modeling soa formation: new insights and more questions ?
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Modeling SOA Formation: New Insights and More Questions ?. Department of Environmental Science and Engineering UNC, Chapel Hill. Mastery of Fire. 400,000 years ago in Europe 100,000 years ago in Africa M. N. Cohne, 1977. - PowerPoint PPT PresentationTRANSCRIPT
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Modeling SOA Formation: Modeling SOA Formation: New Insights and More New Insights and More
QuestionsQuestions??
Department of Environmental Science and Engineering
UNC, Chapel Hill
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MasteryMastery of Fire of Fire
400,000 years ago in Europe 400,000 years ago in Europe
100,000 years ago in Africa100,000 years ago in Africa
M. N. Cohne, 1977M. N. Cohne, 1977
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From a global perspective, fire From a global perspective, fire results in huge emissions of black results in huge emissions of black carbon into the atmospherecarbon into the atmosphere
Biomass burningBiomass burning 6x106x1012 12 gg Fossil fuel burningFossil fuel burning 7x107x1012 12 gg
Biogenic aerosolsBiogenic aerosols 13-60x1013-60x101212gg((presentations by: presentations by: Schnaiter and Jackobson)Schnaiter and Jackobson)
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What are Organic AerosolsWhat are Organic Aerosols??
organic liquid layer
inner solid core inorganic/carbon
H2O
H2SO4
Semi-volatile organics
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Fresh wood soot (0.5 m scale)
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Composition of LA Particulate Matter (adjusted for smoggy days)((Rogge &Cass et al, 1993, Turpin et al, 1991)
NH4 10nitrate 20sulfate 11EC 6other 23OC 30
Percent mass
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PM10 Chemical Characterization in PM10 Chemical Characterization in
BeijingBeijing Xiao-Feng, Min Hua, Ling-Yan Hea, Xiao-Yan Xiao-Feng, Min Hua, Ling-Yan Hea, Xiao-Yan Tang, Tang, Atmos. Environ. 39 (2005) 2819–2827Atmos. Environ. 39 (2005) 2819–2827
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Characteristics of carbonaceous aerosols in Beijing, ChinaYele Suna, Guoshun Zhuang, Ying Wang, Lihui Han, Jinghua Guo, Mo Dan, Wenjie Zhang, Zifa Wang, Zhengping Hao, Atmos, Environ. 38 (2004) 5991–6004
coal burning, traffic exhaust, and dustcoal burning, traffic exhaust, and dust from the long-range transportfrom the long-range transport
Mineral aerosol from outsideMineral aerosol from outside Beijing Beijing accounted for 79% of the total PM10 accounted for 79% of the total PM10 minerals and 37% of the PM2.5 in minerals and 37% of the PM2.5 in winter. It was 19% and 20% in summerwinter. It was 19% and 20% in summer
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Characteristics of carbonaceous aerosols in Beijing, ChinaFengkui Duan, Kebin He, Yongliang Ma, Yingtao Jia,Fengkui Duan, Kebin He, Yongliang Ma, Yingtao Jia,Fumo Yang, Yu Lei, S. Tanaka, T. Okuta,Fumo Yang, Yu Lei, S. Tanaka, T. Okuta, Chemosphere 60 (2005) 355–364Chemosphere 60 (2005) 355–364
OC/EC ratio (on a 1.5 basis showed that OC/EC ratio (on a 1.5 basis showed that SOC accounted more than SOC accounted more than 50%50% for the total for the total organic carbon. In winter, the SOC organic carbon. In winter, the SOC contribution to OC was also significant, and contribution to OC was also significant, and as high as as high as 40%.40%.
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Secondary organic Secondary organic aerosolaerosol (SOA)(SOA) Material as Material as organic compoundsorganic compounds that resides in that resides in the the aerosol phase as a result of aerosol phase as a result of atmospheric reactionsatmospheric reactions that occur in that occur in either the either the gasgas or or particle particle phasesphases..
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Do we see any Do we see any chemical chemical evidence for SOA formation?evidence for SOA formation?
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Leonardo Da Vinci describes blue haze and thinks that plant emissions are its source. (F. W. Went, 1959)
Da Vinci believes that it was due to water moisture emitted from the plants
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F.W.Went published papers on biogenic emissions from vegetation over 40 years ago.
He posed the question, “what happens to the 17.5x107 tons of terpene-like hydrocarbons or slightly oxygenated hydrocarbons once they are in the atmosphere each year?”
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Went suggests that terpenes are removed from the atmosphere by reaction with ozone
attempts to demonstrate “blue haze” formation
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Went suggests that terpenes are removed from the atmosphere by reaction with ozone
attempts to demonstrate “blue haze” formation by adding crushed pine or fir needles to a jar with dilute ozone.
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Over a eucalyptus forest in Over a eucalyptus forest in Portugal Portugal Kavouras et al.Kavouras et al. (1998,1999)(1998,1999) show evidence for show evidence for terpene reaction products in terpene reaction products in aerosolsaerosols
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Terpenes products
Kavouras et al, 1998 ng m-3
pinic acid 0.4 - 85pinonic acid 9 - 141norpinonic acid 0.1 - 38Pinonaldehyde 0.2 - 32
Nopinone 0.0 - 13
-pinene -pinene
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Turpin and co-workersTurpin and co-workers
In the LA area (estimated on smoggy In the LA area (estimated on smoggy
days from days from OC OC //ECEC ratios ratios), as much as ), as much as 50 - 50 - 80%80% of the of the aerosolaerosol organic carbonorganic carbon comes from comes from secondary aerosol secondary aerosol formationformation (1984 and 1987 samples) (1984 and 1987 samples)
In Atlanta in 1999, SOA averaged 46% of the In Atlanta in 1999, SOA averaged 46% of the total OC but with highs of 88% total OC but with highs of 88%
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Turpin Approach for SOA formationTurpin Approach for SOA formation The primary aerosol elemental carbon The primary aerosol elemental carbon (EC)(EC)pripri and and
particle organic content particle organic content (OC)(OC)pripri in an un-reacted in an un-reacted
airshed are measured and a primary ratio of airshed are measured and a primary ratio of {{OC OC //ECEC}}pripri is determined is determined (Turpin et al for 1984 and 1987 aerosol (Turpin et al for 1984 and 1987 aerosol samples)samples)
Under SOA formation OCUnder SOA formation OCtottot and EC and ECtottot are measured are measured
OCOCsecsec= = OCOCtottot- - OCOCpri pri
OCOCpripri = EC = EC {{OCOC /EC} /EC} pripri
On smoggy days in California ~50 - 80% of the organic On smoggy days in California ~50 - 80% of the organic carbon comes from secondary aerosol formationcarbon comes from secondary aerosol formation
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Spyros Pandis also recently looked Spyros Pandis also recently looked at OC/EC ratios (Pittsburgh area)at OC/EC ratios (Pittsburgh area)
He estimates that SOA formation can He estimates that SOA formation can account for 35-50% of the organic account for 35-50% of the organic carboncarbon
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OC/EC Ratio and Photochemical Activity
0
2
4
6
8
10
12
14
15-Jul 16-Jul 17-Jul 18-Jul 19-Jul
OC
/EC
Ra
tio
0
10
20
30
40
50
60
70
80
90
100
O3
(p
pb
)
OC/ECO3
Pittsburgh, 2001
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If we look at the IR spectra of aerosols collected from the smoky mountains, they look like lab aerosols from acid catalyzed
particle phase reactions of carbonyls…
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0
0.001
0.002
0.003
0.004
0.005
5001000150020002500300035004000
wavelength (cm-1)
ab
so
rba
nc
e (
gly
ox
al)
glyoxal/acid-catalyst
Heterogeneous reactions as seen in Heterogeneous reactions as seen in the IR regionthe IR region
0
0.001
0.002
0.003
0.004
0.005
5001000150020002500300035004000
wavelength (cm-1)
ab
so
rba
nc
e (
gly
ox
al)
-0.1
-0.05
0
0.05
0.1
0.15
ab
so
rba
nc
e (
Sm
ok
y M
ou
nta
ins
)
glyoxal/acid-catalyst
Smoky Mountains SOA
C-O-C bonds
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In the 1980s In the 1980s Yamasaki, Bidelman, Yamasaki, Bidelman, PankowPankow began to investigate the began to investigate the equilibrium distribution ofequilibrium distribution of PAHs, PAHs, alkanes, and chlorinated organicsalkanes, and chlorinated organics between the gas and the particle between the gas and the particle phases.phases.
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K PAH
PAH TSPp
part
gas
PAHPAHgas gas + surface + surface PAH PAHpartpart
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log Klog Kp p = -log P= -log Pssoo + const. + const.
Relate solid saturated vapor pressures with Kp
log Pso
log Kp
naphthalenenaphthalene
BaPBaP
PyrenePyrene
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log Klog Kp p = -log P= -log PooLL + const. + const.
PAHs,PAHs, alkanesalkaneschlorinatedchlorinated organics organics
slope = -1
log Po(L)
log Kp
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Problems with the theoryProblems with the theory
many aerosols are composed of 40-100% many aerosols are composed of 40-100% organicsorganics
This gives much more than a mono-layer This gives much more than a mono-layer of coverageof coverage
log Klog Kpp= m log P= m log Poo(L)(L)+ c+ c
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KR T
p M wpLo
7 5 0 1
1 0 9
. fom
In 1994 James Pankow fixes the theory for liquid particles
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Can we chemically / kinetically Can we chemically / kinetically model SOA Formation???model SOA Formation???
Numerical fittingNumerical fitting Semi-explicitSemi-explicit
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From a modelingFrom a modeling perspective perspective Equilibrium Organic Gas-particle Equilibrium Organic Gas-particle partitioningpartitioning provides a context for provides a context for addressing SOA formationaddressing SOA formation
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Gas/Particle PartitioningGas/Particle Partitioning
particleParticle typeCompound Temperature
Humidity
gas
Thermodynamic Equilibrium?
TSPC
CK
gas
partp
Cgas +surf Cpart
Kp will vary with 1/Po
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Odum-Seinfeld Model SOA modelOdum-Seinfeld Model SOA model
Y= MY= Moo / / HC HC
Y Y MK
K Mii
o
i om i
om i oi
,
,( )1
Odum theory
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- pinene- NOx experiments by Odum
Y Mo(g/m3) 1 0.012 1
2 0.028 7
3 0.059 22
4 0.067 34
5 0.078 38
6 0.122 83
7 0.125 94
Y MK
K MM
K
K Mo
om
om oo
om
om o
1 1
1
2 2
21 1,
,
,
,( ) ( )
Y = M= Moo / / HC HC
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-pinene
Y MK
K MM
K
K Mo
om
om oo
om
om o
1 1
1
2 2
21 1,
,
,
,( ) ( )
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Y MK
K MM
K
K Mo
om
om oo
om
om o
1 1
1
2 2
21 1,
,
,
,( ) ( )
Numerical fitting values for Kom and for OH, O3, and NO3 reactions with terpenes and sesquiterpenes were developed by Griffin and Sienfeld et al.
From the averages for OH, O3, and NO3 , the amounts of atmospherically reacted terpenes and sesquiterpenes were estimated ( HC HC ) ) by Griffin and Sienfeld et al.
Y= MY= Moo / / HC HC
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Globally, biogenic emissions
13-24x1012g y-1 of aerosol mass
Gives little insight into the chemical nature of products involve in SOA formation
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From a global perspective, fire From a global perspective, fire results in huge emissions of black results in huge emissions of black carbon into the atmospherecarbon into the atmosphere
Biomass burningBiomass burning 6x106x1012 12 gg Fossil fuel burningFossil fuel burning 7x107x1012 12 gg
Biogenic aerosolsBiogenic aerosols 13-60x1013-60x101212gg((presentations by: presentations by: Schnaiter and Jackobson)Schnaiter and Jackobson)
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Semi explicit models link gas and particle phases
C=OO
cis-pinonaldhyde
particleC=OO
Gas phase reactions
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K
R T
p M wpLo
7 5 0 1
1 0 9
. fom
Kp = kon/koff
[ [ iigasgas] + [part] ] + [part] [ [ iipartpart]] kon
koff
particle
kon
koff
C=OO
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Kp = kon/koff
koff = kbT/h e -Ea/RT
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Particle formation-self nucleationParticle formation-self nucleation
Criegee’s can react with aldehydes and Criegee’s can react with aldehydes and carboxylic groups to form secondary carboxylic groups to form secondary ozonides and ozonides and anhydridesanhydrides..
O=C
C=OCH3
+C
C=O.
CH3
oo.
C
C=OCH3
C
C=OCH3
O
oo
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Secondary Organic Aerosol Secondary Organic Aerosol (SOA) Formation of Toluene(SOA) Formation of Toluene
CH3
+ OH Highly oxygenated gas phase products
Sunlight
NONOxx
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NucleationNucleation
Klotz et al. observed a rapid particle Klotz et al. observed a rapid particle formation from the photolysis of formation from the photolysis of hexendiendial.hexendiendial. CH3
O
O
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C7KETENEC7KETENEO
C O
+
C14KETENE
OC
O
OO
O C
O
C14KETNE + C14KETENEC14KETNE + C14KETENE SEED1 SEED1
2+2
Cycloadditon
PoL ~ 10-21 torr
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Particle Growth from Toluene Particle Growth from Toluene Reaction with Background OHReaction with Background OH
bkg
6 min
10 min
3 min
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CHOOO
CH3
OO
O
Criegee2
Criegee1OO O
-pinene
O3
COOHCOOH
pinic acid
+ otherproducts
O
pinonic acid
CHOO
COOH
+ CO, HO2, OH
COOHO
norpinonaldehyde
norpinonic acid
Mechanism
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pinonaldehyde
OH
OO
O2
+
(a)(b)
(c)
(d)
(e)
pinonaldehyde
acetone
O
OO.
NO2NO
O
O.
pinald-oo
OH
pinonic acid
O
pinO2
OO.
NO2
NO
organic nitrate
+HO2
+NO2
pinald-PAN
=o
=o
=o
=o
=o
=o
=o
OO.
O2
=o
OO=C8=O
C8-oo.
O2
NO2NO
O
+ h
+
+CO+HO2=o
OO.
NO2NO
=o
=o+HO2
+ h
NO2NO
=o
OO.
C8-oo. (C8O2)
+CO+HO2
NO2
NO
(f)
(g)
CO2+
pinO2H2O+
+HO2
O2
OO
H3C-OO.
+oxygenated products
+NO2
+H3C-OONO2PAN
(stab-oxy)
+HO2
norpinonaldehyde
OOH
O=o+
pin-ooH
+OH
O
OO.
=o
NO2
NO
+CO2
norpinaldPAN
+NO2
+HO2
norpinonic acid+norpin-ooH
O
OONO2
=o
+O2
ONO2
=o
+
=o
ONO2
+
organic nitrate
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Overall kinetic MechanismOverall kinetic Mechanism
linked gas and particle phase rate linked gas and particle phase rate expressionsexpressions
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Particle Phase reactions
particle
C=OO
cis-pinonaldhyde
C=OO
polymers
Gas phase reactions
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Particle Phase reactions
particle
C=OO
cis-pinonaldhyde
C=OO
polymers
Gas phase reactions
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Particle Phase reactions
C=OO
cis-pinonaldhyde
C=OO
polymers
Gas phase reactions
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A
B
C
D
[H3O+]
O
OOH
O
O
OH
O
OH
O
[H3O+]
O
OH
OH
OO
O
O
O O
HO
O
O
1
[H3O+]
4
2
OH
H2C
O
O O
[H3O+]
O
O
O
HO
O O
HO
3
O
O
OH
O
O CH2
O
O
OH
2
2
9
O O
HO
4
O
6
O
HOb
a
a
5
b
7 8
O
O
2
2
10 11
A
B
C
D
[H3O+]
O
OOH
O
O
OH
O
OH
O
[H3O+]
O
OH
OH
OO
O
O
O O
HO
O
O
1
[H3O+]
4
2
OH
H2C
O
O O
[H3O+]
O
O
O
HO
O O
HO
3
O
O
OH
O
O CH2
O
O
OH
2
2
9
O O
HO
4
O
6
O
HOb
a
a
5
b
7 8
O
O
2
2
10 11
pinonaldehyde
2 x
Pinonaldehyde dimerization
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ESI-QTOF mass spectrum of SOA from ESI-QTOF mass spectrum of SOA from reaction of reaction of -pinene + O-pinene + O33 + acid seed + acid seed
aerosolaerosol (Tolocka et. al (Tolocka et. al., ., 20042004))
200 300 400 500 600 700 800 900 1000
m/z
337.
18 351.
18
361.
21
377.
2
393.
2
407.
2
423.
2
439.
2
453.
21 489.
32
300 320 340 360 380 400 420 440 460 480 500
321.
21
m/z
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17
7.0
7
19
1.1
2 20
7.1
1
22
5.1
12
33
.14
24
5.1
2
25
5.1
82
61
.11
28
9.1
8
30
1.1
8
31
3.2
3
32
7.1
6
34
1.2
35
9.2
36
0.2
150 200 250 300 350
Inte
nsity,
A.U
.
m/z
O
OH
O
H2C
O
177
207
341
261289
91
77
.07
19
1.1
2 20
7.1
1
22
5.1
12
33
.14
24
5.1
2
25
5.1
82
61
.11
28
9.1
8
30
1.1
8
31
3.2
3
32
7.1
6
34
1.2
35
9.2
36
0.2
150 200 250 300 350
Inte
nsity,
A.U
.
m/z
O
OH
O
H2C
O
177
207
341
261289
9
M Na+ (ESI-QTOF Tolocka et al, 2003)
Particle phase pinonaldehyde dimers Particle phase pinonaldehyde dimers from from -pinene +O-pinene +O3 3 on on acid particlesacid particles
Similar results were obtained by Hartmut Herrmann’s Similar results were obtained by Hartmut Herrmann’s group group (Atmos Envir, 2004)(Atmos Envir, 2004)
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Chemical SystemChemical System
-pinene
+ NOx+ sunlight + ozone----> aerosols
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0.95 ppm -pinene + 0. 44ppm NOx
O3NO
NO2
NO2
model
data
Time in hours EST
pp
mV
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Gas phase pinonaldehdye
OO
mg
/m3
Time in hours EST
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Particle phase
model TSP
mg
/m3
Particle phase
model TSP
mg
/m3
Measured particle mass vs. model
data
Time in hours EST
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Much lower terpene concentrations Much lower terpene concentrations
Different background aerosols which Different background aerosols which have different chemical and physical have different chemical and physical propertiesproperties
Low volatility gas phase products will Low volatility gas phase products will have different interactions with have different interactions with different pre-existing particlesdifferent pre-existing particles
The Real AtmosphereThe Real Atmosphere
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New UNC aerosol smog chamberNew UNC aerosol smog chamber
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Dual 270mDual 270m33 chamber chamber fine particle t fine particle t 1/21/2 >17 h >17 h
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0.1 ppmV Toluene 0.1 ppmV Toluene + 0.1 ppm NOx+ 0.1 ppm NOx
072705S
0.0
0.1
0.2
0.3
0.4
0.5
8:00 10:00 12:00 14:00 16:00
LDT (hours)
To
luen
e, N
Ox-
O3
con
c (p
pm
)
-20
-10
0
10
20
Par
ticl
e m
assc
on
c (
g/m
3)
TSP
O3
Toluene
TotNO3
NO
NO
2
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-pinene SOA formation in -pinene SOA formation in the presence of dilute diesel the presence of dilute diesel and woods soot particlesand woods soot particles
different solubilities of gas different solubilities of gas phase products in the phase products in the different soot matrices different soot matrices
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ss of of -pinene products in diesel -pinene products in diesel
and woods soot and woods soot particles(UNIFAC)particles(UNIFAC)
Compounds Diesel Wood
cis-pinonaldehyde ~5 ~1
pinalic-4-acid ~8 ~1
cis-pinonic acid ~8 ~1
10-hydroxypinonaldehyde ~25 ~1
cis-pinic acid ~11 ~2
* Jang et al. 1997. Envr.Sci.Tech. 31, 2805-2811
Activity Coefficients were estimated at 298 K and 50 RH% by UNIFAC.
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[ [ iigasgas] + [part] ] + [part] [ [ iipartpart]]
KR T
p M wpLo
7 5 0 1
1 0 9
. fom
Kp = kon/koff
kon
koff
kon = koff 7.5 RTfom / { poL Mw109}
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The bottom line???The bottom line???
We could not even come close to We could not even come close to predicting predicting -pinene SOA in the -pinene SOA in the presence of background presence of background diesel seeddiesel seed aerosolaerosol
Our model was consistently Our model was consistently under under predictingpredicting observed SOA formation observed SOA formation by a factor of 5 to 10 by a factor of 5 to 10
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50 50 g/mg/m33 of Diesel Soot Particles of Diesel Soot Particles
0
50
100
150
200
250
8 10 12 14 16 18Time (EDT)
Par
ticl
e m
ass
(ug/
m3 )
North SMPS
North filter
Inject diesel
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250 250 g/mg/m33 of Diesel Soot Particles of Diesel Soot Particles
0
50
100
150
200
250
300
350
400
450
500
8 10 12 14 16 18Time (EDT)
Par
ticl
e m
ass
(ug/
m3 )
South SMPS
South filter
Inject diesel
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Is the polarity of diesel exhaust particles Is the polarity of diesel exhaust particles changing as it ages changing as it ages SOA?? SOA?? Sangdon LeeSangdon Lee (Atmos. Envirn 2004) a(Atmos. Envirn 2004) added dded
deuterated alkanes to the chamber deuterated alkanes to the chamber atmosphere followed by the addition of atmosphere followed by the addition of diesel exhaustdiesel exhaust
Measured gas and particle phase Measured gas and particle phase concentrations and calculated a measured concentrations and calculated a measured
KKpp: : KKpp = d 42 = d 42partpart// {d 42 {d 42gasgasxTSP}xTSP}
Compared to theoryCompared to theory KR T
p M wpLo
7 5 0 1
1 0 9
. fom
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-4.0
-3.5
-3.0
-2.5
-2.0
11 12 13 14 15 16Time in hours (EDT)
Log
Kp
(m3 /u
g)
d42-eicosane_estimated
d42-eicosane_observed
Predicted Kp
Observed Kp
KR T
p M wpLo
7 5 0 1
1 0 9
. fom
Kd42
d42 xTSPp
part
gas
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When When --pinene is present the pinene is present the effect is even greatereffect is even greater
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Diesel particle polarity increases as it Diesel particle polarity increases as it ages and reacts in the presence of ages and reacts in the presence of --
pinenepinene
-3.8
-3.6
-3.4
-3.2
-3.0
-2.8
-2.6
-2.4
-2.2
-2.0
8 9 10 11 12 13 14Time in hours (EDT)
Log
Kp (
m3 /u
g)
d42-eicosane_estimated
d42-eicosane_observed
predicted
observed
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50 50 g/mg/m33 diesel exhaust diesel exhaust + 0.13 + 0.13 ppmppm -pinene-pinene in sunlight in sunlight
Add 0.13 ppmV -pinene
model
data
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Where do we go from here?Where do we go from here?
Begin integrating single compound mechanisms
Expand mechanisms to take into account longer atmospheric aging times
Build better nucleation representations
Build a particle size model which shows the distribution of products with size
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Where do we go from here?Where do we go from here?
Investigate the compounds that are resulting in SOA formation from diesel exhaust
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AcknowledgementsAcknowledgements
Grants from Grants from National Science FoundationNational Science Foundation
USEPA STAR RESEARCH GRANT programUSEPA STAR RESEARCH GRANT program
Gifts of a GC-FTIR-MS system (HP 5890 GC & Gifts of a GC-FTIR-MS system (HP 5890 GC & HP 5965B FT-Infrared Detector) from the HP 5965B FT-Infrared Detector) from the Hewlett Packard Corporation Hewlett Packard Corporation and the Saturn and the Saturn GC-ITMS fromGC-ITMS from the Varian Corpthe Varian Corp..
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Dept. Eviron Sci and Eng,NC Chapel HillNORTH CAROLINA
[email protected]://airsite.sph.unc.edu/~kamens