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: 5. Single-fluid-phase transport

This work is the fifth 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 used to develop models that describe species transport and single-fluid-phase flow through a porous medium system in varying physical regimes. Classical irreversible thermodynamics formulations for species in fluids, solids, and interfaces are developed. Two different approaches are presented, one that makes use of a momentum equation for each entity along with constitutive relations for species diffusion and dispersion, and a second approach that makes use of a momentum equation for each species in an entity. The alternative models are developed by relying upon different approaches to constrain an entropy inequality using mass, momentum, and energy conservation equations. The resultant constrained entropy inequality is simplified and used to guide the development of closed models. Specific instances of dilute and non-dilute systems are examined and compared to alternative formulation approaches

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

TCAT analysis of capillary pressure in non-equilibrium, two-fluid-phase, porous medium systems

Standard models of flow of two immiscible fluids in a porous medium make use of an expression for the dependence of capillary pressure on the saturation of a fluid phase. Data to support the mathematical expression is most often obtained through a sequence of equilibrium experiments. In addition to such expressions being hysteretic, recent experimental and theoretical studies have suggested that the equilibrium functional forms obtained may be inadequate for modeling dynamic systems. This situation has led to efforts to express relaxation of a system to an equilibrium capillary pressure in relation to the rate of change of saturation. Here, based on insights gained from the thermodynamically constrained averaging theory (TCAT) we propose that dynamic processes are related to changes in interfacial area between phases as well as saturation. A more complete formulation of capillary pressure dynamics is presented leading to an equation that is suitable for experimental study

Thermodynamically constrained averaging theory approach for modeling flow and transport phenomena in porous medium systems: 8. Interface and common curve dynamics

This work is the eighth in a series that develops the fundamental aspects of the thermodynamically constrained averaging theory (TCAT) that allows for a systematic increase in the scale at which multiphase transport phenomena is modeled in porous medium systems. In these systems, the explicit locations of interfaces between phases and common curves, where three or more interfaces meet, are not considered at scales above the microscale. Rather, the densities of these quantities arise as areas per volume or length per volume. Modeling of the dynamics of these measures is an important challenge for robust models of flow and transport phenomena in porous medium systems, as the extent of these regions can have important implications for mass, momentum, and energy transport between and among phases, and formulation of a capillary pressure relation with minimal hysteresis. These densities do not exist at the microscale, where the interfaces and common curves correspond to particular locations. Therefore, it is necessary for a well-developed macroscale theory to provide evolution equations that describe the dynamics of interface and common curve densities. Here we point out the challenges and pitfalls in producing such evolution equations, develop a set of such equations based on averaging theorems, and identify the terms that require particular attention in experimental and computational efforts to parameterize the equations. We use the evolution equations developed to specify a closed two-fluid-phase flow model

On the consistency of scale among experiments, theory, and simulation

As a tool for addressing problems of scale, we consider an evolving approach known as the thermodynamically constrained averaging theory (TCAT), which has broad applicability to hydrology. We consider the case of modeling of two-fluid-phase flow in porous media, and we focus on issues of scale as they relate to various measures of pressure, capillary pressure, and state equations needed to produce solvable models. We apply TCAT to perform physics-based data assimilation to understand how the internal behavior influences the macroscale state of two-fluid porous medium systems. A microfluidic experimental method and a lattice Boltzmann simulation method are used to examine a key deficiency associated with standard approaches. In a hydrologic process such as evaporation, the water content will ultimately be reduced below the irreducible wetting-phase saturation determined from experiments. This is problematic since the derived closure relationships cannot predict the associated capillary pressures for these states. We demonstrate that the irreducible wetting-phase saturation is an artifact of the experimental design, caused by the fact that the boundary pressure difference does not approximate the true capillary pressure. Using averaging methods, we compute the true capillary pressure for fluid configurations at and below the irreducible wetting-phase saturation. Results of our analysis include a state function for the capillary pressure expressed as a function of fluid saturation and interfacial area

Modeling the sorption of hydrophobic contaminants by aquifer materials--I. Rates and equilibria

This is the first of a two-part series describing experimental studies and numerical modeling of the sorption of hydrophobic contaminants by aquifer materials. The work focuses on the evaluation of predictive modeling methods for simulating sorption processes in groundwater systems. Equilibrium behavior and rates of approach to equilibrium were investigated for two hydrophobic solutes and three aquifer materials utilizing different reactor configurations. This paper discusses investigations conducted in completely mixed batch reactors. These investigations illustrate that sorption equilibria are nonlinear for the systems studied and that sorption rates involve an initial rapid step followed by a slower continuing uptake that can persist for several days. Alternative models for description of these equilibria and rate conditions are presented and compared. The second paper evaluates the use of sorption model coefficients determined from batch-reactor systems to model column-reactor systems.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/27364/1/0000389.pd

Sorption of hydrophobic organic pollutants in saturated soil systems

Sorption equilibria and rates were characterized for a matrix of four aquifer sands and two slightly to moderately hydrophobic organic solutes (nitrobenzene and lindane), and the effects of sorption on the behavior of these solutes in saturated systems of the soils were determined. Experimental data were used to test and evaluate a variety of mathematical models for predicting contaminant fate and transport in groundwater systems.Observed equilibrium relationships between soil and solution phase solute concentrations were found to be described best by the nonlinear Freundlich isotherm model. It was further determined that the sorption process in the systems tested is rate controlled, requiring several days to approach equilibrium in completely mixed batch reactors. Subsequent modeling of solute transport in continuous flow soil column reactors was found to be most successful when rate-controlled models were used, the best results were obtained with a dual-resistance model incorporating the coupled mass transport steps of boundary-layer and intraparticle diffusion.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/26279/1/0000364.pd