The mechanisms of transport and retaidation processes, chemistry and migration behaviour of radionuclides of fission products and actinides in engineered barriers, especially bentonites, have been summarised. A “critical group of radionuclides” is proposed for thorough investigation of their retardation properties in natural sorbents. The evaluation of accessible data of retardation and transport parameters relevant for the conditions of underground deep repository to be projected is carried out from point of view their possible inclusion into a data-bank. The effect of solubilities and dissolution reactions, diffusion and sorption/desorption, complexation and variations in the aqueous phase composition, pH-value and oxidation-reduction properties and other phenomena on Kd values is discussed. Attention is devoted to thermodynamic modelling and its validation for evaluation of various phenomena in the buffer/backfill-ground water systems.