Impeding 99Tc(IV) mobility in novel waste forms

Lee, Mal-Soon; Um, Wooyong; Wang, Guohui; Kruger, Albert A.; Lukens, Wayne W.; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

doi:10.1038/ncomms12067

Title: Impeding ⁹⁹Tc(IV) mobility in novel waste forms

Journal Article · Thu Jun 30 00:00:00 EDT 2016 · Nature Communications

DOI:https://doi.org/10.1038/ncomms12067· OSTI ID:1282477

Lee, Mal-Soon ^[1]; Um, Wooyong ^[2]; Wang, Guohui ^[3]; Kruger, Albert A. ^[4]; Lukens, Wayne W. ^[5]; Rousseau, Roger ^[1]; Glezakou, Vassiliki-Alexandra ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Fundamental and Computational Sciences Directorate
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy and Environment Directorate; Pohang Univ. of Science and Technology (POSTECH) (South Korea)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy and Environment Directorate
United States Dept. of Energy, Richland, WA (United States). Office of River Protection
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Technetium ( 99 Tc) is an abundant, long-lived radioactive fission product whose mobility in the subsurface is largely governed by its oxidation state. Tc immobilization is crucial for radioactive waste management and environmental remediation. Tc(IV) incorporation in spinels has been proposed as a novel method to increase Tc retention in glass waste forms during vitrification. However, experiments under high-temperature and oxic conditions show reoxidation of Tc(IV) to volatile pertechnetate, Tc(VII). Here we examine this problem with ab initio molecular dynamics simulations and propose that, at elevated temperatures, doping with first row transition metal can significantly enhance Tc retention in magnetite in the order Co > Zn > Ni. Experiments with doped spinels at 700 °C provide quantitative confirmation of the theoretical predictions in the same order. This work highlights the power of modern, state-of-the-art simulations to provide essential insights and generate theory-inspired design criteria of complex materials at elevated temperatures.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830; AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1282477

Alternate ID(s):: OSTI ID: 1436595

Report Number(s):: PNNL-SA-114552; 830403000

Journal Information:: Nature Communications, Vol. 7; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 96 works

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Optimizing radionuclide sequestration in anion nanotraps with record pertechnetate sorption Sun, Qi; Zhu, Lin; Aguila, Briana Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09630-y	journal	April 2019
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The abiotic reductive removal and subsequent incorporation of Tc( iv ) into iron oxides: a frontier review Boglaienko, Daria; Levitskaia, Tatiana G. Environmental Science: Nano, Vol. 6, Issue 12 https://doi.org/10.1039/c9en00903e	journal	January 2019
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