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In Russia, the metrological traceability of certified reference materials for the composition of gas mixtures in cylinders under pressure produced by the manufacturers of certified reference materials is carried out in accordance with GOST 8.578-2014. Certified reference materials for the composition of gas mixtures in cylinders under pressure are applied in type approval testing of measuring instruments, verification, calibration and graduation of gas analytical measuring instruments intended for controlling fire and explosion hazardous gases and vapours, harmful components in the atmospheric and workplace air, emissions of vehicles and industrial enterprises, control of technological processes and quality of hydrocarbon products, etc. In this connection, ensuring the quality of commercially available certified reference materials, which number has recently amounted to about 100,000 cylinders with gas mixtures per year, is an important task. In this paper, we suggest a set of measures aimed at ensuring the quality of certified reference gas mixtures in cylinders under pressure, mass-produced by the manufacturers of certified reference materials: mandatory accreditation of reference material producers (RMPs) for compliance with the requirements of GOST ISO Guide 34-2014 and GOST ISO Guide 35-2015; constant participation of RMPs in proficiency testing programmes through interlaboratory comparisons; updating and revision of the existing set of standards defining the requirements for the entire life cycle of certified reference gas mixtures in cylinders under pressure; improvement of the method for reference material certification by calculating the value of their expanded uncertainty and introducing of a new, “technological reserve”, factor.

The main issues and recent achievements in the field of metrological assurance of carbon isotope-ratio analysis are considered. An overview of the existing methods of carbon isotope-ratio analysis of gaseous, liquid, and solid substances is offered. Recommendations for the development of new carbon isotopic reference gaseous mixtures in vessels under pressure traceable to the international standard VPDB are given. The basic error limits required for their certification are formulated.

The basic principles of development of metrological assurance of quality control of products on the basis of two-phase hydrocarbon systems (stable and unstable gas condensates) are considered.

This paper presents a brief review of the developed laser technologies and lidars with hyperspectral resolution and extremely high sensitivity for the diagnosis of complex impurities in the atmosphere and hydrosphere via Raman spectra. The technological foundations of the research, exploratory, and ecological studies of hydrocarbons are developed using Raman lidars. The prospects of hybridization of Raman spectrometry and video spectrometry in remote probing are considered.

At the highest metrological level, biogas standards are commonly prepared gravimetrically as PSMs (primary standard mixtures). This international key comparison addresses the composition of biogas, to support calibration and measurement services for this renewable energy gas. The mixtures contain nitrogen, carbon dioxide, methane, ethane, propane, hydrogen and oxygen and represent the composition of biogas from landfills. The results in this Track C key comparison on the composition of biogas are generally good. Some of the datasets, especially that of oxygen, showed substantial extra dispersion, that could not be explained by the stated uncertainties. 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).

Application of CCD array photodetector technology is shown to provide record synchronously hundreds of spectral intervals, increase essentially the relative aperture and intensity of echo-signals in the input optical path as well as to reduce the mass – dimension parameters of hyperspectral Raman LIDAR as a whole for geoecological monitoring by aerial and underwater unmanned vehicles.

Forensic application of carbon isotope ratio measurements of honey and honey protein to investigate the degree of adulteration with high fructose corn syrup or other C4 plant sugars is well established. These measurements must use methods that exhibit suitable performance criteria, particularly with regard to measurement uncertainty and traceability – low levels of adulteration can only be detected by methods that result in suitably small measurement uncertainties such that differences of 1‰ or less can be reliably detected. Inter-laboratory exercises are invaluable to assess the state-of-the art of measurement capabilities of laboratories necessary to achieve such performance criteria. National and designated metrology institutes from a number of countries recently participated in an inter-laboratory assessment (CCQM-K140) of stable carbon isotope ratio determination of bulk honey. The same sample material was distributed to a number of forensic isotope analysis laboratories that could not participate directly in the metrological comparison. The results from these studies have demonstrated that the majority of participants provided isotope delta values with acceptable performance metrics; that all participants ensured traceability of their results; and that where measurement uncertainties were reported; these were fit-for-purpose. A number of the forensic laboratories only reported precision rather than full estimates of measurement uncertainty and this was the major cause of the few instances of questionable performance metrics. Reporting of standard deviations in place of measurement uncertainties is common practice outside metrology institutes and the implications for interpretations of small differences in isotopic compositions are discussed. The results have also highlighted a number of considerations that are useful for organisers of similar inter-laboratory studies in the future.

CCQM-K124 was organized by the Inorganic Analysis Working Group (IAWG) of CCQM to assess and document the capabilities of the national metrology institutes (NMIs) or the designated institutes (DIs) to measure the mass fractions of trace elements (As, B, Cd, Ca, Cr, Hg and Mo) and hexavalent chromium (Cr(VI)) in drinking water. The National Metrology Institute of Japan (NMIJ) and the Government Laboratory, Hong Kong SAR (GLHK) acted as the coordinating laboratories. This comparison is divided into two parts. Part A was organized by the NMIJ and the trace elements were the analytes, and Part B was organised by the GLHK and Cr(VI) was the analyte. In Part A, results were submitted by 14 NMIs and nine DIs. The participants used different measurement methods, though most of them used direct measurement using inductively coupled plasma-optical emission spectrometry (ICP-OES), inductively coupled plasma-mass spectrometry (ICP-MS), and isotope dilution technique with ICP-MS. The results of As, B, Cd, Ca and Cr show good agreement with the exception of some outliers. Concerning Hg, instability was observed when the sample was stored in the light. And some participants observed instability of Mo. Therefore, it was agreed to abandon the Hg and Mo analysis as this sample was not satisfactory for KC. In Part B, results were submitted by six NMIs and one DI. The methods applied were direct measurement using 1,5-diphenylcarbazide (DPC) derivatisation UV-visible spectrophotometry, standard addition using ion chromatography-UV-visible spectrophotometry or HPLC—inductively coupled plasma-mass spectrometry (ICP-MS) and isotope dilution technique with ion chromatography—ICP-MS. The results of all participants show good agreement. Accounting for relative expanded uncertainty, comparability of measurement results for each of As, B, Cd, Ca, Cr and Cr(VI) was successfully demonstrated by the participating NMIs or DIs. 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).

Measurement assurance in the identification of ozone-depleting substances is considered. It is indicated thatozone-depleting halogenated hydrocarbons must be monitored, and portable devices for detecting counterfeits in customs border control are needed.

CCQM-K120.a comparison involves preparing standards of carbon dioxide in air which are fit for purpose for the atmospheric monitoring community, with stringent requirements on matrix composition and measurement uncertainty of the CO2 mole fraction. This represents an analytical challenge and is therefore considered as a Track C comparison. The comparison will underpin CMC claims for CO2 in air for standards and calibrations services for the atmospheric monitoring community, matrix matched to real air, over the mole fraction range of 250 μmol/mol to 520 μmol/mol. CCQM-K120.b comparison tests core skills and competencies required in gravimetric preparation, analytical certification and purity analysis. It is considered as a Track A comparison. It will underpin CO2 in air and nitrogen claims in a mole fraction range starting at the smallest participant's reported expanded uncertainty and ending at 500 mmol/mol. Participants successful in this comparison may use their result in the flexible scheme and underpin claims for all core mixtures This study has involved a comparison at the BIPM of a suite of 44 gas standards prepared by each of the participating laboratories. Fourteen laboratories took part in both comparisons (CCQM-K120.a, CCQM-K120.b) and just one solely in the CCQM-K120.b comparison. The standards were sent to the BIPM where the comparison measurements were performed. Two measurement methods were used to compare the standards, to ensure no measurement method dependant bias: GC-FID and FTIR spectroscopic analysis corrected for isotopic variation in the CO2 gases, measured at the BIPM using absorption laser spectroscopy. Following the advice of the CCQM Gas Analysis Working Group, results from the FTIR method were used to calculate the key comparison reference values. KEY WORDS FOR SEARCH FTIR, CO2, GC-FID, Carbon dioxide at background level, Carbon dioxide at urban level, Delta Ray, CO2 gas standards 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).

The management of the production of calibration specimens (of approved type and enterprise-wide) of a composition of hydrocarbon mixtures is considered; special attention is paid to the traceability of the standards to GET 154–2011, the state primary standard of the unit of mole fraction and unit of mass concentration of components in gaseous media.

A complex of studies on the development of a system of metrological assurance of measurement technologies in the recovery, transportation, and delivery of gas to customers in the Russian Federation is considered. A system of metrological assurance for quality control of natural gas developed at the Gazprom company that supports the traceability of the results of measurements to the state primary standard of units of mole fraction and mass concentration of the components in gaseous media (GET 154-01) and renders the results of quality control of natural gas internationally recognizable is presented.

Methods and instruments for ensuring unity of measurements of the ozone content in the surface layer of the atmosphere are described. The uncertainty budget of the standard photometric system based on an SRP-type photometer, forming part of the State Primary Standard of the units of molar fraction and mass concentration of the components in gaseous media (GET 154-01) is presented. The results of international key comparisons carried out under the aegis of the BIPM are presented.

Liquefied hydrocarbon mixtures with traceable composition are required in order to underpin measurements of the composition and other physical properties of LPG (liquefied petroleum gas), thus meeting the needs of an increasingly large industrial market. This comparison aims to assess the analytical capabilities of laboratories for measuring the composition of a Liquid Petroleum Gas (LPG) mixture when sampled in the liquid phase from a Constant Pressure Cylinder. Mixtures contained ethane, propane, propene, i-butane, n-butane, but-1-ene and i-pentane with nominal amount fractions of 2, 71, 9, 4, 10, 3 and 1 cmol mol−1 respectively. 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).

The measurement of trace amounts of water in process gases is of paramount importance to a number of manufacturing processes. Water is considered to be one of the most difficult impurities to remove from gas supply systems and there is strong evidence that the presence of water contamination in semiconductor gases has a measurable impact on the quality and performance of devices. Consequently, semiconductor manufacturers are constantly reducing target levels of water in purge and process gases. As the purity of gases improves, the problem of quantifying contamination and ensuring that the gases are within specification at the point of use becomes more challenging. There are several established techniques for detecting trace water vapour in process gases. These include instruments based on the chilled mirror principle which measures the dew-point of the gas and the quartz crystal adsorption principle which measures the adsorption of water vapour into a crystal with a hygroscopic coating. Most recently, spectroscopic instruments such as those employing cavity ring-down spectroscopy (CRDS) have become available. The calibration of such instruments is a difficult exercise because of the very limited availability of accurate water vapour standards. This CCQM key comparison aims to assess the analytical capabilities of laboratories for measuring the composition of 10 μmol mol-1 water vapour in nitrogen. KEY WORDS FOR SEARCH Metrology, traceability, water vapour, process gas, advance manufacturing 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).

A requirement is substantiated for improving the accuracy of certification for gravimetric standard gas mixtures (GSGM). Principles are developed for external quality control of GSGM for working standards of the zero order with application of statistical monitoring methods for quality according to a quantified characteristic.

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).

The CCQM-K82 comparison was designed to evaluate the degrees of equivalence of NMI capabilities for methane in air primary reference mixtures in the range (1800 to 2200) nmol/mol. The balance gas for the standards was either scrubbed dry real air or synthetic air. CH4 in air standards have been produced by a number of laboratories for many years, with more recent developments focused on standards at atmospheric measurement concentrations and aimed at obtaining agreement between independently produced standards. A comparison of the differences in primary gas standards for methane in air was previously performed in 2003 (CCQM-P41 Greenhouse gases. 1 and 2) with a standard deviation of results around the reference value of 30 nmol/mol and 10 nmol/mol for a more limited set of standards. This can be contrasted with the level of agreement required from field laboratories routinely measuring atmospheric methane levels, set by Data Quality Objectives (DQO) established by the World Meteorological Organization (WMO) to reflect the scientifically desirable level of compatibility for CH4 measurements at the global scale, currently set at 2 nmol/mol (1 sigma). The measurements of this key comparison took place from May 2012 to June 2012. Eight laboratories took part in this comparison coordinated by the BIPM and NIST. Key comparison reference values were calculated based on Cavity Ring Down Spectroscopy Measurements performed at the BIPM, combined with participant's gravimetric values to identify a consistent set of standards. Regression analysis allowed predicted values for each standard to be calculated which acted as the KCRVs. In this comparison reported standard uncertainties by participants ranged from 0.50 nmol/mol to 2.4 nmol/mol and the uncertainties of individual KCRVs ranged from 0.68 nmol/mol to 0.71 nmol/mol. The standard deviation of the ensemble of standards about the KCRV value was 1.70 nmol/mol. This represents a greater than tenfold improvement in the level of compatibility of methane in air standards compared to that demonstrated in 2003. Further improvements in the compatibility of standards will require improved methods and uncertainties for the measurement of trace level methane in balance gases. 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 CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

The increase in renewable sources in the energy matrix of the countries is an effort to reduce dependency on crude oil and the environmental impacts associated with its use. In order to help overcome the lack of widely accepted quality standards for fuel ethanol and to guarantee its competitiveness in the international trade market, the NMIs have been working to develop certified reference materials for bio-fuels and measurement methods. Inorganic impurities such as Cu, Na and Fe may be present in the fuel ethanol and their presence is associated with corrosion and the formation of oxide deposits in some engine parts. The key comparison CCQM-K100 was carried out under the auspices of the Inorganic Analysis Working Group (IAWG) and the coordination of the National Institute of Metrology, Quality and Technology (INMETRO). The objective of this key comparison was to compare the measurement capabilities of the participants for the determination of Cu in fuel ethanol. Ten NMIs participated in this exercise and most of them used the isotopic dilution method for determining the amount of Cu. The median was chosen as key comparison reference value (KCRV). The assigned KCRV for the Cu content was 0.3589 ?g/g with a combined standard uncertainty of 0.0014 ?g/g. In general, there is a good agreement among the participants' 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 (CIPM MRA).

Sulfur dioxide is one of the main contaminants present in the atmosphere due to burning of coal, oil and natural gas, smelting of base metals and production of sulfuric acid. Sulfur dioxide has been the subject of three previous CCQM key comparisons: CCQM-K1.d in 1997, CCQM-K26.b in 2005 and CCQM-K76 in 2010. VNIIM proposed a new COOMET project (No 484/RU/09) in this field, which was registered in the KCDB as key comparison COOMET.QM-K76. It was found that all results were consistent with the reference (gravimetric) values, with observed differences not exceeding ?0.60% and not exceeding either the appropriate assigned expanded uncertainties. VNIIM is the linking laboratory to CCQM-K76. SMU has improved the results obtained in CCQM-K76. The mixtures prepared for this exercise were found to be stable during about one year within the uncertainty of the measurements. 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).

Nitrogen monoxide is one of the main contaminants present in the atmospheric air due to emissions of vehicles and power stations. Taking into account the positive experience of VNIIM in the pilot study CCQM-P73 (Nitrogen monoxide gas standards, 30 ?mol/mol to 70 ?mol/mol), a COOMET project (No 483/RU/09) on the subject was decided and registered in the KCDB as supplementary comparison COOMET.QM-S1. This involved six National Metrology Institutes, aiming to consolidate or support their Calibration and Measurement Capabilities in this field. It was found that most of the results were consistent with the reference (gravimetric) values, with observed differences not exceeding ?1.3% and not exceeding either the appropriate assigned expanded uncertainties. There was, however, one exception: the INMETRO difference from the reference value is slightly higher than the expended uncertainty. The mixtures prepared for this exercise were found to be stable during about one year within the uncertainty of the measurements. 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 COOMET, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Methane is one of the main components of greenhouse gases in the atmosphere. Its measurement is an important issue in monitoring changes in the global environment. The present comparison (methane in synthetic air at the level of 100 ?mol/mol) was proposed in 2011 within the cooperation program in the field of Metrology between VNIIM and INMETRO. It was then registered in the KCDB as a COOMET supplementary comparison with the identifier COOMET.QM-S2. The results of this exercise show that the primary standards of methane in air maintained by INMETRO and VNIIM are in good agreement, the difference of measurements being substantially smaller than its expanded uncertainty. The mixtures prepared for this exercise were found to be stable during about one year within the uncertainty of the measurements. 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 COOMET, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

The results of the first pilot study designed to evaluate the level of comparability of measurements of nitrogen dioxide (NO2) mole fractions in nitrogen based on measurement procedures that rely on FT-IR spectroscopy as an absolute method of quantification with the traceability of measurement results to line strength data are reported. Participants were required to report measurement results using FT-IR for the gas standard (nominal mole fraction of 10??mol/mol NO2 in nitrogen) received from the BIPM as part of the CCQM-K74 exercise. In addition, they were required to provide infrared spectra and instrument parameter information to enable a recalculation of their results by the BIPM's, using only its own synthetic spectra calibration procedure with values traceable to the line parameters contained in HITRAN 2004. The relative standard uncertainties based on FT-IR measurements reported by participating laboratories ranged from 0.6% to 4.3%. The relative standard uncertainty of the reference value for each gas standard was 0.4%, as determined during the CCQM-K74 exercise. Of the ten results submitted, only five agreed with the reference value within their expanded uncertainties. Furthermore, major contributions to the uncertainty of FT-IR measurements arose from the optical path length measurements and the uncertainty that could be attributed to line strength data from the HITRAN molecular database. The inclusion of these uncertainty contributions was estimated by the BIPM to result in achievable relative standard uncertainties of 3.4% for its FT-IR measurements using synthetic spectra calibration procedures. Finally the recalculation of the participants' results by the BIPM using the laboratories' submitted experimental characteristics and infrared spectra showed good agreement with the submitted results, indicating that the calculation algorithms were not in themselves a major reason for the spread of results. 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 key comparison CCQM-K89 was undertaken to demonstrate the capability of participating NMIs and DIs in measuring the contents of incurred trace elements (total arsenic, cadmium and lead) and essential elements (calcium and zinc) at ?g/g (for arsenic, cadmium, lead and zinc) and mg/g (for calcium) levels in a herb matrix sample by various analytical techniques. This key comparison was organized by the Government Laboratory of the Hong Kong Special Administrative Region (GLHK) and agreed at the Inorganic Analysis Working Group Meeting in Hind?s, Sweden in October 2010 as a benchmarking exercise with arsenic (a trace element) and calcium (an essential element) chosen as the 'exemplary' elements. It was also agreed that a pilot study CCQM-P126 would be run in parallel with this key comparison. The key comparison serves to facilitate claims by participants on the Calibration and Measurement Capabilities (CMCs) as listed in Appendix C of the Key Comparison Database (KCDB) under the Mutual Recognition Arrangement of the International Committee for Weights and Measures (CIPM MRA). A total of 20 NMIs/DIs registered for this programme and 18 of them submitted their results. Most of the participants used microwave acid digestion methods for sample dissolution. For the instrumental determination, a variety of techniques like ICP-MS, AAS, INAA, ICP-AES were employed by the participants. For this key comparison, inorganic core capabilities have been demonstrated by concerned participants with respect to methods including ICP-MS (without isotope dilution), ID-ICP-MS, ICP-AES, INAA, AAS and ion chromatography with iteratively matrix-matched calibration on the determination of total arsenic, calcium, cadmium, lead and zinc in a matrix of herb. 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 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).

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).

There is a high international priority attached to activities which reduce NOx in the atmosphere. The current level of permitted emissions is typically between 50 µmol/mol and 100 µmol/mol, but lower values are expected in the future. Currently, ambient air quality monitoring regulations also require the measurement of NOx mole fractions as low as 0.2 µmol/mol. The production of accurate standards at these levels of mole fractions requires either dilution of a stable higher concentration gas standard or production by a dynamic technique, for example one based on permeation tubes. The CCQM-K74 key comparison was designed to evaluate the level of comparability of National Metrology Institutes' measurement capabilities and standards for nitrogen dioxide (NO2) at a nominal mole fraction of 10 µmol/mol. The measurements of this key comparison took place from June 2009 to May 2010. Seventeen laboratories took part in this comparison coordinated by the BIPM and VSL. The key comparison reference value was based on BIPM measurement results, and the standard measurement uncertainty of the reference value was 0.042 µmol/mol. This key comparison demonstrated that the results of the majority of the participants agreed within limits of ±3% relative to the reference value. The results of only one laboratory lay significantly outside these limits. Likewise this comparison made clear that a full interpretation of the results of the comparison needed to take into account the presence of nitric acid (in the range 100 nmol/mol to 350 nmol/mol) in the cylinders circulated as part of the comparison, as well as the possible presence of nitric acid in the primary standards used by participating laboratories. 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).

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).

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).

The key comparison CCQM-K65 was intended to compare the capabilities for the preparation and value assignment of gas standards for methyl and ethyl mercaptans in methane, maintained at the participating national metrological institutes: VNIIM (Russia), KRISS (Korea), VSL (Netherlands) and NPL (United Kingdom). The range of the nominal amount of substance fractions of the comparison gas mixtures was 20 µmol/mol to 30 µmol/mol, which is close to regulatory level (in several countries including Russia) for mercaptans in odorated natural gas. This comparison was proposed at the 12th GAWG meeting in October 2004 and was conducted in 2008. Conclusions are as follows: The results of all laboratories are consistent with the reference values. The observed differences between the reference and reported values are within ±0.9% for methyl mercaptan and ±0.75% for ethyl mercaptan relative to the gravimetric values, and do not exceed the appropriate assigned expanded uncertainties. The prepared mixtures were found to be stable during about a year within the uncertainty of the measurements. The gravimetric values were successfully validated with a dynamic method. 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).

Twenty-two standards of synthetic natural gas standards were submitted from ten different NMIs for a comparison using the harmonization method developed by NPL. All standards had seven components. This method can remove the correlated variation in calibration data for multi-component mixtures and makes a significant improvement in fitting individual points to calibration curves. After removing the non-random variation from the data all the standards showed very good agreement with only a few outliers. The typical deviation from the calibration curves was around 0.05% (relative) for the main components and less than 0.2% for the butanes. 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.

Accurate measurements of sulphur dioxide at the concentrations found in ambient air have become essential to support monitoring and legislation concerned with air quality. In general, the primary element of quality assurance for field instruments is regular calibration using certified gas mixtures. The concentration range chosen for this Key Comparison (240 nmol/mol to 320 nmol/mol) is defined by appropriate European standards and is typical of similar levels used around the world. The travelling standards used for the comparison were prepared commercially by a supplier with a proven track record of preparing stable mixtures of the relevant gases. The coordinating laboratory (NPL) carried out stability checks on the mixtures and determined the amount fraction using a primary gravimetric permeation facility. These data were used to determine the drift rate (and uncertainty) of each standard. The results for the 11 participants in CCQM-K26.b and the one participant in CCQM-P50.b are presented in this report. Degrees of equivalence have been calculated based on a reference value (corresponding to the KCRV) derived from the primary gravimetric facility used by the coordinating laboratory. 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 comparison is the first key comparison in the field of gas analysis organized by Technical Committee 1.8 'Physical Chemistry' COOMET. This comparison is the fourth key comparison on automobile gases. Earlier key comparisons on automobile gases were carried out by the Consultative Committee for Amount of Substance CCQM-K3 (the results were published on 21 November 2001) and by regional metrological organizations EUROMET and APMP (EUROMET.QM-K3?the results were published on 5 July 2002, APMP.QM-K3?the results were published on 14 November 2003). The relevance of the comparison is based on the tightening of requirements on the control of automobile emissions (putting EURO 4 and EURO-5 into operation). The foundation of this comparison is: The formation of circumstances for recognition of the national measurement standards of Belarus and Ukraine, which earlier did not participate in key comparisons, and entering of the calibration and measurement capabilities (CMC) of BelGIM and Ukrmetrteststandard in the field of automobile gases to the international database KCDB in accordance with the Mutual Recognition Arrangement (CIPM MRA) for national measurement standards and for calibration and measurement certificates issued by NMIs; The objective of NMIs which participated in key comparisons on automobile gases earlier (BAM and VNIIM) is to support or improve their calibration and measurement capabilities. All laboratories find the gravimetric value within ?0.7% relative to the gravimetric value. This holds for all three components, CO, CO2 and C3H8 in nitrogen. This is a satisfying result. For all laboratories the observed difference between the gravimetric and reported values does not exceed its combined uncertainty. 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 intended to compare the capabilities for the preparation and value assignment of gas standards for hydrogen sulfide in nitrogen, maintained at the participating national metrology institutes. The range of the nominal amount-of-substance fractions of the comparison standard is 10 µmol/mol, which is close to regulatory levels in most countries. The measurements in this key comparison took place in 2005. There were 7 participants. The KCRV was calculated from the participants' data, and thus represents a consensus value. This was necessary due to the fact that the cylinders could not be prepared gravimetrically as hydrogen sulfide may be absorbed onto the walls of the cylinder, and has been shown to be unstable in cylinders at the comparison concentration. Thus the gas mixtures were procured from a vendor as a homogeneous lot of 12 cylinders, analyzed by the coordinating laboratory for 6 months to determine stability, and then those determined to be stable were shipped to the participants for analysis. After analysis, the cylinders were returned to the coordinating laboratory for reanalysis. Through this protocol the coordinating laboratory could track stability. In parallel, the coordinating laboratory also analyzed a stable reference, a hydrogen sulfide gas mixture that had been shown to be stable over many years. Using the lot stability data, the participant's analytical results, and the coordinating laboratories' analysis of the stable reference, a consensus value could be calculated which represents the concentration of the stable reference. The key comparison demonstrated that the results of the laboratories agreed within 0.5% relative to the consensus value. A subset of 6 participants' results agreed with the consensus value to better than 0.25%. 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).

We report a pilot study organized within the Consultative Committee for Amount of Substance (CCQM), in which the ozone reference standards of 23 institutes have been compared to one common reference, the BIPM ozone reference standard, in a series of bilateral comparisons carried out between July 2003 and February 2005. The BIPM, which maintains as its reference standard a standard reference photometer (SRP) developed by the National Institute of Standards and Technology (NIST, United States), served as pilot laboratory. A total of 25 instruments were compared to the common reference standard, either directly (16 comparisons) or via a transfer standard (9 comparisons). The comparisons were made over the ozone mole fraction range 0 nmol/mol to 500 nmol/mol. Two reference methods for measuring ozone mole fractions in synthetic air were compared, thanks to the participation of two institutes maintaining a gas-phase titration system with traceability of measurements to primary gas standards of NO and NO2, while the 23 other instruments were based on UV absorption. In the first instance, each comparison was characterized by the two parameters of a linear equation, as well as their related uncertainties, computed with generalized least-squares regression software. Analysis of these results using the Birge ratio indicated an underestimation of the uncertainties associated with the measurement results of some of the ozone standards, particularly the NIST SRPs. As a final result of the pilot study, the difference from the reference value (BIPM-SRP27 measurement result) and its related uncertainty were calculated for each ozone standard at the two nominal ozone mole fractions of 80 nmol/mol and 420 nmol/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.

CF4 and SF6 are the global warming chemicals that are used in semiconductor companies. In the Kyoto protocol on climate change in 1997, those chemicals were included in the items for which quantified emission limitation and reduction commitments were required. Accordingly for the measurement of these gases, it is necessary that measurement results are accurate and traceable, in particular because of the fact that CF4 and SF6 are global warming source gases. This part of the project focuses on a comparison of measurement capability for measuring CF4 and SF6 at emission level. This key comparison will cover the comparability of the gas CRMs at the emission level (10 × 10-6 mol/mol – 100 mmol/mol in nitrogen or air) of the following chemicals: CF4, C2F6, CHF3, SF6 and NF3. There is good agreement between the results of the key comparison participants in this comparison for both CF4 and SF6. The results for CF4 agree within 0.5% relative, and for SF6 they agree within 0.1% relative. Even though the concentration is as low as 100 µmol/mol, the comparability between participants on gravimetric preparation plus comparison analysis is excellent for the laboratories that are participating in this key comparison. 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.

Following-up the key comparison CCQM-K1c, EUROMET organized a regional key comparison involving ten laboratories. The objectives of this EUROMET key comparison were essentially the same as for the CCQM-K1c comparison: to compare the measurement capabilities of national metrological institutes (NMIs) in measuring amount of substance fractions of nitrogen monoxide in nitrogen. The nominal amount of substance fraction of the standards used for the comparison was 100 µmol/mol. The pilot laboratory in this key comparison also piloted the CCQM key comparison and has long-term experience in the behaviour of these mixtures and the technical challenges in preparing batches of very similar mixtures. Most participants used chemiluminescence as the measurement method; two participants used UV techniques and one ND-IR. The degrees of equivalence between this comparison and CCQM-K1c were calculated; four laboratories participated in both key comparisons, thus providing sufficient data for demonstrating the comparability. 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, according to the provisions of the Mutual Recognition Arrangement (MRA).

Natural gas is an important energy vector. The determination of its composition is often used as the basis for the calculation of the calorific value. The calorific value in turn is one of the two key parameters used in natural gas trade. In the first series of key comparisons (CCQM-K1e-g), natural gas was already included with three different compositions. These mixtures contained carbon dioxide, nitrogen, ethane, propane and n-butane in methane (matrix) and were only to a limited extent representative of real natural gas. In the past years, national metrology institutes have broadened the range of components by including, e.g., i-butane, neo-pentane, n-pentane, i-pentane and n-hexane. Based on this extended components list, two new mixtures have been defined, one characteristic for a low calorific mixture (type IV) and the other for a high calorific mixture (type V). In the low calorific mixture, helium was also present. Due to presence of the butane and pentane isomers, the mixtures of type IV and V are more demanding with respect to the separation technique than the mixtures used in CCQM-K1e-g. The measurements in this key comparison took place in 2001. There were eight participants and two coordinating laboratories. The key comparison reference value (KCRV) was based on the gravimetric preparation for all components. Even for the heavier hydrocarbons (pentanes and n-hexane) the effects of, e.g., adsorption can be controlled to such an extent that this approach is still valid. The uncertainty evaluation of the KCRVs reflected also the extent to which the preparation data could be demonstrated to be valid. The validity of the preparation data was demonstrated by comparing the composition of the mixtures prepared for this comparison with measurement standards maintained by the coordinating laboratories. The key comparisons demonstrated that the results of the laboratories agreed within 1% relative to the reference value for most components. Even better agreement was obtained for nitrogen in the low calorific mixture (0.5%), carbon dioxide (0.5%), ethane (0,5%), propane (0.5%) and methane (0.1%). In some cases, larger differences were observed, which then also exceeded the associated expanded uncertainty 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 Mutual Recognition Arrangement (MRA).

This key comparison involved primary standards of ethanol in air maintained at eight laboratories. The nominal amount fraction of the standards used for the comparison was 120 µmol/mol, which is typical of the levels used to calibrate evidential breath analysers in many countries. Such standards fulfil the agreed requirements of the International Organization of Legal Metrology (OIML) for the calibration of evidential breath-alcohol analysers and can provide a more accurate calibration at field level than ethanol/water solution-based simulators, which have a high sensitivity to variations in the temperature of the solution. EUROMET.QM-K4 results are linked to CCQM-K4 results.