1. Increased Biomass Burning due to the Economic Crisis in Greece and its Adverse Impact on Winter- time Air Quality in Thessaloniki Full Manuscript of this study is available on-line: Saffari et al., ES&T, 2013 Constantinos Sioutas, Sc.D. Fred Champion Professor of Environmental Engineering University of Southern California (USC) Los Angeles, CA, 90089 Web Site: www.usc.edu/aerosolwww.usc.edu/aerosol

3. Motivation Methodology Results Particle Mass Concentration Organic Carbon and Elemental Carbon Trace Elements and Metals Polycyclic Aromatic Hydrocarbons (PAHs) Organic Wood Smoke Tracers Redox Activity and Reactive Oxygen Species (ROS) measurement Conclusions Overview:

4. Motivations: Thessaloniki: 2 nd largest city in Greece One of the most polluted cities within the EU Change of Residential Heating Method due to the Economic Crisis: Increased fuel oil price (nearly tripling from 2010 to 2013) Wood and Biomass burning for residential heating instead of more expensive fuel oil

5. Motivation: Wood smoke particles Enriched with toxic and carcinogenic organic compounds (e.g. PAHs) Adverse health effects of exposure to wood smoke Pulmonary diseases (Levi et al., 2006) Increased blood pressure (McCracken et al., 2007) Increased inflammatory biomarkers (Barregard et al., 2006) Study Objectives The extent to which biomass burning has increased within the last two years in Thessaloniki Impact of biomass on Particulate Matter (PM) chemical composition and toxicity

6. Methodology: Sampling Protocol: Size Range of interest: PM2.5 Sampler: Low Volume Sampler Location: Municipality of Thessaloniki (Urban background- Eptapyrgion) Period: Feb-Mar 2012 and Jan-Feb 2013 Chemical and Toxicological Analyses: Organic and Elemental Carbon (EC/OC) Trace Elements and Metals (total and water soluble fraction) Polycyclic Aromatic Hydrocarbons (PAHs) Organic Biomass Tracers Oxidative Potential (Macrophage cell-based ROS activity)

7. Results: Particle Mass Reconstruction 30% increase in total PM2.5 in 2013 compared to 2012. 2-fold higher PM2.5 in the evening compared to morning (effect of increased evening-time residential heating) Remarkable increase of Organic Matter in the evening compared to Morning as well as 2013 compared to 2012 (Next Slide)

8. Results: Trace Elements and Metals Species Morning- 2013 Evening- 2013 24-hr 201324-hr 2012 Aluminum 15.2±7.452.0±4.243.7±15.419.3±3 Sulfur 483±266735±326576±1101327±140 Potassium 232±58652±302459±55.6234±33.7 Calcium 95.7±8.3127±9.7171±22.9168±27.4 Titanium 0.9±1.34.7±33.2±1.10.7±0.1 Vanadium 1.4±0.20.8±01.8±0.22.3±0.7 Chromium 0.8±0.21.3±0.80.6±0.11.1±0.1 Iron 76.5±17.5114±44.283.6±11.770.5±11.7 Nickel 0.9±0.21.5±0.81.2±0.21.9±0.5 Copper 7.0±1.913.8±9.83.7±0.83.8±0.8 Zinc 40.7±2.053.7±44.519.3±3.325.4±8.7 Cadmium 0.16±0.030.36±0.110.2±0.020.23±0.04 Antimony 0.53±0.220.64±0.320.52±0.060.91±0.29 Lead10.0±3.811.8±8.66.37±0.837.48±1.99 Concentrations in ng/m 3 ~ 2-3-fold increase in 2013 compared to 2013 and evening compared to morning (increased wood smoke) ~ 40% decrease in V and Ni concentrations in 2013 compared to 2012 (decreased fuel oil combustion)

9. Results: PAHs Species24-hr 201324-hr 2012 Phenanthrene 0.5 ± 0.60.06 ± 0.02 Anthracene 0.02 ± 0.02 Fluoranthene 0.50 ± 0.50.10 ± 0.0 Pyrene 0.74 ± 0.70.04 ± 0.0 Benzo[a]anthracene 1.55 ± 1.50.1 ± 0.1 Chrysene 1.93 ± 1.80.35 ± 0.3 Benzo[e]pyrene 6.64 ± 6.61.33 ± 1.0 Benzo[b]fluoranthene 2.43 ± 1.90.76 ± 0.5 Benzo[k]fluoranthene 1.09 ± 0.80.12 ± 0.1 Benzo[a]pyrene 2.09 ± 1.90.25 ± 0.3 diBenzo[a,h]anthracene 0.53 ± 0.30.03 ± 0.0 Benzo[g,h,i]perylene 3.20 ± 2.60.73 ± 0.4 Indenol[1,2,3-c,d]pyrene 2.32 ± 1.80.78 ± 0.4 Σ13PAHs23.4 ± 20.94.66 ± 3.5 Concentrations in ng/m 3 PAHs may originate from both traffic sources as well as wood and biomass burning. ~10-fold increase in 2013 2013 level is almost 2 times above the EU annual limit 5-fold increase in 2013 compared to 2012, driven by wood and biomass combustion.

10. Results: Organic Markers of Biomass Burning

11. Redox-Activity of PM (Oxidative Potential) Measurement Cellular Reactive Oxygen Species (ROS) assay Rat Alveolar Macrophages (AM) ROS Assay measures the direct capability of PM to generate ROS inside cells. We apply a known amount of PM mass on incubated macrophage cells and measure production of fluorescence Strongly correlated with inflammatory biomarkers in humans (2’7’-dichlorodihydrofluorescin diacetate) (2’7’-dichlorofluorescin) DCF DCFH-DA DCFH (2’7’-dichlorodihydrofluorescin) ROS Rat Alveolar macrophage PM constituents DCFH DCH (non-fluoroscent) (fluoroscent)

12. Results: Redox Activity Volume-normalized ROS activity (Indicator of exposure to toxic PM)  All of the ROS levels in this figure correspond to 2013.

13. Results: Redox Activity SpeciesRp Rp OC0.500.03Zn0.700.03 EC0.580.06As0.700.04 S0.480.07Mo0.490.05 K0.740.02Cd0.640.06 Ti0.420.11Sb0.580.08 V0.430.08Ba0.670.04 Cr0.840.01La0.710.03 Mn0.720.02Pb0.860.01 Fe0.90<0.01PAHs0.400.12 Co0.340.09Levoglucosan0.720.04 Ni0.160.23Mannosan0.650.07 Cu0.160.17Galactosan0.750.04 Association of ROS activity and chemical species in 2013:  Underlined numbers indicate values with R>0.7 and p<0.05 Biomass burning tracers are associated with the ROS activity

15. Size Range StudyLocation Traffic Emissions Fuel Oil Combustion Biomass Burning Secondary Organics FeCuCrPbCoMnZnAsPdCeNiLaVSK Levoglucos an WSOC PM 0.25 Saffri et al. 2013 Los Angeles, USA * * Saffari et al. 2013 Long Beach, USA * * Daher et al. 2014 Beirut, Lebanon * * Saffari et al. 2013 Riverside, USA * * PM 2.5 Verma et al. 2009 Los Angeles, USA **** ** Daher et al. 2014 Beirut, Lebanon *** Daher et al. 2012 Milan, Italy *** * * Saffari et al. 2013 Thessaloniki, Greece ****** * ** Zhang et al. 2008 Denver, USA * * Shafer et al. 2010 Lahore, Pakistan § ***** PM 10-2.5 Cheung et al. 2012 Los Angeles and Riverside, USA ** * Daher et al. 2014 Beirut, Lebanon **

16. Conclusions: Significant increase in concentrations of total PM 2.5 mass and organic tracers of biomass combustion in 2013 compared to 2012 imply the notable deterioration of Thessaloniki’s urban air quality during the period of economic recession. Wintertime PM-induced redox activity in Thessaloniki is strongly associated with wood smoke, originating from residential heating. Active involvement of public authorities and local air quality control agencies is urgently required to implement effective air pollution control strategies in the area. A practical long-term solution could be increased natural gas distribution in residential areas. Catalytic domestic wood burners and increasing the energy efficiency of existing buildings might be additional possible solutions Significant increase in concentrations of total PM 2.5 mass and organic tracers of biomass combustion in 2013 compared to 2012 imply the notable deterioration of Thessaloniki’s urban air quality during the period of economic recession. Wintertime PM-induced redox activity in Thessaloniki is strongly associated with wood smoke, originating from residential heating. Active involvement of public authorities and local air quality control agencies is urgently required to implement effective air pollution control strategies in the area. A practical long-term solution could be increased natural gas distribution in residential areas. Catalytic domestic wood burners and increasing the energy efficiency of existing buildings might be additional possible solutions

17. Acknowledgements: Wisconsin State Laboratory of Hygiene for their assistance with the chemical analyses. USC’s Provost and Viterbi Graduate Fellowships. Mr. Apostolos Kelessis from municipality of Thessaloniki for facilitating the sampling campaign. Mayor’s Office- Municipality of Thessaloniki