Smectite suspensions, at low solids contents, are known to be naturally high in volume with diverse structural properties. The changing structural properties of smectite aqueous suspensions in the absence and presence of calcium ions were investigated using an acoustosizer and an advanced cryo-SEM technique to further understand and thereby control their environmental impact. In the absence of Ca(II) ions, smectite particles are present as a colloidally stable sol due to electrical double layer repulsion of the negatively charged platelets. The smectite network is observed to be extended throughout the suspension via clay platelets networking with an edge-edge (EE) orientation due to high basal surface repulsion. After the initial addition of Ca(II) ions, the smectite negative zeta potential reduces and the smectite platelets coagulate forming 2 mu m aggregates. The platelets are randomly orientated, lettuce-like, coagulated aggregates with a high presence of both edge-edge (EE) and edge-face (EF) orientations. After equilibration, the smectite platelets forming an orientated honeycomb cellular structure comprised of face-face (FF) multiply sheet aggregates. The voids in the cellular structure are larger than prior to Ca(II) addition, measured at 2-8 mu m. The changing structural properties of a smectite suspension in the absence and presence of Ca(II) greatly influence smectite stability and in turn, mineral processing and/or environmental management. Adequate time is required to allow suppression of the initial swelling of the smectite, full Ca(II) exchange and platelet aggregation. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.