Hostname: page-component-cd9895bd7-lnqnp Total loading time: 0 Render date: 2024-12-27T02:39:35.223Z Has data issue: false hasContentIssue false
  • English
  • Français

Perrhenate and Pertechnetate Behavior on Iron and Sulfur-Bearing Compounds

Published online by Cambridge University Press:  19 October 2011

B. Elizabeth Anderson ,
U. Becker ,
K. B. Helean  and
R. C. Ewing
B. Elizabeth Anderson
Affiliation:
[email protected], University of Michigan, Geological Sciences, 2534 C. C. Little Building, 1100 North University Ave, Ann Arbor, 48109-1005, Virgin Islands (U.S.), 337 212 9256, 734 763 4690
U. Becker
Affiliation:
[email protected], University of Michigan, Geological Sciences, 2534 C. C. Little Building, 1100 North University Ave, Ann Arbor, MI, 48109-1005, United States
K. B. Helean
Affiliation:
[email protected], Sandia National Laboratories, Albuquerque, NM, 87123, United States
R. C. Ewing
Affiliation:
[email protected], University of Michigan, Geological Sciences, Material Science, and Nuclear Engineering, Ann Arbor, MI, 49109, United States
Get access

Abstract

Investigations on the behavior of the radioactive element technetium frequently use a stable isotope of rhenium as an analogue. This is justified by citing the elements' similar radii, major oxidation states of +7 and +4, and eH-pH diagrams. However, recent studies (e.g.,[1] have shown this analogy to be imperfect. Therefore, one goal of our study is to compare the behavior of these elements with emphasis on the adsorption of perrhenate and pertechnetate (the major forms of Re and Tc in natural waters) on mineral surfaces.

Quantum mechanical calculations were performed on the adsorption of these two anions on relaxed clusters of the well-characterized sulfide galena (PbS) and some other Fe and S-bearing materials. With these calculations, we gain insight into differences between the anions' adsorption behavior, including geometry, adsorption energies, and electronic structure. Differences between interactions on terraces and step edges, the effects of co-adsorbates such as Na+ and Cl-, and chloride complexation are also explored. The influence of water was calculated using homogeneous dielectric fluids.

As a complement to the calculations, batch sorption tests are in progress involving ReO4-/TcO4- solution in contact with Fe metal, 10% Fe-doped hydroxyapatite, goethite, hematite, magnetite, pyrite, galena, and sphalerite.

Keywords

ReSelectronic structure
Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 985: Symposium NN – Scientific Basis for Nuclear Waste Management XXX , 2006 , 0985-NN12-09
Copyright
Copyright © Materials Research Society 2007

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1. Wharton, M. J., Atkins, B., Charnock, J. M., Livens, F. R., Pattrick, R. A. D., and Collison, D., “An X-ray absorption spectroscopy study of the coprecipitation of Tc and Re with mackinawite (FeS),” Applied Geochemistry, vol.15, pp. 347–354, 2000.Google Scholar
2. Brookins, D. G., “Rhenium as analog for fissiogenic technetium: Eh-pH diagram (25degC a bar) constraints,” Applied Geochemistry, vol.1, pp. 513–517, 1986.Google Scholar
3. Darab, J. G. and Smith, P. A., “Chemistry of technetium and rhenium species during low-level radioactive waste vitrification,” Chemistry of Materials, vol.8, pp. 1004–1021, 1996.Google Scholar
4. Muller, O., White, W. B., and Roy, R., “Crystal Chemistry of Some Technetium-Containing Oxides,” Journal of Inorganic & Nuclear Chemistry, vol.26, pp. 2075–2086, 1964.Google Scholar
5. Colton, R., “Technetium Chlorides,” Nature, vol.193, pp. 872-&, 1962.Google Scholar
6. Volkovich, V. A., May, I., Charnock, J. M., and Lewin, B., “Reactions and speciation of technetium and rhenium in chloride melts: a spectroscopy study,” Physical Chemistry Chemical Physics, vol.4, pp. 5753–5760, 2002.Google Scholar
7. Cataldo, D. A., Wildung, R. E., and Garland, T. R., “Root Absorption and Transport Behavior of Technetium in Soybean,” Plant Physiology, vol.73, pp. 849–852, 1983.Google Scholar
8. Ishii, N., Tagami, K., and Uchida, S., “Physicochemical forms of technetium in surface water covering paddy and upland fields,” Chemosphere, vol.57, pp. 953–959, 2004.Google Scholar
9. Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., M., J. A. Jr, Vreven, T., Kudin, K. N., Burant, J. C., Millam, J. M., Iyengar, S. S., Tomasi, J., Barone, V., Mennucci, B., Cossi, M., Scalman, G., Rega, N., Petersson, G. A., Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J. E., Hratchian, H. P., Cross, J. B., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E., Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Ayala, P. Y., Morokuma, K., Voth, G. A., Salvador, P., etc., “Gaussian 03, Revision C.02.” Wallingford CT: Gaussian, Inc, 2004.Google Scholar
10. Becker, U., Greatbanks, S. P., Rosso, K. M., Hillier, I. H., and Vaughan, D. J., “An embedding approach for the calculation of STM images: Method development and application to galena (PbS),” Journal of Chemical Physics, vol.107, pp. 7537–7542, 1997.Google Scholar
11. Wadt, W. R. and Hay, P. J., “Abinitio Effective Core Potentials for Molecular Calculations -Potentials for Main Group Elements Na to Bi,” Journal of Chemical Physics, vol.82, pp. 284–298, 1985.Google Scholar
12. Check, C. E., Faust, T. O., Bailey, J. M., Wright, B. J., Gilbert, T. M., and Sunderlin, L. S., “Addition of polarization and diffuse functions to the LANL2DZ basis set for p-block elements,” Journal of Physical Chemistry A, vol.105, pp. 8111–8116, 2001.Google Scholar
13. Rashin, A. A. and Honig, B., “Reevaluation of the Born Model of Ion Hydration,” Journal of Physical Chemistry, vol.89, pp. 5588–5593, 1985.Google Scholar
14. Said, B. K., Fattahi, M., Musikas, C., Revel, R., and Abbe, J. C., “The speciation of Tc(IV) in chloride solutions,” Radiochimica Acta, vol.88, pp. 567–571, 2000.Google Scholar
15. Zhang, P. C., Krumhansl, J. L., and Brady, P. V., “Boehmite sorbs perrhenate and pertechnetate,” Radiochimica Acta, vol.88, pp. 369–373, 2000.Google Scholar