High-Precision 13CO2/12CO2 Isotopic Ratio Measurement Using Tunable Diode Laser Absorption Spectroscopy at 4.3 μm for Deep-Sea Natural Gas Hydrate Exploration

For the detection of deep-sea natural gas hydrates, it is very important to accurately detect the 13CO2/12CO2 isotope ratio of dissolved gas in seawater. In this paper, a 13CO2/12CO2 isotope ratio sensor is investigated, which uses a tunable diode laser absorption spectroscopy (TDLAS) technique at 4.3 μm. The proposed sensor consists of a mid-infrared interband cascade laser (ICL) operating in continuous wave mode, a long optical path multi-pass gas cell (MPGC) of 24 m, and a mid-infrared mercury cadmium telluride (MCT) detector. Aiming at the problem of the strong absorption intensity of the two absorption lines of 13CO2 and 12CO2 being affected by temperature, a high-precision temperature control system for the MPGC was fabricated. Five different concentrations of CO2 gas were configured to calibrate the sensor, and the response linearity could reach 0.9992 for 12CO2 and 0.9996 for 13CO2. The data show that the carbon isotope measurement precision was assessed to be 0.0139‰ when the integration time was 92 s and the optical path length was 24 m. The sensor is combined with a gas–liquid separator to detect the 13CO2/12CO2 isotope ratio of CO2 gas extracted from water. Results validate the reported sensor system’s potential application in deep-sea natural gas hydrate exploration.