High-resolution mass spectrometric analysis of secondary organic aerosol produced by ozonation of limonene.

Chemical composition of secondary organic aerosol (SOA) formed from the ozone-initiated oxidation of limonene is characterized by high-resolution electrospray ionization mass spectrometry in both positive and negative ion modes. The mass spectra reveal a large number of both monomeric (m/z < 300) and oligomeric (m/z > 300) condensed products of oxidation. A combination of high resolving power (m/Deltam approximately 60,000) and Kendrick mass defect analysis makes it possible to unambiguously determine the molecular composition of hundreds of individual compounds in SOA samples. Van Krevelen analysis shows that the SOA compounds are heavily oxidized, with average O : C ratios of 0.43 and 0.50 determined from the positive and negative ion mode spectra, respectively. A possible reaction mechanism for the formation of the first generation SOA molecular components is considered. The discussed mechanism includes known isomerization and addition reactions of the carbonyl oxide intermediates generated during the ozonation of limonene. In addition, it includes isomerization and decomposition pathways for alkoxy radicals resulting from unimolecular decomposition of carbonyl oxides that have been disregarded by previous studies. The isomerization reactions yield numerous products with a progressively increasing number of alcohol and carbonyl groups, whereas C-C bond scission reactions in alkoxy radicals shorten the carbon chain. Together these reactions yield a large number of isomeric products with broadly distributed masses. A qualitative agreement is found between the number and degree of oxidation of the predicted and measured reaction products in the monomer product range.

[1]  Peder Wolkoff,et al.  The effect on human eye blink frequency of exposure to limonene oxidation products and methacrolein. , 2005, Toxicology letters.

[2]  Armin Sorooshian,et al.  Characterization of 2-methylglyceric acid oligomers in secondary organic aerosol formed from the photooxidation of isoprene using trimethylsilylation and gas chromatography/ion trap mass spectrometry. , 2007, Journal of mass spectrometry : JMS.

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

[4]  Erik Swietlicki,et al.  Organic aerosol and global climate modelling: a review , 2004 .

[5]  Charles J. Weschler,et al.  Indoor ozone/terpene reactions as a source of indoor particles , 1999 .

[6]  Yong Bin Lim,et al.  Contributions of organic peroxides to secondary aerosol formed from reactions of monoterpenes with O3. , 2005, Environmental science & technology.

[7]  Paul Lioy,et al.  Ozone-initiated reactions with mixtures of volatile organic compounds under simulated indoor conditions. , 2003, Environmental science & technology.

[8]  K. Prather,et al.  Aerosol time‐of‐flight mass spectrometry during the Atlanta Supersite Experiment: 2. Scaling procedures , 2003 .

[9]  B. Turpin,et al.  Origins of primary and secondary organic aerosol in Atlanta: results of time-resolved measurements during the Atlanta Supersite Experiment. , 2002, Environmental science & technology.

[10]  A. Marshall,et al.  Petroleomics: the next grand challenge for chemical analysis. , 2004, Accounts of chemical research.

[11]  John H. Seinfeld,et al.  Atmospheric oxidation of biogenic hydrocarbons : Reaction of ozone with β-pinene, d-limonene and trans-caryophyllene , 1993 .

[12]  D. Murphy,et al.  Observations of organic material in individual marine particles at Cape Grim during the First Aerosol Characterization Experiment (ACE 1) , 1998 .

[13]  Christian Panse,et al.  Ultrahigh mass resolution and accurate mass measurements as a tool to characterize oligomers in secondary organic aerosols. , 2007, Analytical chemistry.

[14]  John H. Seinfeld,et al.  Cloud condensation nucleus activation properties of biogenic secondary organic aerosol , 2005 .

[15]  H. Hansson,et al.  Organic atmospheric aerosols: Review and state of the science , 2000 .

[16]  R. Kamens,et al.  Kinetic mechanism for predicting secondary organic aerosol formation from the reaction of d-limonene with ozone. , 2005, Environmental science & technology.

[17]  Spyros N Pandis,et al.  Secondary organic aerosol formation from limonene ozonolysis: homogeneous and heterogeneous influences as a function of NO(x). , 2006, The journal of physical chemistry. A.

[18]  C. Pio,et al.  Mass balance of organic carbon fractions in atmospheric aerosols , 2002 .

[19]  P. Koutrakis,et al.  Generation and Quantification of Ultrafine Particles through Terpene/Ozone Reaction in a Chamber Setting , 2003 .

[20]  P O Fanger,et al.  Influence of ozone-limonene reactions on perceived air quality. , 2006, Indoor air.

[21]  G. Marston,et al.  Reactions of alkenes with ozone in the gas phase: a matrix-isolation study of secondary ozonides and carbonyl-containing reaction products. , 2000, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[22]  S. Nizkorodov,et al.  Kinetic analysis of competition between aerosol particle removal and generation by ionization air purifiers. , 2007, Environmental science & technology.

[23]  R. Jaenicke,et al.  Organic material in the global troposphere , 1983 .

[24]  James N. Pitts,et al.  Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications , 1999 .

[25]  P Wolkoff,et al.  Formation of strong airway irritants in terpene/ozone mixtures. , 2000, Indoor air.

[26]  M. Mason,et al.  Full-scale chamber investigation and simulation of air freshener emissions in the presence of ozone. , 2004, Environmental science & technology.

[27]  Per Axel Clausen,et al.  Secondary limonene endo-ozonide: A major product from gas-phase ozonolysis of R-(+)-limonene at ambient temperature , 2006 .

[28]  A. Presto,et al.  Ozonolysis Fragment Quenching by Nitrate Formation: The Pressure Dependence of Prompt OH Radical Formation , 2004 .

[29]  Bettina Warscheid,et al.  Direct analysis of highly oxidised organic aerosol constituents by on-line ion trap mass spectrometry in the negative-ion mode. , 2002, Rapid communications in mass spectrometry : RCM.

[30]  Glen R. Cass,et al.  Chemical composition of emissions from urban sources of fine organic aerosol , 1991 .

[31]  R. Corsi,et al.  Ozone reactions with indoor materials during building disinfection , 2007 .

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

[33]  Armin Sorooshian,et al.  Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene. , 2006, The journal of physical chemistry. A.

[34]  Urs Baltensperger,et al.  Real-time measurement of oligomeric species in secondary organic aerosol with the aerosol time-of-flight mass spectrometer. , 2006, Analytical chemistry.

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

[36]  Evert Ljungström,et al.  Impact of humidity on the ozone initiated oxidation of limonene, delta3-carene, and alpha-pinene. , 2006, Environmental science & technology.

[37]  Sunghwan Kim,et al.  Graphical method for analysis of ultrahigh-resolution broadband mass spectra of natural organic matter, the van Krevelen diagram. , 2003, Analytical chemistry.

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

[39]  Jiho Park,et al.  Photochemical aging of secondary organic aerosol particles generated from the oxidation of d-limonene. , 2007, The journal of physical chemistry. A.

[40]  A G Marshall,et al.  Kendrick mass defect spectrum: a compact visual analysis for ultrahigh-resolution broadband mass spectra. , 2001, Analytical chemistry.

[41]  A. Marshall,et al.  Resolution of 11,000 compositionally distinct components in a single electrospray ionization Fourier transform ion cyclotron resonance mass spectrum of crude oil. , 2002, Analytical chemistry.

[42]  S. Paulson,et al.  Measurement of OH radical formation from the reaction of ozone with several biogenic alkenes , 1998 .

[43]  R. Burnett,et al.  Lung cancer, cardiopulmonary mortality, and long-term exposure to fine particulate air pollution. , 2002, JAMA.

[44]  Spyros N. Pandis,et al.  Secondary organic aerosol formation from limonene ozonolysis: homogeneous and heterogeneous influences as a function of NO(x). , 2006, The journal of physical chemistry. A.

[45]  Boris Bonn,et al.  Influence of water vapor on the process of new particle formation during monoterpene ozonolysis , 2002 .

[46]  J. Seinfeld,et al.  Atmospheric Chemistry and Physics: From Air Pollution to Climate Change , 1997 .

[47]  S. Nizkorodov,et al.  Quantification of Ozone Levels in Indoor Environments Generated by Ionization and Ozonolysis Air Purifiers , 2006, Journal of the Air & Waste Management Association.

[48]  Yoshiteru Iinuma,et al.  Laboratory studies on secondary organic aerosol formation from terpenes. , 2005, Faraday discussions.

[49]  William W. Nazaroff,et al.  Cleaning products and air fresheners: exposure to primary and secondary air pollutants , 2004 .

[50]  G. Marston,et al.  OH Yields in the Gas-Phase Reactions of Ozone with Alkenes , 1999 .

[51]  Edward B Rappaport,et al.  Association between air pollution and lung function growth in southern California children: results from a second cohort. , 2002, American journal of respiratory and critical care medicine.

[52]  P. Hatcher,et al.  Identification of black carbon derived structures in a volcanic ash soil humic acid by Fourier transform ion cyclotron resonance mass spectrometry. , 2004, Environmental science & technology.

[53]  D. Dockery,et al.  An association between air pollution and mortality in six U.S. cities. , 1993, The New England journal of medicine.

[54]  D. R. Worsnop,et al.  under a Creative Commons License. Atmospheric Chemistry , 2006 .

[55]  E. Mosley‐Thompson,et al.  New revelations on the nature of organic matter in ice cores , 2006 .

[56]  Kara E. Huff Hartz,et al.  Secondary organic aerosol from limona ketone: insights into terpene ozonolysis via synthesis of key intermediates. , 2007, Physical chemistry chemical physics : PCCP.

[57]  E. Kendrick.  A Mass Scale Based on CH2 = 14.0000 for High Resolution Mass Spectrometry of Organic Compounds. , 1963 .

[58]  W. Carter,et al.  Kinetics and mechanisms of the gas-phase reactions of ozone with organic compounds under atmospheric conditions , 1984 .

[59]  T. Hoffmann,et al.  Direct quantitative analysis of organic compounds in the gas and particle phase using a modified atmospheric pressure chemical ionization source in combination with ion trap mass spectrometry. , 2003, Analytical chemistry.

[60]  C. N. Hewitt,et al.  A global model of natural volatile organic compound emissions , 1995 .

[61]  Y. Nojiri,et al.  Fatty acids in the marine atmosphere: Factors governing their concentrations and evaluation of organic films on sea‐salt particles , 2002 .

[62]  F. Went.  Blue Hazes in the Atmosphere , 1960, Nature.

[63]  Mahoney,et al.  In situ measurements of organics, meteoritic material, mercury, and other elements in aerosols at 5 to 19 kilometers , 1998, Science.

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

[65]  K. Prather,et al.  Aerosol time‐of‐flight mass spectrometry during the Atlanta Supersite Experiment: 1. Measurements , 2003 .

[66]  Frank McGovern,et al.  The 2nd Aerosol Characterization Experiment (ACE-2): general overview and main results , 2000 .