1

2
Evolution of the atmosphere
Solar system condensed out from an interstellar cloud (primordial solar
nebula) 4.6 billion years ago.
Atmosphere of Earth (also of Venus and Mars) formed from volatile
compounds trapped in the planet itself.
3
The early atmosphere formed by degassing of volatiles in earth
consisted of CO
2
, N
2
, H
2
O vapour and trace amounts of H
2
.
Similar to the composition of emissions from volcanoes today.
Some of H
2
O emitted to atmosphere was condensed to form oceans.
Carbon sedimentary carbonate rocks.
N
2
became the most abundant component in the atmosphere.
4
Early atmosphere is slightly , but today it is strongly
oxidizing.
Dramatic increase in O
2
in the atmosphere over the time.
Oxygen did not exist in the early atmosphere. It is produced
as a by-product in the photosynthesis.
Today mixing ratio of O
2
in the atmosphere is approximately
20%.
Reached about 400 million years ago,
Balance between
photosynthesis,
respiration,
oxidation of organic matter
weathering reactions.
5
Comparison of earths atmosphere with the atmospheres of other planets
Table 1 Composition of the atmospheres in solar system
Venus, Earth and Mars inner planets others outer planets.
Table 1. Chemical composition of the atmospheres of planets in the solar system (cm
3
of gas in cm
3
of air)
BODY H
2
He H
2
O CH
4
NH
3
H
2
S CO
2
N
2
O
2
CO
Sun 0.89 0.11 0.001 6.0x10
-4
1.5x10
-4
2.5x10
-5
- - - -
Inner planets
Venus 1x10
-5
2x10
-5
2x10
-5
6x10
-7
- 2x10
-6
0.965 0.035 2x10
-5
3x10
-5

Earth 5.3x10
-7
5.2x10
-6
0.04 1.7x10
-6
<1x10
-8
1x10
-10
3.35x10
-4
0.781 0.209 4x10
-8

Mars - - 3x10
-4
- - - 0.953 0.027 1.3x10
-3
7x10
-4

Outer Planets
Jupiter 0.9 0.1 5x10
-6
2.4x10
-3
2.0x10
-3
? - - - 2x10
-9

Saturn 0.96 0.04 5x10
-6
2.0x10
-3
2.0x10
-3
<4x10
-7
- - - -
Uranus 0.85 0.15 - <1x10
-7
- - - - - -
Neptune 0.85 0.15 - 3x10
-5
- - - - - -
Titan 2x10
-3
3x10
-2
0.82 (Ar 0.12)
6
Outer planets have different atmospheric composition than inner
planets
Atmospheres of outer planets are reducing
high concentrations of H
2
and He
Inner planets have oxidizing atmospheres
high O
2
and CO
2
concentration
Composition of inner planets resembles the composition of early
atmosphere on earth.
Table 1. Chemical composition of the atmospheres of planets in the solar system (cm
3
of gas in cm
3
of air)
BODY H
2
He H
2
O CH
4
NH
3
H
2
S CO
2
N
2
O
2
CO
Sun 0.89 0.11 0.001 6.0x10
-4
1.5x10
-4
2.5x10
-5
- - - -
Inner planets
Venus 1x10
-5
2x10
-5
2x10
-5
6x10
-7
- 2x10
-6
0.965 0.035 2x10
-5
3x10
-5

Earth 5.3x10
-7
5.2x10
-6
0.04 1.7x10
-6
<1x10
-8
1x10
-10
3.35x10
-4
0.781 0.209 4x10
-8

Mars - - 3x10
-4
- - - 0.953 0.027 1.3x10
-3
7x10
-4

Outer Planets
Jupiter 0.9 0.1 5x10
-6
2.4x10
-3
2.0x10
-3
? - - - 2x10
-9

Saturn 0.96 0.04 5x10
-6
2.0x10
-3
2.0x10
-3
<4x10
-7
- - - -
Uranus 0.85 0.15 - <1x10
-7
- - - - - -
Neptune 0.85 0.15 - 3x10
-5
- - - - - -
Titan 2x10
-3
3x10
-2
0.82 (Ar 0.12)
7
Current atmosphere on earth very different
Earths atmosphere was fairly similar to the atmospheres of other
inner planets at the beginning. However, with the evolution
discussed in previous section the composition changed

Table 1. Chemical composition of the atmospheres of planets in the solar system (cm
3
of gas in cm
3
of air)
BODY H
2
He H
2
O CH
4
NH
3
H
2
S CO
2
N
2
O
2
CO
Sun 0.89 0.11 0.001 6.0x10
-4
1.5x10
-4
2.5x10
-5
- - - -
Inner planets
Venus 1x10
-5
2x10
-5
2x10
-5
6x10
-7
- 2x10
-6
0.965 0.035 2x10
-5
3x10
-5

Earth 5.3x10
-7
5.2x10
-6
0.04 1.7x10
-6
<1x10
-8
1x10
-10
3.35x10
-4
0.781 0.209 4x10
-8

Mars - - 3x10
-4
- - - 0.953 0.027 1.3x10
-3
7x10
-4

Outer Planets
Jupiter 0.9 0.1 5x10
-6
2.4x10
-3
2.0x10
-3
? - - - 2x10
-9

Saturn 0.96 0.04 5x10
-6
2.0x10
-3
2.0x10
-3
<4x10
-7
- - - -
Uranus 0.85 0.15 - <1x10
-7
- - - - - -
Neptune 0.85 0.15 - 3x10
-5
- - - - - -
Titan 2x10
-3
3x10
-2
0.82 (Ar 0.12)
8
Evolution of Air Pollution
Before Industrial Revolution
Air pollution started with .......
.
Open fire in the fireplace (no chimneys) for heating
Heavy indoor air pollution due to incomplete combustion.
Eg. Dark walls in caves, in historic churches at rgp, Greme
Outdoor air pollution started with .........

polluted air moved from inside the building to outside.
Coal-based urban air pollution had started.
9
In 20th century coal started to be burned in power plants.
Eliminated coal based air pollution in urban areas, but generated a new
problem called ..........
acid rain.
Obviously air pollution problem due to combustion of coal existed since
prehistoric times.
It changed form in time
The location and altitude of S gases released to atmosphere
changed,
but total amount of coal burned and SO
2
emitted increased with
increasing population.
This problem which started with the invention of fire, finally started to be
eliminated in mid 1980s with reductions in S emission to atmosphere.
10
Contribution of industrial emissions
Industrial air pollution started when .............
People used metal artifacts (Cu, Fe, bronze etc.).
They knew how to purify metals from ores.
Most of the ores are in the form of sulfides of that metal.
Ore processing means roasting ore.
During roasting Sulfur is oxidized to SO
2
and emitted to
atmosphere.
Today smelters
In early days smelting operation was performed within the city.
all SO
2
is emitted to atmosphere along with emissions from space
heating.
11
After industrial revolution
What is industrial revolution
use of steam to move machinary
first half of the 18th century.
Coal the only source of energy for steam generation,
After mid 20th century nuclear power was started to be used
for the same purpose.
Consequently, main forms of air pollution in 18th and 19th centuries was
associated with fossil fuels for steam generation and heating
particularly coal
petroleum started to be used
in the second half of the 19th century
12
Another important feature in this period is rapid increase in motor
vehicles
Table. Number of cars sold in the US annually (Table 1.1 in textbook)
1900 4,192
1925 4,625,330
1950 8,003,056
2000 9,295,732
Invention of electrostatic precipitator Reducing ash emission from
industries
13
1925-1950
Urban air pollution continued to be the main problem.
Episodes occurred which attracted attention to this problem
Meuse valley episode in 1930. 4 people had died
Donora episode (Pennsylvania, US) in 1948, 5 people had died
Paso Rica episode (Mexico) in 1950, 6 died.
First use of natural gas for space heating. Rapid improvement in air quality.
large number of trace compounds were identified
various chemical processes.
14
The time between 1950 and 2004 can be divided into three periods
1950 and end of 60s
Elimination of urban air pollution,
Understanding stratospheric chemistry.
70s and 80s
Acid rain chemistry (S-chemistry),
Long range transport
Chemistry of photochemical smog.

Basics of the atmospheric chemistry were fairly well understood
between 1960 and 1990. What are these?
Currently
chemistry of VOC and NOx in relation to Ozone production
Global warming
15
Studies after 1950s revealed
composition of the atmosphere is changing and humans have
strong influence on this change.
Composition of the early atmosphere Ice core studies
Analysis of ice layers
Analysis of air bubbles trapped in ice
Showed compounds related to human activities increased after 1900
Eg. SO
4
2-
profile in cores Figure 1.
16
17
18
19
20
Pressure change along atmosphere
Pressure changes from 1 atm at the surface to 3x10-7 atm at 100
km.
Relation between P and z is given by barometric equation
P = P
o
e
-(gMz/RT)
or
P/P
o
=e
-(gMz/RT)

P-Presure
g-gravitational acceleration
M-molecular veight of air
z-altitude
R-gas constant
T-temperature
If plug all constants
P = P
o
e
-(1/8)z
21
Barometric equation can also be written as
P/P
o
= e
-(z/H)
Where H is the scale height and given by
H = RT/Mg
22
Layers primarily based on
temperature profile.
Consists of four layers.
Troposphere,
Stratosphere,
Chemospere (or more
commonly known as
mesosphere)
ionosphere (or
thermosphere)
Between layers tropopuse,
stratopuse, and mesopuse,
+1700C
Stratosphere
Troposphere
Mesosphere
Thermosphere
Tropopouse
Stratopouse
Mesopouse
50 km
90 km
11 km
-56C
+2C
-90C
+13C
T
z
Temperature change along the atmosphere and atmospheric layers
23
Stratosphere
Troposphere
Mesosphere
Thermosphere
Tropopouse
Stratopouse
Mesopouse
50 km
90 km
11 km
-56C
+2C
-90C
+13C
T
z
Chemistry and chemical
composition of these layers are
significantly different.
Mesosphere and thermosphere
Effect the radio
communications with
satellites.
Modify the solar spectrum
reaching to the earth.
Affect chemistry in the lower
layers
Protect earth from harmful
UV radiation.
24
Stratosphere
Troposphere
Mesosphere
Thermosphere
Tropopouse
Stratopouse
Mesopouse
50 km
90 km
11 km
-56C
+2C
-90C
+13C
T
z
Stratosphere
important for atmospheric
chemists,
forms a media at which
pollutants can be
transported in the global
scale,
It accommodate O
3

In this course we will primarily
discuss the troposphere, because
it is the part of the
atmosphere in which we
live,
part of the atmosphere
which we pollute and
part of the atmosphere
where most of the
meteorological events
occur.
25
Troposphere
First 11 km of atmosphere
Temp decrease from +13C to -
56C
-56C at the tropopouse is
important keeps H
2
O vapor
Consists of two parts
Boundary layer
Free troposphere
Stratosphere
Troposphere
Mesosphere
Thermosphere
Tropopouse
Stratopouse
Mesopouse
50 km
90 km
11 km
-56C
+2C
-90C
+13C
T
z
26
Boundary layer
First 5 km from surface
Most emissions occur in BL
Concentrations of pollutants
high
Most of the met events
Short residence times
Free troposphere
Between 5 11 km of
atmosphere
No emissions
Low concs
Little meteorology
Long residence time

Stratosphere
Troposphere
Mesosphere
Thermosphere
Tropopouse
Stratopouse
Mesopouse
50 km
90 km
11 km
-56C
+2C
-90C
+13C
T
z
27
UNPOLLUTED AIR
Composition of the atmosphere if there were no humans on
earth.
Only a concept. ..........
Table 1 Gaseous composition of the atmosphere.
background matrix on which chemistry goes on.
Atmospheric vapors. H
2
O and organic vapors
28
Units,
Mixing ratio (%, ppmv, ppbv) vs
concentration (g m
-3
, ng m
-3
, etc)
Conversion of units
1 ppm of gas X = Mol. Wt of X x 44.6 g m
-3

Derivation is homework
1 ppm SO
2
= 64 x 42.6 = 2726 g m
-3
1 ppb SO
2
= 64 x 42.6 x 0.001 = 2.7 g m
-3
5 ppb SO
2
= 64 x 42.6 x 0.001 x 5 = 13.6 g m
-3
5 ppb NO = 30 x 42.6 x 0.001 x 5 = 6.39 g m
-3
29
Importance of water vapour
The H
2
O vapour concentration in the atmosphere is about 2%.
concentration is variable (between 0.5 - 5 %).
Typical concentration is 2%
In tropics it is about 5%
Polar Regions and desert areas <<1%
30
Distribution of H
2
O:
Ocean 97%
Freshwater and lakes 0.6%
Polar ice caps 2.4%
Atmosphere 0.001%
Amount of water in atmosphere is very small
But it is important because:
It absorbs IR radiation and keeps temperature around 13C.
It effects residence times of atmospheric particles and gases,
Crucial for life on earth
Responsible for the uniform distribution of temperature (latent
heat transfer)
31
Latent heat transfer
Energy transfer by evaporation of H
2
O from oceans and
condensation into cloud
has two consequences:
Driving force for large scale atmospheric circulation (winds).
Avoids extreme temperature differences between different
regions.
Can act both source and sink for atmospheric trace constituents
Eg. Sink for CO
2
and source of SO
2

32
PARTICULATE MATTER
Small (m sized) solid material in the air.
Size vary between 1 nm (10
-9
m) and 100 000 nm ( = 100 m = 10
-4
m).
Lower limit measurement technology
Upper limit atmospheric residence time
Particulate material between these sizes stays in the air for an
appreciable time period and are called atmospheric particles, or
atmospheric aerosol.
33
Atmospheric particles are important because:
They effect the energy balance of the earth scatter solar
radiation.
Cause visibility degradation. Figure
They may contain organic or inorganic organic material
Toxic
When they are inhaled they may have health effects
The life cycles of atmospheric particles can be described in three
stages:
Formation
Aging
Removal
34
Primary particles Particles directly injected to atmosphere from various
sources
Secondary particles Particles, which form by reactions between
atmospheric gases
Eg. SO
2
+ h SO
4
2-
Sources
Natural
Eg. .........
sea salt, volcanoes, soil resuspension Figure
Anthropogenic
Eg. ...............
Combustion, industrial etc
35
Aging
processes particles undergo when they are in the atmosphere.
Include
transport over long distances,
scattering of solar radiation
chemical changes
particularly important in terms of aging.
Eg. SO
2
/SO
4
ratio in aerosol is an indication how old (or
aged) the aerosol population is.
36
participation in clouds
Particles also have significant role in cloud formation,
HOW? CCN
No particle condensation of water vapour to cloud
droplet -25C
With CCN -5C
CCN requirement: d<0.1 m., hyroscopic
37
Particle Size distribution.
Concentrations of particles in different size ranges.
Size distribution is one of the most important characteristics of
particles, because: ...........
It determines health effects of particles
It determine their chemistry Figure surface reactions
It determines physical process that particles undergo
(sedimentation transport etc.)
Figure Sizes of various sizes and species
38
There are three types of size distribution:
Number size distribution
#of particles of different sizes in m
-3
air
important for health effects of particles WHY?
Surface distribution
cm
2
of different sizes in m
-3
air
important for chemistry of particles WHY?
Volume (mass) size distribution
cm
3
particle in m
-3
of air, or g particle in m
-3
of air
determines the physical processes that particles undergoes in
the atmosphere, such as transport diffusion etc. WHY?
Volume and mass size distributions are related
d = M/V
M = Vd
39
Figure 1. Number, surface and
volume distributions in Los Angeles
air
1. Number concentrations are
the highest in small
particles (0.01 m).
2. Surface concentration
peaks approximately at
0.1 0.5 m.
3. Volume (mass) distribution
is bimodal (has 2 maxima).
Small size maximum is
at 0.2 1.0 m (fine
particles)
large particle maximum
is at 10 m (coarse
particles)
0.01 0.001 0.1 1 10 100
0
1.0
3.0
Estimated
Number
Surface
Volume
Estimated

N
/
N
T

l
o
g
D
p

S
/
S
T

l
o
g
D
p

V
/
V
T

l
o
g
D
p

2.0
0.01
0
1 10 100
0.1
0.2
0.3
0.4
0.5
0.6
Aerosol mass size
distribution
Antalya
d
C
/
d
l
o
g
D

D (m)
40
Particles in the two modes are generated by different
mechanisms.
Fine particles:
combustion process coagulation of very small particles,
(produced by gas-to-particle conversion)
Coarse particles
Mechanical processes (grinding etc)
41
Large particles have much higher impact on particle mass.
Eg. Three different particles 0.01, 0.1 and 1.0 m
calculate their volume.
0.01 m particle (r = 1x10
-8
m) :
Surface area = r
2
= 3.14 x 10
-16
m
2

V = r
3
= 2.35x10
-24
m
3
= 5.18 x 10
-18
g
0.1 m particle (r=1x10
-7
m)
Surface area = 3.14x10
-14
m
2
Volume = 2.35x10
-21
m
3
= 5.18 x 10
-15
g

1.0 m particle (r=1x10
-6
m)
Surface area = 3.14x10
-12
m
2
Volume = 2.35x10
-18
m
3
= 5.18 x 10
-12
g

42
Note
volume of 1.0 m particle is 10
6
times larger than the volume of the
0.01 m particle.
The same ratio exists in their masses as well (since mass is
proportional to volume through density).
Means that total masses of 1 million 0.01 m particles is equal to the
mass of one single 1.0 m particle.
43
Sinks:
Places to where pollutants are removed from atmosphere and
stored for a long time.
Eg. .............
Soil, sediments vegetation etc.
Storage should be for a long time, but not necessarily permanently.
Scavenging mechanisms:
Mechanisms by which particles are removed from the
atmosphere
wet deposition
dry deposition
Reactions

44
Dry deposition
By sedimentation for large particles
Falling down of particles by the action of gravity
Usually for large particles (particles > 10 m in
diameter).
Small particles can also sediment out, because they can
grow by coagulation

By impaction for small particles
Brownian motion + translational motion.
Some can not follow the movement of air sticks
The roughness of the soil, fibers of the vegetation can all
act like obstacles
45
Wet deposition
removal of particles from air by precipitation such as rain,
snow, dew etc.
Wet scavenging of particles occurs by two mechanisms
Rainout
Particles are incorporated in cloud droplets then fall with
the rain.
Regional process, WHY?
Washout
Particles in the atmosphere are captured by falling rain
droplets.
Local phenomenon WHY?
46
The period during which particles stay in the atmosphere is described
by either half life (t
1/2
) or residence time ()
half life (t
1/2
):
time it takes for half of the pollutants emitted from sources
to be scavenged into sinks
residence time ():
time period between injection and removal of a pollutant
molecule.
= A/f
i
= A/f
o
A: Atmospheric burden
f
i
: input flux
f
o
: output flux
IS ATMOSPHERE IN EQUILIBRIUM?
47
to have long residence time
high concentration in the atmosphere and/or
input and output fluxes should be small.
Eg:

N2
= 1,000,000 yr

O2
= 100,000 yr

Ar
= 10,000,000 yr

CO2
= 4 d
The of H
2
O vapour in the atmosphere is 10 days
48
Table 1. Chemical composition of the atmospheres of planets in the solar system (cm
3
of gas in cm
3
of air)
BODY H
2
He H
2
O CH
4
NH
3
H
2
S CO
2
N
2
O
2
CO
Sun 0.89 0.11 0.001 6.0x10
-4
1.5x10
-4
2.5x10
-5
- - - -
Inner planets
Venus 1x10
-5
2x10
-5
2x10
-5
6x10
-7
- 2x10
-6
0.965 0.035 2x10
-5
3x10
-5

Earth 5.3x10
-7
5.2x10
-6
0.04 1.7x10
-6
<1x10
-8
1x10
-10
3.35x10
-4
0.781 0.209 4x10
-8

Mars - - 3x10
-4
- - - 0.953 0.027 1.3x10
-3
7x10
-4

Outer Planets
Jupiter 0.9 0.1 5x10
-6
2.4x10
-3
2.0x10
-3
? - - - 2x10
-9

Saturn 0.96 0.04 5x10
-6
2.0x10
-3
2.0x10
-3
<4x10
-7
- - - -
Uranus 0.85 0.15 - <1x10
-7
- - - - - -
Neptune 0.85 0.15 - 3x10
-5
- - - - - -
Titan 2x10
-3
3x10
-2
0.82 (Ar 0.12)
Back
49
Greenhouse effect (energy budget of atmosphere)
Acid rain
Indoor air pollution
Chemistry of the stratosphere and upper layers
Long range transport
Photochemical smog
Oxidants.
Revolutionary improvements in measurement technology
There are still uncertainties in the details of the chemistry
Eg. Antarctic ozone hole
50
Years
1970
1950
1930
1910
1890
1870
1990
.
.
.
.
.
.
.
.
.
.
.
.

1500
ICE
Slice
Date
Analyze the ice
Analyze bubbles
51
2000 1900 1950 1600 1650
0.6
1550 1800 1850 1700 1750 1500
0.3
0.9
1.2
0
300
275
325
350
S
O
4
2
-

c
o
n
c
e
n
t
r
a
t
i
o
n

(

g

m
-
3
)

250
C
O
2

m
i
x
i
n
g

r
a
t
i
o

(
p
p
m
)

Back
SO
4
2-
CO
2

Years
52
Back
T
Stratosphere
Troposphere
Mesosphere
Thermosphere
Tropopouse
Stratopouse
Mesopouse
50 km
90 km
11 km
z
-56C
+2C
-90C
+1700C
+13C
53
Composition of UNPOLLUTED
atmosphere
Nitrogen 78.04%
Oxygen 20.95%
Argon 0.91%
CO
2
340 ppm
Neon 19.10 ppm
Helium 5.24 ppm
Methane 1.3 - 1.6 ppm
Krypton 1.14 ppm
Hydrogen 0.5 ppm
N
2
O 0.25 - 0.35 ppm
Xenon 0.087 ppm
Major gases
Minor gases
Trace gases
Back
54
55
Liquid film (water)
Oxidation
SO
2
(aq) + H
2
O
2
SO
4
2-

SO
2
(g)
Particle
Dissolution
(Henrys law)
Chemical reactions on the surfaces of particles
56
Combustion
Nuclei
Aitken
Nuclei
Beach Sand
Cement dust
Fly ash
Tobscco smoke
Clay Silt
Coarse sand
Molecular Clusters

Gravel Fine sand
Carbon black
Atmospheric dust
57
Sattelite picture of dust transport
Dust Storm at Africa
Volcanic eruption Forest fire
58