View
218
Download
2
Tags:
Embed Size (px)
Citation preview
1
Global simulation Global simulation of glyoxalof glyoxal
and methylglyoxal,and methylglyoxal,
and implications for SOAand implications for SOA
Tzung-May Fu, Daniel J. Jacob
Harvard University
April 11, 2007Work supported by EPRI
Thomas Kurosu, Kelly Chance
Harvard/SAO CfA
CHOCHO
CH3C(O)CHO
2
SOA formation through uptake of dicarbonylsSOA formation through uptake of dicarbonyls
CHOCHOSOA
Isoprene (350 Tg C yr-1), monoterpenes, acetone, MBO, C2H4, C3H6
Reversible?
Photolysis
Oxidation
Deposition
[OH]
RH
pH
nuclei
Oligomers?
organic acids?
H* ~ 105
C2H2, C2H4, C3H6, aromatics, acetone, glycolaldehyde, hydroxyacetone
CH3C(O)CHOH* ~ 103
OH, O3, NO3
3
Is dicarbonyl uptake irreversible?Is dicarbonyl uptake irreversible?O
rgan
ic /
su
lfat
e [g
/g]
[Glyx]g = 5 ppb
[Liggio et al., 2005b]
Irreversible
Time
= 2. x 103
For [Glyx]g = 0.1 ppb,
∆[Glyx]particle = 3 g m-3 hr-1
[Kroll et al., 2005]
Reversible
[Glyx]g = 200 ppb
KH* = 2.6 x 107 M atm-1
For [Glyx]g = 0.1 ppb,
[Glyx]particle = 0.003 g m-3
Org
anic
/su
lfa
te [g
g
-1]
4
What What are the irreversible processesare the irreversible processes in the aqueous in the aqueous phase?phase?
H2O
H2O
Oligomers
+ hydrates + H2O
Kalberer et al. [2004]Liggio et al. [2005] Hastings et al. [2005] Zhao et al. [2006]
1
Organic acids
+ OH ?
Ervens et al. [2004]Lim et al. [2005]Warneck et al. [2005]Sorooshian et al. [2006]
2
Altieri et al. [2006]
3
H* ~ 105
H* ~ 103
5
Tracers emitted, non-standard
– ISOP, MONX, MBO, C2H4, PRPE, C2H2, ACET, HAC, BENZ, TOLU, XYLE, GLYX, MGLY, GLYC, MVK, MACR, PAN, PMN, ACRPAN, ENPAN, GPAN, GLPAN, MPAN, NIPAN
Chemistry– New chemical mechanism from MCM v3.1, University of Leeds– JPL 2006 rate constants and photolysis (p-dependent)– Standard SOA from BVOC– Reactive uptake of dicarbonyls by aqueous aerosol and cloud droplets
[Liggio et al., 2005b; Zhao et al., 2006]
Standard emissions– FF + BF: GEIA + regional– BB: GFED2– BG: MEGAN
Non-standard emissions– FF + BF for C2H2: Xiao et al. [2007]– FF + BF for C2H4, arom.: RETRO– BB: Scale GFED2 CO w/ EFs– BG: MEGAN
Dry/wet deposition: – GLYX, MGLY, GLYC, PANs
GEOS-Chem v736 4x5GEOS-Chem v736 4x5 2005 2005/12/12 – 2006 – 2006/11/11 (GEOS4) (GEOS4)
0
5
10
15
20
25
30
35
iso
pre
ne
mo
no
terp
enes
acet
on
e
PR
PE
hyd
roxy
acet
on
e
eth
ene
tolu
ene
acet
ylen
e
xyle
nes
ben
zen
e
gly
oxa
l
gly
cola
ldeh
yde
met
hyl
gly
oxa
l
Em
issi
on
s [
Tg
/ y
r]
Biogenic
Biomass burning
Anthropogenic
40
9
11
0
64
6
New isoprene oxidation – adapted from MCM v3.1New isoprene oxidation – adapted from MCM v3.1
ISOP
IALD
GLYC MGLY
OH, O3
OH
HACGLYX
MVKOH NIALD MVK MACR
NO3
9.8h1h1.5h 2.7h
1.5h 0.7h
High NOx, no RO2 recycling
ISOP + OH 0.045 GLYX + 0.508 GLYC + 0.233 MGLY + 0.197 HAC + 1.033 CH2O
2h 1h0.7h
0.3h
Production of glyoxal
Larger yield of methgylglyoxal, GLYC, HAC
Larger yield of CH2O
7
Are the two Isoprene Are the two Isoprene SOA pathways additive? SOA pathways additive?
SOA via partitioning of SOA via partitioning of semi-volatile products semi-volatile products
from isoprenefrom isoprene
SOA via irreversible SOA via irreversible uptake of glyoxal uptake of glyoxal
from isoprenefrom isoprene
Y = 1~2 % at high [NOx]
Y = 3 % at low [NOx]
YGLYX ~ 10 % at high [NOx]
YGLYX < 5 % at low [NOx]
Experiments by [Kroll et al., 2006] Mechanism from MCM v3.1 (U of Leeds)
Methacrolein is an important intermediate
Methyl vinyl ketone is an important intermediate
Two pathways of SOA formation from isoprene are additive
8
C2H2 + OH 0.636 GLYX
MONX + O3 0.05 GLYX + 0.05 MGLY
MBO + OH 0.63 GLYC + (0.63 ACET)
BENZ + OH 0.252 GLYX
TOLU + OH 0.162 GLYX + 0.124 MGLY
XYLE + OH 0.156 GLYX + 0.230 MGLY
Parameterized chemistryParameterized chemistry
(0.16 - 0.29)
(0.08 - 0.39)
(0.03 – 0.40)
(0.03 - 0.18)
(0.11 - 0.42)
High NOx
C2H4 + OH 0.995 [ GLYC + (1-) ∙ 2 HCHO + HO2], = 0.3 ~ 1
CC22HH44 oxidation – from MCM v3.1 oxidation – from MCM v3.1
9
@ sfc @ 2 km
[ppb] [ppb]
Monthly mean [GLYX], Jul 2006Monthly mean [GLYX], Jul 2006
10-1 ~ 10-2 ppb
~ 10-2 ppb
CHOCHO Inventory 9.3 [Gg]
Production Emission [Tg yr-1] Molar yield [%] 51 [Tg yr-1] Isoprene 408 7.1 + 2.8 21 C2H2 6.9 64 9.8 Glyoxal 5.3 100 5.2 C2H4 12 6.3 1.9 Monoterpenes 110 2.6 1.2 Benzene 6.0 25 1.1 Toluene 7.7 16 0.79 Xylenes 5.9 16 0.51 Glycolaldehyde 3.9 11 0.41 MBO 2.0 6.1 0.08 Loss 51. [Tg yr-1] Photolysis 24 SOA formation 12+6.0 Oxidation 5.9 Dry deposition 1.2 Wet deposition 0.90
10
@ sfc @ 2 km
[ppb] [ppb]
Monthly mean [MGLY], Jul 2006Monthly mean [MGLY], Jul 2006
10-1 ~ 10-2 ppb
~ 10-2 ppb
CH3COCHO Inventory 17 [Gg]
Production Emission [Tg yr-1] Molar yield [%] 159 [Tg yr-1] Isoprene 408 19 + 12 69 Acetone 65 12 + 0.008 9.7 PRPE
(>C3 alkene) 31 14 7.4
Methylglyoxal 3.4 100. 3.4 Monoterpenes 110 2.6 1.5 Xylenes 5.9 23 0.93 Toluene 7.7 12 0.75 Loss 159 [Tg yr-1] Photolysis 103 SOA formation 21+17 Oxidation 16 Dry deposition 1.3 Wet deposition 1.1
11
]p
pt
[
Hourly mean [MGLY], [GLYX]
Local time [h]
Blodgett Forest, CA Aug-Sep 2000
Spaulding et al. [2003]
Tomakomai Forest, Japan Sep 2003
[pp
t]
Ieda et al. [2006]
12
Comparison with SCIAMACHY [Wittrock et al., 2006]Comparison with SCIAMACHY [Wittrock et al., 2006]
SCIAMACHY GLYX VC (10LT)
SCIAMACHY HCHO VC
HCHO VC Dec05-Nov06
GLYX VC Dec05-Nov06 (12-15LT)
13
@ surface
@ 4.2 km
SOASOAglyxglyx+SOA+SOAmglymgly
SOASOA from isoprene from isoprene (Y (Yisopisop = 1~3%) = 1~3%)
SOASOA from from monoterpenes etcmonoterpenes etc
P ~ 6 Tg yr-1 Pglyx ~ 12 + 6 Tg yr-1
Pmgly ~ 21 + 17 Tg yr-1
[ug m-3]
P ~ 10 Tg yr-1
[0.1 ug m-3]
30% 12% 58%
27% 23% 50%
14
ConclusionsConclusions
I. Global simulation of glyoxal and methylglyoxalI. Global simulation of glyoxal and methylglyoxal
– Model sfc concentration same order as rural measurements
– Model glyoxal VC <~ satellite VC measurements
– Isoprene oxidation products well simulated w/ new mechanism
– Isoprene is the largest source dicarbonyls in the free troposphere
– Direct emissions from biomass burning large surface concentrations
II. Reactive uptake of dicarbonyls is significant SOA sourceII. Reactive uptake of dicarbonyls is significant SOA source
– Produces > 18 Tg yr-1 SOA, comparable to other biogenic SOA sources
– SOA from isoprene via glyoxal is independent of SOA from isoprene via
semi-volatile gaseous products
– Anthropogenic and biomass burning emissions produce significant SOA via
uptake of dicarbonyls
15
WHAT DON’T WE UNDERSTAND ABOUT SOA FORMATION?WHAT DON’T WE UNDERSTAND ABOUT SOA FORMATION?
dicarbonyls
Oxidation by OH, O3, NO3
Direct Emission
Terpenes
Nucleation or Condensation
Aromatics
OC
Isoprene
CloudProcessing
FF: 45-80 TgC/yrBB: 10-30 TgC/yr
SOA: >20 Tg/yr
Fossil Fuel Biomass Burning
ANTHROPOGENIC SOURCESBIOGENIC SOURCES
Heterogeneous ReactionsPRECURSORS
CHEMISTRY1. NOx, SO2/acidity2. Multi-step oxidation
FORMATION PATHWAYS
C/o Colette Heald
16
““Reactive uptake of dicarbonyl” Reactive uptake of dicarbonyl” is an attractive mechanism, because it …is an attractive mechanism, because it …
• is a sustained SOA source in aged air masses and free troposphere
• works for both biogenic and anthropogenic precursors
• takes place rapidly in clouds, consistent with field evidence
• produces SOA quickly near the source region. Diurnal variations of SOA concentration more similar to measurements with maximum concentration in the afternoon
• may explain large, heterogeneous source of oxalic acid in aerosols
• may explain observed oligomers in aerosols
17
Experiments needed to determine …Experiments needed to determine …
• Photolysis quantum yield in the visible band
• Reversibility of uptake
• Uptake sensitivity to pH
• Uptake sensitivity to ionic strength
• Total mass contribution of oligomers
• Presence/ID of organic acid hydrate oligomers
• Consistency with ambient aerosol mass spectra
18
Pabstthum, Germany Jul-Aug 1998
Grossmann et al. [2003]
Mexico City Apr 2003
Volkamer et al. [2005b]
]p
pt
[
Hourly mean [MGLY], [GLYX]
Local time [h]
19
Blodget Forest, CABlodget Forest, CAAug-Sep 2000Aug-Sep 2000
Spaulding et al. [2003]
GEOS-ChemGEOS-ChemAug-Sep 2006Aug-Sep 2006
Local time [h]
20
Isoprene oxidation – GEOS-ChemIsoprene oxidation – GEOS-Chem
ISOP
IALD MVK MACR
GLYC MGLY
OH, O3, NO3OH
HACGLYX
High NOx, no RO2 recycling
ISOP + OH 0.317 GLYC + 0.198 MGLY + 0.158 HAC + 0.969 CH2O
2h 1h
9.8h1h1.5h 2.7h
0.8h
No glyoxal production from isoprene
0.3h
21
ORGANIC CARBON AEROSOLORGANIC CARBON AEROSOL
ReactiveOrganicGases
Oxidation by OH, O3, NO3
Direct Emission
Fossil Fuel Biomass Burning
Monoterpenes, etc
Nucleation or Condensation
Aromatics
ANTHROPOGENIC SOURCESBIOGENIC SOURCES
OC
FF: 45-80 TgC/yrBB: 10-30 TgC/yr
Secondary Organic Aerosol (SOA): 8-40 TgC/yrGoldstein and Galbally [2007] 510-910 TgC/yr
*Numbers from IPCC [2001]
Global Model Representation of SOA:1. “Effective primary” yield of semivolatile gas2. Two-product empirical fit to smog chamber data
Isoprene 350 TgC/yr
Partitioning of semivolatile gas?
Heterogeneous rxn of soluble gas?
Other mechanisms?
Volkamer et al. [2006]
C/o Colette Heald
22
[Glyoxal] in ambient air[Glyoxal] in ambient air
Rural
10-1 ~10-2 ppb
Remote and FT
10-1 ~ 10-2 ppb
Location Time [Glyoxal], ppb Statistics Reference Rural Pinnacles, VA
(1037 m) 38º32’N, 78º21’W
Sep 1990 0.044 (<0.02 – 0.35)
Diurnal mean Diurnal range
Munger et al. [1995]
Metter, GA Jul-Aug 1991 0.018 (* - 0.091) 0.016
9-18LT mean 9-18LT maximum midafternoon mean
Lee et al. [1995]
Metter, GA Jun 1992 0.083 (* - 0.19) 0.085
9-18LT mean 9-18LT maximum midafternoon mean
Lee et al. [1995]
Blodgett Forest, CA (1315 m)
38º53’N, 120º37’W
15-19 Aug, 11-15 Sep, 2000
0.020 – 0.054 9-17LT range Spaulding et al. [2002]
Blodgett Forest, CA (1315 m)
38º53’N, 120º37’W
15-19 Aug, 11-15 Sep, 2000
0.027±0.015 (0.006 – 0.083)
Diurnal mean±S.D. Diurnal range
Spaulding et al. [2003]
Tábua, Portugal 40º19’N, 8º3’W
12-24 Aug, 1996 (0 – 0.6) Diurnal range Cerqueira et al. [2003]
Anadia, Portugal 40º25’N, 8º24’W
12-24 Aug, 1996 (0 – 0.2) Diurnal range Cerqueira et al. [2003]
Hokkaido, Japan 44º21’N, 142º15’E
22-29 Aug, 2002 0.018 (<0.001 – 0.065)
Diurnal mean Diurnal range
Matsunaga et al. [2004]
Thuringian Forest, Germany (605 m)
50º37’N, 10º43’E
Oct 2001, Oct 2002
(<0.005 – 0.03) Diurnal range Müller et al. [2005]
Tomakomai Flux Research Site, Japan (140 m)
42º44’N, 141º31’E
3-5 Sep, 2003 0.025 (0.012 – 0.0525) b
Diurnal mean Diurnal range
Ieda et al. [2006]
Salt Point, CA Aug-Sep 2005 <0.020 b 11-14LT range Seaman et al. [2006] Lassen, CA Aug-Sep 2005 <0.035 b 11-14LT range Seaman et al. [2006] Remote Carribean Sea and
Sargasso Sea Oct 1988 – Mar
1989 0.08 Zhou and Mopper [1990]
Free troposphere Southern Nova
Scotia, Canada (1 – 3 km)
28 Aug 1993 (0 – 0.5) 12-14LT range Lee et al. [1996] (pollution event)
Nashville, TN (> 1.9 km)
July 1995 0.026±0.009 (0.01 – 0.06)
Mean±S.D. Range
Lee et al. [1998]
23
[Methyglyoxal] in ambient air[Methyglyoxal] in ambient air
Rural
>1 ~10-2 ppb
Remote and FT
~ 10-2 ppb
Location Time [Methylglyoxal], ppb
Statistics Reference
Rural Pinnacles, VA
(1037 m) 38º32’N, 78º21’W
Sep 1990 <= 0.05 Diurnal range Munger et al. [1995]
Metter GA Jul-Aug 1991 0.031 (* - 0.16) 0.033
9-18LT mean 9-18LT maximum midafternoon mean
Lee et al. [1995]
Metter GA Jun-Jul 1992 0.088 (* - 0.26) 0.08
9-18LT mean 9-18LT maximum midafternoon mean
Lee et al. [1995]
Blodgett Forest, CA (1315 m)
38º53’N, 120º37’W
15-19 Aug, 11-15 Sep, 2000
0.069 – 0.39 9-17LT range Spaulding et al. [2002]
Blodgett Forest, CA (1315 m)
38º53’N, 120º37’W
15-19 Aug, 11-15 Sep, 2000
0.13±0.06 (0.032 – 0.32)
Diurnal mean±S.D. Diurnal range
Spaulding et al. [2003]
Tábua, Portugal 40º19’N, 8º3’W
12-24 Aug, 1996 (0 – 2.0) Diurnal range Cerqueira et al. [2003]
Anadia, Portugal 40º25’N, 8o24’W
12-24 Aug, 1996 (0 – 0.2) Diurnal range Cerqueira et al. [2003]
Hokkaido, Japan 44º21’N, 142º15’E
22-29 Aug, 2002 0.028 (0.004 – 0.088)
Diurnal mean Diurnal range
Matsunaga et al. [2004]
Thuringian Forest, Germany (605 m)
50º37’N, 10º43’E
Oct 2001, Oct 2002 0.015 – 0.15 Diurnal range Müeller et al. [2005]
Tomakomai Flux Research Site, Japan (140 m)
42º44’N, 141º31’E
3-5 Sep, 2003 0.0541 (0.020 – 0.129) b
Diurnal mean Diurnal range
Ieda et al. [2006]
Salt Point, CA Aug-Sep 2005 <0.012 b 11-14LT range Seaman et al. [2006] Lassen, CA Aug-Sep 2005 0.015±0.0056 b 11-14LT range Seaman et al. [2006] Remote Carribean Sea and
Sargasso Sea Oct 1988 – Mar
1989 ~ 0.01 Zhou and Mopper [1990]
Free troposphere Southern Nova
Scotia, Canada (1 – 3 km)
28 Aug 1993 (0 – 1) 12-14LT range Lee et al. [1996] (pollution event)
Nashville, TN (> 1.9 km)
July 1995 0.02 (0 – 0.07)
Mean±S.D. Range
Lee et al. [1998]
24
What What are the irreversible processesare the irreversible processes in the aqueous phase? in the aqueous phase?
I. Hydrate + OH
glyoxylic acid, pyruvic acid
Oxalic acid
II. Hydrate + H2O
Oligomers
Ervens et al. [2004]; Lim et al. [2005]; Warneck et al. [2005]; Sorooshian et al. [2006]
Kalberer et al. [2004]; Liggio et al. [2005]; Hastings et al. [2005]; Zhao et al. [2006]
25
III. Hydrate + OH
glyoxylic acid, pyruvic acid oligomers
oxalic acid oligomers
Altieri et al. [2006]
T = 10 min
T = 202 min