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2008 Field measurements 1
Field Measurements of organic aerosols
Laboratory of Atmospheric Chemistry
LAC :
Head: Urs Baltensperger
15 Scientists/Postdocs
18 Phd students
3 Groups
- Gasphase and Aerosol chemistry
- Aerosol physics
- Ecosystem fluxes
2008 Field measurements 2
Field Measurements of organic aerosols
Emission characterisationEC, OM, inorganic aerosol, elements, acids, gases, aerosol sizeAMS, SR-XRF, IC-MS, aethalometer
TransformationTrace gas oxidation, SOA formation, gasphase-aerosol partitioning, aerosol processingSmogchamber, PTR-MS, AMS, gasphase instruments; Master Chemical mechanism
gas phase organicaerosol, OA
X (g) X (a)
X (oligomer)
X (aq)
aqueous phase
VOCOH HO2
RO2 RO
NO NO2
NONO2
O2
HNO3
NO2
H2O2
HO2
O2 reaction,decomposition orisomerisation
ROOH
HO2
ROH + R-HO
RO2 NO
RONO2
NO2
RO2NO2
h O3O2
Ambient MeasurementsEC, OM, inorganic aerosol, elements, acids, gases, aerosol sizeMobile van, AMS, 14C, s-XRF, IC-MS, Aethalometer; statistical analyses
Chemical Transport ModellingParticulate matter, ozoneCAM-x, MM5, COSMO
2008 Field measurements 3
Field Measurements of organic aerosols
Field experiments
SwitzerlandEuropeGlobal
2008 Field measurements 4
Field Measurements of organic aerosols
Locations with AMS Measurements
Zürich (July/August and January)
Reiden (February)
Roveredo (March, December )
Härkingen (May)
Payerne (June, January)
Massongex (December)
JFJ (Winter, Summer)
Rhine valley (February)
Riviera (June)
Milano (June)
Mobile measurements
2008 Field measurements 5
Field Measurements of organic aerosols
Average compositions in winter (
Zürich (January)
Payerne (January)
9%
75%
2%
9%
4% 1%
18%
45%
8%
16%
9%4%
11%
32%
15%
27%
1%
14%
7%
34%
10%
34%
14%1%
7%
36%
9%
34%
13%1%
Black CarbonOrganic massNitrateSulfateAmmoniumChloride
Roveredo (December)
Massongex (December)
Reiden (February)
2008 Field measurements 6
Field Measurements of organic aerosols
Reiden, Winter
ECfossil
OCfossilOCnonfossil
ECbiomass
Jungfraujoch, Winter
ECfossil
OCfossil
OCnonfossil
ECbiomass
Moleno, Winter
OCfossil
OCnonfossilECfossil
ECbiomass
Zürich, Winter
ECfossil
OCfossil
ECbiomass
OCnonfossil
Roveredo, Winter
ECfossil
OCfossil
OCnonfossil
ECbiomass
Overview over the winter 14C analyses
2008 Field measurements 7
Field Measurements of organic aerosols
ECbiomass/ECtot: Spatial distribution on 29.01.2006
Bern0.14
Dübendorf0.33
Zürich0.33
Tänikon0.40
Payerne0.42
Basel0.38
Reiden0.36
Sedel0.33
Lausanne0.19
Härkingen0.34
2008 Field measurements 8
Field Measurements of organic aerosols
ECfossil8%
OCnonfossil81%
ECbiomass11%
ECfossil13%
OCfossil12%
OCnonfossil66%
ECbiomass9%
Holzverbrennung in Roveredo (GR), Januar 2005
Roveredo (GR)
06:00 – 14:00
18:00 – 02:00
Szidat et al., GRL, 2007
2008 Field measurements 9
Field Measurements of organic aerosols
Aerosol mass spectra
12
8
4
0
2001601208040
m/z
12
8
4
0
% t
o t
ota
l o
rga
nic
s 12
8
4
0
12
8
4
0
12
8
4
0
Levoglucosan
Chestnut, poor burning
Night Filter, March
29
29
2943
43
44 60
60
6073
73
73
115
115
137
137
167
167
167137
Averaged nights, Dec29
43
60
73 115 137 167
2944
55
69 81 91
Haerkingen, May
Levoglucosan
Wood burner (emissions) chestnut, very inefficient burning
Night period in Roveredo in March, more than 80% of OC non-fossil
Average in Roveredo over the whole December
Mass spectra from a Motorway site in May
Alfarra et al. ES&T (2007)
2008 Field measurements 10
Field Measurements of organic aerosols
Dependence of light absorption as a function of wavelength measured by an aethalometer
babs
0.0
2.0
4.0
6.0
8.0
10.0
12.0
350 450 550 650 750 850 950
[nm]
ba
bs(
) /
b ab
s (9
50
nm
)
0.0
2.0
4.0
6.0
8.0
10.0
12.0
350 450 550 650 750 850 950
Absorption exponent : a measure of the strength of the spectral variation in aerosol light absorption
Example power law fit (-2.0)
Wood burninga -1.8 to -2.2
Traffic, diesel soota,b -1.0 to -1.1
a Kirchstetter et al. 2004
b Schnaiter et al. 2003 & 2005
Sandradewi et al., Atmos. Environ., 2008
2008 Field measurements 11
Field Measurements of organic aerosols
Aethalometer model to derive the contribution of woodburning and traffic to PM1
Carbonaceous material (CM)
Sandradewi et al., ES&T, 2008
2008 Field measurements 12
Field Measurements of organic aerosols
Validation of aethalometer model
Sandradewi et al., ES&T, 2008
The variability of OM+BC can be explained at a site with
negligible SOA
Validation of aethalometer analysis with 14C analysis
14C
Aethalometer
2008 Field measurements 13
Field Measurements of organic aerosols
Average diurnal cycle of the carbonaceous material, OC/EC and wood burning versus traffic contributions
Sandradewi et al., ES&T, 2008
2008 Field measurements 14
Field Measurements of organic aerosols
Fractions of BC, OM, NO3, SO4 and NH4 and fossil and non-fossil contribution to EC and OC
Nearly identical composition
Reiden Zürich
Black CarbonOrganic massNitrateSulfateAmmonium
Reiden Zürich
Black CarbonOrganic massNitrateSulfateAmmonium
Z_meanPM10
ECbb4% ECfossil
17%
OCfossil23%
OCnonfossil56%
Z_meanPM10
ECbb4% ECfossil
17%
OCfossil23%
OCnonfossil56%
Reiden Zürich
16%30%
14%
6%
34%Black CarbonOrganic massNitrateSulfateAmmonium
Reiden Zürich
16%30%
14%
6%
34%Black CarbonOrganic massNitrateSulfateAmmonium
R_mean
ECbb5%
ECfossil17%
OCfossil22%
OCnonfossil56%
R_mean
ECbb5%
ECfossil17%
OCfossil22%
OCnonfossil56%
7%
15%
34%11%
33%
Reiden Zürich
Black CarbonOrganic massNitrateSulfateAmmonium
7%
15%
34%11%
33%
Reiden Zürich
Black CarbonOrganic massNitrateSulfateAmmonium
Urban background Highway/rural
2008 Field measurements 15
Field Measurements of organic aerosols
70
60
50
40
30
20
10
0
Mas
s C
once
ntra
tion
(µg
m-3
)
29.01.2006 31.01.2006 02.02.2006 04.02.2006 06.02.2006 08.02.2006 10.02.2006 12.02.2006Date & Time
OrganicNitrateAmmoniumSulfateBC
Reiden
100
80
60
40
20Fra
ctio
nal C
ontr
ibti
on
%
29.01.2006 31.01.2006 02.02.2006 04.02.2006 06.02.2006 08.02.2006 10.02.2006 12.02.2006Date & Time
Chemical composition of PM1 with high time resolution in Zürich and Reiden (Kt. Luzern)
30
25
20
15
10
5
0
Mas
s C
once
ntra
tion
(µg
m-3
)
08.01.2006 11.01.2006 14.01.2006 17.01.2006 20.01.2006 23.01.2006Date & Time
Zurich
OrganicsNitrate SulphateAmmoniumBC
100
80
60
40
20Frac
tiona
l Con
trib
utio
n %
08.01.2006 11.01.2006 14.01.2006 17.01.2006 20.01.2006 23.01.2006Date & Time
2008 Field measurements 16
Field Measurements of organic aerosols
Organic aerosol sources in winter in
Zurich
Statistical analysis of q-AMS data in Zürich (Lanz et al.,
ES&T, 2008)
(ORG)ij = Gi1*F1j+Gi2*F2j+ Gi3*Trafficj
2008 Field measurements 17
Field Measurements of organic aerosols
Verification by comparing source strengths with tracers
Lanz et al., ES&T, 2008
2008 Field measurements 18
Field Measurements of organic aerosols
Carbon apportionment using 14C analysisEstimation of fossil and non-fossil SOA contribution
Z_meanPM10
ECbb4% ECfossil
17%
OCfossil23%
OCnonfossil56%
Zürich (mean)
Use of AMS analysis :
- wood burning 38%
- HOA 7%
Assumptions :
- only SOA, HOA and wood burning present
- OM/OC=2 for wood burning and SOA and OM/OC=1.2 for HOA
- RESULT : SOAnonfossil: 69% SOAfossil: 31%
(biomass burning)
38%
7%17%
38% Wood burning
Traffic
Secondary(fossil)
Secondary(non-fossil)
81%
19%
EC (fossil)
EC (non-fossil)
OM
EC
Lanz et al., ACP, 2007
2008 Field measurements 19
Field Measurements of organic aerosols
Average composition in Zürich in summer and winter
13%
60%
13%
7%
7%
Zürich (July)
11%
32%
15%
27%
1%
14%
Zürich (January)
Black CarbonOrganic massNitrateSulfateAmmonium
2008 Field measurements 20
Field Measurements of organic aerosols
Chemical composition in Zürich summer and Positive Matrix Factorization of the organic matter
Lanz et al., ACP (2007)
Organic mass13%
60%
13%
7%
7%
Zürich (July)
Black CarbonOrganic massNitrateSulfateAmmonium
OOA: Secondary organic aerosol
HOA: mostly traffic
2008 Field measurements 21
Field Measurements of organic aerosols
Identification of two different oxidized organic aerosol components (volatile and non-volatile)
OOA probably corresponds mostly to SOA (secondary organic aerosol)
Lanz et al., ACP (2007)
2008 Field measurements 22
Field Measurements of organic aerosols
Jungfraujoch, Sommer
ECfossil
OCfossil
OCnonfossil
ECbiomass
Zürich, Sommer
ECfossil
OCfossil
OCnonfossil
ECbiomass
Overview over the summer 14C analyses
2008 Field measurements 23
Field Measurements of organic aerosols
Observation of SOA oligomerization by Laser Desorption Ionization mass spectrometer
1500
1000
500
Inte
nsi
ty (
mV
)
1500
1000
500
Inte
nsi
ty (
mV
)
4000
3000
2000
1000Inte
nsi
ty (
mV
)
800700600500400mass m/z
A)
B)
C)
D)
Kalberer et al., Science (2004)
Time after lights on: 3.5 h
4.5 h
6.5 h
• High molecular masses are found that are not predicted by known gasphase oxidation chemistry
2008 Field measurements 24
Field Measurements of organic aerosols
Oligomers also found in the ambient aira
.u.
800700600500400300
pinene-SOA
a.u
.
800700600500400300
Downtown Zurich
a.u
.
800700600500400300
Kpusta, rural Hungary
a.u
.
800700600500400300
trimethylbenzene-SOA
Pattern of Zurichpoints to -pinenerather than TMB(or other anthrop.precursors)
Baltensperger et al.Faraday Disc. (2005)
2008 Field measurements 25
Field Measurements of organic aerosols
Levoglucosan measurements versus 14C and aethalometer analyses
- Are different slopes caused by different emission properties or by atmospheric processing ??Sandradewi et al., ACPD (2008)
2008 Field measurements 26
Field Measurements of organic aerosols
EUROPEAN CARBOSOL project
Gelencser et al., JGR, 2007
2008 Field measurements 27
Field Measurements of organic aerosols
Levoglucosan yearly cycles at different sites in Europe
2008 Field measurements 28
Field Measurements of organic aerosols
Results of source apportionment of OA (PM2.5) during the CARBOSOL project
- SOA, especially non-fossil very important
- EC from fossil fuel mostly more important than EC from biomass burning
- OC from wood burning often more important than from traffic
- OC from primary biogenic sources less than 10%
Gelencser et al., JGR, 2007
2008 Field measurements 29
Field Measurements of organic aerosols
TORCH 2003 campaign site
TORCH campaign at Writtle, Essex July/August 2003
Field measurements by:
Univ. YorkUniv. ManchesterUniv. Leeds Univ. East AngliaUniv. LeicesterUniv. Aberystwyth
2008 Field measurements 30
Field Measurements of organic aerosols
Observed and optimised simulated organic aerosol (MCM) POA: estimated primary organic aerosol
0
2
4
6
8
10
12
26-Jul 29-Jul 1-Aug 4-Aug 7-Aug 10-Aug 13-Aug 16-Aug 19-Aug 22-Aug 25-Aug 28-Aug 31-Aug 3-Sep
co
ncen
trati
on
(mg
m-3)
simulated POA
observed OAoptimised simulated OA (MCM)
Johnson et al., ACP, 2006
2008 Field measurements 31
Field Measurements of organic aerosols
Simulated OA for 9 case studies
Optimisation required:
• Assumption of a background concentration of a persistent (i.e. non-volatile) organic aerosol (model initialisation):
Background (hourly-mean) OA = 0.7 mg m-3
• Scaling of partitioning coefficients for semi-volatile products of VOC oxidation:
Scaling factor = 500(compared with ca. 10 100 for chamber simulations)
Johnson et al., ACP, 2006
2008 Field measurements 32
Field Measurements of organic aerosols
Cabada et al., AS&T, 2004
2008 Field measurements 33
Field Measurements of organic aerosols
Zhang et al., ACP, 2005Cabada et al., AS&T, 2004
Primary versus secondary OC in Pittsburgh from EC-OC method and AMS data
2008 Field measurements 34
Field Measurements of organic aerosols
Measured tracers for different SOA precursors
Kleindienst et al., Atmos. Environ., 2007
2008 Field measurements 35
Field Measurements of organic aerosols
Different SOA, biomass burning and other OC
Kleindienst et al., Atmos. Environ., 2007
2008 Field measurements 36
Field Measurements of organic aerosols
Estimated primary and secondary organic carbon from tracer measurements
Lewandowski et al., ES&T, 2008
2008 Field measurements 37
Field Measurements of organic aerosols
Contribution of different precursors to SOA and SOC
Lewandowski et al., ES&T, 2008
2008 Field measurements 38
Field Measurements of organic aerosols
Weber R. et al., JGR, 2007
2008 Field measurements 39
Field Measurements of organic aerosols
Weber R. et al., JGR, 2007
2008 Field measurements 40
Field Measurements of organic aerosols
Weber R. et al., JGR, 2007
2008 Field measurements 41
Field Measurements of organic aerosols
Weber R. et al., JGR, 2007
2008 Field measurements 42
Field Measurements of organic aerosols
Weber R. et al., JGR, 2007
2008 Field measurements 43
Field Measurements of organic aerosols
Relative composition of organics, sulfate, Relative composition of organics, sulfate, ammonium, nitrateammonium, nitrate
2008 Field measurements 44
Field Measurements of organic aerosols
Relative composition of hydrocarbon-like and oxygenated organic aerosol in different parts of the world
2008 Field measurements 45
Field Measurements of organic aerosols
Summary
Black/elemental carbon in Switzerland mostly due to fossil sources (diesel)
Organic mass is in Switzerland dominated by OOA (probably mostly SOA), in both winter and summer dominated by non-fossil contributions (SOA from biogenic precursors and OA/SOA from wood burning)
In Europe, at many places wood burning is considered to be more important than previously thought. In winter it is and will be more important than traffic because of the emission reductions due to particulate filters of diesel vehicles
Also in the United States, non-fossil OA is dominating over fossil OA. However SOA still seems to be connected to anthropogenic activity.. Explanation not clear..
At many places of the world, the most important fraction of PM1 is the organic aerosol. At most places, the oxygenated aerosol is much more important than the hydrocarbon-like aerosol
Measurements show often more OA (especially OOA or SOA) than expected by models
2008 Field measurements 46
Field Measurements of organic aerosols
FUTURE
More combined off-line and on-line analyses at the same location
More advanced long-term monitoring Combination of various stations and aircraft data like in Mexico
City More smogchamber/flow tube versus field comparisons for
process studies More combination of chemical and physical characterization of
the aerosol Further improvement of models with inclusion of new processes
necessary
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