More theoretical analysis is needed to investigate why a dual-domain model often works better than the classical advection-dispersion (AD) model in reproducing observed breakthrough curves for relatively homogeneous porous media, which do not contain distinct dual domains. Pore-scale numerical experiments presented here reveal that hydrodynamics create preferential flow paths that occupy a small part of the domain but where most of the flow takes place. This creates a flow-dependent configuration, where the total domain consists of a mobile and an immobile domain. Mass transfer limitations may result in nonequilibrium, or significant differences in concentration, between the apparent mobile and immobile zones. When the advection timescale is smaller than the diffusion timescale, the dual-domain mass transfer (DDMT) model better captures the tailing in the breakthrough curve. Moreover, the model parameters (mobile porosity, mean solute velocity, dispersivity, and mass transfer coefficient) demonstrate nonlinear dependency on mean fluid velocity. The studied case also shows that when the Peclet number, Pe, is large enough, the mobile porosity approaches a constant, and the mass transfer coefficient can be approximated as proportional to mean fluid velocity. Based on detailed analysis at the pore scale, this paper provides a physical explanation why these model parameters vary in certain ways with Pe. In addition, to improve prediction in practical applications, we recommend conducting experiments for parameterization of the DDMT model at a velocity close to that of the relevant field sites, or over a range of velocities that may allow a better parameterization.