吴王锁－sorption and precipitation.pptVIP

Ternary ideal SS: EuO(OH) EuH(CO3)2 CaCO3 G* (kJ/mol) = -955 -1775 -1129 cEu pH =8 pH = 6 pH = 13 With the Gibbs Energy Minimization (GEM) technique, it was possible to model data on Eu incorporation in calcite. A ternary solid solution model, with EuO(OH) and EuH(CO3)2 as end-member stoichiometries for Eu, successfully reproduces data obtained at widely different pH-pCO2 conditions Solid solution thermodynamics (4) from: Curti et al. (2005), GCA 69, 1721-1737 Thermodynamic SS models: an example important issues How can we decide: whether adsorption or precipitation will be the relevant uptake mechanism which solids will be the relevant RN host phases in the repository Problems for application of adsorption/precipitation reactions to PA: metastability: thermodynamics sometimes “fails” (e.g. dolomite problem) kinetics of precipitation reactions may be too slow for laboratory scale multitude of host phases with complex chemistry (pick out the right ones) stability of the sorbent surface (recrystallization, phase transformations) Laboratory experiments and natural analogue studies should be combined to resolve these issues Verifying the RN uptake mechanism (1) 4 2 100 m m m 100 mm Swiss nuclear waste reference glass MW corroded during 13 y Ni is trapped in Mg-rich secondary clays (green in XRF map) EXAFS consistent with incorporation as dilute SS in hectorite (Mg-Li-clay) but adsorption cannot be ruled out (low CN for Ni-Mg) m-XRF Na, Mg map Verifying the RN uptake mechanism (2) Uptake of 45Ca during Eu3+ - calcite interaction in cement pore water indicates that - after initial adsorption – Eu3+ is incorporated into recrystallized calcite. Two steps kinetics still unexplained mmol 45Ca exchanged Data integration in PA (1) How are data on radionuclide adsorption and (co)precipitation integrated in safety assessment calculation? Due to... complexity of calculations limited process und