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Distribution and behavior of baseline soil CO<sub>2</sub> were investigated in a candidate geologic CO<sub>2</sub> storage site in Pohang, with measuring CO<sub>2</sub> concentrations and carbon isotopes in the vadose zone as well as CO<sub>2</sub> fluxes and concentrations through ground surface. This investigation aimed to assess the baseline CO<sub>2</sub> levels and to build the CO<sub>2</sub> monitoring system before injecting CO<sub>2</sub>. The gas in the vadose zone was collected using a peristaltic pump from the depth of 60 cm below ground surface, and stored at gas bags. Then the gas components (CO<sub>2</sub>, O<sub>2</sub>, N<sub>2</sub>, CH<sub>4</sub>) and δ<sup>13</sup>C<sub>CO2</sub> were analyzed using GC and CRDS (cavity ringdown spectroscopy) respectively in laboratory. CO<sub>2</sub> fluxes and CO<sub>2</sub> concentrations through ground surface were measured using Li-COR in field. In result, the median of the CO<sub>2</sub> concentrations in the vadose zone was about 3,000 ppm, and the δ<sup>13</sup>C<sub>CO2</sub> were in the wide range between −36.9‰ and −10.6‰. The results imply that the fate of CO<sub>2</sub> in the vadose zone was affected by soil property and vegetations. CO<sub>2</sub> in sandy or loamy soils originated from the respiration of microorganisms and the decomposition of C<sub>3</sub> plants. In gravel areas, the CO<sub>2</sub> concentrations decreased while the δ<sup>13</sup>C<sub>CO2</sub> increased because of the mixing with the atmospheric gas. In addition, the relation between O<sub>2</sub> and CO<sub>2</sub>, N<sub>2</sub>, and the relation between N<sub>2</sub>/O<sub>2</sub> and CO<sub>2</sub> implied that the gases in the vadose zone dissolved in the infiltrating precipitation or the soil moisture. The median CO<sub>2</sub> flux through ground surface was 2.9 g/m<sup>2</sup>/d which is lower than the reported soil CO<sub>2</sub> fluxes in areas with temperate climates. CO<sub>2</sub> fluxes measured in sandy and loamy soil areas were higher (median 5.2 g/m<sup>2</sup>/d) than those in gravel areas (2.6 g/m<sup>2</sup>/d). The relationships between CO<sub>2</sub> fluxes and concentrations suggested that the transport of CO<sub>2</sub> from the vadose zone to ground surface was dominated by diffusion in the study area. In gravel areas, the mixing with atmospheric gases was significant. Based on this study result, a soil monitoring procedure has been established for a candidate geologic CO<sub>2</sub> storage site. Also, this study result provides ideas for innovating soil monitoring technologies.
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