Modeling diffusion processes in the presence of a diffuse layer at charged mineral surfaces: a benchmark exercise

International audienceThe electrostatic properties of clay mineral surfaces play a significant role in their diffusion properties. The negative electrostatic potential field at clay mineral surfaces results in the presence of a diffuse layer that balances the mineral surface charge. The diffusion properties of the porosity fraction that is affected by this phenomenon are different from the diffusion properties of electroneutral bulk water. These properties have attracted growing interest from diverse communities in the past years, especially in the field of study of radioactive waste disposal. The influence of the diffuse layer can be described at the continuum scale by a set of equations that are formulated in terms of the Nernst-Planck equation. The number of codes that can handle the coupling between transport properties in clay affected by the presence of a diffuse layer in the porosity and chemical reactions is very limited, and no benchmark exercises have been published yet that make it possible to validate the numerical implementation of these equations in reactive transport codes. The present study proposes a set of benchmark exercises of increasing complexity that highlight caveats related to the finite difference (volume) treatment of the Nernst-Planck equation in the presence of a diffuse layer in heterogeneous systems. Once these problems are identified and solved, the codes PHREEQC, CrunchClay, and a new Fortran routine written for this study gave results in very good agreement for most of the benchmark exercises. When present, the differences in results were directly traceable to the differences in averaging methods at grid cell boundaries, and to the consideration or the omission of the activity gradient term in the Nernst-Planck equation

Design of a 2-D Cementation Experiment in Porous Medium Using Numerical Simulation

International audienceThe validation and qualification of reactive transport simulation tools has motivated the design and simulation, at a laboratory scale, of an experiment in which flow, advective/dispersive transport of solutes and physicochemical transformation affecting a porous medium are strongly coupled. Several possible experimental setups (or designs) have been evaluated using numerical simulation. The selected experimental design involves the successive precipitation and perforation of a clogging obstacle composed of calcium oxalate. Before an experiment can actually be conducted, this problem is proposed as a numerical benchmark for reactive transport codes and simulated using the coupled reactive transport code Hytec (CIG-École des mines, France)

Solving the Nernst-Planck equation in heterogeneous porous media with finite volume methods: Averaging approaches at interfaces

Molecular diffusion of dissolved species is a fundamental mass transport process affecting many environmental and technical processes. Whereas diffusive transport of single tracers can be described by Fick's law, a multicomponent approach based on the Nernst‐Planck equation is required for charge‐coupled transport of ions. The numerical solution of the Nernst‐Planck equation requires special attention with regard to properties that are required at interfaces of numerical cells when using a finite difference or finite volume method. Weighted arithmetic and harmonic averages are used in most codes that can solve the Nernst‐Planck equation. This way of averaging is correct for diffusion coefficients but inappropriate for solute concentrations at interfaces. This averaging approach leads to charge balance problems and thus to numerical instabilities near interfaces separating grid volumes with contrasting properties. We argue that a logarithmic‐differential average should be used. Here this result is generalized, and it is demonstrated that it generally leads to improved numerical stability and accuracy of concentrations computed near material interfaces. It is particularly relevant when modeling semipermeable clay membranes or membranes used in water treatment processes

Approaches for the simulation of coupled processes in evolving fractured porous media enabled by exascale computing

Models have historically represented fractured porous media with continuum descriptions that characterize the media using bulk parameters. The impact of small-scale features is not captured in these models, although they may be controlling the performance of subsurface applications. Pore-scale models can simulate processes in small-scale features by representing the pore space geometry explicitly but are computationally expensive for large domains. The alternative multiscale approach entails the combination of pore-scale and continuum-scale descriptions in a single framework. We use Chombo-Crunch, a computational capability that discretizes complex geometries with an adaptive, embedded boundary method to contrast these two approaches. Chombo-Crunch takes advantage of recent computational performance and memory bandwidth improvements resulting from the emergence of exascale computing resources. These combined improvements enable the efficient simulation of reactive transport in fractured media with a high degree of fidelity and the ability to capture the control small-scale processes exert on the overall medium evolution