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Natural convection in porous media is a fundamental process for the long-term storage of CO 2 in deep saline aquifers. Typically, details of mass transfer in porous media are inferred from the numerical solution of the volume-averaged Darcy–Oberbeck–Boussinesq (DOB) equations, even though these equations do not account for the microscopic properties of a porous medium. According to the DOB equations, natural convection in a porous medium is uniquely determined by the Rayleigh number. However, in contrast with experiments, DOB simulations yield a linear scaling of the Sherwood number with the Rayleigh number ( $Ra$ ) for high values of $Ra$ ( $Ra\gg 1300$ ). Here, we perform direct numerical simulations (DNS), fully resolving the flow field within the pores. We show that the boundary layer thickness is determined by the pore size instead of the Rayleigh number, as previously assumed. The mega- and proto-plume sizes increase with the pore size. Our DNS results exhibit a nonlinear scaling of the Sherwood number at high porosity, and for the same Rayleigh number, higher Sherwood numbers are predicted by DNS at lower porosities. It can be concluded that the scaling of the Sherwood number depends on the porosity and the pore-scale parameters, which is consistent with experimental studies.