Uptake of Epoxydiol Isomers Accounts for Half of the Particle-Phase Material Produced from Isoprene Photooxidation via the HO2 Pathway

The oxidation of isoprene is a globally significant source of secondary organic material (SOM) of atmospheric particles. The relative importance of different parallel pathways, however, remains inadequately understood and quantified. SOM production from isoprene photooxidation was studied under hydr...

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Published inEnvironmental science & technology Vol. 49; no. 1; pp. 250 - 258
Main Authors Liu, Yingjun, Kuwata, Mikinori, Strick, Benjamin F, Geiger, Franz M, Thomson, Regan J, McKinney, Karena A, Martin, Scot T
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 06.01.2015
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ISSN0013-936X
1520-5851
1520-5851
DOI10.1021/es5034298

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Abstract The oxidation of isoprene is a globally significant source of secondary organic material (SOM) of atmospheric particles. The relative importance of different parallel pathways, however, remains inadequately understood and quantified. SOM production from isoprene photooxidation was studied under hydroperoxyl-dominant conditions for <5% relative humidity and at 20 °C in the presence of highly acidic to completely neutralized sulfate particles. Isoprene photooxidation was separated from SOM production by using two continuously mixed flow reactors connected in series and operated at steady state. Two online mass spectrometers separately sampled the gas and particle phases in the reactor outflow. The loss of specific gas-phase species as contributors to the production of SOM was thereby quantified. The produced SOM mass concentration was directly proportional to the loss of isoprene epoxydiol (IEPOX) isomers from the gas phase. IEPOX isomers lost from the gas phase accounted for (46 ± 11)% of the produced SOM mass concentration. The IEPOX isomers comprised (59 ± 21)% (molecular count) of the loss of monitored gas-phase species. The implication is that for the investigated reaction conditions the SOM production pathways tied to IEPOX isomers accounted for half of the SOM mass concentration.
AbstractList The oxidation of isoprene is a globally significant source of secondary organic material (SOM) of atmospheric particles. The relative importance of different parallel pathways, however, remains inadequately understood and quantified. SOM production from isoprene photooxidation was studied under hydroperoxyl-dominant conditions for <5% relative humidity and at 20 °C in the presence of highly acidic to completely neutralized sulfate particles. Isoprene photooxidation was separated from SOM production by using two continuously mixed flow reactors connected in series and operated at steady state. Two online mass spectrometers separately sampled the gas and particle phases in the reactor outflow. The loss of specific gas-phase species as contributors to the production of SOM was thereby quantified. The produced SOM mass concentration was directly proportional to the loss of isoprene epoxydiol (IEPOX) isomers from the gas phase. IEPOX isomers lost from the gas phase accounted for (46 ± 11)% of the produced SOM mass concentration. The IEPOX isomers comprised (59 ± 21)% (molecular count) of the loss of monitored gas-phase species. The implication is that for the investigated reaction conditions the SOM production pathways tied to IEPOX isomers accounted for half of the SOM mass concentration.The oxidation of isoprene is a globally significant source of secondary organic material (SOM) of atmospheric particles. The relative importance of different parallel pathways, however, remains inadequately understood and quantified. SOM production from isoprene photooxidation was studied under hydroperoxyl-dominant conditions for <5% relative humidity and at 20 °C in the presence of highly acidic to completely neutralized sulfate particles. Isoprene photooxidation was separated from SOM production by using two continuously mixed flow reactors connected in series and operated at steady state. Two online mass spectrometers separately sampled the gas and particle phases in the reactor outflow. The loss of specific gas-phase species as contributors to the production of SOM was thereby quantified. The produced SOM mass concentration was directly proportional to the loss of isoprene epoxydiol (IEPOX) isomers from the gas phase. IEPOX isomers lost from the gas phase accounted for (46 ± 11)% of the produced SOM mass concentration. The IEPOX isomers comprised (59 ± 21)% (molecular count) of the loss of monitored gas-phase species. The implication is that for the investigated reaction conditions the SOM production pathways tied to IEPOX isomers accounted for half of the SOM mass concentration.
The oxidation of isoprene is a globally significant source of secondary organic material (SOM) of atmospheric particles. The relative importance of different parallel pathways, however, remains inadequately understood and quantified. SOM production from isoprene photooxidation was studied under hydroperoxyl-dominant conditions for <5% relative humidity and at 20 °C in the presence of highly acidic to completely neutralized sulfate particles. Isoprene photooxidation was separated from SOM production by using two continuously mixed flow reactors connected in series and operated at steady state. Two online mass spectrometers separately sampled the gas and particle phases in the reactor outflow. The loss of specific gas-phase species as contributors to the production of SOM was thereby quantified. The produced SOM mass concentration was directly proportional to the loss of isoprene epoxydiol (IEPOX) isomers from the gas phase. IEPOX isomers lost from the gas phase accounted for (46 ± 11)% of the produced SOM mass concentration. The IEPOX isomers comprised (59 ± 21)% (molecular count) of the loss of monitored gas-phase species. The implication is that for the investigated reaction conditions the SOM production pathways tied to IEPOX isomers accounted for half of the SOM mass concentration.
Author Geiger, Franz M
Strick, Benjamin F
Thomson, Regan J
Liu, Yingjun
Kuwata, Mikinori
McKinney, Karena A
Martin, Scot T
AuthorAffiliation Department of Chemistry
Northwestern University
School of Engineering and Applied Sciences
Harvard University
Department of Earth and Planetary Sciences
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Snippet The oxidation of isoprene is a globally significant source of secondary organic material (SOM) of atmospheric particles. The relative importance of different...
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SubjectTerms Aerosols - chemistry
Alcohols - chemistry
Atmosphere
Butadienes - chemistry
gases
Hemiterpenes - chemistry
Humidity
Isomerism
isomers
isoprene
Mass Spectrometry - instrumentation
Mass Spectrometry - methods
neutralization
Oxidation-Reduction
Pentanes - chemistry
Photochemical Processes
photooxidation
relative humidity
spectrometers
sulfates
Sulfates - chemistry
Title Uptake of Epoxydiol Isomers Accounts for Half of the Particle-Phase Material Produced from Isoprene Photooxidation via the HO2 Pathway
URI http://dx.doi.org/10.1021/es5034298
https://www.ncbi.nlm.nih.gov/pubmed/25375412
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Volume 49
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