Experimental studies of oxygen isotope fractionation in the carbonic acid system at 15, 25, and 40 (degrees)C
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In light of recent studies that show oxygen isotope fractionation in carbonate minerals to be a function of HCO3 2-; and CO3 2- concentrations, the oxygen isotope fractionation and exchange between water and components of the carbonic acid system (HCO3 2-, CO3 2-, and CO2(aq)) were investigated at 15, 25, and 40 (degrees)C. To investigate oxygen isotope exchange between HCO3 2-, CO3 -2, and H2O, NaHCO3 solutions were prepared and the pH was adjusted over a range of 2 to 12 by the addition of small amounts of HCl or NaOH. After thermal, chemical, and isotopic equilibrium was attained, BaCl2 was added to the NaHCO3 solutions. This resulted in immediate BaCO3 precipitation; thus, recording the isotopic composition of the dissolved inorganic carbon. Data from experiments at 15, 25, and 40 (degrees)C (1 atm) show that the oxygen isotope fractionation between HCO3 2-; and H2O as a function of temperature is governed by the equation: 1000 ;HCO3--H2O = 2.66 + 0.05(106T-2) + 1.18 + 0.52. where is the fractionation factor and T is in kelvins. The temperature dependence of oxygen isotope fractionation between CO32 and H2O is 1000 CO32--H2O = 2.28 + 0.03(106T-2) - 1.50 + 0.29. The oxygen isotope fractionation between CO2(aq) and H2O was investigated by acid stripping CO2(aq) from low pH solutions; these data yield the following equation: 1000 CO2(aq)-H2O = 2.52 + 0.03(106T-2) + 12.12 + 0.33. The kinetics of oxygen isotope exchange were also investigated. The half-times for exchange between HCO3- and H2O were 3.6, 1.4, and 0.25 h at 15, 25, and 40 (degrees)C, respectively. The half-times for exchange between CO2 and H2O were 1200, 170, and 41 h at 15, 25, and 40 (degrees) C, respectively. These results show that the 18O of the total dissolved inorganic carbon species can vary as much as 17 at a constant temperature. This could result in temperature independent variations in the 18O of precipitated carbonate minerals, especially in systems that are not chemically buffered.
Beck, William Cory (2004). Experimental studies of oxygen isotope fractionation in the carbonic acid system at 15, 25, and 40 (degrees)C. Master's thesis, Texas A&M University. Texas A&M University. Available electronically from