Spectroscopic Properties of Tc(I) Tricarbonyl Species Relevant to the Hanford Tank Waste

Levitskaia, Tatiana G.; Andersen, Amity; Chatterjee, Sayandev; Hall, Gabriel B.; Walter, Éric; Washton, Nancy M.

doi:10.2172/1364016

Cited by 5 publications

(13 citation statements)

References 18 publications

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“…The reaction product obtained after 14 days of reaction, consisted of a light straw colored liquid and a dark brown-black precipitate. The 99 Tc NMR of the product showed a sharp resonance at -1006 ppm, which can be attributed to a [Tc(CO) 3 ] + •IDA species based on our previous observations (Levitskaia et al 2015). It is worth mentioning the line-width of the [Tc(CO) 3 ] + •IDA resonance here is significantly narrower compared to that observed for a pure [Tc(CO) 3 ] + •IDA product.…”

Section: Parr Reactionsupporting

confidence: 66%

“…The NMR spectrum bears a strong resemblance with that of observed for the Parr Reaction 1. As in case of the Parr Reaction 1, reaction done at higher pressure, the NMR resonances for the Parr Reaction 5 are significantly narrower than observed for the [Tc(CO) 3 ] + •gluconate complex in simple 5 M NaNO3/0.1 M NaOH solution (Levitskaia et al 2015). Only 5% TcO 4 is observed in the liquid fraction.…”

Section: Figure 22mentioning

confidence: 74%

“…The starting Tc carbonyl complex, (Et 4 N) 2 [Tc(CO) 3 Cl 3 ], was prepared by a two-step reduction procedure starting from NH 4 TcO 4 as described in our previous reports (Levitskaia et al 2014;Levitskaia et al 2015). The tetrameric Tc carbonyl compound, [Tc(CO) 3 (OH)] 4 , was prepared according to a modified literature procedure (Alberto et al 1998) by dissolution of (Et 4 N) 2 [Tc(CO) 3 Cl 3 ] in NaOH solution followed by extraction into diethyl ether, and crystallization from dichloromethane.…”

Section: Synthesis Of Tc(i) Carbonyl Compoundsmentioning

confidence: 99%

“…Studies to evaluate nature and time stability of the non-petechnetate species generated via chemical reduction studies of TcO 4 in Hanford tank supernatant simulant (see Table 1) have been ongoing for last 2.5 years. Experimental conditions and preliminary results are discussed in the FY 2014 and 2015 reports (Levitskaia et al 2015;Chatterjee et al 2015). In brief, the reduction was carried out under four different reaction conditions corresponding to Parr Reactions 1 -4 (Table 2).…”

Section: Synthesis Of Non-pertechnetate Species Through Chemical Redumentioning

confidence: 99%

“…As these complexes have not been chemically isolated previously, a companion effort was to develop a spectroscopic library of [Tc(CO) 3 ] + •chelator complexes. These synthesis and characterization efforts were summarized in a report (Levitskaia et al 2015).…”

Section: Introductionmentioning

confidence: 99%

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Characterization of Non-pertechnetate Species Relevant to the Hanford Tank Waste

Chatterjee

Andersen

et al. 2017

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Among radioactive constituents present in the tank waste stored at the U.S. DOE Hanford Site, technetium-99 (Tc), which is generated from the fission of 235 U and 239 Pu in high yields, presents a unique challenge in that it has a long half-life ( = 292 keV; T 1/2 = 2.1110 5 y) and exists predominately in soluble forms in the liquid supernatant and salt cake fractions of the waste. In the strongly alkaline environments prevalent in most of the tank waste, its dominant chemical form is pertechnetate

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Section: Parr Reactionsupporting

confidence: 66%

Section: Figure 22mentioning

confidence: 74%

Section: Synthesis Of Tc(i) Carbonyl Compoundsmentioning

confidence: 99%

Section: Synthesis Of Non-pertechnetate Species Through Chemical Redumentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Characterization of Non-pertechnetate Species Relevant to the Hanford Tank Waste

Chatterjee

Andersen

et al. 2017

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

et al. 2020

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Technetium-99 (Tc), a high yield fission product generated in nuclear reactors, is one of the most difficult contaminants to address at the U.S. Department of Energy Hanford, Savannah River, and other sites. In strongly alkaline solutions typifying Hanford tank waste, Tc exists as pertechnetate (TcO 4 − ) (oxidation state VII) as well as in reduced forms (oxidation state < VII), collectively known as nonpertechnetate (non-TcO 4 − ) species. Designing strategies for effective Tc management, including separation and immobilization, necessitates understanding the molecular structure of the non-TcO 4 − species and their identification in actual tank waste samples. Identification of non-TcO 4 − species would facilitate the 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(II, IV, V, VII) compounds was generated and applied to the characterization of the actual Hanford AN-102 tank waste supernatant, which was processed to adjust Na concentration to ∼5.6 M and remove 137 Cs by spherical resorcinol-formaldehyde (sRF) ion-exchange resin. Post 137 Cs removal, the cesium-loaded sRF column was eluted with 0.45 M HNO 3 . As-received AN-102, Cs-depleted effluent, and sRF eluate fractions were comprehensively characterized for chemical composition and speciation of Tc using 99 Tc nuclear magnetic resonance spectroscopy and X-ray absorption spectroscopy. It was demonstrated for the first time that non-TcO 4 − Tc present in the 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 first demonstration of multiple non-TcO 4 − species co-existing in the Hanford tank waste, highlighting their importance for the waste processing.

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Oxidative Stability of Tc(I) Tricarbonyl Species Relevant to the Hanford Tank Waste

Chatterjee

Hall

Levitskaia

et al. 2015

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Spectroscopic Properties of Tc(I) Tricarbonyl Species Relevant to the Hanford Tank Waste

Abstract: Planned testing includes obtaining the actual waste samples collected from various Hanford tanks and their characterization for Tc speciation with NMR, EPR, IR, and XAS spectroscopies.

Cited by 5 publications

References 18 publications

Characterization of Non-pertechnetate Species Relevant to the Hanford Tank Waste

Characterization of Non-pertechnetate Species Relevant to the Hanford Tank Waste

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

Oxidative Stability of Tc(I) Tricarbonyl Species Relevant to the Hanford Tank Waste

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