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Abstract Extreme rainfall events in the humid-tropical Luquillo Mountains, Puerto Rico export the bulk of suspended sediment and particulate organic carbon. Using 25 years of river carbon and suspended sediment data, which targeted hurricanes and other large rainstorms, we estimated biogenic particulate organic carbon yields of 65 ± 16 tC km −2 yr −1 for the Icacos and 17.7 ± 5.1 tC km −2 yr −1 for the Mameyes rivers. These granitic and volcaniclastic catchments function as substantial atmospheric carbon-dioxide sinks, largely through export of river biogenic particulate organic carbon during extreme rainstorms. Compared to other regions, these high biogenic particulate organic carbon yields are accompanied by lower suspended sediment yields. Accordingly, particulate organic carbon export from these catchments is underpredicted by previous yield relationships, which are derived mainly from catchments with easily erodible sedimentary rocks. Therefore, rivers that drain petrogenic-carbon-poor bedrock require separate accounting to estimate their contributions to the geological carbon cycle.