HYDROCARBON

VAPORS

Hydrocarbon gases are heavier than air (1.5 to 3 times), and tend to
accumulate in the vicinity of the area where they are generated. A large
amount of gas might exist sometimes in unpredictable locations. The bottom
of the pump room is a typical example.
b) Gases flow to the leeward side, and are dangerous in that they may cause
explosion at space other than where they are generated.
c) The explosion limits or flammable limits (LEL / UEL or LFL / UFL) varies
according to the type of Hydrocarbon gas in question.
Their proportionate mixtures present in the petroleum vapor in question. This
is generally around 1.8% Vol. in Air (Min.) to 9.5% Vol. in Air (Max); whereas
International Chamber of Shipping recommends a range of 1.0% to 10.0 Vol.
%, to assume safer standards.
d) The danger for explosion is far greater in a lightly laden ship, while
loading / unloading cargo, during ballasting operations or during tank
cleaning, rather than when fully laden. This is because on a loaded vessel, the
tank atmosphere contains hydrocarbons concentrations of well over above
UEL

Toxic Hazards of H.C.

Vapors

a) Petroleum gas is noxious and harmful to the body. The table K-01-D-1
shows the concentration of petroleum gas and its effects on the human body.
b) Toxicity can be greatly influenced by the presence of some minor
components such as aromatic hydrocarbons (eg. Benzene and Hydrogen
Sulfide ie H2S).
c) Even if a tank is empty, gases might be regenerated from sludge in the
tank. Precautions are also necessary when working in tanks because
Petroleum Gas or Inert Gas from other tanks might enter the tank due to
leakage from valves.
HC Gas concentration
(Volumetric Proportion in Air) Effects on the Human body0.02% 300ppm
Industry Permissible concentration
(TLV-TWA for 8 Hrs) or 2% LEL
0.1% 1,000ppm Irritation in the eyes within an hour.
0.2% 2,000ppm Irritation in the eyes, nose or throat within
30 minutes, dizziness and unsteadiness.
0.7% 7,000ppm Signs of giddiness within 15 minutes.
1.0% 10,000ppm Sudden giddiness occurs and if the body is exposed to the
same conditions continuously, unconsciousness results, and can sometimes

HYDROGEN SULFIDE
(H2S)

a) H2S is a Highly toxic, corrosive and flammable gas that in low levels will
smell like rotten eggs.
b) It may be present in bukers in dissolved state or as a gas. In may also
be found in certain Natural gases, Crude oils and certain Refined products
such as Naphtha.
b) c) It is Colorless and Heavier than Air, having relative vapor density of
1.189
d) Exposure to high levels of H2S can be fatal after a very short period of
time.
e) H2S is a liquid soluble gas and produces vapor when the liquid is
agitated or heated. It is not possible to predict the likely H2S vapor
concentration present above a liquid in a tank, from any given liquid
concentration but, as an example, an oil containing 70 ppm by weight
has concentration of H2S in liquid has been shown to produce 7000 ppm
byvolume
ppm by Vol. in air) Physiological Effects on the Human body
0.1 0.5 ppm First Detected by smell
10 ppm May cause some nausea, minimal eye irritation
25 ppm Eye and respiratory tract irritation. Strong odour
50 100 ppm Human sense of smell starts to break down. Prolonged
exposure to concentrations at 100 ppm induces a gradual increase in the
severity of these symptoms and death may occur after 4 48 hours of

Precautions for Hydrogen Sulfide (H2S)

a) In cases where H2S concentrations are known to be greater

than 100 ppm in the vapor space and likely to be present in the
atmosphere, Emergency escape Breathing Apparatus shall be
made available to personnel working in the hazardous area, who,
should already have a Personal (pocket-able) H2S gas monitoring
alarm / instrument.
b) The presence of H2S in bunkers should not be ruled out. Empty
bunkers tanks shall be tested for the presence of H2S prior to
bunkering.
If new to be supplied bunkers contains H2S the DPA shall be
informed immediately.

BENZENE
Health Concerns in connection with Benzene
a) Benzene is present in varying concentrations in some
crude oils and the MSDS shall be consulted each time
before cargo handling.
b) Benzene gas has poor warning qualities, as its odour
threshold is well above the TLV-TWA limits. Exposure to
concentrations in excess of 1000 ppm can lead to
unconsciousness and death. Benzene can also be absorbed
through the skin and becomes toxic when ingested.
c) If there is evidence that dissolved benzene is present in
the liquid cargo in quantities of 0.5% by volume or more,
respiratory protection is required when conducting tank
de-mucking or standing up wind from tanks containing
benzene are being vented

MERCAPTANS (THIOL)
Health Concerns of Mercaptans
a) Mercaptans are colorless gas, having a smell similar to rotting
cabbage.
b) They are generated by the de-gradation of natural organisms.
c) They can be detected by smell at concentrations below 0.5 ppm,
although health effects are not experienced until the concentrations
are several times higher than this.
d) The initial effects of Mercaptans on persons are similar to those
caused by H2S exposure.
e) Mercaptans may be found in the following conditions:
i) They may occur on ships where sea water has remained beneath oil
or where oil residues are left in tanks that contain water. (Such as
dirty ballast tank, after it has been completely drained)
ii) They may also be found in water treatment plants and ballast
treatment facilities.
iii) Are also present in vapors of pentane plus cargoes and in some
crude oils.
iv) Are also used as an odorizing agent in natural gas

Inert Gas

Composite of Inert gas

After efficient scrubbing of the inert gas (to reduce
the content of sulfur dioxide), the typical constituents
of a flue gas are as showing the Table :
Inert Gas Percent Present (after scrubber)
Nitrogen N 83%
Carbon Dioxide CO2 12-14%
Oxygen O2 2-4%
Sulfur Dioxide SO2 50 ppm
Carbon Monoxide CO Trace
Nitrogen Oxides NOx 200 ppm
Water Vapor H2O Trace (high, if not effectively dried)
Ash and Soot C Traces
Density 1.044 (heavier than air)

Health Concerns of Inert Gas

a) The main hazard of inert gas is its low oxygen
content.
b) The subsequent hazards such as the presence of
traces of toxic gases in Inert Gas, inside cargo tanks
and spaces of such encountering are reduced and
controlled, by following the companys designated
Procedures for Entry into Enclosed Spaces .
c) By Gas freeing from a Purged condition (HC=2%
VOL) to the Gas free condition(HC=1% LEL),
sufficient dilution of such toxic gases to below their
TLV-TWA limits will have been achieved.

Oxygen-deficient atmosphere

The health effects and consequences because of lack of oxygen

are listed in the table
b) These effects will take place without any warning such as odour
or physical symptoms.
c) 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.
Health effects from lack of oxygen
O2level 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

Hazards of Petroleum Products

FLAMMABILITY
When petroleum is ignited, it is the gas that is progressively given
off by the liquid which burns as a visible flame. The quantity of gas
available to be given off by a petroleum liquid depends on its
volatility which is frequently expressed for purposes of comparison
in terms of Reid Vapour Pressure. A more informative measure of
volatility is the True Vapour Pressure but unfortunately this is not
easily measured. It is referred to in this guide only in connection
with venting problems associated with very volatile cargoes, such
as some crude oils and natural gasolines. Petroleum gases can be
ignited and will burn only when mixed with air in certain
proportions. If there is too little or too much petroleum gas, the
mixture cannot burn. The limiting proportions, expressed as a
percentage by volume of petroleum gas in air, are known as the
Lower and Upper Flammable Limits. These limits vary according to
the different possible components of petroleum gases. For gas
mixtures from petroleum liquids likely to be encountered in normal
tanker trades, the overall range is from a minimum Lower
Flammable Limit of about 1% gas by volume in air to a maximum
Upper Flammable Limit of about 10% gas by volume in air. As a
petroleum liquid is heated, the concentration of gas in air above it

Hazards of Petroleum Products

FLAMMABILITY CLASSIFICATION
There are many classification systems for defining the
flammability characteristics of petroleum liquids, most of which
are based on Flashpoint and Reid Vapour Pressure data. For the
purpose of this guide, which deals primarily with the particular
conditions associated with handling petroleum cargoes in tankers
and terminals, the division of such liquids into the two broad
categories of non-volatile and volatile, as defined below, is in
general sufficient to ensure that proper precautions can be
specified.
Non-Volatile:Flashpoint of 60C or above, as determined by the
closed cup method of testing.
Volatile:Flashpoint below 60C, as determined by the closed cup
method of testing.
If there is any doubt as to the characteristics of a cargo, or if a
non-volatile cargo is being handled at a temperature above its
Flashpoint minus 10C, it should be treated as volatile petroleum.
Owing to their particular characteristics, residual fuel oils should
always be treated as volatile

Hazards of Petroleum Products

TOXICITY
Toxicity is the degree to which a substance or mixture of
substances can harm humans or animals. Toxic substances can
affect humans in four main ways: by being swallowed (ingestion);
through skin contact; through the lungs (inhalation) and through
the eyes. Toxic substances can have local effects, such as skin or
eye irritation, but can also affect other, more distant, parts of the
body (systemic effects). The purpose of this Section is to describe
the adverse effects associated with toxic substances to which
personnel engaged in tanker operations are most likely to be
exposed; to indicate the concentrations at which those adverse
effects are expected to occur in humans through a single or
repeated exposure; and to describe procedures for reducing the
risks of such exposure. Although not strictly a matter of toxicity,
the effects of oxygen deficiency are also described

Hazards of Petroleum Products

Ingestion
Petroleum has low oral toxicity, 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
and 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 impermeable gloves and goggles

Hazards of Petroleum Products

PETROLEUM GASES
Comparatively small quantities of petroleum gas, when inhaled,
can cause symptoms of diminished responsibility and dizziness
similar to drunkenness, with headache and irritation of the
eyes. The inhalation of a sufficient quantity can be fatal. These
symptoms can occur at concentrations well below the Lower
Flammable Limit. However, petroleum gases vary in their
physiological effects and human tolerance to these effects also
varies widely. It should not be assumed that because conditions
can be tolerated the gas concentration is within safe limits. The
smell of petroleum gas mixtures is very variable and in some
cases the gases may dull the sense of smell. The impairment of
smell is especially likely, and particularly serious, if the mixture
contains hydrogen sulphide. The absence of smell
shouldneverbe taken to indicate the absence of gas.

Hazards of Petroleum Products

Perchlorate
Perchlorate is a component of jet fuel. Consequently, it is a common
contaminant at airbases and in the water supplies near bases. It can cause
the health problems described above under petroleum fuels "basic
properties", and also attacks the thyroid gland, which controls many of the
hormones in the body directly or indirectly. People with poor thyroid
function are often tired, they may lose some of their ability to think clearly,
and may also lose their hair or have other signs often confused with aging.
When thyroid function is damaged in pregnant women, their children's
nervous system can be damaged. Studies have found cognitive damage in
their babies, so it is important to be aware of perchlorate exposure during
pregnancy. This is probably an issue of most concern to base families.
Abnormal thyroid function can also impact other parts of the endocrine
system, which are responsible for growth and development, sexual function
and reproduction, levels of testosterone and estrogen and other normal
aspects of physiology. Because these effects can be subtle and attributed
to many other causes (e.g., age, diet, other health conditions), it is easy to
ignore or miss. The identification and treatment of most thyroid diseases
are simple and inexpensive. It is important to be aware of the potential for
thyroid disease if you have been exposed to perchlorate in fuels,
particularly in jet fuel.
Hydrocarbon releases pose more than just the risk of fire and
explosion. Personnel who are in an area where there are such

Hazards of Petroleum Products

Perchlorate
Perchlorate is a component of jet fuel. Consequently, it is a common
contaminant at airbases and in the water supplies near bases. It can cause
the health problems described above under petroleum fuels "basic
properties", and also attacks the thyroid gland, which controls many of the
hormones in the body directly or indirectly. People with poor thyroid
function are often tired, they may lose some of their ability to think clearly,
and may also lose their hair or have other signs often confused with aging.
When thyroid function is damaged in pregnant women, their children's
nervous system can be damaged. Studies have found cognitive damage in
their babies, so it is important to be aware of perchlorate exposure during
pregnancy. This is probably an issue of most concern to base families.
Abnormal thyroid function can also impact other parts of the endocrine
system, which are responsible for growth and development, sexual function
and reproduction, levels of testosterone and estrogen and other normal
aspects of physiology. Because these effects can be subtle and attributed
to many other causes (e.g., age, diet, other health conditions), it is easy to
ignore or miss. The identification and treatment of most thyroid diseases
are simple and inexpensive. It is important to be aware of the potential for
thyroid disease if you have been exposed to perchlorate in fuels,
particularly in jet fuel.
Hydrocarbon releases pose more than just the risk of fire and
explosion. Personnel who are in an area where there are such

TLV
Threshold limit values (TLVs) refer to airborne concentrations of
substances and represent conditions under which it is believed
that nearly all workers may be repeatedly exposed day after day
without adverse health effects
Threshold Limit Value (TLV) Because of wide variation in
individual susceptibility, however, a small percentage of workers
may experience discomfort from some substances at
concentrations at or below the TLV A smaller percentage may
be affected more seriously by aggravation of a preexisting
condition or by development of an occupational illness Continued
7 Threshold Limit Value (TLV) Published by ACGIH Established
in 1946 (updated annually) Approximately 750 chemicals
covered Guidelines not law Documentation of TLVs and BEIs
Method of adoption Balancing of health considerations and
cost to industry ACGIH 1