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Methods of determining molecular oxygen in liquid hydrocarbon fuels are comparatively evaluated. The proposed gas-chromatographic method is based on use of a cryogenic capillary trap for preliminary separation of gaseous contaminants of oxygen, argon, and nitrogen from gasoline vapors, separation of these contaminants into oxygen together with argon and nitrogen in the analytical column of the chromatograph, measurement of the total volume fraction of oxygen and argon with a thermal-conductivity detector, and calculation of the volume fraction of oxygen with introduction of a correction that accounts for the fraction of argon in the overall total with oxygen.

This article presents the report on the COOMET key comparison COOMET.QM-K111, which is linking to the appropriate CCQM comparison—CCQM-K111 'Propane in nitrogen 1000 μmol/mol'. CCQM-K111 was carried out in 2014–2016 and it was one of a series of key comparisons in the gas analysis area assessing core competences. 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).

Carbon monoxide (CO) is reported to mainly be emitted from industries, transportation, and burnings for various usages. Its atmospheric lifetime varies from weeks to months, depending on the mixing ratio of the highly reactive hydroxyl radical. Even though the ambient level of CO varies as a function of regional sources, the mixing ratio ranges from 30 nmol/mol to 300 nmol/mol at the marine boundary layers and from 100 nmol/mol to more than 500 nmol/mol in urban areas(1). In order to study temporal trends and regional variations of the level of CO, the National Oceanic & Atmospheric Administration/Earth System Research Laboratory-Global Monitoring Division (NOAA/ESRL-GMD(2)) has played a key role as the designated Central Calibration Laboratory (CCL) within the frame of the World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) program. NOAA/ESRL-GMD provides natural air standards, analyzed for CO, to WMO GAW participants. Since the structure of WMO traceability chain appears hierarchical and explicit all over the world, WMO intends to improve the CO measurement compatibility to up to 2 ppb (in case of extensive compatibility goal: 5 ppb, GAW report No. 213(3)) in order to ensure compatibility through the GAW network. Nevertheless, accurate measurement of CO at an ambient level has proven to be difficult due to the lack of stability in cylinders. For these reasons, it is necessary that measured results are compared among the values assigned by various NMIs. This key comparison was initially proposed to be aimed at a CO/N2 standard in the 2010 CCQM meeting by KRISS. With participation of FMI, NOAA, and Empa, a modified scheme of CO/air standards was developed for the purpose of atmospheric observations and co-operative support to WMO/GAW activities. Therefore, the purpose of the comparison is to support the measurement capability of CO at an ambient level of 350 nmol/mol. Further, this key comparison is expected to contribute to the establishment of traceability to a single scale of CO between NMIs by means of harmonizing the results from different national standards. The Empa result lies in a different report. 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).

This article presents the report on the COOMET supplementary comparison "Atmospheric air pollutants: CO in Nitrogen, 5 μmol/mol". Carbon monoxide (CO) is present in atmosphere due to different natural and anthropogenic sources. CO is a toxic gas and in concentrations higher than (3-5) μmol/mol it is hazardous to human health. 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).

Dimethyl sulfide (DMS) is an important compound in monitoring climate change and is monitored by the World Meteorological Organization Global Atmospheric Watch Volatile Organic Compounds (WMO-GAW VOC) program at several monitoring sites. It is essential that measurement results are accurate and consistent among the assigned values for primary gas mixtures to meet the WMO requirement. The purpose of this comparison is to compare the measurement capability of DMS at approximately 10 μ­mol/mol and expectation to contribute the establishment of traceability to single measurement scale for DMS between NMIs. 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).

COOMET.QM-S3 is a supplementary comparison of primary standard gas mixtures—'Carbon monoxide in Nitrogen (3 μmol/mol)'. This is a bilateral comparison between VNIIM and INMETRO and it was conducted in 2013. Carbon monoxide is a toxic gas and in concentrations higher than 3–5 μmol/mol it is hazardous to human health. Therefore, it is important for NMIs to have the capability of an accurate carbon monoxide measurements. This comparison has shown that primary standard gas mixtures of carbon monoxide in nitrogen on the level of 3 μmol/mol, prepared in VNIIM and Inmetro, do not agree—the pair-wise degree of equivalence D (0.77%) is higher than the appropriate expanded uncertainty U(D) (0.29%). 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).

Refinery gas is a complex mixture of hydrocarbons and non-combustible gases (e.g., carbon monoxide, carbon dioxide, nitrogen, helium). It is obtained as part of the refining and conversion of crude oil. This key comparison aims to evaluate the measurement capabilities for these types of mixtures. The results of the key comparison indicate that the analysis of a refinery-type gas mixture is for some laboratories a challenge. Overall, four laboratories (VSL, NIM, NPL and VNIIM) have satisfactory results. The results of some participants highlight some non-trivial issues, such as appropriate separation between saturated and unsaturated hydrocarbons, and issues with the measurement of nitrogen, hydrogen and helium. 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).

This key comparison was performed to demonstrate the capability of NMIs to analyse the purity of methane for use as a source gas in the preparation of standard gas mixtures. This capability is an essential requirement for the preparation of accurate standards of natural gas and some other fuels. Since it is difficult to carry out a comparison with individual samples of pure gas, the sample for this comparison was a synthetic mixture of high purity methane with selected added impurities of nitrogen, argon, carbon dioxide and ethane. These mixtures were prepared by a gas company as a batch of 10 cylinders and their homogeneity and stability were evaluated by NMIJ. The KCRVs for the four different analytes in this key comparison are based on a consensus of values reported by participants. The uncertainties in the degrees of equivalence were calculated by combining the reported uncertainties with the homogeneity of the samples and the uncertainty of the KCRV. The results submitted are generally consistent with the KCRV within the estimated uncertainties. Finally, this comparison demonstrates that the analysis of nitrogen, argon, carbon dioxide and ethane in methane at amount fractions of 1 µmol/mol to 5 µmol/mol is generally possible with an uncertainty of 5% to 10%. 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).

The key comparison CCQM-K76 was designed to test the capabilities of the participants to measure and certify sulfur dioxide in nitrogen, and to provide supporting evidence for the CMCs of these institutes for sulfur dioxide. Also, as sulfur dioxide is designated a core compound, and the 100 ?mol/mol concentration is within the designated core compound concentration range, this comparison was also designed to demonstrate core capabilities of institutes which qualify under the rules of the Gas Analysis Working Group. The results of all 16 participants in this key comparison, except for three, are consistent with their key comparisons reference values. The three participants which are outside the KCRV interval are NIM, SMU and NPLI. This comparison may be used to demonstrate core analytical capabilities in accordance with the rules and procedures of the CCQM Gas Analysis Working group. 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).

The first key comparison on carbon monoxide (CO) in nitrogen dates back to 1992 (CCQM-K1a). It was one of the first types of gas mixtures that were used in an international key comparison. Since then, numerous national metrology institutes (NMIs) have been setting up facilities for gas analysis, and have developed claims for their Calibration and Measurement Capabilities (CMCs) for these mixtures. Furthermore, in the April 2005 meeting of the CCQM (Consultative Committee for Amount of Substance) Gas Analysis Working Group, a policy was proposed to repeat key comparisons for stable mixtures every 10 years. This comparison was performed in line with the policy proposal and provided an opportunity for NMIs that could not participate in the previous comparison. NMISA from South Africa acted as the pilot laboratory. Of the 25 participating laboratories, 19 (76%) showed satisfactory degrees of equivalence to the gravimetric reference value. The results show that the CO concentration is not influenced by the measurement method used, and from this it may be concluded that the pure CO, used to prepare the gas mixtures, was not 13C-isotope depleted. This was confirmed by the isotope ratio analysis carried out by KRISS on a 1% mixture of CO in nitrogen, obtained from the NMISA. There is no indication of positive or negative bias in the gravimetric reference value, as the results from the different laboratories are evenly distributed on both sides of the key comparison reference value., JRC.H.2-Air and Climate

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).

Ammonia is an important compound in the chemical industry. It is widely used and is the basis for producing other compounds containing nitrogen. Ammonia is also very hazardous, and consequently emissions of ammonia need be controlled and monitored. In the past years, several national metrology institutes have developed facilities for the preparation of Primary Standard gas Mixtures (PSMs), dynamically generated ammonia mixtures and facilities for comparing and certifying gas mixtures containing ammonia. The amount-of-substance fraction level of ammonia chosen for this key comparison is 30–50 µmol/mol. The results of this key comparison revealed that there is at present no consensus among static and dynamic techniques for gas mixture preparation for this component in this range. As key comparison reference value (KCRV), the mean of the three methods is used. In its uncertainty, no allowance is made for the observed biases. With respect to the KCRV, only two laboratories report consistent results. When grouped in accordance with the employed methods, the results are consistent. Further experimental work is needed. 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).

Industrial stack gas emission measurements are important for process control, control of air pollution, and for implementing legislation regarding carbon dioxide emission rights. Measurements are typically performed using a range of process analysers for carbon monoxide (CO), carbon dioxide (CO2), nitrogen oxides (NOx), sulphur dioxide (SO2) and miscellaneous hydrocarbons. The calibration of these analysers is often performed using a series of binary mixtures of each component in nitrogen. For reasons of efficiency as well as a better match with true stack gas, the use of multi-component mixtures for this purpose would be preferred. The aim of this key comparison is to evaluate the measurement capabilities of national metrology institutes for carbon monoxide, carbon dioxide, nitrogen monoxide, sulphur dioxide and propane in nitrogen. Ten laboratories participated in the key comparison and one in the associated study. The key comparison reference value is based on the gravimetric preparation data. 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).

The pilot study evaluated the level of comparability of laboratories' preparative capabilities for gravimetric nitrogen monoxide/nitrogen primary reference mixtures in the range (30?70) ?mol/mol. The comparison was designed so that measurements would be performed at a central laboratory (the BIPM) and measurement results compared to values assigned by each national metrology institute (NMI) based on gravimetry using regression analysis. The advantages and complications in organizing a comparison with measurements performed at a central laboratory have been clearly demonstrated, notably: analytical measurement uncertainties can be reduced; a degree of equivalence parameter and its uncertainty can be calculated; regression analysis and therefore reference values for the comparison are highly dependent on the data set chosen for regression analysis and the uncertainty ascribed to the analytical measurement system within the central laboratory. Participating laboratories reported standard uncertainties for gravimetric preparation which ranged from 0.01% to 0.22% relative to the nitrogen monoxide mole fraction value. Following FTIR analysis, the standards of three laboratories (six gas standards in total) were omitted from the regression analysis data set, as a significant difference between reported and measured values of impurity contents was observed. An additional standard was removed from the regression analysis set as its deviation from the regression line was of the same order of magnitude as the standards already omitted. A regression line consistent with the remaining calibration data (15 gas standards) could be obtained by increasing estimates of the coordinating laboratory's measurement uncertainty by approximately a factor of three, resulting in analytical standard uncertainties of 0.12% (at 70 ?mol/mol) and 0.27% (at 30 ?mol/mol), and predicted standard uncertainties of the nitrogen monoxide mole fractions of 0.09 ?mol/mol. Reported standard uncertainties related to gravimetric preparation ranged from 0.004 ?mol/mol to 0.11 ?mol/mol with a median of 0.03 ?mol/mol. Nevertheless, comparison of the results of CCQM-P73 to previous key comparisons for nitrogen monoxide in nitrogen at 100 ?mol/mol (CCQM-K1.c and EUROMET.QM-K1.c) illustrates the reductions in uncertainties that can be achieved through a comparison with measurements performed at a central facility. 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-GAWG.

The first key comparison on carbon dioxide in nitrogen dates from 1993–1994 (CCQM-K1.b). Since then, numerous national metrology institutes (NMIs) have been setting up facilities for gas analysis, and have developed claims for their Calibration and Measurement Capabilities (CMCs) for these type mixtures. In the April 2005 meeting of the CCQM Gas Analysis Working Group, a policy was proposed to repeat key comparisons for stable mixtures every 10 years. Consequently in 2007 the key comparison CCQM-K52 'Carbon dioxide in synthetic air' was carried out. This comparison is consistent with the proposed policy and enables NMIs that could not participate in the previous comparison to take part. This report describes the results of a key comparison for carbon dioxide in synthetic air. The amount-of-substance fraction level of carbon dioxide chosen for this key comparison (360 µmol/mol) represents the ambient level of this component in air. In total 18 NMIs and one WMO laboratory participated in the comparison. The agreement of the results in this key comparison is very good. With a few exceptions, the results agree within 0.3% (or better) with the key comparison reference value. Most of the participants that did not participate in CCQM-K1.b do very well. In some cases, the uncertainties claimed are quite large in comparison with the NMIs for which this comparison is a true 'repeat', but the observed differences with the KCRV usually reflect that these claims are realistic. All participants in CCQM-K1.b that participated in this key comparison show improved results. 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).

At the highest metrological level, natural gas standards are commonly prepared gravimetrically as PSMs (primary standard mixtures). This international key comparison is a repeat of CCQM-K1e-g. The mixtures concerned contain nitrogen, carbon dioxide and the alkanes up to butane. The only difference with CCQM-K1e-g is the addition of iso-butane to the list. The results usually agree within 1% (or better) with the key comparison reference value. For ethane, nitrogen and carbon dioxide, the agreement is within 0.5% (or better), and for methane within 0.1% (or better) of 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).