Uranium(VI) Complexation with Lactate and Citrate in Dependence on Temperature (7-65°C)

After disposal in nuclear waste repositories the chemical and migration behavior of actinides depends on many factors. It is estimated that maximum temperatures in the near field of a repository could reach 300°C in dependence on the waste forms [1] and the host rock [2]. Thus, for the long-term safety assessment, knowledge of the interaction of actinides such as uranium with inorganic and organic ligands at elevated temperatures is required. The amount of organic matter in a repository can be separated in humic substances and in low molecular weight organic substances. A not negligible component of low molecular weight organic substances is the group of carboxylic acid. For example, citric acid is used in nuclear reprocessing [3] and acetic, lactic and formic acid were identified in rock extracts and pore water of Opalinus Clay [4]. Reliable experimental data on the complexation of U(VI) in solution at elevated temperatures are still needed.
Therefore, we studied the U(VI) complexation by lactic acid (pH 3) and citric acid (pH 0-10) in the temperature range from 7 to 65°C. Species distribution and complex formation constants were determined by means of UV-Vis and time-resolved laser-induced fluorescence spectroscopy. In the U(VI) lactate system, we identified the formation of 1:1- and 1:2-complexes. In the presence of citrate, we could characterize five U(VI) complexes in dependence on pH value. The complex formation between U(VI) and these both ligands was found to be endothermic and entropy-driven. The complex stability constants of the U(VI) complexes increase with increasing temperature. This could lead to an increased mobility of U(VI) at higher temperatures.