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This presentation will give a general overview of radiation chemistry in the nuclear fuel cycle, and outline some relevant work being conducted in the INL Radiochemical Separations and Radiation Science Department. This will include a discussion of using multiscale modeling to study plutonium radiation chemistry in nitric acid solutions. (Presentation cancelled)
DOE BES Highlight slide for program managers.
NS&T Highlight Slide for DOE
Presentation highlight the INL Center for Radiation Chemistry Research's contributions the Material Recovery & Waste Form Development Campaign on sulfur chloride processing technologies.
This review aims to provide an overview of the current state of radiation chemistry with respect to the actinide elements, thorium through californium. Despite the inherent radioactivity of the actinides, only a few studies explore the effects of ionizing radiation on their redox chemistry and surrounding environment. This fundamental knowledge gap, coupled with the current renaissance in actinide-based technologies such as nuclear power, space exploration, and medicine, underscores the importance of research in this interdisciplinary area. This review will focus on the interactions between reactive species formed by radiolysis with actinides and their complexes, offering an inorganic chemist's perspective on research in radiation chemistry. In addition, a thorough discussion of our current understanding of radiation-induced changes in actinide speciation in both aqueous solution and the solid-state will be provided, focusing on changes in oxidation state distribution, complexation, and secondary coordination effects within inorganic materials. Finally, this review will discuss challenges and opportunities for inorganic chemists to explore this unique intersection of fields.
Given global commitments to significantly increase nuclear energy capacity, it is now more important than ever to develop efficient used nuclear fuel management strategies to improve resource utilization, energy security, and waste minimization. Here, an overview of nuclear energy, backend fuel cycle challenges, and advances in used nuclear fuel reprocessing radiation chemistry will be presented. More specifically, the use of electron pulse irradiation techniques to explore radiation-induced reaction mechanisms in actinide containing solutions and solvent systems.
Actinides are inherently unstable elements that frequently coexist with other radioisotopes, generating intense ionizing radiation fields that drive the formation of non equilibrium oxidation states. These transient species exert a profound mechanistic influence on the radiation response of actinide containing systems due to their unique redox chemistry. Despite their importance, they remain poorly understood, yet such insight is essential for advancing actinide science and accurately predicting radiation driven behavior. Actinide separations—critical for nuclear energy technologies, strategic deterrence, space exploration, and nuclear medicine—depend on precise control of actinide oxidation states to recover targeted elements from complex matrices such as used nuclear fuel. However, during these processes, actinides, their coordination complexes, and the separation media are all exposed to intense, multicomponent (alpha, beta, gamma, etc.) radiation fields that can alter process efficiency, selectivity, and chemical stability. Understanding, controlling, and mitigating radiation induced reactions is therefore key to innovating and optimizing next generation separation technologies. This seminar will provide an overview of the nuclear fuel cycle and non equilibrium actinide radiation chemistry in the context of recovering actinides from used nuclear fuel, with a particular emphasis on direct dissolution–based reprocessing strategies. We will explore time resolved electron pulse radiolysis and alpha and gamma dose accumulation studies, integrated with multiscale computational modeling, to elucidate the molecular level roles of radiation driven, non equilibrium actinide species in process performance and in the radiolytic stability of organic ligands used for actinide recovery. These insights offer new pathways for designing advanced separation methods and next generation solvent systems, with broad implications for the future of the nuclear fuel cycle.
Invited John and Naomi Fackler Lectureship in Chemistry and English seminar at Valparaiso University, IN, USA. Actinides are inherently unstable elements that frequently coexist with other radioisotopes, generating intense ionizing radiation fields that drive the formation of non-equilibrium oxidation states. These transient species exert a profound mechanistic influence on the radiation response of actinide-containing systems due to their unique redox chemistry. Despite their importance, they remain poorly understood, yet such insight is essential for advancing actinide science and accurately predicting radiation-driven behavior. Actinide separations—critical for nuclear energy technologies, strategic deterrence, space exploration, and nuclear medicine—depend on precise control of actinide oxidation states to recover targeted elements from complex matrices such as used nuclear fuel. However, during these processes, actinides, their coordination complexes, and the separation media are all exposed to intense, multicomponent (alpha, beta, gamma, etc.) radiation fields that can alter process efficiency, selectivity, and chemical stability. Understanding, controlling, and mitigating radiation-induced reactions is therefore key to innovating and optimizing next-generation separation technologies. This seminar will provide an overview of the nuclear fuel cycle and non-equilibrium actinide radiation chemistry in the context of recovering actinides from used nuclear fuel, with a particular emphasis on direct-dissolution–based reprocessing strategies. We will explore time-resolved electron pulse radiolysis and gamma dose accumulation studies to elucidate the molecular-level roles of radiation-driven, non-equilibrium actinide species in process performance and in the radiolytic stability of organic ligands used for actinide recovery. These insights offer new pathways for designing advanced separation methods and next-generation solvent systems, with broad implications for the future of the nuclear fuel cycle.
Highlight slides for DOE EM TDO mid-year program review.
Sulfophenyl bistriazinyl pyridine (SO 3 -Ph-BTP) is a hydrophilic organic ligand used to separate actinides and lanthanides. Dose accumulation and time-resolved studies have previously provided insight into the radiolytic stability and degradation pathways of SO 3 -Ph-BTP in reprocessing environments, but no study has yet addressed the impact of minor actinide complexation on the radiation chemistry of this ligand. To begin to fill this knowledge gap, a systematic, time-resolved study exploring the reactivity of the nitrate radical (NO 3 • ) with SO 3 -Ph-BTP in the presence of trivalent americium, Am(III), has been conducted, which demonstrates enhanced reactivity (an order of magnitude faster) upon metal complexation.
The study of steady-state radiolysis of polyhalides is crucial as it simulates the prolonged radiation exposure that materials (e.g., alloys, molten salts) experience in reactor environments. This research provides valuable insights into the long-term effects on material properties, chemical stability, and structural integrity. It is closely linked with fundamental radiation chemistry, which aids in predicting the chemical behavior of accumulation products. Understanding the initial speciation, yield, and chemical evolution of radiolysis products is essential for managing material degradation, controlling corrosion, and ensuring reactor safety.
The uptake of 241 Am, 244 Cm and 249 Cf with LN resin was studied in HCl and HNO3 solutions with concentrations ranging from 0.02 to 2.5 M. There is high uptake at concentrations < 0.1 M in both acids for all three isotopes with decreasing uptake at higher concentrations and negligible extraction at ≥ 0.6 M. Californium has a higher extraction than americium and curium, which are extremely similar. Kinetics studies showed rapid uptake of all three isotopes. Here, column studies were performed to demonstrate the separation of 241 Am and 249 Cf, and a bulk separation including nine stable lanthanides along with 241 Am, 249 Cf, and 88 Y.
Hydrophilic diglycolamides (DGA) ligands have been explored for use as stripping agents in various lanthanide and actinide partitioning processes.1 The separation of lanthanide fission products and transplutonic actinides can serve multifaceted advantages, in that the separation of neutron poisoning rare earth element (REE) fission products from the minor actinides in used nuclear fuel (UNF) can be mutually beneficial to the fundamental research behind REE separations and UNF separations. Considerable efforts have been devoted to understanding the radiation chemistry of hydrophilic DGAs. However, recent studies with lipophilic DGAs have shown that metal ion complexation can promote significant changes in their radiolytic susceptibility.2,3 These effects have been attributed to various parameters, including delocalization of electron density, the presence of radiolytically more susceptible counter ions, and steric hindrance. As such, it is pivotal for these complexation effects to be more thoroughly probed to establish mechanistic knowledge for their effects on hydrophilic DGA molecules. Here we present a time-resolved electron pulse and accumulated gamma dose irradiation study on neodymium ion complexes of tetramethyl diglycolamide (TMDGA) under aqueous solution conditions. References (1) Rostaing, C.; Poinssot, C.; Warin, D.; Baron, P.; Lorrain, B. Development and Validation of the EXAm Separation Process for Single Am Recycling. Procedia Chem. 2012, 7, 367–373. https://doi.org/doi: 10.1016/j.proche.2012.10.057. (2) Horne, G. P.; Conrad, J. K.; McLachlan, J. R.; Rotermund, B. M.; Cook, A. R.; Celis-Barros, C.; Mezyk, S. P. Impact of Lanthanide Complexation and Temperature on the Chemical Reactivity of N,N,N’,N’-Tetraoctyl Diglycolamide (TODGA) with the Dodecane Radical Cation. Phys. Chem. Chem. Phys. 2023, Under Review. (3) Kimberlin, A.; Saint-Louis, G.; Guillaumont, D.; Camès, B.; Guilbaud, P.; Berthon, L. Effect of Metal Complexation on Diglycolamide Radiolysis: A Comparison between Ex Situ Gamma and in Situ Alpha Irradiation. Phys. Chem. Chem. Phys. PCCP 2022, 24 (16), 9213–9228. https://doi.org/10.1039/d1cp05731f.
The separation of the rare earth elements is essential for numerous scientific applications but remains a significant challenge due to the nearly identical chemical properties of the adjacent lanthanide elements. Eichrom’s LN series of extraction chromatographic resins feature organophosphorus extractants and are widely used to achieve adjacent lanthanide separations. While extensive characterization of these resins has been completed for nitric acid matrices, the use of hydrochloric acid is preferred for a variety of applications. Further, the extraction of the rare earth elements, La–Lu and Y, has been characterized on LN and LN2 resins in hydrochloric acid via batch uptake and column chromatographic studies.
Part 1 of 4 presentations summarizing programmatic research progress.
Plutonium plays a critical role in the development of sustainable nuclear fuel cycles, and yet, our fundamental understanding of this element’s inherent radiation-induced redox chemistry and associated impacts on nuclear fuel cycle technologies is limited. Unanticipated changes in oxidation state distribution can influence the speciation and transport of plutonium in a given process. Control of these parameters is especially important for used nuclear fuel reprocessing technologies, wherein the separation and recovery of plutonium is typically achieved by the selective formation, maintenance, and complexation of specific oxidation states. Furthermore, plutonium’s inherent radiation-induced redox chemistry has the capacity to influence the radiolytic behavior of its complexes, the longevity of which are critical in the design of efficient and cost-effective advanced reprocessing technologies. These radiation-induced processes are unavoidable under fuel cycle conditions owing to the inherency of ionizing radiation fields to the decay of plutonium’s isotopes and to the various other radioisotopes generated by nuclear fission and neutron-capture process and the subsequent radioactive decay of their products. As such, mechanistically understanding the response of plutonium’s multiple oxidation states to multi-component ionizing radiation fields is essential for predicting the behavior of this critical element under used nuclear fuel reprocessing conditions. Here, through a combination of time-resolved (electron pulse) and steady-state (alpha and gamma) irradiation experiments complemented by quantitative, multiscale modeling calculations, we present advances in our understanding of radiation-induced plutonium redox chemistry!
LDRD project concluding poster for the LDRD poster presentation.
Plutonium plays a critical role in nuclear fuel cycle technologies, but our understanding of its fundamental radiation-induced redox chemistry is limited. Changes in oxidation states affect the speciation and transport of plutonium ions in solution. For example, solvent extraction techniques used to separate and recover plutonium from used nuclear fuel rely on the selective formation, maintenance, and complexation of specific plutonium oxidation states. However, radiolytically generated radicals, ions, and molecules can drive the oxidation state distribution of plutonium ions far from equilibrium, ultimately changing the physical and chemical properties of the bulk system. These radiation-induced processes are inevitable due to the ionizing radiation fields generated by the radioactive decay of plutonium and its daughter nuclides. Therefore, mechanistically understanding how plutonium's various oxidation states respond to ionizing radiation is essential for predicting its behavior in solution. Here, we present significant advances in our understanding of radiation-induced plutonium redox chemistry by using time-resolved (electron pulse) and dose accumulation (alpha and gamma) irradiation techniques, along with quantitative multiscale modeling methods.