Hazardous Materials

Hazardous Materials
❖ Hazardous materials can be silent killers.

❖ Almost every household and workplace has varying amounts of

chemicals that, if spilled or combined, will cause great harm and even
death.

❖ It is important that you have a basic knowledge of how to recognize

these chemicals, where they may be found, and what to do, or not do,
about hazardous material spills.
Ways that hazardous materials can enter the body:

Inhalation: Through breathing, most rapid way

Absorption: Through skin or eyes

Ingestion: Swallowing

Injection: Penetrating skin

The key to dealing with hazardous material spills is to remember S.I.N.
(Safety, Isolation, Notification).

Safety:

Always assume that spilled chemicals are extremely toxic

Do not approach; stay at a safe distance

Mixtures of chemicals can be very dangerous

- bleach mixed with ammonia creates poisonous gas(es)
Chemical Exposures – Routes of Entry

• Inhalation - Lungs
• Breathe 20,000 – 25,000 Times Per Day
• At Rest – Inhale 10,000 to 14,000 Liters of Air Per Day
• Absorption – Skin
• Ingestion – Digestive Tract
• Injection – Typically Through Sharps
Types of Chemical Exposures
• Acute – Short Term
• Chronic – Over a Long Period of Time
• Chemical Exposures May or May Not Result in Adverse Impact,
Depending on the Amount of the Exposure (i.e., the Dose)
"Dosis facit venenum" - The Dose Makes the Poison

• All substances are poisons; there is none which is

not a poison. The right dose differentiates a
poison…." Paracelsus (1493-1541)
• 10 Grams Caffeine – Usually Fatal
• 150 mg – Stimulate Entire Spinal Cord
• 65 to 350 mg in 8 oz. of Coffee
• 55 mg in 12 oz Can of Mountain Dew®
• 45 mg in 12 oz Can of Coke® or Diet Coke®
Hazardous Materials are an ever-present danger:

In the home or workplace

On roadways
In industrial or commercial areas
In the Home or Workplace
❖ Inventory:

Make a list of hazardous materials

Read the labels on all products you purchase

Segregate and store or dispose of properly

Know what steps to take if chemicals are spilled

Secure and segregate all containers at work

Typical Places Hazardous Materials are Found in the Home:

Kitchen
oven cleaners, drain cleaners, ammonia, bleach

Laundry
bleach, spot removers, cleaners

Garage
gasoline, solvents, pesticides, paints, paint removers, thinners
Cleaning Supplies
• Building Require the Use of “Green Seal Certified”
Cleaning Materials – Undiluted Cleaner:
• Non-Toxic
• Not a Skin Sensitizer
• Does Not Contain Substances Which Contribute to Poor
Indoor Air Quality

• Cleaning Supplies Meet Green Seal Standard #37

• [Link]
Personal Items
• Fragrances,
• Perfumes
• After Shave Lotion
• Nail Polish Remover
• Acetone
• Be Aware of Your Co-Workers
 Asbestos
❖Asbestos is one of the potential hazards that you may encounter in a
damaged building.

❖Asbestos is a human carcinogen, which can be found in a number of

different building materials throughout city and campus buildings.

❖The hazard presented by asbestos varies considerably based upon the

nature of the materials and the likelihood of causing an airborne release
of asbestos fibers.

❖If left un-disturbed, a release is unlikely.

 On Roadways
❖Hazardous materials transported on roadways must carry a Department of
Transportation (DOT) warning label on the package.

❖Vehicles transporting quantities of hazardous materials must have DOT

placards affixed to all sides of the vehicle.

❖Bulk shipments, such as in gasoline tanker trucks, will have a four-digit

numeric code instead of the hazard class in the center of the placard.

❖This number can be referenced in the DOTs "Emergency Response Guide

Book" to determine the identity and the emergency handling for the chemical
involved.
DOT Hazardous Materials Warning Labels:
Color Coding of Labels and Placards:
Orange: Explosive

Red: Flammable Gas and Liquid

White: Poison

Black/White: Corrosive

Yellow: Oxidizer

Green: Non-flammable gas

Yellow/White: Radio Active

Hazardous Materials by Class Numbers

Class 1: Explosive
Class 2: Gasses (Compressed, liquefied or dissolved under pressure)
Class 3: Flammable Liquids
Class 4: Flammable Solids or Substances
Class 5: Oxidizers
Class 6: Poisonous or Infectious Substances
Class 7: Radioactive Substances
Class 8: Corrosives
Class 9: Miscellaneous Dangerous Substances

The class number is the number located on the bottom corner of the label or placard.
In Industrial and Commercial Fixed Sites

Most buildings that contain hazardous materials are identified

by the National Fire Protection Association 704 Diamond
system, which is usually located at the building entrance or in
the storage area.
❖The 4 Diamond is divided into four quadrants.

❖Each quadrant of the diamond has a special meaning and is color-coded.

❖The top quadrant is coded red for fire hazard, the right quadrant is
coded yellow for reactivity, the left quadrant is coded blue for health
hazards, and the bottom quadrant is white and contains information
about special hazards of the particular chemical.

❖Each colored quadrant is also numbered for the degree of hazard from
zero to four, four being the greatest hazard.
Red ... Fire Hazard

4. materials that burn readily

3. materials that can ignite at room temperature
2. materials that ignite if moderately heated
1. materials that ignite after considerable preheating
0. will not burn
Yellow ... Reactivity

4. may detonate
3. shock and heat may detonate
2. violent chemical change
1. unstable if heated
0. stable
Blue ... Health Information

4. deadly
3. extreme hazard
2. hazardous
1. slightly hazardous
0. normal material
Special Information

W: water may cause reaction

COR: corrosive
OXY: oxidizer
ACID: acid
Common Hazardous Material Locations:

Industrial or manufacturing plants

· Shopping centers, supermarkets
· Dry cleaners
· Hardware stores
· Auto repair shops
Signs of Hazardous Material Spills:

· Overturned containers with DOT label especially on roadways

· Pungent or noxious odor you should never intentionally get close

enough to smell it

· Bubbling liquid

· Vapor anything that is letting off a vapor is having a reaction and should
be avoided
If you see one or more of these signs of a hazardous materials spill on roadway
or at a fixed facility, take the following actions:

· Get uphill, and upwind, and a safe distance away from the spill

· Evacuate the surrounding areas if possible, but do not put yourself in

danger of exposure to the spill

· Notify authorities as quickly as possible

❖ "Hazardous Materials" is a very comprehensive subject.

❖ The important concept to understand is recognition.

❖ DOT placards are placed on vehicles, DOT labels are placed on

packages, and the 4 Diamonds are placed on buildings or storage
areas containing hazardous materials.

❖ Being able to recognize warning signs and being able to recognize

that there is a hazardous condition present may save your life and
the lives of others.
❖ Remember, "Hazardous Materials" in the home and workplace should be
segregated and stored in well-marked, unbreakable containers.

❖ They should also be stored in a low cabinet with an earthquake-proof latch.

❖ Dispose of any hazardous materials that are no longer needed.

GHS
• Globally Harmonized System of Classification & Labeling of
Chemicals
GHS
• A system for standardizing and harmonizing the classification and
labeling of chemicals

• Defines health, physical, and environmental hazards of chemicals

• Communicates hazard information, as well as protective measures, on

labels and Safety Data Sheets (SDS).
Current Systems
• Differences in systems within different countries and different
regulatory agencies within the same government lead to inconsistent
protection for those potentially exposed to the chemicals, as well as
creating extensive regulatory burdens on companies producing
chemicals.
GHS
• The GHS itself is not a regulation or a standard.

• Establishes agreed hazard classification and communication

provisions with explanatory information on how to apply the
system.
Why was GHS Developed?

To provide sound management of chemicals that includes a system

through which chemical hazards are identified and communicated to all
who are potentially exposed.
International Mandate

• Adopted in the 1992 United Nations Conference on Environment and

Development (UNCED), often called the "Earth Summit".

• It was recognized that an internationally harmonized approach to

classification and labeling would provide the foundation for all
countries to develop comprehensive national programs to ensure the
safe use of chemicals.
GHS History
• GHS formally adopted by the UN Committee of Experts - The
Transport of Dangerous Goods and GHS in December 2002

• OSHA ANPR on GHS 2006: OSHA's Advance Notice of Proposed

Rulemaking (ANPR) on the Globally Harmonized System (GHS) of Classification
and Labeling of Chemicals, published in September 2006, was the first step in
aligning the Hazard Communication Standard (HCS) with the GHS.

• OSHA NPRM on GHS 2009: In 2009, the Occupational Safety and Health
Administration (OSHA) issued a Notice of Proposed Rulemaking (NPRM) to
align the Hazard Communication Standard (HCS) with the Globally Harmonized
System of Classification and Labeling of Chemicals (GHS).
GHS History

• OSHA revised the Hazard Communication Standard, aligning it with

the GHS on March 26, 2012
• Rule effective 60 days after publication in the Federal Register
• Estimated to prevent 43 fatalities and 521 injuries & illnesses annually
Implementation

• Employers must complete all training regarding new label elements

and SDS format by Dec 1, 2013
• Requiring compliance with all provisions for preparation of new labels
and SDS by June 1, 2015
• Distributors can’t ship containers unless they have a GHS label by Dec
1, 2015
• Employers given an additional year, June 1, 2016 to update their
Hazard Communication programs or any other workplace signs, if
applicable
Application of GHS

• Enhance the protection of human health and the environment by

providing an internationally comprehensible system
• Provide a recognized framework to develop regulations for those
countries without existing systems
• Facilitate international trade in chemicals whose hazards have been
identified on an international basis
• Reduce the need for testing and evaluation against multiple
classification systems
 Overall Benefits of GHS

• To ensure that employers, employees, and the public are provided with
adequate, practical, reliable, and comprehensible information on the
hazards of chemicals, so that they can take effective preventive and
protective measures for their health and safety.
Benefits to Workers/Public

• Improved safety for workers and others through consistent and

simplified communications on chemical hazards and practices to
follow for safe handling and use,

• Greater awareness of hazards, resulting in safer use of chemicals in the

workplace and the home
GHS & Existing Regulations

• The specific hazard criteria, classification processes, label elements,

and SDS requirements within an existing regulation will need to be
modified to be consistent with the harmonized elements of the GHS

• ALL existing hazard communication systems will need to be changed

in order to apply the GHS
Classification

• Classification is the starting point for hazard communication

• Involves the identification of the hazard(s) of a chemical or mixture by

assigning a category of hazard/danger using defined criteria
Hazard Classes

• 16 classes of physical hazards

• 10 classes of health hazards
• 3 classes of environmental hazards
• Explosives GHS Physical Hazards
• Flammable Gases
• Flammable Aerosols
• Oxidizing Gases
• Gases Under Pressure
• Flammable Liquids
• Flammable Solids
• Self-Reactive Substances
• Pyrophoric Liquids
• Pyrophoric Solids
• Self-Heating Substances
• Substances which, in contact
with water emit flammable gases
• Oxidizing Liquids
• Oxidizing Solids
• Organic Peroxides
• Corrosive to Metals
GHS Health Hazards

• Acute Toxicity
• Skin Corrosion/Irritation
• Serious Eye Damage/Eye Irritation
• Respiratory or Skin Sensitization
• Germ Cell Mutagenicity
• Carcinogenicity
• Reproductive Toxicology
• Target Organ Systemic Toxicity - Single Exposure
• Target Organ Systemic Toxicity - Repeated Exposure
• Aspiration Toxicity
GHS Environmental Hazards

• Hazardous to the Aquatic Environment

• Acute aquatic toxicity
• Chronic aquatic toxicity
• Bioaccumulation potential
• Rapid degradability
GHS Hazard Communication

• Once a chemical has been classified, the hazard(s) must be

communicated to target audiences

• Labels and Safety Data Sheets are the main tools for chemical hazard
communication
GHS Label Elements
• Product Identifier
• Signal Word (Danger, Warning)
• Hazard Statement (for each hazard class and category)
• Pictogram(s)
• Precautionary Statement (for each hazard class and category)
• Name, Address, and Tele. # of chemical manufacturers
Signal Words

"Danger" or "Warning" are used to emphasize hazards and indicate the

relative level of severity of the hazard, assigned to a GHS hazard class
and category.

• "Danger" for the more severe hazards

• "Warning" for the less severe hazards.

Hazard Statement
• Hazard statements are standardized and assigned phrases that describe
the hazard(s) as determined by hazard classification
• “Causes eye irritation”
• “Toxic if inhaled”
• “Flammable aerosol”
• “May cause cancer”
• “May cause respiratory irritation”
• “Harmful to aquatic life”
• “Contains gas under pressure; may explode if heated”
Symbols/Pictograms

• Convey health, physical, and environmental hazard information,

assigned to a GHS hazard class and category.

• The GHS symbols have been incorporated into pictograms for use on
the GHS label

• Pictograms will have a black symbol on a white background with a red

diamond frame
Health Hazard

• Carcinogen
• Mutagenicity
• Reproductive Toxicity
• Respiratory Sensitizer
• Target Organ Toxicity
• Aspiration Toxicity
Environment

• Aquatic toxicity
Exclamation Mark

• Irritant (skin and eye)

• Skin Sensitizer
• Acute Toxicity
• Narcotic Effects
• Respiratory Tract Irritant
• Hazardous to Ozone Layer (Non-
Mandatory)
Skull & Crossbones

• Acute toxicity (fatal or toxic)

Gas Cylinder

• Gases Under Pressure

Corrosion

• Skin Corrosion/Burns
• Eye Damage
• Corrosive to Metals
Exploding Bomb

• Explosives
• Self-Reactives
• Organic Peroxides
Flame Over Circle

• Oxidizers
Flame
• Flammables
• Pyrophorics
• Self-Heating
• Emits Flammable Gas
• Self-Reactives
• Organic Peroxides
Physical Hazard Pictograms
Health Hazard Pictograms
Precautionary Statements

• Precautionary Statements are standardized explanations of the

measures to be taken to minimize or prevent adverse effects
- Prevention
- “Wear protective gloves”
- Response
- “If inhaled, move person to fresh air.”
- Storage
- “Store in a well-ventilated place”
- Disposal
- “Waste must be disposed of in accordance with federal, state, and local environmental control
regulations.”
Label Example
Label Example
NFPA Label Changes

Classification – Flammable liquids are classified in one of four categories, as follows:

Category 1 – flashpoint of < 23°C and initial boiling point ≤ 35°C
Category 2 – flashpoint of < 23°C and initial boiling point > 35°C
Category 3 – flashpoint of ≥ 23°C and ≤ 60°C
Category 4 – flashpoint of > 60°C and ≤ 93°C
Hazard Communication
Category 1 – Flame symbol with the “Danger” signal word
Category 2 – Flame symbol with the “Danger” signal word
Category 3 – Flame symbol with the “Warning” signal word
Category 4 – No symbol necessary, but must have the “Warning” signal word
Secondary Containers
• Employers must ensure that each container of hazardous chemicals in
the workplace is labeled, tagged, or marked with either the information
specified under (i) through (v) for labels on shipped containers
• (i) Product identifier;
• (ii) Signal word;
• (iii) Hazard statement(s);
• (iv) Pictogram(s);
• (v) Precautionary statement(s);
OR
Secondary Containers
• Product identifier and words, pictures, symbols, or combination
thereof, which provide at least general information regarding the
hazards of the chemicals, and which, in conjunction with the other
information immediately available to employees under the hazard
communication program, will provide employees with the specific
information regarding the physical and health hazards of the hazardous
chemical.
MSDS’s
• Information that is currently required on a MSDS:
• Identity used on the label
• Physical & chemical characteristics
• Physical hazards
• Health hazards
• Primary routes of entry
• Exposure limits
• Carcinogenic information
• Safe handling
• Control measures (PPE)
• Emergency & First Aid procedures
• Date of preparation
• Chemical mfg. contact info
Safety Data Sheets (SDS)
1. Identification of the substance or mixture and of the supplier
2. Hazards identification
3. Composition/information on ingredients
4. First aid measures
5. Firefighting measures
6. Accidental release measures
7. Handling and storage
8. Exposure controls/personal protection
9. Physical and chemical properties
10. Stability and reactivity
11. Toxicological information
12. Ecological information
13. Disposal considerations
14. Transport information
15. Regulatory information
16. Other information including information on preparation and revision of the SDS