Three-dimensional magnetic resonance imaging (MRI) and micro-computed X-ray tomography (micro-CXT) have been combined to study the entrapment of mercury within nanoporous silica materials following porosimetry. MR images have been used to construct structural models of particular porous media within which several simulations of mercury intrusion and retraction have been performed with variations in the mechanism for the 'snap-off' of the mercury menisci. The simulations gave rise to different predictions for the pattern of the macroscopic (> 10 mu m) spatial distribution of entrapped mercury, depending on 'snap-off' mechanism, which were then compared with corresponding experimental data obtained from micro-CXT images of real pellets containing entrapped mercury. The information obtained from the micro-CXT images, and also from the porosimetry curves themselves, was then used to constrain a model for the microscopic mercury retraction mechanism. Additional predictions of the retraction model were then subsequently confirmed using scanning loop experiments. The simulations showed that the overall level of entrapment of mercury was determined by the close interaction between the pellet macroscopic structure (particularly pore size spatial correlation), and the microscopic mercury retraction mechanism. Hence, it was subsequently possible to explain fully why high mercury entrapment occurred within one particular type of sol-gel silica material, while only low entrapment occurred in another batch of superficially similar material. (c) 2006 Elsevier Ltd. All rights reserved.