Ambient levels of PM2.5‐0.1 in Cork 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) Haulbowline 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.