Removal of TcO4– from Representative Nuclear Waste Streams with Layered Potassium Metal Sulfide Materials

Neeway, James J.; Asmussen, R. Matthew; Lawter, Amanda R.; Bowden, Mark E.; Lukens, Wayne W.; Sarma, Debajit; Riley, Brian J.; Kanatzidis, Mercouri G.; Qafoku, Nikolla P.

doi:10.1021/acs.chemmater.6b01296

Removal of TcO₄^– from Representative Nuclear Waste Streams with Layered Potassium Metal Sulfide Materials

Journal Article · Tue May 17 00:00:00 EDT 2016 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.6b01296· OSTI ID:1480726

Neeway, James J. ^[1]; Asmussen, R. Matthew ^[1]; Lawter, Amanda R. ^[1]; Bowden, Mark E. ^[2]; Lukens, Wayne W. ^[3]; Sarma, Debajit ^[4]; Riley, Brian J. ^[1]; Kanatzidis, Mercouri G. ^[4]; Qafoku, Nikolla P. ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy and Environment Directorate
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). W. R. Wiley Environmental Molecular Sciences Laboratory
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Northwestern Univ., Evanston, IL (United States). Department of Chemistry

Many efforts have focused on the sequestration and immobilization of ⁹⁹Tc because the radionuclide is highly mobile in oxidizing environments and presents serious health risks due to its radiotoxicity and long half-life (t_1/2= 213 000 a). We report that one of the more common methods for Tc removal from solution and immobilization in solids is based on reducing Tc from highly soluble Tc^(VII) to sparingly soluble Tc^(IV). Here, we report results obtained with two potassium metal sulfides (KMS-2 and KMS-2-SS) that are capable of reducing Tc^(VII) to Tc^(IV). Batch sorption experiments were performed in both oxic and anoxic conditions for 15 d in both deionized water (DIW) and a highly caustic (pH ~ 13.6), high ionic strength (8.0 mol L^-1), low-activity waste (LAW) stream simulant solution. Tc removal for both materials in DIW is improved in anoxic conditions compared to oxic conditions as a result of a higher solution pH. In DIW and anoxic conditions, KMS-2 is capable of removing ~45% of Tc, and KMS-2-SS is capable of removing ~90% of Tc. Both materials perform even better in the LAW simulant and remove more than 90% of available Tc after 15 d of contact in anoxic conditions. Postreaction solids analyses indicate that Tc^(VII) is reduced to Tc^(IV) and that Tc(IV)is bonded to S atoms in a Tc₂S₇ complex. Examination of the materials after Tc removal by X-ray diffraction shows that the initially crystalline KMS-2 materials lose much of their initial long-range order. In conclusion, we suggest a Tc removal mechanism wherein the TcO^4- enters the interlayer of the KMS-2 materials where it is reduced by sulfide, which results in a distorted crystalline structure and a solid-state Tc₂S₇ complex.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Environmental Management (EM); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231; AC06-76RL01830

OSTI ID:: 1480726

Alternate ID(s):: OSTI ID: 1326140

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 11 Vol. 28; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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