Compositional data analysis and geochemical modeling of CO ₂ –water–rock interactions in three provinces of Korea

The CO ₂ -rich spring water (CSW) occurring naturally in three provinces, Kangwon (KW), Chungbuk (CB), and Gyeongbuk (GB) of South Korea was classified based on its hydrochemical properties using compositional data analysis. Additionally, the geochemical evolution pathways of various CSW were simulated via equilibrium phase modeling (EPM) incorporated in the PHREEQC code. Most of the CSW in the study areas grouped into the Ca–HCO ₃ water type, but some samples from the KW area were classified as Na–HCO ₃ water. Interaction with anorthite is likely to be more important than interaction with carbonate minerals for the hydrochemical properties of the CSW in the three areas, indicating that the CSW originated from interactions among magmatic CO ₂ , deep groundwater, and bedrock-forming minerals. Based on the simulation results of PHREEQC EPM, the formation temperatures of the CSW within each area were estimated as 77.8 and 150 °C for the Ca–HCO ₃ and Na–HCO ₃ types of CSW, respectively, in the KW area; 138.9 °C for the CB CSW; and 93.0 °C for the GB CSW. Additionally, the mixing ratios between simulated carbonate water and shallow groundwater were adjusted to 1:9–9:1 for the CSW of the GB area and the Ca–HCO ₃ -type CSW of the KW area, indicating that these CSWs were more affected by carbonate water than by shallow groundwater. On the other hand, mixing ratios of 1:9–5:5 and 1:9–3:7 were found for the Na–HCO ₃ -type CSW of the KW area and for the CSW of the CB area, respectively, suggesting a relatively small contribution of carbonate water to these CSWs. This study proposes a systematic, but relatively simple, methodology to simulate the formation of carbonate water in deep environments and the geochemical evolution of CSW. Moreover, the proposed methodology could be applied to predict the behavior of CO ₂ after its geological storage and to estimate the stability and security of geologically stored CO ₂ .