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Title: Biogenic UO_2 _ Characterization and Surface Reactivity

Abstract

Nano-scale biogenic UO{sub 2} is easier to oxidize and more reactive to aqueous metal ions than bulk UO{sub 2}. In an attempt to understand these differences in properties, we have used a suite of bulk and surface characterization techniques to examine differences in the reactivity of biogenic UO{sub 2} versus bulk UO{sub 2} with respect to aqueous Zn(II). Precipitation of biogenic UO{sub 2} was mediated by Shewanella putrefaciens CN32, and the precipitates were washed using two protocols: (1) 5% NaOH, followed by 4 mM KHCO{sub 3}/KCl (NA-wash; ''NAUO2'', to remove surface organic matter), and (2) 4 mM KHCO{sub 3}-KCl (BI-wash; ''BIUO2'', to remove soluble uranyl species). BET surface areas of biogenic-UO{sub 2} prepared using the two protocols are 128.63 m{sup 2}g{sup -1} and 92.56 m{sup 2}g{sup -1}, respectively; particle sizes range from 2-10 nm as determined by FEG-SEM. Surface composition was probed using XPS, which showed a strong carbon 1s signal for the BI-washed samples; surface uranium is > 90% U(IV) for both washing protocols. U L{sub III}-edge XANES spectra also indicate that U(IV) is the dominant oxidation state in the biogenic UO{sub 2} samples. Fits of the EXAFS spectra of these samples yielded half the number of uranium second-shellmore » neighbors relative to bulk UO{sub 2}, and no detectable oxygen neighbors beyond the first shell. At pH 7, the sorption of Zn(II) onto both biogenic and bulk UO{sub 2} is independent of electrolyte concentration, suggesting that Zn(II) sorption complexes are dominantly inner-sphere. Fits of Zn K-edge EXAFS spectra for biogenic UO{sub 2} indicate that Zn(II) sorption is dependent on the washing protocol. Zn-U pair correlations are observed for the NA-washed samples, but not for the BI-washed ones, suggesting that Zn(II) sorbs directly to the UO{sub 2} surface in the first case, and possibly to organic matter in the latter. Further work is required to elucidate the binding mechanism of Zn(II) to bulk UO{sub 2}.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Stanford Linear Accelerator Center (SLAC)
Sponsoring Org.:
USDOE
OSTI Identifier:
896938
Report Number(s):
SLAC-PUB-12230
TRN: US200705%%14
DOE Contract Number:  
AC02-76SF00515
Resource Type:
Conference
Resource Relation:
Journal Name: AIP Conf.Proc.882:277,2007; Conference: Contributed to 13th International Conference on X-ray Absorption Fine Structure (XAFS13), Stanford, California, 9-14 Jul 2006
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; URANIUM DIOXIDE; ACTIVATION ENERGY; SAMPLE PREPARATION; SURFACE AREA; PARTICLE SIZE; CHEMICAL COMPOSITION; SORPTIVE PROPERTIES; VALENCE; ZINC; SORPTION; Other,BIO

Citation Formats

Singer, D.M., Farges, F., Brown, G.E., and Jr. Biogenic UO_2 _ Characterization and Surface Reactivity. United States: N. p., 2007. Web.
Singer, D.M., Farges, F., Brown, G.E., & Jr. Biogenic UO_2 _ Characterization and Surface Reactivity. United States.
Singer, D.M., Farges, F., Brown, G.E., and Jr. Wed . "Biogenic UO_2 _ Characterization and Surface Reactivity". United States. doi:. https://www.osti.gov/servlets/purl/896938.
@article{osti_896938,
title = {Biogenic UO_2 _ Characterization and Surface Reactivity},
author = {Singer, D.M. and Farges, F. and Brown, G.E. and Jr.},
abstractNote = {Nano-scale biogenic UO{sub 2} is easier to oxidize and more reactive to aqueous metal ions than bulk UO{sub 2}. In an attempt to understand these differences in properties, we have used a suite of bulk and surface characterization techniques to examine differences in the reactivity of biogenic UO{sub 2} versus bulk UO{sub 2} with respect to aqueous Zn(II). Precipitation of biogenic UO{sub 2} was mediated by Shewanella putrefaciens CN32, and the precipitates were washed using two protocols: (1) 5% NaOH, followed by 4 mM KHCO{sub 3}/KCl (NA-wash; ''NAUO2'', to remove surface organic matter), and (2) 4 mM KHCO{sub 3}-KCl (BI-wash; ''BIUO2'', to remove soluble uranyl species). BET surface areas of biogenic-UO{sub 2} prepared using the two protocols are 128.63 m{sup 2}g{sup -1} and 92.56 m{sup 2}g{sup -1}, respectively; particle sizes range from 2-10 nm as determined by FEG-SEM. Surface composition was probed using XPS, which showed a strong carbon 1s signal for the BI-washed samples; surface uranium is > 90% U(IV) for both washing protocols. U L{sub III}-edge XANES spectra also indicate that U(IV) is the dominant oxidation state in the biogenic UO{sub 2} samples. Fits of the EXAFS spectra of these samples yielded half the number of uranium second-shell neighbors relative to bulk UO{sub 2}, and no detectable oxygen neighbors beyond the first shell. At pH 7, the sorption of Zn(II) onto both biogenic and bulk UO{sub 2} is independent of electrolyte concentration, suggesting that Zn(II) sorption complexes are dominantly inner-sphere. Fits of Zn K-edge EXAFS spectra for biogenic UO{sub 2} indicate that Zn(II) sorption is dependent on the washing protocol. Zn-U pair correlations are observed for the NA-washed samples, but not for the BI-washed ones, suggesting that Zn(II) sorbs directly to the UO{sub 2} surface in the first case, and possibly to organic matter in the latter. Further work is required to elucidate the binding mechanism of Zn(II) to bulk UO{sub 2}.},
doi = {},
journal = {AIP Conf.Proc.882:277,2007},
number = ,
volume = ,
place = {United States},
year = {Wed Jan 03 00:00:00 EST 2007},
month = {Wed Jan 03 00:00:00 EST 2007}
}

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