The montmorillonite is mostly bi-hydrated in basic and near-neutral conditions whereas it is mostly mono-hydrated at low pH. The transition from the bi-hydrated to the mono-hydrated state occurs through very heterogeneous structures. However, the proportion of the different layer types determined from XRD profile modelling and that derived from chemical modelling using Phreeqc2 code strictly coincide. This correlation shows that the hydration modification is induced by a H3O+-for-Ca2+ exchange at low pH, the two species being distributed in different interlayers. This layer-by-layer exchange process occurs randomly in the layer stack.
Under alkaline conditions, results from XRD profile modelling and from near infrared diffuse reflectance spectroscopy (NIR-DRS) clearly demonstrate that there is no CaOH+-for-Ca2+ exchange at high pH. The apparent increase in Ca sorption in smectite interlayers with increasing pH is thus probably related to the precipitation of Calcium-Silicate-Hydrate (CSH) phases, which also accounts for the decrease in Si concentration under high-pH conditions. This precipitation is thermodynamically favoured.