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Chemometric analyses of XANES data collected on 99Tc bearing silicate glasses

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Abstract

A challenge to the incorporation of 99Tc into a glass matrix is that 99Tc is volatile at vitrification temperatures. Understanding how this volatilization occurs requires knowledge of the multiple chemistries which Tc may take during vitrification. This paper presents an overview of how the localized chemistry of 99Tc has been determined in a series of 99Tc-bearing glasses by chemometric analyses of X-ray absorption near edge spectra (XANES). Linear combination fitting and principal component analysis of the glasses’ XANES spectra suggested that the glasses contained 3–4 chemically distinct Tc environments. The identity of the detected chemistries were pertechnetates, (Tc(VII) as isolated oxyanions, or locally coordinated by Na or K), or isolated Tc(IV) species. The linear combination fitting distribution of local Tc sites agrees with reanalyzed Raman spectra, suggesting that as targeted KTcO4 incorporation increases, a significant ion exchange takes place, and speciation in the glass changes to favor Tc(VII) formation, specifically NaTcO4. Based on the statistical suggestion that not all Tc environments are accounted by the available standards, a new mechanism for the behavior of Tc during vitrification is proposed.

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Acknowledgements

The authors would like to thank Prof. Alain Michalowicz (Université Paris est Créteil Val de Marne), Dr. Steve Wasserman (Lilly Research Laboratories), Prof. Scott Calvin (Sarah Lawrence College) for their guidance in the use of the Straight No Chaser and Athena freewares. They would also like to acknowledge the help provided by Dr. Wayne Lukens in the setup, collection and processing of the XANES data. Special thanks is given to Paul Gassman for assistance with the reinterpretation of the Raman spectra of the Tc glasses. Pacific Northwest National Laboratory is operated by Battelle Memorial Institute for the U.S. DOE under contract DE-AC05-76RL01830. Portions of this work were supported by U.S. Department of Energy, Basic Energy Sciences, Chemical Sciences, Biosciences, and Geosciences Division, Heavy Element Chemistry Program and were performed at Lawrence Berkeley National Laboratory under Contract No. DE-AC02-05CH11231. Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource, a Directorate of SLAC National Accelerator Laboratory and an Office of Science User Facility operated for the U.S. DOE Office of Science by Stanford University. All original data presented in this work are available upon request from the corresponding author.

Funding

This work was supported by the Department of Energy’s Waste Treatment & Immobilization Plant Federal Project Office under the direction of Bill Hamel, Contract DE-EM0002904.

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Authors and Affiliations

  1. Department of Chemistry, Washington State University, Pullman, WA, USA

    Jamie L. Weaver & Nathalie Wall

  2. Pacific Northwest National Laboratory, Richland, WA, USA

    Jamie L. Weaver, Chuck Soderquist & John S. McCloy

  3. School of Mechanical and Materials Engineering, Washington State University, P.O. BOX 642920, Pullman, WA, 99164-292, USA

    John S. McCloy

  4. Office of River Protection, U. S. Department of Energy, Richland, WA, USA

    Albert A. Kruger

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  1. Jamie L. Weaver
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Correspondence to John S. McCloy.

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Weaver, J.L., Soderquist, C., Wall, N. et al. Chemometric analyses of XANES data collected on 99Tc bearing silicate glasses. J Radioanal Nucl Chem 316, 17–27 (2018). https://doi.org/10.1007/s10967-018-5722-7

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