Understanding the Threat from Common Toxic Chemicals. George R. Famini, PhD Director Chemical Security Analysis Center

Transcription

1 Understanding the Threat from Common Toxic Chemicals George R. Famini, PhD Director Chemical Security Analysis Center

2 CSAC is a Force Multiplier for the Homeland Security Enterprise Core Capability Generate Products Impacts Homeland Security 2

3 Is There a Threat From Chemicals? Chemical Uses/Misuse are in the news every day (25-30 S articles/day) Toxic Industrial Chemicals are pervasive and commonly available Toxic Inhalation hazards transported every day Accidents involving TICs happen Common household products can be used to make toxic chemicals Events in Syria/Iraq is driving awareness up Chemical releases continue to occur Although focus still on Chlorine and Sulfur Mustard, other chemicals have been used 3

4 Chemical Incidents in the News Incidents involving chemicals are in the news Foreign reporting is mostly focused on ISIS Many accidents involving mineral acids Pesticides used ( both intentional and accidental) growing Chemical Topics July Chemical Topics August Domestic Foreign Few reports concerning domestic intentional uses Individual acid attacks Acetone/bleach and chemical suicides Foreign reporting concerned mostly with terrorism focused Domestic Foreign From CSAC s Daily Reporting, July and August

5 Recent Chemical Weapons Incidents Iraq Chlorine Attacks, Chlorine 1-ton containers and cylinders Approximately 15 attacks Attacks in Syria, Iraq Chlorine 1-ton containers Chlorine Barrel Bombs Continues to occur Recent attack purported to kill 7 Mustard attacks in Iraq riginally crude preparations Becoming more stable Unconfirmed casualties Methyl Parathion has been used (at least twice) to injure/kill students in Afghanistan schools ther chemicals have been used elsewhere in Middle East, unsuccessfully 5

6 Considering the Threat Most focus is aimed at inhalation threats, but Ingestion, especially classical poisons Certain threats (organic arsenicals, mineral acids, mustards) pose significant dermal threat At present, availability of toxic industrial chemicals make them the most likely agent of choice The most likely used are also the mostly commonly transported or purchased Venue/location must also be considered in identifying chemical threats of interest High BP (low volatility) chemicals are usually not inhalation hazards (but may be ingestional or dermal threats) Solubility and stability based properties will influence threats in food 6

7 CTRA 4.0- A Complex Set of Scenarios 185 chemicals - including pesticides, TICs, CWAs and other chemicals of high concern that may be obtained from 2 locations - foreign or domestic via 4 methods of acquisition - production, theft, purchase or chemical supply chain 6 target classes - Indoor, utdoor, CSC, Food, Water, Dermal, consisting of 37 targets 13 dissemination techniques 3 kinds of terrorist groups - International, Domestic, and Small Groups/Individuals 3 exposure routes - inhalation, ingestion and dermal leading to 3 public health consequences - life threatening, severe, mild/moderate injuries and worried well Economic consequences - health care, loss of life, loss of use, decontamination costs, secondary effects 7

8 CTRA 4.0 Compounds Bold-CSC chemicals Yellow-new CTRA 4.0 Chemical Name CAS N Chemical Name CAS N Chemical Name CAS N Chemical Name CAS N 2,4-Dinitrophenol Chlorine Hexafluoroacetone Phosgene (CG) Butanone peroxide Chloroacetone Hydrazine Phosgene oxime (CX) fluoroethanol Chloroform Hydrogen bromide Phosphamidon isocyanatopropyltriethoxysilane Chloromethyl methyl ether Hydrogen chloride Phosphine quinuclidinyl benzilate Chloropicrin (PS) Hydrogen cyanide Phosphorous oxychloride aminopyridine Chlorosarin Hydrogen fluoride Phosphorous trichloride Acrolein Chlorosoman Hydrogen selenide Picrotoxin Acrylonitrile Chlorosulfonic Acid Hydrogen sulfide Potassium cyanide Adamsite (DM) chlorotrimethylsilane Hydroxyacetonitrile Propionitrile Aldicarb Chlorpyrifos Isobutyronitrile Propyleneimine Allyl Alcohol Cyanogen Chloride (CK) Isopropyl chloroformate R-33 (R-VX) Aluminum phosphide Cyclohexyl isocyanate Lewisite (L) Sarin (GB) Ammonia, anhydrous Cyclohexylamine Malononitrile Sodium arsenite Ammonium metavanadate Cyclosarin (GF) metham-sodium Sodium azide Anatoxin Diacetylmorphine Methanesulfonyl chloride Sodium fluoride Aniline Diborane Methanesulfonyl fluoride Sodium fluoroacetate Aq. Chlorine dioxide Dicrotophos Methanethiol Sodium selenate Aq. Hydrochloric acid Diisopropylfluorophosphate Methomyl Soman (GD) Aq. Hydrogen fluoride Dimethyl mercury Methyl acrylonitrile Strychnine Aq. Ammonia Dimethyl sulfate Methyl fluoroacetate Sulfotep Arsenic Trichloride Diphacinone Methyl hydrazine Sulfur dioxide Arsenic trioxide Diphenylchloroarsine Methyl isocyanate (MIC) Sulfur mustard (HD) Arsine (SA) Diphenylcyanoarsine (DC) Methyl thiocyanate Sulfur tetrafluoride Benzenethiol Diphenylcyanoarsine (DC) Methyl vinyl ketone Sulfur trioxide Bifenthrin Disulfoton Methylphosphonic difluoride (DF) Tabun (GA) bis(chloromethyl)ether Disulfur dichloride Methyltrichlorosilane Tetrachlorosilane Boron trichloride Epichlorohydrin N-Ethylmaleimide Tetraethyl pyrophosphate (TEPP) Boron trifluoride Ethyl chloroacetate Nicotine Tetraethyllead Boron trifluoride Ethyl chloroformate Nitric acid (conc.) Tetrafluorosilane Boron trifluoride etherate Ethyl dichloroarsine (ED) Nitric oxide TETS Brodifacoum Ethyl isocyanate Nitrogen Mustard Thallium sulfate Bromadiolone Ethyl nitrite leum Thiophosphoryl chloride Bromine Ethylene xide smium tetroxide Titanium tetrachloride Bromomethane Ethylenediamine Paraquat dichloride Tungsten hexafluoride Bromopropyne Ethyleneimine (Aziridine) Parathion Vanadium Pentoxide Cadmium oxide Fluorine Pentacarbonyliron VG (AMITN) Caffeine Fluoroacetamide Perchloromethylmercaptan VM (EDEM) Carbofuran Formalin Perfluoroisobutylene VX Carbon disulfide Hexachlorocyclopentadiene Phenyl isocyanate Ziram (HEX) Chlorfenvinphos Phorate α,α-dimethyl benzyl Hydroperoxide

9 CTRA Target Classes and Targets Major Target Representative Targets Major Target Representative Targets Indoor (Theft and Diversion Scenarios for TIH) Chemical Supply Chain Cruise ship Airplane Subway Museums Hospitals ffice Buildings Airport terminal Shopping Mall Religious Center Legislative Building Theaters Arenas Railcar Bulk highway Non-bulk Highway Barge Pipelines Chemical plant Food Representatives selected from 55,000 foods that were analyzed and clustered by like characteristics utdoor (Theft and Diversion Scenarios for TIH) MWS consumption and dermal Dermal Processed cheese Frozen egg patties Milk Bagged Salad Apple juice Ground beef Frozen meat pizza Grapes Seasoned chips Tomato sauce Bottled water Stadium Urban center Urban event Apartment back flush Hydrant back flush Railing Hand cleanser 9

10 Examples of Classes to Consider Pesticides Toxic Industrial Chemicals Chemical Warfare Agents Pharmaceuticals VX Sulfur Mustard Cl 2 HCN TETS Phorate Diacetyl morphine Carbaryl (Sevin) Nitrogen Mustard Methylcyclohexyl Methanol Sarin 10

11 Household Products are Dangerous Commonly available materials can be used to generate toxic inhalation hazards Some materials are toxic themselves NH 4 H + HCl NH 3 H 3 C CH 3 + NaCl CHCl 3 CaS + HCl H 2 S AlP + H 2 /HCl PH 3 HCl + NaCl Cl 2 NH 4 H + NaCl NCl 3 11

12 Most likely Process to Manufacture Sarin Employs precursors and reagents manufactured and sold domestically in bulk quantities. CH 3 P CH 2 CH 3 CH 2 CH 3 Diethyl methylphosphonate SCl 2 CH 3 P Cl Cl Methylphosphonic dichloride CH 3 H NaF CH 3 CH 3 P CH 3 P F F Methylphosphonic difluoride Medium Low Low F CH 3 CH 3 Sarin, GB Chemicals purchased from commercial sources to make Sarin 12

13 Simple Synthesis of ther CWAs Cl Na 2 S H S H HCl or SCl 2 Cl S Cl H 2 - Chloroethanol Sudium sulfide Thiodiglycol Hydrochloric Acid Sulfur Mustard or Thionyl Chloride H 1 mole H 2 N S NH moles H 2 C formaldehyde sulfamide acid catalyst Cl N S N S N N TETS N H H triethanolamine + 3 moles S Cl Cl Cl N Cl + 3S2 + 3HCl thionyl chloride tris ( 2 - chloroethyl) am ine 13

14 Acquisition of Laboratory Equipment for Preparation of Chemical Warfare Agents Sophisticated laboratory equipment is NT needed for the manufacturing of Sarin and Sulfur Mustard. Typical equipment needed for the preparation of Sarin and Sulfur Mustard are shown below and are available on ebay for $ 3 K to $ 4 K. Simple glassware for preparation of Sarin and Sulfur Mustard Reactions can be carried out safely in inexpensive fume hoods. Simple glassware for purification of Sarin and Sulfur Mustard Inexpensive heating mantles are sufficient. 14

15 What Chemicals are Highest Domestic Risk? Depends on target/route of exposure TICs are of concern Higher likelihood of occurring, easier to acquire Will likely not yield high consequences (fatalities) Will cause disruption Examples are: Chlorine, Hydrogen Cyanide and Cyanide salts (Na and K) Chlorine is still being used in the Middle East; typically lower fatalities (but some have been reported) Methyl Parathion has been used at a girl s school in Afghanistan (2X) Sulfur Mustard (bis 2 chloroethyl sulfide, HD) is being used more in Middle East; could be possible to use domestically; will generate large numbers of non-lethal casualties, fewer fatalities Nerve Agents (most G agents) have not been in the news; significantly higher learning curve ; more difficult to make/acquire 15

16 What Threats Can We Mitigate? At present, most commercially available detectors are point detectors only; very little standoff capability This requires more detectors, even in single venue Good chance the cloud will miss a detector Most detectors will not work for all of the highest threats Major weakness is the quality of the libraries (and the proprietary nature) Most detectors will work only for a limited number of chemicals Different detectors will be required to detect the range of chemical threats Sample introduction continues to be a challenge, especially for aerosols 16

17 Jack Rabbit II - verview Problem: DHS and its partners and stakeholders in the HSE must better understand behavior and consequences of large-scale chlorine releases. Millions of tons of chlorine, a potent toxic inhalation hazard (TIH), are shipped annually through highly-populated areas Transported in bulk as a pressurized, liquefied gas via road, water, rail An accidental or intentional release can rapidly generate a lethal vapor cloud Hazard prediction models are not consistent with the evidence, data, and observations from previous fatal chlorine disasters Rapid Cl 2 releases have never been tested at operationally-relevant scales Critical knowledge and data gaps exist for source terms and other phenomena relevant to modeling and emergency response There is insufficient understanding, knowledge, and documentation of large-scale chlorine releases to properly inform, train and prepare emergency responders 2010 Jack Rabbit 1-2 ton chlorine trials identified phenomena and scaling factors that required additional testing. 17

18 Jack Rabbit II - Trials Large-scale chlorine release field trials in to fill critical data and knowledge gaps for improved modeling and emergency response. 5 successful trials in 2015: 5-9 tons Cl 2 5 additional trials in 2016: tons Cl 2 Tracking downwind cloud and concentration to 7+ miles Quantifying source term parameters Simulated urban test grid to study effect of buildings Building infiltration and shelter-in-place studies Emergency vehicles and equipment exposure testing Studies of Cl 2 reactions with environment and surfaces 18

19 Summary The primary concern for a domestic attack with chemical threat materials continues to be commonly available toxic industrial chemicals If an attack were to occur with chemical warfare agents (sarin, soman, tabun, VX), the casualties (fatalities) will be very high. The probability of this occurring is still considered very small. The use of Chlorine and Mustard in the Middle East continues to raise the probability that a similar attack might occur in Europe (most likely) or the US. The optimal chemical for use will depend on the venue/scenario. However, there are multiple possible venues that may be considered, and several routes of exposure that may be employed. Cl 2 Chlorine Phorate Sarin 19

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