Aqueous solubility diagrams for cementitious waste stabilization systems. 4. A carbonation model for Zn-doped calcium...

A thermodynamic Gibbs energy minimization (GEM) solid solution-aqueous solution (SSAS) equilibrium model was used to determine the solubility of Zn from calcium silicate hydrate (CSH) phases doped with 0, 0.1, 1, 5, and 10% Zn at a unity (Ca+Zn)/Si molar ratio. Both the stoichiometry and standard molar Gibbs energy (G(o)298) of the Zn-bearing end-member in the ideal ternary Zn-bearing calcium silicate hydrate (CZSH) solid solution were determined by a "dual-thermodynamic" (GEM-DT) estimation technique. The SSAS model reproduces a complex sequence of reactions suggested to occur in a long-term weathering scenario of cementitious waste forms at subsurface repository conditions. The GEM model of CZSH leaching at several Zn loadings and solid/water (s/w) ratios in a C02-free system showed that, upon complete dissolution of portlandite and calcium zincate phases at decreasing s/w < 0.01 mol x kg(H2O)(-1), the total dissolved concentrations Si(aq), Ca(aq), and Zn(aq) are controlled by a CZSH solid solution of changing composition, with a trough-like Znaq drop by 2-3 orders of magnitude. Carbonation was simulated in another GEM model run series by CO2 titration of the system with initial s/w approximately 0.9 mol/kg(H2O). Formation of (Ca,Zn)-CO3 nonideal solid solution was predicted already at early reaction stage in the presence of both portlandite and calcium zincate hydrate phases. Upon their disappearance, pH, Zn(aq), C(aq), and fCO2 were predicted to change due to the incongruent dissolution of two concurrent CZSH-I and CZSH-II solid solutions, until the total re-partitioning of Ca and Zn into a carbonate solid solution coexisting with amorphous silica at fCO2 > 0.1 bar. Along this solid-phase transition, dissolved Zn(aq) concentrations follow a highly nonlinear trend. The model results predict that at low to moderate Zn loading (< or = 1% per mole Si), CZSH-type compounds can efficiently immobilize Zn in the near field of a cement-stabilized waste repository.