TERRORISM, TOXICITY, AND VULNERABILITY: CHEMISTRY IN DEFENSE OF HUMAN WELFARE

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CHAPTER 13 TERRORISM, TOXICITY, AND
VULNERABILITY CHEMISTRY IN DEFENSE OF HUMAN
WELFARE
From Green Chemistry and the Ten Commandments of
Sustainability, Stanley E. Manahan, ChemChar
Research, Inc., 2006 manahans_at_missouri.edu
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13.1. VULNERABILITY TO TERRORIST ATTACK
Chemicals harming people in terrorist attacks and
accidents Explosive mixture of ammonium nitrate
(a common agricultural fertilizer) and diesel in
the attack on the Alfred P. Murrah Oklahoma City
Federal Building in 1995 Explosives used by
suicide bombers in the Middle East Methyl
isocyanate in the industrial chemical accident in
Bhopal, India, in 1984 Almost 200 killed by
hydrogen sulfide in natural gas released
Chuandongbei natural gas field of southwestern
China in December, 2003
Environment susceptible to terrorist attack
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Protection With Green Chemistry
Green chemistry to mitigate terrorist
threats Uses the safest possible chemicals as
safely as possible Minimizes the accumulation
of hazardous chemicals and eliminates hazardous
chemical wastes Better detection of hazardous
materials Effective substitute materials to
reduce potential for resource blackmail Sustai
nable energy sources to reduce energy blackmail
such as supplies of petroleum and natural
gas Biochemistry and recombinant DNA science to
enable the development of better vaccines against
pathogenic biological warfare agents and
antidotes to chemical and biological toxins
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13.2. PROTECTING THE ANTHROSPHERE
Infrastructure Water purification and
delivery Electricity generation and
distribution Transportation infrastructure Vulne
rability due to interconnectivity Failure of
electrical grids
Cascading failures on complex networks that
operate close to the edge so that a relatively
small failure can rapidly cascade into a major
failure Electrical grids Internet systems
Just in time manufacturing Chemistry can be
applied to infrastructure protection Example
Production of materials that resist heat and flame
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13.3. SUBSTANCES THAT EXPLODE, BURN, OR REACT
VIOLENTLY
Explosives
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Hazardous Substances (Cont.)
Flammable fuels and solvents Corrosive
substances Sulfuric acid Hazardous substances
widely used in industry Practice of industrial
ecology and green chemistry minimizes threats,
producing and using hazardous substances In
minimal quantities Where needed As needed,
just-in-time
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13.4. TOXIC SUBSTANCES AND TOXICOLOGY
Table 13.1. Major Target Systems of Toxic
Substances
Target system
Typical toxic responses
Respiratory system
Emphysema from cigarette smoke, lung cancer from
asbestos
Skin responses
Allergic contact dermatitis, such as from
exposure to dichromate chloracne from exposure
to 2,3,7,8-tetrachlorodibenzo-p-dioxin
(dioxin) skin cancer from exposure to coal tar
constituents
Hepatotoxicity (toxic effects)
Steatosis (fatty liver), such as from exposure to
carbon tetrachloride cirrhosis (deposition and
buildup of fibrous collagen tissue) from
excessive ingestion of ethanol haemangiosarcoma,
a type of liver cancer observed in workers
heavily exposed to vinyl chloride in PVC plastic
manufacture
Reproductive system
Interference with sperm development by some
industrial chemicals, interference with cells
involved with egg formation by chemicals such as
cyclophosphamide
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Table 13.1. Major Target Systems of Toxic
Substances (Cont.)
Blood
Carboxyhemoglobin formation from binding of
carbon monoxide to blood hemoglobin,
methemoglobinemia consisting of conversion of
iron(II) to iron(III) in hemoglobin from exposure
to substances such as aniline or nitrobenzene,
aplastic anemia from exposure to benzene
Immune system effects
Immunosuppression from exposure to radiation,
hypersensitivity from exposure to beryllium
Endocrine system effects
Disruption of endocrine function by endocrine
disruptors such as bisphenol-A
Nervous system
Encephelopathy (brain disorder), such as from
exposure to lead peripheral neuropathy from
exposure to organic solvents inhibition of
acetylcholinesterase enzyme in nerve function by
exposure to organophosphate military poisons
Kidney and urinary tract system
Nephrotoxicity to the kidney by heavy metal
cadmium
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Relative Toxicities
LD50 values are in units of mg of toxicant per
kg of body mass.
Puffer fish toxin

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Relative Toxicities of Insecticidal Parathion and
Nerve Gas Sarin
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Metabolism of Toxic Substances
Xenobiotic substances are those that are normally
foreign to living systems Xenobiotic substances,
are subject to metabolic processes Activate to
more toxic substance Convert to less toxic
substance (detoxication) Two phases of metabolism
of toxic substances Phase I reactions normally
consist of attachment of a functional group,
usually accompanied by oxidation Phase II
reactions consist of binding to an endogenous
conjugating agent, typically glucuronide
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Phase I Reactions

• Most Phase I reactions are microsomal
  mixed-function oxidase
• Reactions
• Catalyzed by the cytochrome P-450 enzyme system
• Associated with cell endoplasmic reticulum
• Occurring most abundantly in the liver of
  vertebrates

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Phase II Reactions
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Phase I and Phase II Reactions and Toxicity
In some cases, Phase I and Phase II reactions
make substances toxic or more toxic
Most human carcinogens are produced
metabolically from non-carcinogenic precursors
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Dynamic Phase of Toxicity
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13.5. TOXIC CHEMICAL ATTACK
Bhopal Accidental release of methyl isocyanate
from a chemical manufacturing operation in
Bhopal, India, during the night of December 2/3,
1984 illustrates potential for terrorist attack
About 40 tons of methyl isocyanate was released
exposing thousands More than 3000 died,
primarily from pulmonary edema (fluid
accumulation in the lung) Immunological,
neurological, ophthalmic (eye), and hematological
effects Methyl isocyanate is the most toxic of
the isocyanates High vapor pressure
Toxicity to multiple organs Cross cell
membranes Reach organs far from exposure site
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Potential Chemical Agents
Carbon monoxide Has killed thousands
accidentally and by suicide Odorless, no warning
Carbon monoxide binding with hemoglobin O2Hb
CO ?? COHb O2 (13.5.1) Effects 10
ppm Impaired visual perception and judgment
100 ppm Dizziness, headache, and fatigue 250
ppm Unconsciousness 1000 ppm Rapid death
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Potential Terrorist Agents (Cont.)
Chlorine (Cl2) Widely used First military poison
in World War I Strong oxidizer that forms acids
and is especially damaging to respiratory
tissue 10-20 ppm Acute respiratory tract
discomfort 1000 ppm Rapidly fatal Hydrogen
cyanide, HCN, is a highly toxic gaseous substance
with potential for attack through the atmosphere
Also toxic as salts, such as KCN (potential
attack through food and water)
Cyanide binds with iron in the 3 oxidation state
of ferricytochrome oxidase enzyme preventing
utilization of O2 leading to rapid death
Antidote is to form iron in the 3 oxidation
state from blood hemoglobin to produce
methemoglobin that binds with cyanide
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Potential Terrorist Agents (Cont.)
Hydrogen sulfide, H2S Colorless gas with a
foul, rotten-egg odor As toxic as hydrogen
cyanide and may kill even more rapidly 1000
ppm Rapid death from respiratory system
paralysis Nonfatal doses can cause excitement
due to damage to the central nervous system
headache and dizziness may be symptoms of exposure
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Military Poisons
Mustard oil, bis(2-chloroethyl)sulfide
Vapors penetrate rapidly and deeply into
tissue Tissue damage and destruction well below
the point of entry Blistering gas producing
severely inflamed lesions that are susceptible to
infection Likely to be fatal in lungs Mutagen
and possible carcinogen
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Nerve Gases
Nerve gas organophosphates are the military
poisons of most concern
Sarin Tokyo subway attack Fatal at a dose of
only about 0.01 milligrams of Sarin per kilogram
of body mass Single drop through the skin can
kill a human
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Action of Organophosphate Poisons
Organophosphate military poisons act on the
nervous system by binding with and inhibiting
acetylcholinesterase enzyme
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Toxins from Biological Sources
Biotoxins Some of the most toxic substances
known Botulinum toxin From Clostridium
botulinum bacteria growing in the absence of
oxygen As little as 1 millionth of a gram can
be fatal to a human In principle, millions of
people could be killed by the amount of botulinum
toxin carried in a terrorists pocket Binds
with nerve terminals causing paralysis of the
respiratory muscles and death
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Ricin Biotoxin
Ricin Very stable proteinaceous material
extracted from castor beans (Ricinus
communis) Injection of an amount about the size
of a pinhead can be fatal Failure of kidneys,
liver, and spleen along with massive blood loss
from the digestive tract Hazard lessened by
need to inject
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13.6. PROTECTING WATER, FOOD, AND AIR
Chemical attack on food supply at a sufficient
scale to cause many poisonings is not
likely Attack on food supply by microorganisms
Anthrax bacteria through air or contact, such
as through mail Shigella dysenteriae bacteria
on food can cause severe dysentery Salmonella
bacteria in contaminated food can cause
debilitating digestive tract effects Although
usually not fatal, Salmonella on food have the
potential to cause temporary disability
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Protection of Water Supplies
Central distribution to large numbers of
people Susceptible to both chemical and
biological attack, though such an attack would be
difficult Arsenic in Bangladesh well water shows
potential of chemical attack A small amount of
botulinus toxin in water could kill
many Microorganism contamination of drinking water
Millions have been killed by waterborne
cholera, typhoid, and dysentery In 1993, more
than 400,000 people in Milwaukee were sickened
and over 50 died from waterborne protozoal
Cryptosporidium parvum In May, 2000,
approximately 3000 people were made ill and seven
died in Walkerton, Ontario, Canada, from drinking
water contaminated with Escherichia coli bacteria
that produced shiga toxin by transfer of DNA from
Shigella dysenteriae bacteria Bacteria that
could be added deliberately to drinking water
include Shigella dysenteriae, Vibrio cholerae,
and Yersinia pestis.
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Attack Through The Atmosphere
Atmosphere as a medium for chemical
attack Means of delivery, such as a low-flying
crop-spraying plane would give warning Atmosphere
as a medium for biological attack Anthrax
spores from Bacillus anthracis are a particular
concern Variola major, which causes
smallpox Francisella tularensis, which causes
tularemia Viruses that cause viral hemorrhagic
fevers, including Ebola, Marburg, Lassa, and
Machupo Bubonic plague caused by Yersinia
pestis bacteria that killed tens of millions
during the Middle Ages
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13.7. DETECTING HAZARDS
Explosives Residues of TNT, RDX, and PETN
explosives detected by sophisticated instruments
including ion mobility spectrometers and
chemiluminecence sensors Nuclear quadrupole
resonance (NQR) may be useful to detect
explosives because it responds to nitrogen, which
all major explosives contain Canine olfactory
detection (dogs nose)
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13.8. GREEN CHEMISTRY TO COMBAT TERRORISM
Safe and sustainable green chemistry can help
combat terrorism
Hazardous substances that might be stolen or
diverted for use in attacks are not made or used
in large quantities Chemical products do what
they are supposed to do and are used in minimum
quantities Materials and processes that are
likely to result in violent reactions, fires,
high pressures, and other extreme conditions are
avoided Potentially hazardous auxiliary
substances and flammable materials are
avoided Minimizes energy consumption, thereby
reducing energetic, high-temperature processes
that might be susceptible to sabotage
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Green Chemistry to Combat Terrorism
Biological processes used in green chemistry
are carried out under the mild, low temperature,
toxic-substance-free, inherently less hazardous
conditions conducive to biochemical
reactions Reduces demand on uncertain sources
of energy and raw materials controlled by
potentially hostile populations that are
inherently subject to disruption and blackmail
The practice of green chemistry requires exacting
process control combined with real-time,
in-process monitoring techniques
Conditions that resist sabotage Passive
safety systems that function by default in the
event of failure of or deliberate damage to
intricate control systems Example Making
methyl isocyanate on site as needed
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13.9. GREEN CHEMISTRY FOR SUSTAINABLE PROSPERITY
AND A SAFER WORLD
Reducing poverty, human misery, and hopelessness
helps alleviate conditions that promote
terrorism People with satisfied material needs
able to lead comfortable and fulfilling lives are
relatively less likely to commit violent acts
Green chemistry fulfills human needs and makes
life more comfortable
Prosperity, narrowly defined, has resulted in
consumption of increasingly scarce resources and
environmental degradation
Quote We are past the days when we can trade
environmental contamination for economic
prosperity that is only a temporary bargain, and
the cost of pollution both economically and on
human health is too high.
Green chemistry and the practice of industrial
ecology can provide high living standards
sustainably
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Abundant, Inexpensive, Sustainable Energy is Key
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Energy (Cont.)
Problems with energy Energy sources tend to be
contentious and competition for them has
precipitated past wars Some major regions of
petroleum of petroleum production are breeding
grounds for terrorists. The provision of adequate
energy independent of such sources would
substantially reduce terrorist threats.
Abundant, sustainable energy can lead to less
terror-prone societies
Production of food through synthesis of
fertilizers (particularly by synthetic fixation
of atmospheric nitrogen) and for irrigation,
cultivation, and reclamation of
farmland Fabricate materials for housing and
provide the heating, cooling, and lighting
required to make dwellings comfortable Pump
water from abundant sources to more arid
regions Purify marginal sources of water and
reclaim water after use Desalinate
water Provide safe, comfortable, non-polluting
transportation systems
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Energy (Cont.)
Abundant, sustainable energy requires the best
practice of green chemistry, green engineering,
and industrial ecology
Increased efficiency of energy utilization is a
key aspect of providing more usable
energy Solar, wind, and biomass energy are
sustainable, renewable energy sources Fossil
fuels will play an interim role, especially if
sequestration of greenhouse gas carbon dioxide
byproduct can be achieved Nuclear fission with
uranium fuel can provide abundant energy safely
with new-generation nuclear reactors and
reprocessing of nuclear fuel.
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Energy (Cont.)
Because wind and solar sources are by nature
intermittent and dispersed and often produce
electricity in locations far from where it is
used, storage and transport of energy are very
important
Superconductor or quantum conductor power
cables are candidates for transport of electrical
energy from source to use Pumped water
hydroelectric storage or high-speed flywheels
coupled with electric motor/generators Elemental
hydrogen, H2, will be widely used for energy
storage and transport as well as for fuel, moved
by pipeline and used to produce electricity
directly in fuel cells Hydrogen from
electrolysis of water Direct photoconversion of
water to hydrogen and oxygen may eventually
become practical