The direct storage of spent fuel (SF) represents a potential alternative to reprocessing as a means of managing nuclear waste. The direct storage of spent fuel in a deep geological environment presents a number of scientific challenges, primarily related to the necessity of developing a comprehensive understanding of the processes involved in the dissolution and release of radionuclides. The objective of this thesis is to develop a comprehensive scientific model that can accurately describe the intricate physico-chemical processes involved, such as the radiolysis of water and the interaction between irradiated fuel and its surrounding environment. The objective is to propose an accurate reactive transport model to enhance long-term predictions of storage performance. This thesis employs a back-and-forth process between modeling and experimentation, with the goal of refining the understanding of alteration mechanisms and validating hypotheses with experimental data. Based on existing models, such as the operational radiolytic model, the work will propose improvements to reduce the current simplifying assumptions. The candidate will contribute to major industrial and societal issues related to nuclear waste management and will help to provide solutions to the associated safety issues.