The Role of Radiation-Induced Non-Equilibrium Plutonium Oxidation States in Solution

Plutonium plays a key role in global actinide research and nuclear fuel cycle technologies, and yet, our fundamental understanding of its inherent radiation-induced chemical behavior is limited. These radiation-induced processes cannot simply be switched off, as they are as fundamentally inherent to plutonium as the impact of relativistic effects on its f-electrons. In less chemically complex actinide systems, such as aqueous solutions of neptunium and americium, both steady-state and transient radiolysis products play a significant role in the redox cycling of their oxidation states, which ultimately impacts their chemistry and transport. However, plutonium's multiple, coexisting, and chemically active oxidation states, which comprise of bare ions and dioxo cations, provide additional redox pathways that complicate the aforementioned radiation-induced competition kinetics. Mechanistically understanding the response of these multiple oxidation states, both equilibrium and non-equilibrium, to intense ionizing radiation fields is essential for predicting the behavior of plutonium under a host of conditions that support technological innovation in global nuclear energy and non-proliferation efforts. Here, advances in radiation-induced plutonium solution chemistry will be presented, including new results from time-resolved electron pulse and steady-state gamma and alpha irradiations.