Influence of Pressure on the Composition of Gaseous Reference Materials

Brewer, Paul J.; Brown, Richard; Resner, Kate; Pearce, Ruth; Worton, David R.; Allen, Nicholas D. C.; Blakley, Kevin C.; Benucci, Daniel; Ellison, Matthew

doi:10.1021/acs.analchem.7b05309

Cited by 13 publications

(25 citation statements)

References 13 publications

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“…After the second cleaning procedure (Table 1d) our results compared reasonably well with the low flow experiments reported in Schibig et al (2018) and Brewer et al (2018). The former setup consisted of higher volume cylinders, and they suggested no 10 difference between the coated and uncoated aluminum cylinders.…”

Section: Discussionsupporting

confidence: 89%

“…A significant difference between this study and the previous studies (Leuenberger et al, 2015;Brewer et al, 2018;Schibig et al, 2018) is the onset of adsorption effects. All previous studies have shown that for high pressure cylinders, usage below 20 bar is problematic.…”

Section: Discussioncontrasting

confidence: 77%

“…Schibig et al (2018) Schibig et al (2018). Due to its higher polarity, H 2 O molecules are expected to occupy the available sites on the cylinder surface, and result in less adsorption of CO 2 molecules, which is supported by Brewer et al (2018). Despite this varying conditions both studies did not observe effects higher than 0.1 µmol mol −1 at low flow conditions for untreated aluminum cylinders.…”

Section: Discussionmentioning

confidence: 60%

“…The enrichment in the CO 2 amount fraction was reported as 0.090 ± 0.009 µmol mol −1 (Schibig et al, 2018). On the contrary, Brewer et al (2018) reported significant differences between the tested treated and untreated aluminum cylinders in their low flow experiments. Their results for the mixtures in untreated aluminum cylinders with high or low water content were 0.1 µmol mol −1 or lower.…”

Section: Discussionmentioning

confidence: 86%

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Investigation of adsorption/desorption behavior of small volume cylinders and its relevance for atmospheric trace gas analysis

Satar¹,

Nyfeler²,

Bereiter³

et al. 2019

Preprint

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Atmospheric trace gas measurements of greenhouse gases are critical in their precision and accuracy. In the past 5 years, atmospheric measurement and gas metrology communities have turned their attention to possible surface effects due to pressure and temperature variations during a standard cylinder's lifetime. This study concentrates on this issue by introducing newly built small volume aluminum and steel cylinders which enable the investigation of trace gases and their affinity for adsorption/desorption on various surfaces over a set of temperature and pressure ranges. The presented experiments 5 are designed to test the filling pressure dependencies up to 30 bar, and temperature dependencies from -10 • C up to 180 • C for these prototype cylinders. We present measurements of CO 2 , CH 4 , CO and H 2 O using a cavity ring down spectroscopy analyzer under these conditions. Moreover, we investigated CO 2 amount fractions using a novel quantum cascade laser spectrometer system enabling measurements at pressures as a low as 5 mbar. This extensive dataset revealed that until pressures as low as 150 mbar the enhancement in the amount fraction of CO 2 relative to its initial value (at 1200 mbar) is limited to 0.12 µmol mol −1 10 for the prototype aluminum cylinder. Up to 80 • C, the aluminum cylinder showed superior results and less response to varying temperature compared to the steel cylinder. For CO 2 , these changes were insignificant at 80 • C for the aluminum cylinder, whereas a 0.11 µmol mol −1 enhancement for the steel cylinder was observed. High temperature experiments showed that for both cylinders irreversible temperature effects occur especially above 130 • C.

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Section: Discussionsupporting

confidence: 89%

Section: Discussioncontrasting

confidence: 77%

Section: Discussionmentioning

confidence: 60%

Section: Discussionmentioning

confidence: 86%

See 2 more Smart Citations

Investigation of adsorption/desorption behavior of small volume cylinders and its relevance for atmospheric trace gas analysis

Satar¹,

Nyfeler²,

Bereiter³

et al. 2019

Preprint

View full text Add to dashboard Cite

show abstract

“…It is NPL practice not to use cylinders that show large initial losses due to concerns over what happens to that adsorbed material during the use of the cylinder. In a recent paper, Brewer et al (2018) have shown that at low pressures (<25 bar), desorption of previous adsorbed gases (carbon dioxide and hydrochloric acid) can affect the mole fraction of reference materials.…”

Section: Oxygenated Vocs (Ovocs)mentioning

confidence: 99%

Stability of gaseous volatile organic compounds contained in gas cylinders with different internal wall treatments

Rhoderick

Cecelski

Miller

et al. 2019

Elementa: Science of the Anthropocene

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Rhoderick, GC, et al. 2019. Stability of gaseous volatile organic compounds contained in gas cylinders with different internal wall treatments. Elem Sci Anth, 7: 28.Measurements of volatile organic compounds (VOCs) have been ongoing for decades to track growth rates and assist in curbing emissions of these compounds into the atmosphere. To accurately establish mole fraction trends and assess the role of these gas-phase compounds in atmospheric chemistry it is essential to have good calibration standards. A necessity and precursor to accurate VOC gas standards are the gas cylinders and the internal wall treatments that aid in maintaining the stability of the mixtures over long periods of time, measured in years. This paper will discuss the stability of VOC gas mixtures in different types of gas cylinders and internal wall treatments. Stability data will be given for 85 VOCs studied in gas mixtures by National Metrology Institutes and other agency laboratories. This evaluation of cylinder treatment materials is the outcome of an activity of the VOC Expert Group within the framework of the World Meteorological Organization (WMO) Global Atmospheric Watch (GAW) program.

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Synthetic Zero Air Reference Material for High Accuracy Greenhouse Gas Measurements

et al. 2018

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The purity analysis of zero air is a significant contributor to the uncertainty in preparing reference materials of high impact greenhouse gases, limiting progress toward coherent and comparable measurements required to assess climate trends. We have produced a commutable synthetic zero air reference material with an oxygen, nitrogen, and argon matrix closely matching atmospheric composition. This is the critical step in preventing systematic biases from pressure broadening effects when using these reference materials to calibrate instruments based on optical spectroscopy. The amount fractions of carbon dioxide, methane, and carbon monoxide, which are present as minor impurities in the zero air reference material, have been accurately quantified using a novel dilution device that can generate gas mixtures of these components at trace amount fractions. These developments will have a significant impact on advancing the state of the art in high accuracy reference materials and for baseline calibration of spectroscopic instrumentation.

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Influence of Pressure on the Composition of Gaseous Reference Materials

Cited by 13 publications

References 13 publications

Investigation of adsorption/desorption behavior of small volume cylinders and its relevance for atmospheric trace gas analysis

Investigation of adsorption/desorption behavior of small volume cylinders and its relevance for atmospheric trace gas analysis

Stability of gaseous volatile organic compounds contained in gas cylinders with different internal wall treatments

Synthetic Zero Air Reference Material for High Accuracy Greenhouse Gas Measurements

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