Core-scale solute transport model selection using Monte Carlo analysis

Model applicability to core-scale solute transport is evaluated using breakthrough data from column experiments conducted with conservative tracers tritium (H-3) and sodium-22, and the retarding solute uranium-232. The three models considered are single-porosity, double-porosity with single-rate mobile-immobile mass-exchange, and the multirate model, which is a deterministic model that admits the statistics of a random mobile-immobile mass-exchange rate coefficient. The experiments were conducted on intact Culebra Dolomite core samples. Previously, data were analyzed using single- and double-porosity models although the Culebra Dolomite is known to possess multiple types and scales of porosity, and to exhibit multirate mobile-immobile-domain mass transfer characteristics at field scale. The data are reanalyzed here and null-space Monte Carlo analysis is used to facilitate objective model selection. Prediction (or residual) bias is adopted as a measure of the model structural error. The analysis clearly shows single- and double-porosity models are structurally deficient, yielding late-time residual bias that grows with time. On the other hand, the multirate model yields unbiased predictions consistent with the late-time -5/2 slope diagnostic of multirate mass transfer. The analysis indicates the multirate model is better suited to describing core-scale solute breakthrough in the Culebra Dolomite than the other two models.