Reactive transport simulations of uranium migration in the Opalinus Clay depend on ion speciation governed by underlying thermodynamic data

Abstract

Abstract. Safety assessments must demonstrate that radionuclides in potential disposal sites are retained within the containment providing rock zone. The impact of thermodynamic data on calculated migration lengths resulting from reactive transport simulations is quantified for the example of uranium in the hydrogeological system of the Opalinus Clay at Mont Terri. In this geochemical system, speciation is controlled by the calcite-carbonate-ion system. Aqueous uranium is mainly present as U(VI) as ternary complexes with calcium or magnesium together with carbonate. Previous simulations using the first NEA update of thermodynamic data for uranium indicated that the anionic complex CaUO2(CO3)32- is the predominant species with a maximum migration distance of 50 m after one million years. The NEA published an update of the thermodynamic data for uranium, what, in turn, changes the predominant species from anionic to almost only the neutral ternary complex Ca2UO2(CO3)3. With identical simulations, except for the application of the second NEA update, a maximum distance of 80 m was obtained. This can be attributed to a decrease in sorption capacity due to a stronger complexation of uranium with calcium and carbonate. Therefore, the impact of the change in the underlying thermodynamic data can be quantified with +30 m. Our work clearly shows how sensitive migration lengths resulting from reactive transport simulations are to the model conceptualisation and selection of underlying data. Consequently, the compilation and further development of data sets and a site specific investigation are indispensable for reliable outcomes of transport simulations, and thus of performance assessments.