Verification and improvement of predictive algorithms for radionuclide migration

This research addresses issues relevant to numerical simulation and prediction of migration of radionuclides in the environment of nuclear waste repositories. Specific issues investigated are the adequacy of current numerical codes in simulating geochemical interactions affecting radionuclide migration, the level of complexity required in chemical algorithms of transport models, and the validity of the constant-k/sub D/ concept in chemical transport modeling. An initial survey of the literature led to the conclusion that existing numerical codes did not encompass the full range of chemical and physical phenomena influential in radionuclide migration. Studies of chemical algorithms have been conducted within the framework of a one-dimensional numerical code that simulates the transport of chemically reacting solutes in a saturated porous medium. The code treats transport by dispersion/diffusion and advection, and equilibrium-controlled proceses of interphase mass transfer, complexation in the aqueous phase, pH variation, and precipitation/dissolution of secondary solids. Irreversible, time-dependent dissolution of solid phases during transport can be treated. Mass action, transport, and sorptive site constraint equations are expressed in differential/algebraic form and are solved simultaneously. Simulations using the code show that use of the constant-k/sub D/ concept can produce unreliable results in geochemical transport modeling. Applications to a field test and laboratory analogs of a nuclear waste repository indicate that a thermodynamically based simulator of chemical transport can successfully mimic real processes provided that operative chemical mechanisms and associated data have been correctly identified and measured, and have been incorporated in the simulator. 17 references, 10 figures