Jeongsoon Lee

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).

Measurement and Characterization of Atmospheric SF 6 at Korea GAW Center in 2007

Korea Global Atmosphere Watch Center (KGAWC), which is located in Anmyeondo and, belongs to the Korea Meteorological Administration (KMA), measures sulfur hexafluoride () in every hour since 2007. In this study, observed in 2007 are discussed. A gas chromatograph-electron capture detector (GC-ECD) with pre-cooled device is applied during the observation, and produced data are qualified by means of periodic calibration with standard gas made by Korea Research Institute of Standard and Science (KRISS). has been greatly paid attention since Kyoto protocol because of its high global warming potential(GWP) with 22,200 times of in the period of 100 years. It is a man-made compound and has been usually used for gas insulation since 1970s and for etching process in the information technology-based industry since 1990. Average mixing ratio of in 2007 was 6.65 pmol/mol at Anmyeondo. According to the GAW report published in 2008, average mixing ratio of in the atmosphere is continuously growing. At present, the average mixing ratio of in the atmosphere is known to be approximately 6.25 pmol/mol at global observatory. value in Anmyeondo shows 0.40 pmol/mol greater than that of the Mauna Loa observatory in 2007.

Validation of spectroscopic gas analyzer accuracy using gravimetric standard gas mixtures: Impact of background gas composition on CO 2 quantitation by cavity ring-down spectroscopy

The effect of background gas composition on the measurement of CO2 levels was investigated by wavelengthscanned cavity ring-down spectrometry (WS-CRDS) employing a spectral line centered at the R(1) of the (3 00 1)III← (0 0 0) band. For this purpose, eight cylinders with various gas compositions were gravimetrically and volumetrically prepared within 2σ = 0.1 %, and these gas mixtures were introduced into the WS-CRDS analyzer calibrated against standards of ambient air composition. Depending on the gas composition, deviations between CRDSdetermined and gravimetrically (or volumetrically) assigned CO2 concentrations ranged from −9.77 to 5.36 μmol mol−1, e.g., excess N2 exhibited a negative deviation, whereas excess Ar showed a positive one. The total pressure broadening coefficients (TPBCs) obtained from the composition of N2, O2, and Ar thoroughly corrected the deviations up to −0.5 to 0.6 μmol mol−1, while these values were −0.43 to 1.43 μmol mol−1 considering PBCs induced by only N2. The use of TPBC enhanced deviations to be corrected to ∼ 0.15 %. Furthermore, the above correction linearly shifted CRDS responses for a large extent of TPBCs ranging from 0.065 to 0.081 cm−1 atm−1. Thus, accurate measurements using optical intensity-based techniques such as WS-CRDS require TPBC-based instrument calibration or use standards prepared in the same background composition of ambient air.

Gravimetric standard gas mixtures for global monitoring of atmospheric SF6

In this study, standard gas mixtures of SF6 in synthetic air were gravimetrically developed as a suite consisting of 6 mixtures with mole fractions of SF6 ranging from 5 to 15 pmol/mol. For precision in weighing the gas fills, an automatic weighing system coupled with a high sensitivity mass balance was used and a gravimetry precision of 3 mg (2σ) was achieved. Impurity profiles of the raw gases were determined by various analyzers. In particular, sub pmol/mol levels of SF6 in the matrix components (N2, O2, and Ar) were carefully measured, since the mole fraction of SF6 in the final step can be significantly biased by this trace amount of SF6 in the raw gases of the matrix components. Gravimetric dilution of SF6 by purity-assessed N2 was performed in 6 steps to achieve a mole fraction of 440 pmol/mol. In the final step, O2 and Ar were added to mimic the atmospheric composition. Gravimetric fractions of SF6 and the associated standard uncertainty in each step were computed according to the ISO 6142 and JCGM 100:2008, respectively, and validated experimentally. Eventually, the SF6 fraction uncertainty of the standard gas mixtures combined by uncertainties of gravimetric preparation and verification measurements were found to be nominally 0.08% at a 95% confidence interval. A comparison with independent calibration standards from NOAA shows agreement within 0.49%, satisfying the extended WMO compatibility goal, 0.05 ppt.

Inspection on the Influence of Asian Dust on the Distribution of Atmospheric Mercury Observed for a Long Time

To evaluate the possibly potent role of Asian Dust (AD) on the long range transport of Hg, statistical analyses were carried out using the hourly concentration data of gaseous elemental mercury (Hg) along with relevant environmental parameters. For the purpose of this study, Hg data were collected from Yang-Jae monitoring station in Seoul, Korea during Sept. 1997 to June 2002. During the study period, Hg concentrations in non-AD period ranged from with a mean , while those in AD period from with a mean . The air quality during AD were typically deteriorated by enhanced PM10 mass concentration (by times) compared to non-AD period, however comparison of the Hg concentration data indicates that they are not critically distinguished between events of AD and non-AD, except for the high minimum level of Hg during AD. The results of correlation and factor analysis also indicated somewhat complex patterns; in the case of AD events, Hg and were assorted concurrently into a same factor. Evidence collected from this study thus suggests that long-range transport of Hg, if occurring, is unlikely to raise statistically Hg concentration levels such as seen during AD event. However, in nighttime of winter season, Hg concentrations are higher during AD (along with PM10 levels) than non-AD period. Although such observations suggest the effect of long range transport on the enhancement of Hg concentrations, more deliberate analysis may be required to track down the effect of such mechanism in relation with various factors including the air mass transport route.

Analysis of trace impurities in neon by a customized gas chromatography.

Excimer lasers, widely used in the semiconductor industry, are crucial for analyzing the purity of premix laser gases for the purpose of controlling stable laser output power. In this study, we designed a system for analyzing impurities in pure neon (Ne) base gas by customized GC. Impurities in pure neon (H2 and He), which cannot be analyzed at the sub-μmol/mol level using commercial GC detectors, were analyzed by a customized pulsed-discharge Ne ionization detector (PDNeD) and a pressurized injection thermal conductivity detector using Ne as the carrier gas (Pres. Inj. Ne-TCD). From the results, trace species in Ne were identified with the following detection limits: H2, 0.378μmol/mol; O2, 0.119μmol/mol; CH4, 0.880μmol/mol; CO, 0.263μmol/mol; CO2, 0.162μmol/mol (PDNeD); and He, 0.190μmol/mol (Pres. Inj. Ne-TCD). This PDNeD and pressurized injection Ne-TCD technique thus developed permit the quantification of trace impurities present in high-purity Ne.

Final report of key comparison APMP.QM-K53—comparison of gravimetric preparative capability with 100 μmol/mol of oxygen in nitrogen (bilateral comparison between NIM and KRISS)

This bilateral comparison, which is traceable to CCQM-K53, was carried out to support NIMs capability for the preparation of stable gas species in nitrogen. The target amount of substance was 100 μmol/mol of oxygen in nitrogen, which was prepared gravimetrically by the participant. The comparison showed that the NIM and KRISS gravimetric values were consistent with each other to within the expanded uncertainty of 0.200 μmol/mol. Therefore the comparison is well linked to the CCQM-K53 and offers a gravimetric preparation capability of oxygen in nitrogen at a level of 100 μmol/mol to the participant. 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).

Final report on CCQM-P151: Halocarbons in dry whole air

The growing awareness of climate change/global warming and continuing concerns regarding stratospheric ozone depletion will require future measurements and standards for many compounds, in particular halocarbons that are linked to these issues. In order to track and control the emissions of these species globally in the atmosphere, it is necessary to demonstrate measurement equivalence at the highest levels of accuracy for assigned values of standards. This report describes the results of a pilot study between National Metrology Institutes and atmospheric research laboratories for several of the more important halocarbons at atmospheric concentration levels. The comparison includes the chlorofluorocarbons (CFCs) dichlorodifluoromethane (CFC 12), trichlorofluoromethane (CFC 11), and 1,1,2-trichlorotrifluoroethane (CFC 113); the hydrochlorofluorocarbons (HCFCs) chlorodifluoromethane (HCFC 22) and 1-chloro-1,1-difluoroethane (HCFC 142b); and the hydrofluorocarbon (HFC) 1,1,1,2-tetrafluoroethane (HFC 134a), all in a dried whole air sample. The objective of this key comparison is to compare the measurement capabilities of the participants for these halocarbons at trace atmospheric levels. Main text. To reach the main text of this paper, click on Final Report. The final report has been peer-reviewed and approved for publication by the CCQM.

Final report on international comparison CCQM-K83: Halocarbons in dry whole air

The growing awareness of climate change/global warming and continuing concerns regarding stratospheric ozone depletion will require future measurements and standards for many compounds, in particular halocarbons that are linked to these issues. In order to track and control the emissions of these species globally in the atmosphere, it is necessary to demonstrate measurement equivalence at the highest levels of accuracy for assigned values of standards. This report describes the results of a key comparison for several of the more important halocarbons at atmospheric concentration levels. The comparison includes the chlorofluorocarbons (CFCs) dichlorodifluoromethane (CFC 12), trichlorofluoromethane (CFC 11), and 1,1,2 trichlorotrifluoroethane (CFC 113); the hydrochlorofluorocarbons (HCFCs) chlorodifluoromethane (HCFC 22) and 1-chloro-1,1-difluoroethane (HCFC 142b); and the hydrofluorocarbon (HFC) 1,1,1,2 tetrafluoroethane (HFC 134a), all in a dried whole air sample. The objective of this key comparison is to compare the measurement capabilities of the participants for these halocarbons at trace atmospheric levels. 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).