Riverine export of particulate organic carbon (POC) to the ocean affects the atmospheric carbon inventory over a broad range of timescales. On geological timescales, the balance between sequestration of POC from the terrestrial biosphere and oxidation of rock-derived (petrogenic) organic carbon sets the magnitude of the atmospheric carbon and oxygen reservoirs. Over shorter timescales, variations in the rate of exchange between carbon reservoirs, such as soils and marine sediments, also modulate atmospheric carbon dioxide levels. The respective fluxes of biospheric and petrogenic organic carbon are poorly constrained, however, and mechanisms controlling POC export have remained elusive, limiting our ability to predict POC fluxes quantitatively as a result of climatic or tectonic changes. Here we estimate biospheric and petrogenic POC fluxes for a suite of river systems representative of the natural variability in catchment properties. We show that export yields of both biospheric and petrogenic POC are positively related to the yield of suspended sediment, revealing that POC export is mostly controlled by physical erosion. Using a global compilation of gauged suspended sediment flux, we derive separate estimates of global biospheric and petrogenic POC fluxes of 157(+74)(-50) and 43(+61)(-25) megatonnes of carbon per year, respectively. We find that biospheric POC export is primarily controlled by the capacity of rivers to mobilize and transport POC, and is largely insensitive to the magnitude of terrestrial primary production. Globally, physical erosion rates affect the rate of biospheric POC burial in marine sediments more strongly than carbon sequestration through silicate weathering. We conclude that burial of biospheric POC in marine sediments becomes the dominant long-term atmospheric carbon dioxide sink under enhanced physical erosion.