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Hazardous Materials: Recognizing and Identifying the Hazards
29 Hazardous Materials: Recognizing and Identifying the Hazards
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Objectives Describe occupancies that may contain hazardous materials.
Describe how your senses can be used to detect the presence of hazardous materials.
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Objectives Describe specific containers and container shapes that might indicate hazardous materials. Describe tanks that could hold hazardous materials. Describe apparatuses that can transport hazardous materials.
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Objectives Describe how to identify the product, owner, and emergency telephone number on a pipeline marker. Describe how to identify a placard and label. Describe how to use the North American Emergency Response Guidebook
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Objectives Describe the NFPA 704 hazard identification system.
Describe the material safety data sheets (MSDS) and shipping papers. Describe CHEMTREC.
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Introduction Scene size-up is important in any emergency.
Even more vital in a hazardous materials incident Situational awareness Ability to read the scene is a critical skill. Must be able to identify sensory clues to be useful and safe.
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Introduction May be possible to identify a hazardous materials incident based on: Information from the dispatcher Knowledge of response area Visual, auditory, or olfactory clues Standard operating procedures (SOPs) and your training level should guide any initial actions.
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Hazardous Material Any material that poses an unreasonable risk of damage or injury to persons, property, or the environment if it is not properly controlled during handling, storage, manufacture, processing, packaging, use and disposal, or transportation
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Recognizing a Hazardous Materials Incident
Scan the scene and interpret visual clues. Dead animals near the release Discolored pavement Dead grass Visible vapors or puddles Identifying labels
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Occupancy and Location
Can occur almost anywhere **Hazardous materials are stored in: Warehouses Hospitals Industrial occupancies Private residences Courtesy of George Roarty/VDEM. Doctors’ offices Hardware stores Other locations
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Occupancy and Location
**Location and type of occupancy are two indicators of the presence of hazardous materials Facilities that pose a significant threat become a part of a comprehensive community plan Alert the fire departments to the need for a pre-incident plan for the site.
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Senses Another way to detect the presence of hazardous materials
Must be done carefully to avoid exposure Getting close enough may expose you. Clues that are seen or heard provide warning information from a distance, enabling you to take precautionary steps.
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Containers Any vessel or receptacle that holds material including storage vessels, pipelines, and packaging
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Container Characteristics
Container type, size, and material provide important clues about the nature of the substance inside. Do not rely solely on the type of container when making a determination about hazardous materials.
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Container Types Steel or polyethylene plastic drums Bags
High-pressure gas cylinders Railroad tank cars Plastic buckets Above-ground and underground storage tanks Truck tankers Pipelines Dewar containers
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Container Volume Bulk storage containers
Includes fixed tanks, large transportation tankers, totes, and intermodal tanks Large-volume containers Liquids: More than 119 gallons Solids: More than 882 pounds Gases: More than 882 pounds
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Container Volume Bulk storage containers found in occupancies that need to store large quantities of a chemical Secondary containment An engineered method to control spilled or released product if the main containment vessel fails
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Container Volume Large-volume horizontal tanks
Above-ground storage tanks (ASTs) Underground storage tanks (USTs) Can hold a few hundred gallons to several thousand gallons of product Usually made of aluminum, steel, or plastic
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Container Volume USTs and ASTs can be pressurized and nonpressurized.
Difficult to relieve internal pressure on these tanks Dangerous when exposed to fire Typically hold flammable or combustible materials
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Container Volume Pressurized horizontal tanks have rounded ends and large vents or pressure-relief stacks. Most above-ground pressurized tanks are liquid propane and liquid ammonia tanks. Can hold a few hundred gallons to several thousand gallons Contain small vapor space
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Tote Portable plastic tanks surrounded by a stainless steel web that adds both structural stability and protection Can hold a few hundred gallons of product and may contain any type of chemical Shipping and storing can be hazardous.
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Intermodal Tanks Shipping and storage vehicles
Hold 5000–6000 gallons of product Pressurized or nonpressurized Surrounded by or part of a boxlike steel framework Courtesy of Eurotainer.
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Intermodal Tanks: IM-101 Have a 6000-gal capacity
Internal working pressures 25–100 psi Typically carry mild corrosives, food-grade products, and flammable liquids
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Intermodal Tanks: IM-102 Have a 6000-gal capacity
Internal working pressures 14–30 psi Primarily carry flammable liquids and corrosives
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Intermodal Tanks: IMO Type 5
High-pressure vessels with internal pressures of several hundred psi Carry liquefied gases like propane and butane
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Intermodal Tanks: IMO Type 7
High-pressure vessels with internal pressures of several thousand psi Carry compressed gases like oxygen and hydrogen **Referred to as a tube module intermodal container and is capable of holding high pressure gases 3,000 psi or higher
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Nonbulk Storage Vessels
Drums Bags Carboys Compressed gas cylinders Cryogenic containers
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Drums **Cylindrical packaging made of metal, plastic, or fiberboard
Used to store a wide variety of substances; material type depends on use. **Transports solids and liquids Courtesy of EMD Chemicals, Inc.
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Drum Openings Closed-head drums have a permanently attached lid with one or more small openings called bungs. Usually have one 2" bung and one ¾" bung **Open-head drum Removable lid fastened to the drum with a ring
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Bags Used to store solids and powders
Plastic, paper, or plastic-lined paper Different sizes and weights Pesticide bags must be labeled with specific information. **Common hazardous materials stored in bags are fertilizers. © USDA.
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Pesticide Bags Warning Label Information
Name of product Statement of ingredients Total amount of product in container Manufacturer’s name and address EPA registration number (US only) Signal words
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Pesticide Bags Warning Label Information
Practical first aid treatment description Directions for use Agricultural use requirements Precautionary statements Storage and disposal information Classification statement
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Pesticide Bags Warning Label Information
**On pesticide labels for materials originating in Canada, the product will have a pest control number which is similar to the EPA registration number in the United States.
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Carboys Transport and store some corrosives and other types of chemicals Made of glass, plastic, or steel Holds 5-gal to 15-gal of product Courtesy of EMD Chemicals, Inc.
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Carboys Often have a protective wood or fiberglass box to help prevent breakage Nitric, sulfuric, and other strong acids are transported and stored in thick glass carboys protected by a wooden or foam crate to shield the glass container
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Cylinders Several types of cylinders are used to hold liquids and gases. Uninsulated compressed gas cylinders Used to store gases such as nitrogen, argon, helium, and oxygen
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Cylinders Oxygen cylinder
Has a pressure reading of 2000 psi Very large compressed gas cylinders found at a fixed facility May have pressure readings of 5000 psi or greater
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Cylinders High pressures can be dangerous.
Rapid release of compressed gas turns the cylinder into a missile. If heated rapidly, it could explode. Compressed gas cylinders have pressure-relief valves.
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Cylinders **A common hazard with cylinders involved in fire is the potential for explosion.
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Low-Pressure Dewar Designed to hold cryogens
Gaseous substances that have been chilled until they liquefy Oxygen, helium, hydrogen, argon, and nitrogen Complex process turns them into liquids. Courtesy of Cryofab, Inc.
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Cryogens Pose a substantial threat if the Dewar fails to maintain the low temperature Have large expansion ratios, Has an expansion ratio of approximately 750 to 1 **Same materials as carried in MC338 Usually have two pressure-relief devices A pressure-relief valve or frangible disk
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Transporting Hazardous Materials
Highway transportation of hazardous materials is the most common method over land. Vehicles often carry the shipments from the station, airport, or dock to the factory or plant.
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MC-306 Flammable Liquid Tanker
Carries gasoline or other flammable and combustible materials Oval-shaped tank pulled by a diesel tractor Courtesy of Polar Tank Trailer, LLC.
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MC-306 Flammable Liquid Tanker
Carries between 6,000 to 10,000 gal Non-pressurized Usually made of aluminum Off-loaded through valves at the bottom of the tank Common highway sight Reliable way to transport chemicals
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MC-307 Chemical Hauler Round or horseshoe-shaped tank
Carries 6000 to 7000 gal Flammable liquids, mild corrosives, and poisons May have a rubber lining Courtesy of Polar Tank Trailer, LLC.
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MC-307 Chemical Hauler **A single or double manhole assembly protected by a flash box and roll-over protection is an identification feature of a MC 307/DOT 407 trailer. Courtesy of Polar Tank Trailer, LLC. **Low pressure chemical carrier is designed to carry chemicals with pressures not to exceed 40.0 psi.
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MC-312 Corrosives Tanker **Sulfuric and nitric acids and other corrosive substances Smaller diameter Reinforcing rings Operates at approximately 75 psi Holds 6,000 gal Courtesy of National Tank Truck Carriers Association.
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MC-312 Corrosives Tanker **A tank truck that carries corrosive liquids, generally acids, and has a narrow diameter with external ribbing is a MC 312 / DOT 412. Courtesy of National Tank Truck Carriers Association.
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MC-331 Pressure Cargo Tanker
Carries materials like ammonia, propane, and butane Rounded ends. Operates at approximately 300 psi Significant explosion hazard Courtesy of Jack B. Kelley, Inc.
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MC-338 Cryogenic Tanker Operates like the Dewar containers
Carries similar substances Tank insulation Boxlike structure Special training to operate valves **Exposure to cryogenic materials may cause freeze burns and frostbite. Courtesy of Jack B. Kelley, Inc.
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Tube Trailers Carry compressed gases
Several individual cylinders banded together and affixed to a trailer Large-volume cylinders operate at 3000 psi to 5000 psi Courtesy of Jack B. Kelley, Inc.
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Tube Trailers One trailer may carry several different gases in individual tubes. Valve control box Each cylinder has its own relief valve. Can frequently be seen at construction sites or at facilities that use great quantities of these materials
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Dry Bulk Cargo Tanks Powders, pellets, fertilizers, or grain
Not pressurized May use pressure to off-load product Generally V-shaped with rounded sides Courtesy of Polar Tank Trailer, LLC.
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Railroad Transportation
Railroads move almost 2 million carloads of freight per year. Relatively few hazardous materials incidents occur. Carry volumes up to 30,000 gal Hazardous materials incidents involving railroad transportation are dangerous.
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Railroad Tank Cars Three basic railcar configurations
Non-pressurized Pressurized Special use Usually labeled with the volume and maximum working pressure inside the tank Dedicated haulers often have the chemical name clearly visible.
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Non-pressurized Railcars
Industrial chemicals and consumer products Easily identified by looking at the top of the car Have visible valves and piping without a dome cover Courtesy of private source.
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Non-pressurized Railcars
**These cars have exposed fittings would and could also be called a low pressure tank **Non-pressure railcars will have a stencil marking of DOT 111 Courtesy of private source.
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Pressurized Railcars Enclosed dome on the top of the railcar
Propane, ammonia, ethylene oxide, and chlorine Internal working pressures ranging from 100 to 500 psi Relief valves Courtesy of private source.
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Special Use Railcars Includes box cars, flat cars, cryogenic , hopper cars, corrosive tank cars, and high-pressure compressed gas tube cars © Mark Gibson/Index Stock/Alamy Images.
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Special Use Railcars **Pneumatically unloaded hopper cars typically carry powdered materials. contents. **High pressure tube cars are considered to be obsolete and no used today. However, they could still be sitting around on rail yards and/or in industrial areas.
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Special Use Railcars The hazard will be unique to the particular railcar and its contents. Do not assume that only the chemical tank cars pose a threat. Until you know what is in a particular car, assume it is a hazardous situation.
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Pipelines Rarely involved in emergencies
Large-diameter pipelines transport natural gas, gasoline, diesel fuel, and other products from delivery terminals to distribution facilities. © Photodisc.
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Pipelines Often buried underground Pipeline right of way
An area, patch, or roadway that extends a certain number of feet on either side of the pipe itself Maintained by the company that owns the pipeline Responsible for placing warning signs
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Pipelines Pipeline warning signs include:
Warning symbol Pipeline owner’s name Emergency contact phone number Complicated events that require specially trained responders Contact the owner immediately.
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Pipelines Information about the pipe’s contents and owner is also found at the vent pipes. Inverted J-shaped tubes Provide pressure relief or natural venting during maintenance and repairs. Vent pipes are clearly marked and are approximately 3' above the ground.
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DOT System Characterized by a system of labels and placards
Emergency Response Guidebook (ERG) Also a part of the system Offers a certain amount of guidance for fire fighters operating at a hazardous materials incident
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Placards Diamond-shaped indicators Measures 10 ¾” on a side
Must be displayed on all four sides of vehicle carrying hazardous materials © Pedro Nogueira/ShutterStock, Inc.
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Labels Smaller version of placards 4" diamond-shaped indicators
Used on the four sides
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Placards and Labels Intended to give fire fighters a general idea of the hazard inside a particular container Placard may identify the broad hazard class that a tanker contains. Labels on a book inside a delivery truck relate only to the potential hazard inside that package.
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Nine Chemical Families
Class 1—Explosives Class 2—Gases **Class 3—Flammable / Combustible liquids **Class 4—Flammable solids Class 5—Oxidizers **Class 6—Poisons Class 7—Radioactive materials Class 8—Corrosives Class 9—Other regulated materials (ORM)
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Class 1 – Explosives
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Class 2 – Gases
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**Class 3 – Flammable / Combustible Liquids
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**Class – Flammable Solids
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Class 5 – Oxidizers
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**Class 6 – Poisons
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Class 7 – Radioactive Materials
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**Class 8 – Corrosives
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Class 9 – Other Regulated Materials (ORM)
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Other Considerations DOT system does not require that all chemical shipments be marked with placards or labels. In most cases, the package or tank must contain a certain amount of hazardous material before a placard is required.
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Placards – must apply placards
Category of material (hazard class or division number and additional description, as appropriate PLACARD NAME Placard design section reference 1.1 EXPLOSIVES 1.1 1.2 EXPLOSIVES 1.2 1.3 EXPLOSIVES 1.3 2.3 POISON GAS 4.3 DANGEROUS WHEN WET 5.2 (organic peroxide, Type B, liquid or solid, temperature controlled ORGANIC PEROXIDE 6.1 (material poisonous by inhalation, see of this subchapter) POISON INHALATION HAZARD 7 (Radioactive Yellow III label only) RADIOACTIVE © Pedro Nogueira/ShutterStock, Inc.
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Placards - 1,001 pounds (or more)
Category of material (Hazard class or division number and additional description, as appropriate) Placard Name Placard design section reference 1.4 EXPLOSIVES 1.4 1.5 EXPLOSIVES 1.5 1.6 EXPLOSIVES 1.6 2.1 FLAMMABLE GAS 2.2 NON-FLAMMABLE GAS 3 FLAMMABLE COMBUSTABLE LIQUID COMBUSTIBLE 4.1 FLAMMABLE SOLID 4.2 SPONTANEOUSLY 5.1 OXIDIZER 5.2 ( Other than organic peroxide, Type B, liquid or solid, temperature controlled) ORGANIC PEROXIDE 6.1 (other than material poisonous by inhalation) POISON 6.2 (NONE) 8 CORROSIVE 9 CLASS 9 (see (f)(9)) ORM-D © Pedro Nogueira/ShutterStock, Inc.
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Using the ERG ERG is a preliminary action guide.
Useful during the initial 10 to 15 minutes of an incident Cannot be used to create a comprehensive action plan Divided into four sections: yellow, blue, orange, green
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Using the ERG The Table of Initial Isolation and Protective Action Distances in the Emergency Response Guidebook is divided into “small spills” and “large spills.” The DOT defines a small spill as a leaking container small than 55 gallons.
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Yellow Section Chemicals are listed in this section numerically by their four-digit UN number. Use when the UN number is known or can be identified. Entries include the name of the chemical and the emergency action guide number.
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Blue Section Chemicals are listed alphabetically by name.
Entry will include the emergency action guide number and the identification number. The same information, organized differently, is in both the blue and yellow sections.
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Orange Section Contains the emergency action guides
Guide numbers are organized by general hazard class and indicate what basic emergency actions should be taken, based on hazard class. **Provides the fire, explosion, and health hazards information for the material identified.
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Green Section Organized numerically by UN identification number and provides the initial isolation distances for certain materials Chemicals included in this section are highlighted in the blue or yellow sections. Toxic inhalation hazardous materials (TIH)
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Green Section If a, in using the ERG, a first responder discovers the entry for the material in question is highlighted and there is no fire involved, the first responder should go directly to the green-bordered section.
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DOT Response Guidebook (ERG)
Can be used during the initial phase of the hazardous materials incident Nine basic hazard classes or families Each exhibits similar properties. “Dangerous” placard indicates more than one hazard class is contained in the same load. DOT system is a broad-spectrum look at chemical hazards.
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DOT Response Guidebook (ERG)
**Control of the scene begins by isolating the site. The process for establishing initial isolation distances can be found in the Emergency Response Guide (ERG).
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DOT Response Guidebook (ERG)
**The two types of potential hazards found in each guide of the Emergency Response Guidebook are health and fire/explosion. erg2008.ppt
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NFPA 704 System Designed for fixed facility use
Found on the outside of buildings, on doorways to chemical storage areas, and on fixed storage tanks
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NFPA 704 System Fire fighters can use the NFPA diamonds to determine a course of action at a hazardous material incident. NFPA 704 hazard identification system uses a diamond-shaped symbol of any size.
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NFPA 704 System Broken into four smaller diamonds, each representing a property or characteristic **Blue diamond indicates the health hazard posed (position 1). **Red diamond indicates flammability (position 2).
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NFPA 704 System Broken into four smaller diamonds, each representing a property or characteristic **Yellow diamond indicates reactivity (position 3). **White diamond is used for special symbols and handling instructions (position 4).
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NFPA 704 System Blue, red, and yellow diamonds each contain a numerical rating of 0–4. 0 is the least hazardous. 4 is the most hazardous.
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NFPA 704 System White quadrant will not have a number but may contain special symbols. Burning O symbolizes oxidizing capability. Three-bladed fan symbolizes radioactivity. **A W with a slash through it symbolizes water reactive.
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NFPA 704 System
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**NFPA 704 System
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HMIS Marking Program for communication of chemical use and hazards to employees Established in 1983 by OSHA Uses diamonds similar to NFPA 704 Voluntary program Intended for employee of a facility Not a response information tool
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Military Hazardous Materials/WMD Markings
The military has their own marking system. Division 1—Considered mass detonation and are identified by a number 1 printed inside an orange octagon. **Division 2–Have explosion-with-fragment hazards and are identified by a number 2 printed inside an orange X.
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Military Hazardous Materials/WMD Markings
The military has their own marking system. Division 3—Mass fire hazards; identified by a number 3 printed inside an inverted orange triangle. Division 4—Moderate fire hazards; identified by a number 4 printed inside an orange diamond.
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Military Hazardous Materials/WMD Markings
3 Military Hazardous Materials/WMD Markings A. B. C. D. A. Mass detonation hazards. B. Explosion-with-fragment hazards. C. Mass fire hazards. D. Moderate fire hazards.
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Other Reference Sources
Material safety data sheets (MSDS) Shipping papers CHEMTREC National Response Center
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MSDS **Developed by the manufacturer listing specific hazards of a product Provides basic information about: The chemical makeup of a substance The potential hazards it presents Appropriate first aid in the event of an exposure Other pertinent data for safe handling of the material
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MSDS Generally an MSDS will include:
Physical and chemical characteristics Physical hazards of the material Health hazards of the material Signs and symptoms of exposure Routes of entry Permissible exposure limits
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MSDS Generally an MSDS will include: Responsible party contact
Precautions for safe handling Applicable control measures, including personal protective equipment Emergency and first-aid procedures Appropriate waste disposal
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MSDS When responding to a hazardous materials incident at a fixed facility, ask the site manager for an MSDS for spilled material. All facilities are required by law to have an MSDS on file.
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MSDS MSDS is not a definitive response tool, but it is a piece of the puzzle. **Firefighters can contact the manufacturer by using the number on the MSDS to obtain hazard and response information.
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Shipping Papers Are required whenever materials are transported from one place to another Names and addresses of the shipper and the receiver Identify the material being shipped Specify the quantity and weight of each part of the shipment
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Bills of Lading Shipping papers for road and highway transportation
Located in the cab of the vehicle Required by law to have a set of shipping papers May have additional information about a hazardous substance
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Packaging Group Designation
Another way used by shippers to identify special handling requirements or hazards Some DOT hazard classes require shippers to assign packaging groups based on the flash point and toxicity. May signal that the material poses a greater hazard
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Packaging Group Designation
Packaging group I: high danger Packaging group II: medium danger Packaging group III: minor danger
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Waybills Shipping papers for railroad transportation
List of every car on the train is called a consist. **Conductor, engineer, or a designated member of the train crew will have a copy of both the waybill and the consist. Care and control of the waybill is the responsibility of the train crew.
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Dangerous Cargo Manifest
Shipping papers on a marine vessel Generally kept in a tube-like container in the wheelhouse in the custody of the captain or master
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Air Bill Shipping paper for air transport
**The Air Bill is usually kept in the cockpit and is the pilot’s responsibility
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Chemical Transportation Emergency Center
Located in Arlington, VA Established by the Chemical Manufacturer’s Association **Available 24 hours per day to provide information about many chemicals to response agencies Phone number
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Calling CHEMTREC Have the following information ready:
Name of the caller and call back telephone number Location of the actual incident or problem Shipper or manufacturer of chemical (if known) Container type
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Calling CHEMTREC Information (continued)
Rail car or vehicle markings or numbers Shipping carrier’s name Recipient of material Local conditions and exact description of the situation
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CHEMTREC Free service that connects fire fighters with chemical manufacturers, chemists, and other product specialists Canadian equivalent of CHEMTREC is known as CANUTEC. Mexican equivalent is SETIQ.
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CHEMTREC **When attempting to collect hazard information during an emergency incident, the responders could contact CHEMTREC for immediate information on the material’s properties, its hazards, and suggested control techniques.
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National Response Center
Operated by the U.S. Coast Guard Central notification point After notification NRC will contact necessary government agencies. NRC must be notified if a spill possibly may enter a waterway. Phone number
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Radiation You must be able to recognize where radioactive materials might be encountered. Typical industries that routinely use radioactive materials include: Food testing labs, hospitals, medical research centers, biotechnology facilities, construction sites
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Radiation Often there will be signs or placards that indicate the presence of radioactive substances. If you suspect a radiation incident at a fixed facility, ask for the radiation safety officer of the facility.
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Radiation If the incident is not at a fixed site, the presence of radiation may never be apparent. Radioactive isotopes are not detected by the senses. Call a hazardous materials team.
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Radiation Significant incidents involving radiation are few and far between. Most incidents you may encounter will involve low-level radioactive sources and can be handled safely. These low-level sources are typically found in Type A packaging.
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Type A Packaging Inner containment vessel and packaging materials
Designed to protect the contents from damage during normal shipping and handling Courtesy of Sandia National Laboratories.
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Type B Packaging More dangerous radioactive sources
Contains materials such as spent radioactive waste and other high-level emitters Courtesy of Sandia National Laboratories.
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Type B Packaging Designed to protect the contents from greater exposure Amount of protection is based on the potential severity of the hazard. Includes small drums and heavily shielded casks weighing more than 100 metric tons
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Potential Terrorist Incident
The difference between a chemical and a biological incident. The major difference is the speed of onset of the health effects. Chemical incidents are typically characterized by rapid onset Biological incidents typically have a delayed onset of symptoms.
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Chemical Agents Terrorist activities involving chemical agents may vary dependent on the complexity of the operation.
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Chemical Agents Some clues to a terrorist activity involving chemical agents may include: Protective equipment, chemical containers, and glass containers Odors Residual chemicals in the area Chemistry books or other reference materials Signs of exposure
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Biological Agents Indicators may include:
Production or containment equipment in the area Microbiology or biology textbooks may be present. Personal protective equipment Abandoned spray devices Signs of exposure
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Radiological Agents Difficult to access Indicators may be:
Production or containment equipment Equipment used for detonation of the radioactive source Personal protective equipment Radiation monitoring equipment Signs of exposure
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Illicit Laboratories There are many indicators of criminal or terrorist activities involving illicit labs. Look for signs of: Terrorist training manuals Suspicious personnel working around the area Surveillance materials Weapon and nonweapon supplies.
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Illicit Laboratories Drug labs are the most common found.
Typically primitive Everyday items modified to produce drugs Large quantities of cold tablets, acid, paint thinner, drain cleaner, and other such products. Should be considered as significant hazardous materials scenes.
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Explosives Indicators fit into four main categories:
Protective equipment Production and containment materials Explosive materials Support materials
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Secondary Devices Indicators include: Trip devices
Common concealment containers
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Summary Fire fighters should use all available resources to provide a greater degree of safety and improve their ability to mitigate the incident. Many resources are readily available and will provide initial guidance for handling the incident.
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Summary Fire fighters should know where to obtain this initial information and how best to use it. Fire fighters should know how to obtain MSDS from various sources, including their department, the scene of the incident itself, or the manufacturer of the material.
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Summary Fire fighters should be able to demonstrate proficiency in determining a proper guide to use when using the NAERG. Fire fighters should be able to name, understand, and locate the various types of shipping papers on various modes of transportation.
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