Air Pollution Sources and Impacts

1. Air Pollution Sources and Impacts

2. Content • Historical Background • Sulphur oxides • Nitrogen oxides • Particulate matter • Ozone depleting substances • MARPOL Annex VI: An overview

3. Activities Pollutants Immediate effects Impacts Transport Human health PM concentration Power Production Acidicdeposits Environment Residences Εutrophication Materials deterioration Agriculture Agricultural cultivation Ozone concentration Industry

4. Historical Background • Prior to the industrial revolution • After the industrial revolution (Engraving showing a foundry in Saar, Germany, 1876) «Αs I was moving far away from the asphyxiating air of Rome and the soot of stacks dispersing poisonous gases around, I felt my mood changing» Senekas, 61 A.C.

5. Historical Background Athens, Greece Las Vegas, USA

6. Sulphur Oxides (SOx) • Properties: Gas, colorless and odorless in low concentrations, but with irritating odor in high • concentrations • Sources:Power plants, oil refineries, chemical plants, paper industry, ships’ main and auxiliary • engines • Sulphur content in crude oil and fuel oils • a) Safety (installation and piping corrosion, poison potential) • b) Operation (fluidized beds of catalysts may be contaminated from the presence of sulphur • compounds) • c) Environment (SOx emissions)

7. Sulphur Oxides (SOx) • Impacts to human health • Short term exposure in high concentrations, might cause bronchoconstriction and increased • asthma symptoms. • Long term exposure might cause serious respiratory problems and deteriorate existing • cardiovascular illnesses London, 1952 4.000 people were fatally exposed to high SOx and smoke concentrations in London (1952)

8. Sulphur Oxides (SOx) • Environmental impacts • Acid rain • In the 70s, more than 18,000 lakes in Swedenwere found with acidity exceeding the natural • limits, and in half of them fish populations had dramatically reduced • The same phenomenon occurred in about 3.000 lakes in US • The transformation of the waters of a lake to acidic does not take place instantaneously but rather • in a period of many years or decades. A forest in Jizera, Czech Republic

9. Sulphur Oxides (SOx) • Acid rain formation mechanism • H2SO4 and HNO3 are formed as a result of the reaction between the water and sulphur as well as • nitrogen oxides with the sun radiation and oxygen as catalysts • Normal rain is slightly acidic (pH 5,5) due to CO2 dissolution and H2CO3 formation • Most lakes have apH ranging from 6 to 8. Values as low as 4.3 have been reported in several • lakes facing acid rain problems

10. Sulphur Oxides (SOx) • Impacts of acid rain • Destruction of sensitive soils, trees and vegetation of forests in high altitudes • Deterioration of materials and paints. Irreversible failures to buildings and monuments that • constitute elements of cultural heritage • Impacts to water dependent ecosystems Forest areas (%) in Europe receiving acid rain

11. Nitrogen Oxides (ΝΟx) • NOx formation in ship’s engines • Very complex mechanism of formation, hundreds of chemical reactions occur • Main source of nitrogen is air combustion • Higher temperatures in cylinders lead to increase NOx emissions • 95% is ΝΟ and about 5% NO2

12. Nitrogen Oxides (ΝΟx) • Impacts to human health • They react with hemoglobin producing inert compounds including methemoglobin hampering the oxygenation of tissues causing tachycardia, high blood pressure, and arrhythmia • >15 μg/m3, irritation of the eyes >25 μg/m3 dyspnea, asthma crisis • > 150 – 200 μg/m3 pulmonary edema

13. Nitrogen Oxides (ΝΟx) Secondary ozone formation ΝΟx + VOCs + sun radiation Ο3 + Photochemical pollution Photochemical smog occurs in sunny periods with high temperatures, low moisture and relatively high levels of nitrogen oxides and hydrocarbons.

14. Particulate matter (PM) • Particles produced during combustion or as secondary products in the atmosphere, that might shift for very long periods far from their point of source. PM 10 PM 2.5 (10 μm) (2,5 μm) Human hair (70 μm diameter)

15. Particulate matter (PM) • Their chemical composition depends on fuel quality. They invariably consist of soot, hydrocarbons, ash, metals (vanadium, nickel, zinc), sulphur and nitrate compounds • The smaller the size of the particles, the deeper penetrate into the human respiratory system.

16. Particulate matter (PM) • Ash significantly reducedfor low sulphur fuel oils (< 1% m/m). • Soot and sulfates are directly depended on the sulfur content.

17. Ozone Depleting Substances(ODS) • Lifetime of gases in atmosphere from several years (HCFCs) until a century (Freon 12). • The ozone layer is going to be back to the level it was before 1980 until 2050. • If ozone was compressed in normal conditions of temperature and pressure, it would have been less than 5 mm thick. • In September 2007, the extent of ozone hole was 24 millionkm2(almost as North America), 18% smaller in relation to 2006.

18. Ships’ engines emissions Exhaust gases (> 99,7%) 75,8% Ν2 13,0% Ο2 5,2% CO2 5,3% H2O Air pollutants (< 0,3%) ΝΟx 0,17% (1500 ppm) SOx 0,15% (800 ppm) HC 0,02% (180 ppm) CO 0,07% (80 ppm) Air 8.5 kgr/KWh 79% Ν2 21% Ο2 Fuel Oil 180 gr/KWh (3,6% S) Lube Oil 1 gr/KWh 97.5% HC 2% Ca 0,5% S

19. An overview to MARPOL, Annex VI

20. Sulphur Oxides (SOx) • Prevention Measures • Μaximum sulphur content (% m/m) • 4,5% before 1 January 2012 • 3,5% after 1 January 2012 • 0,5% after 1 January 2020

21. Sulphur Oxides (SOx) • Prevention Measures • Maximum sulfur content in (S) ECA (North Sea, Baltic Sea, North American) • - 1.0% until 31 December 2014 • - 0.1% after 1 January 2015

22. Sulphur oxides (SOx) • Prevention Measures • Bunker Delivery Note (ΒDN) • Retention for at least 3 years • Must contain information: • Name - Ship ΙΜΟ number • Bunkering port • Date of bunkering • Supplier’s contacts • Name of product • Quantity (in metric tones) • Density at 15° C • Sulphur content (% per weight) • Supplier’s statement about the sulfur content in fuel, that do not contain inorganic acids and other substances which might put at risk the safety of the ship.

23. Sulphur oxides (SOx) • Prevention Measures – Treatment systems

24. Nitrogen oxides (ΝΟx) Prevention measures

25. Nitrogen oxides (ΝΟx) Prevention measures • Tier 3 • Engines fitted in ships constructed after 1 January 2016 and operate within an Emission Control Area (N) (ΕCA). • Emissions must not exceed the following values: • 3,44 g/kWh with n < 130 rpm • 9,0 x n -0,2 g/kWh 130 ≤ n < 2000 rpm • 2,0 g/kWh n ≥ 2000 rpm • If the ship operates outsideECAthen the requirements emissions of Tier II are applicable.

26. Nitrogen oxides (ΝΟx) Prevention measures • NOxemissions by engines of ships constructed from 1/1/1990 –1/1/2020 • Every engine above 5.000 kW, and of displacement per cylinder equal to or greater than 90 liters, must comply to Tier I, under the condition that an Approved Method for this engine has been certified by the Administration of a member state. • Its implementation must not cause power reduction above 1.0%, and increase of specific fuel consumption above 2.0%. • No effect to the reliability or life cycle of the engine and the implementation cost should not be excessive.

27. Nitrogen oxides (ΝΟx) Prevention measures NOx Technical Code Every engine must: • be pre-certified (manufacturer – Class) • Technical File • Installation as approved– Initial Inspection • Annual inspections

28. Nitrogen oxides (ΝΟx) Emissions reduction methods Fuels treatment Engine Technologies Fuel Quality

29. Ozone Depleting Substances(ODS) Firefighting systems Ηalon 1211 Halon 1301 Halon 2402 Air conditioning – Cooling systems CFC-11 CFC-12 CFC – 113 CFC – 114, CFC- 115

30. Ozone Depleting Substances(ODS) • Prevention measures • Refrigerants Management Plan • Record Book • Periodical control of leaks • Use of ODS of low warming potential (greenhouse gases)

31. Thank you for your attention! Questions