Mechanical compaction of smectite clays increases ion exchange selectivity for cesium

A key discussion in radioactive waste disposal is the question of whether adsorption behavior of radionuclides in dispersed and in highly compacted materials is similar. It is common practice to measure sorption data on dispersed systems and to use these data to predict the sorption in compacted systems. The latter represent the situation in a real, deep geological repository system. The discussions focus mainly on items such as the effect of compaction on the accessibility of sorption sites, that is, on sterical effects, and not on the effect of compaction on the thermodynamics of the sorption processes. Here we show that in the case of sorption of cesium on sodium bentonite, material compaction indeed affects the thermodynamics of the sorption process such that sorption increases. This increase is due to a reduction of the interlayer space, leading to a lower ability of the interlayer water for cation hydration. Cations with a low hydration tendency, such as cesium, therefore accumulate in the interlayer space, whereas highly hydrated cations such as sodium tends to accumulate in the bulk water where water is easily available for hydration. The fact that mechanical compaction affects the thermodynamics of ion exchange processes in clay is an important finding and brings in a new aspect in the discussion on the transferability of thermodynamic data from diluted to compacted systems. The common practice of applying chemical and thermodynamic concepts valid for diluted systems to compacted systems must be basically scrutinized.