Ozone–isoprene reactions: Product formation and aerosol potential

Kamens, Richard M.; Gery, M.W.; Jeffries, Harvey E.; Jackson, Maurice; Cole, Edward I.

doi:10.1002/kin.550140902

Cited by 135 publications

(104 citation statements)

References 10 publications

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“…In general, however, despite variations in number and mass, a steady-state CMD was reached, although a MMD was not. The low aerosol yield is consistent with the findings of Kamens et al (1982), who observed a yield of about 1% of homogeneously nucleated aerosol under conditions of 4 ppm isoprene.…”

Section: Discussionsupporting

confidence: 91%

Generation and Quantification of Ultrafine Particles through Terpene/Ozone Reaction in a Chamber Setting

Rohr

Weschler

Koutrakis³

et al. 2003

Aerosol Science and Technology

110

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Terpene/ozone reactions produce gas-and condensed-phase products and thus contribute to both indoor and outdoor aerosol. These reactions may be important in indoor settings, where terpenes are generated from indoor sources and ambient ozone can reach significant levels. Moreover, airway irritation has been observed in mice exposed to terpene oxidation products (OPs). The aim of this study was to characterize a system for generating and quantifying ultrafine particles formed through terpene/ozone reactions in preparation for inhalation toxicology experiments. Two common monoterpenes, α-pinene and d-limonene, and a hemiterpene, isoprene, were investigated. Ozone and gas-phase terpene were introduced continuously into a reaction flow tube, from which reaction products entered a plexiglass chamber. Particle number, mass, and size distribution (∼15-750 nm) were monitored in the chamber for various reactant concentrations and air exchange rates (AERs). In all experiments, ozone was the limiting reagent and the reaction rate was much more rapid than the AER. Particles formed rapidly and in high concentrations in the pinene and limonene systems. Particle formation was slower in the isoprene system and fewer particles were formed; moreover, particle diameters were smaller. In all 3 systems, progressive growth of particles was observed due to condensation and coagulation processes. The isoprene system displayed instability with respect to aerosol characteristics and did not reach steady-state conditions. In the pinene system, ozone concentration was a strong predictor of steady-state particle number and mass concentration and particle diameter. The particle number was greater at higher AERs, but particles were smaller. This study is the first to incorporate measurement of ultrafine particles formed from terpene/ozone reactions into a controlled exposure Address correspondence to Annette C. Rohr, EPRI, 3412 Hillview Avenue, Palo Alto, CA 94304-1395. E-mail: arohr@epri.com chamber setting. Following system characterization, we will conduct mouse exposures to further investigate the respiratory effects of gas-and particle-phase terpene OPs.

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Section: Discussionsupporting

confidence: 91%

Generation and Quantification of Ultrafine Particles through Terpene/Ozone Reaction in a Chamber Setting

Rohr

Weschler

Koutrakis³

et al. 2003

Aerosol Science and Technology

110

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“…Biogenic and anthropogenic VOCs can react with oxidants to produce MeGly and Gly in gas phase in both daytime and nighttime. In daytime, important oxidants are OH radical (Fan and Zhang, 2004) and O 3 (Kamens et al, 1982). In contrast, the main oxidant in nighttime is NO 3 , which only react with biogenic VOCs such as isoprene and monoterpene emitted in the forest area (Warneke et al, 2004).…”

Section: Resultsmentioning

confidence: 99%

Distributions and diurnal changes of low molecular weight organic acids and ^|^alpha;-dicarbonyls in suburban aerosols collected at Mangshan, North China

Kawamura

2010

Geochem. J.

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Aerosol samples were collected at Mangshan in the north of Beijing, China in autumn 2007 and analyzed for α,ω-dicarboxylic acids (C 2 -C 12 ), ketoacids (ωC 2 -ωC 4 , ωC 9 , pyruvic acid) and α-dicarbonyls (glyoxal and methylglyoxal). Oxalic (C 2 ) acid was found as the most abundant species, followed by succinic (C 4 ) and malonic (C 3 ) acids. Concentrations of most compounds, except for C 2 and some other species, were higher in daytime than nighttime, indicating that diacids are produced by photochemical oxidation of organic precursors emitted from anthropogenic sources such as fossil-fuel combustion in Beijing, and are transported to Mangshan area by the northerly wind in daytime. Phthalic acid (Ph) was detected as the 4th most abundant diacid both in daytime and nighttime samples, indicating that anthropogenic sources significantly contribute to the organic aerosols. However, lower adipic (C 6 )/azelaic (C 9 ) acid ratios in nighttime than daytime suggest that biogenic source makes more contribution to the aerosols in nighttime. Higher ratios of C 2 /total diacids in nighttime than daytime suggest the aging of aerosols proceed more in nighttime, probably due to the aqueous phase oxidation of biogenic precursors. This study demonstrates that water-soluble organic aerosols are secondarily produced in the vicinity of Beijing by the oxidation of both anthropogenic and biogenic precursors.

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“…Biogenic and anthropogenic VOCs can react with oxidants to produce methylglyoxal (MeGly) and glyoxal (Gly) in gas phase. During mid-day, OH radicals are important oxidants (Fan and Zhang, 2004) as well as O 3 (Kamens et al, 1982). In contrast, the nighttime oxidant is mainly NO 3 , which attacks biogenic (such as monoterpenes and isoprene) and anthropogenic VOCs (Warneke et al, 2004).…”

Section: Possible Production Of Oxalic Acid In Nighttimementioning

confidence: 99%

Diurnal and temporal variations of water-soluble dicarboxylic acids and related compounds in aerosols from the northern vicinity of Beijing: Implication for photochemical aging during atmospheric transport

He¹,

Kawamura²,

Okuzawa³

et al. 2014

Science of The Total Environment

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Abstract:Aerosol samples were collected in autumn 2007 on day-and nighttime basis in the northern receptor site of Beijing, China. The samples were analyzed for total carbon (TC) and water-soluble dicarboxylic acids (C 2 -C 12 ), oxocarboxylic acids (C 2 -C 9 ), glyoxal and methylglyoxal to better understand the photochemical aging of organic aerosols in the vicinity of Beijing. Concentrations of TC are 50% greater in daytime when winds come from Beijing than in nighttime when winds come from the northern forest areas. Most diacids showed higher concentrations in daytime, suggesting that the organics emitted from the urban Beijing and delivered to the northern vicinity in daytime are subjected to photo-oxidation to result in diacids.However, oxalic acid (C 2 ), which is the most abundant diacid followed by C 3 or C 4 , became on average 30% more abundant in nighttime together with azelaic, ω-oxooctanoic and ω-oxononanoic acids, which are specific oxidation products of biogenic unsaturated fatty acids.Methylglyoxal, an oxidation product of isoprene and a precursor of oxalic acid, also became 29% more abundant in nighttime. Based on a positive correlation between C 2 and glyoxylic acid (ωC 2 ) in nighttime when relative humidity significantly enhanced, we propose a nighttime aqueous phase production of C 2 via the oxidation of ωC 2 . We found an increase in the contribution of diacids to TC by 3 folds during consecutive clear days. This study demonstrates that diacids and related compounds are largely produced in the northern vicinity of Beijing via photochemical processing of organic precursors emitted from urban center and forest areas.

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Ozone–isoprene reactions: Product formation and aerosol potential

Cited by 135 publications

References 10 publications

Generation and Quantification of Ultrafine Particles through Terpene/Ozone Reaction in a Chamber Setting

Generation and Quantification of Ultrafine Particles through Terpene/Ozone Reaction in a Chamber Setting

Distributions and diurnal changes of low molecular weight organic acids and ^|^alpha;-dicarbonyls in suburban aerosols collected at Mangshan, North China

Diurnal and temporal variations of water-soluble dicarboxylic acids and related compounds in aerosols from the northern vicinity of Beijing: Implication for photochemical aging during atmospheric transport

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