6/22/2016
• OSHA Low Hanging Fruit
– Top Violations of OSHA Regulations
• # 1 - Failure to Perform Hazard Assessment for Personal
Protective Equipment (PPE)
• # 2 – Failure to Document Hazard Assessment
• #15 – Failure to Train Employees in Use of PPE
The Chemical Hazard Assessment
Process
Philip C. Mann
Technical Director Kappler, Inc.
• 50% of companies did not perform assessment
• Of the 50% that did, 70% did not document
• How do we select chemical protective clothing?
Overview of Hazard Assessment
– Review rules, regulations & standards
• OSHA
• EPA Levels of Protection
• NFPA, ANSI, ISEA
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•
•
– Test and evaluate performance characteristics
• Chemical Barrier
• Physical Properties
– Perform Hazard Assessment
– Select Chemical Protective Clothing
The Toolbox
QR Codes
WISER
ACGIH TLV’s
Product Specifications
SDS’s
What is the substance?
What is the physical state of the substance?
How is the substance a hazard?
What is the result of contact to the skin?
What is the potential exposure?
What task or operation is being performed?
•The Rules on Protection
Sax’s Dangerous
Properties of
Industrial Materials
Emergency
Response
Guidebook
Hazmatch
NIOSH
Pocket Guide
App
•OSHA 29 CFR 1910.132 - PPE
Personal Protective Equipment for General Industry
•OSHA 29 CFR 1910.120 - ‘Hazwoper’ - Hazardous
Waste Operations and Emergency Response
•OSHA 29 CFR 1910.1030 – Blood-Borne Pathogens
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The Rules on Hazard Evaluation
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ANSI Z129.1
• Precautionary labeling for hazardous materials
• Developed by Chemical Manufacturers Assoc.
• Labeling contains name of chemical and signal
words such as WARNING or DANGER
• May not always provide adequate or complete
information of hazard
ANSI Z129.1
NFPA 704
DOT
HMIS
FMCSA
NFPA 704
NFPA 704
• System uses a color coded diamond with four
quadrants that represent
– Health Hazard (Blue)
– Fire Hazard (Red)
– Reactivity Hazard (Yellow)
– Special Hazards (White)
• Hazards are rated from no unusual hazard (0)
or extreme hazard (4)
Department of Transportation
• Hazard Labeling system uses color coded
diamond
• A symbol and term describe the primary
hazard of the material
Department of Transportation
• Hazard classes include:
– Explosive
– Gases (flammable, non-flammable, corrosive,
poison
– Flammable liquids, flammable solids
– Oxidizers, poisons, radioactive materials
– Corrosives
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Department of Transportation
HMIS
• Hazardous Materials Information System
• National Paint and Coatings Association
• Four part rectangle:
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FMCSA
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Federal Motor Carrier Safety Administration
1) Explosives,
2) Gases,
3) Flamable Liquid and Combustable Liquid,
4) Flammable Solid, Spontanaeously Combusbable and Dangerous
When Wet
5) Oxidizer and Organic Peroxide,
6) Poison (Toxic) and Poison Inhalation Hazard,
7) Radioactive,
8) Corrosive,
9) Miscellaneous, and the general Dangerous placard
Toxicity
• "Irritant:" A chemical, which is not corrosive, but which
causes a reversible inflammatory effect on living tissue
by chemical action at the site of contact. A chemical is
a skin irritant if, when tested on the intact skin of
albino rabbits by the methods of 16 CFR 1500.41 for
four hours exposure or by other appropriate
techniques, it results in an empirical score of five or
more. A chemical is an eye irritant if so determined
under the procedure listed in 16 CFR 1500.42 or other
appropriate techniques.
Blue (Health)
Red (Flammability)
Orange (Physical Hazard)
White (Personal Protection)
Hazardous Characteristics
• Toxicity
• Flammability
• Reactivity
• Physical State
Toxicity
• "Sensitizer:" A chemical that causes a
substantial proportion of exposed people or
animals to develop an allergic reaction in
normal tissue after repeated exposure to the
chemical.
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Toxicity
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•
•
•
"Highly toxic:" A chemical falling within any of the following categories:
(a) A chemical that has a median lethal dose (LD(50)) of 50 milligrams or less per
kilogram of body weight when administered orally to albino rats weighing between
200 and 300 grams each.
(b) A chemical that has a median lethal dose (LD(50)) of 200 milligrams or less per
kilogram of body weight when administered by continuous contact for 24 hours (or
less if death occurs within 24 hours) with the bare skin of albino rabbits weighing
between two and three kilograms each.
(c) A chemical that has a median lethal concentration (LC(50)) in air of 200 parts
per million by volume or less of gas or vapor, or 2 milligrams per liter or less of
mist, fume, or dust, when administered by continuous inhalation for one hour (or
less if death occurs within one hour) to albino rats weighing between 200 and 300
grams each.
Toxicity
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•
•
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Target organ effects
Hepatotoxins: Chemicals which produce liver damage
Nephrotoxins: Chemicals which produce kidney damage
Neurotoxins: Chemicals which produce their primary toxic effects on the nervous
system
Agents which act on the blood or hemato-poietic system
Cyanosis; loss of consciousness
Chemicals which irritate or damage pulmonary tissue
Reproductive toxins: Chemicals which affect the reproductive capabilities including
chromosomal damage (mutations) and effects on fetuses (teratogenesis)
Cutaneous hazards: Chemicals which affect the dermal layer of the body
Eye hazards: Chemicals which affect the eye or visual capacity
Toxicity
•
•
•
•
Benzene
OSHA PEL vs. NIOSH REL
TWA .1 vs 1.0
Why the difference?
Toxicity
•
•
•
•
"Toxic." A chemical falling within any of the following categories:
(a) A chemical that has a median lethal dose (LD(50)) of more than 50 milligrams
per kilogram but not more than 500 milligrams per kilogram of body weight when
administered orally to albino rats weighing between 200 and 300 grams each.
(b) A chemical that has a median lethal dose (LD(50)) of more than 200 milligrams
per kilogram but not more than 1,000 milligrams per kilogram of body weight
when administered by continuous contact for 24 hours (or less if death occurs
within 24 hours) with the bare skin of albino rabbits weighing between two and
three kilograms each.
(c) A chemical that has a median lethal concentration (LC(50)) in air of more than
200 parts per million but not more than 2,000 parts per million by volume of gas
or vapor, or more than two milligrams per liter but not more than 20 milligrams
per liter of mist, fume, or dust, when administered by continuous inhalation for
one hour (or less if death occurs within one hour) to albino rats weighing between
200 and 300 grams each.
Toxicity
• OSHA Permissible Exposure Limits (PELs)
• California Division of Occupational Safety and Health
(Cal/OSHA) Permissible Exposure Limits (PELs)
• National Institute for Occupational Safety and Health
(NIOSH) Recommended Exposure Limits (RELs)
• ACGIH® Threshold Limit Values (TLVs®) and Biological
Exposure Indices (BEIs®)
Flammability
• Flammable vs. Combustible
• DOT definition of a flammable gas (for labeling
purposes)
• NPG says it should be treated as a flammable
gas
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6/22/2016
Flammability
• Flammable liquid means any liquid having a
flashpoint at or below 199.4 °F (93 °C).
Flammable liquids are divided into four
categories as follows:
• Category 1 shall include liquids having
flashpoints below 73.4 °F (23 °C) and having a
boiling point at or below 95 °F (35 °C).
Flammability
• Category 2 shall include liquids having flashpoints below
73.4 °F (23 °C) and having a boiling point above 95 °F (35
°C).
• Category 3 shall include liquids having flashpoints at or
above 73.4 °F (23 °C) and at or below 140 °F (60 °C). When
a Category 3 liquid with a flashpoint at or above 100 °F
(37.8 °C) is heated for use to within 30 °F (16.7 °C) of its
flashpoint, it shall be handled in accordance with the
requirements for a Category 3 liquid with a flashpoint
below 100 °F (37.8 °C). 1910.106(a)(19)(iv)
Flammability
Flammability
• When liquid with a flashpoint greater than
199.4 °F (93 °C) is heated for use to within 30
°F (16.7 °C) of its flashpoint, it shall be
handled in accordance with the requirements
for a Category 4 flammable liquid.
• Category 4 shall include liquids having flashpoints
above 140 °F (60 °C) and at or below 199.4 °F (93
°C). When a Category 4 flammable liquid is
heated for use to within 30 °F (16.7 °C) of its
flashpoint, it shall be handled in accordance with
the requirements for a Category 3 liquid with a
flashpoint at or above 100 °F (37.8 °C).
Flammable vs. Combustible
Reactivity
• https://www.google.com/url?sa=t&rct=j&q=&esr
c=s&source=web&cd=15&cad=rja&uact=8&sqi=2
&ved=0ahUKEwjzmM-FIbNAhVMzmMKHag9AucQtwIIXzAO&url=https%3
A%2F%2Fwww.youtube.com%2Fwatch%3Fv%3D
nPXZhJP1EpM&usg=AFQjCNFEX5sKcBhlog9FS94d
IdKzEe0x7A&bvm=bv.123325700,d.cGc
• Chemical reactivity is the tendency of a substance to
undergo chemical changes in a system.
• Chemical Stability – a measure of how stable a
substance is when in the environment or during normal
use
• Chemical Compatibility – measure of how stable a
substance is when mixed with another substance
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Reactivity
• Fluorine
• Chlorine Trifluoride
• Nitrogen Tetroxide
• Dimethyl Hydrazine
Physical State
• Vapor Pressure Vapor pressure or equilibrium vapor pressure is defined
as the pressure exerted by a vapor in thermodynamic equilibrium with its
condensed phases (solid or liquid) at a given temperature in a closed
system. The equilibrium vapor pressure is an indication of a liquid's
evaporation rate. It relates to the tendency of particles to escape from the
liquid (or a solid). A substance with a high vapor pressure at normal
temperatures is often referred to as volatile. The pressure exhibited by
vapor present above a liquid surface is known as vapor pressure. As the
temperature of a liquid increases, the kinetic energy of its molecules also
increases. As the kinetic energy of the molecules increases, the number of
molecules transitioning into a vapor also increases, thereby increasing the
vapor pressure.
Reactivity
• https://www.google.com/url?sa=t&rct=j&q=&
esrc=s&source=web&cd=1&cad=rja&uact=8&
ved=0ahUKEwiVkLbJiofNAhUH82MKHQAFCwE
QtwIIHDAA&url=https%3A%2F%2Fwww.youtu
be.com%2Fwatch%3Fv%3DHvVUtpdK7xw&us
g=AFQjCNF3cR1oycaQGa3OqtaXmlxMmFZSg&bvm=bv.123325700,d.cGc
NFPA 1992
• Liquids that also present a vapor hazard
• Cannot certify a splash suit if chemical:
– Has a vapor pressure > 5mm Hg at 25 C and
carcinogen per Sax’s or NIOSH Guide
– Has a vapor pressure > 5mm Hg at 25 C and skin
notation per ACGIH
Skin Notation Data for Vapors
• EPA Levels of Protection
• Originally applied to personnel at EPA Superfund Sites
• Adopted and specified in HAZWOPER
• First guidance that addressed garment design
• Recognized the different types of hazards in the workplace
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Rules & Regs
• EPA Level A
• Highest level of respiratory, skin and eye protection available
• Recommends:
– Supplied breathing air
– Fully encapsulated chemical suit
– Inner chemical resistant gloves
– Chemical resistant boots
– Two way radio
• Should be worn when:
– potential for high concentrations of vapors, gases, or liquids
– high potential for splash, immersion or exposure to unexpected
chemicals that are harmful to the skin or capable of being
absorbed through the skin
Rules & Regs
• EPA Level B
• Same level of respiratory protection as Level A, but less skin
protection
• Recommends:
– Supplied breathing air
– Chemical resistant clothing providing total skin protection
– Inner and outer chemical gloves
– Hard hat
– Two way radio
• Should be worn when:
– Type and concentration of substances have been identified and
are not suspected of containing high concentrations of chemicals
harmful to the skin or can be absorbed through skin contact.
Rules & Regs
Rules
& Regs
• EPA Level D
• Same level of skin protection as Level B but a lower level of
respiratory protection
• No respiratory protection, minimal skin protection
• EPA Level C
• Recommends:
– Air purifying respirator
– Chemical resistant clothing
– Inner and outer chemical gloves
– Hard hat and communication
• Should be worn when:
– Contact with chemical contaminants will not adversely affect any
exposed skin
• Recommends:
– Coveralls
– Safety Boots
– Safety glasses or goggles
– Hard Hat
• Should be worn when:
– Atmosphere contains no known hazards
– Work functions have no splashes, immersion or the potential for
contact with hazardous levels of any chemicals
– The atmospheric concentration of chemicals must not exceed
IDLH levels
Test & Evaluate
• American Society for Testing and Materials
• F 23 Committee on Protective Clothing
– ASTM F 739 – Chemical Permeation
– ASTM F 903 – Chemical Penetration
– ASTM F 1052 – Positive Pressure
– ASTM F 1001 – Chemical List
– ASTM D 751 – Physical Properties
Test & Evaluate
• Chemical Resistance of Garment Materials
• Permeation
– Transmission of vapor through material
• Penetration
– Transmission of liquid through material
• Degradation
– Physical change in material from chemical contact
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Test & Evaluate
Test & Evaluate
Chemical Barrier Material
Polymer Membrane
Solution
Diffusion
Evaporation
• ASTM F 739
• Liquid/Vapor Permeation
Testing
• Material is clamped
between two chambers.
• One is filled with chemical.
• Once the chemical is
detected, the rate of
permeation through the
fabric is measured over
time.
Fabric
Fill
Level
Chemical
Test & Evaluate
To Analyzer
Test & Evaluate
• ASTM F 903 Liquid Penetration Testing
– The physical movement of a chemical from one side of
the material to the other through holes and micropores etc
– Test determines if a material is porous to a potentially
hazardous liquid
– Can be applied to seams, closures and interfaces
– Test is typically run for one hour with a one minute
long 2 psi pressure pulse after five minutes
– Visual observation of pass/fail
Test & Evaluate
Test & Evaluate
– ASTM D 751
– Physical Properties
• ASTM F 1358
• Flammability Resistance
• Sample is suspended in the
flame for 3 seconds
– Tensile Strength
• Sample re-enters flame for
an additional 12 seconds
– Sample must not ignite
– Tear Resistance
– Sample can ignite but must
self extinguish in 4 seconds
– Char length must be less than
10 inches
– Bursting Strength
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Selection
Selection
• Solids as Hazards
Overview of Hazard Assessment
– Inhalation, ingestion and skin contact
•
•
•
•
•
•
What is the substance?
What is the physical state of the substance?
How is the substance a hazard?
What is the result of contact to the skin?
What is the potential exposure?
What task or operation is being performed?
Selection
Carcinogens
• Liquids as Hazards
– Primarily skin contact
– Nuisance, irritant, burn and skin absorption
– Some liquids produce vapors
• Vapors as Hazards
– Inhalation and skin contact
Selection Exposure Scenario
• The most critical aspect of the hazard assessment
• Many compounds are known or suspected to cause
cancer from exposure
• Exposure is defined by three things:
– In many cases, cancer results from repeated long term
exposure
– Potential for contact with the substance
– If contact is expected, what is the level of contact
– If contact is expected, what is the length of contact
• Hygienists typically treat carcinogens in the same
way as toxic skin absorbers
• Determine the task or operation being performed
• “Avoid all contact”
Selection
Fabrics, Seams and Styles
• Types of Fabrics
– Impermeable film based fabrics
– Semi-Permeable (microporous) fabrics
– Absorptive fabrics
– Reactive Fabrics
• Types of Seams
– Serged
– Bound
– Ultrasonic Welded
– Heat Sealed/Taped
• Garment Styles
Selection
•
•
•
•
•
Impermeable film based barrier fabrics
Food Packaging
High O2 barrier
Flexible
Long life
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6/22/2016
Selection
Selection
• Coveralls
– Hood, booties
Sewn
- A seam
Heat
Bound
Ultrasonic
Sealed/Taped
Seam
Seam
- ASeam
clean-finished
- ASeam
sealed
- Aseam
very
binding
strong tight
produced
when
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which
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• Totally Encapsulated
– Front or Rear Entry
• Multi-piece ensembles
– Mix and match
Care & Use
Care & Use
• Limitations of Use
• As an employer, we have to:
– Perform a hazard assessment for PPE
– There are uses, environments and chemicals for
which these garments and/or fabrics are
unsuitable. It is the responsibility of the user to
review available data and verify that the garment
and/or fabric is appropriate for the intended use
and meets all specified government and/or
industry standards.
• Specific to chemical hazards
– Document the assessment
– Specify chemical protective clothing for appropriate
protection
– Train the employee in care and use of the chemical
protective clothing
Hazmatch®
• Case Studies
Semiconductor Facility
•
•
•
•
•
Chlorine Triflouride
Used to etch wafers for semiconductors
Reacts with just about everything
Leak in the facility
Isolated to one area in the plant
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6/22/2016
Carbon Fiber Plant
• Acrylonitrile
• Used in the production of fine carbon filament
line/wire for variety of applications
• Chemical brought in by railcar and truck transport
• Truck just offsite rolls over and chemical is
releasing
The Toxic Woman of Riverside County
• Gloria Ramerez – cancer patient admitted to ER
• Staff began experiencing symptoms and
unconsciousness
• Hazmat Team called to respond
• Dimethyl Sulfoxide
• Dimethyl Sulfate
• Methylamine
The Toolbox
Animal Feed Plant
• Propionic Acid CAS# 79-09-4
• Used as drying agent and preservative for the
feed used by reducing mold and bacteria
• Multi story facility
• Large scale release into basement area
• Response and remediation
QR Codes
kappler.com
YouTube Videos
Kappler Univ.
Roadshows
Product Specifications
MSDS’s
Hazmatch
NIOSH
Pocket Guide
App
Thank You for Coming!
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