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Impeding (99)Tc(IV) mobility in novel waste forms.


ABSTRACT: 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.

SUBMITTER: Lee MS 

PROVIDER: S-EPMC4931311 | biostudies-literature | 2016 Jun

REPOSITORIES: biostudies-literature

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Impeding (99)Tc(IV) mobility in novel waste forms.

Lee Mal-Soon MS   Um Wooyong W   Wang Guohui G   Kruger Albert A AA   Lukens Wayne W WW   Rousseau Roger R   Glezakou Vassiliki-Alexandra VA  

Nature communications 20160630


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, T  ...[more]

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