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Stable carbon isotopes of HCO3? in oil-field waters—implications for the origin of CO2
Authors:William W Carothers  Yousif K Kharaka
Institution:U.S. Geological Survey, Menlo Park, CA 94025, U.S.A.
Abstract:The δ13C values of dissolved HCO3? in 75 water samples from 15 oil and gas fields (San Joaquin Valley, Calif., and the Houston-Galveston and Corpus Christi areas of Texas) were determined to study the sources of CO2 of the dissolved species and carbonate cements that modify the porosity and permeability of many petroleum reservoir rocks. The reservoir rocks are sandstones which range in age from Eocene through Miocene. The δ13C values of total HCO3? indicate that the carbon in the dissolved carbonate species and carbonate cements is mainly of organic origin.The range of δ13C values for the HCO3? of these waters is ?20–28 per mil relative to PDB. This wide range of δ13C values is explained by three mechanisms. Microbiological degradation of organic matter appears to be the dominant process controlling the extremely low and high δ13C values of HCO3? in the shallow production zones where the subsurface temperatures are less than 80°C. The extremely low δ13C values (< ?10 per mil) are obtained in waters where concentrations of SO42? are more than 25 mg/l and probably result from the degradation of organic acid anions by sulfate-reducing bacteria (SO42? + CH3COO? → 2HCO3? + HS?). The high δ13C values probably result from the degradation of these anions by methanogenic bacteria (CH3COO? + H2OaiHCO3? + CH4).Thermal decarboxylation of short-chain aliphatic acid anions (principally acetate) to produce CO2 and CH4 is probably the major source of CO2 for production zones with subsurface temperatures greater than 80°C. The δ13C values of HCO3? for waters from zones with temperatures greater than 100°C result from isotopic equilibration between CO2 and CH4. At these high temperatures, δ13C values of HCO3? decrease with increasing temperatures and decreasing concentrations of these acid anions.
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