Lecture Two

Introduction to the physics and chemistry of the atmosphere

(Part II)
Review

Lecture 1: Educational Objectives

 Chemical and physical characteristics of the
atmosphere
 What is “Air pollution” – sources, adverse effect and
historic story
 Understanding of major air pollutants in the
atmosphere
Learning
Objectives
for Today
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.
 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.
 Ozone formation mechanism
• RH + OH  R + H2O
• R + O2 + M  RO2 + M
• RO2 + NO  RO + NO2
• RO + O2  HO2 + aldehydes and ketones
• HO2 + NO  NO2 + O
• 2(NO2 + hv  NO + O)
• 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.
Formation of Tropospheric Ozone
No Hydrocarbons

NO NO2 Needs:
O3 O3 + NO  NO2
O2

With Hydrocarbons
RO2 RO

NO NO2

O2 O3
 The atmosphere is a giant
photoreactor

Emissions of : - carbonyls
Volatile Organic Compounds (VOCs)
+ h - peroxides
Light hydrocarbons, alcohols,
carbonyls, acids, halogenated HC… - Ozone
+ O2
- organic nitrates
and NO + NO2 = NOx
- organic aerosols
Tropospheric ozone concentrations
The background ground-level O3 concentration: 20 – 50 ppbv
during warmer months of the year.
Sources: 1) Photochemical processes
2) The movement of stratospheric O3 in the region of
tropopause folds into the lower atmosphere.
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.
Tropospheric ozone concentrations
In rural areas, elevated O3 levels are often observed due to (1)
transport of O3 precursors such as NOx and less-reactive
NMHCs; (2) less titration by NO.

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
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
 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
 Relevant to Hong Kong
• O3 is a major air pollution problem in HK and
Pearl River Delta.
 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.
Phase-out Schedule of
Ozone Depleting
Substances
PHASE OUT SCHEDULE OF ODSs
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
 PHASE OUT SCHEDULE OF ODS
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
 PHASE OUT SCHEDULE OF ODS
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
 PHASE OUT SCHEDULE OF ODSs
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

Weighted Quantity (tonnes) Consum ption of O zone Depleting Substances in Hong Kong

6000
En a c tm e n t o f th e
O z o n e Lay e r Pro tec tio n O rd in a n c e
5000

4000

3000

2000

1000

0
86 87 88 89 90 91 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06
Year
 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.
 Particle size distribution
• 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

 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.
 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.
Example of Indoor Aerosol Size
Distribution
 Particulate Matter

TSP
PM10 (RSP)
PM2.5 (FSP)
 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

Airborne Dwarfs and Giants
Aerodynamic Diameter

The aerodynamic equivalent

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

Solid sphere  = 2

Hollow sphere  = 0.5 Da = 2 m

Irregular shape  = 2.4

Particles that appear to have different

physical sizes and shapes can have
the same aerodynamic diameter
 Particulate Matter
• 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
 Particulate Matter
• 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
Fine PM is associated
with mortality
 Health Effect of particle number
concentrations

 ambient Ultrafine Fine Particle

concentrations have been associated
with mortality, asthma, lung
diseases, heart diseases and others.
 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
 Particle size distribution
70
Outdoor nighttime hours
Outdoor morning peak hours
Particle number concentration (#/cm)

60
3

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
Acidic Ultrafine 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 ultrafine (d <
100 nm) acid particles, rather than ambient mass, is
an important determining factor affecting lung
injury.
 •Acid Aerosols
• Sulfuric acid and ammonium bisulfate,
both strongly acidic, are important
components of the fine and ultrafine
particle modes in the ambient
atmosphere.
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
 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
Atomization of infectious bioaerosols:
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

Droplet atomization in expiratory activities

Breathing (few; LARGER;

nose)

Speaking (few; SMALL;

front of
Front mouth
the mouth)

Laughing (few;Droplets > 1 m

facial region )

Sneezing (lots; SMALL;

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

SARS
Visibility Reduction
• One of the major
impacts of particles
in the atmosphere
 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
Light scattering and particle size
 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.
 Source apportionment
This can be achieved by:
 Emission inventory
 Modeling – PCA/APCS; PMF; CMB, etc
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% 35%
9%

Mongkok 58.28 μg/m3

Sulfate
1% 3%
16%
35%
Nitrate
5%
Ammonium
EC
40% OC
Others
 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
 Annual average PM2.5 concentration (Teflon) for 00/01 and 04/05 studies
70

60 00/01 study
04/05 study
PM2.5 concentration (µg/m )
3

50

40

30

20

10

0
HT TW MK
 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
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
 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
 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.