Ambient levels of PM2.5‐0.1 in Harbour, Ireland. Chemical analysis and source apportionment

S. Hellebust*, A. Allanic ,I.P. O’Connor and J. R. Sodeau Centre for Research into Atmospheric Chemistry, Department of Chemistry, University College Cork, Cork, Ireland. *e mail : [email protected]

INTRODUCTION TO ELIPSE: ENVIRONMENTAL LINKAGES BETWEEN IN‐PORT SHIP EMISSIONS OF PARTICULATE MATTER TO THEIR CHEMICAL CONTENT AND EFFECTS ON HEALTH

Airborne Particulate Matter (PM) is a mixture of solid and liquid particles suspended in the air. These particles are important in terms of impact of the environment and public health. International policy on air quality, protection of human health and the protection of the environment depends on research on ambient air particulate pollution. Knowledge on the origin of airborne particulate matter, the identification of partic les hdhazardous to the quality of life and the chithemistry of athitmospheric aerosols is essentia l to undtdiderstanding the sources and ftfates of particu la te matter in the envitironment and the ir effec ts on human health.

Since the London Smog event in 1952, where acidic fog mixed with sulfurous smoke and a subsequent influenza epidemic caused about 4000 excess deaths in the winter of 1952/53 compared to the same period in the previous years, this has become a major environmental and epidemiological issue as industrial and population growth has increased and several monitoring networks and legislative measures have been put in place to reduce adverse effects of particulate matter pollution. However, emissions are increasing and abatement strategies need to become more effective in dealing with these problems. The first step in reducing emissions is to determine what measures are cost‐effective and practical without curbing economic growth and development. This requires unequivocal knowledge of what the major sources are in different areas of the world.

It is known that transport and private vehicles are the main culprits in most parts of the world, by virtue of the sheer volume, although industrial activities can dominate in areas of high industrial activity. Ports in particular are economic and industrial hubs connecting rail, road, shipping and air transport, while usually situated in areas of high population density. This fact should make them prime targets for research on air borne pollution, a fact which was overlooked for many years while the emphasis was on road traffic and space heating.

The fact that ports are associated with other forms of transport and economic activity means that emissions measured in‐port are not all attributable to shipping. This also means that a direct link with shipping and ambient levels of pollutants can not be made. Thus, the solution to the problem of high levels of air pollution in port areas is not necessarily to reduce shipping, because it is not known if the main source is shipping emissions or emissions from other associated economic activities. Thus, proper quantification of sources to the air pollution measured in ports has to be carried out before abatement strategies can be effective. If shipping turns out to be a major source, effective measures can be taken without compromising economic growth and shipping volume, such as reduction of sulfur content in the fuel and provision of shore‐power for loading and unloading of goods and hotelling, instead of keeping the ships engines running while alongside quay. Photo: Arnaud Allanic AIMS, SAMPLING LOCATION AND RESULTS

Sampling substrate: The aims of this study are to collect and chemically PM10 and PM2.5 mass per collection (mg) Island: Polyurethane foam 3 characterize airborne particulate matter (PM10,PM2.5, and and ambient concentrations (μg/m ) PM /PM (Dec.’06‐Apr.’08): (PUF). Sampling flow other) present in Cork Harbour. The driving force for the 10 2.5 PM PM rate: 1100 litres per 10‐2.5 2.5‐0.1 studies is based on the world‐wide recognition that ship •12 ions (Ion Chromatography) Sample Sample minute. Sampling Collection Weight PM Weight PM PM / •22 elements (ICP‐OES) 10 2.5 10 emissions comprise a major, relatively unmeasured source 3 3 period: 3 days/4 days, Sampling Dates No (mg) (µg/m ) (mg) (µg/m ) PM2.5 •Weather (T, WS, WD, P, Rain, RH, 06/12/2006 ‐ 10/12/2006 CS 1 7.04 4.47 5.53 3.52 1.3 of pollution with potentially adverse effects on human i.e. weekend/midweek 19/12/2006 ‐ 27/12/2006 CS 2 77.36 8.59 70.11 7.78 1.1 Sunlight) 27/12/2006 ‐ 03/01/2007 CS 3 87.52 7.91 29.44 2.66 3.0 health. 03/01/2007 ‐ 10/01/2007 CS 4 74.72 8.20 21.82 2.40 3.4 10/01/2007 ‐ 17/01/2007 CS 5 6.98 0.63 5.24 0.47 1.3 PM collection programmes are operated at three Cork 17/01/2007 ‐ 24/01/2007 CS 6 77.26 8.55 25.14 2.78 3.1 24/01/2007 ‐ 31/01/2007 CS 7 9.48 0.89 20.78 1.96 0.5 Harbour sites: Tivoli Docks (berth‐side), Haulbowline Island 31/01/2007 ‐ 07/02/2007 CS 8 78.85 8.51 32.15 3.47 2.5 19/04/2007 ‐ 23/04/2007 CS 15 6.88 1.10 11.49 1.83 0.6 23/04/2007 ‐ 27/04/2007 CS 16 10.71 1.68 20.22 3.17 0.5 (mid‐harbour) and Roche’s Point (Outer harbour) using a 27/04/2007 ‐ 01/05/2007 CS 17 15.24 2.41 41.85 6.63 0.4 01/05/2007 ‐ 04/05/2007 CS 18 9.16 1.88 32.12 6.60 0.3 High Volume approach for capture of particles. Photo: Jose Lopez 04/05/2007 ‐ 07/05/2007 CS 19 10.34 2.17 18.39 3.86 0.6 07/05/2007 ‐ 11/05/2007 CS 20 10.97 1.73 10.89 1.71 1.0 Chemical analysis for inorganic compounds found in the 11/05/2007 ‐ 14/05/2007 CS 21 4.28 0.94 8.47 1.86 0.5 Ambient PM levels; Haulbowline Island Cork Harbour 14/05/2007 ‐ 18/05/2007 CS 22 9.10 1.45 9.32 1.48 1.0 PM2.5 fraction employed ion chromatography and 18/05/2007 ‐ 21/05/2007 CS 23 6.46 1.35 8.52 1.78 0.8 21/05/2007 ‐ 25/05/2007 CS 24 7.39 1.18 9.09 1.45 0.8 inductively coupled plasma – optical emission spectroscopy. μg/m3 25/05/2007 ‐ 28/05/2007 CS 25 8.27 1.69 7.97 1.63 1.0 28/05/2007 ‐ 01/06/2007 CS 26 10.12 1.61 11.27 1.79 0.9 14.00 4.0 01/06/2007 ‐ 04/06/2007 CS 27 7.27 1.55 8.41 1.80 0.9 04/06/2007 ‐ 08/06/2007 CS 28 19.12 3.00 39.31 6.17 0.5 A“real‐time” measurement programme for important PM2.5 (µg/m3) PM10/PM2.5 08/06/2007 ‐ 11/06/2007 CS 29 31.73 6.50 12.00 3.0 11/06/2007 ‐ 15/06/2007 CS 30 4.68 0.74 4.25 0.67 1.1 15/06/2007 ‐ 18/06/2007 CS 31 8.73 1.84 atmospheric components such as Elemental and Organic 18/06/2007 ‐ 22/06/2007 CS 32 9.60 1.51 10.28 1.62 0.9 10.00 22/06/2007 ‐ 25/06/2007 CS 33 4384.38 0930.93 5435.43 1151.15 080.8 carbon and theoxida tion of SlfSulfur (IV),asSO2, to SlfSulfur (VI), 202.0 25/06/2007 ‐ 29/06/2007 CS 34 10.88 1.72 7.63 1.20 1.4 29/06/2007 ‐ 02/07/2007 CS 35 12.65 2.66 9.45 1.99 1.3 as sulfate ions is in operation since December 2007. 8.00 02/07/2007 ‐ 06/07/2007 CS 36 10.57 1.66 12.93 2.03 0.8 1.0 06/07/2007 ‐ 09/07/2007 CS 37 3.57 0.78 5.25 1.15 0.7 6.00 09/07/2007 ‐ 13/07/2007 CS 38 4.73 0.73 7.15 1.11 0.7 13/07/2007 ‐ 16/07/2007 CS 39 A second phase of the ELIPSE project is envisioned in which 0.0 16/07/2007 ‐ 20/07/2007 CS 40 6.27 1.00 7.93 1.27 0.8 4.00 20/07/2007 ‐ 23/07/2007 CS 41 7.42 1.64 8.61 1.90 0.9 both toxicological and source apportionment issues 23/07/2007 ‐ 27/07/2007 CS 42 13.94 2.19 8.91 1.40 1.6 27/07/2007 ‐ 30/07/2007 CS 43 7.87 1.66 8.43 1.78 0.9 2.00 -1.0 30/07/2007 ‐ 03/08/2007 CS 44 8.22 1.31 7.84 1.25 1.0 associated with Cork Harbour will be thoroughly addressed. 03/08/2007 ‐ 06/08/2007 CS 45 2.05 0.43 2.19 0.46 0.9 06/08/2007 ‐ 10/08/2007 CS 46 5.23 0.79 5.23 0.79 1.0 0.00 -2.0 10/08/2007 ‐ 13/08/2007 CS 47 3.23 0.68 2.67 0.56 1.2 13/08/2007 ‐17 /08/2007 CS 48 9.09 1.52 6.19 1.03 1.5 17/08/2007 ‐ 20/08/2007 CS 49 5.97 1.25 4.55 0.95 1.3 20/08/2007 ‐ 24/08/2007 CS 50 3.70 0.59 12.48 1.97 0.3 Mass fraction of water soluble ions 24/08/2007 ‐ 27/08/2007 CS 51 3.51 0.72 4.01 0.83 0.9 27/08/2007 ‐ 31/08/2007 CS 52 8.85 1.44 6.68 1.08 1.3 and metals in PM 31/08/2007 ‐ 03/09/2007 CS 53 3.41 0.72 4.19 0.89 0.8 2.5‐0.1 03/09/2007 ‐ 07/09/2007 CS 54 8.99 1.43 14.36 2.28 0.6 07/09/2007 ‐ 10/09/2007 CS 55 12.32 2.75 11.95 2.66 1.0 10/09/2007 ‐ 14/09/2007 CS 56 13.84 2.14 16.90 2.61 0.8 Cl‐, ‐ 2‐ ‐ + + ‐ + NO3 , 3 14/09/2007 ‐ 17/09/2007 CS 57 10.19 2.00 8.73 1.72 1.2 NH4 , 4.77% The main ions are SO4 (15% by mass), NO3 (8%), NH4 (5%), Na (7%) and Cl (9%) Summary statistics (ng/m ) 8.78% 7.90% 17/09/2007 ‐ 21/09/2007 CS 58 17.66 2.97 11.14 1.87 1.6 21/09/2007 ‐ 24/09/2007 CS 59 6.98 1.45 5.24 1.08 1.3 2+ Ca , 0.89% 25/09/2007 ‐ 28/09/2007 CS 60 8.92 1.87 9.79 2.05 0.9 + F‐, 0.17% Na , 7.04% Species Average Minimum Maximum Std. Dev. %BDL 28/09/2007 ‐ 01/10/2007 CS 61 9.48 1.81 20.78 3.96 0.5 2‐ NO ‐, The fluctuation between weekend and midweek samples in the values of PM mass and its chemical PM 01/10/2007 ‐ 05/10/2007 CS 62 11.55 1.91 17.27 2.85 0.7 SO4 , 14.58% 2 10‐2.5 05/10/2007 ‐ 08/10/2007 CS 63 10.13 2.04 28.13 5.66 0.4 3 0.12% (mg/m ) 1.9 0.3 5.5 0.9 0.0 08/10/2007 ‐ 12/10/2007 CS 64 13.08 2.11 15.08 2.43 0.9 2+ Other, 3.35% Mg , 0.88% ‐ content suggests that there is a strong influence of anthropogenic sources in this mid‐harbour 12/10/2007 ‐ 15/10/2007 CS 65 7.55 1.51 16.76 3.35 0.5 PO4 , PM2.5‐0.1 Other (OC, EC, 3 15/10/2007 ‐ 19/10/2007 CS 66 1.76 0.29 8.11 1.33 0.2 0.10% location. Industrial and economic activities are reduced at weekends, but shipping activities are not. (mg/m ) 2.7 0.5 12.9 2.1 0.0 19/10/2007 ‐ 22/10/2007 CS 67 11.29 2.51 14.01 3.12 0.8 non‐water S 333.3 33.6 1918.6 315.6 0.0 22/10/2007 ‐ 24/10/2007 CS 68 6.61 1.00 24.07 3.63 0.3 soluble), 53.57% Zn, 26/10/2007 ‐ 29/10/2007 CS 69 6.88 1.48 11.49 2.47 0.6 + As 090.9 030.3 202.0 040.4 100.0 K , 0.60% 0.29% 29/10/2007 ‐ 02/11/2007 CS 70 11.88 1.83 16.63 2.56 0.7 The high sulfate levels suggest a large component of secondary aerosols. Ships are a major emitter of Sn 0.3 0.0 2.5 0.4 24.6 02/11/2007 ‐ 09/11/2007 CS 71 43.20 3.90 Hg 0.6 0.0 11.5 1.6 55.2 09/11/2007 ‐ 16/11/2007 CS 72 13.33 1.23 22.40 2.07 0.6 Al, 0.09% 16/11/2007 ‐ 23/11/2007 CS 73 SO2. Shipping related elements such as Vanadium and Nickel may be present in ultrafine particles Mo 0.1 0.0 0.7 0.1 76.6 23/11/2007 ‐ 26/11/2007 CS 74 8.43 1.75 18.29 3.81 0.5 Zn 8.1 0.7 40.2 8.5 0.0 26/11/2007 ‐ 30/11/2007 CS 75 10.24 1.56 11.86 1.81 0.9 that do not contribute significantly to total mass. 30/11/2007 ‐ 03/12/2007 CS 76 5.04 1.04 6.52 1.34 0.8 Sb 0.1 0.0 0.7 0.1 58.5 03/12/2007 ‐ 07/12/2007 CS 77 12.04 1.89 10.19 1.60 1.2 Pb 0.4 0.0 2.4 0.5 32.7 07/12/2007 ‐ 10/12/2007 CS 78 10.10 2.24 7.08 1.57 1.4 CORRELATIONS, PRINCIPAL Cd 0.1 0.0 0.2 0.0 95.9 10/12/2007 ‐ 12/12/2007 CS 79 8.71 2.72 16.16 5.05 0.5 14/12/2007 ‐ 17/12/2007 CS 80 14.69 2.86 20.58 4.00 0.7 Levels of Vanadium, which is frequently used as a marker element for heavy bunker fuel, increase at Ni 0.2 0.0 1.8 0.3 9.9 17/12/2007 ‐ 21/12/2007 CS 81 16.92 2.72 41.13 6.62 0.4 Fe 1.1 0.0 9.0 1.5 8.2 21/12/2007 ‐ 24/12/2007 CS 82 11.47 2.56 18.87 4.21 0.6 weekends when there are regular arrivals of international passenger ferries and high levels of 24/12/2007 ‐ 28/12/2007 CS 83 16.77 2.59 23.71 3.67 0.7 COMPONENTS AND Co 0.0 0.0 0.1 0.0 81.9 28/12/2007 ‐ 31/12/2007 CS 84 8.66 1.78 6.96 1.43 1.2 Si 0.5 0.2 1.2 0.2 91.8 31/12/2007 ‐ 04/01/2008 CS 85 17.28 2.71 27.58 4.33 0.6 shipping activities in nearby cargo and cruise terminals. The V/Ni ratios in samples are typical of sites 04/01/2008 ‐ 07/01/2008 CS 86 11.71 2.59 13.04 2.88 0.9 Mn 0.2 0.0 2.9 0.4 12.9 07/01/2008 ‐ 11/01/2008 CS 87 15.38 2.35 12.29 1.88 1.3 SOURCE APPORTIONMENT influenced by shipping emissions, with an average value of 3.4 and a median of 2.9. Cr 0.1 0.0 0.6 0.1 21.1 11/01/2008 ‐ 14/01/2008 CS 88 11.59 2.46 10.69 2.27 1.1 Mg 25.0 1.3 67.1 14.9 0.0 14/01/2008 ‐ 18/01/2008 CS 89 15.21 2.44 15.46 2.48 1.0 'S' 'As' 'Sn' 'Mo' 'Zn' 'Sb' 'Pb' 'Cd' 'Ni' 'Fe' 'Co' 'Si' 'Mn' 'Cr' 'Mg' 'V' 'Ca' 'Cu' 'Ti' 'Al' 'Na+' 'NH4+' 'K+' 'Mg2+' 'Ca2+' 'F-' 'Cl-' 'NO2-' 'Br-' 'NO3-' 'SO42-' 'PO4-' 18/01/2008 ‐ 21/01/2008 CS 90 4.98 1.03 6.03 1.24 0.8 'S' 1 V 0.5 0.1 4.3 0.7 21.6 21/01/2008 ‐ 25/01/2008 CS 91 28.73 4.53 31.62 4.99 0.9 'As' 0.089356 1 Ca 17.7 2.5 131.4 17.2 10.5 25/01/2008 ‐ 28/01/2008 CS 92 6.39 1.37 16.14 3.47 0.4 28/01/2008 ‐ 01/02/2008 CS 93 15.84 2.57 14.40 2.34 1.1 'Sn' 0.578165 0.245766 1 + 2‐ ‐ + ‐ Cu 0.1 0.0 1.0 0.2 60.2 01/02/2008 ‐ 04/02/2008 CS 94 4.58 0.93 10.55 2.15 0.4 0.443548 0.369616 0.713884 1 WHAT IS CORRELATED? Ions group 1: NH4 , SO4 and NO3 (with K and F ) 'Mo' Ti 0.0 0.0 0.4 0.1 12.9 04/02/2008 ‐ 08/02/2008 CS 95 18.44 3.02 14.93 2.44 1.2 'Zn' 0.481643 0.131316 0.150611 0.02222 1 + 2+ ‐ 08/02/2008 ‐ 11/02/2008 CS 96 14.25 2.86 40.03 8.03 0.4 'Sb' 0.141312 0.42448 0.13853 0.075069 0.499191 1 Ions group 2: Na , Mg and Cl Al 2.9 0.0 47.5 6.5 7.0 11/02/2008 ‐ 15/02/2008 CS 97 17.79 3.21 71.34 12.88 0.2 'Pb' 0.566743 0.311679 0.303269 0.23343 0.815113 0.619052 1 Na+ 192.6 7.6 545.7 115.1 0.8 15/02/2008 ‐ 18/02/2008 CS 98 18.77 3.48 56.92 10.56 0.3 'Cd' 0.479114 0.632241 0.556018 0.610477 0.077634 0.234099 0.236671 1 Metals group 1: Mn, Al, Ca, Zn and Cu + 18/02/2008 ‐ 22/02/2008 CS 99 19.62 3.09 55.12 8.67 0.4 NH4 180.3 2.3 1283.4 230.5 0.8 'Ni' 0.467278 0.277118 0.519433 0.518286 0.570319 0.376607 0.673797 0.214547 1 22/02/2008 ‐ 25/02/2008 CS 100 6.89 1.46 7.92 1.68 0.9 K+ 17.8 4.4 72.0 11.2 2.1 25/02/2008 ‐ 29/02/2008 CS 101 14.66 2.31 23.25 3.67 0.6 'Fe' 0.585341 0.153648 0.578838 0.294371 0.764036 0.453789 0.770506 0.193671 0.792417 1 Metals group 2: Pb, Fe, Zn, Cr, V and Ni 2+ 29/02/2008 ‐ 03/03/2008 CS 102 7.60 1.59 8.09 1.69 0.9 0.2413395 0.39485 0.077904 0.138542 0.23715 0.297161 0.37679 0.190292 0.203958 0.154524 1 Mg 24.7 0.7 83.0 16.5 1.3 'Co' 03/03/2008 ‐ 07/03/2008 CS 103 12.66 2.07 10.52 1.72 1.2 2+ 'Si' 0.088318 0.985567 0.240818 0.363313 0.113006 0.416538 0.302881 0.624928 0.272378 0.139621 0.399114 1 Ca 24.2 0.5 203.1 27.7 2.1 07/03/2008 ‐ 10/03/2008 CS 104 9.43 1.95 7.72 1.60 1.2 4.5 'Mn' 0.790637 0.15137 0.552102 0.444396 0.48754 0.35832 0.538687 0.598169 0.310929 0.515927 0.129441 0.145858 1 F‐ 5.1 1.4 38.0 5.8 20.6 10/03/2008 ‐ 12/03/2008 CS 105 7.38 2.16 7.39 2.16 1.0 'Cr' 0.621391 0.388603 0.397813 0.559107 0.357375 0.212376 0.627996 10 0.42984 0.646623 0.53676 0.38948 0.386063 0.457636 1 Fe V NH4+ SO42‐ 2500 and Sulfate 14/03/2008 ‐ 17/03/2008 CS 106 13.12 2642.64 18.04 3633.63 070.7 4 Cl‐ 280.5 8.2 895.4 222.7 0.8 'Mg' 0.232902 0.455413 0.174042 0.301333 ‐0.05667 0.106949 0.081226 0.483095 0.045541 0.006756 0.235128 0.45839 0.245383 0.316819 1 17/03/2008 ‐ 21/03/2008 CS 107 12.64 1.97 17.24 2.68 0.7 )

3 ‐ 'V' 0.634542 0.330645 0.452045 0.441369 0.535494 0.361441 0.7343128 0.344603 0.738246 0.689316 0.284692 0.322461 0.5367 0.852219 0.153585 1 NO2 2.2 0.3 18.3 3.6 83.6 21/03/2008 ‐ 22/03/2008 CS 108 6.63 2.33 7.23 2.55 0.9 3.5 25/03/2008 ‐ 28/03/2008 CS 109 6.64 1.40 7.28 1.54 0.9 'Ca' 0.560806 0.092902 0.4665 0.308775 0.349865 0.27086 0.274921 0.523289 0.062596 0.351344 0.023421 0.084213 0.822568 0.118039 0.390396 0.168204 1 2000 Br‐ 0.7 0.0 2.7 0.7 29.8 28/03/2008 ‐ 31/03/2008 CS 110 13.06 2.85 9.44 2.06 1.4 'Cu' 0.553131 0.045672 0.461375 0.247732 0.556181 0.582647 0.5392046 0.373666 0.304987 0.573117 0.069321 0.030387 0.826511 0.126653 0.093015 0.341507 0.792079 1 3 NO ‐ 352.7 26.8 3846.1 577.5 0.8 31/03/2008 ‐ 04/04/2008 CS 111 16.99 2.65 24.31 3.79 0.7 (ng/m 3 'Ti' 0.665712 0.350603 0.482881 0.635132 0.245926 0.058165 0.452619 0.595687 0.571399 0.445139 0.242473 0.346711 0.529206 0.905029 0.330701 0.724367 0.226715 0.146349 1 04/04/2008 ‐ 07/04/2008 CS 112 7.95 1.72 8.40 1.82 0.9 4 ammonium SO 2‐ 415.9 63.7 2306.7 355.3 0.8 'Al' 0.696875 0.053848 0.529611 0.425183 0.364172 0.24508 0.428273 0.498886 0.198777 0.358673 0.10294 0.054946 0.804353 0.249836 0.210863 0.291082 0.71305 0.691324 0.337003 1 1500 4 07/04/2008 ‐ 11/04/2008 CS 113 6.42 1.02 11.77 1.86 0.5 2.5V ‐ 'Na+' 0.117547 0.379307 0.142014 0.216017 ‐0.17588 0.047633 ‐0.03636 0.365979 ‐0.06584 ‐0.10378 0.139097 0.387614 0.115536 0.1421 0.861196 0.025458 0.277221 0.045198 0.131567 0.171937 1 PO4 2.9 0.1 27.2 5.2 75.2 11/04/2008 ‐ 14/04/2008 CS 114 5.07 1.21 7.62 1.82 0.7 2 'NH4+' 0.2695572 0.087001 0.156369 ‐0.12217 0.692337 0.724765 0.651552 ‐0.01585 0.374627 0.622187 0.167404 0.081244 0.361944 0.035269 ‐0.16015 0.290681 0.295226 0.634344 ‐0.13031 0.294192 ‐0.14495 1 14/04/2008 ‐ 18/04/2008 CS 115 34.35 5.46 39.12 6.22 0.9 'K+' 0.126112 0.341242 0.187723 0.009283 0.363738 0.572569 0.438252 0.206922 0.212792 0.354533 0.271234 0.334808 0.294345 0.083259 0.398185 0.206631 0.379806 0.465212 ‐0.03995 0.245105 0.483308 0.589152 1 1000

Vanadium 0 'Mg2+' 1.50.09384 0.341122 0.102383 0.156386 ‐0.18367 0.019609 ‐0.06415 0.310103 ‐0.07818 ‐0.10268 0.167112 0.34745 0.100975 0.129702 0.90619 0.022566 0.28221 0.016791 0.119228 0.1102 0.92688 ‐0.15015 0.440197 1

'Ca2+' 0.311997 ‐0.02149 0.270824 0.204418 0.073894 0.019411 0.093766 0.227533 0.036954 0.161527 ‐0.06896 ‐0.02233 0.391556 0.025526 0.171692 0.086184 0.446616 0.382176 0.091139 0.342704 0.208052 0.154728 0.186112 0.257781 1 (

‐2 μ and

'F-' 0.167533 0.31457 0.164382 ‐0.03858 0.57214 0.589385 0.524474 0.157882 0.34781 0.47943 0.131828 0.313734 0.276253 0.068944 0.036544 0.296968 0.200611 0.430822 ‐0.05697 0.263452 0.055853 0.751819 0.668997 0.009077 0.032584 1 1 500 g/m SUMMARY 'Cl-' 0.09569 0.528538 0.166786 0.265114 ‐0.14369 0.136403 0.010236 0.482857 ‐0.03695 ‐0.06883 0.129665 0.533952 0.163616 0.207408 0.857133 0.069206 0.32791 0.074397 0.214607 0.158483 0.909415 ‐0.16876 0.415129 0.854279 0.151303 0.039084 1 ‐4

'NO2-' ‐0.50.08839 ‐0.11804 ‐0.09541 0.027287 ‐0.16861 ‐0.19458 ‐0.09395Iron ‐0.09406 ‐0.10341 ‐0.17864 ‐0.16268 ‐0.11435 ‐0.13371 ‐0.10703 ‐0.00322 ‐0.15874 ‐0.16143 ‐0.16138 ‐0.07135 ‐0.00714 0.125608 ‐0.14139 ‐0.02624 0.060604 ‐0.09694 ‐0.13498 0.072617 1 3 'Br-' ‐0.07068 0.210232 ‐0.12793 ‐0.10273 ‐0.15399 0.01063 ‐0.11604 0.092246 ‐0.15776 ‐0.21421 0.035105 0.19402 ‐0.12678 ‐0.04887 0.333629 ‐0.12638 0.067072 ‐0.13141 0.010157 ‐0.14182 0.312179 ‐0.2444 0.016403 0.339952 ‐0.06556 ‐0.19495 0.468542 ‐0.09346 1 ) ‐6 0 'NO3-' 0.2523010 0.128974 0.126556 ‐0.09314 0.696075 0.718548 0.647218 0.031661 0.37066 0.608214 0.097799 0.126961 0.432451 0.064144 ‐0.04553 0.320525 0.370575 0.665114 ‐0.09916 0.315276 ‐0.06248 0.925931 0.616035 ‐0.06217 0.24053 0.766362 ‐0.05819 ‐0.12766 ‐0.24751 1 The majority of the PM2.5‐0.1 fraction of aerosols at this 'SO42-' 0.374980‐0.06528 0.5 0.217703 ‐ 10.0988 0.582905 1.5 0.484083 2 0.524122 CS‐0.09423 23 CS 0.338544 27 CS 0.540211 31 CS0.178819 35 CS‐0.06283 40 0.274921 CS 44‐ CS0.01049 48‐ CS0.08866 52 0.253556 CS 56 0.245646 CS 60 0.517141 CS 64‐0.16705 CS 68 0.336356 CS 72‐0.01981 CS 770.849678 CS 810.554574 CS 85‐0.03421 CS 89 0.186332 CS 93 0.675336 CS 97‐0.15619 CS 101‐0.09941 CS 105‐0.21701 CS 1090.725635 CS 113 1 'PO4-' 0.242535 0.269299 0.283227 0.182931Ni 0.428495 0.384533 0.44985 0.213125 0.442087 0.463283 0.20408 0.269642 0.36569 0.289755 0.054427 0.516554 0.251055 0.364675 0.203811 0.273059 ‐0.06954 0.435718 0.388114 ‐0.03469 0.085793 0.55351 ‐0.00998 ‐0.18466 ‐0.19474 0.492036 0.377003 1 mid‐harbour site is from an anthropogenic, combustion Orthogonally rotated principal components (PCA+Varimax) are shown below left. Analysis performed on The dimension of the dataset is reduced from 16 variables to 4 ambient levels measured (ng/m3) using 16 variables. Four principal components (eigenvalues >1) explain principal components. The Scores (below left) reflect how values related source. The site is located in a predominantly 85.14% of variance in data set. Predicted sample scores for each component are shown below right. The of variables relate to each component. Performing multiple linear marine environment on an island in the middle of the Components are identified as secondary aerosols (SIA), sea salt, a specific shipping/vehicles source and re‐ regression using component scores and ambient PM mass suspended crustal/construction materials. The percent variance explained by each component in brackets. provides an estimate of contribution of each component to shipping lane, so vehicle‐related emissions are not

0.6 10 ambient PM levels (figure below) expected to dominate to the same extent as in an urban 0.4 CS 98 70.00 SIA 5 0.2 CS 63 SIA CONTRIBUTION TO AMBIENT PM MASS: location. The location is influenced by industrial activities 0 (22%) 0 60.00 -0.2 (57%) -0.4 -5 around Cork harbour. Power plants, production plants, Zn Pb Ni Fe Mn Cr V Al Na+NH4+K+Mg2+Ca2+ Cl- NO3-SO42- 0 10 20 30 40 50 60 70 80 90 50.00 0.6 6 collected waste incineration, home heating and shipping emissions 4 0.4 Sea CS 58 2 40.00

0.2 mass salt 0 Crustal/re‐ are all likely to contribute to secondary inorganic aerosol

0 to

-2 (21%) 30.00 Sea salt suspension -0.2 -4 Vehicles, Zn Pb Ni Fe Mn Cr V Al Na+NH4+K+Mg2+Ca2+ Cl- NO3-SO42- 0 10 20 30 40 50 60 70 80 90 (21%) ships, etc. (21%) formation. Shipping emissions are also likely to contribute 0.6 15 Industry/ 20.00 (Cr, V, Ni) 0.4 10 CS 92 to the levels of heavy metals in ambient aerosols. For vehicles/ CS 88 0.2 5 CS 97 contribution source

CS 63 10.00 ships % 0 0 (1%) example, Vanadium levels increase at weekends relative -0.2 (24%) -5 Zn Pb Ni Fe Mn Cr V Al Na+NH4+K+Mg2+Ca2+ Cl- NO3-SO42- 0 10 20 30 40 50 60 70 80 90 0.00 to midweek samples. This may be due to weekend arrivals 0.6 8 CS 98 The main contributor to ambient PM mass are secondary aerosols, Crustal/ 6 0.4 CS 63 sea salt and suspended crustal material, which is also associated constr. 4 CS 89 of passenger ferries and high tonnage cargo ships 0.2 2 0 mat. with construction activities. The anthropogenic input of heavy 0 berthing a few hundred metres to the South West of the -0.2 -2 Zn Pb Ni Fe Mn Cr V Al Na+NH4+K+Mg2+Ca2+ Cl- NO3-SO42- (19%) 0 10 20 30 40 50 60 70 80 90 metals is clearly present, but that source accounts for a small fraction of the ambient PM mass. However, It may have a island and cruise ships berthing in cruise terminal significant contribution to particle counts and toxicity. opposite the receptor site. Acknowledgements References

Project ELIPSE is funded by; Project ELIPSE is supported by; [1] Finlayson‐Pitts, B. J.; Pitts, J. N., Jr. Chemistry of the Upper •National Institute for Public Health and Environment (RIVM), Netherlands. and Lower Atmosphere; Academic Press: New York, 2000. Environmental Protection Agency –Ireland (EPA). • School of Earth Science Cardiff University. [2] “Air pollution from ships”. (European Environmental Bureau, Swedish NGO Secretariat on Acid Rain). 2004. •. Cork City Council. [3] World Health Organisation 2004; Health Aspects of Air •Irish Naval Services. Pollution : Report on a WHO working group meeting, Bonn, Germany: January 2004. Irish Council for Research for Science, (IRCSET). •Health Service Executive Ireland (HSE). •Irish National Meteorological Services (Met Eireann). [4] F. Mazzei et al. “Characterization of particulate matter sources in an urban environment”, Science of the Total Environment (2008), doi:10.1016/j.scitotenv.2008.03.008