Review of zirconolite crystal chemistry and aqueous durability

ABSTRACT Zirconolite (CaZrTi2O7) has been identified as a candidate ceramic wasteform for the immobilisation and disposal of Pu inventories, for which there is no foreseen future use. Here, we provide an overview of relevant zirconolite solid solution chemistry with respect to Ce, U and Pu incorporation, alongside a summary of the available literature on zirconolite aqueous durability. The zirconolite phase may accommodate a wide variety of tri- and tetravalent actinide and rare-earth dopants through isovalent and heterovalent solid solution, e.g. CaZr1–x Pu x Ti2O7 or Ca1–x PuxZrTi2–2x Fe2x O7. The progressive incorporation of actinides within the zirconolite-2M parent structure is accommodated through the formation of zirconolite polytypoids, such as zirconolite-4M or 3T, depending on the choice of substitution regime and processing route. A variety of standardised durability tests have demonstrated that the zirconolite phase exhibits exceptional chemical durability, with release rates of constituent elements typically <10−5 gm−2·d−1. Further work is required to understand the extent to which polytype formation and surrogate choice influence the dissolution behaviour of zirconolite wasteforms.