Gamma radiolysis of hydrophilic diglycolamide ligands in concentrated aqueous nitrate solution

Horne, Gregory P.; Wilden, Andreas; Mezyk, Stephen P.; Twight, Liam; Hupert, Michelle; Stärk, Andrea; Verboom, Willem; Mincher, Bruce J.; Modolo, Giuseppe

doi:10.1039/C9DT03918J

Gamma radiolysis of hydrophilic diglycolamide ligands in concentrated aqueous nitrate solution

Journal Article · Tue Jan 01 00:00:00 EST 2019 · Dalton Transactions

DOI:https://doi.org/10.1039/C9DT03918J· OSTI ID:1596094

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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

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 NO_x 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.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC07-05ID14517; FC02-04ER15533; NE0008406; SC0012704

OSTI ID:: 1596094

Alternate ID(s):: OSTI ID: 1573274

Report Number(s):: INL/JOU--19-56056-Rev000

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 45 Vol. 48; ISSN 1477-9226; ISSN ICHBD9

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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