A master equation for reactive solute transport in porous media

The mean value of a density of a cloud of points described by a generalized Liouville equation associated with a convection dispersion equation governing adsorbing solute transport yields a joint concentration probability density. The general technique can be applied for either linear or nonlinear adsorption; here the application is restricted to linear adsorption in one-dimensional transport. The equation generated for the joint concentration probability density is in the general form of a Fokker-Planck equation, but with a suitable coordinate transformation, it is possible to represent it as a diffusion equation with variable coefficients.     

A meshless method to simulate solute transport in heterogeneous porous media

We derive a meshless numerical method based on smoothed particle hydrodynamics (SPH) for the simulation of conservative solute transport in heterogeneous geological formations. We demonstrate that the new proposed scheme is stable, accurate, and conserves global mass. We evaluate the performance of the proposed method versus other popular numerical methods for the simulation of one- and two-dimensional dispersion and two-dimensional advective–dispersive solute transport in heterogeneous porous media under different Pèclet numbers. The results of those benchmarks demonstrate that the proposed scheme has important advantages over other standard methods because of its natural ability to control numerical dispersion and other numerical artifacts. More importantly, while the numerical dispersion affecting traditional numerical methods creates artificial mixing and dilution, the new scheme provides numerical solutions that are “physically correct”, greatly reducing these artifacts.     

Numerical simulations of non-ergodic solute transport in three-dimensional heterogeneous porous media

Numerical simulations of non-ergodic transport of a non-reactive solute plume by steady-state groundwater flow under a uniform mean velocity, , were conducted in a three-dimensional heterogeneous and statistically isotropic aquifer. The hydraulic conductivity, K(x), is modeled as a random field which is assumed to be log-normally distributed with an exponential covariance. Significant efforts are made to reduce the simulation uncertainties. Ensemble averages of the second spatial moments of the plume and the plume centroid variances were simulated with 1600 Monte Carlo (MC) runs for three variances of log K, _Y²=0.09, 0.23, and 0.46, and a square source normal to of three dimensionless lengths. It is showed that 1600 MC runs are needed to obtain stabilized results in mildly heterogeneous aquifers of _Y²0.5 and that large uncertainty may exist in the simulated results if less MC runs are used, especially for the transverse second spatial moments and the plume centroid variance in transverse directions. The simulated longitudinal second spatial moment and the plume centroid variance in longitudinal direction fit well to the first-order theoretical results while the simulated transverse moments are generally larger than the first-order values. The ergodic condition for the second spatial moments is far from reaching in all cases simulated and transport in transverse directions may reach ergodic condition much slower than that in longitudinal direction.     

Effect of permeability variations on solute transport in highly heterogeneous porous media

The effect of aquifer heterogeneity on flow and solute transport in two-dimensional isotropic porous media was analyzed using the Monte Carlo method. The two-dimensional logarithmic permeability (ln K) was assumed to be a non-stationary random field with its increments being a truncated fractional Lévy motion (fLm). The permeability fields were generated using the modified successive random additions (SRA) algorithm code SRA3DC [http://www.iamg.org/CGEditor/index.htm]. The velocity and concentration fields were computed respectively for two-dimensional flow and transport with a pulse input using the finite difference codes of MODFLOW 2000 and MT3DMS. Two fLm control parameters, namely the width parameter (C) and the Lévy index (α), were varied systematically to examine their effect on the resulting permeability, flow velocity and concentration fields. We also computed the first- and second-spatial moments, the dilution index, as well as the breakthrough curves at different control planes with the corresponding concentration fields. In addition, the derived breakthrough curves were fitted using the continuous time random walk (CTRW) and the traditional advection-dispersion equation (ADE). Results indicated that larger C and smaller α both led to more heterogeneous permeability and velocity fields. The Lévy-stable distribution of increments in ln K resulted in a Lévy-stable distribution of increments in logarithm of the velocity (ln v). Both larger C and smaller α created sharper leading edges and wider tailing edges of solute plumes. Furthermore, a relatively larger amount of solute still remained in the domain after a relatively longer time transport for smaller α values. The dilution indices were smaller than unity and increased as C increased and α decreased. The solute plume and its second-spatial moments increased as C increased and α decreased, while the first-spatial moments of the solute plume were independent of C and α values. The longitudinal macrodispersivity was scale-dependent and increased as a power law function of time. Increasing C and decreasing α both resulted in an increase in longitudinal macrodispersivity. The transport in such highly heterogeneous media was slightly non-Gaussian with its derived breakthrough curves being slightly better fitted by the CTRW than the ADE, especially in the early arrivals and late-time tails.     

A note on benchmarking of numerical models for density dependent flow in porous media

Verification of numerical models for density dependent flow in porous media (DDFPM) by the means of appropriate benchmark problems is a very important step in developing and using these models. Recently, Infinite Horizontal Box (IHB) problem was suggested as a possible benchmark problem for verification of DDFPM codes. IHB is based on Horton–Rogers–Lapwood (HRL) problem. Suitability of this problem for the benchmarking purpose has been investigated in this paper. It is shown that the wavelength of instabilities fails to be a proper criterion to be considered for this problem. However, the threshold of instability formation has been found to be appropriate for benchmarking purpose.     

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.     

A test case for the simulation of three-dimensional variable-density flow and solute transport in discretely-fractured porous media

A test case has been developed for three-dimensional simulations of variable-density flow and solute transport in discretely-fractured porous media. The simulation domain is a low-permeability porous matrix cube containing a single non-planar fracture. The initial solute concentration is zero everywhere. A constant solute concentration is assigned to the top of the domain, which increases near-top fluid density and induces downward density-driven flow. The test case is therefore comparable to downwelling of a dense brine below a saline disposal basin or a waste repository. Numerous fingers and distinct convection cells develop early in the fracture but the fingers later coalesce and convection becomes less apparent. To help test other variable-density flow and transport models, results of the test case are presented both qualitatively (concentration contours and velocity fields) and quantitatively (penetration depth, mass flux, total mass stored, maximum fracture and matrix velocity).     

Nitrate fluctuations at the water table: implications for recharge processes and solute transport in the Chalk aquifer

This study investigates fluctuations in nitrate concentration at the water table to improve understanding of unsaturated zone processes in the Chalk aquifer. Sampling was conducted using a novel multi‐level sampler during periods of water table rise over 5 years at a vertical resolution of 0.05 m. Nitrate concentration increased as the water table seasonally recovered, with similar inter‐annual trends with depth. The rising water table activated horizontal fractures facilitating the delivery of water elevated by up to 10 mg/l of nitrate with respect to the adjacent groundwater below. These fractures are considered to activate via piston displacement of water from the adjoining matrix. Hydrograph analysis identified 16 events which significantly perturbed the water table within 24–48 h of rainfall. Consistent nitrate concentrations indicate recharge through persistent fracture flow from the surface was not generally the primary driver of the rapid water table response during these events. Instead, the response was attributed to the piston displacement of porewater immediately above the water table. However, a single event in November 2012 delivered relatively dilute recharge indicating rapid persistent fracture flow following rainfall was possible to a depth of 14–15 m. Decreases in porewater nitrate concentration around fracture horizons and the dilution of many groundwater samples with respect to porewaters indicate a fresher source of water at depth. This was considered most likely to be a result of near surface water bypassing the matrix because of widespread mineralization on fracture surfaces, which retard water and solute exchange. Therefore, persistent fracture flow maybe considered a frequent process, operating independently of the matrix, and is not necessarily event driven. Copyright © 2015 John Wiley & Sons, Ltd.     

Variable-density groundwater flow and solute transport in porous media containing nonuniform discrete fractures

Variations in fluid density can greatly affect fluid flow and solute transport in the subsurface. Heterogeneities such as fractures play a major role for the migration of variable-density fluids. Earlier modeling studies of density effects in fractured media were restricted to orthogonal fracture networks, consisting of only vertical and horizontal fractures. The present study addresses the phenomenon of 3D variable-density flow and transport in fractured porous media, where fractures of an arbitrary incline can occur. A general formulation of the body force vector is derived, which accounts for variable-density flow and transport in fractures of any orientation. Simulation results are presented that show the verification of the new model formulation, for the porous matrix and for inclined fractures. Simulations of variable-density flow and solute transport are then conducted for a single fracture, embedded in a porous matrix. The simulations show that density-driven flow in the fracture causes convective flow within the porous matrix and that the high-permeability fracture acts as a barrier for convection. Other simulations were run to investigate the influence of fracture incline on plume migration. Finally, tabular data of the tracer breakthrough curve in the inclined fracture is given to facilitate the verification of other codes.     

A multidimensional streamline-based method to simulate reactive solute transport in heterogeneous porous media

We present a new streamline-based numerical method for simulating reactive solute transport in porous media. The key innovation of the method is that both longitudinal and transverse dispersion are incorporated accurately without numerical dispersion. Dispersion is approximated in a flow-oriented grid using a combination of a one-dimensional finite difference scheme and a meshless approximation. In contrast to previous hybrid alternatives to incorporate dispersion in streamline-based simulations, the proposed scheme does not require a grid and, hence, it does not introduce numerical dispersion. In addition, the proposed scheme eliminates numerical oscillations and negative concentration values even when the dispersion tensor includes the off-diagonal coefficients and the flow field is non-uniform. We demonstrate that for a set of two- and three-dimensional benchmark problems, the new proposed streamline-based formulation compares favorably to two state of the art finite volume and hybrid Eulerian–Lagrangian solvers.     

Comparison of theory and experiment for solute transport in weakly heterogeneous bimodal porous media

In this work, the influence of non-equilibrium effects on solute transport in a weakly heterogeneous medium is discussed. Three macro-scale models (upscaled via the volume averaging technique) are investigated: (i) the two-equation non-equilibrium model, (ii) the one-equation asymptotic model and (iii) the one-equation local equilibrium model. The relevance of each of these models to the experimental system conditions (duration of the pulse injection, dispersivity values…) is analyzed. The numerical results predicted by these macroscale models are compared directly with the experimental data (breakthrough curves). Our results suggest that the preasymptotic zone (for which a non-Fickian model is required) increases as the solute input pulse time decreases. Beyond this limit, the asymptotic regime is recovered. A comparison with the results issued from the stochastic theory for this regime is performed. Results predicted by both approaches (volume averaging method and stochastic analysis) are found to be consistent.     

Macroscopic representation of structural geometry for simulating water and solute movement in dual-porosity media

The structure of macroporous or aggregated soils and fractured rocks is generally so complex that it is impractical to measure the geometry at the microscale (i.e., the size and the shape of soil aggregates or rock matrix blocks, and the myriad of fissures or fractures), and use such data in geometry-dependent macroscale flow and transport models. This paper analyzes a first-order type dual-porosity model which contains a geometry-dependent coefficient, β, in the mass transfer term to macroscopically represent the size and shape of soil or rock matrix blocks. As a reference, one- and two-dimensional geometry-based diffusion models were used to simulate mass transport into and out of porous blocks of defined shapes. Estimates for β were obtained analytically for four different matrix block geometries. Values for β were also calculated by directly matching analytical solutions of the diffusion models for a number of selected matrix block geometries to results obtained with the first-order model assuming standard boundary conditions. Direct matching improved previous results for cylindrical macropore geometries, especially when relatively small ratios between the outer soil mantle and the radius of the inner cylinder were used. Results of our analysis show that β is closely related to the ratio of the effective surface area available for mass transfer, and the soil matrix volume normalized by the effective characteristic length of the matrix system. Using values of β obtained by direct matching, an empirical function is derived to estimate macroscopic geometry coefficients from medium properties which in principle are measurable. The method permits independent estimates of β, thus allowing the dual-porosity approach eventually to be applied to media with complex and mixed types of structural geometry.     

Stochastic modeling of solute transport in 3-D heterogeneous porous media with random source condition

During probabilistic analysis of flow and transport in porous media, the uncertainty due to spatial heterogeneity of governing parameters are often taken into account. The randomness in the source conditions also play a major role on the stochastic behavior in distribution of the dependent variable. The present paper is focused on studying the effect of both uncertainty in the governing system parameters as well as the input source conditions. Under such circumstances, a method is proposed which combines with stochastic finite element method (SFEM) and is illustrated for probabilistic analysis of concentration distribution in a 3-D heterogeneous porous media under the influence of random source condition. In the first step SFEM used for probabilistic solution due to spatial heterogeneity of governing parameters for a unit source pulse. Further, the results from the unit source pulse case have been used for the analysis of multiple pulse case using the numerical convolution when the source condition is a random process. The source condition is modeled as a discrete release of random amount of masses at fixed intervals of time. The mean and standard deviation of concentration is compared for the deterministic and the stochastic system scenarios as well as for different values of system parameters. The effect of uncertainty of source condition is also demonstrated in terms of mean and standard deviation of concentration at various locations in the domain.     

Numerical analysis of bacterial transport in saturated porous media

A mathematical model to describe bacterial transport in saturated porous media is presented. Reversible/irreversible attachment and growth/decay terms were incorporated into the transport model. Additionally, the changes of porosity and permeability due to bacterial deposition and/or growth were accounted for in the model. The predictive model was used to fit the column experimental data from the literature, and the fitting result showed a good match with the data. Based on the parameter values determined from the literature experimental data, numerical experiments were performed to examine bacterial sorption and/or growth during bacterial transport through saturated porous media. In addition, sensitivity analysis was performed to investigate the impact of key model parameters for bacterial transport on the permeability and porosity of porous media. The model results show that the permeability and porosity of porous media could be altered due to bacterial deposition and growth on the solid matrix. However, variation of permeability due to bacterial growth was trivial compared with natural permeability variation. Copyright © 2005 John Wiley & Sons, Ltd.     

Analysis of Cryptosporidium parvum oocyst transport in porous media

Cryptosporidium parvum is a protozoan parasite, transmitted through aqueous environments in the form of an oocyst. In this study, a transport model into which sorption, filtration and inactivation mechanisms are incorporated is applied to simulate laboratory column data, and the suitability of a kinetic model to describe the C. parvum oocyst transport and removal in porous media is compared with an equilibrium model. The kinetic model is applied to simulate previous column experimental data and successfully simulates the concentration peak; the late time tailing effect appeared in the breakthrough curves, indicating that the kinetic model is more suitable than the equilibrium one at simulating the fate and transport of the oocysts in porous media. Simulation illustrates that sorption causes retardation along with a tailing in the breakthrough curve. Additionally, filtration acts as a major mechanism of removing the oocysts from the aqueous phase, whereas the role of inactivation in reducing the viable oocyst concentration is minimal. Copyright © 2004 John Wiley & Sons, Ltd.     

Simulation of less‐mobile porosity dynamics in contrasting sediment water interface porous media

Considering heterogeneity in porous media pore size and connectivity is essential to predicting reactive solute transport across interfaces. However, exchange with less‐mobile porosity is rarely considered in surface water/groundwater recharge studies. Previous research indicates that a combination of pore‐fluid sampling and geoelectrical measurements can be used to quantify less‐mobile porosity exchange dynamics using the time‐varying relation between fluid and bulk electrical conductivity. For this study, we use macro‐scale (10 s of cm) advection–dispersion solute transport models linked with electrical conduction in COMSOL Multiphysics to explore less‐mobile porosity dynamics in two different types of observed sediment water interface porous media. Modeled sediment textures contrast from strongly layered streambed deposits to poorly sorted lakebed sands and cobbles. During simulated ionic tracer perturbations, a lag between fluid and bulk electrical conductivity, and the resultant hysteresis, is observed for all simulations indicating differential loading of pore spaces with tracer. Less‐mobile exchange parameters are determined graphically from these tracer time series data without the need for inverse numerical model simulation. In both sediment types, effective less‐mobile porosity exchange parameters are variable in response to changes in flow direction and fluid flux. These observed flow‐dependent effects directly impact local less‐mobile residence times and associated contact time for biogeochemical reaction. The simulations indicate that for the sediment textures explored here, less‐mobile porosity exchange is dominated by variable rates of advection through the domain, rather than diffusion of solute, for typical low‐to‐moderate rate (approximately 3–40 cm/day) hyporheic fluid fluxes. Overall, our model‐based results show that less‐mobile porosity may be expected in a range of natural hyporheic sediments and that changes in flowpath orientation and magnitude will impact less‐mobile exchange parameters. These temporal dynamics can be assessed with the geoelectrical experimental tracer method applied at laboratory and field scales.     

Probabilistic sensitivity and modeling of two-dimensional transport in porous media

A reliability approach is used to develop a probabilistic model of two-dimensional non-reactive and reactive contaminant transport in porous media. The reliability approach provides two important quantitative results: an estimate of the probability that contaminant concentration is exceeded at some location and time, and measures of the sensitivity of the probabilistic outcome to likely changes in the uncertain variables. The method requires that each uncertain variable be assigned at least a mean and variance; in this work we also incorporate and investigate the influence of marginal probability distributions. Uncertain variables includex andy components of average groundwater flow velocity,x andy components of dispersivity, diffusion coefficient, distribution coefficient, porosity and bulk density. The objective is to examine the relative importance of each uncertain variable, the marginal distribution assigned to each variable, and possible correlation between the variables. Results utilizing a two-dimensional analytical solution indicate that the probabilistic outcome is generally very sensitive to likely changes in the uncertain flow velocity. Uncertainty associated with dispersivity and diffusion coefficient is often not a significant issue with respect to the probabilistic analysis; therefore, dispersivity and diffusion coefficient can often be treated for practical analysis as deterministic constants. The probabilistic outcome is sensitive to the uncertainty of the reaction terms for early times in the flow event. At later times, when source contaminants are released at constant rate throughout the study period, the probabilistic outcome may not be sensitive to changes in the reaction terms. These results, although limited at present by assumptions and conceptual restrictions inherent to the closed-form analytical solution, provide insight into the critical issues to consider in a probabilistic analysis of contaminant transport. Such information concerning the most important uncertain parameters can be used to guide field and laboratory investigations.