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

Abstract

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 CH4-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 VSMOW (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 δ2H-CH4 and between -70 and -40% for δ13C-CH4, enveloping the isotope ratios of tropospheric methane (about -85 and -47% for δ2H-CH4 and δ13C-CH4 respectively). Estimated uncertainties, including the full traceability chain, are < 1.5% and < 0.2% for δ2H and δ13C 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 CH4-in-air standards comprise atmospheric oxygen/nitrogen ratios as well as argon, krypton and nitrous oxide mole fractions to prevent gasspecific measurement artefacts. The resulting synthetic CH4-in-air standards are referred to as JRAS-M16 (Jena Reference Air Set - Methane 2016) and will be available to the atmospheric monitoring community. JRAS-M16 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.