Abstract The precise study of adsorption mechanisms at solid–liquid interfaces requires a good analysis of the surface heterogeneity of the studied solids. For that purpose, molecular probe technique is one of the most powerful, especially at solid–gas interfaces. Indeed, low-pressure gas adsorption coupled to modelling of derivative adsorption isotherms as a function of logarithm of pressure allows to study qualitatively and quantitatively the effect of surface heterogeneity on the energy distribution of adsorption centres. The present review points out the interests of that approach to determine the shape of particles, the presence of high-energy adsorption sites and the surface polarity. Results comparing adsorption at solid–gas and solid–liquid interfaces are also mentioned. To cite this article: F. Villiéras et al., C. R. Geoscience 334 (2002) 597–609.