Kinetics of Co-Mingled 99Tc and Cr Removal during Mineral Transformation of Ferrous Hydroxide

Saslow, Sarah A.; Pearce, Carolyn I.; Bowden, Mark E.; Lukens, Wayne W.; Kim, Dong-Sang; Kruger, Albert A.; Um, Wooyong

doi:10.1021/acsearthspacechem.9b00277

Title: Kinetics of Co-Mingled ⁹⁹Tc and Cr Removal during Mineral Transformation of Ferrous Hydroxide

Journal Article · 22 December 2019 · ACS Earth and Space Chemistry

DOI: https://doi.org/10.1021/acsearthspacechem.9b00277 · OSTI ID:1602751

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^[4]; Kruger, Albert A. ^[5];

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Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Pacific Northwest National Laboratory, Richland, Washington 99354, United States
USDOE Office of River Protection (ORP), Richland, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Pohang Univ. of Science and Technology (POSTECH) (Korea, Republic of)

In this work, four simulated waste streams relevant to the vitrification of Hanford nuclear waste were studied to evaluate the removal kinetics of technetium-99 (Tc) and co-mingled Cr(VI) during treatment with solid ferrous hydroxide (Fe(OH)₂(s)). Simulants treated with Fe(OH)₂(s) were reacted for 24 h and sub-sampled periodically to monitor Tc and Cr removal. Solution sample analysis during the reaction was coupled with solid phase characterization, for example, X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD), to establish influence of the solid phase product on Tc and Cr removal rates. Based on these results, the majority of Tc and Cr removal occurs within the first 5 min of simulant contact with Fe(OH)₂(s). However, the order in which Tc and Cr are completely removed from each simulant depends on the simulant chemistry, the preferred reduction pathway, and the solid phase product, for example, magnetite (Fe₃O₄) versus goethite (α-FeOOH). Low pH and low Cr concentrations favor rapid Tc removal, with XRD and XAS confirming that Fe₃O₄ readily incorporates reduced Tc(IV) into its structure. High pH, high Cr concentrations, and the presence of other co-mingled constituents favor heterogeneous removal of Tc early in the reaction (<1 h) with removal rates often faster than those determined for Cr. At reaction times of >1 h, Tc removal slows as homogeneous removal of Cr begins to dominate, concurrent with an increase in the formation of FeOOH as the solid phase reaction product. These results suggest that for complex, high pH waste streams, Tc removal within the first hour after Fe(OH)₂(s) treatment is necessary for complete Tc reduction and improved mineral immobilization.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of River Protection (ORP); National Research Foundation of Korea (NRF)

Grant/Contract Number:: AC02-05CH11231; AC05-76RL01830; AC02-76SF00515

OSTI ID:: 1602751

Alternate ID(s):: OSTI ID: 1685049

Report Number(s):: PNNL-SA--147021

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 2 Vol. 4; ISSN 2472-3452

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Kinetics of Co-Mingled 99Tc and Cr Removal during Mineral Transformation of Ferrous Hydroxide

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Title: Kinetics of Co-Mingled ⁹⁹Tc and Cr Removal during Mineral Transformation of Ferrous Hydroxide