title: Electrochemically modulated separation, concentration, and detection of plutonium using an anodized glassy carbon electrode and inductively coupled plasma mass spectrometry.
abstract: Plutonium is shown to be retained on anodized glassy carbon (GC) electrodes at potentials positive of +0.7 V (vs Ag/AgCl reference) and released upon potential shifts to values negative of +0.3 V. This phenomenon has been exploited for the separation, concentration, and detection of plutonium by the coupling an electrochemical flow cell on-line with an ICPMS system. The electrochemically controlled deposition and analysis of Pu improves detection limits by analyte preconcentration and by matrix and isobaric ion elimination. Information related to the parametric optimization of the technique and hypotheses regarding the mechanism of electrochemical accumulation of Pu are reported. The most likely accumulation scenario involves complexation of Pu(IV) species, produced under a controlled potential, with anions retained in the anodization film that develops during the activation of the GC electrode. The release mechanism is believed to result from the reduction of Pu(IV) in the anion complex to Pu(III), which has a lower tendency to form complexes.
authors.affiliation: Chemical Science Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6375, USA.
authors.forename: William J
authors.initials: WJ
authors.lastname: Clark
authors.forename: Sea H
authors.initials: SH
authors.lastname: Park
authors.forename: Debra A
authors.initials: DA
authors.lastname: Bostick
authors.forename: Douglas C
authors.initials: DC
authors.lastname: Duckworth
authors.forename: Gary J
authors.initials: GJ
authors.lastname: Van Berkel
mesh_terms: D002244:Carbon / Q000737:chemistry*; D002412:Cations; D004563:Electrochemistry / Q000379:methods; D004566:Electrodes; D013058:Mass Spectrometry / Q000379:methods; D017942:Nitric Acid / Q000494:pharmacology; D010084:Oxidation-Reduction; D011005:Plutonium / Q000032:analysis*
chemical_list: D002412:Cations; D017942:Nitric Acid; D011005:Plutonium; D002244:Carbon