Exploring the governing transport mechanisms of corrosive agents in a Canadian deep geological repository.

All nuclear energy producing nations face a common challenge associated with the long-term solution for their used nuclear fuel. After decades of research, many nuclear safety agencies worldwide agree that deep geological repositories (DGRs) are appropriate long-term solutions to protect the biosphere. The Canadian DGR is planned in either stable crystalline or sedimentary host rock (depending on the final site location) to house the used nuclear fuel in copper-coated used fuel containers (UFCs) surrounded by highly compacted bentonite. The copper-coating and bentonite provide robust protection against many corrosion processes anticipated in the DGR. However, it is possible that bisulfide (HS-) produced near the host rock-bentonite interface may transport through the bentonite and corrode the UFCs during the DGR design life (i.e., one million years); although container performance assessments typically account for this process, while maintaining container integrity. Because the DGR design life far exceeds those of practical experimentation, there is a need for robust numerical models to forecast HS- transport. In this paper we present the development of a coupled 3D thermal-hydraulic-chemical model to explore the impact of key coupled physics on HS- transport in the proposed Canadian DGR. These simulations reveal that, although saturation delayed and heating accelerated HS- transport over the first 100s and 10,000s of years, respectively, these times of influence were small compared to the long DGR design life. Consequently, the influence from heating only increased total projected HS- corrosion by <20% and the influence from saturation had a negligible impact (<1%). By comparing the corrosion rate results with a simplified model, it was shown that nearly-steady DGR design parameters governed most of the projected HS- corrosion. Therefore, those parameters need to be carefully resolved to reliably forecast the extent of HS- corrosion.

Prediction of bacterial functional diversity in clay microcosms.

Microorganisms in clay barriers could affect the long-term performance of waste containers in future deep geological repositories (DGR) for used nuclear fuel through production of corrosive metabolites (e.g., sulfide), which is why clay materials are highly compacted: to reduce both physical space and access to water for microorganisms to grow. However, the highly compacted nature of clays and the resulting low activity or dormancy of microorganisms complicate the extraction of biomarkers (i.e., PLFA, DNA etc.) from such barriers for predictive analysis of microbial risks. In order to overcome these challenges, we have combined culture- and 16S rRNA gene amplicon sequencing-based approaches to describe the functional diversity of microorganisms in several commercial clay products, including two different samples of Wyoming type MX-80 bentonite (Batch 1 and Batch 2), the reference clay for a future Canadian DGR, and Avonlea type Canaprill, a clay sample for comparison. Microorganisms from as-received bentonites were enriched in anoxic 10% w/v clay microcosms for three months at ambient temperature with addition of 10% hydrogen along with presumable indigenous organics and sulfate in the clay. High-throughput sequencing of 16S rRNA gene fragments indicated a high abundance of Gram-positive bacteria of the phylum Firmicutes (82%) in MX-80 Batch 1 incubations. Bacterial libraries from microcosms with MX-80 Batch 2 were enriched with Firmicutes (53%) and Chloroflexi (43%). Firmicutes also significantly contributed (<15%) to the bacterial community in Canaprill clay microcosm, which was dominated by Gram-negative Proteobacteria (>70%). Sequence analysis revealed presence of the bacterial families Peptostreptococcaceae, Clostridiaceae, Peptococcaceae, Bacillaceae, Enterobacteriaceae, Veillonellaceae, Tissierellaceae and Planococcaceae in MX-80 Batch 1 incubations; Bacillaceae, along with unidentified bacteria of the phylum Chloroflexi, in MX-80 Batch 2 clay microcosms, and Pseudomonadaceae, Hydrogenophilaceae, Bacillaceae, Desulfobacteraceae, Desulfobulbaceae, Peptococcaceae, Pelobacteraceae, Alcaligenaceae, Rhodospirillaceae in Canaprill microcosms. Exploration of potential metabolic pathways in the bacterial communities from the clay microcosms suggested variable patterns of sulfur cycling in the different clays with the possible prevalence of bacterial sulfate-reduction in MX-80 bentonite, and probably successive sulfate-reduction/sulfur-oxidation reactions in Canaprill microcosms. Furthermore, analysis of potential metabolic pathways in the bentonite enrichments suggested that bacteria with acid-producing capabilities (i.e., fermenters and acetogens) together with sulfide-producing prokaryotes might perhaps contribute to corrosion risks in clay systems. However, the low activity or dormancy of microorganisms in highly compacted bentonites as a result of severe environmental constraints (e.g., low water activity and high swelling pressure in the confined bentonite) in situ would be expected to largely inhibit bacterial activity in highly compacted clay-based barriers in a future DGR.

Iron oxyhydroxide nanoparticles formed by forced hydrolysis: dependence of phase composition on solution concentration.

Nanoparticles of single-phase lepidocrocite (γ-FeOOH) and goethite (α-FeOOH) have been synthesized by forced hydrolysis of ferric nitrate with no other additives, and the particles have been characterized by XRD, FT-IR and TEM. At low Fe(NO(3))(3) concentrations the hydrolysis product is predominantly γ-FeOOH, while at high concentrations it is α-FeOOH. These particles are nanometers in size and fall within narrow particle size distributions. The dependence of the oxyhydoxide phase on ferric nitrate concentration is attributed to two thermodynamic factors, the enthalpy of formation and the surface enthalpy of hydration at the oxide-water interface (which is a function of surface area). Two potential mechanisms for the phase-specific growth are proposed that explain the solution concentration dependence of the phase formed. Three other common nanoscale particles (α-Fe(2)O(3), Fe(3)O(4) and γ-Fe(2)O(3)) have also been prepared by relatively simple thermal/chemical treatment of the γ-FeOOH nanoparticles.