1. Source apportionment for Thessaloniki, Greece Source apportionment for Thessaloniki, Greece a PMF approach and a CAMx approach Aristotle University of Thessaloniki, Greece Scientific Responsible: Prof. Melas D. Poupkou A., Liora N., Karagiannidis A., Markakis K., Giannaros T. APICE - Final Conference, 8th November 2012, Venice University of Western Macedonia, Greece Scientific Responsible: Prof. Bartzis J. D. Saraga, E. Tolis, K. Filiou

2. Thessaloniki’s monitoring campaign PMF results (UOWM) CAMx results (AUTH) Discussion - Main conclusions - Mitigation Measures in the Future - Future Emissions Presentation overview

3. sampling sites Thessaloniki city PORT CITY CENTER (TOWN HALL) PM2.5 sampling at two sites in Thessaloniki

4. PORT

5. CITY CENTER (TOWN HALL)

6. Monitoring campaign schedule SCHEDULLED CANCELLED NEW DATES 1 st period: 14/6/2011- 21/12/2011 2 nd period: 14/2/2012-22/5/2012 322 samples in total

7. 24-hour PM2.5 samples collected on quartz fiber filters using low volume samplers

8. Source apportionment study for Thessaloniki PMF model application results from 1 st period

9. Source apportionment study for Thessaloniki PMF model application Positive Matrix Factorization (PMF) model a widely used receptor model based on factor analysis which provides a flexible modeling approach using a set of data at a receptor site, to indentify the unknown sources and estimate their contribution 2 Selected sites: port & city center (Town hall) period: selected days from June-July-August & November- December 2011 PMF model analysis for one- year data (June 2011 to May 2012) IN PROGRESS ? ? ? Samples (n>50) at receptor site Source 1 Source 2Source n

10. Source apportionment by PMF model Chemical species data used for PMF analysis: 7 (out of 27 measured) PAHs:, Benzo[b]fluoranthene, Benzo[k]fluoranthene, Benzo[e]pyrene, Benzo[a]pyrene, Indeno[cd]pyrene, Dibenzo[a,h]anthracene, Benzo[ghi]perylene. Lighter PAHS were excluded from the analysis because of their volatility 4 (out of 9 measured) ions: NO 3 -, SO 4 2-, Na +, NH 4 + Cl - and Na+ were excluded/ set as weak species respectively because of their large analytical errors. K+, Mg+, Ca2+ ions were excluded as their pair elemental species were used in the analysis (to avoid double counting mass) 13 Metals: Pb, Ni, Cu, V, Mn, Cr, Zn, Mg, K, Ti, Fe, Ca, Al Organic & Elemental carbon: OC, EC. experience obtained from the “Intercomparison source apportionment analysis on Marseille data " was used

11. PMF results Sampling site: Thessaloniki’s port combustion /central heating mixed: Vehicles/Anthropogenic Nitrates/Sulphates Mixed marine origin: sea /fuel oil /ships emissions mineral/ industrial mixed: Crustal/road dust/Incineration? → 5 groups of sources identified

12. PMF resultsSampling site: Thessaloniki’s port combustions/central heating source: elevated during cold period

13. PMF results Sampling site: Thessaloniki’s city center (Town Hall ) → 4 groups of sources identified combustion /central heating mixed: Crustal/ road dust mixed: nitrates /sulphates, anthropogenic Industrial Mineral/Industrial Possibly marine source included

14. PMF results Sampling site: Thessaloniki’s city center (Town Hall ) combustions/central heating source: elevated during cold period mixed source: nitrates /sulphates, anthropogenic, Industrial/ ships emissions: elevated during warm season

15. PMF results Sampling site: Thessaloniki’s port Sampling site: Thessaloniki’s city center (Town Hall) For the examined period: crustal/road dust source + combustions/central heating source: similar contributions to PM2.5 for both sites (appr.30%) secondary aerosol/vehicles/anthropogenic source contribution: elevated at city center area (51%) mixed sea origin + fuel combustion/ships emissions source contribute at the port area

16. Source apportionment study for Thessaloniki CAMx model application

17. Modeling System Set-up CAMx (version 5.3) simulates the Emission, Dispersion, Chemical reaction and Removal of pollutants in the troposphere on three-dimensional grid(s). Meteorology from the application of the meteorological model WRF (version 3.2.1) WRF-CAMx runs for the 2011 SUMMER PERIOD and the winter period 15 NOV TO 15 DEC 2011. Chemical Boundary Conditions Gaseous and Particulate Chemical BCs for the Balkan domain taken from the global modeling system IFS-MOZART (within FP7 EU project MACC). Balkan domain 10km resolution Thessaloniki domain 2km resolution

18. Emission Sources and PM Species Apportioned for Thessaloniki i.Maritime/Harbor activities (e.g. ships, loading/unloading of goods, vehicles/machineries) ii.Road transport iii.Industries iv.Central heating v.Windblown Dust vi.Biogenic NMVOCs vii.Left over sources (e.g. industrial and construction machineries, waste treatment, agriculture, solvent use, distribution of fuels). i.Sulfate (SO4) ii.Particulate nitrate (NO3) iii.Ammonium (NH4) iv.Secondary organic aerosol (SOA) v.Elemental carbon (EC) vi.Primary organic aerosol (POA) vii.Crustal PM viii.Other PM  The pollution transported to Thessaloniki from emission sources OUTSIDE the study domain will NOT be examined in this presentation.

19. Emission Inventory for the Maritime and Harbor Activities Emissions (tn/yr)CONOxSOxNMVOCsNH3PM10PM2.5 Passenger ships60.6736.8010.3812.730.0091.62 Cargo ships881.027022.234537.84113.920.904220.79 Tugs 2.1310.10 0.44 0.390.0040.39 Inland waterways26.7872.87-9.580.0117.597.15 Fishing Boats315.753738.86118.2857.371.30157.72 Harbor Operations (loading, unloading, pilling) -----37.25.64 Vehicles operating in the port----- 0.1810.043 Total1286.3510880.864666.93193.992.23325.56293.36 Most important activities in terms of emissions IN OR NEAR THE PORT:  PM2.5: Ship Hotelling (Cargo ships).  PM10: In-port Processes (loading, unloading and pilling of goods/materials).  SOx, NOx: Ship Maneuvering (Cargo ships); NOx ship hotelling emissions are comparable.  CO, NMVOCs: Ship Hotelling (Ferries). Emissions for the THESSALONIKI STUDY AREA (Reference year 2010)

20. Source Apportionment for PM10 / PM2.5 Port (Summer 2011)  Road transport: Highest contribution to PM10 and PM2.5 mean concentrations.  Maritime/Harbor activities:  Moderate contribution to PM10 (14%)  Small contribution to PM2.5 (6%) despite the emission contribution being ~35% for PM10 and ~15% for PM2.5.

21. Source Apportionment for PM10 / PM2.5 Port (15 Nov – 15 Dec 2011)  Road transport and Central heating: Equal contribution to PM10 levels (~30%).  Central heating: Highest contribution to PM2.5 levels.  Maritime/Harbor activities: Small contribution to PM10 and PM2.5. ~20% for PM10 emissions~10% for PM2.5 emissions

22. Source Apportionment for PM10 / PM2.5 City Hall  The contribution of the Maritime and Harbor activities is very small.

23. Maps of % Contribution to Mean PM2.5 Levels (Summer 2011) Biogenic Dust Left Over Maritime/Harbor IndustriesRoad Transport  Maritime/ harbor contribution over sea:  PM10: up to 50%  PM2.5: between 50% to 75%

24. Maps of % Contribution to Mean PM2.5 Levels (15 Nov - 15 Dec 2011) Dust Biogenic Central Heating Road Transport MaritimeIndustries Left Over  Maritime/harbor contribution to PM10 and PM2.5 over sea: up to 20%

25. 25 CONOxSO2NMVOCsNH3PM10PM2.5 Passenger ships 35.22%25.93%-49.42%33.63%19.21%-6.06% Cargo ships 29.37%40.73%-66.56%40.56%37.72%-63.92% Inland Waterways 2168.66%2142.43%-2152.89% 2163.64%2141.1% Fishing boats -35% Harbour operations (loading, unloading, pilling) -----78.01%77.82% Total emissions 58.48%28.80%-65.71%122.20%5.82%9.42%-1.23% % Difference between present time (2010) and future time (2020) emissions Maritime/Harbor future emissions were calculated considering both the: 1.Port evolution (e.g. 6 th pier extension, construction of a marina) (activity data provided by the Thessaloniki Port Authority SA) 2.Future normative framework according to which the sulfur content in ship fuels should be reduced to 0.50% m/m during cruising mode (sulfur content during maneuvering (in Greece) and hotelling mode is 0.1 % m/m). With a View to the Future…..

26. 26 Mitigation Measures in the Future 1.Cold ironing (zero ship hotelling emissions). 2.Use of chemical wetting agents to control the storage pile emissions (-90% of piling emissions). CONOxSO 2 NMVOCsNH3PM10PM2.5 -4.72%-1.46%-1.68%-4.64%0.01%-23.19%-9.00% % Changes in maritime/harbor future time emissions due to mitigation measures OVER THE WHOLE STUDY DOMAIN CONOxSO 2 NMVOCsNH3PM10PM2.5 -79.72%-45.60%-15.46%-81.51%0.00%-49.74%-52.28% % Changes in maritime/harbor future time emissions due to mitigation measures NEAR and IN THE PORT

27. PORT  CAMx: A) Moderate to small contribution to PM10 (~15%) and PM2.5 (~5%) in summer, B) Small contribution to PM10 (8%) and PM2.5 (3%) in winter.  PMF: contribution to PM2.5 (~22%) CITY HALL  PMF & CAMx: Very small contribution to PM2.5 (<5%) both during summer and winter. Existing discrepancies because of: Two different approaches that identify emission sources that partly match CAMx Maritime/Harbor sector = Ships + (un)Loading of goods + Vehicles/Machineries (possible underestimation of emissions) PMF Marine sector = Ships + Sea Salt (possible overestimation due to the identification of contribution from sources other than ships) OVER THE SEA (CAMx results)  High contribution in summer: Up to 50% for PM10 and more than 50% (up to 75%) for PM2.5.  Moderate contribution in winter: Up to 20% for PM10 and PM2.5. 27 Conclusions – Contribution to PM levels

28. 1.In the year 2020, projected maritime/harbor emissions show:  Small increase in PM10 (~ +10%)  Very small decrease in PM2.5 (~ -1.2%)  Important decrease in SO2 (~ -65%)  Moderate to important increases in CO, NOx, NMVOCs. 2.Mitigation measures like Cold Ironing and the use of Chemical Wetting agents to control the storage pile emissions are expected to decrease by:  - 50% PM10 and PM2.5 emissions in and near the port area  -23% PM10 and -9% PM2.5 over the whole Thessaloniki study domain. 28 Conclusions - Future Emissions