In this study, the ability of laser-induced breakdown spectroscopy (LIBS) to measure the in situ aqueous dissolution of various mineral carbonates with increasing CO2 pressure was examined. Dissolution experiments included four geologically common mineral carbonates (CaCO3, MgCO3, MnCO3, SrCO3) and the CO2 pressure ranged from ambient to 250 bar. The ensuing plasma emission was spectrally analyzed, and the intensities of Ca, Mg, Mn, and Sr emission lines were used to monitor the respective metal cations released to the aqueous solution. The strong emission lines of Ca (Ca II 393.36, Ca II 396.84, Ca I 422.67 nm), Mg (unresolved magnesium doublet: Mg I 383.230, Mg I 383.829 nm), Mn (unresolved manganese triplet: Mn I 403.076, Mn I 403.307, Mn I 403.449 nm), and Sr (Sr II 407.77, Sr II 421.55, Sr I 460.73 nm) were identified in the spectra. The amounts of metals released from their respective carbonates were estimated at different time intervals following the CO2 injection (5 m, 1, 2, 3, 4, 24 h) and at different pressures (50, 100, 150, 200, 250 bar) using calibration models developed at corresponding pressure settings. The results demonstrated that the pressure-induced dissolution of all carbonates was consistent with their expected and selective pH-dependent solubility. The dissolution rate of CaCO3, MgCO3, and SrCO3 was found to be higher than that of MnCO3. The dissolution of constituents in a Mt. Simon sandstone associated with a deep saline reservoir at elevated CO2 pressure was also studied and Ca release was quantified. The results demonstrated that real-time monitoring of carbonate dissolution by LIBS may provide a useful indirect detection system indicative of CO2 leakage from geologic carbon storage sites.