Publikationsrepositorium - Helmholtz-Zentrum Dresden-Rossendorf

A combined approach of optical spectroscopic techniques, such as vibrational and luminescence spectroscopy, classical batch sorption studies and Surface Complexation Modeling (SCM) was applied for the study of the surface speciation of U(VI) and Se(VI/IV) at aqueous-mineral interfaces. In the present study, different single oxides are considered as models for complex natu-rally occurring minerals in a host rock of a nuclear waste repository.
For the ternary sorption system, U(VI)/phosphate/SiO₂, the formation of two binary uranyl surface species was derived from spectroscopic findings irrespective of the presence or absence of phosphate. Additionally, the formation of a phosphate phase precipitate was observed with increasing exposure time. Based on these results, we were able to satisfactorily fit the respective batch results by SCM.[1] For the sorption of selenium(IV) or selenium(VI) on alumina phases, a single predominant inner-sphere selenite and outer-sphere selenate surface species were identi-fied by vibrational spectroscopy. With respect to the bidentate binding mode observed for both oxyanionic surface species, SCM provided excellent fitting results of the batch sorption data.[2,3] Moreover, the final model proposed in our study was used to predict data obtained from a literature survey of recently published batch data related to the Se(VI)/γ-Al₂O₃ binary system. It could be shown that our model is quite capable of predicting literature data collected in the same background electrolyte.[2]
The results of this study demonstrated that the combined approach of in situ spectroscopy and batch sorption studies contributes to an improved performance of future assessments for the mi-gration of radionuclides and fission products in the environment of a repository site.

Ref.:

[1] Comarmond, M. J. et al. (2016) Environ. Sci. Technol. 50, 11610-11618.
[2] Jordan, N. et al. (2018) Environ.-Sci. Nano, in press, DOI: 10.1039/C8EN00293B.
[3] Mayordomo, N. et al. (2018) Environ. Sci. Technol. 52, 581-588.