Photochemical method for removing methane interference for improved gas analysis
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Published:2021-12-23
Issue:12
Volume:14
Page:8041-8067
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ISSN:1867-8548
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Container-title:Atmospheric Measurement Techniques
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language:en
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Short-container-title:Atmos. Meas. Tech.
Author:
Polat MerveORCID, Liisberg Jesper Baldtzer, Krogsbøll Morten, Blunier ThomasORCID, Johnson Matthew S.ORCID
Abstract
Abstract. The development of laser spectroscopy has made it possible to measure minute changes in the concentrations of trace gases and their isotopic analogs. These single or even multiply substituted species occur at ratios from percent to below parts per million and contain important information concerning trace gas sources and transformations. Due to their low abundance, minimizing spectral interference from other gases in a mixture is essential. Options including traps and membranes are available to remove many specific impurities. Methods for removing CH4, however, are extremely limited as methane has low reactivity and adsorbs poorly to most materials. Here we demonstrate a novel method for CH4 removal via chlorine-initiated oxidation. Our motivation in developing the technique was to overcome methane interference in measurements of N2O isotopic analogs when using a cavity ring-down spectrometer. We describe the design and validation of a proof-of-concept device and a kinetic model to predict the dependence of the methane removal efficiency on the methane concentration [CH4], chlorine photolysis rate JCl2, chlorine concentration [Cl2] and residence time tR. The model was validated by comparison to experimental data and then used to predict the possible formation of troublesome side products and by-products including CCl4 and HCl. The removal of methane could be maintained with a peak removal efficiency >98 % for ambient levels of methane at a flow rate of 7.5 mL min−1 with [Cl2] at 50 ppm. These tests show that our method is a viable option for continuous methane scrubbing. Additional measures may be needed to avoid complications due to the introduction of Cl2 and formation of HCl. Note that the method will also oxidize most other common volatile organic compounds. The system was tested in combination with a cavity ring-down methane spectrometer, and the developed method was shown to be successful at removing methane interference.
Publisher
Copernicus GmbH
Subject
Atmospheric Science
Reference42 articles.
1. Atkinson, R., Baulch, D., Cox, R., Hampson Jr., R. F., Kerr, J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: supplement III. IUPAC subcommittee on gas kinetic data evaluation for atmospheric chemistry, J. Phys. Chem. Ref. Data, 18, 881–1097, https://doi.org/10.1063/1.555832, 1989. a 2. Atkinson, R., Baulch, D., Cox, R., Crowley, J., Hampson Jr, R., Kerr, J., Rossi, M., and Troe, J.: Summary of evaluated kinetic and photochemical data for atmospheric chemistry, IUPAC Subcommittee on gas kinetic data evaluation for atmospheric chemistry web version, 1–56, December 2001. a, b, c, d 3. Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I – gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, https://doi.org/10.5194/acp-4-1461-2004, 2004. a 4. Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III – gas phase reactions of inorganic halogens, Atmos. Chem. Phys., 7, 981–1191, https://doi.org/10.5194/acp-7-981-2007, 2007. a, b 5. Baulch, D., Duxbury, J., Grant, S., and Montague, D.: Evaluated kinetic data for high temperature reactions. Volume 4. Homogeneous gas phase reactions of halogen-and cyanide-containing species, J. Phys. Chem. Ref. Data, 10, 129–139, 1981. a
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