Transport in chemically and mechanically heterogeneous porous media IV: large-scale mass equilibrium for solute transport with adsorption

In this article we consider the transport of an adsorbing solute in a two-region model of a chemically and mechanically heterogeneous porous medium when the condition of large-scale mechanical equilibrium is valid. Under these circumstances, a one-equation model can be used to predict the large-scale averaged velocity, but a two-equation model may be required to predict the regional velocities that are needed to accurately describe the solute transport process. If the condition of large-scale mass equilibrium is valid, the solute transport process can be represented in terms of a one-equation model and the analysis is simplified greatly. The constraints associated with the condition of large-scale mass equilibrium are developed, and when these constraints are satisfied the mass transport process can be described in terms of the large-scale average velocity, an average adsorption isotherm, and a single large-scale dispersion tensor. When the condition of large-scale mass equilibrium is not valid, two equations are required to describe the mass transfer process, and these two equations contain two adsorption isotherms, two dispersion tensors, and an exchange coefficient. The extension of the analysis to multi-region models is straight forward but tedious.     

Lattice Boltzmann Models for Flow and Transport in Saturated Karst

Flow and transport simulation in karst aquifers remains a significant challenge for the ground water modeling community. Darcy's law–based models cannot simulate the inertial flows characteristic of many karst aquifers. Eddies in these flows can strongly affect solute transport. The simple two-region conduit/matrix paradigm is inadequate for many purposes because it considers only a capacitance rather than a physical domain. Relatively new lattice Boltzmann methods (LBMs) are capable of solving inertial flows and associated solute transport in geometrically complex domains involving karst conduits and heterogeneous matrix rock. LBMs for flow and transport in heterogeneous porous media, which are needed to make the models applicable to large-scale problems, are still under development. Here we explore aspects of these future LBMs, present simple examples illustrating some of the processes that can be simulated, and compare the results with available analytical solutions. Simulations are contrived to mimic simple capacitance-based two-region models involving conduit (mobile) and matrix (immobile) regions and are compared against the analytical solution. There is a high correlation between LBM simulations and the analytical solution for two different mobile region fractions. In more realistic conduit/matrix simulation, the breakthrough curve showed classic features and the two-region model fit slightly better than the advection-dispersion equation (ADE). An LBM-based anisotropic dispersion solver is applied to simulate breakthrough curves from a heterogeneous porous medium, which fit the ADE solution. Finally, breakthrough from a karst-like system consisting of a conduit with inertial regime flow in a heterogeneous aquifer is compared with the advection-dispersion and two-region analytical solutions.     

Transport in chemically and mechanically heterogeneous porous media: V. Two-equation model for solute transport with adsorption

In this paper we develop the two-equation model for solute transport and adsorption in a two-region model of a mechanically and chemically heterogeneous porous medium. The closure problem is derived and the coefficients in both the one- and two-equation models are determined on the basis of the Darcy-scale parameters. Numerical experiments are carried out for a stratified system at the aquifer scale, and the results are compared with the one-equation model presented in Part IV and the two-equation model developed in this paper. Good agreement between the two-equation model and the numerical experiments is obtained. In addition, the two-equation model is used, in conjunction with a moment analysis, to derive a one-equation, non-equilibrium model that is valid in the asymptotic regime. Numerical results are used to identify the asymptotic regime for the one-equation, non-equilibrium model.     

Transport in chemically and mechanically heterogeneous porous media—III. Large-scale mechanical equilibrium and the regional form of Darcy's law

In this paper we develop the regional form of Darcy's law when the condition of large-scale mechanical equilibrium is valid. This condition occurs for many steady or quasi-steady flows of practical importance, and analytical constraints are presented which define the domain of validity for large-scale mechanical equilibrium. Given a two-region model of a heterogeneous porous medium, the intrinsic region-averaged velocities can be expressed in terms of the large-scale average velocity according to ϕ_η{〈v_β〉_gh}^η = M_βη¹ · {〈v_β〉}, in the η - region ϕ_ω{〈v_β〉_ω}^ω = M_βω¹ · {〈V_β〉}, in the ω - regionHere the mapping tensors M_βη¹ and M_βω¹, are specified by the same closure problem used to determine the effective thermal conductivity tensor for a two-phase system, and they are directly related to the regional permeability tensors K_βν¹ and K_βω¹ Regional permeability tensors are determined for stratified systems, for a nodular model of heterogeneous porous media, and for fractured porous media. These large-scale permeabilities are sensitive to the structure of the mechanical heterogeneities and in general they are not equal to the local permeability that is used to characterize the mechanical heterogeneities.     

Analytical solutions of one-dimensional macrodispersion in stratified porous media by the quadrupole method: convergence to an equivalent homogeneous porous medium

In this article, the quadrupole method is implemented in order to simulate the effects of heterogeneities on one dimensional advective and diffusive transport of a passive solute in porous media. Theoretical studies of dispersion in heterogeneous stratified media can bring insight into transport artefacts linked to scale effects and apparent dispersion coefficients. The quadrupole method is an efficient method for the calculation of transient response of linear systems. It is based here on the Laplace transform technique. The analytical solutions that can be derived by this method assists understanding of upscaled parameters relevant to heterogeneous porous media.First, the method is developed for an infinite homogeneous porous medium. Then, it is adapted to a stratified medium where the fluid flow is perpendicular to the interfaces. The first heterogeneous medium studied is composed of two semi-infinite layers perpendicular to the flow direction each having different transport properties. The concentration response of the medium to a Dirac injection is evaluated. The case studied emphasises the importance in the choice of the boundary conditions.In the case of a periodic heterogeneous porous medium, the concentration response of the medium is evaluated for different numbers of unit-cells. When the number of unit cells is great enough, depending on the transport properties of each layer in the unit cell, an equivalent homogeneous behaviour is reached. An exact determination of the transport properties (equivalent dispersion coefficient) of the equivalent homogeneous porous medium is given.     

On the aquifer's integrated balance equations

A general methodology is presented for describing transport phenomena in porous media at a macroscopic level. Then, these macroscopic balance equations are integrated (or averaged) along the vertical for confined, leaky and phreatic aquifers.The results are employed to derive (averaged) aquifer equations for the flow of water and of a solute (hydrodynamic dispersion). It is shown that in all cases, the resulting equation is identical to that derived on the basis of an assumption of horizontal flow (the Dupuit assumption).Macrodispersion, occurring at the aquifer level, is discussed and appropriate coefficients are proposed.     

Analytical solutions for solute transport in saturated porous media with semi-infinite or finite thickness

Three-dimensional analytical solutions for solute transport in saturated, homogeneous porous media are developed. The models account for three-dimensional dispersion in a uniform flow field, first-order decay of aqueous phase and sorbed solutes with different decay rates, and nonequilibrium solute sorption onto the solid matrix of the porous formation. The governing solute transport equations are solved analytically by employing Laplace, Fourier and finite Fourier cosine transform techniques. Porous media with either semi-infinite or finite thickness are considered. Furthermore, continuous as well as periodic source loadings from either a point or an elliptic source geometry are examined. The effect of aquifer boundary conditions as well as the source geometry on solute transport in subsurface porous formations is investigated.     

Effects of chemical reactions on density-dependent fluid flow: on the numerical formulation and the development of instabilities

A three-dimensional, reactive numerical flow model is developed that couples chemical reactions with density-dependent mass transport and fluid flow. The model includes equilibrium reactions for the aqueous species, kinetic reactions between the solid and aqueous phases, and full coupling of porosity and permeability changes that result from precipitation and dissolution reactions in porous media. A one-step, global implicit approach is used to solve the coupled flow, transport and reaction equations with a fully implicit upstream-weighted control volume discretization. The Newton–Raphson method is applied to the discretized non-linear equations and a block ILU-preconditioned CGSTAB method is used to solve the resulting Jacobian matrix equations. This approach permits the solution of the complete set of governing equations for both concentration and pressure simultaneously affected by chemical and physical processes. A series of chemical transport simulations are conducted to investigate coupled processes of reactive chemical transport and density-dependent flow and their subsequent impact on the development of preferential flow paths in porous media. The coupled effects of the processes driving flow and the chemical reactions occurring during solute transport is studied using a carbonate system in fully saturated porous media. Results demonstrate that instability development is sensitive to the initial perturbation caused by density differences between the solute plume and the ambient groundwater. If the initial perturbation is large, then it acts as a “trigger” in the flow system that causes instabilities to develop in a planar reaction front. When permeability changes occur due to dissolution reactions occurring in the porous media, a reactive feedback loop is created by calcite dissolution and the mixed convective transport of the system. Although the feedback loop does not have a significant impact on plume shape, complex concentration distributions develop as a result of the instabilities generated in the flow system.     

Divergence of solutions to perturbation-based advection-dispersion moment equations

Moment equation methods are popular and powerful tools for modeling transport processes in randomly heterogeneous porous media, but the application of these methods to advection-dispersion equations often leads to erroneous oscillations. Perturbative methods, required to close systems of moment equations, become inaccurate for large perturbations; however, little quantitative theory exists for determining when this occurs for advection-dispersion equations. We consider three different methods (asymptotic approximation, Eulerian truncation, and iterative solution) for closing and solving advection-dispersion moment equations describing transport in stratified porous media with random permeability. We obtain approximate analytical expressions for time above which the asymptotic approximation to the mean diverges, in particular quantifying the impact that dispersion has on delaying—but not eliminating—divergence. We demonstrate that Eulerian truncation and iterative solution methods do not eliminate divergent behavior either. Our divergence criteria provide a priori estimates that signal a warning to the practitioner of stochastic advection-dispersion equations to carefully consider whether to apply perturbative approaches.     

Effects of compound-specific dilution on transient transport and solute breakthrough: A pore-scale analysis

This pore-scale modeling study in saturated porous media shows that compound-specific effects are important not only at steady-state and for the lateral displacement of solutes with different diffusivities but also for transient transport and solute breakthrough. We performed flow and transport simulations in two-dimensional pore-scale domains with different arrangement of the solid grains leading to distinct characteristics of flow variability and connectivity, representing mildly and highly heterogeneous porous media, respectively. The results obtained for a range of average velocities representative of groundwater flow (0.1–10 m/day), show significant effects of aqueous diffusion on solute breakthrough curves. However, the magnitude of such effects can be masked by the flux-averaging approach used to measure solute breakthrough and can hinder the correct interpretation of the true dilution of different solutes. We propose, as a metric of mixing, a transient flux-related dilution index that allows quantifying the evolution of solute dilution at a given position along the main flow direction. For the different solute transport scenarios we obtained dilution breakthrough curves that complement and add important information to traditional solute breakthrough curves. Such dilution breakthrough curves allow capturing the compound-specific mixing of the different solutes and provide useful insights on the interplay between advective and diffusive processes, mass transfer limitations, and incomplete mixing in the heterogeneous pore-scale domains. The quantification of dilution for conservative solutes is in good agreement with the outcomes of mixing-controlled reactive transport simulations, in which the mass and concentration breakthrough curves of the product of an instantaneous transformation of two initially segregated reactants were used as measures of reactive mixing.     

Effective dispersion in a chemically heterogeneous medium under temporally fluctuating flow conditions

We investigate effective solute transport in a chemically heterogeneous medium subject to temporal fluctuations of the flow conditions. Focusing on spatial variations in the equilibrium adsorption properties, the corresponding fluctuating retardation factor is modeled as a stationary random space function. The temporal variability of the flow is represented by a stationary temporal random process. Solute spreading is quantified by effective dispersion coefficients, which are derived from the ensemble average of the second centered moments of the normalized solute distribution in a single disorder realization. Using first-order expansions in the variances of the respective random fields, we derive explicit compact expressions for the time behavior of the disorder induced contributions to the effective dispersion coefficients. Focusing on the contributions due to chemical heterogeneity and temporal fluctuations, we find enhanced transverse spreading characterized by a transverse effective dispersion coefficient that, in contrast to transport in steady flow fields, evolves to a disorder-induced macroscopic value (i.e., independent of local dispersion). At the same time, the asymptotic longitudinal dispersion coefficient can decrease. Under certain conditions the contribution to the longitudinal effective dispersion coefficient shows superdiffusive behavior, similar to that observed for transport in s stratified porous medium, before it decreases to its asymptotic value. The presented compact and easy to use expressions for the longitudinal and transverse effective dispersion coefficients can be used for the quantification of effective spreading and mixing in the context of the groundwater remediation based on hydraulic manipulation and for the effective modeling of reactive transport in heterogeneous media in general.     

New equations for binary gas transport in porous media,: Part 1: equation development

A rigorous understanding of the mass and momentum conservation equations for gas transport in porous media is vital for many environmental and industrial applications. We utilize the method of volume averaging to derive Darcy-scale, closure-level coupled equations for mass and momentum conservation. The up-scaled expressions for both the gas-phase advective velocity and the mass transport contain novel terms which may be significant under flow regimes of environmental significance. New terms in the velocity expression arise from the inclusion of a slip boundary condition and closure-level coupling to the mass transport equation. A new term in the mass conservation equation, due to the closure-level coupling, may significantly affect advective transport. Order of magnitude estimates based on the closure equations indicate that one or more of these new terms will be significant in many cases of gas flow in porous media.     

A stationary principle for non conservative systems

A stationary principle is described to yield governing integral formulations for dissipative systems. Variation is applied on selective terms of energy or momentum functionals resulting with force or mass balance equations respectively. Applying the principle for a motion of a viscous fluid yields the Navier-Stokes equations as an approximation of the functional (i.e. equating to zero part of the integrand). When a Darcy's flow regime in a porous media is considered, implementing a space averaging method on the resultant integral derived by the principle, Forchheimer's law for energy accumulation and solute transport equation for momentum assembling are yielded in differential form approximation of a more extended functional formulation.     

A connection between the Lagrangian stochastic–convective and cumulant expansion approaches for describing solute transport in heterogeneous porous media

The equation describing the ensemble-average solute concentration in a heterogeneous porous media can be developed from the Lagrangian (stochastic–convective) approach and from a method that uses a renormalized cumulant expansion. These two approaches are compared for the case of steady flow, and it is shown that they are related. The cumulant expansion approach can be interpreted as a series expansion of the convolution path integral that defines the ensemble-average concentration in the Lagrangian approach. The two methods can be used independently to develop the classical form for the convection–dispersion equation, and are shown to lead to identical transport equations under certain simplifying assumptions. In the development of such transport equations, the cumulant expansion does not require a priori the assumption of any particular distribution for the Lagrangian displacements or velocity field, and does not require one to approximate trajectories with their ensemble-average. In order to obtain a second-order equation, the cumulant expansion method does require truncation of a series, but this truncation is done rationally by the development of a constraint in terms of parameters of the transport field. This constraint is less demanding than requiring that the distribution for the Lagrangian displacements be strictly Gaussian, and it indicates under what velocity field conditions a second-order transport equation is a reasonable approximation.     

A derivation of the equations for transport of liquid and heat in three dimensions in a fractured porous medium

Governing equations can be derived for transient, three-dimensional transport of heat and mass in compressible, liquid saturated fractured porous media. Recently developed mathematical techniques can be used which relate local space averages of derivatives of medium properties to the derivatives of those averages. Using these techniques, well established thermomechanical transport equations which apply at microscopic points may be transformed into equations in macroscopic variables; i.e. in variables which pertain to the scale of observation. In the absence of chemical reactions, transfer between source entities and the medium may be taken care of in a consistent, physically realistic way, such that macroscopic source terms arise naturally in the course of the macroscopization procedures.     

An exact solution of solute transport by one-dimensional random velocity fields

The problem of one-dimensional transport of passive solute by a random steady velocity field is investigated. This problem is representative of solute movement in porous media, for example, in vertical flow through a horizontally stratified formation of variable porosity with a constant flux at the soil surface. Relating moments of particle travel time and displacement, exact expressions for the advection and dispersion coefficients in the Focker-Planck equation are compared with the perturbation results for large distances. The first- and second-order approximations for the dispersion coefficient are robust for a lognormal velocity field. The mean Lagrangian velocity is the harmonic mean of the Eulerian velocity for large distances. This is an artifact of one-dimensional flow where the continuity equation provides for a divergence free fluid flux, rather than a divergence free fluid velocity.     

An exact solution of solute transport by one-dimensional random velocity fields

The problem of one-dimensional transport of passive solute by a random steady velocity field is investigated. This problem is representative of solute movement in porous media, for example, in vertical flow through a horizontally stratified formation of variable porosity with a constant flux at the soil surface. Relating moments of particle travel time and displacement, exact expressions for the advection and dispersion coefficients in the Focker-Planck equation are compared with the perturbation results for large distances. The first- and second-order approximations for the dispersion coefficient are robust for a lognormal velocity field. The mean Lagrangian velocity is the harmonic mean of the Eulerian velocity for large distances. This is an artifact of one-dimensional flow where the continuity equation provides for a divergence free fluid flux, rather than a divergence free fluid velocity.