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Nuclear field shift effect in isotope fractionation of thallium

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Abstract

Environmental transport of Tl is affected by redox reaction between Tl(I) and Tl(III) and ligand exchange reactions of them. In order to deepen the knowledge of Tl chemistry, we investigated fractionation of Tl stable isotopes (203Tl and 205Tl) in a chemical exchange system. Tl isotopes were fractionated in a liquid–liquid extraction system, in which aqueous and organic phases are hydrochloric acid solution and dichloroethane including a crown ether, respectively. After purification by ion-exchange chemistry, the isotope ratio of 205Tl/203Tl in equilibrated aqueous phase was measured precisely by multiple-collector–inductively-coupled-plasma–mass-spectrometry. A large isotope fractionation >1 ‰ was found. Electronic structures of possible Tl species (hydrated Tl+, Tl3+, and Tl chlorides) were calculated by ab initio methods, and the isotope fractionation factor was theoretically obtained. The isotope fractionation via intramolecular vibrations was calculated to be much smaller than the experimental result. The isotope fractionation via isotopic change in nuclear volume, named the nuclear field shift effect, was calculated to be >1 ‰ in Tl(I)–Tl(III) redox systems and/or ligand exchange systems of Tl(III). The nuclear field shift effect was found to be the major origin of Tl isotope fractionation.

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Acknowledgments

FM acknowledged the support of NASA COSMO #NNX12AH70G, EXO #NNX12AD88G, and ICARES Washington University in St. Louis. AA thanks Conseil Régional de Bretagne for the funding of MS work. MA thanks the Japan Society for the Promotion of Science for the funding of Grant-in-Aid for JSPS Fellows.

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Authors and Affiliations

  1. Research Reactor Institute, Kyoto University, 2-1010 Asashiro Nishi, Kumatori, Sennan, Osaka, 590-0494, Japan

    Toshiyuki Fujii, Akihiro Uehara & Hajimu Yamana

  2. Department of Earth and Planetary Sciences and McDonnell Center for Space Sciences, Washington University in St. Louis, Campus Box 1169, 1 Brookings Drive, Saint Louis, MO, 63130-4862, USA

    Frédéric Moynier

  3. UMR 6538, Domaines Océaniques, Institut Universitaire Européen de la Mer (IUEM), Place Nicolas Copernic, 29820, Plouzané, France

    Arnaud Agranier

  4. Laboratoire de Géochimie et Métallogénie, Département Géosciences Marines, IFREMER, Z.I. Pointe du diable, BP 70, 29280, Plouzané, France

    Emmanuel Ponzevera

  5. Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji-shi, Tokyo, 192-0397, Japan

    Minori Abe

Authors
  1. Toshiyuki Fujii
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  2. Frédéric Moynier
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  4. Emmanuel Ponzevera
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  5. Minori Abe
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  7. Hajimu Yamana
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Correspondence to Toshiyuki Fujii.

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Fujii, T., Moynier, F., Agranier, A. et al. Nuclear field shift effect in isotope fractionation of thallium. J Radioanal Nucl Chem 296, 261–265 (2013). https://doi.org/10.1007/s10967-012-2181-4

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  • DOI: https://doi.org/10.1007/s10967-012-2181-4

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