Photochemical ozone production in the rural southeastern United States during the 1990 Rural Oxidants in the Southern Environment (ROSE) program

Frost, G. J.; Trainer, M.; Allwine, G.; Buhr, M. P.; Calvert, Jack G.; Cantrell, C. A.; Fehsenfeld, F. C.; Goldan, P. D.; Herwehe, Jerold A.; Hübler, G.; Kuster, W. C.; Martin, Randall V.; McMillen, R. T.; Montzka, S. A.; Norton, R. B.; Parrish, D. D.; Ridley, B. A.; Shetter, R. E.; Walega, J. G.; Watkins, B. A.; Westberg, Hal; Williams, E. J.

doi:10.1029/98jd00881

Cited by 76 publications

(68 citation statements)

References 55 publications

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“…This result supports the importance of isoprene photochemistry since approximately 25% of OH formation in the region can be attributed to isoprene photolysis [cf. Lee et al, 1998;Frost et al, 1998]. In addition, analysis of the data from some of the flights indicated that this formaldehyde provided an appreciable source of CO.…”

Section: Role Of Natural Hydrocarbons and Co In Shaping The Odd Hydromentioning

confidence: 99%

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Airborne measurements of isoprene, CO, and anthropogenic hydrocarbons and their implications

Goldan¹,

Parrish²,

Kuster³

et al. 2000

J. Geophys. Res.

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Abstract. Measurements of the mixing ratios of light hydrocarbons (•C6) were made aboard the National Oceanic and Atmospheric Administration Lockheed Orion WP-3 aircraft during June and July of 1994 and 1995 during a series of flights over the region around Nashville, Tennessee. The measurements were carried out as part of the Nashville/ Middle Tennessee Study of the Southern Oxidant Study (SOS) whose purpose was to describe the sources, variation, and distribution of ozone and its precursors in the southeastern United States during the summer season. The spatial (altitude and latitude) distribution of isoprene and anthropogenic nonmethane hydrocarbons (NMHCs) is described. The isoprene distribution measured within the planetary boundary layer over the region is compared to the recent inventories. The correlations between the various anthropogenic hydrocarbons are used to demonstrate the combined influence of OH photochemistry and dilution on their concentrations. Finally, the distributions of those NMHCs that were measured are compared to those of CO and methane and discussed in terms their implications for odd hydrogen photochemistry and our understanding of regional ozone production. In the boundary layer, OH reactions are dominated by isoprene in the southern part of the region explored and by CO and methane in the northern part. The other measured NMHCs are seen to play only a minor role in ozone production in the nonurban atmosphere. IntroductionEpisodes of high concentrations of ozone occur over all parts of the eastern United States every summer, with many areas exceeding current air quality standards for the pollutant [cf. Meagher et al., 1998]. This ozone is thought to be generated by the photochemical reactions of oxides of nitrogen (NOx = NO q-NO2) and nonmethane hydrocarbons (NMHCs) In this connection, one of the principal aims of our aircraft measurements during this study was to better understand the role of NMHCs and CO in the photochemical formation of ozone in this region. An essential feature of our aircraft measurements was the successful development and deployment of instruments to measure the concentrations CO and C2 through C6 NMHCs in the regional atmosphere. The NMHC set includes many of the important anthropogenic NMHCs, as well as isoprene. These measurements, on a regional-wide basis, will allow us to improve our understanding of the relative importance of anthropogenic and biogenic NMHCs and CO in shaping odd hydrogen photochemistry and thereby regional ozone production..In addition, given the number of light NMHCs that can be detected in the atmosphere and their differing chemical and physical properties, a great deal can be learned from the rel- ExperimentThe measurements reported herein were made from the National Oceanic and Atmospheric Administration (NOAA) WP-3 aircraft. The flight tracks and the complement of trace gas measurements made from the aircraft are reported by Hiibler et al. [1998]. Hydrocarbon measurements were made using a gas chromatograph that was housed in the...

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Section: Role Of Natural Hydrocarbons and Co In Shaping The Odd Hydromentioning

confidence: 99%

“…In any case, NO•_ is required for photochemical ozone production through OH-initiated chemistry [cf. Frost et al, 1998]. Further, some species (again such as isoprene) form acyl radicals that form PAN-type compounds, which temporarily sequester NO,..…”

Section: Role Of Natural Hydrocarbons and Co In Shaping The Odd Hydromentioning

confidence: 99%

Airborne measurements of isoprene, CO, and anthropogenic hydrocarbons and their implications

Goldan¹,

Parrish²,

Kuster³

et al. 2000

J. Geophys. Res.

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“…At times, HCHO can be more important than ozone as a source of free radicals to the troposphere [Frost et al, 1998]. Since free radicals are the driving force in tropospheric chemistry, an understanding of formaldehyde sources and sinks is necessary in describing the chemistry of ozone and VOCs.…”

Section: Introductionmentioning

confidence: 99%

Summertime formaldehyde at a high‐elevation site in Quebec

Macdonald¹,

Makar²,

Anlauf³

et al. 2001

J. Geophys. Res.

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Abstract. Measurements of formaldehyde were made during the summer of 1996 at a high-elevation site in Quebec as part of the North American Research Strategy on Tropospheric Ozone-Canada East (NARSTO-CE) measurement program. Gas phase mixing ratios were determined continuously by removing formaldehyde from the air in a glass coil scrubber, and producing a fluorescent dimer through the Hantzsch reaction. Average mixing ratios of formaldehyde were 1.3 and 0.8 ppbv for dry and wet periods, respectively. Highest values of HCHO were observed July 1-2 with a maximum mixing ratio of 4.6 ppbv. Fog water samples were also collected and analyzed for HCHO on five afternoon periods. Comparison of HCHO in the gas and aqueous phases shows reasonable agreement with Henry's law equilibrium. For dry periods July 1-12, relationships were examined between formaldehyde and other chemical species also measured at the site. Data were segregated based on the ratio of NOx to NOy and on the level of anthropogenic hydrocarbons present in the air mass. For the majority of the data, formaldehyde increased with both ozone and products of NOx oxidation (NOz) and was inversely related to the NOx/NOy ratio. During the high HCHO episode July 1-2, HCHO was correlated with neither ozone nor NOz illustrating the different chemistry at the site on these days. A chemical box model was used to examine sources of HCHO July 1-4. The model suggests that biogenic hydrocarbons contribute on average 53% of the locally produced formaldehyde, the remainder resulting from the oxidation of methane (19%), anthropogenic VOCs (16%), acetaldehyde (7%), and organic peroxides (3%). The model cannot account for the July 1-2 formaldehyde mixing ratios from the chemistry measured at the site. This implies that an additional HCHO source not included in the model was responsible for the high levels on those days. IntroductionFormaldehyde, the smallest and most plentiful atmospheric carbonyl compound, plays an important role in the oxidative balance of the atmosphere. Formaldehyde is the first stable product in the oxidation of methane, and in both the background troposphere and the marine atmosphere, methane is its dominant source. In the continental boundary layer, formaldehyde may also be produced via the oxidation of both anthropogenic and biogenic nonmethane hydrocarbons (also referred to as volatile organic compounds or VOCs). Primary sources of formaldehyde include direct emissions from combustion engines, manufacturing, or biomass burning [Warneck, 1988].The photolysis of formaldehyde (HCHO) or its reaction with OH is a source of the hydroperoxy radical in the atmosphere. At times, HCHO can be more important than ozone as a source of free radicals to the troposphere [Frost et al., 1998]. Since free radicals are the driving force in tropospheric chemistry, an understanding of formaldehyde sources and sinks is necessary in describing the chemistry of ozone and VOCs. Air This paper presents measurements of formaldehyde made at the Mt. Sutton site during the NARSTO-CE...

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“…The chemical loss of ozone occurs via three main pathways in this region: photolysis followed by reaction with H 2 O, reaction with HO 2 , and reaction with VOCs (Frost et al, 1998). The loss of O 3 was calculated for each of these pathways, and then integrated over the course of the day to determine total daily ozone loss ( LO 3 ).…”

Section: Calculation Of P O 3 and Effects Of Temperaturementioning

confidence: 99%

Effects of temperature-dependent NO<sub><i>x</i></sub> emissions on continental ozone production

et al. 2018

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Abstract. Surface ozone concentrations are observed to increase with rising temperatures, but the mechanisms responsible for this effect in rural and remote continental regions remain uncertain. Better understanding of the effects of temperature on ozone is crucial to understanding global air quality and how it may be affected by climate change. We combine measurements from a focused ground campaign in summer 2013 with a long-term record from a forested site in the rural southeastern United States, to examine how daily average temperature affects ozone production. We find that changes to local chemistry are key drivers of increased ozone concentrations on hotter days, with integrated daily ozone production increasing by 2.3 ppb • C −1 . Nearly half of this increase is attributable to temperature-driven increases in emissions of nitrogen oxides (NO x ), most likely by soil microbes. The increase of soil NO x emissions with temperature suggests that ozone will continue to increase with temperature in the future, even as direct anthropogenic NO x emissions decrease dramatically. The links between temperature, soil NO x , and ozone form a positive climate feedback.

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Photochemical ozone production in the rural southeastern United States during the 1990 Rural Oxidants in the Southern Environment (ROSE) program

Cited by 76 publications

References 55 publications

Airborne measurements of isoprene, CO, and anthropogenic hydrocarbons and their implications

Airborne measurements of isoprene, CO, and anthropogenic hydrocarbons and their implications

Summertime formaldehyde at a high‐elevation site in Quebec

Effects of temperature-dependent NO<sub><i>x</i></sub> emissions on continental ozone production

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Photochemical ozone production in the rural southeastern United States during the 1990 Rural Oxidants in the Southern Environment (ROSE) program

Cited by 76 publications

References 55 publications

Airborne measurements of isoprene, CO, and anthropogenic hydrocarbons and their implications

Airborne measurements of isoprene, CO, and anthropogenic hydrocarbons and their implications

Summertime formaldehyde at a high‐elevation site in Quebec

Effects of temperature-dependent NO&lt;sub&gt;&lt;i&gt;x&lt;/i&gt;&lt;/sub&gt; emissions on continental ozone production

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About

Effects of temperature-dependent NO<sub><i>x</i></sub> emissions on continental ozone production