Source apportionment of PM 2.5 in Cork Harbour, Ireland using a combination of single particle mass spectrometry and quantitative semi-continuous measurements

Abstract. An aerosol time-of-flight mass spectrometer (ATOFMS) was deployed for the measurement of the size resolved chemical composition of single particles at a site in Cork Harbour, Ireland for three weeks in August 2008. The ATOFMS was co-located with a suite of semi-continuous instrumentation for the measurement of particle number, elemental carbon (EC), organic carbon (OC), sulfate and particulate matter smaller than 2.5 μm in diameter (PM2.5). The temporality of the ambient ATOFMS particle classes was subsequently used in conjunction with the semi-continuous measurements to apportion PM2.5 mass using positive matrix factorisation. The synergy of the single particle classification procedure and positive matrix factorisation allowed for the identification of six factors, corresponding to vehicular traffic, marine, long-range transport, various combustion, domestic solid fuel combustion and shipping traffic with estimated contributions to the measured PM2.5 mass of 23%, 14%, 13%, 11%, 5% and 1.5% respectively. Shipping traffic was found to contribute 18% of the measured particle number (20–600 nm mobility diameter), and thus may have important implications for human health considering the size and composition of ship exhaust particles. The positive matrix factorisation procedure enabled a more refined interpretation of the single particle results by providing source contributions to PM2.5 mass, while the single particle data enabled the identification of additional factors not possible with typical semi-continuous measurements, including local shipping traffic.

[1]  James D. Lee,et al.  Contributions from transport, solid fuel burning and cooking to primary organic aerosols in two UK cities , 2009 .

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

[3]  K. Prather,et al.  Real-Time detection and mixing state of methanesulfonate in single particles at an inland urban location during a phytoplankton bloom. , 2010, Environmental science & technology.

[4]  William A. Welch,et al.  Comprehensive simultaneous shipboard and airborne characterization of exhaust from a modern container ship at sea. , 2009, Environmental science & technology.

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

[6]  B. Doddridge,et al.  Concurrent measurements of black carbon aerosol and carbon monoxide at Mace Head , 1996 .

[7]  K. Velchev,et al.  What can we learn about ship emission inventories from measurements of air pollutants over the Mediterranean Sea , 2009 .

[8]  Philip K. Hopke,et al.  The evolution of chemometrics , 2003 .

[9]  B. Forsberg,et al.  Health impact assessment in case of biofuel peat - Co-use of environmental scenarios and exposure-response functions , 2009 .

[10]  K. Prather,et al.  Interpretation of mass spectra from organic compounds in aerosol time-of-flight mass spectrometry , 2000, Analytical Chemistry.

[11]  P. Bhave,et al.  Comparison of two methods for obtaining quantitative mass concentrations from aerosol time-of-flight mass spectrometry measurements. , 2006, Analytical chemistry.

[12]  R. Harrison,et al.  Chemical characterisation of single airborne particles in Athens (Greece) by ATOFMS , 2006 .

[13]  Hugh Coe,et al.  Source attribution of urban smog episodes caused by coal combustion , 2008 .

[14]  Kimberly A. Prather,et al.  Size and Chemical Characterization of Individual Particles Resulting from Biomass Burning of Local Southern California Species , 1999 .

[15]  A. Wexler,et al.  Identification of sources of atmospheric PM at the Pittsburgh Supersite, Part I: Single particle analysis and filter-based positive matrix factorization , 2006 .

[16]  K. Prather,et al.  On-Line Characterization of Individual Particles from Automobile Emissions , 1997 .

[17]  Erin H. Green,et al.  Mortality from ship emissions: a global assessment. , 2007, Environmental science & technology.

[18]  Single-particle detection efficiencies of aerosol time-of-flight mass spectrometry during the North Atlantic marine boundary layer experiment. , 2006, Environmental science & technology.

[19]  P. Paatero,et al.  Positive matrix factorization: A non-negative factor model with optimal utilization of error estimates of data values† , 1994 .

[20]  Ying Wang,et al.  Characterization of the single particle mixing state of individual ship plume events measured at the Port of Los Angeles. , 2010, Environmental science & technology.

[21]  P. Hopke,et al.  Source characterization of ambient fine particles at multiple sites in the Seattle area , 2008 .

[22]  P. Artaxo,et al.  Trace elements in tropical African savanna biomass burning aerosols , 1995 .

[23]  J. Jimenez,et al.  Interpretation of organic components from Positive Matrix Factorization of aerosol mass spectrometric data , 2008 .

[24]  Ulla Wandinger,et al.  Transport of boreal forest fire emissions from Canada , 2001 .

[25]  M. Andreae,et al.  Size distribution and hygroscopic properties of aerosol particles from dry-season biomass burning in Amazonia , 2005 .

[26]  K. Prather,et al.  Investigations of the diurnal cycle and mixing state of oxalic acid in individual particles in Asian aerosol outflow. , 2007, Environmental science & technology.

[27]  K. Prather,et al.  Using mass spectral source signatures to apportion exhaust particles from gasoline and diesel powered vehicles in a freeway study using UF-ATOFMS , 2008 .

[28]  K. Prather,et al.  Determination of single particle mass spectral signatures from heavy-duty diesel vehicle emissions for PM2.5 source apportionment , 2007 .

[29]  Erik Fridell,et al.  Primary particles in ship emissions , 2008 .

[30]  J J Corbett,et al.  Mitigating the health impacts of pollution from oceangoing shipping: an assessment of low-sulfur fuel mandates. , 2009, Environmental science & technology.

[31]  Hiroshi Furutani,et al.  Impact of emissions from the Los Angeles port region on San Diego air quality during regional transport events. , 2009, Environmental science & technology.

[32]  Min Shao,et al.  Characteristics of particulate carbon emissions from real-world Chinese coal combustion. , 2008, Environmental science & technology.

[33]  D. Rittenberg,et al.  Interpretation of mass spectra of organic compounds , 1965 .

[34]  P. Artaxo,et al.  Wintertime and summertime São Paulo aerosol source apportionment study , 2001 .

[35]  Jay R. Turner,et al.  Estimating the contribution of point sources to atmospheric metals using single-particle mass spectrometry , 2009 .

[36]  Axel Metzger,et al.  Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene , 2008 .

[37]  James F. Pankow,et al.  Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions—2. Dialdehydes, methylglyoxal, and diketones , 2005 .

[38]  S. Russell.  Microorganism characterization by single particle mass spectrometry. , 2009, Mass spectrometry reviews.

[39]  David A Sodeman,et al.  Determination of single particle mass spectral signatures from light-duty vehicle emissions. , 2005, Environmental science & technology.

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

[41]  K. Prather,et al.  Aerosol time‐of‐flight mass spectrometry during the Atlanta Supersite Experiment: 1. Measurements , 2003 .

[42]  M. A. Dreyfus,et al.  Organic aerosol source apportionment from highly time-resolved molecular composition measurements , 2009 .

[43]  Mar Viana,et al.  Chemical tracers of particulate emissions from commercial shipping. , 2009, Environmental science & technology.

[44]  Delbert J. Eatough,et al.  Source apportionment of 1 h semi-continuous data during the 2005 Study of Organic Aerosols in Riverside (SOAR) using positive matrix factorization , 2008 .

[45]  Susanne Krauss-Etschmann,et al.  Health effects of ambient particulate matter--biological mechanisms and inflammatory responses to in vitro and in vivo particle exposures. , 2008, Inhalation toxicology.

[46]  V. Grassian,et al.  N2O5 hydrolysis on the components of mineral dust and sea salt aerosol: Comparison study in an environmental aerosol reaction chamber , 2006 .

[47]  K. Prather,et al.  Direct observations of the atmospheric processing of Asian mineral dust , 2006 .

[48]  V. Ramanathan,et al.  Size‐resolved chemical composition of aerosol particles during a monsoonal transition period over the Indian Ocean , 2008 .

[49]  K. Prather,et al.  In-situ measurements of the mixing state and optical properties of soot with implications for radiative forcing estimates , 2009, Proceedings of the National Academy of Sciences.

[50]  U. Lohmann,et al.  In situ determination of atmospheric aerosol composition as a function of hygroscopic growth , 2008 .

[51]  W. P. Ball,et al.  Characterization of carbonaceous aerosols outflow from India and Arabia: Biomass/biofuel burning and fossil fuel combustion , 2003 .

[52]  Zong-ci Zhao,et al.  Climate change 2001, the scientific basis, chap. 8: model evaluation. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change IPCC , 2001 .

[53]  A. Wexler,et al.  Identification of sources of atmospheric PM at the Pittsburgh Supersite—Part III: Source characterization , 2007 .

[54]  F. Geng,et al.  Particulate nitrate formation in a highly polluted urban area: a case study by single-particle mass spectrometry in Shanghai. , 2009, Environmental science & technology.

[55]  Ernest Weingartner,et al.  Laboratory observation of oligomers in the aerosol from isoprene/NOx photooxidation , 2006 .

[56]  Tracey Holloway,et al.  Intercontinental transport of air pollution: will emerging science lead to a new hemispheric treaty? , 2003, Environmental science & technology.

[57]  J. Godoy,et al.  Coarse and fine aerosol source apportionment in Rio de Janeiro, Brazil , 2009 .

[58]  Ulf Kirchner,et al.  Identification of diesel exhaust particles at an Autobahn, urban and rural location using single-particle mass spectrometry , 2003 .

[59]  Susanne Krauss-Etschmann,et al.  Health Effects of Ambient Particulate Matter—Biological Mechanisms and Inflammatory Responses to In Vitro and In Vivo Particle Exposures , 2008 .

[60]  A. Wexler,et al.  Identification of sources of atmospheric PM at the Pittsburgh Supersite—Part II: Quantitative comparisons of single particle, particle number, and particle mass measurements , 2006 .

[61]  Annmarie G. Carlton,et al.  Atmospheric oxalic acid and SOA production from glyoxal: Results of aqueous photooxidation experiments , 2007 .

[62]  E. Tzannatos.  Ship emissions and their externalities for the port of Piraeus – Greece , 2010 .

[63]  James F. Pankow,et al.  Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions—Part 1: aldehydes and ketones , 2004 .

[64]  K. Prather,et al.  Aerosol time‐of‐flight mass spectrometry during the Atlanta Supersite Experiment: 2. Scaling procedures , 2003 .

[65]  B. Simoneit,et al.  Sugars--dominant water-soluble organic compounds in soils and characterization as tracers in atmospheric particulate matter. , 2004, Environmental science & technology.

[66]  Edward Charles Fortner,et al.  Mexico City Aerosol Analysis during MILAGRO using High Resolution Aerosol Mass Spectrometry , 2009 .

[67]  K. Prather,et al.  Comparison of oil and fuel particle chemical signatures with particle emissions from heavy and light duty vehicles , 2006 .

[68]  K. Prather,et al.  Reproducibility of Single Particle Chemical Composition during a Heavy Duty Diesel Truck Dynamometer Study , 2002 .

[69]  K. Prather,et al.  Single particle characterization of ultrafine and accumulation mode particles from heavy duty diesel vehicles using aerosol time-of-flight mass spectrometry. , 2006, Environmental science & technology.

[70]  X. Querol,et al.  Discriminating the regional and urban contributions in the North-Western Mediterranean: PM levels and composition , 2010 .

[71]  E. S. Lindgren,et al.  Identification and assessment of ship emissions and their effects in the harbour of Göteborg, Sweden , 2001 .

[72]  Xin Yang,et al.  Single particle mass spectrometry of oxalic acid in ambient aerosols in Shanghai: Mixing state and formation mechanism , 2009 .

[73]  U. Lohmann,et al.  Subarctic atmospheric aerosol composition: 2. Hygroscopic growth properties , 2009 .

[74]  R. Harrison,et al.  Characterization of individual airborne particles by using aerosol time‐of‐flight mass spectrometry at Mace Head, Ireland , 2004 .

[75]  Bryan N. Duncan,et al.  Transatlantic transport of pollution and its effects on surface ozone in Europe and North America , 2002 .

[76]  M. Lippmann,et al.  Residual oil combustion: a major source of airborne nickel in New York City , 2009, Journal of Exposure Science and Environmental Epidemiology.

[77]  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.

[78]  P. Hopke,et al.  Comparison of Positive Matrix Factorization and Multilinear Engine for the source apportionment of particulate pollutants , 2003 .

[79]  D. Ceburnis,et al.  Local and regional air pollution in Ireland during an intensive aerosol measurement campaign. , 2006, Journal of environmental monitoring : JEM.

[80]  Stig Hellebust,et al.  Characterisation of single particles from in-port ship emissions , 2009 .

[81]  D. S. Gross,et al.  Relative sensitivity factors for alkali metal and ammonium cations in single-particle aerosol time-of-flight mass spectra. , 2000, Analytical chemistry.

[82]  Ian O'Connor,et al.  The use of real-time monitoring data to evaluate major sources of airborne particulate matter , 2010 .

[83]  Wolfgang Kreyling,et al.  Epidemiological evidence on health effects of ultrafine particles. , 2002, Journal of aerosol medicine : the official journal of the International Society for Aerosols in Medicine.

[84]  Bert Brunekreef,et al.  Concentration response functions for ultrafine particles and all-cause mortality and hospital admissions: results of a European expert panel elicitation. , 2009, Environmental science & technology.

[85]  P. Buseck,et al.  Individual aerosol particles from biomass burning in southern Africa: 2, Compositions and aging of inorganic particles , 2003 .

[86]  John H. Seinfeld,et al.  The formation, properties and impact of secondary organic aerosol: current and emerging issues , 2009 .

[87]  R. Jervis,et al.  Receptor modeling of toronto PM2.5 characterized by aerosol laser ablation mass spectrometry. , 2004, Environmental science & technology.

[88]  Murray V. Johnston,et al.  Source characterization and identification by real-time single particle mass spectrometry. , 2007 .

[89]  Xavier Querol,et al.  Source apportionment of urban fine and ultra-fine particle number concentration in a Western Mediterranean city , 2009 .

[90]  P. Siskos,et al.  Assessment of source apportionment by Positive Matrix Factorization analysis on fine and coarse urban aerosol size fractions , 2009 .

[91]  A. Hoffer,et al.  Molecular distributions of dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in biomass burning aerosols : implications for photochemical production and degradation in smoke layers , 2009 .

[92]  J. Lewtas,et al.  Source apportionment of PM2.5 at an urban IMPROVE site in Seattle, Washington. , 2003, Environmental science & technology.

[93]  Sonia M. Kreidenweis,et al.  Hygroscopic growth behavior of a carbon-dominated aerosol in Yosemite National Park , 2005 .

[94]  J. Kukkonen,et al.  A modelling system for the exhaust emissions of marine traffic and its application in the Baltic Sea area , 2009 .

[95]  Ivan Kourtchev,et al.  Polar organic marker compounds in PM2.5 aerosol from a mixed forest site in western Germany. , 2008, Chemosphere.

[96]  R. Baumann,et al.  Experimental studies on particle emissions from cruising ship, their characteristic properties, transformation and atmospheric lifetime in the marine boundary layer , 2008 .

[97]  Kimberly A Prather,et al.  Recent advances in our understanding of atmospheric chemistry and climate made possible by on-line aerosol analysis instrumentation. , 2005, Analytical chemistry.

[98]  H. Burtscher,et al.  Hygroscopic properties of carbon and diesel soot particles , 1997 .

[99]  B. Morrical,et al.  Real-Time Analysis of Individual Atmospheric Aerosol Particles: Design and Performance of a Portable ATOFMS , 1997 .

[100]  Paul J. DeMott,et al.  In situ detection of biological particles in cloud ice-crystals , 2009 .

[101]  À. Nebot,et al.  PM composition and source reconciliation in Mexico City , 2009 .

[102]  Yuqiu Wang,et al.  Combined source apportionment, using positive matrix factorization–chemical mass balance and principal component analysis/multiple linear regression–chemical mass balance models , 2009 .

[103]  J. Sodeau,et al.  Gas-phase reaction of (E)-β-farnesene with ozone: Rate coefficient and carbonyl products , 2009 .

[104]  P. Hopke,et al.  Atmospheric Chemistry and Physics Source apportionment of PM 2 . 5 in Seoul , Korea , 2009 .

[105]  J. Fuglestvedt,et al.  Impacts of the large increase in international ship traffic 2000-2007 on tropospheric ozone and methane. , 2010, Environmental science & technology.

[106]  Kazuhiko Ito,et al.  Cardiovascular Effects of Nickel in Ambient Air , 2006, Environmental health perspectives.

[107]  W. Kreyling,et al.  Ultrafine particle-lung interactions: does size matter? , 2006, Journal of aerosol medicine : the official journal of the International Society for Aerosols in Medicine.

[108]  P. Paatero.  The Multilinear Engine—A Table-Driven, Least Squares Program for Solving Multilinear Problems, Including the n-Way Parallel Factor Analysis Model , 1999 .

[109]  Almut Arneth,et al.  Subarctic atmospheric aerosol composition: 1. Ambient aerosol characterization , 2009 .

[110]  Philip K. Hopke,et al.  Recent developments in receptor modeling , 2003 .

[111]  Luisa Marelli,et al.  Quantifying the impact of residential heating on the urban air quality in a typical European coal combustion region. , 2009, Environmental science & technology.

[112]  J. Sodeau,et al.  Sources of ambient concentrations and chemical composition of PM2.5–0.1 in Cork Harbour, Ireland , 2010 .

[113]  S. Owega,et al.  On-line analysis of urban particulate matter focusing on elevated wintertime aerosol concentrations. , 2002, Environmental science & technology.

[114]  E. Atlas,et al.  Emissions from biomass burning in the Yucatan , 2009 .

[115]  P. Paatero,et al.  Atmospheric aerosol over Alaska: 2. Elemental composition and sources , 1998 .

[116]  D. Ceburnis,et al.  Major component composition of urban PM10 and PM2.5 in Ireland , 2005 .

[117]  D. Hauglustaine,et al.  Multi-model simulations of the impact of international shipping on Atmospheric Chemistry and Climate in 2000 and 2030 , 2006 .

[118]  Kimberly A Prather,et al.  Real-time, single-particle measurements of oligomers in aged ambient aerosol particles. , 2007, Environmental science & technology.

[119]  J. MacQueen.  Some methods for classification and analysis of multivariate observations , 1967 .

[120]  David R. Musicant,et al.  Environmental chemistry through intelligent atmospheric data analysis , 2010, Environ. Model. Softw..

[121]  Urs Baltensperger,et al.  Real-time measurement of oligomeric species in secondary organic aerosol with the aerosol time-of-flight mass spectrometer. , 2006, Analytical chemistry.

[122]  Frank Arnold,et al.  A Backward Modeling Study of Intercontinental Pollution Transport using Aircraft Measurements , 2003 .

[123]  Robert McLaren,et al.  Reactive uptake of glyoxal by particulate matter , 2005 .

[124]  D. Dabdub,et al.  Modeling the effects of ship emissions on coastal air quality: A case study of southern California , 2008 .

[125]  Panagiotis Symeonidis,et al.  Development of an emission inventory system from transport in Greece , 2004, Environ. Model. Softw..

[126]  Philip B. Russell,et al.  Overview of the Summer 2004 Intercontinental Chemical Transport Experiment–North America (INTEX-A) , 2006 .

[127]  Allen,et al.  Direct observation of heterogeneous chemistry in the atmosphere , 1998, Science.

[128]  M. Molina,et al.  Measurement of ambient aerosols in northern Mexico City by single particle mass spectrometry , 2007 .

[129]  P. Hopke,et al.  Major Source Categories for PM2.5 in Pittsburgh using PMF and UNMIX , 2006 .

[130]  Christoph Hueglin,et al.  Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra , 2007 .