Soil solution and free-flowing soilwater were sampled at various depths for 3 years in a plot of holm oak (Quercus ilex L.) in the Montseny mountains (NE Spain). The soil solution retained at -65M kPa in the mineral soil at depths of 20 and 40 cm had a different chemistry from that of throughflow under the humic layer (H-layer throughflow) and, to a lesser extent, from deep subsurface flow. The dominant mobile anion in the soil solution and the deep flow was SO42-, whereas in the H-layer, SO42- was overridden by alkalinity. H-Layer throughflow chemistry was extremely variable, in consequence of the large number of biogeochemical processes affecting it (e.g. rainfall chemistry, dry deposition, leaching from canopy and litter, decomposition), and of the quantity of water available for transport of solutes. The chemistry of the soil solution was more predictable, as it was governed mainly by nutrient uptake, cation exchange reactions and the seasonal wetting and drying cycles. The chemistry of the deep subsurface flow was often intermediate between that of the soil solution and that of the H-layer throughflow; this suggested a mixture of displaced pre-event soil solution and of H-layer throughflow circulating through preferential flow paths. With humid antecedent conditions, the chemistry of the deep subsurface flow approached that of the soil solution. The cation concentration relationships in the soil solution were strongly linear. In a homogeneous soil, cation exchange theory predicts this to be expected only for cations of the same charge, whereas cations of different charges should follow power relationships. Our results, however, are consistent with a theoretical approach involving cation exchange reactions in a highly heterogeneous environment. Indeed, our study illustrates the heterogeneous nature of the soils, as the power relationship has been obscured completely. Soilwater chemistries were markedly different from those of streamwater, particularly under dry conditions. During baseflow, the stream is fed by groundwater, and the soils are probably disconnected from the stream. During humid periods, the chemistry of the streamwater tends toward that of the deep subsurface flow. Chemical hydrograph separation indicates that, on average, stormflow water comprises an approximately one to one mixture of groundwater and deep subsurface flow. © 1995.