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Geoenvironmental concerns involve unsaturated soils in problems like soil contamination, waste disposal and ground-atmosphere interactions. This paper deals with the two first points. To tackle geoenvironmental problems in unsaturated soils, it is necessary to identify experimentally the retention and transfer phenomena that govern the movements of fluids and chemical species in the unsaturated soil. Some of the experimental techniques used in unsaturated soils can be adapted to face these problems, but extensions accounting for the various physico-chemical processes involved in soil contamination and waste disposal are necessary, including temperature effects and the mechanical couplings resulting from the changes in temperature and chemical concentrations. After an introduction to the geoenvironmental problems that are related to unsaturated soils, the paper presents a series of experimental developments carried out in relation to retention and transfer properties of water (pure or with dissolved species), hydrocarbons and gas, also accounting for temperature effects and chemical effects. The techniques presented are applicable to soil contamination and waste disposal, with a special concern addressed to nuclear waste disposal, in which the effects of desaturation of the geological barrier together with the unsaturated nature of compacted engineered barriers appeared to be quite important.