A significant portion of the carbon sequestration research being performed in the United States involves the risk assessment of injecting large quantities of carbon dioxide into deep saline aquifers. Leakage of CO2 has the potential to affect the quality of groundwater supplies in case contaminants migrate through underlying conduits. New remote sensing and near-surface monitoring technologies are needed to ensure that injection, abandoned, and monitoring wells are structurally sound, and that CO2 remains within the geologic storage reservoir. In this paper, we propose underwater laser-induced breakdown spectroscopy (underwater LIBS) as an analytical method for monitoring naturally occurring elements that can act as tracers to detect a CO2 leak from storage sites. Laboratory-scale experiments were conducted to measure Sr2+, Ca2+, K(+), and Li(+) in bulk solutions to ascertain the analytical performance of underwater LIBS. We compared the effect of NaCl, Na2CO3, and Na2SO4 on the analytes calibration curves to determine underwater LIBS' ability to analyze samples of sodium compounds. In all cases, the calibration curves showed a good linearity within 2 orders of magnitude. The limit of detections (LODs) obtained for K(+) (30±1 ppb) and Li(+) (60±2 ppb) were in ppb range, while higher LODs were observed for Ca(2+) (0.94±0.14 ppm) and Sr(2+) (2.89±0.11 ppm). Evaluation of the calibration curves for the analytes in mixed solutions showed dependence of the lines' intensity with the sodium compounds. The intensities increased respectively in the presence of dissolved NaCl and Na2SO4, whereas the intensities slightly decreased in the presence of Na2CO3. Finally, the capabilities of underwater LIBS to detect certain elements in the ppb or in the low ppm range make it particularly appealing for in situ monitoring of a CO2 leak.