Microbial physiology-based model of ethanol metabolism in subsurface sediments

Dense non-aqueous phase liquids (DNAPLs) present in the subsurface may contain surface active compounds that impact DNAPL migration and distribution. While a number of studies have revealed the role surface active compounds play in altering the wettability of quartz sand, few have considered the implications for other minerals common to contaminated sites. This study extends understanding of DNAPL/surfactant wettability to iron oxide surfaces. Specifically, quartz and iron oxide-coated sands in a tetrachloroethene (PCE)/water system containing the organic base (an organic molecule that acts as a base) dodecylamine (DDA) were compared at a variety of scales. Wettability of the minerals' surfaces, and the impact of wettability on capillary resistance to DNAPL entry, were assessed as a function of pH through: (i) advancing and receding contact angles, (ii) primary drainage capillary pressure-saturation experiments, and (iii) small, two-dimensional, flow cell experiments. The work revealed that, at neutral pH and under identical boundary capillary pressures, DNAPL invaded quartz sand but not iron oxide-coated sand; however, at low pH, DNAPL invaded both sands equally. These differences were demonstrated to be due to wettability alterations associated with the strength of attractive forces between DDA and the mineral surface, dictated by the isolectric point of the minerals and system pH. Observed differences in DNAPL invasion behavior were consistent with measured intrinsic contact angles and P(c)-S relationships, the latter requiring scaling by the operative contact angle inside the porous medium for a meaningful comparison. This study suggests that the distribution of minerals (and, more specifically, their isoelectric points), as well as the aqueous phase pH at a given site, may have a significant impact on the DNAPL source zone architecture.     

Effect of nonionic surfactant partitioning on the dissolution kinetics of residual perchloroethylene in a model porous medium

At concentrations above the critical micelle concentration, surfactants can significantly enhance the solubilization of residual nonaqueous phase liquids (NAPL) and, for this reason, are the focus of research on surfactant-enhanced aquifer remediation (SEAR). As a consequence of their amphiphilic nature, surfactants may also partition to various extents between the organic and aqueous phases, thereby affecting SEAR performance. We report here on the observation and analysis of the effect of surfactant partitioning on the dissolution kinetics of residual perchloroethylene (PCE) by aqueous solutions (1000 mg/L) of the non-ionic surfactant Triton X-100 in a model porous medium. For this fluid system, batch equilibration experiments showed that the surfactant partitions strongly into the NAPL (NAPL-water partition coefficient equal to 12.5). Dynamic interfacial tension (IFT) measurements were employed to study surfactant diffusion and interfacial adsorption. The dynamic IFT measurements were consistent with partitioning of the surfactant between the two liquid phases. PCE dissolution experiments, conducted in a transparent glass micromodel using an aqueous surfactant solution, were contrasted to experiments using clean water. Surfactant partitioning was observed to delay significantly the onset of micellar solubilization of PCE, an observation reproduced by a numerical model. This effect is attributed to the reduction of surfactant concentration in the immediate vicinity of the NAPL-water interface, which accompanies transport of the surfactant into the NAPL. Accordingly, it is suggested that both the rate and the extent of diffusion of the surfactant into the NAPL affect the onset of and the driving force for micellar solubilization. While many surfactants do not readily partition in NAPL, this possibility must be considered when selecting non-ionic surfactants for the enhanced solubilization of residual chlorinated solvents in porous media.     

Transport of a non-volatile contaminant in unsaturated porous media in the presence of colloids

Stable colloidal particles can travel long distances in subsurface environments and carry particle-reactive contaminants with them to locations further than predicted by the conventional advective-dispersive transport equation. When such carriers exist in a saturated porous medium, the system can be idealized as consisting of three phases: an aqueous phase, a carrier phase, and a stationary solid matrix phase. However, when colloids are present in an unsaturated porous medium, the system representation should include one more phase, i.e. the air phase. In the work reported, a mathematical model was developed to describe the transport and fate of the colloidal particles and a non-volatile contaminant in unsaturated porous media. The model is based on mass balance equations in a four-phase porous medium. Colloid mass transfer mechanisms among aqueous, solid matrix, and air phases, and contaminant mass transfer between aqueous and colloid phases are represented by kinetic expressions. Governing equations are non-dimensionalized and solved to investigate colloid and contaminant transport in an unsaturated porous medium. A sensitivity analysis of the transport model was utilized to assess the effects of several parameters on model behavior. The colloid transport model matches successfully with experimental data of Wan and Wilson. The presence of air-water interface retards the colloid transport significantly counterbalancing the facilitating effect of colloids. However, the retardation of contaminant transport by colloids is highly dependent on the properties of the contaminant and the colloidal surface.     

Characterization of pore scale NAPL morphology in homogeneous sands as a function of grain size and NAPL dissolution

In this study, we investigate pore scale morphology of nonaqueous phase liquids (NAPLs) trapped in different pore sizes using tracer techniques. Specific interfacial area and saturation of NAPL trapped in homogeneous sands were measured using the interfacial and partitioning tracer techniques. The observed NAPL-water interfacial areas increased in a log-linear fashion with decreasing sand grain size, but showed no clear trend with residual NAPL saturation formed in the various grain sizes. The measured values were used to calculate the NAPL morphology index, which characterizes the spatial NAPL distribution within the pore space. The NAPL morphology indices, increased exponentially with decreasing grain size, indicating that the NAPL becomes smaller, but more blobs. For a fixed grain size, the specific interfacial area and saturation of the NAPL were measured following changes caused by dissolution using alcohol. The observed interfacial areas showed a decrease linearly as a function of the NAPL saturation.     

Infiltration and redistribution of LNAPL into unsaturated layered porous media

Enhanced understanding of light non-aqueous phase liquid (LNAPL) infiltration into heterogeneous porous media is important for the effective design of remediation strategies. We used a 2-D experimental facility that allows for visual observation of LNAPL contours in order to study LNAPL redistribution in a layered porous medium. The layers are situated in the unsaturated zone near the watertable and they are inclined to be able to observe the effect of discontinuities in capillary forces and relative permeabilities. Two experiments were performed. The first experiment consisted of LNAPL infiltration into a fine sand matrix with a coarse sand layer, and the second experiment consisted of a coarse sand matrix and a fine sand layer. The numerical multi-phase flow model STOMP was validated with regard to the experimental results. This model is able to adequately reproduce the experimental LNAPL contours. Numerical sensitivity analysis was also performed. The capillarity contrast between sands was found to be the main controlling factor determining the final LNAPL distribution.     

Determining effective interfacial tension and predicting finger spacing for DNAPL penetration into water-saturated porous media

The difficulty in determining the effective interfacial tension limits the prediction of the wavelength of fingering of immiscible fluids in porous media. A method to estimate the effective interfacial tension using fractal concepts was presented by Chang et al. [Water Resour. Res. 30 (1994) 125]. We modified the method in that the macroscopic interface length was used instead of the system width. Methods to determine the macroscopic and the microscopic interface length are given. Lab experiments of dense nonaqueous phase liquid (DNAPL) penetrating into water-saturated glass beads were carried out in a two-dimensional (2-D) transparent chamber. The displacement processes were recorded using a 35-mm camera or a video camera, which was directly connected to and controlled by a computer. Unlike the method of Chang et al. (1994), the modified method used here gives a constant value of the effective interfacial tension over time. The predicted wavelengths of fingering are relatively close to those observed except for the fine beads.     

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.     

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.     

The effect of entrapped nonaqueous phase liquids on tracer transport in heterogeneous porous media: laboratory experiments at the intermediate scale

This work considers the applicability of conservative tracers for detecting high-saturation nonaqueous-phase liquid (NAPL) entrapment in heterogeneous systems. For this purpose, a series of experiments and simulations was performed using a two-dimensional heterogeneous system (10x1.2 m), which represents an intermediate scale between laboratory and field scales. Tracer tests performed prior to injecting the NAPL provide the baseline response of the heterogeneous porous medium. Two NAPL spill experiments were performed and the entrapped-NAPL saturation distribution measured in detail using a gamma-ray attenuation system. Tracer tests following each of the NAPL spills produced breakthrough curves (BTCs) reflecting the impact of entrapped NAPL on conservative transport. To evaluate significance, the impact of NAPL entrapment on the conservative-tracer breakthrough curves was compared to simulated breakthrough curve variability for different realizations of the heterogeneous distribution. Analysis of the results reveals that the NAPL entrapment has a significant impact on the temporal moments of conservative-tracer breakthrough curves.     

Non-steady state partitioning of dry cleaning surfactants between tetrachloroethylene (PCE) and water in porous media

Trapped organic solvents, in both the vadose zone and below the water table, are frequent sources of environmental contamination. A common source of organic solvent contamination is spills, leaks, and improper solvent disposal associated with dry cleaning processes. Dry cleaning solvents, such as tetrachloroethylene (PCE), are typically enhanced with the addition of surfactants to improve cleaning performance. The objective of this work was to examine the partitioning behavior of surfactants from PCE in contact with water. The relative rates of surfactants partitioning and PCE dissolution are important for modeling the behavior of waste PCE in the subsurface, in that they influence the interfacial tension of the PCE, and how (or if) interfacial tension changes over time in the subsurface. The work described here uses a flow-through system to examine simultaneous partitioning and PCE dissolution in a porous medium. Results indicate that both nonylphenol ethoxylate nonionic surfactants and a sulfosuccinate anionic surfactant partition out of residual PCE much more rapidly than the PCE dissolves, suggesting that in many cases interfacial tension changes caused by partitioning may influence infiltration and distribution of PCE in the subsurface. Non-steady-state partitioning is found to be well-described by a linear driving force model incorporating measured surfactant partition coefficients.     

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.     

More general capillary pressure and relative permeability models from fractal geometry

More general capillary pressure and relative permeability models were derived theoretically from fractal modeling of a porous medium. It was found that the new capillary pressure model could be reduced to the frequently-used Brooks–Corey capillary pressure model and the Li–Horne imbibition model when the fractal dimension of a porous medium takes specific values. This also demonstrates that the Brooks–Corey model and the Li-Horne model have a further confirmed theoretical basis. Capillary pressure data measured using mercury intrusion techinque were used to verify the model. The results demonstrated that the new capillary pressure model could represent the capillary pressure curves in those rocks with fracures or with great heterogeneity while the existing models cannot. The new relative permeability models can be reduced to the Brooks–Corey relative permeability model in a specific case. It has been proved theoretically that the relative permeability of each phase in a smooth fracture is only a linear function of its own saturation. Relative permeability data were calculated using the new models and the model results were compared with experimental data measured using a steady-state technique. The comparison demonstrated that the relative permeability models and experimental results were consistent with each other.     

Improving the extraction of tetrachloroethylene from soil columns using surfactant gradient systems

In this work, we extend the recently developed gradient approach for surfactant-enhanced remediation of dense non-aqueous phase liquid (DNAPL)-impacted sites. The goal of the gradient approach is to maximize the DNAPL solubilization capacity in swollen micelles (Type I aqueous microemulsions) while at the same time minimizing the potential for DNAPL mobilization. In this work, we introduce a modified version of the capillary/trapping curve that we refer to as the gradient curve to help interpret and/or design the gradient approach. The gradient curve presents the residual DNAPL saturation as a function of interfacial tension and microemulsion viscosity. This approach demonstrates that keeping a low viscosity of the microemulsion phase is not only important for keeping a low head loss during surfactant flooding but also to prevent oil mobilization. Eight microemulsion systems were evaluated in this research; these systems were evaluated based on their tetrachloroethylene (PCE) solubilization capacity, interfacial tension (IFT), viscosity, density, and coalescence kinetics. Two of these systems were chosen for evaluation in site-specific column tests using an increasing electrolyte gradient to produce a decreasing IFT/increasing solubilization gradient system. The column studies were conducted with media from Dover Air Force Base in Dover, DE. Both solubilized and mobilized DNAPL were quantified. During the column studies, we observed that substantial PCE was mobilized when the residual level of PCE in the column was significantly higher than the steady-state residual saturation level being approach (as predicted from the gradient curve). Four column studies were performed, three of which were used to asses the validity of the gradient curve in predicting the residual saturation after each gradient step. From these tests we observed that starting IFTs of less than 1 mN/m all produced the same mobilization potential. In the last column, we used an additional gradient step with an initial IFT above 1 mN/m to dramatically reduce the amount of PCE mobilize. Based on the good agreement between column results and projections based on the gradient curve, we propose this as a preferred method for designing gradient surfactant flushing systems.     

Using aliphatic alcohols as gaseous tracers in determination of water contents and air-water interfacial areas in unsaturated sands

A new type of gaseous tracer utilizing nontoxic aliphatic alcohols for the determination of water content and air-water interfacial area is tested on unsaturated sands of low water content. Alcohol vapors are generated at room temperature and passed through the experimental sand column. Breakthrough curves (BTCs) of these vapors are obtained by monitoring their effluent concentrations using GC-FID. The retardation factor with respect to each vapor transport process is obtained by optimizing BTCs data using the CXTFIT program in the reverse problem mode. The water content and the interfacial area are subsequently calculated from their retardation factors by both equilibrium and nonequilibrium transport models. Experimental results indicate that the pentanol tracer is feasible in the determination of water content at conditions when the degree of water saturation is low. In the determination of air-water interfacial area, decanol is selected due to its interfacial adsorption characteristics. By comparing to interfacial areas from theoretical predictions as well as other conventional tarcer methods, the ones determined from the decanol tracer tests are found to be close to the true interfacial areas when the water content is low.     

Analysis of colloid and tracer breakthrough curves

We consider the dispersion and elution of colloids and dissolved nonsorbing tracers within saturated heterogeneous porous media. Since flow path geometry in natural systems is often ill-characterized macroscopic (mean) flow rates and dispersion tensors are utilized in order to account for the sub-model scale microscopic fluctuations in media structure (and the consequent hydrodynamic profile). Even for tracer migration and dispersal this issue is far from settled.Here we consider how colloid and tracer migration phenomena can be treated consistently. Theoretical calculations for model flow geometries yield two quantitative predictions for the transport of free (not yet captured) colloids with reference to a non-sorbing dissolved tracer within the same medium: the average migration velocity of the free colloids is higher than that of the tracer; and that the ratio of the equivalent hydrodynamic dispersion rates of colloids and tracer is dependent only upon properties of the colloids and the porous medium, it is independent of pathlengths and fluid flux, once length scales are large enough.The first of these is well known, since even in simple flow paths free colloids must stay more centre stream. The second, if validated suggests how solute and colloid dispersion may be dealt with consistently in macroscopic migration models. This is crucial since dispersion is usually ill-characterized and unaddressed by the experimental literature. In this paper we present evidence based upon an existing Drigg field injection test for the validity of these predictions.We show that starting from experimental data the fitted dispersion rates of both colloids and non-sorbing tracers increase with the measured elution rates (obeying slightly different rules for tracers and colloids); and that the ratio of colloid and nonsorbing tracer elution rates, and the ratio of colloid and nonsorbing tracer dispersion rates may be dependent upon properties of the colloids and the medium (not the flow regime).It is important to realize that even for unretarded species, an earlier peak in the breakthrough curve does not necessarily correspond to a faster mean elution rate, or vice versa. But rather that a colloid may elute faster but disperse less than an equivalent tracer. Hence its peak may be retarded compared to that of the tracer, even assuming no retardation. Hence one must consider a combination of mean elution rate and mean dispersion rate, and not rely on “peak times” to corroborate chromatographic effects. The importance of this lies in the fact that these processes are not independent and yet upscale differently. Thus realistic estimates of effective colloid dispersion rates should be upscaled in a way consistent with that adopted for tracers within the same system.     

Contaminant transport in groundwater in the presence of colloids and bacteria: Model development and verification

Colloids and bacteria (microorganisms) naturally exist in groundwater aquifers and can significantly impact contaminant migration rates. A conceptual model is first developed to account for the different physiochemical and biological processes, reaction kinetics, and different transport mechanisms of the combined system (contaminant–colloids–bacteria). All three constituents are assumed to be reactive with the reactions taking place between each constituent and the porous medium and also among the different constituents. A general linear kinetic reaction model is assumed for all reactive processes considered. The mathematical model is represented by fourteen coupled partial differential equations describing mass balance and reaction processes. Two of these equations describe colloid movement and reactions with the porous medium, four equations describe bacterial movement and reactions with colloids and the porous medium, and the remaining eight equations describe contaminant movement and its reactions with bacteria, colloids, and the porous medium. The mass balance equations are numerically solved for two-dimensional groundwater systems using a third-order, total variance-diminishing scheme (TVD) for the advection terms. Due to the complex coupling of the equations, they are solved iteratively each time step until a convergence criterion is met. The model is tested against experimental data and the results are favorable.     

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.