Dissolution of vitrified wastes in a high-pH calcium-rich solution

The current baseline for the conditioning of most UK intermediate-level radioactive waste (ILW) is immobilisation using cement. However, vitrification of some UK ILW is being considered as an alternative. One option for the disposal of the resulting vitrified ILW would be to place it in a geological disposal facility in a high-pH environment with cemented ILW and a cement-based backfill. Therefore, the potential effects of such a high pH (∼12.5), calcium-rich cement-based environment on the dissolution behaviour of simulant ILW glasses have been studied using the product consistency test (PCT). Three non-radioactive waste compositions were assessed: a laboratory simulant ILW vitrified in a borosilicate glass and two full-scale simulant vitrified products (a slag containing simulant plutonium-contaminated material and Magnox sludge; and a glass containing clinoptilolite). Powdered samples were leached in saturated Ca(OH)2 solutions for up to 42 days at temperatures between 30 and 90 °C. In general the rates of dissolution were lower than expected at such a high pH compared to studies in the literature under alkaline conditions. In contrast to the typical dissolution behaviour of high level waste (HLW) glasses, dissolution of the simulant borosilicate ILW glass was initially slow, followed by a period of faster boron and alkali metal release. The saturation/residual regime was not reached within experimental timescales. The rate of dissolution during the period of faster release increased with increasing temperature; the activation energy for this stage of dissolution was calculated to be 47 ± 2 kJ mol-1 based on boron release. The two full-scale simulant glasses, which contained negligible boric oxide, exhibited conventional static dissolution profiles, and entered the residual rate regime after 7-14 days at 50 °C. The greater durability of the full-scale simulants is thought to be due to the greater content of network-forming oxides in these glasses compared to the borosilicate glass. It is also suggested that the formation of calcium borates may delay initial hydration of the borosilicate glass in a similar manner to the retardation of cement hydration by soluble borates. More generally, the formation of calcium- and magnesium-containing precipitates on the surface of the vitrified wastes, and agglomeration of the powder, appeared to act to reduce the dissolution rate. Overall these results suggest that calcium has an important role in the long-term durability of vitrified wastes at high pH.