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History On April 23, 2008 in Konan, Japan, a 14 year old girl locked herself in the bathroom of her family’s apartment. Posting a sign on the door that stated “poison gas being produced”, she mixed the detergent with a liquid cleanser creating enough hydrogen sulfide gas to take her own life and sicken 90 of her neighbors to the point of needing medical intervention. On May 1, 2008 in Otaru, Japan, a 24 year old male mixed the chemicals in his home, prompting the evacuation of 350 nearby residents. His mother, who was home at the time, was found unconscious and in need of immediate medical intervention. Fortunately, she survived the incident.
The first occurred in California in August. A 23-year old man mixed chemicals in his car at a shopping center in Pasadena. He posted a sign in the window of his vehicle to warn first responders not enter his vehicle without proper protection in place. The shopping center was evacuated before the vehicle was ventilated. The second incident occurred in Lake Allatoona, Georgia in December when a young man in his 20’s also mixed chemicals in his car to create hydrogen sulfide gas. He too placed a sign on the window warning first responders of the deadly gas being produced inside. Both cases in the U.S. found the victims locked in their vehicles with hydrochloric acid and bonide, a common insecticide that contains sulfur.
What is Hydrogen Sulfide? Recognition and Response Hydrogen sulfide, H2S, is a colorless gas that has a strong odor of rotten eggs or sulfur associated with it. It is extremely toxic by inhalation, posing a large risk to first responders who do not wear proper respiratory protection when dealing with it or who are unaware of its presence. H2S is an olfactory nerve paralyzer, meaning it will rapidly fatigue the sense of smell, even when present in lower concentrations. Overall, 25% of the deaths associated with hydrogen sulfide gas occur in rescuers, first responders, bystanders, or professionals who deal with it on a regular or routine basis. However, when discussing chemical suicides, there have been no deaths to first responders to date.
Hydrogen sulfide has a vapor density of 1.19, making it heavier than air. As first responders approach the space where a suspected chemical suicide has occurred and they are performing air monitoring tasks, vapors will be found lower to the ground. However, once they enter the space or begin air monitoring within the space, it can be expected that diffusion will have occurred and we will find the space consumed with vapors. Vapors may be knocked down with a water spray if it is felt that that is the best course of action for the incident, however, all runoff created should be contained and disposed of properly as it will be toxic and corrosive. CHEMICAL SUICIDE AWARENESS LOW EXPOSURE: 0 –10 ppm / Caller is complaining of minor irritation in eyes, nose, and throat. MODERATE: 10 –50 ppm / Caller is complaining of headache, dizziness, nausea and vomiting, coughing and difficulty breathing . HIGH : 50 –200 ppm / Caller is complaining of severe respiratory irritation, eye irritation/acute conjunctivitis. Note: This level may also cause shock and convulsions, coma and death.
Hydrogen sulfide is made by mixing hydrochloric acid with a sulfur containing • compound (in a high enough concentration to react with the hydrochloric acid). In many of the cases we have seen, the two chemicals mixed have been hydrochloric acid and lime sulfur. Lime sulfur (bonide) is a 28% solution of calcium polysulfide. • Both products are easy to obtain and can be purchased at a local hardware, grocery, or big box store. • Approximately ½ cup of each product will produce about 1000 ppm H2S inside a • confined space (approximately 3500 cubic feet). The individuals who have mixed these chemicals have been mixing several containers of each product, not increasing the concentration of gas produced but increasing the volume of gas produced. • As one of the chemicals being mixed is an acid and the other a base, a mildly exothermic, somewhat violent reaction can be expected. Because of this, evidence that the reaction has occurred may be visible from outside of the confined space.
Personal protective equipment utilized for dealing with chemical suicide incidents involving hydrogen sulfide should be adequate and appropriate for the degree and type of contamination encountered. Each incident will be slightly different and PPE needs should alter to meet the specific needs of the incident. As the IDLH threshold for hydrogen sulfide is 100 ppm, self contained breathing apparatus must be utilized. Chemical protective clothing is not necessary and is not generally recommended for dealing with hydrogen sulfide gas. Hydrogen sulfide poses a minimal risk through cutaneousabsorption and also a minimal risk of secondary contamination by first responders. Structural firefighting turnout gear or Tyvek suits will provide adequate skin protection for dealing with hydrogen sulfide gas.
By DOT definition, hydrogen sulfide meets the criteria to be considered a flammable gas as the flammable range is 4.3 % - 45%. The auto-ignition temperature is 500degrees Fahrenheit. However, in these particular situations, the flammability risk is fairly low. In the essence of first responder safety, all ignition sources should be eliminated to reduce the flammability risk. A charged hand-line should be made ready in case a source of ignition is found. The vapors in the space should be ventilated properly once all precautions have been taken to safely do so. Decontaminationfor first responders should be set up appropriately for the degree of contamination encountered at the scene. A full technical decontamination setup may not be necessary or appropriate for the incident. At minimum, skin should be washed with water for three to five minutes. If eyes or skin appear to be irritated, continue to flush with water during medical observation and transport to a nearby medical facility.
Summary • The first step to preventing injury or death in response to a chemical suicide is awareness. These incidents typically occur in vehicles, closets, bathrooms, or other small spaces where the concentration of gas can quickly accumulate to lethal levels. • Careful size-up of any situation involving an unresponsive person in an enclosed space is critical for responder safety. As with any incident, size up starts with the initial dispatch. • If responding to an incident involving an unresponsive person in a confined • space and there is a possibility that the individual is sleeping, attempts must be made to waken them. Attempts to waken individuals must be made from a safe distance with the aid of vehicle public address systems, bullhorns, or sirens. • Responders should not approach areas of concern without proper PPE in place and air monitoring equipment to check for unknown presence of vapors.
Warning signs may not be placed on doors or windows to indicate the presence of a deadly gas inside the space. Signs may be placed but may be difficult to detect or understand. • Signs may be obscured by condensation, frost, snow, ice, or vapors • produced by the chemical reaction. Signs might be present but may not be easily interpreted by the person who first found the victim. • Interview any individual who may have approached the scene to learn what they observed. • Indications that a chemical reaction has been initiated include empty • containers of household chemicals, containers that may be used as “mixing vessels”, and visible signs that a chemical reaction has occurred. It is important to keep in mind that improvised mixing vessels may be used such as glove compartments, sinks, or consoles.
Conclusion Structural firefighting clothing and SCBA are recommended for any operations that involve opening the vehicle; decrease the level of personal protective equipment only when air monitoring supports the decision. The reaction of one quart of 30-percent calcium sulfide and one quart of 20-percenthydrochloric acid in a vehicle resulted in a hydrogen sulfide concentration of 4,000 ppm to 8,000 ppm. These concentrations would certainly be fatal in a few minutes. Opening doors or windows for ventilation resulted in a rapid decrease (< 10 minutes) of the hydrogen sulfide concentration.
The temperature of the reaction mixture increased from ~ 45ºF to 75ºF. • Hydrogen sulfide will continue to off-gas from porous media (cloth seats and carpeting in the vehicle and the victim's clothing) after the vehicle is opened. • Passive diffusion of hydrogen sulfide from a closed vehicle was complete in approximately three hours and is dependent on the volume of the vehicle, the tightness of the fit of the windows and doors, and wind speed. • No appreciable quantity of aerosol is generated during the acid/base reaction of calcium sulfide and hydrochloric acid based on no change in color of the pH paper.
Disturbing the container with the reaction mixture results in the generation of more hydrogen sulfide because of the additional mixing. • The recommended Isolation Perimeter (public exclusion zone) is 50 to 75 yards downwind during vehicle ventilation. This suggested exclusion zone is based on the monitoring results from the four-gas meter near the vehicle and an observation of a firefighter downwind during the time the vehicle was vented. The firefighter noted that the odor of hydrogen sulfide was similar to the odor of mercaptan during a natural gas leak.
Case Study On 12-26-2010, Hazmat 7 responded to a Detergent Suicide call, close to the station in SE Portland. This is a synopsis of that incident: At about 7pm, they responded on a UN1 medical call that morphed into a hazmat call. The mother of the victim checked her 50 year old son and found him unresponsive in his pickup. Note the yellow stain on the driveway. This note was found inside the victim’s home, not on the exterior of the vehicle. A likely scenario is that the victim loses consciousness in 60-90 seconds and may die within 5-10 minutes. This family member noticed strong chemical odors when the door was opened. This patient required treatment, while the crew found the victim DOA.
All Very Toxic Products ! ! ! Upon arrival, HM7 noted the odor of rotten eggs, a yellow stain on the ground below the vehicle and the presence of tubs and chemical containers in the back seat. Note the combination of chemicals needed to initiate the exothermic reaction and release of toxic gas. The yellow color in the mixing tub is from the element Sulfur that is present in many of the garden chemicals used in this process. Be aware that Hydrogen Sulfide is only one of many hazardous byproducts of this deadly reaction. HM7 monitors detected dangerous readings at the gaps of the truck doors, even when closed. Levels inside the vehicle triggered high alerts on the 4 gas monitor. Note that H2S will deaden your sense of smell at about 150 ppm, masking estimates of the on scene danger.
LESSONS OBSERVED AND ACTION STEPS • DON’T BECOME COMPLACENT! Always be aware of ALL on scene clues • available to you. Size-up the situation before you act. • IF THERE IS A SMELL OF SULFUR OR ROTTEN EGGS – This may • indicate the presence of H2S gas which is very dangerous even at low levels, • deadening your sense of smell. Back off and don PPE with respiratory • protection before acting. Request fire/hazmat with monitoring capability. • UNRESPONSIVE PATIENT IN A VEHICLE: Warning notes or taped door • and window seams, glass stains or residue on the ground are a sure sign that • you should exercise caution and escalate the response. Call for a hazmat • team and police. • EVIDENCE OF CHEMICALS IN THE VEHICLE – Typical chemicals, tubs • and other equipment mentioned in this bulletin are clues that an active • reaction has filled the vehicle with toxic products. DO NOT ENTER THE • VEHICLE FOR PATIENT ASSESSMENT, WITHOUT DONNING FULL PPE ! • CREATE HAZARD ZONES – Inside the vehicle is a hot zone. Create an • appropriate warm zone around the vehicle. Prohibit entry from anyone not • wearing full PPE. • NOTIFY APPROPRIATE ASSISTANCE – Call the nearest hazardous • materials response team, police and other appropriate agencies. TREAT • THIS AS A HAZMAT SCENE !
In December, 2010, Portland Fire & Rescue responded to its first “Detergent • Suicide” call. There is an increasing potential for more of these calls that may • impact your safety, should you respond on a call to check a patient in a vehicle or • a small room. • “Detergent Suicide” or “Chemical Suicide,” is a new way to commit suicide by • mixing two or more chemicals that can be purchased at local stores. Once mixed, • these chemicals produce a heat releasing or exothermic reaction, creating byproduct gases that quickly fill the enclosed area. This technique that first • originated in Japan, is gaining popularity via instructions posted on the internet. It • is often communicated as a quick and painless way to end one’s life. • There have been hundreds of these incidents in Japan over the last several • years and now have been seen in the United States – specifically in Idaho, • California, Florida and Georgia. This is an overview of the detergent suicide process: • In Japan, a brand of detergent was combined with bath salts – here it is • most likely an inorganic acid and a pesticide or garden product. • Usually, tape will be used to seal joints and seams in the room or the • vehicle, to contain the toxic products inside. • In most but not all incidents, a suicide note will be taped to a door or • window, warning responders of the hazards
Common products from hardware stores are combined in a bucket or tub • and quickly overcome the victim, leaving a crime scene and a hazardous • materials cleanup site. • The main toxic product is Hydrogen Sulfide (H2S), which can cause • coma and death at 1000 parts per million (only 1/10 %) • There will be evidence of this process – you may note the smell of H2S • upon approach (sulfur or rotten eggs) or tubs/buckets in the vehicle, • along with multiple chemical product containers • Common sources for the acids may be: Lysol, toilet cleaner, tile, brick or • drain cleaners Common sources for the sulfur may be: Dandruff shampoo, Epsom salts, pesticides or fungicides. • Possible toxic products could include: H2S, Sulfur Dioxide, Carbon • Monoxide, Acid Gases, Nitrogen Oxides, Phosgene, Carbon • Disulfide, Methyl Isocyanate, Thallium.
ENTRY INTO THE VEHICLE – If the decision is made to enter the vehicle, • use full PPE and completely vent the vehicle first. Position the patient • OUTSIDE the vehicle for assessment. Remember, the atmosphere inside the • vehicle is both an inhalation hazard and possibly an explosive hazard. • IF POLICE NEED TO PERFORM A TACTICAL ENTRY EITHER INTO A • VEHICLE OR A SMALL ROOM – Full SCBA is mandatory and the use of • flash-bang or sting ball devices could cause an explosion because of the • presence of flammable gases. • REMEMBER THAT THIS IS A POSSIBLE CRIME SCENE – Make • immediate notifications to Police, Medical Examiner, etc and avoid disturbing • any evidence. • BE ALERT FOR SECONDARY DEVICES – Scan the vehicle or room for • the presence of anything that looks out of place or suspicious. DO NOT • DISTURB OR TOUCH ANYTHING UNNECCESARILY! • FIRST AID ACTIONS – Remove victim(s) from exposure and if appropriate, • support breathing. Skin contact with corrosive product may cause burns. • DECONTAMINATION – Remove clothing ASAP. For eye or skin exposure, • flush with lukewarm water for 15 minutes.
HAZMAT WASTE – After victim/patient care and legal scene issues, scene • must be treated as a hazmat site. Waste products must be overpacked and • handled as hazardous waste by a licensed contractor. Notify appropriate • environmental agencies as needed.