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The measurement of ammonia (NH3) in ambient air is a sensitive and priority topic due to its impact on ecosystems. NH3 emissions have continuously increased over the last century in Europe because of intensive livestock practices and the enhanced use of nitrogen-based fertilizers. European air quality monitoring networks monitor atmospheric NH3 amount-of-substance fractions. However, the lack of stable reference gas mixtures (RGMs) of atmospheric amount-of-substance fractions of ammonia to calibrate NH3 analyzers is a common issue of the networks, which results in data that are not accurate, traceable, or, thus, geographically comparable. In order to cover this lack, LNE (Laboratoire National de Métrologie et d'Essais) developed, in close collaboration with the company 2M PROCESS, a gas reference generator to dynamically generate NH3 RGMs in air. The method is based on gas permeation and a further dynamic dilution to obtain an amount-of-substance fractions ranging between 1 and 400 nmol mol−1 (also well known as ppb or parts per billion; 1 ppb (NH3) to ≈ 0.7 µg m−3) to cover the amount-of-substance fractions of ammonia measured in ambient air (emissions) and the operating range of the NH3 analyzers used by the monitoring networks. The calibration of the elements of the generator against the LNE primary standards ensures the traceability of the RGMs to the international system of units. Furthermore, the highly accurate flow and oven temperature measurements of the reference generator, together with the associated calibration procedure defined by LNE, guarantee relative expanded uncertainties of the calibration of the NH3 analyzers that are lower than 2 % (coverage factor = 2). This result is very satisfactory, considering the low NH3 amount-of-substance fraction levels (1 to 400 nmol mol−1) and the phenomena of adsorption and desorption, especially in the presence of traces of water on contact surfaces. A bilateral comparison was organized between METAS (Swiss Federal Institute of Metrology) and LNE, which consisted of the calibration of a Picarro G2103 gas analyzer by both national metrology institutes (NMIs). The results highlighted the good agreement between the NH3 reference generators developed by the two institutes and allowed the validation of both LNE's reference generator and calibration procedure. Since the end of 2020, LNE has calibrated several NH3 analyzers from the French air quality monitoring networks (Associations Agréées de Surveillance de la Qualité de l'Air – AASQA) using the newly developed SI-traceable RGMs. The enhanced number of calibrations provided may increase the comparability, accuracy, and traceability of the NH3 measurements carried out on French territory.

Ammonia (NH3) in the atmosphere affects both the environment and human health. It is therefore increasingly recognised by policy makers as an important air pollutant that needs to be mitigated, though it still remains unregulated in many countries. In order to understand the effectiveness of abatement strategies, routine NH3 monitoring is required. Current reference protocols, first developed in the 1990s, use daily samplers with offline analysis; however, there have been a number of technologies developed since, which may be applicable for high time resolution routine monitoring of NH3 at ambient concentrations. The following study is a comprehensive field intercomparison held over an intensively managed grassland in southeastern Scotland using currently available methods that are reported to be suitable for routine monitoring of ambient NH3. In total, 13 instruments took part in the field study, including commercially available technologies, research prototype instruments, and legacy instruments. Assessments of the instruments' precision at low concentrations (< 10 ppb) and at elevated concentrations (maximum reported concentration of 282 ppb) were undertaken. At elevated concentrations, all instruments performed well and with precision (r2 > 0.75). At concentrations below 10 ppb, however, precision decreased, and instruments fell into two distinct groups, with duplicate instruments split across the two groups. It was found that duplicate instruments performed differently as a result of differences in instrument setup, inlet design, and operation of the instrument. New metrological standards were used to evaluate the accuracy in determining absolute concentrations in the field. A calibration-free CRDS optical gas standard (OGS, PTB, DE) served as an instrumental reference standard, and instrument operation was assessed against metrological calibration gases from (i) a permeation system (ReGaS1, METAS, CH) and (ii) primary standard gas mixtures (PSMs) prepared by gravimetry (NPL, UK). This study suggests that, although the OGS gives good performance with respect to sensitivity and linearity against the reference gas standards, this in itself is not enough for the OGS to be a field reference standard, because in field applications, a closed path spectrometer has limitations due to losses to surfaces in sampling NH3, which are not currently taken into account by the OGS. Overall, the instruments compared with the metrological standards performed well, but not every instrument could be compared to the reference gas standards due to incompatible inlet designs and limitations in the gas flow rates of the standards. This work provides evidence that, although NH3 instrumentation have greatly progressed in measurement precision, there is still further work required to quantify the accuracy of these systems under field conditions. It is the recommendation of this study that the use of instruments for routine monitoring of NH3 needs to be set out in standard operating protocols for inlet setup, calibration, and routine maintenance in order for datasets to be comparable.

Ammonia (NH3) in the atmosphere affects both the environment and human health. It is therefore increasingly recognised by policy makers as an important air pollutant that needs to be mitigated. In order to understand the effectiveness of abatement strategies, routine NH3 monitoring is required. Current reference protocols, developed in the 1990s, use daily samplers with offline analysis but there have been a number of technologies developed since, which may be applicable for high time resolution routine monitoring of NH3 at ambient concentrations. The following study is a comprehensive field intercomparison held over an intensively managed grassland in South East Scotland using currently available methods that are reported to be suitable for routine monitoring of ambient NH3. In total 13 instruments took part in the field study. The instruments include: an online ion chromatography system (MARGA, Metrohm-Applikon,NL), two wet chemistry continuous flow analysis systems (AiRRmonia, Mechatronics, NL), a photoacoustic spectrometer (NH3 monitor, LSE, NL), two mini Differential Optical Absorption Spectrometers (miniDOAS; NTB Interstate University of Applied Sciences Buchs, now part of "Eastern Switzerland University of Applied Sciences, CH and RIVM, NL), as well as seven spectrometers using cavity enhanced techniques: a Quantum Cascade Laser Absorption Spectrometer (QCLAS, Aerodyne, Inc. US), Picarro G2103 Analyzer (Picarro US), Economical NH3 Analyser (Los Gatos Research, US), Tiger-i 2000 (Tiger Optics, US) and LaserCEM® gas analyser (AP2E, FR). Assessments of the instruments’ precision at low concentrations (< 10 ppb) and at elevated concentrations (maximum reported concentration of 282 ppb) were undertaken. At elevated concentrations all instruments performed well on precision (r2 > 0.75). At concentrations below 10 ppb however, instruments fell into two distinct groups and the duplicate instruments, miniDOAS, AiRRmonia, LGR and Picarro were split across the two groups. It was found that identical instruments performed differently at low concentrations, highlighting the impact of the setup, inlet design and operation of the instrument used. Accuracy in determining absolute concentrations in the field was assessed using a calibration-free CRDS Optical Gas Standard (OGS, PTB, DE), serving as an instrumental reference standard. Accuracy was also assessed using well established metrological standards for calibration gases, i) a permeation system (ReGaS1, METAS, CH) and ii) Primary Standard gas Mixtures (PSMs) prepared by gravimetry (NPL, UK). This study showed that though the OGS good performance with respect to sensitivity and linearity with reference gas standards, this in itself is not enough for the OGS to be a field reference standard because a closed path spectrometer has limitations due to losses to surfaces in sampling NH3, which need to be taken into account. Overall, the instruments studied performed well against the standard gases but we note that not every instrument could be calibrated using gas standards due to incompatible inlet designs and limitations in the gas flow rates of the standards. This work provides evidence that though NH3 instrumentation have greatly progressed in measurement precision, there is still further work required to quantify the accuracy of these systems under field conditions. It is the recommendation of this study that the use of instruments for routine monitoring of NH3 needs to be set out in standard operating protocols for inlet set-up, calibration and routine maintenance, in order for datasets to be comparable.

The measurement of ammonia (NH3) in ambient air is a sensitive and priority topic due to its harmful effects on human health and ecosystems. NH3 emissions have continuously increased over the last century in Europe, because of intensive livestock practices and enhanced use of nitrogen-based fertilizers. European air quality monitoring networks monitor atmospheric NH3 amount fractions. However, the lack of stable reference gas mixtures (RGMs) at atmospheric amount fractions to calibrate NH3 analyzers is a common issue of the networks, which results in data that are not accurate, traceable and, thus, geographically comparable. In order to cover this lack, LNE developed, in close collaboration with the company 2M PROCESS, a gas reference generator to generate dynamically NH3 RGMs in air. The method is based on gas permeation and further dynamic dilution to obtain an amount fraction range between 1 and 400 nmol/mol. The calibration of the elements of the generator against LNE primary standards ensures the traceability of the RGMs to the international system of units. Furthermore, the highly accurate flow and oven temperature measurements of the reference generator, together with the associated calibration procedure defined by LNE, guarantee relative expanded uncertainties of the calibration of the NH3 analyzer calibrations lower than 2 % (coverage factor = 2). This result is very satisfactory considering the low NH3 amount fraction levels (1 to 400 nmol/mol) and the phenomena of adsorption and desorption, especially in the presence of traces of water on the surfaces in contact. A bilateral comparison was organized between METAS and LNE, consisting on the calibration of a PICARRO G2103 gas analyzer by both national metrology institutes (NMI). The results highlighted the good agreement between the NH3 reference generators developed by the two institutes and allowed to validate both LNE’s reference generator and calibration procedure. The development of the NH3 reference generator has already raised great interest within the French air quality monitoring networks (AASQA). Since the end of 2020, LNE calibrated several NH3 analyzers of the networks. These requests shows the interest of the AASQA in the development of this new gas reference generator to guarantee the traceability of measurements carried out on the French territory.

A critical issue for the long-term monitoring of atmospheric trace gases is precision and accuracy of the measurement systems employed. Both measuring and preparing reference gas mixtures for trace gases are challenging due to, for example, adsorption and desorption of the substances of interest on surfaces; this is particularly critical at low amount fractions and/or for reactive gases. Therefore, to ensure the best preparation and measurement conditions for trace gases in very low amount fractions, usage of coated materials is in demand in gas metrology and atmospheric measurement communities. This study focuses on testing potential adsorption and desorption effects for different materials or coatings that are currently used or that may be relevant in the future for the measurements of greenhouse gases. For this study we used small volume chambers designed to be used for adsorption studies. Various materials with or without coatings were loaded into the small cylinder to test their adsorption and desorption behavior. We used the aluminum cylinder as the measurement chamber and glass, aluminum, copper, brass, steel and three different commercially available coatings as test materials. Inserting the test materials into the measurement chamber doubles the available geometric area for the surface processes. The presented experiments were designed to investigate the pressure dependency of adsorption up to 15 bar and its temperature dependency up to 80 ∘C for the test materials placed in the measurement chamber. Here, we focused on the species CO2, CH4, CO and H2O measured by a cavity ring-down spectroscopy analyzer. Our results show that the materials currently used in atmospheric measurements are well suited. The investigated coatings were not superior to untreated aluminum or to stainless steel at the tested pressure ranges, whereas under changing temperature aluminum showed better performance for CO2 ( µmol mol−1 change in measured amount fractions) than stainless steel (>0.1 µmol mol−1). To our knowledge, this study is one of the first attempts to investigate surface effects of different materials in such a setup for the abovementioned gases.

Monoterpenes play an important role in atmospheric chemistry due to their large anthropogenic and biogenic emission sources and high chemical reactivity. As a consequence, measurements are required to assess how changes in emissions of monoterpenes impact air quality. Accurate and comparable measurements of monoterpenes in indoor and outdoor environments require gaseous primary reference materials (PRMs) that are traceable to the international system of units (SI). PRMs of monoterpenes are challenging to produce due to the high chemical reactivity and low vapour pressures of monoterpenes and also their propensity to convert into other compounds, including other terpenes. In this paper, the long-term stability of gravimetrically prepared static monoterpene PRMs produced in differently passivated cylinders, including sampling canisters, was assessed. We demonstrate that static PRMs of multiple monoterpenes can be prepared and used as a suitable long-term standard. For the first time the effect of cylinder pressure and decanting from one cylinder to another on the chemical composition and amount fraction of monoterpenes was also studied. Gravimetrically prepared PRMs of limonene in high pressure cylinders were compared to a novel portable dynamic reference gas generator based on dilution of pure limonene vapour emitted from a permeation tube.

Volatile organic compounds (VOCs) in gas mixtures at trace level (nmol/mol) are routinely measured by chemical and biochemical laboratories as climate indicators, indoor air quality pollutants from building materials emissions, contaminants in food and beverages, and biomarkers in body fluids (blood, urine, breath) of occupational exposure or human diseases. Current analytical instruments used for measurements are gas chromatographs equipped with various injector and detector configurations. The assurance of measurement quality is done by using a huge amount of certified liquid VOC standard solutions (or gaseous VOC standard cylinders) with multiple dilutions to reach the required trace level. This causes high standard uncertainty in instrument calibrations, high cost, and high consumption of analysis and laboratory personal time. In this paper, we present the implementation of portable generators producing VOC gas standards at trace level for automatic and direct calibration of VOC detectors employed in various contexts, removing the need for preparation of matrix calibration standards in cylinders. Two compact devices in-house developed by two national metrology institutes-the Istituto Nazionale di Ricerca Metrologica (INRIM) and the Federal Institute of Metrology (METAS)-are here used to dynamically generate reference gas mixtures in an SI traceable way. The two devices are based on different technologies: diffusion and permeation, for INRIM and METAS, respectively. A metrological characterization is given and the practical implementation at chemical and biochemical laboratories is discussed. Graphical abstract Onsite calibration with transportable generation system with similar performances to primary laboratory devices.

We report on the development and validation of a compact laser instrument using mid-IR direct absorption spectroscopy (DAS) for high-precision measurements of ethanol in breath-like air mixtures. Leveraging the intermittent continuous wave (iCW) driving for conventional narrow-band distributed feedback (DFB) quantum cascade laser (QCL) emitting around 9.3 µm and using a 25 m path length multiple-pass absorption cell at reduced pressure, a precision of 9 ppb (amount fraction, nmol mol

Main text At the highest metrological level, ammonia gas standards are commonly prepared gravimetrically as Primary Standard Mixtures or using a dynamic standard. This international key comparison addressed the measurement of the amount fraction ammonia in nitrogen, to support calibration and measurement services for mainly environmental applications. The nominal amount fraction was 14 μmol mol-1. The results in this Track C key comparison on the composition of biogas are generally good. 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 https://www.bipm.org/kcdb/. 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 effect of moisture on the adsorption of ammonia was systematically studied using different surface materials and humidity levels. The experimental water amount fractions varied between 6 and 18,000 mu molmol(-1), and the ammonia amount fraction was 400nmolmol(-1). The investigated materials included plain 316L stainless steel and stainless steel cured with Dursan, SilcoNert 2000 and halocarbon wax coatings. Furthermore, Teflon (PTFE) and polyvinylidene difluoride (PVDF) polymer surfaces were studied. Dynamically diluted ammonia, test tubes prepared with the investigated materials, a commercial ammonia analyzer based on cavity ring-down spectroscopy, and a commercial dew-point transmitter were employed. The adsorption was assessed quantitatively using continuous flow conditions and real-time monitoring of the adsorption process. The ammonia adsorption was found to increase substantially in dry conditions for all the studied materials except PVDF. The increase was largest for plain stainless steel which was the most adsorbing material. The coatings applied on stainless steel decreased the adsorption significantly in dry conditions. Polymers PVDF and PTFE were the least-adsorbing materials. In water amount fractions between 1000 and 10,000 mu mol mol(-1), the ammonia adsorption was at its lowest. The adsorption increased again above 1% humidity levels.

Monoterpenes play an important role in atmospheric chemistry due to their large anthropogenic and biogenic emission sources and high chemical reactivity. As a consequence, measurements are required to assess how changes in emissions of monoterpenes impact air quality. Accurate and comparable measurements of monoterpenes in indoor and outdoor environments require gaseous primary reference materials (PRMs) that are traceable to the international system of units (SI). PRMs of monoterpenes are challenging to produce due to the high chemical reactivity and low vapour pressures of monoterpenes and also their propensity to convert into other compounds, including other terpenes. In this paper, the long-term stability of gravimetrically prepared static monoterpene PRMs produced in differently passivated cylinders, including sampling canisters, was assessed. We demonstrate that static PRMs of multiple monoterpenes can be prepared and used as a suitable long-term standard. For the first time the effect of cylinder pressure and decanting from one cylinder to another on the chemical composition and amount fraction of monoterpenes was also studied. Gravimetrically prepared PRMs of limonene in high pressure cylinders were compared to a novel portable dynamic reference gas generator based on dilution of pure limonene vapour emitted from a permeation tube.

Broadly tunable mid-IR laser sources (VECSEL and QCL) open new exciting opportunities for the detection of volatile organic compounds. Real-time, fast, sensitive, and highly specific analysis of human breath with compact instrumentation is demonstrated.

The environmental impacts of ammonia (NH3) in ambient air have become more evident in the recent decades, leading to intensifying research in this field. A number of novel analytical techniques and monitoring instruments have been developed, and the quality and availability of reference gas mixtures used for the calibration of measuring instruments has also increased significantly. However, recent inter-comparison measurements show significant discrepancies, indicating that the majority of the newly developed devices and reference materials require further thorough validation. There is a clear need for more intensive metrological research focusing on quality assurance, intercomparability and validations. MetNH3 (Metrology for ammonia in ambient air) is a three-year project within the framework of the European Metrology Research Programme (EMRP), which aims to bring metrological traceability to ambient ammonia measurements in the 0.5-500 nmol mol-1 amount fraction range. This is addressed by working in three areas: (1) improving accuracy and stability of static and dynamic reference gas mixtures, (2) developing an optical transfer standard and (3) establishing the link between high-accuracy metrological standards and field measurements. In this article we describe the concept, aims and first results of the project.

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).

Dans le cadre du Programme de Recherche Europeen en Metrologie (EMRP), un projet de trois ans a debute en juin 2014 avec l’objectif d’ameliorer la comprehension et la tracabilite metrologique des mesures d’ammoniac (NH3) ambient, dans le domaine 0.5 - 500 nmol/mol. Les trois tâches principales de ce projet sont 1) d’ameliorer l’exactitude et la stabilite de melanges de gaz de reference statiques et dynamiques, 2) de developper un etalon de transfert optique et 3) d’etablir un lien entre les standards metrologiques de haute precision et les mesures de terrain. Les resultats attendus de ce projet vont ameliorer l’exactitude et la fiabilite des estimations d’emissions et ainsi aider a l’evaluation de l’efficacite des mesures de reduction d’emission prescrites par les reglementations internationales. Dans cette publication nous decrivons le concept, les objectifs et les premiers resultats du projet.

The evaluation results of the metrological performance of a dilution and a permeation standard for generating SI-traceable calibration gas mixtures of NO, SO2 and NO2 for ambient air measurements are presented. The composition of the in situ produced reference gas mixtures is calculated from the instantaneous values of the input quantities of the generating standards. In a measurement comparison, the calibration and measurement capabilities of five laboratories were evaluated for the three analytes at limiting amount of substance fractions in ambient air between 20 and 150 nmol mol−1. For the upper generated reference values the target relative uncertainties of ≤2% (for NO and SO2) and ≤3% (for NO2) for evaluating the laboratory results were fulfilled in 12 out of 13 cases. For the analytical results seven out of nine laboratories met the criteria for the upper values for NO and NO2, for SO2 it was one out of four. From the negative degrees of equivalence of all NO2 comparison results it was supposed that the permeation rate of NO2 through the FEP polymer membrane of the permeator was different in air and N2. Subsequent precision permeation measurements with various carrier gases revealed that the permeation rate of NO2 was ≈0.8% lower in synthetic air compared to N2. With the corrected NO2 reference values for air the degrees of equivalence of the laboratory results were improved and closer to be symmetrically distributed.

This key comparison aims to assess the core capabilities of the participants in gas analysis. Such competences include, among others, the capabilities to prepare Primary Standard gas Mixtures (PSMs), perform the necessary purity analysis on the materials used in the gas mixture preparation, the verification of the composition of newly prepared PSMs against existing ones, and the capability of calibrating the composition of a gas mixture. According to the Strategy for Key Comparisons of the Gas Analysis Working Group, this key comparison is classified as an RMO track A key comparison. The artefacts were binary mixtures of propane in nitrogen at a nominal amount-of-substance fraction level of 1000 μmol/mol. The values and uncertainties from the gravimetric gas mixture preparation were used as key comparison reference values (KCRVs). Each transfer standard had its own KCRV. The results are generally good. All results are within ± 1 % 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 (CIPM MRA).

The European Directive (2008/50/EC) sets up, among other things, the limit values i.e. the maximum allowed concentrations at given time average in the air, for specified pollutants. Calibration of the measurement instruments needs to be performed at regular time intervals. In the framework of an European Joint Research Programme (JRP) named Metrology for Chemical Pollutants in Air (MACPoll) one task aims to provide harmonized dilution methods for air pollutant gases at low concentration for calibration and quality control purposes. The study focuses on the reactive gases nitrogen dioxide and sulphur dioxide at concentration levels corresponding to the limit values given in the European Directive (2008/50/EC). Nitrogen oxide (NO) is studied as well as NO2 because both of them are measured simultaneously for NOx. This work consists in improving the dilution methods for generating calibration standards for SO2 , NO, NO2 at limit values and to validate them by an interlaboratory comparison.

This supplementary comparison is designed to test the capabilities of the participants to measure and certify carbon dioxide in nitrogen, and to provide supporting evidence for the CMCs of institutes for carbon dioxide. Indeed this comparison aims to demonstrate the capabilities of IPQ in the production of primary gas mixtures of carbon dioxide in nitrogen and for the participant laboratories to demonstrate their capabilities on certifying primary gas mixtures of percent levels of carbon dioxide in nitrogen. Moreover, a number of NMIs had already participated in the key comparison CCQM-K52, but in a lower range. This EURAMET comparison offers an opportunity to the laboratories to submit CMC in a higher range. In this comparison the laboratories analysed the gas mixtures that are gravimetrically produced and analyzed by IPQ. Each cylinder had its own reference value calculated from the gravimetric preparation. The pressure in the cylinders was approximately 10 MPa; aluminum cylinders of 5 dm3 nominal volume were used. This comparison provides evidence in support of CMCs for carbon dioxide within the range of 1.0 × 10−2 mol/mol to 20.0 × 10−2 mol/mol in a nitrogen/air balance. 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 EURAMET, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

This supplementary comparison (EURAMET.QM-S8) concerns the purity analysis of nitrogen as used in reference gas mixture preparation. This project was carried out without adding impurities to the gas used for this comparison, and is therefore more representative to evaluate the analysis of carbon monoxide, carbon dioxide, methane, oxygen, argon and water impurities in high-purity nitrogen. The analysis of the amount-of-substance fraction water was optional. Two 50 litre high purity nitrogen cylinders were purchased from a well-qualified supplier of specialty gases. The listed components were expected to be present in the pure nitrogen at the target levels as a result of the purification of the nitrogen. From the start of this comparison it was clear that the comparison may not lead to reference values for the constituents analysed. The results indicate that analyses of high purity gases are often limited by the limits of detection of analytical equipment used. The reports of the participating laboratories also indicate that there is no agreed method of determination of the uncertainty on a detection limit value. The results provide useful information on the performance of participants. For all analysed components there is reasonable agreement in results for LNE, VSL, METAS and NPL. For BAM only the argon result is in agreement. 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 EURAMET, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM 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

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).

In the wake of the redefinition of the kilogram, the last unit of the International System of Units (SI) that is still based on a man-made artefact, discussions were launched on the necessity of redefining other units, amongst other the unit mole. Since 1971 the mole is defined as the amount of substance of a system that contains as many elementary entities as there are atoms in 0.012 kilogram of carbon 12. The symbol of the unit is 'mol'. When the mole is used, the elementary entities must be specified and may be atoms, molecules, ions, electrons, other particles, or specified groups of such particles. The definition is based on the pre-existing choice to set the relative atomic mass of carbon 12 equal to 12 exactly. In the proposed new definition the mole is the amount of substance containing exactly 6.022 141 79 × 1023 atoms or molecules, ions, electrons, other particles, or specified groups of such particles, i.e. the Avogardo constant would have a fixed value without an uncertainty. This contribution critically examines the submitted arguments to justify the proposed redefinition of the unit mole by 2011 for their persuasive power to change a scientific and cultural good such as a unit of measurement. As shown, there are no convincing scientific arguments for a redefinition of the mole that stand a closer examination. The current definition is well understood, established in science and technology for almost 50 years and is still up to date.

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.