Chapter 3

Recognizing and Identifying Hazardous Materials

Objectives: Awareness Level Personnel (1 of 3)

• Define hazardous material and weapon of mass destruction (WMD). (NFPA 4.2.1(1), p. 46–47)

• Identify the UN/DOT hazard classes, as well as the primary hazards associated with each. (NFPA 4.2.1(2)(3), p. 64–66)

• Describe the difference between hazardous materials/WMD incidents and other emergencies. (NFPA 4.2.1(4), p. 47)

• Describe occupancies that may contain hazardous materials. (NFPA 4.2.1(5), p. 47)

• Describe some ways you might detect the presence of a hazardous materials release. (NFPA 4.2.1(11), p. 47)

Objectives: Awareness Level Personnel (2 of 3)

• Describe the limitations of using your senses to detect the presence of hazardous materials. (NFPA 4.2.1(11), p. 47–48)

• Describe specific containers and container shapes that might indicate hazardous materials. (NFPA 4.2.1(6), p. 48–53)

• Describe how to identify the product, owner, and emergency telephone number on a pipeline marker. (NFPA 4.2.1(7), p. 57)

• Describe how to identify a placard, label, or other marking used to indicate the presence of a hazardous material. (NFPA 4.2.1(9), 4.2.2, 4.4.1(4), p. 58–60)

Objectives: Awareness Level Personnel (3 of 3)

• Describe the NFPA 704 hazard identification system. (NFPA 4.2.1(8), p. 60–61)

• Describe safety data sheets (SDS) and shipping papers. (NFPA 4.2.1(10), p. 66–71)

• Describe how to identify criminal or terrorist activity involving chemical, biological, or radiological agents. (NFPA 4.2.1(13)(14)(15)(16)(17), p. 73–76)

• Describe how to identify an illicit laboratory, and explosive and secondary devices. (NFPA (18)(19)(20), p. 76–77)

• Use the Emergency Response Guidebook. (NFPA 4.2.3, 4.4.1, p. 63–66)

Objectives: Operations Level Responders (1 of 4)

• Describe occupancies that may contain hazardous materials. • Describe specific containers and container shapes that might

indicate/contain hazardous materials. (NFPA 5.2.1.1, 5.2.1.1.5, 5.2.1.1.6, 5.2.1.2, 5.2.1.2.2, p. 48–53)

• Describe shipping and storage vessels that could hold hazardous materials. (NFPA 5.2.1.1.1, 5.2.1.1.2, 5.2.1.1.2, 5.2.1.1.3, 5.2.1.1.4, p. 48–57)

• Describe various modes of transportation used to transport hazardous materials. (NFPA 5.2.1.1.1, p. 54–57)

• Describe how to identify the product, owner, and emergency telephone number on a pipeline marker. (NFPA 5.2.1.3.1, p. 57)

Objectives: Operations Level Responders (2 of 4)

• Describe how to identify information and its significance on a pesticide label or a radioactive material label. (NFPA 5.2.1.3.2, 5.2.1.3.3, p. 51, 74–76)

• Describe the NFPA 704 hazard identification system.

• Describe safety data sheets and shipping papers. (NFPA 5.2.1.2.1, 5.2.2, 5.2.3(1), p. 66–71)

• Describe assistance provided by CHEMTREC/CANUTEC/SETIQ. (NFPA 5.2.2, 5.2.3(1), p. 73)

Objectives: Operations Level Responders (3 of 4)

• Recognize the surrounding conditions to take note of during a hazardous materials/WMD incident survey. (NFPA 5.2.1.4, p. 46–48)

• Describe ways to verify information obtained from a hazardous materials/WMD incident survey. (NFPA 5.2.1.5, p. 57–73)

• Describe how to identify criminal or terrorist activity involving chemical, biological, or radiological agents. (NFPA 5.2.1.6, 5.2.2, p. 73–76)

• Describe how to identify an illicit laboratory, and explosive and secondary devices.

Objectives: Operations Level Responders (4 of 4)

• Identify the corresponding UN/DOT hazard class and division, given the following:– Blood agents (NFPA 5.2.3(9)(a), p. 66)– Biological agents and biological toxins (NFPA

5.2.3(9)(b), p. 66)– Choking agents (NFPA 5.2.3(9)(c), p. 66)– Irritants (riot control agents) (NFPA 5.2.3(9)(d), p. 66)– Nerve agents (NFPA 5.2.3(9)(e), p. 66)– Radiological materials (NFPA 5.2.3(9)(f), p. 66)– Vesicants (blister agents) (NFPA 5.2.3(9)(g), p. 66)

• Use the Emergency Response Guidebook. (NFPA 5.2.3 (1), p. 63–66)

Introduction (1 of 4)

• Scene size-up is especially important in hazardous materials incidents.

• Train yourself to stop and pay attention.• There is a difference between “looking”

and “seeing.”

Introduction (2 of 4)

• A hazardous materials emergency may be detected based on: – Information from the dispatcher– Information from persons on the scene– Your own knowledge of the response area

Introduction (3 of 4)

• Initial and ongoing activities are guided by:– Departmental standard operating procedures

(SOPs)– Your level of training– Information-gathering efforts at the scene

Introduction (4 of 4)

• More than 4 billion tons of hazardous materials are shipped annually in the United States.

Hazardous Materials

• A hazardous material is any substance or material capable of posing an unreasonable risk to human health, safety, or the environment when transported in commerce, used incorrectly, or not properly contained or stored.

Hazardous Materials/WMD Incidents

• These are different from other types of emergencies.– They generally move more slowly.– The specific chemical or material largely

dictates the actions taken.– There are law enforcement aspects to

consider.

Occupancy and Location

• Two good indicators of the possible presence of a hazardous material

• The materials present at a particular location may already be known.

• The Environmental Health and Safety (EH&S) department of a larger facility should be contacted for information on the hazardous material.

Senses

• Should be used with caution to avoid becoming contaminated or exposed

• Sight and sound are typically safe to use.• Generally, the farther you are from an

incident, the safer you will be.• Rather than “leading with your nose,” use

binoculars from a distance.

Containers (1 of 2)

• A container is a vessel or receptacle that holds a material.

• The type, size, and material that containers are made of often provide information on what might be stored inside.

Containers (2 of 2)

• 55-gallon drums and compressed gas cylinders are found at almost every manufacturing facility.

• Cardboard drums store solids.• Stainless steel containers may hold

dangerous chemicals. • Cold liquids are kept in Thermos-like

Dewar containers.

Bulk Storage Containers

• Liquids greater than 119 gallons• Bulk packaging with net mass greater than

882 pounds• Gases greater than 100-lb water capacity• Examples: fixed tanks, highway cargo

tanks, rail tank cars, totes, intermodal tanks

Secondary Containment (1 of 2)

• An engineered method to control spilled or released product if the main containment vessel fails

• Often surrounds bulk storage containers• Example: a series of short walls forming a

catch basin around a 5000-gallon vertical storage tank

Secondary Containment(2 of 2)

• Typically can hold entire volume of tank, along with percentage of water

Large-Volume Horizontal Tanks (1 of 2)

• Aboveground storage tanks (ASTs) or underground storage tanks (USTs)

• Capacity from a few hundred gallons to several million gallons

• Usually made of aluminum, steel, or plastic

Large-Volume Horizontal Tanks (2 of 2)

• May be pressurized or nonpressurized

• Typically hold flammable or combustible materials, such as gasoline, oil, or diesel fuel

Courtesy of Rob Schnepp

Intermodal Tanks

• Both shipping and storage vessels• Capacity between 5000 and 6000 gallons• Pressurized or nonpressurized• Can be used to ship and store gaseous

substances that have been chilled until they liquefy, such as nitrogen or argon

• A box-like steel framework surrounds an IM tank to facilitate stacking and shipping.

Types of Intermodal Tanks (1 of 2)

• IM-101 portable tanks (IMO type 1 internationally)– 6300-gallon capacity; internal working pressures

between 25.4 and 100 psi; carry mild corrosives, food-grade products, and flammable liquids.

• IM-102 portable tanks (IMO type 2 internationally)– 6300-gallon capacity; internal working pressures

between 14.7 and 25.4 psi; primarily carry nonhazardous materials, but also may carry flammable liquids and corrosives

• Pressure intermodal tanks (IMO type 5 internationally)– High-pressure vessels (100–600 psi); commonly hold

liquefied compressed gases (e.g., propane, butane)

Types of Intermodal Tanks (2 of 2)

• Cryogenic intermodal tanks (IMO type 7 internationally)– Low-pressure vessels, but can be pressurized

up to 600 psi; commonly hold cryogenic materials

• Tube modules– Several high-pressure tubes attached to a

frame; working pressures range as high as 5000 psi; commonly carry hydrogen and oxygen

Nonbulk Storage Vessels

• These are all types of containers other than bulk containers.

• Capacity up to 119 gallons

Drums

• Barrel-like containers that hold a variety of substances (e.g., food-grade materials, corrosives, flammable liquids, grease)

• Closed-head drums have permanent cover with one or more bungs (small openings, removed with a bung wrench).

• Open-head drums have removable lid fastened to drum with a ring.

Bags (1 of 2)

• Commonly store solids and powders (e.g., cement powder, sand, pesticides, soda ash, slaked lime)

• Plastic, paper, or plastic-lined paper• Pesticide labels require:

• Product name• Active ingredients• Hazard statement• Total amount of product in container• Manufacturer’s name and address• EPA registration number• EPA establishment number

Bags (2 of 2)

• Pesticide labels require (cont’d):• Signal words (e.g., “Danger—Poison”)• First-aid treatment description• Directions for use• Agricultural use requirements• Precautionary statements (e.g., mixing directions)• Storage and disposal information• Classification statement on who may use product• “Keep out of reach of children”• PCP number (in Canada)

Carboys

• Glass, plastic, or steel• 5- to 15-gallon capacity• Often placed in protective wood, foam,

fiberglass, or steel box• Some corrosives and other types of

chemicals (e.g., nitric acid, sulfuric acid)

Cylinders• Used to store substances

such as nitrogen, helium, and oxygen

• High-pressure, uninsulated, compressed gas cylinders

• Low-pressure (Dewar) cryogenic containers

Courtesy of Cryofab, Inc.

Ton Containers

• Commonly hold compressed liquefied gases, such as chlorine and sulfur dioxide

• Some may hold refrigerant fluorocarbon gases.

• 2000-lb capacity; 8 feet in length, 3 feet in diameter

• Most have pressure relief valves called fusible plugs.

Intermediate Bulk Containers (1 of 2)

• Volumes inside fall between what is typically found in drums or bags and cargo tanks.

• Capacities greater than 119 gallons, but less than 793 gallons

• Flexible or rigid

Intermediate Bulk Containers (2 of 2)

• Super sacks hold solid material from 500 to several thousand pounds. – Fabric ranges from woven cloth to

polyethylene. • Totes hold variety of substances; capacity

ranges from 119 to 793 gallons. – Can be polyethylene or square metal tank

Transporting Hazardous Materials

• Hazardous materials may be transported by air, sea, and land.

Roadway Transportation• The most common• Important to become familiar with all types

of transport vehicles• Cargo tank as defined by 49 CFR 171.8(2)

or local jurisdictional regulations: – Bulk packaging permanently attached to or

forms a part of a vehicle – Separate from vehicle, but unloaded without

being removed from vehicle

MC-306/DOT 406 Flammable Liquid Tank

• Transports liquid food-grade products, gasoline, or other flammable and combustible liquids

• 6000 to 10,000 gallons• Nonpressurized• Remote emergency shut-

off valvesCourtesy of Polar Tank Trailer L.L.C.

MC-307/DOT 407 Chemical Hauler

• Capacity 6000 to 7000 gallons

• Transports flammable liquids, mild corrosives, poisons

• Insulated (horseshoed) or uninsulated (round)

Courtesy of Polar Tank Trailer L.L.C.

MC-312/DOT 412 Corrosives Tank

• Smaller in diameter than the MC-306/DOT 406 or MC-307/DOT 407

• Capacity about 6000 gallons

• Transports concentrated sulfuric acid, phosphoric acid, sodium hydroxide

Courtesy of National Tank Truck Carriers Association

MC-331 Pressure Cargo Tank• Capacity 1000 to 11,000

gallons• Transports ammonia,

propane, Freon, butane• Explosion threat

– Spring-loaded relief valves unable to keep up with rapidly building internal pressure

Courtesy of Rob Schnepp

MC-338 Cryogenic Tank• Maintains a low

temperature to transport cryogens

• Low pressure• Emits puffs of white

vapor from relief valve to maintain proper internal pressure

• Operation of valves requires special training

Courtesy of Jack B. Kelly, Inc.

Tube Trailer• High-volume transport

container made up of several cylinders banded together and affixed on a trailer

• Transports hydrogen, oxygen, helium, methane

• Working pressures of 3000 to 5000 psi

Courtesy of Jack B. Kelly, Inc.

Dry Bulk Cargo Tank• Transports dry bulk

goods such as powders, pellets, fertilizers, grain

• Not pressurized, but may use pressure to offload the product

• V-shaped with rounded sides that funnel contents to bottom-mounted valves

Courtesy of Polar Tank Trailer L.L.C.

Railroad Transportation (1 of 2)

• Almost 2 million railroad carloads of freight are moved each year in the United States.

• Relatively few hazardous materials incidents, but such incidents can create unique and significant hazards

Railroad Transportation (2 of 2)

• Car type recognition is important to help determine contents.– Each type has a distinctive profile that can be

recognized from a distance.– Rail tank cars are usually labeled on both

sides (revealing the car’s owner, capacity, and specification).

Nonpressurized (General-Service) Rail Tank Car

• Capacity 4000 to 40,000 gallons

• Transports general industrial chemicals, corn syrup, flammable and combustible liquids, mild corrosives

• Newer cars have visible valves and piping.

Courtesy of private source

Pressurized Rail Tank Car• Transports propane,

ammonia, ethylene oxide, chlorine

• High-volume contents can generate long-duration, high-pressure leaks.

• Stopping leaks may require a special kit.

Courtesy of private source

Special-Use Rail Tank Car• Cryogenic tank car is

the most common.• Hazards are specific

to the particular railcar and its contents. © Mark Gibson/Index Stock Images, Inc./Alamy Images

Pipelines (1 of 2)

• Pipelines are rarely involved in emergencies.

• Pipeline incidents present special challenges and require specially trained responders.

• Transport natural gas, gasoline, diesel fuel, other products

• Often buried underground, but may be aboveground in remote areas

Pipelines (2 of 2)

• Pipeline right-of-way: An area, patch, or roadway that extends a certain number of feet on either side of the pipe itself; pipeline owners maintain this area.

• Warning signs are placed along route of pipeline.

• Vent pipes: Inverted J-shaped tubes provide pressure relief.– Clearly marked; contain information about the

pipe’s contents and owner

Transportation and Facility Markings

• Labels, placards, and other markings on buildings, packages, boxes, and containers often make it possible to identify a released chemical.

• Various marking systems are in use.

Department of Transportation (DOT) Marking System (1 of 2)

• Uses labels, placards, and markings• Used when materials are transported in

the United States and Canada• Placards are diamond-shaped indicators

(10¾″ on each side) placed on all four sides of transport vehicles carrying hazardous materials.

Department of Transportation (DOT) Marking System (2 of 2)

• Labels are smaller (4″) diamonds placed on all four sides of boxes and smaller packages being transported.

• Certain hazardous substances require marking only if a certain quantity is being transported.

• Other chemicals are so hazardous shipment of any amount requires the use of labels or placards.

National Fire Protection Association 704 Marking System (1 of 2)

• Uses diamonds found on the outside of buildings, on doorways to chemical storage areas, and on fixed storage tanks

• The diamonds are broken down into four smaller, different-colored diamonds corresponding to different characteristics.

National Fire Protection Association 704 Marking System (2 of 2)

• Blue diamond (9 o’clock position): health hazard

• Top red diamond: flammability• Yellow diamond (3 o’clock position):

reactivity• Bottom white diamond: special hazards

– Burning O: oxidizing capability– Three-bladed trefoil: radioactivity– W with a slash through it: water reactive

Hazardous Materials Information System (HMIS) (1 of 3)

• Helps employers comply with OSHA Hazard Communication Standard

• Similar to NFPA 704 marking system• Meant for employees at a facility

– Gives necessary information to work safely around chemicals

Hazardous Materials Information System (HMIS) (2 of 3)

• Not required by law; voluntary system• Uses a numerical hazard rating, colored

horizontal columns, letters, and icons to describe the hazards posed by a particular substance and provide guidance about choosing PPE

Hazardous Materials Information System (HMIS) (3 of 3)

• HMIS can give responders clues about the presence and nature of hazardous materials in a facility.

Military Hazardous Materials/Weapons of Mass Destruction Markings (1 of 2)

• Mainly identifies detonation, fire, and special hazards

• Divided into four categories based on relative detonation and fire hazards– Division 1: mass detonation hazards– Division 2: explosion-with-fragment hazards– Division 3: mass fire hazards– Division 4: moderate fire hazards

Military Hazardous Materials/Weapons of Mass Destruction Markings (2 of 2)

• Colors depict chemical hazards.– Red: Toxic agents– Yellow: Harassing agents– White: White phosphorous

• Military shipments containing hazardous materials/WMD are not required, by exception, to be placarded.

Chemical References• Many reference

books are available to responders.

The DOT Emergency Response Guidebook (1 of 2)

• Contains information on about 4000 chemicals

• Helpful in deciding on preliminary action to take

• Responders should seek additional specifics about material in question.– Consult appropriate emergency response agency.– Use emergency response number on shipping

document, if applicable.

The DOT Emergency Response Guidebook (2 of 2)

• Organized into four colored sections– Yellow: Chemicals listed by UN/ID number– Blue: Chemicals listed alphabetically by name– Orange: Hazard class, fire/explosion hazards,

health hazards, basic emergency actions– Green: Initial isolation distances

Safety Data Sheets (SDS)

• Provides basic information about the chemical make-up of a substance, its potential hazards, and appropriate first aid

• Facilities that use or store chemicals are required by law to have an SDS on file for each chemical

Shipping Papers (1 of 2)

• Required whenever materials are transported

• Names and addresses of shipper and receiver

• Identify the material being shipped as well as the quantity and weight

• Called bills of lading or freight bills for road and highway transport; located in the cab of the vehicle

Shipping Papers (2 of 2)

• Called waybills for railroad transportation; each car on a train also has a list of contents called consist or train list

• Called dangerous cargo manifest for marine vessels; kept in the wheelhouse in custody of the captain or master

• Called air bills for air transport; kept in the cockpit in custody of the pilot

CHEMTREC (Chemical Transportation Emergency Center)

• Can provide responders with technical chemical information via phone, fax, or other electronic media

• Offers phone conferencing service: puts responder in touch with shippers, substance matter experts, and chemical manufacturers

• CANUTEC—Canadian equivalent • SETIQ—Mexican equivalent

National Response Center (NRC)

• Must be notified when a significant hazardous incident occurs

• Operated by U.S. Coast Guard• Central notification point rather than a

guidance center

Potential Terrorist Incidents

• Potential exists in major metropolitan areas as well as in small towns.

• Responders should be familiar with locations of potential targets in their area.– Infrastructure targets– Symbolic targets– Civilian targets

Chemical Agents

• Overt indicators: chemical-type gloves, chemical suits, respirators, and marked or unmarked containers made of various materials

• Other identifiable signatures: odor, liquid or solid residue, dead insects, foliage

• Personnel may exhibit symptoms of exposure.

Biological Agents• Clues may include Petri dishes, vented

hoods, Bunsen burners, pipettes, microscopes, incubators, and microbiology textbooks.

• Other clues: metal cylindrical cans, red plastic bags or boxes, personal protective equipment

• Personnel may exhibit symptoms of exposure.

Radiological Agents• Clues may include lead or stainless steel

containers, detonators, radiological protective suits, respirators, Geiger counters.

• Personnel may exhibit exposure symptoms such as burns or difficulty breathing.

• Responders must be able to recognize potential situations where radioactive materials might be encountered.– Food testing labs, hospitals, medical research

centers, biotechnology facilities, construction sites, medical laboratories

Radiological Shipments

• Radiological shipments require label when transported.– Require transport index (TI) number,

indicating the highest amount of radiation measured 1 meter away from the surface of the package

Radiological Packaging (1 of 2)

• Excepted packaging: Used to transport materials that meet only general design requirements for hazardous material package; used to transport low-level radioactive substances.

• Industrial packaging: Used to transport low activity material and contaminated objects

Radiological Packaging (2 of 2)

• Type A: Designed to protect the internal radiological contents during normal transportation and in the event of a minor accident

• Type B: More durable than Type A, to prevent release in the case of extreme accidents during transportation

• Type C: For dangerous radioactive substances transported by air; not certified for use in the U.S.

Illicit Laboratories

• Clues may include terrorist training manuals, basement location with multiple vents, buildings with heavy security or obscured windows.

• Drug laboratories are the most common type and use everyday items such as jars, bottles, glass cookware, and tubing.

Explosives

• Clues may include protective equipment, production and containment materials, explosive materials, reference materials.

Secondary Devices (1 of 2)

• A form of explosive or incendiary device designed to harm responders summoned to the scene for some other reason

• Usually takes place as responders begin to treat victims of the initial attack

Secondary Devices (2 of 2)

• Indicators include timers, wires, switches, and concealment containers such as briefcases, backpacks, or propane tanks.

• Perpetrators may watch the site of the primary devices, preparing to manually activate the secondary devices.

Summary (1 of 6)

• Responders must interpret visual clues effectively to improve their ability to mitigate an incident.

• Responders should be able to recognize the various container profiles and understand the general classifications of materials that may be stored inside each type of container.

Summary (2 of 6)

• Responders should be able to name, understand, and locate the various types of shipping papers on various modes of transportation.

Summary (3 of 6)

• Roadway vehicles often transport shipments from the rail station, airport, or dock to the point where the materials will ultimately be used. For this reason, responders must become familiar with all types of chemical transport vehicles.

Summary (4 of 6)

When used correctly, various marking systems indicate the presence of a hazardous material and provide clues about the substance. The DOT, NFPA, HMIS, and military have all developed marking systems specific to their level of response.

Summary (5 of 6)

• Responders should be able to demonstrate proficiency when using the Emergency Response Guidebook.

• Responders should know how to obtain SDS documentation from various sources, including their own department, the scene of the incident itself, or the manufacturer of the material.

Summary (6 of 6)

• Responders should become familiar with the locations of potential terrorist targets in their jurisdiction; the general and specific hazards of chemical, biological, and radiological agents; indicators of illicit laboratories; and basic operational guidelines for dealing with explosive events and identifying the possible indicators of secondary devices.