A wide range of environmental, energy, medical and biological processes rely on dispersive transport through complex media. Yet, because of the stagnant and opaque nature of the microscopic system, the role of disordered flow and structure in the dispersive transport of solutes remains poorly understood. Here, we use a circular porous microfluidic system to investigate the radial dispersion in porous media driven by non-Newtonian fluids with strong advection rate (or at high Péclet number) and low-to-moderate Reynolds numbers. We observe for the first time the presence of diffusion ‘blind zones’ in the microstructure for high solution injection velocities. More specifically, an in-depth analysis uncovers that the circumferential flow frame, coformed by obstacles and vortices especially the ‘twin-vortex’ with same rotation direction, is responsible for the diffusion ‘blind zones’ and transport heterogeneity. The vortices are induced by the coupling of microfluidics and porous structures, and correlated to inertial flow-induced instabilities. The trade-off between diffusion efficiency and quality/completeness with respect to the high Péclet number (or high inlet velocity) serves to enhance our comprehension of intricate fluid dynamics and affords a set of principles to aid a diverse range of practical implementations.