Secondary organic aerosol formation from isoprene photooxidation under high‐NO<sub><i>x</i></sub> conditions

Kroll, J. H.; Ng, N. L.; Murphy, S. M.; Flagan, Richard C.; Seinfeld, John H.

doi:10.1029/2005gl023637

Cited by 332 publications

(412 citation statements)

References 26 publications

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“…Isoprene is also known to have a small but significant yield of SOA mass formation. Depending on seed aerosol, initial precursor concentration and relative NO x levels, SOA yields in the range of 1-5 % were reported in the literature (Kroll et al, 2005;Dommen et al, 2006;Kroll et al, 2006;Dommen et al, 2009). Including SOA from isoprene in calculations of the global SOA burden increases SOA by factors between 0.5 and 2 depending on scenarios used (Henze and Seinfeld, 2006).…”

Section: Resultsmentioning

confidence: 99%

Isoprene in poplar emissions: effects on new particle formation and OH concentrations

Kiendler‐Scharr¹,

Andres²,

Bachner³

et al. 2012

Atmos. Chem. Phys.

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Abstract. Stress-induced volatile organic compound (VOC) emissions from transgenic Grey poplar modified in isoprene emission potential were used for the investigation of photochemical secondary organic aerosol (SOA) formation. In poplar, acute ozone stress induces the emission of a wide array of VOCs dominated by sesquiterpenes and aromatic VOCs. Constitutive light-dependent emission of isoprene ranged between 66 nmol m −2 s −1 in non-transgenic controls (wild type WT) and nearly zero (<0.5 nmol m −2 s −1 ) in isoprene emission-repressed plants (line RA22), respectively. Nucleation rates of up to 3600 cm −3 s −1 were observed in our experiments. In the presence of isoprene new particle formation was suppressed compared to non-isoprene containing VOC mixtures. Compared to isoprene/monoterpene systems emitted from other plants the suppression of nucleation by isoprene was less effective for the VOC mixture emitted from stressed poplar. This is explained by the observed high efficiency of new particle formation for emissions from stressed poplar. Direct measurements of OH in the reaction chamber revealed that the steady state concentration of OH is lower in the presence of isoprene than in the absence of isoprene, supporting the hypothesis that isoprenes' suppressing effect on nucleation is related to radical chemistry. In order to test whether isoprene contributes to SOA mass formation, fully deuterated isoprene (C 5 D 8 ) was added to the stress-induced emission profile of an isoprene free poplar mutant. Mass spectral analysis showed that, despite the isoprene-induced suppression of particle formation, fractions of deuterated isoprene were incorporated into the SOA. A fractional mass yield of 2.3 % of isoprene was observed. Future emission changes due to land use and climate change may therefore affect both gas phase oxidation capacity and new particle number formation.

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Section: Resultsmentioning

confidence: 99%

Isoprene in poplar emissions: effects on new particle formation and OH concentrations

Kiendler‐Scharr¹,

Andres²,

Bachner³

et al. 2012

Atmos. Chem. Phys.

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“…Gly may be associated with pollution sources whereas MeGly may be involved with biogenic sources such as isoprene. These α-dicarbonyls may serve as the precursors to produce secondary organic aerosols through heterogeneous reactions (Kroll et al, 2005;Liggio et al, 2005). Interestingly, levels of α-dicarbonyls in the Mangshan samples (3.5 to 271 ng m -3 , av.…”

Section: α-Dicarbonylsmentioning

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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“…10 Finally, the oxidation of isoprene leads to US and global biogenic SOA formation of 50% and 58%, respectively. 11,12,13 The addition of OH to isoprene results in four distinct hydroxyl alkyl isomers (Figure 1), each of which ultimately leads to different first-generation end products. Although there has been no direct experimental determination of the branching between channels, theoretical work has predicted branching of 0.67, 0.02, 0.02, and 0.29, respectively, for isomers I, II, III, and IV, 14 with an overall rate of (1.0 ( 0.1) × 10 -10 molecule -1 cm 3 s -1 .…”

Section: Introductionmentioning

confidence: 99%

Isomer-Selective Study of the OH-Initiated Oxidation of Isoprene in the Presence of O₂ and NO: 2. The Major OH Addition Channel

et al. 2010

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We report the first isomeric-selective study of the dominant isomeric pathway in the OH-initiated oxidation of isoprene in the presence of O 2 and NO using the laser photolysis-laser induced fluorescence (LP-LIF) technique. The photolysis of monodeuterated/nondeuterated 2-iodo-2-methylbut-3-en-1-ol results exclusively in the dominant OH-isoprene addition product, providing important insight into the oxidation mechanism. On the basis of kinetic analysis of OH cycling experiments, we have determined the rate constant for O 2 addition to the hydroxyalkyl radical to be 1.0 -0.5 +1.7 × 10 -12 cm 3 s -1 , and we find a value of 8.1 -2.3 +3.4 × 10 -12 cm 3 s -1 for the overall reaction rate constant of the resulting hydroxyperoxy radical with NO. We also report the first clear experimental evidence of the (E) form of the δ-hydroxyalkoxy channel through isotopic labeling experiments and quantify its branching ratio to be (10 ( 3)%. This puts a rigorous upper limit on the branching of the (E)-δ-hydroxyalkoxy radical channel. Since our measured isomeric-selective rate constants for the dominant outer channel in OH-initiated isoprene chemistry are similar to the overall rate constants derived from nonisomeric kinetics, we predict that the remaining outer addition channel will have similar reactivity.

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Secondary organic aerosol formation from isoprene photooxidation under high‐NO_x conditions

Cited by 332 publications

References 26 publications

Isoprene in poplar emissions: effects on new particle formation and OH concentrations

Isoprene in poplar emissions: effects on new particle formation and OH concentrations

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

Isomer-Selective Study of the OH-Initiated Oxidation of Isoprene in the Presence of O₂ and NO: 2. The Major OH Addition Channel

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Secondary organic aerosol formation from isoprene photooxidation under high‐NOx conditions

Cited by 332 publications

References 26 publications

Isoprene in poplar emissions: effects on new particle formation and OH concentrations

Isoprene in poplar emissions: effects on new particle formation and OH concentrations

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

Isomer-Selective Study of the OH-Initiated Oxidation of Isoprene in the Presence of O2 and NO: 2. The Major OH Addition Channel

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Secondary organic aerosol formation from isoprene photooxidation under high‐NO_x conditions

Isomer-Selective Study of the OH-Initiated Oxidation of Isoprene in the Presence of O₂ and NO: 2. The Major OH Addition Channel