the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Harmonisation of methane isotope ratio measurements from different laboratories using atmospheric samples
Abstract. Establishing interlaboratory compatibility among measurements of stable isotope ratios of atmospheric methane (δ13C-CH4 and δD-CH4) is challenging. Significant offsets are common because laboratories have different ties to the VPDB or SMOW-SLAP scales. Umezawa et al. (2018) surveyed numerous comparison efforts for CH4 isotope measurements conducted from 2003 to 2017 and found scale offsets of up to 0.5 ‰ for δ13C-CH4 and 13 ‰ for δD-CH4 between laboratories. This exceeds the World Meteorological Organisation Global Atmospheric Watch (WMO-GAW) network compatibility targets of 0.02 ‰ and 1 ‰ considerably.
We employ a method to establish scale offsets between laboratories using their reported CH4 isotope measurements on atmospheric samples. Our study includes data from eight laboratories with experience in high-precision isotope ratio mass spectrometry (IRMS) measurements for atmospheric CH4. The analysis relies exclusively on routine atmospheric measurements conducted by these laboratories at high-latitude stations in the Northern and Southern Hemispheres, where we assume each measurement represents sufficiently well-mixed air at the latitude for direct comparison. We use two methodologies for interlaboratory comparisons: (I) assessing differences between time-adjacent observation data and (II) smoothing the observed data using polynomial and harmonic functions before comparison. The results of both methods are consistent, and with a few exceptions, the overall average offsets between laboratories align well with those reported by Umezawa et al. (2018). This indicates that interlaboratory offsets remain robust over multi-year periods. The evaluation of routine measurements allows us to calculate the interlaboratory offsets from hundreds, in some cases thousands of measurements. Therefore, the uncertainty in the mean interlaboratory offset is not limited by the analytical error of a single analysis but by real atmospheric variability between the sampling dates and stations. Using the same method, we assess this uncertainty by investigating measurements from four high-latitude sites analysed by the INSTAAR laboratory. After applying the derived interlaboratory offsets, we present a harmonised time series for δ13C-CH4 and δD-CH4 at high northern and southern latitudes, covering the period from 1988 to 2023.
Competing interests: One of the co-authors, Thomas Röckmann, is on the editorial board for AMT
Publisher's note: Copernicus Publications remains neutral with regard to jurisdictional claims made in the text, published maps, institutional affiliations, or any other geographical representation in this preprint. The responsibility to include appropriate place names lies with the authors.- Preprint
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