Electrochemicałly-modulated separation and mass spectrometric analysis of actinides in difficult matrices

Electrochemically-modulated separations (EMS) are a straightforward means of isolating and pre-concentrating elements for on-line mass spectrometric analysis. Elements are accumulated at electrochemical working electrodes and subsequently released into a clean carrier solution for spectroscopic analysis. EMS can employ solely aqueous chemistry and uses electrochemical redox adjustment of oxidation state to "trigger" reversible chelation / complexation. Less tractable elements (e.g., uranium and plutonium), based on redox potentials, can therefore be extracted from difficult matrices following redox adjustment and chelation with electrode chelation sites. Simply put, separation is achieved by a small voltage step that is applied to the target electrode to turn "on" or "off" the specific actinide affinity of an electrode. This separation technology employs both redox and chelation chemistry to effect highly selective accumulation of target actinides, and results in element separation, matrix elimination and analyte preconcentration. Prior studies have developed protocols and preliminary insight into EMS processes for U and Pu. U and Pu are released upon oxidation and reduction, respectively, allowing complete separation due to widely divergent redox potentials. The coupling of EMS on-line with ICP-MS for elemental and isotopic analysis of uranium and plutonium is presented, with a focus on analytical performance metrics and applicability to safeguards and process monitoring via nondestructive analyses.