Abstract

Smectite interlayer water plays a key role in the mobility of elements and molecules and affects a variety of geological processes. In trioctahedral smectites, in contrast to saponite and hectorite, the layer charge of which originates from isomorphic substitutions, the stevensite layer charge originates from the presence of octahedral vacancies. Despite its common occurrence in lacustrine environments, stevensite hydration has received little attention compared to saponite and hectorite. Early reports mention a specific hydration behaviour, however, with the systematic presence of a low-angle reflection attributed to the regular interstratification of various hydration states. The present study aims to revisit this specific hydration behaviour in more depth. Within this scope, the hydration behaviour of the three smectite varieties above are compared using synthetic trioctahedral smectites of similar layer charge and various compositions of their octahedral sheets. The chemical composition of the octahedral sheet does not appear to influence significantly smectite hydration for saponite and hectorite. Compared to its saponite and hectorite equivalents, H2O content in stevensite is lower by ~2.0 mmol H2O per g of dry clay. Consistent with this lower H2O content, Zn-stevensite lacks a stable monohydrated state, with dehydrated layers prevailing from 60% to 0% relative humidity. The presence of the regular interstratification of 0W and 1W layers is responsible for the low-angle reflection commonly observed for stevensite under air-dried conditions. Finally, the stevensite identification method based on X-ray diffraction of heated and ethylene glycol-solvated samples is challenged by the possible influence of the octahedral sheet chemical composition (Zn or Mg in the present study) on hectorite swelling behaviour in synthetic Zn-smectites. The origin of this effect remains undetermined and further work is needed to propose a more general identification method.

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