Hazard of Petroleum
Danger
Toxicity
H2S
By Capt. Bambang Purnomo
Subject
1. Refer to
2. Introduction
3. Toxic affect
4. TLV
5. Toxic H2S
6. Procedure Handling cargo containing H2S
7. Company and Terminal Procedure
8. Additional Procedures when Handling Cargoes
with Very High Concentrations of H2S
1. Refer to
ISGOTT 5th Edition
2. INTRODUCTION
Toxicity is the degree to which a substance or
mixture of substances can harm humans or animals.
3.Toxic substances can affect humans
in four main ways :
4 avenues of exposure :
Inhalation
Absorption / Skin Contact
Ingestion
Injection
3.1.Inhalation effect :
Hydrocarbon gas produces narcosis
Eye irritation Low
Headache
Dismissed responsibilities
Drowsiness
Insensibility
Paralysis
Death High
3.2.absorption effect:
Skin & eye irritation
Removal of essential oils
Dermatitis
Serious skin disorders with prolonged & repeated
contact
Carcinogenic
3.3.Ingestion effect:
Low risk of ingestion in operational practice
Low oral toxicity
Acute discomfort & nausea if swallowed
Possible serious consequences if oil enters
lungs during vomiting
3.4. Injection effect:
Ampoule consisting toxic injected passing skin and
Contaminated into blood by view second will given
Effect into body.
4.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.
The toxicity of substance is measured in parts
per million (ppm) of volume of gas in air
The exposure time is also a factor
4.1.TLV-TWA
(time weighted average)
The maximum concentration of vapour in air to
which personnel may be exposed for a normal 8
hour working day or 40 hour working week
without adverse effect
A reference to TLV may be taken to mean
TLV-TWA
4.2. Tlv-stel
( shore term exposure limit )
The maximum concentration of vapour in air
to which personnel can be exposed for a
period of 15 minutes without adverse effect
Maximum 4 such periods per day
Minimum 1 hour between each period
4.3. Ceiling ( TLV-C)
Ceiling (TLV-C) – The concentration that should
not be exceeded during any part of the working
exposure.
5. HYDROGEN SULPHIDE (H2S)
Caracteristic of H2S :
Hydrogen Sulphide (H2S) is a very toxic,
corrosive and flammable gas.
It has a very low odour threshold and a distinctive
odour of rotten eggs.
H2S is colourless and is heavier than air, having a
relative vapour density of 1.189. It is soluble in
water.
5.1.Hydrogen Sulphide ( H2S )
Present in un-stabilised crude
Also in some products
Naptha
Gas oil
“Rotten egg” smell
Precaution : TLV – 10 ppm
5.2. H2s Concentration
The H2S concentration in vapour will vary greatly
and is dependent upon factors such as:
• Liquid H2S content.
• Amount of air circulation.
• Temperature of air and liquid.
• Liquid level in the tank.
• Amount of agitation.
5.3. Hydrogen Sulphide ( H2S )
Detectable by smell only in concentrations <1 ppm
First effect is loss of sense of smell
Smell
nothing ?
5.4. Effect of H2S at
Concentration above TLV
50-100ppm Eye & respiratory tract irritation
after 1 hour.
200-300ppm As above but more severe after 1
hour
500-700ppm Dizziness, headache and nausea
after 15 minutes,
Loss of consciousness and possible
death after 30-60 minutes.
700-900ppm Rapid unconsciousness , death
within a few minutes.
1,000-2,000ppm Instantaneous collapse and
cessation of breathing and then death.
6. Procedures for Handling Cargo and
Bunkers Containing H2S
Vapour Monitoring :
Exposure levels in all work locations should be
monitored by using suitable instrumentation for
detecting and measuring the concentration of the
gas.
Detector tubes should be used if it becomes
necessary to monitor a known high concentration.
6.1. Precaution ! :
High concentrations and the corrosive nature of the
gas can have a damaging effect on many electronic
instruments.
6.2. Precaution ! :
Bunker fuel tanks should be monitored prior to,
during and after bunkering. If H2S has been
detected, the bunker tank should be periodically
tested. Although the concentration in the vapour
space can be successfully lowered by forced air
ventilation, it often increases again when the
bunker fuel is heated, transferred or agitated by
other means.
6.3. Precaution ! :
Bridge, control room, accommodation and engine
spaces should be monitored if H2S may be
present. Ventilation systems should be operated
as far as possible to prevent H2S vapours
entering the accommodation and engine spaces. A
low concentration of H2S over
6.4. Personal Protective Equipment
(PPE)
Procedures should be defined for the use of
respiratory protective equipment, when
concentrations of vapour may be expected to exceed
the TLV-TWA (5 ppm by volume in air).
Consideration should be given to providing
Emergency Escape Breathing Devices to personnel
working in hazardous areas. These are very portable
and can be donned quickly should gas be detected.
6.5. Personnel should be required to wear respiratory
equipment under the following circumstances: -
When TLV-TWAs specified by national or
international authorities are exceeded, or are
likely to be exceeded;
• When monitoring cannot be carried out;
• When closed operations cannot be conducted for
any reason and H2S concentrations could exceed
the TLV-TWA
7. Company and Terminal Procedures
The functional requirements should include, but not be
limited to, the following:
• Training of all crewmembers in the hazards associated
with H2S and the precautions to be taken to reduce
the risks to an acceptable level;
• Safe operating procedures for all operations;
• Gas testing/atmosphere monitoring procedures;
• Maintenance procedures for cargo related systems;
• PPE requirements;
• Contingency planning;
• Emergency response measures;
• Measures to protect visitors from exposure.
8. Additional Procedures when Handling Cargoes with
Very High Concentrations of H2S
Respiratory Protective Equipment
EEBD / SCBA:
This would include the following activities:
• Open gauging and sampling;
• Removing blanks for connecting the cargo hose or
loading arm;
• Cleaning filters;
• Draining lines to open containment; and
• Mopping up spills.
8.1. Warning !
They should not include the use of chemical
cartridge respirators for protection against H2S
vapours, as the vapour concentrations in the
atmosphere may exceed the operational capability of
the respirator being used.
8.2. Corrosion
H2S is very corrosive and enhanced inspection and
maintenance regimes should be put in place if H2S is
likely to be present in high concentrations.
Pressure vacuum valve seats made of brass are more
likely to fail than stainless steel seats.
Mechanical tank gauges are more likely to fail since
H2S has a damaging effect on stainless steel tension
springs and metals such as brass and bronze. An
increase in spare part inventory may be necessary.
Computer and instrument components made of silver
and gold are highly affected by even low H2S
concentrations.
8.3. General Nuisances.
In addition to being a health hazard, the H2S odour is also
considered a public nuisance.
Most local environmental regulations limit or ban the
release of H2S concentrations to the atmosphere and this
is, in any case, good practice. It is therefore necessary to
maintain cargo tank pressures within acceptably low
limits.
The tank vapour pressure will rapidly increase if vapour
space is exposed to heat or the product is agitated.
Crude oil washing may rapidly increase the vapour
pressure and should begin at a relatively low pressure and,
preferably, while maintaining a relatively high discharge
rate.
