Uranium (VI) speciation: modelling, uncertainty and relevance to bioavailability models. Application to uranium uptake by the gills of a freshwater bivalve.
Francis DENISON Thèse de doctorat de l'université d'Aix-Marseille I spécialité Biosciences de l'Environnement, Chimie et Santé, 347p. soutenue le 22 juillet 2004
The effect of varying solution composition on the interactions between uranium (VI) and excised gills of the freshwater Corbicula fluminea have been investigated in well defined solution media. A significant reduction in the uptake of uranium was observed on increasing the concentrations of the uranium complexing ligands citrate and carbonate. Saturation kinetics as a function of uranium concentration at a pH value of 5.0 were observed, indicating that the uptake of uranium is a facilitated process, probably involving one or several trans-membrane systems. A relatively small change in the uptake of uranium was found as a function of pH (factor of ca. 2), despite the extremely large changes to the solution speciation of uranium within the range of pH investigated (5.0 - 7.5).
A comprehensive review of the thermodynamic data relevant to the solution composition domain employed for this study was performed. estimates of the uncertainties for the formation constants of aqueous uranium (VI) species were integrated into a thermodynamic database. A computer program was written to predict the equilibrium distribution of uranium (VI) in simple aqueous systems, using thermodynamic parameter mean-values. The program was extended to perform Monte Carlo and Quasi Monte Carlo uncertainty analyses, incorporating the thermodynamic database uncertainty estimates, to quantitatively predict the uncertainties inherent in predicting the solution speciation of uranium.
The use of thermodynamic equilibrium modelling as a tool for interpreting the bioavailability of uralium (VI) was investigated. Observed uranium (VI) uptake behaviour was interpreted as a function of the predicted changes to the solution speciation of uranium. Different steady-state or pre-equilibrium approches to modelling uranium uptake were tested. Alternative modelling approaches were also tested, considering the potential changes to membrane transport system activity or sorption characteristics on varying solution composition. Finally the effect of uncertainty on the use of thermodynamic equilibrium modelling for interpretation of uranium (VI) bioavailability was assessed.