Analysis of natural organic matter chemistry in bentonite clay under compaction using different dry densities and duration

The Nuclear Waste Management Organization of Canada has adopted an adaptive phased management plan for the long-term storage of used nuclear fuel in a Deep Geological Repository (DGR). The DGR barrier system employs copper-coated used fuel containers (UFCs) surrounded by buffer material which is composed of highly compacted bentonite clay. The natural organic matter (NOM) composition of the compacted bentonite is of practical importance for the safety assessment as it regulates the biogeochemical processes at the interface between the UFCs and the buffer layer. However, insufficient investigations on NOM constituents limits the understanding of biogeochemical dynamics in bentonites compacted under different dry densities. This study analyzed the carbon content and NOM composition using targeted compound analysis and solid-state C-13 nuclear magnetic resonance (NMR) spectroscopy with bentonites compacted at 1.1, 1.4 or 1.6 g/cm(3) dry density for 1, 3, 6, 12 or 18 months. Organic carbon contents were similar across bentonites with different compaction densities at various durations as compared to the reference clay (powdered bentonite sample before compaction). The overall NOM composition measured by solid-state C-13 NMR suggested a predominance of alkyl and aromatic carbon in bentonite samples. No marked variations were observed for the NOM components (i.e., alkyl, O-alkyl and aromatic carbon) between the compacted bentonites and the reference clay. Targeted compound analysis revealed that the extractable lipid concentrations in the compacted clays did not significantly vary from the reference bentonite with only some compounds exhibiting nano-gram level differences. Bentonites with relatively lower dry densities (1.1 and 1.4 g/cm(3)) demonstrated slightly higher extractable compound concentrations, but these differences were not statistically significant. In contrast, the compound concentrations of bentonites compacted to 1.6 g/cm(3) were similar or slightly lower compared with the reference bentonite, likely associated with limited microbial growth under high dry compaction density. Taken together, these results suggested that NOM composition and quantity did not significantly alter in bentonites under various pressures nor with longer experimental durations. These findings highlight that compacted bentonite exhibited geochemical stability under the simulated repository environments, which provides critical insight for design and performance of engineered barrier system in a DGR concept.