Reduction and Simultaneous Removal of 99 Tc and Cr by Fe(OH) 2 (s) Mineral Transformation

Saslow, Sarah A.; Um, Wooyong; Pearce, Carolyn I.; Engelhard, Mark H.; Bowden, Mark E.; Lukens, Wayne; Leavy, Ian I.; Riley, Brian J.; Kim, Dong-Sang; Schweiger, Michael J.; Kruger, Albert A.

doi:10.1021/acs.est.7b02278

Title: Reduction and Simultaneous Removal of ⁹⁹ Tc and Cr by Fe(OH) ₂ (s) Mineral Transformation

Journal Article · Mon Jul 17 00:00:00 EDT 2017 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.7b02278· OSTI ID:1374647

Saslow, Sarah A. ^[1];

^[1]; Pearce, Carolyn I. ^[1]; Engelhard, Mark H. ^[2]; Bowden, Mark E. ^[2];

^[3]; Leavy, Ian I. ^[1];

^[1]; Kim, Dong-Sang ^[1]; Schweiger, Michael J. ^[1]; Kruger, Albert A. ^[4]

Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States
Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
United States Department of Energy, Office of River Protection, P.O. Box 450, Richland, Washington 99352, United States

Technetium (Tc) remains a priority remediation concern due to persistent challenges, including rapid re-oxidation of immobilized Tc, and competing contaminants, e.g. Cr(VI), that inhibit targeted Tc reduction and incorporation into stable mineral phases. Here Fe(OH)₂(s) is investigated as a comprehensive solution for overcoming these challenges, by serving as both the reductant, (Fe(II)), and immobilization agent to form Tc-incorporated magnetite (Fe₃O₄). Trace metal analysis suggests removal of Tc(VII) and Cr(VI) from solution occurs simultaneously; however, complete removal and reduction of Cr(VI) is achieved earlier than the removal/reduction of co-mingled Tc(VII). Bulk oxidation state analysis of the magnetite solid phase by XANES confirms that the majority of Tc is Tc(IV), which is corroborated by XPS. Furthermore, EXAFS results show successful Tc(IV) incorporation into magnetite octahedral sites without additional substitution of Cr or Tc into neighboring Fe octahedral sites. XPS analysis of Cr confirms reduction to Cr(III) and the formation of a Cr-incorporated spinel, Cr2O₃, and Cr(OH)3 phases. Spinel (modeled as Fe₃O₄), goethite, and feroxyhyte are detected in all reacted solid phase samples analyzed by XRD, where Tc(IV) incorporation has little effect on the spinel lattice structure. In the presence of Cr(III) a spinel phase along the magnetite-chromite (Fe₃O₄-FeCr₂O₄) solid-solution line is formed.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1374647

Report Number(s):: PNNL-SA-125836; 48824; 830403000

Journal Information:: Environmental Science and Technology, Vol. 51, Issue 15; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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Thermodynamic description of Tc( iv ) solubility and carbonate complexation in alkaline NaHCO ₃ –Na ₂ CO ₃ –NaCl systems Baumann, A.; Yalçıntaş, E.; Gaona, X. Dalton Transactions, Vol. 47, Issue 12 https://doi.org/10.1039/c8dt00250a	journal	January 2018
Removal of hexavalent chromium, an analogue of pertechnetate, from aqueous solution using bamboo (Acidosasa edulis) shoot shell Hu, Hui; Gao, Yanling; Wang, Tian Journal of Radioanalytical and Nuclear Chemistry, Vol. 321, Issue 2 https://doi.org/10.1007/s10967-019-06606-6	journal	June 2019
The abiotic reductive removal and subsequent incorporation of Tc( iv ) into iron oxides: a frontier review Boglaienko, Daria; Levitskaia, Tatiana G. Environmental Science: Nano, Vol. 6, Issue 12 https://doi.org/10.1039/c9en00903e	journal	January 2019

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