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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Radiation-Induced Effects on the Extraction Properties of Hexa-n-octylnitrilo-triacetamide (HONTA) Complexes of Americium and Europium

The candidate An(III)/Ln(III) separation ligand hexa-n-octylnitrilo-triacetamide (HONTA) was irradiated under envisioned SELECT (Solvent Extraction from Liquid waste using Extractants of CHON-type for Transmutation) process conditions (n-dodecane/0.1 M HNO 3 ) using a solvent test loop in conjunction with cobalt-60 gamma irradiation. The extent of HONTA radiolysis and complimentary degradation product formation was quantified by HPLC-ESI-MS/MS. Further, the impact of HONTA radiolysis on process performance was evaluated by measuring the change in 243 Am and 154 Eu distribution ratios as a function of absorbed gamma dose. HONTA was found to decay exponentially with increasing dose, affording a dose coefficient of d = (4.48 ± 0.19) × 10 –3 kGy –1 . Multiple degradation products were detected by HPLC-ESI-MS/MS with dioctylamine being the dominant quantifiable species. Both 243 Am and 154 Eu distribution ratios exhibited an induction period of ~70 kGy for extraction (0.1 M HNO 3 ) and back-extraction (4.0 M HNO 3 ) conditions, after which both values decreased with absorbed dose. The decrease in distribution ratios was attributed to a combination of the destruction of HONTA and ingrowth of dioctylamine, which is capable of interfering in metal ion complexation. Furthermore, the loss of HONTA with absorbed gamma dose was predominantly attributed to its reaction with the n-dodecane radical cation (R˙ + ). These R˙ + reaction kinetics were measured for HONTA and its 241 Am and 154 Eu complexes using picosecond pulsed electron radiolysis techniques. All three second-order rate coefficients (k) were essentially diffusion limited in n-dodecane indicating a significant reaction pathway: k(HONTA + R˙ + ) = (7.6 ± 0.8) × 10 9 M –1 s –1 , k(Am(HONTA) 2 + R˙ + ) = (7.1 ± 0.7) × 10 10 M –1 s –1 , and k(Eu(HONTA) 2 + R˙ + ) = (9.5 ± 0.5) × 10 10 M –1 s –1 . HONTA-metal ion complexation afforded an order-of-magnitude increase in rate coefficient. Additional nanosecond time-resolved measurements showed that both direct and indirect HONTA radiolysis yielded the short-lived (< 100 ns) HONTA radical cation and a second long-lived (µs) species identified as the HONTA triplet excited state. The latter was confirmed by a series of oxygen quenching picosecond pulsed electron measurements, affording a quenching rate coefficient of k( 3 [HONTA]* + O 2 ) = 2.2 × 10 8 M –1 s –1 . Overall, both the HONTA radical cation and triplet excited state are important precursors to the suite of measured HONTA degradation products.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Ultrafast pre-solvated dodecane hole capture and subsequent damage of used nuclear fuel extraction ligands DEHBA, DEH i BA, HONTA, CMPO, HEH[EHP] and TBP

Here, two classes of used nuclear fuel (UNF) extraction ligands, amide (DEHBA, DEH i BA, HONTA) and organophosphorus (CMPO, HEH[EHP], TBP), were selected to study radiation induced damage at picosecond to nanosecond timescale using electron pulse radiolysis in n-dodecane (DD) and supported by quantum chemical calculations. Spectra after radiolysis of 200 mM extraction ligands were recorded in DD/0.3 M DCM. Absorption peaks at 365, 365, 400 and 387 nm in case of DEHBA, DEH i BA, HONTA and CMPO respectively are assigned to triplet excited states. Additional absorption peaks at 420, 460 and 600 nm of DEHBA, DEH i BA and HONTA respectively were identified as due to ligand radical cations. A concentration dependent absorption peak at 600 nm in the case of CMPO was observed and assigned due to a combination of CMPO˙ + , (CMPO) 2 ˙ + and possibly a radical degradation product of CMPO. Weak absorption peaks at 650 and 550 nm in case of HEH[EHP] and TBP were observed and tentatively assigned to their radical cations. A two-component DD˙ + decay in the presence of ligands was observed due to different ligand oxidation mechanisms: ultrafast capture of pre-solvated DD holes and diffusive capture of solvated DD holes. At high extraction ligand concentrations (>100 mM), the majority of DD holes were captured via the ultrafast pre-solvated pathway in <10 ps with C 37 values of 389, 401, 270, 374, 458 and 340 mM for DEHBA, DEHiBA, HONTA, CMPO, HEH[EHP] and TBP respectively. Following ultrafast capture, the remainder of DD holes became solvated and were captured with k = (2.32 ± 0.13), (1.78 ± 0.12), (1.38 ± 0.2), (0.98 ± 0.081), (1.09 ± 0.08) and (1.77 ± 0.046) × 10 10 for DEHBA, DEH i BA, HONTA, CMPO, HEH[EHP] and TBP respectively. Subsequent hole transfer from the extraction ligands˙ + to the low IP solute tri-p-tolylamine (TTA) showed only 4–16% hole transfer, most likely indicating ligand˙ + degradation in 0.9–4.6 ns.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Impact of f-element complexation on the radiolytic robustness of separations ligands

Impact of f-element complexation on the radiolytic robustness of separations ligands Gregory P. Horne, Makayla R. Baxter, Corey D. Pilgrim, Travis S. Grimes, Center for Radiation Chemistry Research, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID, 83415, USA Cristian Celis Barros, Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306, USA. E-mail: ccelisbarros@fsu.edu Andrew R. Cook, Department of Chemistry, Brookhaven National Laboratory, Upton, New York, 11973, USA Stephen P. Mezyk, Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Boulevard, Long Beach, California, 90840-9507, USA The effects of ionizing radiation are ubiquitous throughout all aspects of a nuclear fuel cycle. However, the complexity and intensity of these effects are greatest during the management of used nuclear fuel, owing to the presence of a wide spectrum of radionuclides from neutron capture and fission processes. With regards to used nuclear fuel (UNF) reprocessing, radiation-induced processes typically promote the destruction of active compounds (e.g., complexants and additives) with the concomitant formation of potentially detrimental degradation products and corresponding changes in physical and chemical properties, which ultimately impact the effectiveness and longevity of a given reprocessing system. Concerning UNF complexants, radiation chemistry studies have historically focused on their radiation robustness in the absence of the metal ions they were designed to selectively complex. This knowledge gap is worrisome as previous studies on aqueous phase complexants have demonstrated significant changes in radiolytic behavior upon metal ion complexation.1-4 More recently, the rate of reaction of the n-dodecane radical cation—believed to be the major organic phase radiation-induced transient species responsible for complexant radiolysis in n-dodecane based solvent systems—with hexa-n-octylnitrilo-triacetamide (HONTA) was shown to increase by an order-of-magnitude upon complexation of europium or americium.5 These findings have significant implications on the projected longevity of complexants in UNF reprocessing solvent systems. Consequently, a thorough understanding of metal ion complexation effects on the radiolytic integrity of UNF complexants is essential to evaluate their potential for process application. Presented here are two recent studies from the Idaho National Laboratory Center for Radiation Chemistry Research group that demonstrate the various impacts of f-element complexation (uranium, americium, and lanthanides) on the radiolytic integrity (gamma and electron pulse) of tributyl phosphate (TBP), N,N-di-(2-ethylhexyl)butyramide (DEHBA), N,N-di-2-ethylhexylisobutryamide (DEHiBA), and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) under UNF reprocessing conditions. References 1) Bhattacharyya and Kundu, Int. J. Radiat. Phys. Chem., 1971, 3, 1. 2) Kundu and Matuura, Int. J. Radiat. Phys. Chem., 1975, 7, 565. 3) Ilan and Czapski, Biochimica et Biophysica Acta, 1977, 498, 386. 4) Buettner, Doherty, and Patterson, Fed. Euro. Biochem. Soc., 1983, 158 (1), 143. 5) Toigawa, Peterman, Meeker, Grimes, Zalupski, Mezyk, Cook, Yamashita, Kumagai, Matsumura, Horne, PCCP, 2021, 23, 1343.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Impact of Actinide Complexation on Ligand Radiolysis

Although the actinides boast many unique physical and chemical properties, their inherent susceptibility to radioactive decay are what make them truly interesting elements to study. The absorption of ionizing radiation from actinide decay leads to the formation of a variety of transient and steady-state radicals, ions, and molecular radiolysis products that can lead to significant changes in the surrounding environment, and ultimately dictate steady-state actinide redox distributions and the longevity of molecules designed for actinide complexation. Radiolysis of the latter leads to complexant destruction and the concomitant formation of degradation products that can complicate actinide studies and processes. However, the radiation chemistry of most actinide complexants have been studied in the absence of the actinides they were designed to complex, which can lead to inaccurate conclusions on longevity and degradation product distributions, as metal ion complexation has been historically shown to influence a ligand’s radiolytic behavior. Consequently, bridging this knowledge gap is important for actinide science. Here, I will discuss the impact of actinide complexation on the steady-state and time-resolved radiation-induced reactivity of a variety of complexants, including, tributyl phosphate (TBP) and N,N,N',N'-tetraoctyl diglycolamide (TODGA) .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

The Role of Pulse Radiolysis in Advanced Nuclear Fuel Cycles

The effects of ionizing radiation are ubiquitous throughout all aspects of a nuclear fuel cycle. The complexity and intensity of these effects are greatest during reactor operations and in the management of used nuclear fuel and waste. Radiation-induced processes typically promote the chemical transformation of molecules and materials with the formation of potentially detrimental degradation products and corresponding changes in physical and chemical properties, which ultimately impact the effectiveness and longevity of nuclear technologies. Consequently, a molecular-level understanding of radiation effects over multiple time, distance, and material domains is essential for the innovation and deployment of next generation nuclear technologies. Attaining this knowledge necessitates a firm grasp of radiation-induced reaction kinetics, for which pulsed electron radiolysis is the methodology of choice. Presented here are several recent studies from our group that demonstrate the critical role of pulsed electron radiolysis techniques in the advancement of our understanding of radiation-induced chemistry under advanced nuclear fuel cycle conditions. Research topics include late actinide redox chemistry, radiation robustness of used nuclear fuel reprocessing complexants, and the behavior of metal cations in high temperature molten salt media.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Fundamental Radiation Chemistry

An overview presentation for the Fundamental Radiation Chemistry component of the Material Recovery and Waste Form Development campaign to be delivered to the campaign team. The overview includes all major findings from FY19 research projects, current state of FY20 research projects, additional projects completed between FY19 and now, and finally our vision for the future direction of the Fundamental Radiation Chemistry component.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗