This paper studies the mechanisms of dispersion in the laminar flow through the pore space of a 3-dimensional porous medium. We focus on pre-asymptotic transport prior to the asymptotic hydrodynamic dispersion regime, in which solute motion may be described by the average flow velocity and a hydrodynamic dispersion coefficient. High performance numerical flow and transport simulations of solute breakthrough at the outlet of a sand-like porous medium evidence marked deviations from the hydrodynamic dispersion paradigm and identify two distinct regimes. The first regime is characterized by a broad distribution of advective residence times in single pores. The second regime is characterized by diffusive mass transfer into low-velocity regions in the wake of solid grains. These mechanisms are quantified systematically in the framework of a time-domain random walk for the motion of marked elements (particles) of the transported material quantity. Particle transitions occur over the length scale imprinted in the pore structure at random times given by heterogeneous advection and diffusion. Under globally advection-dominated conditions, this means Péclet numbers larger than 1, particles sample the intrapore velocities by diffusion, and the interpore velocities through advection. Thus, for a single transition, particle velocities are approximated by the mean pore velocity. In order to quantify this advection mechanism, we develop a model for the statistics of the Eulerian velocity magnitude based on Poiseuille's law for flow through a single pore, and for the distribution of mean pore velocities, both of which are linked to the distribution of pore diameters. Diffusion across streamlines through immobile zones in the wake of solid grains gives rise to exponentially distributed residence times that decay on the diffusion time over the pore length. The trapping rate is determined by the inverse diffusion time. This trapping mechanism is represented by a compound Poisson process conditioned on the advective residence time in the proposed time-domain random walk approach. The model is parameterized with the characteristics of the porous medium under consideration and captures both pre-asymptotic regimes. Macroscale transport is described by an integro-differential equation for solute concentration, whose memory kernels are given in terms of the distribution of mean pore velocities and trapping times. This approach quantifies the physical non-equilibrium caused by a broad distribution of mass transfer time scales, both advective and diffusive, on the representative elementary volume (REV). Thus, while the REV indicates the scale at which medium properties like porosity can be uniquely defined, this does not imply that transport can be characterized by hydrodynamic dispersion.

Pore-scale simulation of fluid flow and solute dispersion in three-dimensional porous media In the present work fluid flow and solute transport through porous media are described by solving the governing equations at the pore scale with finite-volume discretization. Instead of solving the simplified Stokes equation (very often employed in this context) the full Navier-Stokes equation is used here. The realistic three-dimensional porous medium is created in this work by packing together, with standard ballistic physics, irregular and polydisperse objects. Emphasis is placed on numerical issues related to mesh generation and spatial discretization, which play an important role in determining the final accuracy of the finite-volume scheme and are often overlooked. The simulations performed are then analyzed in terms of velocity distributions and dispersion rates in a wider range of operating conditions, when compared with other works carried out by solving the Stokes equation. Results show that dispersion within the analyzed porous medium is adequately described by classical power laws obtained by analytic homogenization. Eventually the validity of Fickian diffusion to treat dispersion in porous media is also assessed. KAUST Repository

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We propose a novel macroscopic model for conjugate heat and mass transfer between a mobile region, where advective transport is significant, and a set of immobile regions where diffusive transport is dominant. Applying a spatial averaging operator to the microscopic equations, we obtain a multi-continuum model, where an equation for the average concentration in the mobile region is coupled with a set of equations for the average concentrations in the immobile regions. Subsequently, by mean of a spectral decomposition, we derive a set of equations that can be viewed as a generalisation of the multi-rate mass transfer (MRMT) model, originally introduced by Haggerty & Gorelick [1]. This new formulation does not require any assumption on local equilibrium or geometry. We then show that the MRMT can be obtained as the leading order approximation, when the mobile concentration is in local equilibrium. The new Generalised Multi-Rate Mode (GMRM) has the advantage of providing a direct method for calculating the model coefficients for immobile regions of arbitrary shapes, through the solution of appropriate micro-scale cell problems. An important finding is that a simple re-scaling or re-parametrisation of the transfer rate coefficient (and thus, the memory function) is not sufficient to account for the flow field in the mobile region and the resulting nonuniformity of the concentration at the interfaces between mobile and immobile regions.

In the upscaling from pore-to continuum (Darcy) scale, reaction and deposition phenomena at the solid-liquid interface of a porous medium have to be represented by macroscopic reaction source terms. The effective rates can be computed, in the case of periodic media, from three-dimensional microscopic simulations of the periodic cell. Several computational and semi-analytical models have been studied in the field of colloid filtration to describe this problem. They often rely on effective deposition rates defined by simple linear reaction ODEs, neglecting the advection-diffusion interplay, and assuming slow reactions (or large Péclet numbers). Therefore, when these rates are inserted into general macroscopic transport equations, they can lead to conceptual inconsistencies and, therefore, often qualitatively wrong results. In this work, we study the upscaling of Brownian deposition on face-centred cubic (FCC) spherical arrangements using a linear effective reaction rate, defined by volume averaging, and a macroscopic advection-diffusion-reaction equation. The case of partial deposition, defined by an attachment probability, is studied and the limit of ideal deposition is retrieved as a particular case. We make use of a particularly convenient computational setup that allows the direct computation of the asymptotic stationary value of effective rates. This allows to drastically reduce the computational domain down to the scale of the single repeating periodic unit: the savings are ever more noticeable in the case of higher Péclet numbers, when larger physical times are needed to reach the asymptotic regime, and thus, equivalently, a much larger computational domain and simulation time would be needed in a traditional setup. We show how this new definition of deposition rate is more robust and extendable to the whole range of Péclet numbers; it also is consistent with the classical heat and mass transfer literature.