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Cast of Characters
AOSC 434
Air Pollution
Russell R. Dickerson
www.atmos.umd.edu/~russ/syllabus434.html
London killer smog
Donora, PA October 29, 1948; 2:00pm LST
1950’s local – 2000’s global.
Washington Post Jan. 25, 2014
Published by AAAS
Pollution and Smog
19
Haagen-Smit (1952) “Photochemical action of
nitrogen oxides oxidized the hydrocarbons and thereby
forms ozone….”
Almost right. 20
Ozone is a national problem
8 - H o u r O z o n e N o n a tta in m e n t A r e a s ( 2 0 0 8 S ta n d a r d )
1 2 /3 1 /2 0 1 7
8 - h o u r O z o n e C la s s i fic a tio n
E x tre m e
S e v e re 1 5
S e r io u s
M o d e ra te
N o n a tt a in m e n t a r e a s a r e in d ic a t e d b y c o lo r. M a r g in a l
W h e n o n ly a p o r t io n o f a c o u n ty is s h o w n in c o lo r,
it in d ic a t e s t h a t o n ly t h a t p a r t o f t h e c o u n ty is w i th in
a n o n a tt a in m e n t a re a b o u n d a ry .
2. Nitrogen Dioxide, NO2
criteria pollutant
Primary
Effects:
1. Lungs (acute chemical pneumonia)
EPA Criteria Pollutant
2. Phytotoxin
3. Catalyst for ozone formation.
4. Atmospheric acidity (about 1/3 of problem and growing)
Effects:
1. Respiration (acute); EPA Criteria Pollutant
2. Cardiovascular system (chronic)
3. Contributor to photochemical smog
4. Changes global HOx cycle (oxidizing capacity of atmosphere).
Limits:
9.0 ppm for 8 hr
35 ppm for 1 hr
50 ppm for 8 hr is the "level of significant harm"
3. Carbon Monoxide, CO (cont…)
Effects:
1. Eye irritation
2. Respiratory tract (carcinogen?)
3. Phytotoxin
Limits: None (too hard to measure)
• Compound "X" in LA smog
• NOx reservoir.
An interesting history
29
5. Polynuclear Aromatic Hydrocarbons, "PAH"
(Also Polycyclic Aromatic Hydrocarbons) See Also Finlayson-Pitts Chapt. 9&10.
Primary
Effects:
1. Carcinogenic (one of the few known
carcinogens in air)
Limits: None
• Low/moderate vapor pressure; divided
between particulate & gas-phases.
• Example: Benzo(a)pyrene (BaP)
• Nitrated PAH even stronger carcinogens .
6. Ethylene, H2C=CH2
Primary
Effects:
1. Ozone formation
2. Plant hormone (e.g. oranges)
Limits: None
• Other biogenic hydrocarbons, isoprene, pinenes.
• Some plants when stressed release more ethylene
7. Formaldehyde, H2CO
Effects:
1. Ozone formation
2. Eye irritant
3. Mutagen, suspected carcinogen
Limits: None
• Indoor air pollutant too, (ureaformaldehyde insulation)
• Produced by HC oxidation
• Represents class of partially oxidized HC
8. Lead, Pb
criteria pollutant
Primary
Effects:
1. Toxic, leads to loss of mental
acuity.
Limits: 0.15 µg/m3 rolling three
month average.
Now primarily a problem of the
developing world.
9. Other Pollutants (toxics)
Halogenated Hydrocarbons
Example: Dioxin
Effects: 1. Teratogen
2. LD50 in guinea pigs is 0.5 to 1.0 g/kg
Limits: None
• Produced as byproduct in 2,4-D and 2,4,5-T synthesis and by incomplete
combustion of chlorine containing refuse such as plastics.
• "Freons" will be considered as part of stratospheric air pollution.
LONDON-TYPE SMOG
Primary
Effects
1. Produces H2SO4 found on particles and in precipitation
- Acid Deposition
2. Cloud Condensation Nuclei (climate)
3. Materials degradation
4. Respiratory tract (esp. bisulfites, HSO3-)
5. Phytotoxin
10. Sulfur Dioxide, SO2 (cont…)
Limits:
Primary 1-hr Standard: 75 ppb (June 2010)
Secondary standard 500 ppb for 3 hr
1 2 /3 1 /2 0 1 7
P M - 2 .5 C l a s s i f i c a t i o n
S e r io u s
M o d e ra te
N o n a tt a in m e n t a r e a s a r e in d ic a t e d b y c o lo r.
W h e n o n ly a p o r t io n o f a c o u n ty is s h o w n in c o lo r,
it in d ic a t e s t h a t o n ly t h a t p a r t o f t h e c o u n ty is w ith in
a n o n a tt a in m e n t a re a b o u n d a ry.
Wet deposition of sulfate
12. Carbon Dioxide, CO2
Primary
CLEAN AIR
(1) O3 + h O2 + O(1D)
(3) OH + O3 HO2 + O2
(4') H + O2 + M HO2 + M
(6') NO2 + h NO + O
(7') O + O2 + M O3 + M
-------------------------------------------------
(3'-7') CO + 2 O2 CO2 + O3 NET
Similar Reaction Sequence For Methane
2H2CO + h H2 + CO
HCO + H
H + O2 + M HO2 + M
HCO + O2 HO2 + CO
--------------------------------------------
2H2CO + 2O2 2CO + 2HO2 + H2
This means two ozone molecules are produced per
formaldehyde. The grand total for methane is four O3
produced! Methane is a good model for all alkanes, but by
itself reacts too slowly to form much ozone locally, it is,
however, important on a global scale. The net production
of ozone requires converting of NO to NO2 without
consuming O2.
International Journal of Chronic Obstructive
Pulmonary Disease, 2014
@AOSC434