Find in Library
Search millions of books, articles, and more
Indexed Open Access Databases
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.