L A Konopelko

Final report on international key comparison CCQM-K53: Oxygen in nitrogen

Gravimetry is used as the primary method for the preparation of primary standard gas mixtures in most national metrology institutes, and it requires the combined abilities of purity assessment, weighing technique and analytical skills. At the CCQM GAWG meeting in October 2005, it was agreed that KRISS should coordinate a key comparison, CCQM-K53, on the gravimetric preparation of gas, at a level of 100 ?mol/mol of oxygen in nitrogen. KRISS compared the gravimetric value of each cylinder with an analytical instrument. A preparation for oxygen gas standard mixture requires particular care to be accurate, because oxygen is a major component of the atmosphere. Key issues for this comparison are related to (1) the gravimetric technique which needs at least two steps for dilution, (2) oxygen impurity in nitrogen, and (3) argon impurity in nitrogen. The key comparison reference value is obtained from the linear regression line (with origin) of a selected set of participants. The KCRV subset, except one, agree with each other. The standard deviation of the x-residuals of this group (which consists of NMIJ, VSL, NIST, NPL, BAM, KRISS and CENAM) is 0.056 ?mol/mol and consistent with the uncertainties given to their standard mixtures. The standard deviation of the residuals of all participating laboratory is 0.182 ?mol/mol. With respect to impurity analysis, overall argon amounts of the cylinders are in the region of about 3 ?mol/mol; however; four cylinders showed an argon amount fraction over 10 ?mol/mol. Two of these are inconsistent with the KCRV subset. The explicit separation between two peaks of oxygen and argon in the GC chromatogram is essential to maintain analytical capability. Additionally oxygen impurity analysis in nitrogen is indispensable to ensure the preparative capability. 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).

Final report on international comparison CCQM-K68: Nitrous oxide in synthetic air

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).

International comparison CCQM-K54: Primary standard gas mixtures of hexane in methane

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).

International comparison CCQM-K82: methane in air at ambient level (1800 to 2200) nmol/mol

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 participants 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).

International comparison CCQM-K46: Ammonia in nitrogen

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).

CCQM-K27-Subsequent: Key Comparison (subsequent) for the Determination of Ethanol in Aqueous Matrix

Ethanol is important both forensically (“drunk driving” or driving while under the influence, “DWI”, regulations) and commercially (alcoholic beverages). Blood-and breath-alcohol testing can be imposed on individuals operating private vehicles such as cars, boats, or snowmobiles, or operators of commercial vehicles like trucks, planes, and ships. The various levels of blood alcohol that determine whether these operators are considered legally impaired vary depending on the circumstances, and locality Accurate calibration and validation of instrumentation is critical in areas of forensic testing where quantitative analysis directly affects the outcome of criminal prosecutions, as is the case with the determination of ethanol in blood and breath. Additionally, the accurate assessment of the alcoholic content of beverages is a commercially important commodity. In 2002, the CCQM conducted a Key Comparison (CCQM-K27) for the determination of ethanol in aqueous matrix with nine participants. A report on this project has been approved by the CCQM and can be found at the BIPM website [1]. CCQM-K27 was comprised of three samples, one at low mass fraction of ethanol in water (nominal concentration of 0.8 mg/g), one at high level (nominal concentration of 120 mg/g), and one wine matrix (nominal concentration of 81 mg/g). Overall agreement among eight participants using gas chromatography with flame ionization detection (GC-FID), titrimetry, isotope dilution gas chromatography/mass spectrometry (GC-IDMS), and gas chromatography-combustion-isotope ratio mass spectrometry (ID-GC-C-IRMS) was good. The ninth participant used a headspace GC-FID method that had not been validated in an earlier pilot study (CCQM-P35).

CCQM-K86/P113.1: Relative quantification of genomic DNA fragments extracted from a biological tissue

Key comparison CCQM-K86 was performed to demonstrate and document the capacity of interested national metrology institutes (NMIs) and designated institutes (DIs) in the determination of the relative quantity of two specific genomic DNA fragments present in a biological tissue. The study provides the support for the following measurement claim: Quantification of the ratio of the number of copies of specified intact sequence fragments of a length in the range of 70 to 100 nucleotides in a single genomic DNA extract from ground maize seed materials. The study was carried out under the auspices of the Bioanalysis Working Group (BAWG) of the Comit? Consultatif pour la Quantit? de Mati?re (CCQM) and was piloted by the Institute for Reference Materials and Methods (IRMM) in Geel (Belgium). The following laboratories (in alphabetical order) participated in this key comparison: AIST (Japan), CENAM (Mexico), DMSc (Thailand), GLHK (Hong Kong), IRMM (European Union), KRISS (Republic of Korea), LGC (United Kingdom), MIRS/NIB (Slovenia), NIM (PR China), NIST (USA), NMIA (Australia), T?BITAK UME (Turkey) and VNIIM (Russian Federation). The following laboratories (in alphabetical order) participated in a pilot study that was organized in parallel: LGC (United Kingdom), PKU (PR China), NFRI (Japan) and NIMT (Thailand). Good agreement was observed between the reported results of eleven participants. 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).

Final Report on International comparison CCQM K23ac: Natural gas types I and III

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).

International comparison CCQM-K77: Refinery gas

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).

Final report on international key comparison CCQM-K65: Gas standards containing methyl and ethyl mercaptans (at the level of 20–30 µmol/mol) in methane

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).