Understanding the formation of biogenic secondary organic aerosol from α-pinene in smog chamber studies: role of organic peroxy radicals

This study focusses on the description of the nucleation process observed during the ozone reaction of the biogenic monoterpene ?-pinene in smog chambers. Therefore, a detailed aerosol dynamics model (UHMA) was extended by a tropospheric chemistry module and a detailed description of the first steps of organic nucleation. We assume secondary ozonides to act as nucleation initiating molecules, which are subsequently activated by reactions with organic peroxy radicals (RO 2 ). With this set-up the observed particle size distributions of an exemplary experiment in Valencia was reproduced, when only the long-lived organic compounds like carboxylic acids and carbonyl compounds are detected by the available aerosol size distribution instruments. Our results indicate that fragile or reactive species might get destroyed because of weak bond breakage during the size classification. This assumption would imply a serious detection problem in nucleation studies to be solved.

[1]  Herbert J. Tobias,et al.  Kinetics of the Gas-Phase Reactions of Alcohols, Aldehydes, Carboxylic Acids, and Water with the C13 Stabilized Criegee Intermediate Formed from Ozonolysis of 1-Tetradecene , 2001 .

[2]  Ari Laaksonen,et al.  Organic aerosol formation via sulphate cluster activation , 2004 .

[3]  G. Moortgat,et al.  Products and Mechanism of the Gas Phase Reaction of Ozone with β-Pinene , 2000 .

[4]  A. Berner,et al.  A new electromobility spectrometer for the measurement of aerosol size distributions in the size range from 1 to 1000 nm , 1991 .

[5]  Tamás Turányi,et al.  Measurement and investigation of chamber radical sources in the European Photoreactor (EUPHORE) , 2006 .

[6]  Spyros N. Pandis,et al.  Evaporation Rates and Vapor Pressures of Individual Aerosol Species Formed in the Atmospheric Oxidation of α- and β-Pinene , 2001 .

[7]  B. Finlayson‐Pitts,et al.  Chemistry of the Upper and Lower Atmosphere , 2000 .

[8]  Geert K. Moortgat,et al.  The Ethene−Ozone Reaction in the Gas Phase , 1998 .

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

[10]  M. Jenkin,et al.  The tropospheric degradation of volatile organic compounds: a protocol for mechanism development , 1997 .

[11]  M. A. Dreyfus,et al.  Chemistry of particle inception and growth during α-pinene ozonolysis , 2006 .

[12]  M. Lawrence,et al.  Influence of Biogenic Secondary Organic Aerosol Formation Approaches on Atmospheric Chemistry , 2005 .

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

[14]  G. Moortgat,et al.  New particle formation during a - and b -pinene oxidation by O 3 , OH and NO 3 , and the influence of water vapour: particle size distribution studies , 2002 .

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

[16]  Hiroaki Minoura,et al.  Temperature dependence of secondary organic aerosol formation by photo-oxidation of hydrocarbons , 2003 .

[17]  G. Moortgat,et al.  Sesquiterpene ozonolysis: Origin of atmospheric new particle formation from biogenic hydrocarbons , 2003 .

[18]  G. Moortgat,et al.  Formation of hydroxymethyl hydroperoxide and formic acid in alkene ozonolysis in the presence of water vapour , 1997 .

[19]  J. Reid,et al.  Heterogeneous atmospheric aerosol chemistry: laboratory studies of chemistry on water droplets. , 2003, Chemical Society reviews.

[20]  Klaus Wirtz,et al.  Is benzene a precursor for secondary organic aerosol? , 2005, Environmental science & technology.

[21]  R. Kamens,et al.  Aerosol formation from the reaction of α-pinene and ozone using a gas- phase kinetics-aerosol partitioning model , 1999 .

[22]  Albert A Presto,et al.  Secondary organic aerosol production from terpene ozonolysis. 2. Effect of NOx concentration. , 2005, Environmental science & technology.

[23]  S. Solberg,et al.  Atmospheric Chemistry and Physics , 2002 .

[24]  S. Koch,et al.  Formation of new particles in the gas phase ozonolysis of monoterpenes , 2000 .

[25]  Adrian Sandu,et al.  Technical note: Simulating chemical systems in Fortran90 and Matlab with the Kinetic PreProcessor KPP-2.1 , 2005 .

[26]  D. Shallcross,et al.  Development and application of a possible mechanism for the generation of cis-pinic acid from the ozonolysis of α- and β-pinene , 2000 .

[27]  H. Akimoto,et al.  Mechanism for the Oxidation of SO_2 in the Atmosphere by the Intermediate Formed in Ozone-Olefin Reactions - Reaction of the Adduct with Water Vapor - , 1992 .

[28]  C. O'Dowd,et al.  Physical characterization of aerosol particles during nucleation events , 2001 .

[29]  M. Molina,et al.  Pressure and Temperature Dependence of the Gas-Phase Reaction of SO3 with H2O and the Heterogeneous Reaction of SO3 with H2O/H2SO4 Surfaces , 1997 .

[30]  Michael E. Jenkin,et al.  Modelling the formation and composition of secondary organic aerosol from α- and β-pinene ozonolysis using MCM v3 , 2004 .

[31]  A. Presto,et al.  Secondary Organic Aerosol Production from Terpene Ozonolysis. 2. Effect of NO x Concentration , 2005 .

[32]  N. Fletcher Size Effect in Heterogeneous Nucleation , 1958 .

[33]  Kari E. J. Lehtinen,et al.  Multicomponent aerosol dynamics model UHMA: model development and validation , 2004 .

[34]  Edward Charles Fortner,et al.  Atmospheric New Particle Formation Enhanced by Organic Acids , 2004, Science.

[35]  J. H. Shaw,et al.  A FT IR spectroscopic study of the ozone-ethene reaction mechanism in oxygen-rich mixtures , 1980 .

[36]  R. C. Weast CRC Handbook of Chemistry and Physics , 1973 .

[37]  A. Wexler,et al.  A hypothesis for growth of fresh atmospheric nuclei , 2002 .

[38]  T. Hoffmann,et al.  On-line characterization of organic aerosols formed from biogenic precursors using atmospheric pressure chemical ionization mass spectrometry. , 2000, Analytical chemistry.

[39]  Roger Atkinson,et al.  Gas-Phase Tropospheric Chemistry of Volatile Organic Compounds: 1. Alkanes and Alkenes , 1997 .

[40]  N. Donahue,et al.  Cycloalkene ozonolysis: collisionally mediated mechanistic branching. , 2004, Journal of the American Chemical Society.

[41]  J. Seinfeld,et al.  Gas/Particle Partitioning and Secondary Organic Aerosol Yields , 1996 .

[42]  H. Akimoto,et al.  Reactions of criegee intermediates in the gas phase , 1994 .

[43]  K. Joback,et al.  ESTIMATION OF PURE-COMPONENT PROPERTIES FROM GROUP-CONTRIBUTIONS , 1987 .

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

[45]  James F. Pankow,et al.  An absorption model of the gas/aerosol partitioning involved in the formation of secondary organic aerosol , 1994 .

[46]  James F. Pankow,et al.  Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions—Part 1: aldehydes and ketones , 2004 .

[47]  I. Barnes J. G. Calvert, R. Atkinson, J. A. Kerr, S. Madronich, G. K. Moortgat, T. J. Wallington, and G. Yarwood: The Mechanisms of Atmospheric Oxidation of the Alkenes , 2001 .

[48]  J. Pankow An absorption model of GAS/Particle partitioning of organic compounds in the atmosphere , 1994 .