The Radiation Induced Chemistry of the Uranyl Cation in Carbonate –Bicarbonate Solutions as Followed by NMR Spectroscopy


Hydrogen peroxide formed by radiolysis of carbonate –bicarbonate media was followed by 13C NMR using dissolved [233UO2(13CO3)3]4- as the alpha source (Dα=12.1 Gy/hr). It is shown that the speciation of the peroxide carbonates (or other species) that are formed in the pH region 5.9 and 11.6 by titration with hydrogen peroxide are common to those formed by hydrogen peroxide generated by radiolysis. Radiolytic generation of hydrogen peroxide was followed by observing the formation of a uranyl peroxide carbonate complex. Complex formation was observed to accelerate for about 1200 hours and to terminate between 1×10-4 and 5×10-4 M. It is assumed that either a steady state H2O2 production rate was established in solution or that some limiting feature of the experiment was responsible for slowing the yield of product.

This is a preview of subscription content, access via your institution.


  1. 1.

    D. Wronkiewicz, E. Buck, Uranium Mineralogy and the Geologic Disposal of Spent Nuclear Fuel, in Uranium: Minerology, Geochemistry and the Environment, Volume 38 P. C. Burns & R. Finch, Eds, Mineralogical Society of America, 2005.

    Google Scholar 

  2. 2.

    B. K. McNamara, E. C. Buck, B. D. Hanson : Mater. Res. Soc.Symp. Proc., 757, 401 (2003).

    CAS  Google Scholar 

  3. 3.

    G. Sattonnay ., C. Ardois, C. Corbel, J. F. Lucchioni, M. F. Barthe, F. Garrido, D. Gosset, J. Nucl. Mater. 288, 11 (2001).

    CAS  Article  Google Scholar 

  4. 4.

    K. A. H. Kubatko, K. B. Helean, P. C. Burns, Science, 302, 1191–1193, 2003.

    Article  Google Scholar 

  5. 5.

    P. K. Glasoe, F. A. Long, J. Phys. Chem., 64, 188 (1960).

    CAS  Article  Google Scholar 

  6. 6.

    G. H. Jeffery, J. Bassett, J. Mendham, R. C. Denney, Vogel’s Textbook of Quantitative Chemical Analysis, 5th Edition, Longman Group UK Limited, Essex CM20 2JE, England, Page 372, 1989.

    Google Scholar 

  7. 7.

    P. G. Allen, J. J. Bucher, D. L. Clark, N. M. Edelstein, S. A. Ekberg, J. W. Gohdes, E. A. Hudson, N. Kaltsoyannis, W. W. Lukens, M. P. Neu, P. D. Palmer, T. Reich, D. K. Shuh, C. D. Tait, and B. D. Zwick, Inorg. Chem., 34, 4797–4807 (1997).

    Article  Google Scholar 

  8. 8.

    M. E. Thompson, K. L. Nash, J. C. Sullivan, Isr. J. Chem., 25 (2) 155 (1985).

    CAS  Article  Google Scholar 

  9. 9.

    R. A. Zehnder, S. M. Peper, B. L. Scott, W. H. Runde, Acta Cryst., C61, i3 (2005).

    Google Scholar 

  10. 10.

    Z. Cai, X. Li, Y. Katsumura, O. Urabe, Nuclear Technology, 136, 231 (2001).

    CAS  Article  Google Scholar 

Download references

Author information



Corresponding author

Correspondence to Bruce McNamara.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

McNamara, B., Snow, L., Soderquist, C. et al. The Radiation Induced Chemistry of the Uranyl Cation in Carbonate –Bicarbonate Solutions as Followed by NMR Spectroscopy. MRS Online Proceedings Library 893, 8930807 (2005).

Download citation