1. The study used single particle mass spectrometry to identify sources of PM2.5 in Cork Harbour, Ireland. Major sources identified were traffic, sea spray, and local combustion including domestic solid fuel burning. 2. While shipping traffic contributed little to PM2.5 mass, it accounted for almost half of total particle number concentration, similar to traffic emissions. 3. Unique mass spectral fingerprints from the single particle technique provided a useful alternative to offline chemical analysis for source apportionment of PM2.5.

1. IAC Helsinki 30/08/2010
Source Apportionment of PM2.5 in Cork Harbour,
Ireland using single particle mass spectrometry
R. M. Healy1, S. Hellebust1, I. Kourtchev1, A. Allanic1, I. O’Connnor1, J. Bell1,
M. Dall’Osto2, D. Ceburnis2, J. Ovadnevaite2, H. Berresheim2, C. O’Dowd2,
J. Sodeau1, J. Wenger1
1Department of Chemistry and Environmental Research Institute, University College Cork, Ireland
2School of Physics and Centre for Climate and Pollution Studies, Environmental Change Institute,
National University of Ireland Galway, Ireland

2. Aims
IAC Helsinki 30/08/2010
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 PM2.5 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 PM2.5 mass
concentration and particle number concentration

3. Sampling Site
IAC Helsinki 30/08/2010
X
B
B
B
0.05 0.1 0.15 0.2
0
45
90
135
180
225
270
315
0 - 2
2 - 4
4 - 6
6 - 8
8+
(m s
-1
)
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

4. Instrumentation
IAC Helsinki 30/08/2010
Instrument Measurement
ATOFMS (TSI, 3800) Size-resolved single particle chemical
composition
SMPS (TSI, 3081) Particle number (20-700 nm)
TEOM (Thermo, 1400a) PM2.5
Thermal-optical carbon analyser
(Sunset, 3rd gen. field model)
ECOC
Sulfate analyser (Thermo, 5020 SPA) Particulate SO4
2-

5. IAC Helsinki 30/08/2010
Data Analysis
1: Over 500,000 particle mass spectra were collected, imported into
ENCHILADA1 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, SO4
2- and hourly integrated SMPS particle
counts for positive matrix factorisation (PMF) in order to reconstruct PM2.5
mass concentrations
1D. Gross et al., Environmental Modelling & Software 25, 760-769, 2010

6. IAC Helsinki 30/08/2010
ATOFMS Results: Shipping
R. M. Healy et al., Atmospheric Environment 43, 6408-6414, 2009
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Ca+
V+
VO+
C2H3
+
Na+
C+
C3
+
Fe+
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
SO3
-
C2
-
CN-
HSO4
-
C3
-
C4
-
50 60 70 80 90 100 110 120 130 140 150
Na2Cl+
Na2Cl+Na2O+
50 60 70 80 90 100 110 120 130 140 150
NaCl2
-
NO3
-
O2
-
SO3
-
NaCl-
NaCl2
-/HSO4
-
m/z m/z
RelativeIntensity
C3
+
A B
DC

7. IAC Helsinki 30/08/2010
ATOFMS Results: Shipping
0
50
100
150
200
250
300
ATOFMScounts
Date
ATOFMS "Shipping" class
10
20
30
40
0
45
90
135
180
225
270
315
ATOFMS "Shipping" class

8. IAC Helsinki 30/08/2010
ATOFMS Results: Shipping
200
150
100
50
0
ATOFMScounts
15:00
23/08/2008
16:00 17:00 18:00 19:00 20:00 21:00 22:00
Time
2
3
4
5
6
7
100
2
3
4
5
6
7
mobilitydiameter(nm)
5x10
5
4
3
2
1
0
(#cm
-3
)
ATOFMS "Shipping" Class

9. IAC Helsinki 30/08/2010
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
C+
C3
+
K+/C3H3
+
C2H3O+
Na+
C2H3
+
C5
+
C4H2
+
C4
+
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
C2
-
CN-
C3
-
CNO-
NO3
-
NO2
-
HSO4
-
SO3
-C4
-
RelativeIntensity
m/z
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
C+
C3
+
K+
C2H3O+
Na+
C2H3
+
C5
+
C4H2
+
C4
+
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
C+
C3
+
K+
C2H3O+
Na+
C2H3
+
C5
+
C4H2
+
C4
+
m/z m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
C2
-
CN-
C3
-
CNO-
C4
-
NO3
-
NO2
-
HSO4
-
Cl-
Cl-
C5
-
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
C2
-
CN-
C3
-
CNO-
NO3
-
NO2
-
HSO4
-
Cl-
Cl-
C5
-
C4
-
RelativeIntensity
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
C+
C3
+
K+
Na+
K+
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
C+
C3
+
K+
Na+
K+
m/z m/z
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
O-
OH-
C2
-
CN-
C3
-
Cl-
Cl-
CNO-
NO2
-
C4
-
NO3
-
C2H3O2
-
HSO4
-
COOHCOO-
C3H3O2
-
KCl2
-
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
O-
OH-
C2
-
CN-
C3
-
Cl-
Cl-
CNO-
NO2
-
C4
-
NO3
-
C2H3O-
C2H3O2
-
C3H3O2
-
HSO4
-
KCl2
-
COOHCOO-
RelativeIntensity
RelativeIntensity
ATOFMS Results: DomesticCombustion
Coal Peat Wood

10. IAC Helsinki 30/08/2010
ATOFMS Results: DomesticCombustion
0
50
100
150
200
250
0
100
200
300
400
500
600
700
800
ATOFMScounts(h-1)
ATOFMScounts(h-1)
Time
coal peat wood

11. IAC Helsinki 30/08/2010
ATOFMS Results: DomesticCombustion

12. IAC Helsinki 30/08/2010
ATOFMS Results: Traffic
1200
EC-domestic Oligomer
0
500
1000
1500
2000
2500
ATOFMScounts(h-1
)
Time
Ca-traffic EC-traffic EC-phos

13. IAC Helsinki 30/08/2010
Semi-continuousResults
OC EC SO4
2- PM2.5
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
Hourly averaged values (µg m-3) 7-28/08/2008

14. IAC Helsinki 30/08/2010
PMFResults
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
PM2.5 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
% Variable contributions to six-factor model and
estimated % contribution to measured PM2.5 mass

15. IAC Helsinki 30/08/2010
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 PM2.5
2: The major sources of PM2.5 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 PM2.5 mass
concentrations, the contribution to particle number concentration is almost
half that of traffic

16. IAC Helsinki 30/08/2010
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!

17. IAC Helsinki 30/08/2010

18. IAC Helsinki 30/08/2010
0
1
2
3
4
5
6
7
0
500
1000
1500
2000
2500
Windspeed(ms-1)
ATOFMScounts(h-1)
Date
Coal-amm-nit Peat-nit Wood-nit Wind speed

19. 0
100
200
300
400
500
600
700
800
900
ATOFMS[NO3]-RelativeIntensity
Time
coal peat wood
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).

20. IAC Helsinki 30/08/2010
Concentration-time profiles for PM2.5
*, SO4
2-*, organic carbon** and elemental
carbon** for 07-28 August 2008. *Hourly averaged mass concentration. **2 hour
averaged mass concentration.
3.0
2.0
1.0
0.0
µgm
-3
07/08/2008
08/08/2008
09/08/2008
10/08/2008
11/08/2008
12/08/2008
13/08/2008
14/08/2008
15/08/2008
16/08/2008
17/08/2008
18/08/2008
19/08/2008
20/08/2008
21/08/2008
22/08/2008
23/08/2008
24/08/2008
25/08/2008
26/08/2008
27/08/2008
28/08/2008
Date
2.0
1.5
1.0
0.5
0.0
µgm
-3 50
40
30
20
10
0
µgm
-3 PM2.5 SO4
2-
OC EC

21. IAC Helsinki 30/08/2010
ATOFMS Results: Traffic
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Ca+
VO+
C2H3
+
Na+
C+
C3
+
Fe+
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
SO3
-
C2
-
CN-
HSO4
-
C3
-
C4
-
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Na2Cl+K+
Na2Cl+Na2O+
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
NaCl2
-
Cl-
NO3
-
NO2
-
SO3
-
Cl-
NaCl-
NaCl2
-/HSO4
-Na-
O-
m/z m/z
RelativeIntensity
RelativeIntensity
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Ca+
Na+
C+
C3
+
C4
+
C5
+
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
C2
-
CN-
HSO4
-
C3
-
C4
-
C5
-
m/z
RelativeIntensity
D
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Ca2O+
Ca+
CaO+
CaOH+
C2H3
+
m/z
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
PO2
-
NO2
-
HSO3
-
CNO-
NO3
-
CN-
PO3
-
PO4
-
RelativeIntensity
C
0 10 20 30 40
C+
C3
+
C2
+
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
C+
C3
+
C4
+
C5
+
C2
+
m/z
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
C2
-
CN-
HSO4
-
C3
-
C4
-
NO3
-
PO3
-
0 10 20 30 40
C2
-
CN-
C3
-
RelativeIntensity
RelativeIntensity
A
K+
C3
+
Na+
K+
C
Ca-Traffic EC-traffic EC-phos

22. IAC Helsinki 30/08/2010
0
20
40
60
80
100
120
140
160
ATOFMScounts(h-1)
Date
EC-phos EC-MSA

23. IAC Helsinki 30/08/2010
Fig. 15: 5 day back-trajectories for air masses arriving at Cork Harbour on at 00:00 h
on 10 (left), 14 (middle) and 26 August 2008 (right).