Air Pollution from shipping - A case study. A long-term, intensive sampling campaign at multiple sites in and
around Cork harbour.
Env. Monitoring: General inventory of exposure levels, Long-term, continuous, Data taken at face value, Fewer
variables, continuous monitoring
Research : Seeks to answer specific questions, Intensive, i.e. expensive, In-depth data analysis, Many
parameters and selected marker variables. Quantification of sources
Particulate Matter = atmospheric aerosols, i.e. solid or liquid particles suspended in the atmosphere
PM10-2.5 Coarse (natural), PM2.5-0.1 Fine (anthr.), PM0.1 Ultrafine (anthr.)
What is PM made of?
Primary Inorganic species: Metals, insoluble minerals, ammonium.
Secondary Inorganic species : Sulfates and nitrates
Primary Organic species: Soot (Impure graphite), polar (e.g. alkanoic acids), and non polar organics (PAH,
alkanes…)
Secondary Organic species: mainly polar organics (multi-functional compounds)
+ Water
PM – sources and fates
Combustion: Diesel vehicles, Ship emissions, Construction, Biomass burning, Incineration, Power generation
Biogenic emissions: Plants (VOC), Agriculture
Resuspension: Rock weathering, wind-blown dust, construction, road dust
EU legislation PM10:
Daily max 50 ug/m3 , max 35 Annual exceedances of 40 ug/m3 from 1 January 2005
Daily max 50 ug/m3 , max 7 Annual exceedances of 20 ug/m3 from 1 January 2010
SO2 – sources and fates: Combustion (dependent on fuel type), biogenic emissions (e.g. dimethylsulfide). In
atmosphere leads to Sulfuric acid, Sulfates, Gas-to-particle conversion. Dry/wet deposition.
NOx – sources and fates: Combustion sources (N2 present in air). In atmosphere produces Ozone, Nitrates.
Dry/wet deposition
Ship emissions:
Can make a significant contribution to air pollution problems. Major sources of emissions of sulphur dioxide
(SO2) and nitrogen oxides (NOx), and also primary particulate matter (PM), which leads to:
acidification and eutrophication, formation of ground level ozone, health problems related to PM and NO2 ,
ozone.
harmful air toxics from ship exhaust can cause breathing problems, cancer and premature death for the people
living next to big harbours.
Harbours:
Urban areas with harbours, often in combination with petrochemical and energy intensive industries are
consequently the first areas to be exposed to ship emissions. ports are inter-modal knots (railway, road and
sea transport) variety of emission sources—trucks, train, loading/unloading activities. harbours emission
estimates is a difficult task. Quantifying harbours emissions is only one side of the air quality problems
presented in coastal urban areas. Other problems are caused by the relationship between primary pollutant
emissions and resulting air quality which is not straightforward. Air quality is affected not only by local
emissions but also by the interactions between these pollutants, their long-range transport in the atmosphere,
natural emissions and meteorological conditions.
Project objectives:
Establish PM Monitoring Programme at Selected In Port Site(s), Total Chemical Analysis – Inorganic & Organic
Physical Characterisation Study of Collected PM, Real Time Monitoring – EC/OC (elemental and organic
carbon) Splits & Sulphate. Development of Source and Partition Model
In other words: Determine the contribution from a specific, non-point source (shipping emissions) to
population exposure levels. Two options:
A) Eliminate other sources
B) Quantify all sources
WHERE TO SAMPLE?
1. Tivoli docks: Ro – Ro (roll on – roll off), Lo – Lo (lift on – lift off), Solid Bulk handling, Liquid Bulk
handling, Break Bulk and Passengers.
2. Haulbowline naval base: Ro – Ro, Solid Bulk, Liquid Bulk, Break Bulk, Near to cruise terminal, pfizer’s
jetty and ringaskiddy deep water port.
3. Roches point – marine background site.
Frequency of sampling, three objectives, three time resolutions:
1. Toxicology: 4 day time resolution. Large samples for exposure to cell cultures. Few samples required.
2. Source apportionment: higher time resolution (24 hours), large number of samples required.
Correlation of daily variation in PM load and chemical composition with Meteorological parameters.
3. Observation of shipping plumes and events: Very High time resolution (15 min).
Equipment:
1. High volume sampler – polyurethane foam substrate: High Volume Cascade Impactor. Collection of
PM onto polyurethane foam substrate. Sampler flow-rate: 900 Lmin-1. Size fractionation into PM10-2.5
and PM2.5- 0.1 by air flow impacting on substrate. Velocity of particles determines cut off point.
2. Other high volume sampler using filter media.
3. Continuous monitoring for observing plume signatures: Simultaneous occurrence of ‘brief’ peaks in
[SO2], [NO], EC/OC and PM number. WEATHER!
Chemical analysis: 22 metals (Inductively Coupled Plasma- optical emission spectroscopy), 12 ions (Ion
Chromatography), EC/OC (coninuous), SO2 (cont.) , SO42- (cont.), NOx (cont.), O3 (cont.). selection of elements
and ions: Source markers!!
Mass loading of inorganic ion & metal component of PM 2.5-0.1:
Inorganic ions and metals composed typically 58% of the mass of the PM 2.5-0.1 collected during the entire
winter sampling campaign. 45% of the mass of PM2.5-0.1 was inorganic ions. Metals accounted for 13% of the
mass of the fine fraction.
Mean ambient concentration of trace metals for Winter 2006/07:
Magnesium, calcium, zinc, silicon and iron most prominent components of PM 2.5-0.1. Lead, mercury, nickel,
chromium, titanium and vanadium present but in less significant quantities. Lead, nickel and vanadium are oil
soluble metals and are contaminants of bunker fuels.
Mean ambient concentration of inorganic ions for Winter 2006/07:
The mean ambient concentration of water soluble inorganic ions shows a high degree of variation between
ionic species. Sulfate, chloride and nitrate most prominent components of PM 2.5-0.1 having concentrations of
93.4 ng m-3, 87.0 ng m-3 and 85.5 ng m-3, respectively. Sodium and ammonium ions are also present in the fine
fraction in relatively significant concentrations.
High correlation coefficients were observed for:
Ca2+, Mg2+, Na+, Cl- suggesting a sea spray source
NH4+/ SO42- and NH4+/ NO3- suggesting a secondary sulfate/nitrate source
Zn and Pb and finally Fe with Ni or Pb suggesting anthropogenic sources.
Bivariate correlation coefficients between selected species in PM2.5 collected in Cork Harbour Ireland:
Mg
Mg
Ca
Zn
Si
Al
Fe
Pb
Ni
Na
Cl
NH4+
NO3-
SO42-
1.0000
Ca
0.6949
Zn
-0.6133 -0.2821
1.0000
Si
-0.0489
0.3755 -0.0088
1.0000
Al
0.1498
0.4310
0.2302
0.2519
1.0000
Fe
-0.4868
0.2688
0.4921
0.5192
0.2835
Pb
-0.6872 -0.1394
0.8264
0.1292
0.5089
0.7050
1.0000
Ni
-0.4310
0.3163
0.5247
0.4176
0.1806
0.9714
0.6713
Na
0.9896
0.6918 -0.5993 -0.0558
0.2405 -0.4616 -0.6443 -0.4302
1.0000
Cl
0.9631
0.7406 -0.5784
0.1202
0.3549 -0.3732 -0.5758 -0.3731
0.9804
NH4+
NO3-
-0.7931 -0.3594
0.8519
0.0100
0.3968
0.5984
0.9716
0.5527 -0.7446 -0.6950
1.0000
-0.6899 -0.0645
0.7561
0.2279
0.4612
0.7817
0.9816
0.7551 -0.6621 -0.5842
0.9272
1.0000
SO42-
-0.5353 -0.4565
0.8005 -0.2743
0.4724
0.1542
0.7683
0.1090 -0.4687 -0.4531
0.8492
0.6382
1.0000
1.0000
1.0000
1.0000
1.0000
Source apportionment: How to separate sulfate from ships from sulfate from power plants? In factor analysis
Source markers (e.g. Vanadium present in heavy fuel oil and bunker fuel used by ships) identify factors
(combined variables, or pollution profiles) as being attributable to specific sources, i.e. a certain amount of
sulfate variation should correlate with vanadium attributable to heavy fuel combustion.
What do we need to know?
Characteristic elements emitted
Emission source
Road transport
Motor vehicle emissions
Engine wear
Catalytic converters
Tyre wear
Road side dust
Br, Pb, Ba, Mn, Cl, Zn, V, Ni, Se, Sb, As
Fe, Al
Rare earths
Zn
EC, Al, Si, K, Ca, Ti, Fe, Zn
Industrial facilities
Bunker f uel and heavy oil combustion
Coal combustion
Ref ineries
Nonf errous smelters
V, Ni
Se, As, Cr, Co, Cu, Al, S, P, Ga
V
As, In (Ni smelting), Cu, Zn
Iron and steel mills
Pb
Plant producing Mn metal and Mn chemicals
Mn
Copper ref inery
Cu
Small combustion
Ref use incineration
Wood smoke
Meat charbroiling emissions
Zn, Sb, Cu, Cd, Hg, K, Pb
Ca, Na, K, Fe, Br, Cl, Cu, Zn
Na, Al, K, Sr, Ba, Cl
Mineral and materials processing
Mg, Al, K, Sc, Fe, Mn
Sea Spray
Na, Cl, S, K
Re-suspended soil
Si, V, Cr, Ca, Ti, Sr, Al, Mn, Sc