Radiolytic evaluation of a new technetium redox control reagent for advanced used nuclear fuel separations

Dang, Anh N.; Rogalski, Maya H.; Pilgrim, Corey D.; Wilbanks, Joseph R.; Peterman, Dean R.; Carrie, Jesse D.; Zalupski, Peter R.; Mezyk, Stephen P.; Horne, Gregory P.

doi:10.1039/d3cp04987f

Title: Radiolytic evaluation of a new technetium redox control reagent for advanced used nuclear fuel separations

Journal Article · 14 January 2024 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/d3cp04987f · OSTI ID:2305464

Dang, Anh N. ^[1]; Rogalski, Maya H. ^[1];

^[2]; Wilbanks, Joseph R. ^[2];

^[2]; Carrie, Jesse D. ^[2];

^[2];

^[1];

^[3]

California State University (CalState), Long Beach, CA (United States)
Idaho National Laboratory (INL), Idaho Falls, ID (United States). Center for Radiation Chemistry Research
Center for Radiation Chemistry Research, Idaho National Laboratory, 1955 N. Freemont Ave., P.O. Box 1625, Idaho Falls, ID, 83415, USA

Technetium is a problematic radioisotope for used nuclear fuel (UNF) and subsequent waste management owing to its high environmental mobility and coextraction in reprocessing technologies as the pertechnetate anion (TcO₄^-). Consequently, several strategies are under development to control the transport of this radioisotope. A proposed approach is to use diaminoguanidine (DAG) for TcO₄^- and transuranic ion redox control. Although the initial DAG molecule is ultimately consumed in the redox process, its susceptibility to radiolysis is currently unknown under envisioned UNF reprocessing conditions, which is a critical knowledge gap for evaluating its overall suitability for this role. To this end, we report the impacts of steady-state gamma irradiation on the rate of DAG radiolysis in water, aqueous 2.0 M nitric acid (HNO₃), and in a biphasic solvent system composed of aqueous 2.0 M HNO₃ in contact with 1.5 M N,N-di-(2-ethylhexyl)isobutyramide (DEHiBA) dissolved in n-dodecane. In addition, we report chemical kinetics for the reaction of DAG with key transients arising from electron pulse radiolysis, specifically the hydrated electron (e_aq^-), hydrogen atom (H^˙), and hydroxyl (^˙OH) and nitrate (NO₃^˙) radicals. The DAG molecule exhibited significant reactivity with the ^˙OH and NO₃^˙ radicals, indicating that oxidation would be the predominant degradation pathway in radiation environments. This is consistent with its role as a reducing agent. Steady-state gamma irradiations demonstrated that DAG is readily degraded within a few hundred kilogray, the rate of which was found to increase upon going from water to HNO₃ containing solutions and solvents systems. This was attributed to a thermal reaction between DAG and the predominant HNO₃ radiolysis product, nitrous acid (HNO₂), k(DAG + HNO₂) = 5480 ± 85 M^-1 s^-1. Although no evidence was found for the radiolysis of DAG altering the radiation chemistry of the contacted DEHiBA/n-dodecane phase in the investigated biphasic system, the utility of DAG as a redox control reagent will likely be limited by significant competition with its degradation by HNO₂.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE; USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC07-05ID14517; FC02-04ER15533

OSTI ID:: 2305464

Report Number(s):: INL/JOU--23-74907-Revision-0

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 5 Vol. 26; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

The reduction of actinide ions by hydroxamic acids Taylor, R. J.; May, I. Czechoslovak Journal of Physics, Vol. 49, Issue S1 https://doi.org/10.1007/s10582-999-1041-0	journal	January 1999
Complexation of uranium(VI) with acetohydroxamic acid Tkac, P.; Matteson, B.; Bruso, J. Journal of Radioanalytical and Nuclear Chemistry, Vol. 277, Issue 1 https://doi.org/10.1007/s10967-008-0705-8	journal	April 2008
Technetium chemistry in a novel group actinide extraction process Aneheim, Emma; Ekberg, Christian; Littley, Alexander Journal of Radioanalytical and Nuclear Chemistry, Vol. 296, Issue 2 https://doi.org/10.1007/s10967-012-1928-2	journal	July 2012
The behavior of technetium in technetium-scrubbing stage of PUREX process Liu, Fang; Zheng, Wei-fang; Zhang, Yu Journal of Radioanalytical and Nuclear Chemistry, Vol. 295, Issue 3 https://doi.org/10.1007/s10967-012-2205-0	journal	September 2012
generators — II. Physicochemical factors in the radiolytic reduction of pertechnetate Heller-Grossman, Lily; Abrashkin, Shmuel; Shafferman, Avigdor The International Journal of Applied Radiation and Isotopes, Vol. 32, Issue 7 https://doi.org/10.1016/0020-708X(81)90126-5	journal	July 1981
The technetium-catalysed oxidation of hydrazine by nitric acid Garraway, John; Wilson, Peter D. Journal of the Less Common Metals, Vol. 97 https://doi.org/10.1016/0022-5088(84)90023-7	journal	February 1984
The formation of hydrophilic Np(IV) complexes and their potential application in nuclear fuel reprocessing May, Iain; Taylor, Robin J.; Brown, Geoff Journal of Alloys and Compounds, Vol. 271-273 https://doi.org/10.1016/S0925-8388(98)00179-0	journal	June 1998
Considerations for choice of a kinetic fig. of merit in process radiation chemistry for waste treatment Mincher, Bruce J.; Curry, Randy D. Applied Radiation and Isotopes, Vol. 52, Issue 2 https://doi.org/10.1016/S0969-8043(99)00161-X	journal	February 2000
Multiple time scales in pulse radiolysis. Application to bromide solutions and dipeptides Hug, Gordon L.; Wang, Yicheng; Schöneich, Christian Radiation Physics and Chemistry, Vol. 54, Issue 6 https://doi.org/10.1016/S0969-806X(98)00303-X	journal	June 1999
Kinetic study of the reactions between chloramine disinfectants and hydrogen peroxide: Temperature dependence and reaction mechanism McKay, Garrett; Sjelin, Brittney; Chagnon, Matthew Chemosphere, Vol. 92, Issue 11 https://doi.org/10.1016/j.chemosphere.2013.03.045	journal	September 2013
A review of technetium and zirconium extraction into tributyl phosphate in the PUREX process George, Kathryn; Masters, Andrew J.; Livens, Francis R. Hydrometallurgy, Vol. 211 https://doi.org/10.1016/j.hydromet.2022.105892	journal	May 2022
On the nature of heptavalent technetium in concentrated nitric and perchloric acid Poineau, Frederic; Burton-Pye, Benjamin P.; Maruk, Alesya Inorganica Chimica Acta, Vol. 398 https://doi.org/10.1016/j.ica.2012.12.028	journal	March 2013
The development of future options for aqueous recycling of spent nuclear fuels Taylor, Robin; Mathers, Gemma; Banford, Anthony Progress in Nuclear Energy, Vol. 164 https://doi.org/10.1016/j.pnucene.2023.104837	journal	October 2023
Simulation of technetium rejection in an advanced PUREX flowsheet Chen, Hongyan; Jobson, Megan; Taylor, Robin Progress in Nuclear Energy, Vol. 164 https://doi.org/10.1016/j.pnucene.2023.104856	journal	October 2023
Radiolytic evaluation of acetohydroxamic acid (AHA) under biphasic (HNO3:n-dodecane and TBP/DEHBA/DEHiBA) used nuclear fuel reprocessing conditions Umpleby, Rachel E.; Conrad, Jacy K.; Wilbanks, Joseph R. Radiation Physics and Chemistry, Vol. 207 https://doi.org/10.1016/j.radphyschem.2023.110799	journal	June 2023
Separation of Technetium from Mixed Fission Products by Solvent Extraction with Tributyl Phosphate. Campbell, M. H. Analytical Chemistry, Vol. 35, Issue 13 https://doi.org/10.1021/ac60206a023	journal	December 1963
Efficient Capture of Perrhenate and Pertechnetate by a Mesoporous Zr Metal–Organic Framework and Examination of Anion Binding Motifs Drout, Riki J.; Otake, Kenichi; Howarth, Ashlee J. Chemistry of Materials, Vol. 30, Issue 4 https://doi.org/10.1021/acs.chemmater.7b04619	journal	January 2018
Distribution Coefficient Model for Zirconium and Technetium Extraction from Nitric Acid Solution Chen, Hongyan; Jobson, Megan; Taylor, Robin J. Industrial & Engineering Chemistry Research, Vol. 61, Issue 1 https://doi.org/10.1021/acs.iecr.1c04103	journal	December 2021
Modeling and Speciation Study of Uranium(VI) and Technetium(VII) Coextraction with DEHiBA Moeyaert, Pauline; Dumas, Thomas; Guillaumont, Dominique Inorganic Chemistry, Vol. 55, Issue 13 https://doi.org/10.1021/acs.inorgchem.6b00595	journal	June 2016
Plutonium and Americium Alpha Radiolysis of Nitric Acid Solutions Horne, Gregory P.; Gregson, Colin R.; Sims, Howard E. The Journal of Physical Chemistry B, Vol. 121, Issue 4 https://doi.org/10.1021/acs.jpcb.6b12061	journal	January 2017
The Chemistry of Aminoguanidine and Related Substances. Lieber, Eugene.; Smith, G. B. L. Chemical Reviews, Vol. 25, Issue 2 https://doi.org/10.1021/cr60081a003	journal	October 1939
Pulse radiolysis studies on pertechnetate and perrhenate in aqueous media. Decay of the technetium(VI) transient Libson, Karen; Sullivan, James C.; Mulac, William A. Inorganic Chemistry, Vol. 28, Issue 2 https://doi.org/10.1021/ic00301a045	journal	January 1989
The Reaction of Nitrous Acid with Diaminoguanidine in Acetic Acid Media. Isolation and Structure Proof of Reaction Products¹ Lieber, Eugene; Levering, Dewey Robert Journal of the American Chemical Society, Vol. 73, Issue 3 https://doi.org/10.1021/ja01147a135	journal	March 1951
The Reaction of Nitrous Acid with Nitroaminoguanidine Lieber, Eugene; Sherman, Edward; Henry, Ronald A. Journal of the American Chemical Society, Vol. 73, Issue 5 https://doi.org/10.1021/ja01149a124	journal	May 1951
Nuclei Formed in Fission: Decay Characteristics, Fission Yields, and Chain Relationships Journal of the American Chemical Society, Vol. 68, Issue 11, p. 2411-2442 https://doi.org/10.1021/ja01215a600	journal	November 1946
The CN ₇ ⁻ Anion Klapötke, Thomas M.; Stierstorfer, Jörg Journal of the American Chemical Society, Vol. 131, Issue 3 https://doi.org/10.1021/ja8077522	journal	January 2009
Temperature Dependence of Hydrogen Atom Reaction with Nitrate and Nitrite Species in Aqueous Solution ^† Mezyk, Stephen P.; Bartels, David M. The Journal of Physical Chemistry A, Vol. 101, Issue 35 https://doi.org/10.1021/jp970934i	journal	August 1997
Technetium Distribution throughout Purex Process Cycles at RT-1 Plant Mashkin, A. N.; Korchenkin, K. K.; Svetlakova, N. A. Radiochemistry, Vol. 44, Issue 1, p. 35-41 https://doi.org/10.1023/A:1014871000568	journal	January 2002
Extraction and Stripping Behavior of U-Np-Tc Ternary System to TBP Kwang, Wook Kim; Soo, Ho Kim; Kee, Chan Song Journal of Radioanalytical and Nuclear Chemistry, Vol. 253, Issue 1, p. 3-10 https://doi.org/10.1023/A:1016585918083	journal	July 2002
Strategic Separation of Technetium and Rare Metal Fission Products in Spent Nuclear Fuel: Solvent Extraction Behavior and Partitioning by Catalytic Electrolytic Extraction Ozawa, M.; Ishida, M.; Sano, Y. Radiochemistry, Vol. 45, Issue 3, p. 225-232 https://doi.org/10.1023/A:1026099707043	journal	May 2003
Removal of TcO ₄ ⁻ ions from solution: materials and future outlook Banerjee, Debasis; Kim, Dongsang; Schweiger, Michael J. Chemical Society Reviews, Vol. 45, Issue 10 https://doi.org/10.1039/C5CS00330J	journal	January 2016
Production, detection, and characterization of transient hexavalent technetium in aqueous alkaline media by pulse radiolysis and very fast scan cyclic voltammetry Deutsch, Edward; Heineman, William R.; Hurst, Roger Journal of the Chemical Society, Chemical Communications, Issue 23 https://doi.org/10.1039/c39780001038	journal	January 1978
The role of intermediate oxidation states of technetium in catalysis of the oxidation of hydrazine by oxo-anions. Part 1. Nitrate ions Kemp, Terence J.; Thyer, Aubrey M.; Wilson, Peter D. Journal of the Chemical Society, Dalton Transactions, Issue 17 https://doi.org/10.1039/dt9930002601	journal	January 1993
Re-evaluation of the thiocyanate dosimeter for pulse radiolysis Buxton, George V.; Stuart, Craig R. Journal of the Chemical Society, Faraday Transactions, Vol. 91, Issue 2 https://doi.org/10.1039/ft9959100279	journal	January 1995
Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O ⁻ in Aqueous Solution Buxton, George V.; Greenstock, Clive L.; Helman, W. Phillips Journal of Physical and Chemical Reference Data, Vol. 17, Issue 2 https://doi.org/10.1063/1.555805	journal	April 1988
Solvent Extraction Behavior of Plutonium (IV) Ions in the Presence of Simple Hydroxamic Acids Carrott, M. J.; Fox, O. D.; Maher, C. J. Solvent Extraction and Ion Exchange, Vol. 25, Issue 6 https://doi.org/10.1080/07366290701634560	journal	October 2007
Solvent Extraction Behavior of Neptunium (IV) Ions between Nitric Acid and Diluted 30% Tri‐butyl Phosphate in the Presence of Simple Hydroxamic Acids Taylor, R. J.; Sinkov, S. I.; Choppin, G. R. Solvent Extraction and Ion Exchange, Vol. 26, Issue 1 https://doi.org/10.1080/07366290701784159	journal	January 2008
Separation of Pertechnetate from Uranium in a Simulated UREX Processing Solution Using Anion Exchange Extraction Chromatography Jarvinen, Gordon D.; Long, Kristy M.; Goff, George S. Solvent Extraction and Ion Exchange, Vol. 31, Issue 4 https://doi.org/10.1080/07366299.2013.800434	journal	July 2013
Radiation chemistry of the branched-chain monoamide di-2-ethylhexyl-isobutyramide Drader, J.; Saint-Louis, G.; Muller, J. M. Solvent Extraction and Ion Exchange, Vol. 35, Issue 7 https://doi.org/10.1080/07366299.2017.1379713	journal	September 2017
Simulation Study on Behavior of Technetium and Its Controlled Strip during Codecontamination Process of Fuel Reprocessing Tachimori, Shoichi Journal of Nuclear Science and Technology, Vol. 31, Issue 5 https://doi.org/10.1080/18811248.1994.9735175	journal	May 1994
Controlling Neptunium and Plutonium within Single Cycle Solvent Extraction Flowsheets for Advanced Fuel Cycles Birkett, J. Eddie; Carrott, Mike J.; Fox, O. Danny Journal of Nuclear Science and Technology, Vol. 44, Issue 3 https://doi.org/10.1080/18811248.2007.9711291	journal	March 2007
The Extraction and Stripping Behavior of Heptavalent Technetium with Trialkyl Phosphine Oxide Xiaogui, Feng; Chongli, Song Solvent Extraction and Ion Exchange, Vol. 19, Issue 1 https://doi.org/10.1081/SEI-100001373	journal	January 2001
Technetium in the Nuclear Fuel Cycle, in Medicine and in the Environment Lieser, K. H. Radiochimica Acta, Vol. 63, Issue s1 https://doi.org/10.1524/ract.1993.63.special-issue.5	journal	January 1993
Oxidation–reduction reactions of simple hydroxamic acids and plutonium(IV) ions in nitric acid Carrott, M. J.; Fox, O. D.; LeGurun, G. Radiochimica Acta, Vol. 96, Issue 6 https://doi.org/10.1524/ract.2008.1502	journal	January 2008
Standard and advanced separation: PUREX processes for nuclear fuel reprocessing Herbst, R. S.; Baron, P.; Nilsson, M. Advanced Separation Techniques for Nuclear Fuel Reprocessing and Radioactive Waste Treatment https://doi.org/10.1533/9780857092274.2.141	book	January 2011
A Review on the Reactivity of 1-Amino-2-Nitroguanidine (ANQ) Wang, Jinghua; Cai, Meng; Zhao, Fengqi Molecules, Vol. 24, Issue 19 https://doi.org/10.3390/molecules24193616	journal	October 2019

Similar Records

Direct Extraction of Uranium Oxides with N,N-Di(2-ethylhexyl)isobutyramide

Journal Article · 2025 · ACS Omega · OSTI ID:2543106

Speelman, Amy L.; Boglaienko, Daria; Tarbet-Mendoza, Avalon B.; +6 more

Extraction of Nitric Acid and Uranium with DEHiBA under High Loading Conditions

Journal Article · 2023 · Inorganic Chemistry · OSTI ID:1973377

Hall, Gabriel B.; Campbell, Emily L.; Bessen, Nathan P.; +5 more

Influence of Metal Ion Complexation on the Radiolytic Longevity of Butyramide Extractants under Direct Dissolution Process Conditions

Journal Article · 2025 · ACS Omega · OSTI ID:2526677

Kynman, Amy E.; Dang, Anh N.; Grimes, Travis S.; +8 more

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Diaminoguanidine
electron pulse irradiation
gamma Irradiation
radical kinetics

Title: Radiolytic evaluation of a new technetium redox control reagent for advanced used nuclear fuel separations

Citation Formats

References (46)

Similar Records

Related Subjects