Hydrograph deconvolution using geochemical tracers is currently widely used for determining the hydrologic mechanisms occurring in watersheds. However, few chemical parameters can be used as tracers because their involvement in biogeochemical processes prevents them from behaving in a conservative way. The aim of this study was to combine several geochemically controlled parameters into a single tracer. Residual alkalinity is a combination of several controlled parameters and is conservative in a wide range of natural environments. It was used in this study for quantifying the contributions of surface runoff and of groundwater flow during a flood in a Mediterranean watershed underlain by sedimentary rock. A preliminary geochemical study revealed that interactions with calcite, dolomite, and the clay-humus complex controlled calcium and magnesium concentrations as well as carbonate alkalinity (Alkc), which prevented using them as tracers. Nevertheless, although residual alkalinity (Alkresidual) is a combination of these three parameters (Alkresidual=Alkc-22+>T-22+>T), it provided results that were highly comparable to those obtained using chloride and Δ18O. Contrary to the most cases in the literature, the contribution of direct runoff was dominant (about 80% at peak discharge). Accuracy estimates, which took into account analytical errors, temporal variations in the isotopic signature of rainfall, and the spatial variability of chemical elements, supported this result and confirmed that residual alkalinity is a useful concept in hydrology. ¿ American Geophysical Union 1996