International Comparison CCQM-P41 Greenhouse gases. 2. Direct comparison of primary standard gas mixtures

In this second part of this study, primary standard gas mixtures (PSMs) as used for calibrations for the greenhouse gases carbon dioxide and methane have been compared. The nominal amount-of-substance fraction levels were 365 µmol/mol for carbon dioxide and 1.8 µmol/mol for methane. The matrix was synthetic air, simulated by a mixture of nitrogen, oxygen (209 mmol/mol) and argon (9.3 mmol/mol). The measurements took place in the spring of 2003. In the protocol, it was foreseen to have the PSMs produced for this study in a small range, enabling regression analysis on the data to assess the consistency of the gas mixtures. The direct comparison of the PSMs shows agreement for carbon dioxide at 365 µmol/mol nominal within 0.52 µmol/mol (0.14% relative) standard uncertainty. One cylinder lies between the 95% and 99% boundaries of the regression line, and after removing this cylinder from the dataset the standard deviation of the x-residuals reduces to 0.18 µmol/mol (0.05% relative). This value for the standard deviation is substantially greater than the stated standard uncertainties for several cylinders. The standard deviation of the x-residuals for methane at 1.8 µmol/mol nominal is 0.011 µmol/mo