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The Canadian deep geological repository (DGR) design consists of copper coated used fuel containers (UFCs) placed within a highly compacted bentonite (HCB) buffer surrounded by a suitable host rock. Although the copper is thermodynamically stable in oxygen-free environments, it is potentially susceptible to microbiologically influenced corrosion from bisulfide (HS-). Therefore, understanding HS- corrosion is important to ensure long-term performance of UFCs. Various reactions in the bentonite barrier of the DGR can affect HS- transport through the HCB and therefore the extent of copper corrosion caused by HS-. Since HS- transport and reactive processes are interconnected, numerical models are required to assess the complex HS- reactive transport dynamics and quantify the influence of reactive processes on HS- transport and corrosion. In this paper, various HS- transport models were coupled with (i) a key geochemical reaction between HS- and iron (i.e., simulating HS- retardation due to iron sulfide formation) or (ii) HS- adsorption. Since HS- is an anion, anion exclusion was also explored. Valuable insight was obtained through validation, comparison, and sensitivity analyses of these models. A comparison between experimental and modelled HS- transport dynamics showed that HS- is being retained by the bentonite due to reactive processes and anion exclusion is occurring. Lastly, HS- transport was simulated for the entire DGR lifespan and was found to be delayed (≈50–800 years) due to FeS formation or HS- adsorption. However, these predicted HS- diffusion delays are relatively short in a DGR lifespan (i.e., 1 million years) and do not impact long-term HS- corrosion.

The disposal of high-level radioactive waste (HLW) and spent nuclear fuel (SF) presents a unique challenge for the prediction of the long-term performance of corrodible structures since the HLW/SF canisters are expected, in some cases, to have lifetimes of one million years or longer. Various empirical and deterministic models have been developed over the past 45 years for making predictions of the long-term corrosion behaviour, including models for uniform and localized corrosion, environmentally assisted cracking and microbiologically influenced corrosion. As well as process models focused on specific corrosion mechanisms (described in Part 1 of this review), there is also a need for performance assessment models as part of the overall analysis of the safety of a deep geological repository (DGR). Performance assessment models are often based on simplified or abstracted process models. The manner in which various international waste management programs have predicted the long-term performance of HLW/SF containers with copper, steel, Ni and Ti alloy corrosion barriers is discussed. Performance assessments are repeated periodically during the development and implementation of a DGR, and the corrosion models are constantly updated in light of new mechanistic understanding and/or more information about the deep geological environment. Two examples of how the container performance assessment models evolve over time are also described. Performance assessment models cannot easily be validated, so it is important to build confidence in the long-term predictions using other methods, including natural analogues and large-scale in situ tests and the use of complementary models.

The disposal of high-level radioactive waste (HLW) and spent nuclear fuel (SF) presents a unique challenge for the prediction of the long-term performance of corrodible structures since HLW/SF containers are expected, in some cases, to have lifetimes of one million years or longer. Various empirical and deterministic models have been developed over the past 45 years for making predictions of long-term corrosion behaviour, including models for uniform and localised corrosion, environmentally assisted cracking, microbiologically influenced corrosion, and radiation-induced corrosion. More recently, fracture-mechanics-based approaches have been developed to account for joint mechanical–corrosion degradation modes. Regardless of whether empirical or deterministic models are used, it is essential to be able to demonstrate a thorough mechanistic understanding of the corrosion processes involved. In addition to process models focused on specific corrosion mechanisms, there is also a need for performance-assessment models as part of the overall demonstration of the safety of a deep geological repository. Performance-assessment models are discussed in Part 2 of this review.

Radiation induced corrosion is one of the possible modes of materials degradation in the concept of long-term management of used nuclear fuel. Depending on the environmental conditions surrounding the used fuel container, a range of radiolysis products are expected to form that could impact the corrosion of the copper coating. For instance, γ-radiolysis of pure water produces molecular oxidants such as H2O2 and the radiolysis of humid air produces compounds such as NOx and HNO3. This review is confined to a discussion of the effect of γ-radiation on the corrosion of copper-coated containers. A simplified mixed-potential model is also presented to calculate the extent of copper corrosion by using the steady-state concentration of H2O2 generated during the first 300 years of emplacement, when the radiation field is significant.