Addressing the Challenge of a Simultaneous Destructive Assay of Plutonium and Uranium: Highly Precise, Robust, Universal, and Reagent-Free Differential Pulse Voltametric Method Development in Biodegradable Methanesulfonic Acid Medium

The destructive assay of bulk uranium and plutonium, a cornerstone for chemical quality control and nuclear material accounting of fuel matrices, mandates robust and precise methodologies. Despite ongoing research, simultaneous, matrix independent determination of U and Pu has eluded solution owing to inherent limitations in aqueous acid medium, viz., coexistence of multiple oxidation states, coupled electrochemical reactions, smaller potential window, and requirement for multistep sample preconditioning and tedious electrode modification. The present study addresses this challenge wherein non-aqueous methanesulfonic acid (MSA) served the dual role of solvent and analyte media with a bare glassy carbon (GC) electrode. Fuel matrices, viz., (U, Pu)C, (U, Pu)O₂, PuO₂, UO₃, UO₂, and U₃O₈, were quantitatively dissolved in biodegradable MSA, without using any additives. Redox speciation of the analytes, U and Pu, in MSA was probed by ultraviolet-visible spectrophotometry and electrometry, revealing the absence of electrocatalytic regeneration and stabilization of single oxidation state, viz., U(VI) and Pu(IV), along with relevant redox-energetic (electron transfer and reversibility) and kinetic data. Bidentate coordination of MSA with the U analyte was indicated by X-ray absorption spectroscopy studies and was corroborated by density functional theory-based investigations, providing the optimized structure, viz., [UO₂(MSA)₂] and [Pu(MSA)₄], binding modes and energy, partial charges, and molecular orbital diagrams. Based on these insights, the feasibility of differential pulse voltammetry (DPV)-based assay method development for U and Pu separately and in different U/Pu ratios, representing assorted fuel matrices, was probed. Analytical figures of merit for both U and Pu (detection limit of ∼10^-5 M, precision of ∼0.2%, accuracy of ∼0.2%, high sensitivity, repeatability, and non-influence of relevant interferences) were determined, method validated employing actual fuel samples, and compared with the established, multi-step biamperometry method. Hence, a universal, simultaneous U and Pu destructive assay method in non-aqueous MSA media based on DPV with a commercial GC electrode was demonstrated.