Polar organic compounds in rural PM2.5 aerosols from K-puszta, Hungary, during a 2003 summer field campaign: sources and diurnal variations

Abstract. In the present study, we examined PM2.5 continental rural background aerosols, which were collected during a summer field campaign at K-puszta, Hungary (4 June-10 July 2003), a mixed coniferous/deciduous forest site characterized by intense solar radiation during summer. Emphasis was placed on polar oxygenated organic compounds that provide information on aerosol sources and source processes. The major components detected at significant atmospheric concentrations were: (a) photo-oxidation products of isoprene including the 2-methyltetrols (2-methylthreitol and 2-methylerythritol) and 2-methylglyceric acid, (b) levoglucosan, a marker for biomass burning, (c) malic acid, an intermediate in the oxidation of unsaturated fatty acids, and (d) the sugar alcohols, arabitol and mannitol, markers for fungal spores. Diel patterns with highest concentrations during day-time were observed for the 2-methyltetrols, which can be regarded as supporting evidence for their fast photochemical formation from locally emitted isoprene. In addition, a diel pattern with highest concentrations during day-time was observed for the fungal markers, suggesting that the release of fungal fragments that are associated with the PM2.5 aerosol is enhanced during that time. Furthermore, a diel pattern was also found for levoglucosan with the highest concentrations at night when wood burning may take place in the settlements around the sampling site. In contrast, malic acid did not show day/night differences but was found to follow quite closely the particulate and organic carbon mass. This is interpreted as an indication that malic acid is formed in photochemical reactions which have a much longer overall time-scale than that of isoprene photo-oxidation, and the sources of its precursors are manifold, including both anthropogenic and natural emissions. On the basis of the high concentrations found for the isoprene oxidation products during day-time, it can be concluded that rapid photo-oxidation of isoprene is an important atmospheric chemistry process that contributes to secondary organic aerosol (SOA) formation at K-puszta during summer.

[1]  D. Smith,et al.  SUGAR ALCOHOLS (POLYOLS) IN FUNGI AND GREEN PLANTS , 1967 .

[2]  K. Kawamura,et al.  Seasonal changes in the distribution of dicarboxylic acids in the urban atmosphere , 1993 .

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

[4]  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 .

[5]  R. Synovec,et al.  Dissolution behavior and surface tension effects of organic compounds in nucleating cloud droplets , 1996 .

[6]  A. Hoffer,et al.  Thermal behaviour of carbonaceous aerosol from a continental background site , 2000 .

[7]  Regina Hitzenberger,et al.  Determination of the carbon content of airborne fungal spores. , 2002, Analytical chemistry.

[8]  Tomas Alsberg,et al.  Estimation of the average molecular weight of humic-like substances isolated from fine atmospheric aerosol , 2003 .

[9]  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.

[10]  Jeffrey R. Brook,et al.  Methods to determine the biological composition of particulate matter collected from outdoor air , 2003 .

[11]  Hans-Christen Hansson,et al.  Surface Tension Effects of Humic-Like Substances in the Aqueous Extract of Tropospheric Fine Aerosol , 2005 .

[12]  M. Claeys,et al.  Improved method for quantifying levoglucosan and related monosaccharide anhydrides in atmospheric aerosols and application to samples from urban and tropical locations. , 2002, Environmental science & technology.

[13]  J. Chow,et al.  Results of the "Carbon Conference" International Aerosol Carbon Round Robin Test Stage I , 2001 .

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

[15]  M. Pelzing,et al.  A new analytical approach for size-resolved speciation of organic compounds in atmospheric aerosol particles: Methods and first results , 2000 .

[16]  R. Flagan,et al.  Organic compounds present in the natural Amazonian aerosol: Characterization by gas chromatography–mass spectrometry , 2003 .

[17]  J. Cafmeyer,et al.  The ''Gent'' stacked filter unit (SFU) sampler for the collection of atmospheric aerosols in two size fractions: Description and instructions for installation and use , 1994 .

[18]  M. Claeys,et al.  Development of a gas chromatographic/ion trap mass spectrometric method for the determination of levoglucosan and saccharidic compounds in atmospheric aerosols. Application to urban aerosols. , 2002, Journal of mass spectrometry : JMS.

[19]  A. Limbeck,et al.  Organic acids in continental background aerosols , 1999 .

[20]  T. Sharkey,et al.  ISOPRENE EMISSION FROM PLANTS. , 2003, Annual review of plant physiology and plant molecular biology.

[21]  J. Penner,et al.  Large contribution of organic aerosols to cloud-condensation-nuclei concentrations , 1993, Nature.

[22]  A. Hoffer,et al.  On the possible origin of humic matter in fine continental aerosol , 2002 .

[23]  Y. Rudich,et al.  New analytical method for the determination of levoglucosan, polyhydroxy compounds, and 2-methylerythritol and its application to smoke and rainwater samples. , 2005, Environmental science & technology.

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

[25]  L. Hildemann,et al.  Characterization of organic compounds collected during southeastern aerosol and visibility study: water-soluble organic species. , 2005, Environmental science & technology.

[26]  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 .

[27]  H. Puxbaum,et al.  Size distribution and seasonal variation of atmospheric cellulose , 2003 .

[28]  E. Pacini.  From anther and pollen ripening to pollen presentation , 2000, Plant Systematics and Evolution.

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

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

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

[32]  B. Simoneit,et al.  Biomass burning — a review of organic tracers for smoke from incomplete combustion , 2002 .

[33]  Glen R. Cass,et al.  Sources of fine organic aerosol. 1. Charbroilers and meat cooking operations , 1991 .

[34]  F. Shafizadeh,et al.  The chemistry of pyrolysis and combustion , 1984 .

[35]  Ruprecht Jaenicke,et al.  The size distribution of primary biological aerosol particles with radii > 0.2 μm in an urban/rural influenced region , 1995 .

[36]  Glen R. Cass,et al.  Allergens in paved road dust and airborne particles , 1999 .

[37]  Tiina Reponen,et al.  Fungal Fragments as Indoor Air Biocontaminants , 2002, Applied and Environmental Microbiology.

[38]  P. Solomon,et al.  High-Volume Dichotomous Virtual Impactor for the Fractionation and Collection of Particles According to Aerodynamic Size , 1983 .

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

[40]  G. Kiss,et al.  Characterization of water-soluble organic matter isolated from atmospheric fine aerosol , 2002 .

[41]  M. Facchini,et al.  Water‐soluble organic compounds in biomass burning aerosols over Amazonia 1. Characterization by NMR and GC‐MS , 2002 .

[42]  K. Kawamura,et al.  Molecular distributions of water soluble dicarboxylic acids in marine aerosols over the Pacific Ocean including tropics , 1999 .

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

[44]  H. Bauer,et al.  The contribution of bacteria and fungal spores to the organic carbon content of cloud water, precipitation and aerosols , 2002 .

[45]  C. Pio,et al.  Water-soluble hydroxylated organic compounds in German and Finnish aerosols , 2003 .