Performance Evaluation and Application of TOC-CRDS for Various Stable Carbon Isotope Analyses in Groundwater

The comprehensive analysis of stable carbon isotopes in dissolved organic carbon (δ13C-DOC) and dissolved inorganic carbon (δ13C-DIC) is essential for understanding carbon cycling in groundwater systems. This study evaluated the performance, stability, and accuracy of a Total Organic Carbon analyzer coupled with Cavity Ring-Down Spectroscopy (TOC-CRDS) for the determination of δ13C-DOC and δ13C-DIC. Long-term stability tests using solid standards (acetanilide) demonstrated an average precision of 0.21‰ over five days, though initial instrument stabilization was found to be critical. Systematic sensitivity experiments revealed a strong dependence of isotopic accuracy on carbon mass. For liquid samples, a minimum carbon threshold of 50 μg C (equivalent to 6.25 mg/L DOC in an 8 mL injection) was established; above this threshold, analytical precision consistently remained better than 0.3‰. Validation using synthetic samples showed excellent agreement between measured and calculated values for both DOC and DIC. Furthermore, comparative analysis of natural groundwater samples revealed that TOC-CRDS results were highly consistent with those obtained by GasBench–Isotope Ratio Mass Spectrometry, with relative deviations within 5% for DOC and 6% for DIC. The study confirms that TOC-CRDS provides a robust, high-precision (<0.3‰), and cost-effective alternative to mass spectrometry for analyzing groundwater carbon isotopes, provided that sample carbon content exceeds the determined thresholds and appropriate calibration strategies are employed.