Abstract Subglacial hyaloclastites from Iceland with ages ranging from 2 ka to 2.2 Ma have been studied from a mineralogical and geochemical standpoint. The chemical composition of palagonite (alteration crust formed on the surface of the glass) is almost identical with that of the clayey material filling the intergranular spaces of the rock. The clayey material is made up of two particle populations: the first is Si-, Mg- and Ca-rich with a smectite structure, while the second is amorphous, Fe−, Ti− and Al-rich, and has a smectite-like morphology. It is suggested that these two types of particles can be formed simultaneously, in the same solution, such that it is not necessary to explain their existence by local or temporary equilibria. The mineralogical sequences observed in natural samples were reproduced using the geochemical computer code DISSOL. The geochemical mass balances calculated with DISSOL also fit quite well with those calculated from Icelandic samples, illustrating the predictive capability of such a calculation code and gives us confidence in applying a similar approach to nuclear waste-form glass problems.