Plutonium Speciation and Oxidation State Distributions in the Presence of Citrate

We explored the speciation and kinetics of the Pu(VI)-citrate and Pu(III)-citrate systems (pH_m = 2.5-11.0, <i>I</i> = 0.1 M NaCl, <i>T</i> = 23 °C, O₂(g) < 2 ppm) using ultraviolet-visible-near-infrared (UV-vis-NIR) spectrophotometry, solvent extraction, and PHREEQC modeling. Formation constants were determined for PuO₂(HcitH)(aq) (log <i>K</i>°_1,1 = 1.09 ± 0.05) and PuO₂(HcitH)(citH)^3- (log <i>K</i>°_1,2 = -0.20 ± 0.07), and evidence for (PuO₂)_<i>m</i>(citH_-<i>k</i>)_<i>n</i>(OH)_<i>x</i>^{2<i>m</i>(3+<i>k</i>)<i>n</i>-<i>x</i>} was identified under alkaline conditions. Pu(VI) species were found to be less stable in the presence of citrate than in the absence of citrate (<i>t</i> ≤ 168 days); the rate of reduction increased with increasing pH. The direct reduction of Pu(VI) to Pu(IV) was required to fit experimental data in the presence of citrate but did not improve the fit for Pu in the absence of citrate. We also observed increased Pu(III) stability in the presence of citrate (<i>t</i> ≤ 293 days), with higher concentrations of Pu(III) favored at lower pH. Finally, we provide evidence of a radiolysis-driven mechanism for the citrate-mediated reduction of plutonium that involves electron transfer from the oxidative breakdown of citrate. Our work highlights the need to investigate the redox effect of organic ligands on plutonium oxidation states under repository-relevant conditions.