Identification and Quantification of Technetium Species in Hanford Waste Tank AN-102

Chatterjee, Sayandev; Holfeltz, Vanessa E.; Hall, Gabriel B.; Johnson, Isaac E.; Walter, Eric D.; Lee, Sungsik; Reinhart, Benjamin; Lukens, Wayne W.; Machara, Nicholas P.; Levitskaia, Tatiana G.

doi:10.1021/acs.analchem.0c02864

Title: Identification and Quantification of Technetium Species in Hanford Waste Tank AN-102

Journal Article · Tue Sep 22 00:00:00 EDT 2020 · Analytical Chemistry

DOI:https://doi.org/10.1021/acs.analchem.0c02864· OSTI ID:1797904

^[1]; Holfeltz, Vanessa E. ^[2];

^[1]; Johnson, Isaac E. ^[1];

^[1];

^[3]; Reinhart, Benjamin ^[3];

^[4]; Machara, Nicholas P. ^[5]; Levitskaia, Tatiana G. ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Montpellier Univ. (France)
Argonne National Lab. (ANL), Argonne, IL (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
US Department of Energy (USDOE), Germantown, MD (United States)

Technetium-99 (Tc), a high yield fission product generated in nuclear reactors, is one of the most difficult contaminants to address at the U.S. Department of Energy Hanford, Savannah River, Tel), and other sites. In strongly alkaline solutions typifying Hanford tank waste, Tc exists as pertechnetate (TcO₄^-) (oxidation state VII) as well as in reduced forms (oxidation state < VII), collectively known as non- pertechnetate (non-TcO₄^-) species. Designing strategies for effective Tc management, including separation and immobilization, necessitates understanding the molecular structure of the non-TcO₄^- species and their identification in actual tank waste samples. Identification of non-TcO₄^- species would facilitate the development of new treatment technologies effective for dissimilar Tc species. Toward this objective, a spectroscopic library of the Tc(I) [fac-Tc(CO₃)]⁺ and Tc(II, IV, V, VII) compounds was generated and applied to the characterization of the actual Hanford AN-102 tank waste supernatant, which was processed to adjust Na concentration to similar to 5.6 M and remove ¹³⁷Cs by spherical resorcinol-formaldehyde (sRF) ion-exchange resin. Here, post ¹³⁷Cs removal, the cesium-loaded sRF column was eluted with 0.45 M HNO₃. As-received AN-102, Cs-depleted effluent, and sRF eluate fractions were comprehensively characterized for chemical composition and speciation of Tc using ⁹⁹Tc nuclear magnetic resonance spectroscopy and X-ray absorption spectroscopy. It was demonstrated for the first time that non-TcO₄^- Tc present in the AN-102 tank waste is composed of several low-valent Tc species, including the Tc(I) [fac-Tc(CO)₃]⁺ and Tc(IV) compounds. This is the first demonstration of multiple non-TcO₄^- species co-existing in the Hanford tank waste, highlighting their importance for the waste processing.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Environmental Management (EM); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-06CH11357; AC02-76SF00515; AC05-76RL01830

OSTI ID:: 1797904

Journal Information:: Analytical Chemistry, Vol. 92, Issue 20; ISSN 0003-2700

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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