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

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

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

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

5. 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

6. 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

7. 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

8. 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

9. DOT Placarding (2 of 2)

10. 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.

11. 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

12. 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

13. 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

14. Class 1: Explosives Division 1.1 – Mass explosion hazard
Division Projectile hazard
Division 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

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

16. 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.

17. 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

18. Class 2: Gases (2 of 2)

19. 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.”

20. 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.

21. Class 3: Flammable Liquids (2 of 2)

22. 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

23. Class 4: Flammable Solids (2 of 2)

24. Class 5 Oxidizers and Organic Peroxides
Division Oxidizers
Division Organic peroxides

25. Oxidizers

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

27. Organic Peroxides

28. 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

29. Class 6: Poisons (2 of 2)

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

31. Class 7: Radioactive (2 of 2)

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

33. Class 8: Corrosives (2 of 2)

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

35. Class 9: Miscellaneous (2 of 2)

36. 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.

37. Dangerous Placard (2 of 2)

38. Specific Name Placards

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

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

41. Other Placards and Labels (1 of 3)

42. Other Placards and Labels (2 of 3)

43. Other Placards and Labels (3 of 3)

44. White Squared Placard

45. Labels Display primary hazard of the package
May display subsidiary hazard

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

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

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

49. Military Warning System

50. Pipeline Marking System
Pipeline contents
Pipeline owner
Emergency contact information

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

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

53. Bottles

54. Bags

55. 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

56. Drums

57. Cylinders

58. Totes

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

60. Specification Plate Located on tank
Provides specific information on the tank

61. 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

62. DOT 406/MC306 (2 of 2)

63. Internal Baffles and Bulkheads

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

65. DOT 407/MC307 (2 of 4)

66. DOT 407/MC307 (3 of 4)

67. DOT 407/MC307 (4 of 4)

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

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

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

71. DOT 412/MC312 (2 of 2)

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

73. MC331 (2 of 2)

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

75. Diagram of a BLEVE

76. 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.

77. 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.

78. 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.

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

80. MC-338 (2 of 2)

81. Tube Trailers
High pressure cylinders
Contain compressed gas

82. Dry Bulk Tanks

83. Hot Materials Tanks

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

85. Intermodal Tanks (2 of 2)

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

87. Types of Rail Cars
Non-pressure
Pressure
Specialized

88. 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

89. Non-pressure Cars (2 of 2)

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

91. Pressure Cars (2 of 2)

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

93. Specialized Rail Cars (2 of 3)

94. Specialized Rail Cars (3 of 3)

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

96. Bulk Storage Tanks
Underground
Aboveground

97. Gasoline Stations

98. Ordinary Tank

99. External Floating Roof

100. Internal Floating Roof

101. Specialized Tanks
Cryogenic tanks
High pressure tanks

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

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

104. State of Matter
Solid
Liquid
Gases

105. Temperature
Melting point
Freezing point
Sublimation

106. Boiling Point
Material turning to a gas or vapor

107. 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

108. 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 2534º F
Sulfuric acid – mm Hg
Ethion – mm Hg
Sarin – 2.1 mm Hg

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

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

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

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

113. Chemical Reactivity
Exothermic
Releases heat
Endothermic
Absorbs heat

114. 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

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

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

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

118. 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.

119. Flammable Range (2 of 2)

120. 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.

121. Summary
Hazard classes
Containers
Chemical and physical properties