Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on delta C-13 values of CO2 to trace the migration of injected CO2 in the subsurface. More recently the use of delta O-18 values of both CO2 and reservoir fluids has been proposed as a method for quantifying in situ CO2 reservoir saturations due to O isotope exchange between CO2 and H2O and subsequent changes in delta O-18(H2O) values in the presence of high concentrations of CO2. To verify that O isotope exchange between CO2 and H2O reaches equilibrium within days, and that delta O-18(H2O) values indeed change predictably due to the presence of CO2, a laboratory study was conducted during which the isotope composition of H2O, CO2, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 degrees C and up to 19 MPa) and varying CO2 pressures. Conditions typical for the Pembina Cardium CO2 Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that delta O-18 values of CO2 were on average 36.4 +/- 2.2 parts per thousand (1 sigma, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5 parts per thousand for the experimental temperatures of 50 degrees C. By using O-18 enriched water for the experiments it was demonstrated that changes in the delta O-18 values of water were predictably related to the fraction of O in the system sourced from CO2 in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO2 is related to the total volumetric saturation of CO2 and water as a fraction of the total volume of the system, it is concluded that changes in delta O-18 values of reservoir fluids can be used to calculate reservoir saturations of CO2 in CCS settings given that the delta O-18 values of CO2 and water are sufficiently distinct. (C) 2011 Elsevier Ltd. All rights reserved.