Characterization of Actinides Complexed to Nuclear Fuel Constituents Using ESI-MS
Abstract
Electrospray ionization-mass spectrometry (ESI-MS) was tested for its use in monitoring spent nuclear fuel (SNF) constituents including U, Pu, dibutyl phosphate (DBP), and tributyl phosphate (TBP). Both positive and negative ion modes were used to evaluate the speciation of U and Pu with TBP and DBP. Furthermore, apparent stability constants were determined for U complexed to TBP and DBP. In positive ion mode, TBP produced a strong signal with and without complexation to U or Pu, but, in negative ion mode, no TBP, U-TBP, or Pu-TBP complexes were observed. Apparent stability constants were determined for [UO2(NO3)2(TBP)2], [UO2(NO3)2(H2O)(TBP)2], and [UO2(NO3)2(TBP)3]. In contrast DBP, U-DBP, and Pu-DBP complexes were observed in both positive and negative ion modes. Apparent stability constants were determined for the species [UO2(DBP)], [UO2(DBP)3], and [UO2(DBP)4]. Analyzing mixtures of U or Pu with TBP and DBP yielded the formation of ternary complexes whose stoichiometry was directly related to the ratio of TBP to DBP. The ESI-MS protocols used in this study will further demonstrate the utility of ESI-MS and its applicability to process control monitoring in SNF reprocessing facilities.
- Authors:
-
- Department of Civil and Environmental Engineering, University of Utah, Salt Lake City, Utah 84112, United States
- Chemical and Biological Signature Sciences Group, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
- CEA, DEN, DANS, Department of Physico-Chemistry, F-91191 Gif-sur-Yvette, France
- Department of Chemistry, Washington State University, Pullman, Washington 99164, United States
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1237779
- Alternate Identifier(s):
- OSTI ID: 1249357
- Report Number(s):
- PNNL-SA-116620
Journal ID: ISSN 0003-2700
- Grant/Contract Number:
- SC0004102; NA0000582; HDTRA11010111; AC05-76RL01830
- Resource Type:
- Published Article
- Journal Name:
- Analytical Chemistry
- Additional Journal Information:
- Journal Name: Analytical Chemistry Journal Volume: 88 Journal Issue: 5; Journal ID: ISSN 0003-2700
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
McDonald, IV, Luther W., Campbell, James A., Vercouter, Thomas, and Clark, Sue B. Characterization of Actinides Complexed to Nuclear Fuel Constituents Using ESI-MS. United States: N. p., 2016.
Web. doi:10.1021/acs.analchem.5b03352.
McDonald, IV, Luther W., Campbell, James A., Vercouter, Thomas, & Clark, Sue B. Characterization of Actinides Complexed to Nuclear Fuel Constituents Using ESI-MS. United States. https://doi.org/10.1021/acs.analchem.5b03352
McDonald, IV, Luther W., Campbell, James A., Vercouter, Thomas, and Clark, Sue B. Thu .
"Characterization of Actinides Complexed to Nuclear Fuel Constituents Using ESI-MS". United States. https://doi.org/10.1021/acs.analchem.5b03352.
@article{osti_1237779,
title = {Characterization of Actinides Complexed to Nuclear Fuel Constituents Using ESI-MS},
author = {McDonald, IV, Luther W. and Campbell, James A. and Vercouter, Thomas and Clark, Sue B.},
abstractNote = {Electrospray ionization-mass spectrometry (ESI-MS) was tested for its use in monitoring spent nuclear fuel (SNF) constituents including U, Pu, dibutyl phosphate (DBP), and tributyl phosphate (TBP). Both positive and negative ion modes were used to evaluate the speciation of U and Pu with TBP and DBP. Furthermore, apparent stability constants were determined for U complexed to TBP and DBP. In positive ion mode, TBP produced a strong signal with and without complexation to U or Pu, but, in negative ion mode, no TBP, U-TBP, or Pu-TBP complexes were observed. Apparent stability constants were determined for [UO2(NO3)2(TBP)2], [UO2(NO3)2(H2O)(TBP)2], and [UO2(NO3)2(TBP)3]. In contrast DBP, U-DBP, and Pu-DBP complexes were observed in both positive and negative ion modes. Apparent stability constants were determined for the species [UO2(DBP)], [UO2(DBP)3], and [UO2(DBP)4]. Analyzing mixtures of U or Pu with TBP and DBP yielded the formation of ternary complexes whose stoichiometry was directly related to the ratio of TBP to DBP. The ESI-MS protocols used in this study will further demonstrate the utility of ESI-MS and its applicability to process control monitoring in SNF reprocessing facilities.},
doi = {10.1021/acs.analchem.5b03352},
journal = {Analytical Chemistry},
number = 5,
volume = 88,
place = {United States},
year = {Thu Feb 11 00:00:00 EST 2016},
month = {Thu Feb 11 00:00:00 EST 2016}
}
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https://doi.org/10.1021/acs.analchem.5b03352
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