Determination of isoprene and alpha-/beta-pinene oxidation products in boreal forest aerosols from Hyytiälä, Finland: diel variations and possible link with particle formation events.

Biogenic volatile organic compounds (VOCs), such as isoprene and alpha-/beta-pinene, are photo-oxidized in the atmosphere to non-volatile species resulting in secondary organic aerosol (SOA). The goal of this study was to examine time trends and diel variations of oxidation products of isoprene and alpha-/beta-pinene in order to investigate whether they are linked with meteorological parameters or trace gases. Separate day-night aerosol samples (PM(1)) were collected in a Scots pine dominated forest in southern Finland during 28 July-11 August 2005 and analyzed with gas chromatography/mass spectrometry (GC/MS). In addition, inorganic trace gases (SO(2), CO, NO(x), and O(3)), meteorological parameters, and the particle number concentration were monitored. The median total concentration of terpenoic acids (i.e., pinic acid, norpinic acid, and two novel compounds, 3-hydroxyglutaric acid and 2-hydroxy-4-isopropyladipic acid) was 65 ng m(-3), while that of isoprene oxidation products (i.e., 2-methyltetrols and C(5) alkene triols) was 17.2 ng m(-3). The 2-methyltetrols exhibited day/night variations with maxima during day-time, while alpha-/beta-pinene oxidation products did not show any diel variation. The sampling period was marked by a relatively high condensation sink, caused by pre-existing aerosol particles, and no nucleation events. In general, the concentration trends of the SOA compounds reflected those of the inorganic trace gases, meteorological parameters, and condensation sink. Both the isoprene and alpha-/beta-pinene SOA products were strongly influenced by SO(2), which is consistent with earlier reports that acidity plays a role in SOA formation. The results support previous proposals that oxygenated VOCs contribute to particle growth processes above boreal forest.

[1]  J. Seinfeld,et al.  Gas‐phase products and secondary aerosol yields from the ozonolysis of ten different terpenes , 2006 .

[2]  Allen H. Goldstein,et al.  Secondary organic aerosols formed from oxidation of biogenic volatile organic compounds in the Sierra Nevada Mountains of California , 2006 .

[3]  M. Facchini,et al.  Size-segregated aerosol chemical composition at a boreal site in southern Finland, during the QUEST project , 2005 .

[4]  Ivan Kourtchev,et al.  Characterization of oxygenated derivatives of isoprene related to 2-methyltetrols in Amazonian aerosols using trimethylsilylation and gas chromatography/ion trap mass spectrometry. , 2005, Rapid communications in mass spectrometry : RCM.

[5]  M. Apostolaki,et al.  Overview of the field measurement campaign in Hyytiälä, August 2001 in the framework of the EU project OSOA , 2003 .

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

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

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

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

[10]  J. M. Mäkelä,et al.  On the formation, growth and composition of nucleation mode particles , 2001 .

[11]  R. Draxler.  An Overview of the HYSPLIT_4 Modelling System for Trajectories, Dispersion, and Deposition , 1998 .

[12]  P. Keronen,et al.  Seasonal variations of trace gases, meteorological parameters, and formation of aerosols in boreal forests , 2005 .

[13]  K. Sellegri,et al.  Measurements of organic gases during aerosol formation events in the boreal forest atmosphere during QUEST , 2004 .

[14]  Pasi Aalto,et al.  Atmospheric Chemistry and Physics a New Feedback Mechanism Linking Forests, Aerosols, and Climate , 2004 .

[15]  M. Claeys,et al.  Hydroxydicarboxylic acids: markers for secondary organic aerosol from the photooxidation of alpha-pinene. , 2007, Environmental science & technology.

[16]  J. Offenberg,et al.  Secondary organic carbon and aerosol yields from the irradiations of isoprene and alpha-pinene in the presence of NOx and SO2. , 2006, Environmental science & technology.

[17]  Peter Harley,et al.  Direct measurement of particle formation and growth from the oxidation of biogenic emissions , 2006 .

[18]  L. Barrie,et al.  Seasonal trends of isoprene, C2–C5 alkanes, and acetylene at a remote boreal site in Canada , 1994 .

[19]  H. Hansson,et al.  Biogenic emissions and gaseous precursors to forest aerosols , 2001 .

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

[21]  Ivan Kourtchev,et al.  Polar organic compounds in rural PM2.5 aerosols from K-puszta, Hungary, during a 2003 summer field campaign: sources and diurnal variations , 2005 .

[22]  M. Boy,et al.  Effects of air masses and synoptic weather on aerosol formation in the continental boundary layer , 2001 .

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

[24]  Ari Laaksonen,et al.  Cluster activation theory as an explanation of the linear dependence between formation rate of 3nm particles and sulphuric acid concentration , 2006 .

[25]  R. Dingenen,et al.  LC-MS analysis of aerosol particles from the oxidation of α-pinene by ozone and OH-radicals , 2003 .

[26]  Ü. Rannik,et al.  Overview of the international project on biogenic aerosol formation in the boreal forest (BIOFOR) , 2001 .

[27]  K. Clemitshaw,et al.  Ozone and other secondary photochemical pollutants: chemical processes governing their formation in the planetary boundary layer , 2000 .

[28]  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 .

[29]  Matti Jussila,et al.  Determination of organic acids in aerosol particles from a coniferous forest by liquid chromatography-mass spectrometry. , 2005, Journal of separation science.

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

[31]  M. D. Maso,et al.  Probability of nucleation events and aerosol particle concentration in different air mass types arriving at Hyytiälä, southern Finland, based on back trajectories analysis , 2005 .

[32]  T. Gnauk,et al.  Biogenic contributions to the chemical composition of airborne particles in a coniferous forest in Germany , 2006 .

[33]  L. Pasternack,et al.  Experimental and modeling studies of secondary organic aerosol formation and some applications to the marine boundary layer , 2001 .

[34]  Hanna Vehkamäki,et al.  Formation and growth rates of ultrafine atmospheric particles: a review of observations , 2004 .

[35]  H. Hakola,et al.  Seasonal variation of VOC concentrations above a boreal coniferous forest , 2003 .

[36]  C. O'Dowd,et al.  Physical characterization of aerosol particles during nucleation events , 2001 .

[37]  Paul J. Crutzen,et al.  The influence of the tropical rainforest on atmospheric CO and CO2 as measured by aircraft over Surinam, South America , 2001 .

[38]  Xiaoyan Xia,et al.  Seasonal variation of 2-methyltetrols in ambient air samples. , 2006, Environmental science & technology.

[39]  Markku Kulmala,et al.  Observation of 2-methyltetrols and related photo-oxidation products of isoprene in boreal forest aerosols from Hyytiälä, Finland , 2005 .

[40]  W. Birmili,et al.  The Hohenpeissenberg aerosol formation experiment (HAFEX): a long-term study including size-resolved aerosol, H 2 SO 4 , OH, and monoterpenes measurements , 2002 .

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

[42]  Liisa Pirjola,et al.  Characteristics of the atmospheric particle formation events observed at a borel forest site in southern Finland , 2000 .

[43]  R. Cary,et al.  Elemental Carbon-Based Method for Monitoring Occupational Exposures to Particulate Diesel Exhaust , 1996 .

[44]  Armin Sorooshian,et al.  Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene. , 2006, The journal of physical chemistry. A.

[45]  Miikka Dal Maso,et al.  Formation and growth of fresh atmospheric aerosols: eight years of aerosol size distribution data from SMEAR II, Hyytiälä, Finland , 2005 .