Dispersion in a commercial polymeric monolith was simulated on a sample geometry obtained by direct imaging using high-resolution electron microscopy. A parallelized random walk algorithm, implemented using a velocity field obtained previously by the lattice-Boltzmann method, was used to model mass transfer. Both point particles and probes of finite size were studied. Dispersion simulations with point particles using periodic boundaries resulted in plate heights that varied almost linearly with flow rate, at odds with the weaker dependence suggested by experimental observations and predicted by theory. This discrepancy resulted from the combined effect of the artificial symmetry in the velocity field and the periodic boundaries implemented to emulate macroscopic column lengths. Eliminating periodicity and simulating a single block length instead resulted in a functional dependence of plate heights on flow rate more in accord with experimental trends and theoretical predictions for random media. The lower values of the simulated plate heights than experimental ones are attributed in part to the presence of walls in real systems, an effect not modeled by the algorithm. On the other hand, analysis of transient dispersion coefficients and comparison of lateral particle positions at the entry and exit hinted at non-asymptotic behavior and a strong degree of correlation that was presumably a consequence of preferential high-velocity pathways in the raw sample block. Simulations with finite-sized probes resulted in particle trajectories that frequently terminated at narrow constrictions of the geometry. The amount of entrapment was predicted to increase monotonically with flow rate, evidently due to the relative contributions to transport by convection that carries particles to choke-points and diffusion that dislodges these entrapped particles. The overall effect is very similar to a flow-dependent entrapment phenomenon previously observed experimentally for adenovirus. (c) 2012 Elsevier B.V. All rights reserved.