Gamma radiolysis of hydrophilic diglycolamide ligands in concentrated aqueous nitrate solution
Abstract
The radiation chemistry of a series of hydrophilic diglycolamides (DGAs: TEDGA, Me-TEDGA, Me2-TEDGA, and TPDGA) has been investigated under neutral pH, concentrated aqueous nitrate solution conditions. A combination of steady-state gamma and time-resolved pulsed electron irradiation experiments, supported by advanced analytical techniques and multi-scale modeling calculations, have demonstrated that: (i) the investigated hydrophilic DGAs undergo first-order decay with an average dose constant of (-3.18 ± 0.23) × 10-6 Gy-1; (ii) their degradation product distributions are similar to those under pure water conditions, except for the appearance of NOx adducts; and (iii) radiolysis is driven by hydroxyl and nitrate radical oxidation chemistry moderated by secondary degradation product scavenging reactions. Overall, the radiolysis of hydrophilic DGAs in concentrated, aqueous nitrate solutions is significantly slower and less structurally sensitive than under pure water conditions, similar to their lipophilic analogs. Acid hydrolysis, not radiolysis, is expected to limit their useful lifetime. These findings are promising for the deployment of hydrophilic DGAs as actinide aqueous phase stripping and hold-back agents, due to the presence of high concentrations of nitrate in envisioned large-scale process conditions.
- Authors:
-
- Idaho National Lab. (INL), Idaho Falls, ID (United States)
- Forschungszentrum Juelich (Germany). Inst. fur Energie- und Klimaforschung (IEK)
- California State Univ. (CalState), Long Beach, CA (United States)
- Forschungszentrum Juelich (Germany)
- Univ. of Twente, Enschede (Netherlands). MESA+ Inst. for Nanotechnology, Molecular Nanofabrication Group
- Publication Date:
- Research Org.:
- Idaho National Lab. (INL), Idaho Falls, ID (United States)
- Sponsoring Org.:
- USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1596094
- Alternate Identifier(s):
- OSTI ID: 1573274
- Report Number(s):
- INL/JOU-19-56056-Rev000
Journal ID: ISSN 1477-9226; ICHBD9; TRN: US2101870
- Grant/Contract Number:
- DE-AC07-05ID14517; FC02- 04ER15533; SC0012704; NE0008406; AC07-05ID14517; FC02-04ER15533
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 48; Journal Issue: 45; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; Hydrophilic Diglycolamides; Gamma Radiolysis; Pulsed Electron Radiolysis; Multi-Scale Modeling
Citation Formats
Horne, Gregory P., Wilden, Andreas, Mezyk, Stephen P., Twight, Liam, Hupert, Michelle, Stärk, Andrea, Verboom, Willem, Mincher, Bruce J., and Modolo, Giuseppe. Gamma radiolysis of hydrophilic diglycolamide ligands in concentrated aqueous nitrate solution. United States: N. p., 2019.
Web. doi:10.1039/C9DT03918J.
Horne, Gregory P., Wilden, Andreas, Mezyk, Stephen P., Twight, Liam, Hupert, Michelle, Stärk, Andrea, Verboom, Willem, Mincher, Bruce J., & Modolo, Giuseppe. Gamma radiolysis of hydrophilic diglycolamide ligands in concentrated aqueous nitrate solution. United States. https://doi.org/10.1039/C9DT03918J
Horne, Gregory P., Wilden, Andreas, Mezyk, Stephen P., Twight, Liam, Hupert, Michelle, Stärk, Andrea, Verboom, Willem, Mincher, Bruce J., and Modolo, Giuseppe. Tue .
"Gamma radiolysis of hydrophilic diglycolamide ligands in concentrated aqueous nitrate solution". United States. https://doi.org/10.1039/C9DT03918J. https://www.osti.gov/servlets/purl/1596094.
@article{osti_1596094,
title = {Gamma radiolysis of hydrophilic diglycolamide ligands in concentrated aqueous nitrate solution},
author = {Horne, Gregory P. and Wilden, Andreas and Mezyk, Stephen P. and Twight, Liam and Hupert, Michelle and Stärk, Andrea and Verboom, Willem and Mincher, Bruce J. and Modolo, Giuseppe},
abstractNote = {The radiation chemistry of a series of hydrophilic diglycolamides (DGAs: TEDGA, Me-TEDGA, Me2-TEDGA, and TPDGA) has been investigated under neutral pH, concentrated aqueous nitrate solution conditions. A combination of steady-state gamma and time-resolved pulsed electron irradiation experiments, supported by advanced analytical techniques and multi-scale modeling calculations, have demonstrated that: (i) the investigated hydrophilic DGAs undergo first-order decay with an average dose constant of (-3.18 ± 0.23) × 10-6 Gy-1; (ii) their degradation product distributions are similar to those under pure water conditions, except for the appearance of NOx adducts; and (iii) radiolysis is driven by hydroxyl and nitrate radical oxidation chemistry moderated by secondary degradation product scavenging reactions. Overall, the radiolysis of hydrophilic DGAs in concentrated, aqueous nitrate solutions is significantly slower and less structurally sensitive than under pure water conditions, similar to their lipophilic analogs. Acid hydrolysis, not radiolysis, is expected to limit their useful lifetime. These findings are promising for the deployment of hydrophilic DGAs as actinide aqueous phase stripping and hold-back agents, due to the presence of high concentrations of nitrate in envisioned large-scale process conditions.},
doi = {10.1039/C9DT03918J},
journal = {Dalton Transactions},
number = 45,
volume = 48,
place = {United States},
year = {2019},
month = {1}
}
Web of Science
Works referenced in this record:
Influence of diluent on radiolysis of amides in organic solution
journal, May 2007
- Sugo, Yumi; Izumi, Yoshinobu; Yoshida, Yoichi
- Radiation Physics and Chemistry, Vol. 76, Issue 5
The Dependence of Radical and Molecular Yields on Linear Energy Transfer in the Radiation Decomposition of 0.8 N Sulfuric Acid Solutions
journal, June 1959
- Barr, Nathaniel F.; Schuler, Robert H.
- The Journal of Physical Chemistry, Vol. 63, Issue 6
The Actinide-Lanthanide Separation Concept
journal, May 2014
- Lumetta, Gregg J.; Gelis, Artem V.; Carter, Jennifer C.
- Solvent Extraction and Ion Exchange, Vol. 32, Issue 4
The LEAF picosecond pulse radiolysis facility at Brookhaven National Laboratory
journal, November 2004
- Wishart, James F.; Cook, Andrew R.; Miller, John R.
- Review of Scientific Instruments, Vol. 75, Issue 11
γ-Radiolysis study of concentrated nitric acid solutions
journal, January 1994
- Jiang, Pei-Yun; Nagaishi, Ryuji; Yotsuyanagi, Tadasu
- J. Chem. Soc., Faraday Trans., Vol. 90, Issue 1
Evaluation of the Hydrophilic Complexant N,N,N’,N’ -tetraethyldiglycolamide (TEDGA) and its Methyl-substituted Analogues in the Selective Am(III) Separation
journal, July 2019
- Klaß, Larissa; Wilden, Andreas; Kreft, Fabian
- Solvent Extraction and Ion Exchange, Vol. 37, Issue 5
Multi-Scale Modeling of the Gamma Radiolysis of Nitrate Solutions
journal, November 2016
- Horne, Gregory P.; Donoclift, Thomas A.; Sims, Howard E.
- The Journal of Physical Chemistry B, Vol. 120, Issue 45
Extraction by N,N'-Tetraalkylmalonamides ii.
journal, October 1987
- Musikas, C.; Hubert, H.
- Solvent Extraction and Ion Exchange, Vol. 5, Issue 5
Time-resolved and steady-state irradiation of hydrophilic sulfonated bis-triazinyl-(bi)pyridines – modelling radiolytic degradation
journal, January 2019
- Horne, Gregory P.; Mezyk, Stephen P.; Moulton, Nicole
- Dalton Transactions, Vol. 48, Issue 14
New Insight into the Americium/Curium Separation by Solvent Extraction using Diglycolamides
journal, December 2014
- Chapron, S.; Marie, C.; Arrachart, G.
- Solvent Extraction and Ion Exchange, Vol. 33, Issue 3
Reduction potential of the nitrate radical in aqueous solution
journal, November 1992
- Jiang, Pei Yun; Katsumura, Yosuke; Ishigure, Kenkichi
- Inorganic Chemistry, Vol. 31, Issue 24
Effects of Track Structure on the Ion Radiolysis of the Fricke Dosimeter
journal, October 2002
- Pimblott, Simon M.; LaVerne, Jay A.
- The Journal of Physical Chemistry A, Vol. 106, Issue 41
Chemistry of Diglycolamides: Promising Extractants for Actinide Partitioning
journal, November 2011
- Ansari, Seraj A.; Pathak, Priyanath; Mohapatra, Prasanta K.
- Chemical Reviews, Vol. 112, Issue 3
Application of quantum mechanical simulations for studying the radiolytic stability of prospective extractants in the nuclear fuel cycle
journal, October 2018
- Koubský, Tomáš; Luštinec, Jakub
- Journal of Radioanalytical and Nuclear Chemistry, Vol. 318, Issue 3
Monte Carlo Simulation of Range and Energy Deposition by Electrons in Gaseous and Liquid Water
journal, January 1996
- Pimblott, Simon M.; LaVerne, Jay A.; Mozumder, Asokendu
- The Journal of Physical Chemistry, Vol. 100, Issue 20
A Comparison of the γ -Radiolysis of TODGA and T(EH)DGA Using UHPLC-ESI-MS Analysis
journal, March 2015
- Zarzana, Christopher A.; Groenewold, Gary S.; Mincher, Bruce J.
- Solvent Extraction and Ion Exchange, Vol. 33, Issue 5
Separation of Americium by Liquid-Liquid Extraction Using Diglycolamides Water-Soluble Complexing Agents
journal, January 2016
- Chapron, S.; Marie, C.; Pacary, V.
- Procedia Chemistry, Vol. 21
Stochastic models of multi-species kinetics in radiation-induced spurs
journal, January 1986
- Clifford, Peter; Green, Nicholas J. B.; Oldfield, Mark J.
- Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 82, Issue 9
The Reactivity of the Nitrate Radical ( • NO 3 ) in Aqueous and Organic Solutions : THE REACTIVITY OF THE NITRATE RADICAL IN AQUEOUS AND ORGANIC SOLUTIONS
journal, July 2017
- Mezyk, Stephen P.; Cullen, Thomas D.; Rickman, Kimberly A.
- International Journal of Chemical Kinetics, Vol. 49, Issue 9
Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
journal, June 2018
- Wilden, Andreas; Mincher, Bruce J.; Mezyk, Stephen P.
- Solvent Extraction and Ion Exchange, Vol. 36, Issue 4
Gamma-radiolytic stability of new methylated TODGA derivatives for minor actinide recycling
journal, January 2015
- Galán, Hitos; Zarzana, Christopher A.; Wilden, Andreas
- Dalton Transactions, Vol. 44, Issue 41
Re-evaluation of the thiocyanate dosimeter for pulse radiolysis
journal, January 1995
- Buxton, George V.; Stuart, Craig R.
- Journal of the Chemical Society, Faraday Transactions, Vol. 91, Issue 2
Development and Validation of the EXAm Separation Process for Single Am Recycling
journal, January 2012
- Rostaing, Christine; Poinssot, Christophe; Warin, Dominique
- Procedia Chemistry, Vol. 7
Formation and decay of peroxynitrous acid: a pulse radiolysis study
journal, June 1993
- Loegager, T.; Sehested, K.
- The Journal of Physical Chemistry, Vol. 97, Issue 25
Complexation and Back Extraction of Various Metals by Water-soluble Diglycolamide
journal, January 2007
- Sasaki, Yuji; Sugo, Yumi; Kitatsuji, Yoshihiro
- Analytical Sciences, Vol. 23, Issue 6
Applications of Diglycolamide Based Solvent Extraction Processes in Spent Nuclear Fuel Reprocessing, Part 1: TODGA
journal, April 2018
- Whittaker, Daniel; Geist, Andreas; Modolo, Giuseppe
- Solvent Extraction and Ion Exchange, Vol. 36, Issue 3
A Study of the γ-Radiolysis of N,N -Didodecyl- N′,N′ -Dioctyldiglycolamide Using UHPLC-ESI-MS Analysis
journal, June 2016
- Roscioli-Johnson, Kristyn M.; Zarzana, Christopher A.; Groenewold, Gary S.
- Solvent Extraction and Ion Exchange, Vol. 34, Issue 5
Preparation of Diglycolamides via Schotten–Baumann Approach and Direct Amidation of Esters
journal, July 2016
- Leoncini, Andrea; Huskens, Jurriaan; Verboom, Willem
- Synlett, Vol. 27, Issue 17
Multiple time scales in pulse radiolysis. Application to bromide solutions and dipeptides
journal, June 1999
- Hug, Gordon L.; Wang, Yicheng; Schöneich, Christian
- Radiation Physics and Chemistry, Vol. 54, Issue 6
Direct Selective Extraction of Trivalent Americium from PUREX Raffinate Using a Combination of CyMe 4 BTPhen and TEDGA—A Feasibility Study
journal, March 2017
- Lange, Steve; Wilden, Andreas; Modolo, Giuseppe
- Solvent Extraction and Ion Exchange, Vol. 35, Issue 3
Studies of geminate ion recombination and formation of excited states in liquid n-dodecane by means of a new picosecond pulse radiolysis system
journal, March 1993
- Yoshida, Y.; Ueda, T.; Kobayashi, T.
- Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 327, Issue 1
New activity coefficients of 0–100 per cent aqueous nitric acid
journal, June 1964
- Davis, W.; De Bruin, H. J.
- Journal of Inorganic and Nuclear Chemistry, Vol. 26, Issue 6
Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O − in Aqueous Solution
journal, April 1988
- Buxton, George V.; Greenstock, Clive L.; Helman, W. Phillips
- Journal of Physical and Chemical Reference Data, Vol. 17, Issue 2
Temperature Dependence of Hydrogen Atom Reaction with Nitrate and Nitrite Species in Aqueous Solution †
journal, August 1997
- Mezyk, Stephen P.; Bartels, David M.
- The Journal of Physical Chemistry A, Vol. 101, Issue 35
The Oxidation of Fe ++ to Fe +++ by the Irradiation with X‐Rays of Solutions of Ferrous Sulfate in Sulfuric Acid
journal, January 1935
- Fricke, Hugo; Hart, Edwin J.
- The Journal of Chemical Physics, Vol. 3, Issue 1
Considerations for choice of a kinetic fig. of merit in process radiation chemistry for waste treatment
journal, February 2000
- Mincher, Bruce J.; Curry, Randy D.
- Applied Radiation and Isotopes, Vol. 52, Issue 2
New Insight into the Americium/Curium Separation by Solvent Extraction Using Diglycolamides
text, January 2015
- Chapron, S.; Marie, C.; Arrachart, G.
- Taylor & Francis
Applications of Diglycolamide Based Solvent Extraction Processes in Spent Nuclear Fuel Reprocessing, Part 1: TODGA
text, January 2018
- Whittaker, Daniel; Geist, Andreas; Modolo, Giuseppe
- Taylor & Francis
A Comparison of the γ-Radiolysis of TODGA and T(EH)DGA Using UHPLC-ESI-MS Analysis
text, January 2015
- Zarzana, Christopher A.; Groenewold, Gary S.; Mincher, Bruce J.
- Taylor & Francis
Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
text, January 2018
- Wilden, Andreas; Mincher, Bruce J.; Mezyk, Stephen P.
- Taylor & Francis
A Comparison of the γ-Radiolysis of TODGA and T(EH)DGA Using UHPLC-ESI-MS Analysis
text, January 2015
- Zarzana, Christopher A.; Groenewold, Gary S.; Mincher, Bruce J.
- Taylor & Francis
Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
text, January 2018
- Wilden, Andreas; Mincher, Bruce J.; Mezyk, Stephen P.
- Taylor & Francis
New Insight into the Americium/Curium Separation by Solvent Extraction using Diglycolamides
text, January 2015
- Chapron, S.; Marie, C.; Arrachart, G.
- Taylor & Francis
Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
text, January 2018
- Wilden, Andreas; Mincher, Bruce J.; Mezyk, Stephen P.
- Taylor & Francis
Applications of Diglycolamide Based Solvent Extraction Processes in Spent Nuclear Fuel Reprocessing, Part 1: TODGA
text, January 2018
- Whittaker, Daniel; Geist, Andreas; Modolo, Giuseppe
- Taylor & Francis
Evaluation of the Hydrophilic Complexant N,N,N’,N’-tetraethyldiglycolamide (TEDGA) and its Methyl-substituted Analogues in the Selective Am(III) Separation
text, January 2019
- Klaß, Larissa; Wilden, Andreas; Kreft, Fabian
- Taylor & Francis