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Technetium stabilization in Portland cement and bentonite clay barriers by thiourea

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Abstract

In this paper we elaborated the prospective approach for the immobilization of technetium in bentonite clay and Portland cement. It includes thiourea (Tu) addition for Tc effective speciation modification from mobile Tc(VII) to immobile Tc species. Based on the resulting compound structure analysis of Tu with technetium, the reductive mechanism of immobilization was proved. A new technetium complex structure with Tu was described by single crystal XRD analysis, where technetium was obtained in the oxidation state + 3. The complex is stable due to the coordination binding of Tc to the sulfur atoms of the Tu molecules and to the chlorine atom, effective charge transfer along the S–Tc bond, and intramolecular hydrogen bonds. XANES spectra characteristics of technetium (VII, IV, III) reference compounds and samples containing Tc–Tu species in a cement matrix and bentonite clay indicates the presence of technetium in bentonite clay in the form of its tetravalent oxidation state during the Fourier transformation.

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Acknowledgements

The authors are grateful to M.S. Grigoriev for invaluable help in analyzing the single crystal data of the Tc-Tu complex. X-ray diffraction experiments were performed at the Center for Shared Use of Physical Methods of Investigation at the Frumkin Institute of Physical Chemistry and Electrochemistry, RAS.

Funding

This work was supported by state assignments from The Ministry of Science and Higher Education of the Russian Federation (#AAAA-A16-11611091001) and performed using the equipment of the Core Facilities Center of IPCE RAS (CKP FMI IPCE RAS). The study was supported by the Ministry of Science and Higher Education of the Russian Federation (program no. 122011300061-3).

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Authors and Affiliations

  1. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russia

    Alexey Safonov, Anton Novikov, Mikhail Volkov, Anastasiia Sitanskaia & Konstantin German

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  1. Alexey Safonov
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  2. Anton Novikov
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  3. Mikhail Volkov
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  4. Anastasiia Sitanskaia
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Contributions

AS: Conceptualization, Investigation, Validation, writing—Original Draft, Supervision, AN: Writing—Original Draft, Investigation, MV: Investigation, Validation, AS: Investigation, Validation, KG: Conceptualization, Methodology, Supervision.

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Correspondence to Alexey Safonov.

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Safonov, A., Novikov, A., Volkov, M. et al. Technetium stabilization in Portland cement and bentonite clay barriers by thiourea. J Radioanal Nucl Chem 332, 2195–2204 (2023). https://doi.org/10.1007/s10967-023-08830-7

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