Streams draining watersheds of the two dominant lithologies (quartz diorite and volcaniclastic rock) in the Luquillo Experimental Forest of eastern Puerto Rico have very high fluxes of bedrock weathering products. The Río Blanco quartz diorite in the Icacos watershed and the Fajardo volcaniclastic rocks in the Mameyes watershed have some of the fastest documented rates of chemical weathering of siliceous rocks in the world. Rapid weathering produces thick, highly leached saprolites in both watersheds that lie just below the soil and largely isolate subsurface biogeochemical and hydrologic processes from those in the soil. The quartz diorite bedrock in the Icacos watershed weathers spheroidally, leaving large, relatively unweathered corestones that are enveloped by slightly weathered rock layers called rindlets. The rindlets wrap around the corestones like an onionskin. Within the corestones, biotite oxidation is thought to induce the spheroidal fracturing that leads to development of rindlets; plagioclase in the rindlets dissolves, creating additional pore spaces. Near the rindlet-saprolite interface, the remaining plagioclase dissolves, hornblende dissolves to completion, and precipitation of kaolinite, gibbsite, and goethite becomes pervasive. In the saprolite, biotite weathers to kaolinite and quartz begins to dissolve. In the soil layer, both quartz and kaolinite dissolve. The volcaniclastic bedrock of the Mameyes watershed weathers even faster than the quartz diorite bedrock of the Icacos watershed, leaving thicker saprolites that are devoid of all primary minerals except quartz. The quartz content of volcaniclastic bedrock may help to control watershed geomorphology; high-quartz rocks form thick saprolites that blanket ridges. Hydrologic flow paths within the weathering profiles vary with total fluid flux, and they influence the chemistry of streams. Under low-flow conditions, the Río Icacos and its tributaries are fed by rainfall and by groundwater from the fracture zones; during storm events, intense rainfall rapidly raises stream levels and water is flushed through the soil as shallow flow. As a result, weathering constituents that shed into streamwaters are dominated by rindlet-zone weathering processes during base flow and by soil weathering processes during stormflow. The upper reaches of the Mameyes watershed are characterized by regolith more than 35 meters thick in places that contains highly fractured rock embedded in its matrix. Weathering contributions to stream chemistry at base flow are predicted to be more spatially variable in the Mameyes watershed than in the Icacos watershed owing to the more complex subsurface weathering profile of the volcaniclastic bedrocks of the Mameyes watershed.