International Comparison of a Hydrocarbon Gas Standard at the Picomol per Mol Level

Rhoderick, George C.; Duewer, David L.; Apel, E. C.; Baldan, Annarita; Hall, B. D.; Harling, Alice M.; Helmig, Detlev; Heo, Gwi Suk; Hueber, Jacques; Kim, Mi Eon; Kim, Yong Doo; Miller, Ben; Montzka, S. A.; Riemer, D. D.

doi:10.1021/ac403761u

Cited by 11 publications

(7 citation statements)

References 24 publications

(49 reference statements)

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“…Reported methane mole fractions are tied to WMO international standards maintained by NOAA/GML (Dlugokencky et al, 2005(Dlugokencky et al, , 2019. BAO NMHCs measured at the site (benzene, propane, i-pentane, n-pentane, i-butane, n-butane, and acetylene) and reported on here (propane, i-pentane, n-pentane and acetylene) are linked to NOAA/ GML laboratory prepared standards, and with the exception of acetylene, have been compared with standards from NIST and other laboratories (Rhoderick et al, 2014).…”

Section: Flask Samplesmentioning

confidence: 99%

Atmospheric oil and natural gas hydrocarbon trends in the Northern Colorado Front Range are notably smaller than inventory emissions reductions

Oltmans¹,

Cheadle

Helmig³

et al. 2021

Elementa: Science of the Anthropocene

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From 2008 to mid-2016, there was more than a 7-fold increase in oil production and nearly a tripling of natural gas production in the Colorado Denver–Julesburg Basin (DJB). This study utilized air samples collected at the Boulder Atmospheric Observatory (BAO) tower in southwestern Weld County in the DJB to investigate atmospheric mole fraction trends of methane and volatile organic compounds (VOCs). Elevated methane and propane mole fractions and low values (<1) in the ratio of i-pentane to n-pentane at BAO were found to be associated with flow patterns that transport air from the northeast (NE) to east (E) sector to the site, the direction where the primary locations of oil and natural gas (O&NG) extraction and processing activities are located. Median mole fractions of the O&NG tracer propane at BAO were 10 times higher than background values when winds came from the NE quadrant. This contrasts with lower mole fractions of O&NG-related constituents in air parcels arriving at BAO from the south, the direction of the major urban area of Denver. None of O&NG tracers, for example, methane and propane, show statistically significant trends in mole fraction (relative to the background) over the study period in air transported from the DJB. Also, longer term acetylene mole fraction changes were not seen in NE quadrant or south sector samples. A significant decline in the mole fraction ratio of i-pentane to n-pentane in the NE sector data provides evidence of an increasing influence of O&NG on the overall composition of VOCs measured at BAO, a change not seen in measurements from the south (urban) sector. These results suggest that O&NG emissions and resulting atmospheric mole fractions have remained relatively constant over 2008–2016. The behavior in the observations is in contrast to the most recent VOC emissions inventory. While the inventory projects O&NG total VOC emission reductions between 2011 and 2020, of –6.5% per year despite the large production increases, the best estimate of the propane emission rate of change for the DJB-filtered data during 2008–2016 is much smaller, that is, –1.5% per year.

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Section: Flask Samplesmentioning

confidence: 99%

Atmospheric oil and natural gas hydrocarbon trends in the Northern Colorado Front Range are notably smaller than inventory emissions reductions

Oltmans¹,

Cheadle

Helmig³

et al. 2021

Elementa: Science of the Anthropocene

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“…In this work, benzene and acetylene mixing ratios (analysed with GC mass spectrometry detection (Rhoderick et al, 2014;Pétron et al, 2012)) from August to September 2011 were utilised, as well as acetylene values from March 2011, as a proxy for mixing ratios during SOAP. Benzene values are calculated from an average of six pairs of flasks (two glass and four stainless steel pairs), while acetylene values are from three pairs of stainless steel flasks in August-September 2011 and a single pair of stainless steel flasks in March 2011.…”

Section: Voc Flask Datamentioning

confidence: 99%

Seasonal in situ observations of glyoxal and methylglyoxal over the temperate oceans of the Southern Hemisphere

et al. 2015

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Abstract. The dicarbonyls glyoxal and methylglyoxal have been measured with 2,4-dinitrophenylhydrazine (2,4-DNPH) cartridges and high-performance liquid chromatography (HPLC), optimised for dicarbonyl detection, in clean marine air over the temperate Southern Hemisphere (SH) oceans. Measurements of a range of dicarbonyl precursors (volatile organic compounds, VOCs) were made in parallel. These are the first in situ measurements of glyoxal and methylglyoxal over the remote temperate oceans. Six 24 h samples were collected in summer (February-March) over the Chatham Rise in the south-west Pacific Ocean during the Surface Ocean Aerosol Production (SOAP) voyage in 2012, while 34 24 h samples were collected at Cape Grim Baseline Air Pollution Station in the late winter (August-September) of 2011. Average glyoxal mixing ratios in clean marine air were 7 ppt at Cape Grim and 23 ppt over Chatham Rise. Average methylglyoxal mixing ratios in clean marine air were 28 ppt at Cape Grim and 10 ppt over Chatham Rise. The mixing ratios of glyoxal at Cape Grim are the lowest observed over the remote oceans, while mixing ratios over Chatham Rise are in good agreement with other temperate and tropical observations, including concurrent Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations. Methylglyoxal mixing ratios at both sites are comparable to the only other marine methylglyoxal observations available over the tropical Northern Hemisphere (NH) ocean. Ratios of glyoxal : methylglyoxal > 1 over Chatham Rise but < 1 at Cape Grim suggest that a different formation and/or loss processes or rates dominate at each site. Dicarbonyl precursor VOCs, including isoprene and monoterpenes, are used to calculate an upper-estimate yield of glyoxal and methylglyoxal in the remote marine boundary layer and explain at most 1-3 ppt of dicarbonyls observed, corresponding to 10 % and 17 % of the observed glyoxal and 29 and 10 % of the methylglyoxal at Chatham Rise and Cape Grim, respectively, highlighting a significant but as yet unknown production mechanism. Surface-level glyoxal observations from both sites were converted to vertical columns and compared to average vertical column densities (VCDs) from GOME-2 satellite retrievals. Both satellite columns and in situ observations are higher in summer than winter; however, satellite vertical column densities exceeded the surface observations by more than 1.5 × 10 14 molecules cm −2 at both sites. This discrepancy may be due to the incorrect assumption that all glyoxal observed by satellite is within the boundary layer, or it may be due to challenges retrieving low VCDs of glyoxal over the oceans due to interferences by liquid water absorption or the use of an inappropriate normalisation reference value in the retrieval algorithm. This study provides much-needed data to verify the presence of these short-lived gases over the remote ocean and provide further evidence of an as yet unidentified source of both glyoxal and also methylglyoxal over the remote oceans.

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“…One of these standards at nominal mole fraction of 200 pmol mol −1 was used as a sample for an international comparison between several NMIs, government agencies, and academia, which resulted in excellent agreement between laboratories. 51 Supporting Figure S2 illustrates the good agreement between laboratories. While a hydrocarbon SRM is not planned in the pmol mol −1 region, the primary calibration scale is in place to certify reference gas mixtures as needed to support the measurement of these hydrocarbons for many atmospheric environments.…”

Section: ■ Discussionmentioning

confidence: 61%

NIST Standards for Measurement, Instrument Calibration, and Quantification of Gaseous Atmospheric Compounds

et al. 2018

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There are many gas phase compounds present in the atmosphere that affect and influence the earth's climate. These compounds absorb and emit radiation, a process which is the fundamental cause of the greenhouse effect. The major greenhouse gases in the earth's atmosphere are carbon dioxide, methane, nitrous oxide, and ozone. Some halocarbons are also strong greenhouse gases and are linked to stratospheric ozone depletion. Hydrocarbons and monoterpenes are precursors and contributors to atmospheric photochemical processes, which lead to the formation of particulates and secondary photo-oxidants such as ozone, leading to photochemical smog. Reactive gases such as nitric oxide and sulfur dioxide are also compounds found in the atmosphere and generally lead to the formation of other oxides. These compounds can be oxidized in the air to acidic and corrosive gases and contribute to photochemical smog. Measurements of these compounds in the atmosphere 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. The National Institute of Standards and Technology has been developing standards of many of these compounds for over 40 years. This paper discusses the development of these standards.

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International Comparison of a Hydrocarbon Gas Standard at the Picomol per Mol Level

Cited by 11 publications

References 24 publications

Atmospheric oil and natural gas hydrocarbon trends in the Northern Colorado Front Range are notably smaller than inventory emissions reductions

Atmospheric oil and natural gas hydrocarbon trends in the Northern Colorado Front Range are notably smaller than inventory emissions reductions

Seasonal in situ observations of glyoxal and methylglyoxal over the temperate oceans of the Southern Hemisphere

NIST Standards for Measurement, Instrument Calibration, and Quantification of Gaseous Atmospheric Compounds

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