Environmental linkage of in-port emissions of PM, their chemical analysis and health effects in Cork Harbour, Ireland

I. P. O’Connor*, A. Allanic, S. Hellebust, D. Healy, R. Healy, C. Jordan, J. Wenger and J. R. Sodeau Centre for Research into Atmospheric Chemistry, Department of Chemistry, University College Cork, Cork, Ireland. *e mail : [email protected] Introduction The chemical/biological composition of particulateparticulate mattermatter (PM) in aerosols can be complex and varies spatially – Cork Harbour between continental and marine environments [1]. Sulfur dioxide is a primary inorganic pollutant that undergoes gas to particle conversion (heterogeneous reactions) and can take part in gas-phase (homogeneous) reactions to form Tivoli Docks secondary inorganic pollutants. These secondary pollutants formed in the atmosphere include acidic sulfate aerosols. Acidic aerosols including bisulfate and sulfate aerosols can react with gaseous ammonia to form Cork City ammonium salt [2]. Hence aerosol acidities are known to be lower in atmospheric regions where ready neutralisation of sulfates by reaction with ammonia occurs [3]. Marino Point Passage West Figure 1 Figure 2 Satellite image Relative 27,000 ppm of ship stack contributions of 10 ppm emissions, sulfur made from Rushbrooke Cobh showing “Ship automobiles and Tracks”. sea-going Haulbowline vessels. Ringaskiddy Whitegate

Ships make significant contributions to the pollution inventories of SO2, CO2, NOx, organic compounds, and PM (especially PM2.5 – fine particulates). Marine residual fuel oil, the residual from crude oil refinement, typically contains sulfur up to 3.5% and vanadium 0.02%. It is estimated that by 2010 emissions from ships will equal three- Crosshaven quarters of the EU total for sulfur [4]. Ships burning the residual fuel are more likely to produce cloud condensing Roches Point nuclei and produce “ship tracks” (Fig. 1). Figure 3 Map of Cork Harbour – showing in-port facilities and monitoring sites (red and green) Sampling Site & Equipment Methodology Polyurethane foam used Haulbowline Project ELIPSE to collect large Island Site amounts of The Environmental Linkage of In-Port Shipping PM (HNB) Emissions project is a wide-ranging ambient monitoring Chemical Analysis (mg) study. The main aims of this project are to identify and apportion pollution sources in the Cork Harbour region. Total Metals by ICP- OES (Perkin & Elmer Optima 2000 series – Phase I – Collection and chemical characterisation of inorganic UV/Vis detector). Figure4 Mid-harbour monitoring site. Figure 5 Particulate collection system . component of PM at Haulbowline (HNB) and Tivoli ª Extraction by microwave acid Chem Vol Model 2400 High Volume Cascade Impactor docks (TP) digestion (HNO3: HF). Phase II – Source apportionment using various methods The collection instrument was set up as follows; including receptor modelling Soluble Inorganic Ions - IC (Dionex ICS 2000) A two stage configuration mode with two Particular attention will be given to assessing acceleration platforms for PM10 – 2.5 and PM 2.5 – 0.1 correlations between the sulfate ions, nitrate ions and ªAqueous extraction (shaking & collections was used. soluble metal indicators with the toxicological endpoints. sonication). 900 L min-1 Total mass loading of ambient PM10-2.5 & 2.5-0.1 by gravimetric Project TACCo 16.3 mg 22.1 mg The Toxicological Analysis and Chemical Correlation for analysis. PM2.5 in transit to Cobh a one-year 42.4 desk % 57.6 study % will provide a toxicological assessment of the airborne particulate matter (PM2.5) seasonally present in Cork Harbour and in transit to Cobh. Source Apportionment Air passed through 32 cm circular nozzles before Receptor modeling techniques will be performed PM was trapped on polyurethane collection Phase I - Identify the most toxic aerosol components substrate on the platforms. in order to identify and apportion pollution sources and will be compared to those previously found for in the Cork Harbour region. A high capacity vacuum pump maintained a samples collected in two Cork City sites (city centre & in- constant flowrate of 900 litres per minute (48m3.hr - Refer to poster – Ambient levels of PM2.5 in Cork 1). port). Harbour, Ireland. T02A046P Tuesday poster session Results - Sampling Campaign at Haulbowline (HNB) (2006- 2007) Future Work A short field campaign has been undertaken at Aerosol Acidity – Ammonium to Sulfate Ratio for Cork Harbour (HNB) Tivoli Docks using an ATOFMS (Aerosol Time- Of-Flight Mass Spectrometer TSI 3800).

6.0

5.0 ] 2- 4 4.0

3.0 ]/ [SO + 4

2.0 [NH 1.0 Figure 6 . Positive and Negative Mass Spectra from a particle analysed at Tivoli docks. Sea-salt particles were readily collected, characterised 0.0 by Na, Mg, Ca & Cl content.

-1.0 May07 June July August September October November December January08 February March April 18/05 /07 -21/05 /07 The ATOFMS will provide information on the Figure5. An indication of the degree of neutralisation of aerosols at Haulbowline, Cork composition of single particles as a function of The ammonium to sulfate ratio is an index used to identify the degree of neutralisation size range. + 2- of acid sulfate in aerosols. Ammonium Rich particles (2 ≥ [NH4 ]/ [SO4 ] ≥ 1.5) are mostly dominant in air at Haulbowline but with significant exceptions at times (Fig. 5 )

Aerosol Acidity – Strong Acidity ( [ H+ ] per m3 ) of air for Cork Harbour (HNB)

) 7.00 -3 6.50

l.m 6.00 o 5.50 Figure 7. Size distribution and composition of a single particle. 5.00

] (nm 4.50 N N N N N N N N N NN N N N NN N NN N N N N NN N N NN N N N N N NN Further intensive field campaigns will take + 4.00 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e place at harbour sites during 2008 & 2009. 3.50 u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u

y [H These will include chemical analysis of PM2.5 3.00 t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r for inorganics, organics and metals.

idit 2.50 a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a 2.00 l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l And 1.50 i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i Real-time aerosol analysis: ng Ac 1.00 s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s o 0.50 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e ª Particulate sulphate analyser: using UV

Str 0.00 d d d d d d d d d d d d d d d d d d d d dd d d d d d d d d dd d d d d 1 fluorescence after catalytic conversion to May June July August September October November December January February March April Figure 6 . An indication of the degree of strong acidity of aerosols at Haulbowline, Cork SO2. ª Elemental & Organic Carbon analyser The strong acidity in terms of nmol of H+ per m3 of air can be a useful indicator of the (EC/OC): collection onto quartz filters and absolute acidity of atmospheric aerosols. It is estimated using an ionic balance of the measurement by NDIR detector system. inorganic ionic species. Using this index it was found that acidic aerosols were associated ª Gas phase monitoring of SO2 using UV with the summer season with a greater degree of variation existing during winter (Fig. 6). fluorescence.

Acknowledgements Project ELIPSE is supported by; References • National Institute for Public Health and Environment (RIVM), Netherlands. Project ELIPSE is funded by; • School of Earth Science Cardiff University. [1] Finlayson-Pitts, B. J.; Pitts, J. N., Jr. Chemistry of the Upper and Lower Atmosphere; Academic Press: New • Port of Cork. York, 2000. Environmental Protection Agency – Ireland (EPA). [2]Spengler, J. D. et al. Acid air and health. Environmental Science and Techbnology, 1990, 24, 946 – 956. • Irish Naval Services. Cork City Council. • Health Service Executive Ireland (HSE). [3]Brook, J. R. et al. Temporal and spatial relationships in fine particle strong acidity, sulphate, PM10, and PM2.5 Irish Council for Research for Science, (IRCSET). across multiple Canadian locations. Atmospheric Environment, 1997, 31, (24). • Irish National Meteorological Services (Met Eireann). [4] “Air pollution from ships”. (European Environmental Bureau, Swedish NGO Secretariat on Acid Rain). 2004.