Chemical Warfare Agents (CWA)

Dr. Pierre Lecavalier

Department of National Defence
Defence R&D Canada Suffield
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 Military Chemical Research

Four areas of interest/concern

Detection
In order to provide the best
Protection solutions/products to counteract
the threat posed by CWA
Decontamination research must be conducted
Equipment with highly toxic chemicals.
Personnel
DRDC Suffield is the host of the
Medical Therapy Canadian National Single
Small-Scale Facility (CNSSSF)

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Location of Defence R&D Canada

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 CWA Outline

History of Chemical Warfare Agents

Categories of CWA
Routes of Entry

}
Nerve Agents
Blister Agents Chemical,physicalproperties
Signsandsymptoms
Choking Agents Medicalcountermeasures
Blood Agents

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Modern Chemical Warfare Begins
Ypres - April 22, 1915
4 mile-front

German soldiers opened the

valves of 1,600 large and
4,130 small cylinders
containing 168 tons of
chlorine

gas formed a thick white

cloud that crossed the first
allied trenches in less than a
minute

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Later Chlorine Attacks

Cylinders opened simultaneously to

provide a continuous, cone-shaped
beam of gas which could penetrate
over a narrow front deep into enemy
territory.

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Early Chemical Munitions

Livens Projectile cross

sectional view; central tube
contains explosive charge;
detonation of fuse released
approx 15kg of agent.

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 WWI Gas Use

Wounded by gas
over 1.3 million
Killed by Gas
over 91,000
Chemicals released
113,000 ton
Gas shells fired
66 million

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9
 Gas Casualties in WWI

Blinded by chlorine
Killed by chlorine
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Respiratory Protection and Training Is Essential

British WW I Respirator

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 Dr. Fritz Haber (1868-1934)
Father of Modern Chemical Warfare

From Dr. Habers Nobel

Prize Acceptance
Speech in 1919:

In no future war will the

military be able to
ignore poison gas. It is
a higher form of killing.

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 Gerhard Schrader
1903-1990
Father of Nerve Agents

Originated from
pesticide research:
1936 GA (Tabun)
1938 GB (Sarin)

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 OtherCWAUse

France and Italy in Northern Africa, 1925 and 1935

700 tons of Mustard delivered by bombs and spray devices

Japan in China, 1937

Tons of CWA left behind. Legacy problem.

Iran-Iraq (1980-88)
Mustard and nerve agents, >10000 casualties

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 Tokyo Subway (1995)

Members of the religious

group Aum Shinrikyo
released sarin (GB) on five
subway trains

12 dead, 50 severely
injured, and > 1000 with
mild symptoms

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 Chemical Warfare Agents

Toxicchemicalswhichcausedeathorinjuryto
humans

chokingagents(e.g.,phosgene,chlorine)
bloodagents(e.g.,hydrogencyanide) lethal
blisteragentsorvesicants(e.g.,mustardgas)
nerveagents(e.g.,sarin,soman,VX)
incapacitatingagents
physical
nonlethal
mental

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 Routes of Entry
Four routes of entry

inhalation
vapour
aerosol with particle size 1-5 m
skin contact
liquid droplets with particle size >70 m
vapour can also be effective (mustard gas, soman)
solids generally not effective
ingestion
injection

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 Nerve Agents
Signs and symptoms
within 1-60mins
Organophosphorus
compounds
Identified by 2 Letter
Code or by name:
GA Tabun
GB Sarin
GD Soman
GF cyclosarin
VX
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 G Nerve Agents - Characteristics

Colourless, odourless
liquid

Modest volatility
(evaporates relatively
quickly/non persistent)

High toxicity

Not easily accessible

GB(Sarin)production
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 V Nerve Agents - Characteristics

Colourless, odourless
liquid

Very low volatility

/persistent agent

Most toxic CWA

Not easily accessible

SamplingVX

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 Nerve Agents: Volatility and Toxicity
Symbol Sarin Soman Cyclosarin Tabun GA VX
GB GD GF
Freezing -56 -42 -30 -50 -51
point

Boiling Point 158 198 239 240 298

0
C

Relative 2500 440 76 55 1

Volatility

IDLH* 0.02 0.01 0.01 0.02 0.0003

(ppm)

*Immediatedangertolifeandhealth,forchlorine10ppm
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Protection

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Processes

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Purification

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 Nerve Agents
Summary

Are the most toxic CWA

V agents are extremely toxic

G agents much more volatile than V

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 Blister Agents

Purpose designed for

warfare
Also called vesicants
Less toxic than Nerve
Agents
Used primarily to inflict
mass casualties

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 Blister Agents

Types identified by Code Letter(s) or name

H sulfur mustard
HD distilled (pure) sulfur mustard
L lewisite
HN nitrogen mustard
CX phosgene oxime

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 H (Sulfur Mustard) - Characteristics
H2 H2
C S C
Cl C C Cl
H2 H2

signs and symptoms delayed 2-48 hours

normally amber to black color (HD is colourless)
garlic or horseradish odour
Freezes at +14.5oC
Relatively persistent agent
Precursor chemicals readily available
Extremely easy to prepare
One of the most difficult agents to destroy

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 L (Lewisite) - Characteristics
ClCHCH AsCl2

effects similar to mustard but more immediate and

painful
Arsenic-based therefore additional toxic threat
geranium odor
Freezes at -1.2oC
relatively persistent agent
often mixed with H (HL) to lower Freezing Point (-25oC)

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Blister Agents: Volatility and Toxicity

HD L

Freezing point (0C) 14.5 -1.2

Boiling point (0C) 217.5 196

Relative volatility
88 619
(versus VX=1)

IDLH* (ppm) 0.1 not available

*Immediatedangertolifeandhealth,VX=0.0003ppm,chlorine10ppm
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 Blister Agents Summary

More likely to cause casualties than deaths

Important characteristics of H
delayed symptoms (2-48 hrs)
freezes at 14oC
Garlic odour

Important characteristics of L
immediate pain
Freezes at -1oC
Geranium odour
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 Choking Agents

Industrial chemicals

Chlorine (Cl) water

purification, bleaching

Phosgene (CG) plastics

manufacture

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 Chlorine (Cl) - Characteristics

Greenish-yellow gas stored in pressurized tank

Odour of bleach, immediate irritation to eyes

Heavier than air

Gas will dissipate quickly, but may remain in

depressions

Can be made using a combination of cleaning

products

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 Chlorine Signs and Symptoms

Attacks lung tissue, powerful irritant; can cause pulmonary

edema within one hour.
Low exposures: immediate ocular & nasal irritation followed
by coughing & choking sensation
Pulmonary edema involves fluid accumulation and swelling
in the lungs.

Treatment
Immediately remove casualty from gas exposure.
Supportive treatment only.

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 Phosgene (CG) - Characteristics

Colourless gas (boiling point 8.2oC), stored

in pressurized tank

Weak odour of freshly cut hay, no

immediate symptoms

Heavier than air

Gas will dissipate quickly, but may remain

in depressions

Causes pulmonary edema

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 Choking Agents Summary

Industrial chemicals

Stored in gas cylinders

Gas will dissipate quickly, but may remain in depressions

Chlorine strong, immediate irritant

Phosgene insidious: no colour, weak odour, no immediate

symptoms

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 Blood Agents

Industrial chemicals

hydrogen cyanide - AC

cyanogen chloride - CK

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 Blood Agents (Source of cyanide)

Hydrogen cyanide AC
Colourless, bitter almond smelling, volatile liquid (bp 26oC)
Flammable
Product of burning nitrile based plastics

Cyanogen chloride CK
Colourless, pungent smelling, liquid or gas (bp 13oC)
Can explosively polymerize

Sodium or potassium cyanide (salts)

Can be mixed with acid to generate AC

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 Blood Agents

Primary inhalation hazard, secondary percutaneous hazard

Acts by inhibiting the enzyme cytochrome oxidase
Respiratory failure is the usual cause of death
in high concentrations, a few breaths may cause death
Supportive therapy can effect the recovery of most casualties
Specific antidotal therapy
sodium nitrate and sodium thiosulfate (IV)

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 Blood Agents Signs and Symptoms

Effects:
Lower Concentrations Higher Concentrations
Weakness Increased depth of
respiration
Vertigo, dizziness
Violent convulsions
Headache, nausea
Coma and cardiac failure
Convulsions and loss of
consciousness

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 Blood Agents Summary

Industrial chemicals (metal processing, plastics

manufacture)

highly volatile, non-persistent

stored in gas cylinders

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 Incapacitating Agents

Most incapacitants are solid

Disseminated pyrotechnically for large scale use

Value of an incapacitating agent lies in the safety margin (ratio):

Ratio (difference) between the lethal dose (LD)

and the incapacitating dose (ID)

ID
lethal agent
LD

ID
Incapacitating agent
LD
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 Incapacitating Agents

Physical Incapacitant

Vomiting Agents
DA, DC, DM

Tear Agents
CS
CN

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 Riot-Control Agents

Irritants, Lachrymators, and Tear Gas

Physical Incapacitant
Mainly solids dispersed as aerosols
Restricted to law enforcement / civilian use

Generally irritate eyes, skin & mucous membranes.

Rapid action and quick end to symptoms post-exposure.
Wide safety margin for use.

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 Riot-Control Agents
O
Cl
N
C Cl CH C HO CH2 R
CH2 C
NH C
C O O
N CH3

CN CS OC

Three Main Agents

CN ICt50 50 mg.min/m3
LCt50 11000 mg.min/m3
CS ICt50 10-20 mg.min/m3
LCt50 10K-60K mg.min/m3
OC ICt50 N/A
LCt50 N/A
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 Incapacitating Agents

Mental Incapacitant

chemicals that produce temporary and non

lethal impairment of performance and
perception by virtue of its
psychobehavioral or CNS effects.

primarily inhalation hazard

secondary ingestion hazard (as food/water
contaminants), injection hazard,
percutaneous hazard

e.g. BZ, LSD, fentanyls

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 BZ: 3-quinuclidinyl benzilate

OH
O
N
O

odorless, non-irritating white solid

relatively easily synthesized
inhalation hazard
normally disseminated as a smoke
stable, persistent in soil and water
~ 4 hours for symptoms to develop, persist for days
ID50 = 0.5 mg/70 kg person (LSD .2 mg, atropine 9.8 mg)

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 Novel Incapacitants
Fentanyl and its analogues

Opioid

Fentanyl analgesicsareexceptionallypotentmorphine
likecompounds
developedbyJanssenPharmaceutica in1960s1970s
upto~10,000xmorphine

Analogues can be multiple times more potent

Dosages measured in thousandths of grams

ID50 (man) 2-3 mg/kg i.v.
LD50 (man) ~11 mg/kg i.v.

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 Fentanyls

SyntheticHeroin

Commonlyusedinmedicineasanesthetic

Effectsinanimalsandmaninclude
analgesia
respiratorydepression
sedation/hypnosis
immobilisation
death(fromrespiratorydepression)

WellknownantidoteNaloxone /Naxolone (Narcan,Nalone,Narcanti)

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 Fentanyls

MoscowTheatreSiege

October23,2002:Approx.50Chechenterroristsheld~800hostagesinaMoscowTheatre

October26:RussianSFusedanaerosolisedagenttorendermostoftheoccupants
unconscious
129hostagesdieddirectlyorindirectlyasaresultoftheagent
further40deathsreportedsince

October30:RussianHealthMinisterconfirmeduseofafentanyl
twoRussiansourcessuggestedtrimethylfentanyl believedtomeancis3
methylfentanyl

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Indicators of CWA Production

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Indicators of CWA Production

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Indicators of CWA Indicent

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Indicators of CWA Indicent

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 CWA Theory Review

What are the 4 categories of CWAs?

Which of the four types is the most toxic?
Which of the four types would inflict mass
casualties vs mass fatalities?
For which CWAs are there no medical
counter measures?

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