Inter-laboratory calibration of natural gas round robins for δ2H and δ13C using off-line and on-line techniques

Compound-specific carbon and hydrogen isotopic compositions of three natural gas round robins were calibrated by ten laboratories carrying out more than 800 measurements including both on-line and off-line methods. Two-point calibrations were performed with international measurement standards for hydrogen isotope ratios (VSMOW and SLAP) and carbon isotope ratios (NBS 19 and L-SVEC CO2). The consensus δ13C values and uncertainties were derived from the Maximum Likelihood Estimation (MLE) based on off-line measurements; the consensus δ2H values and uncertainties were derived from MLE of both off-line and on-line measurements, taking the bias of on-line measurements into account. The calibrated consensus values in ‰ relative to VSMOW and VPDB are:NG1 (coal-related gas):Methane: δ2HVSMOW = − 185.1‰ ± 1.2‰, δ13CVPDB = − 34.18‰ ± 0.10‰Ethane: δ2HVSMOW = − 156.3‰ ± 1.8‰, δ13CVPDB = − 24.66‰ ± 0.11‰Propane: δ2HVSMOW = − 143.6‰ ± 3.3‰, δ13CVPDB = − 22.21‰ ± 0.11‰i-Butane: δ13CVPDB = − 21.62‰ ± 0.12‰n-Butane: δ13CVPDB = − 21.74‰ ± 0.13‰CO2: δ13CVPDB = − 5.00‰ ± 0.12‰NG2 (biogas):Methane: δ2HVSMOW = − 237.0‰ ± 1.2‰, δ13CVPDB = − 68.89‰ ± 0.12‰NG3 (oil-related gas):Methane: δ2HVSMOW = − 167.6‰ ± 1.0‰, δ13CVPDB = − 43.61‰ ± 0.09‰Ethane: δ2HVSMOW = − 164.1‰ ± 2.4‰, δ13CVPDB = − 40.24‰ ± 0.10‰Propane: δ2HVSMOW = − 138.4‰ ± 3.0‰, δ13CVPDB = − 33.79‰ ± 0.09‰All of the assigned values are traceable to the international carbon isotope standard of VPDB and hydrogen isotope standard of VSMOW.

► The first time to calibrate δ2H of natural gas reference materials.
► Calibrated δ13C of the materials, as previous gas standards are to be exhausted.
► Two-point calibrations in off-line measurements assured traceability.
► Uncertainty well controlled.