Equilibrium modeling of U(VI) speciation in high carbonate groundwaters: Model error and propagation of uncertainty

Abstract

► Propagation of uncertainty in uranium speciation is examined by derivative and Monte Carlo methods. ► Predictions of solution speciation are robust with minimal amplification of input uncertainty. ► Predictions of sorption equilibria at low total U(VI) are not robust, with bimodal distributions of predicted speciation. Remediation of U-contaminated sites relies upon thermodynamic speciation calculations to predict U(VI) movement in the subsurface. However, reliability and applicability of geochemical speciation and reactive transport models may be limited by determinate (model) errors and random (uncertainty) errors in the equilibrium speciation calculations. This study examines propagated uncertainty in two types of subsurface calculations: I. Dissolved U(VI) speciation based on measured analytical constraints and solution phase equilibria and II. Overall U(VI) speciation which combined the dissolved phase equilibria with previously published adsorption reactions. Three levels of uncertainty, instrumental uncertainty, temporal variation and spatial variation across a site, were investigated using first-derivative sensitivity calculations and Monte Carlo simulations. Dissolved speciation calculations were robust, with minimal amplification of uncertainty and normal output distributions. The most critical analytical constraints in the dissolved system are pH, DIC, total U and total Ca, with some effect from dissolved SO 4 2 - . When considering adsorption equilibria, calculations were robust with respect to adsorbed U(VI) concentration prediction, but bimodal distributions of dissolved U(VI) concentrations were observed in simulations with background levels of total U(VI) and higher (spatial and temporal variability) estimates of input uncertainty. Consequently, sorption model predictions of dissolved U(VI) may not be robust with respect these higher levels of uncertainty.