We measured the effective diffusion coefficient in regions of microfluidic networks of controlled geometry using the FRAP (Fluorescence Recovery After Photobleaching) technique. The geometry of the networks was based on Voronoi tessellations, and had varying characteristic length scale and porosity. For a fixed network, FRAP experiments were performed in regions of increasing size. Our results indicate that the boundary of the bleached region, and in particular the cumulative area of the channels that connect the bleached region to the rest of the network, are important in the measured value of the effective diffusion coefficient. We found that the statistical geometrical variations between different regions of the network decrease with the size of the bleached region as a power law, meaning that the statistical error of effective medium approximations decrease with the size of the studied medium, although no characteristic length scale could be defined over which the porous medium is equivalent to an effective medium.