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
– 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, nonpoisonous, 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
– 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
– 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
– 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