The fluvial geochemistry of the tributaries of the Orinoco draining the eastern branch of the northern Andes in Colombia and Venezuela is determined by lithology and ranges from rivers dominated by aluminosilicate weathering, mainly of shales and mafic rocks, to those bearing the signatures of dissolution of marine limestones and evaporites and of continental playa deposits. These left bank tributaries of the Orinoco provide the overwhelming proportion of the suspended and dissolved loads transported by the main stem although feeding only half the discharge. However, due to the extreme severity of weathering on the Guayana Shield, the right bank tributaries supply about half the silica and 40% of the K carried by the Orinoco. There is a similar partitioning between the Andes and the lowlands in the Amazon drainage. In contrast the Mackenzie, which drains the northern extremity of the continental arc of the Western Americas, is completely dominated by the weathering of limestones and evaporites and transports very little silica. This, again, appears to be a reflection of lithology since the Yukon, in similar latitudes and terrain, has silica concentrations comparable to the Tropical systems. In addition, a conservative deconvolution of the data gives estimates of the net consumption of atmospheric CO2 by aluminosilicate weathering that follows the same pattern. Thus, the available evidence from the Western Americas indicates that exposure and lithology, rather than the climatic variables, temperature, and runoff, dominate the weathering yields in active orogenic belts. These observations contradict the conventional view of weathering processes and their controls and are at complete variance with the assumptions parameterised in most models of the geochemical cycle.