Assessing Gas-Phase Ion Reactivity of 50 Elements with NO and the Direct Application for ²³⁹Pu in Complex Matrices...

Understanding the reactivity of metal cations with various reaction gases in inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) is important to determine the best gas to use for a given analyte/interference pair. In this study, nitric oxide (NO) was investigated as the reaction gas following previous experimental designs. The reactions with 50 elements were investigated to examine periodic trends in reactivity, validate theoretical modeling of reaction enthalpies as a method to screen reactant gases, and provide a baseline data set for potential in-line gas separation methods. ICP-MS/MS studies involving actinides are typically limited to Th, U, and Pu, with analyses of Np and Am rarely reported in the literature. To date, only two previous methods have investigated the use of NO in ICP-MS/MS analyses. To showcase the utility of NO, a method was developed to measure ²³⁹Pu in the presence of environmental matrix constituent and other actinides, like what could be expected from postdetonation debris, with no chemical separation prior to analysis. ²³⁹Pu⁺ was reacted to form ²³⁹Pu¹⁶O⁺, eliminating interferences derived from the sample matrix by measuring the ²³⁹Pu⁺ intensity at m/z = 255 (²³⁹Pu¹⁶O⁺). To validate NO for ²³⁸U¹H⁺ interference removal in environmental matrices, standard reference materials were diluted to 1 mg/g of solution and spiked to 0.05 pg/g of ²³⁹Pu and 1 μg/g ²³⁸U (Pu/U = 5 × 10^-8). Measured ²³⁹Pu concentrations were within 6% of the spiked value. These results demonstrate that reliable ²³⁹Pu measurements can be made at levels relevant to nuclear forensics without the need for extensive chemical matrix separation prior to analysis.