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/aerosol

• 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:

Motivations:

Thessaloniki:

• 2nd 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

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

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)

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)

Results: Trace Elements and Metals

SpeciesMorning-

2013Evening-

201324-hr 2013 24-hr 2012

Aluminum 15.2±7.4 52.0±4.2 43.7±15.4 19.3±3Sulfur 483±266 735±326 576±110 1327±140

Potassium 232±58 652±302 459±55.6 234±33.7Calcium 95.7±8.3 127±9.7 171±22.9 168±27.4Titanium 0.9±1.3 4.7±3 3.2±1.1 0.7±0.1

Vanadium 1.4±0.2 0.8±0 1.8±0.2 2.3±0.7Chromium 0.8±0.2 1.3±0.8 0.6±0.1 1.1±0.1

Iron 76.5±17.5 114±44.2 83.6±11.7 70.5±11.7Nickel 0.9±0.2 1.5±0.8 1.2±0.2 1.9±0.5Copper 7.0±1.9 13.8±9.8 3.7±0.8 3.8±0.8

Zinc 40.7±2.0 53.7±44.5 19.3±3.3 25.4±8.7Cadmium 0.16±0.03 0.36±0.11 0.2±0.02 0.23±0.04Antimony 0.53±0.22 0.64±0.32 0.52±0.06 0.91±0.29

Lead 10.0±3.8 11.8±8.6 6.37±0.83 7.48±1.99

Concentrations in ng/m3

~ 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)

Results: PAHs

Species 24-hr 2013 24-hr 2012

Phenanthrene 0.5 ± 0.6 0.06 ± 0.02

Anthracene 0.02 ± 0.02 0.02 ± 0.02

Fluoranthene 0.50 ± 0.5 0.10 ± 0.0

Pyrene 0.74 ± 0.7 0.04 ± 0.0

Benzo[a]anthracene 1.55 ± 1.5 0.1 ± 0.1

Chrysene 1.93 ± 1.8 0.35 ± 0.3

Benzo[e]pyrene 6.64 ± 6.6 1.33 ± 1.0

Benzo[b]fluoranthene 2.43 ± 1.9 0.76 ± 0.5

Benzo[k]fluoranthene 1.09 ± 0.8 0.12 ± 0.1

Benzo[a]pyrene 2.09 ± 1.9 0.25 ± 0.3

diBenzo[a,h]anthracene 0.53 ± 0.3 0.03 ± 0.0

Benzo[g,h,i]perylene 3.20 ± 2.6 0.73 ± 0.4

Indenol[1,2,3-c,d]pyrene 2.32 ± 1.8 0.78 ± 0.4

Σ13PAHs 23.4 ± 20.9 4.66 ± 3.5

Concentrations in ng/m3

• 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.

Results: Organic Markers of Biomass Burning

Redox-Activity of PM (Oxidative Potential) MeasurementCellular 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)

DCFDCFH-DA DCFH

(2’7’-dichlorodihydrofluorescin) ROS

Rat Alveolar macrophage

PM constituentsDCFH

DCH(non-fluoroscent) (fluoroscent)

Results: Redox Activity

Volume-normalized ROS activity

(Indicator of exposure to toxic PM)

All of the ROS levels in this figure correspond to 2013.

Results: Redox Activity

Species R p Species R p

OC 0.50 0.03 Zn 0.70 0.03

EC 0.58 0.06 As 0.70 0.04

S 0.48 0.07 Mo 0.49 0.05

K 0.74 0.02 Cd 0.64 0.06

Ti 0.42 0.11 Sb 0.58 0.08

V 0.43 0.08 Ba 0.67 0.04

Cr 0.84 0.01 La 0.71 0.03

Mn 0.72 0.02 Pb 0.86 0.01

Fe 0.90 <0.01 PAHs 0.40 0.12

Co 0.34 0.09 Levoglucosan 0.72 0.04

Ni 0.16 0.23 Mannosan 0.65 0.07

Cu 0.16 0.17 Galactosan 0.75 0.04

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

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PM0.25 PM2.5 PM10-2.5

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1000

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(µg

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Size Range

Study LocationTraffic Emissions

Fuel Oil Combustion

Biomass Burning

Secondary Organics

Fe Cu Cr Pb Co Mn Zn As Pd Ce Ni La V S KLevoglucos

anWSOC

PM0.25

Saffri et al. 2013Los Angeles,

USA * *

Saffari et al. 2013

Long Beach, USA * *

Daher et al. 2014

Beirut, Lebanon * * Saffari et al.

2013Riverside, USA * *

PM2.5

Verma et al. 2009

Los Angeles, USA * * * * * *

Daher et al. 2014

Beirut, Lebanon * * * Daher et al.

2012Milan, Italy * * * * *

Saffari et al. 2013

Thessaloniki, Greece * * * * * * * * *

Zhang et al. 2008

Denver, USA * *Shafer et al.

2010Lahore,

Pakistan§ * * * * *

PM10-2.5

Cheung et al. 2012

Los Angeles and Riverside, USA * * *

Daher et al. 2014

Beirut, Lebanon * *

Conclusions:

• Significant increase in concentrations of total PM2.5 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

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