Reactive oxidation products promote secondary organic aerosol formation from green leaf volatiles

Abstract. Green leaf volatiles (GLVs) are an important group of chemicals released by vegetation which have emission fluxes that can be significantly increased when plants are damaged or stressed. A series of simulation chamber experiments has been conducted at the European Photoreactor in Valencia, Spain, to investigate secondary organic aerosol (SOA) formation from the atmospheric oxidation of the major GLVs cis-3-hexenylacetate and cis-3-hexen-1-ol. Liquid chromatography-ion trap mass spectrometry was used to identify chemical species present in the SOA. Cis-3-hexen-1-ol proved to be a more efficient SOA precursor due to the high reactivity of its first generation oxidation product, 3-hydroxypropanal, which can hydrate and undergo further reactions with other aldehydes resulting in SOA dominated by higher molecular weight oligomers. The lower SOA yields produced from cis-3-hexenylacetate are attributed to the acetate functionality, which inhibits oligomer formation in the particle phase. Based on observed SOA yields and best estimates of global emissions, these compounds may be calculated to be a substantial unidentified global source of SOA, contributing 1–5 TgC yr−1, equivalent to around a third of that predicted from isoprene. Molecular characterization of the SOA, combined with organic mechanistic information, has provided evidence that the formation of organic aerosols from GLVs is closely related to the reactivity of their first generation atmospheric oxidation products, and indicates that this may be a simple parameter that could be used in assessing the aerosol formation potential for other unstudied organic compounds in the atmosphere.

[1]  S. M. Aschmann,et al.  Hydroxyaldehyde products from hydroxyl radical reactions of Z-3-hexen-1-ol and 2-methyl-3-buten-2-ol quantified by SPME and API-MS. , 2003, Environmental Science and Technology.

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

[3]  J. Ortega,et al.  Approaches for quantifying reactive and low-volatility biogenic organic compound emissions by vegetation enclosure techniques - part B: applications. , 2008, Chemosphere.

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

[5]  John H. Seinfeld,et al.  Global secondary organic aerosol from isoprene oxidation , 2006 .

[6]  O. Edenhofer,et al.  Mitigation from a cross-sectoral perspective , 2007 .

[7]  D. Olszyk,et al.  Emission rates of organics from vegetation in California's Central Valley , 1992 .

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

[9]  John H. Seinfeld,et al.  Gas‐phase products and secondary aerosol yields from the photooxidation of 16 different terpenes , 2006 .

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

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

[12]  J. Peñuelas,et al.  Seasonal patterns of non-terpenoid C6-C10 VOC emission from seven Mediterranean woody species. , 2001, Chemosphere.

[13]  Jörg Warnke,et al.  Chapter 9. Organic Aerosols , 2007 .

[14]  A. Winer,et al.  The emission of (Z)-3-hexen-1-ol, (Z)-3-hexenylacetate and other oxygenated hydrocarbons from agricultural plant species , 1991 .

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

[16]  C. Wiedinmyer,et al.  Global Organic Emissions from Vegetation , 2004 .

[17]  B. Lamb,et al.  Biogenic Hydrocarbons in the Atmospheric Boundary Layer: A Review , 2000 .

[18]  Earl L. Bailey,et al.  Secondary organic aerosol formation by glyoxal hydration and oligomer formation: humidity effects and equilibrium shifts during analysis. , 2005, Environmental science & technology.

[19]  Michael E. Jenkin,et al.  Simulating the Formation of Secondary Organic Aerosol from the Photooxidation of Toluene , 2004 .

[20]  P. Crutzen,et al.  High concentrations of reactive biogenic VOCs at a high altitude site in late autumn , 2001 .

[21]  Vincent R. Gray.  Climate Change 2007: The Physical Science Basis Summary for Policymakers , 2007 .

[22]  J. Ortega,et al.  Approaches for quantifying reactive and low-volatility biogenic organic compound emissions by vegetation enclosure techniques - part A. , 2008, Chemosphere.

[23]  J. Lelieveld,et al.  An Atmospheric Chemistry Interpretation of Mass Scans Obtained from a Proton Transfer Mass Spectrometer Flown over the Tropical Rainforest of Surinam , 2001 .

[24]  A. Goldstein,et al.  Known and Unexplored Organic Constituents in the Earth's Atmosphere , 2007 .

[25]  K. T. Paw,et al.  Observations of oxidation products above a forest imply biogenic emissions of very reactive compounds , 2004 .

[26]  I. Galbally,et al.  A Simple Model for Estimating Emissions of Volatile Organic Compounds from Grass and Cut Grass in Urban Airsheds and Its Application to Two Australian Cities , 2004, Journal of the Air & Waste Management Association.

[27]  Tami C. Bond,et al.  Critical assessment of the current state of scientific knowledge, terminology, and research needs concerning the role of organic aerosols in the atmosphere, climate, and global change , 2005 .

[28]  Ü. Niinemets,et al.  Ozone induced emissions of biogenic VOC from tobacco: relationships between ozone uptake and emission of LOX products , 2005 .

[29]  S. M. Aschmann,et al.  Products of the gas-phase reactions of cis-3-hexen-1-ol with OH radicals and O3 , 1997 .

[30]  Annmarie G. Carlton,et al.  Oligomers formed through in-cloud methylglyoxal reactions: Chemical composition, properties, and mechanisms investigated by ultra-high resolution FT-ICR mass spectrometry , 2008 .

[31]  S. Vollenweider,et al.  3-Hydroxypropionaldehyde: applications and perspectives of biotechnological production , 2004, Applied Microbiology and Biotechnology.

[32]  Ronald E. Hester,et al.  Volatile organic compounds in the atmosphere , 1995 .

[33]  John C Wenger,et al.  Characterization of polar compounds and oligomers in secondary organic aerosol using liquid chromatography coupled to mass spectrometry. , 2008, Analytical chemistry.

[34]  M. Glasius,et al.  Gas-Phase OH Oxidation of Monoterpenes: Gaseous and Particulate Products , 2001 .

[35]  S. M. Aschmann,et al.  Rate constants for the gas‐phase reactions of cis‐3‐Hexen‐1‐ol, cis‐3‐Hexenylacetate, trans‐2‐Hexenal, and Linalool with OH and NO3 radicals and O3 at 296 ± 2 K, and OH radical formation yields from the O3 reactions , 1995 .

[36]  J. Franklin,et al.  Photolysis of chloral under atmospheric conditions. , 2004, Environmental science & technology.

[37]  J. Offenberg,et al.  Ozone‐isoprene reaction: Re‐examination of the formation of secondary organic aerosol , 2007 .

[38]  C. N. Hewitt,et al.  Relative contribution of oxygenated hydrocarbons to the total biogenic VOC emissions of selected mid-European agricultural and natural plant species , 1995 .

[39]  John H Seinfeld,et al.  Secondary organic aerosol formation from isoprene photooxidation. , 2005, Environmental science & technology.

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

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

[42]  J. Kesselmeier,et al.  Biogenic Volatile Organic Compounds (VOC): An Overview on Emission, Physiology and Ecology , 1999 .

[43]  B. Ek-Olausson,et al.  Flux of organic compounds from grass measured by relaxed eddy accumulation technique. , 2003, Journal of environmental monitoring : JEM.

[44]  Roger Atkinson,et al.  Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review , 2003 .

[45]  Pasi Miettinen,et al.  Nanoparticle formation by ozonolysis of inducible plant volatiles , 2005 .

[46]  Ulrich Platt,et al.  Primary and Secondary Glyoxal Formation from Aromatics: Experimental Evidence for the Bicycloalkyl−Radical Pathway from Benzene, Toluene, and p-Xylene , 2001 .