A simple and efficient random walk solution of multi-rate mobile/immobile mass transport equations

We extend the particle-tracking method to simulate general multi-rate mass transfer (MRMT) equations. Previous methods for single-rate equations used two-state Markov chains and found that the time a particle spends in the mobile state between waiting time epochs is random and exponentially distributed. Using Bochner’s subordination technique for Markov processes, we find that the random mobile times are still exponential for the stochastic process that corresponds to the MRMT equations. The random times in the immobile phase have a distribution that is directly related to the memory function of the MRMT equation. This connection allows us to interpret the MRMT memory function as the rate at which particles of a certain age, measured by residence time in the immobile zone, exit to become mobile once again. Because the exact distributions of mobile and immobile times are known from the MRMT equations, they can be simulated very simply and efficiently using random walks.