Development and evaluation of a suite of isotope reference gases for methane in air

oleh: P. Sperlich, N. A. M. Uitslag, J. M. Richter, M. Rothe, H. Geilmann, C. van der Veen, T. Röckmann, T. Blunier, W. A. Brand

Format: Article
Diterbitkan: Copernicus Publications 2016-08-01

Deskripsi

Measurements from multiple laboratories have to be related to unifying and traceable reference material in order to be comparable. However, such fundamental reference materials are not available for isotope ratios in atmospheric methane, which led to misinterpretations of combined data sets in the past. We developed a method to produce a suite of synthetic CH<sub>4</sub>-in-air standard gases that can be used to unify methane isotope ratio measurements of laboratories in the atmospheric monitoring community. Therefore, we calibrated a suite of pure methane gases of different methanogenic origin against international referencing materials that define the <span style="" class="text">VSMOW</span> (Vienna Standard Mean Ocean Water) and VPDB (Vienna Pee Dee Belemnite) isotope scales. The isotope ratios of our pure methane gases range between −320 and +40 ‰ for <span style="" class="text"><i>δ</i><sup>2</sup>H–CH<sub>4</sub></span> and between −70 and −40 ‰ for <span style="" class="text"><i>δ</i><sup>13</sup>C–CH<sub>4</sub></span>, enveloping the isotope ratios of tropospheric methane (about −85 and −47 ‰ for <span style="" class="text"><i>δ</i><sup>2</sup>H–CH<sub>4</sub></span> and <span style="" class="text"><i>δ</i><sup>13</sup>C–CH<sub>4</sub></span> respectively). Estimated uncertainties, including the full traceability chain, are &lt; 1.5 ‰ and &lt; 0.2 ‰ for <i>δ</i><sup>2</sup>H and <i>δ</i><sup>13</sup>C calibrations respectively. Aliquots of the calibrated pure methane gases have been diluted with methane-free air to atmospheric methane levels and filled into 5 L glass flasks. The synthetic CH<sub>4</sub>-in-air standards comprise atmospheric oxygen/nitrogen ratios as well as argon, krypton and nitrous oxide mole fractions to prevent gas-specific measurement artefacts. The resulting synthetic CH<sub>4</sub>-in-air standards are referred to as <span style="" class="text">JRAS-M16</span> (Jena Reference Air Set – Methane 2016) and will be available to the atmospheric monitoring community. <span style="" class="text">JRAS-M16</span> may be used as unifying isotope scale anchor for isotope ratio measurements in atmospheric methane, so that data sets can be merged into a consistent global data frame.