Chemical Warfare- Detection of Chemical Weapons

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ABSTRACT

The threat of chemical warfare instills acute fear in both individuals and nations. Since the first significant use of chemical warfare in World War 1, issues surrounding chemical warfare agents are of great importance to national security and world affairs. Unlike other weapons of war, the effects of chemical warfare agents are neither predictable nor controllable. Known as the poor man s atomic bomb, they are relatively cheap to manufacture and deploy. !nce deployed these weapons can have fatal effect within minutes. "t is therefore necessary to develop detection systems and methods that are ine#pensive, portable and which achieve real time detection.

Key Words: Chemical warfare chemical warfare a!ents detection systems

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#$TR%D&CT#%$ This paper begins by describing chemical warfare and the agents used. The detrimental effects of

these agents on the environment1 demand continuous e#perimentation and invention of new detection systems. The paper presents an overview of some of the e#isting detection systems, highlighting the specific uses and benefits of each system and where applicable, developments. The underlying law and policy helps the reader to understand the conte#t of these developments. The paper then sets out some new inventions designed to modify and improve e#isting systems.

$nvironment means %all e#ternal conditions and factors, living and nonliving that affect an organism or other specified system during its lifetime. Source& 'iller (r. ) Tyler, Living in the Environment, Wadsworth )roup. *rooks+,ole, -..-.

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C()*#CA+ WAR,AR) W(AT #S C()*#CA+ WAR,AR) / current definition of chemical warfare is the 0aspects of military operations involving the

employment of lethal and incapacitating chemical munitions or agents.0-".

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C()*#CA+ WAR,AR) A/)$TS / United 1ations report dated 1232 defines chemical warfare 4,W5 agents as 6... chemical

substances, whether gaseous, li7uid or solid, which might be employed because of their direct to#ic effects on man, animals and plants ...0. The ,hemical Weapons ,onvention- defines chemical weapons as including not only to#ic chemicals but also ammunition and e7uipment for their dispersal. To#ic chemicals are stated to be 6... any chemical which, through its chemical effect on living processes, may cause death, temporary loss of performance, or permanent in8ury to people and animals0. "n order to be considered a ,W agent the following must be satisfied& The presumptive agent must not only be highly to#ic but also 0suitably highly to#ic0 so that it is not too difficult to handle. The substance must be capable of being stored for long periods in containers without degradation and without corroding the packaging material. "t must be relatively resistant to atmospheric water and o#ygen so that it does not lose effect when dispersed. "t must withstand the heat developed when dispersed.

The first nerve gas was invented by the )ermans, it is odorless and colorless and attacks the body muscles, including the involuntary muscles. The gases classified as chemical warfare agents are

,onference on 9isarmament, The ,onvention on the :rohibition of the 9evelopment, :roduction, Stockpiling and Use of ,hemical Weapons and on their 9estruction, United 1ations 9ocument ,9+11;. )eneva /ugust 122-.

characteri<ed by poisonous or corrosive nature. These gases can be categori<ed according to the portal of entry into the body and their physiological effects& 1. 0esicants or 1lister !ases= these produce blisters on all body surfaces. $#amples include lewsite and mustard gas. /bout 1. milligrams of mustard gas in the lungs will kill a person. -. ?. @. A. +acrimators such as tear gas produce severe eye irritation> Stern2tators also called vomiting gases cause nausea> $er3e /ases inhibit proper nerve function> +2n! irritants which attack the respiratory tract, causing pulmonary edema.

$er3e A!ents 1erve agents affect the transmission of nerve impulses within the nervous system. They belong to the compound group known as organo=phosphorous compounds 4!:5. !: compounds are stable, easily dispersed, highly to#ic and have rapid effect. "n their pure state they are colorless li7uids with varying volatiles. 1erve agents enter the body through inhalation or through the skin, the port being important for determining the time the agent takes effect. Since nerve agents are fat=soluble they can penetrate the outer layers of the skin so it takes some time before the poison reaches the blood vessels. !n the other hand when it enters through the respiratory system the effect is rapid since the lungs contain numerous more blood vessels facilitating rapid assimilation and transportation to the key organs. 1erve agents include physostigmine 4reversible5 and organophosphorus 4irreversible5

cholinesterase inhibitors, which disable en<ymes responsible for the transmission of nerve impulses. "nitial incapacitating effects of organophosphorus agents occur within 1=1. minutes of e#posure, and death occurs within 1A minutes for Tabun, Sarin, and Soman and from @=@- hours for BC. Some nerve agents include&

Tabun 41/T! military designation, )/5 Sarin 41/T! military designation, )*5 Soman 41/T! military designation, )95 )D 4,yclohe#yl methylphosphonofluoridate5

BC -*ethylphosphonothioic acid S--"--1is-1-methylethyl.amino.ethyl. %-ethyl ester.

)$ (Phosphonofluoridic acid, ethyl-, isopropyl ester)

B$ (Phosphonothioic acid, ethyl-, S-(2-(diethylamino)ethyl) O-ethyl ester)

B) -Amiton.

B' -4hosphonothioic acid methyl- S--"--diethylamino.ethyl. %-ethyl ester.

Blister50esicant A!ents Besicant agents cause blisters on skin and damage the eyes, mucous membranes, respiratory tract, and internal organs. Through chemical processes, mustard agents destroy different substances within cells of living tissue. "nitial effects are somewhat delayed for mustards, occurring 1- to -@ hours after e#posure, but are rapid for other agents. Symptoms are variable and acute mortality is low, but death can occur from complications after lung in8ury. Some blister agents include: Eewisite 4E5 'ustard=Eewisite 4FE5 1itrogen mustards 4F1=1,F1=-, F1=?5 :hosgene o#ime 4,C5 Sulfur mustards 4F, F9, FT5

Blood A!ents /gents are highly volatile, but rapidly acting agents that cause sei<ures, respiratory failure, and cardiac arrest through interference with absorption of o#ygen into the bloodstream. Some blood agents include: ,yanogen chloride 4,K5

Fydrogen cyanide 4/,5

42lmonary A!ents Such agents are li7uids dispersed in a gaseous form that damage the respiratory tract and cause severe pulmonary edema in about four hours, leading to eventual death. $ffects are variable, and can be rapid or delayed depending on the specific agent. Some pulmonary agents include: ,hlorine ,hloropicrin 4:S5 9iphosgene 49:5 :hosgene 4,)5

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CAS) ST&D6: SAR#$- A$ )7A*4+) %, (%W A C()*#CA+ WAR,AR) A/)$T W%RKS Sarin is a nerve agent. !nce inside your body it affects the signaling mechanism that nerve cells

use to communicate with one another. Sarin is a cholinesterase inhibitor == it gums up the cholinesterase en<yme which your nerve cells use to clear themselves of acetylcholine. When a nerve cell needs to send a message to another nerve cell 4for e#ample, to cause a muscle to contract5, it sends the message with the acetylcholine. Without cholinesterase to clear the acetylcholine, muscles start to contract uncontrollably, which eventually causes death by suffocation 4since the diaphragm is a muscle5. Sarin is probably the most feared chemical agent because it has actually been used by terrorists to kill people. "n 122A, the group /um Shinrikyo released sarin gas in the Tokyo subway, wounding thousands and killing 1- people. "t is not particularly difficult to manufacture, and about 1 milligram in the lungs will kill a person.

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:erhaps the most dangerous and worrying feature of chemical weapons is that they are relatively easy and ine#pensive to manufacture and deploy. Dor this reason they are called 0the poor manGs atomic bomb.H !ne group of e#perts has estimated the cost of killing people using chemical weapons would be about I3.. per s7uare kilometer, compared with I-,... per s7uare kilometer using conventional weapons. ,hemical weapons could be dispersed from a crop dusting plane, from aerosols, or by distributing the chemical in water supplies. Sarin, in particular, poses a large threat because it is fairly easy to manufacture. / thimble= si<ed portion of sarin can kill a person in minutes> a few particles can produce death in -@ hours.

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&S) %, C()*#CA+ WAR,AR) ,hemical warfare was first used effectively in World War ", when the )ermans released chlorine

gas against the /llies. Eater in the War they used mustard gas. Soon both sides were using chemical warfare e#tensively leading to the introduction of gas masks. The fear of the detrimental effects of chemical warfare caused many countries to abstain from using it and e#cept for the use of poison gas by the "talians in the war against $thiopia 412?A=?35 and by the (apanese against ,hinese guerrillas 412?;=@-5, chemical warfare was not employed after World War ". This is not to say however, that the military powers of the world did not continue to develop new gases. "t is well known that chemical warfare was used in the "ran="ra7 War. "n fact, "ra7 has used poison gas on its own civilians, in particular the Kurds. "n the :ersian )ulf War, the U1 troops were e7uipped with antidotes for nerve gas, protective clothing, and gas masks in case "ra7 used poison gas. Then there was the release of sarin in a Tokyo subway station in 122A.?

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C%$TR%+ %, C()*#CA+ WAR,AR) A/)$TS "n recognition of the unbridled and disastrous effects of chemical warfare the international

community has negotiated a number of treaties aimed at prohibiting the use of chemical weapons. The first significant attempt was as early as 12-A with the signing of the )eneva :rotocol for the :rohibition of the Use in War of /sphy#iating, :oisonous or !ther )ases, and of *acteriological 'ethods of Warfare. The treaty which went into force in 12-J merely condemned the use of chemical weapons but did not ban the
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supra

development and stockpiling of chemical weapons.

'any States signed the )eneva :rotocol, but

e#pressed the reservation that they should maintain the right to retaliate in kind with chemical weapons, should they or any of their allies be attacked in such a method. 'any signatory States also reserved the right to use chemical weapons against non=signatories to the protocol. "n 122., the United States and the Soviet Union agreed to cut their arsenals by J.K in an effort to create a climate of change that would discourage smaller nations from stockpiling and using such lethal weapons. The most recent and significant treaty is the United 1ations ,hemical Weapons ,onvention@ 4,W,5 signed in 122?. This treaty bans the production, stockpiling A and use of chemical weapons and calls for the establishment of an independent organi<ation to verify compliance. /s of 1- th Debruary -..1 1;@ states had signed or acceded to the treaty and 1@? of them had deposited their ratification.

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D)T)CT#%$ D)T)CT#%$ %, C()*#CA+ WAR,AR) A/)$TS The !rgani<ation for the :rohibition of ,hemical Weapons 4!:,W5 implemented at the )eneva

,onvention in 122- organises e#ercises such as Lound Lobin Tests to verify the presence of ,hemical Weapon /gents. The ne#t step is to develop and test e#isting and new procedures or methods to further the implementation of the chemical weapons convention.. Sarin and Soman are listed in Schedule 1 of the United 1ations ,hemical Weapons ,onvention
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which means that they are chemicals that are deemed to pose a high risk to the purposes of the ,W,, but have very limited, if any, commercial applications. 'ethylphosphponic acid 4':/5 is formed by hydrolsis of these nerve agents. Since ':/ is a more stable product than the nerve agents it is more useful for detection purposes. "t indicates the prior presence of Sarin or Soman. The challenge is that ':/ does not lend itself easily to direct analysis since it is also highly polar and involatile. :resent methods for detection
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,onference on 9isarmament, The ,onvention on the :rohibition of the 9evelopment, :roduction, Stockpiling and Use of ,hemical Weapons and on their 9estruction, United 1ations 9ocument ,9+11;. )eneva /ugust 122-. A *y the year -..; 3 ,onference on 9isarmament, The ,onvention on the :rohibition of the 9evelopment, :roduction, Stockpiling and Use of ,hemical Weapons and on their 9estruction, United 1ations 9ocument ,9+11;. )eneva /ugust 122-.

of methylphosphonic acids are gas chromatography4),5, li7uid chromatography 4E,5 and capillary electrophoresis 4,$5. Using these methods means that the acid must first be derived via sample preparation and analysis. This is very time consuming. What is needed is a simple portable and ine#pensive immunoassay kit which would be valuable to monitor various treaty compliances and during military operations. !ne method developed is the $E"S/ procedure which unlike other methods re7uires only a minimum of sample preparation. -1.

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D)T)CT#%$ S6ST)*S )lectrospray *ass Spectrometry $lectrospray mass spectrometry 4$S='S5 has been evaluated to determine whether it provides a

time=efficient method of detection and analysis of chemical warfare degradation products.

"t was

considered a suitable candidate because it has been shown to be ideal to the analysis of polar non volatile compounds in a7ueous matri#es.-'. These tests revealed that use of $S='S to analy<e degradation products of chemical warfare agents e#tracted from soil samples.

A#R#S The /daptive "nfraLed "maging Spectroradiometer 4/"L"S5 can be used to get wide spectral

coverage at a spectral resolution consistent with the detection of molecular absorption or emission band. /"L"S systems are developed by :hysical Science "nc. 4:S"5 under internal corporate research and development as well as U.S. /rmy *'9! and /ir Dorce Sponsorship. The e#isting /"L"S systems can detect vehicle plume emissions and camouflaged targets in cluttered environments as well as the observation and 7uantification of absorption or emission from specific airborne ha<ardous chemicals. / EW"L /"L"S system is being developed for remote standoff detection of chemical vapor plumes. This can be used in battlefield detection of chemical warfare agent plumes, fugitive emissions monitoring of chemical production facilities and ha<ardous wastes sites. The scientific basis of :S" s /"L"S systems is based on a low order Dabry=:erot interferometer. The benefits of this low order system are wide free spectral range combined with narrow spectral bandwidth, fle#ible and adaptive sampling and processing of the image to isolate spectral features or

signatures, high spatial resolutions and radiance sensitivity. The :S" system is particularly useful because it combines all of this into a compact instrument.

*illimeter Wa3e Technolo!y Unlike e#isting DT"L remote sensing, millimeter wave technology is highly specific and so allows

detection of chemical warfare agents in comple# mi#tures such as water vapor and smoke. The emphasis is on technologies with highly sensitive detection and discrimination capabilities with low false alarm rates. The scientific base is the remote sensing of ha<ardous wastes based on their millimeter wave rotational signature since rotational spectra are very specific to molecular structures. The techni7ue is called the %Dourier Transform 'icrowave 4DT'W5 spectroscopic and it has been proven to have some advantages in detection of chemical warfare agents.-1;.

Chemical A!ent *onitors ,hemical /gent 'onitors 4,/'S5 are a well known detection system. "t s characteristic feature

is its portability. /s stressed throughout this paper, portability is an overriding issue in chemical detection systems. The ,/' has been used by military operations in several countries throughout the world. The ,/' draws samples in continuously . "t uses very little power and can detect atmospheric contaminants.

The 2se of electro<inetic in=ection in Capillary )lectrophoresis ,apillary $lectrophoresis 4,$5 is a method of separating compounds within comple# matri#es. "t

was introduced by (orgenson.; The ,$ method is recogni<ed as a % a powerful separation techni7ue which can be used successfully with small samples. *y employing a buffer system that is highly stable and ine#pensive, the ,$ method reverses the electroosmotic flow and provides e#cellent separation efficiencies within a three minute run. ,$ uses compact lightweight e7uipment smaller samples and reduced wastes. "t is therefore well suited for use in mobile laboratory are the first line of detection and analysis in emergency situations such as a chemical warfare attack. The problem is that the separational efficiency of the ,$ method re7uires a
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See (orgenson, (.W.> Eukacs, K. 9. Anal Chem. 1>?1, A?, 1-2J=1?.-.

high standard of efficiency from the other processes used in analy<ing samples such as the in8ection. Since samples can only be in8ected in limited volumes there is a problem of low concentration sensitivity. $lectrokinetic in8ection is proposed as a viable in8ection method -1'. because it does not re7uire e#tra e7uipment nor add to analysis time. "t therefore does not decrease the efficiency and mobility of the ,$ method and so complements the beneficial usage of ,$. When compared with pressure in8ection, electrokinetic in8ection analysis offers increased analysis sensitivity with very minimal sample, preparation steps. "t s simplicity, ine#pensiveness mean it is suitable for use with the ,$ method in mobile detection units.

S2rface Aco2stic Wa3e -SAW. Chemical Sensor Systems S/W chemical sensors systems have been developed since 12J1 and are conceptually similar to

the bulk acoustic wave sensor reported in 123@ by King J . S/W detects and identifies chemical agents and other to#ic gases or vapors. / S/W chemical sensor is a functionali<ed polymer, a Saw device is coated with a chemoselective material. This coating is gas specific and causes the gas to concentrate on the surface of the S/W device. When the device is in operation, a wave passes across its surface, the sorption of the gas molecules causes the velocity of the S/W to be perturbed. The monitoring of this surface acoustic wave leads to ready detection of gases. The 1aval Lesearch Eaboratory has developed a 61LE=S/WLF"1!H system which is an application of the Saw system designed specifically for vehicular mounted field applications. "t is

described as 6an automated chemical agent detector and alarm, designed for autonomous operation with rapid and reversible responses from low to high concentrations of )=nerve and F=mustard agents.H 411. The 1LE S/WLF"1! also called a %nose for to#ic gases is comprised of a temperature controlled ?=Saw array with an automated dual gas sampling system which has two pneumatic pathways. This means that the device has both immediate detection capability and periodic detection capability. :eriodic detection capability is achieved by the use of a trap and purge gas=solid chromatographic column. /s the name suggests this traps gases which are then sent to the S/W sensors for detection.

King W.F. /nal. ,hem. ?3 4123@5 1;?A=1;?2

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The coating used in the device is specific to a number of nerve and blister agents and can discriminate against a wide range of interferent vapors and gases. Tests of the device commend it with a robust operational performance2 evidenced by 1..K accurate identification of agents with no false alarms. 1ote that while e#perimentation and sampling was done using a ?=Saw array, research at the 1aval Lesearch Eaboratory indicates that real time detection is better achieved by using a A=S/W array.

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#$0)$T#%$S Alarm system for (and (eld Chemical *onitor 4atent $o: &S :1>1:>:-"@. This invention is an alarm system designed for use with chemical agent monitors. 1. ,hemical

agent monitors are hand held soldier operated devices, post attack devices for monitoring chemical agent contamination on people and e7uipment. The alarm system will connect to these monitors so it is

important that they complement their present structure and operation. The inventor aims at providing an alarm system with low power consumption that permits soldiers to easily and 7uickly detach parts while wearing protective gear. The ma8or components are pins, twist lock mechanical connectors, circuit board, a power source, ceramic disk, voicemitter and a housing. When the ,/'+",/' senses the presence of a chemical agent it emits a electric signal to the indicator which emits an audible alarm. This warns of the presence of chemical contamination in an environment. The invention does not take electricity from the ,/'+",/' until it is in alarm and the total power consumption is 3 volts or less.

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Analytical *ethodolo!y for A2alitati3e and A2antitati3e determination of chemical a!ent 3apor 4atent $o &S :1;8;'" -18. The claim is for a method of generating and sampling chemical agent vapor by placing the li7uid

chemical agent in a reservoir purging the chemical agent using dry air and analy<ing the air stream e#iting
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:referably adaptable to the ,hemical /gent 'onitor 4,/'5, "mproved ,hemical /gent 'onitor 4,/'5 and+or other similar chemical monitoring devices.

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the reservoir. The invention is directed to determining BC vapor 11 under various humidity conditions. Since BC is e#tremely to#ic its detection is best accomplished at lowest possible concentrations. When testing chemical detectors using BC vapor it is important to minimi<e the presence of impurities. "mpurities of about AK can affect detector testing. The challenge is that impurities may become the ma8or constituent in a vapor mi#ture when it is vapori<ed. $#isting methods used to 7uantify a BC sample 1- lack the ability to separate or distinguish the relationship between the impurities and BC. "t is therefore desirable to develop an improved methodology for sampling BC. The invention is a method which starts with placing the li7uid agent in a reservoir, the temperature of which is maintained in order to allow vapori<ation of the contaminants in the chemical agent. The contaminant is then purged with dry air. The dry air is then removed which removes the contaminant leaving the retained chemical agent. ,onditioned air is then passed over the retained chemical agent and carries the agent vapors to a sample port where the mi#ture of conditioned air and chemical agent vapors is analy<ed. Unlike e#isting methods it allows the analysis of BC vapor under various humidities.

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Broad Spectr2m 1io-detection of ner3e a!ents or!anophosphates and other chemical

warfare a!ents 4atent $o W% "@@@@8918> The principal thrust of this invention is to provide a method of real time or near real time detection of nerve agents. /s discussed above nerve agents take rapid effect particularly when the route is via the lungs, therefore it is vital that detection e7uipment can produce results as soon as possible. The invention recogni<es that e#isting methods of detection are slow or too bulky which impedes their use where it is needed, on the front line. "t seeks to provide a method and apparatus that provides rapid detection of nerve agents in air and water while being portable and ine#pensive enough to be issued to each individual be a broad band detector which is responsive to a wide variety of !: compounds

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!=ethyl S=4-=diisopropylanimoethyl5, methylphosphonothiolate The Shoenemann reaction, The 'inituari<ed ,ontinous /ir 'onitoring System 4'"1",/'S5

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The invention rests on the scientific observation that protein comple#es can be used with colorimetric compounds to detect the presence of very low concentrations of chemical warfare agents. The instant invention applies this observation to obtain real time detection of chemical warfare agents. The electron distribution in a colorimetric compound is altered by its immediate environment. Therefore an indicator to detect ha<ardous substances may be created by monitoring specific lights wavelengths in the spectrum of a specific colorimetric compound. !ptical changes in the colorimetric indicator are made using preferably both absorbance and fluorescence in the visible region. Fowever the invention uses difference spectra which allows very small wavelength shifts and minute absorbance changes to be identified. This means that over ;;.. different analytes can be identified and their concentration levels can be 7uantified to very small ranges. The second part of the invention is an apparatus which monitors the transforming optical spectrum of a specific colorimetric compound. "t uses real time measurement of the changes in the spectral substrate to indicate the presence of organophospahates. The ma8or components of the apparatus are a light source, a colorimetrically responsive surface and an optical sensitive detector directed toward the illuminated surface. The light source an detector operate continuously in order to achieve immediate identification of changes in the absorptive properties of the detection surface. The apparatus may be as small as a badge so it can be worn continuously by individuals and incorporate some sort of warning element. 1? /dditionally the light source and detector may be maintained separately from the detection surface so that identification tests are conducted at at central location. The invention aims at detection in both a7ueous and air samples.

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4assi3e Remote Sensor of Chemicals 4atent $o W% "@@@99:@" -1@. The invention is a passive remote device and method using differential absorption radiometer

49/L5 or notch filter correlation radiometer 41D,L5 technology to detect chemical weapons. Such a device was deemed necessary because of a number of factors. The first is the spread of chemical warfare technology around the world. There is also the concern about the effects of industrial and vehicular emissions and environmental pollution from pesticides.

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See :atent 1o 1 supra

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$#isting systems such as the ,hemical /gent 'onitor and the $nhanced ,/', both manufactured by the same company, operate on the principle of ion mobility. The limitation of these systems is that they need continuous sampling at the point of measurement and therefore can only detect a gas if the sensor is immersed in it. The S/W system discussed above is critici<ed as lacking specificity and the ability to determine the specific identity of a gas. The invention addresses these deficiencies and the shortcomings of other conventional remote chemical detection techni7ues. The ma8or components are a first optical path, a second optical path, light collecting optics and a sample filter assembly. The sensor mal also include a reference filter assembly which will be positioned in the path of the second optical path after the light collecting optics. The invention also includes a method of determining the presence, concentration and optical density of a target species. This is accomplished by directing the light that has been absorbed from a target species along the two optical paths. / detector output comparison device is then used to compare the sample signal to the reference signal. This produces a signal which indicates the absorption or emission of the light by the target species.

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C%$C+&S#%$ The detection of chemical warfare agents is constantly being developed. The challenge to the

scientific community is to invent methods and devices that are compact, portable and capable of real time detection. /ll of the devices and methods presented above attempt to meet this challenge. !nly some actually achieve it. This area of science is a live one and is interesting to follow, particularly in light of the current threats of global terrorism in the world.

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