Previous studies such as that of Meybeck (1987) estimated the CO2 flux from atmosphere to riverwater due to chemical weathering by assuming that the rate of weathering of silicate rocks and carbonate rocks is proportional to the surface areas of rocks (silicate rocks : carbonate rocks = 7 : 3). However, the dissolution rate of carbonates (calcite and dolomite) is in two to four orders of magnitude higher than silicate (feldspar). This may imply that Meybeck's and other previous approaches lead to a large uncertainty in the estimate of CO2 flux. However, their estimates are nearly similar to that of Gaillardet et al. (1999), who estimated the contribution of the weathering of silicates and carbonates to riverwater chemistry based on a large volume of analytical and runoff data of the world's 60 major rivers.
The thermochemical calculation in the present study indicates that the chemistry of riverwater having a small runoff is controlled by the solubilities of calcite and Na ·Ca-feldspar (Na : Ca = 1 : 1) at atmospheric PCO2 (10 -3.5 atm) and the world-wide average riverwater chemistry plot is close to the Na ·Ca feldspar-calcite-riverwater equilibrium point. This result reasonably explains the similar estimated values of CO2 flux obtained by Meybeck (1987) and others and Gaillardet et al. (1999).
The conditions for riverwater saturated with Na ·Ca feldspar and calcite were derived based on a dissolution kinetics-fluid flow coupling model and were expressed as functions of τ (residence time of groundwater) and A/M (A : surface area of mineral, M : mass of water).