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:
-
[1];
[2];
[3];
[3];
[4];
[4];
[5];
[1];
[2]
- 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}
}
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text, January 2018
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text, January 2015
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- 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