Secondary organic aerosol formation from isoprene photooxidation under high‐NOx conditions

The oxidation of isoprene (2-methyl-1,3-butadiene) is known to play a central role in the photochemistry of the troposphere, but is generally not considered to lead to the formation of secondary organic aerosol (SOA), due to the relatively high volatility of known reaction products. However, in the chamber studies described here, we measure SOA production from isoprene photooxidation under high-NO_x conditions, at significantly lower isoprene concentrations than had been observed previously. Mass yields are low (0.9–3.0%), but because of large emissions, isoprene photooxidation may still contribute substantially to global SOA production. Results from photooxidation experiments of compounds structurally similar to isoprene (1,3-butadiene and 2- and 3-methyl-1-butene) suggest that SOA formation from isoprene oxidation proceeds from the further reaction of first-generation oxidation products (i.e., the oxidative attack of both double bonds). The gas-phase chemistry of such oxidation products is in general poorly characterized and warrants further study.

[1]  Edward Charles Fortner,et al.  Quantification of hydroxycarbonyls from OH-isoprene reactions. , 2004, Journal of the American Chemical Society.

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

[3]  M. Andreae,et al.  Formation of Secondary Organic Aerosols Through Photooxidation of Isoprene , 2004, Science.

[4]  T. Hoffmann,et al.  Formation of Secondary Organic Aerosols , 2003 .

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

[6]  S. C. Liu,et al.  Models and observations of the impact of natural hydrocarbons on rural ozone , 1987, Nature.

[7]  Sonia M. Kreidenweis,et al.  A modeling study of aqueous production of dicarboxylic acids: 1. Chemical pathways and speciated organic mass production , 2004 .

[8]  J. Arey,et al.  Formation and reaction of hydroxycarbonyls from the reaction of OH radicals with 1,3-butadiene and isoprene. , 2005, Environmental science & technology.

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

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

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

[12]  John H. Seinfeld,et al.  Chamber studies of secondary organic aerosol growth by reactive uptake of simple carbonyl compounds , 2005 .

[13]  Annmarie G Carlton,et al.  Isoprene forms secondary organic aerosol through cloud processing: model simulations. , 2005, Environmental science & technology.

[14]  J. Seinfeld,et al.  Atmospheric photooxidation of isoprene part I: The hydroxyl radical and ground state atomic oxygen reactions , 1992 .

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

[16]  J. Seinfeld,et al.  Representation of secondary organic aerosol laboratory chamber data for the interpretation of mechanisms of particle growth. , 2005, Environmental science & technology.

[17]  Ivan Kourtchev,et al.  Formation of secondary organic aerosols from isoprene and its gas-phase oxidation products through reaction with hydrogen peroxide , 2004 .

[18]  P. Shepson,et al.  A study of relationships between isoprene, its oxidation products, and ozone, in the Lower Fraser Valley, BC , 1997 .

[19]  P. Shepson,et al.  Measurement of the organic nitrate yield from OH reaction with isoprene , 1998 .

[20]  Kenneth A. Smith,et al.  Aerosol mass spectrometer for size and composition analysis of submicron particles , 1998 .

[21]  A. Miyoshi,et al.  OH radical‐ initiated photooxidation of isoprene: An estimate of global CO production , 1994 .

[22]  M. Claeys,et al.  Formation of 2-methyl tetrols and 2-methylglyceric acid in secondary organic aerosol from laboratory irradiated isoprene/NOX/SO2/air mixtures and their detection in ambient PM2.5 samples collected in the eastern United States , 2005 .

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

[24]  R. Atkinson,et al.  A product study of the gas-phase reaction of Isoprene with the OH radical in the presence of NOx , 1990 .

[25]  M. Jenkin,et al.  Simulating the Formation of Secondary Organic Aerosol from the Photooxidation of Aromatic Hydrocarbons , 2005 .

[26]  M. Mochida,et al.  Growth of organic aerosols by biogenic semi-volatile carbonyls in the forestal atmosphere , 2003 .

[27]  J. Seinfeld,et al.  Mathematical model for gas-particle partitioning of secondary organic aerosols , 1997 .

[28]  James G. Anderson,et al.  Product analysis of the OH oxidation of isoprene and 1,3‐butadiene in the presence of NO , 2002 .

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