Measurements of secondary organic aerosol from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer.

The Aerodyne aerosol mass spectrometer (AMS) was used to characterize physical and chemical properties of secondary organic aerosol (SOA) formed during ozonolysis of cycloalkenes and biogenic hydrocarbons and photo-oxidation of m-xylene. Comparison of mass and volume distributions from the AMS and differential mobility analyzers yielded estimates of "effective" density of the SOA in the range of 0.64-1.45 g/cm3, depending on the particular system. Increased contribution of the fragment at m/z 44, C02+ ion fragment of oxygenated organics, and higher "delta" values, based on ion series analysis of the mass spectra, in nucleation experiments of cycloalkenes suggest greater contribution of more oxygenated molecules to the SOA as compared to those formed under seeded experiments. Dominant negative "delta" values of SOA formed during ozonolysis of biogenics indicates the presence of terpene derivative structures or cyclic or unsaturated oxygenated compounds in the SOA. Evidence of acid-catalyzed heterogeneous chemistry, characterized by greater contribution of higher molecular weight fragments to the SOA and corresponding changes in "delta" patterns, is observed in the ozonolysis of alpha-pinene. Mass spectra of SOA formed during photooxidation of m-xylene exhibit features consistent with the presence of furandione compounds and nitro organics. This study demonstrates that mixtures of SOA compounds produced from similar precursors result in broadly similar AMS mass spectra. Thus, fragmentation patterns observed for biogenic versus anthropogenic SOA may be useful in determining the sources of ambient SOA.

[1]  Robert P Hodyss,et al.  Particle phase acidity and oligomer formation in secondary organic aerosol. , 2004, Environmental science & technology.

[2]  J. Jimenez,et al.  Characterization of urban and rural organic particulate in the Lower Fraser Valley using two Aerodyne Aerosol Mass Spectrometers , 2004 .

[3]  F. J. Cox,et al.  Formation of oligomers in secondary organic aerosol. , 2004, Environmental science & technology.

[4]  Kenneth A. Smith,et al.  Development of an Aerosol Mass Spectrometer for Size and Composition Analysis of Submicron Particles , 2000 .

[5]  R Zenobi,et al.  Secondary organic aerosols from anthropogenic and biogenic precursors. , 2005, Faraday discussions.

[6]  J. Seinfeld,et al.  Secondary organic aerosol formation from the ozonolysis of cycloalkenes and related compounds. , 2004, Environmental science & technology.

[7]  A. Goldstein,et al.  Submicron aerosol composition at Trinidad Head, California, during ITCT 2K2: Its relationship with gas phase volatile organic carbon and assessment of instrument performance , 2004 .

[8]  J. Jimenez,et al.  A generalised method for the extraction of chemically resolved mass spectra from aerodyne aerosol mass spectrometer data , 2004 .

[9]  Douglas R. Worsnop,et al.  Particle Morphology and Density Characterization by Combined Mobility and Aerodynamic Diameter Measurements. Part 1: Theory , 2004 .

[10]  U. Baltensperger,et al.  Identification of Polymers as Major Components of Atmospheric Organic Aerosols , 2004, Science.

[11]  D. O. De Haan,et al.  Formation of secondary organic aerosol by reactive condensation of furandiones, aldehydes, and water vapor onto inorganic aerosol seed particles. , 2004, Environmental science & technology.

[12]  P. Ziemann,et al.  Effects of Stabilized Criegee Intermediate and OH Radical Scavengers on Aerosol Formation from Reactions of β-Pinene with O 3 , 2003 .

[13]  John H. Seinfeld,et al.  Aromatics, Reformulated Gasoline, and Atmospheric Organic Aerosol Formation , 1997 .

[14]  John H. Seinfeld,et al.  Low-Molecular-Weight and Oligomeric Components in Secondary Organic Aerosol from the Ozonolysis of Cycloalkenes and α-Pinene , 2004 .

[15]  Kenneth L. Demerjian,et al.  Measurement of Ambient Aerosol Composition During the PMTACS-NY 2001 Using an Aerosol Mass Spectrometer. Part II: Chemically Speciated Mass Distributions Special Issue of Aerosol Science and Technology on Findings from the Fine Particulate Matter Supersites Program , 2004 .

[16]  Appendix A : New Particle Formation from Photooxidation of Diiodomethane ( CH 2 I 2 ) * , 2003 .

[17]  Charles E. Kolb,et al.  Chase Studies of Particulate Emissions from in-use New York City Vehicles , 2004 .

[18]  J. Seinfeld,et al.  Marine aerosol formation from biogenic iodine emissions , 2002, Nature.

[19]  John H. Seinfeld,et al.  Aerosol formation in the photooxidation of isoprene and β-pinene , 1991 .

[20]  J. H. Seinfeld,et al.  The Atmospheric Aerosol-Forming Potential of Whole Gasoline Vapor , 1997, Science.

[21]  D. Worsnop,et al.  Measurement of Ambient Aerosol Composition During the PMTACS-NY 2001 Using an Aerosol Mass Spectrometer. Part I: Mass Concentrations Special Issue of Aerosol Science and Technology on Findings from the Fine Particulate Matter Supersites Program , 2004 .

[22]  John H. Seinfeld,et al.  Secondary Organic Aerosol from the Photooxidation of Aromatic Hydrocarbons: Molecular Composition , 1997 .

[23]  J. Seinfeld,et al.  Aircraft‐based aerosol size and composition measurements during ACE‐Asia using an Aerodyne aerosol mass spectrometer , 2003 .

[24]  Richard C. Flagan,et al.  Scanning Electrical Mobility Spectrometer , 1989 .

[25]  Frank M. Bowman,et al.  Formation of Organic Aerosols from the Oxidation of Biogenic Hydrocarbons , 1997 .

[26]  F. McLafferty.  Interpretation of Mass Spectra , 1966 .

[27]  D. Worsnop,et al.  Online mass spectrometric aerosol measurements during the MINOS campaign (Crete, August 2001) , 2003 .

[28]  Qi Zhang,et al.  Insights into the chemistry of new particle formation and growth events in Pittsburgh based on aerosol mass spectrometry. , 2004, Environmental science & technology.

[29]  R C Flagan,et al.  State-of-the-art chamber facility for studying atmospheric aerosol chemistry. , 2001, Environmental science & technology.

[30]  Hugh Coe,et al.  Quantitative sampling using an Aerodyne aerosol mass spectrometer 1. Techniques of data interpretation and error analysis , 2003 .

[31]  R. Kamens,et al.  Heterogeneous Atmospheric Aerosol Production by Acid-Catalyzed Particle-Phase Reactions , 2002, Science.

[32]  John H. Seinfeld,et al.  Organic aerosol formation from the oxidation of biogenic hydrocarbons , 1999 .

[33]  Andreas Limbeck,et al.  Secondary organic aerosol formation in the atmosphere via heterogeneous reaction of gaseous isoprene on acidic particles , 2003 .

[34]  R C Flagan,et al.  Secondary organic aerosol formation from cyclohexene ozonolysis: effect of OH scavenger and the role of radical chemistry. , 2004, Environmental science & technology.

[35]  J. Seinfeld,et al.  New particle formation from photooxidation of diiodomethane (CH2I2) , 2003 .

[36]  Arthur Garforth,et al.  A mass spectrometric study of secondary organic aerosols formed from the photooxidation of anthropogenic and biogenic precursors in a reaction chamber , 2006 .