Compilation of Kinetic Data for Geochemical Calculations

Arthur, R. C,*; Savage, D.*; Sasamoto, Hiroshi   ; Shibata, Masahiro ; Yui, Mikazu

Kinetic data, including rate constants, reaction orders and activation energies, are compiled for 34 hydrolysis reactions involving feldspars, sheet silicates, zeolites, oxides, pyroxenes and amphiboles, and for similar reactions involving calcite and pyrite. The data are compatible with a rate law consistent with surface reaction control and transition-state theoly, which is incorporated in the geochemieal software package EQ3/6 and GWB. Kinetic data for the reactions noted above are strictly compatible with the transition-state rate law only under far-from-equilibrium conditions. It is possiblethat the data are conceptually consistent with this rate law under both far-from-equilibrium and near-to-equilibrium conditions, but this should be confirmed whenever possible through analysis of original experimental results, Due to limitations in the availability of kinetic data for mineral-water reactions, and in order to simplify evaluations of geochemical models of groundwater evolution, it is convenient to assume local-equilibrium in such models whenever possible. To assess whether this assumption is reasonable, a modeling approach accounting for coupled fluid flow and water-rock interaction is described that can be used to estimate spatial and temporal scale of local equiliblium. The approach is demonstrated for conditions involving groundwater flow in fractures at JNC's Kamaishi in-situ tests site, and is also used to estimate the travel time necessary for oxidizing surface waters to migrate to the level of a HLW repository in crystalline rock. The question of whether local equilibrium is a reasonable assumption must be addressed using an appropriate modeling approach. To be appropriate for conditions at the Kamaishi site using the modeling approach noted above, the fracture fill must closely approximate a porous medium, groundwater flow must be purely advective and diffusion of solutes across the fracture-host rock boundary must not occur. Moreover, the ...