4.

1
HAZARDS
Health Hazard
 Definition
• There are many chemicals transported by sea
that can be hazardous. However, in order for
them to affect your health, they must be in
contact with the body or be absorbed into the
body.
• When assessing the potential health effects
from working with a particular material it is
necessary to understand difference between
"toxicity" and "hazard".
• TOXICITY is the ability of a substance to produce an
unwanted effect when the chemical has reached a
sufficient concentration at a certain site in the
body.
• The more toxic a material is, the smaller the
amount of it necessary to be absorbed before
harmful effects are caused.
• The lower the toxicity, the greater the quantity
of it necessary to be absorbed.
• These values are called LD50 (lethal dose) or
LC50 (lethal concentration), and are usually
given in weight of material per kg of body
weight or airborne concentration of material
per set time period respectively.
• HAZARD is the probability that this
concentration in the body will occur.
• Toxicity is an inherent property of the
material.
• A material may be very toxic, but not
hazardous, if it is handled properly and is not
absorbed into the body.
• On the other hand, a material may have a very
low toxicity, but be very hazardous.
 Oil Tanker
• The ability of petroleum to create vapor plays
a major factor.
• Ability to vaporize is known as Volatility.
Volatility increases with temperature.
• An explosive mixture can be produced when
cargo vapour mixed with air
 Oil tanker
• The hazards(toxic effects) to health on board
a oil tanker can be divided as:
– Skin contact with liquid petroleum
– Ingestion (swallowing ) of liquid petroleum
– Inhalation (breathing) of liquid petroleum
– Inhalation (breathing) of petroleum vapour
– Compounds of lead contained in the cargo
 Liquid petroleum on skin
• Skin contact with liquid petroleum causes
irritation and dermatitis because of the
removal of essential natural skin oils.
 Swallowing Liquid Petroleum
• Ingestion of liquid petroleum into the stomach
causes acute discomfort and Nausea.
• The liquid ingested will tend to vaporize and
the vapour could be inhaled into the lungs.
 Inhalation of Liquid Petroleum
• If liquid is inhaled into the lungs there is serious risk
of suffocation through interference with normal
oxygen / CO2 transfer taking place during breathing.
• Cargo vapor in sufficient concentration will exclude
Oxygen and ,even if not toxic ,may cause
asphyxiation.
• Inhalation of petroleum vapour will produce
“Narcosis” , the main symptoms being
– Headache
– Eye irritation
– Dizziness
• with very high concentration may leading to
– Paralysis
– Insensibility
– Possible death
 Chemical Tanker
• All cargoes can be handled safely by showing
the greatest care throughout operation and by
following standing instructions at all times.
• A cargo may present one or all of the following
hazards
– Flammability
– Toxicity
– Corrosives
– Reactivity
 Chemical Tanker
• Cargo vapor in sufficient concentration will
exclude oxygen and ,even if not toxic, may
cause asphyxiation.
• An explosive mixture can be produced when
cargo vapor mixed with air.
• The vapors from some chemicals are toxic by
Inhalation.
• Some chemicals or their vapors are toxic by
absorption through the skin.
 Oxygen deficiency
• The most common of Health Hazard is the Oxygen
Deficiency. The oxygen content of air is 21% by volume
and oxygen content in enclosed spaces may become
lower. The reasons of oxygen deficiency in an enclosed
space could be:
– An inert atmosphere
– Displaced oxygen due to presence of cargo vapour
– Combustion
– Chemical reactions
– Rusting
– Drying paint
• The health effects from lack of oxygen
O2 Level Effects

22 % Oxygen enriched atmosphere

20.8% Normal level (±0.2%)

19.5% Oxygen deficient atmosphere

16% Impaired judgment and breathing

14% Rapid fatigue and faulty judgment

11% Difficult breathing and death in a few

minutes
• Take notes that:
– These effects can take place without any warning
such as odour or physical symptoms.
– In tanks and/or voids of complicated geometry
with high possibility of "pockets of atmosphere"
with low O2-content, and where rescue
operations may be difficult, the use of a portable
oxygen meter with audible alarm is strongly
recommended.
 Harmful Condition
• In certain wind conditions vented gases may descend
down, making the atmosphere on open deck harmful
due to:
– Presence of gases in harmful concentration
– Oxygen deficiency
• If harmful conditions on deck exist, all non-essential
work on deck should cease and only essential personnel
should remain on deck, taking all appropriate
precautions. The symptoms of the effect of oxygen
deficiency as asphyxia.
• Reliance should not be placed on symptoms for
indicating an oxygen-deficient atmosphere.
• The persons have varying susceptibility to oxygen
deficiency but that all will suffer if the oxygen
content drops below 16% by volume.
• If oxygen is less than 21% an atmosphere may be
extremely dangerous unless it is known which gas
has replaced the oxygen.
• The main hazard associated with inert gas is its low
oxygen content, but that it may also contain toxic
gases.
Environmental
Hazards
 Definition
• Hazard to environment can be define as
pollution.
• Pollution is the introduction of contaminants
into the natural environment that cause
adverse change.
• Pollution can take the form of chemical
substances or energy, such as noise, heat or
light.
• Pollutants, the components of pollution, can
be either foreign substances/energies or
naturally occurring contaminants.
• Pollution is often classed as point source or
nonpoint source pollution.
 Law & Regulations
• Carriage of chemicals in bulk is covered by
regulations in:
– SOLAS chapter VII - Carriage of dangerous goods
– MARPOL Annex II - Regulations for the Control of
Pollution by Noxious Liquid Substances in Bulk.
• Both Conventions require chemical tankers built
after 1 July 1986 to comply with the
International Bulk Chemical Code (IBC Code),
which gives international standards for the safe
transport by sea in bulk of liquid dangerous
chemicals, by prescribing the design and
construction standards of ships involved in such
transport and the equipment they should carry
so as to minimize the risks to the ship, its crew
and to the environment, having regard to the
nature of the products carried.
• The basic philosophy is one of ship types
related to the hazards of the products covered
by the Codes.
• Each of the products may have one or more
hazard properties which include flammability,
toxicity, corrosivity and reactivity.
• The IBC Code lists chemicals and their hazards
and gives both the ship type required to carry
that product as well as the environmental
hazard rating.
• Chemical tankers constructed before 1 July
1986 should comply with the requirements of
the Code for the Construction and Equipment
of Ships Carrying Dangerous Chemicals in Bulk
(BCH Code) – the predecessor of the IBC Code.
 Hazard to Environment
• The environmental hazard of shipping includes but
not limited to:
– greenhouse gas emissions
– sound
– oil pollution.
• The International Maritime Organization (IMO)
estimates that Carbon dioxide emissions from
shipping were equal to 3.3% of the global human-
made emissions in 2007 and expects them to rise by
as much as 72 percent by 2020 if no action is taken.
 Ballast Water Pollution
• Ballast water discharges by ships can have a negative
impact on the marine environment.
• Cruise ships, large tankers, and bulk cargo carriers use
a huge amount of ballast water, which is often taken
on in the coastal waters in one region after ships
discharge wastewater or unload cargo, and discharged
at the next port of call, wherever more cargo is loaded.
• Ballast water discharge typically contains a
variety of biological materials, including
plants, animals, viruses, and bacteria.
• These materials often include non-native,
nuisance, invasive, exotic species that can
cause extensive ecological and economic
damage to aquatic ecosystems along with
serious human health problems.
 Bilge Water
• On a ship, oil often leaks from engine and
machinery spaces or from engine
maintenance activities and mixes with water
in the bilge, the lowest part of the hull of the
ship.
• Oil, gasoline, and by-products from the
biological breakdown of petroleum products
can harm fish and wildlife and pose threats to
human health if ingested.
• Oil in even minute concentrations can kill fish or
have various sub-lethal chronic effects. Bilge
water also may contain solid wastes and
pollutants containing high amounts of oxygen-
demanding material, oil and other chemicals.
• A typical large cruise ship will generate an
average of 8 metric tons of oily bilge water for
each 24 hours of operation. To maintain ship
stability and eliminate potentially hazardous
conditions from oil vapors in these areas, the
bilge spaces need to be flushed and periodically
pumped dry.
• However, before a bilge can be cleared out and the
water discharged, the oil that has been
accumulated needs to be extracted from the bilge
water, after which the extracted oil can be reused,
incinerated, and/or offloaded in port.
• If a separator, which is normally used to extract the
oil, is faulty or is deliberately bypassed, untreated
oily bilge water could be discharged directly into
the ocean, where it can damage marine life.
• A number of cruise lines have been charged with
environmental violations related to this issue in
recent years.
 Sound Pollution
• Noise pollution caused by shipping and other
human enterprises has increased in recent history.
• The noise produced by ships can travel long
distances, and marine species who may rely on
sound for their orientation, communication, and
feeding, can be harmed by this sound pollution.
• The Convention on the Conservation of Migratory
Species has identified ocean noise as a potential
threat to marine life.
 Wild life Collision
• Marine mammals, such a whales and manatees, risk being
struck by ships, causing injury and death. For example, if a ship
is travelling at a speed of only 15 knots, there is a 79 percent
chance of a collision being lethal to a whale.
• One notable example of the impact of ship collisions is the
endangered North Atlantic right whale, of which 400 or less
remain. The greatest danger to the North Atlantic right whale
is injury sustained from ship strikes.
• Between 1970 and 1999, 35.5 percent of recorded deaths were
attributed to collisions. During 1999 to 2003, incidents of
mortality and serious injury attributed to ship strikes averaged
one per year. In 2004 to 2006, that number increased to 2.6.
Deaths from collisions has become an extinction threat.
 Atmospheric Pollution
• Exhaust gases from ships are considered to be a
significant source of air pollution, both for conventional
pollutants and greenhouse gases.
• There is a perception that cargo transport by ship is low
in air pollutants, because for equal weight and distance it
is the most efficient transport method, according to
shipping researcher Amy Bows-Larkin.[13] This is
particularly true in comparison to air freight; however,
because sea shipment accounts for far more annual
tonnage and the distances are often large, shipping's
emissions are globally substantial.
• A difficulty is that the year-on-year increasing
amount shipping overwhelms gains in
efficiency, such as from slow-steaming or the
use of kites.
• The growth in tonne-kilometers of sea
shipment has averaged 4 percent yearly since
the 1990s. and it has grown by a factor of 5
since the 1970s. There are now over 100,000
transport ships at sea, of which about 6,000
are large container ships.
• Of total global air emissions, shipping accounts for
18 to 30 percent of the nitrogen oxide and 9 percent
of the sulphur oxides. Sulfur in the air creates acid
rain which damages crops and buildings.
• When inhaled the sulfur is known to cause
respiratory problems and even increase the risk of a
heart attack. According to Irene Blooming, a
spokeswoman for the European environmental
coalition Seas at Risk, the fuel used in oil tankers
and container ships is high in sulfur and cheaper to
buy compared to the fuel used for domestic land
use.
Greenhouse gas pollutants
• 3.5 to 4 percent of all climate change emissions are caused by
shipping.
• Air pollution from cruise ships is generated by diesel engines
that burn high sulphur content fuel oil, also known as bunker
oil, producing sulphur dioxide, nitrogen oxide and particulate,
in addition to carbon monoxide, carbon dioxide, and
hydrocarbons.
• Diesel exhaust has been classified by EPA as a likely human
carcinogen. EPA recognizes that these emissions from marine
diesel engines contribute to ozone and carbon monoxide
nonattainment (i.e., failure to meet air quality standards), as
well as adverse health effects associated with ambient
concentrations of particulate matter and visibility, haze, acid
deposition, and eutrophication and nitrification of water.
• EPA estimates that large marine diesel engines accounted for
about 1.6 percent of mobile source nitrogen oxide emissions
and 2.8 percent of mobile source particulate emissions in the
United States in 2000.
• Contributions of marine diesel engines can be higher on a
port-specific basis. Ultra-low sulfur diesel (ULSD) is a standard
for defining diesel fuel with substantially lowered sulfur
contents. As of 2006, almost all of the petroleum-based diesel
fuel available in Europe and North America is of a ULSD type.
• As one way to reduce the impact of greenhouse gas emissions
from shipping, vetting agency RightShip has developed an
online “GHG Emissions Rating” as a systematic way for the
industry to compare a ship’s CO2 emissions to peer vessels of
a similar size and type. Using higher rated ships can deliver
significantly lower CO2 emissions across the voyage length.
 Oil Spills
• Most commonly associated with ship pollution are oil spills. While less
frequent than the pollution that occurs from daily operations, oil spills
have devastating effects.
• While being toxic to marine life, polycyclic aromatic hydrocarbons
(PAHs), the components in crude oil, are very difficult to clean up, and
last for years in the sediment and marine environment.
• Marine species constantly exposed to PAHs can exhibit developmental
problems, susceptibility to disease, and abnormal reproductive cycles.
• One of the more widely known spills was the Exxon Valdez incident in
Alaska. The ship ran aground and dumped a massive amount of oil into
the ocean in March 1989. Despite efforts of scientists, managers, and
volunteers over 400,000 seabirds, about 1,000 sea otters, and
immense numbers of fish were killed.
 Sewage
• The cruise line industry dumps 255,000 US gallons (970 m3) of
greywater and 30,000 US gallons (110 m3) of blackwater into the
sea every day.
• Blackwater is sewage, wastewater from toilets and medical
facilities, which can contain harmful bacteria, pathogens,
viruses, intestinal parasites, and harmful nutrients.
• Discharges of untreated or inadequately treated sewage can
cause bacterial and viral contamination of fisheries and shellfish
beds, producing risks to public health.
• Nutrients in sewage, such as nitrogen and phosphorus, promote
excessive algal blooms, which consumes oxygen in the water
and can lead to fish kills and destruction of other aquatic life.
• A large cruise ship (3,000 passengers and crew)
generates an estimated 55,000 to 110,000 liters per
day of blackwater waste.
• Due to the environmental impact of shipping, and
sewage in particular marpol annex IV was brought into
force September 2003 strictly limiting untreated waste
discharge.
• Modern cruise ships are most commonly installed
with a membrane bioreactor type treatment plant for
all blackwater and greywater, such Zenon or Rochem
which produce near drinkable quality effluent to be
re-used in the machinery spaces as technical water.
 Wastewater
• Greywater is wastewater from the sinks, showers, galleys,
laundry, and cleaning activities aboard a ship. It can
contain a variety of pollutant substances, including fecal
coliforms, detergents, oil and grease, metals, organic
compounds, petroleum hydrocarbons, nutrients, food
waste, medical and dental waste.
• Sampling done by the EPA and the state of Alaska found
that untreated greywater from cruise ships can contain
pollutants at variable strengths and that it can contain
levels of fecal coliform bacteria several times greater
than is typically found in untreated domestic wastewater.
• Greywater has potential to cause adverse
environmental effects because of
concentrations of nutrients and other oxygen-
demanding materials, in particular. Greywater
is typically the largest source of liquid waste
generated by cruise ships (90 to 95 percent of
the total).
• Estimates of greywater range from 110 to 320
liters per day per person, or 330,000 to
960,000 liters per day for a 3,000-person
cruise ship.
 Solid Waste
• Solid waste generated on a ship includes glass, paper,
cardboard, aluminium and steel cans, and plastics. It can be
either non-hazardous or hazardous in nature.
• Solid waste that enters the ocean may become marine debris,
and can then pose a threat to marine organisms, humans,
coastal communities, and industries that utilize marine
waters.
• Cruise ships typically manage solid waste by a combination of
source reduction, waste minimisation, and recycling.
However, as much as 75 percent of solid waste is incinerated
on board, and the ash typically is discharged at sea, although
some is landed ashore for disposal or recycling.
• Marine mammals, fish, sea turtles, and birds can be
injured or killed from entanglement with plastics and
other solid waste that may be released or disposed off of
cruise ships.
• On average, each cruise ship passenger generates at least
two pounds of non-hazardous solid waste per day. With
large cruise ships carrying several thousand passengers,
the amount of waste generated in a day can be massive.
• For a large cruise ship, about 8 tons of solid waste are
generated during a one-week cruise. It has been
estimated that 24 percent of the solid waste generated by
vessels worldwide (by weight) comes from cruise ships.
• Most cruise ship garbage is treated on board
(incinerated, pulped, or ground up) for
discharge overboard.
• When garbage must be off-loaded (for
example, because glass and aluminium cannot
be incinerated), cruise ships can put a strain
on port reception facilities, which are rarely
adequate to the task of serving a large
passenger vessel.
Reactivity Hazards
 Reactivity
• Many pure substances (i.e. uninhibited) can undergo vigorous
polymerization quite easily by themselves when they are
heated slightly or exposed to light. These include:
– acrylic acid
– acrylonitrile
– cyclopentadiene
– diketene
– ethyl acrylate
– hydrocyanic acid
– methacrylic acid
– methyl acrylate
– vinyl acetate
• The most common form of self-reaction is
polymerization.
• Polymerization generally results in the
conversion of gases or liquids into viscous
liquids or solids.
• It may be a slow, natural process which only
degrades the product without posing any
safety hazards to the ship or the crew, or it
may be a rapid, exothermic reaction evolving
large amounts of heat and gases.
• Heat produced by the process can accelerate it.
Such a reaction is called a run-off polymerization
that poses a serious danger to both the ship and
its personnel. Products that are susceptible to
polymerization are normally transported with
added inhibitors to prevent the onset of the
reaction.
• An inhibited cargo certificate should be provided
to the ship before a cargo is carried. The action to
be taken in case of a polymerization situation
occurring while the cargo is on board should be
covered by the ship's emergency contingency plan.
 Reaction with air
• Certain cargoes react with air in a way that
could pose a danger to both the ship and its
personnel. Toxic gases may be evolved. The
most noticeable examples are the isocyanates;
such cargoes are carried under dry and inert
condition.
 Reaction with water
• Certain cargoes react with water in a way that could
pose a danger to both the ship and its personnel.
• Toxic gases may be evolved. The most noticeable
examples are the isocyanates; such cargoes are
carried under dry and inert condition.
• Other cargoes react with water in a slow way that
poses no safety hazard, but the reaction may
produce small amounts of chemicals that can
damage equipment or tank materials, or can cause
oxygen depletion.
• Certain chemical cargoes, mostly ethers and
aldehydes, may react with oxygen in air or in
the chemical to form unstable oxygen
compounds (peroxides) which, if allowed to
build up, could cause an explosion. Such
cargoes can be either inhibited by an anti-
oxidant or carried under inert conditions.
 Reaction with other materials
• The materials used in construction of the
cargo systems must be compatible with the
cargo to be carried, and care must be taken to
ensure that no incompatible materials are
used or introduced during maintenance (e.g.
by the material used for replacing gaskets).
• Some materials may trigger a self-reaction
within the product.
• In other cases, reaction with certain alloys will
be non-hazardous to ship or crew, but can
impair the commercial quality of the cargo or
render it unusable.
Corrosion Hazards
 Corrosity
• Acids, anhydrides and alkalis are among the most commonly
carried corrosive substances.
• They can rapidly destroy human tissue and cause irreparable
damage.
• They can also corrode normal ship construction materials,
and create a safety hazard for a ship. Acids in particular react
with most metals, evolving hydrogen gas which is highly
flammable.
• The IMO Codes address this, and care should be taken to
ensure that unsuitable materials are not included in the cargo
system. Personnel likely to be exposed to these products
should wear suitable personal protective equipment
Explosion and Flammability
Hazards
Ability of petroleum to create vapor
plays a major factor in fire and
explosion related hazards.
Almost all tanker cargoes
presently transported in bulk by
sea, with the exception of Chlorine
and Nitrogen are Flammable.
It is not the liquids, but the vapor
emitted from them, that burn.
62
Ability to vaporize is known as volatility
Volatility increases with temperature and
reaches a maximum at the boiling
temperature of the petroleum
When hydrocarbon vapor is mixed with
oxygen ,in air an explosive mixture is
produced

63
The mixture of hydrocarbon vapor
and oxygen will only ignite and
burn if its composition is within
the “flammable range “ and
exposed to ignition source.
The working flammable range of a
mixture of petroleum vapor and
air can be taken to be 1 to 10% by
volume.

64
The ‘flashpoint’ of a cargo is the
lowest temp at which the cargo will
give off sufficient vapor to form a
flammable gas mixture with air near
the surface of the cargo.
Auto ignition temp is the lowest
temp to which a fuel to be raised to
cause self-sustained combustion
without a source of ignition.
65
Three essentials for a fire
Oxygen
Flammable material (Fuel)
Source of ignition (Heat)
The complete triangle
represents active fire.
The removal of any one side
will extinguish the fire
66
 Three main methods of
controlling a fire are:
1.Removal of oxygen (Smothering)
2.Removal of heat (Cooling)
3.Removal of fuel (Starvation)
Removal of the flammable
materials is usually not possible
with petroleum in bulk.
Generally the use of an IG
displaces or reduce oxygen below
flammable mixtures.
67
A diagram illustrating ,relationship between
composition / flammability of mixtures of
cargo vapor, oxygen and inert gas ; enable
procedures to be developed avoiding
flammable mixtures at all times.
Every point on the diagram represents a
mixture of oxygen , flammable vapor and
inert gas- in terms of its vapor and oxygen
content by % volume 68
69
LEL / LFL
Concentration of a Hydrocarbon gas in
oxygen below which there is insufficient
Hydrocarbon (fuel) to support and
propagate Combustion.
UEL / UFL
Concentration of a Hydrocarbon gas in
oxygen above which there is insufficient
oxygen to support and propagate
combustion
70
71
Range of Hydrocarbon gas concentrations
in oxygen between the LEL and UEL (LFL
and UFL) and are capable of being ignited
and of burning.
The values differ for different cargoes

72
73
Too Lean
A tank atmosphere, incapable of burning by the
deliberate reduction of the hydrocarbon
content (fuel content) below the LFL
Too Rich
A tank atmosphere, incapable of burning by the
deliberately maintaining the hydrocarbon
content (fuel content) over the UFL

74
75
In practice the following figures used for
Hydrocarbons gas
LEL / LFL - 1% by volume
UEL / UFL - 10% by volume
O2 - FR at least 10 % by volume
O2 - Safety margin< 8% by volume
For each Liquefied Gas Cargo – refer to
the ICS CDS for fire and explosion data

76
77
Electrostatic hazard

78
 Electrostatic hazards

 Electrostatic discharge can ignite

flammable hydrocarbon gas
 Electrostatic discharge completes
fire triangle (“heat”source)
 3 stages lead to electrostatic
hazard
– 1-charge generation
– 2-charge accumulation
– 3-electrostatic discharge

79
Charge separation

 2 dissimilar materials in
contact.An imbalance of
charge occur at interface

 The 2 materials separated

by mechanical action.One
carry an excess positive
charge other an excess
negative charge

80
 Charge separation

 Separated charges attempt to

combine.When one body poor
conductor - recombination limited
 Difference in charge(pd) exist
between 2 bodies. A voltage
distribution set up throughout
neighboring space- electrostatic
field present

81
 Charge accumulation

 Separated charges
accumulate.Degree of accumulation
depend on
-rate of charge generation
-rate of charge decay (charge
relaxation)
 Accumulation occurs best on
materials of slow charge decay (poor
conductors).Large voltage sets up.

82
 Electrostatic discharge

 Accumulated charge establishes an

electric field between it - nearby
earthed bodies.Electric field,in air or
petroleum gases when exceeds app.
3000kv/m- an electrostatic disc
occurs.
 Type of disc depend on
-Conduction property
-Electrostatic field strength
83
 Electrostatic discharge

 A body - low conductivity

- A brush corona disc
- Only part stored energy disc-
repetitive

 Body a conducting materials

- A spark disc occurs
- All energy stored on the body
move freely
and dissipated in single jump
- More incendiary properties
84
 Instantaneous release of energy

 Conductors
- Solids - metals
- Liquids - sea water /
human body
- Incapable holding a charge
unless insulated
- If insulated-a spark
discharge is possible

85
 Instantaneous release of energy
 Non conductors - liquids

- Received charge retained for

very long period (static
accumulators)
- Conductivity < 50 picosiemens/ m
- Relaxation time > 0.35sec
- An antistatic additive added to
petroleum distillate (clean oils)
to inc conductivity

86
 Instantaneous release of energy

 Non - conductors -solids

- highly insulating materials

- become conductive as
surfaces contaminated with
dirt / moisture

87
 Instantaneous release of energy

 Intermediate liquid / solid conductors

- Liquids-black/crude oils
conductivities >
50ps/m- non-static accumulator

- Solids-wood/cork
Readily absorb water and become
more
conductive

88
 Instantaneous release of energy

Gases

- Highly insulating
- Water-relaxation of charge on
droplets hindered by insulating
properties of surrounding
gases
- Fine particles in IG charged
- Gradual charge relaxation occurs
- Particles / droplets settles with 89
 Electrostatic charge generation
in tankers

 Steaming cargo tank

 Pipeline flow
 Oil mixing with water
 Oil splashing / spraying
 Un bonded intermediate flanges
 Protruding object-charged oil surface

90
 Operational practice avoiding electrostatic

 Only fixed apparatus for steaming

operations
 Steam velocity as minimum as
possible
 No earthed probe until tank clear
of steam
 Initial loading stage - flow rate
minimum
 Do not load tanks in overall
manner
 Use antistatic additive in oil
 Do not breach design safeties

91
 Operational practice avoiding electrostatic

 Keep tanks inert

 Use non conductive ullage tape
 Use permanently installed
ullaging device
 Take ullage through sounding
pipes
 Use sampling can made of non-
conductive materials + non-
conductive line
92
 Explosion due electrostatic discharge

 Charge accumulated -an

electric field exist
 Gas mixture-flammable

 Electric discharge-
A spark-intensity sufficient
to ignite gas mixture

93
 Avoiding electrostatic hazards

 Prevent charge accumulation

and generation -built in safety
features
 Prevent electrostatic disc
being dangerous-correct
operating procedures

 Prevent gas mixtures being

flammable – IG system
94
Toxicity
Hazards
 Definition
• TOXICITY –
– the ability of a substance to produce
an unwanted effect when the chemical has
reached a sufficient concentration at a certain
site in the body.
– The more toxic a material is, the smaller the amount of it
necessary to be absorbed before harmful effects are caused.
– The lower the toxicity, the greater the quantity of it
necessary to be absorbed. The toxicity of a chemical is
generally measured by experiments on animals (quite often
rats).
• If it is measured in terms of the amounts of material
necessary to cause death in 50% of the test animals.
These values are called LD50 (lethal dose) or LC50
(lethal concentration), and are usually given in
weight of material per kg of body weight or airborne
concentration of material per set time period
respectively.
• HAZARD is the probability that this
concentration in the body will occur.
• Toxicity is an inherent property of the
material. A material may be very toxic, but not
hazardous, if it is handled properly and is not
absorbed into the body. On the other hand, a
material may have a very low toxicity, but be
very hazardous.
 Threshold Limit Value (TLV)

• Airborne concentrations of substances under which

it is believed that nearly all workers may be exposed
day after day with no adverse effect. TLVs are
advisory exposure guidelines, not legal standards,
and are based on industrial experience and studies.
• There are three different types of TLVs:
- Time Weighted Average (TLV-TWA)
- Short Term Exposure Limit (TLV-STEL)
- Ceiling (TLV-C)
Time Weighted Average (TLV-TWA)

– The airborne concentration of a toxic

substance averaged over an 8 hour period,
usually expressed in parts per million (ppm).
 Short Term Exposure Limit (TLV-STEL)

– The airborne concentration of a toxic

substance averaged over any 15 minute
period, usually expressed in parts per million
(ppm).
 Ceiling (TLV-C)

– The concentration that should not be

exceeded during any part of the working
exposure
 Occupational Exposure Limit (OEL).
• Limits established to protect workers from workplace exposure to
certain chemical substances or physical agents. OELs have many
sources among them are legal standards (i.e., set by OSHAS)
Prevention of exposure is achieved through a combination of cargo
containment, which prevents toxic fumes or liquid from
contaminating the workplace, and the use of personal protective
equipment (PPE).

• To ensure safety on board one must adhere to the following points:

– knowledge,
– training and
– strict routine.
• It is a clear responsibility for the Owner, the master
and the officers to inform their personnel about the
cargoes to be carried, safety procedures etc. and to
arrange for the proper training.

• Information should be given partly in the form of

written notices combined with informal meetings
with the entire crew present when new cargoes are
to be loaded or when inexperienced personnel are to
be signed on.
• Among other things the following information
should be given:
– Cargoes to be loaded; their characteristics as
regards handling, pumping, toxicity, corrosiveness,
first aid etc.
– The cargo loading plan to be posted in places
where it will be clearly seen by everyone on board
and at the accommodation ladder, when in port.
– Post cargo information cards for products to be
loaded or are contained on board. For "new"
products ask the shipper for safety brochures and
leaflets.
– the personal safety equipment to be used by
those involved in cargo handling, pumping,
sampling etc.
– Have available on board literature on chemical
cargoes, medical advice, etc,
– Inform in particular if the cargo to be loaded has
an odour threshold which is higher than the TLV-
value. Of, and that danger cannot always be
sensed in advance (e g. carbon tetra chloride,
ethylene dichloride, etc).
– Most hydrocarbon vapours are heavier than air and
have a tendency to accumulate in lower spaces.
Therefore work below gratings in pump rooms,
cofferdams, pipe tunnels etc is extra dangerous.
– Never take work clothes into your cabin! Soiled
clothes must be washed before being used again or
in the case of toxic products, destroyed.
– Wash your hands before meals!
– Give information about firefighting methods for
each type of cargo on board.
– Give information if the cargo is water-reactive or
reactive to other cargoes on board. Give
information on segregation required.
– For some very toxic cargoes mouth to mouth
artificial breathing might be dangerous to the
rescuer (e.g. acrylonitrile, acetone etc.).
– Information must be given particularly if the cargo
danger lies primarily in vapour inhalation (e.g.
acrylonitrile, trichloroethylene) or skin contact
(e.g. phenol, caustic soda, sulphuric acid).
– State where eye washing bottles are located (deck
office, at cargo manifolds on deck, in pump rooms,
on fore deck, etc.).
– Insist on that nobody should work with cargo gear
without anyone standing by. Have people report
when going to and returning from pump rooms.
– Give information if any cargo is so toxic that an
escape breathing mask must be used in an
emergency.
 Vapour leaks and clouds

• These clouds would directly affect the surrounding

areas. In the case of flammable substances the greatest
danger arises from sudden massive escape of volatile
liquids.
• If the cloud were ignited, the effects of combustion
would depend on many factors, such as wind speed and
the extent to which the cloud was diluted.
• The area affected would generally be limited to a few
hundred metres from the location of release and would
cover all gas dangerous and gas safe areas.
• The procedures mentioned below are guidelines in event of
an accidental vapour leaks on tankers

– Raise alarm
– If in port, advise terminal
– Stop any Cargo Operations and then Shut Tank and Manifold Gate
Valves
– All crew to muster inside accommodation and close all doors
– Stop air conditioning / ventilation to living and working
spaces. (But maintain to operate the Pump Room Exhaust Fans, if
applicable)
– Notify nearest coast state and other vessels in vicinity
– If at sea, Master to alter course, if possible, to blow vapors away
from accommodation
– Check MSDS for emergency procedures
– Crew, wearing SCBA and PPE, go about to isolate source of leak.
Precautions when discovery of a leaks

• DO NOT create any sparks or heat sources

which could ignite escaping gas or liquids
• DO NOT approach a suspected vapour cloud
resulting from a leak
 4.2
HAZARD
CONTROLS
 Inerting
• Inert gas - gas or a mixture of gases containing insufficient
oxygen to support the combustion of hydrocarbons.
• Used in cargo tanks:
– To reduce oxygen in the tank atmosphere in order to prevent fire
and explosion
– To reduce hydrocarbons in an already inerted tank atmosphere
– To protect the cargo from polymerization, oxidation and humidity
• Purging (inerting) is done by replacing hydrocarbon vapours
with an inert gas until the concentration of vapours is below
2 % by volume
 Water padding
• Filling the ullage spaces of cargo tanks with a
liquid, gas or vapour to separate the cargo
from air and maintaining that condition
 Drying agents
• Filling the cargo tanks and associated piping or
where required spaces surrounding the tank
with moisture
• Free vapour having a dew point below -40°
Centigrade at atmospheric pressure and
maintaining that condition
• Prevents the access of water or water vapour
to the cargo
 Monitoring techniques
• Monitoring ullage spaces and other gas
dangerous spaces for safety and correct
atmospheric controls is provided
 Anti-static measure
• To avoid electrostatic hazard:-
– An important counter measure is to bond all metal
objects together
– Bonding to earth is effectively accomplished by
connecting all metal objects to the ship’s structure
– The ship’s hull could be earthed through the
seawater
• Anti-static measure to be taken:
– Safe flow rates
– Safe procedures for ullaging, sampling and gauging
 Ventilation
• Mechanical ventilation, normally of the extraction type, is
provided for spaces normally entered during cargo operations
(e.g. pump-rooms) of an oil and chemical tanker
• Ventilation intakes are so arranged as to minimize the possibility
of recycling hazardous vapours from any ventilation discharge
opening
• Ventilation ducts are not led through engine-rooms,
accommodation, working spaces or other similar spaces to ensure
cargo vapours do not enter into the safe zone. Engine-rooms and
accommodation spaces are kept in a positive pressure condition
• Ventilation fans should be properly earthed for operation in
explosive atmospheres when flammable cargoes are carried
aboard the ship
 Cargo segregation
• Residues of cargoes or mixtures containing cargoes, which react in a
hazardous manner with other cargoes, residues or mixtures, shall:-
– Be segregated from such other cargoes by means of cofferdam,
void space, cargo pump-room, pump-room, empty tank, or tank
containing a mutually compatible cargo
– Have separate pumping and piping systems which shall not pass
through other cargo tanks containing such cargoes, unless
encased in a tunnel; and have separate tank venting systems
 Cargo inhibitation
• Products that are susceptible to
polymerization are normally transported with
added inhibitors to prevent the onset of the
reaction
• Inhibited cargo certificate should be provided
to ship before a cargo is carried
 Importance of cargo compatibility
• Transporting of dangerous and noxious liquid
chemicals in bulk involved various risk factors.
• Between some chemicals violent reactions may
occur if the chemicals are mixed in certain
proportions.
• The result may possibly be an eruption and tank
rupture. Such an occurrance must be prevented.
Water may also have to be considered in this
respect.
• Leakages through bulkheads occur at times in any tanker.
Normally, however, such leakages are only minor seep ages.
• They will not cause any violent reaction due to the great
disproportion in mixture from dangerous proportions.
• But legislation as expressed in the IMO Chemicals Bulk Code ref
(25), and in the US Coast Guard Rules ref (18) and Appendix 3
expressly prohibits the placement of inter-reactive cargoes on
both sides of a bulkhead.
• There must be an empty tank, a cofferdam or a tank with a cargo
neutral to both products in between.
• This requirement causes some headaches in cargo planning.
"Diagonal contact'' between tanks is normally considered as
sufficient separation between reactive cargoes.
• More important, however, is the complete separation
of piping systems so that one product cannot
inadvertently be pumped into another.
• To this effect strategic pipe bends may have to be
removed and blind flanges fitted on each pipe end.
• Modern chemical tankers will have blind flange valves
fitted .
• Such a blind flange valve must have a double
separation between the products with a drain in the
interspace.
• A single blind flange is not acceptable.
• Remember also to separate drain lines or slop
connections to avoid the possibility of cargo mixing.
• The cargo inter- reactions may be of type:

a) Chemical reaction:
– Strong ( inorganic) acid plus alikali (or water) causes heat, e g
sulphuric acid plus caustic soda or water.
– Therefore sulphuric acid may not be carried in tanks bordering
the side shell or filled ballast tanks.
– Similarly sulphuric acid may react with a number of
hydrocarbons except parraffines (petroleum oils).
– Amines ( aniline, diethylamine) may react with esters
( butyl, acetate, ethyl acetate).
– Caustic soda will react violently with acrolein, acrylonitrile and
allyl alcohol.
• b) Oxidation :
– An Oxygen-rich compound like propylene oxide
may react with an amine (e g diethylamine) or an
aldehyde (e g acetaldehyde).
– An ether (e g ethyl ether) may react with oxygen
and from a peroxide which is an explosive hazard.
– The ether should be inhibited and carried in an
inerted (N 2 ) tank.
• c) Auto- reaction :
– Certain hydrocarbons compounds have a tendency
to polymerize with time, accelerated by heat, light,
sometimes air or other matter such as rust.
– Polymerization means that several molecules of the
same kind binding together to bigger molecules.
– The compound tends to become more viscous or
eventually solidify. Heat is liberated , which
accelerates further polymerization.
 Atmospheric control
• For oil tanker:
– Oil tankers using an inert gas system should
maintain their cargo tanks in a non-flammable
condition at all
– Tanks should be kept in an inert condition at all
times, except when it is necessary for them to be
gas free for inspection or work
– Oxygen content should be not more than 8% by
volume and the atmosphere should be maintained
at a positive pressure
• Atmosphere within the tank should make the transition from the inert condition to the
gas free condition without passing through the flammable condition
• Before any tank is gas freed, it should be purged with inert gas until the hydrocarbon
content of the tank atmosphere is below the critical dilution line
• For chemical tanker
– The IBC Code requires vapour spaces within cargo tanks to
have specially controlled atmospheres, principally when the
cargo is either air reactive resulting in a hazardous situation, or
has low auto-ignition temperature, or has a wide flammability
range.
– The correct atmosphere in a tank can be established either by
inerting to prevent the formation of flammable mixtures of
cargo vapour and air, or by padding to prevent chemical
reaction between oxygen and the cargo.
– It may also be necessary to reduce the humidity (dew point)
– Of the atmosphere within the cargo systemn
– The extent of atmosphere control to protect the
quality of the cargo will normally be specified by
the cargo shippers
– Some cargoes are extremely sensitive to
contamination or discoloration, and for quality
control reasons are carried under a blanket of
nitrogen that is very pure and which must often be
obtained from shore
 Gas testing
Evaluation of tank atmosphere shall be done
before:
Prior to entry by personnel
During inert, gas-freeing
and purging operations
To establish a gas-free
condition
As a quality control before
changing cargoes
Information to be obtained during the
evaluation of a tank atmosphere are
Type of atmosphere (constituent gases)
Flammability
Toxicity
Oxygen deficiency
Reactivity
The atmosphere in a cargo tank or enclosed
space may be dangerous due to flammability,
toxicity and /or lack of oxygen. No personnel
should enter or work in a tank or enclosed
space until safe working conditions have
been created. It is the responsibility of the
master or officer on duty to ensure that safe
working conditions are created.
Evaluation of the tank atmosphere is
essential to safe working conditions. As a
rule, a tank or enclosed space should not be
entered. When entry is necessary,
‘precautions for safe working condition’
should be observed and all relevant checklist
used to full extent.
• Before entry in enclosed spaces make sure:-
– Oxygen content must be 21% by volume
– Hydrocarbon content must be less than 1% LFL
– Toxic gas concentration must be less than 50%
• After tank washing, manual removal of residue
may be necessary
– residue removal may generate more hydrocarbon
gas
– gas testing operations must therefore be
continuous
• Adjacent bulkheads, pipelines and leaking
heating coils may constitute additional sources
of hydrocarbon gas
• Venting/ inert gas supply to the tank should
be shut off during the testing
• Carbon monoxide in the inert gas can be a
potential hazard as during gas freeing
operation carbon monoxide may not be easily
displaced from the tank
Material Safety Data Sheet (MSDS)
• A Material Safety Data Sheet (MSDS) is a document that contains
information on
– the potential hazards (health, fire, reactivity and environmental)
– how to work safely with the chemical product.
• It is an essential starting point for the development of a complete health
and safety program.
• It also contains information on the use, storage, handling and emergency
procedures all related to the hazards of the material.
• The MSDS contains much more information about the material than the
label.
• MSDSs are prepared by the supplier or manufacturer of the material.
• It is intended to tell what the hazards of the product are, how to use the
product safely, what to expect if the recommendations are not followed,
what to do if accidents occur, how to recognize symptoms of
overexposure, and what to do if such incidents occur.