The formation of hydrated zirconium molybdate in simulated spent nuclear fuel reprocessing solutions

Hydrated zirconium molybdate (ZMh) is known to precipitate from solutions of dissolved spent nuclear fuel, particularly from the waste fission product solution after the uranium and plutonium have been extracted during reprocessing. Its precipitation can cause major problems during waste treatment, and therefore a complete understanding of its chemical behaviour, especially with regard to its role in the nuclear fuel cycle, is desirable. We have used a number of complementary analytical techniques to elucidate the hitherto incompletely understood chemistry of formation of ZMh in synthetic fuel reprocessing solutions. We have demonstrated that ZMh formation was governed by multi-step surface reactions and does not involve the formation of colloids or particulates in solution. The first step in the deposition of ZMh onto surfaces is the formation of an amorphous film with a Zr:Mo ratio close to unity. It is followed by the formation, growth and nucleation of ZMh particles of varying degrees of crystallinity with a Zr:Mo ratio close to 0.5. The X-ray di3raction pattern of deposited ZMh particles is in agreement with the reported crystallographic data. The structural features of the film and ZMh were also examined at the nanometer scale.