Real-time analysis of <i>δ</i><sup>13</sup>C- and <i>δ</i>D-CH<sub>4</sub> in ambient air with laser spectroscopy: method development and first intercomparison results

oleh: S. Eyer, B. Tuzson, M. E. Popa, C. van der Veen, T. Röckmann, M. Rothe, W. A. Brand, R. Fisher, D. Lowry, E. G. Nisbet, M. S. Brennwald, E. Harris, C. Zellweger, L. Emmenegger, H. Fischer, J. Mohn

Format: Article
Diterbitkan: Copernicus Publications 2016-01-01

Deskripsi

In situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called trace gas extractor (TREX). This unit enhances CH<sub>4</sub> mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N<sub>2</sub>O and CO<sub>2</sub>. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, µmole mole<sup>−1</sup>) methane is 0.1 and 0.5 ‰ for <i>δ</i><sup>13</sup>C- and <i>δ</i>D-CH<sub>4</sub> at 10 min averaging time. <br><br> Based on repeated measurements of compressed air during a 2-week intercomparison campaign, the repeatability of the TREX–QCLAS was determined to be 0.19 and 1.9 ‰ for <i>δ</i><sup>13</sup>C and <i>δ</i>D-CH<sub>4</sub>, respectively. In this intercomparison campaign the new in situ technique is compared to isotope-ratio mass spectrometry (IRMS) based on glass flask and bag sampling and real time CH<sub>4</sub> isotope analysis by two commercially available laser spectrometers. Both laser-based analyzers were limited to methane mole fraction and <i>δ</i><sup>13</sup>C-CH<sub>4</sub> analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX–QCLAS data and bag/flask sampling–IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for <i>δ</i><sup>13</sup>C- and <i>δ</i>D-CH<sub>4</sub>, respectively. This also displays the potential to improve the interlaboratory compatibility based on the analysis of a reference air sample with accurately determined isotopic composition.