationships. PCE mass distributions, estimated by image analysis of digital photographs taken during the infiltration event, were compared to simulation results. Although both relative permeability models were qualitatively able to predict the PCE retention in the organic-wet layers, simulations with the Mualem model failed to capture the observed rate of PCE migration. A traditional multiphase simulator, incorporating water-wet capillary retention relations, failed to predict both PCE pathways and retention behavior. This study illustrates the potential influence of subsurface wettability variations on DNAPL migration and entrapment and supports the use of modified capillary relations in conjunction with the Burdine model in multiphase flow simulators.     

Effects of heterogeneities on capillary pressure-saturation-relative permeability relationships

In theories of multiphase flow through porous media, capillary pressure-saturation and relative permeability-saturation curves are assumed to be intrinsic properties of the medium. Moreover, relative permeability is assumed to be a scalar property. However, numerous theoretical and experimental works have shown that these basic assumptions may not be valid. For example, relative permeability is known to be affected by the flow velocity (or pressure gradient) at which the measurements are carried out. In this article, it is suggested that the nonuniqueness of capillary pressure-relative permeability-saturation relationships is due to the presence of microheterogeneities within a laboratory sample. In order to investigate this hypothesis, a large number of "numerical experiments" are carried out. A numerical multiphase flow model is used to simulate the procedures that are commonly used in the laboratory for the measurement of capillary pressure and relative permeability curves. The dimensions of the simulation domain are similar to those of a typical laboratory sample (a few centimeters in each direction). Various combinations of boundary conditions and soil heterogeneity are simulated and average capillary pressure, saturation, and relative permeability for the "soil sample" are obtained. It is found that the irreducible water saturation is a function of the capillary number; the smaller the capillary number, the larger the irreducible water saturation. Both drainage and imbibition capillary pressure curves are found to be strongly affected by heterogeneities and boundary conditions. Relative permeability is also found to be affected by the boundary conditions; this is especially true about the nonaqueous phase permeability. Our results reveal that there is much need for laboratory experiments aimed at investigating the interplay of boundary conditions and microheterogeneities and their effect on capillary pressure and relative permeability.     

The influence of field-scale heterogeneity on the infiltration and entrapment of dense nonaqueous phase liquids in saturated formations

Numerical simulations are used for the systematic exploration of the migration and entrapment of dense nonaqueous phase liquids (DNAPLs) in heterogeneous formations. Ensembles of realizations of random, spatially correlated permeability fields are generated and employed in model simulations of a spill event. Statistical techniques are then used to quantify the sensitivity of model predictions to input parameters, thereby identifying the parameters or processes that may be of primary importance in the determination of organic liquid distributions in heterogeneous systems. Results of the study indicate that the most critical factors in modeling organic entrapment include the spill release rate, reliable estimates of the mean, variance, and vertical correlation scale of the formation permeability, and an accurate representation of the correlation between the capillary pressure–saturation function and the permeability. In contrast, the hydraulic gradient and cross-correlation of residual saturations with permeabilities are found to have only minor influence on organic liquid distributions in such heterogeneous formations.     

A pragmatic approach for estimation of source-zone emissions at LNAPL contaminated sites

When considering natural attenuation as a remediation strategy at a site contaminated by a light non-aqueous phase liquid (LNAPL), it is important to consider the emission of contaminants from the source zone. A quantification of source-zone emissions is essential both for comparison with down-gradient mass fluxes to provide an estimate of fractional mass flux reduction, as well as for estimating the source lifetime. Because the spatial distribution of LNAPL at a field site is strongly dependent on both the spill circumstances and the heterogeneity of the geologic materials, which can be problematic for in-situ determination, alternative methods for estimating source-zone emissions are needed. In this work, a three-dimensional multiphase flow and transport modelling approach is used to investigate the relationship between the lateral extent of an LNAPL body and the emission of contaminants to groundwater at a contaminated site. For simulations involving an LNAPL release in an aquifer comprised of heterogeneous porosity and permeability distributions that were generated geostatistically, it is shown that a simple linear relationship exists between the lateral extent of the LNAPL body in the capillary fringe and the emission to the aqueous phase. The parameters describing the relationship are found to be linear functions of the groundwater flow velocity and the vertical infiltration rate. This site-specific relationship provides a simple method to estimate contaminant emissions to groundwater at LNAPL contaminated sites.     

Insights into the use of time-lapse GPR data as observations for inverse multiphase flow simulations of DNAPL migration

Perchloroethylene (PCE) saturations determined from GPR surveys were used as observations for inversion of multiphase flow simulations of a PCE injection experiment (Borden 9 m cell), allowing for the estimation of optimal bulk intrinsic permeability values. The resulting fit statistics and analysis of residuals (observed minus simulated PCE saturations) were used to improve the conceptual model. These improvements included adjustment of the elevation of a permeability contrast, use of the van Genuchten versus Brooks-Corey capillary pressure-saturation curve, and a weighting scheme to account for greater measurement error with larger saturation values. A limitation in determining PCE saturations through one-dimensional GPR modeling is non-uniqueness when multiple GPR parameters are unknown (i.e., permittivity, depth, and gain function). Site knowledge, fixing the gain function, and multiphase flow simulations assisted in evaluating non-unique conceptual models of PCE saturation, where depth and layering were reinterpreted to provide alternate conceptual models. Remaining bias in the residuals is attributed to the violation of assumptions in the one-dimensional GPR interpretation (which assumes flat, infinite, horizontal layering) resulting from multidimensional influences that were not included in the conceptual model. While the limitations and errors in using GPR data as observations for inverse multiphase flow simulations are frustrating and difficult to quantify, simulation results indicate that the error and bias in the PCE saturation values are small enough to still provide reasonable optimal permeability values. The effort to improve model fit and reduce residual bias decreases simulation error even for an inversion based on biased observations and provides insight into alternate GPR data interpretations. Thus, this effort is warranted and provides information on bias in the observation data when this bias is otherwise difficult to assess.     

A pore-scale investigation of a multiphase porous media system

Pore-scale processes govern fundamental behavior in multiphase porous media systems. A high-resolution, three-dimensional image of the interior of a multiphase porous media system was obtained using synchrotron X-ray tomography. The system was imaged at a resolution of 12.46 mum following entrapment of the nonwetting phase at residual saturation. First, the physically representative network structure of the porous media system is extracted from the void space. This provides a direct mapping of the pore bodies and throats and enables pore-level calculations of coordination numbers, aspect ratios, and pore body and throat correlations. Next, algorithms developed to calculate properties of the entrapped nonwetting phase, such as volume, sphericity, interfacial area, and orientation, are applied to the residual nonwetting phase blobs. Finally, correlations between the pore network structure and nonwetting phase characteristics are examined. As expected, it was found that the nonwetting phase was trapped primarily in the largest pore spaces, the pore bodies with the highest aspect ratios, and the pore bodies with the highest coordination numbers. This work shows that, while there may be limitations related to the ability to capture REV-sized domains for some of the multiphase flow properties and phenomena, high-resolution X-ray tomography is able to provide the high quality datasets needed to observe and quantify the pore-scale phenomena and processes that govern multiphase flow in unconsolidated porous media systems.     

Effective parameters for two-phase flow in a porous medium with periodic heterogeneities

Computational simulations of two-phase flow in porous media are used to investigate the feasibility of replacing a porous medium containing heterogeneities with an equivalent homogeneous medium. Simulations are performed for the case of infiltration of a dense nonaqueous phase liquid (DNAPL) in a water-saturated, heterogeneous porous medium. For two specific porous media, with periodic and rather simple heterogeneity patterns, the existence of a representative elementary volume (REV) is studied. Upscaled intrinsic permeabilities and upscaled nonlinear constitutive relationships for two-phase flow systems are numerically calculated and the effects of heterogeneities are evaluated. Upscaled capillary pressure-saturation curves for drainage are found to be distinctly different from the lower-scale curves for individual regions of heterogeneity. Irreducible water saturation for the homogenized medium is found to be much larger than the corresponding lower-scale values. Numerical simulations for both heterogeneous and homogeneous representations of the considered porous media are carried out. Although the homogenized model simulates the spreading behavior of DNAPL reasonably well, it still fails to match completely the results form the heterogeneous simulations. This seems to be due, in part, to the nonlinearities inherent to multiphase flow systems. Although we have focussed on a periodic heterogeneous medium in this study, our methodology is applicable to other forms of heterogeneous media. In particular, the procedure for identification of a REV, and associated upscaled constitutive relations, can be used for randomly heterogeneous or layered media as well.     

Simulation of organic liquid flow in porous media using estimated and measured transport properties

Many numerical models which describe the movement of a separate organic liquid phase in the subsurface require information about the relationships between capillary pressure and saturation, and between relative permeability and saturation. An evaluation of the information available for these relationships suggests that substantial discrepancies may be introduced into simulations if estimated, rather than measured, data are employed. The purpose of this study was to quantify these deviations. Two-phase displacement simulations were performed in one and two dimensions for several organic liquid-water systems. Both constant-head and constant-flux boundary conditions were employed at a variety of flow rates and time scales, using both measurements and estimates of capillary pressure and relative permeability for a sandy aquifer material. The results demonstrate that the use of estimated transport relationships produces significantly different predictions of organic liquid migration. The magnitude of the deviations between predictions may be as high as 25% or more after relatively short displacement periods, depending on the boundary conditions of the simulated scenario, as well as on the physical characteristics of the two-phase system. For the systems examined, most of the deviations resulted from the estimates for relative permeability to the organic liquid. Thus, improved methods for the estimation of the relative permeability to the organic liquid are needed to reduce the uncertainty in displacement simulations.     

A multi-flowpath model for the interpretation of immiscible displacement experiments in heterogeneous soil columns

This work focuses on the phenomenon of the immiscible two-phase flow of water and oil in saturated heterogeneous soil columns. The goal is to develop a fast and reliable method for quantifying soil heterogeneities for incorporation into the relevant capillary pressure and relative permeability functions. Such data are commonly used as input data in simulators of contaminant transport in the subsurface. Rate-controlled drainage experiments are performed on undisturbed soil columns and the transient response of the axial distribution of water saturation is determined from electrical measurements. The transient responses of the axial distribution of water saturation and total pressure drop are fitted with the multi-flowpath model (MFPM) where the pore space is regarded as a system of parallel paths of different permeability. The MFPM enables us to quantify soil heterogeneity at two scales: the micro-scale parameters describe on average the effects of pore network heterogeneities on the two-phase flow pattern; the macro-scale parameters indicate the variability of permeability at the scale of interconnected pore networks. The capillary pressure curve is consistent with that measured with mercury intrusion porosimetry over the low pressure range. The oil relative permeability increases sharply at a very low oil saturation (< 10^− 3) and tends to a high end value. The water relative permeability decreases abruptly at a low oil saturation (~ 0.1), whereas the irreducible wetting phase saturation is quite high. The foregoing characteristics of the two-phase flow properties are associated with critical (preferential) flowpaths that comprise a very small percentage of the total pore volume, control the overall hydraulic conductivity, and are consistent with the very broad range of pore-length scales usually probed in soil porous matrix.     

A composite medium approximation for unsaturated flow in layered sediments

Saturated-unsaturated flow in strictly layered sediments proceeds via conductors in parallel in the direction parallel to bedding, and via resistors in series in the direction perpendicular to bedding. On sufficiently small scales of space and time, flow in such media will be subject to approximate capillary equilibrium locally, which provides a basis for approximating the effective hydraulic conductivity of a composite multi-layer medium in terms of the conductivities of the individual layers. Equations for the hydraulic conductivity tensor in "composite medium approximation" (COMA) are given in a coordinate system aligned with bedding. Hydraulic conductivity parallel to bedding is generally larger than in the perpendicular direction. The anisotropy depends on the spread of the conductivity distribution, and tends to increase for dryer conditions. The COMA model was implemented in a multi-phase flow simulator and tested by comparison with high-resolution simulations in which all layering heterogeneity is resolved explicitly. Under favorable conditions, COMA is found to accurately represent sub-grid scale flow and transport processes, providing a practical method for simulating field-scale flow and transport in layered media. The approximation improves when layers are thinner, and when flow rates are smaller.     

Multidimensional validation of a numerical model for simulating a DNAPL release in heterogeneous porous media

A fixed-volume release of 1,2-DCE, tracked in space and time with a light transmission/image analysis system, provided a data set for the infiltration, redistribution, and immobilisation of a dense non-aqueous phase liquid (DNAPL) in a heterogeneous porous medium. The two-dimensional bench scale flow cell was packed with a spatially correlated, random heterogeneous distribution of six sand types. In order to provide the necessary modelling parameters, detailed constitutive relationships were measured at the local scale for the six sands. These experiments revealed that nonwetting phase (NWP) relative permeability-saturation (k(rN)-S(W)) relationships are strongly correlated to sand type. Trends in the best-fit k(rN)-S(W) parameters reflected a positive correlation between mean grain diameter and the maximum NWP relative permeability, k(rN)(max). Multiphase flow simulations of the bench scale experiment best reproduced the experimental observations, producing excellent matches in both time and space, when the measured, correlated local scale k(rN)-S(W) relationships were employed.     

Entrapment and dissolution of DNAPLs in heterogeneous porous media

Two-dimensional multiphase flow and transport simulators were refined and used to numerically investigate the entrapment and dissolution behavior of tetrachloroethylene (PCE) in heterogeneous porous media containing spatial variations in wettability. Measured hydraulic properties, residual saturations, and dissolution parameters were employed in these simulations. Entrapment was quantified using experimentally verified hydraulic property and residual saturation models that account for hysteresis and wettability variations. The nonequilibrium dissolution of PCE was modeled using independent estimates of the film mass transfer coefficient and interfacial area for entrapped and continuous (PCE pools or films) saturations. Flow simulations demonstrate that the spatial distribution of PCE is highly dependent on subsurface wettability characteristics that create differences in PCE retention mechanisms and the presence of subsurface capillary barriers. For a given soil texture, the maximum and minimum PCE infiltration depth was obtained when the sand had intermediate (an organic-wet mass fraction of 25%) and strong (water- or organic-wet) wettability conditions, respectively. In heterogeneous systems, subsurface wettability variations were also found to enhance or diminish the performance of soil texture-induced capillary barriers. The dissolution behavior of PCE was found to depend on the soil wettability and the spatial PCE distribution. Shorter dissolution times tended to occur when PCE was distributed over large regions due to an increased access of flowing water to the PCE. In heterogeneous systems, capillary barriers that produced high PCE saturations tended to exhibit longer dissolution times.     

表面活性剂冲洗修复多氯联苯污染土壤多相流研究

多氯联苯(PCBs)是一种具有持久性、抗生物降解性、脂肪溶性和明显的生物毒性等特性的持久性有机污染物,PCBs在土壤中难于准确定位、难被分解和强烈吸附,去除土壤中PCBs比较困难.表面活性剂冲洗法可以通过提高PCBs溶解度和降低水-PCBs界面张力来实现PCBs从土壤中去除;表面活性剂冲洗PCBs污染土壤涉及气相、水相、NAPLs相和固相等物质,是多相共存并相互发生作用的过程,发生相对渗透率、饱和度和毛细压力的变化;另外,为研究表面活性剂冲洗土壤中PCBs的去除机理,并降低PCBs对研究人员的危害,采用微观孔隙结构网络模型是一种较新颖的和效果显著的研究方法.开展表面活性剂冲洗PCBs污染土壤多相流研究,可以为PCBs污染场地修复提供理论基础和实验支持,并促进我国POPs履约工作的顺利进行.     

Multispectral image analysis method to determine dynamic fluid saturation distribution in two-dimensional three-fluid phase flow laboratory experiments

The need for measuring dynamic fluid saturation distribution in multi-dimensional three-fluid phase flow experiments is hampered by lack of appropriate techniques to monitor full field transient flow phenomena. There is no conventional technique able to measure dynamic three-fluid phase saturation at several array points of the flow field at the same time. A multispectral image analysis technique was developed to determine dynamic NAPL, water and air saturation distribution in two-dimensional three-fluid phase laboratory experiments. Using a digital near-infrared camera, images of sand samples with various degrees of NAPL, water and air saturation were taken, under constant lighting conditions and within three narrow spectral bands of the visible and near-infrared spectrum. It was shown that the optical density defined for the reflected luminous intensity was a linear function of the NAPL and the water saturation for each spectral band and for any two and three-fluid phase systems. This allowed the definition of dimensionless lump reflection coefficients for the NAPL and the water phase within each spectral band. Consequently, at any given time, two images taken within two different spectral bands provided two linear equations which could be solved for the water and the NAPL saturation. The method was applied to two-dimensional three-phase flow experiments, which were conducted to investigate the migration and the distribution of LNAPL in the vadose zone. The method was used to obtain continuous, quantitative and dynamic full field mapping of the NAPL saturation as well as the variation of the water and the air saturation during NAPL flow. The method provides a non-destructive and non-intrusive tool for studying multiphase flow for which rapid changes in fluid saturation in the entire flow domain is difficult to measure using conventional techniques.     

Investigation of the Contamination of Fractured Formations by Non-Newtonian Oil Pollutants

In many practical applications, non-aqueous phase liquid (NAPL) pollutants exhibiting a clearly non-Newtonian rheological behavior (e.g. crude oil, suspensions of engine oils, asphalt, creosote, etc.) may migrate through fractured formations and contaminate aquifers. The present work is the first step toward the development of non-Darcian models concerning the non-linear NAPL flow in single fractures, and detemiination of the coupled effects of non-Newtonian NAPL rheology and flow rate on the transient immiscible displacement of an aqueous phase by a NAPL. Initially, a protocol is developed for the preparation and rheological characterization of synthetic non-Newtonian NAPLs, which are based on waxy oils. Then, an artificial transparent glass-etched single fracture of controlled morphology is fabricated and used for the measurement of the non-linear pressure gradient--superficial velocity relationship for the flow of NAPL of varying rheology. Pore network simulations and effective medium approximation (EMA) are used for the interpretation of the experimental results and derivation of an analytic non-Darcian one-phase flow model. Visualization experiments of the immiscible displacement of an aqueous phase by Newtonian and non-Newtonian NAPLs are performed on the artificial fracture under controlled values of the viscosity ratio and capillary number (ratio of viscous to capillary forces). Comparative study of the Newtonian and non-Newtonian NAPL flow patterns allows us to evaluate the interactive effects of NAPL rheology, flow rates and fracture morphology on the spatial and temporal distribution of such liquid pollutants within single fractures     

Predictive modelling of NAPL injection tests in variable aperture spatially correlated fractures.

In preparation for a field experiment where a NAPL will be injected into a fractured sandstone aquifer, a 2D invasion percolation model of DNAPL migration in a single horizontal fracture with varying aperture has been developed. This simulation investigated the effect of spatially correlated fracture aperture fields on pressure-saturation relationships as a function of variable aperture mean, standard deviation, and spatial correlation statistics under hydrostatic conditions. Results from spatially correlated variable aperture fields can be significantly different from random fields. Longer ranges decreased entry pressures and higher standard deviations decreased nonwetting phase saturations. Mean aperture is the major control on displacement pressure, entry pressure and the form of the pressure-saturation curve. Simulation results using statistical parameters for a variable aperture natural sandstone fracture as described by Yeo et al. [International Journal of Rock Mechanics and Mining Sciences 35 (1998) 1051] closely resemble a Brooks-Corey pressure-saturation function, and exhibit a distinct entry pressure followed by a rapid increase in nonwetting phase saturation. Graphical estimates of entry pressure provide a good approximation of the critical aperture controlling the formation of a continuous nonwetting phase pathway in a variable aperture fracture. Consequently, we show that multiphase flow concepts developed for porous media can successfully be applied to variable aperture fractures. Entry pressure correlates well to the mean aperture in these simulations when using a Gaussian distribution of fracture aperture. Interpreted aperture distributions from NAPL injection experiments do not fit the true distribution well at low nonwetting phase saturations, but do at higher saturations above the entry pressure. Consequently, true, mechanical aperture variation within a fracture plane cannot be determined from NAPL injection experiments either in the field or laboratory.     

Investigation of the Contamination of Fractured Formations by Non-Newtonian Oil Pollutants

In many practical applications, non-aqueous phase liquid (NAPL) pollutants exhibiting a clearly non-Newtonian rheological behavior (e.g. crude oil, suspensions of engine oils, asphalt, creosote, etc.) may migrate through fractured formations and contaminate aquifers. The present work is the first step toward the development of non-Darcian models concerning the non-linear NAPL flow in single fractures, and determination of the coupled effects of non-Newtonian NAPL rheology and flow rate on the transient immiscible displacement of an aqueous phase by a NAPL. Initially, a protocol is developed for the preparation and rheological characterization of synthetic non-Newtonian NAPLs, which are based on waxy oils. Then, an artificial transparent glass-etched single fracture of controlled morphology is fabricated and used for the measurement of the non-linear pressure gradient—superficial velocity relationship for the flow of NAPL of varying rheology. Pore network simulations and effective medium approximation (EMA) are used for the interpretation of the experimental results and derivation of an analytic non-Darcian one-phase flow model. Visualization experiments of the immiscible displacement of an aqueous phase by Newtonian and non-Newtonian NAPLs are performed on the artificial fracture under controlled values of the viscosity ratio and capillary number (ratio of viscous to capillary forces). Comparative study of the Newtonian and non-Newtonian NAPL flow patterns allows us to evaluate the interactive effects of NAPL rheology, flow rates and fracture morphology on the spatial and temporal distribution of such liquid pollutants within single fractures.     

The effect of multicomponent diffusion on NAPL dissolution from spherical ternary mixtures

This paper investigates the dissolution characteristics of ternary nonaqueous phase liquid (NAPL) mixtures with the goal of comparing the relative contributions of multicomponent (intra-NAPL) diffusion, film transfer and thermodynamic nonideality. These contributions are compared at the pore scale and intermediate scale (several centimeters downstream from the source). Trichloroethene (TCE), tetrachloroethene (PCE) and 1,1,1-trichloroethane (TCA) were selected to model a reasonably ideal mixture; TCE, PCE and octanol were selected as a relevant nonideal mixture. A multicomponent diffusion-based dissolution model incorporating hydrodynamic theory was formulated to estimate intra-NAPL concentration gradients and associated aqueous interfacial concentrations for ideally shaped (spherical) NAPL blobs. Pore scale dissolution times for this model were compared to those generated using the conventional well-mixed NAPL dissolution model, applying the same film transfer boundary condition in both cases. Activity coefficients (spatially and temporally variable for the diffusion model, temporally variable for the well-mixed model) were estimated using UNIFAC. NAPL interfacial concentration histories generated using the pore scale models were used as input in a three-dimensional groundwater transport model (MT3DMS) to compare downstream concentration distributions. For the relatively large NAPL bodies simulated (r=0.6 cm), intra-NAPL diffusion effects were found to be significant at the pore scale and were strongly impacted by the mixture's thermodynamic ideality. At the intermediate scale, and for the conditions tested, modest differences in the simulations suggested that intra-NAPL diffusion effects would be negligible compared to those associated with mixture composition uncertainty, dissolution rate processes related to NAPL-induced permeability effects and hydrodynamic issues associated with flow field heterogeneity.     

Two-dimensional laboratory simulation of LNAPL infiltration and redistribution in the vadose zone

A quantitative two-dimensional laboratory experiment was conducted to investigate the immiscible flow of a light non-aqueous phase liquid (LNAPL) in the vadose zone. An image analysis technique was used to determine the two-dimensional saturation distribution of LNAPL, water and air during LNAPL infiltration and redistribution. Vertical water saturation variations were also continuously monitored with miniature resistivity probes. LNAPL and water pressures were measured using hydrophobic and hydrophilic tensiometers. This study is limited to homogeneous geological conditions, but the unique experimental methods developed will be used to examine more complex systems. The pressure measurements and the quantification of the saturation distribution of all the fluids in the entire flow domain under transient conditions provide quantitative data essential for testing the predictive capability of numerical models. The data are used to examine the adequacy of the constitutive pressure-saturation relations that are used in multiphase flow models. The results indicate that refinement of these commonly used hydraulic relations is needed for accurate model prediction. It is noted in particular that, in three-fluid phase systems, models should account for the existence of a residual NAPL saturation occurring after NAPL drainage. This is of notable importance because residual NAPL can act as a non negligible persistent source of contamination.