7.1 7.

1 TANK ATMOSPHERE EVALUATION

The evaluation of the atmosphere is fundamental to ensuring that there are safe working
conditions in any cargo tank or enclosed space.

7.1.1 7.1.1 Flammability and explosion

Combustion is a chemical reaction, initiated by a source of ignition, in which a flammable
vapor combines with oxygen in suitable proportions to produce carbon dioxide, water vapor
and heat. Under ideal conditions the reaction for propane can be written as follows:

C3H8 + 502 Combustion 3CO2 + 4H2O + Heat

propane oxygen ® carbon water
dioxide vapor

Under certain circumstances when, for example, the oxygen supply to the source of fuel is
restricted, carbon monoxide or carbon can also be produced.

The three requirements for combustion to take place are fuel, oxygen and ignition. The
proportions of flammable vapor to oxygen or to air must be within the flammable limits.

The gases produced by combustion are heated by the combustion reaction. In open,
unconfined spaces the consequent expansion of these gases is unrestricted and the
combustion reaction may proceed smoothly without undue overpressures developing. If the
free expansion of the hot gases is restricted in any way, pressures will rise and the speed of
flame travel will increase, depending upon the degree of confinement encountered. Increased
flame speed in turn gives rise to more rapid increase in pressure with the result that damaging
overpressures may be produced and, even in the open, if the confinement resulting from
surrounding pipework, plant and buildings is sufficient, the combustion can take on the nature
of an explosion. In severely confined conditions, as within a building or ship's tank where the
expanding gases cannot be adequately relieved, the internal pressure and its rate of increase
may be such as to disrupt the containment. Here, the resultant explosion is not so much
directly due to high combustion rates and flame speed as to the violent expulsion of the
contained high pressure upon containment rupture.

The term flammable range gives a measure of the proportions of flammable vapor to air
necessary for combustion to be possible. The flammable range is the range between the
minimum and maximum concentrations of vapor (per cent by volume) in air which form a
flammable mixture. These terms are usually abbreviated to LFL (lower flammable limit) and
UFL (upper flammable limit). This concept is illustrated for propane in Figure 7.1.

All the liquefied gases, with the exception of chlorine, are flammable but the values of the
flammable range are variable and depend on the particular vapor. These are listed in Table
7.2. The flammable range of a particular vapor is broadened in the presence of oxygen in
excess of that normally in air; the lower flammable limit is not much affected whereas the
upper flammable limit is considerably raised. Comparative flammable ranges in air and in
oxygen are quoted in Table 7.3 for propane, n-butane and vinyl chloride monomer. All
flammable vapors exhibit this property and as a result oxygen should not normally be
introduced into an atmosphere where flammable vapors exist. The oxygen cylinders
associated with oxyacetylene burners and oxygen resuscitators should only be introduced into
hazardous areas under strictly controlled conditions.
Figure 7.1. Flammable range for propane
Table 7.2. Ignition properties for various gases

Flammable range (% by volume)

(in air) (in oxygen)

Propane 2.1 - 9.5 2.1 - 55.0

n-Butane 1.8 - 8.5 1.8 - 49.0

VCM 4.0 - 33.0 4.0 - 70.

Table 7.3. Flammability range in air/oxygen for various

liquefied gases
The flash point of a liquid is the lowest temperature at which that liquid will evolve sufficient
vapor to form a flammable mixture with air. High vapor pressure liquids such as liquefied
gases have extremely low flash points, as seen from Table 7.2.
The auto-ignition temperature of a substance is the temperature to which its vapor in air must
be heated for it to ignite spontaneously. The auto-ignition temperature is not related to the
vapor pressure or to the flash point of the substance and, since most ignition sources in
practice are external flames or sparks, it is the flash point rather than the autoignition
characteristics of a substance which is generally used for the flammability classification of
hazardous materials. Nevertheless, in terms of the ignition of escaping vapor by steam pipes
or other hot surfaces, the auto-ignition temperature of vapors of liquefied gases are worthy of
note and are also listed in Table 7.2.
As mentioned above, the most common inadvertent sources of ignition of a flammable vapor
mixture are flames, thermite sparks (due to metal to metal impact) and electric sparks. The
minimum ignition energy necessary to initiate combustion of hydrocarbon vapors is very low,
particularly when the vapor concentration is in the middle of the flammable range. Minimum
ignition energies for flammable vapor mixtures of the liquefied gases in air are typically less
than one millijoule, an energy level which is substantially exceeded by any visible flame, by
most electric lighting or power circuit break sparks or by electrostatic discharges down to the
lowest level generally detectable by human contact. The presence of oxygen in excess of its
normal proportion in air further lowers the minimum ignition energy. be gradually dispersed
downwind. The vapor cloud or plume would be flammable only over part of its downwind
travel. The situation is illustrated in general terms in Figure 7.3. The region B immediately
adjacent to the spill area A would be non-flammable because it is over-rich, i.e. it contains too
low a percentage of oxygen to be flammable. Region D would also be non-flammable because
it is too lean, i.e. it contains too little vapor to be flammable. The flammable zone would be
between these two regions as indicated by C.

Figure 7.4. Flammable vapor zones emanating from a gas spill

7.1.2 7.1.2 Suppression of flammability by

inert gas

Whereas increasing the oxygen concentration in a flammable mixture causes a broadening of

the flammable range and a lowering of the energy necessary for ignition, decreasing the
oxygen availability causes the flammable range to be narrowed and the minimum ignition
energy to be increased. If the oxygen availability is reduced to a sufficient extent, the mixture
will become non-flammable no matter what the combustible vapor content may be. Figure 7.5
illustrates this general concept for a typical hydrocarbon gas in mixtures of air and nitrogen.
The mixtures are represented on the horizontal axis by the resultant overall percentage
oxygen content in the total mixture. The diagram provides a wealth of useful information. The
narrowing of the flammable range as the oxygen in the total mixture is reduced can be seen
from the shape of the area labeled "flammable". It is also clear that an oxygen content of less
than that at the left hand extremity of the flammable envelope, renders the mixture inert.
While this value for most hydrocarbon vapors is around 10 per cent to 12 per cent by volume,
the generally accepted requirement, as defined by the IMO, for an atmosphere which is
adequately inert is one which contains less than 8 per cent by volume oxygen. This allows for
a degree of inhomogeneity in practical circumstances.

Fig. 7.5. Flammable limits of a typical hydrocarbon gas

mixtures of air and nitrogen

The diagram is also useful in illustrating proper inerting and gasfreeing procedures. For
example, assume that the atmosphere in a cargo tank has been determined by adequate
sampling and is represented by point A. If the tank is then gas-freed directly by air, the
composition of the tank atmosphere will move along the line AB to the fully gas-free point B. In
so doing, the atmosphere will have passed through the flammable envelope.
This can be avoided by first purging the tank with inert gas along, say, the line AC to a point
below the critical dilution tine. Gas freeing by air to point B may then be undertaken without
the atmosphere composition passing through the flammable envelope. This result can only be
achieved with certainty if regular and extensive measurements are taken using properly
calibrated instruments to evaluate the atmosphere throughout the tank at the various stages.
In this process it is important to use reasonable margins of safety since the precise shape of
the flammable envelope cannot be known for mixtures and a degree of inhomogeneity in tank
atmosphere must be allowed for.

7.1.3 7.1.3 Sources of ignition

The principal method of protection against fire and explosion on gas carriers and jetties is
achieved through operational procedures which control atmospheres and avoid liquid spills or
leakages and vapor released to atmosphere. Added protection is essential, though more
difficult to achieve, by means of controlling sources of ignition. A source of ignition is an ever-
present hazard because of the possibility of human error and because its occurrence is usually
unexpected.
Smoking is perhaps the most common source of ignition to be found in hazardous areas and,
to minimize this, smoking activities and utensils should always be restricted to pre-defined and
approved locations. Considerable care must be taken to enforce these regulations during
cargo-handling operations at the jetty, particularly when visitors are present who may not
appreciate the nature of the cargo being handled.
Hot and cold work should only be permitted under conditions of strict control. This can best be
achieved by the use of work permits which make use of a checklist approach. Atmospheres in
areas which could become hazardous should be continuously monitored during hot and cold
work operations, preferably with instruments which are capable of alarming automatically on
the detection of flammable vapor.
The use of "safety" tools in hazardous areas often create a false sense of security.
Constructed from soft copper alloys, these tools are often referred to as "non-sparking" but, it
should be appreciated that fragments of steel can easily become imbedded in the heads of
these tools.

Static electricity can arise when liquids or gases are pumped at high velocity. Non-conducting
liquids (static accumulators), emulsions, carbon dioxide and steam are common sources of
static electricity. In general terms, static generation increases with velocity of flow. The
removal of clothing in hazardous areas, particularly in dry atmospheric conditions, can also
give rise to static discharge. Helicopters are also efficient static generators, the risk being
greatest in dry atmospheric conditions. Immediately before approaching any ship for winching
or landing, it is generally recommended that the helicopter should drop an earthing cable into
the sea to dissipate any static charge in advance.

Electrical instruments used for essential purposes in hazardous areas should be of flameproof
or intrinsically safe design. The use of wandering electric power leads should be discouraged.

Electrical sparks may occur when making or breaking cargo connections between ship and
shore if the cargo connection hose or hard arm provides an electrical path between ship and
jetty structures. Electrical current will flow through this path due to differences in the
electrolytic potential of the ship's structure and of the jetty structure in relation to the
surrounding seawater. Such differences as may occur naturally due to the different steels or
protective coatings of the two structures may be increased by an imbalance between the
degree of cathodic protection being applied to each structure.
Although the resultant potential difference between ship and jetty will never be more than a
fraction of a volt, the electrolytic cells involved are large and electrical resistances in the
ship/sea water/jetty/cargo connection circuit are small. As a result, a heavy current of many
amperes may flow through the cargo connection and this current, on being established or
interrupted, may produce a spark of incendive energy.

The intention of the bonding cable traditionally connected between jetty and ship was to
provide an alternative path for this current but, in practical terms, such cables have been
shown to be quite ineffective for this purpose. Since it is ineffective and itself presents some
hazard bv virtue of the current it carries, the use of the bonding cable is now not
recommended. The introduction of an electrical discontinuity in the cargo connection by
means of an insulating flange or a length of electrically discontinuous hose, as appropriate, is
completely effective in eliminating the cargo connection current and any resultant sparking
due to its making or breaking. For reasons of accessibility and to avoid the possibility of
sparking due to electromagnetic induction in the hard arm length, insulating flanges are
usually located at the lower end of the outer arm of the hard arm.

7.1.4 7.1.4 Static Electricity Precautions

In normal operations, the presence of inert gas prevents the existence of flammable gas
mixtures inside cargo tanks. Hazards due to static electricity may arise, however, mainly in
the case of a failure of the inert gas system. To avoid these hazards the following procedures
are recommended:

  If the inert gas plant breaks down during discharge, operations should be suspended; if
air has entered the tank, no dipping, ullaging, sampling or other equipment should be
introduced into the tank until at least 30 minutes have elapsed since the injection of inert
gas ceased. After this period equipment may be introduced provided that all metallic
components are securely earthed. This restriction should be applied until a period of five
hours has elapsed since the injection of inert gas ceased.

  During any necessary re-inerting of a tank following a failure and repair of the inert gas
system, or during initial inerting of a non-gas free tank, no dipping, ullaging, sampling or
other equipment should be inserted until it has been established that the tank is in an inert
condition. This should be done by monitoring the gas vented from the tank being inerted.
Should it be necessary, however, to introduce a gas sampling system into the tank for this
purpose, at least 30 minutes should elapse after stopping the injection of inert gas before
inserting the sampling system. Metallic components of the sampling system should be
electrically continuous and securely earthed.

7.1.5 7.1.5 Tank Washing

Before each tank is washed, the oxygen level must be determined, both at a point 1 meter
below the deck and at the middle level of the ullage space. At neither of these locations
should it exceed 8% by volume. Where tanks have a complete or partial swash bulkhead, the
measurement should be taken from similar levels in each section of the tank. The oxygen
content and pressure of the inert gas being delivered during the washing process should be
continuously recorded.
If during washing:

  the oxygen level in the tank exceeds 8% by volume, or

  the pressure of the atmosphere in the tanks is no longer positive,

washing must be stopped until satisfactory conditions are restored.

7.1.6 7.1.6 Purging

When it is required to gas free a tank after washing, it should first be purged with inert gas to
reduce the hydrocarbon content to 2% or less by volume so that during the subsequent gas
freeing no portion of the tank atmosphere is brought within the flammable range. The tank
may then be gas freed.
The hydrocarbon content must be measured with an appropriate meter designed to measure
the percentage of hydrocarbon gas in an oxygen deficient atmosphere. The usual flammable
gas indicator is not suitable for this purpose.
If the dilution method of purging is used, it should be carried out with the inert gas system set
for maximum capacity to give maximum turbulence within the tank. If the displacement
method is used, the gas inlet velocity should be lower to prevent undue turbulence.

7.1.7 7.1.7 Preparation for Tank Entry

To ensure the dilution of the toxic components of inert gas to below their Threshold Limit
Values (TLV), gas freeing should continue until tests with an oxygen analyzer show a steady
oxygen reading of 21 % by volume and tests with a flammable gas indicator show not more
than 1 % LFL.
If the presence of a toxic gas such as benzene or hydrogen sulphide is suspected, gas freeing
should be continued until tests indicate that its concentration is below its TLV.
Positive fresh air ventilation should be maintained throughout the period that personnel are in
a tank, and frequent tests should be made of both oxygen and hydrocarbon content of the
tank atmosphere.
When other tanks in an inert condition are either adjacent or interconnected (e.g. by a
pipeline) to the tank being entered, personnel should be alert to the possibility of inert gas
leaking into the gas free tank through, for example, bulkhead fractures or defective valves.
The risk of this occurring can be minimized by maintaining a small but positive inert gas
pressure.
When a gas free tank is re-connected to the inert gas main it should immediately be reinerted.

7.1.8 7.1.8 Hazards associated with the

handling and carriage of petroleum
The toxic hazards to which personnel are exposed in tanker operations arise almost entirely
from contact with gases of various kinds.
A convenient indicator of the toxicity of gases and the avoidance of health hazards is provided
by the Threshold Limit Value - Time-Weighted Average (TLV-TWA) (in this compendium, all
references to TLVs are to time-weighted average TLVS).
TLV-TWAs are kept under regular review and the values quoted in this guide are those adopted
at the American Conference of Governmental Industrial Hygienists in 1983. The values are
expressed as parts per million (ppm) by volume of gas in air.

7.1.9 7.1.9 Toxicity of petroleum

  Liquid petroleum
The risk of swallowing significant quantities of liquid petroleum during normal tanker and
terminal operations is very slight. Petroleum has low oral toxicity to man, but when swallowed
it causes acute discomfort and nausea. There is then a possibility that liquid petroleum may
be drawn into the lungs during vomiting; this can have serious consequences, especially with
higher volatility products such as gasolines and kerosenes.

  Skin contact
Many petroleum products, especially the more volatile ones, cause skin irritation and remove
essential oils from the skin, leading to dermatitis. They are also irritating to the eyes. Certain
heavier oils can cause serious skin disorders on repeated and prolonged contact.
Direct contact with petroleum should always be avoided by wearing the appropriate protective
equipment, especially gloves and goggles.

  Petroleum gases
The main effect of petroleum gas on humans is to produce narcosis. The symptoms include
headache and eye irritation, with diminished responsibility and dizziness similar to
drunkenness. At high concentrations these symptoms are followed by paralysis, insensibility
and death.
The toxicity of petroleum gases can vary widely, depending on the major hydrocarbon
constituents of the gases. It can be greatly influenced by the presence of some minor
components such as aromatic hydrocarbons (e.g. benzene) and hydrogen sulphide. A TLV of
300 ppm corresponding to about 2% LFL, has been established for gasoline vapors. Such a
figure may be used as a general guide for petroleum gases, but must not be taken as
applicable to gas mixtures containing benzene or hydrogen sulphide.
Since TLV is an indication of how much of a toxic substance is acceptable during working hours
(8) day after day, the human body can tolerate concentrations somewhat greater than the TLV
for short periods. The following are typical effects at higher concentrations:

Concentration % LEL Effects

0.1 % vol. (1,000 ppm) 10 % Irritation of the eyes within 1 hour
0.2 % vol. (2,000 ppm) 20 % Irritation of the eyes, nose and throat,
dizziness and unsteadiness within an hour.
0.7 % vol. (7,000 ppm) 70 % Symptoms as of drunkenness within 15
minutes
1.0 % vol. (10,000 ppm) 100 % Rapid onset of drunkenness which may lead
to unconsciousness and death if exposure
continues
2.0 % vol. (20,000 ppm) 200 % Paralysis and death occur very rapidly

The smell of petroleum gas mixtures is very variable, and in some cases the gases may fool
the sense of smell. The impairment of smell is especially serious if the mixture contains
hydrogen sulphide. It must be stressed that the absence of smell should therefore never be
taken to indicate the absence of gas.

  Benzene and other aromatic hydrocarbons

The aromatic hydrocarbons include benzene, toluene and xylene. They are components, in
varying proportions, of many typical petroleum cargoes such as gasolines, gasoline blending
components, naphtas and special-boiling-point solvents.
The TLV of aromatic hydrocarbons is generally lower than that of the other hydrocarbons in
petroleum gases. In particular, benzene has a TLV of 10 ppm an exposure level that should
not be exceeded. Exposure to benzene vapors in high concentration leads to chronic disorders
of the blood and of the bone marrow. Precautions should be taken to avoid harmful exposure
during the loading of cargoes containing benzene.
The concentration must be reduced to below the TLV of 35 ppm by dilution or by displacement
with air. Carbon monoxide poisoning is caused by carbon monoxide combining with the
blood's hemoglobin instead of oxygen, so that the blood loses its ability to take up oxygen in
the lungs. This results in internal suffocation, and death occurs when 60 to 70% of the
hemoglobin has combined with carbon monoxide. The symptoms are headache and
drowsiness, deterioration of consciousness and vomiting. In the treatment of carbon monoxide
poisoning it is of the utmost importance to supply oxygen, if necessary in combination with
artificial respiration.
Nitrous gases are present as nitrogen monoxide (also known as nitric oxide) (NO) and nitrogen
dioxide (NO2) in concentrations of about 0.02% by volume in inert gas after it has passed
through the scrubber, corresponding to 200 ppm. The TLV for nitrogen monoxide is 25 ppm
and that for nitrogen dioxide is 5 ppm by volume. Nitrous gases form acids by reaction with
the moisture in the air, and may destroy the lung tissue.
The sulphur dioxide content of inert gas will be very low, provided the scrubber is efficient.

7.1.10 7.1.10 Oxygen deficiency

Oxygen deficiency must always be suspected in any enclosed space which has not been
ventilated for some time. It may be caused by vapor emitted from volatile liquids, by the
displacement of air by inert gas or by the consumption of the available oxygen in the air by
chemical reactions such as rusting or the drying of paint. Air contains 21 % oxygen, and
spaces should not be entered before establishing that the oxygen content of the atmosphere
that is to be entered is in fact 21 %.

TEST…VENTILATE…TEST
DON'T BE A FOOL,
USE YOUR OXYGEN METER AS YOUR TOOL.

MAKE SURE IT’S SAFE!!!

Before personnel enter tanks which have contained petroleum products such as those listed
above, the tanks should be ventilated to a reading of not more than 1 % LFL on a combustible
gas indicator and then checked to ensure that the TLV of 10 ppm is not exceeded. Tests for
benzene at this low concentration can only be made with a special chemical tube indicator.

  Gasolines containing tetraethyl-lead or tetramethyl-lead

The amounts of tetraethyl-lead (TEL) or tetramethyl-lead (TML) normally added to gasolines
are insufficient to render the gases from these products significantly more toxic than those
from unleaded gasolines. The effects of the gases from leaded gasolines are therefore similar
to those described above for petroleum gases.

7.1.11 7.1.11 Toxicity of inert gas

Cargo tanks filled with an inert atmosphere must be ventilated with air before they are
entered, both to increase the oxygen content from less than 5% by volume to 21 % by volume
and to sufficiently reduce the amounts of carbon monoxide, nitrous gases and sulphur dioxide.
Carbon monoxide (CO) may typically be present in a concentration of about 0. 0 1 % by
volume in inert gas, corresponding to 100 ppm. In certain cases it may become significantly
higher.

7.1.12 7.1.12 Carriage of Products Having a

Flashpoint Exceeding 60°C
The 1974 SOLAS Convention, as amended, implies that tankers may carry petroleum products
having a flashpoint exceeding 60o C (i.e. bitumens, lubricating oils, heavy fuel oils, high
flashpoint jet fuels and some diesel fuels, gas oils and special boiling point liquids) without
inert gas systems having to be fitted or, if fitted, without tanks containing such cargoes having
to be kept in the inert condition.

However, when cargoes with a flashpoint exceeding 60 o C are carried at a cargo temperature
higher than their flashpoint less 5o C, the tanks should be maintained in an inert condition
because of the danger that a flammable condition may occur.
It is recommended that, if inert gas systems are fitted, cargo tanks are maintained in an inert
condition whenever there is a possibility that the ullage space atmosphere could be within the
flammable range.
When a non-volatile cargo is carried in a tank that has not been previously gas freed, the tank
should be maintained in an inert condition.