Observations on the mechanism of oxidation of UO2 in air and results from X-ray photoelectron spectroscopy surface analyses of UO2 electrodes exposed to aqueous solutions show that the dissolving solid under oxic conditions is essentially U3O7 formed by oxygen diffusion on the UO2 surface. Saturation effects with respect to U3O7 can be of importance for the overall reaction rate if oxygen transport to the dissolving surface is limited. The release of soluble radionuclides in solid solution with the UO2 matrix appears to be limited by the mass transfer rates for the conversion of U3O7 to alteration products such as schoepite. The rates of 90Sr and 137Cs release decrease with the square root of time under uranium-saturated conditions. This time dependence may be explained by either grainboundary diffusion or by oxygen diffusion through the alteration product phase.