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A-1 APPENDIX A Chemical Threat Information A.1 POSSIBLE TYPES OF AGENTS VX, and soman. Other chemicals mentioned include: Prussic acid (hydrocyanic acid), lysergic acid (LSD), aminazin, There is a wide range of chemicals that are potentially pheromones, pure nicotine, phosgene oxime (CX), arsenic, attractive to terrorists, whether at a fixed site or during trans- Cobalt-60, compound 1080 (sodium fluoroacetate), arsine, portation. There are numerous sources that can be consulted nickel carbonyl, and strychnine. Toxic chemicals can be cat- for lists of such chemicals, among them being the following: egorized as shown below based upon Cordesman, 1996. The EPA Risk Management Program (RMP) 40 CFR Part NERVE AGENTS: Agents that quickly disrupt the nervous 68 lists 77 regulated toxic chemicals. See www.epa.gov/ system by binding to enzymes critical to nerve functions, ceppo. causing convulsions and/or paralysis. Must be ingested, The OSHA Process Safety Management (PSM) Standard inhaled, and absorbed through the skin. Very low doses cause 29 CFR 1910.119 provides a list of 136 toxic and highly a running nose, contraction of the pupil of the eye, and diffi- reactive hazardous chemicals. See (www.osha.gov). culty in visual coordination. Moderate doses constrict the The FBI Community Outreach Program for Manufactur- bronchi, cause a feeling of pressure in the chest, and weaken ers and Suppliers of Chemical and Biological Agents, the skeletal muscles and cause fibrillation. Large doses Materials, and Equipment has a table of 42 industrial cause death by respiratory or heart failure. (Can be absorbed chemical materials and agents that "may be more likely through inhalation or skin contact.) Reaction normally to be used in furtherance of WMD terrorism." See (http:// occurs in 12 minutes. Death from lethal doses occurs within www.aiche.org/ccps/pdf/fbi_wmd.pdf) minutes, but artificial respiration can help and atropine and The Australia Group list of chemical and biological the oximes act as antidotes. The most toxic nerve agents kill weapons provides a list of 54 chemical weapons pre- with a dosage of only 10 milligram-minutes per cubic meter, cursors. See www.australiagroup.net versus 400 for less lethal gases. Recovery is normally quick, The Chemical Weapons Convention (CWC) provides if it occurs at all, but permanent brain damage can occur. three toxic chemicals and 11 precursors under Sched- Examples of nerve agents are: ule 2 and 17 toxic chemicals under Schedule 3. See www.cwc.gov. Tabun (GA) The Department of Transportation's (DOT's) 2004 Sarin (GB)--nearly as volatile as water and delivered by Emergency Response Guidebook contains guides to air. A dose of 5 mg-min/m3 produces casualties, a respi- responding to dangerous goods/hazardous materials ratory dose of 100 mg-min/m3 is lethal. Lethality lasts incidents. Each guide is designed to cover a group of 12 days. materials that have similar chemical and toxicologi- Soman (GD) cal properties. This may be obtained online through GF http://hazmat.dot.gov/pubs/erg/gydebook.htm. VR-55 (Improved Soman) A thick oily substance which persists for some time. The above sources list at most a few hundred chemicals. In VK/VX/VE/VM/VG/VS--Persistent agents are roughly actuality there may be "literally tens of thousands of poiso- as heavy as fuel oil. A dose of 0.5 mg-min/m3 produces nous chemicals" that might be of some use to terrorists (Kup- casualties, a respiratory dose of 10 mg-min/m3 is lethal. perman and Kamen 1989). Mullen (1978) cites an estimate of Lethality lasts 116 weeks. "well over 50,000" for the number different organophosphate (of which sarin is one) alone. Purver (1995) provides a list of BLISTER AGENTS: Cell poisons that destroy skin and chemical agents specifically mentioned in the then-current lit- tissue, cause blindness upon contact with the eyes, and erature on terrorism: insecticides such as nicotine sulfate, which can result in fatal respiratory damage. Can be col- DFP (diisopropylphosphorofluoridate), parathion, and TEPP; orless or black oily droplets. Can be absorbed through herbicides such as 2,4D and 2,4, 5T (against plants), TCDD inhalation or skin contact. Serious internal damage if (dioxin), and benzidine (112-14); "blood agents" such as inhaled. Penetrates ordinary clothing. Some have delayed hydrogen cyanide and cyanogen chloride; "choking agents" and some have immediate action. Actual blistering nor- such as chlorine, phosgene (carbonyl chloride), and chloropi- mally takes hours to days, but effects on the eyes are much crin; "blistering agents" such as sulfur mustard, nitrogen mus- more rapid. Mustard gas is a typical blister agent and expo- tard, and lewisite; and "nerve agents" such as tabun, sarin, sure to concentrations of a few milligrams per cubic meter

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A-2 over several hours generally causes blisters and swollen Produce highly fatal poisoning characterized by general eyes. When the liquid falls onto the skin or eyes it has the weakness, headache, dizziness, double vision and dilation of effect of second or third degree burns. It can blind and the pupils, paralysis of muscles, and problems in speech. cause damage to the lungs leading to pneumonia. Severe Death is usually by respiratory failure. Antitoxin therapy has exposure causes general intoxication similar to radiation limited value, but treatment is mainly supportive. An exam- sickness. HD and HN persist up to 12 hours. L, HL, and ple is Botulin toxin (A), of which there are six distinct types CX persist for 12 hours. Short of preventing exposure, the Four of these are known to be fatal to man. An oral dose of only treatment is to wash the eyes, decontaminate the skin, 0.001 mg is lethal. A respiratory dose of 0.02 mg-min/m3 is and treat the resulting damage like burns. Examples of also lethal. blister agents are: DEVELOPMENTAL WEAPONS: A new generation of Sulfur Mustard (H or HD): A dose of 100 mg-min/m3 chemical weapons is under development (this statement writ- produces casualties, a dose of 1,500 mg-min/m3 is lethal. ten in 1996). The only publicized agent is perfluoroisobutene Residual lethality lasts up to 28 weeks. (PFIB), which is an extremely toxic, odorless, and invisible Distilled Mustard (DM) substance produced when PFIB (Teflon) is subjected to Nitrogen Mustard (HN) extreme heat under special conditions. It causes pulmonary Lewisite (L) edema or dry-land drowning when the lungs fill with fluid. Phosgene Oxime (CX) Short exposure disables and small concentrations cause Mustard Lewisite (HL) delayed death. Activated charcoal and most existing protec- tion equipment offer no defense. Some sources refer to CHOKING AGENTS: Agents that cause the blood vessels "third" and "fourth" generation nerve gases, but no technical in the lungs to hemorrhage, and fluid to build-up, until the literature seems to be available. victim chokes or drowns in his or her own fluids (pulmonary edema). Provide quick warning though smell or lung irrita- RIOT CONTROL AGENTS: Agents that produce tempo- tion. Can be absorbed through inhalation. Immediate to rary irritating or disabling effects. They cause flow of tears delayed action. The only treatment is inhalation of oxygen and irritation of upper respiratory tract and skin when in con- and rest. Symptoms emerge in periods of seconds up to three tact with the eyes or inhaled. They can cause nausea and vom- hours after exposure. Examples of choking agents are: iting: can cause serious illness or death when used in confined spaces. CS is the least toxic gas, followed by CN and DM. Symptoms can be treated by washing the eyes and/or removal Phosgene (CG) from the area. Exposure to CS, CN, and DM produces imme- Diphosgene (DP) diate symptoms. Staphylococcus produces symptoms in 30 PS Chloropicrin minutes to four hours, and recovery takes 2448 hours. Treat- Chlorine Gas ment of Staphylococcus is largely supportive: BLOOD AGENTS: Kill through inhalation. Provide little Tear Gases: warning except for headache., nausea, and vertigo. Interferes Chlororacetophenone (CN) with use of oxygen at the cellular level. CK also irritates the O-Chlorobenzyl-malononitrile (CS) lungs and eyes. Rapid action and exposure either kills by Vomiting Gases: (cause irritation, coughing, severe inhibiting cell respiration or it does not--casualties will headache, tightness in chest, nausea, and vomiting): either die within seconds to minutes of exposure or recover Adamsite (DM) in fresh air. Most gas masks have severe problems in pro- Staphylococcus viding effective protection against blood agents, examples of which are: INCAPACITATING AGENTS: Agents that normally cause short term illness and psychoactive effects (delirium and hal- Hydrogen Cyanide (AC)--a dose of 2,000 mg-min/m3 lucinations). Can be absorbed through inhalation or skin produces casualties. A dose of 5,000 mg-min/m3 is lethal. contact. The psychoactive gases and drugs produce unpre- Lethality lasts 14 hours. dictable effects, particularly in the sick, small children, Cyanogen Chloride (CK)--a dose of 7,000 mg-min/m3 elderly, and individuals who already are mentally ill. In rare produces casualties. A dose of 11,000 mg-min/m3 is cases they kill. In others, they produce a permanent psychotic lethal. Lethality lasts 15 minutes to one hour. condition. Many produce dry skin, irregular heart beat, uri- nary retention, constipation, drowsiness, and a rise in body BIOLOGICAL TOXINS : Biological poisons causing neu- temperature, plus occasional maniacal behavior. A single romuscular paralysis hours or days after exposure. Formed in dose of 0.1 to 0.2 milligrams of LSD-25 will produce food or cultures by the bacterium Clostridium botulinum. profound mental disturbance within a half hour that lasts

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A-3 10 hours. The lethal dose is 100 to 200 milligrams. Examples tially the most current attempts to develop toxicity lim- of incapacitating agents are: its that are useful in the context of emergency response. AEGL-1 is the airborne concentration (expressed as BZ parts per million or milligrams per cubic meter (ppm LSD or mg/m3)) of a substance above which it is predicted LSD Based BZ that the general population, including susceptible indi- Mescaline viduals, could experience notable discomfort, irrita- Psilocybin tion, or certain asymptomatic nonsensory effects. Benzilates However, the effects are not disabling and are transient and reversible upon cessation of exposure. AEGL-2 is the airborne concentration (in ppm or A.2 MEASURES OF TOXICITY mg/m3) of a substance above which it is predicted that The routes of exposure for chemicals can be one or more the general population, including susceptible individ- of inhalation, ingestion, or absorption through the skin. uals, may have irreversible or serious long-lasting health effects, or impaired ability to escape. AEGL-3 is the airborne concentration (expressed as Inhalation ppm or mg/m3) of a substance above which it is pre- dicted that the general population, including suscep- In the context of accidental or deliberately engineered tible individuals, could experience life-threatening releases of toxic chemicals, there are several toxicity indica- health effects or death. tors. Examples are: Table A-1 displays the relative inhalation toxicity of some LC50: the "Lethal Concentration" in air that will prove of the chemicals mentioned above. The measure provided is fatal to 50% of the people exposed to it. This quantity is the AEGL-2 for one hour, the ERPG-2, or the TEEL-2, a function of exposure time. There are other, similar depending on which is available. measures, such as the LC10 (10% probability of fatal- ity) and LC01 (1% probability of fatality). The probit Pr is a concise summary of the available data Dermal Exposure on a specific chemical. For a given exposure concentra- tion and duration, there is a chemical-specific equation Some chemicals can produce hazardous health effects by from which the probit can be calculated. There is then a being absorbed through the skin. For example, the blister one-to-one relationship between the value of the probit agent sulfur mustard is specifically designed to do this. As and the probability that the exposed individual will suf- noted above, it is persistent so that people handling contam- fer fatality. inated clothing or touching contaminated surfaces can also The Emergency Response Planning Guidelines (ERPGs) be affected hours or days after the release. The most effec- are published by the American Industrial Hygiene Asso- tive way in which percutaneous absorption might occur is ciation (AIHA). As of 2002, AIHA had published ERPGs for 100 chemicals. There are three levels: (1) TABLE A-1 Relative Measures of Acute Toxicity of ERPG-1--mild irritation; (2) ERPG-2--a threshold for Chemical Agents irreversible health effects; and (3) ERPG-3--a threshold Chemical 1-hr AEGL-2/ERPG-2/ for fatalities. Each ERPG is tied to an exposure time of TEEL-2 (mg/m3) one hour. EPA uses the ERPG-2 or equivalent as the Ammonia 105.0 Hydrogen chloride 30.0 toxic endpoint for hazards analysis in its Risk Manage- Hydrogen Fluoride 16.4 ment Program. Vinyl Chloride 12.5 Temporary Emergency Exposure Limits (TEELs) are Hydrogen Cyanide 11.1 published by DOE for 2234 chemicals at http://tis.eh.doe. Sodium Cyanide 5.0 Nicotine Sulfate 9.0 gov/web/chem_safety/teel.html. Where ERPGs exist, the Chlorine 7.5 TEELs are the same. Otherwise, TEELs are intended to Benzidene 3.5 be temporary surrogates for ERPGs. Chloropicrin 2.0 Acute Exposure Guideline Limits (AEGLs) are essen- Parathion 1.0 tially time-dependent ERPGs and are applicable to five TEPP 1.0 Phosgene 0.8 emergency exposure periods (10 and 30 min, 1 h, 4 h, Phosphine 0.7 and 8 h). A five-minute AEGL is available for some Sulfur Mustard 0.02 chemicals. The latest information on AEGLS is at http:// Sarin 0.006 www.epa.gov/oppt/aegl/chemlist.htm. They are essen- VX 0.00027

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A-4 when there is liquid on the skin. Both sarin and sulfur mus- this could well be attractive. Similar arguments apply tard are effective in this way. In both cases, vapor can also be even in the case of ammonia, which has the highest of absorbed through the skin, but this is a much less efficient all the toxicity levels in the above table. mechanism. In short, the terrorist's choice of a chemical will be driven by several factors: Ingestion Toxicity Both sarin and sulfur mustard can be fatal if ingested. Persistence However, on the face of it, this does not seem a promising Vapor pressure (i.e., ease of getting airborne) avenue for a terrorist who wishes to cause large numbers of Ease of availability or manufacture of the chemical casualties. It is conceivable that persons whose skin is cont- Mass available, and (last but not least) aminated by liquid sarin or sulfur mustard could ingest some Objectives (e.g., maximize fatalities, maximize economic of the agent, but this particular exposure pathway is not con- disruption, maximize cleanup problems). sidered further here. A.3 ATMOSPHERIC DISPERSION OF CHEMICAL AGENTS Factors Potentially Influencing Terrorists' Choice of Chemical Agents There is a huge variety of ways in which toxic chemicals can be released and subsequently dispersed in the atmosphere. All other things being equal, one would choose to use The following are some examples pertinent to possible ter- chemicals near the bottom of the Table A-1 for maximum rorist activities in the transportation system. effect. However, there are many other factors that influence the likelihood of successfully achieving terrorist objectives. Gases Liquefied Under Pressure and Transported in Bulk Examples are as follows: Ammonia and chlorine are transported as gases liquefied under pressure in amounts up to 90 tons in railcars. The The vapor pressure of VX at 20 oC is 0.00063 mm/Hg. If attractiveness of these toxic materials from the terrorist per- spilled on the floor, it will evaporate extremely slowly. spective is that it is possible to release large quantities very Sarin is about 20 times less toxic, but its vapor pressure quickly, as is explained below. is 1.48 mm/Hg at 20 oC so that, under given conditions it will evaporate about 200 times more rapidly than VX. Thus, Sarin spilled on the floor of a railcar in the Tokyo Chlorine Subway attack evaporated rapidly enough to cause fatal- ities and severe injuries: VX would not have. On the In its usual transportation containers, (150lb or 1 ton cylin- other hand, VX is a persistent agent. If the terrorists' ders, 17 ton road tankers or 90 ton railcars) chlorine is a gas intention had been to cause severe cleanup problems, liquefied under pressure. For example, at 77 oF (25 oC) the VX would have been a better choice than sarin. vapor pressure of chlorine is 8 atm1. When the liquid is Both VX and sarin would be more effectively dispersed released, part of it (about 20%) flashes to vapor and the rest if they were aerosolized by some kind of spray device can be fragmented into fine liquid droplets. Unless the or explosion. Both of them cause severe health effects if emerging release encounters an obstacle (e.g. impinges on absorbed through the skin. Dispersing them as fine the ground or adjacent structures), all of the vapor and droplets in a crowded area would be an effective way of droplets can remain airborne. If the size of the rupture in the ensuring skin contact. However, building effective chlorine container is sufficiently large, most if not all of the aerosolizing devices is more difficult than simply whole contents can become airborne in a time that varies arranging for a liquid to be spilled. from virtually at once to a few minutes2. Thus, a terrorist On its face, chlorine is much less attractive as a poten- could put a large quantity of highly toxic chlorine into the air tial WMD. Its toxicity as measured by the 1-hr AEGL- in a time so short that measures to minimize the release can- 2 is one thirty thousandth that of VX. However, chlorine not be implemented. As air is entrained, the liquid droplets is available in extremely large quantities on the nation's transportation networks (e.g. 90 ton railcars). Its vapor pressure at 20 oC is approximately 8 atm. When released 1 Physical properties of chlorine (vapor pressure, boiling point, flash fraction, fraction of liquid droplets remaining airborne, etc.) obtained from Appendix A of CCPS (1996). catastrophically, as explained below, all of the chlorine 2 Appendix A of CCPS (1996) calculates the rate of release of chlorine through a hole may well become and remain airborne and cover many of diameter 3" in the liquid space of a chlorine vessel at 25 oC as 44.16 kg/s.~97 lb/s. This would empty a 17 ton road tanker in about 6 minutes. If terrorists used explosives square miles with potentially dangerous concentrations to blow a one-foot diameter hole in the side of the road tanker, the vessel could empty within a few minutes. From the terrorist perspective, in about 20 seconds.

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A-5 evaporate. The cloud is denser than air, partly because the is entrained virtually instantaneously (as much as 1020 molecular weight is 70, partly because the flashing release is times as much air as the mass of ammonia released). This initially at the boiling point of chlorine (about 30 oF), and evaporates the liquid droplets and, within less than a minute, partly because initially entrained air is cooled as it evaporates the cloud consists of air at the boiling point of ammonia the droplets. mixed with a few percent of ammonia. This mixture is heav- One characteristic of heavy vapor clouds is an initial ier than air and slumps as was described for chlorine above, slumping phase when they behave much as would a liquid. becoming very broad and backing up against the wind They become very broad and can even back up against the (Kaiser 1989)4. wind. For 20 ton or 90 ton releases, the backup can be sev- The principal difference between chlorine and ammonia as eral hundred meters and the cloud can become a kilometer or an effective means of causing mass casualties lies in the very more 3in width within a few minutes. Another consequence different levels of toxicity. From Table 7.2.2, the AEGLs for of the pseudo-liquid-like behavior of heavy vapor clouds is Ammonia are 50150 times as large as those for chlorine. that they will tend to run into depressions, ditches, drains, Therefore, a release of ammonia will propagate to a much and basements of buildings (if released in an urban area). smaller distance than would the release of the same mass of They can persist there for several hours if the windspeed is chlorine before falling below levels such as AEGL-2 or low or if internal volumes are not well ventilated. This can ERPG-2. This is evidenced by results from RMP*Comp, be dangerous for unwary members of the public and emer- which show that 17 tons of ammonia would propagate up to gency rescue personnel. 2.1 miles at an urban site or 3.3miles at a rural site before Once the initial slumping phase is over, during which the falling below the ERPG-2 of 150 ppm. The corresponding chlorine is considerably diluted by air entrained due to tur- distances for a 90 ton railcar are 4.9 miles and 7.8 miles bulence generated within the cloud itself, the vapor begins to respectively. As for chlorine, it is extremely unlikely that behave more like a passive plume in which the predominant such conservative distances would actually be realized as a dilution mechanism is the entrainment of air by the action of result of an ammonia release. A study (Kaiser et al. 1999) atmospheric turbulence. Conservative atmospheric disper- that compiled data from 12 accidental releases of ammonia, sion models, such as that used by EPA in its guidance on including railcars and road tankers (Markham 1986), large- atmospheric dispersion modeling for Risk Management Pro- scale anhydrous ammonia release experiments (Goldwire et grams (EPA 1999) as embodied in RMP*Comp (EPA 2004), al. 1985), and dispersion models showed that concentrations show that a 17 ton release of chlorine in unfavorable weather of 20,000 ppm (which is the LC50 for durations of cloud pas- conditions can propagate up to 5.8 miles at an urban site or sage of a few minutes) are never exceeded beyond a few hun- 12 miles at a rural site before falling below the ERPG-2 of dred meters from the point of release. Concentrations in the 3 ppm. The corresponding distances for a 90 ton railcar are range 1,00010,000 ppm are not seen or predicted beyond 14 miles and > 25 miles respectively. While it is exceedingly about 2 km. This observation is pertinent for emergency unlikely that such distances will actually be achieved, never- responders in that, in practice, distances predicted by con- theless it is entirely possible that a broad chlorine vapor servative models with conservative endpoints like those in cloud would cover many square miles with concentrations RMP*Comp are extremely unlikely to be encountered. that could prove highly injurious or fatal, and that this could happen within a few minutes. Materials That Are Liquids at Typical Ambient Temperatures Many toxic chemicals have boiling points that are above Anhydrous Ammonia any reasonably anticipated ambient temperature. For exam- ple, sarin has a boiling point of 316.4 oF5. Therefore, if spilled, Anhydrous ammonia is also transported as a gas liquefied it will initially form a slowly evaporating pool on the ground. under pressure in road tankers or 90 ton railcars. Many peo- For such pools, the subsequent rate of evaporation is limited ple believe that, because ammonia is less dense than air, it by mass transfer from the pool to the atmosphere and is will rise when it is released. This is true if the release con- dependent on vapor pressure (1.4 mm/Hg at 68 oF ~ 1,800 tains only pure vapor. However, it is well established that sudden, large releases of ammonia from pressurized contain- ment behave in much the same way as do large releases of 4 On May 11 1976, a road tanker carrying 19 metric tons of anhydrous ammonia crashed through a barrier on an elevated section of motorway near Houston, TX. The pressurized chlorine. There is an initial flashing phase when typically tank burst on falling to the roadway below and the contents were rapidly released. ~ 20% of the ammonia vaporizes and fragments the remain- (McMullen 1976). After about one minute the observed breadth of the cloud was 400600m. The maximum upwind distance, measured by observing burnt grass, was ing liquid. Because the situation is highly turbulent, much air 200m. These observations are substantiated by photographs in Fryer and Kaiser (1979). In 1977, a train derailment in Pensacola, Florida punctured the tank head on a rail car so that 50% of the contents, amounting to some 40 metric tons, quickly vaporized. (NTSB, 3 For the 3" hole described in footnote 2, Appendix A predicts that the chlorine vapor 1978). After about five minutes, the cloud was already "about a mile across." 5 cloud will be 3.4 km wide at a distance downwind of 1 km in atmospheric stability cate- Physical data on Sarin from the National Institute of Occupational Safety and Health gory F with a windspeed of 2 m/s. However, this predicted width is reduced by a factor (NIOSH) Emergency Response Card for Sarin, available at http://www.bt.cdc.gov/ of 5 in atmospheric stability category D with a windspeed of 5 m/s. agent/sarin/erc107-44-8pr.asp.

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A-6 ppm), the area within which it is confined or over which it tanks containing this ammonia were to be ruptured (perhaps spreads, and the windspeed (CCPS 1996, Section 4.2.5). Sarin by a USS Cole-type attack), up to 40% of the refrigerated is likely to be available to terrorists only in small quantities. ammonia could be vaporized (Raj et al. 1974). What happens For example, on March 20, 1995 a terrorist cult released a few is that, as ammonia dissolves in the water, heat is released, liters of sarin in commuter trains on three different Tokyo which is responsible for vaporizing the aforementioned 40%. subway lines. They concealed the sarin in lunch boxes and Raj et al. also show that the resulting vapor cloud is slightly soft-drink containers and placed it on subway train floors. buoyant (i.e., the liquid droplet effects described for the pres- It was released as terrorists punctured the containers with surized release are not important in this instance). However, umbrellas before leaving the trains so that the sarin spilled this does appear to be a potential mechanism for rapidly onto the floor of the subway cars and began to evaporate vaporizing up to a thousand tons of ammonia. (Ohbu et al. 1997). Therefore, it is more likely to be used in an attack on the transportation system than in an open-air release. A.4 METHODS FOR INTRODUCING AND DISPERSING CHEMICALS In point of fact, pouring agents like sarin and sulfur mus- tard on the ground or floor is a relatively inefficient way of The means of maliciously introducing and dispersing dispersing them. If terrorists were able to obtain or manufac- chemical agents discussed above can be summarized as ture chemical munitions, they could cause a more devastat- follows: ing impact. For example, as quoted by Purver (1995) from Berkowitz et al. (1972): Hijack a railcar or road tanker of chlorine or ammonia, "In the open, six pounds of Sarin distributed by a three move it to an optimum location and rupture the con- pound burster charge at a height of 15 feet creates a dosage tainment with an explosion. Within a short time, an area of 3500mg-min/m3 20 yards from the burst within 10 sec- potentially encompassing many square miles could be onds; in 25 seconds the cloud expands to a 50-yard radius covered by a vapor cloud that is potentially dangerous with a minimum dosage of 100 mg/m3 (Robinson, 1967). or fatal to those exposed. A minute after the burst, anyone in an area of over 70,000 square feet around the burst will have received at least a Cause a highly toxic chemical such as sarin to be spilled median lethal dose, and probably much more than that. In a in a confined space such as a subway car. It will evapo- confined space (banquet hall, auditorium), the effects will be rate and cause adverse or fatal health effects through even greater." inhalation. Obtain a chemical munition containing an agent such as Similar comments about effects could be applied to a con- sarin and explode it in a large confined volume such as fined space such as a crowded airport terminal. The impact an airport terminal. Individuals would be affected both would be further enhanced by the use of a persistent agent through inhalation and by liquid droplets impinging such as sulfur mustard. on exposed skin. The adverse consequences could be Note that Purver (1995) states that "Chemical weapons enhanced by using a persistent agent such as sulfur mus- such as nerve agents are generally credited with being capa- tard whereby surfaces would be dangerously contami- ble of causing casualties in the range of hundreds to a few nated by deposited liquid for hours or days. thousand." Thus the magnitude of the consequences would Introduce a toxic gas into the HVAC system of a build- not be as great as could potentially be obtained from biolog- ing such as an airport or marine terminal, or the HVAC ical or nuclear weapons. system of a ship. Hijack and blow up a barge or ship containing a large HVAC Systems quantity of material such as ammonia. Gases could potentially be introduced into the HVAC sys- tems of large buildings such as airport terminals or large Note that these are only meant to be examples of a much vessels such as passenger liners. For example, it might be larger number of scenarios that can be imagined. possible to release the contents of a 150 lb cylinder of chlo- rine into the HVAC intake. It would also be possible to envisage pouring the contents of a container of sarin the size A.5 EXAMPLES OF CHEMICAL INCIDENTS of a milk bottle into the HVAC system. The following subsections provide summaries of chemical Releases into or onto Water events that are examples of the potential effects of a terrorist As an example of potential terrorist interest in the trans- attack using a chemical agent. Some of the summarized portation of toxic chemicals, consider the transportation of events are hypothetical, most are actual accidents that have anhydrous ammonia by barge. This occurs extensively on occurred. These examples are grouped as: chemical weapons inland and coastal waterways in the U.S. in barges typically events, chemical transportation incidents, and releases from containing 2,500 tons of refrigerated liquid ammonia. If the fixed facilities.

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A-7 A.5.1 Chemical Weapons Events by sarin went to work in spite of their symptoms. Most of these left and sought medical treatment as the symptoms The following are examples of actual or potential attacks worsened. Several of those affected were exposed to sarin on transportation systems. only by helping passengers from the trains (these include passengers on other trains, subway workers and health care The Tokyo Subway Attack--Sarin workers). Recent surveys of the victims show that many are The most notorious chemical attack on an element of the still suffering, particularly from post-traumatic stress disor- transportation system was the use of sarin in an assault on the der. In one survey, 20% of 837 respondents complained that Tokyo subway system on March 20, 19956. Members of a they feel insecure whenever riding a train, while 10 percent Japanese millenarian cult, Aum Shinrikyo released sarin gas answered that they try to avoid any gas-attack related news. on several lines of the Tokyo subway. As a result, 12 people Over 60 percent reported chronic eyestrain and said their died and thousands were injured. vision has worsened (Mainichi Online 2001). Aum Shinrikyo was a Japanese millenarian cult centered Purver (1995) provides a detailed review of the then-current on the charismatic leader Asahara Skoko, whose teachings information about the subway attack. He suggests that Aum combined elements of Buddhism and Hinduism as well as Shinrikyo experimented with poison gas before March 20, millenarian Christianity. Central to the group's teachings is 1995. For example, in the mountain resort of Matsumoto, 125 that the apocalypse is near. The Aum cult attracted people miles northwest of Tokyo, late in the evening of 27 June 1994, from all walks of life, and had as many as 10,000 followers a substance later identified as sarin seeped through the open at its peak. Members lived in communes, cut off relations windows of apartments and houses, killing or injuring every with outsiders, and gave all their savings to the cult. It was living thing inside an area 500 yards long by 100 yards wide. believed that the cult was to become more powerful than the Seven people were killed and 264 sought hospital treatment. state, and needed the most advanced weapons of mass A report in the London Sunday Times of 19 March 1995 (just destruction to achieve this end. one day before the subway attack) reported that there had been Monday, 20 March, 1995 was for most a normal workday, "an intensive investigation involving a special sarin unit of though the following day was a national holiday. The attack Tokyo's metropolitan police department criminal investiga- came at the peak of the Monday morning rush hour on one of tion laboratory, the national police agency, and the security the world's busiest commuter transport systems. The liquid services that had concluded that "the attack was a trial run by sarin was contained in plastic bags which each team then terrorists of the delivery system" of a chemical agent. wrapped in newspapers. Each of the five perpetrators carried Purver also indicated that commentators expressed sur- two packets of sarin totaling approximately 1 liter of sarin, prise that, given the toxicity of sarin and the nature of the except for one who carried three bags. Thus, there was a total target, the casualty toll had not been much higher. Had the of only about 5 liters used in the attack. A single drop of pure terrorists implemented a means of aerosolizing the sarin, sarin the size of the head of a pin can kill an adult. However rather than simply letting it evaporate from the floor of the the sarin used was diluted, possibly to cause slower effects subway cars, many more people would have been killed, and thereby allow more people to be exposed. although the rapidly falling bodies would have prevented Carrying their packets of sarin and umbrellas with sharp- others from entering the train, thus possibly exposing fewer ened tips, the perpetrators boarded their appointed trains; at people to the sarin. Police raids on Aum Shinrikyo com- prearranged stations, each perpetrator dropped his package pounds uncovered the capacity to make much larger quanti- and punctured it several times with the sharpened tip of his ties of sarin, other agents such as tabun (which is ten times umbrella before escaping to his accomplice's waiting get- as toxic as sarin), evidence of experimentation with biolog- away car. The Tokyo subway system transports millions of ical weapons including botulism, and evidence of attempts passengers daily. During rush hour trains are frequently so to obtain the Ebola virus and Q-fever. crowded that it is impossible to move. As noted above, 12 people were killed in the attacks. An Aborted Attack on the Tokyo Subway-- Symptoms included choking, coughing, foaming at the Hydrogen Cyanide mouth, and fading vision as victims staggered from the On Friday May 5, 1995, Tokyo subway guards responded trains. Those that received the highest doses fell to the to a fire in a public restroom, and averted a potential mass- ground, writhing in convulsions. At one subway station in casualty incident (Purver 1995). The incident it attributed to particular, the subway entrance was described as resembling Aum Shinrikyo cult. Two plastic bags, one containing two a battlefield, where the injured simply lay on the ground, liters of powdered sodium cyanide already in flames and the struggling for breath. In other areas, many of those affected other containing 1.5 liters of diluted sulphuric acid, were found side-by-side on the floor of a men's bathroom in Tokyo's 6 The primary source for this summary, except as otherwise noted, is "Protecting Pub- busiest subway station, Shinjuku. The bags reportedly were lic Surface Transportation Against Terrorism and Serious Crime: Continuing Research and Best Security Practices," published by the Mineta Transportation Institute (2001), arranged so that a reaction producing hydrogen cyanide gas and available at. http://www.transweb.sjsu.edu/publications/terrorism_final.pdf. would have occurred if contents from the two bags had mixed.

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A-8 Four subway guards who doused the flames with water were inhalation", 59% of the annually transported tonnage moves overcome by fumes and briefly hospitalized, but otherwise by rail, amounting to 5,766,000 tons. Based on ton-miles, a there were no casualties. Chemical experts later estimated that much larger proportion of chemicals (i.e., 95% or, 4,940x106 the amount of cyanide gas that could have been released may ton-miles) are transported by rail (GAO, 2003a). To exem- have been sufficient to kill between 10,000 and 20,000 people. plify the variety of hazardous bulk chemicals shipped in the US, Table A-2 shows the volumes of hazardous materials Hypothetical Scenario--Persistent Agent shipped by rail from 19982001. The authors are unaware of Several workers move drums labeled as cleaning agents any deliberate, large-scale release of a highly toxic chemical into a large shopping mall, large public facility, subway, train from the transportation system. The scenarios presented after station, or airport. They dress as cleaners and are wearing Table A-2 are examples of accidental releases that could what appear to be commercial dust filters or have taken the potentially be replicated by terrorists. antidote for the agent they will use. They mix the feedstocks for a persistent chemical agent at the site during a peak traf- Ammonia Release from Road Tank Truck-- fic period. Large-scale casualties result, and draconian secu- Houston, TX rity measures become necessary on a national level. A series Between 11.09 am and 11.15 am on May 11, 1976, a tank of small attacks using similar "binary" agents virtually para- truck crashed through a guard rail at the Southwest Freeway lyze the economy, and detection is impossible except to iden- and Loop 610 West Interchange, landing on a street some 30 tify all canisters of liquid (Cordesman 1996). feet below. The tank ruptured on impact, releasing 19 tons of anhydrous ammonia. The accident resulted in the imme- A.5.2 Chemical Transportation Incidents diate death of four people and injury to more than one-hun- dred others. Two other victims died later as a result of their Bulk chemicals are transported by truck, rail, barge, and injuries. (McMullen, 1976). One of the most striking fea- ocean-going vessels. For chemicals categorized as "toxic by tures of this accident was that the ammonia cloud exhibited TABLE A-2 The Top 20 Hazardous Materials Shipped by Rail By Volume 19982001a Hazardous Material Estimated Total Estimated Annual Carloads, 1998-2001b Average No. of Carloads Freight Forwarder Trafficc 1,188,109 297,027 All freight rate shipments, not elsewhere coded (NEC) or trailer on flatcar shipments, commercial, except where 716,177 179,044 identified by commodity. Sulfur liquid or molten nonmetallic minerals except 273,005 68,251 fuels Liquefied Petroleum Gas, NEC, compressed 253,234 63,308 Sodium (soda), caustic (sodium hydroxide) 236,455 59,114 Asphalt pitches or tars, from petroleum, coal tar, coke 222,163 55,541 ovens, or natural gas Sulfuric acid or oil of vitriol 200,875 50,219 Anhydrous ammonia 163,057 40,764 Chlorine 128,600 32,150 Gasolines, blended, consisting of motor fuels containing 97,192 24,298 50% or more of gasoline Ethyl alcohol, anhydrous denatured in part with petroleum products and/or chemicals (not to exceed 95,333 23,833 5 wt%) Phosphate fertilizer solution, containing not more than 90,779 22,695 77 wt% of phosphoric anhydride Chemical, NEC 86,854 21,713 Vinyl Chloride (chloroethane or chloroethylene) 73,033 18,258 Methanol (methyl or wood alcohol liquid) 67,903 16,976 Propane gas, liquefied 65,702 16,425 Carbon dioxide gas, liquefied or carboic acid gas 63,020 15,755 Ammonium nitrate fertilizer 62,563 15,641 Muriatic (hydrochloric) acid 58,165 14,541 Styrene (liquid) 55,910 13,977 Footnotes for Table A-1 a. Reproduced from GAO (2003a), Appendix III, Table 4 b. Extrapolated from a 1% sample of waybills c. Non-bulk, mixed

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A-9 and fragments the remaining liquid. Because the situation is highly turbulent, much air is entrained virtually instantaneously (as much as 1020 times as much air as the mass of ammonia released). This evaporates the liquid droplets and, within less than a minute, the cloud consists of air at the boiling point of ammonia mixed with a few percent of ammonia. This mixture is heavier than air (Haddock and Williams 1978) and slumps as was described for chlorine above, becoming very broad and backing up against the wind (Kaiser 1989). Depending on the weather conditions and the amount of Figure A-1. Cloud of ammonia fumes spreading over the ammonia released, the vapor cloud can be considerably larger west loop 610 overpass, Houston, TX, May 11, 1976. Photo than that observed in Houston. See the discussion of the Pen- reproduced from Fryer and Kaiser (1979). Photograph sacola accident below for an example. taken by Carrol S. Grevemberg. This incident is also relevant to potential large-scale delib- erate or accidental releases of chlorine. In fact, McMullen (1976) explicitly states "Had the truck been loaded with chlo- the ground-hugging features of a dense vapor cloud. Figure rine the potential for disaster would be further com- A-1 was taken about a minute after the after the crash from pounded." To the authors' knowledge, there has not been a the Transco tower in the Houston Galleria complex. large chlorine spillage during transportation that has resulted One can see that as the vapor cloud propagates downwind in the immediate or near-immediate release of the contents of (from right to left), it appears to decrease in height. This is the transportation vessel and which resulted in reasonably characteristic of a slumping, heavy vapor cloud. In addition, good documentation of the size of the vapor cloud. However, the cloud is backing up against the wind towards the right of there is no doubt that chlorine would behave in much the the picture. This is reinforced by Figure A-2, which was taken same way as ammonia. If anything, the slumping effects for from a Houston Air Pollution Control Program Enforcement chlorine would be even greater because chlorine, even as a helicopter after the ammonia had dispersed. pure vapor, is already denser than air. Section 7.1.2.4 cites a The photograph shows the area where the grass had been calculation Appendix A of CCPS (1996) calculates the rate burnt by the ammonia. The wind was blowing from left to of release of chlorine through a hole of diameter 3" in the liq- right. One can clearly see that the plume spread a consider- uid space of a chlorine vessel at 25 oC as 44.16 kg/s.~97 lb/s. able distance both across the wind and upwind. The upwind This would empty a 17 ton road tanker in about 6 minutes7. boundary is at about 200m and the cloud is about 600m Appendix A predicts that the chlorine vapor cloud will be across just downwind of the overpass (Kaiser 1979). 3.4 km wide at a distance downwind of 1 km in atmospheric As was briefly discussed above, it is well established that stability category F with a windspeed of 2 m/s8. sudden, large releases of ammonia from pressurized contain- ment behave as denser-than-air vapor clouds. There is an initial Ammonia Release from Railcar--Pensacola flashing phase when typically ~ 20% of the ammonia vaporizes About 6.06 pm on November 9, 1977, 2 SD-45 locomotives and 35 cars of Louisville and Nashville freight train No. 407 derailed at Pensacola, Florida (NTSB 1978). The adjacent tank heads of the 18th and 19th cars were punctured and this released anhydrous ammonia into the atmosphere. Two persons died and 43 were injured. NTSB established that, within ten minutes, about 50 per- cent of the contents of the 19th car quickly vaporized, so that about 40 tons became airborne. The air traffic controller at the Pensacola Airport first observed the ammonia cloud on radar at about 6.10 pm (i.e., only 4 minutes after the accident). At that time, "It appeared to be about one mile in diameter and about 125 feet high." This substantiated the statement, made above, that clouds that are considerably broader than that observed in the aftermath of the Houston road tanker crash are possible. 7 If terrorists used explosives to blow a one-foot diameter hole in the side of a 17-ton road tanker, the vessel could empty in about 20 seconds. Figure A-2. Photo of the Houston ammonia tank truck 8 Note, however, that this predicted width is reduced by a factor of 5 in atmospheric crash site after the ammonia had dispersed. stability category D with a windspeed of 5 m/s.

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A-10 Other Ammonia Transportation Accidents plume." For comparison, the chlorine AEGL-2 for a 1-hour Crete, Nebraska, February 18, 1969: At about 6.30 am on exposure is 2 ppm (6,000 g/m3--see Table 7.2.2). No chlo- February 18, 1969, Chicago, Burlington, and Quincy (CB&Q) rine concentrations above 1 g/m3 were observed after 8 am train No. 64 derailed the 72nd to the 90th cars as the train was on November 15. entering Crete, Nebraska (NTSB, 1971). The derailed cars It is apparent that the chlorine was leaking slowly over a struck Train 824, standing on a track north of the main track. A period of days. Thus, the Mississauga derailment and subse- tank car in train 824 was completely fractured by the impact quent chlorine leak is not an example of a catastrophic release and rapidly released 29,200 gallons (about 76 metric tons) to that might be engineered by a terrorist, although presumably the atmosphere. NTSB states that "A cloud was formed which a terrorist would be gratified by the dislocation caused by the blanketed the immediate area. The cloud extended westward need to evacuate nearly a quarter of a million people for sev- beyond the (nearby) Blue River and for several blocks north eral days. and south of the railroad. The concentrated cloud of ammonia vapor was retained in the area for a considerable period of time. Howard Street Tunnel Fire--Baltimore, MD Unfortunately, the NTSB report provides no further data on the At 3:04 pm on Wednesday, July 18, 2001, the 60-car CSX size of the cloud. Three trespassers riding on rain 64 were killed freight train L412-16 entered the Howard Street Tunnel in as a result of the derailment. Six people were killed and 53 were downtown Baltimore, MD (Carter et al. 2002)9. The train car- injured as a result of exposure to the ammonia cloud. The ambi- ried 29 loaded and 31 empty cars, including several tanker ent temperature was 4 oF and the wind was calm. cars. At 3.07 pm, the train lurched and came to a rough stop Minot, North Dakota, January 18, 2002: On January 18, as several cars derailed. The engineers uncoupled the three 2002, a 112-car train derailed one mile west of Minot, ND in diesel engines and exited the tunnel in order to report the the Souris River valley. Eleven anhydrous ammonia cars and event. From the amount of smoke exiting the tunnel, it was two granular urea cars released their contents. In excess of clear that there was a fire somewhere among the cars. 300,000 pounds (about 136 metric tons) of anhydrous ammo- Baltimore City firefighters received notification of the nia was released from the ruptured tanker cars. One tanker event between 3.35 pm and 4.15 pm. After reviewing the bill car was propelled over 600 feet in the air and skidded another of lading firefighters discovered that the freight train was car- 500 feet on the ground, crashing through a corner of a nearby rying a variety of hazardous materials including tripropylene house. Part of another tanker car landed on the ice of the and hydrochloric acid. Souris River. A dense anhydrous ammonia cloud drifted One of the immediate problems was to determine the poten- through low-lying areas of the city. A temperature inversion, tial environmental impact from the hazardous materials and with sub-zero temperatures and no wind, prevented the cloud whether downtown Baltimore needed to be evacuated. This from dissipating. One fatality occurred, 15 people were hos- problem was solved by the Maryland Department of the Envi- pitalized, and eventually over 1600 people sought medical ronment's (MDE's) Emergency Response Division (ERD). treatment for anhydrous ammonia exposure (Radig 2003). Following a review of the bill of lading, ERD personnel con- GAO (2003a) states that the vapor plume was 5 miles long tacted members of the South Baltimore Industrial Aid Plan and 21/2 miles wide. It caused 1 death and more than 300 (SBIMAP), a voluntary consortium of manufacturers, emer- injuries and affected 15,000 people. This was in a relatively gency response personnel, Baltimore City environmental and lightly populated rural area. NTSB has not yet released its emergency management personnel, and MDE. SBIMAP pro- report on this accident. vided two chemists, who quickly determined that, individually or in combination, the hazardous chemicals involved in the fire Chlorine Release from Railcar--Mississauga would not present a serious environmental hazard and that it Just before midnight on Saturday, November 10, 1979, a was not necessary to evacuate downtown Baltimore. derailment occurred involving 24 railway tanker cars of a 106- At 10.30 am on July 19, 2001, firefighters found small leaks car Canadian Pacific Railway Train in the city of Mississauga, in one of the hydrochloric acid cars. This necessitated the Ontario. One railcar containing 90 tons of liquid chlorine arrangement of acid transfer activities. The damaged HCl car began to leak. More than 200,000 Mississauga residents were was finally removed from the tunnel at 11.30 am on July 22. evacuated for their protection against potentially harmful This incident, like the one at Mississauga, is thus more exposure to chlorine drifting away from the site, and as a pre- notable for the disruption it caused over a period of several caution against the possibility of further explosions, which days and the indications it gives of the potential danger. Had might have released more chlorine. (SCIEX 1980). there been a car load of chlorine and had the crash caused a SCIEX performed numerous measurements of airborne significant rupture, the released chlorine would have flowed chlorine concentrations from November 11, 1979 at 1 pm down the 4.8% grade of the tunnel and poured out into down- until 10 am on November 19 at numerous locations ranging town Baltimore. This accident is interesting because of its from about 0.5 km to 5 km from the point of release. The highest recorded concentrations were about 400 g/m3 and 9 This description of the Howard Street Tunnel derailment draws freely upon and the most serious health effects noted were "Eye irritation in quotes from the work by Carter et al. (2002).

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A-11 effects on transportation systems in and around Baltimore. It 24 to 36 hours. Some freight that would normally have used had a major effect on rail transportation, road transportation the tunnel was diverted as far west as Ohio. and transit. It had some effect on marine transportation (the Medium-term transportation impacts of the July 18, 2001 inner harbor was briefly closed to traffic) and some effect on Howard Street Tunnel fire continued until July 19 to 23, air (to the extent that transportation to and from BWI airport 2001. These impacts included the following: was affected. These are documented by Carter et al. (2002). Suppression of and Initial Clean-up from the Tunnel The short-term transportation impacts of the July 18, 2001 Fire took approximately 5 days. All cars were removed Howard Street Tunnel fire lasted up to 36 hours and included from the tunnel and inspected for damage, and all haz- the following: ardous materials were off-loaded and removed. The tunnel Closing of Major Highways into Baltimore: at the request of was inspected for structural damage and reopened to rail the Incident Commander, Maryland State authorities closed traffic on July 23. major highways into the city, including I-83 southbound, MD- Miscellaneous: On Monday morning, July 23, when city 295 northbound (the Baltimore-Washington Parkway), Route and state employees returned to work after taking advantage 40 eastbound and I-395 northbound. These roadways were of liberal leave at the end of the previous week, traffic was reopened on the morning of July 19. backed up for more than a mile on northbound I-95 before Closing of City Streets in the Vicinity of the Tunnel and the the junction with thI-395 spur that takes traffic downtown. Rerouting of Passenger, Bus, and Commercial Vehicle Traf- Street closures in the vicinity of Howard and Lombard fic: Howard Street and the surrounding area were closed to Streets caused MTA officials to divert approximately 23 bus traffic, cutting Baltimore's central business district in half routes. Light rail service continued to rely on buses to trans- and closing off east-west traffic flows (Howard Street runs port riders between the Patapsco and North Avenue Station North-South for 1.7 miles over the tunnel). This resulted in stops around the section of track damaged by the water main gridlock, but once traffic management was put in place the break. For five days following the accident, streets in the City was cleared of traffic within 2 hours of the normal end vicinity of the tunnel and the water main break remained of rush hour (8pm instead of 6pm). closed, and all vehicle traffic was diverted. On July 24, Closing of the Metro Subway's State Center Station: the nearly all of the streets were reopened to traffic. Only a two- station was closed due to smoke accumulation from the fire. block stretch of Howard Street and a portion of Lombard However, Metro officials conducted an inspection of the Street remained closed. Metro tunnel running under the Howard Street tunnel and Metro: commuters took advantage of Metro services to determined that no damage had occurred. They were able to travel into Baltimore during this time. Ridership on Monday keep the trains running. The State Center Station itself was July 24 was 7,000 higher than normal. reopened on July 21, 2001. East Coast Rail Network: the East Coast network became The Disruption of Light Rail Service: light rail track runs increasingly constrained with each day that the major north- along Howard Street. In the immediate vicinity of the fire a south artery through the Howard Street tunnel remained water main ruptured and washed away the track bed, neces- closed. Freight trains were delayed, cancelled, or diverted sitating the closure of the light rail service. Metro set up a bus hundreds of miles throughout the Middle Atlantic States. bridge between nearby stations to carry passengers around MARC Rail Service on the Camden Line was also disrupted the break. until the fire was suppressed. Service ended at the Dorsey The Disruption of Maryland Commuter (MARC) rail and Street Station near BWI airport. However, there was not a sig- Oriole Game Day Service: MARC trains were stopped at the nificant decrease in ridership because MARC commuters to Dorsey Station near BWI Airport and bus bridge was set up and from Washington D.C. took advantage of free parking at by the MTA to bring passengers into the city. The bus bridge the Dorsey Street station. was only needed for July 18. 2,000 Orioles employees and Longer-term transportation impacts of the July 18, 2001 between 2,500 and 5,000 fans were evacuated. Howard Street Tunnel fire included only the 55 days it took The Disruption of Bus Services: disruptions were system- to repair the damage to the Central Light Rail Line caused by wide. the bursting water main. Relatively speaking, there were no The Closing of the Inner Harbor: the U.S. Coastguard long-term impacts as might have been the case in the event (USCG) closed the inner harbor to boat traffic at 5.00 pm and of a radiological incident. set up booms to minimize potential contamination from Table A-3 summarizes the agencies that were involved chemicals seeping from leaking rail cars. and their roles and responsibilities. The Disruption of Rail Freight Along the East Coast: the Howard Street Tunnel is one of only two direct northeast- southeast freight lines along the East Coast. Losing access to A.5.3 Releases from Fixed Installations the tunnel required CSX to divert or delay a significant por- tion of rail traffic along the Eastern Seaboard. Freight moving There is a vast range of releases of toxic chemicals from from the northeast to Florida was advised to expect delays of fixed installations. The following are a couple of examples.

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A-12 TABLE A-3 Incident Response and Agency Responsibilities (Table 5 from Carter et al 2000) Jurisdiction Modal Role in Incident Area of Concern Administration Response or Agency Baltimore City Fire Department Incident Command Fire Suppression. Police Traffic Enforcement Closing of streets crossing over the Howard Street Tunnel. Department Department of Infrastructure Repairs Repairs to water main and street surface at Howard and Public Works Traffic Management Lombard Streets. Traffic control in Baltimore. Office of Interagency Media information. Emergency Coordination & Management Public Information Maryland Headquarters Coordination of DOT Worked with Baltimore Department of Public Works (DPW) to Department of Response Activities establish a plan on how to repair the infrastructure damage once Transportation the fire was extinguished (procurement issueshaving a contractor in place, developing a plan on how repair work would be implemented once the "green light" was received, plans for site survey, traffic diversion, etc.). State Highway Traffic Management Through CHART system10, posted notices on fixed and mobile Administration on Interstate System DMS advising that major routes into the city were closed. Mass Transit Rail and Bus Transit Light rail and bus operations. Establishing bus bridge between Administration Operations in north and south segments of light rail. MARC operations. Baltimore City Metro subway operationstunnel inspection. Maryland Traffic management Ensured that I-395 route into Baltimore was closed off during Transportation on I-95 approaches to initial incident response activities. Authority Ft. McHenry Tunnel & I-395 Maryland Emergency Air Quality, Water Obtained information possible environmental impact of train Department of Response Quality, Hazardous fire (hazardous materials). Monitored air and water quality in the Environment Division Materials, area around the tunnel and the Inner Harbor. Checked railcars (MDE) Leaks/Discharges pulled from tunnel for structural integrity. Coordinated removal and disposal of hazardous materials from the train. Maryland N/A Coordination of State Coordinating activities of state agencies. Media relations and Emergency Government rumor control. Management Emergency response Agency and Incident Management Activities U.S. Coast USDOT Supported MDEI Implemented waterway safety measures, including closing of Guard (USCG) Inner Harbor. Supported hazardous material detection and containment. U.S. N/A Supported MDE Assisted with monitoring of air quality and water Environmental Protection Agency (EPA) Methyl Isocyanate Release--Bhopal 1988). A toxic cloud of MIC drifted over the hundreds of The Union Carbide India Ltd. (UCIL) pesticide plant in dwellings in a crowded shanty town outside the plant, killing Bhopal, India produced Methyl Isocyanate (MIC) by reacting more than 3,800 people and leaving 11,000 more with perma- monomethylamine with phosgene in the plant's MIC produc- nent disabilities (figures provided by the Indian Government tion unit. The MIC was used to make SEVIN carbaryl and sev- in 1991). Investigations proved that the introduction of water eral other carbamate pesticides. The MIC was stored in two was deliberate (Browning 1993). horizontal, mounded, 15,000-gallon, stainless steel tanks. On Once the toxic cloud had dispersed and drifted away, there the night of December 23, 1984, the 41 metric tons of MIC appeared to be no lasting impact on transportation systems in one of the tanks underwent a chemical reaction which was around the plant. The water was introduced by a disgruntled caused by the introduction of water into the tank (Kalelkar employee who may not have been aware that the conse- quences would be so catastrophic. However, it does illustrate 10 The CHART (Chesapeake Highways Advisories Routing Traffic) program the potential for terrorists to work with an insider to engineer started in the mid-1980s as the "Reach the Beach" initiative, focused on improving travel to and from Maryland's eastern shore. It has become so successful that it is catastrophic releases of toxic chemicals. now a multi-jurisdictional and multi-disciplinary program extending statewide. This comprehensive, advanced traffic management system is enhanced by a newly con- structed state-of-the-art command and control center called the Statewide Opera- Hydrogen Fluoride Release--Texas City tions Center (SOC). The SOC is the "hub" of the CHART system, functioning 24 hours-a-day, seven days a week with satellite Traffic Operations Centers (TOCs) At 5.20 pm on October 30, 1987, a crane was moving a spread across the state to handle peak-period traffic. 50-foot, multi-ton convection section from a vertical heating

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A-13 vessel to a semi-truck trailer in Marathon Petroleum Com- When exposed to CAs, it can change color according to the pany's Texas City refinery. The crane was located immedi- type of agent. If an aerosolized droplet encounters the paper, ately east of the HF acid vessel, which was part of the plant's the diameter and density of the spot can be used to determine HF alkylation unit. The crane dropped the convection section the droplet size of the agent and the degree of contamination. while it was above the HF vessel (Ryan 1988). The convec- Chemical detection paper lacks specificity and is prone to tion section severed two lines attached to the HF vessel. error because it reacts with contaminants such as brake fluid, Marathon reported that 53,200 pounds of HF were released antifreeze, and insect repellent, resulting in false-positive over a 44-hour period. Shortly after the accident, Marathon readings. False readings are especially undesirable in civilian directed a water spray at the HF cloud. situations because they may lead to mass panic. Therefore, As of November 16, 1987, local area hospital reported a chemical detection paper should always be used with another total of 1,037 patients who were treated for HF exposure. Of modality for accuracy of detection. these, 97 were hospitalized, two of whom were in critical condition. There were no fatalities. 85 square blocks and M8/M9 chemical detection paper approximately 4,000 residents were evacuated. M8 and M9 CA detection papers, commonly used by the Reports of the incident do not indicate that the HF cloud military, are available commercially to HAZMAT response hampered the activities of emergency responders. teams. M8 paper is packaged in 25 perforated sheets, 2.5 in by 4 in, and is blotted on liquids that arouse suspicion. It iden- tifies CAs by changing colors within 30 seconds of exposure: A.6 CHEMICAL DETECTION dark green for vesicants, yellow for nerve agents, and red for Chemical detection equipment (CDE) is an essential com- blister agents. ponent of hazardous material (HAZMAT) emergency M9 paper has adhesive backing that allows it to be attached response. This equipment should detect the harmful agent, to clothing and equipment. M9 paper detects the same agents correctly identify the agent, and define the area of exposure. as M8 paper but does not change color to enable identifica- Rapid detection is essential so that responders and military tion. M9 paper tends to react faster than M8 paper and can be targets can recognize a threat and don protective gear (ide- attached to vehicles that are entering areas filled with vapor to ally in 9 s). It also is important to know the extent of con- determine contamination. Vehicles thus equipped are limited tamination. During several documented chemical attacks, to a speed of 30 km/h. first responder casualties have been vast enough to delay the rescue. During the Tokyo subway sarin attack in 1995, 9% of M256A1 chemical agent detection kit emergency medical services (EMS) providers suffered the The M256 CA detector kit originally was released in 1978 affects of acute exposure. Effective CDE may help prevent and was modified in 1987 to the M256A1, which is sensitive these occurrences. to lower concentrations of nerve agents. It was used exten- Several different technologies are used today to detect sively during the Gulf War but also is available commercially. chemical agents (CAs). CAs are defined as chemicals It is another common component of CDE provided to civilian intended to kill or seriously injure human beings. CDE usu- response teams. This portable kit detects nerve gas, mustard ally detects the most common CAs: nerve agents, blister gas, and cyanide and usually is used to define areas of conta- agents, and arsenical vesicants. A large variety of equipment mination. The M256A1 contains a package of M8 paper, is available that is capable of identifying liquid droplets of detailed instructions, and a vapor sampler (12 enzymatic tick- CAs on surfaces and in vapors. Laboratory-based equipment ets that contain laboratory filter paper for detecting CA can detect agents in water. The main challenges with these vapors). The vapor sampler employs wet chemistry technol- technologies are ensuring an appropriate sample for analysis ogy, in which ampoules containing different substrates are and filtering out nonhazardous environmental chemicals that crushed so that the liquids interact with strips of filter paper, may be present. This article focuses on the technologies and chromatographic media, and glass fiber filter. These substrates devices that may be used by first responder teams in the field. then are exposed to the vapor under suspicion. The reaction Laboratory detection techniques are beyond the scope of this causes a color change, alerting the user to the presence of a discussion. CA. The reactions typically take 15 minutes to occur. The M256A1 can detect nerve gas concentrations of 0.005 Chemical Detection Paper mg/m3, hydrogen cyanide concentrations of 11mg/m3, and Chemical detection paper is a very sensitive technique for mustard gas concentrations of 0.02 mg/m3. This is one of the detecting CAs. It is one of the least sophisticated and thus least military's most sensitive devices for detecting CAs and expensive methods of detection. It is used to detect liquids and detects all agents at levels below those that can kill or injure aerosols and is a common means for defining a contaminated people. It is prone to false-positive results, similar to other area. Chemical detection paper is composed of 2 dyes soluble enzymatic detection techniques, but has not been demon- in CAs and a pH indicator integrated into cellulose fibers. strated to produce false-negative results in real situations.

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A-14 Colorimetric tubes slightly larger and has a communications interface that is use- Colorimetric tubes such as those available from Draeger ful in combat. and RAE systems use enzymatic techniques to identify CAs. ETG provides a commercial version of an IMS stand- A hand pump is used to draw a sample into a specific tube, alone detector called the Fixed Site/Remote Chemical and the concentration of the substance is read from the tube. Agent Detector. This system detects and identifies nerve This is another simple and inexpensive way of detecting and and blister agents and offers superior reliability from identifying a CA. It is used extensively in civilian response interference. The alarm information can be transmitted via units for this reason, but it has some disadvantages. Avail- radio, satellite, or hardwiring. This system can be useful able are 160 substance-specific reagent tubes identifying dif- if placed in hospital wards or at victim collection sites to ferent agents. For each agent, a different tube must be used. detect contamination Efficient use of this system demands knowledge of which CA is likely to be present in a given environment. If a tube Infrared Detection for vesicants is used to sample the air and the CA is a nerve Infrared radiation (IR) is employed in several CA detec- agent, the tube reports a false-negative result. A tube for each tors, including long-range detectors and point detectors. IR possible CA must be used for thorough detection. can be used to excite molecules, and each agent has a unique infrared pattern referred to as a fingerprint. Several different Ion Mobility Spectroscopy detection techniques use IR, including photoacoustic Ion mobility spectroscopy (IMS) is used in many handheld infrared spectroscopy, filter-based infrared spectroscopy, and stand-alone detection devices that can be used to scan forward-looking infrared spectroscopy (FLIR), and Fourier equipment, surfaces, and people for contamination. This tech- transform spectroscopy. These include photoacoustic nology involves drawing a gaseous sample into a reaction infrared spectroscopy, filter-based infrared spectroscopy, chamber using an air pump. The air molecules then are ionized, differential absorption light detection and ranging, and pas- most commonly using radioactive beta emitters such as nickel- sive infrared detection 63 or americium-241. The ionized particles then are passed The military uses the M21 Remote Sensing Chemical through a weak electrical field toward an ion detector. Conta- Agent Alarm (RSCAAL) based on passive infrared detec- minants are identified according to the time it takes to traverse tion. It is the first fielded standoff chemical detection device. the distance to the detector. This time is proportional to the This system can detect a vapor cloud from 5 km with an 87% mass of the molecule. The pattern is compared to a sample of detection rate. The M21 RSCAAL continuously monitors a clean air; if the pattern is markedly different and unique to cer- background and notes the change in spectral information if a tain types of agents, the alarm sounds. These systems are capa- vapor cloud obstructs the background. It automatically scans ble of detecting and distinguishing between nerve gas, mustard along a 60 angle, allowing the operator to monitor horizon- gas, and vesicants. Its sensitivity ranges from 0.03 mg/m3 for tal movement. The M21 can be set up in 10 minutes and is nerve gases such as sarin to 0.1 mg/m3 for mustard gas. unaffected by low light conditions. However, the M21 is lim- IMS has certain advantages. It is less sensitive to contami- ited in that it must be stationary and can be obstructed by nants, because it relies on a clean air sample for calibration. snow and rain. Thus, if an area has a certain baseline nonhazardous environ- mental vapor present, it is not detected. CDE in Civilian response to Terrorist Attacks CDE technology has advanced primarily as a result of mili- Stand-alone detectors--M8A1, Automatic tary necessity. More recently, the need for civilian preparedness Chemical Agent Alarm, and Fixed Site/Remote for terrorist attacks with CA has been recognized. Civilian Chemical Agent Detector response is different from military response in many ways, and Many stand-alone detectors also use IMS technology. The the choice of CDE must take this into account. Key differences military employs the M8A1 detector that consists of a stand- include the following: alone detector, which continuously monitors the environment for hazardous vapors and aerosols, and up to 5 alarms that can Civilian responders tend to be less experienced in chem- be dispersed throughout an area. The M8A1 detects nerve ical attacks. agents and blister agents when the concentration is 0.1 mg/m3 Civilian responders have less information concerning or greater and alarms within 12 minutes. M8A1 is an ideal the origin and type of attack and may not recognize that device for protection from off-target attacks, in which a vapor it is a CA attack initially. is released upwind from the targets. However, it is less effec- Civilian responders have more stringent budget restraints tive for on-target attacks, in which the CA is released in large and thus must use cost-effective equipment. amounts within seconds. In this situation, the alarm sounds Civilian responders have less latitude in incorrectly after the personnel have been exposed. This system was used identifying a CA. during the Gulf War and has been upgraded to the Automatic Civilian responders are deployed primarily to provide Chemical Agent Alarm (ACAA) system. The ACAA is medical care, leaving detection as a secondary goal.

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A-15 In the civilian setting, EMS or other medical providers are Davis, G. and Kelen, P. (2001). CBRNE Chemical Detection Equip- the first to arrive. Most EMS providers do not carry CDE to ment, emedicine, http://www.emedicine.com/emerg/topic924.htm detect CAs and thus initially must recognize the potential threat EPA (U.S. Environmental Protection Agency) 1999. Risk Man- in order to notify specialized HAZMAT response teams. These agement Program Guidance for Offsite Consequence Model- ing Analysis, EPA 550-B-99-009, Washington, D.C. Available teams exist in many cities and are at a minimum equipped with at http://yosemite.epa.gov/oswer/ceppoweb.nsf/vwResources- pH paper and combustible gas indicators. This equipment is ByFilename/oca-all.PDF/$File/oca-all.PDF inadequate in identifying most CAs. Other teams now are EPA (U.S. Environmental Protection Agency), 2004. RMP*Comp equipped with colorimetric tubes Colorimetric tubes are much Modeling Program for Risk Management Plans. Available at http:// less expensive than more technical devices, such as the ICAM, yosemite.epa.gov/oswer/ceppoweb.nsf/content/rmp-comp.htm. and can be distributed generally. Major cities in the US have a Fryer, L.S., and G.D. Kaiser (1979). DENZ A Computer Program Metropolitan Medical Strike Response System (MMRS) orga- for the Calculation of the Dispersion of Dense Toxic or Explosive nized by the Public Health Service. These are highly special- Gases in the Atmosphere, United Kingdom Atomic Energy Author- ized, fully equipped, deployable teams to combat civilian ity Report SRD R 152, Culcheth, Cheshire, UK. threats from weapons of mass destruction. They are primarily GAO (U.S. General Accounting Office) 2003a. Rail Safety and medical providers who provide EMS services, decontamina- Security: Some Actions Already Taken to Enhance Rail Security, but Risk-Based Plan Required, GAO-03-435, Washington, D.C. tion, detection, and treatment. The first such team was orga- Goldwire, Jr., H.C., T.G. McRae, G.W. Johnson, D.L. Hipple, R.P. nized in 1995 in Washington, DC, and a second was organized Koopman, J.W. McLure, L.K. Morris, and R.T. Cedarwall, (1985). for the 1996 Olympics in Atlanta. MMRS teams are often bet- Desert Tortoise Series Data report 1983 Pressurized Ammonia ter equipped to respond to CA attacks than HAZMAT response Spills, Lawrence Livermore National Laboratories Report UCID- teams. Even so, wide variability exists in the type of detection 20562, Livermore, CA. devices used. A recent study by the National Guard recognized Haddock, S.R. and R.J. Williams (1978). The Density of an Ammonia that no standards regulate the detection devices among differ- Cloud in the Early Stages of its Atmospheric Dispersion, United ent civilian emergency response units. MMRS teams can Kingdom Atomic Energy Authority Safety and Reliability Direc- employ any of the devices and technologies described above. torate Report SRD R103, Culcheth, Warrington, Cheshire, UK. They commonly use inexpensive CDE such as SAW detectors Kaiser, G.D. (1979). Examples of the Successful Application of a and enzymatic techniques such as M9 paper and the M256 kit. Simple Model for the Atmospheric Dispersion of Dense, Cold Vapors to the Accidental Release of Anhydrous Ammonia from Some teams also use IMS devices such as the APD2000 and a Pressurized Containers, United Kingdom Atomic Energy Author- modified ICAM for domestic preparedness. ity Safety and Reliability Directorate Report SRD 150, Culcheth, Warrington, Cheshire, UK. Kaiser, G.D. (1989). A Review of Models for Predicting the Disper- A.7 REFERENCES FOR APPENDIX A sion of Ammonia in the Atmosphere, Plant/Operations Progress Vol. 8, No. 1, pp 5864. Berkowitz, B.J. et al. (1972). 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