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

Schmidt, Moritz; Lee, Sang Soo; Wilson, Richard E.; Knope, Karah E.; Bellucci, Francesco; Eng, Peter J.; Stubbs, Joanne E.; Soderholm, L.; Fenter, P.

doi:10.1021/es4037258

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

Journal Article · Fri Nov 15 00:00:00 EST 2013 · Environmental Science and Technology

DOI:https://doi.org/10.1021/es4037258· OSTI ID:1508049

Schmidt, Moritz ^[1]; Lee, Sang Soo ^[1]; Wilson, Richard E. ^[1]; Knope, Karah E. ^[1]; Bellucci, Francesco ^[1]; Eng, Peter J. ^[2]; Stubbs, Joanne E. ^[2]; Soderholm, L. ^[1]; Fenter, P. ^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Chicago, Chicago, IL (United States)

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.

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Research Organization:: Univ. of Chicago, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: FG02-94ER14466

OSTI ID:: 1508049

Report Number(s):: DOE-UCHICAGO-14466-11

Journal Information:: Environmental Science and Technology, Vol. 47, Issue 24; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 24 works

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Redox-mediated formation of plutonium oxide nanoparticles Romanchuk, Anna Yu.; Plakhova, Tatiana V.; Egorov, Alexander V. Dalton Transactions, Vol. 47, Issue 32 https://doi.org/10.1039/c8dt02396d	journal	January 2018

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58 GEOSCIENCES
plutonium
colloids
nanoparticles
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sorption
crystal truncation rods
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