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Title: Surface-Mediated Formation of Pu(IV) Nanoparticles at the Muscovite-Electrolyte Interface

Abstract

The formation of Pu(IV)-oxo-nanoparticles from Pu(III) solutions by a surface-enhanced redox/polymerization reaction at the muscovite (001) basal plane was discovered with a continuous increase in plutonium coverage observed in situ over several hours. The sorbed Pu extended >70 Å from the surface with a maximum concentration at 10.5 Å and a total coverage of >9 Pu atoms per unit cell area of muscovite (0.77 μg Pu/cm2) (determined independently by in situ resonant anomalous X-ray reflectivity and by ex-situ alpha-spectrometry). The presence of discrete nanoparticles was proved by high resolution atomic force microscopy. The formation of these Pu(IV) nanoparticles from an otherwise stable Pu(III) solution can be explained by the combination of a highly concentrated interfacial Pu-ion species, the Pu(III)–Pu(IV) redox equilibrium, and the strong proclivity of tetravalent Pu to hydrolyze and form polymeric species. These findings are the first direct observation of such behavior of plutonium on a naturally occurring mineral, providing insights into understanding the environmental transport of plutonium and other contaminants capable of similar redox/polymerization reactions.

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [2];  [1];  [1]
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  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Univ. of Chicago, Chicago, IL (United States)
Publication Date:
Research Org.:
Univ. of Chicago, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1508049
Report Number(s):
DOE-UCHICAGO-14466-11
Journal ID: ISSN 0013-936X
Grant/Contract Number:  
FG02-94ER14466
Resource Type:
Accepted Manuscript
Journal Name:
Environmental Science and Technology
Additional Journal Information:
Journal Volume: 47; Journal Issue: 24; Journal ID: ISSN 0013-936X
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES; plutonium; colloids; nanoparticles; X-ray scattering; sorption; crystal truncation rods; resonant anomalous x-ray reflectivity

Citation Formats

Schmidt, Moritz, Lee, Sang Soo, Wilson, Richard E., Knope, Karah E., Bellucci, Francesco, Eng, Peter J., Stubbs, Joanne E., Soderholm, L., and Fenter, P. Surface-Mediated Formation of Pu(IV) Nanoparticles at the Muscovite-Electrolyte Interface. United States: N. p., 2013. Web. doi:10.1021/es4037258.
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Schmidt, Moritz, Lee, Sang Soo, Wilson, Richard E., Knope, Karah E., Bellucci, Francesco, Eng, Peter J., Stubbs, Joanne E., Soderholm, L., & Fenter, P. Surface-Mediated Formation of Pu(IV) Nanoparticles at the Muscovite-Electrolyte Interface. United States. https://doi.org/10.1021/es4037258
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Schmidt, Moritz, Lee, Sang Soo, Wilson, Richard E., Knope, Karah E., Bellucci, Francesco, Eng, Peter J., Stubbs, Joanne E., Soderholm, L., and Fenter, P. Fri . "Surface-Mediated Formation of Pu(IV) Nanoparticles at the Muscovite-Electrolyte Interface". United States. https://doi.org/10.1021/es4037258. https://www.osti.gov/servlets/purl/1508049.
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@article{osti_1508049,
title = {Surface-Mediated Formation of Pu(IV) Nanoparticles at the Muscovite-Electrolyte Interface},
author = {Schmidt, Moritz and Lee, Sang Soo and Wilson, Richard E. and Knope, Karah E. and Bellucci, Francesco and Eng, Peter J. and Stubbs, Joanne E. and Soderholm, L. and Fenter, P.},
abstractNote = {The formation of Pu(IV)-oxo-nanoparticles from Pu(III) solutions by a surface-enhanced redox/polymerization reaction at the muscovite (001) basal plane was discovered with a continuous increase in plutonium coverage observed in situ over several hours. The sorbed Pu extended >70 Å from the surface with a maximum concentration at 10.5 Å and a total coverage of >9 Pu atoms per unit cell area of muscovite (0.77 μg Pu/cm2) (determined independently by in situ resonant anomalous X-ray reflectivity and by ex-situ alpha-spectrometry). The presence of discrete nanoparticles was proved by high resolution atomic force microscopy. The formation of these Pu(IV) nanoparticles from an otherwise stable Pu(III) solution can be explained by the combination of a highly concentrated interfacial Pu-ion species, the Pu(III)–Pu(IV) redox equilibrium, and the strong proclivity of tetravalent Pu to hydrolyze and form polymeric species. These findings are the first direct observation of such behavior of plutonium on a naturally occurring mineral, providing insights into understanding the environmental transport of plutonium and other contaminants capable of similar redox/polymerization reactions.},
doi = {10.1021/es4037258},
journal = {Environmental Science and Technology},
number = 24,
volume = 47,
place = {United States},
year = {Fri Nov 15 00:00:00 EST 2013},
month = {Fri Nov 15 00:00:00 EST 2013}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/es4037258
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Cited by: 24 works
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Figures / Tables:

Table 1 Table 1: Surface loading, determined by alpha-spectrometry ($α$) and resonant anomalous x-ray reflectivity (RAXR) in units of number of Pu atoms (NPu) per area of the muscovite unit cell (AUC); Experimental conditions correspond to those described in the references, for details refer to the Supporting Information (S.I.); Reaction time beforemore » the start of the in situ CTR/RAXR or ex situ AFM experiments, respectively; Solution removed from the surface by blow-drying with N2 before experiment« less
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    Works referencing / citing this record:

    Redox-mediated formation of plutonium oxide nanoparticles
    journal, January 2018

    • Romanchuk, Anna Yu.; Plakhova, Tatiana V.; Egorov, Alexander V.
    • Dalton Transactions, Vol. 47, Issue 32
    • DOI: 10.1039/c8dt02396d
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