Fluctuation of redox conditions in radioactive waste disposal cell: characterisation of corrosion layers formed on archaeological analogues.

<title/> Oxygen trapped during the operational phase in disposal cells of an underground radioactive waste repository is often considered to be quickly consumed, notably by corrosion of metallic materials or reducing microorganisms. This would lead to anoxic conditions in most of each disposal cell. In addition to this, a shift from anoxic to oxic conditions could not be excluded locally in disposal cells after their closure due to the ventilation in handling drifts that could contribute to the regeneration of oxygen at the head of each disposal cell. The impact of these transient phases on corrosion processes may affect the confinement properties of metallic components and should thus be assessed. To this end, ferrous archaeological analogues are studied. The present paper focuses on the characterisation of nails that have undergone such transient phases. First, a sample exposed for several hundred years to an aerated environment and then to an anoxic carbonated environment in laboratory for 3 years has been analysed. Corrosion layers after the oxic phase contain mostly oxihydroxides (such as goethite) and some layers perpendicular or parallel to the interface, which is in good agreement with an aerated corrosion. After 3 years under anoxic conditions, the main phase of the corrosion layer is siderite. Second, a sample exposed to an anoxic environment for several hundred years has been immersed in an aerated solution for 5 weeks. The main phases of the corrosion layer after the anoxic phase are iron carbonates and a goethite layer formed on the outer part of the corrosion layer after the immersion in an aerated solution. In both cases, the formation of new phases in the corrosion layer is in good agreement with predictions of thermodynamic modelling based on the respective environmental conditions. [ABSTRACT FROM AUTHOR]