CCQM-K90, formaldehyde in nitrogen, 2 μmol mol− 1 Final report

The CCQM-K90 comparison is designed to evaluate the level of comparability of national metrology institutes (NMI) or designated institutes (DI) measurement capabilities for formaldehyde in nitrogen at a nominal mole fraction of 2 μmol mol−1. The comparison was organised by the BIPM using a suite of gas mixtures prepared by a producer of specialty calibration gases. The BIPM assigned the formaldehyde mole fraction in the mixtures by comparison with primary mixtures generated dynamically by permeation coupled with continuous weighing in a magnetic suspension balance. The BIPM developed two dynamic sources of formaldehyde in nitrogen that provide two independent values of the formaldehyde mole fraction: the first one based on diffusion of trioxane followed by thermal conversion to formaldehyde, the second one based on permeation of formaldehyde from paraformaldehyde contained in a permeation tube. Two independent analytical methods, based on cavity ring down spectroscopy (CRDS) and Fourier transform infrared spectroscopy (FTIR) were used for the assignment procedure. Each participating institute was provided with one transfer standard and value assigned the formaldehyde mole fraction in the standard based on its own measurement capabilities. The stability of the formaldehyde mole fraction in transfer standards was deduced from repeated measurements performed at the BIPM before and after measurements performed at participating institutes. In addition, 5 control standards were kept at the BIPM for regular measurements during the course of the comparison. Temporal trends that approximately describe the linear decrease of the amount-of-substance fraction of formaldehyde in nitrogen in the transfer standards over time were estimated by two different mathematical treatments, the outcomes of which were proposed to participants. The two treatments also differed in the way measurement uncertainties arising from measurements performed at the BIPM were propagated to the uncertainty of the trend parameters, as well as how the dispersion of the dates when measurements were made by the participants was taken into account. Upon decision of the participants, the Key Comparison Reference Values were assigned by the BIPM using the largest uncertainty for measurements performed at the BIPM, linear regression without weight to calculate the trend parameters, and not taking into account the dispersion of dates for measurements made by the participant. Each transfer standard was assigned its own reference value and associated expanded uncertainty. An expression for the degree of equivalence between each participating institute and the KCRV was calculated from the comparison results and measurement uncertainties submitted by participating laboratories. Results of the alternative mathematical treatment are presented in annex of this report

Final report, on-going key comparison BIPM.QM-K1, ozone at ambient level, comparison with JRC, July 2019

As part of the ongoing key comparison BIPM.QM-K1, a comparison has been performed between the ozone standard of the European Commission maintained by the Joint Research Centre (JRC) and the common reference standard of the key comparison, maintained by the Bureau International des Poids et Mesures (BIPM). The instruments have been compared over a nominal ozone amount-of-substance fraction range from 0 nmol/mol to 500 nmol/mol.JRC.C.5-Air and Climat

CCQM-K120 (Carbon dioxide at background and urban level)

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

International Comparison CCQM-P28: Ozone at Ambient Level

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.JRC.H.4-Transport and air qualit

Absorption cross-sections of Ozone in the ultraviolet and visible spectral regions – Status report 2015

International audienceThe activity “Absorption Cross-Sections of Ozone” (ACSO) started in 2008 as a joint initiative of the International Ozone Commission (IO3C), the World Meteorological Organization (WMO) and the IGACO (“Integrated Global Atmospheric Chemistry Observations”) O3/UV subgroup to study, evaluate, and recommend the most suitable ozone absorption cross-section laboratory data to be used in atmospheric ozone measurements. The evaluation was basically restricted to ozone absorption cross-sections in the UV range with particular focus on the Huggins band. Up until now, the data of Bass and Paur published in 1985 (BP, 1985) are still officially recommended for such measurements. During the last decade it became obvious that BP (1985) cross-section data have deficits for use in advanced space-borne ozone measurements. At the same time, it was recognized that the origin of systematic differences in ground-based measurements of ozone required further investigation, in particular whether the BP (1985) cross-section data might contribute to these differences.In ACSO, different sets of laboratory ozone absorption cross-section data (including their dependence on temperature) of the group of Reims (France) and , 1992, 1995, abbreviated as BDM, 1995) and those of [8], and [7], (abbreviated as SER, 2014) were examined for use in atmospheric ozone measurements in the Huggins band.In conclusion, ACSO recommends:- The spectroscopic data of BP (1985) should no longer be used for retrieval of atmospheric ozone measurements.- For retrieval of ground-based instruments of total ozone and ozone profile measurements by the Umkehr method performed by Brewer and Dobson instruments data of SER (2014) are recommended to be used. When SER (2014) is used, the difference between total ozone measurements of Brewer and Dobson instruments are very small and the difference between Dobson measurements at AD and CD wavelength pairs are diminished.- For ground-based Light Detection and Ranging (LIDAR) measurements the use of BDM (1995) or SER (2014) is recommended.- For satellite retrieval the presently widely used data of BDM (1995) should be used because SER (2014) seems less suitable for retrievals that use wavelengths close to 300 nm due to a deficiency in the signal-to-noise ratio in the SER (2014) dataset

Advances in reference materials and measurement techniques for greenhouse gas atmospheric observations

We present the global research landscape which aims to deliver a measurement infrastructure to underpin atmospheric observations of key greenhouse gases governing changes in the Earth’s climate. These measurements present a significant challenge to the metrological community, analytical laboratories and major producers of reference materials. The review focuses on the progress made in the Gas Analysis Working Group of the Consultative Committee for Amount of Substance: Metrology in Chemistry and Biology (CCQM-GAWG) in establishing the primary realisation of the amount-of-substance fraction for carbon dioxide, methane and nitrous oxide in an air matrix. It also focuses on the importance of providing traceable measurements of isotopic composition of these components for commutability of reference materials and for isotope ratio measurements for greenhouse gas source attribution. The review examines the developments in the Global Atmosphere Watch (GAW) Programme of the World Meteorological Organisation (WMO) for providing the framework for the development and implementation of integrated greenhouse gas observations, which is vital for understanding the global carbon cycle and the role greenhouse gases play in climate change. The developments in analytical techniques are also discussed which have shaped the direction of the metrology required to meet the evolving and future needs of stakeholders