Precise U and Pu isotope ratio measurements in nuclear samples by hyphenating capillary electrophoresis and MC-ICPMS

Abstract : Precise isotopic and elemental characterization of spent nuclear fuel is a major concern for the validation of the neutronic calculation codes and waste management strategy in the nuclear industry. Generally, the elements of interest, particularly U and Pu which are the two major elements present in spent fuel, are purified by ion exchange or extractant resins before off-line measurements by thermal ionization mass spectrometry. The aim of the present work was to develop a new analytical approach based on capillary electrophoresis (CE) hyphenated to a multicollector inductively coupled plasma mass spectrometer (MC-ICPMS) for online isotope ratio measurements. An electrophoretic separation protocol of U, Pu and the fraction containing fission products and minor actinides (Am and Cm) was developed using acetic acid as the electrolyte and complexing agent. The instrumentation for CE was designed to be used in a glove box and a laboratory-built interface was developed for hyphenation with MC-ICPMS. The separation was realized with only a few nL of a solution of spent nuclear fuel and the reproducibilities obtained on the U and Pu isotope ratios were on the order of a few which is comparable to those obtained by thermal ionization mass spectrometer (TIMS). This innovative protocol allowed a tremendous reduction of the sample amounts classically required for analysis sample masses from et956;g to ng and sample volumes from et956;L to nL. also a drastic reduction of the liquid waste production from mL to et956;L. In addition, the measurement process was shorted by at least three orders of magnitude. All of these improved parameters are of major interest for nuclear applications.