Thermodynamically constrained averaging theory approach for modeling flow and transport phenomena in porous medium systems: 4. Species transport fundamentals

This work is the fourth in a series of papers on the thermodynamically constrained averaging theory (TCAT) approach for modeling flow and transport phenomena in multiscale porous medium systems. The general TCAT framework and the mathematical foundation presented in previous works are built upon by formulating macroscale models for conservation of mass, momentum, and energy, and the balance of entropy for a species in a phase volume, interface, and common curve. In addition, classical irreversible thermodynamic relations for species in entities are averaged from the microscale to the macroscale. Finally, we comment on alternative approaches that can be used to connect species and entity conservation equations to a constrained system entropy inequality, which is a key component of the TCAT approach. The formulations detailed in this work can be built upon to develop models for species transport and reactions in a variety of multiphase systems.     

Thermodynamically constrained averaging theory approach for modeling flow and transport phenomena in porous medium systems: 2. Foundation

This paper is the second in a series that details the thermodynamically constrained averaging theory (TCAT) approach for modeling flow and transport phenomena in porous medium systems. In this work, we provide the mathematical foundation upon which the theory is based. Elements of this foundation include definitions of mathematical properties of the systems of concern, previously available theorems needed to formulate models, and several theorems and corollaries, introduced and proven here. These tools are of use in producing complete, closed-form TCAT models for single- and multiple-fluid-phase porous medium systems. Future work in this series will rely and build upon the foundation laid in this work to detail the development of sets of closed models.     

Thermodynamically constrained averaging theory approach for modeling flow and transport phenomena in porous medium systems: 3. Single-fluid-phase flow

This work is the third in a series of papers on the thermodynamically constrained averaging theory (TCAT) approach to modeling flow and transport phenomena in multiscale porous medium systems. Building upon the general TCAT framework and the mathematical foundation presented in previous works in this series, we demonstrate the TCAT approach for the case of single-fluid-phase flow. The formulated model is based upon conservation equations for mass, momentum, and energy and a general entropy inequality constraint, which is developed to guide model closure. A specific example of a closed model is derived under limiting assumptions using a linearization approach and these results are compared and contrasted with the traditional single-phase-flow model. Potential extensions to this work are discussed. Specific advancements in this work beyond previous averaging theory approaches to single-phase flow include use of macroscale thermodynamics that is averaged from the microscale, the use of derived equilibrium conditions to guide a flux–force pair approach to simplification, use of a general Lagrange multiplier approach to connect conservation equation constraints to the entropy inequality, and a focus on producing complete, closed models that are solvable.     

Thermodynamically constrained averaging theory approach for modeling flow and transport phenomena in porous medium systems: 6. Two-fluid-phase flow

This work is the sixth in a series of papers on the thermodynamically constrained averaging theory (TCAT) approach for modeling flow and transport phenomena in multiscale porous medium systems. Building upon the general TCAT framework and the mathematical foundation presented in previous works, the limiting case of connected two-fluid-phase flow is considered. A constrained entropy inequality is developed based upon a set of primary restrictions. Formal approximations are introduced to deduce a general simplified entropy inequality (SEI). The SEI is used along with secondary restrictions and closure approximations consistent with the SEI to produce a general functional form of a two-phase-flow model. The general model is in turn simplified to yield a hierarchy of models by neglecting common curves and by neglecting both common curves and interfaces. The simplest case considered corresponds to a traditional two-phase-flow model. The more sophisticated models including interfaces and common curves are more physically realistic than traditional models. All models in the hierarchy are posed in terms of precisely defined variables that allow for a rigorous connection with the microscale. The explicit nature of the restrictions and approximations used in developing this hierarchy of models provides a clear means to both understand the limitations of traditional models and to build upon this work to produce more realistic models.     

Thermodynamically constrained averaging theory approach for modeling flow and transport phenomena in porous medium systems: 1. Motivation and overview

We give several examples of weaknesses in classical, empirically derived models of transport phenomena in porous medium systems. We also place recent attempts to develop improved multiscale porous medium models using averaging theory in context and note deficiencies in these approaches. These deficiencies are found to arise in part from the manner in which thermodynamics is introduced into a constrained entropy inequality, which is used to guide the formation of closed models. Because of this, we briefly examine several established thermodynamic approaches and outline a framework to develop macroscale models that retain consistency with microscale physics and thermodynamics. This framework will be detailed and applied in future papers in this series.     

Thermodynamically constrained averaging theory approach for modeling flow and transport phenomena in porous medium systems: 7. Single-phase megascale flow models

This work is the seventh in a series that introduces and employs the thermodynamically constrained averaging theory (TCAT) for modeling flow and transport in multiscale porous medium systems. This paper expands the previous analyses in the series by developing models at a scale where spatial variations within the system are not considered. Thus the time variation of variables averaged over the entire system is modeled in relation to fluxes at the boundary of the system. This implementation of TCAT makes use of conservation equations for mass, momentum, and energy as well as an entropy balance. Additionally, classical irreversible thermodynamics is assumed to hold at the microscale and is averaged to the megascale, or system scale. The fact that the local equilibrium assumption does not apply at the megascale points to the importance of obtaining closure relations that account for the large-scale manifestation of small-scale variations. Example applications built on this foundation are suggested to stimulate future work.     

Block-effective macrodispersion for numerical simulations of sorbing solute transport in heterogeneous porous formations

Heterogeneity is prevalent in aquifers and has an enormous impact on contaminant transport in groundwater. Numerical simulations are an effective way to deal with heterogeneity directly by assigning different hydraulic property values to each numerical grid block. Because hydraulic properties vary on different scales, but they cannot be sampled exhaustively and the number of numerical grid blocks is limited by computational considerations, the dispersive effects of unmodeled heterogeneity need to be accounted for. Dispersion tensors can be used to model the dispersion caused by unmodeled heterogeneity. The concept of block-effective macrodispersion tensors for modeling the effects of small-scale variability on solute transport introduced by Rubin et al. [Rubin Y, Sun A, Maxwell R, Bellin A. The concept of block-effective macrodispersivity and a unified approach for grid-scale- and plume-scale-dependent transport. J Fluid Mech 1999;395:161–80] is extended in this paper for use with reactive solutes. The tensors are derived for reactive solutes with spatially variable retardation factors and for solutes experiencing spatially uniform rate-limited sorption. The longitudinal block-effective macrodispersion coefficient is largest for perfect negative correlation between the log-hydraulic conductivity and the retardation factor. Because dispersion tensors, as they are usually implemented in numerical simulations, produce symmetric spreading, the applicability of the concept depends on the portion of the plume asymmetry caused by small-scale variability. The presented results show that the concept is applicable for rate-limited sorption for block sizes of one and two integral scales.     

Stochastic modeling of reactive transport in wetlands

This study describes the development of a general model for reaction in and performance of spatially heterogeneous bioreactors such as treatment wetlands. The modeled domain possesses local-scale velocities, reaction rates and transverse dispersion coefficients that are functions of an underlying heterogeneity variate representing one or more controlling biophysical attributes, for example, reactive surface area (submerged plant) density. Reaction rate coefficients are treated as related to local velocities in an inverse square fashion via their mutual dependence upon the variate. The study focuses on the solution for the steady-state case with constant inlet concentration. Results compare well with exact solutions developed for laterally-bounded systems in which the heterogeneity is represented explicitly. Employing the bicontinuum analogue of a second-order model, an expression for an effective longitudinal dispersion coefficient as a function of travel distance is developed using the method of moments. The result provides insights into the behavior of concentration as transverse mixing drives the system asymptotically toward Fickian longitudinal dispersion. The model may represent an improvement over other approaches for characterizing treatment wetland performance because it accounts for evolving shear flow dispersion, and because parameters are few in number, physically based, and invariant with mean velocity.     

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.     

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.     

Two-dimensional modeling of contaminant transport in porous media in the presence of colloids

It has long been known that colloids can facilitate the transport of contaminants in groundwater systems by reducing the effective retardation factor. A significant effort has been devoted to study colloid-facilitated contaminant transport during the past decade. Many of the previous studies were restricted to one-dimensional analyses and comparisons with finite-column experiments. In this work, a two-dimensional numerical model is developed and used to study the different interactions between colloids, contaminants, and porous media under homogeneous conditions. The numerical formulation of the model is based on discretizing mass balance equations and reaction equations using finite differences having a third-order, total variance-diminishing scheme for the advection terms. This scheme significantly reduces numerical dispersion and leads to greater accuracy compared to the standard central-differencing scheme. The model is tested against analytical solutions under simplified conditions as well as against experimental data, and the results are favorable. The model is used to investigate the impact of the various reaction rates and parameter values on the movement of contaminant plumes in two dimensions. The model is also used to investigate the hypothesis that colloids may increase the effective retardation factor of contaminant plumes. The analysis shows that assuming kinetic mass exchange between contaminant and colloids with constant reaction rate coefficients that are not related to the concentrations may lead to inaccurate results. These inaccurate results are exemplified in the finding that under the kinetic assumption the ratio of the initial concentration of colloids to the initial concentration of contaminant does not affect the amount of facilitation or retardation that occurs in the system. It is also found that colloids can increase the effective retardation factor for the contaminant under certain combinations of reaction rates and distribution coefficients. A quantitative empirical expression to identify whether colloids retard or facilitate the contaminant movement is presented.     

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.     

First-principles derivation of reactive transport modeling parameters for particle tracking and PDE approaches

Both Eulerian and Lagrangian reactive transport simulations in natural media require selection of a parameter that controls the “promiscuity” of the reacting particles. In Eulerian models, measurement of this parameter may be difficult because its value will generally differ between natural (diffusion-limited) systems and batch experiments, even though both are modeled by reaction terms of the same form. And in Lagrangian models, there previously has been no a priori way to compute this parameter. In both cases, then, selection is typically done by calibration, or ad hoc. This paper addresses the parameter selection problem for Fickian transport by deriving, from first principles and D (the diffusion constant) the reaction-rate-controlling parameters for particle tracking (PT) codes and for the diffusion–reaction equation (DRE). Using continuous time random walk analysis, exact reaction probabilities are derived for pairs of potentially reactive particles based on D and their probability of reaction provided that they collocate. Simultaneously, a second PT scheme directly employing collocation probabilities is derived. One-to-one correspondence between each of D, the reaction radius specified for a PT scheme, and the DRE decay constant are then developed. These results serve to ground reactive transport simulations in their underlying thermodynamics, and are confirmed by simulations.     

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.     

Analysis of biodegradation in a 3-D heterogeneous porous medium using nonlinear stochastic finite element method

Probabilistic analysis by Monte Carlo Simulation method (MCSM) is a computationally prohibitive task for a reactive solute transport involving coupled PDEs with nonlinear source/sink terms in 3-D heterogeneous porous media. The perturbation based stochastic finite element method (SFEM) is an attractive alternative method to MCSM as it is computationally efficient and accurate. In the present study SFEM is developed for solving nonlinear reactive solute transport problem in a 3-D heterogeneous medium. Here the solution of the biodegradation problem involving a single solute by a single class of microorganisms coupled with dynamic microbial growth is attempted using this method. The SFEM here produces a second-order accurate solution for the mean and a first-order accurate solution for the standard deviation of concentrations. In this study both the physical parameters (hydraulic conductivity, porosity, dispersivity and diffusion coefficient) and the biological parameters (maximum substrate utilization rate and the coefficient of cell decay) are considered as spatially varying random fields. A comparison between the MCSM and SFEM for the mean and standard deviation of concentration is made for 1-D and 3-D problem. The effects of heterogeneity on the degradation of substrate and growth of biomass concentrations for a range of variances of input parameters are discussed for both 1-D and 3-D problems.     

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.     

Adaptive multi-scale parameterization for one-dimensional flow in unsaturated porous media

In the analysis of the unsaturated zone, one of the most challenging problems is to use inverse theory in the search for an optimal parameterization of the porous media. Adaptative multi-scale parameterization consists in solving the problem through successive approximations by refining the parameter at the next finer scale all over the domain and stopping the process when the refinement does not induce significant decrease of the objective function any more. In this context, the refinement indicators algorithm provides an adaptive parameterization technique that opens the degrees of freedom in an iterative way driven at first order by the model to locate the discontinuities of the sought parameters. We present a refinement indicators algorithm for adaptive multi-scale parameterization that is applicable to the estimation of multi-dimensional hydraulic parameters in unsaturated soil water flow. Numerical examples are presented which show the efficiency of the algorithm in case of noisy data and missing data.     

Total variation diminishing schemes for pollutant transport in porous media

A bidimensional numerical model has been used in order to simulate the contaminant transport in the coastal groundwater area (Atlantic margin of the Rharb basin, Morocco). This groundwater is materialized by means of the salt contamination derived from several factors: evapotranspiration, lithological series formations, marine intrusion, and processes of interaction between water and rocks. In order to reduce the numerical diffusion and limit the numerical dispersion, we use the Superbee flux limiter as a total variation diminishing scheme to discretize the convective operator. This kind of discretization was applied to the coastal groundwater of the Rharb basin (Morocco). The results show that the Superbee flux limiter is efficient at drawing the path of the contaminant front with high accuracy. Consequently, this scheme could constitute an approach in water management and allows one to prevent the risks of pollution and to manage the groundwater resource from a durable development perspective. Copyright © 2007 John Wiley & Sons, Ltd.