Hydrogen

Sulfide
Gas
h2s
Amirkabir University of Technology
(Tehran Polytechnic)

Dr B.Taheri
H.Allahyar (8334007)
M.A.Albooyeh(833480
1)

If you wait for a warning, it may be too late

Hydrogen sulfide is a powerful and deadly gas which
smells like rotten eggs at low concentrations and has
a sweet smell at high concentrations. But workers
should not rely on the smell as a warning. At high
concentrations H2S may overcome one's sense of
smell. The result could be instant death. Long
exposure to low concentrations will also deaden the
sense of smell.

What it is?

H2S is explosive - it will ignite and explode when subjected to

a spark or ordinary flame - in any concentration from 4% to
44% of the air. It is also soluble in water and oil, so it may
flow for a considerable distance from its origin before
escaping above ground or in an entirely unexpected place.
Because the vapor (gas) is heavier than air, it may travel for
a long way until ignited and then flash back towards the
source.

Where is it found?

Hydrogen sulfide is found in large amounts in natural gas

and petroleum. Any worker involved in extracting gas and
petroleum from the ground, or in storing, transporting or
processing gas is at risk from exposure to H2S Hydrogen
sulfide exists in solution in crude oil, and workers are
exposed when the gas begins to "pass off" as it reaches the
surface or comes into contact with air. This can occur at any
point, including all stages of the refining operation, and it is
accelerated by heat or hot weather.

H2S Sources

H2S is found widely in industry and few workers are warned

of its dangers or their exposure. It is formed by the
decomposition of organic materials, so it is found in natural
gas and oil, in mines, wells, fertilizers, sewers, and
cesspools. It is given off as a by-product in the manufacture
of rayon, synthetic rubber, dyes and the tanning of leather.

Some of
h2s
propertie
s

Hydrogen sulfide is colorless, transparent, and flammable,

smells like "rotten eggs" at very low concentrations, and is
denser than air and thus may accumulate in low places.
The slightest presence of H2S in the air is normally
detectable by its characteristic "rotten-egg" odor;
however, it is dangerous to rely on odor as a means of
detecting life-threatening concentrations because the
sense of smell is lost rapidly, allowing lethal concentrations
to accumulate without warning.

Health Effects
Of
H2S acute exposure

First of all, and most important, H2S can kill you. The extent
of acute poisoning danger depends on the concentration of
H2S in the atmosphere.
When you breathe in H2S, it goes directly through your lungs
and into your bloodstream. To protect itself, your body
"oxidizes" (breaks down) the H2S as rapidly as possible into a
harmless compound. If you breathe in so much H2S that your
body can't oxidize all of it, the H2S builds up in the blood and
you become poisoned. The nervous centers in your brain
which control breathing are paralyzed. Your lungs stop
working and you are asphyxiated - just as though someone
had come up and put their hands around your neck and
strangled you. A worker can be overcome by H2S and lose
consciousness in a few seconds; luckily if he is rescued in
time and is given artificial respiration within a few minutes,
the worker may recover. Either artificial mouth-to-mouth or
an oxygen supply system of resuscitation will work if it is
done in time, because, with an adequate source of oxygen
and no further H2S intake, the body will quickly break down
the H2S still in the blood.

This is acute poisoning. It can occur with no warning at all,

since even the sense of smell may be overcome, and it can
be fatal within a few seconds.
Although acute poisoning is deadly if it is not caught in
time, when caught and treated it is reversible and this is
why rescue attempts with proper safety equipment are so
important.
Recent evidence has shown irreversible brain damage from
acute high doses.

Chronic effects
H2S can also cause a wide range of sub-acute and chronic
effects. At very low concentrations of 10-100 ppm.)
headache, dizziness, nausea and vomiting may develop,
together with irritation of the eyes and respiratory tract (the
lungs and trachea and bronchi, or air pipes from the nose
and mouth to the lungs). The eyes become red, sore,
inflamed, and sensitive to light. Respiratory system effects
include cough, pain in the nose and throat, and pain on
breathing.

If exposure at low levels continues, the worker may

develop a state of chronic poisoning. In addition to eye and
respiratory tract irritation, there will be a slowed pulse
rate, fatigue, insomnia, digestive disturbances, and cold
sweats. More dangerous, if exposure at the level of 100
ppm (which results in eye and respiratory tract irritation
and drowsiness after 15 minutes) lasts for several hours, it
may result in death within the next 48 hours. Symptoms of
chronic exposures at low levels are conjunctivitis (eye
infections), headache, attacks of dizziness, diarrhea, and
loss of weight.
Chronic hydrogen sulfide intoxication is marked by
headaches, eye disorders, chronic bronchitis, and a greygreen line on the gums. Reports of nervous system
disorders including paralysis, meningitis, and neurological
problems has been reported, but not confirmed.

A study of workers and community residents of a California

refinery engaged in extracting sulfur from crude oil, which is
rich in H2S, complained of headaches, nausea, vomiting,
depression, personality changes, nosebleeds and breathing
difficulties. When compared to a non-exposed group of
people, the exposed people showed abnormalities of color
discrimination, eye-hand coordination, balance, and mood
disturbances.
In rats, exposure to hydrogen sulfide has caused
teratogenic effects.

Effects of hydrogen sulfide.

Concentration of H2S
Effect
(%)
(ppm) (g/100 ft3)
0.001 10
0.65
Obvious and unpleasant odor; safe for
8 hr
0.002 20
1.3
Safe for 4 hr exposure
0.01 100
6.48
Kills sense of smell in 315 min; may
sting
eyes and throat
0.02 200
12.96
Kills sense of smell; stings eyes and
throat
0.05 500
32.96
Dizziness; breathing ceases in
minutes;
need prompt artificial
respiration
0.07 700
45.26
Unconscious quickly; death will result
if not
rescued promptly
0.1
1000 64.8
Unconscious immediately, followed by
death
within minutes

How much is safe?

The OSHA Permissible Exposure Limit (PEL) for a ceiling

concentration is 20 ppm hydrogen sulfide, a level which
may not ever be exceeded. The acceptable maximum
peak, for 10 minutes only, once during an 8 hour day if
there is no other measurable exposure, is 50 ppm.
There is no time-weighted average because H2S is so fastacting that no fluctuations above 20 ppm are safe; only
one peak per day is allowed.
This level is too high and recent recommendations are
that it be lowered to 10 ppm. You should remember,
however, that H2S is an invisible gas, floating freely and
unpredictably, and a reading even below a 10 ppm
Permissible Exposure Limit (PEL) may not guarantee your
safety.

There are no particular medical exams for exposure to H2S.

Whenever you enter a confined space such as a tank, make
sure that you follow strict work practices, including a permit
system. Make sure that the Confined Space Entry Standard
1910.146 is followed, that the air is continually monitored for
the presence of H2S, and that a buddy be stationed outside a
confined space. Both of you should wear supplied air and
lifelines and rescue equipment must be immediately
available.

If you work with H2S make sure that:

* Your employer has trained you in the hazards of H2S.
* Your employer has appropriate rescue equipment on-site.

Following are excerpts from a Hazard Bulletin issued

by OSHA after a fatality due to H2S exposure.

Fundamentally, employers and employees must be alert to

the fact that working with a "closed system" does not
always ensure safety. Operations involving the opening of
valves or pumps on otherwise closed systems or working
on such equipment that is not isolated or locked out are
particular sources of danger. When a normally closed
system is opened, the potential exists for releasing
hazardous chemicals to the workers' breathing zones in
unknown concentrations.

Examples of accidents

OSHA reviewed previous fatality inspections involving

valves or industrial piping systems and found the following
incidents where one or more workers had died. Some
examples of these types of accidents included:

* In 1988, two workers were operating a sodium purification

system. One worker attempted to pump a sodium sulfhydrate
solution into a tank and accidentally opened the valve to
another tank which contained an acidic solution. The mixture
of the two compounds generated and released hydrogen
sulfide gas to which the victim was exposed.

* In 1988, a refinery employee received a fatal exposure to

hydrogen sulfide gas while draining the contents of a
knockout drum to an oily water sewer, rather than activating
a closed system to pump out the drum. The worker failed to
observe procedures calling for the use of a closed system,
and the valve to the sewer was not locked out.

* In 1993, employees were working in a coker unit that

thermally cracks heavy residual feed through a process
called delayed coking. The workers were preparing to
switch the feed to the core drum, which necessitated
opening and closing a number of valves. Three workers
were involved with opening and closing the valve, each
working at a different location. As the operation was
proceeding, a loud noise was heard and a vapor cloud was
observed in the vicinity of the pumps feeding the process.
The vapor cloud ignited, fatally burning two of the workers.

* In 1994, an employee was killed when disconnecting a line

from an ammonia valve causing liquid ammonia to be
released, striking the worker on his face and body.

* In 1994, a tragic fatality caused by exposure to hydrogen

sulfide was reported by the Billings, Mont. OSHA Area Office. The
accident was associated with opening a valve to a sewer cup
during the draining of a fuel gas knockout drum in a hydro
treating unit of a petroleum refinery. Normal work procedures
included periodically opening a valve that carried a water-gas
mixture to a separator which removed and vented hydrocarbon
gases to a flare.

During the preceding winter, the piping to the separator

froze, and the drum was temporarily drained to the sewer.
OSHA believes that, due to unclear procedures, the
temporary practice of draining some of the water-gas
mixture to the sewer in some instances may have been
continued, or was incorporated by some workers into the
normal draining procedures.
The worker who was killed is thought to have opened the
valve to the sewer believing it to be part of the draining
procedure, resulting in the release of toxic and fatal
amounts of hydrogen sulfide.
Common factors and problems
A common theme running through many industrial
fatalities is that they involve situations where a closed
industrial system is opened through a valve or pump either
to perform maintenance work, vent by-products, or remove
condensate.

The hazards inherent in these operations

should be addressed by one or more of
the following measures:

1. Perform a process hazard analysis to address the

hazards of the process and engineering and other control
measures to ensure worker safety, including a complete
evaluation and assessment of process systems handling
waste products, by-products, and/or unreacted process
components. Recommendations made by the PHA team,
including recommended engineering changes, should be
promptly implemented.
2. Assure that the system is locked out, including
draining and purging of lines and equipment, prior to
working on the system.
3. Assure that written procedures are clear and that they
provide complete instructions for the safe performance of
work activities.
4. Assure that employees, including contract employees,
are trained in applicable procedures and safe work
practices, and that the employees understand and adhere
to the current operating procedures of the process.

While the risk of accidents cannot be entirely eliminated,

these procedures and practices will reduce the potential for
accidental exposure to hazardous chemicals.

Applicable control
measures:
*Engineering controls
*Monitoring and detection equipment
*Training
*Respiratory protection

Engineering controls

completely assessed to assure that valves capable of

releasing the toxic agent to the atmosphere are permitted
to be opened only when absolutely necessary and are then
vented to a safe location. The valves must also be capable
of being locked out.
Sewer systems for draining tanks or drums which present
potential exposure to hazardous chemicals should be
constructed so that they are closed, vented to a safe
location, or not open to the atmosphere. Alternatively,
appropriate respiratory protection should be worn before
these systems are used.
A valve configuration on an industrial process should be
such that only the valves used for routine use as part of the
normal process are readily capable of being opened. If the
valves are required to be opened for occasional shutdown
operations, they must be locked and tagged in the closed
position to preclude erroneous opening during routine plant
operations.
Valves that must remain available for immediate use in
emergency operations should be clearly labeled as such so
that they are not accidentally opened during routine
operations.

Monitoring and detection equipment

Operators working on units where there is potential

exposure to hazardous chemicals may need to be supplied
with personal monitoring equipment. Alternatively,
stationary monitors could be installed. Personal or stationary
monitors must be capable of sounding an audible alarm or
warning.

Training

All current and new employees should receive training in

standard operating procedures covering all aspects of the
job, with emphasis on safe work practices. Where
appropriate, training should also include field observations
(on-the-job training) by qualified supervisory personnel,
including verification that workers have satisfied the
training requirements.
Training must include proper procedures for working
around areas of potential exposure to hazardous chemicals
and include the hazards of exposure. While labeling of
pipes cannot be required, the hazard communication
standard does require that the employer address the
hazards of unlabeled piping systems in a written hazard
communication program and that the information be
provided through training to workers.

Respiratory protection

Respirators must be provided by the employer when

effective engineering controls are not feasible, or while
they are being instituted, when such equipment is
necessary to protect the health of the worker. The
employer must provide respirators that are applicable for
the purpose intended.
Written procedures must be developed for the safe use of
respirators during the performance of operations
presenting a potential exposure to hazardous chemicals.

Hydrogen Sulfide gas is very corrosive and causes metals to

become brittle. Therefore, employers need to take special
precautions when choosing equipment when they may
reasonably expect to encounter H2S. This may include
appropriate H2S trimming of equipment in accordance with
National Association of Corrosion Engineers (NACE)
Standards.
All well-drilling sites should be classified according to areas
of potential and/or actual exposure to H2S. The
recommendations and employee instruction will vary
depending on the type of area.

No Hazard Condition
API Condition I - Low Hazard
API Condition II - Medium Hazard
API Condition III - High Hazard

No Hazard Condition

Any well that will not penetrate a known Hydrogen Sulfide

formation would be categorized as a No Hazard Area.
Special Hydrogen Sulfide equipment is not required.

API Condition I - Low Hazard

Work locations where atmospheric concentrations of H2S are

less than 10ppm.

Recommended for Area:

Hydrogen Sulfide warning sign with green flag warning device present
Keep all safety equipment in adequate working order.
Store the equipment in accessible locations.

API Condition II - Medium Hazard

Work locations where atmospheric concentrations of H2S

are greater than 10ppm and less than 30ppm.

Recommended for Area:

Legible Hydrogen Sulfide warning sign with yellow flag
warning device present.
Keep a safe distance from dangerous locations if not
working to decrease danger.
Pay attention to audible and visual alarm systems.
Follow the guidance of the operator representative.
Keep all safety equipment in adequate working order.
Store the equipment in accessible locations.
An oxygen resuscitator.
A properly calibrated, metered hydrogen sulfide detection
instrument.

API Condition III - High Hazard

Work locations where atmospheric concentrations of H2S

are greater than 30ppm.

Recommended for Area:

Post legible Hydrogen Sulfide warning sign with red flag
warning device.
Post signs 500 feet from the location on each road leading
to the location, warning of the hydrogen sulfide hazard.
Check all Hydrogen Sulfide safety equipment to ensure
readiness before each tour change.
Establish a means of communication or instruction for
emergency procedures and maintain them on location,
along with contact information of persons to be informed
in case of emergencies.
Ensure usability of two exits at each location.

Do not permit employees on location without hydrogen

Sulfide safety training. (Employees may be permitted on
location for specific Hydrogen Sulfide training purposes that
does not include general rig training.)
Pay attention to audible and visual alarm systems.
Store the equipment in accessible locations.
Two Hydrogen Sulfide detectors should be present (one
should be a properly calibrated, metered detection
instrument, and the other should be a pump type with
detector tubes. The maximum permissible exposure limit
(PEL) is 20 ppm. Respiratory protection would be required if
periodic testing indicates employee exposures to H2S at
concentrations above the PEL.

SOURCES
*Neurobehavioral Impairment from H2S. Kaye H. Kilburn,
M.D. and Raphael H. Warshaw, B. A., University of Southern
California School of Medicine, Environmental Sciences
Laboratory: Los Angeles, CA, 1991.
*ILO Encyclopaedia of Occupational Health and Safety
Third Edition. International Labor Office, Geneva, 1983.
*Proctor and Hughes' Chemical Hazards of the Workplace,
Third Edition. Van Nostrand Reinhold, New York, 1991.
*And Internet Sites.