Secondary organic aerosol formation in northern Europe: A model study

This paper describes a set of studies which has attempted to make a first estimate of the contribution of biogenic emissions to secondary organic aerosol (SOA) formation over the Nordic countries. The studies comprise first simulations of smog-chamber experiments and second atmospheric modeling. The α-pinene chemical mechanism suggested by Kamens et al. [1999] has been extended for use in regional oxidant models. Inclusion of dimer-formation in this scheme substantially improved performance for some experimental conditions. Although the modified scheme is necessarily tentative, it fits with experimental findings over a wide range of conditions, covering α-pinene concentrations of between 20 and 900 ppb and NOx concentrations of between zero and 240 ppb. The EMEP oxidant model has been used to estimate SOA formation in northern Europe using this chemical scheme and modified gas/particle partitioning methods. The results suggest that biogenic volatile organic compounds (VOCs) contribute far more than anthropogenic VOC to SOA formation. SOA is calculated to be a very variable fraction, between 2 and 50%, of total organic carbon mass in aerosols over the Nordic countries. This fraction is least at coastal sites in southern Norway and Denmark, and much greater for inland sites and sites further north, reflecting the relative distribution of biogenic precursors. There are great uncertainties in these figures, however, and we have had to neglect important primary sources of organic carbon (OC), notably plant waxes, which probably also contribute significantly to total OC. Further progress will be difficult until more measurements are available to characterize the ambient organic aerosol.

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

[2]  R. Barthelmie,et al.  A model mechanism to describe oxidation of monoterpenes leading to secondary organic aerosol: 1. α‐pinene and β‐pinene , 1999 .

[3]  G. Seufert,et al.  Fluxes of biogenic VOC from Mediterranean vegetation by trap enrichment relaxed eddy accumulation , 1997 .

[4]  R. Valentini,et al.  Emission of reactive terpene compounds from orange orchards and their removal by within‐canopy processes , 1999 .

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

[6]  J. Heintzenberg.  Fine particles in the global troposphere. A review , 1989 .

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

[8]  B. Simoneit,et al.  Characterization of Organic Constituents in Aerosols in Relation to Their rigin and Transport: A Review , 1986 .

[9]  J. Seinfeld,et al.  Atmospheric Chemistry and Physics: From Air Pollution to Climate Change , 1997 .

[10]  S. M. Aschmann,et al.  Products of the gas phase reactions of the OH radical with α‐ and β‐pinene in the presence of NO , 1998 .

[11]  I. Barnes,et al.  Evidence for formation of a PAN analogue of pinonic structure and investigation of its thermal stability , 1998 .

[12]  John H. Seinfeld,et al.  Identification of Products Containing −COOH, −OH, and −C=O in Atmospheric Oxidation of Hydrocarbons , 1998 .

[13]  Ken Nelson,et al.  COMPOSITION OF LIGHT-DUTY MOTOR VEHICLE EXHAUST PARTICULATE MATTER IN THE DENVER, COLORADO AREA , 1999 .

[14]  Evert Ljungström,et al.  Atmospheric fate of carbonyl oxidation products originating from α-pinene and Δ3-carene : Determination of rate of reaction with OH and NO3 radicals, UV absorption cross sections, and vapor pressures , 1997 .

[15]  P. Mcmurry,et al.  Vapor pressures and surface free energies of C14-C18 monocarboxylic acids and C5 and C6 dicarboxylic acids , 1989 .

[16]  D. Simpson,et al.  Long-period modelling of photochemical oxidants in Europe. Model calculations for July 1985 , 1992 .

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

[18]  R. A. Cox,et al.  Organic peroxy radicals: Kinetics, spectroscopy and tropospheric chemistry , 1992 .

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

[20]  R. Kamens,et al.  A Thermodynamic Approach for Modeling Partitioning of Semivolatile Organic Compounds on Atmospheric Particulate Matter: Humidity Effects , 1998 .

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

[22]  H. Hakola,et al.  Modeling speciated terpenoid emissions from the European boreal forest , 2000 .

[23]  A.J.H. Visschedijk,et al.  Particulate matter emissions (PM 10 - PM 2.5 - PM 0.1 ) in Europe in 1990 and 1993 , 1997 .

[24]  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 .

[25]  F. Lurmann,et al.  Modeling potential ozone impacts from natural hydrocarbons—I. Development and testing of a chemical mechanism for the nox-air photooxidations of isoprene and α-pinene under ambient conditions , 1983 .

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

[27]  R. Atkinson,et al.  Atmospheric lifetimes and fates of a series of sesquiterpenes , 1995 .

[28]  H. Lihavainen,et al.  Observations of ultrafine aerosol particle formation and growth in boreal forest , 1997 .

[29]  Frank M. Bowman,et al.  Formation of Organic Aerosols from the Oxidation of Biogenic Hydrocarbons , 1997 .

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

[31]  R. Atkinson.  Gas-Phase Tropospheric Chemistry of Organic Compounds , 1994 .

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

[33]  J. Seinfeld,et al.  Observation of gaseous and particulate products of monoterpene oxidation in forest atmospheres , 1999 .

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

[35]  D. Simpson,et al.  Comparison of the chemical schemes of the EMEP MSC-W and IVL photochemical trajectory models , 1999 .

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

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

[38]  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 .

[39]  J. Seinfeld,et al.  Characterization of photochemical aerosols from biogenic hydrocarbons , 1990 .

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

[41]  I. Wängberg,et al.  Product and Mechanistic Study of the Reaction of NO3 Radicals with α-Pinene , 1997 .

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

[43]  Y. Andersson-Sköld,et al.  Photochemical ozone creation potentials (POCP) and replacement of solvents in Europe , 2000 .

[44]  B. Simoneit,et al.  Organic matter of the troposphere — V: Application of molecular marker analysis to biogenic emissions into the troposphere for source reconciliations , 1989 .

[45]  C. N. Hewitt,et al.  Biogenic emissions in Europe: 1. Estimates and uncertainties , 1995 .

[46]  D. Simpson,et al.  Photochemical model calculations over Europe for two extended summer periods: 1985 and 1989. Model results and comparison with observations , 1993 .

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

[48]  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 .

[49]  F. Kirchner,et al.  A new mechanism for regional atmospheric chemistry modeling , 1997 .

[50]  R. Atkinson,et al.  Rate constants for the gas‐phase reactions of O3 with a series of Terpenes and OH radical formation from the O3 reactions with Sesquiterpenes at 296 ± 2 K , 1994 .

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

[52]  H. Hakola,et al.  Product formation from the gas-phase reactions of OH radicals and O3 with a series of monoterpenes , 1994 .

[53]  Glen R. Cass,et al.  Source contributions to atmospheric fine carbon particle concentrations , 1998 .

[54]  R. Janson.  Monoterpene emissions from Scots pine and Norwegian spruce , 1993 .

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

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

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

[58]  Tuomas Laurila,et al.  Canopy scale monoterpene emissions of Pinus sylvestris dominated forests , 2000 .

[59]  D. Simpson,et al.  Biogenic emissions in Europe: 2. Implications for ozone control strategies , 1995 .