Abstract: This paper studies the mechanisms of dispersion in the laminar flow through the pore space of a -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 identifies 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 region in the wake of solute 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. 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.
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