Optically Switched Dual-Wavelength Cavity Ring-Down Spectrometer for High-Precision Isotope Ratio Measurements of Methane δD in the Near Infrared

• Published in: Analytical chemistry (Washington) 2021-04, Vol.93 (16), p.6375-6384
• Main Authors: Chen, Tzu-Ling, Ober, Douglas C, Miri, Robin, Bui, Thinh Q, Shen, Linhan, Okumura, Mitchio
• Format: Article
• Language: English
• Subjects: Abundance; Analytical chemistry; Cavity ringdown; Chemistry; Frequency stabilization; Infrared spectrometers; Isotope ratios; Isotopes; Methane; Near infrared radiation; Optical switching; Spectroscopy; Switches; Temperature; Waveguides; Wavelength; Wavelengths
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/acs.analchem.0c05090

We report a spectrometer employing optically switched dual-wavelength cavity ring-down spectroscopy (OSDW-CRDS) for high-precision measurements of methane isotope ratios. A waveguide optical switch rapidly alternated between two wavelengths to detect absorption by two isotopologues using near-infrared CRDS. This approach alleviated common-mode noise that originated primarily from temperature and frequency fluctuations. We demonstrated the measurement of δD in natural abundance methane to a precision of 2.3 ‰, despite the lack of active temperature or frequency stabilization of the cavity. The ability of alternating OSDW-CRDS to improve the isotope precision in the absence of cavity stabilization were measured by comparing the Allan deviation with that obtained when frequency-stabilizing the cavity length. The system can be extended to a wide variety of applications such as isotope analysis of other species, kinetic isotope effects, ortho–para ratio measurements, and isomer abundance measurements. Furthermore, our technique can be extended to multiple isotope analysis or two species involved in kinetics studies through the use of multiport or high-speed optical switches, respectively.