Characterization of a redox-modified clay mineral with respect to its suitability as a barrier in radioactive waste confinement

Engineered barriers for high-level nuclear waste (HLW) consist of excavated repositories in sub-surface rock formations where canisters holding the radionuclide are stored. Clay minerals, particularly the swelling 2:1 types, are used as backfill material, both in the canisters and in the bore hole, in order to prevent radionuclide transport to surrounding groundwater. One of the most important risks that can occur is the corrosion of the canister, which could be coupled with reduction of iron (Fe) in the clay structure. Such changes could greatly decrease the long-term stability of the clay and, consequently, of the barriers themselves. In order to test the potential effects of such redox interactions, an Fe-bearing clay mineral from a commercial source located in the Kutch region, India, was selected for study. This particular mineral is one of the candidate clay minerals to serve as such a barrier material, and is the one with the largest structural Fe content. Results from it should, therefore, provide maximum insight into the potential effects of redox interactions between the barrier and its surroundings. The unaltered clay was characterized by X-ray powder diffractometry (XRD), thermal gravimetric analysis (TGA/DTGA), Fourier-transform infrared (FTIR) spectroscopy, and variable-temperature Mössbauer spectroscopy. The chemically reduced and reoxidized forms of the clay were characterized by variable-temperature Mössbauer spectroscopy and chemical analysis. In the unaltered state the clay is comprised of smectite, maghemite, superparamagnetic goethite, and hematite, with a possible trace of kaolinite. In the reduced state the Fe (oxyhydr)oxides were dissolved. Upon reoxidation no six-line pattern was observed, indicating that the Fe remained only in the structure of the silicates. The final structure of the reduced–reoxidized clay contained more defects than the original clay, as revealed by greater quadrupole splitting values for structural Fe(III) in the clay. These findings indicate that upon exposure to natural redox cycles the Kutch clay could undergo permanent changes in its mineralogical composition and clay mineral structure, but further study is required to ascertain the effects that such changes would have on its long-term stability as a barrier material.