Background

Introduction
A review of chemical agents and tear gases
Application of chemical agents in the context of armed
conflict is as old as organized warfare. Examples frequently cited are the use of poisoned
arrows and various kinds of irritant, toxic, or hypnotic smokes.
In the war between Athenians and Spartans (431 - 404 BC), a
chemical compound was developed consisting of wood saturated with sulphur and pitch and
burned under the walls of besieged cities in order to generate choking fumes. In the war
of Constantine against the Saracens in 673 AD, a compound known as "Greek Fire"
was composed of sulphur, quicklime, pitch, resin, and petroleum. This was a flaming
mixture, usually delivered against the enemy by means of syringe-like objects having the
form of dragons and other monsters with widely opened jaws. It was also used by the
Saracens against the Christians during the Crusades.
Chemical weaponry was first used in the United States in
the Civil War at the siege of Charleston. Wood was saturated with sulphur and burned under
the parapets around the city hoping that favorable winds would propel huge clouds of
choking smoke to drive out the defenders.
French law enforcement is reputed to have been the first
police organization to have used a chemical lacrimator (tear-producing) in a hand-thrown
device. At the start of World War I (1914-1918) the French Army had limited stocks of hand
and rifle grenades, loaded with a liquid tear-producing agent called Ethylbromacetate.
Scarcely a week goes by without press reports of tear gas
being used in a public setting, typically the dispersal of demonstrators or the subduing
of a barricaded criminal. Recent years have seen the use of large amounts of tear gas in
several countries including Chile, Panama, South Korea, and Israel. Some 15 chemicals have
been used worldwide as tear gas agents. Four of these Chloroacetophenone (CN),
O-chloro-benzylidene-malononitrile (CS), 10-chloro-5, 10-dihydrophenarsazine, and
bromo-tolunitrile have been used extensively. In the United States, Britain, and Europe,
CN and CS have been employed most widely.
The highlighted agents above are described in detail
in following pages since they are the most widely known and, historically, most widely
used agents.
Health Hazards and Toxicology of Chemical Agents
Most of the lacrimator and the common blistering agents are
alkylating agents, tending to attach themselves to atoms such as oxygen, nitrogen, and
sulfur. All three of these atoms occur in proteins, and oxygen and nitrogen are found in
nucleic acids - both DNA and RNA. Once proteins (enzymes) or nucleic acids become
alkylated, they are generally unable to function normally; the ultimate result may vary
from a mild irritation to cancer. Thus, alkylating agents have been implicated as the
causative agents in carcinogenesis, mutagenesis, and teratogenesis1.
CS (Orthochlorobenzylidenemalononitrile) for example is an effective alkylating agent because
the two strongly electron-withdrawing nitrile (CN) groups,
reinforced by the chlorobenzene ring, place a positive charge on the bridge carbon atom.
The result is a hyperactive bridge carbon that can be attacked directly with nucleophilles
such as water or thiol groups.
Toxicological Terminology
While studying the chemical agents, it is important to
understand the hazardous effects of these agents on humans and animals. The following are
basic toxicological terminologies:
LD50: Lethal Dose 50, also called
"Median Lethal Dose", is the quantity of a chemical compound that, when applied
directly to test organisms, is estimated to be fatal to 50% of those organisms under the
stated conditions of the test by any route other than inhalation. LD50 is usually
expressed as milligrams or grams of material per kilogram of animal weight (mg/kg or g/kg,
where 5000 mg = 5g = 1 teaspoonful). The phrase "Rat, Oral, LD50 : 200 mg/kg"
for example means that 200 milligrams of the chemical per each kilogram of body weight is
the lethal dose that killed 50% of a group of test rats. These data are used to help
establish the degree of hazard to man.
1 "Harvest of Death", by J.B. Neilands &
Gordon H. Orians. Published by "Collier-Macmillan Limited", London, 1972.
LC50: Lethal Concentration 50, also called
"Median Lethal Concentration", is the concentration of a material in air
(air-borne) that is expected to kill 50% of a group of test animals when administered as a
single exposure in a specific time period, usually 1 hour through inhalation and
respiratory route. The LC50 is expressed as parts of material per million parts of air, by
volume (ppm) for gases and vapors, as micrograms of material per liter of air, or
milligrams of material per cubic meter of air (mg/m3) for dusts and mists, as well as for
gases and vapors.
TLV: Threshold Limit Value, refers to
airborne concentrations of substances and represents conditions and levels under which it
is believed that nearly all those exposed repeatedly, day after day, will experience no
adverse health effects.
ICt50: Median incapacitating dosage. This
is the concentration of chemical multiplied by the time (duration) of exposure that will
affect 50% of an exposed population.