Decision-Making in Chemical Warfare Agent (CWA) Response There Is a Lot of Fear Associated with Chemical Will Act Accordingly

Home , Arsenical, Pepper spray

Application Note: 102 Decision-Making in Chemical Warfare Agent (CWA) Response There is a lot of fear associated with Chemical will act accordingly. If the first responders Warfare Agents (CWAs). The misnomer over-react and immediately jump into full “Nerve Gas” quickly brings horrible images to encapsulation protection it could panic the the minds of many civilians. But if we lay aside public and cause unnecessary worry and the politics and fear, CWA detection should even injury. treated like other gas/vapor detection challenges. It should be a collaborative Over Protection Can Be Dangerous process encompassing physical clues, threat to the Responder scenario, biological clues, and a variety of Heat stress is the number one injury in sensing technologies. No one clue or HazMat response and immediately jumping technology is always correct. Experience and into full Level A encapsulation is a good way the use of multiple clues and technologies are of overheating oneself. Level A the keys to successful CWA response. encapsulation also makes one much more Understanding what the clues are and how to susceptible to slip, trip and fall injuries. layer them to make a decision is critical to Finally, over protection makes it harder to get successful CWA response. things done. When properly used, detection allows responders to respond at lower levels Why is Gas Detection Important? of Personal Protective Equipment (PPE) to Responders cannot rely on their senses for provide the highest levels of safety to decision-making. Without effectively knowing themselves and to the community that they how to use detection techniques responders protect. are unable to properly identify threats and make decisions that are appropriate to the CWA Response Is a 5-Step actual hazard. Detection technologies Process supplement the responder’s senses when 1. Clues: are the making decisions in potentially hazardous physical clues, environments. Relying on the senses alone threat scenario can be dangerous in chemical response; and biological detectors become our eyes and ears when clues consistent those senses fail us. Proper use of detection with a CWA technologies coupled with the clues present at release the scene allow for better decision making. 2. Location: survey tools or Over Responding Can Be Dangerous “sniffers” will to the Community help find out where “it” is coming from. If Risked Based Response (RBR) is a common you can find “it” you have a much better concept in the first responder community. The chance to figure out what “it” is idea is to respond at the lowest level necessary 3. Classification: will narrow down the to prevent undue risk to the responder whilst problem to give a general idea of the protecting the public. Over-responding can be chemical you are dealing with to dangerous to the community because panic is understand how to proceed. It is not as effective a killer as bullets, bombs or necessary to differentiate between GA chemical attacks. One example of how panic and GB to administer antidote! can kill occurred in 2003 when more than 1,500 4. Identification: using clues, common people were in the Epitome Night Club in sense or an instrument to gain the Chicago when someone released pepper spray specific identify of a chemical or a into the air. 21 people were crushed to death in mixture of chemicals the resulting stampede to evacuate the club 5. Ask the Right Questions: responders from the unknown chemical release. The have to interpret the clues AND ask the community will echo how the first responders right questions. act. If the first responders are calm, civilians Copyright © 6/14/2012 Chris Wrenn Environics USA, Inc. 1308 Continental Drive, Suite J, Abingdon, MD 21009 Tel: (410) 612-1250, Fax: (410) 612-1251 [email protected], www.EnvironicsUSA.com Page 1 of 24

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

Why Worry About CWAs? CWAs are chemicals designed to either kill or . In 2003 US made Chloropicrin shells debilitate an opposing military. They are often were found in a Baltimore, MD basement, derived from civilian Toxic Industrial Chemicals live but not armed (TICs) such as insecticides, chlorine and hydrogen cyanide. In 1994 the Japanese Cult Aum Shinrikyo released Sarin spray from a refrigerated box truck in a quiet neighborhood of Matsumoto, Japan with the intent to kill three judges who were due to rule against the cult. Seven people were killed and 200 hospitalized. In 1995, the Aum cult again used Sarin to terrorize the Tokyo subways by simultaneously spilling Sarin liquid in a number of subway cars. Twelve people were killed, about 1000 were hospitalized and thousands became ill. In Iraq, insurgents have used chemical munitions to make roadside IEDs (Improvised Explosive Devices). With terrorist groups having demonstrated their ability to make and use CWAs, responders must look at ways to . In 2010 Mustard contaminated clams effectively detect and respond to these were dredged out of Long Island Sound compounds. and burned some of the fishermen . CWAs can be stolen from poorly CWAs are Accessible maintained regulated stockpiles. Until that last few years one of the most Terrorists in Iraq and Afghanistan have common ways to dispose of chemical munitions used CWAs as IEDs either intentionally was to bury it, or dump it off our coasts, and it or inadvertently. often has been lost track of. Abandoned . Aum Shinrikyo has twice demonstrated munitions and lab materials at military or that they can make and disperse Sarin research facilities can provide easy access to and it can be expected that others can CWAs. and will follow Aum’s example. . After WWII the Germans left 296,103 tons of chemical weapons. The US share was 30-40K tons which they disposed of in 6/1946-8/1948 by sinking 9 ships in the Baltic Sea and 2 in the North Sea in operation “Davy Jones Locker” . From 1967-68 four ships containing CWAs were sunk in a three mile area between Florida and the Bahamas as part of “Operation CHASE” (Cut Holes and Sink ‘Em) . In 1995 “mustard” shells from WWI were dug up during the construction of subdivision outside of Washington, DC

Copyright © 6/14/2012 Chris Wrenn Environics USA, Inc. 1308 Continental Drive, Suite J, Abingdon, MD 21009 Tel: (410) 612-1250, Fax: (410) 612-1251 [email protected], www.EnvironicsUSA.com Page 2 of 24

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

the weather is fickle, and when the wind changed it carried the chlorine gas back Physical Clues over to the Germans. . Any signs of . What was needed was a stable and dissemination persistent chemical that would stay techniques? where it was needed. Mustard “gas,” . Is there a also called Yperite or Ypercite, was used valid/credible for the first time near Ypres in the autumn threat? of 1917. Mustard is a liquid at normal . Is there any temperatures and it is very persistent. physical evidence? That is, it is not a gas and it stays where . Are there any dead it is put. Mustard is so pervasive that is animals or ones still remains in the soil and water around that display SLUDGEM /DUMBBELLS type Ypres. Modern farmers have sat down symptoms? on freshly cut tree stumps and suffered . Are there any human victims displaying severe burns to their rear ends because SLUDGEM /DUMBBELLS symptoms? the trees draw up the mustard in the soil and water and concentrate it in their sap. A Brief History of CWAs In Edgewood, MD, Mustard contaminated CWAs are chemical compounds designed to soil is remediated with trees. either kill or debilitate opposing militaries. With . Chemical Weapons came of age in WWI terrorist groups having demonstrated their o By the beginning of 1918 one in four ability to make and use CWA, responders must projectiles were chemical look at ways to effectively measure these o By November 1918 one in two shells compounds. Chemical warfare is not a 20th were chemical century development: o While Phosgene caused the most . The Chinese used arsenical smokes in deaths in WWI, Mustard caused the 1000 BC. most casualties . The Spartans used noxious smoke and . 6/17/1925 The Geneva Protocol flame against the Athenian allied cities in prohibits the first use of chemical and the Peloponnesian War in 429 and 424BC. biological weapons . Leonardo DaVinci proposed a powder of sulfur and verdigris (oxidized copper) as a th Modern “Nerve Agents” weapon in the 17 century. . On December 23, 1936 Dr. Gerhard . The Strasbourg Agreement of 1675 is the Schrader of I.G. Farben invented Tabun first international agreement banning the (GA) as an insecticide. Because of a use of chemical weapons and was created 1935 Nazi decree it was reported to the in response to the use of poisoned bullets Ministry of War as an invention of . John Doughty, a New York City school possible military significance. teacher, proposed chlorine filled 10 inch . In 1938 Sarin was invented and was shells during the US Civil War but was named for its discoverers Schrader, turned down because the weapon was too Ambros, Rigriger and Vad Der Linde. inhumane. . The V-series of agent was invented by . The Hague Convention of 1899 prohibited the US in the 1960s. “the Use of Projectiles the Object of Which is the Diffusion of Asphyxiating or . Novichok was invented by the Russians Deleterious Gases” in the 1990s. . On April 22, 1915 the Germans used . On January 13, 1993 the US and Russia chlorine against the Allied trenches in entered into the Chemical Weapons Ypres, Belgium with 5,000 fatalities and an Convention (CWC) that prohibits the use additional 10,000 casualties. One of the and manufacture of chemical weapons. lessons from using chlorine is that it is not persistent. Wind easily carried the chlorine gas over to the English trenches. However,

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

injectors that are used for military nerve CWA Classes and Characteristics agents to address organophosphate pesticide  Nerve exposures. Nerve agents are cumulative o Liquids at normal temperatures hazards, repeated exposures to low o Stable & persistent concentrations may produce symptoms.  Blister  GA/Tabun o Liquids at normal temperatures o Chemical Name: o Stable & persistent Ethyl N, N-  Choke/Blood dimethylphosphor o Gases at normal temperatures that oamidocyanidate are normally treated by first o Synonym: responders as TICs Dimethylaminocy o As the gas detection protocols for anophosphoric acid ethyl ester TICs are well developed the  GB/Sarin balance of this paper will only o Chemical Name: address nerve and blister agents Isopropyl Nerve: agents are more toxic than other methylphosphonofluo agents. At sufficient concentrations they can ridate cause effects within seconds and death within o Synonym: minutes. Nerve agents are divided into two Methylphosphonofluo classes G and V agents: ridic acid isopropyl 1. G, or “German” agents are older and ester more volatile and are more of a vapor  GD/Soman hazard o Chemical Name: 2. V or “Venom” agents are newer, less Pinacolyl methyl volatile, more persistent, more toxic phosphonofluoridate (~2x) and more of a contact hazard o Synonym: Nerve agents are stable and persistent liquids Methylphosphonofluoridic acid 1,2,2- at normal temperatures that can vary from clear trimethylpropyl ester & colorless to light amber to dark brown  GF/Cyclo-sarin depending on purity and age. GB recovered o Chemical Name: from Guam during the US demilitarization Cyclohexyl process was the color of coffee and still 98% methylphosphonoflu pure. oridate o Synonym: Phosphonofluoridic acid, methyl-, cyclohexyl ester  VX o Chemical Name: O-Ethyl-S-(2- diisopropyla minoethyl) methyl phosphonot hiolate o Synonym: Nerve agents are organophosphates which are Phosphonot defined by a phosphorous-oxygen double bond hioic acid, at the heart of their chemical structure. They methyl-, S- are similar to insecticides but 100-500 times (2- more powerful, although technical grade, highly (diisopropyla concentrated organophosphate pesticides, mino)ethyl) O-ethyl ester such as parathion, are only about 3 times less toxic than military nerve agents. Because of this EMS in big agricultural states routinely carry and use the same atropine/2 pam auto- Copyright © 6/14/2012 Chris Wrenn Environics USA, Inc. 1308 Continental Drive, Suite J, Abingdon, MD 21009 Tel: (410) 612-1250, Fax: (410) 612-1251 [email protected], www.EnvironicsUSA.com Page 4 of 24

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

In all of the “Nerve” agents we . VX can see that chemically they o Chemical Name: O-Ethyl-S-(2- all contain phosphorous (P) , diisopropylaminoethyl) methyl which we will later see is phosphonothiolate important for at least one o Synonym: Phosphonothioic acid, detection methyl-, S-(2- technology, and they are all (diisopropylamino)ethyl) O-ethyl organophosphates. Other ester organophosphates such as That fact that all of the Nerve agents are DMMP (Dimethyl esters may be the cause of cross-sensitivities methylphosphonate with other compounds that are or contain commonly used as a flame esters such as some cleaning compounds retardant) and TEP (Triethyl phosphate often and brake fluids. used as a plasticizer) can be used as Nerve agent simulants. Blister: Agents are colorless to Organophosphate dark brown oily liquids at pesticides are chemically normal temperatures (HD Gels similar to nerve and will below 50oF,14.5oC) that are often give nerve alarms stable and persistent. Blister on CWA detectors. agents can take minutes to hours to develop blisters. We can also see that all the They often do not Nerve agents are immediately kill their victims complicated acidic esters like nerve agents. But blister (the author has added bold agents certainly make it italics to the ester parts in difficult for soldiers to each of the synonyms to perform their tasks. When illustrate that they are all complicated organic, inhaled, blister agents can fill acidic esters). their victims’ lungs with fluid and can cause . GA/Tabun chemical pneumonia. Because Blister Agent o Chemical Name: Ethyl N, N- symptoms take time to develop and it does dimethylphosphoroamidocyanidate not immediately cause death, many people o Synonym: do not consider blister agents an effective Dimethylaminocyanophosphoric acid WMD agent. ethyl ester  HD/Mustard . GB/Sarin o Chemical Name: o Chemical Name: Isopropyl Bis (2-chloroethyl) methylphosphonofluoridate sulfide o Synonym: Methylphosphonofluoridic  HN-1/Nitrogen Mustard-1 acid isopropyl ester o Chemical Name: . GD/Soman 2,2’- o Chemical Name: Pinacolyl methyl Dichlorotriethylamine phosphonofluoridate  HN-2/Nitrogen Mustard-2 o Synonym: Methylphosphonofluoridic o Chemical Name: Bis- acid 1,2,2-trimethylpropyl ester (2- . GF/Cyclo-sarin chloroethyl)methylami o Chemical Name: Cyclohexyl ne methylphosphonofluoridate  HN-3/Nitrogen Mustard-3 o Synonym: Phosphonofluoridic acid, o Chemical Name: 2, 2’, methyl-, cyclohexyl ester 2”- Trichlorotriethylamine

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

 L/Lewisite technologies. So if a sample beads upon on o Chemical Name: M8 paper it probably is not a CWA. Dichloro(2- Vapor Pressure tells us how readily a liquid chlorovinyl)arsine (or solid) wants to evaporate into a vapor. The “blister” agents don’t Low vapor pressure chemicals do not want to have a common defining make vapors while high vapor pressure chemical element like the chemicals want to become gases. Any nerve agents. From the previous brief chemical with a vapor pressure over 1 ATM, summary we can see that blister agents can be 760 mm/Hg, 14.7 PSIA or 1,701 mb is a gas. sulfur (HD), amine (HN) or arsine (L) based. Vapor pressures of over 40 mm/Hg are more We will later see how these likely to move around and are considered to elements/compounds are important for at least be an inhalation or vapor hazard. As a one detection technology and they also can reference point, water has a vapor pressure lead to some cross-sensitivities with other of 20 mm/Hg. compounds that contain sulfur and amines. A chemical’s boiling point is another way to Nitrogen Mustard is known to depress white understand how readily a liquid wants to blood cell count. Because Leukemia is too move to a vapor state. A liquid’s boiling point many white blood cells in is the temperature at which it transitions to a 1954 doctors in the US gas. Low boiling point chemicals want to Army’s Edgewood labs become vapors and have relatively higher tried injecting Nitrogen vapor pressures making them easier to Mustard into a critically measure in air. An example is gasoline. terminal leukemia patient High boiling point chemicals do not want to and found the first become vapors, have relatively low vapor effective chemotherapy for pressures and are harder to measure in air. leukemia. Nitrogen An example is diesel. Mustard is still an ingredient in some oncology drugs and has A Summary of CWA Chemical Properties Name Abbreviation Melting Vapor Boiling been found in the personal effects of retired o o Point Pressure Point C/ F oncologists o o ( C)/ ( F) mm/Hg o Blood or Choke: agents are gases at normal (@20 C) temperatures that are neither stable nor persistent. They include chlorine, phosgene, Tabun GA -50/-58 0.07 246/475 hydrogen cyanide and cyanogen chloride. They act by choking, or preventing the blood Sarin GB -57/-70 1.48 147/297 stream from taking up oxygen by preferentially binding to hemoglobin. Typically these TICs Soman GD -80/0112 0.92 190/374 still have legitimate industrial uses and can be Cyclo- Sarin GF -12/10 0.93 228/442 encountered in “routine” HazMat calls so they will not be focused on in the rest of this paper. Mustard HD 14/57 0.11 217/422

A Brief Review of Chemical Lewisite L -18/-0.4 0.35 190/374 Properties When discussing CWAs it is important to VX VX -51/-59 0.0007 298/568 understand their chemical properties. CWAs are complex organic compounds and are not Water H2O 0 17.54 100/212 very water soluble. This can provide a clue. 160-371/ Diesel Diesel 0.40 320-700 For example, water will bead up on M8 paper and M9 tape while organic chemicals and Heavy 176-648/ CWAs quickly soak right into these colorimetric Fuel Oil #6 Fuel Oil <5.2 350-1200 All of the CWAs have vapor pressures less than 40mm/Hg (an arbitrary “vapor threat” pressure), less than 20mm/Hg for water Copyright © 6/14/2012 Chris Wrenn Environics USA, Inc. 1308 Continental Drive, Suite J, Abingdon, MD 21009 Tel: (410) 612-1250, Fax: (410) 612-1251 [email protected], www.EnvironicsUSA.com Page 6 of 24

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

(which is not that volatile), less than diesel, and propellant charge. Then when it even less than #6 fuel oil (essentially crank reaches the proper altitude a case oil). secondary “dispersant” charge is detonated to turn the heavy liquid into a mist or a spray that spreads out over the opposing military.  Big explosions burn up chemical like a fuel-air bomb, but small ones spread it effectively. The army will There Is No Such dispose of unstable chemical Thing as “Nerve ordinance in place, rather than taking Gas” the risk of transporting it, by blowing Owing to their low it up in place. vapor pressure and  If witnesses/victims talk of hearing a high boiling points, “pop” without a fireball that is a good CWAs do not represent sign of a dispersant charge much of a vapor threat  If they speak of a big boom or unless they have been whoomp followed by a fireball it is aerosolized in some highly probable that the explosion way. They are heavier than air and tend to stay consumed the CWA low to the ground.  Explosions that dispense liquids, mists or gases should be suspected CWAs are stable and persistent liquids, as dispersant charges. opposed to gases, because the army that  Explosions that seem to only destroy deploys them wants them to stay on their a package or bomb itself should be enemy and not float back. Compared to gases suspected as dispersant charges. like chlorine, hydrogen fluoride, and ammonia, 2. Pneumatic Dissemination which all can move readily in air, CWAs are  Can be as simple as garden very toxic but they are not that tough to contain. sprayers. Aum’s first strike was Unlike most other atmospheric threats (like lack against judges in Masumoto, Japan of oxygen) there are antidotes for CWA using a garden sprayer that killed 7. exposure. Without some means of  Unscheduled or unusual sprays dissemination via aerosolization, CWAs will should be suspected as dispersant take some time to produce vapors that would incidents affect people at room temperature of  o o Abandoned spray devices should be ~20 C/65 F. suspected as dispersant devices. Dissemination Is the Key 3. Mechanical Action Dissemination  Plastic bags inside paper bags or If one were to solely look at CWAs chemical boxes that were poked with characteristics they do not appear that sharpened umbrella tips in Tokyo threatening. While they are very toxic, they do proved to be a poor dissemination not want to move and “chase” us as gases like method. This seems to indicate that chlorine and ammonia can and will do. The key their intent may have been to create to successful deployment of CWAs is more of a distraction than to kill large dissemination, which is a fancy name for the numbers of people. techniques used to spread the CWAs around.  There are four dissemination techniques which Glass bottles dropped from above or can provide a clue as to the nature of the plastic bottles with holes in them that attack/event: allow agent to splash down the station steps may have been more 1. Explosive Dissemination effective.  The military has honed their skills on 4. Chemical Reaction Dissemination using low level explosive (dispersant)  charges to disseminate chemicals. A Cyanide tablets plus acid = gas CWA shell is lofted into the air by its Copyright © 6/14/2012 Chris Wrenn Environics USA, Inc. 1308 Continental Drive, Suite J, Abingdon, MD 21009 Tel: (410) 612-1250, Fax: (410) 612-1251 [email protected], www.EnvironicsUSA.com Page 7 of 24

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

Dissemination is the key to killing a lot of cramps or can feel like a bad hangover. people. With proper dissemination, Tokyo could Nerve agents are cumulative poisons, have been the first 9/11 type of event with repeated exposures to low concentrations thousands of fatalities. However, because may produce symptoms. Animals displaying CWAs all have low vapor pressures, after the characteristic symptoms of effective dissemination it is likely that a film will organophosphate exposure (DUMMBELLS or be left on flat, smooth, non-porous surfaces. SLUDGEM) are good clues to a Nerve agent CWAs are not gases, and they will take hours release. But human victims displaying the to days to break down even in direct sunlight. If characteristic symptoms of organophosphate there has been a valid dissemination technique exposure (DUMMBELLS or SLUDGEM) are used then look for clues on surfaces in the area always the ultimate and best nerve agent near the dissemination. detector. Is There a Valid Threat Scenario? Agent Toxicity When responding to potential CWA releases Before discussing the toxicity of the CWAs responders should first think about what the it’s important to understand how toxicity is potential threat scenario is. Terrorists are most defined: likely to use CWAs against high-visibility . Dosage: is the amount of substance targets: administered per body weight . Transportation: subways in Tokyo . ECt50: Median Effective Dosage of a . Public venues: sports arenas, vapor or aerosol is the effective dosage conventions that will cause some defined effect in . Dignitary visits 50% of exposed, unprotected people Terrorists are not as likely to use CWAs against . ED50: Median Effective Dosage of a normal everyday people unless they are part of liquid agent is the amount expected to a large crowd, big event or part of the cause some defined effect (like collapse transportation system (like subways). or convulsions) in 50% of exposed, unprotected people . LCt50: Medial Lethal Dosage of a Nerve Agent Actions chemical agent vapor or aerosol is the Vertebrate nervous systems are hybrid dosage that is lethal to 50% of exposed, electrical-chemical systems. Electrical pulses unprotected people for a defined minute travel down the neurons and chemicals volume (MV) and exposure duration complete the transfer to the next nerve at the . LD: Lethal Dose synapses. Organophosphates Nerve agents . LD50: Median Lethal Dosage of a liquid quickly shut down the nervous system by chemical agent is the amount expected blocking acetyl cholinesterase (AChE) to kill 50% of a group of exposed, transmission at the nerve synapses and unprotected people because of this they are also known as acetyl . MV(L): Minute Volume in liters cholinesterase inhibitors. AChE normally binds . ROE: Route Of Entry and hydrolyzes the neurotransmitter ACh, which ends the activity of ACh at the receptor sites. Nerve agents bind to AChE, making it unable to bind with ACh. ACh is not hydrolyzed and it builds up causing an hyperactivity/ overstimulation of the body organs stimulated by cholinergic neurons. Essentially the affected nerves go into “overdrive.” At high dose IDLH (Immediately Dangerous to Life and Health) levels they produce muscles twitches, foaming at the mouth, tremors, and lungs constrict & fill with fluids. At low dose TWA (Time Weighted Average or 8 hour dosage) levels they can produce pinpoint pupils, watery eyes, stomach

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

GB Toxicity Estimates HD Toxicity Estimates

VX Toxicity Estimates HN1 Toxicity Estimates

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

Biological Detection DUMBBELLS Humans can smell Sulfur Mustard (HD) at D - Diarrhea (Diaphoresis-excessive about 0.1 ppm while the LCt50 is 1500 ppm. sweating) Smell is not a reliable indicator as it can vary U - Urination (peeing) with individual, batch, purity. Exposure to even M - Miosis (constriction of the pupil of the very low levels of nerve agent vapor produces: eye) . Observable signs: Miosis and runny nose B - Bronchospasm (difficulty breathing) . Symptoms: Headache, blurred or dim B - Bradycardia (slow heart beat) vision E - Excite skeletal muscle and CNS emesis Nerve agent will kill other species, and dosage (vomiting) is dependent on the size and the metabolism of L - Lacrimation (tearing) the animal. Smaller animals with fast L - Lethargy (fatigue) metabolisms will be affected faster than large S - Salivation (excessive drooling) animals with slower metabolisms. Insects, amphibians, reptiles, birds and small mammals SLUDGEM will all be affected by nerve agents before S - salivation (excessive drooling) humans. However, humans are biological L - lacrimation (tearing) indicators for large animals like horses and U – urination elephants. Because of its low vapor pressure D - defecation / diarrhea and high vapor density, nerve agents will not G - GI upset (cramps) E - emesis (vomiting) M - muscle (twitching, spasm, "bag of worms”)

Severity of symptoms is dose dependent. Here are some more specific symptoms to look for: . stay aerosolized, meaning that they will quickly Nose: runny nose (Rhinorrhea) . fall to the ground, affecting ground dwelling and Airways: tightness in chest, difficulty grazing species first. The characteristic breathing, wheezing (Dyspnea) . symptoms of CWA exposure, both in humans GI Tract: nausea, vomiting, diarrhea . and in animals, are one of the best and most Glands: increase of secretions sweat, unequivocal means of establishing the nasal, salivary, bronchial . presence of CWAs. Skeletal: muscle twitching . Central Nervous System (CNS): Nerve Agent Symptoms confusion, agitation, forgetfulness, There are two major mnemonics used to insomnia, irritability, impaired judgment, remember human (and animal) nerve agent seizures, coma symptoms: DUMBBELLS and SLUDGEM. . Eyes: pinpoint pupils (Miosis ) Each captures many of the same symptoms “The eyes may be the window to the soul, somewhat differently. Irritated eyes and but they also can serve as an agent throats are NOT found in the SLUDGEM or alarm” (i.e. Miosis) (Brad Rowland, DPG) DUMBBELLS acronyms and are NOT valid clues to the presence of CWAs. Bird Kill Examples In 12/2000 there was a bird kill at the Texas State house in Austin, TX. As George H.W. Bush was governor and president-elect there was a viable threat scenario in this case. Upon questioning the building maintenance people it was found that they had baited the area for “nuisance” birds. In about the same time there was a bird kill at a low-income apartment complex in Woonsocket, RI. Upon questioning the building maintenance people Copyright © 6/14/2012 Chris Wrenn Environics USA, Inc. 1308 Continental Drive, Suite J, Abingdon, MD 21009 Tel: (410) 612-1250, Fax: (410) 612-1251 [email protected], www.EnvironicsUSA.com Page 10 of 24

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response it was found that they had baited the area for “nuisance” birds. CWA Location

Certainly the Austin response had a higher Why Are Survey threat scenario and required a higher level of Sensors response. However, over-responding in the Important? Woonsocket scenario could have caused Survey sensors or fearful apartment dwellers to harm themselves “sniffers” are one of even when there was no threat to them. the best tools to Clues Summary quickly identify if . Any signs of dissemination techniques? something is out o A dissemination technique MUST be there and where it is used to effectively spread CWAs located. If you can’t – Explosion that dispensed liquids, find “it” you will mists or gases never figure out what “it” is. On their own, – Explosion that seemed to only survey sensors will not tell what that destroy a package or the bomb “something” is, but they can often quickly (<3- itself 10 seconds) tell where it is coming from and – Unscheduled or unusual spray how much is there. “Classification” and – Abandoned spray devices “Identification” devices may be too slow to . Is there a valid/credible threat? “sniff.” . Is there any physical evidence? M9 tape o If liquid samples are found do they M9 is a “dumb” survey bead up or are they quickly absorbed technique. M9 tape is a into M8? simple colorimetric o Classic CWAs are not “gasses” and technology. It is there will be strong clues if they have designed to be taped to been used personnel (on boots and o CWAs are heavy, low-vapor pressure the bottom of pant legs) and liquids, after effective dissemination the to vehicle bumpers. It only indicates red as a area should appear to be coated with it positive response and is best used with a o Days after dissemination/spills CWAs classification technology. on outdoor surfaces exposed to  Advantages sunlight will have degraded but CWAs o Simple can still be found in protected areas o Stores well (keep cool) such as soils, groundwater o Inexpensive (<$7 for 10m roll) . Are there any biological clues?  Disadvantages o Are there any dead animals or ones o A liquid sample is required that display SLUDGEM /DUMBBELLS o Red color change can’t be read with type symptoms? night vision filters (red) on flashlights o Are there any human victims displaying o Many organics will provide positive SLUDGEM /DUMBBELLS symptoms? response including cleaning solvents, o Irritated eyes and throats are NOT ammonia, some petroleum products found in the SLUDGEM or and even high temperatures. DUMBBELLS acronyms and are NOT valid clues to the presence of CWAs PIDs and FIDs o If no human signs or symptoms take a A Photoionization Detector (PID) or Flame breather and figure it out, do not rush Ionization Detector (FID) may provide faster to antidotes and decon “sniffing” for the location of CWA than most CWA classifiers because they not only respond faster but can display below the alarm threshold so that concentration gradients can be “seen.” CWA classifiers Copyright © 6/14/2012 Chris Wrenn Environics USA, Inc. 1308 Continental Drive, Suite J, Abingdon, MD 21009 Tel: (410) 612-1250, Fax: (410) 612-1251 [email protected], www.EnvironicsUSA.com Page 11 of 24

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response often require more time to detect, therefore, when sampling, the user often must check for The ChemPro100i can Locate and potential contamination slowly and Classify Simultaneously methodically, much like when checking for One product, the ChemPro100i, can locate or alpha radiation contamination. Coupled with “sniff” and classify simultaneously. It clues (e.g. chemical pools, clouds, dead provides a rolling line graph and audible animals, victims, placards and waybills) that “Geiger-Counter” style beep so users can provide identification of a chemical, some “see” and “hear” areas of higher survey sensors like PIDs and FIDs can quickly concentrations. It can be easily used as a tell how much is there when the proper scaling survey tool, much like a Photoionization factors (Correction Factors) are used, but they Detector (PID) “on steroids” to quickly “see” 241 are broad-band detectors that respond to a concentration trends. The AM (Americium- wide variety of chemicals other than CWAs. 241) NRC exempt source of the ChemPro100i produces approximately 60KeV (60,000eV) so it can “see” hundreds of gases & vapors with high ionization potentials (like chlorine, carbon tetrachloride, etc.) that go unseen by most PIDs which are limited to just 10.6eV.

 Advantages o Relatively inexpensive to purchase o Can detect many CWAs in air o Fast response time o Store well o Inexpensive to use <$0.25/hr for PID <$1.00hr for FID  Disadvantages o PIDs with 10.6eV lamps can’t “see” hi IP chemicals (Sarin is borderline, can’t see chlorine or phosgene) o Non specific

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

the sample pads for faster response than CWA Classification waiting for an airborne sample). The test Classification may process takes 12-25 minutes and the take more time than instructions are complicated and hard to read location. Classifiers off of the dark green packaging material. It is will typically come up counter-intuitive that the G series indication is with an answer a lack of color change where the other pads quicker on real agent do change colors. Most colorimetric than on cross- techniques make a positive color change, sensitive chemicals. from white to a new color, in the presence of There are two the target chemical. fundamental types of  Advantages CWA classification o Cheapest way into vapor detection of techniques, chemical color change CWAs ($140 per kit) technologies (colorimetrics) and direct reading o Can do liquids too devices. Properly used in conjunction with o Stores well (keep cool) each other and the other clues at a scene,  Disadvantages these technologies can provide a very high o 15-25 minute test time degree of confidence. o Complicated instructions o “Trainer” kits are only differentiated M8 Paper from the real thing by a hard to see M8 Paper is blue band around the dark olive one of the green package. simplest o Interferents: some smokes, high means of temperatures and petroleum classifying products CWAs. o Per use cost of $140 is high if Some have multiple samples are required called it “pH paper” for CWA. Detection is based upon solubility of dyes in CWA. Nerve Colorimetric Tubes indicates yellow, Blister indicates red and VX indicates green. . Advantages Often referred to as “Draeger” tubes after the o Simple German manufacturer, a colorimetric tube is o Stores well (when kept cool) a glass tube filled with a silica substrate o Inexpensive (<$5 per book) coated with reagent that will produce a color . Disadvantages change when exposed to the chemical of o A liquid sample is required interest. The user draws a predetermined o Many organics will also dissolve the sample through the tube and reads the scale dyes including cleaning solvents, like reading an old glass thermometer. The ammonia, some petroleum products tube is calibrated at the factory and this and even high temperatures. calibration is printed on the side of the tube as a scale. Calibration is typically valid for M256A1 Kit operation life of tube (2 years). The M256A1 kit is an organic chemistry set on a paper card to provide classification of nerve, blister and blood agent gas, vapors and liquids (an undocumented feature of the M256A1 kit is that drops of chemical samples can be put on

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

Some common Tubes for WMD Chemical Draeger Sensidyne PN Detects Species PN Phosphoric 6728461 (132LL) GA, GB, GD esters Dichlorovos/ Trichloroethylene Carbon 8101791 Chloropicrin Tetrachloride Organic CH26303 (19LA) Arsine Lewisite Arsenic Compounds Thioether CH25803 N/A Mustard (HD) (Qualitative) Organic Basic CH25903 Mustard Nitrogen acetone is used by one manufacturer to help Nitrogen Mustard absorb moisture. Membranes, sieve packs (Qualitative) and dopants are expensive consumables that Phosgene CH28301 (16) Blood/Choke have to be periodically replaced (typically HCN CH25701 (12L) Blood/Choke annually depending on use). So metimes Cyanogen CH19801 Blood Chloride change out is predictable but they can fail Cyanide 6728791 Blood/Choke unpredictably when presented with gross Chlorine 6728411 Blood/Choke contaminants. The membrane slows  Advantages response time, especially on VX, and also o Proven technology slows recovery when the detector is exposed o Factory calibrated (no expensive to high chemical concentrations. Some calibration gas required) closed loop IMS CWA detectors need to be o Relatively inexpensive vapor detection “exercised” or run once per day/week/month technique ($2-10 per sample) or else they will not work when an emergency comes. To “exercise” a detector, turn it on,  Disadvantages wait for it to stabilize, challenge it with o “Snap Shots,” non-continuous, no simulant and then wait for it to clear. This alarms can result in sampling error process may take over an hour. o Respond in minutes rather than  seconds Advantages o o 15-25% accuracy Piston/Bellows style Sensitive Instrument good for vapor o Readings subject to interpretation detection o o Does not store well, tubes expire and a Military proven technology o large stock is expensive to keep up to Quick response time o date (keep cool) Good detection of class (i.e., G vs. H)  Disadvantages Traditional “Closed Loop” IMS o False positives to many common Ion Mobility Spectroscopy (IMS) uses a urban chemicals radiation source (ionizing and non-ionizing) to o Small to none TIC capability until break down a sample into ions that then travel $20-30K detectors down a magnetic drift tube where the ions are o Some use radioactive sources that separated to generate a characteristic spectra require NRC license and periodic or “picture.” This picture is matched up against wipe testing pictures in the detector’s library to provide a o Unpredictable maintenance intervals, positive identification. One simplistic way to if the sieve gets chemically look at IMS is “ion distillation.” In traditional contaminated it will not work closed loop IMS, the ion cell is separated from o Membranes slow response time ambient air by a membrane to keep o Stores poorly, must be exercised contaminants from affecting the signal. Clean o Can be expensive to maintain lifetime air, provided by a sieve pack, keeps the inside costs of +$2/hr of use of the ion cell perfectly clean. Sometimes chemical dopants are also used to keep contaminant under control. For example, Copyright © 6/14/2012 Chris Wrenn Environics USA, Inc. 1308 Continental Drive, Suite J, Abingdon, MD 21009 Tel: (410) 612-1250, Fax: (410) 612-1251 [email protected], www.EnvironicsUSA.com Page 14 of 24

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

 Disadvantages Open Loop or “Aspirated” IMS o False positives to many common The open-loop IMS sensor uses a Nuclear urban chemicals (typically shown as Regulatory Commission (NRC) exempt 241Am a “Chemical Threat” alarm) (Americium) ionization source. As safe as a smoke detector, it does not require periodic Surface Acoustical Wave (SAW) 63 nuclear wipe tests like Ni (Nickel) sources in SAW sensors convert acoustic waves to some other IMS products. The IMS sensor is electrical signals by exploiting the open to the environment, no membrane or piezoelectric effect of certain materials. Their sieve pack is used to maintain cleanliness in use for CWA detection originated in the US the sensor. Because of this, the open loop IMS Naval Research Labs. A waveform (sound) can provide much faster response and clearing is generated on a quartz substrate. The times than closed loop IMS, allowing for open- substrate is coated with a polymer that has loop IMS to also be used for location or an affinity with the chemical to be detected. “sniffing.” The high ionization potential of its When the target chemical bonds with the 241 Am source allows it to be used to sniff for polymer coating, the wave form frequency GB, chlorine and other high ionization potential changes (tone changes) indicating that the chemicals largely unseen by PIDs with a target chemical is present. Selectivity comes 10.6eV lamp. Life-cycle costs and logistical from the choice of the polymer coating. footprint are much less than those of traditional Simplified, a SAW is essentially a polymer closed-loop IMS and flame-spectrophotometer (“paint”) on a quartz substrate; the chemical based devices because it does not require of interest is absorbed into the paint and costly membranes and sieves to keep the changes the tone. sensor clean and it does not use expensive hydrogen gas.

While an elegant solution SAWs have two problems. First, while specific they lack low end sensitivity relative to IMS and flame  Advantages spectrophotometry. Second o Sensitive instrument good for vapor they are very susceptible to detection chemical contamination of their o Military proven technology polymer coatings. To illustrate o Quick response time this, consider a handprint by a o Good detection of class (i.e., G vs. H) light switch on the wall. After o Good TIC capability (>40) cleaning the handprint o As safe as a smoke detector (especially with small children) it eventually o Predictable service intervals comes back. Eventually cleaning the o Stores well, no need to exercised handprint is not enough and the wall must be o Inexpensive to maintain, lifetime costs repainted. As the paint (polymer) in a SAW <$0.50/hr of use absorbs chemical, some of that chemical Copyright © 6/14/2012 Chris Wrenn Environics USA, Inc. 1308 Continental Drive, Suite J, Abingdon, MD 21009 Tel: (410) 612-1250, Fax: (410) 612-1251 [email protected], www.EnvironicsUSA.com Page 15 of 24

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

(either target or interferent) is left behind. As burn in a colorless hydrogen flame. Fireworks take advantage of this characteristic to produce the desired colors. In the case of spectrophotometry for CWA detection the detector looks for the spectra that are specific to phosphorous, sulfur, arsine and nitrogen compounds that are a defining characteristic of nerve and blister agents. It provided relative quantification by the intensity of the color. The brighter the color the more chemical is present. It is very sensitive and quick to respond to chemicals that contain sulfur (blister), phosphorous (nerve), amines (nitrogen mustard) and arsine (lewisite). However, this technology is perhaps the least specific to CWAs of any of the competing technologies because ANY chemical containing phosphorous, sulfur, amines and arsine will give false positive alarms. Product manuals warn against locating near exhausts which can produce false blister alarms because sulfur dioxide is a by-product of the combustion process. Phosphorous is not just in chemical is left behind the baseline signal rises, organophosphates. The second largest use eventually the baseline signal rises to the point of phosphorous in the world is as a fabric that it equals the signal level and detection is safe whitener in detergents. So if one does no longer possible. A new sensor is needed not rinse clothing thoroughly, a Flame and SAW sensors are expensive to replace. Spectrophotometry detector could improperly . Advantages identify detergent residue as nerve agent o Specific vapor detector contamination. These devices only classify o Proven technology to the main chemical species and are not as o Stores well (assuming no specific as IMS and SAW detectors, which contaminants in the air) are much more specific to organophosphates . Disadvantages and blister agents. o Some common vapors (like alcohols) . Advantages may ruin the polymer coating o Military proven technology o Less sensitive, alarms well above o Quick response time military levels o Stores well, no memory affect o Unpredictable end of life . Disadvantages o Lifetime costs can be significantly o EXPENSIVE to purchase higher than IMS based products o False positives to exhausts, fuel (~$9/hour of use) spills and detergent o Does not measure TICs (unless they Flame Spectrophotometry contain sulfur, phosphorous, amines Chemicals produce characteristic or arsine) electromagnetic spectra (colors) when they o Run time constrained by hydrogen size to 12 hours per cylinder (@$100 per cylinder) o Long-term operations can be hindered by the requirement for hydrogen gas o Hydrogen gas is difficult to ship by air, which hinders air deployment of Copyright © 6/14/2012 Chris Wrenn Environics USA, Inc. 1308 Continental Drive, Suite J, Abingdon, MD 21009 Tel: (410) 612-1250, Fax: (410) 612-1251 [email protected], www.EnvironicsUSA.com Page 16 of 24

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

this technology (hydrogen fill station longer to come up with a solution when costs $75K) presented with simulants than if presented o >$12/hour to run with the real thing. Orthogonal Detectors CWA Simulants/Cross-sensitivities for “Orthogonal” means to Classifiers look at something from . Brake fluid (nerve on some IMS, SAW many different angles and and M8) orthogonal detectors do . Anti-freeze (blister on some IMS) this by using a variety of . Anything with methyl salicylate (oil of sensors rather than just wintergreen) including: Skoal, one type to come to a Wintergreen Altoids, Peppermint Oil, conclusion. Each sensor Mennen “Speed Stick,” “Deep Heat,” Ben has its strengths and Gay, (blister on some IMS) weaknesses. “Sensor . Detergent residue on clothing due to the fusion” takes advantage of phosphorous in “whiteners” (nerve-Flame this by utilizing the Spectrophotometry) strengths of a number of . Sulfur compounds in fuel products or sensors to come to a final conclusion. exhaust (blister-Flame Advanced signal processing is used to match Spectrophotometry) the pattern from the sensor array to a library of . Fingernail polish remover (nerve-M8) compounds. By using multiple sensors the . Cleaners that containing esters including: goal is to increase sensitivity while reducing “Super Gleam” glass cleaner, ACE Brand false alarms. Another way of looking at this is window cleaner, “Spray-9” industrial that redundancy is built into the detector. cleaner (nerve on some IMS) . Advantages . Real toxic materials (chemically similar to o Less false alarms nerve) o More chemicals detected than just a o Parathion, Malathion (nerve) short CWA list o DMMP: Dimethyl Methyl o Great when they cost less or the same Phosphonate (nerve) also possibly as the sum of the various detectors that found in flame retardants they replace o TEP: Triethyl Phosphate (nerve) also . Disadvantages found in plasticizers so decon tents o Can be very expensive and Level A suits possibly could give o Can be larger and heavier “nerve” alarms on some detectors o Their value is questionable when they o Tributoxyethyl phosphate (TBEP) cost much more than the sum of the found in Acolade floor polish is also detection technologies they include US Army VX simulant CWA Classifiers Can Be Fooled Every detector will have some false positives. Typically different detector technologies will have different false positives. Most CWA classification techniques were designed for the battlefield environment and do not always take into account cross-sensitivities from common chemicals found in the urban environment. Low vapor pressure for most CWAs complicates classification because other low vapor pressure chemicals can fool the algorithms. This is not a condemnation of CWA classifiers, just a realization that multiple confirmational techniques may be required in CWA response. CWA classifiers tend to take

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

handle mixtures varies with vendor although CWA Identification some products will not be able to see a After a chemical has component in a mixture if it accounts for 10% been located and or less of the mixture. They typically have classified in some the advantage of low lifetime costs but they special situations it is can be expensive ($10’s of thousands) to necessary to identify purchase. it. Speciation  Advantages (typically o Can identify many solids, liquids, spectroscopy) pastes, gases & vapors technologies are used o Relatively easy to use to identify chemicals o Low calibration and logistical so that additional requirements actions can be taken. “Spectroscopy” is the o Stores well study of how electromagnetic radiation interacts . Disadvantages with the atoms and molecules: o Either solids or gases not both . “Infrared” or FTIR spectroscopy is the study o Some difficulty with mixtures of how infrared light is absorbed by the o Some are heavy and bulky bonds between atoms that form molecules o Very expensive to purchase . Mass Spectroscopy ionizes pure chemical peaks, produced by a gas chromatograph, Gas Chromatography/Mass which breaks down into characteristic and Spectroscopy identifiable pieces; this spectral “fingerprint” GC/MS is the combination of two is unique to a particular chemical and can technologies to help identify gases or vapors: be matched to a library. Gas Chromatography (GC): separates high Essentially spectroscopy is the science of boiling from low boiling chemicals (low vapor taking a “picture” and matching that picture to pressure from high vapor pressure) and puts another known “picture” in a library. Once a them into “peaks” that represent their spectrum is acquired the system software can characteristic travel time through a perform a search analysis for the “unknown” in chromatography column (a small very small question. capillary tube). High boiling (low vapor pressure) compounds have longer retention FTIR Spectroscopy time in the capillary than low boiling (high In Fourier Transform Infrared (FTIR) vapor pressure) compounds. The resulting spectroscopy, infrared (IR) radiation is passed graph is called a “chromatogram” which through a sample. Wavelengths of IR light that shows a series of peaks representing a chemical absorbs determines what that different chemicals separated by the time that chemical is (fingerprint). Each molecular each takes through the column. structure has a unique combination of atoms and produces a unique infrared spectrum (identification = qualitative). When FTIR is used for gas/vapor measurement, thanks to the Beer-Lambert Law the amount of IR that is absorbed (intensity) determines how much chemical is there (concentration = quantitative). FTIR is a proven technology for chemical identification used for over 50 years in applications from laboratories to law enforcement and industry. FTIR can be used to identify some solids, pastes and liquids including CWAs. FTIR can also be used to identify some gases and vapors Mass Spectroscopy (MS): ionizes these including CWAs. FTIR analyzers are typically pure chemical peaks which break down into fast acting and easy to use. Their ability to characteristic and identifiable pieces. This

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response spectral “fingerprint” is unique to a particular chemical and can be matched to a spectral Ask the Right library. In the Ionizer a corona discharge ionizes the peaks into ions. In the Quadrupole Questions Rods the ions are electronically filtered and Asking the proper separated before they reach the Detector which questions may be measures their response. the key to an effective CWA response. We Some portable GC/MS have a survey mode in addition to the GC/MS mode. In this survey can’t be overly mode the GC is by-passed and the sample is dependent on drawn directly into the MS. This gives quicker technology. We response time of about 2 minutes versus the have to also use 15-25 minute process time for GC/MS mode. common sense. Survey mode can analyze relatively pure If the classical samples to 10’s of ppm but had difficulty with signs of CWA exposure are NOT present in mixtures and providing low levels of sensitivity. both animal and human victims then it can be assumed that CWAs are NOT present no In GC/MS mode the GC separates each matter what other detection techniques are chemical into peaks and then each peak is showing. . further separated into ions for identification by Take a “breather” and work the clues to the MS. This mode is most useful for solve the problem separating mixtures and has high sensitivity If it is not an obvious CWA attack, but some (10’s of ppb) but it takes much longer, 15-25 detection technologies are giving false minutes per sample. alarms, responders need to ask questions to . Advantages see if there have been any recent changes to o The “Gold Standard” of gas detection the environment that are causing the false o Very accurate alarms: . o Very specific Dissemination questions o . Disadvantages Has there been an explosion that dispensed liquids, mists or gases? o Very expensive to purchase ($60- o $100K) Has there been an explosion that o “Snap Shots,” non-continuous (MS can seemed to only destroy a package or run continuous) the bomb itself? o o Respond in minutes rather than Has there been an unscheduled or seconds (~2 min in survey ~20 min in unusual spray? o GC/MS mode) Has there been any abandoned o Very complicated & training intensive spray devices? . o Very heavy and bulky Is there a valid/credible threat? o o Does not store well (NEG vacuum Are there any high profile individuals pumps prefer constant rather than visiting? o intermittent use) Is a high profile event taking place? . o ~$35/hr to use Is there any physical evidence? o If liquid samples are found do they CWA Identification Technology bead up or are they quickly absorbed Summary into M8? While typically more expensive to purchase and o CWAs are heavy, low-vapor pressure while they may take longer to make a liquids, is the area coated with measurement, they provide a “quality check” on anything, are droplets or pools of faster and cheaper colorimetric and direct liquid present? reading technologies. o Days after dissemination/spills CWAs on outdoor surfaces exposed to sunlight will have degraded but

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

CWAs can still be found in protected areas such as soils, groundwater Integrating Gas . What has changed, what is different from before the incident? Detection o SHOW ME . Technologies Have there been any recent cleaning Every technology has activities? its strengths and o Esters in some professional cleaners weakness. In the can mimic G-series agents because following chart there nerve agents are esters are three continuums. o Some professional floor waxes/sealers The top line moves contain VX simulant from broadband o SHOW ME detection to very . Have there been any recent construction specific gaseous activities? detection. The second o Can include gluing, painting, cleaning line is a metaphoric line and the lowest line and exhausts from construction represents speed of detection. A PID can machinery locate contamination in seconds. o SHOW ME Metaphorically speaking the PID can get to . Have there been any recent applications the right state in seconds. An IMS product of pesticides? can classify in 10’s of seconds. o Some pesticides are chemically similar Metaphorically speaking it can get to the right to G-series and they will alarm as town in 20-30 seconds. A GC/MS can “Nerve” even if levels are not high identify a gas/vapor in 25 minutes. enough to provide symptoms in human Metaphorically speaking it can identify the victims correct “address” in 25 minutes. So a PID o SHOW ME can be used to find contamination while an . Have there been any recent attempts at IMS can classify it. While classification is removal of nuisance species using adequate for making antidote decisions in the chemicals or bait? field it is not good enough for evidence and a o Dead birds, rodents and small animals GC/MS or FTIR analysis of the sample probably are not signs of chemical provides more solid identification. agent attack if people are not affected o SHOW ME . Are there any internal combustion engines running nearby? o Diesel exhaust can set off some CWA detectors . Could there be a lot of plastics in the area? o Plasticizers like TEP, used in rubberized tents and Level A suits can Detection Limits are Important simulate nerve agents Make sure that you understand the detection limits of your CWA detection technology. Ask the Right Questions Summary Limits of Detection (LOD) can vary widely The questions you ask are perhaps the most with detection techniques. IMS and Flame important part of CWA response. If the answer Spectrophotometry can provide fast results to to any of these questions is “yes,” investigate very low levels. SAW detectors can have further before concluding the presence of much higher limits of detection as the CWAs. If you find chemicals, look at their following two charts demonstrate. While ingredients or MSDS to see if they contain any FTIR can be very accurate, one common compounds that might provide a cross-sensitive gaseous FTIR detector has a LOD of 50ppm! response.

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

also the cost of ownership. Some products Handheld CWA Classifier Sensitivity need expensive consumables or services Comparison which can mean very expensive hourly run- Agent Environics Bruker MSA Proengin Smiths Mild rate costs. Some products have unusual Effects logistics demands (like requiring unusual ChemPro100i RAID- HazMat AP2C LCD gases to operate) that may not be readily M 100 CAD Plus 3.3 available during a national emergency. GB 0.04-0.1 0.05 0.2- 0.01 mg/m3 0.1 (0.4 mg/m3 mg/m3 0.9/0.13- mg/m3 Some products may not store well (requiring mg/m3) 25 mg/m3 weekly/monthly “exercising”) or may need a VX (0.1 0.04-0.1 0.05 0.2- 0.03 mg/m3 0.1 long time to “warm up” (as long as an hour or mg/m3) mg/m3 mg/m3 0.9/0.13- mg/m3 two) after extended periods of storage. When 3 25 mg/m looking to purchase, make sure the entire HD (25 0.5-2.0 0.35 1.2- 1 mg/m3 1 mg/m3) mg/m3 mg/m3 1.4/0.23- mg/m3 story is revealed! The following chart 0.31 compares CWA detectors as cost per hour of mg/m3 use: HN1 0.5-2.0 0.35 1.2- - 2 (25 mg/m3 mg/m3 1.4/0.23- mg/m3 mg/m3) 0.31 mg/m3 Sensitivity is nothing without specificity. One of the most sensitive detectors is the least specific.

In addition to purchase cost, look for products that have low cost of ownership (if all else is equal). Look for products that have multiple uses. This allows operators to become familiar with their performance across a wide range of applications. Single use products like CWA only detection technologies tend to get underutilized and users quickly lose their aptitude when they are not frequently using a detection technology. Another way of looking at this is that multi-use products don’t not have to sit around and “gather dust” waiting for a CWA response. The other side of this is that with routine use the user skills on the product don’t gather dust either.

Life Cycle Costs and Sustainability When purchasing expensive detection technologies for CWA response one should consider not only the cost of acquisition but

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

Putting It All Nerve alarm in a Sports Stadium Together The HazMat team for a state capitol did a In this diagram, each security sweep for the local college football circle represents team prior to a big game. On a sweep the whether or not a day before an event they consistently got particular “Nerve” alarms on their ChemPro100. Upon technique/clue is questioning the custodial staff they found that providing a positive they had just sprayed the stadium with response. By pesticide. By closely inspecting the pesticide overlaying multiple they found that it was an organophosphate techniques one can zoom in on the solution just pesticide that should give “Nerve” alarms. like a detective uses multiple clues to solve a They scanned the morning of the day of crime. Use multiple techniques until the event and found no pesticide readings. If solution reveals itself. they had found 1. Clues pesticide  Any signs of dissemination techniques? readings the day  Is there a valid/credible threat? of event the  Is there any physical evidence? ChemPro100 allows users to  Are there any dead animals or ones that display SLUDGEM /DUMBBELLS zero out this type symptoms? background and still alarm if  Are there any human victims displaying levels were to SLUDGEM /DUMBBELLS symptoms? rise. 2. Location devices 1. Clues  Using PID, FID, M9 are there any  Any signs of dissemination areas of higher concentrations? techniques? NO 3. Classification devices  Is there a valid/credible threat? YES  What are the color change  technologies telling you? Is there any physical evidence? NO  Are there any dead animals or ones  What is your CWA detection that display SLUDGEM technology(s) telling you? /DUMBBELLS type symptoms? 4. Identification devices NO  Are there any human victims  Verify the above clues with an displaying SLUDGEM /DUMBBELLS identification technology symptoms? 5. Ask the Right Questions NO 2. Location devices  Using PID, FID, M9 are there any areas of higher concentrations? NO 3. Classification devices  What are the color change technologies telling you? Not used  What is your CWA detection technology(s) telling you? “Nerve” alarm on a ChemPro100 4. Identification devices  Verify the above clues with an identification technology Not used 5. Ask the Right Questions Pesticide

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

Nerve Gas in a Catholic High Irritated Eyes & Throats in an Office School Building A HazMat team was called to a Catholic High A fire department was called to an office School for “irritated throats.” They checked building for irritated eyes and throats; no classic with a PID and found nothing. They checked CWA toxicity symptomology was noted. There with a 4 gas monitor and found nothing. was no threat scenario, no dispersant They checked with an APD2000, came up technique, no other physical evidence. No “Nerve.” Based upon this single reading they reading on the PID but an APD2000 gave a called the local “Nerve” alarm. The floors were very shiny. CST, set up a HazMat asked building maintenance if anything mass decon line had changed overnight (no symptoms were and noticed the prior day). Building maintenance decontaminated said that a floor contractor had polished the approximately floor overnight. HazMat found some of the floor 300 students. polish and found that it contained Let’s review the Tributoxyethyl clues: phosphate 1. Clues (TBEP). Not  Any signs knowing that of dissemination techniques? TBEP was VX NO  simulant, the Is there a valid/credible threat? NO  HazMat officer Is there any physical evidence? NO concluded that  Are there any dead animals or ones the phosphorous that display SLUDGEM in the floor polish /DUMBBELLS type symptoms? NO was setting off  Are there any human victims their APD2000. displaying SLUDGEM /DUMBBELLS 1. Clues symptoms? NO  Any signs of dissemination techniques? 2. Location devices NO  Using PID, FID, M9 are there any  Is there a valid/credible threat? NO areas of higher concentrations? NO  Is there any physical evidence? NO 3. Classification devices   Are there any dead animals or ones What are the color change that display SLUDGEM /DUMBBELLS technologies telling you? May have type symptoms? NO been a good next step   Are there any human victims displaying What is your CWA detection SLUDGEM /DUMBBELLS symptoms? technology(s) telling you? “Nerve” NO alarm on an APD2000 2. Location devices 4. Identification devices   Using PID, FID, M9 are there any Verify the above clues with an areas of higher concentrations? NO identification technology May have 3. Classification devices been a good next step for the CST  What are the color change 5. Ask the Right Questions NOT DONE technologies telling you? Not used  What is your CWA detection technology(s) telling you? “Nerve” alarm on an APD2000 4. Identification devices  Verify the above clues with an identification technology Not used 5. Ask the Right Questions TBEP in the floor polish

AP-102: Decision-making in Chemical Warfare Agent (CWA) Response

Irritant in a Thrift Shop There is No “Tricorder”: A major metropolitan HazMat team was called In the future represented by the classic TV to a thrift shop for “irritated throats.” They show “Star Trek,” one of the characters “Mr. checked with PID and found nothing. They Spock” used a “Tricorder” to analyze checked with a RAID-M and found unknown environments. But even in this Mace/Pepper Spray. They checked with an future the Tricorder was given to the smartest HGVI that came up “Nerve,” and they checked guy on the spaceship. In present day CWA with AP2C and got response we must be smart in coming to nothing. Most HazMat decisions using not only the high-tech teams don’t have detection technologies that we are provided access to this many with, but also the clues that we can see with meters, but in this our own eyes. case the multiple meters help to define References the problem. Let’s  Combating WMD Journal, Chemical review the clues: Warfare: Part I, Mr. A. Mark Diglio, pages 1. Clues 56-60, issue #3, January 2009  Any signs of  Combating WMD Journal, Chemical dissemination techniques? NO Warfare: Part II, Mr. A. Mark Diglio,  Is there a valid/credible threat? NO pages 30-35, issue #4, December 2009  Is there any physical evidence? NO  Detection Technologies for Chemical  Are there any dead animals or ones Warfare Agents and Toxic Vapors, Yin that display SLUDGEM /DUMBBELLS Sun and Kwok Y. Ong, 2005 CRC Press type symptoms? NO  Emergency Response to Incidents  Are there any human victims displaying Involving Chemical and Biological SLUDGEM /DUMBBELLS symptoms? Warfare Agents, John Medici, Steve NO Patrick, NFPA Supplement 14, 1997 2. Location devices  Potential Military Chemical/Biological  Using PID, FID, M9 are there any Agents and Compounds, FM 3-11.9, areas of higher concentrations? NO January 2005 3. Classification devices  What are the color change About the Author technologies telling you? Not used Christopher Wrenn is the Sr. Director of  What is your CWA detection Sales and Marketing for Environics USA a technology(s) telling you? HGVI: provider of sophisticated gas & vapor “Nerve, ” Bruker: “Mace,” AP2C detection solutions for the military, 1st nothing (very good layering of responder, safety and homeland security classifiers) markets. Previously Mr. Wrenn was a key 4. Identification devices member of the RAE Systems team. Chris  Verify the above clues with an has been a featured speaker at more than 20 identification technology Not used international conferences and has written 5. Ask the Right Questions Never proved numerous articles, papers and book chapters it but suspect that Pepper spray went off on gas detection in HazMat and industrial in a purse safety applications.