Stratospheric Ozone

•Stratospheric ozone is important in the earth system because it absorbs

ultraviolet radiation from the sun, protecting life on earth.

Ozone is found in two regions of the atmosphere:

•In the stratosphere at heights around 20–30 km, where it is produced by
sunlight. This is good ozone. It is critical for life because it protects all life on
earth from dangerous solar ultraviolet radiation, especially UVB, a band of
ultraviolet radiation with wavelengths from 280–320 nanometers produced by
the sun. Ultraviolet radiation with wavelengths from 320–400 nanometers, UVA,
is not absorbed, and it is much less dangerous to life.

•Close to the surface, where it is produced by sunlight acting on

atmospheric pollutants. It is produced from nitrogen oxides and volatile
carbon-based compounds when there is intense sunshine, above all in the
spring and summer. This is bad ozone. It causes respiratory illness; it damages
plants; and it attacks rubber.

Remember: Good up high. Bad nearby.

Ozone Absorption in the UV Band

 UV radiation includes wavelengths from 200 to 400 nm

 UV-A 320-400 nm
 UV-B 200-320 nm
 UV-C 200-290 nm

 UV-C
• Nearly all UV-C is absorbed in the upper atmosphere
 UV-B
• 90% of UV-B is absorbed by the atmosphere, mostly by O3
 UV-A
• Not strongly absorbed by the atmosphere
 Stratospheric Ozone Depletion

 Results from large-scale industrial manufacture and

release of synthetic compounds (chlorofluorocarbons,
CFCs) in quantities that can interfere with chemical
processes in the Earth’s atmosphere
History

 1974: Molina & Rowland (1974) Nature 249, 810-812

– Paper calls attention to dangers of CFC’s in ozone breakdown

 1978: U.S. bans CFCs as propellants

 1987: Montreal Protocol calls for decrease in CFC to
50% of 1986 levels by 1999
 1990: London Amendments call for complete CFC
phaseout by 2000
 1992: Copenhagen Amendments accelerate phase out
to 1996
 1995: Molina & Rowland win Nobel Prize in Chemistry
Ozone (O3)

 Blue colored, strong smelling molecule

 Absorbs UV radiation (more in a moment…)

 Unstable: constantly breaks down, reforms in

stratosphere
– Breakdown can be accelerated by certain chemicals (catalysts)

 Also a primary constituent of photochemical smog in the

troposphere
 Ozone partial pressure (mPa)
0 5 10 15 20 25
50
Stratosphere
40

36

32

28 Ozone concentration curve “Ozone layer”

Altitude (km)

24

20

16

12 Troposphere
8

4 Pressure gradient

0
0 0.2 0.4 0.6 0.8 1.0
Atmospheric Pressure (atm)
Ozone Formation in the Atmosphere

 Solar radiation striking the

Earth’s atmosphere is
absorbed by air molecules

 O2 strongly absorbs in the

UV band

 Absorption of UV by
molecular oxygen splits the
O=O bond, forming •O free
radicals

 These •O free radicals

combine with molecular
oxygen to form O3 (ozone)
In terms of equivalent
thickness of pure Ozone

How many molecules

Of Ozone does 1m2
Contain?
Chapman’s theory could not explain the observed O3 in the atmosphere
Depletion of stratospheric ozone
Mechanism of ozone depletion

Water derived from CH4 through a

series of reaction involving O2
These show massive Ozone depletion during spring time
ClO+NO2-----ClONO2
Cl+CH4------CH3+HCl

Contains solidified
HNO3.3H2O
Ice

ClONO2 + H2O-----HOCl + HNO3 HOCl + hv --------OH + Cl

ClONO2 + HCl------Cl2 +HNO3 Cl2 + hv------2Cl
ACID RAIN
Sandstone portal
Figure on Herten
Castle in Ruhr
district of Germany.
Sculpted 1702;
photographed in
1908.
Same sandstone
portal figure
photographed in
1969.
 SOURCES OF ACID RAIN
• Natural vs. Manmade
– Natural sources include forest fires, volcanoes,
– Man-made sources include industrial factories, car
emissions, and coal- and oil-fired power plants
(electricity from burning fossil fuels)
– The #1 cause of acid rain is from human activity
 NATURAL pH OF RAIN
• Equilibrium with natural CO2 (280 ppmv) results in a rain pH of 5.7:


H 2O
CO2 ( g )   CO2  H 2O K H  3 102 M atm-1

 HCO3  H  K1  9 107 M
CO2  H 2O 


 CO32  H 
HCO3 
 K 2  7  1010 M

 [ H  ]  ( K1K H PCO2 )1/ 2

• This pH can be modified by natural acids (H2SO4, HNO3, RCOOH…)
and bases (NH3, CaCO3) e natural rain has a pH in range 5-7

“Acid rain” refers to rain with pH < 5 e damage to ecosystems

 CHEMICAL COMPOSITION OF PRECIPITATION

Neutralization by NH3 is illusory because NH4+ g NH3 + H+ in ecosystem

ACID RAIN in the U.S.
Formation and Composition
Gas Phase production of nitric acid:
OH + NO₂ + M → HNO₃ + M

Aqueous phase production of nitric acid:

NO₂ + O₃ → NO₃ + O₂
NO₃ + NO₂ + M = N₂O₅ + M
N₂O₅ + H₂O(l) → 2HNO₃(aq)
 EFFECTS OF ACID RAIN
• Harmful to aquatic life and
vegetation
– Increased acidity in bodies of
water
– Increased acidity in soil
• Harmful to human health
– Respiratory problems, asthma, dry
coughs, headaches and throat
irritations
• Harmful to stone and metal
– Weathering of statues and
buildings is accelerated
 WHAT CAN WE DO?
• Reduce amount of sulfur dioxide and oxides of
nitrogen released into the atmosphere
– Use less energy (hence less fuel burnt)
– Use cleaner fuels
• Coal that contains less sulfur
• "Washing" the coal to reduce sulfur content
• Natural Gas
• Bio-fuel
– Use other sources of electricity (i.e. nuclear power,
hydro-electricity, wind energy, and solar energy)