Lecture Two

Introduction to the physics

and chemistry of the
atmosphere
(Part II)
Professor S.C. Lee
Department of Civil and Environmental Engineering
The Hong Kong Polytechnic University
ZS943
Email: ceslee@polyu.edu.hk,
Tel: (+852) 2766-6011, Fax: (852) 2334-6389

1
 Educational Objectives

Understanding the mechanism of

photochemical oxidants and ozone
formation
Knowledge of particulate matters - particle
number and particle mass; particle size
distributions; types of particle modes;
sources and adverse effects.

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 ???

What factors determine the O3 concentrations

in the troposphere?
Concentrations dependent on
Intensity of sunlight
NO2/NO ratios
Reactive HC type and concentration
Concentrations of aldehydes/CO

8
Tropospheric ozone concentrations (1)

The background ground-level O3 mixing ratio: 20 – 50 ppbv

during warmer months of the year.
Sources: 1) Photochemical processes
2) Stratospheric ozone intrusion.

In large, economically developed landmasses: O3 levels are

often significantly higher than background. – associated with
anthropogenic emissions of NMHCs and NOx, biogenic
emissions of reactive NMHCs, and subsequent photochemical
reactions summarized previously.

9
Tropospheric ozone concentrations (2)

In rural areas, elevated O3 levels are often observed due to

(1)long-range transport of O3 aloft; (2) transport of O3
precursors such as NOx and less-reactive NMHCs.

In the U.S., the highest 1-hr average O3 level reached 400

ppbv. In Mexico City, it was recorded as high as 480 ppbv.
In southern England, it exceeded 250 ppbv.
In Hong Kong, the highest O3 recorded was 204 ppbv

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

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Daily evolution of photochemical
air pollution

Rush-hour emissions of NO and HCs

followed by:
Rapid conversion of NO → NO2
and formation of aldehydes
Then build-up of O3, peaking at
noon

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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
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 Relevant to Hong Kong

◼ O3 is a major air pollution problem in HK and

Pearl River Delta.

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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.

◼ Chlorofluorocarbons (CFCs): CFCl3 (CFC-11), CF2Cl2 (CFC-12), and

C2Cl3F3 (CFC-113)

◼ low reactivity, low toxicity, thermal and solvent properties, widely used
as aerosol propellants, refrigerant, degreasers, and foaming agents

◼ because of their roles in stratospheric ozone depletion, they are being

phased out.

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18
Phase-out Schedule of
Ozone Depleting
Substances

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PHASE OUT SCHEDULE OF ODSs (1)

CFCs 75 % reduction of consumption by 1

January 1994
Total phase-out by 1 January 1996

Halons Total phase-out by 1 January 1994

Carbon tetrachloride 85 % reduction of consumption by 1

January 1995
Total phase-out by January 1, 1996

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PHASE OUT SCHEDULE OF ODSs (2)

1,1,1-trichloroethane 50 % reduction of consumption by 1 January

(Methyl Chloroform) 1994
Total phase out by 1 January 1996

HBFCs Total phase out by 1 January 1996

Methyl Bromide Restrict to quarantine and pre-shipment

applications starting 1 January 1995

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PHASE OUT SCHEDULE OF ODSs (3)

1,1,1-trichloroethane 50 % reduction of consumption by 1 January

(Methyl Chloroform) 1994
Total phase out by 1 January 1996

HBFCs Total phase out by 1 January 1996

Methyl Bromide Restrict to quarantine and pre-shipment

applications starting 1 January 1995

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PHASE OUT SCHEDULE OF ODSs (4)

HCFCs Freeze consumption at base level starting 1

January 1996

35 % reduction of consumption by 1.1. 2004

65 % reduction of consumption by 1.1.2010

90 % reduction of consumption by 1.1.2015

二零
99.5% reduction of consumption by 1.1. 2020

Total phase out by 1.1. 2030

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26
 Particulate Matter
◼ Particulate matter is a collective term used to describe small solid
and liquid particles in the atmosphere.

◼ It is of a major air-quality concern because it is

1) an inhalation hazard to humans and animals,
2) reduces visibility,
3) affects climate on regional and global scales.

◼ Particle size is a very important characteristics because it determines

atmospheric lifetime, effects on light scattering, deposition in human
lungs.

◼ 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

Size characteristics of atmospheric particles

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 Particle size distribution (2)

⚫ Aerosols are divided into two major fractions based

on their size, origin, and physical properties: Coarse
particles Dp > 2.5 μm; fine particles Dp < 2.5 μm

⚫The fine particle fraction includes three modes:

Ultrafine, Aitken nuclei, and accumulation modes.
Particle diameter ranges of these modes are <0.01, 0.01
to 0.08, and ~0.10 to 1.2 μm, respectively.

⚫Most atmospheric particles are fine particles. It is

composed of 1/3 of the particulate mass found in non-
urban areas and 1/2 in urban areas.

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 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.

Both fine and coarse particles up to size range of 10 μm tend to remain

suspended.
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Example of Indoor Aerosol Size Distribution

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 Particulate Matter

TSP
PM10 (RSP)
PM2.5 (FSP)

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 Bacteria: 10 m

Road Dust: 5 m

Coal Dust: 2 m

Human Hair: 100 m

Viruses: 0.4 m

Vehicle Emission: 0.2 m

Relative Particle Size

33
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

The aerodynamic equivalent

diameter refer to a spherical
particle of unit density (1g/cm3)
that settles at a standard velocity.

36
Aerodynamic Diameter

Solid sphere g = 2

Hollow sphere g = 0.5 Da = 2 m

Irregular shape g = 2.4

Particles that appear to have different

physical sizes and shapes can have
the same aerodynamic diameter

37
 Question ???

True or False: The aerodynamic diameter of a

specific particle is the diameter of a particle
with unit density that will settle at the same
rate as the particle in question
a. True
b. False

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

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 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?

Chemical composition of particles reflects

the nature of sources from which they
were emitted, particle formation in the
atmosphere, and their atmospheric history.

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Fine PM is associated with mortality

42
 Health Effect of particle number
concentrations

⚫ Ambient Ultrafine Fine Particle

concentrations have been associated with
mortality, asthma, lung diseases, heart
diseases and others.

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 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)

Indoor and outdoor particle NUMBER concentrations in an air-

conditioned classroom in Brisbane

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)

Particle size distribution in a rural sampling

location in Australia
45
Contour plots of the average diurnal variations of particle size distribution and
diurnal patterns of the meteorological data and the concentrations of airborne
pollutants on 28 October 2010 at TMS 46
 Acidic Ultra-fine Particles

Ambient-particle-associated acidity is more closely

correlated with total mortality and hospital
admissions for respiratory disease than indices of
total particulate mass.
Evidence indicates the number of ultra-fine (d <
100 nm) acid particles, rather than ambient mass, is
an important determining factor affecting lung
injury.

47
 Acid Aerosols

Sulfuric acid and ammonium bisulfate,

both strongly acidic, are important
components of the fine and ultra-fine
particle modes in the ambient
atmosphere.

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)

▪ Virus: A bio-aerosol that could travel a certain

distance and infect human beings (from
physical point of view)

SARS virus

50
 Atomization of infectious bio-aerosols:
humans and their activities

Expiratory activities: breathing,

speaking, coughing, sneezing

Sewage atomization from

toilets and its transport in
building downpipe systems

Showering, using tap water

Wet - cleaning of indoor surfaces 51

Droplet atomization in expiratory activities

Breathing (few; LARGER;

nose)

Speaking (few; SMALL;

front of the mouth)
Front mouth
Laughing (few;Droplets > 1 m
facial region )

Sneezing (lots; SMALL;

front of the mouth, nose,
facial) 52
Example: SARS spread in Amoy Gardens in
Hong Kong

SARS
53
 Visibility Reduction

One of the major

impacts of particles in
the atmosphere

54
 Factors affecting visibility

Most light scattering caused by fine

particles
Particles with diameters equal to
wavelengths of visible light most effective
in scattering light
Scattering of visible light described as Mie
scattering

55
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

58
 Relevance to Hong Kong

◼ Particulate matter is a major air pollution

problem in HK.
◼ Vehicles, particularly diesel vehicles, are the
most important source.
◼ Acidic particles and bio-aerosol pollution
needs more studies.

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

This can be achieved by:

⚫ Emission inventory
⚫ Modeling – PCA/APCS; PMF; CMB, etc

61
PM2.5 composition in background, urban and
roadside locations (Source: HKEPD)

Hok Tsui 23.53 μg/m3 Tsuen Wan 34.12 μg/m3

3% 9% 4%
19%
16% 27%
7% 37%

9%
25% 9% 35%

Mongkok 58.28 μg/m3

Sulfate
1% 3%
16%
35%
Nitrate
5%
Ammonium
EC
40% OC
Others
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Major sources of fine particles in Hong Kong

➢ Sulfate particles – Regional contribution

➢ Organic carbons – local sources (primary
OC) and regional sources (Secondary OC).
➢ Elemental carbons – Local sources

63
 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

40% Crustal Material

Trace Species (30-element)
20% Unidentified

0%
HT (00/01) HT (04/05) MK MK TW (00/01) TW (04/05)
(00/01) (04/05)
Site

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 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

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 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%
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 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

Mass, mg Mass Fraction Device Efficiency Overall Efficiency

4.5 0.0049 0.1 0.00049
179.5 0.195 0.35 0.06825
368 0.4  0.75 0.3 =
276 0.3 0.9 0.27
73.5 0.08 0.98 0.0784
18.5 0.02 1 0.02
TOTAL: TOTAL:
920 0.73714
400
73.7%
350 100% 100%
90% 90%
300
80% 80%

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

We have discussed photochemical oxidants and

particulate matter. Chemical reactions can be very
complicated for photochemical oxidants.

 Understanding of above fundamental aspects is

important for the management of air pollution.

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 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

This is about 6 times the height of the tallest man-

made structure, and far beyond our current structural
engineering capabilities.

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 SO2 emission calculation

A China coal is burned at a rate of 1.00 kg/second. If the

analysis of the coal reveals a sulfur content of 3.00%, what is
the annual rate of emission of SO2? (the sulfur in the ash is 5%
of input sulfur)
Hint:
Using the mass-balance approach by drawing a mass-balance
diagram:
SO2 (SSO2)

Sulfur in (Sin)

SO2 (Sash)

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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

The sulfur in the ash is 5% of input sulfur:

Sash = (0.05)(9.46*105 kg/y) = 4.73 *104 kg/y

The amount of sulfur available for conversion to SO2:

SSO2 = Sin – Sash = 9.46*105 – 4.73*104 = 8.99*105 kg/y
The amount of sulfur formed is determined from the proportional weights of the
oxidation reaction:
S + O2 → SO2
The amount of SO2 formed is then 64/32 of the S available for conversion:
SSO2 = 64/32*(8.99*105 kg/y) = 1.80*106 kg/y
74