Generalized Taylor-Aris moment analysis of the transport of sorbing solutes through porous media with spatially-periodic retardation factor

Taylor-Aris dispersion theory, as generalized by Brenner, is employed to investigate the macroscopic behavior of sorbing solute transport in a three-dimensional, hydraulically homogeneous porous medium under steady, unidirectional flow. The porous medium is considered to possess spatially periodic geochemical characteristics in all three directions, where the spatial periods define a rectangular parallelepiped or a unit-element. The spatially-variable geochemical parameters of the solid matrix are incorporated into the transport equation by a spatially-periodic distribution coefficient and consequently a spatially-periodic retardation factor. Expressions for the effective or large-time coefficients governing the macroscopic solute transport are derived for solute sorbing according to a linear equilibrium isotherm as well as for the case of a first-order kinetic sorption relationship. The results indicate that for the case of a chemical equilibrium sorption isotherm the longitudinal macrodispersion incorporates a second term that accounts for the eflect of averaging the distribution coefficient over the volume of a unit element. Furthermore, for the case of a kinetic sorption relation, the longitudinal macrodispersion expression includes a third term that accounts for the effect of the first-order sorption rate. Therefore, increased solute spreading is expected if the local chemical equilibrium assumption is not valid. The derived expressions of the apparent parameters governing the macroscopic solute transport under local equilibrium conditions agreed reasonably with the results of numerical computations using particle tracking techniques.