Laboratory Studies of Peroxy Radicals, Carbonyl Compounds and Ozonolysis Reactions of Tropospheric Importance

Moortgat, G. K.; Bauer, Dieter; Burrows, J. P.; Crowley, John N.; Helleis, Frank; Horie, Osamu; Koch, S. W.; Limbach, Stefan; Neeb, Peter; Raber, W.; Sauer, Frank; Schäfer, Christian; Schneider, Wolfgang; Simon, F.; Zahn, Chr.

doi:10.1007/978-3-642-59216-4_15

Cited by 3 publications

(2 citation statements)

References 17 publications

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“…Soil organic matter and organic films are often rich in alkenes (Vancampenhout et al, 2009;Donaldson et al, 2005;Simpson et al, 2006), which undergo ozonolysis reactions in the presence of O 3 (Criegee, 1975;Wolff et al, 1997). Hydroxyalkyl hydroperoxides formed via the ozonolysis of alkenes can further decompose to alkanoic acids (Moortgat et al, 1997;Anglada et al, 2002;Hasson et al, 2003;. O 3 mixing ratios measured at the site were relatively high at nighttime (∼ 40 ppb v ; Fig.…”

Section: Alkanoic Acidsmentioning

confidence: 93%

Tropospheric sources and sinks of gas-phase acids in the Colorado Front Range

et al. 2018

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Abstract. We measured organic and inorganic gas-phase acids in the Front Range of Colorado to better understand their tropospheric sources and sinks using a high-resolution time-of-flight chemical ionization mass spectrometer. Measurements were conducted from 4 to 13 August 2014 at the Boulder Atmospheric Observatory during the Front Range Air Pollution and Photochemistry Éxperiment. Diurnal increases in mixing ratios are consistent with photochemical sources of HNO 3 , HNCO, formic, propionic, butyric, valeric, and pyruvic acid. Vertical profiles taken on the 300 m tower demonstrate net surface-level emissions of alkanoic acids, but net surface deposition of HNO 3 and pyruvic acid. The surface-level alkanoic acid source persists through both day and night, and is thus not solely photochemical. Reactions between O 3 and organic surfaces may contribute to the surface-level alkanoic acid source. Nearby traffic emissions and agricultural activity are a primary source of propionic, butyric, and valeric acids, and likely contribute photochemical precursors to HNO 3 and HNCO. The combined diel and vertical profiles of the alkanoic acids and HNCO are inconsistent with dry deposition and photochemical losses being the only sinks, suggesting additional loss mechanisms.

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Section: Alkanoic Acidsmentioning

confidence: 93%

Tropospheric sources and sinks of gas-phase acids in the Colorado Front Range

et al. 2018

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“…Soil organic matter and organic films are often rich in alkenes (Vancampenhout et al, 2009;Donaldson et al, 2005;Simpson et al, 2006), 35 which undergo ozonolysis reactions in the presence of O3 (Criegee, 1975;Wolff et al, 1997). Hydroxyalkyl hydroperoxides formed via the ozonolysis of alkenes can further decompose to alkanoic acids (Moortgat et al, 1997;Anglada et al, 2002;Hasson et al, 2003;Millet et al, 2015). O3 mixing ratios measured at the site were relatively high at nighttime (~ 40 ppbv) (Fig.…”

Section: Alkanoic Acids 35mentioning

confidence: 96%

Tropospheric sources and sinks of gas-phase acids in the Colorado Front Range

Mattila¹,

Brophy²,

Kirkland³

et al. 2018

Preprint

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A new mechanism for regional atmospheric chemistry modeling

Stockwell¹,

Kirchner²,

Kühn³

et al. 1997

J. Geophys. Res.

1,015

718

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Abstract. A new gas-phase chemical mechanism for the modeling of regional atmospheric chemistry, the "Regional Atmospheric Chemistry Mechanism" (RACM) is presented. The mechanism is intended to be valid for remote to polluted conditions and from the Earth's surface through the upper troposphere. The RACM mechanism is based upon the earlier Regional Acid Deposition Model, version 2 (RADM2) mechanism ] and the more detailed Euro-RADM mechanism [Stockwell and Kley, 1994]. The RACM mechanism includes rate constants and product yields from the most recent laboratory measurements, and it has been tested against environmental chamber data. A new condensed reaction mechanism is included for biogenic compounds: isoprene, a-pinene, and d-limonene. The branching ratios for alkane decay were reevaluated, and in the revised mechanism the aldehyde to ketone ratios were significantly reduced. The relatively large amounts of nitrates resulting from the reactions of unbranched alkenes with NO 3 are now included, and the production of HO from the ozonolysis of alkenes has a much greater yield. The aromatic chemistry has been revised through the use of new laboratory data. The yield of cresol production from aromatics was reduced, while the reactions of HO, NO3, and 03 with unsaturated dicarbonyl species and unsaturated peroxynitrate are now included in the RACM mechanism. The peroxyacetyl nitrate chemistry and the organic peroxy radical-peroxy radical reactions were revised, and organic peroxy radical + NO 3 reactions were added. IntroductionThe gas-phase chemical mechanism is one of the most important components of an atmospheric chemistry model. These models require high-quality gas-phase chemical mechanisms to calculate the concentrations of atmospheric chemical species. The concentrations of ozone and other air pollutants are determined by the emissions of nitrogen oxides and reactive organic species, gas-and aqueous-phase chemical reaction rates, deposition, and meteorological conditions. There are several important mechanisms which are widely used for modeling the chemistry of the troposphere including the mechanism of Lurmann et al. chemistry on a regional scale, we have named it the "Regional Atmospheric Chemistry Mechanism" (RACM). The RACM mechanism was created to be capable of simulating the troposphere from the Earth's surface through the upper troposphere and to be valid for simulating remote to polluted urban conditions.The mechanism includes 17 stable inorganic species, 4 inorganic intermediates, 32 stable organic species (4 of these are primarily of biogenic origin), and 24 organic intermediates (Table 1). The RACM mechanism includes 237 reactions ( Table 2). The mechanism and its use are described in the subsequent text. The text is divided into section 2 on the inorganic chemistry and section 3 on the organic chemistry. The organic chemistry section includes a description of the aggregation procedures for emissions and the development of the chemistry for alkanes, carbonyls, alkenes, aromatics; the decomposition...

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Laboratory Studies of Peroxy Radicals, Carbonyl Compounds and Ozonolysis Reactions of Tropospheric Importance

Cited by 3 publications

References 17 publications

Tropospheric sources and sinks of gas-phase acids in the Colorado Front Range

Tropospheric sources and sinks of gas-phase acids in the Colorado Front Range

Tropospheric sources and sinks of gas-phase acids in the Colorado Front Range

A new mechanism for regional atmospheric chemistry modeling

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