Download - Improved Prediction of In-Cloud Biogenic SOA
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Improved Prediction of In-Cloud Biogenic SOA: Experiments and CMAQ Model Refinements
Barbara Turpin, PISybil Seitzinger, Co-I
Rutgers UniversityNew Brunswick, NJ
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SOA –
a major fine particle constituent
Zhang GRL 2007
organicsulfateammoniumnitrate
OOAHOA
Aerosol Mass Spectrometer Data
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CondensationEvaporation
VolatileOrganicCompound>C7
Oxidation (+OH, NO3 , O3 )
Semi-volatile Products
pre-existing particlePartitioning into OM
SOAVolatileproducts
Gas-phaseReactions
Pankow 1994, AE
Odum 1996, ES&T
Traditional “smog chamber”
SOA
Precursors must be large (>C7) to produce high yields because partitioning depends on product vapor pressure
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Dept of Environmental SciencesWhile important, fails to explain:
•Predictive models capture organic aerosol poorly (Hallquist ACP 2009)
•Atmospheric O/C > smog chamber O/C (Aiken EST 2008)
atmos. HOA = 0.06 – 0.1atmos. OOA-SV = 0.5 – 0.6atmos. OOA-LV = 0.8 – 1.0
sm. chamber SOA = 0.3 – 0.5
•Liquid water may be more accessible than OMe.g., high humidities of eastern US
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Cloud evaporation
SOA
·OH
·OH
·OH
NOx
·OH
·OH
·OH
NOx
NOx, alkenes, aromatics
O
OO
O
·OH O3
·OH
Isoprene
In Clouds and Fogs:Hypothesis: Blando and Turpin, AtmosEnv, 2000
Gelencser and Varga, ACP, 2005
Organic gases are oxidized forming water-soluble compounds.
These partition into cloud droplets and react further (e.g., by ·OH).
Cloud droplets evaporate, lower volatility products remain, forming SOA.
and in Aerosol Water:Hypothesis: Carlton AtmosEnv, 2007
Volkamer GRL, 2007
Water-soluble gases partition into aerosol water and react.
Lower volatility products remain, forming SOA.
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SOA through Aqueous Chemistry: Partitioning driven by water solubility
isoprene
Wet aerosol
SOAglyoxal OH
PartitioningOH
oligomerization
Aerosol water(LWC)
Organic/inorganic
constituents
Partitioning
low volatilityproducts
OH
oligomerization
Clouddroplet
SOACloud Droplet Evaporation
Volatile butHighly water soluble
~M
~0.1- 10M
glyoxal uptake
glyoxal evaporation
Implications•organic PM loading •vertical distribution•different precursors
(Volkamer ACP, 2009)
•product O/C
1
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Carlton GRL 2006, AE 2007; Altieri EST 2006, AE 2008; Perri AE 2009
Previous research:Major products of OH radical oxidation verified (≥1mM)
Phase transfersRxs with •OH
Aqueous phase
ISOPRENE + oxidants (·OH, O3, NO3)
HOCH2CHO CHOCHO CH3COCHO(glycolaldehyde) (glyoxal) (methylglyoxal)
HOCH2CH(OH)2 (OH)2CHCH(OH)2 CH3COCH(OH)2
HOCH2COOH CH3COCOOH(glycolic acid) (pyruvic acid)
(OH)2CHCOOH CH3COOH(glyoxylic acid) (acetic acid)
HOOCCOOH CH2(OH)2(oxalic acid) (formaldehyde - hydrated)
CO2 HCOOH(formic acid)
Gas phase
(hydrated glyoxal)
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Demonstrate kinetic feasibility of SOA formation through cloud processing using (mostly) measured rate const.
Rate constants available from cloud and wastewater literature Herrmann, Monod, Stefan and Bolton
Questions:How does precursor concentration matter?How do high molecular weight products form?Can the chemical model reproduce experiments?How do anthropogenic emissions impact biogenic
“aqueous” SOA formation?
Warneck AE 2003; Ervens JGR 2004; Lim EST 2005
Previous research:Cloud chemistry/parcel model predictions
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Overall Goal:Improve the simulation of secondary organic aerosol (SOA)
formation through atmospheric aqueous chemistry
Approach:• Conduct aqueous experiments at cloud concentrations and
HNO3 (glyoxal/ methylglyoxal + OH)
• Validate/refine aqueous chemical mechanisms; update the cloud chemistry model
• Add in-cloud SOA formation to CMAQ
• Begin to explore the magnitude of in-cloud SOA formation and role of NOx /HNO3 in SOA formation from isoprene through cloud processing
Improved Prediction of In-Cloud Biogenic SOA
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Roles of NOx in Aqueous SOA from Isoprene:
1. Gas phase formation of atmospheric oxidants
2. Gas phase formation of water soluble carbonyls
3. Aqueous NO3 catalysis, organic nitrogen products?
Project Experiments
Modeling (collaborators)
This Project
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On-line ESI MS; IC-ESI-MS; FT-ICR MS; ESI-MS-MS, UV or IC for organic acids, DOC for mass balance, H2 O2
Experiments 10 ‐
3000 M ORG H2
O2
+hν ∙OH (10‐12 M)2‐5 pH± HNO3
, NH4
ORG: glyoxal, methylglyoxal
Controls ORG+Prod+UV
± HNO3
, NH4
ORG+Prod+H2
O2
± HNO3
, NH4UV+H2
O2
Aqueous-Phase Reactions with Product Analysis
Goal: Validate/Refine Aqueous Chemistry Model
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Precursor/products modeled in reaction vessel: C
once
ntra
tion
(M
)
Time (min)
Methylglyoxal + OH radical
methylglyoxal
pyruvic acid
acetic acid
glyoxylic acid, formic acid, formaldehyde
oxalic acid
Methylglyoxal
Acetic acid
Glyoxylicacid
Pyruvic acid
formic acid
H2O2
·OH
Oxalic acid
Formaldehyde
Tan AE, 2010
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Dilute aqueous chemistry model reproduces oxalic, pyruvic acid and total organic carbon at 30 M
0 50 100 150 2000
5
10
15
20
25
30
35
0 50 100 150 2000
50
100
150
200
250
0 50 100 150 2000
200
400
600
800
1000
(a)
30 M glyoxal
(b)
300 M glyoxal
Oxa
lic A
cid
Con
cent
ratio
n (
M)
Model Prediction No H2SO4
280 M H2SO4
840 M H2SO4
(c)
3000 M glyoxal
Time (min)
0
2
4
6
8
10
0
20
40
60
80
100
0 100 200 300 4000
100
200
300
400
without H2SO4
280 M H2SO4
840 M H2SO4
model prediction
Oxa
lic a
cid
(M
)
Time (min)
30 M methylglyoxal + 0.15 mM H2O2
300 M methylglyoxal+ 1.5 mM H2O2
MethylglyoxalGlyoxal
Cloud relevant ~30 M
300 M
3000 M
Oxa
lic A
cid
(M
)
Oxa
lic A
cid
(M
)
Time (min) Time (min)
Tan EST 2009; AE 2010
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Methylglyoxal (3000 M) + OH radical (10-12 M)
Oxalate formation verified with IC ESI-MSMethylglyoxal
Acetic acid
Glyoxylic acid
Pyruvic acid
formic acid
H2 O2
·OH
Oxalic acid
Formaldehyde
Oxalic acid (pk I, m/z- 89)
Pyruvic acid
40
30
20
10
00 5 10
Abu
ndan
ce
93
J
I
H
contaminant 1
CA+B
JI
H
contaminant 1
C
117
89
11997
92
87
14175 A+BConductivity (S)
Tim
e (m
in)
1000
2000
3000
1x105
2x105
2000
4000
1x104
2x104
1x105
2x105
0 100 200 300
3x104
6x104
m/z-
IC ESI-MS
Acetic acid
Oxalic acid
Tim
e (m
in)
m/z-
(180 min)
Tan AE, 2010
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40
35
30
25
20
15
10
5
00 10 20 30 40 50
157143131
8789
89
191
C
A
unknown 1
C
Aunknown 1
Conductivity (S)
Tim
e (m
in)
0
2x104
4x104
6x104
8x104
0
1x105
2x105
3x105
abun
danc
e
0 100 200 3000
2x104
4x104
6x104
8x104
m/z-
40
35
30
25
20
15
10
5
00 20 40 60 80
113 199
191B
A+B
A
Conductivity (S)
Tim
e (m
in)
0 100 200 3000
2x104
4x104
6x104
m/z-
Methylglyoxal (3000 M) + UV
Methylglyoxal experiment with IC ESI-MS
IC ESI-MS IC ESI-MS
Methylglyoxal (3000 M) + H2 O2
Acetic acidPyruvic acid
Oxalic acid
Tim
e (m
in)
m/z-
m/z-
Oxalic acid forms only in the presence of OH radical
No oxalic acid forms in control experimentsNo oxalic acid
forms in control experiments
(180 min)
Tan AE, 2010
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Little effect on oxalate (slighly faster decay with nitric acid)No change in nitrate or sulfate throughout the reactionNo discernable change in IC ESI-MSMight still form enough organic-N to observe by FT-ICR MS
Addition of HNO3
(1.7 mM) or (NH4
)2
SO4
(0.84 mM)to glyoxal (1 mM) and OH radical (10‐12
M)
Kirkland, in prep
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0 10 20 30 40 50 600.3
0.4
0.5
0.6
0.7
0.8
0.0 0.1 0.2 0.3 0.40.3
0.4
0.5
0.6
0.7
0.8
0.0 0.1 0.2 0.3 0.43
4
5
6
7
8
9
10
0 10 20 30 40 50 60
Y c [%
]
3
4
5
6
7
8
9
10
[min h-1]
[min h-1]
Y c [%
]
Y c [%
]Y c
[%]
LWCav [g m-3]
LWCav
[g m-3]
(a) VOC/NOx = 5 r2 = 0.72
(b) VOC/NOx = 5 r2 = 0.45
(d) VOC/NOx = 100 r2 = 0.55
(c) VOC/NOx = 100 r2 = 0.69
0.1 1 10 10005
1015202530354045
Trajectory 1Trajectory 2Trajectory 3
VOC/NOx
Y c [%
]
Impact of NOx on SOA from isoprene through cloud proc.
Note: higher SOA yields with higher NOx because more gas phase production of water soluble carbonyls
Ervens GRL 2008Ervens ACP 2010
Yield (%) = mass C in SOAmass isoprene C
Feingold microphys. cloud model
•multiple cycles •stratocumulus•partitioning of wsoc•gas+aq chem•Ervens aq chem •altered Gly, PA chem
Cloud contact time
VOC/NOx
Yiel
d c(%
)
Yiel
d c(%
)
Yiel
d c(%
)
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Model deviates from measurements at higher concentrations – what happens in wet aerosols?
0 50 100 150 2000
5
10
15
20
25
30
35
0 50 100 150 2000
50
100
150
200
250
0 50 100 150 2000
200
400
600
800
1000
(a)
30 M glyoxal
(b)
300 M glyoxal
Oxa
lic A
cid
Con
cent
ratio
n (
M)
Model Prediction No H2SO4
280 M H2SO4
840 M H2SO4
(c)
3000 M glyoxal
Time (min)
0
2
4
6
8
10
0
20
40
60
80
100
0 100 200 300 4000
100
200
300
400
without H2SO4
280 M H2SO4
840 M H2SO4
model prediction
Oxa
lic a
cid
(M
)
Time (min)
30 M methylglyoxal + 0.15 mM H2O2
300 M methylglyoxal+ 1.5 mM H2O2
MethylglyoxalGlyoxal
Cloud relevant ~30 M
Aerosol relevant ~1-10 M
Oxa
lic A
cid
(M
)
Oxa
lic A
cid
(M
)
Time (min) Time (min)
300 M
3000 M
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(a) ESI-MS 69 min. neg mode
(b) ESI FT-ICR MS69 min. neg mode
Peak Location300 350 400 450 500
Peak
Hei
ght
0
20
40
m/z50 100 150 200 250 300 350 400 450 500 550 6001000
Ion
abun
danc
e
0
2000
4000
6000
8000
10000
C14H17O12377.070380
C17H13O11393.044360
C16H19O14435.075940
C13H15O12363.054800
C23H13O20465.177920
C12H13O20476.99925
m/z0 100 200 300
Ion
abun
danc
e
0100000200000300000400000500000
73
87
89
PA
GA
•High MW products
•O/C ~ 1
•Not seen in std mix (not ESI artifact)
•Not in controls (·OH involved)
Ultra high resolution FT-ICR MS (9.4 T) provides exact elemental comp. > m/z 300
OA
Methylglyoxal (1mM) + ∙OH
*Electrospray ionization Fourier transform-ion cyclotron resonance mass spectrometry
Altieri AE 2008
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40
35
30
25
20
15
10
5
00 10 20
Abu
ndan
ce
unknown 2
221 263249
235
89
119177
133177
175161
87
75
177
103
117
177
131
unknown 3
I
H
F
E
unknown 2
A+B+C
unknown 3
IH
FE
A+B+C
Conductivity (S)
Tim
e (m
in)
02x104
4x104
0
3x105
6x105
03x105
6x105
05x104
1x105
0
1x104
2x104
01x105
2x105
0 100 200 3000
3x104
6x104
m/z-
Chemistry at Higher Concentrations―Methylglyoxal
Higher-MW ions
Oxalic acid (peak I, m/z- 89)
RT of Succinic acid (m/z- 117)
RT of Malonic acid (m/z- 103)
Formation of higher C# products
Tan AE, 2010
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0 100 200 300 4000
100
200
300
400
Oxa
lic a
cid
(M
)
Time (min)
Chemistry at Higher Concentrations―Methylglyoxal
Larger acids are important products at higher concentrations.
Formation of higher C# products suggests radical-
radical reactions0
100
200
300
peak F quantified as malonic acid
peak E quantified as succinic acid
Con
cent
ratio
n (
M)
without H2SO4
280 M H2SO4
840 M H2SO4
0 100 200 300 4000
50
100
150
200
Con
cent
ratio
n (
M)
Time (min)(Tan AE 2010)
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OO 2 H2O OHHO
OHHOH+
OH
H2O
OHHO
OHHO
O2OHHO
OHHO
OHO
OHHO
OO
RO2
OHHO
OHHOO
HO
HO+ O
OH
OH
O2 HO2
O
HO
glyoxal(hydrated)
1 glyoxylic acid(hydrated)
2 formic acid
+ HO2
OHO
OHHO
O2OHO
OHHOOO
OO
OHHO3 oxalic acid
+ HO2
OHO
OHHOO
OHO
OHHOO +
OO
OHO
O
HO+ CO2
CO2
CO2
glyoxal
decomposition
+ O2
+ O2
OH
H2O
RO2decomposition
decomposition
decomposition
O2 HO2
OH
H2O
O2 HO2
decomposition
R*1
R*3
R*2
R*4
R*4
4(hydrated)
4
4
4
4(hydrated)
Aqueous Mechanism - Glyoxal Y Lim ACPD 2010
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Y Lim ACPD 2010
Mass o
xalat
e
formed
per m
ass
glyox
al rea
cted
Mass high MW
products formed
per mass glyoxal
reacted
Model produces oxalate at cloud‐relevant concentrations and oligomers at aerosol‐relevant
glyoxal concentrations (OH radical = 10‐12
M)
Cloud wet aerosol
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Chemistry in wet aerosols –
complex
•Photolysis and photooxidation reactions
•Reactions of organics with ammonium and amines to form organic-nitrogen compounds
•Reactions of organics with sulfate to form organic-sulfates
•Acid and ammonium catalyzed oligomerization
Investigators include:Anastasio, Claeys, Cordova, de Haan, Flagan, Galloway, Grgic, Guzman, Hoffmann, Jimenez, Keutsch, Liu, Maenhaut, Michaud, McNeill, Monod, Noziere, Sareen, Seinfeld, Shapiro, Sun, Tolbert, Volkamer, Wortham, Yasmeen, Zhang
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SOA formation from glyoxal
increases with LWC
SOA formation faster with OH radical (light)
Volkamer ACP 2009
(Seed: ammonium bisulfate + humic acid salt; acetylene; hydrogen peroxide; light/dark) Dark reaction
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(Carlton EST 2008)
Improved model
performance;
ICARTT
SOA through cloud processing now in CMAQ (yields)
“Aqueous” comparable in magnitude to “smog chamber” SOA(Chen ACP 2007; Fu JGR 2008; Carlton EST 2008; Fu Atmos.Environ. 2009)
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Dept of Environmental SciencesOverview
(Lim et al., ACPD 2010)
•Predictive models capture organic aerosol poorlyaqueous SOA precursors different (Volkamer ACP 2009)improved with “aqueous” SOA (Carlton EST 2008)
•Atmospheric O/C > smog chamber O/C (Aiken EST 2008)
atmos. OOA-LV = 0.8 – 1.0 atmos. OOA-SV = 0.5 – 0.6sm. chamber SOA = 0.3 – 0.5aqueous SOA = 1-2
•Sometimes liquid water is more accessible than OM e.g., high humidities of eastern US
•Atlanta - SOA is correlated with liquid waterAtlanta (Hennigan GRL 2008; Hennigan ACP 2009)
•Anthropogenic pollutants generate biogenic SOAhigher yields for aqueous SOA from isoprene at high NOx (Ervens GRL 2008)
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Secondary Organic Aerosol
Past/present Students, PostdocsHo Jin LimKatie AltieriYi TanMark PerriYong Bin LimDiana Ortiz SupportMary Moore U.S. EPA – STARAnjuli RamosPhyllis KuoJeff Kirkland
Acknowledgements