Modeling carbonaceous aerosol over Europe: Analysis of the CARBOSOL and EMEP EC/OC campaigns

In this paper the European Monitoring and Evaluation Programme (EMEP) MSC-W model is used to assess our understanding of the sources of carbonaceous aerosol in Europe ( organic carbon (OC), elemental carbon (EC), or their sum, total carbon (TC)). The modeling work makes use of new data from two extensive measurement campaigns in Europe, those of the CARBOSOL project and of the EMEP EC/OC campaign. As well as EC and OC measurements, we are able to compare with levoglucosan, a tracer of wood-burning emissions, and with the source apportionment ( SA) analysis of Gelencser et al. ( 2007), which apportioned TC into primary versus secondary and fossil fuel versus biogenic origin. The model results suggest that emissions of primary EC and OC from fossil fuel sources are probably captured to better than a factor of two at most sites. Discrepancies for wintertime OC at some sites can likely be accounted for in terms of missing wood-burning contributions. Two schemes for secondary organic aerosol (SOA) contribution are included in the model, and we show that model results for TC are very sensitive to the choice of scheme. In northern Europe the model seems to capture TC levels rather well with either SOA scheme, but in southern Europe the model strongly underpredicts TC. Comparison against the SA results shows severe underprediction of the SOA components. This modeling work confirms the difficulties of modeling SOA in Europe, but shows that primary emissions constitute a significant fraction of ambient TC.

[1]  S. Pandis,et al.  Water Absorption by Secondary Organic Aerosol and Its Effect on Inorganic Aerosol Behavior , 2000 .

[2]  G. Seufert,et al.  Novel maps for forest tree species in Europe , 2001 .

[3]  C. Sternhufvuda,et al.  Particulate matter emissions and abatement options in residential wood burning in the Nordic countries , 2004 .

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

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

[6]  P. Warneck.  Chemistry of the natural atmosphere , 1999 .

[7]  J. Huntzicker,et al.  Vapor adsorption artifact in the sampling of organic aerosol: Face velocity effects , 1986 .

[8]  D. Streets,et al.  A technology‐based global inventory of black and organic carbon emissions from combustion , 2004 .

[9]  K. Yttri,et al.  Determination of monosaccharide anhydrides in atmospheric aerosols by use of high-performance liquid chromatography combined with high-resolution mass spectrometry. , 2005, Analytical chemistry.

[10]  J. Lelieveld,et al.  Gas/aerosol partitioning 2. Global modeling results , 2002 .

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

[12]  Sönke Szidat,et al.  Contributions of fossil fuel, biomass-burning, and biogenic emissions to carbonaceous aerosols in Zurich as traced by 14C , 2006 .

[13]  J. Seinfeld,et al.  Global distribution and climate forcing of carbonaceous aerosols , 2002 .

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

[15]  M. Legrand,et al.  Modeling historical long‐term trends of sulfate, ammonium, and elemental carbon over Europe: A comparison with ice core records in the Alps , 2007 .

[16]  Christian Seigneur,et al.  Uncertainties in modeling secondary organic aerosols: three-dimensional modeling studies in Nashville/western Tennessee. , 2003, Environmental science & technology.

[17]  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 .

[18]  Erik Berge,et al.  A regional scale multilayer model for the calculation of long‐term transport and deposition of air pollution in Europe , 1998 .

[19]  Glen R. Cass,et al.  Chemical Characterization of Fine Particle Emissions from Fireplace Combustion of Woods Grown in the Northeastern United States , 2001 .

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

[21]  Christer Johansson,et al.  Is Levoglucosan a Suitable Quantitative Tracer for Wood Burning? Comparison with Receptor Modeling on Trace Elements in Lycksele, Sweden , 2006, Journal of the Air & Waste Management Association.

[22]  C. Spirig,et al.  Eddy covariance flux measurements of biogenic VOCs during ECHO 2003 using proton transfer reaction mass spectrometry , 2005 .

[23]  Ulrich Pöschl,et al.  Atmospheric aerosols: composition, transformation, climate and health effects. , 2005, Angewandte Chemie.

[24]  Seasonal variation of primary biological aerosol particles , 1995 .

[25]  Alexandre Caseiro,et al.  Climatology of aerosol composition (organic versus inorganic) at nonurban sites on a west-east transect across Europe , 2007 .

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

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

[28]  Judith C. Chow,et al.  The dri thermal/optical reflectance carbon analysis system: description, evaluation and applications in U.S. Air quality studies , 1993 .

[29]  J. Putaud,et al.  INTERCOMP2000: the comparability of methods in use in Europe for measuring the carbon content of aerosol , 2004 .

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

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

[32]  Yinon Rudich,et al.  Atmospheric HULIS : how humic-like are they ? A comprehensive and critical review , 2005 .

[33]  Barbara J. Turpin,et al.  Measuring and simulating particulate organics in the atmosphere: problems and prospects , 2000 .

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

[35]  Leiv Håvard Slørdal,et al.  Quantification of Monosaccharide Anhydrides by Liquid Chromatography Combined with Mass Spectrometry: Application to Aerosol Samples from an Urban and a Suburban Site Influenced by Small-Scale Wood Burning , 2005, Journal of the Air & Waste Management Association.

[36]  C. Serves,et al.  Acetone and monoterpene emissions from the boreal forest in northern Europe , 2001 .

[37]  Judith C. Chow,et al.  Comparison of IMPROVE and NIOSH Carbon Measurements , 2001 .

[38]  Christian Seigneur,et al.  Secondary organic aerosol 2. Thermodynamic model for gas/particle partitioning of molecular constituents , 2002 .

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

[40]  Peter Wåhlin,et al.  A European aerosol phenomenology—1: physical characteristics of particulate matter at kerbside, urban, rural and background sites in Europe , 2004 .

[41]  T. Laurila,et al.  Upscaling the BIPHOREP Results - Regional Biogenic VOC Emissions in the European Boreal Zone , 1999 .

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

[43]  Glen R. Cass,et al.  Sources of fine organic aerosol. 2. Noncatalyst and catalyst-equipped automobiles and heavy-duty diesel trucks , 1993 .

[44]  G R Cass,et al.  Measurement of emissions from air pollution sources. 3. C1-C29 organic compounds from fireplace combustion of wood. , 2001, Environmental science & technology.

[45]  S. Jennings,et al.  Importance of organic and black carbon in atmospheric aerosols at Mace Head, on the West Coast of Ireland (53°19'N, 9°54'W) , 2002 .

[46]  D. Ceburnis,et al.  Advances in characterization of size-resolved organic matter in marine aerosol over the North Atlantic , 2004 .

[47]  C. N. Hewitt,et al.  Screening of 18 Mediterranean plant species for volatile organic compound emissions , 1997 .

[48]  R. Koppmann,et al.  Monoterpene emissions from Scots pine (Pinus sylvestris): Field studies of emission rate variabilities , 2002 .

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

[50]  C. N. Hewitt,et al.  A highly spatially and temporally resolved inventory for biogenic isoprene and monoterpene emissions: Model description and application to Great Britain , 2003 .

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

[52]  J. Hansen,et al.  Aerosol organic carbon to black carbon ratios: Analysis of published data and implications for climate forcing , 2005 .

[53]  Martin Adams,et al.  Inventory Review 2004. Emission data reported to CLRTAP and under the NEC Directive. , 2004 .

[54]  Kostas Tsigaridis,et al.  Atmospheric Chemistry and Physics Global Modelling of Secondary Organic Aerosol in the Troposphere: a Sensitivity Analysis , 2003 .

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

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

[57]  R. Kamens,et al.  Heterogeneous Atmospheric Aerosol Production by Acid-Catalyzed Particle-Phase Reactions , 2002, Science.

[58]  Allen L Robinson,et al.  Critical factors determining the variation in SOA yields from terpene ozonolysis: a combined experimental and computational study. , 2005, Faraday discussions.

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

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

[61]  G. Seufert,et al.  Seasonal Variation in Amount and Composition of Monoterpenes Emitted by Young Pinus pinea Trees – Implications for Emission Modeling , 2000 .

[62]  Jos Lelieveld,et al.  Gas/aerosol partitioning: 1. A computationally efficient model , 2002 .

[63]  Jostein K. Sundet,et al.  Calculation of Ozone and Other Pollutants for the Summer 1996 , 1999 .

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

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

[66]  R. Kamens,et al.  Modeling aerosol formation from alpha-pinene + NOx in the presence of natural sunlight using gas-phase kinetics and gas-particle partitioning theory. , 2001, Environmental science & technology.

[67]  Michel Legrand,et al.  Summary of the CARBOSOL project: Present and retrospective state of organic versus inorganic aerosol over Europe , 2007 .

[68]  Yvonne Andersson-Sköld,et al.  Secondary organic aerosol formation in northern Europe: A model study , 2001 .

[69]  I. J. Ackermann,et al.  Modeling the formation of secondary organic aerosol within a comprehensive air quality model system , 2001 .

[70]  P. Hari,et al.  Temperature and light dependence of the VOC emissions of Scots pine , 2004 .

[71]  M. Andreae,et al.  Emission of trace gases and aerosols from biomass burning , 2001 .

[72]  John H. Seinfeld,et al.  Modeling the Formation of Secondary Organic Aerosol (SOA). 2. The Predicted Effects of Relative Humidity on Aerosol Formation in the α-Pinene-, β-Pinene-, Sabinene-, Δ3-Carene-, and Cyclohexene-Ozone Systems , 2001 .

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

[74]  D. Ceburnis,et al.  Elemental and organic carbon in PM 10 : a one year measurement campaign within the European Monitoring and Evaluation Programme , 2007 .

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

[76]  M. Scholtz,et al.  Speciation of volatile organic compound emissions for regional air quality modeling of particulate matter and ozone , 2003 .

[77]  Alexandre Caseiro,et al.  Levoglucosan levels at background sites in Europe for assessing the impact of biomass combustion on the European aerosol background , 2007 .

[78]  J. Randerson,et al.  Interannual variability in global biomass burning emissions from 1997 to 2004 , 2006 .

[79]  Z. Klimont,et al.  Modeling of elemental carbon over Europe , 2007 .

[80]  H. Hansson,et al.  High Natural Aerosol Loading over Boreal Forests , 2006, Science.

[81]  Patrick R. Zimmerman,et al.  Natural volatile organic compound emission rate estimates for U.S. woodland landscapes , 1994 .

[82]  Z. Klimont,et al.  Primary emissions of fine carbonaceous particles in Europe , 2007 .

[83]  S. Sandler.  Chemical and engineering thermodynamics , 1977 .

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

[85]  Renato Zenobi,et al.  Seasonal variation of high-molecular-weight compounds in the water-soluble fraction of organic urban aerosols , 2005 .

[86]  C. N. Hewitt,et al.  An overview of the Castelporziano experiments , 1997 .

[87]  L. Luckner,et al.  International Institute for Applied Systems Analysis, A-2361 Laxenburg, Austria , 1985 .

[88]  H. Hakola,et al.  Seasonal variation of mono- and sesquiterpene emission rates of Scots pine , 2005 .

[89]  John H. Seinfeld,et al.  Modeling the formation of secondary organic aerosol. 1. Application of theoretical principles to measurements obtained in the α-pinene/, β-pinene/, sabinene/, Δ3-carene/, and cyclohexene/ozone systems , 2001 .

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

[91]  B. J. Turpind,et al.  Sampling methods used for the collection of particle-phase organic and elemental carbon during ACE-Asia , 2003 .

[92]  John H. Seinfeld,et al.  Estimating the vapor pressures of multi-functional oxygen-containing organic compounds using group contribution methods , 2002 .

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

[94]  R Zenobi,et al.  Secondary organic aerosols from anthropogenic and biogenic precursors. , 2005, Faraday discussions.

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

[96]  M Y O S E O N J A N G,et al.  A Thermodynamic Approach Using Group Contribution Methods to Model the Partitioning of Semivolatile Organic Compounds on Atmospheric Particulate Matter , 1997 .

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

[98]  R. Jaenicke,et al.  Examination of atmospheric bioaerosol particles with radii >0.2 μm , 1994 .

[99]  M. Kulmala,et al.  Characterization of aerosol particle episodes in Finland caused by wildfires in , 2005 .

[100]  Alexandre Caseiro,et al.  Source apportionment of PM2.5 organic aerosol over Europe: Primary/secondary, natural/anthropogenic, and fossil/biogenic origin , 2007 .

[101]  Donald Dabdub,et al.  A Coupled Hydrophobic-Hydrophilic Model for Predicting Secondary Organic Aerosol Formation , 2003 .