changes of chemical composition of pm10 - eco research

Materials Science & Technolog y

Changes of chemical composition of PM10 and the assessment of long‐term trends

A. Ulrich, M.F.D. Gianini, A. Wichser, A. Fischer, N. Heeb, R. Gehrig, C. Hueglin

Empa, Swiss Federal Laboratories for Materials Science and Technology,, [email protected]

Materials Science &Technolog y

Workshop Bozen 2011 [email protected]

Dimensions of particulate matter in ambient air

PM 101A 1nm 10nm 100nm 1µ m 10µ m 100µ m 1m m 1cm

PM 1ultrafine particles

diesel soot ca. 100 nmcom bustion generated soot

pollen 10 -100 µm

sea salt 0.2 -10 µm

mineral dust 0.2 -10 µm

Ammonium sulfate ca. 100 nm



Particle deposition in human lungs

PM 10

1A 1nm 10nm 100nm 1µ m 10µ m 100µ m 1m m 1cm

PM 1ultrafine particles

Pharyngeal / mucosa> 10 µm

Larynx 5 – 6 µm

Trachea / main bronchia

3 – 5 µm

Terminal bronchia 1 ‐ 4 µm

Alveole < 1 µm



Ch. Hueglin, Empa 22nd AKPF Meeting

13 Mar 2009

4Federal Office for the Environment (FOEN) Mater ials Science & Technolog y



Suburban

Urban kerbside

Urban background

Rural –South of the Alps

Rural – North of the Alps

5 different sampling site typesSampling sites



Sampling of PM 10

C. Hueglin et al, Atm Environ 2005, 39(4), 637‐651M. Gianini et. al., Atm Environ 2011, submitted


Workshop Bozen 2011 [email protected] [email protected]

Analysis of PM 10


EC/OC Thermal‐optical analysis EC = elemental carbon (soot) OC = organic carbon

Plasma Mass Spectrometry ICPMS 35 Elements (e.g. Al, V, Fe, Ni, Cu, Se, Rb, Mo,……)

Ionic Chromatography IC 8 Ions (Na+, K+, NH4

+, Mg2+, Ca2+, Cl‐, NO3‐, SO4

2‐)



Trend of PM10 (annual mean) from 1991 ‐ 2009

Source: BAFU, Luftbelastung 2009

µg/m3

Urban kerbside

Urban kerbside

Urban background

Rural at m otorway

Rural

Suburban



Change of Fleet in CH from 2006 to 2010



Zurich –Urban background

20.7 g/m3

Basel ‐ suburbanPayerne ‐ rural

Magadino ‐ ruralBern –Urban roadside

20.9 g/m319.0 g/m329.4 g/m3

Chemical composition of PM10 (Aug. 2008 – Jul. 2009)

South of the AlpsNorth of the Alps



PM10

Sulfat

Ammon

ium

Nitrat

OM EC

Min.Staub

Sp.Elemen

te

rel. Verän

derung

200

8/09

- 19

98/99 (%

)

-40

-20

0

20

40 BER - Stadt, VerkehrZUE - Stadt, Hintergrund

BAS - VorstadtPAY - Land

Change in chemical composition of PM10 (1998/1999 – 2008/2009)




Annual mean(g/m3)

Daily mean(g/m3)

Hourly mean

(g/m3)

½-Hourly mean(g/m3)

EU 40a --- 200a,b ---

Switzerland 30 80 --- 100c

WHO AQG 2005

40d --- 200d ---

a compliance by 1 Jan 2010b not to be exceeded on more than 18 occasionsc 95‐percentiled Guideline values

NO2 air quality standards and guideline values



0 10 20 30 40 50 60

010

2030

4050

60

PM10 (ug/m 3)

NO2 (ug/m3)

B

B

C

D

H

J

L

L

M

P

R

S

T

Z

urban, kerbsideurban, backgroundrural, m otorwaysuburbanruralrural, above 1000 m asl.high-alpineother sites (cantons, cities)

NO2 vs. PM10 (annual means 2006)

NO2 at Swiss measurement sites



NOx Sources (NOx = NO+NO2)

BAFU Report 256



Trend of annual NO, NO2, NOxat urban roadsite site (Bern)

BER

NOx, NO, N

O2 (ppb

)

NOxNONO2

020

6010

014

018

0

Year

NO2/NOx (%

)

1990 1995 2000 2005

020

4060

80

Year

O3 (ppb

)

1990 1995 2000 2005

020

40

NO + O3 → NO2 + O2 (1)k1 = 1.4∙10‐12 ∙ exp(‐1310/T)cm3s‐1

k1

NO2 + h → NO + O(3P) < 420nm (2)

O(3P) + O2 + M → O3 + M (3)

(1) – (3) tend to establish an equilibrium, the

Photostationary State (Leighton, 1961)

2NO

312JOk

NONO

Total oxidant Ox = NO2 + O3 conserved in eqs. (1) – (3)

NO2 stable



Trend of annual NO, NO2, NOx at other urban sitesLAU

NOx, NO, N

O2 (ppb

)

NOxNONO2

020

4060

80

Year

NO2/NOx (%

)

1990 1995 2000 2005

020

4060

80

Year

O3 (ppb

)

1990 1995 2000 2005

020

40

ZUE

NOx, NO, N

O2 (ppb

)

NOxNONO2

020

4060

8010

0

LUG

NOx, NO, N

O2 (ppb

)

NOxNONO2

020

4060

8010

0

YearNO2/NOx (%

)

1990 1995 2000 2005

020

4060

80

Year

NO2/NOx (%

)

1990 1995 2000 2005

020

4060

80

Year

O3 (ppb

)

1990 1995 2000 2005

020

40

Year

O3 (ppb

)

1990 1995 2000 2005

020

40

Lausanne, roadside Zurich, urban bkg. Lugano, urban bkg.

NO2 konstant or less decrease



View to eastern direction View to north‐eastern direction

Haerkingen: A rural site 20m from a motorway

0

20'000

40'000

60'000

80'0001

2

3

4

5

6

7

8

9

10

11

12

0

10

20

30

401

2

3

4

5

6

7

8

9

10

11

12

0

20

40

60

80

1001

2

3

4

5

6

7

8

9

10

11

12

particle number conc. (#/cm3) PM10 and PM1 (µg/m3) nitrogen oxides (ppb)

NONO2

PM10

PM1

N



Possible Reasons

• Reduced S in Fuel from 350 ppm to <10 ppmSO2 replaced by NOx‐species in redox processes

• Increase of diesel vehicles in Switzerland from 3 to 25 % measure in car import to fulfill demands for CO2 reduction

• Diesel vehicles equipped with oxidation catalysts and diesel particle filter (DPF)

Denovo formation of NO2 in some types of DPFs?NO oxidation from reduction to oxidation argent

Sulphur Limits in CHFuel 2001 2005 since 2004 Petrol 150 ppm 50 ppm additonal levy for all fuels

with S content >10 ppmDiesel 350 ppm 50 ppm additonal levy for all fuels

with S content >10 ppm


Workshop Bozen 2011 [email protected]. Ulrich, Spring Meeting SCG Industrie 2009, 4. June 2009 19

Passenger cars EU 42 % dieselCH 20 % diesel

Heavy duty >90 % diesel

Ship engines >95 % diesel

Locomotive: EU 55 % diesel

Diesel vehicle types (2008)



1.27.8

14.516.9

19.822.223.323.726.2

38.739.642.1

45.358

6467.4

71.4

GreeceSweden

FinnlandIreland

SwitzerlandNorway

DenmarkNetherlands

UKGermanyPortugal

Western Europe AverageItaly

SpainLuxembourg

FranceAustria

Percentage of diesel personal cars in Europe (2008)



Development of diesel fleet without and with particle filter in CH



According to emission limits – NO EFFECT!Nitrogen species (NOx, NO, NO2)

Nitrogen behavior in diesel particle filters

Heeb et al. Env. Sci. Tech. 2010, 44, 1078‐1084.Heeb et al. , Atm. Env. 2011, 45, 3203‐3209.



According to emission limits – NO EFFECT!Nitrogen species (NOx, NO, NO2)

Nitrogen behavior in diesel particle filters2 types of filter families, one which reduces NO2

and the second forms NO2!

Heeb et al. Env. Sci. Tech. 2010, 44, 1078‐1084.Heeb et al. , Atm. Env. 2011, 45, 3203‐3209.



Changes in chemical composition of PM101998/1999 ‐ 2008/2009

Reduction of SO2emission regulations

e.g. less S in fuel


New road pavem ents in Baselshortly before 2008/2009 cam paign

Reduction of re-suspensionof m ineral and road dust.

Reduction of EC emissionsEuro vehicle standards

changes of fleet, DPF for diesel vehicles,

DPF mandatory for construction machinery

Exchange of SO2 by NOx species DeNovo-formation of NO2

in some DPF types



SSANSA

Changes of average source contributions in PM10 (1998/1999 – 2008/2009)




Acknowledgements

M.F.D. Gianini

A. Wichser

A. Fischer

N. Heeb

R. Gehrig

C. Hueglin



Thank you for your attention

16th ETH‐Conference on Combustion Generated NanoparticlesJune 24. ‐ 27 , 2012 Zurich, CH www.lav.ethz.ch/nanoparticle_conf/

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changes of chemical composition of pm10 - eco research

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