Download - Tzung-May Fu, Daniel J. Jacob Department of Earth and Planetary Sciences Harvard University
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Global Budgets of Atmospheric Glyoxal and Global Budgets of Atmospheric Glyoxal and
Methylglyoxal and Implications for Formation of Methylglyoxal and Implications for Formation of
Secondary Organic AerosolsSecondary Organic Aerosols
Tzung-May Fu, Daniel J. JacobDepartment of Earth and Planetary Sciences
Harvard University
Folkard Wittrock, John P. Burrows, Mihalis VrekoussisInstitute of Environmental Physics and Remote Sensing
University of Bremen
Fu et al. [2007b] submittedThis work is supported by EPRI
CHOCHO
(glyoxal)
CH3C(O)CHO
(methylglyoxal)
US EPA November 8 2007
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Organic Aerosols: Primary vs. SecondaryOrganic Aerosols: Primary vs. Secondary
Fossil fuel burning
Biomass burning
Direct emission
Primary Organic Aerosols (POA)
Secondary Organic Aerosols (SOA)
Isoprene Terpenes Aromatics
BIOGENIC SOURCES ANTHROPOGENIC SOURCES
Semi-volatile organic gases
Oxidation by OH, O3, NO3
Nucleation
Reversible partitioning on existing particles
FF: 45-80 TgC y-1
BB: 10-30 TgC y-1
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ACE-Asia: OC aerosol measurements in the free troposphere ACE-Asia: OC aerosol measurements in the free troposphere
Mean ObservationsMean Simulation (GEOS-Chem global CTM)Observations+
Concentrations of OC in the FT were under-predicted by a factor of 10-100Current knowledge is missing a large SOA source
[Mader et al., 2002] [Huebert et al., 2003] [Maria et al., 2003]
(ACE-Asia aircraft campaign conducted off of Japan April/May 2001)
Heald et al. [2005], GRL
c/o Colette Heald
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Where is the large missing SOA source?Where is the large missing SOA source?
Secondary Organic Aerosols (SOA)
Isoprene
400 Tg y-1
Terpenes Aromatics
BIOGENIC SOURCES ANTHROPOGENIC SOURCES
Semi-volatile organic gases
Oxidation by OH, O3, NO3
Volkamer et al. [2006]
SO
Ao
bs /
SO
Am
od
el
Nucleation
Reversible partitioning on existing particles
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SOA formation by reactive uptake of dicarbonylsSOA formation by reactive uptake of dicarbonyls
glyoxalSOA
Isoprene (400 Tg y-1), monoterpenes, acetone, MBO, C2H4, C3H6
Photolysis
Oxidation
Deposition
Oligomers?
organic acids?
~ 2.9 hr
Acetone, C2H2, isoalkanes, alkenes, aromatics, glycolaldehyde, hydroxyacetone, primary emissions
methylglyoxal
OH, O3, NO3
~ 1.6 h
Our goal: build global model
Irreversible uptake?
Fu et al. [2007b]
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What What are the irreversible processesare the irreversible processes in the AQ phase? in the AQ phase?
H2O
H2O
Oligomers
+ hydrates + H2O
Kalberer et al. [2004]Liggio et al. [2005] Hastings et al. [2005] Zhao et al. [2006]Loeffler et al. [2006]
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Organic acids
+ OH ?
Ervens et al. [2004]Lim et al. [2005]Carlton et al. [2006, 2007]Warneck et al. [2005]Sorooshian et al. [2006]
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Altieri et al. [2006]
3
H* ~ 105
H* ~ 103
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First detailed global simulation of glyoxal and methylglyoxalFirst detailed global simulation of glyoxal and methylglyoxal
glyoxalSOA
Isoprene (400 Tg y-1), monoterpenes, acetone, MBO, C2H4, C3H6
Irreversible uptake
Photolysis
Oxidation
Deposition
lifetime ~ 2.9 hr
Acetone, C2H2, isoalkanes, alkenes, aromatics, glycolaldehyde, hydroxyacetone, primary emissions
methylglyoxal
OH, O3, NO3
lifetime ~ 1.6 hr
Built on GEOS-Chem global 3D CTM
Fu et al. [2007b]
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New New isoprene oxidation adapted from MCM v3.1isoprene oxidation adapted from MCM v3.1
Isoprene + OH
0.046 Glyoxal + 0.16 Glycolaldehyde + 0.13 Methylglyoxal + 0.15 Hydroxyacetone
ON
O
O
O OH
OOH
O O O
OO
HO
OO
O
O
OH
Isoprene
C5 carbonylsHydroxy-
methylvinyl ketone Methylvinyl ketone Methacrolein
Glyoxal Glycolaldehyde Methylglyoxal Hydroxyacetone
Methyl-nitroxy butenal
25% 12% 37% 26%
18%33% 32%62%
29% 51% 24%39%
87%16%
45%52%
+ OH+ NO3
+ NO + NO
16%
84%
16%
84%
2%
andisomers
0.5%
Organicnitrates
Organicnitrates
Fu et al. [2007b]
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Result: Sources of glyoxal and methylglyoxalResult: Sources of glyoxal and methylglyoxal
1 Isoprene is largest source for both glyoxal (47%) and methylglyoxal (79%).
2 Second largest sources C2H2 and acetone long lifetime dicarbonyl background
3 Glyoxal is more sensitive to non-biogenic emissions
Isoprene 110
Monoterpenes 3.5
Aromatics 1.4
Hydroxyacetone 3.6
Isoalkanes 3.7
>C2 alkenes 4.1
Methylglyoxal 5
Acetone 10
Glyoxal 45 Tg y-1 Methylglyoxal 140 Tg y-1
55%
20% 17%
8%
87%
5%
3%
5%BiogenicBiomass burningBiofuel useAnthropogenic
Isoprene 21
Acetylene8.9
Glyoxal 7.7 Ethene 2.5
Monoterpenes 1.8
Aromatics 2.0
Glycolaldehyde 0.54
MBO 0.35
(47%)
(79%)
Fu et al. [2007b]
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Result: Photolysis is the dominant sink of dicarbonylsResult: Photolysis is the dominant sink of dicarbonyls
Glyoxal Methylglyoxal
PhotolysisOxidationSOA formationDry depositionWet deposition
2.9 hours 1.6 hoursLifetime:
1 Photolysis is the dominant sink for both dicarbonyls
2 SOA formation must compete against photolysis and oxidation
3 90% of SOA formation is in clouds
45 Tg y-1 140 Tg y-1Sink:
15 Gg 25 GgBurden:
Fu et al. [2007b]
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Simulated global concentrations of glyoxalSimulated global concentrations of glyoxal
Isoprene 21
C2H2 8.9
Glyoxal 7.7 C2H4 2.5
Monoterpenes 1.8
Aromatics 2.0
Glycolaldehyde 0.54
MBO 0.35
2 Northern mid-latitude summertime model glyoxal ~ 10-100 ppt
1 Biomass burning: highest surface concentration
3 Acetylene: hemispheric background and anthropogenic outflow
Fu et al. [2007b]
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Simulated global concentrations of methylglyoxalSimulated global concentrations of methylglyoxal
Isoprene 110
Monoterpenes 3.5
Aromatics 1.4
Hydroxyacetone 3.6
Isoalkanes 3.7
>C2 alkenes 4.1
Methylglyoxal 5
Acetone 10 2 Northern mid-latitude summertime model methylglyoxal ~ 20-150 ppt, w/ stronger biogenic pattern
1 Biomass burning: highest surface concentration
3 Acetone: global background and anthropogenic outflow
Fu et al. [2007b]
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Simulated dicarbonyl concentrations are Simulated dicarbonyl concentrations are consistent with available in situ measurementsconsistent with available in situ measurements
Glyoxal Methylglyoxal
Northern mid-latitudes (summer)Marine boundary layer
Free troposphere
1 Northern mid-latitudes summertime dicarbonyl concentrations consistent with measurements
2 Marine boundary layer model underestimates dicarbonyls?Fu et al. [2007b]
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Simulated glyoxal pattern consistent w/ satellite over landSimulated glyoxal pattern consistent w/ satellite over land
Wittrock et al. [2006a,b]
Overall error ~ 4 x 1014 molec cm-2
Over land: simulated glyoxal column pattern agrees well with satellite observations, but model concentrations are 50% lower
Satellite product has error ~ 4 x 1014 molec cm-2 and issues with clouds [Wittrock et al., 2006b]
Fu et al. [2007b]
SCIAMACHY GEOS-Chem
1~3.5 x 1014 molec cm-2 0.5~2 x 1014 molec cm-2
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Is there a large unknown marine source of glyoxal?Is there a large unknown marine source of glyoxal?
Wittrock et al. [2006a]
Over tropical ocean: satellite retrieve high glyoxal column
interference by chlorophyll?
unknown marine emissions or precursors?
Fu et al. [2007b]
SCIAMACHY
MODIS chlorophyll 2006
GEOS-Chem
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Terpenes Isoprene Aromatics Glyoxal +Methylglyoxal
An
nu
al S
OA
so
urc
e [T
g C
y-1]
Dicarbonyls produce large amounts of SOA!Dicarbonyls produce large amounts of SOA!
6.7
9.0
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1.8
Reversible partitioning Irreversible uptake by aerosol (10%) and clouds (90%)
SOA production via irreversible uptake of dicarbonyls comparable
to SOA production from reversible partitioning
Glyoxal 2.6
Methyl-gyloxal 8.0
AnthropogenicBiofuel useBiomass burningBiogenic
Fu et al. [2007b]
20%
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Are the reversible / irreversible production of SOA Are the reversible / irreversible production of SOA from isoprene oxidation products additive?from isoprene oxidation products additive?
Kroll et al. [2006], Surrat et al. [2006]
Isoprene
Methacrolein
Methyl vinyl ketone
SOA from reversible partitioningX
It is unclear, BUT
Experiments conducted at RH < 10% no aqueous reaction
(glyoxal and methylglyoxal)
(methylglyoxal)
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Major findings : Global budgets of dicarbonyls Major findings : Global budgets of dicarbonyls and their SOA productionand their SOA production
OH, NO3, O3
CHOCHO+
CH3COCHOIrreversible uptake
SOA production from dicarbonyls 11 Tg C y-1
Current simulated SOA sources from biogenic terpenes (9 Tg C y-1), isoprene (7 Tg C y-1) and aromatics are too small!
Isoprene, monoterpenes, acetone, MBO, C2H4, C3H6
Acetone, C2H2, isoalkanes, alkenes, aromatics, glycolaldehyde, hydroxyacetone, primary emissions
Isoprene is the largest source of dicarbonyls
20% of SOA produced via dicarbonyls are from non-biogenic emissions, especially in FT
Fu et al. [2007b]
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Contribution of dicarbonyl SOA in U.S.Contribution of dicarbonyl SOA in U.S.
Aircraft measurements during ICARTT (summer 2004)
Water Soluble Organic Carbon by Rodney Weber at Georgia Tech
Samples influenced by biomass burning removed
Observed WSOC
Modelw/ dicarbonyl
SOA
Modelw/o dicarbonyl
SOA
Observed WSOCModel w/ dicarbonyl SOAModel w/o dicarbonyl SOA
Alt
itu
de
[km
]
WSOC [g C m-3 STP][g C m-3 STP]
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Observed WSOC
Model WSOC including SOA from dicarbonyl
Model WSOC without SOA from dicarbonyls
Correlation coefficient (r)
ICARTT WP3 measurements in FT (2 to 6 km), without biomass burning samples
WSOC correlation with other measured tracersWSOC correlation with other measured tracers
Dicarbonyl SOA
captures a lot of the observed variation
correlates with sulfate (aqueous processes) and toluene (anthropogenic precursors)0 0.1 0.2 0.3 0.4 0.5
OBS WSOC
CO
Sulfate
Methanol
Ammonium
Benzene
Toluene
PAN
Acetylene
Methyl nitrate
Ethyl nitrate
Isopropyl nitrate
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WSOC production in cloud – need regional modelWSOC production in cloud – need regional model
Measurements on Twin Otter during ICARTT (summer 2004)Sorooshian et al. [2006]
SO4OxalateNH4 NO3
Power plant plume in cloudsMeasured oxalate consistent with toluene being precursor
SO4 [nmol m-3]
Oxa
late
[
nm
ol
m-3]
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Using suite of satellite observations to diagnose Using suite of satellite observations to diagnose regional pollutant emission and chemistryregional pollutant emission and chemistry
NO2 June 2005 Glyoxal June 2005 SO2 June 2005
c/o KNMI c/o KNMIc/o T. Kurosu
July 25
2005
July 26
2005
July 27
2005
Glyoxal HCHO NO2Volkamer et al. [2006]