Chemical Resolution of Pu~(+) from U~(+) and Am~(+) Using a Band-Pass Reaction Cell Inductively Coupled Plasma Mass Spectrometer

摘要

Determination of the concentration and distribution of the Pu and Am isotopes is hindered by the isobaric overlaps between the elements themselves and U, generally requiring time-consuming chemical separation of the elements. A method is described in which chemical resolution of the elemental ions is obtained through ion-molecule reactions in a reaction cell of an ICPMS instrument. The reactions of "natural" U~(+), ~(242)Pu~(+), and ~(243)Am~(+) with ethylene, carbon dioxide, and nitric oxide are reported. Since the net sensitivities to the isotopes of an element are similar, chemical resolution is inferred when one isobaric element reacts rapidly with a given gas and the isobar (or in this instance surrogate isotope) is unreactive or slowly reactive. Chemical resolution of the m/z 238 isotopes of U and Pu can be obtained using ethylene as a reaction gas, but little improvement in the resolution of the m/z 239 isobars is obtained. However, high efficiency of reaction of U~(+) and UH~(+) with CO_(2), and nonreaction of Pu~(+), allows the sub-ppt determination of ~(239)Pu, ~(240)Pu, and ~(242)Pu (single ppt for ~(238)Pu) in the presence of 7 orders of magnitude excess U matrix without prior chemical separation. Similarly, oxidation of Pu~(+) by NO, and nonreaction of Am~(+), permit chemical resolution of the isobars of Pu and Am over 2-3 orders of magnitude relative concentration. The method provides the potential for analysis of the actinides with reduced sample matrix separation.