Diffusion coefficients and effective, or transport, porosities are important parameters in the assessment of the fate and transport of contaminants in fractured rock systems and when contaminant transport needs to be considered in zones of low to negligible advective flows. This study presents and discusses various solutions, analytical and semianalytical, to Fick's law for the typical through-diffusion experiment and applies these solutions to the results of three through-diffusion experimental data sets. These through-diffusion experiments were conducted on two natural breccia samples, with bulk measured porosities of approximately 13.7% and 16.8%, and one manufactured porous plate sample with a bulk measured porosity of 40.9%, such that the samples displayed order of magnitude differences in their diffusivities. For each experiment, the derived effective porosities and intrinsic diffusion coefficients for each method are compared. It was shown that the semianalytical solution provides an improved method for reliably estimating the effective porosity from through-diffusion experimental data; however, there is little difference between methods in the derived intrinsic diffusion coefficients.