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

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

doi:10.1021/acs.analchem.0c02864

Cited by 20 publications

(12 citation statements)

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“…Detailed knowledge about the coordination chemistry of technetium with small inorganic ligands is imperative to assess the possible speciation of technetium in the environment and at problematic nuclear waste sites such as the Hanford wastewater tanks. Particularly, interactions with small nitrogen-containing ligands such as nitrite, nitrate, or azide may contribute to the omnipresent potential explosion hazard formed by transition-metal complexes in conjunction with the high level of radioactivity present in these containers. − The existence of low-valent organotechnetium compounds such as carbonyls in nuclear waste solutions has been proven, and thus, an assessment of hitherto unknown complexes of technetium carbonyl complexes with small inorganic ligands also becomes important.…”

Section: Introductionmentioning

confidence: 99%

Technetium(I) Carbonyl Chemistry with Small Inorganic Ligands

2022

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[Tc(OH2)(CO)3(PPh3)2](BF4) has been used as a synthon for reactions with small inorganic ligands with relevance for the treatment of nuclear waste solutions such as nitrate, nitrite, pseudohalides, permetalates (M = Mn, Tc, Re), and BH4 –. The formation of bond isomers and/or a distinct reactivity has been observed for most of the products. [Tc(NCO)(CO)3(PPh3)2], [Tc(NCS)(CO)3(PPh3)2], [Tc(CN)(CO)3(PPh3)2], [Tc(N3)(CO)3(PPh3)2], [Tc(NCO)(OH2)(CO)2(PPh3)2], [Tc(η2-OON)(CO)2(PPh3)2], [Tc(η1-NO2)(CO)3(PPh3)2], [Tc(η2-OONO)(CO)2(PPh3)2], [Tc(η1-ONO2)(CO)3(PPh3)2], [Tc(η2-OO(CCH3))(CO)2(PPh3)2], [Tc(η2-SSC(SCH3))(CO)2(PPh3)2], [Tc(η2-SSC(OCH3))(CO)2(PPh3)2], [Tc(η2-SSC(CH3))(CO)2(PPh3)2], [Tc(η2-SS(CH))(CO)2(PPh3)2], [Tc(OTcO3)(acetone)(CO)2(PPh3)2], [Tc(OTcO3)(CO)3(PPh3)2], and [Tc(η2-HHBH2)(CO)2(PPh3)2] have been isolated in crystalline form and studied by X-ray crystallography. Additionally, the typical reactivity patterns (isomerization, thermal decomposition, hydrolysis, or decarbonylation) of the products have been studied by spectroscopic methods. 99Tc NMR spectroscopy has proved to be a particularly useful tool for the evaluation of such reactions of the diamagnetic technetium(I) compounds in solution.

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Section: Introductionmentioning

confidence: 99%

Technetium(I) Carbonyl Chemistry with Small Inorganic Ligands

2022

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“…Under the extreme conditions to which technetium compounds are exposed at nuclear waste sites, several unexpected reactions may proceed. Thus, high-valent technetium compounds are present in such solutions, and the reduction of technetium to low-valent compounds such as Tc(I) or Tc(II) carbonyls or nitrosyls has been observed under the influence of the radiation level present. − …”

Section: Introductionmentioning

confidence: 99%

Unlocking Air- and Water-Stable Technetium Acetylides and Other Organometallic Complexes

Jungfer

Abram

2022

Inorg. Chem.

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The first technetium complexes containing anionic alkynido ligands in an end-on coordination mode have been prepared by using the nonprotic, cationic precursor mer,trans-[Tc(SMe2)(CO)3(PPh3)2]+. This cation acts as a functional analogue of the highly reactive 16-electron metallo Lewis acid {Tc(CO)3(PPh3)2}+ in reactions with alkynes, acetylides, and other organometallic reagents. Such reactions give a variety of organometallic technetium complexes in excellent yields and enable the preparation of [Tc(CH3)(CO)3(PPh3)2], [Tc(Ph)(CO)3(PPh3)2], [Tc(Cp)(CO)2(PPh3)], [Tc(CCH2CH2CH2O)(CO)3(PPh3)2]+, [Tc(CCH2CH2CH2CH2O)(CO)3(PPh3)2]+, [Tc(CC–H)(CO)3(PPh3)2], [Tc(CC–Ph)(CO)3(PPh3)2], [Tc(CC– t Bu)(CO)3(PPh3)2], [Tc(CC– n Bu)(CO)3(PPh3)2], [Tc(CC–SiMe3)(CO)3(PPh3)2], and [Tc{CC–C6H3(CF3)2}(CO)3(PPh3)2]. The bonding situation in the alkynyl complexes is compared to that in corresponding alkyl- and arylnitrile and -isonitrile complexes. [Tc(NC–Ph)(CO)3(PPh3)2](BF4), [Tc(CN–Ph)(CO)3(PPh3)2](BF4), [Tc(NC– t Bu)(CO)3(PPh3)2](BF4), and [Tc(CN– t Bu)(CO)3(PPh3)2](BF4) were prepared in high yields by ligand exchange reactions starting from mer,trans-[Tc(OH2)(CO)3(PPh3)2](BF4). The novel complexes were characterized by single-crystal X-ray diffraction and spectroscopic methods. In particular, 99Tc nuclear magnetic resonance spectroscopy proved to be an invaluable and sensitive tool for the characterization of the complexes. Density functional theory calculations strongly suggest similar bonding situations for the related alkynyl, nitrile, and isonitrile complexes of technetium.

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“…Development). A full suite of non-pertechnetate species can be identified using a combination of nuclear magnetic resonance spectroscopy and X-ray adsorption spectroscopy (Chatterjee et al 2020). Additional information on the topic of non-pertechnetate chemistry is provided in SRNL-STI-2017-00382, Literature Review of the Potential Impact of Glycolic Acid on the Technetium Chemistry of SRS Tank Waste).…”

Section: Determination Of Non-pertechnetate Speciesmentioning

confidence: 99%

“…First, if technetium is to be removed from LAW to enable a grout waste form, most of the known technetium removal methods have only been shown to be effective for the pertechnetate ion. However, removal of a Tc(I)(CO)3 species has been shown using spherical resorcinol formaldehyde resin (Chatterjee et al 2020). No removal methods have been developed specifically for all of the non-pertechnetate form(s) and only very limited testing has been performed on methods to convert non-pertechnetate to pertechnetate.…”

Section: Non-pertechnetate Behavior In Grout Waste Formsmentioning

confidence: 99%

“…The predominant form of technetium in tank waste is pertechnetate ion, TcO4 -. There is also a form of technetium in Hanford tank waste known as "non-pertechnetate" (LA-UR-95-4440, Technetium Partitioning for the Hanford Tank Waste Remediation System: Anion Exchange Studies for PartitioningChatterjee et al, 2020). The complete speciation and distribution of technetium in Hanford tank waste is not known.…”

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Follow-On Report of Analysis of Approaches to Supplemental Treatment of Low-Activity Waste at the Hanford Nuclear Reservation (Volumes I & II)

BATES¹,

HERMAN²,

Langton³

et al. 2023

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The Hanford Site, in southeast Washington State, is preparing to disposition approximately 56,000,000 gallons (56 Mgal) of radioactive and chemically hazardous wastes currently stored in underground tanks at the site. Tank wastes will be divided into a high-activity fraction and a low-activity fraction for subsequent treatment and disposition. A waste processing and treatment facility, the Waste Treatment and Immobilization Plant (WTP), will include the high-level waste (HLW) vitrification facility (WTP HLW Vitrification Facility) for immobilizing the high-activity fraction and a low-activity waste (LAW) vitrification facility (WTP LAW Vitrification Facility) for immobilizing the low-activity fraction. Both facilities will use vitrification technology to immobilize the Hanford tank wastes in a glass waste form.The volume of LAW to be treated and disposed of following waste retrieval and WTP operations will exceed the planned processing capacity of the WTP LAW Vitrification Facility. ORP-11242, River Protection Project System Plan, 1 estimates a shortfall in LAW treatment capacity of approximately 56 Mgal, approximately 50% of the projected LAW volume. 2 To maintain the planned tank waste processing mission schedule, the U.S. Department of Energy (DOE) will require additional LAW treatment capacity (termed "supplemental LAW") external to the WTP process. LAW must be solidified by a treatment technology before the waste can be permanently disposed of in an approved DOE on-site disposal facility or a commercial (state or U.S. Nuclear Regulatory Commission [NRC]-licensed) off-site mixed low-level waste disposal facility. A decision on the approach to supplemental LAW treatment, processing, and disposal has not yet been made. SRNL-STI-2023-00007 Revision 0 Volume I | viii SRNL-STI-2023-00007 Revision 0 Volume I | ix The FFRDC team makes the following recommendation: DOE should expeditiously secure and implement multiple pathways for off-site grout solidification/ immobilization and disposal of LAW in parallel with the direct-feed low-activity waste (DFLAW) vitrification process.

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

Cited by 20 publications

References 50 publications

Technetium(I) Carbonyl Chemistry with Small Inorganic Ligands

Technetium(I) Carbonyl Chemistry with Small Inorganic Ligands

Unlocking Air- and Water-Stable Technetium Acetylides and Other Organometallic Complexes

Follow-On Report of Analysis of Approaches to Supplemental Treatment of Low-Activity Waste at the Hanford Nuclear Reservation (Volumes I & II)

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