The chemical/biological composition of particulate matter (PM) in

aerosols can be complex and varies spatially – between continental and

marine environments [1]. One source of PM that contributes to air

pollution is that derived from ship emissions. Seagoing ships are not

subject to the stringent air quality legislation which is applied to land-

based transport. Ships make significant contributions to the pollution

inventories of SO2, CO2, NOx, organic compounds, and PM (especially

PM2.5 – fine particulates). The average sulfur content of marine heavy fuel

oil (“bunker fuel”) used in European waters is 27,000 ppm and it is

estimated that by 2010 emissions from ships will equal three-quarters of

the EU total for sulfur [2].

16.3 mg 22.1 mg12.2 mg

42.4 % 57.6 %

Project ELIPSE is funded by;

Environmental Protection Agency – Ireland (EPA).

Cork City Council.

Irish Council for Research for Science, (IRCSET).

Acknowledgements References

[1] Finlayson-Pitts, B. J.; Pitts, J. N., Jr. Chemistry of the Upper

and Lower Atmosphere; Academic Press: New York, 2000.

[2] “Air pollution from ships”. (European Environmental

Bureau, Swedish NGO Secretariat on Acid Rain). 2004.

Project ELIPSE is supported by;

• National Institute for Public Health and Environment (RIVM), Netherlands.

• School of Earth Science Cardiff University.

• Port of Cork.

• Irish Naval Services.

• Health Service Executive Ireland (HSE).

• Irish National Meteorological Services (Met Eireann).

Results - Sampling Campaign 2008 – Inorganic Ions, Aerosol Acidity & Metals.

Environmental linkage of in-port emissions of PM, their

chemical analysis and health effects in Cork Harbour,

IrelandI. P. O’Connor*, A. Allanic, S. Hellebust, Ivan Kourchev, D. Healy, Robert Healy, J. Wenger and J. R. Sodeau

Centre for Research into Atmospheric Chemistry, Department of Chemistry,

University College Cork, Cork, Ireland.

*e mail : i.p.oconnor@student.ucc.ie

Introduction Aims

Project ELIPSE is a wide-ranging ambient air

monitoring study. The main aim of this study is to assess

the contribution that a range of products associated with

marine diesel (bunker fuel) combustion in-port make to

the ambient air pollution of Cork City and Harbour.

Receptor modelling techniques will be performed in

order to identify and apportion pollution sources in the

Cork Harbour region. Chemical characterisation and

physico-toxicological assessment will identify the most

toxic aerosol components.

10 ppm

27,000 ppm

Figure 1. Ships use “Bunker Fuel” – high sulfur emissions

Figure 2. Satellite image of ship stack emissions, showing

“Ship Tracks”.

The ammonium to sulfate ratio is an index to identify

the degree of neutralisation of acid sulfate in aerosols.

Ammonium Rich particles (2 ≥ [NH4+]/ [SO4

2-] ≥ 1.5) are

mostly dominant in air at Tivoli Docks but with significant

exceptions at times (Fig5)

Figure5 . An indication of the degree of neutralisation of aerosols at Tivoli Docks, Cork

Figure 4. Comparison of concentration of major inorganic ions in Cork Harbour & City

Figure7 . Concentration of Ni & Vin ambient air at Mid-Harbour, Cork

Figure6 . Concentration of Ni & V in ambient air at Tivoli Docks, CorkFigure 8 . A Positive and Negative Mass Spectra from a particle

analysed at Tivoli docks

Ambient Air Concentration of Inorganic Ions in Cork Harbour

0.00

100.00

200.00

300.00

400.00

500.00

600.00

700.00

800.00

900.00

Winter - Mid-Harbour

(HNB)

Winter - Tivoli Docks

(TP)

Winter - City Centre

(OSR)

Summer - City Centre

(OSR)

Summer - Mid-Harbour

(HNB)

Sampling Period

Co

ncen

trati

on

(n

g/m

3)

Sulphate Nitrate Chloride Ammonium Sodium Potassium Magnesium Calcium

Aerosol Acidity of Cork Harbour - Tivoli Docks

-1.00

-0.50

0.00

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

07/09/2007 - 10/09/2007 24/09/2007 - 28/09/2007 12/10/2007 - 15/10/2007 29/10/2007 - 02/11/2007

Sampling Period

Am

mo

nia

to

Su

lph

ate

Rati

o

Fine particulate ions are us formed as secondary particles,

often origination as primary emissions or as primary

airborne particles from combustion sources. Sulphate

particles (SO42-), were found in highest concentration at

Tivoli Docks during the winter (Fig. 4)

The correlation between Nickel and Vanadium is stronger at Tivoli Docks compared

with Mid-Harbour(Fig.5&6). This could indicate the existence of one dominant source

of these trace metal particles, such as combustion of oil.

Ambient Air Concentrations of of Nickel & Vanadium - Tivoli Docks

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

1.60

1.80

2.00

07/09/2007 - 10/09/2007 25/09/2007 - 28/09/2007 12/10/2007 - 15/10/2007 29/10/2007 - 02/11/2007

Sampling Periods

Co

ncen

trati

on

(n

g/m

3) Ni V

The oil soluble metals vanadium (V), nickel (Ni) are found naturally in crude oil.

Fuels which are crude oil derivatives have different Nickel to Vanadium ratios

depending on the degree of refining undergone. This Nickel to Vanadium ratio is a

useful marker in the identification of particulate pollution from the combustion of

crude oil products such as the Bunker Fuel used by large ocean-going vessels.

Ambient Air Concentrations of of Nickel & Vanadium - Mid-Cork Harbour

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

07/09/2007 - 10/09/2007 25/09/2007 - 28/09/2007 12/10/2007 - 15/10/2007 29/10/2007 - 02/11/2007

Sampling Periods

Co

ncen

trati

on

(n

g/m

3)

Ni V

Future Work

A short field campaign has been undertaken at

Tivoli Docks using an ATOFMS (Aerosol Time-

Of-Flight Mass Spectrometer TSI 3800). Sea-salt

particles have readily collected, characterised by

Na, Mg, Ca and Cl content (Fig. 8)

The ATOFMS will allow for the identification

of different particle size range and information

on the composition of single particles.

Figure 9. Size distribution and composition of a single particle.

900 L min-1

High time resolution PM

collection using high volume

sampler (300-1200 L min-1)

with quartz fibre filter or

Polyurethane foam collection

substrate.

Sampling Campaign Cork Harbour – 2007 & 2008

Sampling Equipment

Tivoli Docks Real-time aerosol analysis:

Particulate sulphate analyser:

using UV fluorescence after

catalytic conversion to SO2.

Elemental & Organic Carbon

analyser (EC/OC): collection

onto quartz filters and

measurement by NDIR

detector system.

Gas phase monitoring of SO2

using UV fluorescence.

Haulbowline

•ATOFMS (Aerosol Time-Of-Flight

Mass Spectrometer TSI 3800)

instrument for the measurement of

aerodynamic size and chemical

composition of single particles.

NUMBERS of particles counted

•Particles are accelerated through an

aerodynamic lens and sized based

on their flight time between two

sizing lasers (532 nm)

•Upon leaving the sizing region,

particles are ionised using a UV

laser (266 nm) and the ions then

enter a bipolar time-of-flight mass

spectrometer

•A positive and a negative mass

spectrum is generated from EACH

particle

ATOFMS (Aerosol Time-Of-Flight Mass

Spectrometer TSI 3800)

Total Metals by ICP- OES (Perkin & Elmer Optima 2000 series – UV/Vis detector).

Extraction by microwave acid digestion (HNO3: HF).

Soluble Inorganic Ions - IC (Dionex ICS 2000)

Aqueous extraction (shaking & sonication).

Total mass loading of ambient PM 2.5-0.1 by gravimetric analysis.

Chemical Analysis

Cobh

Passage WestMarino Point

Haulbowline

Whitegate

Roches Point

Crosshaven

Ringaskiddy

Rushbrooke

Tivoli Docks

Monitoring Sites & In-Port Shipping Facilities

Roches Point

Tapered Element Oscillating

Microbalance (TEOM) system

for determination of real-time

mass loading of PM in ambient.

Collection of PM2.5 on quartz

fibre filters for chemical

analysis of metal and inorganic

ions.

Figure3. A satellite map showing location of monitoring sites & port facilities in Cork

Harbour