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

Chen, Tzu-Ling and Ober, Douglas C. and Miri, Robin and Bui, Thinh Q. and Shen, Linhan and Okumura, Mitchio (2021) Optically Switched Dual-Wavelength Cavity Ring-Down Spectrometer for High-Precision Isotope Ratio Measurements of Methane δD in the Near Infrared. Analytical Chemistry, 93 (16). pp. 6375-6384. ISSN 0003-2700. doi:10.1021/acs.analchem.0c05090. https://resolver.caltech.edu/CaltechAUTHORS:20210415-104125351

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Abstract

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.analchem.0c05090DOIArticle
ORCID:
AuthorORCID
Chen, Tzu-Ling0000-0002-2243-5780
Bui, Thinh Q.0000-0001-6090-0930
Shen, Linhan0000-0003-3871-655X
Okumura, Mitchio0000-0001-6874-1137
Additional Information:© 2021 American Chemical Society. Received: December 4, 2020; Accepted: March 16, 2021; Published: April 12, 2021. The authors wish to thank Dr. Charles R. Markus and Dr. Ofir Shoshanim for their helpful discussions. This work was supported by the National Aeronautics and Space Administration (NASA), Mars Fundamental Research Grant NNX12AI01G, and Solar Systems Working program, contract number 80NSSC18K0263. T.-L.C. was supported by the grant of 2019 Postdoctoral Research Abroad Program from the Taiwan Ministry of Science and Technology. R.M. was supported by a Master PHYTEM Internship from the Ecole Normale Supérieure de Cachan and the Université de Sorbonne. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NASANNX12AI01G
NASA80NSSC18K0263
Ministry of Science and Technology (Taipei)UNSPECIFIED
Ecole Normale Supérieure de CachanUNSPECIFIED
Université de SorbonneUNSPECIFIED
Issue or Number:16
DOI:10.1021/acs.analchem.0c05090
Record Number:CaltechAUTHORS:20210415-104125351
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210415-104125351
Official Citation:Optically Switched Dual-Wavelength Cavity Ring-Down Spectrometer for High-Precision Isotope Ratio Measurements of Methane δD in the Near Infrared. Tzu-Ling Chen, Douglas C. Ober, Robin Miri, Thinh Q. Bui, Linhan Shen, and Mitchio Okumura Analytical Chemistry 2021 93 (16), 6375-6384; DOI: 10.1021/acs.analchem.0c05090
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:108741
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:19 Apr 2021 18:26
Last Modified:03 May 2021 18:00

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