28 | Loss Prevention Bulletin 215 October 2010
Lessons not learned – part 6
Failure to recognise hydrogen sulphide
hazards
Key lessons
• Hydrogen sulphide (also known as dihydrogen
sulphide) is an extremely poisonous chemical which
affects the central nervous system through inhalation.
• At low levels H2S has a characteristic ‘rotten egg’
odour. Never turn a blind eye if you detect this
odour — H2S gradually dulls the sense of smell, and
exposure may then continue to dangerous levels,
unbeknown to the victim.
• Always wear prescribed Personal Protective
Equipment and carry personal H2S alarms in potential
H2S areas. A regular maintenance/calibration
program for H2S devices should be established with
regular training provided on their use.
• Rescuers must be fully trained, have the correct
equipment and strictly follow safe rescue procedures.
• Whenever sulphur containing substances are in use
then there is potential for H2S development/release.
A robust Hazard identification process is essential.
Introduction
Over the past years, several articles on the subject of
hydrogen sulphide (H2S) poisoning have been published in
Loss Prevention Bulletin1–5. The two incidents described
below share several common features related to the failure
to properly recognise the hazards of hydrogen sulphide.
• In both cases, there was insufficient detailed knowledge of
the process being undertaken and personnel were unaware
that dangerous levels of H2S could be generated. This
resulted in inadequate provision of risk mitigation measures.
• Personnel in the vicinity of both incidents were aware of
the presence of hydrogen sulphide by its unpleasant
smell, but no-one had thought it necessary to act upon
it. In the first incident there had even been complaints
received from off-site.
• Another common feature was the way in which colleagues
entered the area in an attempt to rescue a collapsed
colleague without wearing suitable respiratory protection.
In the first incident, the two colleagues were fortunate in
securing a rescue without causing harm to themselves. Two
would-be rescuers in the second incident were less lucky.
Hydrogen sulphide toxicology
Hydrogen sulphide (also known as dihydrogen sulphide) is
an extremely poisonous chemical. Its toxicity is comparable
to that of the better-known poison, hydrogen cyanide
(HCN). Its occupational exposure level (eight-hour TWA) is
5 ppm, and short-term exposure level (STEL 15 minutes) is
10 ppm. The STEL for hydrogen cyanide is also 10 ppm.
Hydrogen sulphide affects the central nervous system
through inhalation. It also has the effect of ‘fatiguing’ the
sense of smell in those exposed to it so that exposure
continues beyond dangerous levels without the victim being
fully aware of the effects—sometimes with fatal results. This
effect starts to manifest itself at levels in air of 50–100 ppm
and it starkly illustrates the need for monitoring of
occupational levels starting at much lower levels than this. If
levels likely to lead to a fatality are present, however, it will not
be detected by smell as its impact on the nasal nerve endings
are too rapid for someone to notice. The obnoxious of H2S at
lower concentrations indicate that appropriate measures such
as monitors and breathing approaches are required. Optimum
systems of worker protection against H2S would incorporate
personal gas detectors, with audio/visual alarms and
respiratory protection. In the second incident described, it is
possible that the release was sudden and dramatic. If that were
the case, then the ‘fatiguing’ effect would have been irrelevant.
It is sometimes forgotten that hydrogen sulphide is extremely
flammable (between limits of 4% and 56% in air), and has an
exceptionally low minimum ignition energy of approximately
0.08mJ – cf 0.8mJ for petrol vapour. The main combustion
product is highly toxic sulphur dioxide.
Incident 1: Hydrogen sulphide exposure
A maintenance worker entered a wastewater treatment
plant to retrieve a tool. His path brought him directly
alongside a clarifier — an open top tank for settling solids.
The worker noticed a ‘rotten egg’ odour, and suddenly felt
unable to breathe. He tried to leave the area but was
overcome and collapsed. He was pulled to safety by fellow
employees and recovered with no injuries.
The process involved
The hazardous waste facility was a treatment, storage and
disposal facility consisting of a series of tanks and filters that
received, stored, chemically treated, filtered, and settled
solids out of water-based waste streams. The aqueous
portion of this waste would be consolidated in a storage
tank, and sampled and treated by adding chemicals to react
with the various contaminants, adjusting for pH, and
filtering. The treated solution was held in a clarifier, and if
the pollutants were within permitted limits, the liquid would
be decanted into a storage tank, and filtered again, before
finally being discharged to the municipal sewer. Figure 1
shows a simplified diagram of the process.
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Figure 1: Simplified flow diagram
Description of the incident
On the morning of the incident, the waste treatment
operator sampled treated liquid in the clarifier and noted
that the mercury content was above the discharge permit
level. The operator added sodium sulphide flake to the
clarifier to precipitate mercury sulphide. As the clarifier was
not equipped with a mixer, the operator connected a plant
air hose to the vessel to provide mixing. After decanting,
tests showed that the mercury was within limits, but the pH
was too high due to the alkalinity of the sodium sulphite.
The operator then added an acidic chemical –
polyaluminium chloride (PAC) – to the clarifier in order to
cause flocculation of the mercury salts and to adjust the pH
towards neutral. Three 55-gallon drums of PAC were added
over a few hours.
At approximately 2.00pm, the facility compliance
coordinator was alerted to an H2S smell. He entered the
wastewater treatment area, noticed the odour and left to get
a portable gas detector.
A few minutes later, a maintenance worker entered the
area to retrieve a tool. He also noticed the odour but was
unconcerned because he had smelled it before with no ill
effects. However, as he walked towards the tool, he
suddenly became unable to breathe and he collapsed.
The compliance coordinator returned to the plant with a
supervisor and a gas detector to further investigate the odour
and they discovered the mechanic lying unconscious on the
floor and not breathing. At the same moment, the gas
detector began to alarm. The two men (who were not wearing
breathing apparatus) pulled the victim from the room in the
fresh air, where he began breathing again. He was taken to
hospital for evaluation, but suffered no lasting effects.
The investigation and causes
• The operator used air to mix the contents of the clarifier
(a vessel designed for settling its contents) rather than
transferring the batch back to the treatment tank which
had adequate mixing and ventilation. The air did not
provide sufficient mixing to completely dissolve the
sodium sulphide flake and distribute the PAC. These two
chemicals combined to produce hydrogen sulphide,
which was released from the top of the vessel.
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Loss Prevention Bulletin 215 October 2010 | 29
• The facility had no written procedures for operating the
wastewater treatment plant and no written instructions
specifying what to do in the event that a waste failed to
meet discharge limits after treatment.
• Communication was inadequate to inform facility
personnel of the hazards of H2S. Employees did not
respond appropriately when they smelled the
characteristic odour because they did not fully appreciate
the dangers. Employees were not warned when waste
treatment operations had the potential to release H2S.
This lack of awareness is evidence by the fact that several
employees entered the area immediately after the
incident without respiratory protection.
• There was no calibration and inspection programme for
the H2S detector. It did not alarm on the day of the
incident and failed to warn employees of a dangerously
high concentration of H2S in the area. The investigation
found that it was not functioning due to a faulty sensor.
From US Chemical Safety and Hazard Investigation Board
http://www.csb.gov/investigations/detail.
aspx?SID=44&Type=2&pg=1&F_All=y
Incident 2: Fatalities result from a hydrogen
sulphide release
Three men died as a result of inhaling hydrogen sulphide
released during the emptying of molecular sieve from a gas
drier.
The process involved
The plant concerned produced lean gas and natural gas
liquids (NGL) from associated gas from oil wells. The
associated gas contained water vapour and H2S. The process
comprised compression of gas, followed by refrigeration to
condense and separate liquids, dehydration of vapours and
liquids, and final separation of lean gas and NGL cryogenically.
The natural gas liquids were dried by passing through a bed of
molecular sieve prior to the cryogenic stage. When this bed
became saturated with water, it was regenerated by passing
hot gas through it then cooled with cold gas.
After some 3-4 years, beds have to be replaced. To do
this, the sieve would be regenerated, cooled and purged
with nitrogen, then put into a truck for disposal.
30 | Loss Prevention Bulletin 215 October 2010
Description of the incident
A drier was prepared for discharge of sieve in a way that had
been done many times before over the past twenty years.
The operators entering the drier to remove the top guard
and mesh used breathing apparatus and personal H2S moni-
tors, demonstrating that the hazards of this gas were well
understood for this operation. The sieve was then removed
by raking it from the drier onto a chute carrying it to just
above a high-sided tipper truck. The truck floor and the dis-
charged sieve were water-wetted to restrict dust (it was
windy) and to reduce the risk from any pyrophoric material.
After a while, a mound of sieve accumulated at the back of
the truck. A man entered the truck via a ladder to level the
mound by shovelling it to the front of the truck. Ten minutes
later, a second man joined him to help with the levelling.
This man collapsed very soon after entry. The first man tried
to help him and was joined by a third man who actually
jumped down into the truck from the platform on the drier.
All three became unconscious and died. A fourth man, who
also entered the truck via the ladder, to render assistance,
collapsed but was rescued. The emergency response was
delayed by unclear radio communications.
Investigation and cause of the incident
It was established that the H2S concentration in the truck was
sufficient to overcome workers in a few minutes and lead to
death unless they were rescued very quickly. The rear of the
high-sided truck, in effect, constituted a confined space in
which ventilation by natural air circulation was insufficient to
reduce the concentration of any toxic vapours.
The workers in the truck, who were contractors, were
not provided with breathing apparatus, escape masks or
personal monitors. The possibility of H2S release from the
sieve at this stage was not fully understood or foreseen and
this resulted in inadequate management of the potential
risks. The initial emergency response was not effective.
The mechanism for release of H2S in fatal quantities was
described as follows. The regeneration gas used prior to sieve
discharge, contained approximately 830 ppm of H2S which
begins to be adsorbed by the sieve during cooling. It is then
retained, not removed, during the nitrogen purge stage. Then,
since the molecular sieve’s affinity for water is much greater
than its affinity for H2S, the latter is released on contact with
water, in this case when it was wetted in the truck. More
trapped H2S would have been physically released while the
sieve was being levelled by shovelling. There was little or no
prior knowledge amongst company staff or contractors about
this mechanism for release of H2S though it is hard to imagine
that it had never happened before in 20 years. Perhaps it was
just fortuitous that no tragic accident had occurred previously.
Other important findings of the investigation were:
• The mechanism for H2S release from the sieve in this
way was not known to either the company personnel or
to the contractors.
• The induction training given to contractors was not
effective. There was no testing of understanding, records,
or recognition of any literacy or language difficulties.
• There were no signs posted in or around the driers to
warn of possible hazardous concentrations of H2S.
• Personnel in the vicinity of the disposal operation did not
react to the very unpleasant smell which was apparent
for some time before the incident. This was a crucial
factor in allowing events to proceed to the tragic scale
that they did.
• The management of safety and risk assessment systems
had a number of shortcomings. Disposal of the sieve was
not included in the planning of the overall sieve
replacement job. No risk assessment was carried out
specifically for the disposal stage. Multiple jobs requiring
different precautions were carried out under the one
Permit to Work, in contravention of company safety
procedures. There was no company supervision at the
sieve unloading location.
• No standby personnel were posted at the scene to pro-
vide, for example, breathing apparatus or rescue services.
This is perhaps not surprising since the hazard that was
present was not recognized. Because of this, and other
factors, the immediate first aid response was inadequate.
• The fact that the high-sided truck, in effect, constituted a
confined space in which concentrations of toxic gas could
be confined and accumulate, was not taken into account.
A risk assessment would probably have identified this.
Lessons from this incident
The company did take this tragic accident most seriously and
put into place systems and improvements to address all of
the above considerations. Thus:
• Hazards identification, including potential incident scenar-
ios and job safety analysis would be carried out with the
involvement of first line supervisors. Method statements,
containing clear roles, responsibilities and control features,
would be prepared in advance of the starting of jobs.
• The understanding, communication and application of
manufacturer’s recommended safe practices would be
enhanced.
• Safety induction would take account of different
languages and levels of literacy and its effectiveness
would be checked. Follow-up refresher training would
be provided as necessary.
• The awareness of the specific hazards of H2S would be
enhanced, tested and made the subject of routine
refresher training.
• Enforcement of the use of personal protective equipment,
in particular breathing apparatus, would be ensured, and
emergency drills would cover a range of all identifiable
scenarios and include all personnel who have a role to play.
From LPB 194, April 2007
References
1. Man overcome by hydrogen sulphide fumes, LPB 184,
August 2005
2. Hydrogen sulphide release from a process vessel, LPB
168, December 2002
3. Supply of wrong chemical leads to a release of
hydrogen sulphide gas, LPB 159, June 2001
4. A hydrogen sulphide release affects four workers, LPB
155, October 2000
5. Hydrogen sulphide releases during oil tanker
operations, LPB 155, October 2000
6. Hazardous substances in refineries, BP Process Safety
Series, IChemE, ISBN 978 0 85295 482 9
© Institution of Chemical Engineers
0260-9576/10/$17.63 + 0.00