Stromatolitic limestone and calcareous shale belonging to Chattisgarh Supergroup of Proterozoic age dominate the upper part of the Mahanadi river basin. X-ray diffractogram (XRD) of limestone rocks show presence of a significant amount of calcite, dolomite and ankerite. Shales of various colours contain calcite and dolomite. It is observed that congruent dissolution of carbonate minerals in the Charmuria pure limestone has given rise to a typical karst topography. On the other hand, limestones are also seen to support red and black soil profiles. This indicates that the limestone bedrock undergoes a parallel incongruent weathering, which leaves a residue of decomposed rock. The XRD analyses reveal that the limestone soils thus formed contain an assemblage of quartz, clays and Fe-oxides. It is likely that the silicate component trapped during deposition of the stromatolitic limestone weathers incongruently resulting in diverse soil profiles. Carbonate and silicate mineral weathering schemes have been worked out to explain the soil formation, fixation of Al in clay minerals, and Fe in goethite. The water quality parameters such as Ca, Mg and HCO3 in the river water suggest under saturation with respect to calcite and dolomite. The mineral stability diagrams indicate that kaolinite and Ca-smectite are stable in the river water environment, hence they occur in suspended sediments and soils. The dominant influence of carbonate weathering on the water quality is observed even in the downstream part of the river outside the limestone terrain.