presentation slides for chapter 11, part 1 of fundamentals of atmospheric modeling 2 nd edition
DESCRIPTION
Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition. Mark Z. Jacobson Department of Civil & Environmental Engineering Stanford University Stanford, CA 94305-4020 [email protected] March 21, 2005. Types of Gases. Inorganic gases - PowerPoint PPT PresentationTRANSCRIPT
![Page 1: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/1.jpg)
Presentation Slides for
Chapter 11, Part 1of
Fundamentals of Atmospheric Modeling 2nd Edition
Mark Z. JacobsonDepartment of Civil & Environmental Engineering
Stanford UniversityStanford, CA [email protected]
March 21, 2005
![Page 2: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/2.jpg)
Types of GasesInorganic gases
Contain O, N, S, Cl, Br, and maybe H or C, but not both
Nitric oxide --
Organic gasesContain both H and C, but may also contain other atoms
Carbon dioxide --
Formaldehyde --
Acetone --
Peroxyacetylnitrate --
N O O C O
H C
O
H
H C
H
C
H
O
C
H
H
H
C C
O
O
H
H
H
O
N
O
O
![Page 3: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/3.jpg)
HydrocarbonsOrganic gases that contain only hydrogen and carbon
Propane --
Alkanes - Carbons bonded by a single bond
Cyclobutane --
Ethene (ethylene) --
Cycloalkanes - A ring of alkanes
Alkenes - Carbons bonded by a double bond
H C
H
C
H
H
C
H
H
H
H
H2
C
H2
C CH2
CH2
C C
H
H
H
H
![Page 4: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/4.jpg)
Hydrocarbons
Toluene --
Aromatics - Carbons that form a benzene ring
Isoprene --
Terpenes - Biogenic hydrocarbons
CH3
H
C C
H2
CCH
2
CH3
![Page 5: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/5.jpg)
DefinitionsNon-methane hydrocarbons (NMHC)
Hydrocarbons, except for methane
Oxygenated hydrocarbonsHydrocarbons with oxygenated functional groups, such as aldehydes, ketones, alcohols, acids, and nitrates, added to them
Reactive organic gas (ROG)The sum of oxygenated and NMHC
Total organic gas (TOG)The sum of ROG and methane
![Page 6: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/6.jpg)
Photostationary State Relationship(11.1)
(11.2)
(11.3)
NO + O3
NO2
+ O2
NO2
+ h ν + NO O λ < 420 nm
O + O2
+ M O3
+ M
d NO2[ ]dt
=k1 NO[ ] O3[ ]−J NO2[ ]
O3[ ]=J NO2[ ]k1 NO[ ]
Time rate of change of nitrogen dioxide (11.4)
Steady state --> photostationary state relationship (11.5)
![Page 7: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/7.jpg)
Photostationary State RelationshipExample 11.1:Estimate ozone mixing ratio when
pa = 1013 hPa T = 298 KNO = 5 pptv NO2 = 10 pptvk1 = 1.8x10-14 cm3 molec.-1 s-1 J = 0.01 s-1
Solution:[O3] = 1.1x1012 molec. cm-3
Nd = 2.46 x 1019 molec. cm-3
O3 = 44.7 ppbv
![Page 8: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/8.jpg)
Other Reactions Affecting OzonePhotodissociation of ozone (11.6)
(11.7)
Conversion of excited to ground-state atomic oxygen (11.8)
O3
+ h νO
2 + (O
1
D ) λ < 310 nm
O3
+ h ν O2
+ O λ > 310 nm
O(
1
D ) O
M
![Page 9: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/9.jpg)
Hydroxyl Radical SourcesMajor (11.9)
Minor (11.10-13)
O(1
D ) + H2
O 2OH
HONO + h ν + OH NO λ < 400 nm
HNO3
+ h ν + OH NO2
λ < 335 nm
H2
O2
+ h ν 2OH λ < 355 nm
HO2
NO2
+ h ν
HO2
+ NO2
+ OH NO3
λ < 330 nm
λ < 330 nm
![Page 10: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/10.jpg)
Scavenging by Hydroxyl Radical(11.14-17)
OH + O3
HO2
+ O2
OH + H2
H2
O + H
OH + HO2
H2
O + O2
OH + H2
O2
HO2
+ H2
O
![Page 11: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/11.jpg)
Scavenging by Hydroxyl Radical(11.19-23)
M
OH + NO2
HNO3
OH + SO2
HSO3
M
OH + CO H + CO2
OH + CH4
H2
O + CH3
![Page 12: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/12.jpg)
Hydroperoxy Radical Production
(11.27)
(11.28)
M
H + O2
HO2
HO2
NO2
HO2
+ NO2
M
![Page 13: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/13.jpg)
Hydroperoxy Radical Loss
Hyrdoxyl radical reactions in presence of NO (11.29)
(11.30)
(11.31)
(NO > 10 pptv)
(NO 3-10 pptv)
(NO < 3 pptv)
M
H O2
+ NO OH + NO2
HO2
+ NO2
HO2
NO2
HO2 +
O3
OH + 2O2
HO2
+ HO2
H2
O2
+ O2
![Page 14: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/14.jpg)
Nighttime Nitrogen Chemistry
Production of nitrate radical (11.32)
Dinitrogen pentoxide formation / decomposition (11.33)
NO2
+ O3
NO3
+ O2
M
NO2
+ NO3
N2
O5
![Page 15: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/15.jpg)
Nighttime Nitrogen Chemistry
Dinitrogen pentoxide reaction, photolysis (11.34)
Nitrate radical photolysis (lifetime of minutes) (11.35)
(11.36)
N2
O5
+ H2
O(aq) 2HNO3
(aq)
N2
O5
+ h ν NO2
+ NO3
λ < 385 nm
NO3
+ h ν
NO2
+ O
+ NO O2
410 <nm λ < 670 nm
590 < nm λ < 630 nm
![Page 16: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/16.jpg)
Ozone From Carbon Monoxide
(11.37-41)CO + OH CO2
+ H
M
H + O2
HO2
NO + HO2
NO2
+ OH
NO2
+ h ν + NO O λ < 420 nm
O + O2
+ M O3
+ M
![Page 17: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/17.jpg)
Ozone Formation From Methane(11.42)
(11.43)
CH4
+ OH CH3
+ H2
O
+ O2
, M
C
H
H
H
Methyl
radical
C
H
H
H
O
O
Methylperoxy
radical
H
C O
H
H
Methoxy
radical
O2
NO2
+ NO
+ HO2
H C
H
O
H
O H
Methyl
hydroperoxide
H C
O
H
Formaldehyde
+ O2
HO2
(11.40)
(11.41)
NO2
+ h ν + NO O λ < 420 nm
O + O2
+ M O3
+ M
![Page 18: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/18.jpg)
Methyl Hydroperoxide Decomposition
(11.44)
H C
O
H
Formaldehyde
+ O2
HO2
H
C O
HOH
Methoxy
radical
H C
H
O
H
O H
+ h ν
C
H
H
H
O
O
Methylperoxy
radical
Methyl
hydroperoxide
λ < 360 nm
H
+ OH
H2
O
![Page 19: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/19.jpg)
Ethane Oxidation
Methylperoxy radical production and loss (11.45)
Ethane
H C
H
C
H
H
H
H C
H
C
H
H
H
Ethyl radical
H
H C
H
C
H
O
H
H
O
Ethylperoxy radical
+ O2
, M
+ OH
H2
O
![Page 20: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/20.jpg)
Ethane Oxidation(11.46)
H C
H
C
H
O
H
H
O
Ethylperoxy radical
H C
H
C
H
H
H
Ethoxy radical
O
NO2
+ NO
Acetaldehyde
H C
H
C
H
O
H
+ O2
HO2
+ NO2
M
H C
H
C
H
H
O
H
Ethylperoxynitric acid
O
N
O
O
![Page 21: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/21.jpg)
Propane OxidationMethylperoxy radical production and loss (11.47)
+ O2
, M
H C
H
C
H
H
C
H
H
HH C
H
C
H
H
C
H
H
Propane n -Propyl radical
H H
H C
H
C
H
H
C
H
H
O
H
n -Propylperoxy radical
O
+ OH
H2
O
NO2
+ NO
H C
H
C
H
H
H
n -Propoxy radical
C
H
H
O H C
H
C
H
O
C
H
H
H
Acetone
+ O2
HO2
![Page 22: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/22.jpg)
Formaldehyde/Acetaldehyde PhotolysisFormaldehyde (11.48)
Acetaldehyde (11.49)
Eormyl radical (11.50)
H C
O
H
Formaldehyde
+ h ν
+ H
Formyl
radical
+ CO H2
λ < 334 nm
λ < 370 nm
C
HO
+ h ν
C
H
H
H
CH C
H
C
H
Acetaldehyde Methyl radical Formyl radical
+
O
H
O
H
λ < 325 nm
Formyl
radical
C
O
H
CO
+ O2
HO2
![Page 23: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/23.jpg)
Formaldehyde/Acetaldehyde ReactionFormaldehyde (11.51)
Acetaldehyde (11.52)
CH C
Formaldehyde Formyl radical
O
H
O
H
+ OH
H2
O
C C
O
H
H
H
H
Acetaldehyde Acetyl radical
C C
OH
H
H
Peroxyacetyl
radical
C C
O
O
H
H
H
O
+ OH
H2
O
+ O2
, M
![Page 24: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/24.jpg)
Formaldehyde/Acetaldehyde Reaction
PAN formation (11.53)
Peroxyacetyl
radical
C C
O
O
H
H
H
O
Acetyloxy radical
C C
O
O
H
H
H
Peroxyacetyl nitrate
C C
O
O
H
H
H
O
N
O
O
NO2
+ NO
+ NO2
, M
![Page 25: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/25.jpg)
Acetone Photolysis
(11.55)
H C
H
C
H
O
C
H
H
H
Acetone
+ h νC
H
H
H
Methyl radical
+
Acetyl radical
C C
OH
H
H
![Page 26: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/26.jpg)
Sulfur PhotochemistryBiogenic sulfur
H2S -- hydrogen sulfide
CH3SH -- methyl sulfide
CH3SCH3 -- dimethyl sulfide (DMS)
CH3SSCH3 -- methyl disulfide
Volcanic sulfur
CS2 -- carbon disulfide
OCS -- carbonyl sulfide
SO2 -- sulfur dioxide
H2S -- hydrogen sulfide
![Page 27: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/27.jpg)
Sulfur Photochemistry
Sulfuric acid formation from sulfur dioxide (11.74)
S
OO
O
S
HO O
O
S
O O
+ OH, M+ H
2O
Sulfur
dioxide
Bisulfite Sulfur
trioxide
Sulfuric
acid
S
O
OH
O OH
+ O2
HO2
![Page 28: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/28.jpg)
DMS Abstraction Pathway
Sulfur dioxide production from dimethyl sulfide (DMS) (11.56)
+ O2
H C
H
S
H
C
H
H
H H C
H
S
H
C
H
H
H C
H
S
H
C
H
H
O
O
Dimethyl sulfide (DMS) DMS radical DMS peroxy radical
+ OH
H2
O
H C
H
S
H
C
H
H
O H C
H
S
H
+
H C
O
H
DMS oxy radical Methanethiolate
radical
Formaldehyde
M
NO2
+ NO
![Page 29: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/29.jpg)
DMS Abstraction Pathway
Methanethiolate radical reaction (11.57)
H C
H
S
H
H C
H
S
H
O
O
Methanethiolate
radical
Excited methanethiolate
peroxy radical
*
H C
H
S
H
O
O
Methanethiolate oxy
radical
Methanethiolate
peroxy radical
M
H C
H
S
H
O
+ O2
, M
NO2
+ NO
![Page 30: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/30.jpg)
DMS Abstraction Pathway
Methanethiolate oxy radical reaction (11.58)
H C
H
H
Methyl
radical
H C
H
S
H
O
+
H C
H
S
H
O
O
S O
Sulfur monoxide
Methanethiolate
peroxy radical
Methanethiolate oxy
radical
M
+ O3
O2
![Page 31: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/31.jpg)
DMS Abstraction Pathway
Sulfur dioxide production from sulfur oxide (11.59)
Sulfur dioxide production from sulfur oxide (11.60)
S
OO
OSulfur
monoxide
S O
Sulfur
dioxide
+ O2
S
OO
H C
H
H
+H C
H
S
H
O
O
Methyl radical Sulfur dioxideMethanethiolate
peroxy radical
M
![Page 32: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/32.jpg)
DMS Addition Pathway
Methanethiolate oxy radical reaction (11.61)
H C
H
S
H
C
H
H
H
+ OH
Dimethyl sulfide (DMS)
H C
H
S
H
C
H
H
H
OH
H C
H
H
H C
H
S
H
O
H
O
S C
O
C
H
H
H
H
H
H
+
Dimethyl sulfone (DMSO2
)
Methanesulfenic
acid
Methyl
radical
DMS-OH adduct
M
+ OH, 2O2
2 HO2
![Page 33: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/33.jpg)
DMS Addition Pathway
Methanesulfenic acid oxidation (11.62)
Methanethiolate oxy
radical
H C
H
S
H
O
H
Methanesulfenic
acid
H C
H
S
H
O
+ OH
H2
O
![Page 34: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/34.jpg)
DMDS Reaction
OH addition (11.63)
Photolysis (11.64)
H C
H
S
H
S C
H
H
H H C
H
S
H
O
H
H C
H
S
H
+
Dimethyl disulfide (DMDS) Methanesulfenic
acid
Methanethiolate
radical
+ OH
H C
H
S
H
S C
H
H
HH C
H
S
H
2
Dimethyl disulfide (DMDS)Methanethiolate
radical
+ h ν
![Page 35: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/35.jpg)
Biogenic SulfurHydrogen sulfide oxidation (11.65)
Hydrogen sulfide radical reaction (11.66)
Sulfur dioxide production from sulfur oxide (11.59)
S
HH
S
H
Hydrogen
sulfide
Hydrogen
sulfide radical
+ OH
H2
O
+ O2
S
H
OH
Hydrogen
sulfide radical
Sulfur
monoxide
S O
S
OO
OSulfur
monoxide
S O
Sulfur
dioxide
+ O2
![Page 36: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/36.jpg)
Volcanic SulfurSulfur monoxide production from carbonyl sulfide (11.68)
(11.69)
(11.70)
+ OHO C S
S
H
Hydrogen sulfide
radical
+ CO2
Carbonyl
sulfide
Carbonyl
sulfide
O C S +
Carbon
monoxide
Atomic
sulfur
+ h ν λ < 260 nmCO S
O
+ O2
Sulfur
monoxide
S O
Atomic
sulfur
S
![Page 37: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/37.jpg)
Volcanic SulfurSulfur oxide production from carbon disulfide (11.71)
(11.72)
(11.73)
+ OHS C S
S
H
O C S+
Carbon
disulfide
Hydrogen sulfide
radical
Carbonyl
sulfide
S C S +C S
Carbon
disulfide
Carbon
monosulfide
Atomic
sulfur
+ h ν S λ < 340 nm
+ O2
C S
Carbon
monosulfide
+ OO C S
Carbonyl
sulfide
![Page 38: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/38.jpg)
Urban PhotochemistryOzone production in smog (11.75-8)
NO + ROG * NO2
+ ROG **
NO + O3
NO2
+ O2
NO2
+ h ν + NO O λ < 420 nm
O + O2
+ M O3
+ M
![Page 39: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/39.jpg)
0 0.5 1 1.5 2
0
0.05
0.1
0.15
0.2
0.25
ROG (ppmC)
NO
x
(g) (ppmv)
0.4
0.32
0.24
0.16
0.08 = O
3
(g), ppmv
Ozone Isopleth
Fig. 11.1Contours are ozone (ppmv)
NO
x (pp
mv)
0.24
0.08
0.32
0.16
![Page 40: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/40.jpg)
Sea Breeze
Fig. 11.2
0
1
2
3
4
5
6
7
0 6 12 18 24 30 36 42 48 54 60 66 72
Wind speed (m s
-1
)
Hour of day
Day 1 Day 2
Day 3
Win
d sp
eed
(m s
-1)
![Page 41: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/41.jpg)
Source/Receptor Regions in Los Angeles
0
0.1
0.2
0.3
0 6 12 18 24
Volume mixing ratio (ppmv)
Hour of day
O
3
NO
2NO
Central Los Angeles
August 28, 1987
Vol
ume
mix
ing
rati
o (p
pmv)
Fig. 11.2
0
0.1
0.2
0.3
0 6 12 18 7224
Volume mixing ratio (ppmv)
Hour of day
O
3
NO
2
NO
San Bernardino
August 28, 1987
Vol
ume
mix
ing
rati
o (p
pmv)
![Page 42: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/42.jpg)
Daily Los Angeles Emission (1987)
Table 11.2
Gas Emission (tons/day) Percent of totalCarbon monoxide 9796 69.3
Nitric oxide 754Nitrogen dioxide 129Nitrous acid 6.5
Total NOx+HONO 889.5 6.3Sulfur dioxide 109Sulfur trioxide 4.5
Total SOx(g) 113.5 0.8Alkanes 1399Alkenes 313Aldehydes 108Ketones 29Alcohols 33Aromatics 500Hemiterpenes 47
Total ROGs 2429 27.2Methane 904 6.4
Total emission 14,132 100
![Page 43: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/43.jpg)
Percent Emission by Source
Nitric oxide from combustion (11.79)
N N O O N O+ 2+ heat
Table 11.4
Source Category CO(g) NOx(g) SOx(g) ROG Stationary 2 24 38 50Mobile 98 76 62 50Total 100 100 100 100
![Page 44: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/44.jpg)
Organic Gases Emitted in Greatest Abundance in Los Angeles (1987)
Table 11.3
1. Methane2. Toluene3. Pentane4. Butane5. Ethane6. Ethylene7. Octane8. Xylene
9. Heptane10. Propylene11. Chloroethylene12. Acetylene13. Hexane14. Propane15. Benzene
![Page 45: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/45.jpg)
Most Important Gases in Smog in Terms of Ozone Reactivity and Abundance
Table 11.6
1. m- and p-Xylene2. Ethene3. Acetaldehyde4. Toluene5. Formaldehyde6. i-Penane7. Propene8. o-Xylene9. Butane10. Methylcyclopentane
![Page 46: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/46.jpg)
Lifetimes of ROGs Against Loss in Urban Air
Table 11.5
ROG Species Phot. OH HO2 O NO3 O3 n-Butane --- 22 h 1000 y 18 y 29 d 650 ytrans-2-butene --- 52 m 4 y 6.3 d 4 m 17 mAcetylene --- 3 d --- 2.5 y --- 200 dFormaldehyde 7 h 6 h 1.8 h 2.5 y 2 d 3200 yAcetone 23 d 9.6 d --- --- --- ---Ethanol --- 19 h --- --- --- ---Toluene --- 9 h --- 6 y 33 d 200 dIsoprene --- 34 m --- 4 d 5 m 4.6 h
![Page 47: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/47.jpg)
OH Sources in Polluted AirEarly morning source (11.80)
Mid-morning source (11.81)
(11.82)
(11.83)
λ < 400 nmOH + NOHONO + h ν
HCHO + h ν λ < 334 nm + H HCO
M
H + O2
HO2
HCO + O2
HO2
+ CO
(11.84)NO + HO
2NO
2 + OH
![Page 48: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/48.jpg)
Hydroxyl Rad. Sources in Polluted Air
Afternoon source (11.88)
(11.86)
O3
+ h ν O2
+ (O1
D ) λ < 310 nm
O(1
D ) + H2
O 2 OH
![Page 49: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/49.jpg)
Alkene Reaction With Hydroxyl Radical
Ethene oxidation (11.87)
C C
H
H
H
H
Ethene
C C
H
H
H
H
Ethanyl radical
OH
C C
H
H
H
H
Ethanolperoxy
radical
OH
O
O
C C
H
H
H
H
Ethanoloxy
radical
OH
O
+ OH, M + O2
, M
NO2
+ NO
![Page 50: Presentation Slides for Chapter 11, Part 1 of Fundamentals of Atmospheric Modeling 2 nd Edition](https://reader033.vdocuments.net/reader033/viewer/2022051418/5681585a550346895dc5b615/html5/thumbnails/50.jpg)
Alkene Reaction With Hydroxyl Radical
Ethanoloxy radical oxidation (11.88)
Formaldehyde
C O
H
H
C C
H
H
H
H
Ethanoloxy
radical
OH
O
C C
H
H
O
H
OH
Glycol aldehyde
72% 2
28%
+ O2
HO2