Stability of Th(IV) polymers measured by electrospray mass spectrometry and laser-induced breakdown detection

  • Clemens WaltherEmail author
  • Markus Fuss
  • Sebastian Büchner
  • Horst Geckeis


The formation of polynuclear thorium hydroxide complexes in acidic aqueous solutions is observed by electrospray mass spectrometry. Size, number of hydroxide ligands and charge of all complexes in solution are identified independently. By repeated measurements over a time span of up to 418 days the stability of the polymers is observed. At concentrations above [Th(IV)]tot = 10 mM pentamers and dimers are the dominant stable species. In contrast, the fractions of pentamers initially present at [Th(IV)]tot = 0.2 mM decrease within less than 4 weeks, correlated with the formation of nm-sized colloids observed by LIBD indicating an Ostwald-ripening like process.


Thorium Polymerization Colloid Electrospray Laser-induced breakdown detection 



We thank Marcus Altmaier (INE) for preparation of the stock solution and, together with Volker Neck, for many fruitful discussions. We also thank Oliver Schwindt for LIBD and the INE analytics group for ICP MS measurements. Finally, we acknowledge financial support by the “Programm Nuklear” and by the “Helmholtz Russia Joint Research Group” of the Helmholtz Gemeinschaft Deutscher Forschungszentren (HGF).


  1. 1.
    Choppin GR (2007) J Radioanal Nucl Chem 273:695CrossRefGoogle Scholar
  2. 2.
    Johnson GL, Toth LM (1978) In Report ORNL/Oak Ridge National Laboratory, TennesseeGoogle Scholar
  3. 3.
    Wickleder M, Fourest B, Dorhout P (2006) In: Morss LR, Edelstein NM, Fuger J, Katz JJ (eds) The chemistry of actinide and transactinide elements. Springer, Berlin, p 117Google Scholar
  4. 4.
    Rand MH, Fuger J, Grenthe I, Neck V, Rai D (2008) Chemical thermodynamics of thorium. In: Mompean F, Perrone MIJ (eds) OECD nuclear energy agency, data bank. Elsevier, North-Holland, AmsterdamGoogle Scholar
  5. 5.
    Moll H, Denecke MA, Jalilehvand F, Sandstrom M, Grenthe I (1999) Inorg Chem 38:1795CrossRefGoogle Scholar
  6. 6.
    Rothe J, Denecke MA, Neck V, Müller R, Kim JI (2002) Inorg Chem 41:249CrossRefGoogle Scholar
  7. 7.
    Baes CF Jr, Meyer NJ, Roberts CE (1965) Inorg Chem 5:518CrossRefGoogle Scholar
  8. 8.
    Neck V, Kim JI (2001) Radiochim Acta 89:1CrossRefGoogle Scholar
  9. 9.
    Johannson G (1968) Acta Chem Scand 22:389CrossRefGoogle Scholar
  10. 10.
    Johannson G (1968) Acta Chem Scand 22:399CrossRefGoogle Scholar
  11. 11.
    Wilson RE, Skanthakumar S, Sigmon G, Burns PC, Soderholm L (2007) Inorg Chem 46:2368CrossRefGoogle Scholar
  12. 12.
    Bundschuh T, Knopp R, Müller R, Kim JI, Neck V, Fanghänel T (2000) Radiochim Acta 88:625CrossRefGoogle Scholar
  13. 13.
    Neck V, Müller R, Bouby M, Altmaier M, Rothe J, Denecke MA, Kim JI (2002) Radiochim Acta 90:485CrossRefGoogle Scholar
  14. 14.
    Bitea C, Müller R, Neck V, Walther C, Kim JI (2003) Colloid Surf A 217:63CrossRefGoogle Scholar
  15. 15.
    Katz JJ (1986) Chemistry of the actinide elements. Chapman and Hall, LondonGoogle Scholar
  16. 16.
    Fanghänel T, Neck V (2002) Pure Appl Chem 74:1895CrossRefGoogle Scholar
  17. 17.
    Moulin C, Amekraz B, Hubert S, Moulin V (2001) Anal Chim Acta 441:269CrossRefGoogle Scholar
  18. 18.
    Walther C, Fuss M, Büchner S (2008) Radiochim Acta 96:411CrossRefGoogle Scholar
  19. 19.
    Hietanen S, Sillen LG (1959) Acta Chem Scand 13:533CrossRefGoogle Scholar
  20. 20.
    Walther C, Rothe J, Fuss M, Büchner S, Koltsov S, Bergmann T (2007) Anal Bioanal Chem 388:409CrossRefGoogle Scholar
  21. 21.
    Wilm M, Mann M (1996) Anal Chem 68:1CrossRefGoogle Scholar
  22. 22.
    Kitamori T, Matsui T, Sakagami M (1989) Chem Lett 89:2205CrossRefGoogle Scholar
  23. 23.
    Kim JI, Walther C (2007) In: Lead J, Wilkinson K (eds) Environmental colloids and particles: behaviour, separation and characterisation. Wiley, West Sussex, p 555Google Scholar
  24. 24.
    Walther C, Büchner S, Filella M, Chanudet V (2006) J Colloid Interface Sci 301:532CrossRefGoogle Scholar
  25. 25.
    Ostwald W (1896) Lehrbuch der Allgemeinen Chemie. Leipzig, GermanyGoogle Scholar
  26. 26.
    Nabivanets BI, Kudritskaya LN (1964) Ukr Khim Zh 30:891Google Scholar
  27. 27.
    Ryan JL, Rai D (1987) Inorg Chem 26:4140CrossRefGoogle Scholar
  28. 28.
    Rai D, Moore DA, Oakes CS, Yui M (2000) Radiochim Acta 88:297CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2009

Authors and Affiliations

  • Clemens Walther
    • 1
    Email author
  • Markus Fuss
    • 1
  • Sebastian Büchner
    • 1
  • Horst Geckeis
    • 1
  1. 1.Institute for Nuclear Waste Disposal, Forschungszentrum KarlsruheKarlsruheGermany

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