Time domain random walk Continuous time random walk Dual multirate mass transfer model a b s t r a c t We study the upscaling of pore-scale transport of passive solute in a carbonate rock sample. It is characterized by microporous regions displaying heterogeneous porosity distribution that are accessible due to diffusion only, and a strongly heterogeneous mobile pore space, characterized by a broad distribution of flow velocities. We observe breakthrough curves that are characterized by strong tailing, which can be attributed to velocity variability in the flowing medium portion, and solute retention in the microporous space. Using accurate numerical flow and transport simulations, we separate these two mechanisms by analyzing the statistics of residence times in the mobile phase, and the trapping and residence time statistics in the mmobile phase. We employ a continuous time random walk framework in order to upscale transport using a particle based implementation of mobile-immobile mass transfer, and heterogeneous advection. This approach is based on the statistics of the characteristic mobile and immobile residence times, and mass transfer rates between the two continua. While classical mobile-immobile approaches model mass transfer as a constant rate process, we find that the trapping rate increases with increasing mobile residence times until it reaches a constant asymptotic value. Based on these findings and the statistical characteristics of travel and retention times, we derive an upscaled Lagrangian transport model that separates the processes of heterogeneous advection and diffusion in the immobile microporous space, and provides accurate descriptions of the observed non-Fickian breakthrough curves. These results shed light on transport upscaling in highly complex dual-porosity rocks for which mobile-immobile mass transfer are controlled by a dual multirate process controlled by the heterogeneity of both the flow field in the connected porosity and the diffusion in the no-flow regions.