Chemistry of the Interaction and Retention of TcVII and TcIV Species at the Fe3O4(001) Surface

The pertechnetate ion TcVIIO4- is a nuclear fission product whose major issue is the high mobility in the environment. Experimentally, it is well known that Fe3O4 can reduce TcVIIO4- to TcIV species and retain such products quickly and completely, but the exact nature of the redox process and products is not completely understood. Therefore, we investigated the chemistry of TcVIIO4 - and TcIV species at the Fe3O4(001) surface through a hybrid DFT functional (HSE06) method. We studied a possible initiation step of the TcVII reduction process. The interaction of the TcVIIO4- ion with the magnetite surface leads to the formation of a reduced TcVI species without any change in the Tc coordination sphere through an electron transfer that is favored by the magnetite surfaces with a higher FeII content. Furthermore, we explored various model structures for the immobilized TcIV final products. TcIV can be incorporated into a subsurface octahedral site or adsorbed on the surface in the form of TcIVO2 center dot xH2O chains. We propose and discuss three model structures for the adsorbed TcIVO2 center dot 2H2O chains in terms of relative energies and simulated EXAFS spectra. Our results suggest that the periodicity of the Fe3O4(001) surface matches that of the TcO2 center dot 2H2O chains. The EXAFS analysis suggests that, in experiments, TcO2 center dot xH2O chains were probably not formed as an inner-shell adsorption complex with the Fe3O4(001) surface.