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R. M. Healy TXB Galway 08/09/2010 Identification and Apportionment of sources of PM 2.5  in Cork Harbour using single particle mass spectrometry R. M. Healy 1 , S. Hellebust 1 , I. Kourtchev 1 , A. Allanic 1 , I. O’Connnor 1 , J. Bell 1 ,  D. Healy 1 , M. Dall’Osto 2 , D. Ceburnis 2 , J. Ovadnevaite 2 , H. Berresheim 2 ,  C. O’Dowd 2 , J. Sodeau 1 , J. Wenger 1   1 Department of Chemistry and Environmental Research Institute, University College Cork, Ireland 2 School of Physics and Centre for Climate and Pollution Studies, Environmental Change Institute, National University of Ireland Galway, Ireland
Aims 1: To measure the size-resolved chemical composition of single particles in Cork Harbour using Aerosol Time-of-Flight Mass Spectrometry (ATOFMS) 2: To use this information to identify sources of PM 2.5  with an emphasis on local shipping emissions 3: To combine ATOFMS data with other semi-continuous measurements in order to estimate the contribution of each source to ambient PM 2.5  mass concentration and particle number concentration R. M. Healy TXB Galway 08/09/2010
Sampling Site Sampling carried out at Tivoli Docks, Cork Harbour for three weeks (7-28/08/2008) R. M. Healy et al., Atmos. Chem. Phys. Discuss.  10 , 1035-1082, 2010 R. M. Healy TXB Galway 08/09/2010
Instrumentation R. M. Healy TXB Galway 08/09/2010 Aerodynamic lens Sizing Region (2 sizing lasers 532 nm) Ionization laser (266 nm) Positive and negative time-of-flight mass spectrometers
Instrumentation R. M. Healy TXB Galway 08/09/2010 Instrument Measurement ATOFMS (TSI, 3800) Size-resolved single particle chemical composition SMPS (TSI, 3081) Particle number (20-700 nm) TEOM (Thermo, 1400a) PM 2.5 Thermal-optical carbon analyser (Sunset, 3 rd  gen. field model) ECC  Sulfate analyser (Thermo, 5020 SPA) Particulate SO 4 2-
Data Analysis 1: Over 500,000 particle mass spectra were collected, imported into ENCHILADA 1  and clustered using the  K -means algorithm ( K =50) 2: 50 clusters reduced to 14 ATOFMS classes;  Peat, Coal, Wood, Sea salt, Shipping, Ca-traffic, EC-traffic, EC-phos, EC-MSA, EC-domestic, EC-background, EC-oil, ECOC, and Oligomer 3: ATOFMS counts for each class were sorted into hourly bins and used along with hourly averages of EC/OC, SO 4 2-  and hourly integrated SMPS particle counts for positive matrix factorisation (PMF) in order to reconstruct PM 2.5  mass concentrations 1 D. Gross et al., Environmental Modelling & Software  25 , 760-769, 2010 R. M. Healy TXB Galway 08/09/2010
ATOFMS Results: Shipping R. M. Healy et al., Atmospheric Environment  43 , 6408-6414, 2009 R. M. Healy TXB Galway 08/09/2010
ATOFMS Results: Shipping R. M. Healy TXB Galway 08/09/2010
ATOFMS Results: Shipping R. M. Healy TXB Galway 08/09/2010
ATOFMS Results: Domestic Combustion Coal Peat Wood R. M. Healy TXB Galway 08/09/2010
ATOFMS Results: Domestic Combustion R. M. Healy TXB Galway 08/09/2010
ATOFMS Results: Domestic Combustion R. M. Healy TXB Galway 08/09/2010
ATOFMS Results: Traffic R. M. Healy TXB Galway 08/09/2010
ATOFMS Results: Long-range transport? R. M. Healy TXB Galway 08/09/2010
ATOFMS Results: Long-range transport? R. M. Healy TXB Galway 08/09/2010 5 day back-trajectories for air masses arriving at Cork Harbour on at 00:00 on 10/08/2008 (left), 14/08/2008 (middle) and 26/08/2008 (right).
Semi-continuous Results Hourly averaged values (µg m -3 ) 7-28/08/2008 R. M. Healy TXB Galway 08/09/2010 OC EC SO 4 2- PM 2.5 Mean 1.13 0.61 0.49 9.67 Median 1.02 0.55 0.45 8.55 Maximum 3.41 2.90 2.14 49.80 Minimum 0.22  0.00 0.04 1.50
PMF Results % Variable contributions to six-factor model and  estimated % contribution to measured PM 2.5  mass Robert Healy TXB Galway 08/09/2010   Traffic Domestic Combustion Various Combustion Marine Long-range Shipping Quantitative measurements:             OC mass 21 21 16 20 18 4 EC mass 43 20 18 5 11 4 Sulfate mass 9 11 40 23 15 2 Particle number (SMPS) 42 14 13 6 7 18 PM 2.5  mass 23 5 11 14 13 1 ATOFMS classes: Coal 5 52 30 3 7 3 Peat 3 84 5 2 3 2 Wood 11 63 5 13 6 1 Sea salt 1 0 2 86 10 1 Shipping 0 0 0 0 0 100 Ca-traffic 83 0 0 4 8 4 EC-traffic 59 25 6 1 3 6 EC-phos 82 9 3 0 6 0 EC-MSA 1 0 3 6 90 0 EC-domestic 0 91 0 0 2 7 EC-background 28 18 35 1 11 6 EC-oil 52 24 24 1 0 0 ECOC 0 0 69 0 31 0 Oligomer 0 76 8 15 0 1
Conclusions 1: Unique mass spectral fingerprints and high time resolution of ATOFMS are suited to source identification and apportionment, representing a useful alternative to off-line chemical analysis of PM 2.5 2: The major sources of PM 2.5  in Cork Harbour during the summer are traffic and sea spray, followed by local combustion processes including a contribution from domestic solid fuel burning 3: Although shipping traffic contributes very little to PM 2.5  mass concentrations, the contribution to particle number concentration is almost half that of traffic R. M. Healy TXB Galway 08/09/2010
Acknowledgements Port of Cork for providing a suitable sampling site Higher Education Authority, Environmental Protection Agency and Science Foundation Ireland for providing funding for this research Thank you for your attention! R. M. Healy TXB Galway 08/09/2010
R. M. Healy TXB Galway 08/09/2010
Robert Healy TXB Galway 08/09/2010
Hourly averaged signal for nitrate for the Coal, Peat and Wood ATOFMS classes for the 4 low wind speed events (11-12 August 2008, 13-15 August 2008 and 22-23 August 2008).  R. M. Healy TXB Galway 08/09/2010
Concentration-time profiles for PM 2.5 * , SO ­ 4 2-* , organic carbon **  and elemental carbon **  for 07-28 August 2008.  * Hourly averaged mass concentration.  ** 2 hour averaged mass concentration. R. M. Healy TXB Galway 08/09/2010
ATOFMS Results: Traffic Ca-Traffic EC-traffic EC-phos Robert Healy TXB Galway 08/09/2010

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Identification and Apportionment of sources of PM2.5 in Cork Harbour using single particle mass spectrometry - R M Healy, UCC

  • 1. R. M. Healy TXB Galway 08/09/2010 Identification and Apportionment of sources of PM 2.5 in Cork Harbour using single particle mass spectrometry R. M. Healy 1 , S. Hellebust 1 , I. Kourtchev 1 , A. Allanic 1 , I. O’Connnor 1 , J. Bell 1 , D. Healy 1 , M. Dall’Osto 2 , D. Ceburnis 2 , J. Ovadnevaite 2 , H. Berresheim 2 , C. O’Dowd 2 , J. Sodeau 1 , J. Wenger 1 1 Department of Chemistry and Environmental Research Institute, University College Cork, Ireland 2 School of Physics and Centre for Climate and Pollution Studies, Environmental Change Institute, National University of Ireland Galway, Ireland
  • 2. Aims 1: To measure the size-resolved chemical composition of single particles in Cork Harbour using Aerosol Time-of-Flight Mass Spectrometry (ATOFMS) 2: To use this information to identify sources of PM 2.5 with an emphasis on local shipping emissions 3: To combine ATOFMS data with other semi-continuous measurements in order to estimate the contribution of each source to ambient PM 2.5 mass concentration and particle number concentration R. M. Healy TXB Galway 08/09/2010
  • 3. Sampling Site Sampling carried out at Tivoli Docks, Cork Harbour for three weeks (7-28/08/2008) R. M. Healy et al., Atmos. Chem. Phys. Discuss. 10 , 1035-1082, 2010 R. M. Healy TXB Galway 08/09/2010
  • 4. Instrumentation R. M. Healy TXB Galway 08/09/2010 Aerodynamic lens Sizing Region (2 sizing lasers 532 nm) Ionization laser (266 nm) Positive and negative time-of-flight mass spectrometers
  • 5. Instrumentation R. M. Healy TXB Galway 08/09/2010 Instrument Measurement ATOFMS (TSI, 3800) Size-resolved single particle chemical composition SMPS (TSI, 3081) Particle number (20-700 nm) TEOM (Thermo, 1400a) PM 2.5 Thermal-optical carbon analyser (Sunset, 3 rd gen. field model) ECC Sulfate analyser (Thermo, 5020 SPA) Particulate SO 4 2-
  • 6. Data Analysis 1: Over 500,000 particle mass spectra were collected, imported into ENCHILADA 1 and clustered using the K -means algorithm ( K =50) 2: 50 clusters reduced to 14 ATOFMS classes; Peat, Coal, Wood, Sea salt, Shipping, Ca-traffic, EC-traffic, EC-phos, EC-MSA, EC-domestic, EC-background, EC-oil, ECOC, and Oligomer 3: ATOFMS counts for each class were sorted into hourly bins and used along with hourly averages of EC/OC, SO 4 2- and hourly integrated SMPS particle counts for positive matrix factorisation (PMF) in order to reconstruct PM 2.5 mass concentrations 1 D. Gross et al., Environmental Modelling & Software 25 , 760-769, 2010 R. M. Healy TXB Galway 08/09/2010
  • 7. ATOFMS Results: Shipping R. M. Healy et al., Atmospheric Environment 43 , 6408-6414, 2009 R. M. Healy TXB Galway 08/09/2010
  • 8. ATOFMS Results: Shipping R. M. Healy TXB Galway 08/09/2010
  • 9. ATOFMS Results: Shipping R. M. Healy TXB Galway 08/09/2010
  • 10. ATOFMS Results: Domestic Combustion Coal Peat Wood R. M. Healy TXB Galway 08/09/2010
  • 11. ATOFMS Results: Domestic Combustion R. M. Healy TXB Galway 08/09/2010
  • 12. ATOFMS Results: Domestic Combustion R. M. Healy TXB Galway 08/09/2010
  • 13. ATOFMS Results: Traffic R. M. Healy TXB Galway 08/09/2010
  • 14. ATOFMS Results: Long-range transport? R. M. Healy TXB Galway 08/09/2010
  • 15. ATOFMS Results: Long-range transport? R. M. Healy TXB Galway 08/09/2010 5 day back-trajectories for air masses arriving at Cork Harbour on at 00:00 on 10/08/2008 (left), 14/08/2008 (middle) and 26/08/2008 (right).
  • 16. Semi-continuous Results Hourly averaged values (µg m -3 ) 7-28/08/2008 R. M. Healy TXB Galway 08/09/2010 OC EC SO 4 2- PM 2.5 Mean 1.13 0.61 0.49 9.67 Median 1.02 0.55 0.45 8.55 Maximum 3.41 2.90 2.14 49.80 Minimum 0.22 0.00 0.04 1.50
  • 17. PMF Results % Variable contributions to six-factor model and estimated % contribution to measured PM 2.5 mass Robert Healy TXB Galway 08/09/2010   Traffic Domestic Combustion Various Combustion Marine Long-range Shipping Quantitative measurements:             OC mass 21 21 16 20 18 4 EC mass 43 20 18 5 11 4 Sulfate mass 9 11 40 23 15 2 Particle number (SMPS) 42 14 13 6 7 18 PM 2.5 mass 23 5 11 14 13 1 ATOFMS classes: Coal 5 52 30 3 7 3 Peat 3 84 5 2 3 2 Wood 11 63 5 13 6 1 Sea salt 1 0 2 86 10 1 Shipping 0 0 0 0 0 100 Ca-traffic 83 0 0 4 8 4 EC-traffic 59 25 6 1 3 6 EC-phos 82 9 3 0 6 0 EC-MSA 1 0 3 6 90 0 EC-domestic 0 91 0 0 2 7 EC-background 28 18 35 1 11 6 EC-oil 52 24 24 1 0 0 ECOC 0 0 69 0 31 0 Oligomer 0 76 8 15 0 1
  • 18. Conclusions 1: Unique mass spectral fingerprints and high time resolution of ATOFMS are suited to source identification and apportionment, representing a useful alternative to off-line chemical analysis of PM 2.5 2: The major sources of PM 2.5 in Cork Harbour during the summer are traffic and sea spray, followed by local combustion processes including a contribution from domestic solid fuel burning 3: Although shipping traffic contributes very little to PM 2.5 mass concentrations, the contribution to particle number concentration is almost half that of traffic R. M. Healy TXB Galway 08/09/2010
  • 19. Acknowledgements Port of Cork for providing a suitable sampling site Higher Education Authority, Environmental Protection Agency and Science Foundation Ireland for providing funding for this research Thank you for your attention! R. M. Healy TXB Galway 08/09/2010
  • 20. R. M. Healy TXB Galway 08/09/2010
  • 21. Robert Healy TXB Galway 08/09/2010
  • 22. Hourly averaged signal for nitrate for the Coal, Peat and Wood ATOFMS classes for the 4 low wind speed events (11-12 August 2008, 13-15 August 2008 and 22-23 August 2008). R. M. Healy TXB Galway 08/09/2010
  • 23. Concentration-time profiles for PM 2.5 * , SO ­ 4 2-* , organic carbon ** and elemental carbon ** for 07-28 August 2008. * Hourly averaged mass concentration. ** 2 hour averaged mass concentration. R. M. Healy TXB Galway 08/09/2010
  • 24. ATOFMS Results: Traffic Ca-Traffic EC-traffic EC-phos Robert Healy TXB Galway 08/09/2010