REFRIGERANTS AND

ENVIRONMENT

MARPOL
73/78
Annexe VI contains Regulations for the

Prevention of Air Pollution from Ships.

Divided into 3 chapters
Chapter I -General having 4 Regulations (1-4)
Chapter II- Survey Certification of Means of
Control having 7 Regulations (5-11)
Chapter III- Requirements for Control of
Emission from Ships having 8 Regulations (12-19)

MARPOL 73/78 Contd.

CHAPTER I
Regulation 1-Applications
Regulation 2- Definitions
Regulation 3- General Exceptions
Regulation 4- Equivalents

MARPOL 73/78 Contd.

CHAPTER II
Regulation 5-Surveys and Inspections
Regulation 6-Issue of International Air
Pollution Prevention Certificate
Regulation 7-Issue of Certificate by
another Government.
Regulation 8-Form of Certificate

MARPOL 73/78 Contd.

CHAPTER II Contd.
Regulation 9-Duration and Validity of
Certificate
Regulation 10-Port State Control on
operational requirements
Regulation 11-Detection of violations and
enforcement

MARPOL 73/78 Contd.

CHAPTER III
Regulation 12- Ozone Depleting
Substances
Regulation 13- Nitrogen Oxides (NOx)
Regulation 14- Sulphur Oxides (SO x)
Regulation 15-Volatile Organic
Compounds

MARPOL 73/78 Contd.

CHAPTER III Contd.
Regulation 16- Shipboard Incineration
Regulation 17-Reception Facilities
Regulation 18- Fuel Oil Quality
Regulation 19- Requirements for
platforms and drilling rigs

MARPOL 73/78 Contd.

Regulation 12 deals with Ozone Depleting
Substances
Definition: Ozone Depleting Substances
means controlled substances defined in
Paragraph 4 of article 1 of the Montreal
Protocol on Substances that Deplete the
Ozone Layer, 1987.

MARPOL 73/78 Contd.

Definition Contd.
The following Halons are listed
Halon 1211 Bromochlorofluoromethane
Halon 1301 Bromotrifluoromethane
Halon 2402 1,2-Dibromo-1,1,2,2tetrafluoro ethane (also known as Halon
114B2)

MARPOL 73/78 Contd.

Definition Contd.
The following Refrigerants are listed
CFC-11 Trichlorofluouromethane
CFC-12 Dichlorodifluouromethane
CFC-113 1,1,2-Trichloro-1,2,2-trifluoroethane
CFC-114 1,2-Dichloro-1,1,2,2-tetrafluoroethane
CFC-115 Chloropentafluoroethane

MARPOL
73/78
Contd
.
Regulation 12 is about Ozone Depleting Substances
Subject to the provisions of Regulation 3, any
deliberate emissions of ozone depleting substances
shall be prohibited.
Deliberate emissions include emissions in the course
of maintaining, servicing, repairing or disposing of
systems or equipment except that deliberate
emissions do not include minimal releases associated
with the recapture or recycling of an ODS.

MARPOL
73/78
Contd
.
Regulation 12 Contd.
Emissions arising from leakage of an ODS,
whether or not the leaks are deliberate, may be
regulated by Parties to the Protocol of 1997.
New installations which contain ODSs shall be
prohibited on all ships, except that new
installations containing hydrochlorofluoro
carbons (HCFCs) are permitted until 1 January
2020.

MARPOL 73/78 Contd.

Regulation 12 Contd.
The substances referred to in this
regulation and equipments
containing such substances, shall be
delivered to appropriate reception
facilities when removed from ships.

WHAT ARE THE VARIOUS

THAT CAN
CFCs and SUBSTANCES
HCFCs used in following
applications:
CAUSE OZONE DEPLETION?

Air Conditioning
Refrigeration
Pesticides
Plastic Foams
Solvents

Fire fighting
Adhesives
Aerosols
Chemical feedstock etc.

VARIOUS
REFRIGERANTS
CFCs- R-12,R-11, R-113, R-114,
R-115 etc.
HCFCs- R-22, R-123, R-124 etc.
HFCs- R-134a, R-125, R-148a,
R-152a etc.

VARIOUS REFRIGERANTS
Contd.
Freon is Duponts trademark for its
fluorocarbon refrigerants.
All Refrigerants have one Carbon
atom as their origin is from Methane
(CH4) or Ethane C2H6 where one or 2
Hydrogen atoms have been replaced
with Chlorine, Fluorine or Bromine.

VARIOUS REFRIGERANTS
Contd.
Methane Derived Refrigerants
R No. viz. R-11, R-12, R-22 etc.
First figure shows the number of
Hydrogen atoms plus one.
Second figure
shows the number of
Fluorine atoms.
The total number of Hydrogen and other
replacement atoms should be 4

VARIOUS REFRIGERANTS
Methane Derived Refrigerants Contd. Contd.

R-11: CCl3F CFC

R-13: CClF3 CFC
R-22: CHClF2 HCFC
R-12:CCl2F2 DichlorodifluoroMethane CFC
R 113: CCl2F/CClF2
R 501:Mixture 75%-R22 and 25%-R12
R 502:Mixture 75%-R12 and 25%-R22

VARIOUS REFRIGERANTS
Contd.
Ethane Derived Refrigerants
R No: viz. R 113, R 114, R 115 etc.

First Figure shows number

of
Carbon atoms minus 1
Second figure shows number of
Hydrogen atoms plus 1 Third figure
shows number of
Fluorine atoms.

VARIOUS REFRIGERANTS
Ethane Derived Refrigerants Contd. Contd.
R-113- 1,1,2 Trichloro 1,2,2 Trifluoro ethane
R-114- 1,2 Dichloro
1,1,2,2
Tetrafluoroethane
R-115- Chloropentafluoroethane
R-134a C2H2F4 Tetra Fluoro Ethane (a
stands for isomer- same chemical composition
but different atomic arrangement)

KEY REFRIGERANT
CHARACTERISTICS
Ozone Depletion Potential ODP
AFFECTING
Global Warming
Potential GWP
ENVIRONMENT
Chlorine leading Potential
Atmospheric Life (years)

MONTREAL PROTOCOL
Signed on September 16, 1987 under the
auspecies of IMO.
Seeks to inhibit production, consumption
and trade of ozone depleting compounds.
Also distinguishes between developed
countries with higher consumption and
developing countries with lower countries.

UNEP CONFERENCE
Dated 25 November 1992.
New CFCs will be stopped production
after 1995 and HFCs after 2020.

ENVIRONMENT
Definition
The conditions and
influences of the place in which
an organism lives.
In laymans terms, it is known as
Surroundings.

ECOLOGY
Definition
The Study of
relationship between living
organisms and their
Environment.

ATMOSPHERE
Definition
The layer of gas surrounding
a planet or a star.
Earths Atmosphere Composition
Oxygen: 21% Nitrogen: 78%
CO2, H2, Argon and other Gases: 1%

ATMOSPHERE
Contd
.
Earths Atmosphere consists of the following layers
TROSPHERE Closest to Earths surface upto 14
kms height STRATOSPHERE upto 44 km
height IONOSPHERE consisting of
MESOSPHERE upto 80 km height
and
THERMOSPHERE above 80 km height
Each of these layers is seperated by TROPOPAUSE,
STRATOPAUSE,AND MESOPAUSE respectively.

OZONE
Formed by the action of Ultra Violet Light from the
sun on Oxygen in the atmosphere.
Boiling Point is -112 deg C.
Chemically very active, can readily react with any
other chemical atoms present closeby.
It has a great affinity to Chlorine and can engage in a
catalytic reaction in which each chlorine fragment can
destroy upto 100000 ozone molecules before the
chemical processes remove the chlorine from the
atmosphere.

OZONE LAYER
Present in Stratosphere at heights 11 km to 50
km above Earths surface. Stratosphere
temperature ranges from -56 deg C to -2 deg C.
Most concentrated at height of 22 km.
Highest concentration of about 10 ppm.
It accounts for less than one-millionth part of
Earths Atmosphere.
But it is of vital importance for Earths life-form.

OZONE LAYER Contd.

The ozone layer is not constantly thick all over
the earths surface.
Ozone Molecules are formed over the tropics
and are delivered along with the chlorine to the
Arctic and Antarctic with atmospheric Motion.
A circulation pattern called Antarctic and
Acrtic Polar Vortex traps the ozone near the
poles for several months.

OZONE LAYER Contd.

IMPORTANCE OF OZONE LAYER
It absorbs the UV-B rays while allowing the heat
generating infra-red rays to reach the earth.
This heat is life-sustaining on the planet
keeeping the temperatures of planet at desired
levels.
It influences the weather by stabilizing the
stratosphere which acts as a cap to the turbulent
weather system in the troposphere.

FORMATION OF OZONE
Ultra Violet Radiation below 190 nm LAYER
is removed
before it reaches Stratosphere by atmospheric
nitrogen and oxygen.
U V Radiation between 190 nm and 340 nm is
removed in Stratosphere by the reaction O 2 + hV
= O + O*
There is continuous cyclic formation and
destruction of ozone due to foll: reactions
O+
O* =O3 + M*; O3 + hV = O3 + O O3 + O2 = 2 O2

FORMATION OF OZONE
The absorption of UVRadiation in Stratosphere
LAYER
Contd.
prevents virtually all radiation
below 290 nm
and
mostly between 290 nm and 320 nm from reaching
the earth.
Above the Stratosphere, the density of gases is so low
that O2 atoms rarely find other molecules to collide
with; so ozone is not found in abundance.
Below the ozone layer, too little solar radiation
penetrates to allow appreciable amounts of ozone to
form.

DEPLETION OF OZONE
LAYER Contd.

Process
Chlorine in Stratosphere becomes trapped
in so called reservoir compounds such as
Hydrogen Chloride and Chlorine Nitrate
which themselves do not destroy Ozone.
Once Stratosphere becomes cold enough to
freeze closed particles, ice crystals provide
surfaces on which reactions can occur.

DEPLETION OF OZONE
Contd.
LAYER Contd.

Process
Chlorine Nitrate ClONO2 reacts with
Hydrochloric Acid present on ice surface,
producing molecular chlorine and Nitric Acid.
Nitric Acid remains bonded to the ice and
molecular Chlorine is quickly broken down into
Atomic Chlorine which reacts with Ozone
destroying it through production of chlorine
Monoxide and Molecular Oxygen.

DEPLETION OF OZONE
LAYER Contd.
Process Contd.
Chlorine Monoxide undergoes further
reactions that reform a chlorine atom which
is free to destroy another Ozone molecule.
The Ozone depleted is transported from the
polar regions to lower latitudes through
wind in the late spring when antarctic
Vortex breaks up.

DEPLETION OF OZONE
LAYER Contd.
Process Contd.
Ozone depletion process is accelerated
during presence of sunlight and low
temperatures.

DEPLETION OF OZONE
LAYER Contd.

Where does the Chlorine come from?

CFCs are one particular class of Refrigerants and
Fire Extinguishing Mediums containing Chlorine and
Fluorine Atoms. Ex. R-12, R-11.
They are chemically very stable and remain
unchanged in the lower atmospheric layer
(Troposphere).
Upon reaching Stratosphere, they encounter high
energy Ultra Violet light which breaks them releasing
Chlorine atoms.

DEPLETION OF OZONE
LAYER Contd.
Chlorine Levels in Stratosphere
1970 - 1.2 parts per billion
1985 - 3.0 parts per billion
2050 projected - 8.2 parts per billion
1 Chlorine Atom can destroy upto 100000
ozone molecules before the chemical
processes remove the Chlorine from the
Atmosphere.

DEPLETION OF OZONE
LAYER Contd.
Ozone Hole keeps forming over
Antarctica during certain months of the
year.
The lowest ozone levels were recorded
over South Pole in the first 2 weeks of
October 1987.

DEPLETION OF OZONE
LAYER
Contd.
What happens if the atmospheric Ozone Layer gets
depleted?
Ultra Violet rays from sunlight can reach the Earth
can damage human immune system, can cause
cataracts,
increase incidence of skin cancer.
Every 1% depletion of Stratospheric Ozone, results
in 2% rise in skin cancer.
In USA, 3000000 to 4000000 new cases of skin
cancer are reported every year.

DEPLETION OF OZONE
LAYER Contd.
Effects on Plants: Reduced leaf size,
stunted growth, poor seed quality,
susceptibility to weeds, disease and pests.
Marine Food Chain can be killed with
significant UV Radiation.
Lesser amounts of UV Radiation causes
slowdown of Photosynthesis.

OBLIGATIONS OF MARINE
FRATERNITY

Do not vent out CFCs and HCFCs into the

atmosphere.
Use CFC to HFC conversion kits that are
available for existing equipment.
When ordering for new Equipment /Machinery
for Refrigeration and Air Conditioning, ensure
to use only HFC Refrigerant based Machinery.
Educate and Train the floating staff regarding
the importance of these steps.

Reefer Cargo Temperature Log

M/V ___________________________

SAILED PORT ___________________

ON : ____________

VOY NO. __________

ARRIVED PORT ___________________

ON : ____________

Note : AlltemperaturestobeenteredinDegreesCelsius

DATE
TIME
Pulp temp
A DECK

Co2
Humidity
Pulp temp

B DECK

Co2
Humidity
Pulp temp

HOLD NO

C DECK

Co2
Humidity
Pulp temp

D DECK

Co2
Humidity
Pulp temp

E DECK

Co2
Humidity