Hiroshi Sasamoto

POLYMER MODEL OF ZEOLITE THERMOCHEMICAL STABILITY

The polymer model provides a relatively simple and robust basis for estimating the standard Gibbs free energies of formation (ΔGfo) and standard enthalpies of formation (ΔHfo) of clay minerals and other aluminosilicates with an accuracy that is comparable to or better than can be obtained using alternative techniques. The model developed in the present study for zeolites entailed the selection of internally consistent standard thermodynamic properties for model components, calibration of adjustable model parameters using a linear regression technique constrained by ΔGfo and ΔHfo values retrieved from calorimetric, solubility, and phase-equilibrium experiments, and assessments of model accuracy based on comparisons of predicted values with experimental counterparts not included in the calibration dataset. The ΔGfo and ΔHfo predictions were found to average within ±0.2% and ±0.3%, respectively, of experimental values at 298.15 K and 1 bar. The latter result is comparable to the good accuracy that has been obtained by others using a more rigorous electronegativity-based model for ΔHfo that accounts explicitly for differences in zeolite structure based on differences in framework density and unit-cell volume. This observation is consistent with recent calorimetric studies indicating that enthalpies of transition from quartz to various pure-silica zeolite frameworks (zeosils) are small and only weakly dependent on framework type, and suggests that the effects on ΔHfo of differences in framework topology can be ignored for estimation purposes without incurring a significant loss of accuracy. The relative simplicity of the polymer model, together with its applicability to both zeolites and clay minerals, is based on a common set of experimentally determined and internally consistent thermodynamic properties for model components. These attributes are particularly well suited for studies of the effects of water-rock-barrier interactions on the long-term safety of geologic repositories for high-level nuclear waste (HLW).

An Evaluation of the Long-Term Stagnancy of Porewater in the Neogene Sedimentary Rocks in Northern Japan

A groundwater dating for very old porewater using 36Cl and 4He was applied to the Koetoi and Wakkanai formations distributed in the northernmost part in Japan. Measured 36Cl/Cl in the Koetoi Formation was 2.6 ± 2.0 × 10−15 and that in the Wakkanai Formation was 8.1 ± 2.5 × 10−15. These values are similar to 36Cl/Cl in situ secular equilibrium calculated from chemical compositions of core suggesting that Cl− ions and porewater have remained in the formations for much longer than half-life of 36Cl . He concentration in porewater ranged from 1.1 × 10−6 to 2.6 × 10−5 ( ) and it is much higher than water saturated with air indicating that both formations contain very old porewater. However, the possibility of mixing of young water was indicated because He concentration was lower than that calculated by multiplication of in situ He production and time after the uplift. This possibility was also supported by Cl−, δD, and δ18O data. After combining information on 36Cl/Cl, 4He, and δD and δ18O, it was inferred that the porewater in the deep part of the Wakkanai Formation might have been stagnant since the uplift. The porewater in the Koetoi Formation and the shallow part of the Wakkanai Formation were found to be affected by young surface water.

Mineralogical, physical and chemical investigation of compacted Kunigel V1 bentonite in contact with a steel heater in the ABM test package 1 experiment, Aspo laboratory, Sweden

Abstract In many countries, compacted bentonite is a candidate engineering barrier material for safe disposal of high-level radioactive waste. The Swedish Nuclear Fuel and Waste Management Company (SKB) set up an in situ experiment (the ABM project) to compare the stability of different bentonites under the conditions of exposure to an iron source and to elevated temperature (up to 130°C) at the Äspö Hard Rock Laboratory, Sweden. Results for the Japanese bentonite (Kunigel V1) are summarized in the present study. Mineralogical investigation using X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) suggested no transformation of smectite or neoformed clay phases. However, a distinct change in exchangeable cations of smectite was indicated (i.e. from Na type to Fe type and/or Ca type) in the bentonite in the vicinity of the steel heater. Measurements of hydraulic conductivity and swelling properties suggest that no significant changes occurred in the bentonite even in the vicinity of the steel heater. This is attributed to the limited portion of the bentonite affected by the iron-bentonite interactions and the incomplete ion-exchange reactions. The methylene blue cation exchange capacity and the determination of the exchangeable cations showed that the lateral distribution for these parameters was constant. However, the total exchangeable cation population has changed significantly compared to the initial sample.