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Title: 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:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [5]
  1. Idaho National Laboratory
  2. California State University Long Beach
  3. Forschungszentrum Jülich
  4. Retired INL
  5. University of Twente
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) (SC-22)
OSTI Identifier:
1596094
Alternate Identifier(s):
OSTI ID: 1573274
Report Number(s):
INL/JOU-19-56056-Rev000
Journal ID: 0
Grant/Contract Number:  
DE-AC07-05ID14517; AC07-05ID14517; FC02-04ER15533; SC0012704; NE0008406
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 48; Journal Issue: 45
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, Mezyk, Stephen S, Wilden, Andreas, Hupert, Michelle, Stark, Andrea, Modolo, Giuseppe, Mincher, Bruce J, Twight, Liam, and Verboom, Willem. Gamma radiolysis of hydrophilic diglycolamide ligands in concentrated aqueous nitrate solution. United States: N. p., 2019. Web. doi:10.1039/C9DT03918J.
Horne, Gregory P, Mezyk, Stephen S, Wilden, Andreas, Hupert, Michelle, Stark, Andrea, Modolo, Giuseppe, Mincher, Bruce J, Twight, Liam, & Verboom, Willem. Gamma radiolysis of hydrophilic diglycolamide ligands in concentrated aqueous nitrate solution. United States. doi:10.1039/C9DT03918J.
Horne, Gregory P, Mezyk, Stephen S, Wilden, Andreas, Hupert, Michelle, Stark, Andrea, Modolo, Giuseppe, Mincher, Bruce J, Twight, Liam, and Verboom, Willem. Mon . "Gamma radiolysis of hydrophilic diglycolamide ligands in concentrated aqueous nitrate solution". United States. doi:10.1039/C9DT03918J.
@article{osti_1596094,
title = {Gamma radiolysis of hydrophilic diglycolamide ligands in concentrated aqueous nitrate solution},
author = {Horne, Gregory P and Mezyk, Stephen S and Wilden, Andreas and Hupert, Michelle and Stark, Andrea and Modolo, Giuseppe and Mincher, Bruce J and Twight, Liam and Verboom, Willem},
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 = {10}
}

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