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

Chatterjee, Sayandev; Holfeltz, Vanessa E.; Hall, Gabriel B.; Johnson, Isaac; Walter, Eric D.; Lee, Sungsik; Reinhart, Benjamin; Lukens, Wayne W.; Machara, N; 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 Oct 20 00:00:00 EDT 2020 · Analytical Chemistry

DOI:https://doi.org/10.1021/acs.analchem.0c02864· OSTI ID:1734563

Chatterjee, Sayandev ^[1]; Holfeltz, Vanessa E. ^[1];

^[1];

^[1]; Lee, Sungsik ^[2]; Reinhart, Benjamin ^[2]; Lukens, Wayne W. ^[3]; Machara, N ^[4];

^[1]

BATTELLE (PACIFIC NW LAB)
Argonne National Laboratory
Lawrence Berkeley National Laboratory
U.S. Department of Energy

Technetium-99 (Tc) generated from the fission of 235U and 239Pu in high yields is one of the most difficult contaminants to be addressed at the U.S. Department of Energy Hanford Site. 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 species. Designing strategies for effective Tc management, including separation and immobilization, necessitates understanding the molecular structure of the non- pertechnetate species and their identification in the actual tank waste samples, which would facilitate development of new treatment technologies effective for dissimilar Tc species. Toward this objective, a spectroscopic library of the Tc(I) [fac-Tc(CO)3]+ and Tc(IV, VII) compounds was generated using a range of techniques and applied to the characterization of the actual tank waste supernatant collected from the tank 241-AN-102 at Hanford, WA. A sample of the 241-AN-102 tank waste supernatant was processed to adjust Na concentration to about 5.6 M and remove 137Cs by spherical resorcinol-formaldehyde (sRF) ion exchange resin. Cesium-loaded sRF column was eluted with 0.5 M HNO3. As received AN-102, Cs-depleted AN-102 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-pertechnetate Tc present in the 241-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 second experimental observation of the [fac-Tc(CO)3]+ species in the Hanford tank waste and the first demonstration of multiple forms of non-pertechnetate species existing simultaneously in the waste, cumulatively highlighting their importance for the waste processing.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

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

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1734563

Report Number(s):: PNNL-SA-142972

Journal Information:: Analytical Chemistry, Vol. 92, Issue 20

Country of Publication:: United States

Language:: English

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