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 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).

Identified sources of uncertainty within the ELISA methodology included pipetting, data fitting, model selection and instrument/plate variation.

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.

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 uncertaintyMain 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).