Secondary organic aerosol formation in the atmosphere via heterogeneous reaction of gaseous isoprene on acidic particles

Water‐soluble macromolecular substances with spectral properties of “humic‐like substances” (HULIS) were recently found to form the major identified fraction of the organic aerosol at urban and rural sites in Europe. With primary sources identified so far (e.g., biomass combustion) it is not possible to explain the observed HULIS levels in Europe, therefore there is an ongoing search for other sources ‐ which form HULIS in situ in the atmosphere. Here we show that secondary aerosol formation of atmospheric polymers occurs by heterogeneous reaction of isoprenoid or terpenoid emissions in the presence of a sulfuric acid aerosol catalyst. Competing oxidants such as ozone or the presence of humidity decreased the reaction yield, but the formation of humic–like substances was not disabled. Calculations indicate that the presented reaction pathway could be an additional source for HULIS in the continental aerosol.

[1]  D. Riemer,et al.  The chemical processing of gas-phase carbonyl compounds by sulfuric acid aerosols: 2,4-pentanedione , 2003 .

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

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

[4]  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.

[5]  U. Baltensperger,et al.  Study on the Chemical Character of Water Soluble Organic Compounds in Fine Atmospheric Aerosol at the Jungfraujoch , 2001 .

[6]  J. Seinfeld,et al.  Reshaping the Theory of Cloud Formation , 2001, Science.

[7]  S. Weiss,et al.  Chemical physics. Single-molecule spectroscopy comes of age. , 2001, Science.

[8]  John H. Seinfeld,et al.  Modeling the Formation of Secondary Organic Aerosol (SOA). 2. The Predicted Effects of Relative Humidity on Aerosol Formation in the α-Pinene-, β-Pinene-, Sabinene-, Δ3-Carene-, and Cyclohexene-Ozone Systems , 2001 .

[9]  Ü. Rannik,et al.  Biogenic aerosol formation in the boreal forest , 2000 .

[10]  M. Scholes,et al.  Mass balance of the atmospheric aerosol in a South African subtropical savanna (Nylsvley, May 1997) , 2000 .

[11]  C. O'Dowd,et al.  Stable sulfate clusters as a source of new atmospheric particles , 2000 .

[12]  L. Pirjola,et al.  Stable sulphate clusters as a source of new atmospheric particles , 2000, Nature.

[13]  P. Warneck Chemistry of the natural atmosphere , 1999 .

[14]  M. Facchini,et al.  Cloud albedo enhancement by surface-active organic solutes in growing droplets , 1999, Nature.

[15]  Jeffrey T. Roberts,et al.  Chemistry at and near the Surface of Liquid Sulfuric Acid: A Kinetic, Thermodynamic, and Mechanistic Analysis of Heterogeneous Reactions of Acetone , 1999 .

[16]  Hans-Christen Hansson,et al.  Inorganic, organic and macromolecular components of fine aerosol in different areas of Europe in relation to their water solubility , 1999 .

[17]  C. N. Hewitt,et al.  Inventorying emissions from nature in Europe , 1999 .

[18]  L. Barrie,et al.  Physical and chemical characteristics of aerosols at Spitsbergen in the spring of 1996 , 1999 .

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

[20]  Ian Barnes,et al.  Aerosol and Product Yields from NO3 Radical-Initiated Oxidation of Selected Monoterpenes , 1999 .

[21]  Thorsten Hoffmann,et al.  Molecular composition of organic aerosols formed in the α‐pinene/O3 reaction: Implications for new particle formation processes , 1998 .

[22]  N. Mihalopoulos,et al.  Formation of atmospheric particles from organic acids produced by forests , 1998, Nature.

[23]  M. Facchini,et al.  Partitioning of the organic aerosol component between fog droplets and interstitial air , 1998 .

[24]  Jeffrey T. Roberts,et al.  A new sulfate‐mediated reaction: Conversion of acetone to trimethylbenzene in the presence of liquid sulfuric acid , 1998 .

[25]  D. Klockow,et al.  Spectroscopic Characterization of Humic-Like Substances in Airborne Particulate Matter , 1998 .

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

[27]  P. Saxena,et al.  Water-soluble organics in atmospheric particles: A critical review of the literature and application of thermodynamics to identify candidate compounds , 1996 .

[28]  Glen R. Cass,et al.  Quantification of urban organic aerosols at a molecular level: Identification, abundance and seasonal variation , 1993 .

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

[30]  V. N. Cheshchevoi,et al.  Cyclization and oxidation of isoprene oligomers during polymerization on kaolinite , 1987 .

[31]  H. Mukai,et al.  Characterization of a humic acid-like brown substance in airborne particulate matter and tentative identification of its origin , 1986 .

[32]  J. W. Winchester,et al.  Strong and weak acidity of aerosols collected over the northeastern United States , 1983 .