[en] Cementitious materials in radioactive waste repositories establish high pH which brings many benefits. The pH will change with time as the chemical constituents responsible for it are leached away. This has been simulated in the laboratory for a Sulphate Resisting Portland Cement (SRPC), a slag-modified cement composed of 90% Blast Furnace Slag (BFS) and 10% Ordinary Portland Cement (OPC) and an ash-modified cement containing 90% Pulverized Fuel Ash (PFA) and 10% OPC. They have been leached in demineralised water and a synthetic groundwater typical of a clay environment. Leachate analyses for a variety of elements showed that the leachate was not usually in equilibrium with any of the solid phases. Nevertheless the experimental evolution of pH was not too different from that predicted by assuming equilibrium and the predictions offer a means of estimating a lower bound for pH as it evolves in a real repository. The experiments with synthetic groundwater showed that the dominant effect influencing pH was precipitation of CaCO₃ from bicarbonates in the groundwater resulting in a reduction in both pH and buffer capacity. The ash-modified cement has particularly poor pH-buffering performance which is exacerbated in the groundwater. (author)