We present a comparative study of two offline methods, a newly developed method and an existing one, for the measurement of the stable carbon isotopic composition (δ(13)C) of dissolved inorganic carbon (DIC; δ(13)CDIC) in natural waters. The measured δ(13)CDIC values of different water samples, prepared from laboratory Na2CO3, ground and oceanic waters, and a laboratory carbonate isotope standard, are found to be accurate and reproducible to within 0.5 ‰\ (1σ). The extraction of CO2 from water samples by these methods does not require pre-treatment or sample poisoning and can be applied to a variety of natural waters to address carbon cycling in the hydrosphere. In addition, we present a simple method (based on a two-end-member mixing model) to estimate the silicate-weathering contribution to DIC in a river system by using the concentration of DIC and its δ(13)C. This approach is tested with data from the Krishna River system as a case study, thereby quantifying the contribution of silicate and carbonate weathering to DIC, particularly during peak discharge.