Applying laboratory methods for durability assessment of vitrified material to archaeological samples

Laboratory testing used to assess the long-term chemical durability of nuclear waste forms may not be applicable to disposal because the accelerated conditions may not represent disposal conditions. To address this, we examine the corrosion of vitrified archeological materials excavated from the near surface of a ~1500-year old Iron Age Swedish hillfort, Broborg, as an analog for the disposal of vitrified nuclear waste. We compare characterized site samples with corrosion characteristics generated by standard laboratory durability test methods including the product consistency test (PCT), the vapor hydration test (VHT), and the EPA Method 1313 test. Results show that the surficial layer of the Broborg samples resulting from VHT displays some similarities to the morphology of the surficial layer formed over longer timescales in the environment. This work provides improved understanding of long-term glass corrosion behavior in terms of the thickness, morphology, and chemistry of the surficial features that are formed.

On Alteration Rate Renewal Stage of Nuclear Waste Glass Corrosion

The three generically accepted stages of glass corrosion are reviewed with focus on final stage termed alteration rate renewal (or resumption) stage when the glass may re-start corroding with the rate similar to that at the initial stage. It is emphasized that physical state and physical changes that occur in the near-surface layers can readily lead to an effective increase of leaching rate which is similar to alteration rate renewals. Experimental data on long-term (during few decades) corrosion of radioactive borosilicate glass K26 designed to immobilize high-sodium operational NPP radioactive waste evidence on resumption-like effects of radionuclides (137,134Cs) leaching. The cause of that was however related not to chemical changes in the leaching environment but rather to physical state of glass surface due to formation of small cracks and new pristine glass areas in contact with water.

In situ nuclear-glass corrosion under geological repository conditions

Silicate glasses are durable materials but laboratory experiments reveal that elements that derive from their environment may induce high corrosion rates and reduce their capacity to confine high-level radioactive waste. This study investigates nuclear-glass corrosion in geological media using an in situ diffusion experiment and multi-component diffusion modelling. The model highlights that the pH imposed by the Callovo–Oxfordian (COx) claystone host rock supports secondary-phase precipitation and increases glass corrosion compared with pure water. Elements from the COx rock (mainly Mg and Fe) form secondary phases with Si provided by the glass, which delay the establishment of a passivating interface. The presence of elements (Mg and Fe) that sustain glass alteration does not prevent a significant decrease in the glass-alteration rate, mainly due to the limited species transport that drives system reactivity. These improvements in the understanding of glass corrosion in its environment provide further insights for predictive modelling over larger timescales and space.