Transitions from functionalization to fragmentation reactions of laboratory Secondary Organic Aerosol (SOA) generated from the OH oxidation of alkane precursors

Andrew T. Lambe, Timothy B. Onasch, David R. Croasdale, Justin P. Wright, Alexander T. Martin, Jonathan P. Franklin, Paola Massoli, Jesse H. Kroll, Manjula R. Canagaratna, William Henry Brune, Douglas R. Worsnop, Paul Davidovits

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Abstract

Functionalization (oxygen addition) and fragmentation (carbon loss) reactions governing secondary organic aerosol (SOA) formation from the OH oxidation of alkane precursors were studied in a flow reactor in the absence of NOx. SOA precursors were n-decane (n-C10), n-pentadecane (n-C15), n-heptadecane (n-C17), tricyclo[5.2.1.0 2,6]decane (JP-10), and vapors of diesel fuel and Southern Louisiana crude oil. Aerosol mass spectra were measured with a high-resolution time-of-flight aerosol mass spectrometer, from which normalized SOA yields, hydrogen-to-carbon (H/C) and oxygen-to-carbon (O/C) ratios, and C xHy +, CxHyO+, and C xHyO2 + ion abundances were extracted as a function of OH exposure. Normalized SOA yield curves exhibited an increase followed by a decrease as a function of OH exposure, with maximum yields at O/C ratios ranging from 0.29 to 0.74. The decrease in SOA yield correlates with an increase in oxygen content and decrease in carbon content, consistent with transitions from functionalization to fragmentation. For a subset of alkane precursors (n-C10, n-C15, and JP-10), maximum SOA yields were estimated to be 0.39, 0.69, and 1.1. In addition, maximum SOA yields correspond with a maximum in the CxHyO+ relative abundance. Measured correlations between OH exposure, O/C ratio, and H/C ratio may enable identification of alkane precursor contributions to ambient SOA.

Original languageEnglish (US)
Pages (from-to)5430-5437
Number of pages8
JournalEnvironmental Science and Technology
Volume46
Issue number10
DOIs
StatePublished - May 15 2012

Fingerprint

Alkanes
Aerosols
alkane
fragmentation
aerosol
oxidation
Oxidation
Carbon
carbon
Oxygen
Hydrogen
hydrogen
laboratory
oxygen
aerosol formation
Petroleum
Mass spectrometers
Diesel fuels
crude oil
relative abundance

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Environmental Chemistry

Cite this

Lambe, Andrew T. ; Onasch, Timothy B. ; Croasdale, David R. ; Wright, Justin P. ; Martin, Alexander T. ; Franklin, Jonathan P. ; Massoli, Paola ; Kroll, Jesse H. ; Canagaratna, Manjula R. ; Brune, William Henry ; Worsnop, Douglas R. ; Davidovits, Paul. / Transitions from functionalization to fragmentation reactions of laboratory Secondary Organic Aerosol (SOA) generated from the OH oxidation of alkane precursors. In: Environmental Science and Technology. 2012 ; Vol. 46, No. 10. pp. 5430-5437.
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title = "Transitions from functionalization to fragmentation reactions of laboratory Secondary Organic Aerosol (SOA) generated from the OH oxidation of alkane precursors",
abstract = "Functionalization (oxygen addition) and fragmentation (carbon loss) reactions governing secondary organic aerosol (SOA) formation from the OH oxidation of alkane precursors were studied in a flow reactor in the absence of NOx. SOA precursors were n-decane (n-C10), n-pentadecane (n-C15), n-heptadecane (n-C17), tricyclo[5.2.1.0 2,6]decane (JP-10), and vapors of diesel fuel and Southern Louisiana crude oil. Aerosol mass spectra were measured with a high-resolution time-of-flight aerosol mass spectrometer, from which normalized SOA yields, hydrogen-to-carbon (H/C) and oxygen-to-carbon (O/C) ratios, and C xHy +, CxHyO+, and C xHyO2 + ion abundances were extracted as a function of OH exposure. Normalized SOA yield curves exhibited an increase followed by a decrease as a function of OH exposure, with maximum yields at O/C ratios ranging from 0.29 to 0.74. The decrease in SOA yield correlates with an increase in oxygen content and decrease in carbon content, consistent with transitions from functionalization to fragmentation. For a subset of alkane precursors (n-C10, n-C15, and JP-10), maximum SOA yields were estimated to be 0.39, 0.69, and 1.1. In addition, maximum SOA yields correspond with a maximum in the CxHyO+ relative abundance. Measured correlations between OH exposure, O/C ratio, and H/C ratio may enable identification of alkane precursor contributions to ambient SOA.",
author = "Lambe, {Andrew T.} and Onasch, {Timothy B.} and Croasdale, {David R.} and Wright, {Justin P.} and Martin, {Alexander T.} and Franklin, {Jonathan P.} and Paola Massoli and Kroll, {Jesse H.} and Canagaratna, {Manjula R.} and Brune, {William Henry} and Worsnop, {Douglas R.} and Paul Davidovits",
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month = "5",
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Lambe, AT, Onasch, TB, Croasdale, DR, Wright, JP, Martin, AT, Franklin, JP, Massoli, P, Kroll, JH, Canagaratna, MR, Brune, WH, Worsnop, DR & Davidovits, P 2012, 'Transitions from functionalization to fragmentation reactions of laboratory Secondary Organic Aerosol (SOA) generated from the OH oxidation of alkane precursors', Environmental Science and Technology, vol. 46, no. 10, pp. 5430-5437. https://doi.org/10.1021/es300274t

Transitions from functionalization to fragmentation reactions of laboratory Secondary Organic Aerosol (SOA) generated from the OH oxidation of alkane precursors. / Lambe, Andrew T.; Onasch, Timothy B.; Croasdale, David R.; Wright, Justin P.; Martin, Alexander T.; Franklin, Jonathan P.; Massoli, Paola; Kroll, Jesse H.; Canagaratna, Manjula R.; Brune, William Henry; Worsnop, Douglas R.; Davidovits, Paul.

In: Environmental Science and Technology, Vol. 46, No. 10, 15.05.2012, p. 5430-5437.

Research output: Contribution to journalArticle

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T1 - Transitions from functionalization to fragmentation reactions of laboratory Secondary Organic Aerosol (SOA) generated from the OH oxidation of alkane precursors

AU - Lambe, Andrew T.

AU - Onasch, Timothy B.

AU - Croasdale, David R.

AU - Wright, Justin P.

AU - Martin, Alexander T.

AU - Franklin, Jonathan P.

AU - Massoli, Paola

AU - Kroll, Jesse H.

AU - Canagaratna, Manjula R.

AU - Brune, William Henry

AU - Worsnop, Douglas R.

AU - Davidovits, Paul

PY - 2012/5/15

Y1 - 2012/5/15

N2 - Functionalization (oxygen addition) and fragmentation (carbon loss) reactions governing secondary organic aerosol (SOA) formation from the OH oxidation of alkane precursors were studied in a flow reactor in the absence of NOx. SOA precursors were n-decane (n-C10), n-pentadecane (n-C15), n-heptadecane (n-C17), tricyclo[5.2.1.0 2,6]decane (JP-10), and vapors of diesel fuel and Southern Louisiana crude oil. Aerosol mass spectra were measured with a high-resolution time-of-flight aerosol mass spectrometer, from which normalized SOA yields, hydrogen-to-carbon (H/C) and oxygen-to-carbon (O/C) ratios, and C xHy +, CxHyO+, and C xHyO2 + ion abundances were extracted as a function of OH exposure. Normalized SOA yield curves exhibited an increase followed by a decrease as a function of OH exposure, with maximum yields at O/C ratios ranging from 0.29 to 0.74. The decrease in SOA yield correlates with an increase in oxygen content and decrease in carbon content, consistent with transitions from functionalization to fragmentation. For a subset of alkane precursors (n-C10, n-C15, and JP-10), maximum SOA yields were estimated to be 0.39, 0.69, and 1.1. In addition, maximum SOA yields correspond with a maximum in the CxHyO+ relative abundance. Measured correlations between OH exposure, O/C ratio, and H/C ratio may enable identification of alkane precursor contributions to ambient SOA.

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