Interlaboratory comparison of δ13C and δD measurements of atmospheric CH4 for combined use of data sets from different laboratories
Taku Umezawa1,2,Carl A. M. Brenninkmeijer1,Thomas Röckmann3,Carina van der Veen3,Stanley C. Tyler4,5,Ryo Fujita6,Shinji Morimoto6,7,Shuji Aoki6,Todd Sowers8,Jochen Schmitt9,Michael Bock9,Jonas Beck9,Hubertus Fischer9,Sylvia E. Michel10,Bruce H. Vaughn10,John B. Miller10,James W. C. White10,Gordon Brailsford11,Hinrich Schaefer11,Peter Sperlich11,Willi A. Brand12,Michael Rothe12,Thomas Blunier13,David Lowry14,Rebecca E. Fisher14,Euan G. Nisbet14,Andrew L. Rice15,Peter Bergamaschi16,Cordelia Veidt17,and Ingeborg Levin17Taku Umezawa et al.Taku Umezawa1,2,Carl A. M. Brenninkmeijer1,Thomas Röckmann3,Carina van der Veen3,Stanley C. Tyler4,5,Ryo Fujita6,Shinji Morimoto6,7,Shuji Aoki6,Todd Sowers8,Jochen Schmitt9,Michael Bock9,Jonas Beck9,Hubertus Fischer9,Sylvia E. Michel10,Bruce H. Vaughn10,John B. Miller10,James W. C. White10,Gordon Brailsford11,Hinrich Schaefer11,Peter Sperlich11,Willi A. Brand12,Michael Rothe12,Thomas Blunier13,David Lowry14,Rebecca E. Fisher14,Euan G. Nisbet14,Andrew L. Rice15,Peter Bergamaschi16,Cordelia Veidt17,and Ingeborg Levin17
Received: 31 Jul 2017 – Discussion started: 09 Aug 2017 – Revised: 16 Jan 2018 – Accepted: 17 Jan 2018 – Published: 02 Mar 2018
Abstract. We report results from a worldwide interlaboratory comparison of samples among laboratories that measure (or measured) stable carbon and hydrogen isotope ratios of atmospheric CH4 (δ13C-CH4 and δD-CH4). The offsets among the laboratories are larger than the measurement reproducibility of individual laboratories. To disentangle plausible measurement offsets, we evaluated and critically assessed a large number of intercomparison results, some of which have been documented previously in the literature. The results indicate significant offsets of δ13C-CH4 and δD-CH4 measurements among data sets reported from different laboratories; the differences among laboratories at modern atmospheric CH4 level spread over ranges of 0.5 ‰ for δ13C-CH4 and 13 ‰ for δD-CH4. The intercomparison results summarized in this study may be of help in future attempts to harmonize δ13C-CH4 and δD-CH4 data sets from different laboratories in order to jointly incorporate them into modelling studies. However, establishing a merged data set, which includes δ13C-CH4 and δD-CH4 data from multiple laboratories with desirable compatibility, is still challenging due to differences among laboratories in instrument settings, correction methods, traceability to reference materials and long-term data management. Further efforts are needed to identify causes of the interlaboratory measurement offsets and to decrease those to move towards the best use of available δ13C-CH4 and δD-CH4 data sets.
Isotope measurements are useful for separating different methane sources. However, the lack of widely accepted standards and calibration methods for stable carbon and hydrogen isotopic ratios of methane in air has caused significant measurement offsets among laboratories. We conducted worldwide interlaboratory comparisons, surveyed the literature and assessed them systematically. This study may be of help in future attempts to harmonize data sets of isotopic composition of atmospheric methane.
Isotope measurements are useful for separating different methane sources. However, the lack of...