Reduction of Plutonium(VI) to (V) by Hydroxamate Compounds at Environmentally Relevant pH

Natural organic matter is known to influence the mobility of plutonium (Pu) in the environment via complexation and reduction mechanisms. Hydroxamate siderophores have been specifically implicated due to their strong association with Pu. Hydroxamate siderophores can also break down into di and monohydroxamates and may influence the Pu oxidation state, and thereby its mobility. In this study we explored the reactions of Pu­(VI) and Pu­(V) with a monohydroxamate compound (acetohydroxamic acid, AHA) and a trihydroxamate siderophore desferrioxamine B (DFOB) at an environmentally relevant pH (5.5–8.2). Pu­(VI) was instantaneously reduced to Pu­(V) upon reaction with AHA. The presence of hydroxylamine was not observed at these pHs; however, AHA was consumed during the reaction. This suggests that the reduction of Pu­(VI) to Pu­(V) by AHA is facilitated by a direct one electron transfer. Importantly, further reduction to Pu­(IV) or Pu­(III) was not observed, even with excess AHA. We believe that further reduction of Pu­(V) did not occur because Pu­(V) does not form a strong complex with hydroxamate compounds at a circum-neutral pH. Experiments performed using desferrioxamine B (DFOB) yielded similar results. Broadly, this suggests that Pu­(V) reduction to Pu­(IV) in the presence of natural organic matter is not facilitated by hydroxamate functional groups and that other natural organic matter moieties likely play a more prominent role