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Technetium Incorporation into Hematite (α-Fe2O3)

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Pacific Northwest National Laboratory, Richland, Washington, U.S.A.
* Corresponding author phone: +1-509-371-6368; fax: +1-509-371-6354; e-mail: [email protected]
†In memorium.
Cite this: Environ. Sci. Technol. 2010, 44, 15, 5855–5861
Publication Date (Web):July 13, 2010
Copyright © 2010 American Chemical Society

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    Quantum-mechanical methods were used to evaluate mechanisms for possible structural incorporation of Tc species into the model iron oxide, hematite (α-Fe2O3). Using periodic supercell models, energies for charge-neutral incorporation of Tc4+ or TcO4 ions were calculated using either a Tc4+/Fe2+ substitution scheme on the metal sublattice, or by insertion of TcO4 as an interstitial species within a hypothetical vacancy cluster. Although pertechnetate incorporation is found to be invariably unfavorable, incorporation of small amounts of Tc4+ (at least 2.6 wt %) is energetically feasible. Energy minimized bond distances around this impurity are provided to aid in future spectroscopic identification of these impurity species. The calculations also show that Fe2+ and Tc4+ prefer to cluster in the hematite lattice, attributed to less net Coulombic repulsion relative to that of Fe3+−Fe3+. These modeling predictions are generally consistent with observed selective association of Tc with iron oxide under reducing conditions, and in residual waste solids from underground storage tanks at the U.S. Department of Energy Hanford Site (Washington, U.S.). Here, even though relatively high pH and oxidizing conditions are dominant, Tc incorporation into iron oxides and (oxy)hydroxides is prospectively enabled by prior reduction of TcO4 to Tc4+ via interaction with radiolytic species.

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    Additional computational details are included, along with Eh-pH diagrams illustrating the overlapping stability fields of aqueous Tc and Fe species and their corresponding solid phases. This material is available free of charge via the Internet at

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