George C. Rhoderick

Creation of 0.10-cm-1 resolution quantitative infrared spectral libraries for gas samples

The National Institute of Standards and Technology (NIST) and the Pacific Northwest National Laboratory (PNNL) are independently creating quantitative, approximately 0.10 cm-1 resolution, infrared spectral libraries of vapor phase compounds. The NIST library will consist of approximately 100 vapor phase spectra of volatile hazardous air pollutants (HAPs) and suspected greenhouse gases. The PNNL library will consist of approximately 400 vapor phase spectra associated with DOEs remediation mission. A critical part of creating and validating any quantitative work involves independent verification based on inter-laboratory comparisons. The two laboratories use significantly different sample preparation and handling techniques. NIST uses gravimetric dilution and a continuous flowing sample while PNNL uses partial pressure dilution and a static sample. Agreement is generally found to be within the statistical uncertainties of the Beers law fit and less than 3 percent of the total integrated band areas for the 4 chemicals used in this comparison. There does appear to be a small systematic difference between the PNNL and NIST data, however. Possible sources of the systematic difference will be discussed as well as technical details concerning the sample preparation and the procedures for overcoming instrumental artifacts.

Development of hydrocarbon gas standards

Abstract Methodology is described for the gravimetric preparation and analytical evaluation of accurate, stable, multicomponent gas standards in compressed gas

Methane Standards Made in Whole and Synthetic Air Compared by Cavity Ring Down Spectroscopy and Gas Chromatography with Flame Ionization Detection for Atmospheric Monitoring Applications

There is evidence that the use of whole air versus synthetic air can bias measurement results when analyzing atmospheric samples for methane (CH4) and carbon dioxide (CO2). Gas chromatography with flame ionization detection (GC-FID) and wavelength scanned-cavity ring down spectroscopy (WS-CRDS) were used to compare CH4 standards produced with whole air or synthetic air as the matrix over the mole fraction range of 1600-2100 nmol mol(-1). GC-FID measurements were performed by including ratios to a stable control cylinder, obtaining a typical relative standard measurement uncertainty of 0.025%. CRDS measurements were performed using the same protocol and also with no interruption for a limited time period without use of a control cylinder, obtaining relative standard uncertainties of 0.031% and 0.015%, respectively. This measurement procedure was subsequently used for an international comparison, in which three pairs of whole air standards were compared with five pairs of synthetic air standards (two each from eight different laboratories). The variation from the reference value for the whole air standards was determined to be 2.07 nmol mol(-1) (average standard deviation) and that of synthetic air standards was 1.37 nmol mol(-1) (average standard deviation). All but one standard agreed with the reference value within the stated uncertainty. No significant difference in performance was observed between standards made from synthetic air or whole air, and the accuracy of both types of standards was limited only by the ability to measure trace CH4 levels in the matrix gases used to produce the standards.

NIST gravimetrically prepared atmospheric level methane in dry air standards suite.

The Gas Metrology Group at the National Institute of Standards and Technology was tasked, by a congressional climate change act, to support the atmospheric measurement community through standards development of key greenhouse gases. This paper discusses the development of a methane (CH(4)) primary standard gas mixture (PSM) suite to support CH(4) measurement needs over a large amount-of-substance fraction range 0.3-20,000 μmol mol(-1), but with emphasis at the atmospheric level 300-4000 nmol mol(-1). Thirty-six CH(4) in dry air PSMs were prepared in 5.9 L high-pressure aluminum cylinders with use of a time-tested gravimetric technique. Ultimately 14 of these 36 PSMs define a CH(4) standard suite covering the nominal ambient atmospheric range of 300-4000 nmol mol(-1). Starting materials of pure CH(4) and cylinders of dry air were exhaustively analyzed to determine the purity and air composition. Gas chromatography with flame-ionization detection (GC-FID) was used to determine a CH(4) response for each of the 14 PSMs where the reproducibility of average measurement ratios as a standard error was typically (0.04-0.26) %. An ISO 6134-compliant generalized least-squares regression (GenLine) program was used to analyze the consistency of the CH(4) suite. All 14 PSMs passed the u-test with residuals between the gravimetric and the GenLine solution values being between -0.74 and 1.31 nmol mol(-1); (0.00-0.16)% relative absolute. One of the 14 PSMs, FF4288 at 1836.16 ± 0.75 nmol mol(-1) (k = 1) amount-of-substance fraction, was sent to the Korea Research Institute of Standards and Science (KRISS), the Republic of Koreas National Metrology Institute, for comparison. The same PSM was subsequently sent to the National Oceanic and Atmospheric Administration (NOAA) for analysis to their standards. Results show agreement between KRISS-NIST of +0.13% relative (+2.3 nmol mol(-1)) and NOAA-NIST of -0.14% relative (-2.54 nmol mol(-1)).

Preparation and Validation of Fully Synthetic Standard Gas Mixtures with Atmospheric Isotopic Composition for Global CO2 and CH4 Monitoring

We report the preparation and validation of the first fully synthetic gaseous reference standards of CO2 and CH4 in a whole air matrix with an isotopic distribution matching that is in the ambient atmosphere. The mixtures are accurately representative of the ambient atmosphere and were prepared gravimetrically. The isotopic distribution of the CO2 was matched to the abundance in the ambient atmosphere by blending (12)C-enriched CO2 with (13)C-enriched CO2 in order to avoid measurement biases introduced by measurement instrumentation detecting only certain isotopologues. The reference standards developed here have been compared with standards developed by the National Institute of Standards and Technology and standards from the WMO scale. They demonstrate excellent comparability.

Hydrocarbon Gas Standards at the pmol/mol Level to Support Ambient Atmospheric Measurements

Studies of climate change increasingly recognize the diverse influences exerted by hydrocarbons in the atmosphere, including roles in particulates and ozone formation. Measurements of key non-methane hydrocarbons (NMHCs) suggest atmospheric concentrations ranging from low pmol/mol to nmol/mol, depending on location and compound. To accurately establish concentration trends and to relate measurement records from many laboratories and researchers, it is essential to have good calibration standards. Several of the worlds National Metrology Institutes (NMIs) are developing primary and secondary reference gas standards at the nmol/mol level. While the U.S. NMI, the National Institute of Standards and Technology (NIST), has developed pmol/mol standards for halocarbons and some volatile organics, the feasibility of preparing well-characterized, stable standards for NMHCs at the pmol/mol level is not yet established. NIST recently developed a suite of primary standards by gravimetric dilution that contains 18 NMHCs covering the concentration range of 60 pmol/mol to 230 pmol/mol. Taking into account the small but chemically significant contribution of NMHCs in the high-purity diluent nitrogen used in their preparation, the relative concentrations and short-term stability (2 to 3 months) of these NMHCs in the primary standards have been confirmed by chromatographic analysis. The gravimetric values assigned from the methods used to prepare the materials and the analytical concentrations determined from chromatographic analysis generally agree to within +/-2 pmol/mol. However, anomalous results for several of the compounds reflect the difficulties inherent in avoiding contamination and making accurate measurements at these very low levels.

Stability of compressed gas mixtures containing low level volatile organic compounds in aluminum cylinders

Compressed gas mixtures containing up to twenty-six volatile organic compounds (VOCs) in a balance of nitrogen have been prepared and analyzed at the National Institute of Standards and Technology (NIST). The mixtures are contained in aluminum cylinders and the hydrocarbons included are aromatic or aliphatic, both saturated and unsaturated and some containing a halogen, oxygen or nitrogen atom. The individual compounds are present at concentrations ranging from 0.1–3000 nmol/mol and the relative standard uncertainty in the concentration of each is between ±2–5%. The stability of the mixtures over various time intervals is discussed.

Development of a gas standard reference material containing eighteen volatile organic compounds

SummaryA procedure to prepare primary gas cylinder standards for eighteen volatile organic compounds (VOCs) at the 1–15 nmol/mol (ppb) level was developed. The gas standards that were prepared by this procedure were intercompared by using gas chromatography with flame ionization detection (GC-FID) and electron capture detection (GC-ECD). The data, gravimetric concentration of the standards versus the respective GC peak area response, were plotted for each compound and fitted using linear regression. The regression analysis showed excellent agreement among the standards for each compound. These gas standards were evaluated over a period of 2 years and were determined to be stable and accurate. This research resulted in the development of Standard Reference Material (SRM) 1804, which contains these 18 volatile organic compounds in nitrogen at a nominal concentration of 5 nmol/mol for each compound. A batch of cylinders containing the mixture was procured from a commercial supplier. Each cylinder in the batch was analyzed for each of the 18 components. The data showed that the batch was homogeneous and stable for 15 of the 18 organic compounds, resulting in certification and issuance of SRM 1804.

Stability assessment of gas mixtures containing monoterpenes in varying cylinder materials and treatments.

Studies of climate change increasingly recognize the diverse influences exerted by monoterpenes in the atmosphere, including roles in particulates, ozone formation, and oxidizing potential. Measurements of key monoterpenes suggest atmospheric mole fractions ranging from low pmol/mol (parts-per-trillion; ppt) to nmol/mol (parts-per-billion; ppb), depending on location and compound. To accurately establish the mole fraction trends, assess the role of monoterpenes in atmospheric chemistry, and relate measurement records from many laboratories and researchers, it is essential to have good calibration standards. The feasibility of preparing well-characterized, stable gas cylinder standards for monoterpenes at the nmol/mol level was previously tested using treated (Aculife IV) aluminum gas cylinders at NIST. Results for 4 of the 11 monoterpenes, monitored versus an internal standard of benzene, indicated stability in these treated aluminum gas cylinders for over 6 months and projected long-term (years) stability. However, the mole fraction of the key monoterpene β-pinene decreased, while the mole fractions of α-pinene, d-limonene (R-(+)-limonene), p-cymene, and camphene (a terpene not present in the initial gas mixture) increased, indicating a chemical transformation of β-pinene to these species. A similar pattern of decreasing mole fraction was observed in α-pinene where growth of d-limonene, p-cymene, and camphene has been observed in treated gas cylinders prepared with a mixture of just α-pinene and benzene as the internal standard. The current research discusses the testing of other cylinders and treatments for the potential of long-term stability of monoterpenes in a gas mixture. In this current study, a similar pattern of decreasing mole fraction, although somewhat improved short-term stability, was observed for β-pinene and α-pinene, with growth of d-limonene, p-cymene, and camphene, in nickel-plated carbon steel cylinders. β-Pinene and α-pinene showed excellent stability at over 6 months in aluminum cylinders treated with a different process (Experis) than used in the original study.

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).