Comparison of theory and experiment for solute transport in highly heterogeneous porous medium

In this work we compare the recently developed two-region mass transfer theory reported by Ahmadi et al. [A. Ahmadi, M. Quintard, S. Whitaker (1998), Transport in chemically and mechanically heterogeneous porous media, V, two-equation model for solute transport with adsorption, Adv. Water Resour. 1998;22:59–86] with experimental results reported by Zinn et al. [Zinn, B., L. C. Meigs, C. F. Harvey, R. Haggerty, W. J. Peplinski, C. F. Von Schwerin. Experimental visualization of solute transport and mass transfer processes in two-dimensional conductivity fields with connected regions of high conductivity. Environ Sci Technol 2004;38:3916–3926]. We find that the constant mass transfer coefficient predicted by the steady-state closure to the theory, when used with the macroscale transport equation, provides a reasonable prediction of the observed breakthrough curve. However, the use of a constant mass transfer coefficient does not allow good representation of the tailing that is observed in the data. We show that the mass transfer coefficient can be represented in terms of the eigenvalue expansion of a Green’s function. For a steady solution to the closure problem, this expansion leads to the effective mass transfer coefficient being defined in terms of the harmonic average of the eigenvalues of the expansion; this is consistent with previous work on this topic. To further investigate the influence of using a single, constant value for the mass transfer coefficient, we examine the solution to the mass transfer problem in terms of a mixed model, where the eigenvalues of one region (the inclusions) are kept, while the second region (the matrix) is treated as a homogenized material. The results from this comparison indicate that the mass transfer coefficient predicted via volume averaging using a quasi-steady closure could potentially be improved upon by development of new methods that retain more of the eigenvalues of the system.