OZONE DEPLETION

Causes Effects and Human Contribution...

Submitted By:
Jahanzaib Khan Khalid
Asad Zahid
Mirza Sikandar Izhar

An Overview
The ozone layer is a layer in Earth's atmosphere which contains relatively high
concentrations of ozone (O3). This layer absorbs 93-99% of the sun's high
frequency ultraviolet light, which is potentially damaging to life on earth. Over
91% of the ozone in Earth's atmosphere is present here. It is mainly located in the
lower portion of the stratosphere from approximately 10 km to 50 km above Earth,
though the thickness varies seasonally and geographically. The ozone layer was
discovered in 1913 by the French physicists Charles Fabry and Henri Buisson. Its
properties were explored in detail by the British meteorologist G. M. B. Dobson.
Between 1928 and 1958 Dobson established a worldwide network of ozone
monitoring stations which continues to operate today. There are many situations
where human activities have significant effects on the environment. Ozone layer
damage is one of them. The objective of this paper is to review the origin, causes,
mechanisms and bio effects of ozone layer depletion as well as the protective
measures of this vanishing layer. The chlorofluorocarbon and the halons are
potent ozone depletors. One of the main reasons for the widespread concern about
depletion of the ozone layer is the anticipated increase in the amounts of
ultraviolet radiation received at the surface of the earth and the effect of this on
human health and on the environment. Ultraviolet radiations are absorbed by
Ozone layer and are high energy electromagnetic waves emitted by the sun which
if enters the earths atmosphere can lead to various environmental issues including
global warming, and also a number of health related issues for all living organisms.
Thanks to the ozone layer which protects us from these harmful rays.

CAUSES OF OZONE LAYER DEPLETION

Following are the main causes
1) Low temperatures.
2) Increase in the level of chlorine and bromine gases in the upper stratosphere
3) Production and emission of chlorofluorocarbons (CFCs). This is what which
leads to almost 80 percent of the total ozone layer depletion! (And hence the
major most factor)
4) Hydro chlorofluorocarbons (HCFCs) and volatile organic compounds (VOCs).
Such substances are found in vehicular emissions, by-products of industrial
processes, aerosols sprays and refrigerants. All these ozone depleting substances
remain stable in the lower atmospheric region, but as they reach the stratosphere,
they get exposed to the ultra violet rays. This leads to their breakdown and
releasing of free chlorine atoms which reacts with the ozone gas, thus leading to
the depletion of the ozone layer by breaking the tri oxygen molecule and creating

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simple oxygen gas and free oxygen ions.

Different types of Refrigerants

Freons (Halo carbons):
Usually synthetic. Depending on whether they include chemical elements
hydrogen (H), carbon (C), chlorine (Cl) and fluorine (F) they are named after as
follows:
CFCs (Chlorofluorocarbons): R11, R12, R113, R114, R115
HCFCs (Hydro chlorofluorocarbons): R22, R123
HFCs (Hydrofluorocarbons): R134a, R404a, R407C, And R410a

Azeotropic refrigerants:
are mixtures of two or more refrigerants whose vapor and liquid phases retain
identical compositions over a wide range of temperatures. Typical examples of
azeotropic mixtures can be seen below:
R-503: 40.1% R23 and 59.9% R13
R-502: 8.8% R22 and 51.2% R115

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Zeotropic refrigerants
is one whose composition in liquid phase differs to that in vapor phase. The word
Zeotropic is a combination of the Greek words zeo (boiling) and tropi (change).
I.e. different components of the mixture would vapor out at different temperature
levels.
Some common examples are:
R404a: R125/143a/134a (44%, 52%, 4%)
R407c: R32/125/134a (23%, 25%,
R410a: R32/125 (50%, 50%)

The chemical reaction behind ozone depletion

Hydro chlorofluorocarbons (HCFCs)

These are refrigerants that contain Hydrogen, Chlorine, Fluorine, and Carbon. They
have only about 10% of the ozone depleting potential as CFCs. They are energy efficient, low-in-toxicity, cost effective and can be used safely. They have allowed
the CFCs consumption of the world to fall by about 75%. Unfortunately HCFCs
are Greenhouse gases, despite their very low atmospheric concentrations
When chlorofluorocarbons reaches stratosphere ultraviolet rays cause free
chlorine ions to be discharged from them which then react with ozone.
CFCl3 + UV Light --> CFCl2 + Cl
Cl + O3 --> ClO + O2
ClO + O --> Cl + O2

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The free chlorine ion produced in this step is then free to attack another ozone
molecule
Cl + O3 --> ClO + O2
ClO + O --> Cl + O2
And again...
Cl + O3 --> ClO + O2
ClO + O --> Cl + O2
And this cycle continues causing hazardous effects in the atmosphere.
2ClO + 2O 2Cl + 2O2
______________________
NET = 203 t

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Ozone and CFCs Chain Reaction

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Principal Steps in Depletion of Stratospheric

Ozone
Emission
The process begins with the emission, at Earths surface, of source gases containing
the halogens chlorine and bromine. The halogen source gases, often referred to as
ozone-depleting substances (ODSs), include manufactured chemicals released to
the atmosphere in a variety of applications, such as refrigeration, air conditioning,
and foam blowing. Chlorofluorocarbons (CFCs) are an important example of
chlorine-containing gases. Emitted source gases accumulate in the lower
atmosphere (troposphere) and are transported to the stratosphere by natural air
motions.

Accumulation
The accumulation occurs because most source gases are highly unreactive in the
lower atmosphere. Small amounts of these gases dissolve in ocean waters. The low
reactivity of these manufactured halogenated gases is one property that makes them
well suited for specialized applications such as refrigeration. Some halogen gases are
emitted in substantial quantities from natural sources.

Transport
These emissions also accumulate in the troposphere, are transported to the
stratosphere, and participate in ozone destruction reactions. These naturally
emitted gases are part of the natural balance of ozone production and destruction
that predates the large release of manufactured halogenated gases.

Conversion
Halogen source gases do not react directly with ozone. Once in the stratosphere,
halogen source gases are chemically converted to reactive halogen gases by
ultraviolet radiation from the Sun . The rate of conversion is related to the
atmospheric lifetime of a gas ). Gases with longer lifetimes have slower conversion
rates and survive longer in the atmosphere after emission. Lifetimes of the principal
ODSs vary from 1 to 100 years . Emitted gas molecules with atmospheric lifetimes
greater than a few years circulate between the troposphere and stratosphere
multiple times, on average, before conversion occurs.

Reaction
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The reactive gases formed from halogen source gases react chemically to destroy
ozone in the stratosphere. The average depletion of total ozone attributed to
reactive gases is smallest in the tropics and largest at high latitudes. In Polar
Regions, surface reactions that occur at low temperatures on polar stratospheric
clouds (PSCs) greatly increase the abundance of the most reactive chlorine gas,
chlorine monoxide (ClO). This results in substantial ozone destruction in Polar
Regions in late winter and early spring. After a few years, air in the stratosphere
returns to the troposphere, bringing along reactive halogen gases.

Removal
These gases are then removed from the atmosphere by rain and other precipitation
or deposited on Earths land or ocean surfaces. This removal brings to an end the
destruction of ozone by chlorine and bromine atoms that were first released to the
atmosphere as components of halogen source gas molecules. Tropospheric
conversion. Halogen source gases with short lifetimes (less than 1 year) undergo
significant chemical conversion in the troposphere, producing reactive halogen
gases and other compounds. Source gas molecules that are not converted are
transported to the stratosphere. Only small portions of reactive halogen gases
produced in the troposphere are transported to the stratosphere because most are
removed by precipitation. Important examples of halogen gases that undergo some
tropospheric removal are the hydro chlorofluorocarbons (HCFCs), methyl bromide
(CH3Br), and gases containing iodine.

Effects of Ozone Layer Depletion

The depletion of ozone layer allows entering of UV rays from sun into the earths
atmosphere which is associated with a number of health related and
environmental issues. Let us see its major impacts on human beings

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Skin Cancer: exposure to UV rays from sun can lead to increased risk for
developing of several types of skin cancers. Malignant melanoma, basal and
squamous cell carcinoma are the most common cancers caused by exposure to UV
rays.
Eye Damage: UV rays are harmful for our eyes too. Direct exposure to UV rays can
lead to Cataract problems, and also Photokeratitis or snow blindness.
Damage to Immune system: our immune system is also highly vulnerable to UV
rays. Increased exposure to UV rays can lead to weakening of the response of
immune system and even impairment of the immune system in extreme cases.
Aging of skin: exposure to UV rays can lead to acceleration of the aging process of
your skin. This will result in you looking older than what you actually are. It can
also lead to photo allergy that result in outbreak of rashes in fair skinned people
In humans, exposure to UV rays can also lead to difficulty in breathing, chest pain,
and throat irritation and can even lead to hampering of lung function.
UV rays affect other life forms too. It adversely affects the different species of
amphibians and is one of the prime reasons for the declining numbers of the
amphibian species. It affects them in every stage of their life cycle; from hampering
the growth and development in the larvae stage, deformities and decreases
immunities in some species and to even retinal damage and blindness in some
species

Ways to prevent ozone depletion

1. Limit private vehicle driving
A very easy way to control ozone depletion would be to limit or reduce the amount
of driving as vehicular emissions eventually result in smog which is a culprit in the
deterioration of the ozone layer. Carpooling, taking public transport, walking, using
a bicycle would limit the usage of individual transportation

2. Use eco-friendly household cleaning products

Usage of eco-friendly and natural cleaning products for household chores is a great
way to prevent ozone depletion. This is because many of these cleaning agents
contain toxic chemicals that interfere with the ozone layer. A lot of supermarke ts
and health stores sell cleaning products that are toxic-free and made out of natural
ingredients.

3. Avoid using pesticides

Pesticides may be an easy solution for getting rid of weed, but are harmful for the
ozone layer. The best solution for this would be to try using natural remedies, rather

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than heading out for pesticides. You can perhaps try to weed manually or mow your
garden consistently so as to avoid weed-growth.

4. Developing stringent regulations for rocket launches

The world is progressing in scientific discoveries by leaps and bounds. A lot of rocket
launches are happening the world over without consideration of the fact that it can
damage the ozone layer if it is not regulated soon. A study shows that the harm
caused by rocket launches would outpace the harm caused due to CFCs. At present,
the global rocket launches do not contribute hugely to ozone layer depletion, but
over the course of time, due to the advancement of the space industry, it will become
a major contributor to ozone depletion. All types of rocket engines result in
combustion by products that are ozone-destroying compounds that are expelled
directly in the middle and upper stratosphere layer near the ozone layer.

5. Banning the use of dangerous nitrous oxide

Due to the worldwide alarm caused by a study in the late 70s about the alarming
rate at which the ozone was being depleted, nations around the globe got together
and formed the Montreal Protocol in the year 1989 with a strong aim to stop the
usage of CFCs. However, the protocol did not include nitrous oxide which is the
most fatal chemical that can destroy the ozone layer and is still in use. Governments
across the world should take a strong stand for banning the use of this harmful
compound to save the ozone layer.

Recent International Developments in Saving the

Ozone Layer
191 Countries Agree to Strengthen Protection of the Earth's Ozone Layer
At the 19th Meeting of the Parties in Montreal on September 17-21, 2007, the Parties
agreed to more aggressively phase out ozone-depleting hydrochlorofluorocarbons
(HCFCs). The final agreement resulted from discussion of six proposals submitted
by governments from both developed and developing countries - Argentina and
Brazil; Norway, Iceland and Switzerland; the United States; Mauritania; Mauritius;
and the Federated States of Micronesia.

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HCFCs originally emerged as replacement chemicals for use in air conditioning,

some forms of refrigeration equipment and foams.

MONTREAL PROTOCOL- CONTROL SCHEDULE

HALOCARBON REFRIGERANTS

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Halocarbon Refrigerant are all synthetically produced and were developed as

the Freon family of refrigerants.
Examples :
CFCs : R11, R12, R113, R114, R115
HCFCs : R22, R123
HFCs : R134a, R404a, R407C, R410a

HFCs
Remain a popular choice especially for R22 phase out
Good efforts at improving leakage performance
e.g. Real Zero project
Interest in R407A to replace R404A
50% reduction in GWP

HCFC

Transitional compounds with low ODP

Partially halogenated compounds of hydrocarbon
Remaining hydrogen atom allows Hydrolysis and can be absorbed.
R22, R123

HCFC

Production frozen at 1996 level

35% cut by 2005,65% by 2010
90% by 2015,100 % by 2030
10 year grace period for developing countries.

R22

ODP-0.05, GWP-1700
R22 has 40% more refrigerating capacity
Higher pressure and discharge temp and not suitable for low temp
application

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Extensively used in commercial air-conditioning and frozen food storage

and display cases

R123

ODP-0.02,GWP-90
As a replacement for R11 as similar thermodynamic properties.
Very short atmospheric life but classified as carcinogen
Retrofit alternative to R11

HFC

Zero ODP as no chlorine atom contains only Hydrogen and Flurodine

Very small GWP values
No phase out date in Montreal Protocol
R134a and R152 a Very popular refrigerants
HFC refrigerants are costly refrigerants

R134a

ODP-0, GWP-1300
Used as a substitute for R12 and to a limited range for R22
Good performance in medium and high temp application
Toxicity is very low
Not miscible with mineral oil

R152a

ODP-0,GWP-140
R152a is another attractive HFC with similar properties to R12.
GWP is one order less than HFC134a but it is slightly flammable.
Also it has lower energy consumption. Hence the Environmental Protection
Agency of Europe prefers HFC152a to HFC134a

HYDROCARBONS REFRIGERANTS

Very promising non-halogenated organic compounds

With no ODP and very small GWP values
Their efficiency is slightly better than other leading alternative refrigerants
They are fully compatible with lubricating oils conventionally used with
CFC12.
Extraordinary reliability- The most convincing argument is the reliability of
the hydrocarbon system because of fewer compressor failures.
But most of the hydrocarbons are highly flammable and require additional
safety precaution during its use as refrigerants.
Virtually no refrigerant losses
Hydrocarbons have been used since the beginning of the century and now
being considered as long term solutions to environmental problems,
Dominant in domestic market like household refrigerators and freezers

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Growing use in very small commercial systems like car air-conditioning

system
Examples: R170, Ethane, C2H6
R290 , Propane C3H3
R600, Butane, C4H10
R600a, Isobutane, C4H10

R290

ODP-0,GWP-3
Compatible with copper.Miscible with mineral oil
Highest latent heat and largest vapour density
A third of original charge only is required when replacing halocarbons
refrigerant in existing equipment

Energy saving : up to 20% due to lower molecular mass and vapour pressure

R 600a

ODP-0,GWP-3
Higher boiling point hence lower evaporator pressure
Discharge temp is lowest
Very good compatibility with mineral oil

Azeotropic Refrigerants

A stable mixture of two or several refrigerants whose vapour and liquid

phases retain identical compositions over a wide range of temperatures.
Examples : R-500 : 73.8% R12 and 26.2% R152
R-502 : 8.8% R22 and 51.2% R115
R-503 : 40.1% R23 and 59.9% R13

Zeotropic Refrigerants

A zeotropic mixture is one whose composition in liquid phase differs to that

in vapour phase. Zeotropic refrigerants therefore do not boil at constant
temperatures unlike azeotropic refrigerants. The fact that zeotropic
refrigerants do not boil and condense and condense at constant
temperature, can present an advantage. This phenomenon known as
temperature glide is used to match the pressure drop in heat in heat
exchangers thereby increasing their efficiency. This in turn results in an
improved COP of the refrigeration cycle.

Examples :R404a : R125/143a/134a (44%,52%,4%)

R407c : R32/125/134a (23%, 25%, 52%)

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R410a : R32/125 (50%, 50%)

R413a : R600a/218/134a (3%, 9%, 88%)

INORGANIC REFRIGERANTS
Carbon Dioxide

Zero ODP & GWP

Non Flammable, Non toxic
Inexpensive and widely available
Its high operating pressure provides potential for system size and weight
reducing potential.

Drawbacks:

Operating pressure (high side) : 80 bars

Low efficiency

AMMONIA- A natural Refrigerant

ODP = 0
GWP = 0
Excellent thermodynamic characteristics: small molecular mass, large latent
heat, large vapour density and excellent heat transfer characteristics
High critical temperature (132C) : highly efficient cycles at high condensing
temperatures
Its smell causes leaks to be detected and fixed before reaching dangerous
concentration
Relatively Low price

Some Drawbacks of Ammonia as Refrigerant

Toxic
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Flammable ( 16 28% concentration )

Not compatible with copper
Temperature on discharge side of compressor is higher compared to other
refrigerants

WATER:

Zero ODP & GWP

Water as refrigerant is used in absorption system .New developing
technology has created space for it for use in compression cycles also.
But higher than normal working pressure in the system can be a factor in
restricted use of water as refrigerant

APPLICATION OF NEW ECO-FRIENDLY REFRIGERANTS

Application
HFCs used
Possible
Eco-friendly refrigerant

Domestic refrigeration
R134a,R152a
HC600a and blends
Commercial refrigeration
R134a,R404A,R407C
HC
blends,NH3 ,CO2 **
Cold storage ,food processing
And industrial refrigeration
R134a,R404A,R507A
NH3 ,HCs,CO2 **
Unitary air conditioners
R410A,R407C
CO2 ,
HC s
Centralized AC (chillers)
R134a,R410A,R407C
NH3 ,HCs,CO2, water **
Transport refrigeration
R134a,R404A
CO 2,
Mobile air conditioner
R134a
CO2 ,HCs
Heat pumps
R134a,R152a,R404A
NH3 ,HCs,CO2, water **

R407C,R410A

SURVEY OF REFRIGERANTS

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COMPARISON OF ALTERNATIVES:

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