CCQM Activities in the Gas Analysis Working Group

Summary

NIST's Chemical Sciences Division Gas Sensing Metrology Group has participated in over 40 Consultative Committee for Amount of Substance-Metrology in Chemistry (CCQM) Gas Analysis Working Group (GAWG) Key Comparison and Pilot studies since 1993. The CCQM conducts international Key comparisons to establish equivalence among measurements made by National Metrology Institutes (NMIs). GAWG Key Comparisons during the past five years included measurement of BTEX, ammonia, carbon dioxide, monoterpenes, propane, hydrogen chloride, nitrous oxide, and automotive emissions gases.  In addition to key comparison activities, the Gas Sensing Metrology Group routinely contributes to GAWG task group activities.

Description

Credit: Lane Sander

The results from these Key comparisons will be used to benchmark the appropriate Calibration and Measurement Claims (CMCs) of the participating NMIs. CMCs are basically the declared capabilities that an NMI offers to customers, and they are included in a searchable database at the BIPM web site. CMCs that are common among the NMIs are identified appropriate comparisons proposed. NIST CMCs are benchmarked based on carefully designed and executed comparisons using the methods normally used for those analyses for NIST's customers.

In addition to Key comparisons, NIST often participates in task group activities of the Gas Analysis Working Group (GAWG).  Task groups are often formed to address technical issues and develop guidance for the NMI community.  Examples of task groups NIST members of the Gas Sensing Metrology Group have participated in over the past five years include:  Task Group on Designing Key Comparisons, Broad Scope Claims Harmonization Task Group, Task Group on Purity Analysis, GAWG Strategy Task Group, and Task Group on Developing Guidelines to Support New CMCs.  Recently, GAWG has included expert institutions and external stakeholders in task group activities.  Listed below are two additional large task groups which include external stakeholders:

• Launch of Greenhouse Gas Scale Task Group:  expanding accessibility to standards for CO2 atmospheric monitoring and emissions authentication  https://www.bipm.org/en/-/2021-04-01-co2-tg
• CCQM Task Group for Ozone Cross-Section Change Management:  establishing guidance for implementing the change in the ozone cross-section value used world-wide for surface ozone measurements to the CCQM.O3.2019 value https://doi.org/10.1088/1681-7575/ab0bdd.

Major Accomplishments

• CCQM-K46, Key Comparison of 30 to 40 µmol/mol Ammonia
• CCQM-K51, Key Comparison of 5 µmol/mol Carbon Monoxide
• CCQM-K53, Key Comparison (Preparative) of 100 µmol/mol Oxygen
• CCQM-K54, Key Comparison (Preparative) of 100 µmol/mol Hexane
• CCQM-K66 Purity of Methane
• CCQM-K68 320 nmol/mol Nitrous Oxide in Air
• CCQM-K71, Key Comparison emission levels of Sulfur Dioxide, Nitric Oxide, Propane, Carbon Monoxide, and Carbon Dioxide
• CCQM-K76, Key Comparison of 100 µmol/mol Sulfur Dioxide in Nitrogen (Coordinating Laboratory)
• CCQM-K82, Key Comparison of Methane in Air at Ambient Level (1800-2200) nmol/mol (Preparative) (Co-Coordinating Laboratory)
• CCQM-K93, Key Comparison of 120 µmol/mol Ethanol in Nitrogen or Air
• BIPM.QM-K1, Key Comparison of Ozone
• CCQM-K10.2018: BTEX in nitrogen at 5 nmol mol−1
• CCQM-K117 ammonia
• CCQM-K120 Carbon dioxide at background and urban level
• CCQM-K121 Monoterpenes in nitrogen at 2.5 nmol mol-1
• CCQM-K111 Propane in nitrogen
• CCQM-K175 hydrogen chloride (ongoing)
• CCQM-P225 Ambient CO2 in Air (ongoing)
• CCQM-K68.2019 Ambient N2O in Air (ongoing)
• CCQM-K3.2019 Automotive Emission Gases (ongoing)

Additional Technical Details

The technical approaches used for the GAWG Key Comparisons are the same as those used for the CMCs. In this way, the CMCs can be benchmarked through the CCQM studies. The GAWG has decided to conduct two types of Key Comparisons: 1) the Core Key Comparisons and 2) Analytical Challenge Key Comparisons. The Core Key Comparisons will test an NMI's core capabilities to produce gas standards, and each NMI will be required to participate in these exercises periodically. An example of a current active Core Key Comparison is 1000 µmol/mol propane of which NIST is a participant. These comparisons will be very broad in scope and cover a large number of non-reactive gas CMCs. The Analytical Challenge Key Comparisons will cover a very narrow scope, usually only the compound being compared. An example of these comparisons is the recent ammonia key comparison which covers only ammonia in the concentration range of 10 µmol/mol to percent levels.

Associated Publications

1. van der Veen, A. M. H., van Wijk, J. I. T., Harris, K., Goodman, C., Hodges, J., Uehara, S., Kang, J. H., Kim, Y. D., Kim, D. H., and Lee, S., "International comparison CCQM-K117 ammonia," Metrologia, 58, (2021). 

2. Liaskos, C., Rhoderick, G., Hodges, J., Possolo, A., and Wilke, O., "Pilot comparison CCQM-P177-monoterpenes in nitrogen at 2.5 nmol mol(-1) final report," Metrologia, 57, (2020). 

3. Viallon, J., Idrees, F., Moussay, P., Wielgosz, R., Ming, K. F., Hui, W. L., Jie, F., Cui, Y. X., Norris, J. E., and Hodges, J. T., "Final report, on-going key comparison BIPM.QM-K1, ozone at ambient level, comparison with NMC, A-STAR, July 2018," Metrologia, 57, (2020). 

4. Viallon, J., Flores, E., Idrees, F., Moussay, P., Wielgosz, R. I., Oh, S. H., Lee, S., Kim, B. M., Nieuwenkamp, G., Van der Veen, A., Efremova, O. V., Konopelko, L. A., Kustikov, Y. A., Kolobova, A. V., Shuguo, H., Carney, J., Kelley, M. E., Rhoderick, G. C., Hodges, J. T., Uehara, S., Akima, D., Brewer, P., Worton, D., Van Aswegen, S., Mace, T., Smeulders, D., Fuko, J., Ntsasa, N., Leshabane, N., Ramahala, K., Tshilongo, J., Cieciora, D., Shimosaka, T., and Matsumoto, N., "CCQM-K137, nitrogen monoxide (NO) in nitrogen," Metrologia, 57, (2020). 

5. Viallon, J., Idrees, F., Moussay, P., Wielgosz, R., Norris, J. E., and Hodges, J. T., "Final report, on-going key comparison BIPM.QM-K1, ozone at ambient level, comparison with NIST, June 2019," Metrologia, 57, (2020). 

6. Liaskos, C., Rhoderick, G., Hodges, J., Possolo, A., Goodman, C., Kim, Y. D., Kim, D. H., Lee, S., Allen, N., Corbel, M., Worton, D., Brown, R., and Brewer, P., "CCQM-K121-Monoterpenes in Nitrogen at 2.5 nmol mol(-1) Final Report," Metrologia, 55, (2018). 

7. Rhoderick, G., Guenther, F., Duewer, D., Lee, J., Kim, J. S., Hall, B., Weiss, R., Harth, C., Reimann, S., and Vollmer, M., "CCQM-P151 Final Report Pilot Study CCQM P151 Halocarbons in Dry Whole Air," Metrologia, 51, (2014). 

8. Rhoderick, G., Guenther, F., Duewer, D., Lee, J., Moon, D., Lee, J., Lim, J., and Kim, J. S., "CCQM-K83 Final Report International Comparison CCQM-K83 Halocarbons in Dry Whole Air," Metrologia, 51, (2014). 

9. Urquiza, M. P., Torres, M. M., Mitani, Y., Schantz, M. M., Duewer, D. L., May, W. E., Parris, R. M., Wise, S. A., Kaminski, K., Philipp, R., Win, T., Rosso, A., Kim, D. H., Ishikawa, K., Krylov, A. I., Kustikov, Y. A., and Baldan, A., "CCQM Key Comparison - Organic Solutions CCQM-K47 Volatile Organic Compounds in Methanol Final Report," Metrologia, 50, (2013).