Secondary Organic Aerosol Formation from Isoprene Photooxidation

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

doi:10.1021/es0524301

Cited by 786 publications

(944 citation statements)

References 56 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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“…The gas collected in these canisters was analyzed off-line using the gas chromatographic system with several columns and detectors described by Sive et al [2005] and White et al [2010], allowing for accurate quantification of over 100 different VOC compounds. Specifically, a-pinene and isoprene are used as indicators of BVOC precursors to SOA [Hoffmann et al, 1997;Kroll et al, 2006], toluene is used as an indicator of a mixed biogenic-anthropogenic [White et al, 2009] primary aromatic precursor to SOA , and isopropyl nitrate is used as an additional indicator of secondary processing of anthropogenic emissions [deGouw et al, 2005].…”

Section: Measurementsmentioning

confidence: 99%

Characterization of aerosol associated with enhanced small particle number concentrations in a suburban forested environment

Ziemba¹,

Griffin²,

Cottrell³

et al. 2010

J. Geophys. Res.

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Two elevated particle number/mass growth events associated with Aitken‐mode particles were observed during a sampling campaign (13–29 September 2004) at the Duke University Free‐Air CO2 Enrichment facility, a forested field site located in suburban central North Carolina. Aerosol growth rates between 1.2 and 4.9 nm hr−1 were observed, resulting in net increases in geometric mean diameter of 21 and 37 nm during events. Growth was dominated by addition of oxidized organic compounds. Campaign‐average aerosol mass concentrations measured by an Aerodyne quadrupole aerosol mass spectrometer (Q‐AMS) were 1.9 ± 1.6 (σ), 1.6 ± 1.9, 0.1 ± 0.1, and 0.4 ± 0.4 μg m−3 for organic mass (OM), sulfate, nitrate, and ammonium, respectively. These values represent 47%, 40%, 3%, and 10%, respectively, of the measured submicron aerosol mass. Based on Q‐AMS spectra, OM was apportioned to hydrocarbon‐like organic aerosol (HOA, likely representing primary organic aerosol) and two types of oxidized organic aerosol (OOA‐1 and OOA‐2), which constituted on average 6%, 58%, and 36%, respectively, of the apportioned OM. OOA‐1 probably represents aged, regional secondary organic aerosol (SOA), while OOA‐2 likely reflects less aged SOA. Organic aerosol characteristics associated with the events are compared to the campaign averages. Particularly in one event, the contribution of OOA‐2 to overall OM levels was enhanced, indicating the likelihood of less aged SOA formation. Statistical analyses investigate the relationships between HOA, OOA‐1, OOA‐2, other aerosol components, gas‐phase species, and meteorological data during the campaign and individual events. No single variable clearly controls the occurrence of a particle growth event.

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“…Owing to its high concentration and reactivity with OH radicals, isoprene plays an important role in the photochemistry occurring within the atmospheric boundary layer. Recently, it has been shown that the photooxidation of isoprene leads to the formation of low volatility species that condense to form SOA (Claeys et al, 2004;Edney et al, 2005;Kroll et al, 2005;Dommen et al, 2006;Kroll et al, 2006;Surratt et al, 2006); SOA yields as high as ∼3% have been observed (Kroll et al, 2005;Kroll et al, 2006). Global SOA production from isoprene photooxidation has been estimated to be about 13 Tg yr −1 (Henze et al, 2007).…”

Section: Introductionmentioning

confidence: 99%

Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO<sub>3</sub>)

et al. 2008

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Abstract. Secondary organic aerosol (SOA) formation from the reaction of isoprene with nitrate radicals (NO 3 ) is investigated in the Caltech indoor chambers. Experiments are performed in the dark and under dry conditions (RH<10%) using N 2 O 5 as a source of NO 3 radicals. For an initial isoprene concentration of 18.4 to 101.6 ppb, the SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) ranges from 4.3% to 23.8%. By examining the time evolutions of gas-phase intermediate products and aerosol volume in real time, we are able to constrain the chemistry that leads to the formation of lowvolatility products. Although the formation of ROOR from the reaction of two peroxy radicals (RO 2 ) has generally been considered as a minor channel, based on the gas-phase and aerosol-phase data it appears that RO 2 +RO 2 reaction (self reaction or cross-reaction) in the gas phase yielding ROOR products is a dominant SOA formation pathway. A wide array of organic nitrates and peroxides are identified in the aerosol formed and mechanisms for SOA formation are proposed. Using a uniform SOA yield of 10% (corresponding to M o ∼ =10 µg m −3 ), it is estimated that ∼2 to 3 Tg yr −1 of SOA results from isoprene+NO 3 . The extent to which the results from this study can be applied to conditions in the atmosphere depends on the fate of peroxy radicals in the nighttime troposphere.

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Secondary Organic Aerosol Formation from Isoprene Photooxidation

Cited by 786 publications

References 56 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

Characterization of aerosol associated with enhanced small particle number concentrations in a suburban forested environment

Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO<sub>3</sub>)

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Secondary Organic Aerosol Formation from Isoprene Photooxidation

Cited by 786 publications

References 56 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

Characterization of aerosol associated with enhanced small particle number concentrations in a suburban forested environment

Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO&lt;sub&gt;3&lt;/sub&gt;)

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Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO<sub>3</sub>)