Effect of acidic seed on biogenic secondary organic aerosol growth

Abstract Secondary organic aerosol (SOA) growth in the presence of acid aerosols was studied in twin 500 l Teflon bags and in a 4 m flow reactor. In Teflon bags, isoprene, acrolein and α-pinene were all made to react individually with ozone and exposed to either acid or non-acid inorganic seed aerosols to determine the effect of acid-catalyzed heterogeneous reactions on SOA growth. α-Pinene and ozone were made to react in a flow reactor to assess the immediate effect of mixing an acid aerosol with SOA at high and low relative humidity levels. In all cases, exposure to acid seed aerosol increased the amount of SOA mass produced. Fourier transform infrared spectra of the SOA in acid systems confirmed the transformation of carbonyl functional groups through acid-catalyzed heterogeneous reactions when SOAs formed in acidic environments or were exposed to acidic aerosols. Organic products initially produced from ozonation in the gas phase partition onto the inorganic seed aerosol and react heterogeneously with an acid catalyst forming low vapor pressure products. These acid-catalyzed heterogeneous reactions are implicated in generating the increased SOA mass observed in acidic aerosol systems as they transform predominantly gas phase compounds of high volatility into low vapor pressure predominantly particle phase products.

[1]  R. Kamens,et al.  Newly characterized products and composition of secondary aerosols from the reaction of α-pinene with ozone , 1999 .

[2]  Reinhold Busen,et al.  First direct sulfuric acid detection in the exhaust plume of a jet aircraft in flight , 1998 .

[3]  D. Kotzias,et al.  Gas Phase Terpene Oxidation Products. A Review. , 1999 .

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

[5]  R. Kamens,et al.  A thermodynamic approach using group contribution methods to model the partitioning of semivolatile organic compounds on atmospheric particulate matter , 1997 .

[6]  Jack G. Calvert,et al.  The mechanisms of atmospheric oxidation of aromatic hydrocarbons , 2002 .

[7]  R. A. Cox,et al.  Evaluated Kinetic, Photochemical and Heterogeneous Data for Atmospheric Chemistry: Supplement V. IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry , 1997 .

[8]  M. Gery,et al.  A continuous stirred tank reactor investigation of the gas‐phase reaction of hydroxyl radicals and toluene , 1985 .

[9]  L. Hammett,et al.  A SERIES OF SIMPLE BASIC INDICATORS. I. THE ACIDITY FUNCTIONS OF MIXTURES OF SULFURIC AND PERCHLORIC ACIDS WITH WATER1 , 1932 .

[10]  Dimitrios Kotzias,et al.  Carboxylic Acids in Secondary Aerosols from Oxidation of Cyclic Monoterpenes by Ozone , 2000 .

[11]  E. Atlas,et al.  Particle growth in urban and industrial plumes in Texas , 2003 .

[12]  Edward S. Rubin,et al.  Toxic releases from power plants , 1999 .

[13]  M. Jacobson.  Isolating nitrated and aromatic aerosols and nitrated aromatic gases as sources of ultraviolet light absorption , 1999 .

[14]  M. Gery,et al.  Investigation of hydroxyl radical reactions with o-xylene and m-xylene in a continuous stirred tank reactor. , 1987, Environmental science & technology.

[15]  R. Kamens,et al.  Characterization of secondary aerosol from the photooxidation of toluene in the presence of NOx and 1-propene. , 2001, Environmental science & technology.

[16]  Y. Yokouchi.  Seasonal and diurnal variation of isoprene and its reaction products in a semi-rural area , 1994 .

[17]  P. Warneck,et al.  Oxidation of toluene in NO? free air: Product distribution and mechanism , 1996 .

[18]  R. Schwarzenbach,et al.  Environmental Organic Chemistry , 1993 .

[19]  Donald Dabdub,et al.  Estimate of global atmospheric organic aerosol from oxidation of biogenic hydrocarbons , 1999 .

[20]  G. Moortgat,et al.  Formation of hydrogen peroxide in the ozonolysis of isoprene and simple alkenes under humid conditions , 1999 .

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

[22]  G. Moortgat,et al.  Formation of OH radicals in the gas-phase reaction of propene, isobutene and isoprene with O3: Yields and mechanistic implications , 1999 .

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

[24]  J. Hansen,et al.  Trends of measured climate forcing agents , 2001, Proceedings of the National Academy of Sciences of the United States of America.

[25]  R. Kamens,et al.  Atmospheric secondary aerosol formation by heterogeneous reactions of aldehydes in the presence of a sulfuric acid aerosol catalyst. , 2001, Environmental science & technology.

[26]  P. Crutzen,et al.  Atmospheric aerosols: Biogeochemical sources and role in atmospheric chemistry , 1997 .

[27]  Stephen E. Stein,et al.  Estimation of normal boiling points from group contributions , 1994, J. Chem. Inf. Comput. Sci..

[28]  W. Shiu,et al.  Vapor-pressure correlations for low-volatility environmental chemicals , 1982 .

[29]  J. Yu,et al.  Atmospheric photooxidation of alkylbenzenes-I. Carbonyl product analyses , 1997 .

[30]  R. W. Waytulonis,et al.  Chemical analysis of diesel engine nanoparticles using a nano-DMA/thermal desorption particle beam mass spectrometer. , 2001, Environmental science & technology.

[31]  I. Barnes,et al.  Product study and mechanisms of the reactions of α‐pinene and of pinonaldehyde with OH radicals , 1999 .

[32]  S. M. Aschmann,et al.  Product study of the gas-phase reactions of monoterpenes with the OH radical in the presence of NO x , 1990 .

[33]  G. Cass,et al.  Source-oriented model for air pollutant effects on visibility , 1996 .

[34]  M. Gery,et al.  Ozone–isoprene reactions: Product formation and aerosol potential , 1982 .

[35]  R. Kamens,et al.  Mass balance of gaseous and particulate products analysis from α-pinene/NOx/air in the presence of natural sunlight , 2001 .

[36]  G. Cass,et al.  Los Angeles Summer Midday Particulate Carbon: Primary and Secondary Aerosol , 1991 .

[37]  A. Lambert,et al.  Properties of the Mt. Pinatubo Aerosol Cloud Determined from ISAMS Measurements at 12.1 μm , 1996 .

[38]  S. Twomey,et al.  Aerosols, clouds and radiation , 1991 .

[39]  T. Kleindienst,et al.  Primary Product Distribution from the Reaction of Hydroxyl Radicals with Toluene at ppb NOX Mixing Ratios , 1998 .

[40]  Richard M. Kamens,et al.  Organic aerosol growth by acid-catalyzed heterogeneous reactions of octanal in a flow reactor , 2003 .

[41]  S. Yalkowsky,et al.  A modification of Trouton's rule by simple molecular parameters for hydrocarbon compounds , 1999 .

[42]  Dimitrios Kotzias,et al.  cis-Pinic acid, a possible precursor for organic aerosol formation from ozonolysis of α-pinene , 1998 .

[43]  B. Turpin,et al.  Identification of secondary organic aerosol episodes and quantitation of primary and secondary organic aerosol concentrations during SCAQS , 1995 .

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

[45]  John H. Seinfeld,et al.  Gas-Phase Ozone Oxidation of Monoterpenes: Gaseous and Particulate Products , 1999 .

[46]  E. Grosjean,et al.  Atmospheric chemistry of acrolein , 1994 .

[47]  B. Mader,et al.  Gas/solid partitioning of semivolatile organic compounds (SOCs) to air filters. 3. An analysis of gas adsorption artifacts in measurements of atmospheric SOCs and organic carbon (OC). WHen using teflon membrane filters and quartz fiber filters. , 2001, Environmental science & technology.

[48]  J. Coakley,et al.  Climate Forcing by Anthropogenic Aerosols , 1992, Science.

[49]  H. Akimoto,et al.  Reactions of ozone with α‐pinene and β‐pinene in air: Yields of gaseous and particulate products , 1989 .

[50]  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 .

[51]  S. M. Aschmann,et al.  OH radical formation from the gas-phase reactions of O3 with a series of terpenes , 2002 .

[52]  J. Seinfeld,et al.  Effects of aerosols on tropospheric photolysis rates in clear and cloudy atmospheres , 1999 .

[53]  T J Wallington,et al.  Organic aerosol formation during the atmospheric degradation of toluene. , 2001, Environmental science & technology.

[54]  R. Kamens,et al.  Modeling aerosol formation from alpha-pinene + NOx in the presence of natural sunlight using gas-phase kinetics and gas-particle partitioning theory. , 2001, Environmental science & technology.

[55]  Ping Li,et al.  Predicting the Entropy of Boiling for Organic Compounds , 1999, J. Chem. Inf. Comput. Sci..

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

[57]  N. Mihalopoulos,et al.  Formation and gas/particle partitioning of monoterpenes photo‐oxidation products over forests , 1999 .

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

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

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

[61]  David R. Cocker,et al.  The effect of water on gas–particle partitioning of secondary organic aerosol. Part I: α-pinene/ozone system , 2001 .

[62]  J. Pankow.  Common y-intercept and single compound regressions of gas-particle partitioning data vs 1/T , 1991 .

[63]  P. Ziemann,et al.  Thermal desorption mass spectrometric analysis of organic aerosol formed from reactions of 1-tetradecene and O3 in the presence of alcohols and carboxylic acids , 2000 .