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Chemical Agents of Opportunity for Terrorism: TICs & TIMs Module Two: Toxic Industrial Gases
Mark Su, MD
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Chemical Agents of Opportunity for Terrorism: TICs & TIMs
Course Overview
1. Introduction – Why Toxic Industrial Chemicals? 2. Inhalation of Toxic Industrial Gases 3. Neurotoxins 4. Agricultural Chemicals of Concern 5. Cyanide and Fumigants 6. Water, Food & Medication as Vectors 7. Delayed-Onset Toxins 8. Psychological Consequences of Mass Chemical Exposure 9. Tabletop Exercise
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Faculty Disclosure
• Faculty: Mark Su, MD – Relationships with commercial interests: none – Speakers Bureau/Honoraria: none – Consulting Fees: none – Other: none
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Learning Objectives
• Review history of important industrial gas exposures and regulatory response • Identify major industrial gases of interest • Understand the clinical picture created by the gases and be able to relate this to their physical properties and toxicity • Address methods to decrease likelihood of exposure and illness
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Key Learning Points
• Legislation to regulate TICs/TIMs generated by toxic gas concerns • Releases of large volumes of gas most likely TIC/TIM scenario • Toxicity of a gas is determined by – Dose – Inherent toxicity – Water solubility – Warning properties
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Participant Question
• Which of the following events resulted in the largest number of casualties? A. The sinking of the Titanic, 1912 B. The Bhopal disaster, 1984 C. The carbon dioxide release from Lake Nyos, 1986 D. Terrorist attacks of September 11th, 2001
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The Bhopal Disaster (1984)
• Best example of large scale toxic industrial gas release • More casualties and from this event than any terrorist event to date. • Methyl isocyanate (MIC) release
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Bhopal Disaster (1984)
• Occurred in middle of the night • Staffing levels low / Plant was shutting down • Water entered a tank believed to be empty – 57,000L of Methyl isocyanate – Accident vs. sabotage • Exothermic (heat releasing) reaction • 40+ tons of methyl isocyanate released – Some combustion products
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Bhopal Disaster • Safety system failures – Unreliable pressure gauges – Nonfunctional refrigeration – Inoperable gas scrubber – Alarm failure – Inadequate spray “knock-down”
http://www.lenntech.com/environmental-disasters.htm
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Bhopal
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Bhopal Disaster
• Plume drifted over shanty-town – 250,000 people exposed – Blinding fog at night • Temperature inversion trapped plume • No actual measurements of the Methyl isocyanate concentration – Modeled mean methylisocyanate conc: 27 ppm (0.1-86 ppm) with a median concentration of 1.8 ppm • Concerning gas levels as AEGL3 only 0.40 ppm – Acute Exposure Guideline Level -3 is concentration at which the general population is expected to experience life threatening health effects. Level 3 = highest level (NNN)
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Bhopal Disaster • Unprecedented human toll – 2500 fatalities within 1 week (pulmonary) – Thousands more died weeks-months later – Chronic disability for > 100,000+ • Chronic pulmonary complaints • Ocular inflammation
Dhara et al, Arch Environ Health 2002; 57:391-404
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Methyl Isocyanate (MIC): • Chemical intermediary – Insecticides, polyurethane foam and some plastics • Used in large industrial amounts • Properties – Colorless, flammable liquid at room temperature – Easily vaporizes – Boiling point 39.5 ºC – Has a pungent odor but not enough to provide warning – Water soluble, but releases heat with water – Heavier than air (Vapor density: 1.4) • It is not cyanide and does not produce cyanide*
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Methyl Isocyanate: Clinical Effects
• Ocular/Dermal – Blindness/unable to escape exposure – Irritation and ulceration • Respiratory – Irritation upper and lower respiratory tract – Life-threatening pulmonary edema – Residual chronic lung disease • Reactive Airways Dysfunction Syndrome (RADS) – Asthmatic condition following large exposure to certain irritants – Non-immunologic
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Chemical Agents of Opportunity for Terrorism: TICs & TIMs Reactive Airways Dysfunction Syndrome (RADS) • A form of chemically induced asthma • Syndrome Diagnosis requires: – No prior chronic respiratory illness (including asthma) – Documented significant exposure to chemical irritant – Symptom onset (cough, dyspnea, wheezing) within 24 hours and persistence for >3 months – Bronchial hyper-responsiveness on pulmonary function testing – Lack of another competing pulmonary diagnosis
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SARA • Reponses to tragedy US Congress passed several laws • SARA Title III-Emergency Planning and Community Right-to-Know Act (1986) – State Emergency Response Commission – Local Emergency Planning Committees – Chemical facilities required to submit annual hazardous chemicals inventory reports • Law focus on accidental releases
http://www.access.gpo.gov/nara/cfr/waisidx_04/40cfr372_04.html Module Two: Inhalation of Toxic Industrial Gases 17
Chemical Agents of Opportunity for Terrorism: TICs & TIMs Clean Air Act Amendments of 1990: Risk Management Plans (RMP) • Regulated businesses required to prepare RMP – Greater than threshold amounts present of 77 toxic or 63 flammable substances • RMP must include – Type and amounts of hazardous materials – Accident history during past 5 years* – Hazards associated with chemical processes – Process controls, passive mitigation, detection systems • Off-site consequence analysis (OCA) – Accidental release scenario
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Chemical Agents of Opportunity for Terrorism: TICs & TIMs Chemical Facility Anti-Terrorism Standards (CFATS, 2014) • Certain chemical facility covered by act – Risk based focus (Consequence, capability) – Security vulnerability assessments – Site security plans – Audits and inspections • Penalties for non-compliance/ facility shut down • Recognition of need to coordinate but also protection of sensitive information from public disclosure
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Chemical Agents of Opportunity for Terrorism: TICs & TIMs Chemical Accidents (not explosive) in US Industry under RMP for 2000-2015 Anhydrous Ammonia 965 (16) Chlorine 548 (3) Sulfur Dioxide 175 (0) Hydrogen Fluoride 137 (4) Ammonia (>20%) 121 (15) Hydrogen Sulfide 89 (2) Formaldehyde 63 (2) Hydrogen Chloride 58 (0) Fuming Sulfuric acid 57 (2) 1,3 Butadiene 54 (4) Propylene oxide 54 (1) Carbon Disulfide 50 (1) Number of accidents with Chlorine Dioxide 47 (1) number of fatalities in Vinyl Chloride 47 (5) parenthesis Phosgene 36 (0*)
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Chemical Agents of Opportunity for Terrorism: TICs & TIMs Inhalational Exposure: Determinants of Toxicity • Dose = Respiratory rate x tidal volume • Exposure circumstances – Concentration – Duration • Health of Individual exposed • Properties of Agent – Water solubility – pH – Volatility/Vapor density – Mixtures and particle size
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Chemical Agents of Opportunity for Terrorism: TICs & TIMs Clinical Effects Based on Properties of Agent High water Low water Solubility Solubility
Onset of Symptoms Rapid Delayed
Warning Properties Good Poor
Airway Upper with Lower with lung Injury irritation injury
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Ammonia > Phosgene • Ammonia AEGL3 = 1600 ppm
Phosgene > Ammonia • Phosgene AEGL3 = 1.5 ppm
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Railway Accident: Minot, ND 2002
• Derailment of 31 cars • Immediate release of ~150,000 gallons of anhydrous ammonia • 5 cars released • One car airborne ¼ mile striking a house • Plume 300 feet high spreading 5 miles downwind
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Video Derailment
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Minot ND Ammonia Leak • Even though lighter than air, this release resulted in significant ground-level [NH3] • The visible fog represents significant hazard to: – Contact – Upper airway – Inhalation hazard • Highly water soluble gas • Sheltering in place was the appropriate response to this event – In home or in vehicle
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Response and Outcomes
• Shelter-in-place order • Difficulty with communication (no overnight TV crew) • Exposed population: 11,600 • Minor symptoms: 322 • Serious symptoms: 11 • Fatal: 1
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Anhydrous Ammonia (NH3)
• Third highest production volume chemical in U.S. – ~9 million metric tons • Manufacture of fertilizer as nitrogen source (>80%) • Other uses: plastics, fibers and resins, explosives, cleaning disinfectants, refrigeration • Transported as liquefied gas under pressure via pipeline, railcar, tanker truck, and refrigerated barge
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Ammonia: Physical Properties • Colorless gas with pungent odor • Low odor threshold; good warning properties – Odor threshold 25 ppm <<< IDLH 500 ppm • Highly water soluble • Boiling point – 33º C – Requires high pressures/low temperature storage • Vapor density 0.6 (lighter than air*) • Combustible in narrow range • Highly reactive gas
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Clinical Effects
• Damage from alkali burn and thermal reaction (frost) Ammonium NH3 + H2O Æ NH4OH Hydroxide
• Low concentration: irritant to nose, throat, upper respiratory tract • Higher concentrations or more prolonged contact cause skin burns • Lower airway inflammation with pneumonitis and pulmonary edema
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Anhydrous Ammonia
• Concentration x duration determines clinical effect – Minor irritation to blindness with extensive scar formation • Center picture shows fluorescein uptake indicating diffuse corneal injury
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Homemade WWI Warfare Agent
• 29 yr old man with acute respiratory distress after cleaning toilet with mixture he made • RR 36/min, HR 128/min, BP 148/76 • Lip and throat swelling • Diffuse wheezing • Required intubation and positive pressure ventilation • Hypoxia with CXR
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Participant Question
• What chemical agent was made? A. Anhydrous Ammonia B. Chlorine C. Phosgene D. Sulfur Mustard
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Chlorine
Non-cardiogenic pulmonary edema
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Dangerous combination
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Chlorine Gas
• Multiple Uses – Manufacturing chemicals – Pulp and paper industry – Commercial & household bleaching agents – Water purification & waste treatment • 1998 US production > 14 million tons – One of most produced chemicals – Shipped as liquefied compressed gas
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Chlorine: Physical Properties
• Green-yellow, pungent gas • Low odor threshold; – Moderate warning properties (≈3ppm) • Intermediate water solubility
– Less than NH3, more than phosgene • Boiling point –34 ºC • Vapor density 2.5 (heavier than air) • Reacts explosively with many http://www.amazingrust.com/ compounds Experimentshow_to/Images/ Module Two: Inhalation of Toxic Industrial Gases Chlorine_gas.jpg 37
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Chlorine: Clinical Effects • Intermediate water-solubility • Low concentrations: Cl2 + H2O ↔ HCl + HOCl – irritant to eyes, nose, throat, upper respiratory tract – May not be detected so the victim remains in environment • Higher concentrations: – Acute pulmonary edema – Chemical pneumonitis • Chronic sequelae: – RADS http://www.aliciapatterson.org/APF1403/Borg/Borg04.jpg Module Two: Inhalation of Toxic Industrial Gases 38
Chemical Agents of Opportunity for Terrorism: TICs & TIMs Chlorine: 1st Successful Chemical Warfare Agent, WW I
Wind-borne Chlorine Attack, WWI
Battle of Ypres-168 tons of Cl2 released from 5700 canisters; 50% mortality Chlorine Gas Respirators Module Two: Inhalation of Toxic Industrial Gases 39
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One 90 ton tanker ruptured, releasing gas for ¼ - ½ mile
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Consequences Graniteville Train Accident • 9 deaths – 1 train engineer – 6 mill workers – 1 in home – 1 in truck • 529 sought medical care • 69 hospitalized, 11 critical • 18 were treated at area physicians’ offices • 5,400 evacuated in 1 mile radius of crash • Initial report : "sodium nitrate" • Chlorine was not reported to ED for 1 hour Public Health Consequences from Hazardous Substances Acutely Released During Rail Transit ---South Carolina, 2005; Selected States, 1999-2004. MMWR 54(3):64-67. http://sav-cdn.com/sites/default/files/imagecache/superphoto/editorial/images/savannah/mdControlled/cms/2006/07/18/24773370.jpg Module Two: Inhalation of Toxic Industrial Gases 41
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Chlorine Transport in the US
Rail transportation of chlorine and other toxic gases is common in highly populated cities.
photo: Jim Dougherty July 9, 2004
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Chemical Agents of Opportunity for Terrorism: TICs & TIMs Chlorine Gas used in terrorism • Reports of chlorine gas being used in Syria and by ISIS – Partial augmentation in IED weapon lethality – Also using just the gas • Transient breathing problems most common.
http://www.bbc.com/news/world-middle-east-31847427 Module Two: Inhalation of Toxic Industrial Gases 43
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Chlorine Bombs
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Phosgene • Used in the manufacture of – Organic chemicals: dyestuffs, isocyanates – Plastics – Insecticides – Pharmaceuticals • 80% used for isocyanate production • US production: estimated 1 million tons/year • Also formed as a combustion product when chlorine-containing compounds are burned
• Formula Cl2C=O; Not same as phosphine
Module Two: Inhalation of Toxic Industrial Gases http://www.newworldencyclopedia.org/entry/Phosgene 45
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Phosgene: History
• Synthesized in 1812 • 1st used in WWI, Ypres, Belgium (December 1915) – Germans shelled British with 88 tons of phosgene – 1100 casualties, 120 deaths
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Chemical Agents of Opportunity for Terrorism: TICs & TIMs Phosgene: Community Threat Assessment • 99.9% of production is “used on-site” • Storage and transport as liquefied compressed gas
http://www.chemicaldesign.com/Phosgene.htm
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Phosgene
• BASF Plant Ascension Parish, LA • 1981: Plant operator killed • 1982: 28 workers injured • 1986: Phosgene plume over unpopulated parts of http://commons.wikimedia.org/wiki/ Ascension Parish Image:Map_of_Louisiana_highlighting_Ascen sion_Parish.svg – Only chemical releases considered
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Phosgene: Physical Characteristics
• Colorless gas (Odor of musty hay) • Low water solubility • Higher odor threshold; poor warning properties • Vapor density 3.5 (heavier than air) • Boiling point 8.3 ºC – Can be stored in pressurized cylinders
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Video
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• Odor threshold: Phosgene 0.5 - 1.5 ppm – Olfactory fatigue • 10 min AEGL-2: 0.60 ppm – Severe symptoms • 10 min AEGL-3: 3.6 ppm – Life threatening symptoms
(AEGL= Acute Exposure Guideline Level; 3=NNN) Module Two: Inhalation of Toxic Industrial Gases 51
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Phosgene: Clinical Effects
• Limited initial symptoms – Eyes, nose, upper airways irritation – Airway spasm with high concentration • Low water solubility – delayed onset • Slow hydrolysis to HCl
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Phosgene: Clinical Effects
• Latent development of pulmonary edema – Onset 1 to 24 hours after exposure – Pulmonary function abnormalities – May be fatal • Chronic airway disease • Other possible mechanism of damage include linking molecules together and making acid.
COCl2 + 2 R-NH2 Æ CO(NH-R)2 + 2HCl
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Phosgene: Delayed Lung Injury
6 hrs post-exposure 10 hrs post-exposure
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Hydrofluoric Acid
• Known as HF • Used in # industrial processes/consumer products: – Catalyst in oil refineries – Manufacture of silicon semiconductor chips – Separating uranium isotopes – Etching glass or enamel – Cleaning brass, crystal and as a rust remover (dilute) • Production in U.S. is < 1 million tons/year • Transported as pressurized anhydrous liquid by rail
Module Two: Inhalation of Toxic Industrial Gases http://www.viewimages.com/Search.aspx?mid=1307009&epmid=1&partner=Google 55
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HF: Physical Properties
• Colorless, non-flammable- irritating odor • Fuming liquid or gas • Highly water soluble • Low odor threshold; good warning property • Weak acid (does not mean unable to harm!) – Penetrates tissue well • Boiling point 20 ºC • Vapor density 0.7 (less than air)
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HF: Clinical Effects
• Corrosive (concentration dependent): Irritating • Onset of pain and skin changes may be delayed for hours with dilute (<20%) solutions – Near instant/immediate injury with 50%+ solutions • Release of fluoride ion results in binding to calcium and magnesium – Unique and severe systemic effects – Tissue necrosis – Hypocalcemia, hypomagnesemia, hyperkalemia – Cardiac dysrhythmia and death • Small burns with concentrated HF can be fatal Module Two: Inhalation of Toxic Industrial Gases 57
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Chemical Agents of Opportunity for Terrorism: TICs & TIMs Texas City, TX Industrial Accident Releasing HF (October 31, 1987) • ~30,000 pounds of hydrofluoric acid leaked from an HF alkylation reactor drum – Convection unit was dropped on the vessel • Estimate of critical levels (AEGL3) ~3/4 mile away – ~4000 residents evacuated for 3 days – >1000 people to hospital with skin, eye, nose/throat irritation and pulmonary symptoms • No fatalities
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Chemical Agents of Opportunity for Terrorism: TICs & TIMs Prevention • Importance of plant security/ Hardening • Plant used to store 500,000 lbs HF
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Chemical Agents of Opportunity for Terrorism: TICs & TIMs Prevention • Proximity to Oakland coliseum
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Gas Summary
AGENT PHYSICAL PROPERTIES EXPECTED CLINICAL EFFECTS
H2O Odor / Vapor Mucosal / Lower Systemic Solubility Warning Density Upper Airway Airway MIC High Pungent / 1.4 Yes Possible No Inadequate methylisocyanate NH High Pungent / 0.5 Yes Possible No 3 Good Ammonia Pungent / Fair Cl2 Interm. 2.5 Yes Yes No Chlorine COCl Low Mown Hay/ 3.5 Unlikely Yes No 2 Inadequate Phosgene HF High Pungent / 0.7 Yes Possible Electrolyte & Good Cardiac Hydrofluoric Rhythm
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Participant Question
• Which chemical agent has the lowest water solubility and often the longest symptom onset time? A. Anhydrous Ammonia B. Chorine C. Hydrofluoric Acid D. Phosgene
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Treatment for Irritant Gas Exposure
• Remove from exposure • Irrigation of eyes or skin if involved – Extensive decontamination usually not necessary unless liquid exposure – Delays can impede care and have other negative effects • Oxygen • Nebulized beta-agonists (e.g. albuterol) for wheezing or dyspnea
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• National planning guidance available about decon • Recommendations based on available (minimal) evidence
http://www.dhs.gov/publication/mass-decontamination-guidance Module Two: Inhalation of Toxic Industrial Gases 64
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Treatment for Irritant Gas Exposure
• Consider adding sodium bicarbonate to nebulizer in chlorine gas exposures • Intravenous and inhaled calcium gluconate, and continuous cardiac monitoring are important for hydrogen fluoride exposure • Observe patients for late pulmonary effects, particularly in those with severe early symptoms • Concern for late pulmonary effects for agents with low water solubility agents
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Questions?
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