Detailed chemical characterization of unresolved complex mixtures in atmospheric organics: Insights into emission sources, atmospheric processing, and secondary organic aerosol formation

被引：62

作者：

Chan, Arthur W. H. ^{[1
,2
]}

Isaacman, Gabriel ^{[1
]}

Wilson, Kevin R. ^{[3
]}

Worton, David R. ^{[1
,4
]}

Ruehl, Christopher R. ^{[1
,3
]}

Nah, Theodora ^{[5
]}

Gentner, Drew R. ^{[6
]}

Dallmann, Timothy R. ^{[6
]}

Kirchstetter, Thomas W. ^{[6
,7
]}

Harley, Robert A. ^{[6
,7
]}

Gilman, Jessica B. ^{[8
,9
]}

Kuster, William C. ^{[9
]}

deGouw, Joost A. ^{[8
,9
]}

Offenberg, John H. ^{[10
]}

Kleindienst, Tadeusz E. ^{[10
]}

Lin, Ying H. ^{[11
]}

Rubitschun, Caitlin L. ^{[11
]}

Surratt, Jason D. ^{[11
]}

Hayes, Patrick L. ^{[8
,12
]}

Jimenez, Jose L. ^{[8
,12
]}

Goldstein, Allen H. ^{[1
,6
,7
]}

机构：

[1] Univ Calif Berkeley, Dept Environm Sci Policy & Management, Berkeley, CA 94720 USA

[2] Univ Toronto, Dept Chem Engn & Appl Chem, Toronto, ON M5S 3E5, Canada

[3] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Div Chem Sci, Berkeley, CA 94720 USA

[4] Aerosol Dynam Inc, Berkeley, CA USA

[5] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

[6] Univ Calif Berkeley, Dept Civil & Environm Engn, Berkeley, CA 94720 USA

[7] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Environm Energy Technol Div, Berkeley, CA 94720 USA

[8] Univ Colorado, Cooperat Inst Res Environm Sci, Boulder, CO 80309 USA

[9] NOAA, Div Chem Sci, Boulder, CO USA

[10] US EPA, Natl Exposure Lab, Off Res & Dev, Res Triangle Pk, NC 27711 USA

[11] Univ N Carolina, Dept Environm Sci & Engn, Gillings Sch Global Publ Hlth, Chapel Hill, NC USA

[12] Univ Colorado, Dept Chem & Biochem, Boulder, CO 80309 USA

来源：

JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES | 2013年 / 118卷 / 12期

基金：

美国海洋和大气管理局;

关键词：

semivolatile organic compounds; secondary organic aerosol; urban emissions; unresolved complex mixture; gas chromatography mass spectrometry; 2-DIMENSIONAL GAS-CHROMATOGRAPHY; AIR-POLLUTION SOURCES; DUTY DIESEL TRUCKS; MASS-SPECTROMETER; VOLATILITY DISTRIBUTION; N-ALKANES; SEMIVOLATILE; HYDROCARBONS; EVOLUTION; PHOTOOXIDATION;

D O I：

10.1002/jgrd.50533

中图分类号：

P4 [大气科学（气象学）];

学科分类号：

0706 ; 070601 ;

摘要：

Recent studies suggest that semivolatile organic compounds (SVOCs) are important precursors to secondary organic aerosol (SOA) in urban atmospheres. However, knowledge of the chemical composition of SVOCs is limited by current analytical techniques, which are typically unable to resolve a large number of constitutional isomers. Using a combination of gas chromatography and soft photoionization mass spectrometry, we characterize the unresolved complex mixture (UCM) of semivolatile aliphatic hydrocarbons observed in Pasadena, California (similar to 16km NE of downtown Los Angeles), and Bakersfield, California, during the California Research at the Nexus of Air Quality and Climate Change 2010. To the authors' knowledge, this work represents the most detailed characterization of the UCM in atmospheric samples to date. Knowledge of molecular structures, including carbon number, alkyl branching, and number of rings, provides important constraints on the rate of atmospheric processing, as the relative amounts of branched and linear alkanes are shown to be a function of integrated exposure to hydroxyl radicals. Emissions of semivolatile branched alkanes from fossil fuel-related sources are up to an order of magnitude higher than those of linear alkanes, and the gas-phase OH rate constants of branched alkanes are similar to 30% higher than their linear isomers. Based on a box model considering gas/particle partitioning, emissions, and reaction rates, semivolatile branched alkanes are expected to play a more important role than linear alkanes in the photooxidation of the UCM and subsequent transformations into SOA. Detailed speciation of semivolatile compounds therefore provides essential understanding of SOA sources and formation processes in urban areas.

引用

页码：6783 / 6796

页数：14

共 47 条

[1] Emission ratios of anthropogenic volatile organic compounds in northern mid-latitude megacities: Observations versus emission inventories in Los Angeles and Paris [J].

Borbon, Agnes ;

Gilman, J. B. ;

Kuster, W. C. ;

Grand, N. ;

Chevaillier, S. ;

Colomb, A. ;

Dolgorouky, C. ;

Gros, V. ;

Lopez, M. ;

Sarda-Esteve, R. ;

Holloway, J. ;

Stutz, J. ;

Petetin, H. ;

McKeen, S. ;

Beekmann, M. ;

Warneke, C. ;

Parrish, D. D. ;

de Gouw, J. A. .

JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 2013, 118 (04) :2041-2057

[2] On-Road Measurement of Gas and Particle Phase Pollutant Emission Factors for Individual Heavy-Duty Diesel Trucks [J].

Dallmann, Timothy R. ;

DeMartini, Steven J. ;

Kirchstetter, Thomas W. ;

Herndon, Scott C. ;

Onasch, Timothy B. ;

Wood, Ezra C. ;

Harley, Robert A. .

ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2012, 46 (15) :8511-8518

[3] Field-deployable, high-resolution, time-of-flight aerosol mass spectrometer [J].

DeCarlo, Peter F. ;

Kimmel, Joel R. ;

Trimborn, Achim ;

Northway, Megan J. ;

Jayne, John T. ;

Aiken, Allison C. ;

Gonin, Marc ;

Fuhrer, Katrin ;

Horvath, Thomas ;

Docherty, Kenneth S. ;

Worsnop, Doug R. ;

Jimenez, Jose L. .

ANALYTICAL CHEMISTRY, 2006, 78 (24) :8281-8289

[4] Resolving the unresolved complex mixture in petroleum-contaminated sediments [J].

Frysinger, GS ;

Gaines, RB ;

Xu, L ;

Reddy, CM .

ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2003, 37 (08) :1653-1662

[5]

Gary J.H., 2007, Petroleum Refining: Technology and Economics

[6] Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of organic carbon emissions [J].

Gentner, Drew R. ;

Isaacman, Gabriel ;

Worton, David R. ;

Chan, Arthur W. H. ;

Dallmann, Timothy R. ;

Davis, Laura ;

Liu, Shang ;

Day, Douglas A. ;

Russell, Lynn M. ;

Wilson, Kevin R. ;

Weber, Robin ;

Guha, Abhinav ;

Harley, Robert A. ;

Goldstein, Allen H. .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2012, 109 (45) :18318-18323

[7] Ozone variability and halogen oxidation within the Arctic and sub-Arctic springtime boundary layer [J].

Gilman, J. B. ;

Burkhart, J. F. ;

Lerner, B. M. ;

Williams, E. J. ;

Kuster, W. C. ;

Goldan, P. D. ;

Murphy, P. C. ;

Warneke, C. ;

Fowler, C. ;

Montzka, S. A. ;

Miller, B. R. ;

Miller, L. ;

Oltmans, S. J. ;

Ryerson, T. B. ;

Cooper, O. R. ;

Stohl, A. ;

de Gouw, J. A. .

ATMOSPHERIC CHEMISTRY AND PHYSICS, 2010, 10 (21) :10223-10236

[8] Known and unexplored organic constituents in the earth's atmosphere [J].

Goldstein, Allen H. ;

Galbally, Ian E. .

ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2007, 41 (05) :1514-1521

[9] Constraining the Volatility Distribution and Gas-Particle Partitioning of Combustion Aerosols Using Isothermal Dilution and Thermodenuder Measurements [J].

Grieshop, Andrew P. ;

Miracolo, Marissa A. ;

Donahue, Neil. M. ;

Robinson, Allen L. .

ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2009, 43 (13) :4750-4756

[10] The formation, properties and impact of secondary organic aerosol: current and emerging issues [J].

Hallquist, M. ;

Wenger, J. C. ;

Baltensperger, U. ;

Rudich, Y. ;

Simpson, D. ;

Claeys, M. ;

Dommen, J. ;

Donahue, N. M. ;

George, C. ;

Goldstein, A. H. ;

Hamilton, J. F. ;

Herrmann, H. ;

Hoffmann, T. ;

Iinuma, Y. ;

Jang, M. ;

Jenkin, M. E. ;

Jimenez, J. L. ;

Kiendler-Scharr, A. ;

Maenhaut, W. ;

McFiggans, G. ;

Mentel, Th. F. ;

Monod, A. ;

Prevot, A. S. H. ;

Seinfeld, J. H. ;

Surratt, J. D. ;

Szmigielski, R. ;

Wildt, J. .

ATMOSPHERIC CHEMISTRY AND PHYSICS, 2009, 9 (14) :5155-5236

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