Frank Guenther

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/mol. Main text. To reach the main text of this paper, click on Final Report. The final report has been peer-reviewed and approved for publication by the CCQM.

Final report on international comparison CCQM-K68: Nitrous oxide in synthetic air

Nitrous oxide (N2O) is one of six greenhouse gases that are regulated by the Kyoto Protocol and has a Global Warming Potential (GWP) that is 296 times that of carbon dioxide. Global levels of nitrous oxide have increased at a rate of 0.25%/yr (0.8 ppb/yr) during the last ten years. In order to monitor levels of nitrous oxide in the atmosphere, it is necessary to use measurement standards with demonstrated equivalence at the highest level of accuracy. This report describes the results of a key comparison of standard gas mixtures of nitrous oxide in synthetic air at an amount fraction of 320 nmol/mol. This key comparison is part of the programme of the Gas Analysis Working Group (GAWG) of the CCQM to demonstrate the equivalence of the standards and measurement capabilities of the NMIs for greenhouse gases. It will support the development of measurement capability at the NMIs for nitrous oxide with uncertainties within the target set by the Global Atmospheric Watch (GAW) programme of the WMO for its global monitoring networks. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA).

International comparison CCQM-K54: Primary standard gas mixtures of hexane in methane

The aim of this comparison is to evaluate the gravimetry and purity verification of gas mixtures prepared by introducing a liquid into a gas cylinder. This type of preparation is well known from, e.g., ethanol in nitrogen/air (CCQM-K4), and n-hexane in synthetic natural gas (CCQM-K16). The choice for n-hexane in methane is based on the relevance of natural gas primary standard mixtures and higher hydrocarbons in synthetic natural gas (for, e.g., dew point calibrations). Furthermore, n-hexane is relatively straightforward to analyse using a GC/FID (gas chromatograph equipped with a flame ionisation detector) with good repeatability. Eight laboratories participated. After the data evaluation, the result of one laboratory was eliminated to arrive at a consistent subset. The quality of the fitted line was not overly good, leading to small discrepancies in the degrees-of-equivalence calculated for three other laboratories. Only four laboratories are consistent with the KCRV. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA).

International comparison CCQM-P41 Greenhouse gases. 1. Measurement capability

The measurement of greenhouse gases in the atmosphere is one of the activities to monitor changes in the global environment, as some of these gases are presumed to contribute to climate change. The CCQM Gas Analysis Working Group has organised a pilot comparison for carbon dioxide and methane at ambient levels to compare primarily the capabilities of national metrology institutes (NMIs) for measuring these species in air. The participation in this comparison was not limited to signatories of the MRA, as is usually the case. Laboratories from the World Meteorological Organisation (WMO) were invited as well, and two participated. The project has been split in two parts, a comparison of the (analytical) measurement capability, and a high-accuracy comparison of primary standard gas mixtures for greenhouse gases. In this first part, the measurement capability was compared between NMIs and WMO laboratories. The nominal amount-of-substance fraction levels are 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. The protocol used for this comparison was the same as used so far in the gas analysis area for key comparisons and studies of this type. The reference values were assigned to each gas mixture on the basis of the gravimetric preparation, taking into account the results from the purity verification. In particular for the value assignment of methane, traces of methane in the matrix gases (nitrogen, oxygen and argon) can influence the value assigned to the gas mixture appreciably. The results for methane agree within 4% relative, and for most participants even within 2% relative at an amount of substance fraction level of 1.8 µmol/mol. For carbon dioxide all results agree within 1% relative, and for most the agreement is even better: within 0.5% relative at an amount of substance fraction level of 365 µmol/mol. The methane data show a discrepancy of approximately 0.025 µmol/mol between the averages of the WMO laboratories and the NMIs, which confirms results of earlier comparisons. Measurement traceability is quite differently established in NMIs and WMO laboratories, and may account for this difference. Further work is needed to find out the causes of this difference. Main text. To reach the main text of this paper, click on Final Report. The final report has been peer-reviewed and approved for publication by the CCQM.

Final report of the ongoing key comparison BIPM.QM-K1: Ozone at ambient level, comparison with CHMI (September 2013)

As part of the ongoing key comparison BIPM.QM-K1, a comparison has been performed between the ozone standard of the Czech Republic maintained by the Czech Hydrometeorological Institute (CHMI) and the common reference standard of the key comparison, maintained by the Bureau International des Poids et Mesures (BIPM). The instruments have been compared over a nominal ozone amountof-substance fraction range of 0 nmol/mol to 500 nmol/mol.

Final report on CCQM-K93: Preparative comparison of ethanol in nitrogen

This report presents the results of CCQM-K93, a key comparison between 13 National Measurement Institutes (NMIs), which tested the capability of the NMIs to prepare standard gas mixtures of ethanol at a nominal amount fraction of 120 µmol/mol in nitrogen. This composition is typical of the levels used to calibrate evidential breath analysers in many countries. Such standards fulfill the agreed requirements of the International Organization of Legal Metrology (OIML) for the calibration of evidential breath-alcohol analysers. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

SIM.QM-S1: Bilateral comparison of NIST and CENAM binary gas mixtures

Ten compressed gas cylinders from NIST containing binary mixtures with propane, carbon monoxide, carbon dioxide or nitric oxide, all of them with nitrogen balance, were shipped to CENAM for the purpose of bilateral comparison between CENAM and NIST. CENAM utilized its own gravimetrically prepared Primary Reference Materials (PRM) to measure the respective concentrations and reported to NIST. The cylinders were shipped back to NIST for verification of their value. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by SIM, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA).

Final report, on-going key comparison BIPM.QM-K1: Ozone at ambient level, comparison with UBA, 2007

As part of the on-going key comparison BIPM.QM-K1, a comparison has been performed between the ozone national standard of the Umweltbundesamt (UBA) and the common reference standard of the key comparison, maintained by the Bureau International des Poids et Mesures (BIPM), via a transfer standard maintained by the National Institute of Standards and Technology (NIST). The instruments have been compared over a nominal ozone mole fraction range of 0 nmol/mol to 500 nmol/mol.

Final report, on-going key comparison BIPM.QM-K1: Ozone at ambient level, comparison with NIM, 2008

As part of the on-going key comparison BIPM.QM-K1, a comparison has been performed between the ozone national standard of the National Institute of Standards and Technology (NIST) and the common reference standard of the key comparison, maintained by the Bureau International des Poids et Mesures (BIPM). The instruments have been compared over a nominal ozone mole fraction range of 0 nmol/mol to 500 nmol/mol.

Final report, on-going key comparison BIPM.QM-K1: Ozone at ambient level, comparison with JRC, 2008

As part of the on-going key comparison BIPM.QM-K1, a comparison has been performed between the ozone national standard of the Directorate General Joint Research Centre (JRC) and the common reference standard of the key comparison, maintained by the Bureau International des Poids et Mesures (BIPM), via a transfer standard maintained by the National Institute of Standards and Technology (NIST). The instruments have been compared over a nominal ozone mole fraction range of 0 nmol/mol to 500 nmol/mol.