Jin Bok Lee

Direct determination of arsine in gases by inductively coupled plasma-dynamic reaction cell-mass spectrometry.

Reliable determination of arsine (AsH(3)) in gases is of great importance due to stringent regulations associated with health, safety and environmental issues. It is, however, challenging for an analyst to determine trace airborne arsine concentrations without specifically designed collection procedures using adsorption, desorption, dissolution or impinging techniques. To circumvent such technical barrier, we have newly developed a direct analytical method, characterized by introduction of an arsine gas sample into stable plasma stream, followed by gas-phase oxidation of arsine with molecular oxygen in a dynamic reaction cell (DRC) equipped within the inductively coupled plasma-mass spectrometry (ICP/MS) system, followed by subsequent detection of AsO(+) ion. This preliminary work used trace arsine concentrations (161 microg m(-3), 322 microg m(-3), and 645 microg m(-3)) gravimetrically prepared in N(2) balance. The proposed method was optimized for the important experimental parameters such as the flow rates of the reaction gas, the arsine sample, and the carrier gas. This method was then validated by demonstrating good figure-of-merits including the low limit of detection (0.10 microg m(-3)), good linearity (r(2)>0.9915), low measurement uncertainty (0.66%), and high speed of analysis (<6 min). The proposed method is expected to be potentially applicable to the determination of arsine in real workplace air after appropriate modifications are made.

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).

Effect of variation in argon content of calibration gases on determination of atmospheric carbon dioxide.

Carbon dioxide (CO(2)) is a greenhouse gas that makes by far the largest contribution to the global warming of the Earths atmosphere. For the measurements of atmospheric CO(2) a non-dispersive infrared analyzer (NDIR) and gas chromatography are conventionally being used. We explored whether and to what degree argon content can influence the determination of atmospheric CO(2) using the comparison of CO(2) concentrations between the sample gas mixtures with varying Ar amounts at 0 and 18.6 mmol mol(-1) and the calibration gas mixtures with Ar at 8.4, 9.1, and 9.3 mmol mol(-1). We newly discovered that variation of Ar content in calibration gas mixtures could undermine accuracy for precise and accurate determination of atmospheric CO(2) in background air. The differences in CO(2) concentration due to the variation of Ar content in the calibration gas mixtures were negligible (<+/-0.03 micromol mol(-1)) for NDIR systems whereas they noticeably increased (<+/-1.09 micromol mol(-1)) especially for the modified GC systems to enhance instrumental sensitivity. We found that the thermal mass flow controller is the main source of the differences although such differences appeared only in the presence of a flow restrictor in GC systems. For reliable monitoring of real atmospheric CO(2) samples, one should use calibration gas mixtures that contain Ar content close to the level (9.332 mmol mol(-1)) in the ambient air as possible. Practical guidelines were highlighted relating to selection of appropriate analytical approaches for the accurate and precise measurements of atmospheric CO(2). In addition, theoretical implications from the findings were addressed.