Development and application of an advection-dispersion model for data analysis of electromigration experiments with...

An advection-dispersion model was developed for interpreting the experimental results of electromigration in granitic rock cores. The most important mechanisms governing the movement of the tracer ions, i.e. electromigration, electroosmosis and dispersion were taken into account by the advection-dispersion model, but the influence of aqueous chemistry was ignored. An analytical solution in the Laplace domain was derived and then applied to analyze the measured results of a series of experiments, performed in an updated experimental device using different applied voltages. The modelling results suggested that both studied tracers, i.e. iodide and selenite, are effectively non-sorbing in the intact rock investigated. The effective diffusivities and formation factors evaluated from the model were also found to be in good agreement with data reported in literature and the associated uncertainties are much smaller than those obtained from the classical ideal plug-flow model, which accounts only for the dominant effect of electromigration on ionic transport. To explore further how the quality of parameter identifications would be influenced by neglect of aqueous chemistry, a reactive transport model was also implemented, which may be regarded as a multi-component version of the advection-dispersion model. The analysis showed that the advection-dispersion model works equally well as the reactive transport model but requires much less computational demand. It can, therefore, be used with great confidence to interpret the experimental results of electromigration for studies of diffusion and sorption behavior of radionuclides in intact rock cores.