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.     

Variable-density groundwater flow and solute transport in irregular 2D fracture networks

Numerical simulations of variable-density flow and solute transport have been conducted to investigate dense plume migration for various configurations of 2D fracture networks. For orthogonal fractures, simulations demonstrate that dispersive mixing in fractures with small aperture does not stabilize vertical plume migration in fractures with large aperture. Simulations in non-orthogonal 2D fracture networks indicate that convection cells form and that they overlap both the porous matrix and fractures. Thus, transport rates in convection cells depend on matrix and fracture flow properties. A series of simulations in statistically equivalent networks of fractures with irregular orientation show that the migration of a dense plume is highly sensitive to the geometry of the network. If fractures in a random network are connected equidistantly to the solute source, few equidistantly distributed fractures favor density-driven transport. On the other hand, numerous fractures have a stabilizing effect, especially if diffusive transport rates are high. A sensitivity analysis for a network with few equidistantly distributed fractures shows that low fracture aperture, low matrix permeability and high matrix porosity impede density-driven transport because these parameters reduce groundwater flow velocities in both the matrix and the fractures. Enhanced molecular diffusion slows down density-driven transport because it favors solute diffusion from the fractures into the low-permeability porous matrix where groundwater velocities are smaller. For the configurations tested, variable-density flow and solute transport are most sensitive to the permeability and porosity of the matrix, which are properties that can be determined more accurately than the geometry and hydraulic properties of the fracture network, which have a smaller impact on density-driven transport.     

Scale effect and calibration of contaminant transport models

The influence on solute transport of the small-scale spatial variation of aquifer hydraulic conductivity (K) was analyzed by comparing results from fine-grid (2 m by 2 m) simulations of a synthetic heterogeneous aquifer to those from coarse-grid (8 m by 4 m) simulations of an equivalent homogeneous aquifer. Realizations of the K field of the heterogeneous aquifer were generated, using the Monte Carlo approach, from a lognormal distribution with mean log K of 2 (K in m/d) and three levels of log K variance of 0.1, 0.5, and 1.0. Numerical simulation results show that the average standard deviation of point concentrations increased from 1.21 to 5.78 when the value of log K variance was increased from 0.1 to 1.0. The average discrepancy between modeled concentrations (obtained from a coarse-grid deterministic numerical simulation) and the actual mean point concentrations (obtained from fine-grid Monte Carlo numerical simulations) increased from 0.91 to 4.23 with the increase in log K variance. The results from this study illustrate the uncertainty in predictions from contaminant transport models due to their inability to simulate the effects of heterogeneities at scales smaller than the model grid.     

Geostatistical Borehole Image‐Based Mapping of Karst‐Carbonate Aquifer Pores

Quantification of the character and spatial distribution of porosity in carbonate aquifers is important as input into computer models used in the calculation of intrinsic permeability and for next‐generation, high‐resolution groundwater flow simulations. Digital, optical, borehole‐wall image data from three closely spaced boreholes in the karst‐carbonate Biscayne aquifer in southeastern Florida are used in geostatistical experiments to assess the capabilities of various methods to create realistic two‐dimensional models of vuggy megaporosity and matrix‐porosity distribution in the limestone that composes the aquifer. When the borehole image data alone were used as the model training image, multiple‐point geostatistics failed to detect the known spatial autocorrelation of vuggy megaporosity and matrix porosity among the three boreholes, which were only 10 m apart. Variogram analysis and subsequent Gaussian simulation produced results that showed a realistic conceptualization of horizontal continuity of strata dominated by vuggy megaporosity and matrix porosity among the three boreholes.     

Effects of rate-limited mass transfer on water sampling with partially penetrating wells

Nonequilibrium concentration type curves are numerically developed and sensitivity analyses are performed to examine the relationships between effluent concentrations in partially penetrating monitoring/extraction wells, the vertical plume shape, and the mass transfer characteristics of the aquifer. The governing two-dimensional, axisymmetric nonequilibrium solute transport equation is solved in three stages using an operator-splitting approach. In the first two stages, the advection and dispersion terms are solved with the Eulerian-Lagrangian method, based on the backward method of characteristics for advection and the standard implicit Galerkin finite element method for dispersion. In the third step, the first-order, immobile-mobile domain mass transfer term is computed analytically for both two-site and lognormally distributed, multirate models. Effluent concentration variations with time and contour plots of the pore water concentration distribution in the aquifer are compared for a wide range of field- and laboratory-measured mass transfer rates, various plume shapes, and relevant physical/chemical parameter values, including pumping rate, vertical anisotropy ratio, retardation factor, and porosity. The simulation results show that rate-limited mass transfer can have a significant impact on sample and aquifer pore water concentrations during three-dimensional transport to a partially penetrating well. An alternative dimensionless form of the nonequilibrium solute transport equation is derived to illustrate the key parameter groupings that quantify rate-limited sorption effects and show the relative importance of individual parameters. A hypothetical field application example demonstrates the fitting of dimensional type curves to discrete-interval sampling data in order to evaluate the mass transfer characteristics of an aquifer and shows how type curve superposition can be used to model complex plume shapes.     

The Dual-Domain Porosity Apparatus: Characterizing Dual Porosity at the Sediment/Water Interface

The characterization of pore-space connectivity in porous media at the sediment/water interface is critical in understanding contaminant transport and reactive biogeochemical processes in zones of groundwater and surface-water exchange. Previous in situ studies of dual-domain (i.e., mobile/less-mobile porosity) systems have been limited to solute tracer injections at scales of meters to hundreds of meters and subsequent numerical model parameterization using fluid concentration histories. Pairing fine-scale (e.g., sub-meter) geoelectrical measurements with fluid tracer data over time alleviates dependence on flowpath-scale experiments, enabling spatially targeted characterization of shallow sediment/water interface media where biogeochemical reactivity is often high. The Dual-Domain Porosity Apparatus is a field-tested device capable of variable rate-controlled downward flow experiments. The Dual-Domain Porosity Apparatus facilitates inference of dual-domain parameters, i.e., mobile/less-mobile exchange rate coefficient and the ratio of less mobile to mobile porosity. The Dual-Domain Porosity Apparatus experimental procedure uses water electrical conductivity as a conservative tracer of differential loading and flushing of pore spaces within the region of measurement. Variable injection rates permit the direct quantification of the flow-dependence of dual-domain parameters, which has been theorized for decades but remains challenging to assess using existing experimental methodologies.     

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.     

Contaminant transport in a small deformation aquitard affected by the delayed drainage phenomenon

This paper presents a formulation accounting for the effect of delayed drainage phenomenon (DDP) on the breakthrough of contaminant flux in an aquitard, by considering the movement of soil particles, porosity variation, hydraulic head variation, and transient flow during the consolidation. The water flow equation in an aquitard was based on the Terzaghi's consolidation theory, and the contaminant transport equation was derived on the basis of the mass balance law. Two cases were used to illustrate the effect of DDP on the contaminant transport in an aquitard of small deformation. It is found that the breakthrough time of contaminant in an aquitard is very long, which is mainly ascribed to the low permeability of aquitard and sorption of soil particles. It is also found that the increase of depletion, which is in general induced by the increase of thickness and specific storativity and the decrease of hydraulic conductivity, enhances the impact of DDP on the contaminant transport in an aquitard. A larger delay index (τ₀) of DDP gives a greater delay breakthrough time (DBT) of solute transport in an aquitard, which controls the difference of the breakthrough time of contaminant transport in aquitards with and without the occurrence of DDP. For the cases where advection plays a dominant role during the process of solute transport, τ₀ is almost linearly correlated with DBT, and the ratio of DBT over the breakthrough time without consideration of DDP also approximately shows a linear relationship with the ratio of specific storativity to porosity, given a fixed drawdown in the adjacent aquifer with the sorption being ignored.     

Can Contaminant Transport Models Predict Breakthrough?

A solute breakthrough curve measured during a two-well tracer test was successfully predicted in 1986 using specialized contaminant transport models. Water was injected into a confined, unconsolidated sand aquifer and pumped out 125 feet (38.3 m) away at the same steady rate. The injected water was spiked with bromide for over three days; the outflow concentration was monitored for a month. Based on previous tests, the horizontal hydraulic conductivity of the thick aquifer varied by a factor of seven among 12 layers. Assuming stratified flow with small dispersivities, two research groups accurately predicted breakthrough with three-dimensional (12-layer) models using curvilinear elements following the arc-shaped flowlines in this test.
Can contaminant transport models commonly used in industry, that use rectangular blocks, also reproduce this breakthrough curve? The two-well test was simulated with four MODFLOW-based models, MT3D (FD and HMOC options), MODFLOWT, MOC3D, and MODFLOW-SURFACT.
Using the same 12 layers and small dispersivity used in the successful 1986 simulations, these models fit almost as accurately as the models using curvilinear blocks. Subtle variations in the curves illustrate differences among the codes. Sensitivities of the results to number and size of grid blocks, number of layers, boundary conditions, and values of dispersivity and porosity are briefly presented. The fit between calculated and measured breakthrough curves degenerated as the number of layers and/or grid blocks decreased, reflecting a loss of model predictive power as the level of characterization lessened. Therefore, the breakthrough curve for most field sites can be predicted only qualitatively due to limited characterization of the hydrogeology and contaminant source strength.     

Nonlinear iteration methods for nonequilibrium multiphase subsurface flow

Fully implicit, fully coupled techniques are developed for simulating multiphase flow with nonequilibrium mass transfer between phases, with application to groundwater contaminant flow and transport. Numerical issues which are addressed include: use of MUSCL or Van Leer flux limiters to reduce numerical dispersion, use of full or approximate Jacobian for flux limiter methods, and variable substitution for increased Newton iteration efficiency. A comparison of the performance of equilibrium and nonequilibrium models is also presented.     

Tidal influence on BTEX biodegradation in sandy coastal aquifers

A numerical study was conducted to investigate the influence of tides on the fate of terrestrially derived BTEX discharging through an unconfined aquifer to coastal waters. Previous studies have revealed that tide-induced seawater circulations create an active salt–freshwater mixing zone in the near-shore aquifer and alter the specific subsurface pathway for contaminants discharging to the coastal environment. Here the coupled density-dependent flow and multi-species reactive transport code PHWAT was used to examine the impact of these tidal effects on the aerobic biodegradation of BTEX released in a coastal aquifer and its subsequent loading to coastal waters. Simulations indicated that tides significantly enhance BTEX attenuation in the near-shore aquifer. They also reduce the rate of chemical transfer from the aquifer to the ocean and exit concentrations at the beach face. For the base case consisting of toluene transport and biodegradation, 79% of toluene initially released in the aquifer was attenuated prior to discharge with tides present, compared to only 1.8% for the non-tidal case. The magnitude of tidal forcing relative to the fresh groundwater flow rate was shown to influence significantly the extent of biodegradation as it controls the intensity of salt–freshwater mixing, period of exposure of the contaminant to the mixing zone and rate of oxygen delivery to the aquifer. The oxygen available for biodegradation also depends on the rate at which oxygen is consumed by natural processes such as organic matter decomposition. While simulations conducted with heterogeneous conductivity fields highlighted the uncertainties associated with predicting contaminant loadings, the study revealed overall that BTEX may undergo significant attenuation in tidally influenced aquifers prior to discharge.     

Modeling Transport in Transient Ground-Water Flow: An Unacknowledged Approximation

Abstract. During unsteady or transient ground-water flow, the fluid mass per unit volume of aquifer changes as the potentiometric head changes, and solute transport is affected by this change in fluid storage. Three widely applied numerical models of two-dimensional transport partially account for the effects of transient flow by removing terms corresponding to the fluid continuity equation from the transport equation, resulting in a simpler governing equation. However, fluid-storage terms remaining in the transport equation that change during transient flow are, in certain cases, held constant in time in these models. For the case of increasing heads, this approximation, which is unacknowledged in these models'documentation, leads to transport velocities that are too high, and increased concentration at fluid and solute sources. If heads are dropping in time, computed transport velocities are too low. Using parameters that somewhat exaggerate the effects of this approximation, an example numerical simulation indicates solute travel time error of about 14 percent but only minor errors due to incorrect dilution volume. For horizontal flow and transport models that assume fluid density is constant, the product of porosity and aquifer thickness changes in time: initial porosity times initial thickness plus the change in head times the storage coefficient. This formula reduces to the saturated thickness in unconfined aquifers if porosity is assumed to be constant and equal to specific yield. The computational cost of this more accurate representation is insignificant and is easily incorporated in numerical models of solute transport.     

Monte Carlo evaluation of microbial-mediated contaminant reactions in heterogeneous aquifers

Monte Carlo simulations are conducted to evaluate microbial-mediated contaminant reactions in an aquifer comprised of spatially variable microbial biomass concentrations, aquifer hydraulic conductivities, and initial electron donor/acceptor concentrations. A finite element simulation model is used that incorporates advection, dispersion, and Monod kinetic expressions to describe biological processes. Comparisons between Monte Carlo simulations of heterogeneous systems and simulations using homogeneous formulation of the same two-dimensional transport problem are presented. For the assumed set of parameters, physical aquifer heterogeneity is found to have a minor effect on the mass of contaminant biodegraded/transformed when compared to a homogeneous system; however, it noticeably changes the dispersion, skewness, and peakness of contaminant concentration distributions. Similarly, for low microbial growth rate, given favorable microbial growth characteristics, biological heterogeneity has minor effect on the mass of contaminant biodegraded/transformed when compared to a homogeneous system. On the other hand, when higher effective growth rates are assumed, biological heterogeneity and spatial heterogeneities in essential electron donor/acceptors reduce the efficiency of biotic contaminant reactions; consequently, model simulations derived from heterogeneous biomass distributions predict remediation time scales that are longer than those simulated for homogeneous systems. When correlations between physical aquifer and biological heterogeneities are considered, the assumed correlation affects predicted mean and variance of contaminant concentration and biomass distributions. For example, an assumed negative correlation between hydraulic conductivity and the initial biomass distribution produces a plume where less efficient biotic contaminant reactions occur at the leading edge of the plume; this is consistent with less degradation/transformation occurring over regions of higher groundwater velocities. However, the presence and absence of these correlations do not appear to affect the efficiency of microbial-mediated contaminant attenuation.     

Effective macroscopic transport parameters between parallel plates with constant concentration boundaries

A macroscopic transport model is developed, following the Taylor shear dispersion analysis procedure, for a 2D laminar shear flow between parallel plates possessing a constant specified concentration. This idealized geometry models flow with contaminant dissolution at pore-scale in a contaminant source zone and flow in a rock fracture with dissolving walls. We upscale a macroscopic transient transport model with effective transport coefficients of mean velocity, macroscopic dispersion, and first-order mass transfer rate. To validate the macroscopic model the mean concentration, covariance, and wall concentration gradient are compared to the results of numerical simulations of the advection–diffusion equation and the Graetz solution. Results indicate that in the presence of local-scale variations and constant concentration boundaries, the upscaled mean velocity and macrodispersion coefficient differ from those of the Taylor–Aris dispersion, and the mass transfer flux described by the first-order mass transfer model is larger than the diffusive mass flux from the constant wall. In addition, the upscaled first-order mass transfer coefficient in the macroscopic model depends only on the plate gap and diffusion coefficient. Therefore, the upscaled first-order mass transfer coefficient is independent of the mean velocity and travel distance, leading to a constant pore-scale Sherwood number of 12. By contrast, the effective Sherwood number determined by the diffusive mass flux is a function of the Peclet number for small Peclet number, and approaches a constant of 10.3 for large Peclet number.     

Transport and fate of nonaqueous phase liquid (NAPL) in variably saturated porous media with evolving scales of heterogeneity

 A stochastic simulation is performed to study multiphase flow and contaminant transport in fractal porous media with evolving scales of heterogeneity. Numerical simulations of residual NAPL mass transfer and subsequent transport of dissolved and/or volatilized NAPL mass in variably saturated media are carried out in conjunction with Monte Carlo techniques. The impact of fractal dimension, plume scale and anisotropy (stratification) of fractal media on relative dispersivities is investigated and discussed. The results indicate the significance of evolving scale of porous media heterogeneity to the NAPL transport in the subsurface. In general, the fractal porous media enhance the dispersivities of NAPL mass plume transport in both the water phase and the gas phase while the influence on the water phase is more significant. The porous media with larger fractal dimension have larger relative dispersivities. The aqueous horizontal dispersivity exhibits a most significant increase against the plume scale.     

Non-equilibrium interphase heat and mass transfer during two-phase flow in porous media—Theoretical considerations and modeling

Mass and heat transfer occurring across phase-interfaces in multi-phase flow in porous media are mostly approximated using equilibrium relationships or empirical kinetic models. However, when the characteristic time of flow is smaller than that of mass or heat transfer, non-equilibrium situations may arise. Commonly, empirical approaches are used in such cases. There are only few works in the literature that use physically-based models for these transfer terms. In fact, one would expect physical approaches to modeling kinetic interphase mass and heat transfer to contain the interfacial area between the phases as a variable. Recently, a two-phase flow and solute transport model was developed that included interfacial area as a state variable [36]. In that model, interphase mass transfer was modeled as a kinetic process.     

Hydrogeophysical Methods for Analyzing Aquifer Storage and Recovery Systems

Hydrogeophysical methods are presented that support the siting and monitoring of aquifer storage and recovery (ASR) systems. These methods are presented as numerical simulations in the context of a proposed ASR experiment in Kuwait, although the techniques are applicable to numerous ASR projects. Bulk geophysical properties are calculated directly from ASR flow and solute transport simulations using standard petrophysical relationships and are used to simulate the dynamic geophysical response to ASR. This strategy provides a quantitative framework for determining site‐specific geophysical methods and data acquisition geometries that can provide the most useful information about the ASR implementation. An axisymmetric, coupled fluid flow and solute transport model simulates injection, storage, and withdrawal of fresh water (salinity ～500 ppm) into the Dammam aquifer, a tertiary carbonate formation with native salinity approximately 6000 ppm. Sensitivity of the flow simulations to the correlation length of aquifer heterogeneity, aquifer dispersivity, and hydraulic permeability of the confining layer are investigated. The geophysical response using electrical resistivity, time‐domain electromagnetic (TEM), and seismic methods is computed at regular intervals during the ASR simulation to investigate the sensitivity of these different techniques to changes in subsurface properties. For the electrical and electromagnetic methods, fluid electric conductivity is derived from the modeled salinity and is combined with an assumed porosity model to compute a bulk electrical resistivity structure. The seismic response is computed from the porosity model and changes in effective stress due to fluid pressure variations during injection/recovery, while changes in fluid properties are introduced through Gassmann fluid substitution.     

Using wind run to predict sand drift

Conventional aeolian sand transport models relate mass transport rate to wind speed or shear velocity, usually expressed and empirically tested on a 1-s time scale. Projections of total sand delivery over long time scales based on these models are highly sensitive to any small bias arising from statistical fitting on empirical data. We analysed time series of wind speed and sand transport rate collected at 14 independent measurement stations on a beach during a prior field experiment. The results show that relating total sand drift to cumulative above-threshold wind run yields models which are more statistically robust when fitted on empirical data, generating smaller prediction errors when projected to longer time scales. Testing of different power exponents indicates that a linear relationship between sand drift and above-threshold wind run yields the best results. These findings inspire a speculative novel phenomenological model relating the mass flow of air in the boundary layer to the mass transport of sand over the surface. © 2020 John Wiley & Sons, Ltd.