Jump to ContentJump to Main Navigation
Show Summary Details
More options …

Radiochimica Acta

International Journal for chemical aspects of nuclear science and technology

Editor-in-Chief: Qaim, Syed M.

12 Issues per year


IMPACT FACTOR 2017: 1.202

CiteScore 2017: 1.22

SCImago Journal Rank (SJR) 2017: 0.409
Source Normalized Impact per Paper (SNIP) 2017: 0.869

Online
ISSN
2193-3405
See all formats and pricing
More options …
Volume 98, Issue 9-11

Issues

Molecular interactions of plutonium(VI) with synthetic manganese-substituted goethite

Yung-Jin Hu / Luna Kestrel Schwaiger / Corwin H. Booth
  • 3 Lawrence Berkeley National Laboratory, Chemical Sciences Division, Berkeley, CA 94720, U.S.A.
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Ravi K. Kukkadapu / Elena Cristiano
  • 5 Lawrence Berkeley National Laboratory, Nuclear Sciences Division, Berkeley, CA 94720, U.S.A.
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Daniel Kaplan / Heino Nitsche
Published Online: 2010-11-23 | DOI: https://doi.org/10.1524/ract.2010.1766

Abstract

Plutonium(VI) sorption on the surface of well-characterized synthetic manganese-substituted goethite minerals (Fe1−xMnxOOH) was studied using X-ray absorption spectroscopy. We chose to study the influence of manganese as a minor component in goethite because goethite rarely exists as a pure phase in nature. Manganese X-ray absorption near-edge structure measurements indicated that essentially all the Mn in the goethite existed as Mn(III), even though Mn was added during mineral synthesis as Mn(II). Importantly, energy dispersive X-ray analysis demonstrated that Mn did not exist as discrete phases and that it was homogeneously mixed into the goethite to within the limit of detection of the method. Furthermore, Mössbauer spectra demonstrated that all Fe existed as Fe(III), with no Fe(II) present. Plutonium(VI) sorption experiments were conducted open to air and no attempt was made to exclude carbonate. The use of X-ray absorption spectroscopy allows us to directly and unambiguously measure the oxidation state of plutonium in situ at the mineral surface. Plutonium X-ray absorption near-edge structure measurements carried out on these samples showed that Pu(VI) was reduced to Pu(IV) upon contact with the mineral. This reduction appears to be strongly correlated with mineral solution pH, coinciding with pH transitions across the point of zero charge of the mineral. Furthermore, extended X-ray absorption fine structure measurements show evidence of direct plutonium binding to the metal surface as an inner-sphere complex. This combination of extensive mineral characterization and advanced spectroscopy suggests that sorption of the plutonium onto the surface of the mineral was followed by reduction of the plutonium at the surface of the mineral to form an inner-sphere complex. Because manganese is often found in the environment as a minor component associated with major mineral components, such as goethite, understanding the molecular-level interactions of plutonium with such substituted mineral phases is important for risk assessment purposes at radioactively contaminated sites and long-term underground radioactive waste repositories.

Keywords: Plutonium; XAS; Redox; Sorption; Manganese-substituted goethite

About the article

* Correspondence address: University of California at Berkeley, Departement of Chemistry, 1 Cyclotron Road, MS70A-1150, CA 94720 Berkeley, U.S.A.,


Published Online: 2010-11-23

Published in Print: 2010-11-01


Citation Information: Radiochimica Acta International journal for chemical aspects of nuclear science and technology, Volume 98, Issue 9-11, Pages 655–663, ISSN (Print) 0033-8230, DOI: https://doi.org/10.1524/ract.2010.1766.

Export Citation

© by Oldenbourg Wissenschaftsverlag, Berkeley, Germany.Get Permission

Citing Articles

Here you can find all Crossref-listed publications in which this article is cited. If you would like to receive automatic email messages as soon as this article is cited in other publications, simply activate the “Citation Alert” on the top of this page.

[1]
Amy E. Hixon and Brian A. Powell
Environmental Science: Processes & Impacts, 2018
[2]
D. R. Brookshaw, R. A. D. Pattrick, J. R. Lloyd, and D. J. Vaughan
Mineralogical Magazine, 2012, Volume 76, Number 03, Page 777
[3]
Ugras Kaplan, Samer Amayri, Jakob Drebert, Andre Rossberg, Daniel Grolimund, and Tobias Reich
Environmental Science & Technology, 2017, Volume 51, Number 14, Page 7892
[4]
Stefan Hellebrandt, Sang Soo Lee, Karah E. Knope, Aaron J. Lussier, Joanne E. Stubbs, Peter J. Eng, L. Soderholm, Paul Fenter, and Moritz Schmidt
Langmuir, 2016, Volume 32, Number 41, Page 10473
[5]
Daniel I. Kaplan, Ravi Kukkadapu, John C. Seaman, Bruce W. Arey, Alice C. Dohnalkova, Shea Buettner, Dien Li, Tamas Varga, Kirk G. Scheckel, and Peter R. Jaffé
Science of The Total Environment, 2016, Volume 569-570, Page 53
[6]
Pihong Zhao, James D. Begg, Mavrik Zavarin, Scott J. Tumey, Ross Williams, Zurong R. Dai, Ruth Kips, and Annie B. Kersting
Environmental Science & Technology, 2016, Volume 50, Number 13, Page 6948
[7]
Boris F. Myasoedov and Stepan N. Kalmykov
Mendeleev Communications, 2015, Volume 25, Number 5, Page 319
[8]
Clare L. Thorpe, Katherine Morris, Jonathan R. Lloyd, Melissa A. Denecke, Kathleen A. Law, Kathy Dardenne, Christopher Boothman, Pieter Bots, and Gareth T.W. Law
Applied Geochemistry, 2015, Volume 63, Page 303
[9]
Tashi Parsons-Moss, Jinxiu Wang, Stephen Jones, Erin May, Daniel Olive, Zurong Dai, Mavrik Zavarin, Annie B. Kersting, Dongyuan Zhao, and Heino Nitsche
J. Mater. Chem. A, 2014, Volume 2, Number 29, Page 11209
[10]
Brian A. Powell, Daniel I. Kaplan, Steven M. Serkiz, John T. Coates, and Robert A. Fjeld
Journal of Environmental Radioactivity, 2014, Volume 131, Page 47
[11]
Anna Yu. Romanchuk, Stepan N. Kalmykov, Alexander V. Egorov, Yan V. Zubavichus, Andrey A. Shiryaev, Olga N. Batuk, Steven D. Conradson, Denis A. Pankratov, and Igor A. Presnyakov
Geochimica et Cosmochimica Acta, 2013, Volume 121, Page 29
[12]
Amy E. Hixon, Yuji Arai, and Brian A. Powell
Journal of Colloid and Interface Science, 2013, Volume 403, Page 105
[13]
Horst Geckeis, Johannes Lützenkirchen, Robert Polly, Thomas Rabung, and Moritz Schmidt
Chemical Reviews, 2013, Volume 113, Number 2, Page 1016
[14]
Dien Li and Daniel I. Kaplan
Journal of Hazardous Materials, 2012, Volume 243, Page 1
[15]
Drew Gorman-Lewis, Baikuntha P. Aryal, Tatjana Paunesku, Stefan Vogt, Barry Lai, Gayle E. Woloschak, and Mark P. Jensen
Inorganic Chemistry, 2011, Volume 50, Number 16, Page 7591

Comments (0)

Please log in or register to comment.
Log in