Chemical alteration of cement materials in a radioactive waste repository environment. 3. Development of reactive transport computational code combined with incongruent dissolution model of calcium silicate hydrates

For long-term performance assessment of a cementitious disposal system for TRU waste, a so-called reactive transport computational code, being a numerical simulation code coupled a geochemical model suited to the system includes cement hydrate and a solute transport model, so-called reactive transport computational code, has been developed. The thermodynamic model previously developed in our institute for incongruent dissolution of calcium silicate hydrate (C-S-H) gel, which is a principal product of hydrated cement phase, was incorporated into a geochemical code, Harphrq, to evaluate chemical equilibrium conditions containing cement hydrates. This modification of the code enables a user to evaluate adequately the chemical equilibrium of a system including cement hydrate, such as a dissolution/precipitation of C-S-H gel and/or a change of Ca/Si ratio in C-S-H gel. The modified geochemical code was coupled onto a simplified solute transport code using a compartment model. The coupled code could simulate the processes where various chemical species in aqueous phase migrate through the homogeneous porous materials while locally maintaining chemical equilibrium. The developed reactive transport computational code was verified by comparison with experimental results on batch-type dissolution tests and column-type alteration tests under flow-through conditions of ordinary Portland cement hydrate. Predictive calculation results by the developed code were reasonably accordant with the experimental results, e.g. the distribution of constituent minerals and the composition of pore water in altered ordinary Portland cement hydrate. The validity of the developed code was therefore verified. Analysis on the results by the calculation could indicates special features such as a distribution of Ca/Si ratio in C-S-H gel along the water-flow in the column, and a re-precipitation of C-S-H gel in the downstream side of the dissolution front of C-S-H gel. (author)