Ozone Layer Depletion

Introduction
 Ozone is a bluish gas located in the stratosphere which
protects the earth by absorbing UV-B and prevents this
harmful radiation from reaching the earth.
 Research has shown that the ozone is slowly being
depleted.
 We will discuss:
 The causes of ozone depletion
 The impacts ozone depletion has on the environment
 The current status of the ozone
 Solutions to the problem
 What is ozone?
Ozone is a stable molecule
composed of three oxygen
atoms.
While stable, it is highly reactive. The Greek word
ozein means “to smell” and O3 has a strong
pungent odor. Electric discharges in air often
produce significant quantities of O3 and you may
have smelled O3 near these sources.
Ozone in the atmosphere
The ozone layer
 Ultraviolet protection by ozone

Ozone absorbs UV light in the solar irradiation that is

harmful to life
Ultraviolet protection by ozone

The overlap of ground level radiation with the

sunburn sensitivity curve would be much greater
without the filtering effects of the ozone layer.
Ozone formation and destruction in the
stratosphere
 Chapman Theory

• O2+ hv (<242nm) -> 2O formatio

b) O+O2+M -> O3+M n

c) O3 + hv (<320nm)O +O2
Destructio
d) O + O32O2 n
Where M is a random air molecule (O2 or
N2)
Steady-state [O3] k a kb [M ] 1/ 2
=( )
O3 [O 2] kc kd
concentration
Chapman theory describes how sunlight converts the various
forms of oxygen from one to another, explains why the highest
content of ozone occur in the layer between 15 and 50 km,
Prediction by Chapman theory vs.
Observation

Using Chapman theory

 There must be other O3 destruction
pathways Catalytic ozone destruction
X + O3 = XO + O2
XO + O = X + O2
Net reaction O + O3 = 2 O2

X is a regenerated in the process – act as a

catalyst.
The chain reaction continues until X is removed by
some side reaction.
 The important catalysts for
stratospheric O3 destruction
 Hydroxy radical (OH)
.
OH + O3 = HO2. + O2
HOx cycle
HO2. + O = .OH + O2
Net: O + O3 = 2 O2
 Chlorine and bromine (Cl and Br)
. . ClOx cycle
Cl + O3 = ClO + O2
ClO. + O = Cl. + O2
Net: O + O3 = 2 O2
 Nitric oxide (NO) NOx cycle
NO + O3 = NO2 + O2
NO2 + O = NO + O2
Net: O + O3 = 2 O2
 The two-sided effect of NOx
 NOx provides a catalytic chain
mechanism for O3 destruction.
 NOx inhibit the HOx and ClOx cycles for
O3 destruction by removing radical
species in the two cycles.
 The relative magnitude of the two effects
is altitude dependent.
 >25 km, the net effect is to destruct O3.
 (NOx accounts for >50% of total ozone
destruction in the middle and upper
troposphere.)
 In the lower stratosphere, the net effect is to
protect O3 from destruction.
The catalytic destruction reactions described so
far, together with the Chapman cycle, account
for the observed average levels of stratospheric
ozone, they are unable to account for the ozone
hole over Antarctica.

The ozone depletion in the Antarctica is limited

both regionally and seasonally. The depletion is
too great and too sudden. These observations
can not be explained by catalytic O3 destruction
by ClOx alone.
 Causes of Depletion
 According to the Environmental Protection Agency,
the discovery of an “ozone hole” over Antarctica in 1985
focused attention on the idea that humans can have a
significant impact on the global environment. There are
also a number of natural causes of ozone depletion.

 When the following substances reach the stratosphere,

they break down under intense ultraviolet light, and
release chlorine or bromine atoms, which degrade the
ozone.
Chlorofluorocarbons (CFCs)
 CFCs is the abbreviated form of
ChloroFluoroCarbons, a collective name given to
a series of compounds containing chlorine,
fluorine and carbon atoms. Examples: CFCl3,
CF2Cl2, and CF2ClCFCl2.
 Related names
 HCFCs: Hydrochloroflorocarbons,
halocarbons containing hydrogen atoms in
addition to chlorine, fluorine and carbon
atoms.
 HFCs: hydroflorocarbons, halocarbons
containing atoms of hydrogen in addition to
fluorine and carbon atoms.
 Perhalocarbons: halocarbons in which every
available carbon bond contains a haloatoms.
 Halons: bromine-containing halocarbons,
Chlorine atom
Sources:
Photolysis of Cl-containing compounds in the
stratosphere.
CFCl3 + hv (185-210nm) CFCl2. + Cl.
CF2Cl2 + hv (185-210nm) CF2Cl. + Cl.
Subsequent reactions of CFCl2 and CF2Cl more Cl
atoms
The principal Cl-containing species are:
CF2Cl2, CFCl3,
Sources CFCl2, CF2Cl,
for Cl-containing CCl4, CH3CCl3,
compounds (need to be
CF2HCl,inCH3Cl
long-lived the troposphere)
•Man-made: e.g. CFCs
•Natural: e.g. methyl chloride from biomass
burning.
Chlorine atom (Continued)
Termination reactions for Cl
Cl. + CH4  CH3. + HCl
Stable in the stratosphere
Removed from air by precipitation
when it migrates to the troposphere

ClO. + NO2 + M ClONO2 + M

Reservoir species
Relatively unreactive but can
regenerate reactive species upon
suitable conditions
ClONO2 + hv
ClO + NO2
Nitric oxide
 NO is produced abundantly in the troposphere,
but all of it is converted into NO2 HNO3
(removed through precipitation)
 NO in the stratosphere produced from nitrous
oxide (N2O), which is much less reactive than
NO.
N2O + hv N2 + O (90%)
N2O + O 2 NO (~10%)
 Removal processes: Inhibit the
NO2 + .OH HNO3 HOx and ClOx
cycles
ClO. + NO2 ClONO2
Hydroxy radical
 Accounts for nearly one-half of the total ozone
destruction in the lower stratosphere (16-20
km).
 Sources
O3 + hv (<325nm) = O2 + O1D (2%)
= O2 + O3P (98%)
O1D + H2O = 2 .OH (major)

O1D + CH4 = .OH +CH3. (minor)

 Termination reaction
.
OH + NO2 HNO3
 How Humans Cause Depletion
 CFC’s (chlorofluorocarbons)
 Coolants for refrigerators
 Aerosol propellants
 Cleaning solvents
 Electric equipment
 Blowing agents to produce plastic foam and
insulation
 Halon
 Fire Extinguishing agent (only until 1994)
 Carbon Tetra Chloride
 Fire Extinguishers
 Aerosol Spray Propellants
 Dry Cleaning
 Methyl Chloroform
 Industrial Solvents
Natural Causes of Ozone Depletion
 Aerosols emitted from:
 Volcanic Eruptions
 The Ocean
 Cow Farts
 Burning Fossil Fuels
Ozone Depletion Potential (ODP)
The ratio of the impact on ozone of a chemical compared
to the impact of a similar mass of CFC-11.
Ozone Depletion Potentials (ODP)

7
6
5
ODP 4
(averages) 3
2
1
0
CFC's Halons Carbon Tetra Methyl
Chloride Chloroform

Substances
 Environmental Impacts
 Increase in UV-B reaching the earth’s
surface, which causes harm to :
 Humans
 Animals
 Plants and Agriculture
 The Ocean and Aquatic Ecosystems
Impact on Humans and Animals
 Damaging health effects primarily with skin,
eyes, and immune system
 Reduced air quality
 Human exposure to UV-B depends on
 Individual’s location
 Duration and timing of outdoor activities
 Precautionary behavior
 Skin color and age
 Plants and Agriculture
 Reduction of air quality reduces crop yields
 Decrease in photosynthetic activity
 Susceptibility to disease
 Changes in plant structure and pigmentation
 Retardation of growth
 Field Study: Soybean Harvests
Ocean and Aquatic Ecosystems
 Diminishes productivity of the oceans
 Decreases species such as fish and shrimp
 Humans and other consumers are dependent
on these higher species
 Populations outside the local ecosystem are
potentially at risk
Status of Ozone Depletion
 Ban of production and consumption of
compounds that deplete the ozone layer.
 Air Quality Improvements
 Statistically
 New Technology
Solutions
 Many substitute products have been made
 Increased public knowledge of ozone
depletion
 New Technology
 Policy and Regulations
Policy
 1987, The Montreal Protocol was signed
 Ban of CFC production
 More than 160 countries have signed the
treaty
 1990 Clean Air Act Amendments
 Established U.S. regulatory program to
protect the stratospheric ozone layer
 Individual and Corporate Responsibility