Abstract.Residual soils (saprolites) developed on crystalline rocks appear to form by an essentially isovolumetric process (i.e. without dilation or compaction). Isovolumetric geochemical analysis of a suite of saprolite samples developed on a common parent rock can be used to estimate the relative rates of long-term losses of P and Si during weathering. Using the export of dissolved Si in rivers as a weathering index, one can then estimate the rate of P release due to chemical weathering by means of the P-Si loss ratio in saprolite. For three basins where data are available (Liberty Hill, SC; Amazon River, Brazil: Rio Negro, Brazil) estimated P weathering release rates are 163,457, and 242molesP km-' yr-', respectively. These compare to precipitation inputs of 684, 700 and 630 moles P km-* yr-' and total river exports of 256,449O and 820 moles P km-' yr-', respectively. The Rio Negro shows a near perfect balance between the input of P via precipitation and chemical weathering and the riverine output of dissolved and suspended P. This system, however, raised the unsolved problem of the source that supports the atmospheric P input.