AP 3050 Air Pollution
Air Pollution and Global Warming:
History, Science, and Solutions
Chapter 3: Urban Air Pollution
Lecturers: Neng-Huei Lin and Guey-Rong Sheu
Spring 2016
By Mark Z. Jacobson
Cambridge University Press (2012)
Urban-scale air pollution types
• London type smog
• Photochemical smog
Smog = Smoke + Fog
Athens
Pollution due to
metal production
wood burning
www.worst-city.com
Pb/Ag mining
Hong et al.
1994
Rome
Heavy heavens
Metal smelting
wood burning
I238.photobucket.com
Horace, Wiki
Sea Coal, KE I, Lime Kiln, Slaked Lime
In London during the Middle Age
1285 – commission
1306 - ban
www.communigate.co.uk
Middletemple.org.uk
www.texcenproperties.com
CaCO3 + heat
 CaO
CaO + H2O
 Ca(OH)2
www.nsiuk.org
Forge, Glass & Brick Furnaces, Brewery
1300-1800 AD
www.exponent.com
www.prestonservices.co.uk
www.yahushua.org.uk
Wheeling.weirton.lib.wv.us
John Evelyn (1620-1706)
“London by reason of the
excessive coldness of the air,
hindering the ascent of the
smoke, was so filled with the
fuliginous (sooty) steam of
sea-coal, that hardly could
one see across the street,
and this filling the lungs
with its gross particles
exceedingly obstructed the
breast, so as one would
scarce breathe.” (Diary,
1684)
Papin Pressure Cooker (1679)
Denis Papin
1647-1712
Pressure-cooker.org.uk
Savery Steam Engine (1698)
Thomas Savery
1650-1715
Step 1: Evaporate water in
boiler, then spray liquid to
recondense vapor in vessel,
creating vacuum to draw water
from well into vessel.
Step 2: Evaporate water in boiler to
force water in vessel up delivery
pipe.
www.mgsteam.btinternet.co.uk/savery2
Newcomen Steam Engine (1712)
Thomas Newcomen
1663-1729
Step 1: Boil water to
create steam to push
piston up.
Step 2: squirt liquid
water into steam
chamber to recondense
vapor to create vacuum
that pulls piston down.
www.csa.com
Watt Steam Engine (1769 ff.)
James Watt
1736-1819
Separate chamber for condensing steam
Motion circular rather than up and down
Brewster (1832)
Early U.K. Regulations
Railway Clauses Act (1845)
“Every locomotive steam engine to be used on a
railway shall, if it use coal or other similar fuel
emitting smoke, be constructed on the principle of
consuming, and so as to consume its own smoke.”
Smoke Nuisance Abatement (Metropolis) Act (1853)
Inspector to reduce nuisance from the smoke of
furnaces in London and steam vessels below London
Bridge.
Alkali Act (1863)
Monet’s House of Parliament (1899-1901)
Early U.S. Regulations
Pittsburgh (1869) Outlawed burning soft coal in
locomotives in city
Cincinnati (1881) Required smoke reductions,
appointed inspector
Chicago (1881) Smoke reduction law, supported
by judiciary
St. Louis (1893) Outlawed “dense black or thick
gray smoke”
London-Type Smog
Smog
Harold Antoine Des Voeux of London’s Coal
Smoke Abatement Society, introduced word in
1905 to describe combination of smoke and fog
visible in several cities in Great Britain.
London-type smog:
Arises from coal- and chemical-combustion
smoke in presence of fog or low-lying
temperature inversion.
Reading, Pennsylvania (c. 1909)
Library of Congress Prints and Photographs Division, Washington, D. C.
Youngstown, Ohio (c. 1910)
Library of Congress Prints and Photographs Division, Washington, D. C.
Gary, Indiana (c. 1912)
Library of Congress Prints and Photographs Division, Washington, D. C.
Thomas Midgley (1889-1944)
Edgar Fahs Smith Collection, U. Penn. Library
Leaded Gasoline
1921: Invented leaded gasoline and named it Ethyl.
1923: Midgley suffered lead poisoning, but
defended lead:
"The exhaust does not contain enough lead to
worry about, but no one knows what legislation
might come into existence fostered by
competition and fanatical health cranks.”
Leaded Gasoline
1923-5: 17 workers died, 149 injured due to lead poisoning
1925: Despite working on ethanol/benzene blends, iron carbonyl
alternatives, Midgley countered,
"...tetraethyl lead is the only material available which can bring
about these (antiknock) results, which are of vital importance to
the continued economic use by the general public of all
automotive equipment, and unless a grave and inescapable
hazard exists in the manufacture of tetraethyl lead, its
abandonment cannot be justified"
1925: U.S. Surgeon General organized committee to investigate lead.
Observed drivers/garage workers did not experience poisoning
--> “no grounds for prohibiting the use of Ethyl gasoline.”
Leaded Gasoline
1930s: 90 percent of vehicles leaded
1936: Federal Trade Commission outlawed commercial criticism of
lead:
"...entirely safe to the health of (motorists) and to the public in
general when used as a motor fuel, and is not a narcotic in its
effect, a poisonous dope, or dangerous to the life or health of a
customer, purchaser, user or the general public."
1959: U.S. Public Health Service
"...regrettable that the investigations recommended by the
Surgeon General's Committee in 1926 were not carried out by
the Public Health Service."
1975: Catalytic converter invented; lead deactivates catalyst
1977: Lead regulated as criteria air pollutant in the U.S.
Donora, Pa (1948)
www.eoerth.org
Noon, Donora, Pa. Oct. 29, 1948
Pittsburgh Post-Gazette
London Smog (1952) 4000 deaths
www.virginmedia.com
U.S. Library of Congress
Also events in 1873, 1880, 1892, 1948, 1956, 1957, 1962
Los Angeles, California
(December 3, 1909)
Library of Congress Prints and Photographs Division, Washington, D. C.
Los Angeles (1920s)
www.airfields-freeman.com
Media-2.web.britannica.com
Los Angeles (1930s)
Images.encarta.msn.com
Uplaod.wikimedia.org
www.nottingham.ac.uk
Los Angeles 1940s
www.aqmd.gov
Open Waste Incineration LA (1945)
Los Angeles Public Library
Los Angeles 1950s
Time, Inc.
Los Angeles 1958
Los Angeles Public Library
Los Angeles 1964
Los Angeles Public Library
Daytime in Pittsburgh (1945) and NY
City (1953)
U.S. Library of Congress
LA Effects of Air Pollution
Smog damage to sugar beets
LA nonsmoker’s lungs
www.aqmd.gov
Arie Haagen-Smit (1900-1977)
The Archives, California Institute of Technology
Backyard Incinerator Ban (1957)
Herald-Examiner Photo Collection, Los Angeles Public Library
Warning of Backyard Incinerator
Ban (1960)
Los Angeles Public Library
Los Angeles (July 23, 2000)
Mark Z. Jacobson
Chemistry of Background
Troposphere and Polluted Air
Background troposphere
Inorganic gases
Long-lived, light organic gases
Naturally-emitted short-lived heavy organic gases
Polluted air
Inorganic gases
Short-lived light and heavy organic gases
Photostationary State Ozone
NO(g) + O 3(g)
Nitric
Ozone
oxide
NO2 (g) + O 2(g)
Nitrogen Molecular
dioxide
oxygen
NO(g) + O(g)
l < 420 nm
Nitric
Atomic
oxide
oxygen
M
O(g) + O 2(g)
O3(g)
Ground- Molecular
Ozone
state atomic oxygen
oxygen
(4.1) - (4.3)
NO2 (g) + hn
Nitrogen
dioxide
Photostationary State Ozone
cO =(J/Ndk1)(cNO
3
2
(g)/cNO(g))
(4.4)
J = photolysis rate coefficient of NO2(g)+hn-->NO(g)+O(g)
k1 = rate coefficient of NO(g)+O3(g)-->NO2(g)+O2(g)
Example 4.1:
Estimate ozone mixing ratio when
pd
= 1013 mb
T
= 298 K
cNO(g) = 5 pptv
cNO (g) = 10 pptv
2
-14
3
-1
-1
k1
= 1.8x10 cm molec. s J
= 0.01 s-1
---->
Nd
----> c
O
3
(g)
= 2.46 x 1019 molec. cm-3
= 45.2 ppbv
Daytime Nitrogen Oxide Removal
NO2(g) + OH(g)
Nitrogen Hydroxyl
dioxide
radical
M
HNO3(g)
Nitric
acid
(4.5)
Hydroxyl Radical Production
O3(g) + hn
Ozone
O2 (g) + O(1D)(g)
Molecular Excited
oxygen
atomic
oxygen
O(1D)(g) + H 2O(g)
Excited
Water
atomic
vapor
oxygen
l < 310 nm
2OH(g)
Hydroxyl
radical
(4.6) - (4.7)
Nighttime Nitrogen Chemistry
NO2 (g) + O3 (g)
Nitrogen Ozone
dioxide
NO3 (g) + O2(g)
Nitrate Molecular
radical
oxygen
M
NO2 (g) + NO3 (g)
Nitrogen
dioxide
Nitrate
radical
N2O5 (g) + H 2O(aq)
Dinitrogen Liquid
pentoxide
water
N2O5 (g)
Dinitrogen
pentoxide
2HNO3 (aq)
Dissolved
nitric acid
(4.8) - (4.10)
Ozone From Carbon Monoxide
CO(g) + OH(g)
Carbon Hydroxyl
monoxide radical
CO2(g) + H(g)
Carbon Atomic
dioxide hydrogen
M
H(g) + O2(g)
Atomic Molecular
hydrogen oxygen
NO(g) + HO2(g)
Nitric Hydroperoxy
oxide
radical
NO2 (g) + hn
Nitrogen
dioxide
HO2(g)
Hydroperoxy
radical
NO2(g) + OH(g)
Nitrogen Hydroxyl
dioxide
radical
NO(g) + O(g)
Nitric
Atomic
oxide
oxygen
M
O(g) + O 2(g)
O3(g)
Ground- Molecular
Ozone
state atomic oxygen
oxygen
l < 420 nm
(4.11) - (4.15)
Ozone From Methane
CH4(g) + OH(g)
Methane Hydroxyl
radical
CH3(g) + O 2(g)
Methyl Molecular
radical
oxygen
NO(g) + CH 3O2(g)
Nitric Methylperoxy
oxide
radical
NO2 (g) + hn
Nitrogen
dioxide
CH3(g) + H2O(g)
Methyl Water
radical vapor
M
CH3O2 (g)
Methylperoxy
radical
NO2(g) + CH 3O(g)
Nitrogen
Methoxy
dioxide
radical
NO(g) + O(g)
Nitric
Atomic
oxide
oxygen
M
O(g) + O 2(g)
O3(g)
Ground- Molecular
Ozone
state atomic oxygen
oxygen
l < 420 nm
(4.16) - (4.20)
Ozone From Ethane
C2H6(g) + OH(g)
Ethane Hydroxyl
radical
C2H5(g) + O 2(g)
Ethyl Molecular
radical
oxygen
NO(g) + C 2H5O2(g)
Nitric
Ethylperoxy
oxide
radical
NO2 (g) + hn
Nitrogen
dioxide
C2H5(g) + H2O(g)
Ethyl
Water
radical
vapor
M
C2H5O2 (g)
Ethylperoxy
radical
NO2(g) + C 2H5O(g)
Nitrogen
Ethoxy
dioxide
radical
NO(g) + O(g)
Nitric
Atomic
oxide
oxygen
l < 420 nm
M
O(g) + O 2(g)
Ground- Molecular
state atomic oxygen
oxygen
O3(g)
Ozone
(4.26) - (4.30)
Formaldehyde and
Acetaldehyde Formation
Formaldehyde
CH3O(g) + O2(g)
Methoxy Molecular
radical
oxygen
HCHO(g) + HO2 (g)
Formal- Hydroperoxy
dehyde
radical
Acetaldehyde
C2H5O(g) + O 2(g)
Ethoxy Molecular
radical
oxygen
CH3CH(=O) + HO2 (g)
Acetaldehyde Hydroperoxy
radical
(4.21), (4.31)
Ozone From Formaldehyde
HCHO(g) + hn
Formaldehyde
HCHO(g) + OH(g)
FormalHydroxyl
dehyde
radical
HCO(g) + H(g)
Formyl Atomic
radical hydrogen
l < 334 nm
CO(g) + H2(g)
Carbon Molecular
monoxide hydrogen
l < 370 nm
HCO(g) + H 2O(g)
Formyl
Water
radical
vapor
HCO(g) + O 2(g)
CO(g) + HO2(g)
Formyl Molecular
Carbon Hydroperoxy
radical
oxygen
monoxide
radical
M
H(g) + O2(g)
HO2(g)
Atomic Molecular
Hydroperoxy
hydrogen oxygen
radical
--> Form O3 from both CO and HO2
(4.22) - (4.25)
PAN From Acetaldehyde
CH3C(=O)(g) + H2O(g)
Acetyl
Water
radical
vapor
CH3CH(=O)(g) + OH(g)
Acetaldehyde Hydroxyl
radical
CH3C(=O)(g) + O2(g)
Acetyl
Molecular
radical
oxygen
M
CH3C(=O)O2(g)
Peroxyacetyl
radical
M
CH3C(=O)O2(g) + NO2(g)
Peroxyacetyl
Nitrogen
radical
dioxide
CH3C(=O)O2NO2(g)
Peroxyacetyl nitrate
(PAN)
(4.32) - (4.34)
Photochemical Smog Formation
NO(g) + RO2(g)
Nitric
Organic
oxide
peroxy
radical
NO(g) + O 3(g)
Nitric
Ozone
oxide
NO2 (g) + hn
Nitrogen
dioxide
NO2 (g) + RO(g)
Nitrogen Organic
dioxide
oxy
radical
NO2 (g) + O 2(g)
Nitrogen Molecular
dioxide
oxygen
NO(g) + O(g)
Nitric
Atomic
oxide
oxygen
M
O(g) + O 2(g)
O3(g)
Ground- Molecular
Ozone
state atomic oxygen
oxygen
l < 420 nm
(4.37) - (4.40)
Ozone Isopleth
0.25
0.15
0.1
0.32
0.24
NOx(g) (ppmv)
0.2
0.16
0.08 = O3(g), ppmv
0.4
0.05
0
0
0.5
Contours are ozone (ppmv)
1
ROG (ppmC)
1.5
2
Figure 4.12
0.3
Volume mixing ratio (ppmv)
Volume mixing ratio (ppmv)
Source/Receptor Regions in Los
Angeles
Central Los Angeles
August 28, 1987
0.2
NO(g)
NO2(g)
O3(g)
0.1
0
0
6
12
18
Hour of day
24
0.3
San Bernardino
August 28, 1987
0.2
O3(g)
NO2(g)
0.1
0
0
NO(g)
6
12
18
Hour of day
24
Figure 4.13
Lifetimes of ROGs Against
Chemical Loss in Urban Air
ROG Species
n-Butane
trans-2-butene
Acetylene
Formaldehyde
Acetone
Ethanol
Toluene
Isoprene
Phot.
------7h
23 d
-------
OH
22 h
52 m
3d
6h
9.6 d
19 h
9h
34 m
HO2
------1.8 h
---------
Table 4.3
O
--6.3 d
----------4d
NO3
29 d
4m
--2d
----33 d
5m
O3
--17 m
----------4.6 h
Most Important Gases in Smog in Terms
of Ozone Reactivity and Abundance
1. m- and p-Xylene
2. Ethene
3. Acetaldehyde
4. Toluene
5. Formaldehyde
6. i-Pentane
7. Propene
8. o-Xylene
9. Butane
10. Methylcyclopentane
Table 4.4
Early Morning OH Source in
Polluted Air
HONO(g) + hn
Nitrous
acid
OH(g) + NO(g)
Hydroxyl
radical
l < 400 nm
Nitric
oxide
(4.42)
Mid-Morning OH Source in
Polluted Air
HCHO(g) + hn
Formaldehyde
HCO(g) + H(g)
Formyl Atomic
radical hydrogen
l < 334 nm
M
H(g) + O2(g)
Atomic Molecular
hydrogen oxygen
HCO(g) + O 2(g)
Formyl
radical
Molecular
oxygen
NO(g) + HO2(g)
Nitric Hydroperoxy
oxide
radical
HO2(g)
Hydroperoxy
radical
CO(g) + HO2(g)
Carbon Hydroperoxy
monoxide
radical
NO2(g) + OH(g)
Nitrogen Hydroxyl
dioxide
radical
(4.43) - (4.46)
Afternoon OH Source in
Polluted Air
O3(g) + hn
Ozone
l < 310 nm
O2 (g) + O(1D)(g)
Molecular Excited
oxygen
atomic
oxygen
O(1D)(g) + H 2O(g)
Excited
Water
atomic
vapor
oxygen
2OH(g)
Hydroxyl
radical
(4.47) - (4.48)
Isoprene Reaction with OH
HO
HO CH
3
H
C C
(4)
O
H
C
C
O
23.6% 2
H2
CH3
CH C
(1) O O
C
CH2
16.4%
H2
H
C
H2C
CH3
C
CH 2
+ OH(g),
O2(g)
O
(2)
12.3% HO
O
O
CH C
C
H2
Isoprene
(3)
12.3% HO
C
H2
CH3
C
C
H2
O
H
C
CH3
C
H2C
CH2
H
C
O
(5)
21.2%
CH3
O
(6)
14.1%
O
C
H2
H
C
O
Isoprene peroxy radicals
OH
C
H2
CH3
C
OH
C
H2
(4.54)
Alcohol Reactions with OH
+ O2(g)
+ OH(g)
85% CH2OH(g)
HO2(g) Formaldehyde
CH3OH(g)
Methanol
HCHO(g)
H2O(g)
15% CH3O(g)
Methoxy radical
5%
CH2CH2OH(g)
+ O2(g)
+ OH(g)
90% CH3CHOH(g)
C2H5OH(g)
Ethanol
CH3CHO(g)
HO2(g)
H2O(g)
5%
CH3CH2O(g)
Ethoxy radical
Acetaldehyde
(4.57) - (4.58)
Percent Changes E85 Minus Gas From
Data
NMOG
NOx
+ 45%
- 30%
Benzene
1,3-butadiene
Acetaldehyde
Formaldehyde
- 64%
- 66%
+ 4500%
+ 200%
E85 = 81% ethanol
19% gasoline
Whitney (2007)
Ozone isopleth
0.25
0.15
0.1
0.32
0.16
3
NO (g) (ppmv)
x
0.2
0.24
0.08 = O (g), ppmv
0.4
0.05
0
0
0.5
Contours are ozone (ppmv)
1
1.5
ROG (ppmC)
2
Effect in 2020 of E85 vs. Gasoline on
Ozone and Health in Los Angeles
0
-118
250
-116
Change in ozone deaths/yr due to E85:
Changes in cancer/yr due to E85:
1000
750
33.5
750
750
750
50000
0
33
1000
00
5100
-1
250
0
33.5
00
5100
0
250
250
Aug. day+night ozone diff. (ppbv) E85 minus gas
Los Angeles model domain population
3
00
00
200000
0
0
750
750
5
5
1 00 1000
1 00 1000
34.5
34.5
100
100
0
0
2
1
1
150000
250000 750500
250000 750500
105000
105000
34
34
7
7
1
100000
33
-118
+120 (+9%) (47-140)
-3.5 to +0.3
-116
2020 U.S. Effects of E85 vs. Gasoline
Aug. 24-hr ozone diff. (ppbv) E85 minus gas
4
45
40
0
0
2
35
-2
30
-4
25
0
0
0
-120
-100
-80
Additional ozone deaths/yr:
+185 (72-213)
E85, regardless of source, causes as much or more U.S. air pollution
mortality from the tailpipe as gasoline