9/11/15 Chemical Agents of Opportunity for Terrorism: TICs & TIMs Module Two: Toxic Industrial Gases Mark Su, MD 1 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 Module Two: Inhalation of Toxic Industrial Gases 2 Chemical Agents of Opportunity for Terrorism: TICs & TIMs Faculty Disclosure • Faculty: Mark Su, MD – Relationships with commercial interests: none – Speakers Bureau/Honoraria: none – Consulting Fees: none – Other: none Module Two: Inhalation of Toxic Industrial Gases 3 1 9/11/15 Chemical Agents of Opportunity for Terrorism: TICs & TIMs Please help us improve this course by filling out the module evaluation. 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Module Two: Inhalation of Toxic Industrial Gases 4 Chemical Agents of Opportunity for Terrorism: TICs & TIMs 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 Module Two: Inhalation of Toxic Industrial Gases 5 Chemical Agents of Opportunity for Terrorism: TICs & TIMs 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 Module Two: Inhalation of Toxic Industrial Gases 6 2 9/11/15 Chemical Agents of Opportunity for Terrorism: TICs & TIMs 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 Module Two: Inhalation of Toxic Industrial Gases 7 Chemical Agents of Opportunity for Terrorism: TICs & TIMs 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 Module Two: Inhalation of Toxic Industrial Gases 8 Chemical Agents of Opportunity for Terrorism: TICs & TIMs 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 Module Two: Inhalation of Toxic Industrial Gases 9 3 9/11/15 Chemical Agents of Opportunity for Terrorism: TICs & TIMs 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 Module Two: Inhalation of Toxic Industrial Gases 10 Chemical Agents of Opportunity for Terrorism: TICs & TIMs Bhopal Module Two: Inhalation of Toxic Industrial Gases 11 Chemical Agents of Opportunity for Terrorism: TICs & TIMs 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) Module Two: Inhalation of Toxic Industrial Gases 12 4 9/11/15 Chemical Agents of Opportunity for Terrorism: TICs & TIMs 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 Module Two: Inhalation of Toxic Industrial Gases 13 Chemical Agents of Opportunity for Terrorism: TICs & TIMs 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* Module Two: Inhalation of Toxic Industrial Gases 14 Chemical Agents of Opportunity for Terrorism: TICs & TIMs 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 Module Two: Inhalation of Toxic Industrial Gases 15 5 9/11/15 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 Module Two: Inhalation of Toxic Industrial Gases 16 Chemical Agents of Opportunity for Terrorism: TICs & TIMs 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 Module Two: Inhalation of Toxic Industrial Gases 18 6 9/11/15 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 Module Two: Inhalation of Toxic Industrial Gases 19 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*) Module Two: Inhalation of Toxic Industrial Gases 20 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 Module Two: Inhalation of Toxic Industrial Gases 21 7 9/11/15 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 Module Two: Inhalation of Toxic Industrial Gases 22 Chemical Agents of Opportunity for Terrorism: TICs & TIMs Comparative Toxicity Of Likely Terrorist Industrial Gases Ammonia > Phosgene • Ammonia AEGL3 = 1600 ppm Phosgene > Ammonia • Phosgene AEGL3 = 1.5 ppm Module Two: Inhalation of Toxic Industrial Gases 23 Chemical Agents of Opportunity for Terrorism: TICs & TIMs 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 Module Two: Inhalation of Toxic Industrial Gases 24 8 9/11/15 Chemical Agents of Opportunity for Terrorism: