Amorphous, biogenic Si (ASi) is stored in large amounts in terrestrial ecosystems. The study of terrestrial ASi mobilization remains in the pioneer research stage: most Si budget studies have not included the biogenic amorphous Si stock and fluxes. This hampers our ability to accurately quantify terrestrial mobilization of Si, which is—through ocean carbon burial and CO2 uptake during terrestrial Si weathering—intricately linked to global carbon budgets. We studied detailed concentration and load patterns of dissolved (DSi) and ASi during several high-discharge events in eight first-order river basins. Based on high frequency discharge measurements and concurrent analysis of ASi and DSi concentrations at base flow and during intense precipitation events, we were able to attribute a percentage of yearly ASi and DSi fluxes to both base flow and precipitation event related surface run-off. Our results show ASi and DSi concentrations in upstream river basins to be intricately linked to each other and to discharge, and ASi transport constitutes an important part to the total transport of Si even through first-order river basins (up to 40%). Based on our observations, increased occurrence of peak-discharge events with global climatic changes, and lowered importance of base flow, will coincide with drastic changes in ASi and DSi dynamics in the river continuum. Our work clearly shows ASi dynamics should be incorporated in global Si budgets now, even in low-order small river basins