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Title: Can Mineral Growth by Oriented Attachment Lead to Incorporation of Uranium(VI) into the Structure of Goethite?

Abstract

Oriented aggregation (OA), whereby crystals grow by successive attachment of precursor nanoparticles that are crystallographically co-aligned with the growing crystal, is a fundamental process by which many low solubility phases and minerals reach maturity in aqueous solution. Here, we investigated whether U(VI) can be incorporated into the structure of goethite that grows by OA. Wet chemical analysis and acid treatments showed that the additions of U(VI) early in the OA process hindered crystallization and increased the recalcitrant fraction of sorbed U(VI) relative to later addition of U(VI). Over time, however, the recalcitrant fraction of U(VI) decreased and converged to similar values for both early and late additions of U(VI). Electron microscopy indicated a portion of the acid resistant sorbed U(VI) was likely associated with grain boundaries between aggregating particles, not nanopores; and that these features were annealed out with increasing reaction time. Further, time elapsed imaging of U atom diffusion, that was stimulated by the electron beam, indicated that most sorbed U(VI) was not incorporated into the structure of goethite. This was confirmed and more rigorously quantified by ab initio molecular dynamics informed extended X-ray absorption fine structure spectra which indicated that only up to 5% of the recalcitrant U(VI)more » might be incorporated with an upper solubility limit of only U/Fe ~ 0.02 atom % in goethite where U(VI) was added early in the process. We conclude that most of the recalcitrant U(VI) is simply strongly adsorbed to the surface and that it is the uranyl oxygens that both inhibit crystallization of goethite as well as incorporation of U into the structure of goethite.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1];  [1];  [1]
  1. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1577088
Report Number(s):
PNNL-SA-145133
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Environmental Science Nano
Additional Journal Information:
Journal Volume: 6; Journal Issue: 10
Country of Publication:
United States
Language:
English

Citation Formats

Soltis, Jennifer A., McBriarty, Martin E., Qafoku, Odeta, Kerisit, Sebastien N., Nakouzi, Elias, De Yoreo, James J., and Ilton, Eugene S. Can Mineral Growth by Oriented Attachment Lead to Incorporation of Uranium(VI) into the Structure of Goethite?. United States: N. p., 2019. Web. doi:10.1039/c9en00779b.
Soltis, Jennifer A., McBriarty, Martin E., Qafoku, Odeta, Kerisit, Sebastien N., Nakouzi, Elias, De Yoreo, James J., & Ilton, Eugene S. Can Mineral Growth by Oriented Attachment Lead to Incorporation of Uranium(VI) into the Structure of Goethite?. United States. doi:10.1039/c9en00779b.
Soltis, Jennifer A., McBriarty, Martin E., Qafoku, Odeta, Kerisit, Sebastien N., Nakouzi, Elias, De Yoreo, James J., and Ilton, Eugene S. Tue . "Can Mineral Growth by Oriented Attachment Lead to Incorporation of Uranium(VI) into the Structure of Goethite?". United States. doi:10.1039/c9en00779b.
@article{osti_1577088,
title = {Can Mineral Growth by Oriented Attachment Lead to Incorporation of Uranium(VI) into the Structure of Goethite?},
author = {Soltis, Jennifer A. and McBriarty, Martin E. and Qafoku, Odeta and Kerisit, Sebastien N. and Nakouzi, Elias and De Yoreo, James J. and Ilton, Eugene S.},
abstractNote = {Oriented aggregation (OA), whereby crystals grow by successive attachment of precursor nanoparticles that are crystallographically co-aligned with the growing crystal, is a fundamental process by which many low solubility phases and minerals reach maturity in aqueous solution. Here, we investigated whether U(VI) can be incorporated into the structure of goethite that grows by OA. Wet chemical analysis and acid treatments showed that the additions of U(VI) early in the OA process hindered crystallization and increased the recalcitrant fraction of sorbed U(VI) relative to later addition of U(VI). Over time, however, the recalcitrant fraction of U(VI) decreased and converged to similar values for both early and late additions of U(VI). Electron microscopy indicated a portion of the acid resistant sorbed U(VI) was likely associated with grain boundaries between aggregating particles, not nanopores; and that these features were annealed out with increasing reaction time. Further, time elapsed imaging of U atom diffusion, that was stimulated by the electron beam, indicated that most sorbed U(VI) was not incorporated into the structure of goethite. This was confirmed and more rigorously quantified by ab initio molecular dynamics informed extended X-ray absorption fine structure spectra which indicated that only up to 5% of the recalcitrant U(VI) might be incorporated with an upper solubility limit of only U/Fe ~ 0.02 atom % in goethite where U(VI) was added early in the process. We conclude that most of the recalcitrant U(VI) is simply strongly adsorbed to the surface and that it is the uranyl oxygens that both inhibit crystallization of goethite as well as incorporation of U into the structure of goethite.},
doi = {10.1039/c9en00779b},
journal = {Environmental Science Nano},
number = 10,
volume = 6,
place = {United States},
year = {2019},
month = {10}
}

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