Modelling iron–clay interactions in deep geological disposal conditions

Abstract

In the context of deep geological disposal of high level radioactive wastes, the interactions between iron and clay-rich materials may lead to adverse transformations of clay minerals with a potential loss of confining properties such as swelling and capacity to exchange cations. Such transformations have been experimentally observed at temperatures starting at ca. 80 °C, where smectites contained in a mixture of bentonite and iron powder are transformed into iron-rich serpentine-type minerals. The reaction-transport code CRUNCH is used to investigate the iron–clay interactions at 50 °C over a period of 10,000 years, which are the conditions considered here to represent the mean temperature value and the expected timescale for the corrosion stage. The aim is to predict the nature and quantity of corrosion product, calculate the chemistry of water (essentially the pH) and the mineralogical transformation in the system containing the canister, an optional engineered barrier (bentonite) and the host-rock (argillite). The results of the calculations show that at the interface with the canister, where steel corrosion occurs, the iron is partly immobilized by the precipitation of iron oxides (essentially magnetite) and small amounts of siderite. The pH stabilizes at high values, between 10 and 11, at this location. In the bentonite or the argillite in contact with the container, the primary clay minerals are destabilized and iron-rich serpentine-like minerals precipitate as observed in the experiments (cronstedtite and berthierine). These minerals show low cation exchange and swelling capacities. The results also show that the interactions between iron and clay may lead to significant porosity changes in the system. A reduction of the porosity is predicted at the surface of the steel canister, due to the precipitation of iron oxides. Porosity increase is predicted in the clay material due to the dissolution of the primary clay minerals. The effect of these porosity changes have yet to be observed experimentally and assessed with regard to the confinement capability of the repository near field, especially by considering the mechanical aspects in the case with and without the engineered barrier.