This study investigates the dissolution of CeO2, an isostructural analogue for UO2 and ThO2, which was synthesized to closely approximate the microstructure of a spent nuclear fuel matrix. Dissolution of CeO2 particles was performed in simplified solutions representative of saline, near-neutral and alkaline ground waters that may be encountered in geological disposal scenarios, and in acidic medium for comparison. The normalized mass loss of cerium was found to be significantly influenced by the formation of colloidal particles, especially in the near-neutral and alkaline solutions investigated. The normalized dissolution rate, RL(Ce), k
(g m-2 d-1), in these two solutions was found to be similar, but significantly lower than in a nitric acid medium. The activation energies based on the normalized release rate of cerium, at 40°C, 70°C and 90°C in each solution, were in the range of 24 ± 3 kJ mol-1 to 27 ± 7 kJ mol-1, indicative of a surface-mediated dissolution mechanism. The mechanism of dissolution was postulated to be similar in each of the solutions investigated, and further work is proposed to investigate the role of carbonate on the CeO2 dissolution mechanism.