Search

The most challenging problems in the field of chemico- and bioanalytical measurements are described. These problems are being solved, in particular, by participating in new international comparisons organized by the Consultative Committee for Amount of Substance: Metrology in Chemistry and Biology of the International Committee of Weights and Measures (CCQM CIPM). Solutions of these challenging problems are presented. The objectives and tasks of developing key comparisons in the following areas are described: isotopic measurements; determination of the purity of substances; organic analysis; bioanalytical measurements; measurements of aerosol particle parameters; measurements in the field of gas analysis and electrochemistry. It is shown that participation in international key comparisons allows obtaining valid and reliable results of measurements of the composition and properties of gas and liquid media, as well as solid substances and materials.

This article develops the issues of building up the federal state educational standards, major professional academic programs for specialists in the field of metrology, taking into account occupational standards. The regulatory documents characterizing the metrology specialists activities have been analyzed. A structure to build up an occupational standards system in the field of metrology has been put forward.

Main text The CCQM-K10.2018 comparison aimed to evaluate the capabilities of national metrology institutes (NMIs) to prepare and/or value assign primary reference mixtures containing benzene, toluene, ethylbenzene, p-xylene, m-xylene and o-xylene (subsequently referred to as BTEX) in nitrogen. This key comparison was separated into two parallel studies. The first study, deemed the "gravimetric study", evaluated the level of compatibility of BTEX standards provided by NMIs. Seven participating laboratories each submitted one standard at nominal 5 nmol mol-1 BTEX in nitrogen. Comparison measurements were performed by the National Institute of Standards and Technology (NIST) from July to October 2018. The second study, deemed the "comparative study", compared the capabilities of NMIs to measure the amount fractions of BTEX in a mixture provided by NIST. NIST prepared one standard at nominal 5 nmol mol-1 BTEX in nitrogen, which was measured consecutively by three participating laboratories. The participants' measurements took place from August 2018 to March 2019. The comparison protocol adopted for CCQM-K10.2018 was more challenging than for the original comparison, CCQM-K10 in 2001, and the results provide an extended evaluation of the level of compatibility of BTEX in nitrogen standards. 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).

Main text Dimethyl sulfide (DMS) is produced mainly by the metabolic activities of oceanic phytoplankton and the most abundant natural sulfur compound in the atmosphere. DMS plays an important role for climate change since it is oxidized and forms sulfate aerosols in the atmosphere, affecting the Earth's radiation budget directly and indirectly. DMS is designated as one of the target reactive gases and monitored in the World Meteorological Organization (WMO) Global Atmospheric Watch (GAW) programme. It is important to accurately monitor its global background levels with SI traceability for better understanding of the role of DMS in climate change. This comparison is organized by Korea Research Institute of Standards and Science (KRISS). Gas mixtures gravimetrically prepared by KRISS are used for demonstrating measurement equivalence at the highest metrological level. This comparison (Track C) is designed to underpin participants' measurement capabilities of trace level DMS in nitrogen at the nominal amount fraction of 5 nmol mol-1. 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).

Main text CCQM-K118 was an international key comparison on natural gas composition with two types of gases, i.e., a low calorific hydrogen-enriched natural gas and a high calorific LNG type of gas. There were 14 participating laboratories. The traveling standards (i.e., 14 mixtures each) were obtained from an external source and checked for homogeneity and stability before and after the participants' measurements at the two coordinating laboratories. The data evaluation was performed using a consensus value and a laboratory effect model. The results of the participants were benchmarked against a key comparison reference value computed from the largest consistent subset (LCS) of the submitted results, adjusted for the differences between the travelling standards. For the first time in a key comparison in gas analysis, the model included a term to account for excess variability in the LCS. Most of the participants reported one or a few (slightly) discrepant results. Partly this is due to the heterogeneity and heteroscedasticity of the datasets. In all, the results in this key comparison demonstrate the good comparability of the national measurement standards for natural gas composition maintained by the participating NMIs. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA). 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 introduction of interference–polarization filters (IPFs) in the structure of an optical–absorption analyzer makes it possible to pick out a harmonic (a Fourier component of the absorption spectrum) providing measurement with the highest sensitivity. The selectivity of such a method of analysis is determined by overlapping the oscillations of the measured and interfering components. By the example of measurement in benzene in the presence of an interfering component (toluene), the possibility is considered for the optimization of selectivity due to the variation of the path-difference dispersion for ordinary and extraordinary interfering rays. The metrological characteristics of the interference–polarization analyzer of C6H6 confirming the results of calculations are given.

A new analytical method of optical absorption analysis, based on selection of a Fourier component of the absorption spectrum (characteristic of the material under study) by a polarization interference filter, has been proposed and tested experimentally.

We developed a Raman lidar with ultraspectral resolution for automatic airborne monitoring of pipeline leaks and for oil and gas exploration. Test flights indicate that a sensitivity of 6 ppm for methane and 2 ppm for hydrogen sulfide has been reached for leakage detection.

The key comparison CCQM-K137 was aimed at evaluating the level of compatibility of laboratories' preparative capabilities for gravimetric nitrogen monoxide/nitrogen primary reference mixtures at mole fractions of 30 μmol mol-1 and 70 μmol mol-1. The comparison was organised by the BIPM. It consisted in the simultaneous comparison of a suite of 2n primary gas standards, two standards to be prepared by each of the n participating laboratories at the nominal values of 30 μmol mol-1 and 70 μmol mol-1. Two independent analytical methods were used by the BIPM to analyse the amount fraction of nitrogen monoxide (NO) in nitrogen; UV spectrophotometry and chemiluminescence (CLD). The agreement between the results obtained with the two main techniques served to highlight possible issues in the preparation of the standards. During this comparison, standards prepared by two participants appeared to result in a larger bias between the analysers than observed for others. These observations were explained by the analysis of all standards by Fourier Transform Infrared Spectroscopy (FTIR) which identified the presence of a larger amounts of water vapour (H2O), nitrous oxide (N2O) and nitrogen dioxide (NO2) in these standards, which are the three main impurities which can appear in mixtures of NO in nitrogen. The above observations were used to underpin the selection of standards (at each nominal NO mole fraction) which can be considered as a consistent set, allowing the calculation of a calibration line by a Generalised Least-Square regression. Key Comparison Reference Values were then proposed for all participants as predicted values from the calibration lines. Interferences caused in the response of the CLD analyser by impurities (verified by FTIR measurements) led to only the results from the UV analyser being proposed for the KCRV and Degrees of Equivalence calculations. Good agreement was observed between all participants who could prepare their standards with minimum levels of impurities. The key comparison CCQM-K137 is considered to present an analytical challenge at both nominal mole fractions and therefore considered as a Specialised (Track C) comparison in the CCQM nomenclature. 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-P106 pilot study was organized by the inorganic working group of the Comite Consultatif pour la Quantite de Matiere (CCQM) as a feasibility comparison to study the applicability of different analysis methods to the polypropylene sample and test the abilities of the participants for measuring the Cd, Cr, Hg and Pb in polypropylene. National Institute of Metrology P.R. China (NIM) acted as the coordinating laboratory of this pilot study. There were 21 laboratories that submitted the final results. The median values of the mass fraction of Cd, Cr, Hg and Pb were 36.12 mg kg−1 (the median absolute deviation about the median (MADe) = 0.46 mg kg−1), 252.5 mg kg−1 (MADe = 3.4 mg kg−1), 387.0 mg kg−1 (MADe = 10.1 mg kg−1) and 466.2 mg kg−1 (MADe = 8.9 mg kg−1), respectively. Isotope dilution mass spectrometry (IDMS), inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasma-optical emission spectrometry (ICP-OES), atomic absorption spectrometry (AAS), instrumental neutron activation analysis (INAA) and X-ray fluorescence (XRF) measurement methods were used, and microwave digestion was used by the most of the participants. In general, very good agreement of the results was observed. Moreover, compared to the results of other methods, the results of IDMS still showed less spread amongst laboratories and had a smaller uncertainty. In addition, the results of some analytes used by XRF and INAA also got satisfactory agreement with the median value.

Characteristic features of identification procedures of chemical substances are described and the metrological requirements for identification are discussed. The procedures are considered to be rigorous enough, if quantitative criteria such as the measure of similarity between physicochemical properties or spectra of the unknown substance and reference materials are used. Identification involves expert opinion which is of prime importance in the analysis of samples of unknown composition. The reliability of substance recognition can be increased by selecting highly qualified personnel, establishing a good information supply, using an on-line combination of separation and detection instruments such as chromatography-spectrometry and estimating the probability of identification. Standard conditions for reliable identification including quantitative criteria are examined using gas chromatography-mass spectrometry as an example.

The characteristic features and the constituents of an identification procedure for chemical substances are discussed. This procedure is a screening of identification hypotheses followed by experimental testing of each one. The testing operation consists of comparison of the values of the quantities measured with other measurement results or reference data, resulting in the Student's ratio, the significance level, the matching of spectra, etc. The performance and the correctness of identification are expressed as "identification uncertainty", i.e. the probability of incorrect identification. The statistical significance level and other similarity values in spectra, chromatography retention parameters, etc. are the particular measures of uncertainty. Searching of prior data and estimation of the prior probability of the presence of particular compounds in the sample (matrix) to be analysed simplifies the setting up and cancelling of hypotheses during screening. Usually, identification is made by the analyst taking into account measurement results, prior information and personal considerations. The estimation of uncertainty and rules for the incorporation of prior data, make the result of identification less subjective.

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