Characterization of natural organic matter in Wyoming-type bentonites irradiated at varied moisture levels

Wyoming-type bentonite clay (MX-80; Wyoming, USA) will be used in a deep geological repository (DGR) for the long-term storage of used nuclear fuel in Canada. The natural organic matter (NOM) found in bentonite may serve as a microbial nutrient source and potentially compromise the performance of the used fuel containers. Previous investigations indicate that NOM is present in low concentrations in MX-80 and has undergone extensive diagenetic alteration, though limited knowledge is available regarding NOM chemistry under simulated DGR conditions. Of particular concern is the possibility for gamma-radiation to alter NOM dissolution and reactivity due to the presence of reactive species generated by water radiolysis in Wyoming-type bentonites. In this study, NOM chemistry was investigated using complementary molecular-level techniques following exposure to a total gamma-radiation dose of 100 kGy (1.08 kGy/h for 93 h) at varied moisture levels (20%, 40%, 60% and 80%) and room temperature. Treated samples exhibited relatively low total organic carbon concentrations (0.074–0.232%), with no evidence of any major changes in total, organic, and inorganic carbon concentrations. Solid-state ¹³C NMR spectroscopy detected no changes in solid-phase NOM chemistry after irradiation. Solubilization of NOM increased significantly with radiation exposure at 80% moisture, suggesting higher levels of water saturation may enhance dissolved organic matter (DOM) production. Solution-state ¹H nuclear magnetic resonance (NMR), and UV–Vis analyses did not identify any significant differences in DOM composition. More sensitive, targeted compound analysis revealed significant decreases in total n-alkanol concentration at lower moisture content levels (20% and 40%). Several individual compound concentrations also differed significantly at the nanogram-level, including n-octacosanol and several n-alkanoic acids at elevated moisture levels (60% and 80%). These findings suggest the majority of NOM in MX-80 remains chemically stable under the anticipated initial conditions of the proposed DGR.