Hazardous Materials Incidents by Chris Hawley CHAPTER 2: Recognition and Identification

Chapter 2: Overview Introduction Location and occupancy Placards, labels, and markings Other identification systems Containers Use of senses Chemical and physical properties Summary

HAZMAT Clues (1 of 2) It is through recognition and identification (R & I) that you can impact your ability to stay alive.

HAZMAT Clues (2 of 2) Location and occupancy Placards, labels, and markings Container types Senses

Location and Occupancy The size of the community does not impact the potential for hazardous materials; every community has hazardous materials Major transportation corridors Buildings that store chemicals

Some Examples Hardware stores, hospitals Auto part supply stores Dry cleaners Manufacturing facilities Print shops Doctors’ offices Photo labs Agricultural supply stores Semi-conductor manufacturing facilities Electronic manufacturing Light to heavy industrial Marine terminals Rail yards Airport terminals and fueling areas Pool chemical stores Paint stores Hotels Swimming pools Food manufacturing Many others

Placards, Labels, and Markings The Department of Transportation (DOT) regulates the movement of hazardous materials (dangerous goods in Canada) by air, rail, water, roadway, and pipeline which can be located in 49 CFR 170-180.

DOT Placarding (1 of 2) Table 1 placards Table 2 placards Require placarding at any amount Table 2 placards Require placarding at 1,001 pounds

DOT Placarding (2 of 2)

DOT Hazard Classes (1 of 2) DOT has established 9 hazard classes. Classes 1-8 are specific. Class 9 is a miscellaneous category. Some classes have subdivisions.

DOT Hazard Classes (2 of 2) Class 1: Explosives Class 2: Gases Class 3: Flammable liquids Class 4: Oxidizers and organic peroxides Class 5: Flammable solids, water reactives, and spontaneously reactive Class 6: Poisons Class 7: Radioactives Class 8: Corrosives Class 9: Miscellaneous hazards

Placards Fixed on the four sides of a vehicle 10 ¾ by 10 ¾ inches Provide warning by: Color Division number Name or UN number Picture

Labels Used on two sides of shipping packages Affixed near shipping name 3.9 x 3.9 inches in size Smaller versions of the placards Required for most hazardous materials packages

Class 1: Explosives Division 1.1 – Mass explosion hazard Division 1.2 - Projectile hazard Division 1.3 - Fire hazard or minor blast hazard Division 1.4 – Minor explosion hazard Division 1.5 – Very insensitive explosives Division 1.6 –Also very insensitive explosives

Explosives and Fires Extremely dangerous Withdrawing usually best option Consult DOT ERG 1988 Kansas City, MO, lost six firefighters to a fire involving explosives.

Packing Groups Some materials may not be shipped with others. They have established packing groups. Packing group I – greatest danger Packing group 2 – medium danger Packing group 3 – minor danger DOT rules state which materials can be shipped with the various packing groups.

Class 2: Gases (1 of 2) Division 2.1 – Flammable gases Division 2.2 – Non-flammable, non-poisonous, and compressed gas Liquefied gas Pressurized cryogenic gas Compressed gas in solution Division 2.3 – Poisonous gases

Class 2: Gases (2 of 2)

Hazard Zones DOT has established hazard zones that signify the amount of toxicity a particular material may present. Hazard zones are listed as A-D. A material listed with “Hazard zone A” is extremely toxic and presents significant inhalation risk. Hazard zone D is also severely toxic, but not as toxic as “A.”

Class 3: Flammable Liquids (1 of 2) Flammable liquids are those that have flash points below 141º F. Combustible liquids are those that have flash points above 141º F.

Class 3: Flammable Liquids (2 of 2)

Class 4: Flammable Solids (1 of 2) Division 4.1 – Flammable solids Division 4.2 – Spontaneously combustible materials Division 4.3 – Dangerous when wet materials

Class 4: Flammable Solids (2 of 2)

Class 5 Oxidizers and Organic Peroxides Division 5.1 - Oxidizers Division 5.2 - Organic peroxides

Oxidizers

Organic Peroxides Ability to polymerize May be violently reactive or explosive May violently rupture container, if contained Sensitive to shock, heat, or contamination

Organic Peroxides

Class 6: Poisons (1 of 2) Division 6.1 – Materials that present a risk to humans during transportation Division 6.2 – Microorganisms, or their toxins, that can cause disease Has two hazard zones

Class 6: Poisons (2 of 2)

Class 7: Radioactive (1 of 2) There are no sub-divisions for radioactives. There are three labels. Radioactive I Radioactive II Radioactive III

Class 7: Radioactive (2 of 2)

Class 8: Corrosives (1 of 2) Includes acids and bases Capable of causing destruction to humans and metal

Class 8: Corrosives (2 of 2)

Class 9: Miscellaneous (1 of 2) Present hazard not listed in previous classes Dry ice Molten sulfur Hazardous waste

Class 9: Miscellaneous (2 of 2)

Dangerous Placard (1 of 2) Placard means mixed load is being carried. Load consists of two materials that would require placarding. More than 2, 205 lbs. requires dangerous placard and specific hazard placard.

Dangerous Placard (2 of 2)

Specific Name Placards

Primary Placards Provides primary hazard and subsidiary hazard. Subsidiary hazard does not have class/division number. Subsidiary placard is below primary hazard.

Placard and Identification Numbers ID number indicates a bulk shipment. More than 119 gallons in one container

Other Placards and Labels (1 of 3)

Other Placards and Labels (2 of 3)

Other Placards and Labels (3 of 3)

White Squared Placard

Labels Display primary hazard of the package May display subsidiary hazard

Facility Markings: NFPA 704 Four-tiered system Health Fire Reactivity Special hazards Numerical rating system 0-4

Ratings 4 – Severe hazard 3 – Serious hazard 2 – Moderate hazard 1 – Slight hazard 0 – Minimal hazard

Hazardous Materials Information System (HMIS) On containers Used by employers to comply with hazard communication regulation

Military Warning System

Pipeline Marking System Pipeline contents Pipeline owner Emergency contact information

Pesticide Markings Label signal words Pesticide control # Danger Warning Caution Pesticide control #

Containers Small, household Medium-sized containers Large-scale containers Fortified containers

Bottles

Bags

Drums Fiberboard Fiberboard plastic lined Plastic (poly) Steel Stainless steel Aluminum Dry, granular Wetted materials, slurries Corrosives Flammables Hazardous corrosives Pesticides or steel reacting materials

Drums

Cylinders

Totes

Highway Transportation Box trucks Land sea container (sea box) Atmospheric tank truck Chemical hauler Corrosive tank Pressurized tanks Inter-modal containers

Specification Plate Located on tank Provides specific information on the tank

DOT 406/MC306 (1 of 2) Atmospheric tank truck 2-5 compartments Commonly called gasoline tank truck 2-5 compartments Up to 11,000 gallons Aluminum construction Elliptical in shape Rollover protection

DOT 406/MC306 (2 of 2)

Internal Baffles and Bulkheads

DOT 407/MC307 (1 of 4) Chemical workhorse Two types Insulated Non-insulated 2000-7000 gallons (5000 normal) Usually one compartment

DOT 407/MC307 (2 of 4)

DOT 407/MC307 (3 of 4)

DOT 407/MC307 (4 of 4)

Insulated 407/307 Typically one compartment Inner tank surrounded by insulation and outer shell Steam lines or heated lines in insulation Horseshoe shaped

Non–Insulated 407/307 Reinforced rings Typically one compartment Round in shape

DOT 412/MC312 (1 of 2) Corrosive tank trucks Single compartment Usually less than 5,000 gallons

DOT 412/MC312 (2 of 2)

MC331 (1 of 2) Pressurized tank Compressed gases Up to 11,500 gallons Low to high pressure Significant BLEVE risk

MC331 (2 of 2)

BLEVE They pose significant risk to responders. Fires involving sealed containers can violently rupture. Propane tanks are common examples

Diagram of a BLEVE

BLEVE Recommendations (1 of 2) Withdraw immediately in case of rising sound from venting relief valves or discoloration of the tank. Fight the fire from a distance with unstaffed hose holders or monitor nozzles. Cool the tank with flooding quantities long after the fire is out. A minimum of 500 gpm at the point of flame impingement is recommended by the NFPA.

BLEVE Recommendations (2 of 2) If the water is vaporizing on contact, you are not putting enough water on the tank. Water should be running off the tank if you are cooling the tank. Do not direct water at relief valves or safety devices, as icing may occur which would block the venting material causing an increase in pressure inside the tank. The tank may fail from any direction, but avoid the ends of the tank. For massive fire, use unmanned hose holders or monitor nozzles. If impossible, withdraw from the area and let fire burn.

Dangers Associated with BLEVEs The fireball can engulf responders and exposures. Metal parts of the tank can fly considerable distance. Liquid propane can be released into the surrounding area and be ignited. The shock wave, air blast, or flying metal parts created by a BLEVE can collapse buildings, or move responders and equipment.

MC-338 (1 of 2) Cryogenic containers Vacuum-sealed inner container Well insulated Low pressure

MC-338 (2 of 2)

Tube Trailers High pressure cylinders Contain compressed gas

Dry Bulk Tanks

Hot Materials Tanks

Intermodal Tanks (1 of 2) Non-pressure Pressure High pressure

Intermodal Tanks (2 of 2)

Rail Tank Cars Increased volume Limited access Up to 30,000 gallons for HAZMAT Limited access

Types of Rail Cars Non-pressure Pressure Specialized

Non-pressure Cars (1 of 2) Up to 100 psi pressure Known as General Service cars All piping valves, lines, relief valves on the outside

Non-pressure Cars (2 of 2)

Pressure Cars (1 of 2) Over 100 psi pressure Liquefied gases All pipes, valves, and fittings under a protective dome

Pressure Cars (2 of 2)

Specialized Rail Cars (1 of 3) Trailers of flat car Box cars Cryogenic cars Tube cars

Specialized Rail Cars (2 of 3)

Specialized Rail Cars (3 of 3)

Markings on Rail Cars Placards Dedicated cars labeled Specifications on side Tank car #

Bulk Storage Tanks Underground Aboveground

Gasoline Stations

Ordinary Tank

External Floating Roof

Internal Floating Roof

Specialized Tanks Cryogenic tanks High pressure tanks

Senses Touch, taste, smell are dangerous tools to use for recognition and identification. Sight and sounds are acceptable, but always maintain distance.

Chemical and Physical Properties Follow the science to guide your response.

State of Matter Solid Liquid Gases

Temperature Melting point Freezing point Sublimation

Boiling Point Material turning to a gas or vapor

Vapor Pressure Indication of vapor production Material moves to a gas or vapor Measure of the force of the vapors 760 mm HG = 1 ATM = 14.7 psi

Common Vapor Pressures Water – 25 mm Hg Acetone – 180 mm Hg Gasoline – 300 mm Hg Ethyl ether – 440 mm Hg Methyl alcohol – 100 mm Hg Diesel fuel – 5 mm Hg Sodium hydroxide – 1 mm Hg @ 2534º F Sulfuric acid – 0.001 mm Hg Ethion – 0.0000015 mm Hg Sarin – 2.1 mm Hg

Vapor Density Relationship with air Air given value of 1 Less than 1 rise in air Greater than 1 stay low

Specific Gravity Relationship with water Water given value of 1 Less than 1 float on water Greater than 1 sink

Corrosivity Acids have a value of 0-6.9. Bases are 7.1-14. Neutral is a pH of 7.

Common pHs Water – 7 Stomach acid – 2 Orange juice – 3 Drain cleaner – 14 Potassium hydroxide – 14 Sulfuric acid – 1 Pepsi – 2 Ammonia - 12

Chemical Reactivity Exothermic Releases heat Endothermic Absorbs heat

Flash Point Temperature of the liquid when, while being heated, an ignition source is introduced into the vapor/air mixture located above the liquid, causing a flash fire

Common Flashpoints Gasoline – 45º F Isopropyl alcohol – 53º F Acetone – -4º F Diesel fuel – >100º F Motor oil 300 – -450º F Xylene – 90º F

Autoignition Temperature Material is heated and ignites on its own without the presence of an ignition source.

SADT Self Accelerating Decomposition Temperature Temperature at which the material will rapidly decompose Usually reacting violently or burning

Flammable Range (1 of 2) Lower Explosive Limit (LEL) Minimum amount in air needed to have a fire Upper Explosive Limit (UEL) Maximum amount in air to have a fire Range in between LEL and UEL is the flammable range. Fires and explosions occur in the flammable range.

Flammable Range (2 of 2)

Toxic Products of Combustion When most materials burn, smoke is usually very toxic. Even wood, wool, hay, and many other common items present a significant risk. Smoke from plastic burning is extremely toxic. Respiratory protection should always be worn in the presence of smoke.

Summary Hazard classes Containers Chemical and physical properties