Professional Documents
Culture Documents
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Educational Objectives
2
Photochemical oxidants
◼ Produced in the atmosphere via:
HCs +NOx +O2 + sunlight → O3, NO2, PAN,
H2O2, +RO2 etc.
CH3C=OOO + NO2 + M → CH3=OOONO2 (PAN)
◼ Ozone (O3)
the major component and has received major
scientific and regulatory attention. It has important
health and ecological implications.
3
Question ???
Ozone is formed in the atmosphere when molecular
oxygen reacts with ground state atomic oxygen
[O(3P)]. The source of O(3P) is
(a)Photolysis of nitrogen dioxide
(b) oxidation of hydrocarbons
(c) photodissociation of existing ozone
(d) none of the above
NO2 + hv -→ NO + O(3P); O2 + O(3P) →O3
Nitrogen dioxide photolysis results in little actual net O3 increase, but
cannot explain much higher levels present in troposphere
4
Ozone formation mechanism
◼ RH + ·OH → R·+ H2O
◼ R·+ O2 + M → RO2·+ M (M is an energy-absorbing molecule, e.g. N2 or O2)
◼ RO2·+ NO → RO·+ NO2
◼ RO·+ O2 → HO2·+ aldehydes and ketones
◼ HO2·+ NO → NO2 + HO·
◼ 2(NO2 + hv → NO + O·) (hv is a photon of light energy)
◼ 2 (O·+ O2 + M → O3 + M)
◼ Net: RH + 4O2 + hv → 2O3 + H2O + aldehydes/ketones
◼ NOx (NO + NO2) serves as a catalyst in the above chain
reaction.
◼ Major sink for O3 is surface deposition and chemical
reactions involving UV photolysis and reaction with NO.
5
The atmosphere is a giant photoreactor
Emissions of : - carbonyls
Volatile Organic Compounds (VOCs)
+ hn - peroxides
Light hydrocarbons, alcohols,
carbonyls, acids, halogenated HC… - Ozone
+ O2
- organic nitrates
and NO + NO2 = NOx
- organic aerosols
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7
Question ???
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Tropospheric ozone concentrations (1)
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Tropospheric ozone concentrations (2)
10
Photochemical Smog
In both developed and developing countries, the major threat to clean air is posed
by traffic emissions in summer.
The archetype is the Los Angeles photochemical smog, first described in 1948
and now plaguing cities from Athens to Mexico City.
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Formation of Tropospheric Ozone
No Hydrocarbons
NO NO2 Needs:
O3 O3 + NO → NO2
O2
With Hydrocarbons
RO2• RO•
NO NO2
O2 O3
12
Daily evolution of photochemical
air pollution
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Ozone Sinks
1. Surface destruction or deposition
- reaction with plants, bare land, ice and snow, and man-made
structures
- deposition of O3 is at its greatest over forests and croplands
during daylight hours.
2. Photochemical reactions
-photodissociation on absorption of UV light and subsequent
formation of OH radicals.
- In polluted atmosphere, O3 reacts with NO to produce NO2 +
O2
- during nighttime hours, it reacts with NO2 to produce HNO3
14
Relevant to Hong Kong
15
16
Halogenated Hydrocarbons
◼ A variety of halogenated HCs are present in the atmosphere. They
contain one or more atoms of Cl, Br, F.
◼ Some are toxic, and others can contribute to O3 depletion and climate
warming.
◼ low reactivity, low toxicity, thermal and solvent properties, widely used
as aerosol propellants, refrigerant, degreasers, and foaming agents
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18
Phase-out Schedule of
Ozone Depleting
Substances
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PHASE OUT SCHEDULE OF ODSs (1)
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PHASE OUT SCHEDULE OF ODSs (2)
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PHASE OUT SCHEDULE OF ODSs (3)
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PHASE OUT SCHEDULE OF ODSs (4)
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24
25
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Particulate Matter
◼ Particulate matter is a collective term used to describe small solid
and liquid particles in the atmosphere.
◼ Most atmospheric particles are very small (<0.1 μm), whereas most
aerosol mass is associated with particles > 0.1 μm.
27
Particle size distribution (1)
◼ UFP mode: generated by poorly
understood gas-to-particle
conversion.
◼ Nuclei mode: from condensation of
low vapor pressure substances and
gas-to-particle conversion
◼ Accumulation mode: grown from
nuclei mode particles through
coagulation and condensation
◼ Coarse mode: generated by
mechanical processes
29
Particle size distribution (3)
⚫ UFPs: contributes little to particulate mass but they are often present
in large numbers.
⚫ Aitken nuclei: their number rapidly diminish as they coagulate with
each other to form larger particles.
⚫ Accumulation mode particles:
- they don’t grow into coarse particles because of growth-limiting
physical factors.
- the mode appears to be bimodal in relatively polluted urban areas,
with peaks at ~0.2 and 0.7 μm
⚫ Coarse particles:
- most coarse particles are in the 2.5- to 10-μm size range.
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Particulate Matter
TSP
PM10 (RSP)
PM2.5 (FSP)
32
Bacteria: 10 m
Road Dust: 5 m
Coal Dust: 2 m
Viruses: 0.4 m
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Airborne Dwarfs and Giants
34
Question ???
How do coarse and fine particles differ relative to their
size, mechanisms of formation, and chemical
composition?
Coarse particles are typically >2.5 μm aerodynamic diameter,
produced by mechanical processes, and consist of the same
chemicals as the materials from which they were formed.
Fine particles are typically <2.5 μm aerodynamic diameter, often
produced by photochemical reactions, and condense to produce
droplet particles that scatter sunlight; their chemical composition
depends on their atmospheric history.
35
Aerodynamic Diameter
36
Aerodynamic Diameter
Solid sphere g = 2
37
Question ???
38
Particulate Matter (1)
◼ Source
Primary
◼ Natural – volcanos, forest fires, ocean sprays,
biologic sources (mold, pollen, bacteria etc.)
◼ Anthropogenic – transportation, fuel combustion in
stationary sources, and other activities such as
industrial processes, construction and agricultural
activity
Secondary
◼ from chemical processes involving gases, aerosol particles and
moisture
39
Particulate Matter (2)
◼ Chemical composition:
major components include organic and elemental
carbon (OC and EC), sulfate, nitrate, and a variety
of trace metal.
In Hong Kong, C ~ 50% of PM10 mass; sulfate
~17%, nitrate~6%
◼ Sink:
wet and dry deposition
40
Question ???
Atmospheric particles vary in their chemical
composition. Why is this the case?
41
Fine PM is associated with mortality
42
Health Effect of particle number
concentrations
43
1.60E+04
Indoor particle number concentration
Outdoor particle number concentration
Particle number concentration (#/cm3)
1.40E+04
1.20E+04
1.00E+04
8.00E+03
6.00E+03
4.00E+03
2.00E+03
0.00E+00
6/09/2006 7/09/2006 7/09/2006 8/09/2006 8/09/2006 9/09/2006 9/09/2006
12:00:00 0:00:00 12:00:00 0:00:00 12:00:00 0:00:00 12:00:00
Time (sec)
44
Particle size distribution
70
Outdoor nighttime hours
Outdoor morning peak hours
Particle number concentration (#/cm3)
60
Nucleation Outdoor daytime hours
50 Outdoor afternoon peak hours
40
30
20
10
0
1 10 100 1000
Diameter (nm)
47
Acid Aerosols
48
Image of a scan of an iron nanofilm detector exposed in the
MOI-EAS for 2 days in summer 1 sampling session. The ringed
reaction sites produced by acidic particles are clearly different
from the sites produced by non-acidic particles. Tuxedo NY
outdoor: 48 hr. July 14-16, 1999, 10 x 10μm 49
Bio-aerosols (biological particles)
SARS virus
50
Atomization of infectious bio-aerosols:
humans and their activities
SARS
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Visibility Reduction
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Factors affecting visibility
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Light scattering and particle size
56
Question ???
What are the sizes of particles most
responsible for visibility reduction?
a. 300 to 800 nm
b. 0.1 to 5 mm
c. 2.5 to 10 mm
57
Question ???
An object is visible to the eye because it
contrasts with its background. The apparent
contrast of an object can be described
mathematically as ___________ function of
the distance between the observer and the
object.
a. A Linear
b. An Exponential
c. A Logarithmic
d. Don’t know
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Relevance to Hong Kong
59
Question ???
Describe how physical/chemical properties of
particles affect their atmospheric behavior.
Larger, heavier particles settle out more rapidly than
smaller, lighter particles. Particles with diameters in the
range of visible light scatter light very effectively.
Hygroscopic particles absorb H2O. Small particles can
collide with each other and grow into larger particles.
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Source apportionment
61
PM2.5 composition in background, urban and
roadside locations (Source: HKEPD)
9%
25% 9% 35%
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Annual average PM2.5 concentration (Teflon) for 00/01 and 04/05 studies
70
60 00/01 study
PM2.5 concentration (µg/m3 )
04/05 study
50
40
30
20
10
0
HT TW MK
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Material balance for 00/01 and 04/05 studies
100%
Ammonium Sulfate
80%
Ammonium Nitrate
Percentage (%)
Elemental Carbon
60%
Organic Matter
0%
HT (00/01) HT (04/05) MK MK TW (00/01) TW (04/05)
(00/01) (04/05)
Site
65
Particle Mass Distribution
400
350
300
Total mass = 920 mg
Mass, mg
250
200
150
100
50
0
0-2 2-5 5-9 9-15 15-25 >25
Size Range, um
66
Mass Fraction in Size Range
100%
90%
80%
Mass Fraction
70%
60%
50%
40%
30%
20%
10%
0%
0-2 2-5 5-9 9-15 15-25 >25
Size Range, um
Mass fraction in this size range = 179.5 / 920 = 19.5%
Mass fraction in this size range = 368 / 920 = 40%
67
Device Removal Efficiency
100%
90%
80%
Removal Efficiency
70%
60%
50%
40%
30%
20%
10%
0%
0-2 2-5 5-9 9-15 15-25 >25
Size Range, um
68
Overall Efficiency
Removal Efficiency
Mass, mg
250
70%
Mass Fraction
70%
200 60% 60%
150 50% 50%
40% 40%
100
30% 30%
50 20%
20%
0 10%
10%
0-2 2-5 5-9 9-15 15-25 >25 0%
0%
Size Range, um 0-2 2-5 5-9 9-15 15-25 >25
0-2 2-5 5-9 9-15 15-25 >25
Size Range, um
Size Range, um
69
Summary
70
Question ???
Dirty air removal or emission control?
The area of Los Angeles basin is 4083 square miles. The
heavily polluted air layer is assumed to be 2000 ft thick on
average. One solution to Los Angeles’ problems would be to
pump this contaminated air away. Suppose that we wish to
pump out the Los Angeles basin every day and that the air must
be pumped 50 miles to the desert. Assume also that the average
velocity in the pipe is 40 ft/s. Estimate the required pipe
diameter. (1 mile = 5280 ft)
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The flow rate required is
AH 4083mi 2 2000 ft (5280 ft / mi) 2
Q= = •
t 24h 3600s / h
3 3
ft m
= 2.63 109 = 7.47 107
s s
And the required pipe diameter is
4Q 4 2.63 109 ft 3 / s
D= = = 9158 ft = 2791m
V 40 ft / s
72
SO2 emission calculation
Sulfur in (Sin)
SO2 (Sash)
73
The mass balance equation may be written as
Sin = Sash + SSO2
From the problem data, the mass of “sulfur in” is
Sin = 1.00 kg/s x 0.030 = 0.030 kg/s
In one year,
Sin = 0.030 kg/s x 86,400 s/d x 365 d/y = 9.46 * 105 kg/y