On-line technique for preparingand measuring stable carbon isotopeof total dissolved inorganic carbonin water samples ( d13CTDIC)

A fast and completely automated procedure is proposed for the preparation and determination of d13C of total inorganic carbon dissolved in water ( d13CTDIC). This method is based on the acidification of water samples transforming the whole dissolved inorganic carbon species into CO2. Water samples are directly injected by syringe into 5.9 ml vials with screw caps which have a pierciable rubber septum. An Analytical Precision «Carbonate Prep System» was used both to flush pure helium into the vials and to automatically dispense a fixed amount of H3PO4. Full-equilibrium conditions between produced CO2 and water are reached at a temperature of 70°C (± 0.1°C) in less than 24 h. Carbon isotope ratios (13C/ 12C) were measured on an AP 2003 continuous flow mass spectrometer, connected on-line with the injection system. The precision and reproducibility of the proposed method was tested both on aqueous standard solutions prepared using Na2CO3 with d13C=-10.78 per mil versus PDB (1 s= 0.08, n = 11), and at five different concentrations (2, 3, 4, 5 and 20 mmol/l) and on more than thirty natural samples. Mean d13CTDIC on standard solution samples is ?10.89 < per mil versus PDB (1 s= 0.18, n = 50), thus revealing both a good analytical precision and reproducibility. A comparison between average d13CTDIC values on a quadruplicate set of natural samples and those obtained following the chemical and physical stripping method highlights a good agreement between the two analytical methods