CE-ICP-MS investigation of the carbonate complexation of Am(III), Th(IV), Np(V), and U(VI) and the influence of alkali cations

Abstract

Capillary electrophoresis inductively coupled plasma mass spectrometry (CE-ICP-MS) was used to investigate the carbonate complexation of Am(III), Th(IV), Np(V), and U(VI) at environmentally relevant concentrations. Experiments were conducted at an ionic strength of 0.33 M in different alkali chloride solutions (Li+, Na+, and K+). Formation constants for the three successive actinide carbonate complexes were determined for Am(III), Np(V), and U(VI). For Th(IV), the CE-ICP-MS measurements posed some challenges. The complexation of U(VI) with carbonate was determined to be stronger than previously assumed. A strong influence of alkali cations on the electrophoretic mobility μ of highly negatively charged actinide carbonate complexes was observed and attributed to the association of cations to those complexes. The electrophoretic mobility of negatively charged An-CO3 complexes was found to follow the trend |μLi| ≤ |μNa| < |μK|. Furthermore, the reaction of UO2(CO3)34– with different alkali cations (Me+ = Li+–Cs+) was studied. Complex formation constants for MeUO2(CO3)33– and Me2UO2(CO3)32– for all investigated cations were determined.