Application of a novel gas phase synthesis approach to carbonyl complexes of accelerator-produced 5d transition metals

Gtz, M.*; Yakushev, A.*; Gtz, S.*; Di Nitto, A.*; Dllmann, Ch. E.*; Asai, Masato; Kindler, B.*; Krier, J.*; Lommel, B.*; Nagame, Yuichiro*; et al.

Radiochimica Acta, 110(2), p.75 - 86, 2022/02

https://doi.org/10.1515/ract-2021-1028

The study of volatile superheavy element carbonyl complexes requires more efficient methods because the yield of transactinide elements decreases with increasing atomic number. This is achieved by using a newly developed double chamber system to separate the recoil chamber and the reaction one, thereby avoiding the decomposition of reactive molecules by the projectile ion beam, which hinders the synthesis of carbonyl complexes. The feasibility of this method was verified by synthesizing 5d metal short-lived isotopes as homologous element isotopes of the light transactinide elements Sg, Bh, Hs, and Mt at the Japan Atomic Energy Agency tandem accelerator and conducting model experiments.

Gas phase synthesis of 4d transition metal carbonyl complexes with thermalized fission fragments in single-atom reactions

Gtz, M.*; Gtz, S.*; Kratz, J.-V.*; Ballof, J.*; Dllmann, Ch. E.*; Eberhardt, K.*; Mokry, C.*; Renisch, D.*; Runke, J.*; Sato, Tetsuya; et al.

Radiochimica Acta, 109(3), p.153 - 165, 2021/03

https://doi.org/10.1515/ract-2020-0052

We report on a novel two-chamber approach for the synthesis of volatile complexes that allows spatial decoupling of thermalization and gas-phase carbonyl complex synthesis. Neutron induced fission on U and spontaneous fission of Cm were employed for the production of the fission products. These were stopped inside a gas volume behind the target and flushed with an inert-gas flow into a second chamber. This was flushed with carbon monoxide to allow the gas-phase synthesis of carbonyl complexes. Parameter studies of the transfer from the first into the second chamber as well as on the carbonyl complex formation and transport processes have been performed. High overall efficiencies of more than 50% were reached rendering this approach interesting for studies of superheavy elements. Our results show that carbonyl complex formation of thermalized fission products is a single-atom reaction, and not a hot-atom reaction.

Simultaneous separation of Am and Cm from Nd and Sm by multi-step extraction using the TODGA-DTPA-BA-HNO system

Sasaki, Yuji; Morita, Keisuke; Matsumiya, Masahiko*; Nakase, Masahiko*

Radiochimica Acta, 108(9), p.689 - 699, 2020/09

https://doi.org/10.1515/ract-2019-3215

The simultaneous separation of Am and Cm from lanthanides is important for atomic energy fields. All lanthanides, Am, and Cm can be extracted by diglycolamide (DGA). In addition, relatively high separation factors between An and Ln were obtained by the extraction system of TODGA, DTPA (diethylenetriamine-pentaacetic acid) and HNO. In this work, DTPA-BA (diethylenetriamine-triacetic-bisamide), which is an improved version of DTPA, was employed for the separation of Ln and An. A relatively high separation factor (approximately 8) for actinides/lanthanides was obtained. Then, the multi-step extraction was performed. Thus, the recoveries of 94.7% for Nd and 4.7% for Am and Cm in organic phase, and 5.3% Nd and 95.3% for Am and Cm in aqueous phase were obtained.

Contamination of Fukushima Daiichi Nuclear Power Station with actinide elements

Koma, Yoshikazu; Murakami, Erina

Radiochimica Acta, 107(9-11), p.965 - 977, 2019/09

https://doi.org/10.1515/ract-2019-3126

Fukushima Daiichi Nuclear Power Station, which is owned by Tokyo Electric Power Company, suffered from the great earthquake and Tsunami on 11 March 2011, and serious contamination with radioactive nuclides occurred. To investigate methodologies of waste management, contaminated materials have been radiochemically analyzed. This paper reviews the analytical data for actinide elements. Actinide nuclides are detected in the contaminated water. The contaminated water is chemically decontaminated, although actinide concentration does not decrease with time. This suggests that actinides come from the damaged fuel with slow dissolution. From the topsoil at the site, Pu, Am and Cm were detected and come from the damaged fuel, whereas U from natural. TRU would slowly move to deeper. Contamination of rubble is nonuniform and actinides are detected as well as fission products. For vegetation, TRU nuclides were found from fallen leaves near the reactor buildings.

From SRAFAP to ARCA and AIDA; Developments and implementation of automated aqueous-phase rapid chemistry apparatuses for heavy actinides and transactinides

Schdel, M.*; Nagame, Yuichiro

Radiochimica Acta, 107(7), p.561 - 585, 2019/07

https://doi.org/10.1515/ract-2019-3103

Extraction behavior of rutherfordium as a cationic fluoride complex with a TTA chelate extractant from HF/HNO acidic solutions

Yokoyama, Akihiko*; Kitayama, Yuta*; Fukuda, Yoshiki*; Kikunaga, Hidetoshi*; Murakami, Masashi*; Komori, Yukiko*; Yano, Shinya*; Haba, Hiromitsu*; Tsukada, Kazuaki; Toyoshima, Atsushi*

Radiochimica Acta, 107(1), p.27 - 32, 2019/01

https://doi.org/10.1515/ract-2018-2949

A Thermodynamic model for the solubility of HfO(am) in the aqueous K - HCO - CO - OH - HO system

Rai, D.*; Kitamura, Akira; Rosso, K.*

Radiochimica Acta, 105(8), p.637 - 647, 2017/08

https://doi.org/10.1515/ract-2016-2623

Solubility of HfO(am) was determined as a function of KHCO concentrations ranging from 0.001 mol.kg to 0.1 mol.kg. The solubility of HfO(am) increased dramatically with the increase in KHCO concentrations, indicating that Hf(IV) makes strong complexes with carbonate. Thermodynamic equilibrium constants for the formation of Hf-carbonate complexes were determined using both the Pitzer and SIT models. The dramatic increase in Hf concentrations with the increase in KHCO concentrations can best be described by the formation of Hf(OH-)(CO) and Hf(CO). The log K values for the reactions [Hf + 2 CO +2 OH Hf(OH)(CO)] and [Hf + 5 CO Hf(CO)], based on the SIT model, were determined to be 44.53 0.46 and 41.53 0.46, respectively.

Decomposition studies of group 6 hexacarbonyl complexes, 1; Production and decomposition of Mo(CO) and W(CO)

Usoltsev, I.*; Eichler, R.*; Wang, Y.*; Even, J.*; Yakushev, A.*; Haba, Hiromitsu*; Asai, Masato; Brand, H.*; Di Nitto, A.*; Dllmann, Ch. E.*; et al.

Radiochimica Acta, 104(3), p.141 - 151, 2016/03

https://doi.org/10.1515/ract-2015-2445

Conditions of the production and decomposition of hexacarbonyl complexes of short-lived Mo and W isotopes were investigated to study thermal stability of the heaviest group 6 hexacarbonyl complex Sg(CO). A tubular flow reactor was tested to decompose the hexacarbonyl complexes and to extract the first bond dissociation energies. A silver was found to be the most appropriate reaction surface to study the decomposition of the group 6 hexacarbonyl. It was found that the surface temperature at which the decomposition occurred was correlated to the first bond dissociation energy of Mo(CO) and W(CO), indicating that the first bond dissociation energy of Sg(CO) could be determined with this technique.

An Attempt to select thermodynamic data and to evaluate the solubility of radioelements with uncertainty under HLW disposal conditions

Yamaguchi, Tetsuji; Takeda, Seiji; Nishimura, Yuki; Iida, Yoshihisa; Tanaka, Tadao

Radiochimica Acta, 102(11), p.999 - 1008, 2014/11

https://doi.org/10.1515/ract-2014-2248

http://www.degruyter.com/view/j/ract.2014.102.issue-11/ract-2014-2248/ract-2014-2248.xml?format=INT

An attempt was made to select thermodynamic data with uncertainties and to evaluate the solubility of radioelements with uncertainties considering variation in groundwater chemistry. The thermodynamic data was selected by reviewing the JAEA-TDB released in 2012. Data for Nb, Pd and Pa were revised from the viewpoint of the consistency of the data selection process. Data for Se, U and Pa were revised from the viewpoint of the conservativeness. Up-to-date ternary calcium-metal(IV)-OH complexes were adopted for Zr, Th, U, Np and Pu. A Monte Carlo-based probabilistic calculation code, PA-SOL, was used for probabilistic analysis of the solubility.

Thermodynamic model for the solubility of Ba(SeO, SO) precipitates

Rai, D.*; Felmy, A. R.*; Moore, D. A.*; Kitamura, Akira; Yoshikawa, Hideki; Doi, Reisuke; Yoshida, Yasushi*

Radiochimica Acta, 102(8), p.711 - 721, 2014/08

https://doi.org/10.1515/ract-2013-2207

The solubility of Ba(SeO, SO) precipitates was determined as a function of the BaSeO mole fractions, ranging from 0.0015 to 0.3830, and time with an equilibration period extending to as long as 302 days. Equilibrium/steady state conditions in this system are reached in 65 days. Pitzer's ion interaction model was used to calculate solid and aqueous phase activity coefficients. Thermodynamic analyses showed that the data do not satisfy Gibbs-Duhem equation, thereby demonstrating that a single-solid solution phase does not control both the selenate and sulfate concentrations. Our extensive data with [Ba], [SeO], and [SO] can be explained with the formation of an ideal BaSeO solid solution phase that controls the selenium concentrations and a slightly disordered/less-crystalline BaSO(s) that controls the sulfate concentrations. In these experiments the BaSO component of the solid solution phase never reaches thermodynamic equilibrium with the aqueous phase. Thermodynamic interpretations of the data show that both the ideal BaSeO solid solution phase and less-crystalline BaSO(s) phase are in equilibrium with each other in the entire range of BaSeO mole fractions investigated in this study.