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Socratescbw2.Pdf Principles of Environmental Toxicology Imponderabilities “The decisive battles of any war are not won by the physical destruction of the enemy but by psychic imponderabilities which induce them in a decisive moment to lose the will to fight and to feel defeated.” –Fritz Haber The Socrates Award Lecture Chemical and Biological Warfare Agents Eric Croddy Monterey Institute of International Studies Center for Non Proliferation Studies CBW Non Proliferation Project Principles of Environmental Toxicology Principles of Environmental Toxicology Chemical Warfare (CW) Agent Categories Ypres, Chlorine Gas attack, April 1915 CW agent type Example • Lung irritants • Phosgene Cl2 + H2O • Vesicants • Mustard, Lewisite HCl + HOCl •Blood (systemic) • Cyanide •Nerve •Sarin • Harassing • Tear gas – Riot Control • Psychoincapacitants •BZ • Herbicides • Agent Orange • Olfactory agents • Skunk: Skatole (!) Principles of Environmental Toxicology Principles of Environmental Toxicology Bleach, Ammonia and Terrorism World War I • Chloramines (NH2Cl, NHCl2) are generally • The following CW agents were more toxic than chlorine gas. responsible for most casualties in • Under some conditions, World War I: chlorine gas can be – Chlorine (Cl2) High mortality produced from civilian – Phosgene High mortality products. – Mustard High morbidity 1 Principles of Environmental Toxicology Principles of Environmental Toxicology Physical Properties Comparative Toxicities CW agent Toxicity, inhalation At least as important as toxicity in chemical warfare. 3 (LCt50) mg x min/m 3 Hydrogen cyanide* 2,500-5,000 CW agent Volatility, mg/m Sarin (GB) 100 Hydrogen cyanide 1,000,000 Sulfur mustard (HD) 1,500 Sarin (GB) 22,000 VX 10 Sulfur mustard (HD) 900 VX 10 *oddball Principles of Environmental Toxicology Principles of Environmental Toxicology Hydrogen Cyanide Blood agent NaCN or KCN + H2SO4 = Bad news About 10-20% of adults have a hereditary inability to detect the characteristic odor. Principles of Environmental Toxicology “Sour Gas” The Ku Klux Klowns… Wise County, Texas Hydrogen Sulfide (H2S)* *Or, the case that wasn’t… 2 Principles of Environmental Toxicology Principles of Environmental Toxicology Hydrogen Sulfide: Highly Toxic Flammable Gas Tanks H2S = Blood agent, similar toxicodynamics to cyanide poisoning TLV-TWA Hydrocyanic acid 10 ppm (11 mg/m3) Hydrogen sulfide 10 ppm (14 mg/m3) Compare: Methyl isocyanate 0.02 ppm (0.047mg/m3) Principles of Environmental Toxicology Principles of Environmental Toxicology Vessicants • Mustard (sulfur, nitrogen) • No evidence that the Wise County – “King of CW agents” until nerve gas agents conspirators ever intended to release appeared in 1937. toxic gas. • Lewisite – Extremely nasty. – Not used much (yet). Principles of Environmental Toxicology Principles of Environmental Toxicology Blister Agents (Vesicants) Sulfur Mustard: Vesicant CH2 CH2 Cl H Cl S Cl C C As CH2 CH2 Cl H Cl Sulfur mustard Lewisite CH2 CH2 Cl N CH2 CH2 Cl CH2 CH2 Cl Nitrogen mustard 3 Principles of Environmental Toxicology Principles of Environmental Toxicology Sulfonium Ion Formation Base Reaction O CH2 CH Cl CH2CH2SCH2CH2Cl 2 CH2 S + N S CH HN + 2 C CH2 CH2 Cl CH2CH2Cl N Sulfur mustard H2N Sulfur adjunct Guanine Guanine CH2 Sulfonium ion O + Cl- O CH2CH2S+ CH2 N + HN HN N + CH2 S CH2 + C C N Sulfonium ion CH2CH2Cl N H2N H2N formed again… Principles of Environmental Toxicology Principles of Environmental Toxicology Mustard Toxicity: Two views? This can only spell trouble…. Choose your poison: or: O CH2CH2SCH2CH2 O DNADNA Glutathione N + Alkylationalkylation reactions HN N NH C C Denaturing of N N DNA H2N NH breaks Transcription thiol proteins 2 and protein synthesis Loss of Guanine Guanine Poly (ADP- inhibition calcium ribose) polymerase Lipid peroxidation, Cross linking of DNA (G-G) Phospholipases and membrane damage activated nucleases disinhibited Glycolysis Cell stops, loss Autolysis death of ATP Principles of Environmental Toxicology Principles of Environmental Toxicology Cell Death by Mustard (Sulfur) Mustard: Burns Alkylation of DNA Depurination DNA of DNA Breaks Active poly (ADPRibose) - polymerase Enzyme Cellular activation NAD+ depletion Hexose monophosphate Release of Inhibition of shunt activation proteases Mustard burns begin glycolosis with redness and itching. 4 Principles of Environmental Toxicology Principles of Environmental Toxicology Compare with Diphtheria Pathology Mustard: Airway Blockage Pseudo-membrane formation - probably worst outcome. Principles of Environmental Toxicology Principles of Environmental Toxicology Mustard: Eye Injury July 1917, Ypres, Belgium Eye injury is serious, Most of these men would be fit for duty but not necessarily permanent . after a few months. Principles of Environmental Toxicology Principles of Environmental Toxicology Long Term Ocular Sequelae Mustard Toxicity Summary • Exposure to 100 mg x min/m3 of sulfur “Single exposures, even if severe, as in mustard vapor causes acute blindness military service, are not associated with for 24-48 hours. statistically verifiable increases in mortality • Permanent blindness usually from tuberculosis and cancer; but repeated occurred about 14 years small exposures, such as occur after acute corneal in industrial operations, do injury by mustard. increase cancer deaths significantly.” National Research Council Possible Long-Term Effects of Short-Term Exposure to Chemical Agents Volume 2, 1984, p128. 5 Principles of Environmental Toxicology Principles of Environmental Toxicology Lewisite Lewisite: Toxicity Mechanisms H Reactions with Glutathione sulfhydryl groups of reactions Cl enzymes Cl C C Denaturing of As thiol proteins Inhibits pyruvate dehydrogenase Cl complex Loss of H calcium Glycolysis inhibited Lipid peroxidation, Toxicity data limited to membrane damage mostly animal studies. ATP loss, Cell cell death death Principles of Environmental Toxicology Principles of Environmental Toxicology Mustard/Lewisite Mixture Spray Tank Mustard Munition 500 kg, approx.168 kg fill 1,500 kg Aerial Munition Mustard/Lewisite 636 kg fill Principles of Environmental Toxicology Principles of Environmental Toxicology Nerve Agents Nerve Agents Soman (GD): A bad actor, even among other nerve agents O CH3 P F Leaving group O CH3 CHAging group CH3 C CH3 CH3 O Aging O P Leaving group F group CH3 GF (cyclosarin): Not far behind 6 Principles of Environmental Toxicology Principles of Environmental Toxicology V-Agents (VX, V-gas, etc.) Inhibition of Acetylcholinesterase VX (US) CH3 Nerve agent (sarin) O CH CH3 CH3 CH2 OSP CH2 CH2 N CH3 CH3 CH CH CH3 3 Leaving O P O C H (Sarin) group CH3 F CH3 CH3 CH O OH 3 CH2 OSP CH CH2 CH2 CH2 N (Serine) anionic site CH CH3 CH3 2 CH3 Soviet V-gas Acetylcholinesterase (AChE) Principles of Environmental Toxicology Principles of Environmental Toxicology AChE Inhibition, cont’d Soman: Notoriously “age prone” CH Phosphoryated CH CH resistance to 3 3 3 Aged hydrolysis CH3 OH CH C CH enzyme O P O C H (Sarin) enzyme 3 (Sarin) O PO CH 3 CH O 3 HF CH3 O (Serine) anionic site (Serine) anionic site Acetylcholinesterase (AChE) Acetylcholinesterase (AChE) Principles of Environmental Toxicology Principles of Environmental Toxicology Nerve Agent Intoxication V-gaz Neuromuscular Autonomic CNS V-gaz was thickened • Twitching • Reduced Vision • Headache further by the • Weakness • Small pupil size •Convulsions Soviets, with methyl • Paralysis • Drooling •Coma methacrylate • Respiratory failure • Sweating • Respiratory arrest polymer… • Diarrhea • Confusion • Nausea • Slurred speech SCUD-type warhead, 555 kg • Abdominal pain • Depression • Respiratory thickened VX (VR-55) fill. depression 7 Principles of Environmental Toxicology Principles of Environmental Toxicology Making Demil: More Complicated US Chemical Field Doctrine (cr. 1950s) CH3 CH O “The coverage of a target to a dosage of 100 mg- 3 CH2 CH CH OSP CH CH N 3 2 2 2 min/m (the LCt50) has not been considered, since the CH CH3 CH3 2 total casualties resulting therefrom can be largely in CH3 Soviet V-gas excess of that required to achieve the desired effect +K -O CH 2 CH CH3 + HO CH2 CH CH3 75% + on target. Logistically, it is more desirable to achieve CH3 CH3 Potassium isobutyrate this effect on target with the minimum Isobutyl alcohol expenditures. Therefore, coverages N-methyl pyrrolidinone 25% of targets to a dosage of only N CH3 3 50 mg-min/m (the ICt50) have CH3 CH3 been calculated.”— CH2 CH3 +K - O PO CH2 CH S CH2 CH2 N + Dept. of the Army, Air Force O “Capabilities and Employment CH2 CH3 CH3 of Toxic Chemicals” CH2 October 13, 1958, p36. CH3 CH CH3 Principles of Environmental Toxicology Principles of Environmental Toxicology 1958: 105 mm Sarin Howitzer Shell Honest John Warhead w/ Sarin Bomblets Target Area Coverage Calculation Table Principles of Environmental Toxicology Principles of Environmental Toxicology US MLRS Chinese MLRS US M55 Rocket (GB, VX) Multiple Launch Rocket System Video still photograph, 1979 Sino-Vietnamese war. Probably a precursor to the Type 83, 24-round, Chinese multiple launch rocket system (122mm), or a variant of the BM21. 8 Principles of Environmental Toxicology Principles of Environmental Toxicology Binary Shells Mixing Munition Left: Chinese depiction of a binary (nerve) shell. Below: the US M687 binary (GB) howitzer shell. 1. Conical warhead 2. Agitation/mixing device 3. Mixing blade 4. Mixing chamber 5. Fill spout 6. Belt cable 7. ‘A’ Component section 8. ‘B’ Component section 9. Spray pipe 10. Dissemination device/aperture* Principles of Environmental Toxicology Principles
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