Radiolytic modelling of spent fuel oxidative dissolution mechanism. Calibration against UO2 dynamic leaching experiments

Calibration and testing are inherent aspects of any modelling exercise and consequently they are key issues in developing a model for the oxidative dissolution of spent fuel. In the present work we present the outcome of the calibration process for the kinetic constants of a UO2 oxidative dissolution mechanism developed for using in a radiolytic model. Experimental data obtained in dynamic leaching experiments of unirradiated UO2 has been used for this purpose. The iterative calibration process has provided some insight into the detailed mechanism taking place in the alteration of UO2, particularly the role of OH radicals and their interaction with the carbonate system. The results show that, although more simulations are needed for testing in different experimental systems, the calibrated oxidative dissolution mechanism could be included in radiolytic models to gain confidence in the prediction of the long-term alteration rate of the spent fuel under repository conditions.