changes of chemical composition of pm10 - eco research
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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,, Switzerlandandrea.ulrich@empa.ch
Materials Science &Technolog y
Workshop Bozen 2011 2andrea.ulrich@empa.ch
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
Materials Science &Technolog y
Workshop Bozen 2011 3andrea.ulrich@empa.ch
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
Materials Science &Technolog y
Workshop Bozen 2011 4andrea.ulrich@empa.ch
Ch. Hueglin, Empa 22nd AKPF Meeting
13 Mar 2009
4Federal Office for the Environment (FOEN) Mater ials Science & Technolog y
Materials Science &Technolog y
Workshop Bozen 2011 5andrea.ulrich@empa.ch
Suburban
Urban kerbside
Urban background
Rural –South of the Alps
Rural – North of the Alps
5 different sampling site typesSampling sites
Materials Science &Technolog y
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Sampling of PM 10
C. Hueglin et al, Atm Environ 2005, 39(4), 637‐651M. Gianini et. al., Atm Environ 2011, submitted
Materials Science &Technolog y
Workshop Bozen 2011 andrea.ulrich@empa.ch 77andrea.ulrich@empa.ch
Analysis of PM 10
C. Hueglin et al, Atm Environ 2005, 39(4), 637‐651M. Gianini et. al., Atm Environ 2011, submitted
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‐)
Materials Science &Technolog y
Workshop Bozen 2011 8andrea.ulrich@empa.ch
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
Materials Science &Technolog y
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Change of Fleet in CH from 2006 to 2010
Materials Science &Technolog y
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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
Materials Science &Technolog y
Workshop Bozen 2011 11andrea.ulrich@empa.ch
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)
C. Hueglin et al, Atm Environ 2005, 39(4), 637‐651M. Gianini et. al., Atm Environ 2011, submitted
Materials Science &Technolog y
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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
Materials Science &Technolog y
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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
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NOx Sources (NOx = NO+NO2)
BAFU Report 256
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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
Materials Science &Technolog y
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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
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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
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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
Materials Science &Technolog y
Workshop Bozen 2011 19andrea.ulrich@empa.chA. 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)
Materials Science &Technolog y
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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)
Materials Science &Technolog y
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Development of diesel fleet without and with particle filter in CH
Materials Science &Technolog y
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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.
Materials Science &Technolog y
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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.
Materials Science &Technolog y
Workshop Bozen 2011 andrea.ulrich@empa.ch 2424andrea.ulrich@empa.ch
Changes in chemical composition of PM101998/1999 ‐ 2008/2009
Reduction of SO2emission regulations
e.g. less S in fuel
C. Hueglin et al, Atm Environ 2005, 39(4), 637‐651M. Gianini et. al., Atm Environ 2011, submitted
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
Materials Science &Technolog y
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SSANSA
Changes of average source contributions in PM10 (1998/1999 – 2008/2009)
C. Hueglin et al, Atm Environ 2005, 39(4), 637‐651M. Gianini et. al., Atm Environ 2011, submitted
Materials Science &Technolog y
Workshop Bozen 2011 26andrea.ulrich@empa.ch
Acknowledgements
M.F.D. Gianini
A. Wichser
A. Fischer
N. Heeb
R. Gehrig
C. Hueglin
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