Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing
Abstract
© 2016 Author(s). Nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. We find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices.more »
- Authors:
-
[1];
[3]
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Nuclear and Chemical Sciences Division
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Materials Science Division
- Publication Date:
- Research Org.:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA), Office of Defense Nuclear Nonproliferation; USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1262187
- Alternate Identifier(s):
- OSTI ID: 1253655; OSTI ID: 1408398
- Report Number(s):
- LLNL-JRNL-681003
Journal ID: ISSN 0021-8979; JAPIAU
- Grant/Contract Number:
- AC52-07NA27344; AC02-05CH11231; AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Applied Physics
- Additional Journal Information:
- Journal Volume: 119; Journal Issue: 19; Journal ID: ISSN 0021-8979
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 54 ENVIRONMENTAL SCIENCES; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Citation Formats
Pacold, J. I., Lukens, W. W., Booth, C. H., Shuh, D. K., Knight, K. B., Eppich, G. R., and Holliday, K. S. Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing. United States: N. p., 2016.
Web. doi:10.1063/1.4948942.
Pacold, J. I., Lukens, W. W., Booth, C. H., Shuh, D. K., Knight, K. B., Eppich, G. R., & Holliday, K. S. Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing. United States. https://doi.org/10.1063/1.4948942
Pacold, J. I., Lukens, W. W., Booth, C. H., Shuh, D. K., Knight, K. B., Eppich, G. R., and Holliday, K. S. Wed .
"Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing". United States. https://doi.org/10.1063/1.4948942. https://www.osti.gov/servlets/purl/1262187.
@article{osti_1262187,
title = {Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing},
author = {Pacold, J. I. and Lukens, W. W. and Booth, C. H. and Shuh, D. K. and Knight, K. B. and Eppich, G. R. and Holliday, K. S.},
abstractNote = {© 2016 Author(s). Nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. We find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. The resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.},
doi = {10.1063/1.4948942},
journal = {Journal of Applied Physics},
number = 19,
volume = 119,
place = {United States},
year = {Wed May 18 00:00:00 EDT 2016},
month = {Wed May 18 00:00:00 EDT 2016}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 8 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Local structure of iron in tektites and natural glass: An insight through X-ray absorption fine structure spectroscopy
journal, January 2013
- Wang, Ling; Yoshiasa, Akira; Okube, Maki
- Journal of Mineralogical and Petrological Sciences, Vol. 108, Issue 5
Groundwater Nanoparticles in the Far-Field at the Nevada Test Site: Mechanism for Radionuclide Transport
journal, March 2009
- Utsunomiya, Satoshi; Kersting, Annie B.; Ewing, Rodney C.
- Environmental Science & Technology, Vol. 43, Issue 5
Release of Actinides from Defense Waste Glass Under Simulated Repository Conditions
journal, May 1986
- Apted, M. J.; McVay, G. L.; Wald, J. W.
- Nuclear Technology, Vol. 73, Issue 2
Chemical investigation of Australasian tektites
journal, December 1969
- Chapman, Dean R.; Scheiber, Leroy C.
- Journal of Geophysical Research, Vol. 74, Issue 27
Time Scales for Sorption−Desorption and Surface Precipitation of Uranyl on Goethite
journal, August 2001
- Giammar, Daniel E.; Hering, Janet G.
- Environmental Science & Technology, Vol. 35, Issue 16
Multiplet effects in X-ray spectroscopy
journal, January 2005
- Groot, Frank de
- Coordination Chemistry Reviews, Vol. 249, Issue 1-2
On the evaluation of groundwater contamination from underground nuclear tests
journal, March 2002
- Tompson, A.; Bruton, C.; Pawloski, G.
- Environmental Geology, Vol. 42, Issue 2-3
Radionuclide Fractionation in Bomb Debris: The fractionation systematics for high-yield bursts at sea-water and coral surfaces are delineated
journal, June 1961
- Freiling, E. C.
- Science, Vol. 133, Issue 3469
Oxidation state and coordination of Fe in minerals: An Fe K- XANES spectroscopic study
journal, May 2001
- Wilke, Max; Farges, François; Petit, Pierre-Emmanuel
- American Mineralogist, Vol. 86, Issue 5-6
Secondary ion mass spectrometry measurements of volcanic tuffs containing radionuclides from underground nuclear tests
journal, January 2000
- Rose, T. P.; Smith, D. K.; Phinney, D. L.
- Radiochimica Acta, Vol. 88, Issue 8
Trinitite redux: Mineralogy and petrology
journal, February 2015
- Eby, G. N.; Charnley, N.; Pirrie, D.
- American Mineralogist, Vol. 100, Issue 2-3
Postdetonation nuclear debris for attribution
journal, November 2010
- Fahey, A. J.; Zeissler, C. J.; Newbury, D. E.
- Proceedings of the National Academy of Sciences, Vol. 107, Issue 47
Confirmation of standard error analysis techniques applied to EXAFS using simulations
journal, November 2009
- Booth, Corwin H.; Hu, Yung-Jin
- Journal of Physics: Conference Series, Vol. 190
The chemistry of uranium in glass-forming aluminosilicate melts
journal, May 1983
- Schreiber, Henry D.
- Journal of the Less Common Metals, Vol. 91, Issue 1
Actinide Valences in Borosilicate Glass
journal, January 1982
- Karraker, D. G.
- Journal of the American Ceramic Society, Vol. 65, Issue 1
Etude expérimentale du comportement de l'uranium dans les magmas: États d'oxydation et coordinance
journal, September 1979
- Calas, Georges
- Geochimica et Cosmochimica Acta, Vol. 43, Issue 9
The structure of uranium (VI) sorption complexes on silica, alumina, and montmorillonite
journal, July 2000
- Sylwester, E. R.; Hudson, E. A.; Allen, P. G.
- Geochimica et Cosmochimica Acta, Vol. 64, Issue 14
Colloidal Cutin-Like Substances Cross-Linked to Siderophore Decomposition Products Mobilizing Plutonium from Contaminated Soils
journal, November 2008
- Xu, C.; Santschi, P. H.; Zhong, J. Y.
- Environmental Science & Technology, Vol. 42, Issue 22
X-ray-absorption fine-structure standards: A comparison of experiment and theory
journal, September 1995
- Li, G. G.; Bridges, F.; Booth, C. H.
- Physical Review B, Vol. 52, Issue 9
Characterization of Nuclear Explosive Melt Debris
journal, January 1995
- Smith, David K.
- Radiochimica Acta, Vol. 69, Issue 3
Modeling Ground Water Flow and Radioactive Transport in a Fractured Aquifer
journal, September 1999
- Pohll, Greg; Hassan, Ahmed E.; Chapman, Jenny B.
- Ground Water, Vol. 37, Issue 5
Physical and Radiochemical Properties of Fallout Particles
journal, January 1966
- Crocker, G. R.; OʼConnor, J. D.; Freiling, E. C.
- Health Physics, Vol. 12, Issue 8
Colloid Transport of Plutonium in the Far-Field of the Mayak Production Association, Russia
journal, October 2006
- Novikov, A. P.; Kalmykov, S. N.; Utsunomiya, S.
- Science, Vol. 314, Issue 5799
X-ray absorption fine structure of aged, Pu-doped glass and ceramic waste forms
journal, April 1998
- Hess, N. J.; Weber, W. J.; Conradson, S. D.
- Journal of Nuclear Materials, Vol. 254, Issue 2-3
X-ray microprobe analysis of iron oxidation states in silicates and oxides using X-ray absorption near edge structure (XANES)
journal, December 1994
- Bajt, S.; Sutton, S. R.; Delaney, J. S.
- Geochimica et Cosmochimica Acta, Vol. 58, Issue 23
Migration of plutonium in ground water at the Nevada Test Site
journal, January 1999
- Kersting, A. B.; Efurd, D. W.; Finnegan, D. L.
- Nature, Vol. 397, Issue 6714
Constraints on fallout melt glass formation from a near-surface nuclear test
journal, July 2014
- Eppich, Gary R.; Knight, Kim B.; Jacomb-Hood, Timothy W.
- Journal of Radioanalytical and Nuclear Chemistry, Vol. 302, Issue 1
Solvations of redox ions in glass-forming silicate melts
journal, February 1995
- Schreiber, Henry D.; Todd Coolbaugh, M.
- Journal of Non-Crystalline Solids, Vol. 181, Issue 3
Number of relevant independent points in x-ray-absorption fine-structure spectra
journal, October 1993
- Stern, Edward A.
- Physical Review B, Vol. 48, Issue 13
Mineral Associations and Average Oxidation States of Sorbed Pu on Tuff
journal, July 1999
- Duff, M. C.; Hunter, D. B.; Triay, I. R.
- Environmental Science & Technology, Vol. 33, Issue 13
Determinations of Uranium Structures by EXAFS: Schoepite and Other U(VI) Oxide Precipitates
journal, January 1996
- Allen, P. G.; Shuh, D. K.; Bucher, J. J.
- Radiochimica Acta, Vol. 75, Issue 1
Microanalytical X-ray Imaging of Depleted Uranium Speciation in Environmentally Aged Munitions Residues
journal, January 2014
- Crean, Daniel E.; Livens, Francis R.; Stennett, Martin C.
- Environmental Science & Technology, Vol. 48, Issue 3
Investigation of Aquo and Chloro Complexes of UO 2 2+ , NpO 2 + , Np 4+ , and Pu 3+ by X-ray Absorption Fine Structure Spectroscopy
journal, October 1997
- Allen, P. G.; Bucher, J. J.; Shuh, D. K.
- Inorganic Chemistry, Vol. 36, Issue 21
Radioactivity Trapped in Melt Produced by a Nuclear Explosion
journal, May 1975
- Borg, I. Y.
- Nuclear Technology, Vol. 26, Issue 1
Environmental Speciation of Actinides
journal, June 2012
- Maher, Kate; Bargar, John R.; Brown, Gordon E.
- Inorganic Chemistry, Vol. 52, Issue 7
Australasian microtektites from Antarctica: XAS determination of the Fe oxidation state
journal, April 2014
- Giuli, Gabriele; Cicconi, Maria Rita; Eeckhout, Sigrid Griet
- Meteoritics & Planetary Science, Vol. 49, Issue 4
Actinide Association with Groundwater Colloids in a Coastal Plain Aquifer
journal, January 1994
- Kaplan, D. I.; Bertsch, P. M.; Adriano, D. C.
- Radiochimica Acta, Vol. 66-67, Issue s1
Uranium co-precipitation with iron oxide minerals
journal, October 2002
- Duff, Martine C.; Coughlin, Jessica Urbanik; Hunter, Douglas B.
- Geochimica et Cosmochimica Acta, Vol. 66, Issue 20
Kinetic Desorption and Sorption of U(VI) during Reactive Transport in a Contaminated Hanford Sediment
journal, May 2005
- Qafoku, Nikolla P.; Zachara, John M.; Liu, Chongxuan
- Environmental Science & Technology, Vol. 39, Issue 9
Multi-spectroscopic study of Fe(II) in silicate glasses: Implications for the coordination environment of Fe(II) in silicate melts
journal, September 2005
- Jackson, William E.; Farges, Francois; Yeager, Mark
- Geochimica et Cosmochimica Acta, Vol. 69, Issue 17
Iron local structure in tektites and impact glasses by extended X-ray absorption fine structure and high-resolution X-ray absorption near-edge structure spectroscopy
journal, December 2002
- Giuli, Gabriele; Pratesi, Giovanni; Cipriani, Curzio
- Geochimica et Cosmochimica Acta, Vol. 66, Issue 24
Transport of colloidal contaminants in groundwater: radionuclide migration at the Nevada test site
journal, September 1988
- Buddemeier, Robert W.; Hunt, James R.
- Applied Geochemistry, Vol. 3, Issue 5
An Electromotive Force Series in a Borosilicate Glass-Forming Melt
journal, June 1984
- Schreiber, Henry D.; Balazs, G. Bryan; Carpenter, Barbara E.
- Journal of the American Ceramic Society, Vol. 67, Issue 6
Electrochemical determination of reduction potentials in glass-forming melts
journal, October 1998
- Medlin, Michael W.; Sienerth, Karl D.; Schreiber, Henry D.
- Journal of Non-Crystalline Solids, Vol. 240, Issue 1-3
Compositional dependence of redox equilibria in sodium silicate glasses
journal, November 1994
- Schreiber, Henry D.; Kochanowski, Brian K.; Schreiber, Charlotte W.
- Journal of Non-Crystalline Solids, Vol. 177
XANES calibrations for the oxidation state of iron in a silicate glass
journal, July 2003
- Berry, Andrew J.; O’Neill, Hugh St. C.; Jayasuriya, Kasthuri D.
- American Mineralogist, Vol. 88, Issue 7
Thermodynamic assessment of the uranium–oxygen system
journal, August 2002
- Guéneau, C.; Baichi, M.; Labroche, D.
- Journal of Nuclear Materials, Vol. 304, Issue 2-3
Real-space multiple-scattering calculation and interpretation of x-ray-absorption near-edge structure
journal, September 1998
- Ankudinov, A. L.; Ravel, B.; Rehr, J. J.
- Physical Review B, Vol. 58, Issue 12
Analysis of radionuclide migration through a 200-m Vadose zone following a 16-year infiltration event
journal, February 2006
- Tompson, Andrew F. B.; Hudson, G. Bryant; Smith, David K.
- Advances in Water Resources, Vol. 29, Issue 2
When the dust settles: stable xenon isotope constraints on the formation of nuclear fallout
journal, November 2014
- Cassata, W. S.; Prussin, S. G.; Knight, K. B.
- Journal of Environmental Radioactivity, Vol. 137
Determination of the iron oxidation state in basaltic glasses using XANES at the K-edge
journal, July 2005
- Wilke, Max; Partzsch, Georg M.; Bernhardt, Ralf
- Chemical Geology, Vol. 220, Issue 1-2
Chemistry of uranium (V)
journal, October 1969
- Selbin, Joel; Ortego, J. D.
- Chemical Reviews, Vol. 69, Issue 5
Sources of anthropogenic radionuclides in the environment: a review
journal, June 2010
- Hu, Qin-Hong; Weng, Jian-Qing; Wang, Jin-Sheng
- Journal of Environmental Radioactivity, Vol. 101, Issue 6
Stabilization of Plutonium Nano-Colloids by Epitaxial Distortion on Mineral Surfaces
journal, April 2011
- Powell, Brian A.; Dai, Zurong; Zavarin, Mavrik
- Environmental Science & Technology, Vol. 45, Issue 7
A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes
journal, July 1997
- Westre, Tami E.; Kennepohl, Pierre; DeWitt, Jane G.
- Journal of the American Chemical Society, Vol. 119, Issue 27
Progress in the thermodynamic modelling of the O–U binary system
journal, May 2002
- Chevalier, P. -Y.; Fischer, E.; Cheynet, B.
- Journal of Nuclear Materials, Vol. 303, Issue 1
Oxygen and phosphorus coordination around iron in crystalline ferric ferrous pyrophosphate and iron-phosphate glasses with UO 2 or Na 2 O
journal, June 1999
- Booth, C. H.; Allen, P. G.; Bucher, J. J.
- Journal of Materials Research, Vol. 14, Issue 6
Redox processes in glass-forming melts
journal, July 1986
- Schreiber, Henry D.
- Journal of Non-Crystalline Solids, Vol. 84, Issue 1-3
Spectroscopic and Diffraction Study of Uranium Speciation in Contaminated Vadose Zone Sediments from the Hanford Site, Washington State
journal, May 2004
- Catalano, Jeffrey G.; Heald, Steven M.; Zachara, John M.
- Environmental Science & Technology, Vol. 38, Issue 10
Pu(V) and Pu(IV) Sorption to Montmorillonite
journal, May 2013
- Begg, James D.; Zavarin, Mavrik; Zhao, Pihong
- Environmental Science & Technology, Vol. 47, Issue 10
Cerium, uranium, and plutonium behavior in glass-bonded sodalite, a ceramic nuclear waste form
journal, May 2000
- Morss, L. R.; Lewis, M. A.; Richmann, M. K.
- Journal of Alloys and Compounds, Vol. 303-304, p. 42-48
Organic Nature of Colloidal Actinides Transported in Surface Water Environments
journal, September 2002
- Santschi, Peter H.; Roberts, Kimberly A.; Guo, Laodong
- Environmental Science & Technology, Vol. 36, Issue 17
Plutonium Transport in the Environment
journal, June 2012
- Kersting, Annie B.
- Inorganic Chemistry, Vol. 52, Issue 7
Properties of redox ions in glasses: An interdisciplinary perspective
journal, October 1980
- Schreiber, Henry D.
- Journal of Non-Crystalline Solids, Vol. 42, Issue 1-3
Crystal chemistry of iron in natural grandidierites: an X-ray absorption fine-structure spectroscopy study
journal, October 2001
- Farges, F.
- Physics and Chemistry of Minerals, Vol. 28, Issue 9
Lead Isotopic Composition of Trinitite Melt Glass: Evidence for the Presence of Canadian Industrial Lead in the First Atomic Weapon Test
journal, July 2013
- Bellucci, Jeremy J.; Simonetti, Antonio; Wallace, Christine
- Analytical Chemistry, Vol. 85, Issue 15
High-precision determination of iron oxidation state in silicate glasses using XANES
journal, November 2009
- Cottrell, Elizabeth; Kelley, Katherine A.; Lanzirotti, Antonio
- Chemical Geology, Vol. 268, Issue 3-4
Investigating incorporation and distribution of radionuclides in trinitite
journal, September 2011
- Belloni, F.; Himbert, J.; Marzocchi, O.
- Journal of Environmental Radioactivity, Vol. 102, Issue 9
Assessing field-scale migration of radionuclides at the Nevada Test Site: “mobile” species
journal, October 2008
- Hu, Q. H.; Rose, T. P.; Zavarin, M.
- Journal of Environmental Radioactivity, Vol. 99, Issue 10
Structural environments of incompatible elements in silicate glass/melt systems: II. UIV, UV, and UVI
journal, December 1992
- Farges, François; Ponader, Carl W.; Calas, Georges
- Geochimica et Cosmochimica Acta, Vol. 56, Issue 12
Iron oxidation states in silicate glass fragments and glass inclusions with a XANES micro-probe
journal, August 2001
- Bonnin-Mosbah, Michelle; Simionovici, Alexandre S.; Métrich, Nicole
- Journal of Non-Crystalline Solids, Vol. 288, Issue 1-3