FOREWORD
This manual is a reference guide for students enrolled in scheduled training courses of the U.S.
Environmental Protection Agency (EPA). While it will be useful to anyone who needs information
on the subjects covered, it will have its greatest value as an adjunct to classroom presentations
involving discussions among the students and the instructional staff.
This manual has been developed with a goal of providing the best available current information.
Individual instructors may provide additional material to cover special aspects of their presentations.
Because of the limited availability of the manual, it should not be cited in bibliographies or other
publications.
References to products and manufacturers are for illustration only; they do not imply endorsement
by EPA.
Constructive suggestions for the improvement in the content and format of the manual are welcome.
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HAZARDOUS MATERIALS INCIDENT RESPONSE OPERATIONS
(165.5)
This course is designed for personnel who are involved with the investigation and remediation of
uncontrolled hazardous waste sites. To a lesser extent, it is designed for personnel who respond to
accidents or releases of hazardous materials. It provides basic information needed to meet the
requirements of 29 CFR 1910.120, "Hazardous Waste Operations and Emergency Response."
After completing the course, participants will be able to:
• Identify methods and procedures for recognizing, evaluating, and controlling hazardous
substances.
• Identify concepts, principles, and guidelines to properly protect site and response personnel.
• Discuss regulations and action levels to ensure the health and safety of the workers.
• Discuss the fundamentals needed to develop organizational structure and standard operating
procedures.
• Demonstrate the selection and use of dermal and respiratory protective equipment.
• Demonstrate the use and calibration of direct-reading air monitoring instruments.
The course is designed so that personnel will be more knowledgeable in hazardous waste site
operations, team functions, personnel health and safety, and field monitoring equipment.
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Emergency and Remedial Response
Environmental Response Team
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CONTENTS
Section 1:
Day 1
Hazard Recognition
Air Monitoring Instruments I
Air Monitoring Instruments II
Section 2: Day 2
Toxicology
Respiratory Protection: Air-Purifying Respirators
Respiratory Protection: Supplied-Air Respirators
Levels of Protection and Chemical Protective Clothing
Section 3:
Day 3
Site Entry and Reconnaissance
Radiation Survey Instruments
Decontamination
Section 4:
Section 5:
Day 4
Supplementary
Reading
Response Organization
Hazard Recognition
Air Monitoring Instruments
Toxicology and Exposure Guidelines
Respiratory Protection
Chemical Protective Clothing
Site Entry and Reconnaissance
Decontamination
Radiation
Response Organization
Section 6: Appendix A
Appendix B
Appendix C
Appendix D
29 CFR 1910.120 - "Hazardous Waste
Operations and Emergency Response"
Warning Concentrations of Various Chemicals
Hazardous Materials Identification Systems
Glossary and Acronym List
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Section 1
-------
Hazard Recognition
HAZARDOUS INCIDENT RESPONSE
• Recognition
• Evaluation
• Control
Recognition
Identification of the substances involved,
the associated hazards, and the degree
of hazard.
NOTES
Day 1
Hazard Recognition/p.1
-------
NOTES
Day 1
p.2/Hazard Recognition
Evaluation
Assessing impact or risk that the substances
pose to public health, response personnel,
and the environment.
Control
Methods to eliminate or reduce the
impact of the hazard.
CHEMICAL HAZARDS
• Toxic
• Combustion
• Explosive
• Chemical Reactive
• Corrosive
-------
Toxic Hazards
Combustion Hazards
- fires
- explosions
Combustion Hazards
Practical Considerations
Most dangerous substances:
• low ignition temperature
• low LEL
• wide flammable range
Additional hazards:
• Shockwave, heat, flying objects
• initiation of secondary fires
• release of toxic & corrosive compounds
NOTES
Day 1
Hazard Recognition/p.3
-------
NOTES
Day 1
p.4/Hazard Recognition
Hazards Due to
Chemical Reactivity
Chemical Incompatibility
The combination of two or more reactive
materials resulting in uncontrollable,
undesirable conditions.
Some Results of Chemical Reactions
• heat generation
• fire
• explosion
• formation of toxic vapors
• volatilization of toxic or
flammable substances
• violent polymerization
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Oxidizers
Materials that contain large amounts of
chemically bound oxygen that is easily
released, especially when heated, and
that will stimulate the burning of
combustible material.
EXAMPLES OF OXIDIZERS
HALOGENS
Chlorine
Fluorine
PEROXIDES
Hydrogen Peroxide
Benzoyl Peroxide
OZONE
HYPOCHLORITES
Oxidation Hazards
Practical Considerations
• Destruction of metals and organics.
• Ignition of combustible materials.
• Organic peroxides may be
shock sensitive.
NOTES
Day 1
Hazard Recognition/ft.5
-------
NOTES
Day 1
p.6/Hazard Recognition
Corrosion Hazards
Corrosion
The electrochemical degradation of metals
or alloys due to reaction with their
environment, which is accelerated by
presence of acids or bases.
pH Scale
>0 ACID
< I I I I I
, BASE 14
| I I I I I I >
7.0
Neutral
-------
EXAMPLES OF CORROSIVES
ACIDS
Acetic Acid
Hydrochloric Acid
Sulfuric Acid
BASES (Caustics)
Sodium Hydroxide
Potassium Hydroxide
Ammonia
Corrosive Hazards
Practical Considerations
• What is the toxicity of the corrosive?
• What structural damage can occur?
• What other hazards can this lead to?
• Can the corrosive be monitored?
PHYSICAL PROPERTIES
• DENSITY
• VAPOR PRESSURE
• SOLUBILITY
NOTES
Day 1
Hazard Recognition/p.7
-------
NOTES
Day 1
p.8/Hazard Recognition
PHYSICAL HAZARDS
Drum/Container Handling
labels or placards?
sound or undamaged?
rusted or corroded?
bulging or leaking?
CONTAINER HANDLING PROCEDURES
Assume all containers are hazardous
Inspect all containers BEFORE moving them
Brief all personnel on potential hazards
Develop a spill prevention and containment
plan
SPILL CONTAINMENT & CONTROL
• Reduces the spread of contamination
• Minimizes cleanup efforts
• Reduces exposure to hazardous materials
-------
SPILL CONTAINMENT & CONTROL PLAN
• Define the hazards of materials on site
• Assess the potential for leaks
• Evaluate influencing physical factors
• Provide spill control equipment
• Implement a leak detection system
• Train staff
SPILL PREVENTION GOALS
Prevent operational errors
Minimize through training
and awareness.
Prevent equipment failures
Minimize by selecting proper
equipment and performing
proper maintenance.
OTHER PHYSICAL HAZARDS
Kinetic
Thermal
Electrical
Acoustic
Biological
Radiological
Heat Stress/Cold Exposure
NOTES
Day 1
Hazard Recognition/p.9
-------
NOTES
Day 1
p.10/Hazard Recognition
HEAT RELATED ILLNESSES & EMERGENCIES
• Heat Rash
• Heat Cramps
• Heat Exhaustion
• Heat Stroke
COLD EXPOSURE
• Frostbite
• Hypothermia
CONFINED SPACE HAZARDS
• Atmospheric
• Safety
-------
Confined Space
A space which by design has
limited openings for entry and exit;
unfavorable natural ventilation; and
which is not intended for continuous
employee occupancy.
CONFINED SPACE HAZARDS
Atmospheric Hazards:
• Oxygen deficient
• Toxic
• Flammable
• Irritant (corrosive)
CONFINED SPACE HAZARDS
Safety Hazards:
• Slip/trip/fall
• Mechanical/electrical
• Limited entry/exit
• Physiological stress
• Entrapment
NOTES
Day 1
Hazard Recognition/p.11
-------
NOTES
Day 1
p.12/Hazard Recognition
Reference Materials
and
Resources
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Air Monitoring Instruments
Part I
FIELD AIR MONITORING INSTRUMENTS
Collection of 'Real Time' data to aid
in decisions concerning:
• Hazards & Risks to Public & Personnel
• Personal Protective Equipment Selection
• Site Work Zones
• Effects on Environment
• Mitigative Actions
DESIRED CHARACTERISTICS
of Field Instruments
• Portable and Rugged
• Easy to Operate
• Inherently Safe
• Reliable and Useful Results
NOTES
Day 1
Air Monitoring l/p.1
-------
NOTES
Day 1
p.2/Air Monitoring I
RELIABLE & USEFUL RESULTS
• Response Time
• Sensitivity
• Selectivity
• Accuracy
• Precision
HAZARDOUS ATMOSPHERES
National Electrical Code
Definition of a Hazardous Atmosphere:
• Concentration between the Lower
Explosive Limit and Upper Explosive
Limit (LEL - UEL)
• Presence of an Ignition Source
• Exothermic Reaction
INHERENT SAFETY APPROVAL
Electrical devices, such as portable
air monitoring instruments, are to
be constructed in such a fashion
to eliminate the possibility of
igniting a combustible atmosphere.
-------
SAFETY STANDARDS
Inherent Safety
National Electrical Code (NEC) consensus
standard, presented by National Fire
Protection Association (NFPA) defining:
• Hazardous Locations
• Approval Criteria
HAZARDOUS LOCATIONS
Inherent Safety
3LASS
I Combustible Gases & Vapors
II Combustible Dusts
III Combustible Fibers, Flyings
3ROUP
A,B,C,D Gases & Vapors found in
Class I Atmosphere
E.F.G Dusts found in Class II Atmosphere
DIVISION
HAZARDOUS LOCATIONS
Inherent Safety
1 Location in which hazardous
concentrations exist continuously,
intermittently, or periodically
under NORMAL operating conditions
2 Location in which hazardous
concentrations do NOT normally
exist under normal operating
conditions
NOTES
Day 1
Air Monitoring l/p.3
-------
NOTES
Day 1
p.4/Air Monitoring I
INSTRUMENT PROTECTION CRITERIA
• Class I, Division 1, Groups A.B.C, & D
"Instrinsically Safe'
"Explosion-Proof
'Purged System'
• Class I, Division 2, Groups A,B,C, & D
"Non-lncendive"
• Class II, Division 1 & 2, Groups E,F, & G
'Dust-Ignition Proof
DEFINITIONS
INTRINSICALLY SAFE
Designed so that parts are not exposed to
explosive atmosphere or, if so, there is
insufficient energy for ignition.
EXPLOSION PROOF
Designed to contain an explosion and cool
gases to prevent spread.
PURGED SYSTEM
Inert gas filled system; positive pressure
to prevent explosive gases or vapors from
entering.
OXYGEN INDICATORS
Oxygen in the Atmosphere
To Determine:
• Types of Respirator Protection
• Combustion Risk
• Use of Other Instruments
• Presence of Contaminants
-------
OXYGEN INDICATORS
• Exterior Sensor
• Interior Sensor
- manual pump
- automatic pump
• Combination Units
OXYGEN INDICATORS
Theory of Operation
• Oxygen diffusion into detector cell
• Chemical reaction establishes current
proportional to oxygen concentration
O2O2O2 O2 O2
Ihermlator I I I I I
.Protective Disk
T~l 1 1 I I
.Telfon Mem.
- Au Electrode
-KOH
- Pb Electrode
OXYGEN INDICATORS
Limitations/Precautions
Atmospheric Pressure (Altitude)
Interfering Gases
Operating Temperature
NOTES
Day 1
Air Monitoring l/p.S
-------
NOTES
Day 1
p.6/Air Monitoring I
OXYGEN INDICATORS
Interpretation of Data
• Instantaneous Response
• Specific, Quantitative Results
0-25% Oxygen
0-100% Oxygen
• Calibrate to Ambient Oxygen (20.8%)
ALTITUDE/OXYGEN METER READING
17.3*
5000 FT
20.8%
SEA LEVEL
ALTITUDE/OXYGEN INDICATION
Altitude
-1000 feet
Sea Level
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
Oxygen Indication
21.6%
20.8
20.1
19.3
18.6
18.0
17.3
16.7
16.1
15.4
14.9
14.3
-------
COMBUSTIBLE GAS INDICATORS
(CGIs)
To Determine:
• Risk of Fire/Explosion
• Indication of Contaminants
COMBUSTIBLE GAS INDICATORS
• Manual vs. Automatic Pumps
• "Super-Sensitive" Unit
• Combination Units (CGI-Oxygen)
COMBUSTIBLE GAS INDICATOR
Theory of Operation
n the presence of a combustible gas. a heated
:atalytic filament (or bead) burns the gas, increasing
he filament's temperature. An electrical resistance
s created causing an imbalance in a Wheatstone
fridge circuit.
Battery —
I
Display,
Qas Sample
Compensating Filament
WHEATSTONE BRIDGE CIRCUIT
NOTES
Day 1
Air Monitoring l/p.7
-------
NOTES
Day 1
p.8/Air Monitoring I
CONCENTRATION
0
LEL
6%
-H
UEL
15%
(Methane)
0 100%
METER READING
UEL
COMBUSTIBLE GAS INDICATORS
Limitations/Precautions
• Temperature
• Oxygen Requirements
• Interfering Gases
Lead
Sulfur
Silicone
Hydrogen Chloride
Hydrogen Fluoride
• Relative Response
100
BO
BO
70
BO
BO
40
30
20
10
COMBUSTIBLE GAS INDICATORS
Relative Response Curve
Acetylene (2.5%)
Pentane
Methane (6.0%)
Ethyl Chloride
(38%)
1,4-Dloxane
(2.0%)
Xylene (1.1%)
0 10 20 30 40 60 60 70 BO BO 100
Percent LEL (MSA 260)
-------
COMBUSTIBLE GAS INDICATORS
Relative Response
Chemical LEL Concentration *LEL Meter Response %LEL
Methane (5.0%)
Acetylene (2.6%)
Pentane (1.6%)
Ethyl
Chloride (3.8%)
1.4 Dloxane (2.0%)
Xylene (1.1%)
80
60
60
60
60
60
86
60
63
37
37
27
TOXIC ATMOSPHERE MONITORS
To Determine:
• Health Risks to Workers /Public
• Personal Protective Equipment
• Work Zones/Safety Plans
TOXIC ATMOSPHERE MONITORS
Types
• Detector Tube System
• Monitors for Specific Agents
(i.e. CO, Hydrogen Sulfide)
• Total Vapor Analyzers
^ ~u u
• Gas Chromatograph
. FID)
NOTES
Day 1
Air Monitoring l/p.9
-------
NOTES
Day 1
p.W/Air Monitoring I
DETECTOR TUBE SYSTEMS
Components
• Pump
piston
bellows
• Tubes
specific chemicals
general chemicals
concentration ranges
DETECTOR TUBE SYSTEM
Theory of Operation
Glass Tube w/ Indicating Chemical
Specific Volume of Air
Color Change
Stain Length - Concentration
DETECTOR TUBE SYSTEMS
Limitations/Precautions
• Accuracy
• Temperature/Humidity/Pressure
• Expiration Date
• Chemical Group/Specific
• Lot #
• Color Change/Endpoint
• Pump Strokes/Volume/Time
• Interferences
• Reusable
-------
DETECTOR TUBE SYSTEM
Plug
Glass Tube
i i r
0 10 20 30
Pre-filter
Plug
Indicating Chemical
NOTES
Day 1
Air Monitoring l/p.11
-------
Air Monitoring Instruments
Part II
PHOTOIONIZATION
\YA
AMPLIFIER
XI '
xl
METER uv
. I . LAMP
O '/
SAMPLE OUT iV ~"
Jn n h.
ELECTRODE " ELECTRODE
SAMPLE IN
NOTES
Day 1
Air Monitoring ll/p.1
-------
NOTES
Day 1
p.2/Air Monitoring II
PHOTOIONIZATION
R + hu
R • chemical absorbing UV
h(nu) • photon with energy i
lonization Potential (IP)
of chemical
lonization Potentials
CHEMICAL IP(eV)
Carbon Monoxide 14.0
HCN 13.9
Methane 13.0
Water 12.6
HCI 12.7
Oxygen 12.1
Chlorine 11.5
Propane 11.1
Hydrogen Sulfide 10.5
Hexane 10.2
Ammonia 10.1
Acetone 9.7
Trichloroethylene 9.45
Benzene 9.2
Triethyl Amine 7.5
Examples of Lamp Energies
and Detectable Chemicals
IP
Helocarbona
Melhanol
Other tingle C compound!
11.7
102
Vinyl Chloride
MEK
MIBK
TCE
Other 2-4 C compound!
9.5
Aromatic*
Large moleculei
Lamp
-------
SELECTIVE DETERMINATION OF
COMPOUND
Carbon dioxide
Propane
Vinyl chloride
Acetone
VINYL CHLORIDE
IE
13.8
11.1
10.0
9.7
PHQTOIONIZATION
Considerations
• Lamp Energy/Chemical IP
• Dust/Humidity
• High Methane
• Electromagnetic Radiation
• Lamp Aging
• Relative Response
• High Concentrations
RELATIVE RESPONSES FOR HNU
PI-101 WITH
CHEMICAL
m-Xylene
Benzene
Phenol
Isobutylene
Acetone
Hexane
Ammonia
10.2 eV PROBE
_BB
1.12
1.00
0.78
0.56
0.63
0.22
0.03
_!E
8.56
9.25
8.69
9.25
9.69
10.18
10.15
NOTES
Day 1
Air Monitoring ll/p.3
-------
NOTES
Day 1
p.4/Air Monitoring II
800-
— 400-
|
- soo-
Benzene
(gain • 9.8)
100 300 600 700
ppm (by volume)
ooo
Uttir
Readout
Battery
-
Lamp PoMr
Supply
Ion ChimbM
Bl»
/
\
Ion Ckambir
1.
f rti
' pump i — ,n
Prtimp 1 «LJ
< LJ
PROBE
FLAME IONIZATION
DETECTOR
H,
SAMPLE
(AIR)
-------
FLAME IONIZATIQN
Considerations
• Detects only organics
• Sensitive to methane
• Relative Response
• Hydrogen gas needed
• Electromagnetic radiation
NOTES
Day 1
Air Monitoring ll/p.5
-------
Section 2
-------
NOTES
Toxicology and
Exposure Guidelines
Which chemical
poses the greatest risk?
• Chlorine
• Ammonia
• Toluene
• Benzene
• Methyl Alcohol
• Hydrogen Cyanide
• Lead
• Mercury
• Asbestos
• Polychlorinated Biphenyls
RISK ASSESSMENT
FOR CHEMICALS
WHAT IS THE TOXICITY OF THE COMPOUND?
WHAT IS THE PROBABILITY OF EXPOSURE?
Day 2
Toxicology/p.1
-------
NOTES
Day 2
p.2/Toxicology
What is the toxicity of the compound?
m Dose-Response Relationship
• Adverse Effects
TOXICITY
The ability of a substance to produce
injury once it reaches a susceptible
site in or on the body.
TOXICOLOGY
CLASSIC DEFINITION:
"Science of Poisons"
MODERN CONCEPT:
•Limits of Safety*
-------
NOTES
"All things are poisons, for there is
nothing without poisonous qualities.
It is only the dose which makes a
thing poison."
Paracelsus
(1493 - 1541)
TYPES OF TOXICITY INFORMATION
• Epidemiologic Data
• Animal Bioassays
• Short-Term Studies
• Comparisons to Molecular Structure
DOSE-RESPONSE CURVE
100-
%
A
C
D
DOSE
Day 2
Day 2
Toxicology/p.3
-------
NOTES
Day 2
p.4/Toxicology
EXAMPLES OF DOSE-RESPONSE INDICES
ENDPOINT - L _ : Lethality
T _ : Toxlclty
E _ : Effectiveness
ROUTE - — D : Dose based on all routes
except inhalation
_ C : Concentration based
upon inhalation only
RESPONSE - Percentage of experimental population
Lo - Lowest dose at which effect
was observed
LETHAL DOSE FIFTY
(LD50)
The dose of a substance which is
expected to cause the death of
50% of a defined experimental
animal population.
Relationship of LD50 to Dose-Response
100—
Rnpentf
60—
LD60
DOSE (MG/KQ)
-------
LIMITATIONS OF
DOSE-RESPONSE DATA
NOTES
SPECIES VARIATION
BASED ON SINGLE DOSE
STATISTICAL VALUE
pose-l
Response Curves for Two Substances
100—
InpOflM
60—
20—
DOSE (MG/KG)
ADVERSE EFFECTS
• LOCAL EFFECTS
• SYSTEMIC EFFECTS
• ASPHYXIATION
- simple
- chemical
• SENSITIZATION
• TERATOGENIC
• MUTAGENIC
• CARCINOGENIC
Day 2
Toxicology/p.5
-------
NOTES
Day 2
p.6/Toxicology
What is the probability of exposure?
m Route of exposure
• Duration and frequency of exposure
• Personal characteristics
• Chemical interactions
ROUTES OF EXPOSURE
• INHALATION
. ABSORPTION
Skin
Eyes
• INJECTION
• INGESTION
PERSONAL
CHARACTERISTICS
• gender
• genetic factors
• health status
• age
-------
Types of Chemical Interactions
EXAMPLES
ADDITION (2*2 - 4)
SYNERGISM (2 + 2-6)
POTENTIATION (0 + 2 - 4)
ANTAGONISM (2*2-2)
EXPOSURE GUIDELINES
OSHA
Permissible Exposure Limits (PEL)
Enforced standards
NIOSH
Recommended Exposure Limits (REL)
Research agency, recommendations for OSHA
ACGIH
Threshold Limit Values (TLV)
Recommended workplace exposure levels
EXPOSURE LIMITS
(29 CFR PART 1910.120)
• Permissible Exposure Limits
29 CFR Part 1910.1000. Subparts G & Z
(OSHA)
• 'Published Exposure Levels*
'NIOSH Recommendations for
Occupational Health Standards,' 1986
ACGIH's TLVs and BEIs for 1987-1988
NOTES
Day 2
Toxicology/p.7
-------
NOTES
?ay 2
j.8/Toxicology
EXPOSURE LIMITS
are used to determine:
m Site Characterization
• Medical Surveillance
• Exposure Controls
- engineered controls
- work practices
- PPE selection
29 CFR 1910.120
TIME WEIGHTED AVERAGE (TWA)
• Averages the concentrations of exposure
• Based on duration of exposure
EXAMPLE: ACETONE TLV-TWA 750 ppm (ACQIH)
1000 ppm for 3 hours
500 ppm for 2 hours
200 ppm for 3 hours
For an 8 hour TWA:
- (3 hraHIOOO) * (2 hrsXSOQ) • (3 hraKZOO)
8
575 ppm
TIME WEIGHTED AVERAGE
(TWA)
c
o
N
C
E
N
T
R
A
T
I
O
N
750
TWA-EL
6AM
10 AM
TIME
3PM
-------
SHORT TERM EXPOSURE LIMIT (STEL)
The concentration to which workers can be
exposed continuously for a short period of
time without suffering from:
• Irritation
• Chronic or Irreversible tissue damage
• Narcosis
NOTES
SHORT TERM EXPOSURE LIMIT
(STEL)
c
o
N
C
E
N
T
R
A
T
I
O
N
1000
750
6 AM
10AM
TIME
3PM
C
0
N
C
E
N
T
R
A
T
I
O
N
CEILING
(C)
Celling
6AM
10AM
TIME
3PM
Day 2
. Toxicology/p. 9
-------
NOTES
THRESHOLD LIMIT VALUES
are not intended for use:
• as a relative index of toxicity
• in the evaluation or control of community
air pollution nuisances
• in estimating the toxic potential of continuous,
uninterrupted exposures or other extended
work periods
• as proof or disproof of an existing
disease or physical condition
• for adoption by countries whose working
conditions differ from those in the U.S.
ACGIH TLVs and BEIs (current version)
Day 2
p. 10/Toxicology
-------
Respiratory Protection:
Air-Purifying Respirators
REQUIREMENTS FOR A MINIMAL
ACCEPTABLE PROGRAM
OSHA 29 CFR 1910.134(B)
1. WRITTEN STANDARD OPERATING
PROCEDURES
2. SELECTION BASED ON HAZARD
3. TRAINING
4. CLEAN AND DISINFECT
5. STORAGE
6. INSPECTION
7. MONITORING
8. PROGRAM EVALUATION
9. PHYSICALLY FIT
10. APPROVED OR ACCEPTED RESPIRATORS
APPROVED RESPIRATORS
MSHA: Establish Testing Criteria
NIOSH: Conduct Approval Testing
NOTES
Day 2
Air-Purifying Respirators/p. 1
-------
NOTES
Day 2
p.2/Air-Purifying Respirators
PHYSIOLOGICAL AND PSYCHOLOGICAL
LIMITATIONS FOR RESPIRATOR WEARERS
Respiratory Impairment
Anemia
Epilepsy
Punctured Eardrum
Facial Hair
Cardiovascular Impairment
Diabetes
Claustrophobia
Comfort
Vision
Adapted from ANSI Z88.2-1980. APPENDIX A4
OXYGEN REQUIREMENTS
• ACGIH TLVS
• ANSI STANDARDS •
• OSHA REGULATIONS
• USEPA GUIDES
18%
19.5%
16-19.5%
19.5%
Z88.2 (198*0)
IMMEDIATELY DANGEROUS TO LIFE OR HEALTH
(IDLH)
A concentration that represents the maximum
concentration from which, in the event of
respirator failure, one could escape within
30 minutes without a respirator and without
experiencing any escape-impairing or
irreversible health effects.
Reference: NIOSH Pocket Guide to Chemical Hazards
-------
AIRBORNE CONTAMINANTS
• Gases
• Vapors
• Aerosols
dust
fumes
mist
NIOSH APPROVED
PARTICULATE FILTERS
• DUST
• MIST
• FUME
• HEPA
• RADON DAUGHTERS
• ASBESTOS
• SINGLE-USE
• ABRASIVE BLASTING
PARTICULATE CLASSIFICATION
Dust & Mist
80 - 90% efficiency 0.6/x
Fume
90 - 99% efficiency 0.6^i
HEPA
99.97% efficiency 0.3^t
Exposure limit < 0.05 mg/m3
NOTES
Day 2
Air-Purifying Respirators/p.3
-------
NOTES
Day 2
p.4/Air-Purifying Respirators
Vapor & Gas Removing Respirators
• Organic vapors
• Acid gases
• Ammonia
• Combinations (gases, vapors & participates)
• Specific conditions/approvals required
- carbon monoxide
- hydrogen sulfide
- hydrogen cyanide
- vinyl chloride
- formaldehyde
WARNING PROPERTIES
Adequate warning properties can be assumed
when the substance's odor, taste, or irritation
effects are detectable and persistent at
concentrations 'at or below* the Permissible
Exposure Limit.
SOURCE: NIOSH/OSHA RESPIRATOR DECISION LOGIC
SOLVENTS
1% Breakthrough Time
(Minutes)
• BENZENE 73
• CHLOROFORM 33
• ETHANOL 28
• METHANOL 0.2
• METHYL CHLORIDE 0.05
• VINYL CHLORIDE 3.8
• CARBON TETRACHLORIDE 77
-------
WARNING PROPERTIES
iHEMICAL
kCETONE
1UTYLAMINE
5ARBON MONOXIDE
MRBON TETRACHLORIDE
IYDROQEN SULFIDE
SULFUR DIOXIDE
IUTVL MERCAPTAN
WARNING
CONCENTRATION
0 1 - 699
01-6
ODORLESS
2 - 700
0.00001 - 14 (fatigue)
0.3 -6 (taste)
00008-0038
EL
760
C-6
36
C-2
C-10
2
C-0.6
PROTECTION
RESPIRATOR TYPE
AIR-PURIFYING
QUARTER MASK
HALF MASK
FULL MASK
SUPPLIED- AIR
Demand
HALF MASK
FULL MASK
Pressure -Demand
FULL MASK SCBA
FACTORS
NIOSH
6
10
60
10
60
10.000
MUC = PF X EL
? = 10 X 10 ppm
500 = ? X 5 ppm
NOTES
Day 2
Day 2
Air-Purifying Respirators/p.S
-------
NOTES
Day 2
p.6/Air-Purifying Respirators
RESPIRATOR SELECTION
SUBSTANCE
IDENTIFIED
1
OPEN |-
IOXYQEN CONTENT | *\ INSUFFICIENTJ-
{
KNOWN
CONCENTRATIC
k |> mi
IN ' Lll:!.
RESPIRATOR PROTECTION 1 ^
FACTOR |
1
< 50 x EL |-
H|
HI
> 50
xEL
»
— » ISCBA |
— HSCBA 1
» ISCBA
FULL-FACE
APR
RESPIRATOR SELECTION
• Nature of Hazard
• Characteristics of Operation & Worker
Activity
• Location Of Hazardous Area
• Duration Of Respirator Use
• Respirator Capabilities And Limitations
ANSI Z88.2-1980
-------
Respiratory Protection:
Supplied-Air Respirators
SUPPLIED-AIR RESPIRATORS
Benefits:
• Provide breathing air
• No filter/sorbent limitations
• Better protection factors
SUPPLIED AIR RESPIRATORS
Modes of Operation
> NEGATIVE PRESSURE
- pressure inside facepiece can become negative
- leakage in
- 'demand*
> POSITIVE PRESSURE
- pressure inside facepiece stays positive
- leakage out
- 'pressure-demand'
NOTES
Day 2
Supplied-Air Respirators/p.1
-------
NOTES
Day 2
Day 2
p.2/Supplied-Air Respirators
COMPARISON OF
RESPIRATOR PROTECTION FACTORS
TYPE OF RESPIRATOR
Negative Pressure
Full facepiece APR
Full facepiece SAR
Positive Pressure
Full facepiece air-line
(without SCBA)
Full facepiece SCBA
ASSIGNED PROTECTION
FACTORIfAPFl
50
50
2000
10000
SUPPLIED-AIR RESPIRATORS
Types
• Hose Mask
• Airline
• Self-Contained Breathing Apparatus
(SCBA)
• Combination Airline/SCBA
• Escape SCBA
TYPES OF SCBAs
CLOSED CIRCUIT
OPEN CIRCUIT
-------
BREATHING AIR SPECIFICATIONS
(Compressed Gas Association)
Characteristics GRADE D
% Oxygen
Water
Hydrocarbons
Carbon Monoxide
Odor
Carbon Dioxide
atm/19.5-23.5
varies
5 mg/m3
20 ppm
none
1000 ppm
GRADE E
atm/19.5-23.5
varies
5 mg/m3
10 ppm
none
500 ppm
NOTES
Day 2
Supplied-Air Respirators/p.3
-------
Levels of Protection
and
Chemical Protective Clothing
SELECTING LEVELS OF PROTECTION
• Known vs. Unknown
• Chemical hazard recognition
• Actual concentrations vs.
exposure guidelines
• Work function
• Work location
• Weather conditions
LEVEL D
Should not be worn on any site with respiratory
or skin hazards. Level D is primarily a work
uniform providing minimal protection.
NOTES
Day 2
Levels of Protection/p.1
-------
NOTES
Day 2
p.2/Levels of Protection
Level D protection is used when:
• Atmosphere contains no known hazard
• Work function precludes the potential
for unexpected exposure to hazardous
levels of any substances
Level D Equipment
• Coveralls
• Gloves •
• Safety Boots/Shoes
(leather or chemical resistant)
• Disposable Boot Covers •
• Safety Glasses or Chemical
Splash Goggles •
• Hard Hat (face shield*)
• Escape Mask •
• OPTIONAL
LEVEL C
Should be selected when the types of airborne
contaminants are known, the concentrations are
measured, and the criteria for using air-purifying
respirators are met.
-------
Level C protection is used when:
• Criteria for the use of APRs are met
• Air contaminants have been identified
and concentrations measured
• Direct contact does not pose a
severe skin hazard
Level C Equipment
• Air-Purifying Respirator
(full-face, canister)
• Hooded Chemical Resistant Clothing
• Inner Clothing
• Chemical Resistant Gloves
(inner and outer)
• Chemical Resistant Safety Boots
• Disposable Boot Covers •
• Hard Hat (face shield-)
• Escape Mask •
• 2-Way Radio (inherently safe)
LEVEL B
Should be selected when the highest level of
respiratory protection is needed and some
degree of skin protection is required.
Level B is the minimum recommendation for
initial site entry.
NOTES
Day 2
Levels of Protection/p.3
-------
NOTES
Day 2
p.4/Levels of Protection
Level B protection is used when:
• Air contaminants are unknown
• Air .contaminants have been identified and
the criteria for using APRs are not met
• IDLH air concentrations exist
• The atmosphere contains less than
19.5% oxygen
• Direct contact does not pose a severe
skin hazard
Level B Equipment
• Supplied-Air Respirator
Pressure-Demand
• Hooded Chemical Resistant Clothing
• Inner Clothing
• Chemical Resistant Gloves
(inner and outer)
• Chemical Resistant Safety Boots
• Disposable Boot Covers •
• Hard Hat (face shield*)
• 2-Way Radio (inherently safe)
LEVEL A
Should be worn when the highest level of
respiratory, skin, and eye protection
is required.
-------
Level A protection is used when:
Conditions are unknown
The hazardous substance has been identified
and It requires the highest level of protection
for skin, eyes, and respiratory system
Operations are being conducted in confined,
poorly ventilated areas
Work function involves a high potential
for splash, immersion, or exposure to
unexpected skin hazards
Level A Equipment
• Supplled-AIr Respirator
Pressure-Demand
• Fully Encapsulating
Chemical Resistant Suit
• Inner Clothing
• Chemical Resistant Gloves
(inner and outer)
• Chemical Resistant Safety Boots
• Outer Clothing (disposable protective
suit, gloves, and boot covers) •
• Hard Hat • (under suit)
• Cooling Unit •
• 2-Way Radio (Inherently safe)
Le
Level A
Level B
Level C
Level D
vels of Prote
Chemical
Protective
Clothing
FES
Splash
Suit
None
ction
Pespiretory
Protection
SAR
APR
None
NOTES
Day 2
Levels of Protection/p.S
-------
NOTES
Day 2
p.6/Levels of Protection
PERFORMANCE QUALITIES
Chemical Resistance
Durability
Flexibility
Temperature Resistance
Aging Resistance
Cleanability
Design (color)
Comfort (size)
CHEMICAL RESISTANCE
• Penetration
• Degradation
• Permeation
PENETRATION (a physical process)
The flow of a chemical through closures,
porous materials, seams, and pinholes
or other imperfections in a protective
clothing material on a nonmolecular level.
ASTM F739
-------
DEGRADATION (a chemical process)
A deleterious change in one or more
physical properties of a protective
clothing material due to contact
with a chemical.
ASTM F739
PERMEATION (a chemical process)
The process by which a chemical
moves through a protective clothing
material on a molecular level.
ASTM F739
PERMEATION involves:
1. Sorption of molecules of the chemical
into the contacted (outside) surface
of a material,
2. Diffusion of the sorbed molecules in
the material; and
3. Desorption of the molecules from the
opposite (inside) surface of the
material into the collecting medium.
ASTM F739
NOTES
Levels of Protection/p
ay 2
/P.7
-------
NOTES
Day 2
p.8/Levels of Protection
MEASURED PARAMETERS
BREAKTHROUGH TIME
PERMEATION RATE (STEADY-STATE)
PERMEATION/DEGRADATION RESISTANCE GUIDE
NITRILENBR NEOPRENE • PVC
Aoiuni
"issr
Hydralluoilo
Acid 146%)
»"—
1.1.1-
TilcblorMlfeaiii
oa
NR
E
E
F
F
PBT
-
HO
Zhr.
lOmln
16 hr
pa
-
-
-
F
f
OR
a
E
E
NR
NR
PBT
6mln
• 6 hi
1hr
-
-
PR
F
-
-
-
•
OR
NR
E
a
NR
NR
?" VCSSSISSTi.*?1*'1""11*" Tm" Na • ioi'a»eo"iMi«n
PBT
-
4hr
lOmin.
-
-
i/r/iif 0
d
pa
•
-
•
•
-
"' ""
BLENDS and LAYERS
NEOPRENE and LATEX RUBBER (Gloves)
VITON^NEOPRENE (FES - MSA Vautex. Draeger)
VITON^BUTYL (FES - Trellborg)
PVC/NITRILE (Boots)
PVC/PARACRIL (Splash Suit)
-------
PROTECTIVE CLOIHIKIU
REFERENCES
• Manufacturers' data
• Published studies
• Guidelines tor the Selection of
Chemical Protective Clothing
(Arthur D. Little. Inc.)
• Personal Protective Equipment for
Hazardous Material Incidents:
A Selection Guide (NI03H)
• Quick Selection Guide to
Chemical Protective Clothing
(K. Forsberg/S.Z. Mansdorf)
• Computer Systems
• Field Test Kit
PERSONAL PROTECTIVE EQUIPMENT
OSHA REGULATION
29 CFR 1910.133
EYE AND FACE PROTECTION
29 CFR 1910.134
RESPIRATORY PROTECTION
29 CFR 1910.135
HEAD PROTECTION
29 CFR 1910.136
FOOT PROTECTION
SOURCE
41 CFR 60-204.7
ANSI Z87.M968
(REV. 1989)
ANSI Z88.2-1969
(REV. 1980)
ANSI Z89.V1969
(REV. 1986)
ANSI Z41H967
(REV. 1983)
NOTES
Day 2
Levels of Protection/p.9
-------
Section 3
-------
Site Entry
and Reconnaissance
SITE SAFETY PLAN REQUIREMENTS
As a Minimum, the Plan MUST-
• Name Key Personnel, Alternates. Health
and Safety Personnel
• Task/Operation Safety & Health Risk Analysis
• Employee Training
• Personal Protective Equipment
• Air Monitoring Program
• Sampling Techniques
• Personnel Medical Monitoring
SITE SAFETY PLAN REQUIREMENTS
(Con't)
• Site Control Measures
• Decontamination Procedures
• Emergency Planning/Medical Facilities
• Confined Space Procedures
• Medical Surveillance Program
• Weather-Related Problems
• Buddy System
• Communications (Visual/Verbal)
• Spill Containment
NOTES
Day 3
Site Entry/p.1
-------
NOTES
THREE
• Support Zone (Cold)
- Command Post
- No Contamination
- Normal Work Clothes
• Contamination Reduction Zone (Warm)
- Decon Line
- Buffer
- PPE Required
• Exclusion Zone (Hot)
- Hot Line
- Contamination
- PPE Required
HOT LINE
ACCESS CONTROL
h— POINTS
PERSONNEL
DECONTAMINATION
CORRIDOR
CONTROL
LINE
EXCLUSION ZONE / CONTAMINATION
REDUCTION ZONE
SUPPORT ZO
DIAGRAM OF SITE WORK ZONES
SITE CONTROL
• Security/Physical Barriers
• Minimize Personnel/Equipment
• Work Zones
• Access Control Points
• Control Airborne Dispersion
• Decontamination Procedures
Day 3
p.2/Site Entry
-------
Interviews/Records Research
Habitation
Site Location and Size
Response Activities/Emergency
Duration of Employee Activity
Site Topography
Geologic and Hydrologic Data
Accessibility by Air/Road
Hazardous Substances Involved
Pathways of Dispersion
Previous Surveying/Sampling
NOTES
PERIMETER RECONNAISSANCE
• Site Maps
• Historical/Current Photographs
• Container/Vehicle Markings
• Condition of Containers/Vehicles
• Biologic Indicators
• Unusual Conditions
• Unusual Odors
• Air Monitoring at Site Perimeter
• Off Site Samples
On-Site Survey
PRIMARY ENTRY OBJECTIVE
Monitor air for IDLH atmospheres
- combustibles or explosives
- oxygen deficiency
- radiation
- toxic substances
Day 3
Site Entry/p. 3
-------
NOTES
EPA ACTION GUIDELINE
Combustible Gas Indicators
METER READING
< 10% LEL
10-25%
> 25%
ACTION
Continue investigation
with caution.
Continue on-site monitoring
with extreme caution as
higher levels are encountered,
Explosion hazard! Withdraw
from area immediately.
EPA ACTION GUIDELINE
Oxygen Indicators
METER READING
< 19.5%
19.5-25%
> 25%
ACTION
Monitor wearing SCBA.
Note: CGI readings may
not be valid.
Continue investigation with
caution. SCBA not needed
based only on oxygen content.
Discontinue investigation;
fire hazard potential.
EPA ACTION GUIDELINE
Radiation Survey
METER READING ACTION
< 1 mR/hr
>. 1 mR/hr
If levels are above backgrounc
continue investigation with
caution. Perform thorough
monitoring. Consult health
physicist.
Potential radiation hazard.
Evacuate site. Continue
monitoring only upon advice
of a health physicist.
Day 3
p.4/Site Entry
-------
EPA ACTION GUIDELINE
Total Gas/Vapor Meters
NOTES
METER READINGS
Unknowns
Background
0-5
5-500
500 -/OOO
Knowns
ACTION
Level D
Level C
Level B
Level A
Consider explosive
Compare to Exposure Guide
IDLH/PEL/REL/TLV
On-Site Survey
PRIMARY ENTRY OBJECTIVE
Visually observe for signs of IDLH
conditions
- confined spaces
- visible vapor clouds
- biological indicators
On-Site Survey
ENTRY OBJECTIVE
Note types of containers
- paper or wood packages
- metal or plastic barrels/drums
- underground tanks
- above ground tanks
- compressed gas cylinders
- pits, ponds or lagoons
Day 3
Site Entry/p.S
-------
NOTES
On-Site Survey
ENTRY OBJECTIVE
• Note condition of containers
and storage systems
- sound (undamaged)
- rusted or corroded
- leaking
- bulging
- types & quantities of material
- labels
On-Site Survey
ENTRY OBJECTIVE
Note physical condition of materials
- solid, liquid, or gas
- color & turbidity
- behavior (corroding, foaming,
or vaporizing)
- conditions conducive to splash
or contact
On-Site Survey
ENTRY OBJECTIVE
Note indicators of potential exposure
- biological indicators
- dust or spray in the air
- pools of liquid
- foams or oils on liquid surfaces
- possible landfilled areas
Day 3
p.6/Site Entry
-------
Radiation Survey Instruments
RADIOACTIVITY
The tendency of unstable atoms to
undergo radioactive decay.
Radioactive atoms are called
radionuclides.
Radioactive Decay
NOTES
Day 3
Radiation/p. 1
-------
NOTES
Day 3
p.2/Radiation
Radiation
Characteristics of the Three Major Types
Sourct
ALPHA
BETA
QAMMA
Symbol
a
0
7
Form
Parllcl*
Pamela
Elaclro-
Magnallc
Energy
JM«flM
Mm
(Ch»ra*l
<•»>
000066
(•/-I)
0
(0)
*ot
loalzttloni
/em In Air
100,00 O't
»0'«
1
Pmlh
Ltrtgth
In Air
• 1 1nch
1 malar
Bavaral
matara
10
kllomatara
Hiztra
Laotian
ot Sourct
Inlarnal
Internal/
Exlirnal
Intarnal/
Extarnal
Definitions
Roentgen - The unit of measure for X or
gamma radiation in air.
Rad - The unit of measure for radiation
energy transferred to an absorbing tissue.
Quality Factor - The factor by which
absorbed doses are multiplied to obtain
a quantity that expresses the risk
associated with the dose.
Rem - The unit of measure which represents
the risk associated with the radiation exposure.
Rad X OF
Rem
Gamma 1 Rad X 1 • 1 Rem
Beta 1 Rad X (1 to 2.6) • 1 to 2.6 Rem
Alpha 1 Rad X 20 - 20 Rem
-------
Subunits
1000 mRem • 1 Rem
1000 \L Rem • 1 mRem
Acute Exposure Risk
700 Rem - LD100
600 Rem - LD99
450 Rem - LD50
200 Rem = LDLo
100 Rem • TDLO
25 Rem - EDLO
Chronic Exposure Risk
A normal U.S. citizen has a 25% risk
of cancer. 1 Rem increases risk to 25.03%
100 Rem increases risk to 28%.
NOTES
Day 3
Radiation/p.3
-------
NOTES
Background Radiation
• is unavoidable
• comes from cosmic sources and
earth materials
• averages .01 - .02 mR/hr gamma
in the USA
US EPA Action Level:
1 mR/hr gamma above background
Maintain exposure ALARA
(As Low As Reasonably Achievable)
Day 3
p.4/Radiation
-------
Exposure Reduction Mechanisms
Time
Distance
Shielding
NOTES
Purpose of Radiation Monitoring
• Determine risk of exposure
• Determine types of radiation
Interpretation of Instrument Data
mR/hr (beta/gamma) -
used to make exposure estimates
cpm (alpha or beta) -
used to determine activity of the source
Day 3
Radiation/p.5
-------
NOTES
Limitations and Considerations
Annual calibration (minimum)
Instruments are calibrated for one
type of radiation
Day 3
p.6/Radiation
-------
Decontamination
DECONTAMINATION
The process of removing potentially harmful
contaminants from exposed individuals and
equipment in order to:
• reduce the spread of contamination
from the work area, and
• prevent inadvertent and unnecessary
contact with contaminated materials
EXCLUSION ZONE
CONTAMINATION
REDUCTION ZONE
jUlEXIT POINT
(""^ENTRANCE
*** POINT
CONTROL LINE
DREMOUT .
SUPPORT ZONE
. : REDRESS
NOTES
Day 3
Decontamination/p. 1
-------
NOTES
Day 3
p.2/Decontamination
FACTORS THAT DETERMINE
EXTENT OF DECONTAMINATION
Type of Contaminants
Amount of Contaminants
Level of Protection
Work Function
Location of Contaminants
Reason for Leaving Site
DECONTAMINATION PLAN
SHOULD PROVIDE FOR:
• proper level of decontamination
• suitable location
• decontamination worker protection
• appropriate decon methods
• program evaluation
• disposal of decontamination materials
• emergency decontamination procedures
-------
DECONTAMINATION PROCEDURES
• assume personnel grossly contaminated
• determine level of protection and specific
equipment to be worn
• remove protective clothing starting with
the most heavily contaminated, ending with
the least contaminated
• wash and rinse each piece of protective
clothing at least once
• separate each operation by a minimum of 3 ft.
• adapt original decon plan to actual conditions
DECONTAMINATION WORKERS
DETERMINE LEVEL OF PROTECTION BY:
• expected or visible contamination on entry team
• type of contaminant and associated respiratory
and skin hazards
• contaminant concentrations in the contamination
reduction corridor (CRC)
• results of swipe tests
NOTES
Day 3
Decontamination/p.3
-------
NOTES
Day 3
p.4/Decon tarn/nation
oeuitiOHiom
IUPPORT mug
-------
Section 4
-------
Response Organization
RESPONSE IMPLEMENTATION
• Organize
• Evaluate situation
• Develop plan of action
Make preliminary off-site survey
Make initial on-site reconnaissance
• Modify original plan of action
• Complete planned cleanup and restoration
KEY REQUIREMENTS
• Establish a chain-of-command
• Assign job functions/duties
• Develop personnel requirements
• Establish internal communications
NOTES
Day 4
Response Organization/p.1
-------
NOTES
Day 4
p.2/Response Organization
Bty
cer
Co
1
Field
Officer
PR and
mmumcations
Sole
Advl
1
Aaat. S
Advl
PERSONNEL
• Project leader/on-scene coordinator/
Incident manager •
• Scientific advisor
• Safety officer •
• Field leader
• Public information officer
• Security officer
• Recordkeeper
• Operations officer
• Team leaders
• Financial officer
• Logistics officer
• Medical officer
• Speclfiod by 1910 120
ON-SITE PERSONNEL
PROJECT TEAM LEADER
• Directs response operations.
• Prepares & organizes work plan, site
safety plan, and field team.
• Ensures that the work plan is completed
and on schedule.
-------
ON-SITE PERSONNEL
SAFETY & HEALTH OFFICER
Recommends stopping work when
conditions warrant.
Selects personal protective equipment
& takes care of storage/maintenance.
Confirms team member's suitability for
work based on physician's recommendation.
Coordinates emergency medical care.
Monitors on-site hazards & conditions.
ON-SITE PERSONNEL
FIELD TEAM LEADER
• Responsible for field team operations.
• Executes work plan & schedule.
• Enforces site control & safety.
• Documents field activities & sample
collection.
ON-SITE PERSONNEL
SCIENTIFIC ADVISOR
• Advises on field monitoring, sample
collection & analysis, scientific
studies, data interpretation and
remedial plans.
NOTES
Day 4
Response Organization/p.3
-------
NOTES
Day 4
p.4/Response Organization
ON-SITE PERSONNEL
PUBLIC INFORMATION OFFICER
• Releases information to the news media
& public concerning site activities.
ON-SITE PERSONNEL
LOGISTICS/EQUIPMENT OFFICER
• Plans & mobilizes facilities, materials
and personnel required for response.
ON-SITE PERSONNEL
RECORD KEEPER
• Maintains official records of site
activities.
-------
ON-SITE PERSONNEL
DECONTAMINATION OFFICER
• Sets up decon lines.
• Controls decon of all equipment,
personnel, and samples.
• Ensures that all required equipment
is available.
ON-SITE PERSONNEL
ENTRY TEAM/WORK PARTY
• Safely completes the on-site tasks.
• Complies with site safety plan.
• Notifies safety officer of unsafe
conditions.
ON-SITE PERSONNEL
SECURITY OFFICER
• Manages site security.
NOTES
Day 4
Response Organization/p.5
-------
NOTES
Da
lay 4
.6/Response Organization
AS-NEEDED PERSONNEL
FIREFIGHTERS
BOMB SQUAD/EXPLOSION EXPERTS
ENVIRONMENTAL SCIENTISTS
HAZARDOUS CHEMICAL EXPERTS
HEALTH PHYSICISTS
INDUSTRIAL HYGIENISTS
TOXICOLOGISTS
EFFECTIVE ORGANIZATION
Designate leader
Determine objectives
' Establish authority
1 Develop policy and procedures
Assign duties
Plan and direct operations
Establish internal communications
Manage resources
Establish external communications
-------
Section 5
-------
HAZARD RECOGNITION
A hazardous material incident is a situation in which a hazardous material has escaped or may escape
into the environment. Hundreds of thousands of different chemicals are produced stored,
transported, and used annually. Because of the hazardous nature of many of them, safeguards are
established to prevent them from causing harm. If these safeguards are accidentally or purposefully
disregarded, the material is no longer under effective control. Then a situation is established that
can have dangerous effects. Hazardous material incidents vary considerably. Considerations are
chemicals and quantities involved, types of hazard, response efforts required, number of responders
needed, and effects produced. They may require immediate control measures (emergency) or long
term cleanup activities (remedial action) to restore acceptable conditions.
Activities that are required when responding to incidents can be divided into five broad, interacting
elements.
• Recognition: identification of the substance involved and the characteristics which
determine its degree of hazard.
• Evaluation: impact or risk the substance poses to the workers, public health and the
environment.
• Control: methods to eliminate or reduce the impact of the incident.
• Information: knowledge gained about the conditions or circumstances particular to
an incident. Information is often called intelligence. In a response you gather
intelligence and disseminate it.
• Safety: protection of responders from harm.
These elements make up a system—an orderly arrangement of components that interact to accomplish
a task (Figure 1). In response work, the task is to prevent or reduce the impact of the incident on
people, property, and the environment, and to restore conditions to as near normal as possible. To
achieve this goal response personnel undertake a variety of activities; for example, firefighting,
sampling, developing safety plans, erecting fences, installing a physical treatment system,
recordkeeping, evaluation, etc. These activities are all related; what occurs in one affects or is
affected by the others.
Five elements classify all response activities. Recognition, evaluation, and control describe
performance-oriented elements. There is an outcome - a sample needs collected, a treatment system
installed, a chemical identified or a risk determined. Information and safety are supportive elements.
They are the results that come from recognizing, evaluating, and controlling.
Understanding the system provides some insight into how response activities relate to each other.
It helps explain, in broad terms, the processes involved in responding to a hazardous material
incident.
6/93 1 Hazard Recognition
-------
INFORMATION
RECOGNITION
EVALUATION
CONTROL
» S-4FE7V
FIGURE 1
THE INCIDENT RESPONSE SYSTEM
Recognition
Recognizing the type and degree of the hazard present is usually one of the first steps in responding
to an incident. The substance involved must be identified. Then the physical and chemical
properties which may make it hazardous - capable of causing harm - are determined. These inherent
properties are used, on a preliminary basis, to predict the behavior and anticipated problems
associated with a material.
Recognition may be easy. For example, the placard on a railroad tank car carrying a hazardous
material is used to quickly identify its content. At a hazardous waste site, which may contain
hundreds of different chemicals, complete identification is more difficult. The element of
recognition, therefore, involves use of all available information (e.g., sampling results, historical
data, visual observation, instruments, package labels, shipping manifests, existing documentation,
witnesses, and other sources) to identify the substances.
Hazard Recognition
6/93
-------
An incident involves more than the mere presence of a hazardous material. It is a situation in which
the normal safeguards associated with the materials are compromised, thus creating the chance of
undesirable effects. For instance, gasoline can do harm because its vapors can ignite and explode.
However, the usual safety techniques for handling gasoline prevent this from happening. Problems
caused by the release of gasoline into the environment can be anticipated based on its chemical and
physical properties. The harm that gasoline will do if released at a site, however, depends on site-
specific conditions.
Thousands of substances exhibit one or more characteristics of flammability, radioactivity,
corrosiveness, toxicity, or other properties which classify them as hazardous. For any particular
hazardous category, the degree of hazard varies depending on the substance. The degree of hazard
is a relative measure of how hazardous a substance is. For instance, the Immediately Dangerous to
Life or Heath (IDLH) concentration of butyl acetate in air is 10,000 parts per million (ppm); the
IDLH for sulfur dioxide is 100 ppm. Sulfur dioxide, therefore, is much more acutely toxic (has a
higher degree of hazard) when inhaled at IDLH concentrations than butyl acetate. Vapors from butyl
acetate, however, have a higher degree of explosive hazard than tetrachloroethane vapors, which are
not explosive.
Once the substance(s) has been identified, its hazardous properties and its degree of hazard is
determined using reference material. Although appropriate references give information about the
substance's physical/ chemical properties and may give indications of its environmental behavior,
additional data is required. Most frequently, monitoring and sampling data is used to: (1) identify
substances, (2) determine concentrations, (3) confirm dispersion patterns, and (4) verify the presence
of material.
Evaluation
Recognition provides basic data about the substance. Evaluation is defined as determining its effects,
or potential impact, on public health, property, and the environment. A hazardous substance is a
threat due to its physical and chemical characteristics. Its actual impact however, depends on the
location of the release, on weather, and other site-specific conditions. Two measures of impact are:
(1) the adverse effects that have occurred, and (2) the potential impact of the substance if released.
Risk is the chance of harm being done, a measure of the potential impact or effect. The presence
of a hazardous substance is a risk, but if the material is under control, the risk is low; if
uncontrolled, the risk increases. For harm to be done, a critical receptor must be exposed to the
uncontrolled material, as when people live in the area, property will be impacted, or a sensitive
ecological habitat will be affected. Chlorine gas, for instance, is highly toxic and represents a risk.
If chlorine gas is released in a densely populated area, the risk to people is very great, while the
human risk associated with a release of chlorine gas in an unpopulated area is very low. If the
substance was carbon dioxide rather than chlorine, the human risk in both situations would be
substantially less, since carbon dioxide is much less toxic than chlorine.
Evaluating risk in these two examples is relatively simple. Much more complex are those episodes
where many compounds are involved and a higher degree of uncertainty exists regarding their
behavior in the environment and their contact with and effects on receptors. For instance: what is
the risk if a few thousand people drink from a water supply obtained from an aquifer underlying soil
containing a few parts per billion of styrene?
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The completeness of information must also be assessed. Is additional sampling and monitoring of
air, water, and soil necessary to provide more comprehensive information on what the material is,
where it is, how it moves through the environment, what it will contact, and what is the associated
risk? To evaluate completely the effects of a hazardous materials incident, all substances must be
identified, their dispersion pathways established, and for toxic chemicals, concentrations determined.
Risk is then assessed based on exposure (or potential exposure) to the public or other critical
receptors.
Identifying the materials involved in an incident and evaluating the impact the incident may have,
is frequently termed site characterization. Site characterization may be easy and rapid, or as in the
case of an abandoned waste site, a process that may take a long time to completely accomplish.
Control
Control is a method (or methods) which prevents or reduces the impact of the incident. Preliminary
control actions are instituted as rapidly as possible in emergency situations. As additional
information is developed through recognition and evaluation, initial control actions are modified or
others instituted. Releases that do not require immediate action allow more time for planning and
instituting remedial measures. Control measures include physical, chemical, and biological treatment
and cleanup techniques for restoring the area to prerelease conditions. It also includes public health
countermeasures, for example, evacuation or the shutdown of a drinking water supply, to prevent
contact of people with the substance.
Information
An integral part of response is information. All response activities evolve having information that
is readily available or subsequently obtained. Information is a support element to recognition,
evaluation, and control. It is an input to the three performance elements and provides data for
decision-making. It is also an outcome of these elements. A sample is collected and analyzed. The
results provide an input to determine treatment options, an outcome. Information comes from three
sources:
• Intelligence: Information obtained from existing records or documentation, placards,
labels, signs, special configuration of containers, visual observations, technical
reports, and others.
• Direct-reading instruments: Information relatively quickly obtained from
instruments.
• Sampling: Information obtained from collecting representative portions of
appropriate media or material and subsequent laboratory analysis.
Information acquisition, analyses, and decision-making are iterative processes that define the extent
of the problem and the array of possible response actions. For incident response to be effective, an
information base must be established which is accurate, valid, and timely. Throughout the lifetime
of the incident, a continuous stream of information is collected, processed, and applied. Sound
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decisions are based on (1) receipt and evaluation of good information and (2) development of a good
knowledge base concerning the situation.
Safety
All hazardous material responses pose varying dangers to responders. An important consideration
in all response activities is to protect the health and safety of the responders. To do this requires
that the chemical and physical hazards associated with each operation be assessed and methods
implemented to prevent or reduce harm to responders. Safety considerations are an input to every
activity that and are an outcome of each response activity. For example, an outcome of identifying
a specific chemical may be changes in safety requirements. Each response organization must have
an effective health and safety program including medical surveillance and health monitoring,
appropriate safety equipment, standardized safety procedures, and an active training program.
Relationship of Elements
Recognition, evaluation, control, information, and safety describe the five elements of response.
Each includes a variety of activities or operations. Elements are not necessarily sequential steps for
responding. In some situations, control measures can start before the substances are completely
identified. In others, a more thorough evaluation of the material's dispersion needs completed before
effective control actions can be determined. Likewise, safety measures for workers may be instituted
before the materials are identified or all the hazardous conditions fully known.
Each element and activity are interrelated. A dike (control), to contain the runoff water from
fighting a fire at a warehouse suspected of containing pesticides, is built. Once determined that the
runoff contains no hazardous chemicals (recognition), or that concentrations in the runoff are below
acceptable values (evaluation), no treatment is necessary and the dike is removed. This knowledge
(information) also changes the safety requirements for responders (safety).
A constant flow of information is needed to characterize the incident and to make decisions. For
example, an option to use carbon absorption for water treatment may require additional sample
collection and analysis to identify completely the substances involved. In turn, this would require
reevaluating the effectiveness of carbon absorption for the identified chemicals.
Additional information regarding where and how the substance is migrating may change the
requirements for sampling.
The response system is a concept explaining, in general terms, the processes involved in incident
response. All responses require the performance elements of recognizing, evaluating, and
controlling. To support these, information is needed and responder safety must be considered.
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CHEMICAL HAZARDS
Chemical hazards may be classified according to one of many groups. These groups may include
toxic, fire and explosive, corrosive, and chemical reactive. A material may elicit more than one
chemical hazard. For example, toxic vapors can be released during chemical fires. The hazard may
be a result of the physical/chemical properties of the material or of its chemical reactivity with other
materials or the environment to which it is exposed.
Toxic Hazards
Toxic materials cause local or systemic detrimental effects in an organism. Exposure to such
materials does not always result in death, although that is often the most immediate concern. Types
of toxic hazards are categorized by the physiological effect they have on the organism. A material
may induce more than one physiological response that may include: asphyxiation, irritation allergic
sensitization, systemic poisoning, mutagenesis, teratogenesis and carcinogenesis.
The likelihood that any of these effects will be experienced by an organism depends on: (1) the
inherent toxicity of the material itself (as measured by its lethal dose); (2) the magnitude of the
exposure (acute or chronic) and; (3) the route of exposure (ingestion, inhalation, skin absorption).
Fire and Explosion Hazards
Combustibility is the ability of a material to act as a fuel. Materials that can be readily ignited and
sustain a fire are considered combustible. Those that do not are called noncombustible. Three
components are required for combustion to occur: fuel, oxygen, and heat. The concentration of fuel
and oxygen must be high enough to allow ignition and to maintain the burning process. Combustion
is a chemical reaction that requires heat to proceed:
heat
fuel -I- oxygen > products
Heat is either supplied by the ignition source and maintained by the combustion, or is supplied from
an external source. The relationship of these three components is illustrated by the fire triangle
(Figure 2). Most fires can be extinguished by removing one of the three components. For example,
water applied to a fire removes the heat, thereby extinguishing the fire. When a material by itself
generates enough heat to self-ignite and combust, spontaneous combustion occurs, either as a fire
or explosion.
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FUEL / \ HEAT
OXYGEN
FIGURE 2
FIRE TRIANGLE
While oxygen is the usual oxidizing agent during the combustion process, there are chemicals that
can burn without oxygen being present. For example, calcium and aluminum will burn in nitrogen.
Therefore, the first side of the fire tetrahedron (Figure 3) is an oxidizing agent that permits the fuel
to burn.
The fuel is the material that oxidized. Since the fuel becomes chemically charged by the oxidizing
process, it is a reducing agent. This makes the second side of the tetrahedron. Fuels can be
anything from elements (carbon, hydrogen, magnesium) to compounds (cellulose, wood, paper,
gasoline, petroleum compounds).
Some mixtures of reducing agent and oxidizing agent remain stable under certain conditions.
However, when there is some activation energy, a chain reaction is started, which causes
combustion. The factor that can trigger this chemical reaction can be as simple as exposing the
combination to light. Once the chain reaction begins, extinguishment must take place by interrupting
the chain reaction.
Scientists have known for many years that certain chemicals act as excellent extinguishing agents.
However, they were at a loss to explain how these chemicals actually accomplished extinguishment,
given the triangle of the fire model. With the development of the tetrahedron model and the
inclusion of the uninhibited chain reaction, a scientifically sound theory could be postulated. With
this as the basis, the extinguishing capabilities of the halons and certain dry chemicals were possible.
The final side of the tetrahedron is temperature. The fact that temperature is used instead of heat
is deliberate. Temperature is the quantity of the disordered energy, which is what initiates
combustion. It is possible to have a high heat as indicated by a large reading of Btu and still not
have combustion. The temperature is therefore the key ingredient and the one that influences the
action of the tetrahedron.
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Temperature
Fuel
(Reducing
Agent)
Oxidizing
Agent
Uninhibited
Chain Reactions
FIGURE 3
FIRE TETRAHEDRON
Flammability is the ability of a material (liquid or gas) to generate enough concentration of
combustible vapors under normal conditions to be ignited and produce a flame. It is necessary to
have a proper fuel-to-air ratio (expressed as the percentage of fuel in air) to allow combustion.
There is a range of fuel concentrations in air for each material that is optimal for the ignition and
the sustenance of combustion. This is the Flammable Range. The lowest concentration of fuel in
this range is the Lower Flammable Limit (LFL). Concentrations less than the LFL are not
flammable because there is too little fuel—that is, the mixture is too "lean." The highest ratio that
is flammable is the Upper Flammable Limit (UFL).
Concentrations greater than the UFL are not flammable because there is too much fuel displacing
the oxygen (resulting in too little oxygen). This mixture is too "rich." Fuel concentrations between
the LFL and UFL are optimal for starting and sustaining fire. Example: the LFL for benzene is
1.3% (13,000 ppm), the UFL is 7.1% (71,000 ppm), thus the flammable range is 1.3% to 7.1%.
A flammable material is considered highly combustible if it can burn at ambient temperatures
(Table 1). But a combustible material is not necessarily flammable, because it may not be easily
ignited or the ignition maintained. For example some pyrophoric materials will ignite at room
temperature in the presence of a gas or vapor or when a slight friction or shock is applied.
It is important to note that the U. S. Department of Transportation (DOT), the Occupational Safety
and Health Administration (OSHA), the National Institute for Occupational Safety and Health
(NIOSH), and the National Fire Protection Association (NFPA) have established strict definitions
for flammability based on the flash point of a material.
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TABLE 1
FLAMMABLE COMPOUNDS AND ELEMENTS
Flammable Liquids
Flammable Solids
Aldehydes
Ketones
Amines
Ethers
Aliphatic hydrocarbons
Aromatic hydrocarbons
Alcohols
Nitroaliphatics
Water-Reactive Flammable Solids
Potassium
Sodium
Lithium
Phosphorus
Magnesium dust
Zirconium dust
Titanium dust
Aluminum dust
Zinc dust
Pvrophoric Liquids
Organometallic compounds
Dimethyl zinc
Tributyl aluminum
An explosive is a substance that undergoes a very rapid chemical transformation producing large
amounts of gases and heat. The gases produced, for example, nitrogen, oxygen, carbon monoxide,
carbon dioxide, and steam, due to the heat produced, rapidly expand at velocities exceeding the speed
of sound. This creates both a Shockwave (high pressure wave front) and noise.
Explosive gases/vapors exhibit an explosive range, which is the same as the flammable range. The
upper explosive limit (UEL) and lower explosive limit (LEL) are the UFL and LFL but in confined
areas. Most reference books list either explosive limits or flammable limits which are identical.
A gas or vapor explosion is a very rapid, violent release of energy. If combustion is extremely
rapid large amounts of kinetic energy, heat, and gaseous products are released. The major factor
contributing to the explosion is the confinement of a flammable material.
When vapors or gases cannot freely dissipate, they enter the combustion reaction more rapidly.
Confinement also increases the energy associated with these molecules, which enhances the explosive
process. Poorly ventilated buildings, sewers, drums, and bulk liquid containers are examples of
places where potentially explosive atmospheres may exist.
There are several types of explosive hazards:
• High or detonating: Chemical transformation occurs very rapidly with detonation
rates as high as 4 miles per second. The rapidly expanding gas produces a shock
wave which may be followed by combustion.
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• Primary high explosive: detonating wave produced in an extremely short period of
time. May be detonated by shock, heat, or friction. Examples are lead azide,
mercury fulminate, and lead styphnate.
• Secondary high explosive: generally needs a booster to cause them to detonate.
Relatively insensitive to shock, heat, or friction. Examples are tetryl, cyclonite,
dynamite, and TNT.
• Low or deflagrating: Rate of deflagration up to 1000 feet per second. Generally
combustion followed by a shock wave. Examples are smokeless powder, black
powder, and solid rocket fuel.
High or low does not indicate the explosion hazard (or power) but only the rate of chemical
transformation. Explosions can occur as a result of reactions between many chemicals not
ordinarily considered as explosives. Ammonium nitrate, a fertilizer, can explode under the right
conditions. Alkali metals and water explode; as will water and peroxide salts. Picric acid and
certain ether compounds become highly explosive with age. Gases, vapors, and finely divided
particulates, when confined, can also explode if an ignition source is present.
In summary, fires and explosions require fuel, air (oxygen), and an ignition source (heat). At a
hazardous materials incident, the first two are not easily controlled. Consequently, while working
on-site where a fire hazard may be present, the concentration of combustible gases in air must be
monitored, and any potential ignition source must be kept out of the area.
The most dangerous flammable substances:
• are easily ignited (e.g., pyrophorics).
• require little oxygen to support combustion.
• have low LFL/LEL and a wide flammable/explosive range.
Hazards related to fires and explosions cause:
• physical destruction due to shock waves, heat, and flying objects.
• initiation of secondary fires or creation of flammable conditions.
• release of toxic and corrosive compounds into the surrounding environment.
Corrosive Hazards
Corrosion is a process of material degradation. Upon contact, a corrosive material may destroy
body tissues, metals, plastics, and other materials. Technically, corrosivity is the ability of material
to increase the hydrogen ion or hydronium ion concentration of another material; it may have the
potential to transfer electron pairs to or from itself or another substance. A corrosive agent is a
reactive compound or element that produces a destructive chemical change in the material upon
which it is acting. Common corrosives are the halogens, acids, and bases (Table 2). Skin irritation
and burns are typical results when the body contacts an acidic or basic material.
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The corrosiveness of acids and bases can be compared on the basis of their ability to dissociate (form
ions) in solution. Those that form the greatest number of hydrogen ions (H+) are the strongest acids,
while those that form the most hydroxide ions (OH') are the strongest bases. The H+ ion
concentration in solution is called pH. Strong acids have a low pH (many H+ in solution) while
strong bases have a high pH (few H+ in solution; many OH'in solution). The pH scale ranges from
0 to 14 as follows:
< Increasing acidity Neutral Increasing basicity >
012 3 4 5 6 7 8 9 10 11 12 13 14
Measurements of pH are valuable because they can be quickly done on-site, providing immediate
information on the corrosive hazard.
TABLE 2
CORROSIVES
HALOGENS
Bromine
Chlorine
Fluorine
Iodine
Sulfuric acid
BASES (CAUSTICS)
Potassium hydroxide
Sodium hydroxide
ACIDS
Acetic acid
Hydrochloric acid
Hydrofluoric acid
Nitric acid
When dealing with corrosive materials in the field, it is imperative to determine:
• How toxic is the corrosive material? Is it an irritant or does it cause severe burns?
• What kind of structural damage does it do, and what other hazards occur? For
example, will it destroy containers holding other hazardous materials, releasing them
into the environment?
Chemical Reactivity
A reactive material is one that undergoes a chemical reaction under certain specified conditions.
Generally, the term "reactive hazard" is used to refer to a substance that undergoes a violent or
abnormal reaction in the presence of either water or normal ambient atmospheric conditions. Among
this type of hazard are the pyrophoric liquids which will ignite in air at or below normal room
temperature in the absence of added heat, shock, or friction, and the water-reactive flammable solids
which will spontaneously combust upon contact with water (Table 1).
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A chemical reaction is the interaction of two or more substances, resulting in chemical changes.
Exothermic chemical reactions, which give off heat, can be the most dangerous. A separate source
of heat is required to maintain endothermic chemical reactions. Removing the heat source stops the
reaction.
Chemical reactions usually occur in one of the following ways:
• Combination A + B > AB
• Decomposition AB > A + B
• Single replacement A + BC > B + AC
• Double replacement AB + CD > AD + CB
The rate at which a chemical reaction occurs depends on the following factors:
• Surface area of reactants available at the reaction site (for example, a large chunk of
coal is combustible, but coal dust is explosive)
• Physical state of reactant - solid, liquid, or gas
• Concentration of reactants
• Temperature
• Pressure
• Presence of a catalyst.
If two or more hazardous materials remain in contact indefinitely without reaction, they are
compatible. Incompatibility, however, does not necessarily indicate a hazard. For example, acids
and bases (both corrosive) react to form salts and water, which may not be corrosive.
Many operations on waste or accident sites involve mixing or unavoidable contact between different
hazardous materials. It is important to know ahead of time if such materials are compatible. If they
are not, then any number of chemical reactions could occur. The results could range from the
formation of an innocuous gas to a violent explosion. Table 3 illustrates what happens when some
incompatible materials are combined.
The identity of unknown reactants must be determined by chemical analysis to establish
compatibility. On the basis of their properties, a chemist then should be able to anticipate any
chemical reactions resulting from mixing the reactants. Judging the compatibility of more than two
reactants is very difficult; analysis should be performed on a one-to-one basis.
Response personnel who must determine compatibilities should refer to A Method for Determining
the Compatibility of Hazardous Wastes (EPA 600/2-80-076), published by EPA's Office of Research
and Development. Final decisions about compatibilities should only be made by an experienced
chemist.
Sometimes the identity of a waste is impossible to ascertain due to money and time constraints. In
this event, simple tests must be performed to determine the nature of the material or mixture. Tests
such as pH, oxidation-reduction potential, and flash point are useful. In addition, very small
amounts of the reactants may be carefully combined to determine compatibility.
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If materials are compatible they may be stored together in bulk tanks or transferred to tank trucks
for ultimate disposal. It is necessary, then, to establish the compatibility of the materials through
analyses prior to bulking them. Compatibility information is also very important in evaluating an
accident involving several different hazardous materials. The ultimate handling and treatment of the
materials may be partially based on such information.
TABLE 3
HAZARDS DUE TO CHEMICAL REACTIONS (INCOMPATIBILITIES)
Heat Generation
Fire
Explosion
Toxic Gas or Vapor Production
Flammable Gas or Vapor Production
Formation of a Substance with Greater
Toxicity than the Reactants
Formation of Shock or Friction Sensitive
Compounds
Pressurization of Closed Vessels
Solubilization of Toxic Substances
Dispersal of Toxic Dusts and Mists
Violent Polymerization
Acid and Water
Hydrogen Sulfide and Calcium Hypochlorite
Picric Acid and Sodium Hydroxide
Sulfuric Acid and Plastic
Acid and Metal
Chlorine and Ammonia
Peroxides and Organics OR
Liquid Oxygen and Petroleum Products
Fire Extinguisher
Hydrochloric Acid and Chromium
Sodium or Potassium Cyanide and Water or
Acid Vapor
Ammonia and Acrylonitrile
Properties of Chemical Hazards
Chemical compounds possess inherent properties which determine the type and degree of the hazard
they represent. Evaluating risks of an incident depends on understanding these properties and their
relationship to the environment.
The ability of a solid, liquid, gas or vapor to dissolve in a solvent is solubility. An insoluble
substance can be physically mixed or blended in a solvent for a short time but is unchanged when
it finally separates. The solubility of a substance is independent of its density or specific gravity.
The solubility of a material is important when determining its reactivity, dispersion, mitigation, and
treatment. Solubility can be given in parts per million (ppm) or milligrams per liter (mg/L)
The density of a substance is its mass per unit volume, commonly expressed in grams per cubic
centimeter (g/cc). The density of water is 1 g/cc since 1 cc has a mass of 1 g.
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Specific gravity (SpG) is the ratio of the density of a substance (at a given temperature) to the
density of water at the temperature of its maximum density (4°C). Numerically, SpG is equal to the
density in glee, but is expressed as a pure number without units. If the SpG of a substance is greater
than 1 (the SpG of water), it will sink in water. The substance will float on water if its SpG is less
than 1. This is important when considering mitigation and treatment methods.
The density of a gas or vapor can be compared to the density of the ambient atmosphere. If the
density of a vapor or gas is greater than that of the ambient air, then it will tend to settle to the
lowest point. If vapor density is close to air density or lower, the vapor will tend to disperse in the
atmosphere. Vapor density is given in relative terms similar to specific gravity. In settling, dense
vapor creates two hazards. First, if the vapor displaces enough air to reduce the atmospheric
concentration of oxygen below 16%, asphyxia may result. Second, if the vapor is toxic, then
inhalation problems predominate even if the atmosphere is not oxygen deficient. If a substance is
explosive and very dense, the explosive hazard may be close to the ground rather than at the
breathing zone (normal sampling heights).
The pressure exerted by a vapor against the sides of a closed container is called vapor pressure.
It is temperature dependent. As temperature increases, so does the vapor pressure. Thus, more
liquid evaporates or vaporizes. The lower the boiling point of the liquid, the greater the vapor
pressure it will exert at a given temperature. Values for vapor pressure are most often given as
millimeters of mercury (mm Hg) at a specific temperature.
The boiling point is the temperature at which a liquid changes to vapor - that is, it is the temperature
where the pressure of the liquid equals atmospheric pressure. The opposite change in phases is the
condensation point. Handbooks usually list temperatures as degrees Celsius (°C) or Fahrenheit (°F).
A major consideration with toxic substances is how they enter the body. With high-boiling-point
liquids, the most common entry is by body contact. With low-boiling-point liquids, the inhalation
route is the most common and serious.
The temperature at which a solid changes phase to a liquid is the melting point. This temperature
is also the freezing point, since a liquid can change phase to a solid. The proper terminology
depends on the direction of the phase change. If a substance has been transported at a temperature
that maintains a solid phase, then a change in temperature may cause the solid to melt. The
particular substance may exhibit totally different properties depending on phase. One phase could
be inert while the other highly reactive. Thus, it is imperative to recognize the possibility of a
substance changing phase due to changes in the ambient temperature.
The minimum temperature at which a substance produces enough flammable vapors to ignite is its
flash point. If the vapor does ignite, combustion can continue as long as the temperature remains
at or above the flash point. The relative flammability of a substance is based on its flash point. An
accepted relation between the two is:
Highly flammable: Flash point less than 100°F
Moderately flammable: Flash point greater than 100°F but
less than 200°F
Relatively inflammable: Flash point greater than 200°F
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SAFETY HAZARDS
Safety is the condition of being secure from undergoing or causing hurt, injury, or loss. In this
definition, safety requires a twofold posture - offensive and defensive. The offensive posture
provides protection for actions one can control. The defensive posture is the awareness of factors
or situations others may create. Care must be taken that actions to protect or reduce accident
potentials for one person do not set up conditions ("booby traps") for subsequent accidents by others.
Kinetic/Mechanical
Generally referred to as "slip-trip-fall" type injuries, the kinetic/mechanical category includes
"struck-by" injuries along with the "striking" injuries.
Workers must walk cautiously at a site to avoid tripping. Abandoned wastes usually are not kept
neat and tidy. Train or other vehicle wrecks can produce debris that can increase the possibility of
tripping. Problems at a hazardous waste site and an accident scene can be compounded by uneven
terrain and mud, caused by rain or leaking chemicals.
Walking on drums is dangerous. Not only can they tip over, but they can be so corroded that they
cannot support a person's weight. If it is necessary to walk over drums, place a piece of plywood
over several drums and stand on this. This distributes the walker's weight over several drums. In
some cases, a drum grappler can be used to move drums to a more accessible location.
Extra precautions must be taken if guardrails or railing are absent. The precautions generally include
the use of a safety belt with lifeline.
Electrical
Electrical hazards can exist at accident sites because of downed power lines or improper use of
electrical equipment. The presence of underground electric lines must be checked before any digging
or excavating. When using cranes or material handlers, care must be taken that the machinery does
not come in contact with any energized lines. There should be a 10-foot clearance between a crane
and electric power lines unless the lines have been deenergized or an insulating barrier has been
erected. Shock is the primary hazard from electrical tools. Electrical shock may cause death or
burns or falls that lead to injury.
Ways for protecting personnel from shock are:
• Grounding equipment. Grounding drains current, due to a short circuit, to earth.
The ground wire is the third wire on three prong plugs. Equipment can also be
grounded by a separate wire attached to the metal parts of equipment.
• Using double-insulated tools. These tools do not need to be grounded because they
are: encased by a nonconductive material which is shatterproof, or have a layer of
insulating material isolating the electrical components from a metal housing (used for
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more rugged design). This insulation is in addition to that found in regular tools.
Double-insulated tools are identified by writing on the tool or by the symbol of a
square within a square ([D]).
• Having overcurrent devices such as: (1) fuses, which interrupt current by melting
a fusible metal strip, or (2) circuit breakers, which operate by temperature change or
magnetic difference.
Overcurrent devices open the circuit automatically if the current is high from accidental
ground, short circuit or overload. They should be selected based on type of equipment and
capacity. A ground fault circuit interrupter (GFCI) device can be used to protect personnel
and equipment. This device breaks a circuit when it detects low levels of current leaking to
ground. It is fast-acting to keep the size of the current and its duration so low that it cannot
produce serious injury. This device only operates on line-to-ground fault currents and not
on line-to-line contact. It is commonly used on construction sites and in hospitals.
Additionally, tools and flexible cords should be inspected for damage that could lead to
shock. For more detailed information check the National Electrical Code (National Fire
Protection Association Section 70).
Acoustic
Excessive acoustic energy can destroy the ability to hear and may also put stress on other parts of
the body, including the heart. There is no cure for most effects of noise, therefore prevention is the
only way to avoid health damage. The damage depends mainly on the intensity and length of
exposure. The frequency or pitch can also have some effect and high-pitched sounds are more
damaging than low-pitched ones.
Noise may tire out the inner ear, causing hearing loss. After a period of time off, hearing may be
restored. Under some circumstances the damage may become permanent because cells in the inner
ear have been destroyed and can never be replaced or repaired. Permanent damage can be caused
by long-term exposure to loud noise, or in some cases, by brief exposure to very loud noises
(explosions, shock waves).
Although research on the effects of noise on other parts of the body is not complete, it appears that
excessive noise can quicken the pulse rate, increase blood pressure, and narrow blood vessels. Over
a long period of time, these may place an added burden on the heart.
Excessive noise may also put stress on other parts of the body by causing the abnormal secretion of
hormones and tensing of muscles. Workers exposed to noise sometimes complain of nervousness,
sleeplessness, and fatigue. Excessive noise exposure also can reduce job performance and may cause
high rates of absenteeism.
OSHA regulation 29 CFR 1910.95 limits a worker's noise exposure to 90 decibels -A weighted
(dBA) for an 8-hour exposure. Time limits are shorter for higher noise levels. Decibel is the unit
used in sound level measurements. Instruments generally are designed to use an A-weighted scale
so that the instrument responds to the different sound frequencies in the same way as the human ear.
Hazard Recognition 16 6/93
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When daily noise exposure is composed of two or more periods of different noise levels, their
combined effect should be considered, rather than the individual effect of each. If the sum—a time-
weighted average (TWA)—of the following fractions Cj/Tl + C2/T2 .... Cn/Tn exceeds 1, then
the mixed exposure should be considered to exceed the limit value. Cn indicates the total time of
exposure at a specific noise level, and Tn indicates the total time of exposure permitted at that level.
Recent rule-making by OSHA requires a continued, effective hearing conservation program whenever
worker noise exposures equal or exceed an 8-hour time-weighted average sound level (TWA) of 85
decibels measured on the A scale (dBA) or, equivalently, a dose of SO percent.
The main elements of the hearing conservation program are:
• Monitoring of workers' exposures.
• An audiometric testing program for those exposed above a 85 dBA TWA. This
requires a "baseline" audiogram for comparison and annual retesting to see if there
is any hearing loss.
• Hearing protection available for those exposed to above 85 dBA TWA. If the TWA
is above 90 dBA, or if it is above 85 dBA and the worker shows a permanent
significant hearing loss, then hearing protection is required to be worn.
• Informing exposed workers about noise hazards (or effects) and the elements of a
hearing conservation program.
The U.S. Environmental Protection Agency (EPA) recommends that, for an 8-hour work day,
workers should not be exposed to noise levels above 85 dBA TWA. EPA's goal is to reduce that
level to 75 dBA. EPA also recommends that individuals should not be exposed to 70 dBA TWA for
an entire 24-hour day.
BIOLOGICAL HAZARDS
Animal bites, insect stings, contact with plants and microbes, and exposure to medical/infectious
wastes are examples of biological hazards that response personnel may encounter.
Animal bites or insect stings are usually nuisances (localized swelling, itching, and minor pain) that
can be handled by first aid treatments. The bites of certain snakes, lizards, spiders, and scorpions
contain sufficient poison to warrant medical attention.
There are diseases that can be transmitted by animal bites. Examples are Rocky Mountain spotted
fever (tick), rabies (mainly dogs, skunks and foxes), malaria, and equine encephalitis (mosquito).
The biggest hazard and most common cause of fatalities from animal bites—particularly bees, wasps,
and spiders—is a sensitivity reaction. Anaphylactic shock due to stings can lead to severe reactions
to the circulatory, respiratory, and central nervous system, and it can also cause death.
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Toxic effects from plants are generally due to ingestion of nuts, fruits, or leaves. Of more concern
to response personnel are certain plants, including poison ivy, poison oak, and poison sumac, which
produce adverse effects from direct contact.
The usual effect is dermatitis - inflammation of the skin. The protective clothing and
decontamination procedures used for chemicals also reduce the exposure risk from the plant toxins.
Cleaning the skin thoroughly with soap and water after contact will reduce the risk.
Another source of infection for response workers is poor sanitation. Water borne and food borne
diseases can be a problem if adequate precautions are not taken. Examples of water borne diseases
are cholera, typhoid fever, viral hepatitis, salmonellosis, bacillary dysentery, and amebic dysentery.
In an emergency response related to a disaster, water supplies may be affected. The source of water
for a long-term remedial action is also important. In some locations, it may be necessary to transport
water and food to the site. They must be handled properly and come from an uncontaminated
source.
The response team must also avoid creating any sanitation problems by making sure that properly
designed lavatory facilities are available at the worksite.
Microbial hazards can occur when the materials the workers are handling have biological as well
as chemical contamination. This can be a problem if a chemical spill is into or mixed with sewage.
Most bacteria that affect humans prefer a neutral environment (pH 7). Thus an extremely acid or
alkaline environment would destroy or inhibit bacterial growth. However, during neutralization, the
environment could become more conducive to bacteria growth. In these situations, the normal
decontamination procedures will usually alleviate the problem.
Medical/infectious wastes include blood borne pathogens which are regulated by OSHA 29 CFR
1910.1030. This standard specifically addresses proper engineering controls, work practices, and
personal protective equipment to reduce the risk of contact with blood borne pathogens.
RADIATION HAZARDS
Radioactive materials that may be encountered at a site can emit three types of harmful radiation:
alpha particles, beta particles, and gamma waves. All three forms harm living organisms by
imparting energy which ionizes molecules in the cells. Therefore, the three are referred to as
ionizing radiation. lonization may upset the normal cellular function causing cell dysfunction or
death.
An alpha particle is positively charged. The beta is an electron possessing a negative charge. Both
particles have mass and energy. Both are emitted from the nucleus. They travel short distances in
material before interactions with the material causes them to lose their energy. The outer layers of
the skin and clothing generally protect against these particles. Therefore, they are considered
hazardous primarily when they enter the body through inhalation or ingestion.
Hazard Recognition 18 6/93
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Gamma radiation is pure electromagnetic energy and is wave-like rather than paniculate. Gamma
waves pass through all materials to some degree. Clothing, including protective gear, will not
prevent gamma radiation from interacting with body tissue.
Unlike many hazardous substances that possess certain properties which can alert response personnel
to overexposures (odor, irritation, or taste), radiation has no such warning properties. Therefore,
preventing radiation material from entering the body or protecting against external radiation is the
best protection. As with biological and chemical hazards, the use of respiratory and personnel
protective equipment, coupled with scrupulous personal hygiene, will afford good protection against
radioactive particulates.
CONFINED SPACE HAZARDS
NIOSH defines a confined space as any space which by design has limited openings for entry and
exit; unfavorable natural ventilation which could contain or produce dangerous air contaminants, and
which is not intended for continuous worker occupancy. Examples of confined spaces would include
storage tanks, holds of ships, process vessels, pits, silos, boilers, ventilation and exhaust ducts,
sewers, tunnels, underground utility vaults, and pipelines.
The NIOSH classifications of confined spaces use a checklist to prepare for and carry out confined
space operations safely. These checklists are found in NIOSH's Criteria for a Recommended
Standard: Working in Confined Spaces. This document should be studied completely by anyone
responsible for the oversight of confined space work. Particular professional judgement, skill, and
experience is required to conduct confined space operations safely. All items listed on the checklist
must be in place and in use to ensure worker health and safety during the most dangerous hazardous
materials work activity: that of confined space work.
Although complete data are not available, working in confined spaces is recognized as the most
dangerous type of work involving hazardous materials. The very nature of a confined space
increases the likelihood of encountering a toxic atmosphere because the confined space encourages
the accumulation of gases and vapor. A very high rate of accidents involving worker fatalities is
associated with confined spaces. Again, while complete data are impossible to obtain, studies have
suggested that as many as two-thirds of all confined space fatalities are would-be rescuers. For every
worker that initially is overcome and eventually dies as a result to a confined space exposure,
perhaps two would-be rescuers are succumbing also. The main reason that this occurs is that
workers do not recognize the hazard presented by the confined space.
A closed building or room are examples of confined spaces that response personnel may encounter.
Procedures for entry into a confined space are very similar to entry into a site. Because of poor
ventilation, high concentrations of gases or vapors are more likely to exist in a confined space than
at an open site. Also, certain confined spaces may contain hazardous materials. For example,
hydrogen sulfide and methane are often in sewers. Also, a large amount of organic material in an
enclosed space can combine with oxygen in the surrounding air to produce an oxygen deficient
atmosphere.
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Besides the problem with possible high concentration of gases or vapors, confined spaces also present
an entrance and exit problem. Most of the spaces mentioned earlier have only small openings for
entry and exit. This can interfere with use of equipment like self-contained breathing apparatus
(SCBA). In some cases an airline respirator may have to be used in place of an SCBA. Because
of this problem, and in case a worker is injured, a lifeline is often attached to the worker to aid in
pulling him out. That way rescuers would not have to enter the space. A lifeline is especially
important in spaces where access is through an opening in the top of the space.
Lockout, blocking, or equivalent measures may be needed to ensure that deactivated systems are
not reactivated at inopportune times (Figure 4). These procedures are usually used when someone
is working on or around equipment that could cause injury if it is accidentally turned on.
The general procedure is to turn off the equipment at a point where it can be locked so that the
equipment cannot be turned on. An example is the main power disconnect on a fuse box. Most
boxes have a tab and hole where a lock can be placed so the switch cannot be turned back on. For
piping systems, not only can the valve be turned off, but the pipes can be disconnected or a "blank" -
a flat plate inserted in the pipeline. These two methods may be used in lieu of actually locking a
valve. The advantage of using an actual lock is that only one person has a key; therefore, only he
can reactivate the equipment after he is done with repair work. In some cases, there may be several
workers, each using a different lock on a switch so that all locks have to be removed before
equipment can be used.
Hazard Recognition 20 6/93
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a.
b.
d.
VALVES
(CLOSED)
FIGURE 4
LOCKOUT, BLOCKING, AND TAGGING
(a) Multiple locks
(b) Block on switch
(c) Tag
(d) Disconnecting and "blanking" pipeline
6/93
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Hazard Recognition
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MEDICAL EMERGENCIES
Hazardous material environments pose unique health hazards for personnel. A medical program is
necessary to assess and monitor the workers' health and fitness both prior to work and during the
course of work activities. It is important for personnel to recognize medical emergencies and to be
trained on emergency procedures and treatment.
Heat Stress
The human body is designed to function at a certain internal temperature. When metabolism or
external sources (fire, hot summer day) cause the body temperature to rise, the body seeks to protect
itself by triggering cooling mechanisms. Excess heat is dissipated by two means:
• Changes in blood flow to dissipate heat by convection, which can be seen as
"flushing" or reddening of the skin in extreme cases.
• Perspiration, the release of water through skin and sweat glands. While working in
hot environments, evaporation of perspiration is the primary cooling mechanism.
Protective clothing worn to guard against chemical contact effectively stops the evaporation of
perspiration. Thus the use of protective clothing increases heat stress problems.
The major disorders due to heat stress are heat cramps, heat exhaustion, and heat stroke. Heat
cramps are painful spasms which occur in the skeletal muscles of workers who sweat profusely in
the heat and drink large quantities of water, but fail to replace the body's lost salts or electrolytes.
Drinking water while continuing to lose salt tends to dilute the body's extracellular fluids. Soon
water seeps by osmosis into active muscles and causes pain. Muscles fatigued from work are usually
most susceptible to cramps.
Heat exhaustion is characterized by extreme weakness or fatigue, dizziness, nausea, and headache.
In serious cases, a person may vomit or lose consciousness. The skin is clammy and moist,
complexion pale or flushed, and body temperature normal or slightly higher than normal. Treatment
is rest in a cool place and replacement of body water lost by perspiration. Mild cases may recover
spontaneously with this treatment; severe cases may require care for several days. There are no
permanent effects.
Heat stroke is a very serious condition caused by the breakdown of the body's heat regulating
mechanism. The skin is very dry and hot with a red, mottled or bluish appearance.
Unconsciousness, mental confusion, or convulsions may occur. Without quick and adequate
treatment, the result can be death or permanent brain damage. Get medical assistance quickly! As
first aid treatment, the person should be moved to a cool place. Body heat should be reduced
artificially, but not too rapidly, by soaking the person's clothes with water and fanning them.
Hazard Recognition 22 6/93
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Steps that can be taken to reduce heat stress are:
• Acclimatize the body. Allow a period of adjustment to make further heat exposure
endurable. It is recommended that a new worker start at 50% of the anticipated total
work load for the first day and increase the work load gradually each succeeding day
for about a week. Acclimatization can be "lost" if a worker is away from the heat
for two weeks.
• Drink more liquids to replace body water lost during sweating.
• Rest frequently.
• Increase salt consumption. Sweat is mostly water with smaller amounts of sodium
and potassium salts. Replacement fluids should be similar in composition. Thus, salt
tablets usually are not necessary and can be harmful. It is better to increase salt on
food or drink commercially available preparations that provide the proper balance of
water and salts.
• Wear personal cooling devices. There are two basic designs; units with pockets for
holding frozen packets and units that circulate a cooling fluid from a reservoir
through tubes to different parts of the body. Both designs can be in the form of a
vest, jacket, or coverall. Some circulating units also have a cap for cooling the head.
• Wear supplied air suits or respirators that are equipped with a vortex tube that either
cools or warms the air being supplied. The vortex tube is not used with self-
contained breathing apparatus because it uses large amounts of compressed air during
operation.
• Wear cotton long underwear under chemical protective clothing. The cotton will
absorb perspiration and will hold it close to the skin. This will provide the body with
the maximum cooling available from the limited evaporation that takes place beneath
chemical resistant clothing. It also allows for rapid cooling of the body when the
protective clothing is removed.
There are instruments that measure air temperature, radiant heat, and humidity to give a heat index.
NIOSH, the American Conference of Governmental Industrial Hygienists (ACGIH), and other groups
use this index in their guidelines on heat stress. However, these guidelines are usually valid only
for acclimatized personnel wearing light summer clothing and not chemical resistant or insulating
protective gear.
Cold Exposure
Cold temperatures can also cause medical problems. The severe effects are frostbite and
hypothermia.
Frostbite is the most common injury resulting from exposure to cold. The extremities of the body
are most often affected. The signs of frostbite are: the skin turns white or grayish-yellow, pain is
6/93 23 Hazard Recognition
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sometimes felt early but subsides later (often there is no pain), and the affected part feels intensely
cold and numb.
Standard first aid for frostbite includes getting the victim to a warm shelter. Put frozen parts in
warm water (100-105°F) but not hot water. Handle parts gently and do not rub or massage them.
If toes and finger are affected, put dry, sterile gauze between them after warming them. Loosely
bandage the injured parts. If the part has been thawed and refrozen, rewarm it at room temperature.
Hypothermia is characterized by shivering, numbness, drowsiness, muscular weakness and a low
internal body temperature when the body feels warm externally. This can lead to unconsciousness
and death. In the case of hypothermia, professional medical care should be sought immediately.
A victim should be taken out of the cold and into dry clothing. The body should be warmed slowly.
Medical Surveillance
Medical surveillance is important in two ways. First, since response workers are handling materials
that can damage their bodies, they must be checked to determine if any damage is occurring. There
are medical tests for determining if a worker has too much of a chemical in their system. For
example, blood tests can detect lead and carbon monoxide, urine tests can detect arsenic, and there
are tests to determine if the liver is functioning properly. Exhaled air and hair and nail clippings can
also be analyzed for the presence of chemicals. Workers showing an abnormal amount of chemical
in their systems should be removed from their assignments or have their operating procedures
reevaluated.
The second reason for medical surveillance is to ensure the worker is capable of doing the job.
Using respiratory protection strains the pulmonary system. OSHA General Industry Standard 29
CFR 1910.134(b)(10) states that "Persons should not be assigned to tasks requiring use of respirators
unless it has been determined that they are physically able to perform the work and use the
equipment." Heat stress can be a problem for workers wearing protective clothing. Thus, in some
situations, it would be advisable to check workers for symptoms of heat stress.
Emergencies and First Aid
OSHA Construction Industry Standard 29 CFR 1926.50 - Medical Services and First Aid requires
that:
• Medical personnel be available for advice and consultation on matters of occupational
health.
• Prior to start of the project, provisions be made for prompt medical attention in case
of serious injury.
• At least one and preferably more persons at the worksite be trained in first aid. The
American Red Cross, some insurance carriers, local safety councils, and other
organizations provide acceptable training.
Hazard Recognition 24 6/93
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• First aid supplies approved by a consulting physician be readily available. The
supplies should be in sanitary and weatherproof containers with individually sealed
packages for material such as gauze, bandages, and dressings that must be sterile.
• Proper equipment be provided for prompt transportation of an injured person to a
physician or hospital, or a communication system for contacting necessary ambulance
service.
• The telephone numbers of the physicians, hospitals, or ambulances be conspicuously
posted.
Medical assistance will probably be available at an emergency response such as a truck or train
wreck. It is important to remember that first aid is immediate temporary treatment given in the event
of accident or illness before the doctor arrives. Some states have laws establishing limits on first
aid given by the lay person. Trained employees should understand where first aid ends and
professional medical treatment begins.
Additionally, OSHA's Medical Services and First Aid Standard (29 CFR 1910.151) for general
industry require that the areas where workers may be exposed to splashes of corrosive materials
should have facilities for flushing the chemicals out of eyes and from the body. If a decontamination
line has been set up, it may provide the protection needed. Otherwise, additional facilities will be
needed. For example, eyewashes and drench showers (Figure 5) may be necessary in such areas
as laboratories, solvent-dispensing areas, and battery recharging stations where harmful material may
be splashed in the eyes or on the skin. Such units can be hooked to a water line or may be portable
with a self-contained water supply. It is important to remove chemicals from the body immediately
even if protective clothing is worn because the clothing does not stop penetration or permeation of
all chemicals.
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FIGURES
COMBINATION DRENCH SHOWER AND EYEWASH
Source: "Occupational Safety and Health in Vocational Education". (NIOSH, 1979) page 97.
Hazard Recognition
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REFERENCES
American Red Cross, Standard Safety First Aid and Personal Safety, Doubleday and Co., Inc.,
Garden City, NY, 1979.
Doull, John, et. al., Toxicology: The Basic Science of Poisons, MacMillan Publishing Co., Inc.,
New York, NY, 1980.
Dreisbach, Robert H., Handbook of Poisoning, Lange Medical Publications, Los Altos, CA, 1980.
Guthrie, Rugus K., Food Sanitation, Avi Publishing Co., Inc., Westport, CT, 1972.
Industrial Commission of Ohio - Division of Safety and Hygiene, Safety in the Manual Handling of
Materials, Columbus, OH, 1974.
Justrite Manufacturing Co., How to Handle Flammable Liquids Safely, Des Plaines, IL, 1977.
National Fire Protection Association, National Electrical Code, Boston, MA, 1981.
National Safety Council, Accident Prevention Manual for Industrial Operations, 7th Edition,
Chicago, IL, 1974.
Proctor, Nick H., and James P. Hughes, Chemical Hazards of the Workplace, J. B. Lippincott Co.,
Philadelphia, PA, 1978.
Smith, Alice Lorraine, Principles of Microbiology, C. V. Mosby Co., St. Louis, MO, 1973.
U.S. Department of Health, Education, and Welfare - National Institute for Occupational Safety and
Health, Working Safely with Flammable and Combustible Liquids", Publication No. 78-206,
Cincinnati, OH, 1978.
U.S. Department of Health and Human Services - National Institute for Occupational Safety and
Health, Occupational Safety and Health in Vocational Education: A Guide for Administrators,
Faculty, and Staff, Publication No. 79-138, Cincinnati, OH, 1979.
U.S. Department of Labor - Occupational Safety and Health Administration, Construction Industry
Standards 29 CFR 1926, Washington, DC, 1980.
U.S. Department of Labor - Occupational Safety and Health Administration, General Industry
Standards 29 CFR 1910, Washington, DC, 1977.
U.S. Department of Labor - Occupational Safety and Health Administration, Noise Control - A Guide
for Workers and Employers, OSHA Publication No. 3048, Washington, DC, 1980.
U.S. Department of Labor - Occupational Safety and Health Administration, The Principles and
Techniques of Mechanical Guarding, OSHA Publication No. 2057, Washington, DC, 1973.
6/93 27 Hazard Recognition
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U.S. Department of Health, Education, and Welfare - National Institute for Occupational Safety and
Health, Criteria for a Recommended Standard: Working in Confined Spaces, Publication No. 80-
106, Washington, DC, 1979.
U.S. Department of Health and Human Services - National Institute for Occupational Safety and
Health, Alert - Request for Assistance in Preventing Occupational Fatalities in Confined Spaces,
Publication No. 86-110, Cincinnati, OH, 1986.
U.S. Department of Health and Human Services - National Institute for Occupational Safety and
Health, A Guide to Safety in Confined Spaces, Publication No. 87-113, Morgantown, WV, 1987.
Hazard Recognition 28 6/93
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AIR MONITORING INSTRUMENTS
Airborne contaminants can present a significant threat to human health. Identifying and quantifying
these contaminants by air monitoring are essential components of a health and safety program at a
hazardous waste site. Air monitoring data is useful for:
• Assessing the health risks to the public and response workers.
• Selecting personal protective equipment.
• Delineating areas where protection is needed.
• Determining actual or potential effects on the environment.
• Selecting actions to mitigate the hazards safely and effectively.
Direct-reading instruments were developed as early warning devices for use in industrial settings,
where leaks or an accident could release a high concentration of a known chemical. Today, some
direct-reading instruments can detect low concentrations of contaminants as little as one part
contaminant per million parts of air (ppm). Direct-reading instruments provide information at the
time of sampling and do not require sending samples to a laboratory for subsequent analysis. This
characteristic of direct-reading instruments enables rapid decision-making.
Characteristics of Air Monitoring Instruments
To be useful air monitoring instruments must be:
• Portable and rugged.
• Easy to operate.
• Able to generate reliable and useful results.
• Inherently safe.
Portability. A prime consideration for field instruments is portability. Transportation shock
resulting from the movement from one place to another, together with unintentional abuse, shortens
the usable life of an instrument. To reduce the effects of this trauma, instruments should be selected
that have reinforced shells or frames, shock-mounted electronic packages, or padded containers for
shipment.
Exposure to the elements and to the test atmosphere itself is of concern for those instruments
repeatedly used in adverse conditions or as long-term monitors. Anodized or coated finishes,
weather resistant packaging and remote sensors are effective in reducing downtime and increasing
portability.
5/pj 1 Air Monitoring Instruments
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An internal power supply is important for portability. Some instruments use replaceable or
rechargeable batteries and some do not require a power supply.
An instrument should not be so heavy or bulky that it is difficult for a response worker to carry.
Ease Of Operation. Because many of these instruments were designed for industrial use,
allowances may not have been made for using the instrument while wearing protective equipment.
One must consider how easy it is to use the instrument while wearing gloves or how difficult it is
to read the meter while wearing a respirator. Also, how quickly a worker can learn to operate the
instrument correctly should be considered.
Preparation time for use of the instrument should be short. Rapid warm-up, easy attachment of
accessories, and quick instrument checks shorten preparation time.
Reliable and Useful Results. The response time, sensitivity, selectivity, accuracy and precision of
an instrument are important in evaluating the reliability and usefulness of the data the instrument
generates.
Response time, the interval between an instrument "sensing" a contaminant and generating data, is
important to producing reliable and useful results in the field. Response time depends on: test(s) to
be performed, dead time between sample periods (the time for analysis, data generation, and data
display), and the sensitivity of the instrument. Response times for direct-reading instruments may
range from a few seconds to several minutes.
Sensitivity is important when slight concentration changes can be dangerous. Sensitivity is defined
as the ability of an instrument to accurately measure changes in concentration. Sensitive instruments
can detect small changes in concentration. The lower detection limit is the lowest concentration to
which instrument will respond to. The operating range is the lower and upper use limits of the
instrument. It is defined by the lower detection limit at one end and the saturation concentration at
the other end. It is important to use an instrument with an operating range that will accurately
measure the concentration in the range of concern.
Amplification, a term often used synonymously (and incorrectly) with sensitivity, is the instrument's
ability to increase very small electronic signals emanating from the detector to the readout.
Changing the amplification of the detector does not change its sensitivity. However, it may be useful
in calibration. Instruments with amplifier circuits can be affected by radio frequency from pulsed
DC or AC power lines, transformers, generators, and radio wave transmitters.
Accuracy is defined as the relationship between a true value and the instrument reading. Precision
is the indication of the reproducability. These factors can be indicated by the error factor. For
example, some detector tubes may have an error factor of ±35% of the true value; meaning the
actual concentration of the chemical being measured is within a range of 35% higher and lower than
the tube reading.
Selectivity is the ability of an instrument to detect and measure a specific chemical or group of
similar chemicals. Additionally, selectivity is dependent upon interfering compounds which may
produce a similar response. Selectivity and sensitivity must be reviewed and interpreted together.
Interferences can affect the accuracy of the instrument reading.
Air Monitoring Instruments 2 6/93
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Another consideration is that the instrument must give results that are immediately useful.
Instruments should be direct reading, with little or no need to interpolate, integrate, or compile large
amounts of data.
When selecting an instrument, compare the desired sensitivity, range, accuracy, selectivity, and
ability to vary amplification of detector signals with the available instrument characteristics.
Inherent Safety. The portable instrumentation used to characterize hazardous material spills or
waste sites must be safe to use. Electrical devices, including instruments, must be constructed in
such a fashion as to prevent the ignition of a combustible atmosphere. The sources of this ignition
could be: an arc generated by the power source itself or the associated electronics, or a flame or
heat source necessary for function of the instrument. Several engineering, insurance, and safety
organizations have standardized test methods, established inclusive definitions, and developed codes
for testing electrical devices used in hazardous locations. The National Fire Protection Association
(NFPA) has created minimum standards in its National Electrical Code (NEC) published every 3
years. This code spells out types of areas in which hazardous atmospheres can be generated and the
types of materials that generate these atmospheres, and design safeguards acceptable for use in
hazardous atmospheres.
Hazardous Atmospheres
Depending upon the response worker's background, the term "hazardous atmosphere" conjures up
situations ranging from toxic air contaminants to flammable atmospheres. For NEC purposes, an
atmosphere is hazardous if it meets the following criteria:
• It is a mixture of any flammable material in air whose concentration is within the
material's flammable range (i.e., between the material's lower flammable limit and
its upper flammable limit).
• There is the potential for an ignition source to be present.
• The resulting exothermic reaction could propagate beyond where it started.
To adequately describe hazardous atmospheres, the NEC categories them according to their Class,
Group, and Division.
Class and Group
Class is a category describing the type of flammable material that produces the hazardous
atmosphere:
• Class I is flammable vapors and gases, such as gasoline and hydrogen. Class I is
further divided into groups A, B, C, and D on the basis of similar flammability
characteristics (Table 1).
67P3 3 Air Monitoring Instruments
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• Class II consists of combustible dusts like coal or grain and is divided into groups E,
F, and G (Table 2).
• Class III is ignitable fibers such as produced by cotton milling.
TABLE 1
SELECTED CLASS I CHEMICALS BY GROUPS
Group A Atmospheres
acetylene
Group B Atmospheres (not sealed in conduit 1/2 inch or larger)
1,3-butadiene
ethylene oxide
formaldehyde (gas)
hydrogen
manufactured gas (containing greater than 30% H2 by volume)
propylene oxide
propyl nitrate
allyl glycidyl ether
n-butyl glycidyl ether
Group C Atmospheres (selected chemicals)
acetaldehyde
carbon monoxide
crotonaldehyde
dicyclopentadiene
diethyl ether
ethylene glycol
monoethyl ether acetate
methylacetylene
epichlorohydrin
ethylene
ethyl mercaptan
hydrogen cyanide
hydrogen selenide
hydrogen sulfide
dimethylamine
nitropropane
tetrahydrofuran
triethylamine
ethylene glycol
monoethyl ether
furfural
chloroacetaldehyde
tetramethyl lead
(39 others)
Group D Atmospheres (selected chemicals)
acetone
methanol
ammonia
propane
chlorobenzene
methane
acrylonitrile
naphtha
butane
vinyl chloride
acetonitrile
methyl ethyl ketone
benzene
styrene
Source: Classification of Gases. Vapors, and Dusts for Electrical Equipment in Hazardous (classified} Locations. 1986.
National Fire Protection Association ANSI/NFPA 497M.
Air Monitoring Instruments
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Division
Division is the term describing the "location" of generation and release of the flammable
material.
• Division 1 is a location where the generation and release are continuous, intermittent,
or periodic into an open, unconfmed area under normal conditions.
• Division 2 is a location where the generation and release are only from ruptures,
leaks or other failures from closed systems or containers.
A hazardous atmosphere can be routinely and adequately defined. As an example, an abandoned
waste site containing intact closed drums of methyl ethyl ketone, toluene and xylene would be
considered a Class I, Division 2, Group D environment. However, when transferring of the
flammable liquids takes place at the site, or if releases of flammable gases/vapors is considered
normal, the areas would be considered Class I, Division 1.
TABLE 2
SELECTED CLASS II CHEMICALS BY GROUPS
Group E Conductive Dusts
Atmospheres containing metal dusts, including aluminum, magnesium, and their
commercial alloys, and other metals of similarly hazardous characteristics.
Group F Semivolatile Dusts
Atmospheres containing carbonaceous dusts such as: charcoal, carbon black, coal or
coke dust with more than 8% volatile material.
Group G Nonconductive Dusts
Atmospheres containing flour, starch, grain, chemical thermoplastic, thermosetting
and molding compounds.
Source: Classification of Gases. Vapors, and Dusts for Electrical Equipment in Hazardous
(classified] Locations. 1986, National Fire Protection Association ANSI/NFPA 497M.
Instrument Controls
The following three methods of construction exist to prevent a potential source from igniting a
flammable atmosphere:
• Explosion-proof: Explosion-proof instruments allow the flammable atmosphere to
enter. If an arc is generated, the ensuing explosion is contained within the specially
built enclosure. Within it, any flames or hot gases are cooled prior to exiting into
6/93 5 Air Monitoring Instruments
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the ambient flammable atmosphere so that the explosion does not spread into the
environment.
Intrinsically Safe: The potential for arcing among components is reduced by
encasing them in a solid insulating material. Also, reducing the instrument's
operational current and voltage below the energy level necessary for ignition of the
flammable atmosphere provides protection. An "intrinsically safe" device, as defined
by the National Electrical Code, is incapable "of releasing sufficient electrical or
thermal energy under normal or abnormal conditions to cause ignition of a specific
hazardous atmospheric mixture in its most easily ignited concentration. Abnormal
conditions shall include accidental damage to any wiring, failure of electrical
components, application of over-voltage, adjustment and maintenance operations and
other similar conditions."
Purged: The arcing or flame-producing device is buffered from the flammable
atmosphere with an inert gas. In a pressurized or "purged" system, a steady stream
of, nitrogen or helium is passed by the potential arcing device, keeping the flammable
atmosphere from the ignition source. This type of control, however, does not
satisfactorily control analytical devices that use flame or heat for analysis, such as a
combustible gas indicator (CGI). It also requires a source of gas which would reduce
instrument portability.
Certification
A device, certified as explosion-proof, intrinsically safe, or purged for a given Class, Division, and
Group, which is used, maintained, and serviced according to the manufacturer's instructions, will
not contribute to ignition. The device is not, however, certified for use in atmospheres other than
those indicated. All certified devices must be marked to show Class, Division, and Group
(Figure 1). Any manufacturer wishing to have an electrical device certified must submit a prototype
to a laboratory for testing. If the unit passes, it is certified as submitted. However, the
manufacturer agrees to allow the testing laboratory to randomly check the manufacturing plant at any
time, as well as any marketed units. Furthermore, any change in the unit requires the manufacturer
to notify the test laboratory, which can continue the certification or withdraw it until the modified
unit can be retested. NFPA does not do certification testing. Testing is done by such organizations
as Underwriters' Laboratory Inc. (UL) or Factory Mutual Research Corp. (FM). Currently, these
are the only two testing labs recognized by OSHA.
To ensure personnel safety, it is recommended that only approved instruments be used on-site and
only in atmospheres for which they have been certified. When investigating incidents involving
unknown hazards, the monitoring instruments should be rated for use in the most hazardous
locations.
The following points will assist in selection of equipment that will not contribute to ignition of a
hazardous atmosphere:
• The mention of a certifying group in the manufacturer's equipment literature does not
guarantee certification.
Air Monitoring Instruments 5 6/93
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Some organizations test and certify instruments for locations different from the NEC
classification. The Mine Safety and Health Administration (MSHA) tests instruments
only for use in methane-air atmospheres and in atmospheres containing coal dust.
In an area designated Division 1, there is a greater probability of generating a
hazardous atmosphere than in Division 2. Therefore, the test protocols for Division
1 certification are more stringent than those for Division 2. Thus a device approved
for Division 1 is also permitted for use in Division 2, but not vice versa. For most
response work this means that devices approved for Class I (vapors, gases), Division
1 (areas of ignitable concentrations), Groups A, B, C, D should be chosen whenever
possible. At a minimum, an instrument should be approved for use in Division 2
locations.
There are so many Groups, Classes, and Divisions that it is impossible to certify an
all-inclusive instrument. Therefore, select a certified device based on the chemicals
and conditions most likely to be encountered. For example, a device certified for a
Class II, Division 1, Group E (combustible metal dust) would offer little protection
around a flammable vapor or gas.
1
flfll=7±l
Combustible Gas
.«,.«™i mode, 2
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tnliiniicillr Silf lor ait In huirdovi
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6. C. »nd D «hin vied -ilh MSA C
MUST BE OPERATED IN ACCORDAI
MPO. BY
MINE SAFETY APPLIAN
PITTSBURGH. PENNSriVAN
VIM TV 1 US FAT HO l.OII. Ml MUM
and 02 Alarm
60 part no. 449900
Pen Lane
locilioni Clill 1. Oivitlon |.
in Cltn 1. Qivmon 2. Ciaupt A
• ncry. Pin no '57839.
*CE WITH INSTRUCTIONS
^S COMPANY
A. U S A. 15208
0 II CANADA Illl 11131}
FIGURE 1
CERTIFICATION LABEL FROM MSA MODEL 260
COMBUSTIBLE GAS AND O2 INDICATOR
6/93
Air Monitoring Instruments
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Calibration and Relative Response
For an instrument to function properly in the field, it should be calibrated prior to use. Calibration
is the process of adjusting the instrument readout so that it corresponds to the actual concentration.
Calibration involves checking the instrument results with a known concentration of a gas or vapor
to see that the instrument gives the proper response. For example, if a combustible gas meter is
calibrated with a gas that is 20% of the lower explosive limit (LEL), then the instrument should read
20% of the LEL. If it does not read accurately, it is out of calibration and should be adjusted until
accurate readings are obtained. Although an instrument is calibrated to give a one-to-one response
for a specific chemical (the calibration gas), its response to other chemicals may be different. This
variability is called relative response. A combustible gas indicator calibrated to pentane will give
a higher instrument reading for methane than the actual concentration (Table 3).
The relative response of an instrument to different chemicals can be calculated by dividing the
instrument reading by the actual concentration and is expressed as a ratio or a percent. Note that
for the calibration standard the relative response should be 1.00 or 100%.
If the instrument is being used for a chemical that is not the calibration standard, then it may be
possible to look at the manufacturer's information to get the relative response of that instrument for
the chemical. Then the actual concentration can be calculated. For example, if the instrument's
relative response for xylene is 0.27 (27%) and the reading is 100 ppm (parts per million), then the
actual concentration is 370 ppm (.27 x actual concentration = 100 ppm, then actual concentration
= 100/.27 = 370 ppm). If there is no relative response data for the chemical in question, it may
be possible to recalibrate the instrument. If the instrument has adjustable settings and a known
concentration is available, the instrument may be adjusted to read directly for the chemical. As
recalibration takes time, this is usually done only if the instrument is going to be used for many
measurements of the special chemical.
TABLE 3
RELATIVE RESPONSE FOR A COMBUSTIBLE GAS
INDICATOR CALIBRATED TO PENTANE
Chemical
Methane
Acetylene
Pentane
1 ,4-Dioxane
Xylene
Concentration
(% LEL)
50
50
50
50
50
Meter Response
(% LEL)
85
60
53
37
27
Relative
Response
170%
120%
106%
74%
54%
Source: Portable Gas Indicator. Model 250 & 260. Response Curves. Mine Safety Appliances
Company, Pittsburgh, PA.
Air Monitoring Instruments
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TYPES OF DIRECT-READING INSTRUMENTS
Many hazards may be present when responding to hazardous materials spills or uncontrolled waste
sites. There are several types of instrumentation for detecting hazardous atmospheres. These are
commonly referred to as oxygen indicators, combustible gas indicators, and toxic atmosphere
monitors.
Oxygen Indicators
Oxygen indicators are used to evaluate an atmosphere for the following:
• Oxygen content for respiratory purposes. Normal air is 20.9% oxygen. Generally,
if the oxygen content decreases below 19.5% it is considered oxygen deficient and
special respiratory protection is needed.
• Increased risk of combustion. Generally, concentrations above 25% are considered
oxygen-enriched and increase the risk of combustion.
• Use of other instruments. Some instruments require sufficient oxygen for operation.
For example, some combustible gas indicators do not give reliable results at oxygen
concentrations below 10%. Also, the inherent safety approvals for instruments are
for normal atmospheres and not for oxygen enriched ones.
• Presence of contaminants. A decrease in oxygen content can be due to the
consumption (by combustion or a reaction such as rusting) of oxygen or the
displacement of air by a chemical. If it is due to consumption then the concern is the
lack of oxygen. If it is due to displacement then there is something present that could
be flammable or toxic.
Oxygen-deficient atmospheres may occur in unventilated areas or may be due to terrain variations
in cases where heavier than air vapors may collect. Most indicators have meters which display the
oxygen concentration from 0-25%. There are also oxygen indicators available which measure
concentrations from 0-5% and 0-100%. The most useful range for response is the 0-25% oxygen
content readout since decisions involving air-supplying respirators and the use of combustible gas
indicators fall into this range.
Many instrument manufacturers make oxygen meters. They can be small hand-held units with or
without pumps to draw the sample across the detector cell. Some pumps are single aspirating (hand-
squeeze) bulbs, others are battery powered diaphragm pumps. Units that combine 02 meters and
combustible gas indicators into one instrument are available from a number of manufacturers. Also,
flashing and audible alarms can be found on many instruments. These alarms go off at a preset
oxygen concentration to alert the users even if they are not watching the meter.
Principle of Operation. Oxygen indicators have two principle components for operation. These
are the oxygen sensor and the meter readout. In some units air is drawn into the oxygen detector
with an aspirator bulb or pump; in other units, the ambient air is allowed to diffuse to the sensor.
6/93 9 Air Monitoring Instruments
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The oxygen detector uses an electrochemical sensor to determine the oxygen concentration in air.
A typical sensor consists of: two electrodes; a housing containing a basic electrolytic solution; and
a semipermeable Teflon membrane (Figure 2).
Oxygen molecules (02) diffuse through the membrane into the solution. Reactions between the
oxygen, the solution and the electrodes produce a minute electric current proportional to the oxygen
content. The current passes through the electronic circuit. The resulting signal is shown as a needle
deflection on a meter or digital reading.
Limitations and Considerations. The operation of oxygen meters depends on the absolute
atmospheric pressure. The concentration of natural oxygen (to differentiate it from manufactured
or generated oxygen) is a function of the atmospheric pressure at a given altitude. While the actual
percentage of oxygen does not change with altitude, at sea level the weight of the atmosphere above
is greater, and more O2 molecules (and the other components of air) are compressed into a given
volume than at higher elevations. As elevation increases, this compression decreases, resulting in
fewer air molecules being "squeezed" into a given volume. Consequently, an 02 indicator calibrated
at sea level and operated at an altitude of several thousand feet will falsely indicate an oxygen
deficient atmosphere because less oxygen is being "pushed" into the sensor. Therefore, it is
necessary to calibrate at the altitude the instrument is used.
High concentrations of carbon dioxide (CO2) shorten the useful life of the oxygen sensor. As a
general rule, the unit can be used in atmospheres greater than 0.5% CO2 only with frequent replacing
or rejuvenating of the sensor. Lifetime in a normal atmosphere (0.04% CO2) can be from one week
to one year depending on the manufacturer's design.
Temperature can affect the response of oxygen indicators. The normal operating range for them is
between 32°F and 120°F. Between 0°F and 32°F the response of the unit is slower. Below 0°F the
sensor may be damaged by the solution freezing. The instrument should be calibrated at the tem-
perature at which it will be used.
Strong oxidizing chemicals, like ozone and chlorine, can cause increased readings and indicate high
or normal O2 content when the actual content is normal or even low.
Air Monitoring Instruments \Q 6/93
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thermistor
020202 02 02
Protective Disk
. Telfon Membrane
Au Electrode
KOH
Pb Electrode
FIGURE 2
SCHEMATIC OF OXYGEN SENSOR
Selection from Product Literature. Rexnard Electronic Products Division. Biomarine Oxygen Sensor.
by Rexnard, Inc., reprinted with permission of publisher.
Combustible Atmosphere Indicators
Combustible gas indicators (CGIs) measure the concentration of a flammable vapor or gas in air,
indicating the results as a percentage of the lower explosive limit (LEL) of the calibration gas.
The LEL (or LFL, lower flammable limit) of a combustible gas or vapor is the minimum
concentration of the material in air which will propagate flame on contact with an ignition source.
The upper explosive limit (UEL) is the maximum concentration. Above the UEL, the mixture is too
"rich" to support combustion so ignition is not possible. Below the LEL there is insufficient fuel
to support combustion. Concentrations between the LEL and the UEL are considered flammable.
CGIs are available in many styles and configurations. AH units have some type of pump to draw
'the air sample into the detector. The pumps are either hand operated square bulbs or automatic
(battery-powered) diaphragm types. Many units are "combination meters". This means they have
an 02 meter and CGI (and sometimes one or two specific gas indicators) combined in the same
instrument. Flashing and audible alarms are options on many units. The alarms go off at a preset
concentration to warn the instrument operator of potentially hazardous concentrations. Other options
such as larger sampling lines, moisture traps, and dust filters are also available.
6/93
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Air Monitoring Instruments
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Principle of Operation. Combustible gas indicators use a combustion chamber containing a filament
that combusts the flammable gas. To facilitate combustion the filament is heated or is coated with
a catalyst (like platinum or palladium), or both. The filament is part of a balanced resistor circuit
called a Wheatstone Bridge. The hot filament combusts the gas on the immediate surface of the
element, thus raising the temperature of the filament. As the temperature of the filament increases
so does its resistance. This change in resistance causes an imbalance in the Wheatstone Bridge.
This is measured as the ratio of combustible vapor present compared to the total required to reach
the LEL. For example, if the meter reads 0.5 (or 50%, depending upon the readout), this means
that 50% of the concentration of combustible gas needed to reach a flammable or combustible
situation is present. If the LEL for the gas is 5% then the meter indicates that a 2.5% concentration
is present. Thus, the typical meter readout indicates concentration up to the LEL of the gas
(Figure 3a).
If a concentration greater than LEL and lower than the UEL is present, then the meter needle will
stay beyond the 1.0 (100%) level on the meter (Figure 3b). This indicates that the ambient
atmosphere is readily combustible. When the atmosphere has a gas concentration above the UEL
the meter needle will usually rise above the 1.0 (100%) mark and then return to zero. (Figure 3c)
This occurs because the gas mixture in the combustion cell is too rich to burn. This permits the
filament to conduct a current just as if the atmosphere contained no combustibles at all. Some
instruments have a lock mechanism that prevents the needle from returning to zero when it has
reached 100% and must be reset in an atmosphere below the LEL.
Limitations and Considerations. The response of the instrument is temperature dependent. If the
temperature at which the instrument is zeroed differs from the sample temperature, the accuracy
of the reading is affected. Hotter temperatures raise the temperature of the filament and produce a
higher than actual reading. Cooler temperatures will reduce the reading. It works best to calibrate
and zero the instrument at the sample temperature.
The instruments are intended for use only in normal oxygen atmospheres. Oxygen-deficient
atmospheres will produce lowered readings. Also the safety guards that prevent the combustion
source from igniting a flammable atmosphere are not designed to operate in an oxygen-enriched
atmosphere.
Organic lead vapors (e.g., gasoline vapors), sulfur compounds, and silicone compounds will foul the
filament. Acid gases (e.g., hydrogen chloride and hydrogen fluoride) can corrode the filament.
Most units have an optional filter that protects the sensor from leaded vapors.
There is no differentiation between petroleum vapors and combustible gases. If the flammability of
the combined vapors and gases in an atmosphere is the concern this is not a problem. However, if
the instrument is being used to detect the presence of a released flammable liquid - like gasoline -
in a sewer system where methane may be present, the operator can not tell if the reading is the
contaminant or the methane. A pre-filter can be used to remove the vapors but will not remove the
methane. Thus, if readings are made with and without the filter, the user can compare the readings
and can conclude that differences in the values indicate that a petroleum vapor (i.e., the contaminant)
is present.
Air Monitoring Instruments \i 6/93
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% LEL
Lower than
the LEL
% LEL
Between the
LEL and UEL
% LEL
Above the
UEL
FIGURES
COMPARISON OF METER READINGS TO
COMBUSTIBLE GAS CONCENTRATIONS
Toxic Atmosphere Monitors
Along with oxygen concentration and flammable gases or vapors, there is a concern about chemicals
present at toxic concentrations.
This usually involves measurements at concentrations lower than would be indicated by oxygen
indicators or combustible gas indicators. There is a need to determine if toxic chemicals are present
6/93
13
Air Monitoring Instruments
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and identify them so the environmental concentration can be compared to exposure guidelines. Toxic
atmosphere monitoring is done to:
• Identify airborne concentrations that could pose a toxic risk to response workers and
the public.
• Evaluate the need for and type of personal protective equipment.
• Set up work zones or areas where contaminants are or are not present.
There are several different groups of instruments that can be used for these functions.
Colorimetric Indicator Tubes (Detector Tubes)
Principle of Operation. Colorimetric indicator tubes consist of a glass tube impregnated with an
indicating chemical (Figure 4). The tube is connected to a piston- or bellows- type pump. A known
volume of contaminated air is pulled at a predetermined rate through the tube by the pump. The
contaminant reacts with the indicator chemical in the tube, producing a change in color whose length
is proportional to the contaminant concentration.
Detector tubes are normally chemical specific. There are different tubes for different gases; for
example, chlorine detector tube for chlorine gas, acrylonitrile tube for acrylonitrile gas, etc. Some
manufacturers do produce tubes for groups of gases, e.g., aromatic hydrocarbons, alcohols.
Concentration ranges on the tubes may be in the ppm or percent range. A preconditioning filter may
precede the indicating chemical to:
• Remove contaminants (other than the one in question) that may interfere with the
measurement. Many have a prefilter for removing humidity.
• React with a contaminant to change it into a compound that reacts with the indicating
chemical.
Hazmat kits are available from at least two manufacturers. These kits identify or classify the
contaminants as a member of a chemical group such as acid gas, halogenated hydrocarbon, etc. This
is done by sampling with certain combinations of tubes at the same time by using a special multiple
tube holder or by using tubes in a specific sampling sequence. Detector tube manufacturers are listed
at the end of this manual section.
Air Monitoring Instruments 14 6/93
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Plug
Glass Tube
10 20 30
Pre-filter
Plug
Indicating Chemical
FIGURE 4
DIRECT-READING COLORIMETRIC
INDICATOR TUBE
Limitations and Considerations. Detector tubes have the disadvantage of poor accuracy and
precision. In the past, the National Institute for Occupational Safety and Health (NIOSH) tested and
certified detector tubes that were submitted to them. For the tubes they tested they certified the
accuracy to be ±35% at concentrations at one-half the OSHA Permissible Exposure Limit (PEL) and
±25% at 1-5 times the PEL. NIOSH has discontinued testing and certification. Special studies
have reported error factors of 50% and higher for some tubes.
The chemical reactions involved in the use of the tubes are affected by temperature. Cold weather
slows the reactions and thus the response time. To reduce this problem it is recommended that the
tubes be kept warm (for example, inside a coat pocket) until they are used if the measurement is
done in cold weather. Hot temperatures increase the reaction and can cause a problem by discoloring
the indicator when a contaminant is not present. This can happen even in unopened tubes.
Therefore, the tubes should be stored at a moderate temperature or even refrigerated during storage.
Some tubes do not have a prefilter to remove humidity and may be affected by high humidity. The
manufacturer's instructions usually indicate if humidity is a problem and list any correction factors
to use if the tube is affected by humidity.
The chemical used in the tubes deteriorates over time. Thus the tubes are assigned a shelf life. This
varies from 1-3 years. Shelf life can be extended by refrigeration, but the tube should equilibrate
to ambient temperature before use.
6/93
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An advantage that detector tubes have over some other instruments is that it is possible to select a
tube that is specific to a chemical. However, some tubes will respond to interfering compounds.
Fortunately, the manufacturers provide information with the tubes on interfering gases and vapors.
Interpretation of results can be a problem. Since the tube's length of color change indicates the
contaminant concentration, the user must be able to see the end of the stain. Some stains are
diffused and are not clear cut; others may have an uneven endpoint. When in doubt use the highest
value that would be obtained from reading the different aspects of the tube.
The total volume to be drawn through the tube varies with the tubes. The volume needed is given
as the number of pump strokes needed, i.e., the number of times the piston or bellows is
manipulated. Also, the air does not instantaneously go through the tube. It may take 1 to 2 minutes
for each volume (stroke) to be completely drawn. Therefore, sampling times can vary from 1 to 30
minutes per tube. This can make the use of detector tubes time consuming.
Because of these many considerations, it is very important to read the instructions that are provided
with and are specific to a set of tubes. The information includes the number of pump strokes
needed, time for each pump stroke, interfering gases and vapors, effects of humidity and
temperature, shelf life, proper color change, and whether the tube is reusable.
While there are many limitations and considerations for using detector tubes, detector tubes allow
the versatility of being able to measure a wide range of chemicals with a single pump. Also, there
are some chemicals for which detector tubes are the only direct-reading indicators.
Specific Chemical Monitors
There are several gas monitors that use electrochemical cells or metal oxide semiconductors (MOS)
for detecting specific chemicals. MOS detectors change conductivity when exposed to certain gases
or vapors. They can be designed to respond to a large group of chemicals or to a specific chemical.
The most common monitors are used to detect carbon monoxide or hydrogen sulfide, but there are
also monitors available for hydrogen cyanide, ammonia, and chlorine. They are more accurate than
detector tubes but there are only about a dozen different chemicals they can monitor.
Photoionization Detectors
These instruments detect concentrations of gases and vapors in air by utilizing an ultraviolet light
source to ionize the airborne contaminant. Once the gas or vapor is ionized in the instrument, it can
be detected and measured.
Principle of Operation. All atoms and molecules are composed of particles: electrons, protons,
and neutrons. Electrons, negatively charged particles, rotate in orbit around the nucleus, the dense
inner core. The nucleus consists of an equal number of protons (positively charged particles) as
electrons found in the orbital cloud. The interaction of the oppositely charged particles and the laws
of quantum mechanics keep the electrons in orbits outside the nucleus.
Air Monitoring Instruments 16 6/93
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The energy required to remove the outermost electron from the molecule is called the ionization
potential (IP) and is specific for any compound or atomic species (Table 4). Ionization potentials
are measured in electron volts (eV). High frequency radiation (ultraviolet and above) is capable of
causing ionization and is hence called ionizing radiation. When a photon of ultraviolet radiation
strikes a chemical compound, it ionizes the molecule if the energy of the radiation is equal to or
greater than the IP of the compound. Since ions are charged particles, they may be collected on a
charged plate and produce a current. The measured current will be directly proportional to the
number of ionized molecules (Figure 5).
AMPLIFIER
/
METER
/
SAMPLE OUT
UV
LAMP
Jd
ELECTRODE
ELECTRODE
SAMPLE IN
FIGURES
DIAGRAM OF PHOTOIONIZATION DETECTOR
LAMP AND COLLECTING ELECTRODES
6/93
17
Air Monitoring Instruments
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The photoionization process can be illustrated as:
R + h -* R+ + e
where R is an organic or inorganic molecule and h represents a photon of UV light with
energy equal to or greater than the ionization potential of that particular chemical species.
R* is the ionized molecule.
PIDs use a fan or a pump to draw air into the detector of the instrument where the contaminants are
exposed to UV light and the resulting negatively charged particles (ions) are collected and measured.
TABLE 4
IONIZATION POTENTIALS OF SELECTED CHEMICALS
Chemical
Hydrogen cyanide
Carbon dioxide
Methane
Hydrogen chloride
Water
Oxygen
Chlorine
Propane
Hydrogen sulfide
Hexane
Ammonia
Vinyl chloride
Acetone
Benzene
Phenol
Ethyl amine
Ionization Potential (eV)
13.9
13.8
13.0
12.5
12.6
12.1
11.5
11.1
10.5
10.2
10.1
10.0
9.7
9.2
8.5
8.0
Limitations and Considerations. Because the ability to detect a chemical depends on the ability to
ionize it, the IP of a chemical to be detected must be compared to the energy generated by the UV
lamp of the instrument. As can be seen from Table 4, there is a limit imposed by the components
of air. That is, the lamp cannot be too energetic or oxygen and nitrogen will ionize and interfere
with the readings for contaminants. The energy of lamps available are 8.3, 8.4, 9.5, 10.2, 10.6,
10.9, 11.4, 11.7, and 11.8 eV. Not all lamps are available from a single manufacturer. One use
of the different lamps is for selective determination of chemicals. For example, if a spill of propane
and vinyl chloride were to be monitored with a PID, the first check would be to see whether they
could be detected. The IP of propane is 11.1 eV and the IP of vinyl chloride is 10.0 eV. To detect
both, a lamp with an energy greater than 11.1 eV is needed (e.g., 11.7 or 11.8). If vinyl chloride
was the chemical of concern, then a lamp with an energy greater than 10.0 but less than 11.1 (such
as 10.2 or 10.6) could be used.
The propane would neither be ionized nor detected. Thus, propane would not interfere with the
vinyl chloride readings. The sample drawn into the instrument passes over the lamp to be ionized.
Air Monitoring Instruments
18
6/93
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Dust in the atmosphere can collect on the lamp and block the transmission of UV light. This will
cause a reduction in instrument reading. This problem will be detected during calibration and the
lamp should be cleaned on a regular basis.
Humidity can cause two problems. When a cold instrument is taken into a warm moist atmosphere,
the moisture can condense on the lamp. Like dust this will reduce the available light. Moisture in
the air also reduces the ionization of chemicals and cause a reduction in readings.
Because an electric field is generated in the sample chamber of the instrument, radio-frequency
interference from pulsed DC or AC power lines, transformers, generators, and radio wave
transmission may produce an error in response.
As the lamp ages the intensity of the light decreases. It will still have the same ionization energy,
but the response will decline. This will be detected during calibration and adjustments can be made.
However, the lamp will eventually burn out.
Photoionization detectors are calibrated to a single chemical. The instrument's response to chemicals
other than the calibration gas/vapor can vary. Table 5 shows the relative responses of several
chemicals for a specific PID. In some cases, at high concentrations the instrument response can
decrease. While the response may be linear (i.e., 1 to 1 response) from 1 to 600 ppm for an
instrument, a concentration of 900 ppm may only give a meter response of 700.
Units that use photoionization include the HNU PI 101, the Photovac TIP, and the Thermo
Environmental Instrument's Model 580A.
TABLE 5
RELATIVE RESPONSES FOR SELECTED CHEMICALS USING
THE HNU MODEL PI 101 WITH 10.2 eV PROBE CALIBRATED TO BENZENE
Chemical
m-Xylene
Benzene
Phenol
Vinyl chloride
Acetone
Hexane
Phosphine
Ammonia
Relative Response
1.12
1.00
0.78
0.63
0.50
0.22
0.20
0.03
Source: Instruction Manual for Model PI 101. Portable Phntniomzation Anafaer. HNU Systems,
Inc., Newton, MA, 1986.
19 Air Monitoring Instruments
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HNU PI 101 Photoionization Detector
The HNU PI 101 consists of two modules connected via a single power cord (Figure 6):
• A readout unit consisting of a 4.5-inch analog meter, a rechargeable battery, and
power supplies for operation of the amplifier and the UV lamp.
• A sensor unit consisting of the UV light source, pump, ionization chamber, and a
preamplifier.
The unit has a separate sensor unit because the lamps available—8.3, 9.5, 10.2 (standard),
and 11.7 eV—require separate electronic circuits. To change the energy of ionization the
whole sensor or probe has to be switched and not just the lamp. Lamps are replaceable.
Photovac TIP (Total ionizables present)
The TIP has components similar to those of the HNU, but they are all contained in an 18-
and 2.5-inch diameter unit. The standard lamp is 10.6 eV, but it can easily be replaced with
an 8.4, 9.5, 10.2, or 11.7 eV lamp. A separate sensor is not used. The readout is digital
with a range of 0 to 2000. The instrument also has a replaceable dust filter to eliminate
collection on the lamp.
Thermo Environmental Instruments Model 580A
The Organic Vapor Meter (OVM) is 5 inches by 5 inches by 10 inches with a handle on top
and in the center. It can use any of four different lamps—9.5, 10.0,10.6 (standard), or 11.8
eV. The instrument has a digital readout with a range of 0 to 2000. It has a maximum hold
feature so that you can get two readings: the current concentration or the maximum
concentration during the survey. The meter has a lockout if the readout exceeds 2000 so that
high concentrations are not missed. It must be reset in an area of low concentrations. The
instrument has a microprocessor for assistance in calibration and lamp changing.
The unit also has connections and software for interfacing the unit with a personal computer
and a data logger for recording readings at coded locations so that the readings can be looked
at later or unloaded into a computer.
Photoionization detectors are also used in gas chromatographs made by Photovac, HNU and
Thermo Environmental Instruments. Gas chromatography will be discussed later in this
section.
Air Monitoring Instruments 20 6/93
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Readout Unit
Ion Chamber
y
Pump
\
Preamp
— SAMPLE
PROBE
FIGURE 6
PORTABLE PHOTOIONIZATION DETECTOR
Selectionfrom Instruction Manual for Model PI 101 Photoionization Detector, by HNU Systems, Inc.,
copyright 1975 by HNU Systems, Inc., reprinted with permission of publisher.
Flame lonization Detectors (FID)
These units use combustion as the means to ionize airborne contaminants. Once they are ionized,
they can be detected and measured.
Principle of Operation. Flame ionization detectors use a hydrogen flame as the means to ionize
organic (toxic) vapors. FID responds to virtually all organic compounds, that is, compounds that
contain carbon-hydrogen or carbon-carbon bonds. The flame detector analyzes by the mechanism
of breaking bonds as the following reaction indicates:
RH + 0 - RHO
e- - CO + H0
Inside the detector chamber, the sample is exposed to a hydrogen flame which ionizes the organic
vapors. When most organic vapors burn, positively charged carbon-containing ions are produced
which are collected by a negatively charged collecting electrode in the chamber. An electric field
exists between the conductors surrounding the flame and a collecting electrode. As the positive ions
are collected, a current proportional to the hydrocarbon concentration is generated on the input
6/93
21
Air Monitoring Instruments
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electrode. This current is measured with a preamplifier which has an output signal proportional to
the ionization current. A signal conducting amplifier is used to amplify the signal from the preamp
and to condition it for subsequent meter or external recorder display.
Flame ionization detectors have a more generalized response in detecting organic vapors. This
generalized sensitivity is due to the breaking of chemical bonds which require a set amount of energy
and is a known reproducible event. When this is compared to Photoionization (PID), a major
difference should be noted between the detectors. PID detection is dependent upon the ionization
potential (eV) and the ease in which an electron can be ionized (displaced) from a molecule. This
mechanism is variable, highly dependent on the individual characteristics of a particular substance.
This results in a more variable response factor for the vast majority of organics that are ionizable.
Therefore, in general, one does not see large sensitivity shifts between different substances when
using an FID as compared to a PID. Flame ionization detectors are the most sensitive for saturated
hydrocarbons, alkanes, and unsaturated hydrocarbons alkenes. Substances that contain substituted
functional groups such as hydroxide (OH~), and chloride (Cl~), tend to reduce the detector's
sensitivity; however, overall, the detectabilities remain good.
Companies that manufacture FIDs include Beckman Industrial, The Foxboro Company and Thermo
Environmental Instruments. The Foxboro Century Organic Vapor Analyzer (OVA) will be discussed
as an example later.
Limitations and Considerations. Flame ionization detectors respond only to organic compounds.
Thus, they do not detect inorganic compounds like chlorine, hydrogen cyanide, or ammonia.
As with all instruments, flame ionization detectors respond differently to different compounds.
Table 6 is a list of the relative responses of the Foxboro CENTURY OVA to some common organic
compounds. Since that instrument is factory calibrated to methane, all responses are relative to
methane and are given by percentage, with methane at 100%.
Thus with all survey-type instruments, the identity of the chemical of interest must be ascertained
before its concentration can be determined. However, the CENTURY OVA can be purchased as
a dual mode survey-gas chromatograph and can separate and define the components present in a gas
mixture. As with all instruments, individuals should be trained for best operation and performance.
Experience in gas chromatography is an important aspect to successful operation of the
chromatographic option.
Air Monitoring Instruments 22
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TABLE 6
RELATIVE RESPONSES FOR SELECTED CHEMICALS
USING THE OVA CALIBRATED TO METHANE
Compound
Relative Response
Methane
Ethane
Propane
n-Butane
n-Pentane
Ethylene
Acetylene
Benzene
Toluene
Acetone
Methyl ethyl ketone
Methyl isobutyl ketone
Methanol
Ethanol
Isopropyl alcohol
Carbon tetrachloride
Chloroform
Trichlorethylene
Vinyl chloride
100
90
64
61
100
85
200
150
120
100
80
100
15
25
65
10
70
72
35
Selection from Product Literature. The Foxboro Company, with permission of the Foxboro Company.
Foxboro Century Organic Vapor Analyzer (OVA}
The Foxboro CENTURY OVA consists of two major parts: (1) a 12-pound package
containing the sampling pump, battery pack, support electronics, flame ionization detector,
hydrogen gas cylinder, and an optional gas chromatography (GC) column and (2) a hand-held
meter/sampling probe assembly (Figure 7).
The OVA is generally calibrated to methane, but can be calibrated to the species of interest.
The OVA can operate in two modes:
Survey mode. During normal survey mode operation, a sample is drawn into the probe and
transmitted to the detector chamber by an internal pumping system. When the sample
reaches the FID it is ionized as described before and the resulting signal is translated on the
meter for direct-reading concentration as total organic vapors or recorded as a peak on a
chart. The meter display is an integral part of the probe/readout assembly and has a scale
from 0 to 10 which can be set to read 0-10, 0-100, or 0-1000 ppm.
Gas chromatography mode. Gas chromatography (GC) is a technique for separating
components of a sample and qualitatively and quantitatively identifying them. The sample
6/93
23
Air Monitoring Instruments
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to be separated is injected into a column packed with an inert solid. As the carrier gas (for
the OVA it is hydrogen) forces the sample through the column, the separate components of
the sample are retained on the column for different periods of time. The amount of time a
substance remains on the column, which is called its retention time, is a function of its
affinity for the column material, column length, column temperature, and flow rate of the
carrier gas. Under preset instrumental conditions, each component elutes from the column
at a different, but reproducible, length of time. Separate peaks are recorded for each
component by connecting the output of the detector to a strip chart recorder. This readout
is called a gas chromatogram (qualitative identification is made by measuring retention time).
Signal Processor Chart Recorder
^p^flf
^^®
^^y-^^'U-a
Detector
Meier fr
Sample
/ Sample Pump
FIGURE?
ORGANIC VAPOR ANALYZER SCHEMATIC
Selection from Product Literature. TheFoxboro Company, with permission of the Foxboro Company.
Retention time is the time that elapses between the injection of the compound into the column and
the elution of that compound as represented by a peak. Retention is expressed as a function of either
time, or the measured distance, between the injection point and the peak on the strip chart recorder.
Air Monitoring Instruments
24
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The unknown is tentatively identified if the retention time of an unknown chemical agrees with the
retention time of a chemical recorded under the same set of analytical conditions.
Also, the area under the peak is proportional to the concentration of the corresponding sample
component. Concentration of the sample components can be calculated by comparing these areas
to the areas of standards recorded under identical analytical conditions.
Catalytic Combustion Detectors
There are toxic monitors which use the same detection system as CGIs but are more sensitive. In
a sense they are super sensitive CGIs with readouts in ppm instead of %LEL. Since the detection
method is similar, they have the same limitations and considerations as CGIs.
Some of these instruments (e.g., the Bacharach TLV Sniffer), give only readings in parts per million
(ppm). There are combination units (e.g., Gastec Models 1238 and 1314) that give ppm readings
along with % LEL and oxygen readings.
Aerosol Monitors
Not all toxic materials dispersed in air are in the form of a gas or vapor. Solids and liquids can
become suspended in air by combustion, splashing liquids or by disturbing soil.
There are direct-reading instruments that measure aerosols, i.e., dust, mist, fume, smoke, fog, spray.
Most of them use a light source and a light sensor that measures the amount of light scattered by the
aerosol. Readouts are in milligrams per cubic meter (mg/m3). Some examples are MIE Incorporated
RAM-1 and MINIRAM and TSI Incorporated's Model 5150.
Other methods of detection are the piezoelectric crystal mass monitor and beta attenuation. The
piezoelectric crystal mass monitor uses a crystal that resonates at a certain frequency as electric
current is applied to it. As particles collect on the crystal its resonant frequency changes and the
change is measured. An instrument using this detector is TSI Incorporated's Model 3500.
Beta attenuation measures the attenuation of beta radiation by particles collected on a surface between
the beta source and a beta detector. GCA Corporation's Model RDM-101 is an instrument using this
type of detector.
Accessories for these types of instruments include (1) an attachment that only allows collection of
"respirable" particles (i.e., ones that collect in the lungs) instead of the total particles in air and (2)
integrators for giving average concentrations.
It is important to remember that these instruments give the total amount of paniculate and not the
type of paniculate. Individual content, e.g., lead or arsenic, must be analyzed separately. However,
if the content of the sample is known, then the direct-reading instrument could be used if content of
the dust is assumed to remain constant. For example, if the dust being detected is 5% lead and
1 % arsenic and the concentration of dust is 2 mg/m3 then the concentration of lead and arsenic are
25 Air Monitoring Instruments
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0.1 mg/m3 and 0.02 mg/m3 respectively (0.05 x 2 mg/m3 = 0.1 mg/m3 and 0.01 x 2 mg/m3 =
0.02 mg/m3).
Accessories/Options
As mentioned earlier, instruments combining more than one detector can be found. For examples,
"trimeters" and "quadmeters" combine an oxygen indicator, a combustible gas indicator, and one or
two toxic monitors. Also there are units with alarms that indicate readings that are above or below
a concentration of concern, strip chart (printed) outputs, and electronic outputs for data storage.
Some instruments have an integrator that averages concentrations while the instrument is operating
or over a specified time (e.g., IS minutes). This permits use of the instrument as a long-term
monitor as well as a direct-reading instrument.
One of the more recent additions is the microprocessor. This can be used with a gas chromatograph
so the microprocessor "reads" the output and compares it to calibration information in its memory.
That way the instrument instead of the operator qualifies and quantifies the chemicals. In some cases
the operator asks the microprocessor to check for a chemical and the unit uses its memory to match
retention time and peak height. Microsensor's Micromonitor, the Photovac 10S50, and the Sentex
Scentor use this capability. The main limitation with the microprocessors are the number of
chemicals in their memory or "library." What the microprocessor doesn't recognize, it can't
identify. Most portable units have libraries for up to 100 chemicals. Also the detection method
(PID, FID, etc.) used must be considered as that limits the number of chemicals that can be
identified.
Air Monitoring Instruments 26
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REFERENCES
American Conference of Governmental Industrial Hygienists. Air Sampling Instruments for
Evaluation of Atmospheric Contaminants. 6th Edition. 6500 Glenway Avenue, Building D-7,
Cincinnati, OH.
Cee, R.J., J.C. Septon, J.C. Ku, and T. Wilczek. An Evaluation of Commercial Detector Tube
Systems. Paper presented at American Industrial Hygiene Conference, Montreal, Canada, June 1987.
Clayton, G.D., and F.E. Clayton (ed.). Patty's Industrial Hygiene and Toxicology. 3rd review
edition, Volume I: General Principles. John Wiley and Sons, New York, NY, 1978.
Clayton, George D. (ed.). The Industrial Environment - Its Evaluation and Control. 3rd edition.
Public Health Services Publication, 1973.
Conley, Robert. InfraredSpectroscopy. 2nd edition. Allyn and Bacon, Inc., Boston, MA, 1972.
Klinsky, Joseph (ed.). Manual of Recommended Practice for Combustible Gas Indicators and
Portable Direct-Reading Hydrocarbon Detectors. 1st edition. American Industrial Hygiene
Association, Akron, OH, 1980.
National Fire Prevention Association. National Electrical Code. Volume 70. 470 Atlantic Ave.,
Boston, MA 02210, 1986.
27 Mr Monitoring Instruments
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TOXICOLOGY AND EXPOSURE GUIDELINES
"All substances are poisons; there is none which is not a poison. The right dose differentiates a
poison and a remedy."
This early observation concerning the toxicity of chemicals was made by Paracelsus (1493-1541).
The classic connotation of toxicology was "the science of poisons." Since that time, the science has
expanded to encompass several disciplines. Toxicology is the study of the interaction between
chemical agents and biological systems. While the subject of toxicology is quite complex, it is
necessary to understand the basic concepts in order to make logical decisions concerning the
protection of personnel from toxic injuries.
Toxicity can be defined as the relative ability of a substance to cause adverse effects in living
organisms. This "relative ability" is dependent upon several conditions. As Paracelsus suggests,
the quantity or the dose of the substance determines whether the effects of the chemical are toxic,
nontoxic or beneficial. In addition to dose, other factors may also influence the toxicity of the
compound such as the route of entry, duration and frequency of exposure, variations between
different species (interspecies) and variations among members of the same species (intraspecies).
To apply these principles to hazardous materials response, the routes by which chemicals enter the
human body will be considered first. Knowledge of these routes will support the selection of
persona! protective equipment and the development of safety plans. The second section deals with
dose-response relationships. Since dose-response information is available in toxicology and
chemistry reference books, it is useful to understand the relevance of these values to the
concentrations that are actually measured in the environment. The third section of this chapter
includes the effects of the duration and frequency of exposure, interspecies variation and intraspecies
variation on toxicity. Finally, toxic responses associated with chemical exposures are described
according to each organ system.
Routes of Exposure
There are four routes by which a substance can enter the body: inhalation, skin (or eye) absorption,
ingestion, and injection.
• Inhalation: For most chemicals in the form of vapors, gases, mists, or particulates,
inhalation is the major route of entry. Once inhaled, chemicals are either exhaled or
deposited in the respiratory tract. If deposited, damage can occur through direct
contact with tissue or the chemical may diffuse into the blood through the lung-blood
interface.
Upon contact with tissue in the upper respiratory tract or lungs, chemicals may cause
health effects ranging from simple irritation to severe tissue destruction. Substances
absorbed into the blood are circulated and distributed to organs which have an affinity
for that particular chemical. Health effects can then occur in the organs which are
sensitive to the toxicant.
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• Skin (or eye) absorption: Skin (dermal) contact can cause effects that are
relatively innocuous such as redness or mild dermatitis; more severe effects
include destruction of skin tissue or other debilitating conditions. Many
chemicals can also cross the skin barrier and be absorbed into the blood
system. Once absorbed, they may produce systemic damage to internal
organs. The eyes are particularly sensitive to chemicals. Even a short
exposure can cause severe effects to the eyes or the substance can be
absorbed through the eyes and be transported to other parts of the body
causing harmful effects.
• Ingestion: Chemicals that inadvertently get into the mouth and are swallowed
do not generally harm the gastrointestinal tract itself unless they are irritating
or corrosive. Chemicals that are insoluble in the fluids of the gastrointestinal
tract (stomach, small, and large intestines) are generally excreted. Others
that are soluble are absorbed through the lining of the gastrointestinal tract.
They are then transported by the blood to internal organs where they can
cause damage.
• Injection: Substances may enter the body if the skin is penetrated or
punctured by contaminated objects. Effects can then occur as the substance
is circulated in the blood and deposited in the target organs.
Once the chemical is absorbed into the body, three other processes are possible: metabolism,
storage, and excretion. Many chemicals are metabolized or transformed via chemical reactions in
the body. In some cases, chemicals are distributed and stored in specific organs. Storage may
reduce metabolism and therefore, increase the persistence of the chemicals in the body. The various
excretory mechanisms (exhaled breath, perspiration, urine, feces, or detoxification) rid the body,
over a period of time, of the chemical. For some chemicals elimination may be a matter of days or
months; for others, the elimination rate is so low that they may persist in the body for a lifetime and
cause deleterious effects.
The Dose-Response Relationship
In general, a given amount of a toxic agent will elicit a given type and intensity of response. The
dose-response relationship is a fundamental concept in toxicology and the basis for measurement of
the relative harmfulness of a chemical. A dose-response relationship is defined as a consistent
mathematical and biologically plausible correlation between the number of individuals responding and
a given dose over an exposure period.
Dose Terms. In toxicology, studies of the dose given to test organisms is expressed in terms of the
quantity administered:
• Quantity per unit mass (or weight). Usually expressed as milligram per kilogram
of body weight (mg/kg).
• Quantity per unit area of skin surface. Usually expressed as milligram per square
centimeter (mg/cm2).
Toxicology and Exposure Guidelines 2 6/93
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• Volume of substance in air per unit volume of air. Usually given as microliters
of vapor or gas per liter of air by volume (ppm). Particulates and gases are also
given as milligrams of material per cubic meter of air (mg/m3).
The period of time over which a dose has been administered is generally specified. For example,
5 mg/kg/3 D is 5 milligrams of chemical per kilogram of the subject's body weight administered
over a period of three days. For dose to be meaningful it must be related to the effect it causes.
For example, SO mg/kg of chemical "X" administered orally to female rats has no relevancy unless
the effect of the dose, say sterility in all test subjects, is reported.
Dose-Response Curves. A dose-response relationship is represented by a dose-response curve. The
curve is generated by plotting the dose of the chemical versus the response in the test population.
There are a number of ways to present this data. One of the more common methods for presenting
the dose-response curve is shown in Graph 1. In this example, the dose is expressed in "mg/kg"
and depicted on the "x" axis. The response is expressed as a "cumulative percentage" of animals
in the test population that exhibit the specific health effect under study. Values for "cumulative
percentage" are indicated on the "y" axis of the graph. As the dose increases, the percentage of the
affected population increases.
Dose-response curves provide valuable information regarding the potency of the compound. The
curves are also used to determine the dose-response terms that are discussed in the following section.
O
V) Q
UJ 5
01 UJ
U EC
UJ CO
o z
EC <
UJ
100
50
INCREASING DOSE
DOSE (mg/kg)
GRAPH 1
HYPOTHETICAL DOSE-RESPONSE CURVE
Dose-Response Terms. The National Institute for Occupational Safety and Health (NIOSH) defines
a number of general dose-response terms in the "Registry of Toxic Substances" (1983, p. xxxii).
A summary of these terms is contained in Table 1.
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• Toxic dose low (TD^): The lowest dose of a substance introduced by any route,
other than inhalation, over any given period of time, and reported to produce any
toxic effect in humans or to produce tumorigenic or reproductive effects in animals.
• Toxic concentration low (TCu,): The lowest concentration of a substance in air to
which humans or animals have been exposed for any given period of time that has
produced any toxic effect in humans or produced tumorigenic or reproductive effects
in animals.
• Lethal dose low (LD^): The lowest dose, other than LD50, of a substance
introduced by any route, other than inhalation, which has been reported to have
caused death in humans or animals.
• Lethal dose fifty (LD50): A calculated dose of a substance which is expected to
cause the death of 50 percent of an entire defined experimental animal population.
It is determined from the exposure to the substance by any route other than
inhalation.
• Lethal concentration low (LC^,): The lowest concentration of a substance in air,
other than LCSO, which has been reported to have caused death in humans or animals.
• Lethal concentration fifty (LC50): A calculated concentration of a substance in air,
exposure to which for a specified length of time is expected to cause the death of SO
percent of an entire defined experimental animal population.
Limitations of Dose-Response Terms. Several limitations must be recognized when using dose-
response data. First, it is difficult to select a test species that will closely duplicate the human
response to a specific chemical. For example, human data indicates that arsenic is a carcinogen,
while animal studies do not demonstrate these results. Second, most lethal and toxic dose data are
derived from acute (single dose, short-term) exposures rather than chronic (continuous, long-term)
exposures. A third shortcoming is that the LDSO or LCSO is a single value and does not indicate the
toxic effects that may occur at different dose levels. For example, in Graph 2 Chemical A is
assumed to be more toxic than Chemical B based on LDSO, but at lower doses the situation is
reversed. At LD20, Chemical B is more toxic than Chemical A.
Toxicology and Exposure Guidelines 4 6/93
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TABLE 1
SUMMARY OF DOSE-RESPONSE TERMS
Category
TDu,
TCo)
LDuj
LD50
LCuj
LC50
Exposure
Time
Acute or chronic
Acute or chronic
Acute or chronic
Acute
Acute or chronic
Acute
Route of Exposure
All except inhalation
Inhalation
All except inhalation
All except inhalation
Inhalation
Inhalation
Toxic Effects
HUMAN ANIMAL
Any nonlethal
Any nonlethal
Death
Not applicable
Death
Not applicable
Reproductive,
Tumorigenic
Reproductive,
Tumorigenic
Death
Death
(statistically
determined)
Death
Death
(statistically
determined)
DOSE (mg/kg)
GRAPH 2
COMPARISON OF DOSE-RESPONSE CURVES FOR TWO SUBSTANCES
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Factors Influencing Toxicity. Many factors affect the reaction of an organism to a toxic chemical.
The specific response that is elicited by a given dose varies depending on the species being tested
and variations that occur among individuals of the same species. These must be considered when
using information such as that found in (Table 2).
• Duration and Frequency of Exposure. There is a difference in type and severity
of effects depending on how rapidly the dose is received (duration) and how often the
dose is received (frequency). Acute exposures are usually single incidents of
relatively short duration—a minute to a few days. Chronic exposures involve
frequent doses at relatively low levels over a period of time ranging from months to
years.
If a dose is administered slowly so that the rate of elimination or the rate of
detoxification keeps pace with intake, it is possible that no toxic response will occur.
The same dose could produce an effect with rapid administration.
TABLE 2
CLASSIFICATION OF FACTORS INFLUENCING TOXICITY
Type
Factors related to the
chemical
Factors related to exposure
Factors related to person
exposed
Factors related to
environment
Examples
Composition (salt, free base, etc.); physical characteristics
(particle size, liquid, solid, etc.); physical properties
(volatility, solubility, etc.); presence of impurities; break
down products; carrier.
Dose; concentration; route of exposure (ingestion, skin
absorption, injection, inhalation); duration.
Heredity; immunology; nutrition; hormones; age; sex; health
status; preexisting diseases.
Carrier (air, water, food, soil); additional chemical present
(synergism, antagonism); temperature; air pressure.
Routes of Exposure. Biological results can be different for the same dose, depen-
ding on whether the chemical is inhaled, ingested, applied to the skin, or injected.
Natural barriers impede the intake and distribution of material once in the body.
These barriers can attenuate the toxic effects of the same dose of a chemical. The
effectiveness of these barriers is partially dependent upon the route of entry of the
chemical.
Interspecies Variation. For the same dose received under identical conditions, the
effects exhibited by different species may vary greatly. A dose which is lethal for
one species may have no effect on another. Since the toxicological effects of
chemicals on humans is usually based on animal studies, a test species must be
selected that most closely approximates the physiological processes of humans.
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• Intraspecies Variations. Within a given species, not all members of the population
respond to the same dose identically. Some members will be more sensitive to the
chemical and elicit response at lower doses than the more resistant members which
require larger doses for the same response.
Age and Maturity. Infants and children are often more sensitive to toxic
action than younger adults. Elderly persons have diminished physiological
capabilities for the body to deal with toxic insult. These age groups may be
more susceptible to toxic effects at relatively lower doses.
Gender and Hormonal Status. Some chemicals may be more toxic to one
gender than the other. Certain chemicals can affect the reproductive system
of either the male or female. Additionally, since women have a larger
percentage of body fat than men, they may accumulate more fat-soluble
chemicals. Some variations in response have also been shown to be related
to physiological differences between males and females.
Genetic Makeup. Genetic factors influence individual responses to toxic
substances. If the necessary physiological processes are diminished or
defective the natural body defenses are impaired. For example, people
lacking in the G6PD enzyme (a hereditary abnormality) are more likely to
suffer red blood cell damage when given aspirin or certain antibiotics than
persons with the normal form of the enzyme.
State of Health. Persons with poor health are generally more susceptible to
toxic damage due to the body's decreased capability to deal with chemical
insult.
• Environmental Factors. Environmental factors may contribute to the response for
a given chemical. For example, such factors as air pollution, workplace conditions,
living conditions, personal habits, and previous chemical exposure may act in
conjunction with other toxic mechanisms.
• Chemical Combinations. Some combinations of chemicals produce different effects
from those attributed to each individually:
Synergists: chemicals that, when combined, cause a greater than additive
effect. For example, hepatotoxicity is enhanced as a result of exposure to
both ethanol and carbon tetrachloride.
Potentiation: is a type of synergism where the potentiator is not usually toxic
in itself, but has the ability to increase the toxicity of other chemicals.
Isopropanol, for example, is not hepatotoxic in itself. Its combination with
carbon tetrachloride, however, increases the toxic response to the carbon
tetrachloride.
Antagonists: chemicals, that when combined, lessen the predicted effect.
There are four types of antagonists.
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(1) functional: Produces opposite effects on the same physiologic function.
For example, phosphate reduces lead absorption in the gastrointestinal tract
by forming insoluble lead phosphate.
(2) chemical: Reacts with the toxic compound to form a less toxic product.
For example, chelating agents bind up metals such as lead, arsenic, and
mercury.
(3) dispositional: Alters absorption, metabolism, distribution, or excretion.
For example, some alcohols use the same enzymes in their metabolism:
ethanol > acetaldehyde > acetic acid
methanol > formaldehyde > formic acid
The aldehydes cause toxic effects (hangover, blindness). Ethanol is more
readily metabolized than methanol, so when both are present, methanol is not
metabolized and can be excreted before forming formaldehyde. Another
dispositional antagonist is Antabuse which, when administered to alcoholics,
inhibits the metabolism of acetaldehyde, giving the patient a more severe
prolonged hangover.
(4) receptor: Occurs when a second chemical either binds to the same tissue
receptor as the toxic chemical or blocks the action of receptor and thereby
reduces the toxic effect. For example, atropine interferes with the receptor
responsible for the toxic effects of organophosphate pesticides.
Sources of Toxicitv Information
Information on the toxic properties of chemical compounds and dose-response relationships is
obtained from animal studies, epidemiological investigations of exposed human populations, and
clinical studies or case reports of exposed humans.
• Toxicity Tests. The design of any toxicity test incorporates:
a test organism, which can range from cellular material and selected strains
of bacteria through higher order plants and animals
a response or biological endpoint, which can range from subtle changes in
physiology and behavior to death
an exposure or test period
a dose or series of doses.
The objective is to select a test species that is a good model of humans, a response that is
not subjective and can be consistently determined for a given dose, and a test period that is
relatively short.
Toxicology and Exposure Guidelines 8 6193
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Epidemiological and Clinical Studies. Epidemiological investigations and clinical
cases are another means of relating human health effects and exposure to toxic
substances. Epidemiological investigations are based upon a human population
exposed to a chemical compared to an appropriate, nonexposed group. An attempt
is made to determine whether there is a statistically significant association between
health effects and chemical exposure. Clinical cases involve individual reports of
chemical exposure.
Uses of Toxicity Information
Comparison of Toxicity Data. Comparing the LD50 of chemicals in animals gives a relative ranking
of potency or toxicity of each. For example, DDT (LD50 for rats = 113 mg/kg) would be
considered more toxic than ethyl alcohol (LDJO for rats = 14,000 mg/kg). Using the LDJO (mg/kg)
for a test species and multiplying by 70 kg (average mass of man) gives a rough estimate of the toxic
potential of the substance for humans, assuming that humans are as sensitive as the subjects tested.
Because the extrapolation of human data from animal studies is complex, this value should only be
considered as an approximation for the potency of the compound and used in conjunction with
additional data (Tables 3 and 4).
Establishing Exposure Guidelines. Toxicity data from both animal experimentation and
epidemiological studies is used to establish exposure guidelines. The method for deriving a guideline
is dependent upon the type of chemical as well as duration and frequency of exposure. It is also
important to make the distinction between an experimental dose (mg/kg) and an environmental
concentration (mg/m3 or ppm). In order to make safety decisions, exposure guidelines are presented
as concentrations so that these values can be compared to concentrations measured by air monitoring
instrumentation.
TABLE 3
TOXICITY RATING
Toxicity Rating or Class
Oral Acute LD50 for Rats
Extremely toxic
Highly toxic
Moderately toxic
Slightly toxic
Practically nontoxic
1 mg/kg or less (dioxin, botulinum toxin)
1 to 50 mg/kg (strychnine)
50 to 500 mg/kg (DDT)
0.5 to 5 g/kg (morphine)
5 to 15 g/kg (ethyl alcohol)
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TABLE 4
VALUES FOR RATS FOR A GROUP OF WELL-KNOWN CHEMICALS
Chemical
LD,,, (mg/kg)
Sucrose (table sugar)
Ethyl alcohol
Sodium chloride (common salt)
Vitamin A
Vanillin
Aspirin
Chloroform
Copper sulfate
Caffeine
Phenobarbital, sodium salt
DDT
Sodium nitrite
Nicotine
Aflatoxin Bl
Sodium cyanide
Strychnine
29,700
14,000
3,000
2,000
1,580
1,000
800
300
192
162
113
85
53
7
6.4
2.5
Health Effects
Human health effects caused by exposure to toxic substances fall into two categories: short-term and
long-term effects. Short-term effects (or acute effects) have a relatively quick onset (usually minutes
to days) after brief exposures to relatively high concentrations of material (acute exposures). The
effect may be local or systemic. Local effects occur at the site of contact between the toxicant and
the body. This site is usually the skin or eyes, but includes the lungs if irritants are inhaled or the
gastrointestinal tract if corrosives are ingested. Systemic effects are those that occur if the toxicant
has been absorbed into the body from its initial contact point, transported to other parts of the body,
and cause adverse effects in susceptible organs. Many chemicals can cause both local and systemic
effects.
Long-term effects (or chronic effects) are those with a long period of time (years) between exposure
and injury. These effects may occur after apparent recovery from acute exposure or as a result of
repeated exposures to low concentrations of materials over a period of years (chronic exposure).
Health effects manifested from acute or chronic exposure are dependent upon the chemical involved
and the organ it effects. Most chemicals do not exhibit the same degree of toxicity for all organs.
Usually the major effects of a chemical will be expressed in one or two organs. These organs are
known as target organs which are more sensitive to that particular chemical than other organs. The
organs of the body and examples of effects due to chemical exposures are listed below.
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Respiratory Tract. The respiratory tract is the only organ system with vital functional elements in
constant, direct contact with the environment. The lung also has the largest exposed surface area
of any organ on a surface area of 70 to 100 square meters versus 2 square meters for the skin and
10 square meters for the digestive system.
The respiratory tract is divided into three regions: (1) Nasopharyngeal—extends from nose to larynx.
These passages are lined with ciliated epithelium and mucous glands. They filter out large inhaled
particles, increase the relative humidity of inhaled air, and moderate its temperature. (2) Tracheo-
bronchial—consists of trachea, bronchi, and bronchioles and serves as conducting airway between
the nasopharyngeal region and alveoli. These passage ways are lined with ciliated epithelium coated
by mucous, which serves as an escalator to move particles from deep in the lungs back up to the oral
cavity so they can be swallowed. These ciliated cells can be temporarily paralyzed by smoking or
using cough suppressants. (3) Pulmonary acinus—is the basic functional unit in the lung and the
primary location of gas exchange. It consists of small bronchioles which connect to the alveoli. The
alveoli, of which there are 100 million in humans, contact the pulmonary capillaries.
Inhaled particles settle in the respiratory tract according to their diameters:
• 5-30 micron particles are deposited in the nasopharyngeal region.
• 1-5 micron particles are deposited in the tracheobronchial region.
• Less than 1 micron particles are deposited in the alveolar region by diffusion and
Brownian motion.
In general, most particles 5-10 microns in diameter are removed. However, certain small inorganic
particles, settle into smaller regions of the lung and kill the cells which attempt to remove them. The
result is fibrous lesions of the lung.
Many chemicals used or produced in industry can produce acute or chronic diseases of the
respiratory tract when they are inhaled (Table 5). The toxicants can be classified according to how
they affect the respiratory tract.
• Asphyxiants: gases that deprive the body tissues of oxygen
• Simple asphyxiants are physiologically inert gases that at high concentrations
displace air leading to suffocation. Examples: nitrogen, helium, methane, neon,
argon.
• Chemical asphyxiants are gases that prevent the tissues from getting enough oxygen.
Examples: carbon monoxide and cyanide. Carbon monoxide binds to hemoglobin
200 times more readily than oxygen. Cyanide prevents the transfer of oxygen from
blood to tissues by inhibiting the necessary transfer enzymes.
• Irritants: chemicals that irritate the air passages. Constriction of the airways occurs
and may lead to edema (liquid in the lungs) and infection. Examples: hydrogen
fluoride, chlorine, hydrogen chloride, and ammonia.
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• Necrosis producers: Chemicals that result in cell death and edema. Examples:
ozone and nitrogen dioxide.
• Fibrosis producers: Chemicals that produce fibrotic tissue which, if massive, blocks
airways and decreases lung capacity. Examples: silicates, asbestos, and beryllium.
• Allergens: Chemicals that induce an allergic response characterized by
bronchoconstriction and pulmonary disease. Examples: isocyanates and sulfur
dioxide.
• Carcinogens: Chemicals that are associated with lung cancer. Examples: cigarette
smoke, coke oven emissions, asbestos, and arsenic.
Not only can various chemicals affect the respiratory tract, but the tract is also a route for chemicals
to reach other organs. Solvents, such as benzene and tetrachloroethane, anesthetic gases, and many
other chemical compounds can be absorbed through the respiratory tract and cause systemic effects.
TABLE 5
EXAMPLES OF INDUSTRIAL TOXICANTS THAT PRODUCE
DISEASE OF THE RESPIRATORY TRACT
Toxicant
Ammonia
Arsenic
Asbestos
Chlorine
Isocyanates
Nickel Carbony
Ozone
Phosgene
Toluene
Xylene
Site of Action
Upper airways
Upper airways
Lung parenchyma
Upper airways
Lower airways,
alveoli
Alveoli
Bronchi, alveoli
Alveoli
Upper airways
Lower airways
Acute Effect
Irritation, edema
Bronchitis, irritation,
pharyngitis
Cough, irritation, asphyxiant
(by muscle cramps in larynx)
Bronchitis, pulmonary edema,
asthma
Edema (delayed symptoms)
Irritation, edema, hemorrhage
Edema
Bronchitis, edema,
bronchospasm
Edema, hemorrhage
Chronic Effect
Bronchitis
Cancer, bronchitis,
laryngitis
Fibrosis, cancer
Emphysema, bronchitis
Bronchitis, fibrosis,
pneumonia
Skin. The skin is, in terms of weight, the largest single organ of the body. It provides a barrier
between the environment and other organs (except the lungs and eyes) and is a defense against many
chemicals.
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The skin consists of the epidermis (outer layer) and the dermis (inner layer). In the dermis are sweat
glands and ducts, sebaceous glands, connective tissue, fat, hair follicles, and blood vessels. Hair
follicles and sweat glands penetrate both the epidermis and dermis. Chemicals can penetrate through
the sweat glands, sebaceous glands, or hair follicles.
Although the follicles and glands may permit a small amount of chemicals to enter almost
immediately, most pass through the epidermis, which constitutes the major surface area. The top
layer is the stratum corneum, a thin cohesive membrane of dead surface skin. This layer turns over
every 2 weeks by a complex process of cell dehydration and polymerization of intracellular material.
The epidermis plays the critical role in skin permeability.
Below the epidermis lies the dermis, a collection of cells providing a porous, watery, nonselective
diffusion medium. Intact skin has a number of functions:
Epidermis: Prevents absorption of chemicals and is a physical barrier to bacteria.
Sebaceous glands: Secrete fatty acids which are bacteriostatic and fungistatic.
Melanocytes (skin pigment): Prevent damage from ultraviolet radiation in sunlight.
Sweat glands: Regulate heat.
Connective tissue: Provides elasticity against trauma.
Lymph-blood system: Provide immunologic responses to infection.
The ability of skin to absorb foreign substances depends on the properties and health of the skin and
the chemical properties of the substances. Absorption is enhanced by:
Breaking top layer of skin by abrasions or cuts.
Increasing hydration of skin.
Increasing temperature of skin which causes sweat cells to open up and secrete sweat,
which can dissolve solids.
Increasing blood flow to skin.
Increasing concentrations of the substance.
Increasing contact time of the chemical on the skin.
Increasing the surface area of affected skin.
Altering the skin's normal pH of 5.
Decreasing particle size of substance.
Adding agents which will damage skin and render it more susceptible to penetration.
Adding surface-active agents or organic chemicals. DMSO, for example, can act as
a carrier of the substance.
Inducing ion movement by an electrical charge.
Absorption of a toxic chemical through the skin can lead to local effects through direct contact, such
as irritation and necrosis, and systemic effects.
Many chemicals can cause a reaction with the skin resulting in inflammation called dermatitis. These
chemicals are divided into three categories:
• Primary irritants: Act directly on normal skin at the site of contact (if chemical is
in sufficient quantity for a sufficient length of time).Skin irritants include: acetone,
benzyl chloride, carbon disulfide, chloroform, chromic acid and other soluble
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chromium compounds, ethylene oxide, hydrogen chloride, iodine, methyl ethyl
ketone, mercury, phenol, phosgene, styrene, sulfur dioxide, picric acid, toluene,
xylene.
• Photosensitizes: Increase in sensitivity to light, which results in irritation and
redness. Photosensitizers include: tetracyclines, acridine, creosote, pyridine
furfural, and naphtha.
• Allergic sensitizers: May produce allergic-type reaction after repeated exposures.
They include: formaldehyde, phthalic anhydride, ammonia, mercury, nitrobenzene,
toluene diisocyanate, chromic acid and chromates, cobalt, and benzoyl peroxide.
Eyes. The eyes are affected by the same chemicals that affect skin, but the eyes are much more
sensitive. Many materials can damage the eyes by direct contact:
• Acids: Damage to the eye by acids depends on pH and the protein-combining
capacity of the acid. Unlike alkali burns, the acid burns that are apparent during the
first few hours are a good indicator of the long-term damage to be expected. Some
acids and their properties are:
sulfuric acid. In addition to its acid properties, it simultaneously removes
water and generates heat.
picric acid and tannic acid. No difference in damage they produce in entire
range of acidic pHs.
hydrochloric acid. Severe damage at pH 1, but no effect at pH 3 or greater.
• Alkalies: Damage that appears mild initially but can later lead to ulceration,
perforation, and clouding of the cornea or lens. The pH and length of exposure have
more bearing on the amount of damage than the type of alkali. Some problem
alkalies are:
sodium hydroxide (caustic soda) and potassium hydroxide.
ammonia penetrates eye tissues more readily than any other alkali; calcium
oxide (lime) forms clumps when it contacts eye tissue and is very hard to
remove.
• Organic solvents: Organic solvents (for example, ethanol, toluene, and acetone)
dissolve fats, cause pain, and dull the cornea. Damage is usually slight unless the
solvent is hot.
• Lacrimators: Lacrimators cause instant tearing at low concentrations. They are
distinguished from other eye irritants (hydrogen chloride and ammonia) because they
induce an instant reaction without damaging tissues. At very high concentrations
lacrimators can cause chemical burns and destroy corneal material. Examples are
chloroacetophenone (tear gas) and mace.
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In addition, some compounds act on eye tissue to form cataracts, damage the optic nerve, or damage
the retina. These compounds usually reach the eye through the blood system having been inhaled,
ingested or absorbed rather than direct contact.
Examples of compounds that can provide systemic effects damaging to the eyes are:
Naphthalene: Cataracts and retina damage.
Phenothiazine (insecticide): Retina damage
Thallium: cataracts and optic nerve damage.
Methanol: Optic nerve damage.
Central Nervous System. Neurons (nerve cells) have a high metabolic rate but little capacity for
anaerobic metabolism. Subsequently, inadequate oxygen flow (anoxia) to the brain kills cells within
minutes. Some may die before oxygen or glucose transport stops completely.
Because of their need for oxygen, nerve cells are readily affected by both simple asphyxiants and
chemical asphyxiants. Also, their ability to receive adequate oxygen is affected by compounds that
reduce respiration and thus reduce oxygen content of the blood (barbiturates, narcotics). Other
examples are compounds such as arsine, nickel, ethylene chlorohydrin, tetraethyl lead, aniline, and
benzene that reduce blood pressure or flow due to cardiac arrest, extreme hypotension,
hemorrhaging, or thrombosis.
Some compounds damage neurons or inhibit their function through specific action on parts of the
cell. The major symptoms from such damage include: dullness, restlessness, muscle tremor,
convulsions, loss of memory, epilepsy, idiocy, loss of muscle coordination, and abnormal sensations.
Examples are:
Fluoroacetate: Rodenticide.
Triethyltin: Ingredient of insecticides and fungicides.
Hexachlorophene: Antibacterial agent.
Lead: Gasoline additive and paint ingredient.
Thallium: Sulfate used as a pesticide and oxide or carbonate used in manufacture of
optical glass and artificial gems.
Tellurium: Pigment in glass and porcelain.
Organomercury compounds: Methyl mercury used as a fungicide; is also a product
of microbial action on mercury ions. Organomercury compounds are especially
hazardous because of their volatility and their ability to permeate tissue barriers.
Some chemicals are noted for producing weakness of the lower extremities and abnormal sensations
(along with previously mentioned symptoms):
Acrylamide: Soil stabilizer, waterproofer.
Carbon disulfide: Solvent in rayon and rubber industries.
n-Hexane: Used as a cleaning fluid and solvent. Its metabolic product, hexanedione,
causes the effects.
Organophosphoms compounds: Often used as flame retardants (triorthocresyl
phosphate) and pesticides (Leptofor and Mipafox).
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Agents that prevent the nerves from producing proper muscle contraction and may result in death
from respiratory paralysis are DDT, lead, botulinum toxin, and allethrin (a synthetic insecticide).
DDT, mercury, manganese, and monosodium glutamate also produce personality disorders and
madness.
Liver. Liver injury induced by chemicals has been known as a toxicologic problem for hundreds
of years. It was recognized early that liver injury is not a simple entity, but that the type of lesion
depends on the chemical and duration of exposure. Three types of response to hepatotoxins can be
identified:
• Acute. Cell death from:
carbon tetrachloride: Solvent, degreaser.
chloroform: Used in refrigerant manufacture solvent.
trichloroethylene: Solvent, dry cleaning fluid, degreaser.
tetrachloroethane: Paint and varnish remover, dry cleaning fluid.
bromobenzene: Solvent, motor oil additive.
tannic acid: Ink manufacture, beer and wine clarifier.
kepone: Pesticide.
• Chronic. Examples include:
cirrhosis: a progressive fibrotic disease of the liver associated with liver
dysfunction and jaundice. Among agents implicated in cirrhosis cases are
carbon tetrachloride, alcohol, and aflatoxin.
carcinomas: malignant, growing tissue. For example, vinyl chloride (used
in polyvinyl chloride production) and arsenic (used in pesticides and paints)
are associated with cancers.
• Biotransformation of toxicants. The liver is the principal organ that chemically
alters all compounds entering the body. For example:
ethanol—> acetaldehyde—> acetic acid—> water+carbon dioxide
This metabolic action by the liver can be affected by diet, hormone activity, and alcohol
consumption. Biotransformation in the liver can also lead to toxic metabolities. For
example:
carbon tetrachloride— > chloroform
Kidneys. The kidney is susceptible to toxic agents for several reasons: (1) The kidneys constitute
1 percent of the body's weight, but receive 20-25 percent of the blood flow (during rest). Thus,
large amounts of circulating toxicants reach the kidneys quickly. (2) The kidneys have high oxygen
and nutrient requirements because of their work load. They filter one-third of the plasma reaching
them and reabsorb 98-99% of the salt and water. As they are reabsorbed, salt concentrates in the
kidneys. (3) Changes in kidney pH may increase passive diffusion and thus cellular concentrations
of toxicants. (4) Active secretion processes may concentrate toxicants. (5) Biotransformation is
high.
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A number of materials are toxic to the kidneys:
Heavy metals, may denature proteins as well as produce cell toxicity. Heavy metals
(including mercury, chromium, arsenic, gold, cadmium, lead, and silver) are readily
concentrated in the kidneys, making this organ particularly sensitive.
Halogenated organic compounds, which contain chlorine, fluorine, bromine, or
iodine. Metabolism of these compounds, like that occurring in the liver, generates
toxic metabolites. Among compounds toxic to the kidneys are carbon tetrachloride,
chloroform, 2,4,5-T (a herbicide), and ethylene dibromide (a fumigant).
Miscellaneous, including carbon disulfide (solvent for waxes and resins) and ethylene
glycol (automobile antifreeze).
Blood The blood system can be damaged by agents that affect blood cell production (bone
marrow), the components of blood (platelets, red blood cells, and white blood cells), or the oxygen-
carrying capacity of red blood cells.
Bone Marrow. Bone marrow is the source of most components in blood. Agents that suppress the
function of bone marrow include:
Arsenic, used in pesticides and paints.
Bromine, used to manufacture gasoline antiknock compounds, ethylene dibromide,
and organic dyes.
Methyl chloride, used as a solvent, refrigerant, and aerosol propellant.
Ionizing radiation, produced by radioactive materials and x-rays is associated with
leukemia.
Benzene, a chemical intermediate associated with leukemia.
Blood Components. Among platelets (thrombocytes) are blood components that help prevent blood
loss by forming blood clots. Among chemicals that affect this action are:
Aspirin, which inhibits clotting.
Benzene, which decreases the number of platelets.
Tetrachloroethane, which increases the number of platelets.
Leukocytes (white blood cells) are primarily responsible for defending the body against foreign
organisms or materials by engulfing and destroying the material or by producing antibodies.
Chemicals that increase the number of leukocytes include naphthalene, magnesium oxide, boron
hydrides, and tetrachloroethane. Agents that decrease the number of leukocytes include benzene and
phosphorous.
Erythrocytes (red blood cells) transport oxygen in the blood. Chemicals that destroy (hemolyze) red
blood cells include arsine (a gaseous arsenic compound and contaminant in acetylene), naphthalene
(used to make dyes), and warfarin (a rodenticide).
Oxygen Transport. Some compounds affect the oxygen carrying capabilities of red blood cells.
A notable example is carbon monoxide which combines with hemoglobin to form
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carboxyhemoglobin. Hemoglobin has an affinity for carbon monoxide 200 times greater than that
for oxygen.
While carbon monoxide combines reversibly with hemoglobin, some chemicals cause the hemoglobin
to change such that it cannot combine reversibly with oxygen. This condition is called
methemoglobinemia. Some chemicals that can cause this are:
Sodium nitrite, used in meat curing and photography.
Aniline, used in manufacture of rubber accelerators and antioxidants, resins, and
varnishes.
Nitrobenzene and dinitrobenzene, used in manufacture of dyestuffs and explosives.
Trinitrotoluene (TNT), used in explosives.
Mercaptans, used in manufacture of pesticides and as odorizers for hazardous
odorless gases.
2-nitropropane, used as a solvent.
Spleen. The spleen filters bacteria and paniculate matter (especially deteriorated red blood cells)
from the blood. Iron is recovered from the hemoglobin for recycling. In the embryo, the spleen
forms all types of blood cells. In the adult, however, it produces only certain kinds of leukocytes.
Examples of chemicals that damage the spleen are:
Chloroprene, used in production of synthetic rubber.
Nitrobenzene, used as chemical intermediate.
Reproductive System. Experimental results indicate that certain agents interfere with the
reproductive capabilities of both sexes, causing sterility, infertility, abnormal sperm, low sperm
count, and/or affect hormone activity in animals. Many of these also affect human reproduction.
Further study is required to identify reproductive toxins and their effects. Some examples of
chemicals that have been implicated in reproductive system toxicity include:
Male: Anesthetic gases (halothane, methoxyflurane) cadmium, mercury, lead, boron,
methyl mercury, vinyl chloride, DDT, kepone, chlordane, PCBs, dioxin, 2,4-D,
2,4,5-T, carbaryl, paraquat, dibromochloropropane, ethylene dibromide, benzene,
toluene, xylene, ethanol, radiation, and heat.
Female: DDT, parathion, carbaryl, diethylstilbestrol (DES), PCBs, cadmium,
methyl mercury, hexafluoroacetone, and anesthetic gases.
Tvoes of Toxic Effects
Teratogenic. Teratology is derived from Latin and means the study of monsters. In a modern
context, teratology is the study of congenital malformations. Teratology is a relatively new discipline
that started in 1941 with the correlation of German measles to birth defects. In the 1960s, the first
industrial link to teratogens was discovered. The chemical involved was methyl mercury.
The following conditions have been associated with congenital malformations: heredity, maternal
diseases such as German measles and viral infections during pregnancy, maternal malnutrition,
physical injury, radiation, and exposure to chemicals.
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Most major structural abnormalities occur during the embryonic period, 5-7 weeks, whereas
physiologic and minor defects occur during the fetal period, 8-36 weeks. Studies using lab animals
show the need to evaluate exposure of chemicals for each day of pregnancy. Thalidomide, for
example, caused birth defects in rats only when administered during the 12th day of gestation.
A number of chemicals are reactive or can be activated in the body during the gestation period. The
degree and nature of the fetal effects then depend upon:
Developmental state of embryo or fetus when chemical is administered.
Dose of chemical, route, and exposure interval.
Transplacental absorption of chemical and levels in tissues of embryo/fetus.
Ability of maternal liver and placenta to metabolize or detoxify chemical.
Biologic half-life of chemical or metabolites.
State of cell cycle when chemical is at toxic concentrations.
Capacity of embryonic/fetal tissues to detoxify or bioactivate chemicals.
Ability of damaged cells to repair or recover.
Teratogenic potential has been suggested by animal studies under various conditions:
Dietary deficiency: Vitamins A, D, E, C, riboflavin, thiamine, nicotinamide, folic
acid, zinc, manganese, magnesium, and cobalt.
Hormonal deficiency: Pituitary, thyroxin, and insulin.
Hormonal excess: Cortisone, thyroxin, insulin androgens, estrogens, and
epinephrine.
Hormone and vitamin antagonists: 3-acetylpyridine, 6-aminonicotinamide, and
thiouracils.
Vitamin excess: Vitamin A and nicotinic acid.
Antibiotics: Penicillin, tetracyclines, and streptomycin.
Heavy metals: Methyl mercury, mercury salts, lead, thallium, selenium, and
chelating agents.
Azo dyes: Trypan blue, Evans blue, and Niagara sky blue 6B.
Producers of anoxia: Carbon monoxide and carbon dioxide.
Chemicals: Quinine, thiadiazole, salicylate, 2,3,7,8-TCDD, caffeine, nitrosamines,
hydroxyurea, boric acid, insecticides, pesticides, DMSO, chloroform, carbon
tetrachloride, benzene, xylene, cyclohexanone, propylene glycol, acetamides,
formamides, and sulfonamides.
Physical conditions: hypothermia, hyperthermia, radiation, and anoxia.
Infections: Ten viruses (including German measles and cytomegalovirus), syphilis,
and gonorrhea.
Far fewer agents have been conclusively shown to be teratogenic in humans: anesthetic gases,
organic mercury compounds, ionizing radiation, german measles and thalidomide.
Mutagenic. Mutagens are agents that cause changes (mutations) in the genetic code, altering DNA.
The changes can be chromosomal breaks, rearrangement of chromosome pieces, gain or loss of
entire chromosomes, or a changes within a gene.
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Among agents shown to be mutagenic in humans are:
Ethylene oxide, used in hospitals as a sterilant.
Ethyleneimine, an alkylating agent.
Ionizing radiation.
Hydrogen peroxide, a bleaching agent.
Benzene, a chemical intermediate.
Hydrazine, used in rocket fuel.
The concern over mutagenic agents covers more than the effect that could be passed into the human
gene pool (germinal or reproductive cell mutations). There is also interest in the possibility that
somatic cell mutations may produce carcinogenic or teratogenic responses.
Carcinogenic. Two types of carcinogenic mechanisms have been identified.
• Genotoxic: Electrophilic carcinogens that alter genes through interaction with DNA.
There are three types:
Direct or primary carcinogens: Chemicals that act without any bioactivation;
for example, bis(chloromethyl) ether, ethylene dibromide, and dimethyl
sulfate.
Procarcinogens: Chemicals that require biotransformation to activate them
to a carcinogen; for example, vinyl chloride and 2-naphthylamine.
Inorganic carcinogen: Some of these are preliminarily categorized as
genotoxic due to potential for DNA damage. Other compounds in the group
may operate through epigenetic mechanisms.
• Epigenetic: These are carcinogens that do not act directly with genetic material.
Several types are possible:
Cocarcinogen: Increases the overall response of a carcinogen when they are
administered together; for example, sulfur dioxide, ethanol, and catechol.
Promoter: Increases response of a carcinogen when applied after the
carcinogen but will not induce cancer by itself; for example, phenol and
dithranol.
Solid-state: Works by unknown mechanism, but physical form vital to effect;
for example, asbestos and metal foils.
Hormone: Usually is not genotoxic, but alters endocrine balance; often acts
as promoter (e.g., DES and estrogens).
Immunosuppressor: Mainly stimulates virally induced, transplanted, or
metastatic neoplasms by weakening host's immune system (e.g.,
antilymphocytic serum, used in organ transplants).
Genotoxic carcinogens are sometimes effective after a single exposure, can act in a cumulative
manner, or act with other genotoxic carcinogens which affect the same organs. Some epigenetic
carcinogens, however, only cause cancers when concentrations are high and exposure long. The
implication is that while there may be a "safe" threshold level of exposure for some carcinogens,
others may have "zero" threshold; that is, one molecule of the chemical can induce a cancer.
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Various considerations indicate that DNA is a critical target for carcinogens:
Many carcinogens are or can be metabolized so that they react with DNA. In these
cases, the reaction can usually be detected by testing for evidence of DNA repair.
Many carcinogens are also mutagens.
Inhibitors and inducers of carcinogens affect mutagenic activity.
Chemicals often are tested for mutagenic and carcinogenic activity in the same cell
systems.
Defects in DNA repair predispose to cancer development.
Several inheritable or chromosomal abnormalities predispose to cancer development.
Initiated dormant tumor cells persist, which is consistent with a change in DNA.
Cancer is inheritable at the cellular level and, therefore, may result from an alteration
of DNA.
Most, if not all, cancers display chromosomal abnormalities.
Although cancer ranks as the second most common cause of death in the United States, the process
of carcinogenesis is not yet clearly defined. As a result, there are several problems encountered
when evaluating the carcinogenic potential of various agents in the environment. First, human health
can be affected by a wide range of factors including the environment, occupation, genetic
predisposition and lifestyle (i.e., cigarette smoking and diet). Therefore, it is often difficult to
determine the relationship between any one exposure and the onset of cancer. Second, many cancers
are latent responses; that is, the disease may not be manifested until many years after the initial
exposure. Third, the mechanisms for carcinogenesis may differ according to the type and the site
of cancer.
EXPOSURE GUIDELINES
It is necessary, during response activities involving hazardous materials, to acknowledge and plan
for the possibility that response personnel will be exposed to the materials present at some time and
to some degree. Most materials have levels of exposure which can be tolerated without adverse
health effects. However, it is most important to identify the materials involved and then determine
(1) the exposure levels considered safe for each of these materials; (2) the type and extent of
exposure; and (3) possible health effects of overexposure.
Several reference sources are available that contain information about toxicological properties and
safe exposure limits for many different materials. These sources can be grouped into two general
categories: 1) sources that provide toxicological data and general health hazard information and
warnings and 2) sources that describe specific legal exposure limits or recommended exposure
guidelines.
Both types of sources, considered together, provide useful information that can be used to assess the
exposure hazards that might be present at a hazardous materials incident. In the following
discussion, these sources are described in greater detail.
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General Guidelines
The effects of chemical exposure with the route and dosage required can be found in NIOSH's
Registry of Toxic Effects of Chemical Substances. However, because most of the data is for animal
exposures, there may be problems in trying to use the data for human exposure guidelines.
Other sources give some general guides on chemical exposure. They may say that the chemical is
an irritant or corrosive, or they may give a warning like "AVOID CONTACT" or "AVOID
BREATHING VAPORS." This gives the user information about the possible route of exposure and
effects of the exposure. However, this does not give a safe exposure limit. One may question
whether the warning means to "AVOID ANY POSSIBLE CONTACT" or whether there is a certain
amount that a person can contact safely for a certain length of time.
Two sources of information go a little further and use a ranking system for exposure to chemicals.
Irving Sax, in Dangerous Properties of Industrial Materials, gives a Toxic Hazard Rating (THR) for
certain chemicals. These ratings are NONE, LOW, MODERATE, and HIGH. The route of
exposure is also given. For example, butylamine is listed as a HIGH toxic hazard via oral and
dermal routes and a MODERATE toxic hazard via inhalation. HIGH means that the chemical is
"capable of causing death or permanent injury due to the exposures of normal use; incapacitating and
poisonous; requires special handling."
In the book, Fire Protection Guide on Hazardous Materials, the National Fire Protection Association
(NFPA) also uses a ranking system to identify the toxic hazards of a chemical. These numbers are
part of the NFPA 704 M identification system. The numbers used range from 0 to 4 where 0 is for
"materials which on exposure under fire conditions would offer no health hazard beyond that of
ordinary combustible material" and 4 is for materials where "a few whiffs of the gas or vapor could
cause death; or the gas, vapor, or liquid could be fatal on penetrating the fire fighters' normal full
protective clothing which is designed for resistance to heat." The degree of hazard is based upon
the inherent properties of the chemical and the hazard that could exist under fire or other emergency
conditions. This rating is based on an exposure of "a few seconds to an hour" and the possibility
of large quantities of material being present. Thus it is not completely applicable to long-term
exposure to small quantities of chemicals. It is more useful for spills or fires where a person could
come in contact with a large amount of the chemical.
The Sax and NFPA sources provide information about the routes of exposures and some effects
along with a rating system which indicates which chemicals require extra precaution and special
protective equipment.
Sources for Specific Guidelines for Airborne Contaminants
While there are many sources for general exposure guidelines, there are only a few that give more
specific information about what is considered a safe exposure limit. Many of the following
organizations have exposure guidelines for exposures to hazards other than airborne contaminants
(e.g., heat stress, noise, and radiation). This part will deal only with chemical exposures.
American Conference of Governmental Industrial Hygienists (ACGIH). One of the first groups
to develop specific exposure guidelines was the American Conference of Governmental Industrial
Toxicology and Exposure Guidelines 22 6/93
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Hygienists (ACGIH). In 1941, ACGIH suggested the development of Maximum Allowable
Concentrations (MACs) for use by industry. A list of MACs was compiled by ACGIH and
published in 1946. In the early 1960s, ACGIH revised those recommendations and renamed them
Threshold Limit Values (TLVs).
Along with the TLVs, ACGIH publishes Biological Exposure Indices (BEIs). BEIs are intended to
be used as guides for evaluation of exposure where inhalation is not the only possible route of
exposure. Since the TLVs are for inhalation only, they may not be protective if the chemical is
ingested or is absorbed through the skin. Biological monitoring (e.g., urine samples, breath analysis)
can be used to assess the overall exposure. This monitoring uses information about what occurs in
the body (e.g., metabolism of benzene to phenol) to determine if there has been an unsafe exposure.
The BEIs serve as a reference for biological monitoring just as TLVs serve as a reference for air
monitoring.
The TLVs are reviewed yearly and are published in their booklet, Threshold Limit Values and
Biological Exposure Indices.
American National Standards Institute (ANSI). The American National Standards Institute (ANSI)
has published standards that are a consensus of the people who have a concern about the subject the
standard covers (e.g., hard hats and respirators). An ANSI standard is intended as a guide to aid
manufacturers, consumers, and the general public. ANSI has standards covering many aspects of
the working environment. Many of these have been adopted by OSHA (see later discussion) as legal
requirements.
Some of the standards were exposure guidelines. They gave "acceptable concentrations" which were
"concentrations of air contaminants to which a person may be exposed without discomfort or ill
effects." These exposure limits were withdrawn in 1982. However, some were adopted by OSHA
before the withdrawal and still may be in use.
Occupational Safety and Health Administration (OSHA). In 1971, the Occupational Safety and
Health Administration (OSHA) promulgated Permissible Exposure Limits (PELs). These limits were
extracted from the 1968 TLVs, the ANSI standards, and other federal standards. The PELs are
found in 29 CFR 1910.1000. Since then, additional PELs have been adopted and a few of the
originals have been changed. These have been incorporated into specific standards for chemicals
(e.g., 29 CFR 1910.1028 - Benzene). There are also standards for thirteen carcinogens in which
there is no allowable inhalation exposure.
In 1989, OSHA published major revisions to the PELs. Since only a few of the PELs had been
updated since 1971, it was decided to update the entire list of PELs by changing existing ones and
adding new ones. Again, OSHA looked to the TLVs, but also considered recommendations from
the National Institute for Occupational Safety and Health (NIOSH).
Because OSHA is a regulatory agency, their PELs are legally enforceable standards and apply to all
private industries and federal agencies. They may also apply to state and local employees depending
upon the state laws.
National Institute for Occupational Safety and Health (NIOSH). The National Institute for
Occupational Safety and Health (NIOSH) was formed at the same time as OSHA to act as a research
5Y93 23 Toxicology and Exposure Guidelines
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organization. It is charged in part, with making recommendations for new standards and revising
old ones as more information is accumulated. The exposure levels NIOSH has researched have been
used to develop new OSHA standards, but there are many Recommended Exposure Limits (RELs)
that have not been adopted. Thus, they are in the same status as the exposure guidelines of ACGIH
and other groups. The RELs are found in the "NIOSH Recommendations for Occupational Health
Standards" (see Appendix II).
American Industrial Hygiene Association (AIHA). The American Industrial Hygiene Association
has provided guidance for industrial hygienists for many years. In 1984, AIHA developed exposure
guidelines that it calls Workplace Environmental Exposure Level Guides (WEELs). These are
reviewed and updated each year. Appendix HI has the current list of WEELs. While the list is not
as large as others, AIHA has chosen chemicals for which other groups do not have exposure
guidelines. Thus, they are providing information to fill the gaps left by others.
Types of Exposure Guidelines
Several organizations develop exposure guidelines. However, the types of guidelines they produce
are similar.
Time-Weighted Average (TWA). This exposure is determined by averaging the concentrations of
the exposure with each concentration weighted based on the duration of exposure. For example, an
exposure to acetone at the following concentrations and durations:
1000 ppm for Shows
SOOppmfor 2 hours
200ppmfor 3 hours
would have an 8-hour, TWA exposure of:
(3 hrsHlOOO pom) + f2 hrsifSOO onm) + (3 hrs}(200 nnm\
8hrs
3000 pom + 1000 ppm + 600 ppm
8
= 575 ppm
This exposure would be compared to an 8-hour TWA exposure limit.
A TWA can be the average concentration over any period of time. However, most TWAs are the
average concentration of a chemical most workers can be exposed to during a 40-hour week and a
normal 8-hour work day without showing any toxic effects. NIOSH TWA recommendations, on the
other hand, can also be based on exposures up to 10 hours. The time-weighted average permits
exposure to concentrations above the limit, when they are compensated by equal exposure below the
TWA. (Graph 3) shows an example that illustrates this point for a chemical with a TWA exposure
limit of 750 ppm.
Toxicology and Exposure Guidelines 24 6/93
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TIME WEIGHTED AVERAGE
(TWA)
750
UJ
O
z
O
O
TWA-EL
6AM
10 AM
TIME
3 PM
GRAPHS
EXAMPLE OF AN EXPOSURE COMPARED TO A TWA EXPOSURE LIMIT
Short-Term Exposure Limit (STEL). The excursions allowed by the TWA could involve very high
concentrations and cause an adverse effect, but still be within the allowable average. Therefore,
some organizations felt there was a need for a limit to these excursions. In 1976, ACGIH added
STELs to its TLVs. The STEL is a 15 minute, TWA exposure. Excursions to the STEL should
be at least 60 minutes apart, no longer than IS minutes in duration and should not be repeated more
than 4 times per day. Because the excursions are calculated into the 8-hour TWA, the exposure must
be limited to avoid exceeding the TWA. Graph 4 illustrates an exposure that exceeds the IS minute
limit for an STEL of 1000 ppm.
The STEL supplements the TWA. It reflects an exposure limit that protects against acute effects
from a substance which primarily exhibits chronic toxic effects. This concentration is set at a level
to protect workers against irritation, narcosis, and irreversible tissue damage. OSHA added STELs
to its PELs with the 1989 revisions.
6/93
25
Toxicology and Exposure Guidelines
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AIHA has some short-term TWAs similar to the STELs. The times used vary from 1 to 30 minutes.
These short-term TWAs are used in conjunction with, or in place of, the 8-hour TWA. There is no
limitation on the number of these excursions or the rest period between each excursion.
SHORT TERM EXPOSURE LIMIT
(STEL)
<
DC
UJ
O
z
O
O
1000
750
TWA-EL
6AM
10AM
TIME
3 PM
GRAPH 4
EXAMPLE OF AN EXPOSURE COMPARED TO AN STEL AND A TWA
Ceiling (Q. Ceiling values exist for substances where exposure results in a rapid and particular type
of response. It is used where a TWA (with its allowable excursions) would not be appropriate.
ACGIH and OSHA state that a ceiling value should not be exceeded even instantaneously. They
denote a ceiling value by a "C" preceding the exposure limit.
NIOSH also uses ceiling values. However, their ceiling values are more like a STEL. Many have
time limits (from 5 to 60 minutes) associated with the exposure. Graph 5 illustrates an exposure
that does not exceed a ceiling value of 5 ppm.
Toxicology and Exposure Guidelines
26
6/93
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CEILING
(C)
Ceiling
111
o
z
o
o
6 AM
10 AM
TIME
3 PM
GRAPH 5
EXAMPLE OF AN EXPOSURE COMPARED TO A CEILING EXPOSURE LIMIT
Peaks. Until recently ANSI, and OSHA where they have adopted ANSI standards, had used a peak
exposure limit. This peak exposure is an allowable excursion above their ceiling values. The
duration and number of exposures at this peak value is limited. For example, ANSI allowed the 25
ppm ceiling value for benzene to be exceed to 50 ppm but only for 10 minutes during an 8 hour
period. ANSI withdrew its exposure limit standards in 1982. With the revision of the PELs in
1989, OSHA has dropped most of its peak values.
"Skin" Notation. While these exposure guidelines are based on exposure to airborne concentrations
of chemicals. However, OSHA, NIOSH, ACGIH and AIHA recognize that there are other routes
of exposure in the workplace. In particular, there can be a contribution to the overall exposure from
skin contact with chemicals that can be absorbed through the skin. Unfortunately, there is very little
data available that quantifies the amount of allowable skin contact. But some organizations provide
qualitative information about skin absorbable chemicals. When a chemical has the potential to
contribute to the overall exposure by direct contact with the skin, mucous membranes or eyes, it is
given a "skin" notation.
6/93
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Toxicology and Exposure Guidelines
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This "skin" notation not only points out chemicals that are readily absorbed through the skin, but also
notes that if there is skin contact, the exposure guideline for inhalation may not provide adequate
protection. The inhalation exposure guidelines are designed for exposures only from inhalation. If
additional routes of exposure are added, there can be detrimental effects even if the exposure
guideline is not exceeded.
Immediately Dangerous to Life or Health (IDLH). In the May 1987 "NIOSH Respirator Decision
Logic", IDLH is defined as a condition "that poses a threat of exposure to airborne contaminants
when that exposure is likely to cause death or immediate or delayed permanent adverse health effects
or prevent escape from such an environment. The purpose of establishing an IDLH exposure level
is to ensure that the worker can escape from a given contaminated environment in the event of failure
of the respiratory protection equipment."
Other organizations, such as ANSI, OSHA, and the Mine Safety and Health Administration (MSHA),
have defined IDLH similarly. It is accepted by all of these groups that IDLH conditions include not
only toxic concentrations of contaminants, but also oxygen-deficient atmospheres and explosive, or
near-explosive (above, at, or near the lower explosive limits), environments.
At hazardous material incidents, IDLH concentrations should be assumed to represent concentrations
above which only workers wearing respirators that provide the maximum protection (i.e., a positive-
pressure, full-facepiece, self-contained breathing apparatus [SCBA] or a combination positive-
pressure, full-facepiece, supplied-air respirator with positive-pressure escape SCBA) are permitted.
Specific IDLH concentrations values for many substances can be found in the NIOSH "Pocket Guide
to Chemical Hazards." Guidelines for potentially explosive, oxygen deficient, or radioactive
environments can be found in the U.S. EPA "Standard Operating Safety Guidelines" and the
NIOSH/OSHA/USCG/EPA Occupational Safety and Health Guidance Manual for Hazardous Waste
Site Activities.
Exposure Limits for Chemical Mixtures
The exposure limits that have been discussed are based upon exposure to single chemicals. Since
many exposures include more than one chemical, values are adjusted to account for the combination.
When the effects of the exposure are considered to be additive, a formula can be used to determine
whether total exposure exceeds the limits. The calculation used is:
Em = (C,*L, + C^LJ + ... (CH+LJ
where:
Em is the equivalent exposure for the mixture.
C is the concentration of a particular contaminant.
L is the exposure limit for that substance.
The value ofEm should not exceed unity (1).
Toxicology and Exposure Guidelines 28 6/93
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An example using this calculation would be as follows:
Chemical A C = 200 ppm L = 750 ppm
Chemical B C = 100 ppm L = 500 ppm
Chemical C C = 50 ppm L = 200 ppm
Em = 200+750 + 100+500 + 50+200
Em = 0.27 + 0.20 + 0.25
Em = 0.72
Since Em is less than unity, the exposure combination is within acceptable limits.
This calculation applies to chemicals where the effects are the same and are additive. If the
combination is not additive, the calculation is not appropriate.
Application of Exposure Guidelines
In 29 CFR 1910.120, "Hazardous Waste Operations and Emergency Response" standard, OSHA
specifies the use of certain exposure limits. The exposure limits specified are OSHA's permissible
exposure limits (PELs) and "published exposure levels." The "published exposure levels" are used
when no PEL exists. A "published exposure level" is defined as "the exposure limits published in
'NIOSH Recommendations for Occupational Health Standards' dated 1986 incorporated by reference.
If none is specified, the exposure limits published in the standards specified by the American
Conference of Governmental Industrial Hygienists in their publication Threshold Limit Values and
Biological Exposure Indices.
Engineered Controls and Work Practices. 29 CFR 1910.120 (g) (1) (i) states "Engineering
controls and work practices shall be instituted to reduce and maintain employee exposure to or below
the permissible exposure limits for substances regulated by 29 CFR Part 1910, to the extent required
by Subpart Z, except to the extent that such controls and practices are not feasible." (emphasis
added) Whenever engineering controls and work practices are not feasible, personal protective
equipment shall be used to reduce and maintain exposures.
For those substances or hazards where there is no PEL, the published exposure levels, published
literature and material safety data sheets (MSDS) will be used for evaluation. In these
circumstances, a combination of engineering controls, work practices and PPE shall be used to
reduce and maintain exposures.
Personal Protective Equipment. Since PPE must be selected based on the hazards present at the
site, the exposure limits are used to evaluate the effectiveness of the PPE. Comparing the actual or
expected exposure to the PEL or other exposure limits gives the wearer information on selection of
the proper PPE.
Medical Surveillance. 29 CFR 1910.120(0(2)0) requires a medical surveillance program for all
employees exposed to substances or hazards above the PEL for 30 or more days per year. If there
is no PEL, then the published exposure levels are used for evaluation. The exposures are considered
even if a respirator was being used at the time of exposure.
5/pj 29 Toxicology and Exposure Guidelines
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Limitations/Restrictions of Exposure Guideline Use
The exposure guidelines discussed in this part are based on industrial experience, experimental
human studies, experimental animal studies, or a combination of the three. The guidelines were
developed for workers in the industrial environment. Thus, they are not meant to be used for other
purposes. ACGIH in its Threshold Limit Values and Biological Exposure Indices for 1992-1993
states:
These limits are intended for use in the practice of industrial hygiene as guidelines
or recommendations in the control of potential health hazards and for no other use,
e.g., in the evaluation or control of community air pollution nuisances, in estimating
the toxic potential of continuous, uninterrupted exposures or other extended work
periods, as proof or disproof of an existing disease or physical condition, or adoption
by countries whose working conditions differ from those in the United States of
America and where substances and processes differ. These limits are not fine lines
between safe and dangerous concentration nor are they a relative index of toxicity,
and should not be used by anyone untrained in the discipline of industrial hygiene.
As can be seen from this qualifier, these exposure limits are not intended as exposure limits for
exposure by the public.
There is the limitation on the use of the exposure guideline as a relative index of toxicity. This is
because the exposure limits are based on different effects for different chemicals. For example, the
TLV-TWA for acetone is chosen to prevent irritation to the eyes and respiratory system. The TLV-
TWA for acrylonitrile is chosen to reduce the risk to cancer. Exposures to these chemicals at other
concentration levels could lead to other effects. Thus, when evaluating the risk of chemical
exposure, all toxicological data should be consulted.
Toxicology and Exposure Guidelines 30 6/93
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REFERENCES
Ariens, Everhard, A.M. Simonis, and J. Offermeir. Introduction to General Toxicology. Academic
Press, New York, NY, 1976.
Doull, John, Curtis D. Klaassen, Mary O. Amdur. Casarett and Doull's Toxicology: The Basic
Science of Poisons. Macmillan Publishing Co., Inc., New York, NY, 1986.
Loomis, Ted A. Essentials of Toxicology. Lea and Febiger, Philadelphia, PA, 1970.
National Institute for Occupational Safety and Health. Registry of Toxic Effects of Chemical
Substances. DHHS (NIOSH) Publication No. 83-107, Volumes 1-3, U.S. Government Printing
Office, Washington, DC, 1983.
National Institute for Occupational Safety and Health. The Industrial Environment: Its Evaluation
and Control. U.S. Government Printing Office, Washington, DC, 1973.
National Institute for Occupational Safety and Health. Occupational Diseases: A Guide to Their
Recognition. U.S. Government Printing Office, Washington, DC, 1977.
Proctor, Nick H., and James P. Hughes. Chemical Hazards of the Workplace. J.B. Lippincott Co.,
Philadelphia, PA, 1978.
U.S.-Department of Labor. Occupational Safety and Health Toxicology Training Course 100-124-9,
December 8-16, 1981, Chicago, IL.
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RESPIRATORY PROTECTION
The respiratory system is able to tolerate exposures to toxic gases, vapors, and particulates, but only
to a limited degree. Some chemicals can impair or destroy portions of the respiratory tract, or they
may be absorbed directly into the bloodstream from the lungs. Chemicals that enter the blood may
eventually affect the function of other organs and tissues. The respiratory system can be protected
by avoiding or minimizing exposure to harmful substances. Engineering controls such as ventilation
help decrease exposure. When these methods are not feasible respirators may provide protection.
Certain respirators can filter gases, vapors, and particulates in the ambient atmosphere, other
respirators are available which can supply clean breathing air to the wearer.
The use of respirators is regulated by the Occupational Safety and Health Administration (OSHA).
Regulations stipulate the use of approved respirators, proper selection, and individual fitting of
respirator users.
Respiratory protection must be used when the concentration of a substance in the ambient atmosphere
exceeds a personal exposure limit. Several exposure limits used to determine the need for respiratory
protection. In order of precedence, these are the OSHA Permissible Exposure Limits (PELs),
NIOSH Recommended Exposure Limits (RELs), and the ACGIH Threshold Limit Values (TLVs).
If none of these are available, other published data may be used.
Respiratory Hazards
The normal atmosphere consists of 78% nitrogen, 21 % oxygen, 0.9% inert gases, and 0.04% carbon
dioxide. An atmosphere containing toxic contaminants, even at very low concentrations, could be
a hazard to the lungs and body. A concentration large enough to decrease the percentage of oxygen
in the air can lead to asphyxiation, even if the contaminant is an inert gas.
Oxygen Deficiency. The body requires oxygen to live. If the oxygen concentration decreases, the
body reacts in various ways (Table 1). Death occurs rapidly when the concentration decreases to
6%.
Physiological effects of oxygen deficiency are not apparent until the concentration decreases to 16%.
The various regulations and standards dealing with respirator use recommend that concentrations
ranging from 16 to 19.5 % be considered indicative of an oxygen deficiency. Such numbers take into
account individual physiological responses, errors in measurement, and other safety considerations.
In hazardous materials response operations 19.5% oxygen in air is considered the lowest "safe"
working concentration. Below 19.5% available oxygen, a supplied air respirator must be used.
6/93 1 Respiratory Protection
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TABLE 1
PHYSIOLOGICAL EFFECTS OF OXYGEN DEFICIENCY
% Oxygen
(by volume)
at Sea Level
21-16
16-12
12-10
10-6
<6
Effects
Nothing abnormal.
Loss of peripheral vision, increased breathing volume, accelerated
heartbeat, impaired attention and thinking, impaired coordination.
Very faulty judgment, very poor muscular coordination, muscular
exertion causes fatigue that may cause permanent heart damage,
intermittent respiration.
Nausea, vomiting, inability to perform vigorous movement, or loss
of all movement, unconsciousness, followed by death.
Spasmatic breathing, convulsive movements, death in minutes.
Aerosols. Aerosol is a term used to describe fine particulates (solid or liquid) suspended in air.
Particulates ranging in diameter from 5 to 30 microns are deposited in the nasal and pharyngeal
passages. The trachea and smaller conducting tubes collect particulates 1-5 microns in diameter.
For particulates to diffuse from the bronchioles into alveoli they must be less than 0.5 microns in
diameter. Larger particles do reach the alveoli due to gravity. The smallest particulates may never
be deposited in the alveoli and so may diffuse back into the conducting tubes to be exhaled.
Aerosols can be classified in two ways: by their physical form and origin and by the physiological
effect on the body.
• Physical Classification Examples:
Mechanical dispersoid: liquid or solid particle mechanically produced.
Condensation dispersoid: liquid or solid particle often produced by
combustion.
Spray: visible liquid mechanical dispersoid.
Fume: extremely small solid condensation dispersoid.
Mist: liquid condensation dispersoid.
Fog: mist dense enough to obscure vision.
Smoke: liquid or solid organic particles resulting from incomplete
combustion.
Smog: mixture of smoke and fog.
• Physiological Classification Examples:
Nuisance: no lung injury but proper lung functioning inhibited.
Inert pulmonary reaction causing: non-specific reaction.
Respiratory Protection 2 6/93
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Pulmonary fibrosis causing: effects ranging from nodule production in lungs
to serious diseases such as asbestosis.
Chemical irritation: irritation, inflammation, or ulceration of lung tissue.
Systemic poison: diseases in other parts of the body.
Allergy-producing: causes allergic hypersensitivity reactions such as itching
or sneezing.
Gaseous Contaminants. Gases and vapors are filtered to some degree on their trip through the
respiratory tract. Soluble gases and vapors are absorbed by the conducting tubes en route to the
alveoli. Not all will be absorbed so that along with insoluble gases, they finally diffuse into the
alveoli where they can be directly absorbed into the bloodstream.
Gaseous contaminants can be classified as chemical and physiological hazards.
• Chemical Contaminants:
Acidic: acids or react with water to form acids.
Alkaline: bases or react with water to form bases.
Organic: compounds which contain carbon; may range from methane to
chlorinated organic solvents.
Organometallic: organic compounds containing metals.
Hydrides: compound in which hydrogen is bonded to another metal.
Inert: no chemical reactivity.
• Physiological Contaminants:
Irritants: corrosive substances which injure and inflame tissue.
Asphyxiants: substances which displace oxygen or prevent the use of oxygen
in the body.
Anesthetics: substances which depress the central nervous system, causing
a loss of sensation or intoxication.
Systemic poisons: substances which can cause disease in various organ
systems.
Respirator Use and Selection
The health of a respirator wearer is based on how the respirator is used. The American National
Standards Institute (ANSI) has prepared the American National Standard Practices for Respiratory
Protection and updates it periodically. The latest version, Z88.2-1980, was issued in 1980 as a
voluntary standard. It addresses all phases of respirator use and is highly recommended as a guide
to respiratory protection.
The Occupational Safety and Health Administration (OSHA), in 29 CFR Part 1910.120, refers to
29 CFR Part 1910.134 as the source of respiratory protection regulations issued in 1975. In 29 CFR
Part 1910.134, OSHA cites ANSI Z88.2-1969 as the reference for these enforceable regulations.
6/93 3 Respiratory Protection
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Section b of 29 CFR 1910.134, as well as Z88.2-1980, requires a "minimal acceptable program" to
ensure sound respiratory protection practices. The balance of the regulations discusses specific
requirements for respiratory use. The requirements for a minimal acceptable program are quoted
from 29 CFR 1910.134 as follows:
• Written standard operating procedures governing the selection and use of respirators
shall be established.
• Respirators shall be selected on the basis of the hazards to which the worker is
exposed.
• The user shall be instructed and trained in the proper use of respirators and their
limitations.
• Respirators shall be regularly cleaned and disinfected. Those used by more than one
worker shall be thoroughly cleaned and disinfected after each use.
• Respirators shall be stored in a convenient, clean, and sanitary location.
• Respirators used routinely shall be inspected during cleaning. Worn or deteriorated
parts shall be replaced. Respirators for emergency use such as self-contained devices
shall be thoroughly inspected at least once a month and after each use.
• Appropriate surveillance of work area conditions and degree of employee exposure
or stress shall be maintained.
• There shall be regular inspection and evaluation to determine the continued
effectiveness of the program.
• Persons should not be assigned to tasks requiring use of respirators unless it has been
determined that they are physically able to perform the work and use the equipment.
The local physician shall determine what health and physical conditions are pertinent.
The respirator user's medical status should be reviewed periodically (for instance
annually).
• Approved respirators shall be used. The respirator furnished shall provide adequate
respiratory protection against the particular hazard for which it is designed in
accordance with approvals established by the National Institute for Occupational
Safety and Health (NIOSH).
In general ANSI Z88.2-1980 states that the selection of the proper approved respirator depends upon:
• The nature of the hazard.
• The characteristics of the hazardous operation or process.
• The location of the hazardous area with respect to a safe area having respirable air.
Respiratory Protection 4 6/93
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• The period of time for which respiratory protection may be needed.
• The activity of workers in the hazardous area.
• The physical characteristics, functional capabilities, and limitations of respirators of
various types.
• The respirator/protection factors and respirator fit.
All of these criteria must be considered in the selection of a respirator. The Joint NIOSH/OSHA
Standards Completion Respirator Committee devised a "Respirator Decision Logic" based on the
above criteria. ANSI Z88.2-1980 also describes the suitability of a particular respiratory protective
device for oxygen deficient or immediately dangerous to life or health (IDLH) atmosphere. This
information supplies only a portion of the information required to select the appropriate respirator.
Respirator Approval
OSHA regulations require the use of approved respirators. Respirators are tested at the NIOSH
Testing Laboratory in Morgantown, West Virginia, in accordance with the requirements of 30 CFR
Part 11 and are jointly approved by the Mine Safety and Health Administration (MSHA).
An MSHA/NIOSH approval indicates that the respirator in use is identical to the one submitted for
the original approval. If a manufacturer changes any part of the respirator without resubmitting it
to the NIOSH Testing Lab, the approval is invalid and will be rescinded. This is intended to protect
the respirator user. Also, any unauthorized changes or hybridization of a respirator by the user
invalidates the respirator approval and all the guarantees understood with the approval.
Many agencies were responsible for respirator certification at one time or another. Thus respirators
in use today may bear approval numbers issued to the manufacturers by the Bureau of Mines,
MESA, and MSHA. The approval number must be displayed on the respirator or its container. It
consists of the prefix TC (Testing and Certification), the schedule number, followed by the approval
number. For example in TC-13F-69, "13" is the schedule for self-contained breathing apparatus,
"F" indicates the number of revisions to the schedule, and 69 is the consecutive approval number.
Also, the approval label includes the certifying agencies.
Periodically, NIOSH publishes a list of all approved respirators and respirator components. The
current edition, issued in 1991, is entitled the NIOSH Certified Equipment List as of December 31,
1991 (DHHS [NIOSH] Publication No. 91-101). This document is used to answer two basic
questions about respiratory protection:
• Is this respirator appropriate (approved) for the existing work conditions?
• Is this respirator (mask and purifying-elements) an approved assembly?
If the answer to either of these questions is "no," then the worker is prohibited from using that
respirator (or type of respirator).
Respiratory Protection
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AIR-PURIFYING RESPIRATORS
Air-purifying respirators (APRs) refer to respirators that remove contaminants by passing the
breathing air through a purifying element. There is a wide variety of APRs available to protect
against specific contaminants but they all fall into two subclasses: (1) paniculate APRs that employ
a mechanical filter element and (2) gas and vapor removing APRs that use chemical sorbents
contained in a cartridge or canister.
APRs may be used only if all of the following requirements are met:
• The identity and concentration of the contaminant are known.
• The ambient concentration of a contaminant is below the IDLH concentration.
• The oxygen content in the atmosphere is greater than 19.5%.
• The respirator assembly is approved for protection against the specific concentration
of a contaminant.
• There is periodic monitoring of the work area.
• The respirator assembly has been successfully fit-tested on the user.
Requirements for APR Use
The use of an APR is contingent upon a number of criteria. If the conditions spelled out in this
section of the text cannot be met, then use of an APR is prohibited.
• Oxygen Content. The normal atmosphere contains approximately 21 % oxygen. The
physiological effects of reduced oxygen begin to be evident at 16%. Without regard
to contaminants, the atmosphere must contain a minimum of 19.5% oxygen to permit
use of an APR. This is a legal requirement of 30 CFR Part 11 and a
recommendation of ANSI Z88.2 - 1980. Below 19.5% oxygen, atmosphere-
supplying respirators must be used instead.
• Identification of Contaminants. It is absolutely imperative that the contaminant(s)
be known so that: the toxic effects of inhaling the contaminant can be determined;
appropriate paniculate filters or cartridges/canisters can be chosen; it can be
determined that adequate warning properties exist for the contaminant; and, the
appropriate facepiece be selected (full-face mask is necessary if the agent causes eye
irritation).
• Known Contaminant Concentration. The maximum concentration depends on the
contaminant and the respirator: the concentration must not exceed IDLH; the
Maximum Use Limit of the respirator cannot be exceeded (MUL = APF x EL); the
Maximum Use Concentration of a particular type and size cartridge or canister must
Respiratory Protection 6
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not be surpassed; and the expected service life (cartridge/canister efficiency) should
be determined.
• Periodic Monitoring of Hazards. Because of the importance of knowing the identity
and concentration of the contaminant(s), monitoring of the work area with appropriate
equipment must occur at least periodically during the work day. This is done to
ensure that no significant changes have occurred and the respirators being used are
adequate for the work conditions.
• Approval of Respirators. The respirator assembly (facepiece and air-purifying
elements) is approved for protection against the contaminant at the concentration
which is present in the work area. The concentration must not exceed the
NIOSH/MSHA designated MUC for that type and size cartridge or canister.
• Fit-test. The wearer must pass a qualitative fit-test for the make, model, and size
of air-purifying device used. The OSHA regulations, in 29 CFR 1910.134(e)(5)(i),
state:
Every respirator wearer shall receive fitting instructions including demonstrations and
practice in how the respirator is worn, how to adjust it, and how to determine if it
fits properly.
Respirators shall not be worn when conditions prevent a good face seal. Such
conditions may be growth of beard, sideburns, a skull cap that projects under the
facepiece, or temple pieces on glasses. Also, the absence of one or both dentures can
seriously affect the fit of a facepiece. The worker's diligence in observing these
factors shall be evaluated by periodic check. To assure proper protection, the
facepiece fit shall be checked by the wearer each time he puts on the respirator. This
may be done by giving fitting instructions.
Air-Purifying Elements
Respiratory hazards can be broken down into two classes: particulates and vapors/gases.
Particulates are filtered by mechanical means, while vapors and gases are removed by sorbents that
react chemically with them. Respirators using a combination of mechanical filter and chemical
sorbent will effectively remove both hazards.
• Particulate-Removing Filters
Particulates can occur as dusts, fumes, or mists. The particle size can range from
macroscopic to microscopic, and their toxicological effects can be severe or innocuous. The
hazard posed by a paniculate can be determined by its exposure limit (EL). A nuisance
paniculate will have an EL of 10 mg/m3, while a toxic paniculate may have an EL well
below 0.05 mg/m3.
Mechanical filters are classified according to the protection for which they are approved
under schedule 21C of 30 CFR Part 11. Most paniculate filters are approved only for dusts
7 Respiratory Protection
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and/or mists with ELs equal to or greater than 0.05 mg/m3. These dusts are usually
considered to produce pneumoconiosis and fibrosis. Such filters have an efficiency of
80-90% for 0.6-micron particles.
Respirators approved for fumes are more efficient, removing 90-99% for 0.6-micron
particles. This type of respirator is approved for dusts, fumes, and mists with ELs equal to
or greater than 0.05 mg/m3.
Finally there is a high-efficiency filter, which is 99.97% effective against particles
0.3 microns in diameter. It is approved for dusts, mists, and fumes with an EL less than
0.05 mg/m3.
Mechanical filters load with particulates as they are used. As they do, they become more
efficient, but also become more difficult to breathe through. When a mechanical filter
becomes difficult to breathe through it should be replaced.
• Gas and Vapor-Removing Cartridges and Canisters
When selecting a gas- or vapor-removing element, it must be chosen for protection against
a specific type of contaminant. Some of the commonly employed types of chemical
cartridges and canisters and their OSHA-required color coding are listed in Table 2. This
table has been excerpted from the OSHA respirator regulations for general industry (29 CFR
1910.134).
Gas and vapor elements are available in different styles. The physical differences are: (1)
size and (2) means of attachment to the facepiece. The smallest elements are cartridges
which contain 50-200 cm3 of sorbent and attach directly to the facepiece, usually in pairs.
Chin canisters have a volume of 250-500 cm3 and are attached to a full-facepiece. Gas
mask, or industrial-size canisters contain 1000-2000 cm3 and are attached by a harness to the
wearer's front or back and connected to the full-facepiece by a breathing hose.
The difference in applications is the Maximum Use Concentration (MUC) for which the
cartridge or canister can be used in accordance with its NIOSH/MSHA approval. For
example, organic vapors can be removed by the appropriate cartridges, chin canister, or gas-
mask canister. Cartridges are approved for use in atmospheres up to 1,000 ppm (0.1%)
organic vapors, chin style canisters up to 5000 ppm (0.5%), and gas mask canisters up to
20,000 ppm (2.0%). However, no air-purifying respirator is permitted in an IDLH
atmosphere.
Each sorbent has a finite capacity for removing contaminants and when this limit is reached
the cartridge or canister is said to be saturated. At this point the element will allow the
contaminant to pass through and enter the facepiece. The length of time a cartridge or
canister will effectively sorb the contaminant is known as the service life of the element.
Service life of a type of cartridge or canister is dependent on several factors: the breathing
rate of the wearer, contaminant concentration, and sorption efficiency.
Respiratory Protection 8 6/93
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TABLE 2
CHEMICAL CARTRIDGE TYPES AND COLOR CODING
§1910.134 and 29 CFR Ch. XVII (7-1-86 Edition)
Atmospheric Contaminants to be
Protected Against
Acid gases
Hydrocyanic acid gas
Chlorine gas
Organic vapors
Ammonia gas
Acid gases and ammonia gas
Carbon monoxide
Acid gases and organic vapors
Hydrocyanic acid gas and chloropicrin
vapor
Acid gases, organic vapors, and
ammonia gases
Radioactive materials, excepting
tritium and noble gases
Particulates (dusts, fumes, mists, fogs,
or smokes) in combination with any of
the above gases or vapors
All of the above atmospheric
contaminants
Colors Assigned1
White
White with 1/2-inch green stripe completely around
the canister near the bottom
White with 1/2-inch yellow stripe completely around
the canister near the bottom
Black
Green
Green with 1/2-inch white stripe completely around
the canister near the bottom
Blue
Yellow
Yellow with 1/2-inch blue stripe completely around
the canister near the bottom
Brown
Purple (Magenta)
Canister color for contaminant, as designated above,
with 1/2-inch gray stripe completely around the
canister near the top
Red with 1/2-inch gray stripe completely around the
canister near the top
1 Gray shall not be assigned as the main color for a canister designed to remove acids or vapors.
Note: Orange shall be used as a complete body or as a stripe color to represent gases not included
in this table. The user will need to refer to the canister label to determine the degree of protection
the canister will afford.
6/93
Respiratory Protection
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If the breathing rate of the user is rapid, the flow rate of the contaminated air drawn
through the cartridge is greater than it is at a moderate or slow respiration rate. A higher
flow rate brings a larger amount of contaminant in contact with the sorbent in a given period
of time which, in turn, increases the rate of sorbent saturation and shortens service life.
The expected service life of an organic vapor cartridge decreases as ambient contaminant
concentration increases. As concentration goes up, the mass flow rate increases, bringing
more contaminant in contact with the sorbent in a given period of time. For example, at any
constant breathing rate, ten times as much contaminant contacts the element when the
concentration is 500 ppm compared to SO ppm.
Chemical sorbents vary in their ability to remove contaminants from air. Table 3 compares
the efficiency of organic vapor cartridges for a number of solvents by recording the amount
of time until a 1% breakthrough concentration was measured in the cartridge-filtered air. The
initial test concentration is 1000 ppm of solvent vapor; the breakthrough concentration is 10
ppm. From the table it can be seen that it takes 107 minutes for chlorobenzene to reach a
1% breakthrough, while it only takes 3.8 minutes for vinyl chloride. The sorbent (activated
carbon) in the organic vapor cartridge is much better for removing chlorobenzene than vinyl
chloride under the test conditions. Cartridge efficiencies need to be considered when
selecting and using APRs.
A warning property is used as a sign that a cartridge or canister in use is beginning to lose
its effectiveness. A warning property can be detected as an odor, taste, or irritation. At the
first such signal, the old cartridge or canister must be exchanged for a fresh one. Without
a warning property, respirator efficiency may drop without the knowledge of the wearer,
ultimately causing a health hazard.
Most substances have warning properties at some concentration. A warning property
detected only at dangerous levels—that is, greater than EL—is not considered adequate. An
odor, taste, or irritation detected at extremely low concentrations is also not adequate because
the warning is being given all the time or long before the filter begins to lose its
effectiveness. In this case, the wearer would never realize when the filter actually becomes
ineffective.
The best concentration for a warning property to be first detected is around the EL. For
example, toluene has an odor threshold of 40 ppm and an EL of 100 ppm. This is usually
considered an adequate warning property. Conversely, dimethylformamide has an EL of 10
ppm and an odor threshold of 100 ppm. An odor threshold ten times the EL is not an
adequate warning property.
If a substance causes rapid olfactory fatigue (i.e., the sense of smell is no longer effective),
its odor is not an adequate warning property. For example, upon entering an atmosphere
containing hydrogen sulfide, the odor is quite noticeable. After a short period of time, it is
no longer detectable.
Respiratory Protection 10 6/93
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TABLE 3
EFFECTS OF SOLVENT VAPOR ON RESPIRATOR CARTRIDGE EFFICIENCY1
Solvent
Time to Reach 1% Breakthrough (10 ppm)
(minutes2)
Aromatics3
Benzene
Toluene
Ethyl benzene
m-Xylene
Cutnene
Mesitylene
73
94
84
99
81
86
Alcohols3
Methanol
Ethanol
Isopropanol
Ally! alcohol
n-Propanol
sec-Butanol
Butanol
2-Methoxyethanol
Isoamyl alcohol
4-Methyl-2-pentanol
2-Ethoxyethanol
Amyl alcohol
2-Ethyl-l-butanol
0.2
28
54
66
70
96
115
116
97
75
77
102
76.5
Monochlorides3
Methyl chloride
Vinyl chloride
Ethyl chloride
Allyl chloride
1-Chloropropane
1-Chlorobutane
Chlorocyclopentane
Chlorobenzene
1-Chlorohexane
0-Chlorotoluene
1-Chloroheptane
3-(Chloromethyl heptane)
0.05
3.8
5.6
31
25
72
78
107
77
102
82
63
1 Nelson, G.O , and C A. Harder Respirator Cartridge Efficiency Studies, University of California, Livermore. 1976.
2 Cartridge pairs tested at 1000 ppm, 50% relative humidity, 22°C, and 53.3 liters/minute (equivalent to a moderately heavy
work rate). Pair cartridges preconditioned at room temperature and 50% relative humidity for at least 24 hours
pnor to testing.
3 Mine Safety Appliances Cartridges.
6/93
11
Respiratory Protection
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Determining Respirator Protection
The protection provided the wearer is a function of how well the facepiece (mask) fits. No matter
how efficient the purifying element, there is little protection afforded if the respirator mask does not
provide a leak-free facepiece-to-face seal. Facepieces are available in three basic configurations
which relate to their protective capacity:
• A quarter-mask fits over the bridge of the nose, along the cheek, and across the top
of the chin. The headbands which hold the respirator in place are attached at two or
four places of the mask. Limited protection is expected because the respirator can
be easily dislocated, creating a breach in the seal.
• A half-mask fits over the bridge of the nose, along the cheek, and under the chin.
Headbands have a four-point suspension. Because they maintain a better seal and are
less likely to be dislocated, half-masks give better protection than quarter masks.
• A full-facepiece fits across the forehead, down over the temples and cheeks, and
under the chin. They typically have a head harness with a five or six-point
suspension. These masks give the greatest protection because they are held in place
more securely and because it is easier to maintain a good seal along the forehead than
it is across the top of the nose. An added benefit is the eye protection from the clear
lens in the full-facepiece.
The use of respirators is prohibited when conditions prevent a good facepiece-to-face seal. Some
examples of these conditions are facial hair, skullcaps, long hair, makeup, temple pieces on
eyeglasses. Because maintaining a leak-free seal is so important, personnel required to wear
respirators must successfully pass a fit-test designed to check the integrity of the seal.There are two
types of fit-tests: quantitative and qualitative. The quantitative test is an analytical determination
of the concentration of a test agent inside the facepiece compared to that outside the mask. This
concentration ratio is called the assigned protection factor (APF) and is a measure of the relative
protection offered by a respirator. For example, if the ambient concentration of the test agent is
1000 and the concentration inside the mask is 10 ppm, the respirator gives the tested individual an
APF of 100. Therefore:
Concentration outside mask
APF = Concentration inside mask
Because quantitative tests are expensive and tedious, qualitative tests are most often performed to
check respirator fit. A qualitative fit-test is not an analytical measurement. It is a subjective test
where an irritant or aroma is used to determine if there is a good facepiece-to-face seal. If the test
subject does not respond (by smelling, tasting, coughing, etc.) to the test agent, he/she can wear the
tested respirator with the APF for that type of mask. Table 4 lists several types of respirators and
their APFs.
A protection factor is used to determine the maximum use limit (MUL) of a successfully fit-tested
respirator. The MUL is the highest concentration, not exceeding IDLH concentration, of a specific
contaminant in which a respirator can be worn:
MUL = APF x TLV
Respiratory Protection 12
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For example, if a contaminant has a TLV-TWA of 10 ppm, then the MUL for any half-mask
respirator is 100 ppm. The MUL for a full-facepiece APR or demand self-contained breathing
apparatus (SCBA) is 1000 ppm. If the ambient concentration is greater than 1000 ppm, then a
pressure-demand SCBA is required because the MUC for organic vapor cartridges is 1000 ppm.
Fit testing and assigned protection factors are only two of the several considerations for selecting the
proper type of respirator.
TABLE 4
RESPIRATOR ASSIGNED PROTECTION FACTORS1
Type of Respirator
Air-purifying
Quarter-mask
Half-mask
Air-line
Quarter-mask
Half-mask
Hose mask
Full facepiece
SCBA, demand
Quarter-mask
Half-mask
Air-purifying
Full facepiece
Air-line, demand
Full facepiece
SCBA, demand
Full facepiece
Air-line, pressure-demand,
with escape provision
Full facepiece (no test required)
SCBA, pressure-demand or
positive pressure
Full facepiece (no test required)
NIOSH APF (Qualitative Test)
5
10
10
10
10
10
10
50
50
50
10,000
10,000
1 For more detailed information consult Table 5, "Respirator Protection Factors" in ANSI
Z88.2-1980.
6/93
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Respiratory Protection
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ATMOSPHERE-SUPPLYING RESPIRATORS
Atmosphere-supplying respirators refer to another classification of respirators. These types of
respirators provide a substitute source of breathing air. The respirable air may.be supplied to the
wearer by a portable breathing air source (SCBA) or by a stationary source such as an air-line (a
supplied-air respirator).
Types of Atmosphere-Supplying Respirators
Respiratory apparatus must frequently be used during response to hazardous materials incidents. If
the contaminant is unknown, or the requirements for using air-purifying respirators cannot be met,
then an atmosphere-supplying respirator is required. Several types of atmosphere-supplying devices
are available.
• Hose Mask. This type of respirator consists of a facepiece attached to a large diameter hose
which transports clean air from a remote area. In units where the wearer breathes the air in,
the hose lines can go up to 75 feet. With powered units the hose length can vary from 50
to 250 feet.
• Airline Respirator. The airline respirator is similar to the hose mask, except that breathing
grade air is delivered to the wearer under pressure; either from a compressor or a bank of
compressed air cylinders. The air may flow continuously, or it may be delivered as the
wearer breathes (demands it). The air source must not be depletable, and no more than 300
feet of airline is allowed. An SCBA escape device is required for entry into an IDLH
atmosphere.
• Oxygen-Generating. One of the oldest respirators is the oxygen-generating respirator,
which uses a canister of potassium superoxide. The chemical reacts with water vapor to
produce oxygen which replenishes the wearer's exhaled breath. Exhaled CO2 is removed by
a scrubber device containing LiOH. This reoxygenated air is then returned to the wearer.
Oxygen-generating respirators have been used by the military and for escape purposes in
mines. It generally is not used for hazardous material applications because of the chemical
reaction taking place within the respirator itself.
• Self-Contained Breathing Apparatus. The SCBA consists of a facepiece and regulator
mechanism connected to a cylinder of compressed air or oxygen carried by the wearer. The
SCBA is generally used because it allows the wearer to work without being confined by a
hose or airline. The wearer of the SCBA depends on it to supply clean breathing air.
Modes of Operation
The SCBA and the supplied-air respirator may be differentiated by the type of air flow supplied to
the facepiece:
Respiratory Protection 14 6/93
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Negative-pressure. In a negative-pressure mode (also referred to as demand mode),
a negative pressure is created inside the facepiece and breathing tubes when the
wearer inhales (Table 5). This negative pressure draws down a diaphragm in the
SCBA's regulator. The diaphragm depresses and opens the admission valve,
allowing air to be inhaled. As long as the negative pressure remains, air flows to the
facepiece.
The problem with demand operation is that the wearer can inhale contaminated air
through any gaps in the facepiece-to-face sealing surface. Hence, a demand
apparatus with a full facepiece is assigned a protection factor of only 100, the same
as for a full-face, air-purifying respirator.
Positive-pressure. In the positive-pressure mode (also referred to as a pressure-
demand mode) a positive pressure is maintained inside the facepiece at all times. The
system is designed so that the admission valve remains open until enough pressure
is built up to close it. The pressure builds up because air is prevented from leaving
the system until the wearer exhales. Less pressure is required to close the admission
valve than is required to open the spring-loaded exhalation valve.
At all times, the pressure in the facepiece is greater than the ambient pressure outside
the facepiece. If any leakage occurs, it is outward from the facepiece. Because of
this, the pressure-demand (positive-pressure) SCBA has been assigned a protection
factor of 10,000.
TABLE 5
RELATIVE PRESSURE INSIDE AND OUTSIDE SCBA FACEPIECE
Action
Inhalation
Exhalation
Static (between breaths)
Demand
+
same
Pressure Demand
(positive pressure)
+
+
+
Types of SCBAs
There are two types of SCBA apparatus: closed-circuit, which use compressed oxygen, and open-
circuit, which use compressed air. SCBAs may operate in one of two modes, demand (negative-
pressure) or pressure-demand (positive-pressure). The length of time an SCBA operates is based on
the air supply. The units available operate from 5 minutes to over 4 hours. The pressure-demand
(positive pressure) is the only approved type of open-circuit SCBA for use in hazardous environments
by the U.S. Environmental Protection Agency (EPA) and NFPA.
• Closed-Circuit SCBA
The closed-circuit SCBA (Figure 1), commonly called the rebreather, was developed
especially for oxygen-deficient situations. Because it recycles exhaled breath and
6/93 15 Respiratory Protection
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carries only a small oxygen supply, the service time can be considerably greater than
an open-circuit device, which must carry all of the user's breathing air.
HctdHirntli
Fiupleu
Exhalation Tube.,
Silivi Trip
and Pressure
fttllefVilvt
Mjln Vjlvt
Cr»nulir Solid Adsorbent lor Carbon Dloiloe
ComprtSMd —
Oryjen Tank
Inhilitlon Tube
Breithlnj tf)
Admission Valve
Pressure Plilt
Bypass Valve
Bypjsi Lint
FIGURE 1
CLOSED-CIRCUIT SCBA
The air for breathing is mixed in a flexible breathing bag. This air is inhaled, deflating the
breathing bag. The deflation depresses the admission valve, allowing the oxygen to enter the
bag. There it mixes with exhaled breath, from which carbon dioxide has just been removed
by passage through a C02 scrubber.
Most rebreathers operate in the demand mode. Several rebreathers are designed to provide
a positive pressure in the facepiece. The approval schedule 13F under 30 CFR Part II for
closed-circuit SCBA makes no provisions for testing "demand" or "pressure-demand"
rebreathers. The approval schedule was set up to certify only rebreathers that happen to
operate in the demand mode. Thus, rebreathers designed to operate in the positive pressure
mode can be approved strictly as closed-circuit apparatus. Since regulations make no
distinction, and selection is based on approval criteria, rebreathers designed to maintain a
positive pressure can only be considered as a demand-type apparatus. Rebreathers use either
compressed oxygen or liquid oxygen. To assure the quality of the air to be breathed, the
oxygen must be at least medical grade breathing oxygen which meets the requirements set
by the "U.S. Pharmacopeia."
Respiratory Protection
16
6/93
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• Open-Circuit SCBA
The open-circuit SCBA requires a supply of compressed breathing air. The user simply
inhales and exhales. The exhaled air is exhausted from the system. Because the air is not
recycled, the wearer must carry the full air supply, which limits a unit to the amount of air
that the wearer can easily carry. Available SCBAs can last from 5 to 60 minutes. Units that
have 5- to 15-minute air supplies are only applicable to escape situations.
The air used in open-circuit apparatus must meet the requirements in the Compressed Gas
Association's Pamphlet G-7.1, which calls for at least "Grade D." Grade D air must contain
19.5 to 23.5% oxygen with the balance being predominantly nitrogen. Condensed
hydrocarbons are limited to 5 mg/m3, carbon monoxide to 20 parts per million (ppm) and
carbon dioxide to 1,000 ppm. An undesirable odor is also prohibited. Air quality can be
checked using an oxygen meter, carbon monoxide meter and detector tubes.
Components of an Open-Circuit. Positive-Pressure SCBA
The user should be completely familiar with the SCBA being worn. Checkout procedures have been
developed for inspecting an SCBA prior to use, allowing the user to recognize potential problems.
An individual who checks out the unit is more comfortable and confident wearing it. If the wearer
is not properly trained to wear the SCBA or it is not properly cared for, then it may fail to provide
the protection expected.
• Backpack and harness. A backpack and harness support the cylinder and regulator,
allowing the user to move freely. Weight should be supported on the hips not the
shoulders.
•
Cylinder. Compressed air is considered a hazardous material. For this reason, any
cylinder used with an SCBA must meet the Department of Transportation's (DOT)
"General Requirements for Shipments and Packaging" (49 CFR Part 173) and
"Shipping Container Specifications" (49 CFR Part 178).
A hydrostatic test must be performed on a cylinder at regular intervals: for steel &
aluminum cylinders, every 5 years; for composite cylinders (glass fiber/aluminum),
every 3 years. Composite cylinders are relatively new, designed with fiberglass.
Composite cylinders have a DOT exemption because there are no set construction
requirements at this time. Overall difference is in weight. The construction
technology reduces the weight of the cylinder and thereby the overall weight of the
SCBA.
Air volume of 45 cubic feet of Grade D air at a pressure of 2,216 pounds per square
inch (psi) is needed for a 30-minute supply. Cylinders are filled using a compressor
or a cascade system of several large cylinders of breathing air. If the cylinder is
overfilled, a rupture disc releases the pressure. The rupture disc is located at the
cylinder valve, along with a cylinder pressure gauge to be accurate within ±5%.
Because the gauge is exposed and subject to abuse, it should be used only for judging
if the cylinder is full, and not for monitoring air supply to the wearer.
17 Respiratory Protection
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• High-Pressure Hose. The high-pressure hose connects the cylinder and the
regulator. The hose should be connected to the cylinder only by hand, never with
a wrench. An O-ring inside the connector assures a good seal.
• Alarm. A low-pressure warning alarm is located near the connection to the cylinder.
This alarm sounds to alert the wearer that only 20-25% of the full cylinder air supply
is available for retreat, usually 5 to 8 minutes.
• Regulator Assembly. Air travels from the cylinder through the high-pressure hose
to the regulator (Figure 2). There it can travel one of two paths. If the by-pass
valve is opened, air travels directly through the breathing hose into the facepiece.
If the mainline valve is opened, air passes through the regulator and is controlled by
that mechanism. Also at the regulator (before air enters one of the valves) is another
pressure gauge which also must be accurate to + 5%. Because it is visible and well
protected, this gauge should be used to monitor the air supply.
Under normal conditions, the bypass valve is closed and the mainline valve opened
so air can center the regular. Once in the regulator, the air pressure is reduced from
the actual cylinder pressure to approximately 50-100 psi by reducing mechanism. A
pressure relief valve is located after the pressure reducer for safety should the
pressure reducer malfunction.
• Breathing Hose and Facepiece. The breathing hose connects the regulator to the
facepiece. Rubber gaskets at both ends provide tight seals. The hose is usually
constructed of neoprene and is corrugated to allow stretching.
Above the point in the mask where the hose is connected, is a one way check valve.
This valve allows air to be drawn from the hose when the wearer inhales but prevents
exhaled air from entering the breathing hose. If the check valve is not in place, the
exhaled air may not be completely exhausted from the facepieces.
The facepiece is normally constructed of neoprene, but sometimes of silicone rubber.
Five- or six-point suspension is used to hold the mask to the face. The visor lens is
made of polycarbonate or other clear, shatter proof, and chemically resistant material.
At the bottom of the facepiece is an exhalation value. Some masks include an air-
tight speaking diaphragm, which facilitates communications while preventing
contaminated air from entering.
Respiratory Protection 18
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exhalation , •
valve body ~
exhalation valve -
spring
exhalation
valve cover
diaphragm-
regulator cover'
by-pnss valve
pressure
gauge
high pressure
cylinder
main line
valve
high-pressure
relief valve
admission
valve
levers
spring
low-pressure
relief valve
FIGURE 2
REGULATOR ASSEMBLY
Selected from MSA Product Literature, by Mine Safety Appliances Co. Copyright by Mine
Safety Appliances Co.; reprinted with permission of publisher.
SCBA Inspection and Checkout
The SCBA must be inspected according to manufacturer and 29 CFR recommendations. In addition,
the SCBA should be checked out immediately prior to use. Checkout and inspection procedures
should be followed closely to ensure safe operation of the unit.
6/93
19
Respiratory Protection
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A cylinder on an SCBA typically carries the following information (Figure 3):
DOT exemption for composite cylinder
DOT rated pressure and air volume
Cylinder number
Manufacturer's name, symbol and part number
Original hydrostatic test date, month/year
'
CONTENTS: AIR; 45 SCF, AT 2216 PSIG
~ "~ APPLIANCES CO.--
NO. "460320
FIGURE 3
INFORMATION ON TYPICAL SCBA CYLINDER LABEL
National Fire Protection Association Standards for SCBAs
The National Fire Protection (NFPA) has developed a standard for performance requirements and
appropriate testing procedures designed to simulate various environmental conditions that fire
fighter's SCBA can be exposed to during use and storage. These requirements are in addition to the
basic NIOSH/MSHA certification requirements. This Standard, NFPA 1981, now applies only to
open circuit SCBA.
• Basic Design Requirements. The basic design requirements for SCBA units under
1981 are:
That the units be NIOSH/MSHA certified positive-pressure.
The maximum weight shall not exceed 35 pounds, in accordance with
NIOSH/MSHA certification.
Respiratory Protection
20
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The rated service time shall be 30 minutes or more.
No positive-pressure unit that can be switched to demand mode.
The unit shall not be approved under the Bureau of Mines Schedule.
The manufacturer shall provide with each SCBA instructions on maintenance,
storage, disinfecting, inspection, use, operations, limitations, and training
materials.
• General Requirements. Additionally, SCBA units must meet certain general
requirements, which include:
Labeling showing that the unit meets the requirements.
Initial, annual and fifth year testing of the SCBA.
Retesting of unit after any modifications.
Test series to include three categories, with one SCBA used per category.
• Performance Tests: Airflow. This test increases the current NIOSH breathing
machine requirements of 40 liters per minute to 100 liters per minute. The 100 liters
per minute volume was derived from a review of several studies indicating that a
ventilation rate of 100 standard liters per minute encompasses the 98th percentile of
all firefighters' studies.
Note: An airflow test is then performed after each of the following tests, with the
exception of the fabric component test, to ensure breathing apparatus performance.
• Thermal Resistance Test. This series of test expose the breathing apparatus to
various temperature extremes and temperature cycles that breathing apparatus might
be exposed to during actual firefighting operations.
• Vibration and Shock. This test is designed to provide a reasonable level of
assurance that when the breathing apparatus is exposed to vibration, such as being
carried on a rig that often travels over rough road surfaces, the apparatus will
perform and function properly.
• Fabric Components Test. Flame, heat and thread tests are added to provide a
reasonable level of assurance that the fabric components of a harness assembly used
to hold the backplate to the wearer's body will remain intact during firefighting
operations.
• Accelerated Corrosion Resistance Test. This test is to provide a reasonable level
of assurance that the breathing apparatus is designed to resist corrosion that may form
and interfere with the apparatus performance and function.
• Particulate Resistance Test. This test exposes the breathing apparatus to a specified
concentration of particulates to provide a reasonable level of assurance that the
apparatus is designed to properly function when exposed to dust conditions commonly
present during firefighting operations.
6/93 21 Respiratory Protection
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Facepiece Lens Abrasion Resistance Test. This test is designed to provide a
reasonable level of assurance that the facepiece lens of the breathing apparatus is not
easily scratched during firefighting operations that could result in reduced visibility
for the fire fighter.
Communications Test. This test is designed to assure that the facepiece of the
breathing apparatus does not significantly reduce a fire fighter's normal voice
communications.
Respiratory Protection 22
-------
CHEMICAL PROTECTIVE CLOTHING
Chemical protective clothing (CPC) is worn to prevent harmful chemicals from coming in contact
with the skin or eyes. It provides a barrier between the body and chemicals which have a
detrimental effect on the skin or which can be absorbed through the skin affecting other organs.
Used with respiratory protection, properly selected clothing can protect personnel who work in
chemical environments.
Protecting workers against skin exposure requires using the most effective CPC. Of primary
importance is selecting clothing made from a material which is the most resistant against the attack
chemical. Other selection criteria which should be considered include style, the probability of being
exposed, ease of decontamination, mobility while wearing clothing, durability of clothing, and to a
lesser degree, cost.
A variety of manufactured materials are used as the fabric for CPC. Each of these materials
provides a degree of skin protection against a range of chemicals. Not one material affords the
maximum protection against all chemicals. The CPC that is selected must be made from a material
that affords the greatest deterrent against the chemicals known or expected to be encountered.
Properly selected clothing can minimize risk of exposure to chemical substances, but may not protect
against physical hazards such as fires, radiation hazards and electrical hazards. The use of other
personal protective equipment must also be determined for complete protection. Head protection is
provided by hard hats, eye and face protection by goggles or impact-resistant lenses, hearing
protection by earmuffs or earplugs, and foot protection by impact- and chemical-resistant safety
boots.
Performance Requirements for Chemical Protective Clothing
A number of performance requirements must be considered when selecting the appropriate protective
material. Their relative importance is determined by the particular work activity and site specific
conditions.
• Chemical Resistance: The ability of a material to withstand chemical and physical
change. A material's chemical resistance is the most important performance
requirement. The material must maintain its structural integrity and protective
qualities upon contact with a hazardous substance.
• Durability: The ability to withstand wear. The ability to resist punctures, abrasions,
and tears. The materials' inherent strength.
• Flexibility: The ability to bend or flex; pliability. It is extremely important both for
glove and full-body suit materials, for it directly impacts the worker's mobility,
agility, and range of motion.
Chemical Protective Clothing
-------
• Temperature Resistance: The ability of a material to maintain its chemical
resistance during temperature extremes (especially heat) and to remain flexible in cold
weather. A general tendency for most materials is that higher temperatures reduce
their chemical resistance; lower temperatures reduce flexibility.
• Service Life: The ability of a material to resist aging and deterioration. Factors
such as chemicals, extreme temperatures, moisture, ultraviolet light, oxidizing agents,
and others decrease a material's service life. Storage away from and proper care
against these conditions can help prevent aging. Manufacturers should be consulted
regarding any recommendations on a suit's shelf-life.
• Cleanability: The ability to effectively decontaminate protective materials.
Cleanability is a relative measure of the ability of a material to release the contact
substance. Some materials are nearly impossible to decontaminate, so it may be
important to cover those materials with disposable garments to prevent gross
contamination.
• Design: The way a suit is constructed, including its general type and special
features. A variety of suit styles and features that should be considered are:
Fully encapsulating or nonencapsulating
One, two, or three piece suits
Hoods, facepieces, gloves, and boots (attached or unattached)
Location of zipper, buttons, storm flaps, and seams (front, side and back)
Pockets, cloth collars, and velcro straps
Exhalation valves or ventilation ports
Ease of compatibility with wearing respiratory protection
• Size: The physical dimensions or proportions of clothing. Size is directly related to
comfort and influences the number of unnecessary physical accidents. Ill-fitting
clothing limits a worker's mobility, dexterity and concentration. Manufacturers offer
standard sizes in boots and gloves for both men and women, however standard suit
sizes for women are not available.
• Color: Brightly colored suit material make it easier to maintain visual contact
between personnel. Suits of darker colors (black, green) absorb radiant heat from
external sources and transfer it to the worker increasing heat related problems.
• Cost: The cost of CPC varies considerably. Cost will often play a role in the
selection and frequency of use of CPC. In many situations, less expensive, single
use garments are more appropriate and as safe as more costly clothing. Other sit-
uations require high quality, costly clothing which may have to be discarded after
limited use.
Chemical Protective Clothing
-------
Chemical Resistance
The effectiveness of materials to protect against chemicals is based on their resistance to penetration,
degradation, and permeation. Each of these properties must be evaluated when selecting the style
of CPC and the material from which it is made. In choosing protective materials, remember that:
• There is no protective material that is impermeable,
• There is no one material that affords protection against all chemicals, and
• For certain contaminants and chemical mixtures there are no materials available that
will protect for more than an hour after initial contact.
Penetration is the transport of chemicals through openings in a garment. A chemical may penetrate
due to design or garment imperfections. Stitched seams, button holes, pinholes, zippers, and woven
fabrics can provide an avenue for the chemical to penetrate the garment. A well-designed and
constructed garment prevents this by using self-sealing zippers, seams overlaid with tape, flap
closures, and nonwoven fabrics. Rips, tears, punctures, or abrasions to the garment also allow
penetration.
Degradation is a chemical action involving the molecular breakdown of the material due to chemical
contact. Degradation is evidenced by physical changes to the material. The action may cause the
material to shrink or swell, become brittle or soft, or completely change its chemical properties.
Other changes may be a slight discoloration, rough or gummy surface, or cracks in the material.
Such changes may enhance permeation or allow penetration by the contaminant.
Degradation test data for specific chemical or generic classes of chemical (Table 1) is available from
product manufacturers, suppliers, or other sources. The published data provides the user with a
general degradation resistance rating. The rating is subjectively expressed as excellent, good, fair,
or poor. Degradation data can help in assessing the protective capability of a material but should
not replace permeation test data. The reason for this is that a material with excellent degradation
resistance can have poor permeation properties. Degradation and permeation are not directly related
and cannot be used interchangeably. The manufacturer should be consulted by the user to determine
on which degradation changes the rating is based.
Permeation is a chemical action involving the movement of chemicals, on a molecular level, through
intact material. Permeation is a process which involves the sorption of the chemical on the outside
surface, diffusion through, and desorption of the chemical from the inside surface of the protective
material. A concentration gradient (high on the outside, low on the inside) is established. Because
the tendency is to achieve concentration equilibrium, molecular forces "drive" the chemical into the
material toward the area of no or lower concentration. Eventually the highest flow of permeating
chemical exists and is referred to as the steady flow state.
Permeation is measured as a rate. Permeation rate is the quantity of chemical that will move through
an area of protective material in a given time. It is usually expressed in micrograms of chemical
permeated per square centimeter per minute of exposure (/ig/cm2/min). Several factors influence the
rate of permeation including the type of material and thickness. A general rule of thumb is that the
6/93 3 Chemical Protective Clothing
-------
permeation rate is inversely proportional to the thickness (2 x thickness = 1/2 x permeation rate).
Other important factors are chemical concentration, contact time, temperature, material grade,
humidity, and solubility of the material in the chemical.
TABLE 1
EFFECTIVENESS OF PROTECTIVE MATERIALS AGAINST
CHEMICAL DEGRADATION (BY GENERIC CLASS)1
Generic Class
Alcohols
Aldehydes
Amines
Esters
Ethers
Halogenated hydrocarbons
Hydrocarbons
Inorganic acids
Inorganic bases and salts
Ketones
Natural fats and oils
Organic acids
Butyl
Rubber
E
E-G
E-F
G-F
G-F
G-P
F-P
G-F
E
E
G-F
E
Polyvinyl
Chloride
E
G-F
G-F
P
G
G-P
F
E
E
P
G
E
Neoprene
E
E-G
E-G
G
E-G
G-F
G-F
E-G
E
G-F
E-G
E
Natural
Rubber
E
E-F
G-F
F-P
G-F
F-P
F-P
F-P
E
E-F
G-F
E
1 E - Excellent
G - Good
F - Fair
P - Poor
Source: Survey of Personal Protective Clothing and Respiratory Apparatus. U.S. Department of
Transportation, U.S. Coast Guard, Office of Research and Development (September, 1974).
Note: For material and thickness, a general rule of thumb is that the permeation rate is inversely
proportional to the thickness (2 x thickness - 1/2 x permeation rate). Other important factors are
chemical concentration, contact time, temperature, material grade, humidity, and solubility of the
material in the chemical.
Another measure of permeation is breakthrough time, expressed in minutes. Breakthrough is the
elapsed time between initial contact of a chemical with the outside surface and detection at the inside
surface of the material. Like permeation rate, breakthrough time is chemical specific for a particular
Chemical Protective Clothing
6/93
-------
material and is influenced by the same factors. A rule of thumb concerning breakthrough time is
that it is directly proportional to the square of the thickness (2 x thickness = 4 x breakthrough time).
Permeation and breakthrough test data are available from manufacturers which give specific rates and
times (Table 2). A given manufacturer's recommendations serve as a relative guideline to properly
selecting their products. This data is obtained using the American Society for Testing and Materials
(ASTM) standard test method F739-81. Although ASTM has a standard method for permeation
testing, considerable variation exists between manufacturer's test data. The differences are due to
material thickness and grade, manufacturing processes, temperature, chemical concentrations, and
analytical detection method. Therefore, caution should be used when comparing different manufac-
turers results. The results for the same material/chemical combination will differ considerably
between manufacturers. ASTM also has test methods for penetration and degradation resistance.
The best protective material against a specific chemical is one that has a low permeation rate (if any)
and a long breakthrough time. However, these properties do not always correlate. Compare propyl
acetate (Table 2) and 1,1,1-trichloroethane against nitrile NBR or dimethyl sulfoxide and acetone
against neoprene. As indicated, a long breakthrough time does not always correlate with a low
permeation rate or vice versa. A long breakthrough time is usually desired.
The literature on material testing also notes that permeation rates and breakthrough times are not
tested for those materials which receive a poor degradation rating; only breakthrough time is
measured for those chemicals (especially corrosives) which are known to be direct skin hazards. The
data also reflects the testing of pure substances and not mixtures.
In addition to the manufacturer's chemical resistance data, the best general reference for selection
of CPC is Guidelines For The Selection Of Chemical Protective Clothing, ACG1H (1985). This
reference compiles degradation and permeation test data from manufacturers, vendors, and
independent laboratories with recommendations for over 300 chemicals. Table 3 illustrates
information presented in this particular reference. Additional information is also available on
computer databases.
Specific chemicals are rated against a variety of protective materials. The ratings (RR, rr, NN, nn)
are based on two criteria; breakthrough times and vendor chemical resistance data. Each rating
represents a combination of performance, number of sources confirming that performance, and
consistency of the data. The number and size of the letters indicate this.
The available test data and recommendations for all CPC is extremely limited in scope and use. The
user must consider these restrictions when selecting CPC and use the guidelines in the way they were
intended to be used.
6/93 5 Chemical Protective Clothing
-------
TABLE 2
PERMEATION/DEGRADATION RESISTANCE FOR EDMONT GLOVES
Acetone
Cellosolve acetate
Dimethyl sulfoxide
(DMSO)
Hydrofluoric acid, 48%
Propyl acetate
Toluene
1,1,1-
Trichloroethane
Nitrile NBR
Degradation Rating
NR
F
E
E
F
F
F
Permeation: Breakthrough
-
1.5 hr.
<4hr.
2hr.
20 min.
10 min.
1.5 hr.
Permeation Rate
-
G
VG
-
G
F
P
Neoprene
Degradation Rating
B
G
E
E
P
NR
NR
Permeation: Breakthrough
5 min.
1.25 hr.
ND
Ihr.
-
.
-
Permeation Rate
F
VG
E
-
-
-
-
PVC
•f
1
Q
NR
NR
NR
G
NR
NR
NR
Permeation: Breakthrough
3hr.
•
-
40 min.
-
-
-
Permeation Rate
-
-
-
-
-
-
-
ND
E
VG
G
F
P
NR
KEY TO PERMEATION RATE
None detected during 6-hour test
(Equivalent to Excellent)
Excellent; permeation rate of less
Very Good; permeation rate of less
than 9 jig/cnr/min.
Good; permeation rate of less than
90 pg/cm2/min.
Fair; permeation rate of less than
900 pg/cm2/min.
Poor; permeation rate of less than
9000 /ig/cm2/min.
Not recommended; permeation rate
greater than 9000 /ig/cm2/min.
Simply stated, drops per hour through a glove
(eyedropper-size drop).
NONE
0 to 1/2 drop
1 to 5 drops
6 to SO drops
SI to 500 drops
SOI to 5000 drops
>5001 drops
Note: The current revision to the ASTM standard permeation test calls for permeation to be reported in micrograms
of chemical permeated per square centimeter of garment exposed per minute of exposure, >g/cm2/min."
Chemical Protective Clothing
6/93
-------
TABLE 3
GUIDELINES FOR THE SELECTION OF CHEMICAL PROTECTIVE CLOTHING (ACGIH)
Inorganic Salts
Inorganic Salts (34)
Ammonium fluoride
Ammonium fluoride, 30-70%
Ammonium sulfate
Arsenic trichloride
Bromine trifluoride
Calcium chloride
Calcium hypochlorite
Copper chloride
Copper sulfate
Cupric chloride
Cupric sulfate
Ferric chloride
1
r
r
r
r
r
r
a
u
Viton/Neoprene
n
n
Natural Rubber
IT
R
R
R
n
n
n
n
r
Neoprene
IT
R
R
R
r
R
R
R
R
I
#
jg
'S
2
r
r
r
r
r
r
£
'£
z
IT
r
r
r
r
r
r
a
!
fc
g
rr
R
R
R
r
R
R
R
R
I
>
Butyl/Neoprene
n
n
OTHER
MATERIALS
Neop+Nat Rub
Polyurethane (R)
Polyurethane (r)
Polyurethane (r)
Polyurethane (r)
Polyurethane (r)
Polyurethane (r)
Polyurethane (r)
Polvurethane (r)
I
Note: For explanation of recommendation codes (e.g. r, rr, R, n, etc.) refer to Arthur D. Little, Inc.
-------
Classification of Chemical Protective Clothing
• Style:
Fully Encapsulating Suit (FES). Fully encapsulating CPC is a one-piece garment
that completely encloses the wearer. Boots, gloves, and facepiece are an integral part
of the suit, but may be removed. If removable they are connected to the suit by
devices that provide a vapor or gas proof seal. These are gas tight suits and must be
periodically pressure tested to insure integrity.
Respiratory protection and breathing air are provided to the wearer by a positive-
pressure, self-contained breathing apparatus (SCBA) worn under the suit or by an air-
line respirator that maintains a positive-pressure inside the suit. Fully encapsulating
suits are primarily for protecting the wearer against toxic vapors, gases, mists, or
particulates in air. Concomitantly, they protect against splashes of liquids. The
protection they provide against a specific chemical depends upon the material from
which they are constructed.
Nonencapsulating Suit. Nonencapsulating CPC (frequently called splash suits) does
not have a facepiece as an integral part of the suit. A positive pressure SCBA or air-
line respirator is worn outside the suit, or an air-purifying respirator is used. Splash
suits are of two types: a one-piece "coverall" or a two-piece "pants and coat."
Either type may include a hood and other accessories.
Nonencapsulating suits are not designed to provide maximum protection against
vapors, gases, or other airborne substances but they do provide protection against
splashes. In effect, splash suits can be made (by taping wrist, ankle and neck joints)
to totally enclose the wearer such that no part of the body is exposed but they still
are not considered to be gas tight. They may be an acceptable substitute for a fully
encapsulating suit if the concentration of airborne contamination is low and the
material is not extremely toxic to the skin.
• Protective Material:
Elastomers. Polymeric (plastic-like) materials, after being stretched, return to about
their original shape. Most protective materials are elastomers. These include:
polyvinyl chloride, neoprene, polyethylene, nitrile, polyvinyl alcohol, viton, Teflon®,
butyl rubber and others. Elastomers may be supported (layered on to cloth-like
material) or unsupported.
Nonelastomers. Materials that do not have the quality of stretchability.
Nonelastomers include tyvek, tyvek-coated garments, and other materials.
• Single-Use Suits:
A third classification is single use or disposable garment. This classification is
relative and based on cost, ease of decontamination and quality of construction.
Disposable CPC is commonly considered to be less than $25.00 per garment. In
Chemical Protective Clothing g 6/93
-------
situations where decontamination is a problem, more expensive clothing may be
considered disposable.
Protective Materials
There are a wide variety of protective materials. The following is a list of the more common
materials used in CPC segregated as elastomers or nonelastomers. The elastomers are not listed in
any particular priority. The classes of chemicals rated as "good for" or "poor for" represent test
data for both permeation breakthrough and permeation rate. They are general recommendations;
there are many exceptions within each chemicals class. Sources consulted for this information
included Guidelines for the Selection of Chemical Protective Clothing (ACGIH Volume 1,1985) and
manufacturer's literature.
• Elastomers
Natural Rubber: (Polyisoprene)
Good for: alcohols, dilute acids and bases, flexibility
Poor for: organic chemicals, aging (affected by ozone)
Polvvinvl Alcohol: (PVA)
Good for: almost all organics, ozone resistance
Poor for: esters, ethers, acids and bases, water and water solutions flexibility
Chlorinated Polyethylene: (Cloropel, CPE)
Good for: aliphatic hydrocarbons, acids and bases, alcohols, phenols, abrasion
and ozone
Poor for: amines, esters, ketones, halogenated hydrocarbons, cold temperature
(becomes rigid)
Nitrite Rubber: (Acrylonitrile rubber, Buna-N, NBR, hycar, paracril, krynac)
Good for: phenols, PCBs, oils and fuels, alcohols, amines, bases, peroxides,
abrasion and cut resistance, flexibility
Poor for: aromatic & halogenated hydrocarbons, amides, ketones, esters, cold
temperature
Note: The higher the acrylonitrile concentration, the better the chemical resistance;
but also increases stiffness.
Poivvinvl Chloride: (PVC)
Good for: acids and bases, some organics, amines, peroxides
Poor for: most organic compounds, cut and heat resistance, decontamination
6/93 9 Chemical Protective Clothing
-------
Neoprene: (Chloroprene)
Good for: bases and dilute acids, peroxides, fuels and oils, aliphatic
hydrocarbons, alcohols, glycols, phenols, abrasion and cut resistance
Poor for: halogenated hydrocarbons, aromatic hydrocarbons, ketones,
concentrated acids
Butvl Rubber:
Good for: bases and many organics heat and ozone resistance decontamination
Poor for: aliphatic and aromatic hydrocarbons, gasoline, halogenated
hydrocarbons, abrasion resistance
Viton:
Good for: aliphatic and aromatic hydrocarbons, halogenated hydrocarbons,
acids, decontamination, physical properties
Poor for: aldehydes, ketones, esters (oxygenated solvents), amines
Teflon'8:
Teflon® has become available for chemical protective suits. Limited permeation test
data is published on Teflon®. Teflon®, similar to viton, is thought to afford excellent
chemical resistance against most chemicals.
Polyurethane:
Good for: bases, aliphatic hydrocarbons, alcohols, abrasion resistance, flexibility
- especially at cold temperatures
Poor for: halogenated hydrocarbons
Blends/Layers:
CPC Manufacturers have developed a technique of layering materials to improve
chemical resistance. Essentially one suit is designed with multiple layers. Some
examples of layered fully encapsulating suits are viton/butyl (Trelleborg),
viton/neoprene (MSA Vautex and Draeger), and butyl/neoprene (MSA Betex).
• Nonelastomers
Tyvek: (nonwoven polyethylene fibers)
Good for: dry particulate and dust protection decontamination (disposable)
lightweight
Poor for: chemical resistance (penetration/degradation) durability
Recommendations: Used against toxic particulates but provides no chemical
protection; worn over other CPC to prevent gross
Chemical Protective Clothing 10 6/93
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contamination of nondisposable items and under suits to
replace cotton.
Polyethylene: (coated tyvek)
Good for: acids and bases, alcohols, phenols, aldehydes, decontamination
(disposable), lightweight
Poor for: halogenated hydrocarbons, aliphatic and aromatic hydrocarbons
physical properties (durability) penetration (stitched seams)
Recommendations: Provides limited chemical protection against concentrated
liquids and vapors. Useful against low concentrations and
those activities which do not create a high risk of splash; also
worn over CPC to prevent gross contamination of
nondisposables.
Saranex: (laminated tyvek)
Good for: acids and bases, amines, some organics, PCBs, decontamination
(disposable), lightweight, durable
Poor for: halogenated hydrocarbons, aromatic hydrocarbons, stitched seams
(penetration may occur)
Recommendations: Provides greater chemical resistance and overall protection
compared to polyethylene coated tyvek; used to prevent
contamination of nondisposable clothing.
Personal Cooling Devices
Wearing chemical-resistant clothing and respirators increases the risk of heat stress. They cause
additional strain on the body by adding weight, increasing breathing resistance, and restricting
movement. They can also reduce the body's natural cooling mechanisms. The body releases heat
by convecting heat to cooler air, radiating heat to cooler surfaces in the surroundings, and
evaporating moisture from the skin. Chemical-resistant clothing interferes with these processes.
This can lead to heat illness, heat fatigue, heat rash, heat cramps, heat syncope (fainting), heat
exhaustion, or even heat stroke. Methods used to prevent heat illness include frequent rest breaks,
reduced work loads, increased consumption of fluids, acclimatization, and working during the cooler
times of the day. Another method that is available is the use of personal cooling devices to remove
heat from the user's body.
There are many different types of personal cooling devices. When selecting a unit, one main
consideration is whether it is compatible with the other protective equipment worn. Mobility, weight
and duration of use must also be considered. Worker acceptance is also an important consideration.
Whatever device is used, it must be remembered that the device reduces but doesn't eliminate the
heat stress.
6/93 11 Chemical Protective Clothing
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Cooling devices are divided into two types: those that use a coolant source external to the wearer
(an umbilical system) or self-contained systems that are not connected to an outside source.
• External Coolant Systems
Devices using an external cooling source need a connection between the wearer and
the coolant source. The coolant can be compressed air or a liquid.
Compressed Air Systems
Compressed air systems use cool, dry air to aid in cooling the body. Generally the
air is distributed to the ankles, wrists, and head by an arrangement of air tubes worn
on the body or attached to the protective clothing (Figure 1). Some systems can be
found in the form of a hood or vest. Many manufacturers of fully encapsulating suits
have air distribution systems built into their suits.
TEE ASSEMBLY
FIGURE 1
FULLY ENCAPSULATING SUIT WITH AIR DISTRIBUTION SYSTEM
Used with permission of Mine Safety Appliances, Pittsburgh, PA.
The air is delivered to the units from a compressor or a large compressed air
container (like a cascade system). The air acts as an insulator from external heat and
increases evaporation of sweat because of the constant flow of dry air. If additional
cooling is needed, a vortex cooler to chill the air can be connected into the airline at
the user's end. The vortex cooler (Figure 2) takes compressed air, increases its
velocity, directs it into an outer "hot" tube, and forms a vortex. The air spirals down
Chemical Protective Clothing
12
6/93
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the tube and a fraction escapes through a valve in the end. The remaining air forms
a second vortex which passes through the center of the outer vortex—flowing in the
opposite direction—and exits from the "cold" tube. The outer vortex takes heat from
the inner vortex. How much heat is transferred is determined by how much air the
valve releases; more hot air out, more cold air to user. The vortex cooler is attached
to a belt or other support. It must be worn on the outside of any protective clothing
so that the heat can be vented.
It is important to remember that NIOSH does not have a specific testing and
certification schedule for supplied air suits. Thus, the suits should not be used for
respiratory protection. Some suits and hoods have a NIOSH/MSHA respiratory
approval under the SCBA or airline testing schedules. If a vortex tube is used with
a unit for respirator protection, then the respirator must be tested and approved with
the vortex tube.
HOOD OK HCl MET
VOflTEX TUBE -t-
BELT OK «UPPOHT
LINE TO OOurFIEBBEO
AIM BOUBOE
FIGURE 2
VORTEX TUBE; SCHEMATIC OF VORTEX TUBE;
VORTEX TUBE CONNECTED TO AIR-SUPPLIED HOOD
Used with permission ofFyrepel Products, Inc., Newark, OH.
Compressed air systems have two advantages. They are able to cool the whole body
and they allow the wearer to work as long as desired. However, they have several
disadvantages. They restrict mobility because of the airline umbilical. Since the
system is continuous flow, they use a lot of air - especially if using a vortex cooler.
One unit with a vortex cooler uses 25 cubic feet of air per minute to deliver 15 cubic
feet of usable air to the wearer. A normal airline respirator uses 6-8 cubic feet per
6/93
13
Chemical Protective Clothing
-------
minute. Also, the hot air from the vortex tube—as hot as 162°F—can add heat to the
environment or to the outside surface of the protective clothing.
Liquid-Cooled Devices
There is only one device in this category. Water is circulated through tubing in a
garment resembling long Johns. It can use an external water supply - which can be
chilled - or a portable chilling unit for recirculated water.
This unit has the same advantages and disadvantages of the air-supplied systems. It
has additional disadvantages. There is additional weight due to the water in the
system. At the present, fully encapsulating suits do not have liquid line connections.
One advantage is that the cooling system can be located away from the user and thus
not add heat to the user's immediate area.
Self-Contained Systems
Self-contained systems have all of the heat-exchanging elements as part of the
wearer's ensemble. Thus, they are not hooked to an outside coolant source. These
systems are usually of two types: those that use ice to cool the wearer and those that
circulate a liquid cooled by a heat-exchange system.
Ice Vests/Jackets
These systems use ice in a vest or jacket or in removable packets. The size and
number of packets vary from manufacturer to manufacturer. Some systems come
with an inner vest to prevent direct contact with the skin. Some have an outer vest
to reduce external heat effects on the ice (Figure 3).
These systems have several advantages. They are simple to use, have no moving
parts, and do not restrict mobility. They can be worn under protective clothing or
an SCBA. They also have disadvantages. They are usually limited to a maximum
of 1 hour of cooling. If more time is needed, extra packets are needed. If the unit
has no removable packets, the whole vest has to be refrozen. After the ice melts, the
wearer is carrying extra weight with no cooling benefit. They weigh from 12 to 15
pounds. If there is no inner insulation, they may be too cold.
Chemical Protective Clothing 14 6/93
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Honeycombed v*ct
FUkng connection
Booy bee
Fisiemng bunon- too
F«»i»n«9 bunon - booom
Outt' »»»t
Filling icctssory
\
D
Q
FIGURES
WATER-FILLED ICE VEST
(Entire jacket is frozen prior to use)
Used with permission of National Draeger, Pittsburgh, PA.
Circulating Systems
Circulating systems use a water or a water/alcohol mixture circulated through the vest
to cool the wearer. The liquid is cooled by ice or other frozen liquid contained in
a pouch or container carried by the wearer (Figure 4). In some cases, the melting
ice becomes part of the circulating system. There are a couple of experimental
models that use dry ice to cool the circulating liquid.
The circulating systems have some of the same advantages and disadvantages as the
ice vests. They have the additional disadvantage of using an electric circulator. This
requires battery pack to power the circulator. Thus, more weight is added. Also,
while the units have waterproof and sparkproof connections, none have received an
inherent safety rating. Their main advantage is that the cooling rate can be controlled
by controlling the flow of the liquid through the vest. They can be worn under
protective clothing and an SCBA. There is one model that is incorporated into a
fully encapsulating suit. The ice can be replenished without removing the suit.
6/93
15
Chemical Protective Clothing
-------
FIGURE 4
COOL VEST® MODEL 19
(The back of the unit has a battery-operated pump
and pouch containing ice and circulating water)
Used with permission oflLC Dover, Frederica, DE.
Chemical Protective Clothing
16
6/93
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SITE ENTRY AND RECONNAISSANCE
The primary objective when responding to a hazardous material incident is the prevention, or
reduction, of detrimental effects to public health or environment. To accomplish this it is necessary
to:
• Identify the substance involved.
• Evaluate its behavior when released and its effects on public health and the
environment.
• Initiate actions to prevent or modify its effects.
A high priority, from start to finish of an incident, is obtaining the necessary information to evaluate
its impact. This is called incident characterization and is the process of identifying the substance
involved and evaluating actual, or potential, impact on public health or the environment.
Characterization is relatively straightforward in incidents where the substance involved is known or
easily identified, the pathways of dispersion are clearly defined, and the effect or potential impact
is demonstrated. For example, the effects of a large discharge of vinyl chloride on fish in a small
stream is relatively easy to evaluate. However, an incident such as an abandoned waste site
containing 60,000 55-gallon drums is more complex because there generally is not enough initial
information to determine the hazards and to evaluate their impact.
Evaluating a hazardous substance incident is generally a two-phase process: (1) an initial
characterization and (2) a more comprehensive characterization.
Preliminary Assessment
At site responses where the hazards are largely unknown and where there is no need to go on-site
immediately, conduct an off-site reconnaissance by: (1) making visual observations; (2) monitoring
atmospheric hazards near the site; and (3) collecting off-site samples that may indicate on-site
conditions or migration from the incident.
An off-site reconnaissance and information gathering should also include:
• Collections of information not available from, or needed to verify or supplement, the
preliminary assessment.
• General layout and map of the site.
• Monitoring ambient air with direct-reading instruments for: oxygen deficiency;
combustible gases; radiation; organic vapors, gases, and particulates; inorganic
vapors, gases, and particulates; and specific materials if known.
• Placards, labels, markings on containers or transportation vehicles.
(5/93 i Site Entry and Reconnaissance
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• Configuration of containers, tank cars, and trailers.
• Types and number of containers, buildings, and impoundments.
• Biological indicators - dead vegetation, animals, insects, and fish.
• Unusual odors or conditions.
• Visual observation of vapors, clouds, or suspicious substances.
• Off-site samples (surface water, drinking water, site run-off, groundwater, soil, air).
• Interviews with inhabitants, observers, or witnesses.
Initial Characterization
The initial characterization is based on information that is readily available or that can be quickly
obtained. This information is used to determine: (1) what hazards exist and (2) whether immediate
protective measures are necessary. During this initial phase, a number of key decisions must be
made as follows:
• Imminent or potential risk to public health and to the environment.
• Immediate need for protective actions to prevent or reduce the impact.
• Protection of the health and safety of response personnel.
Once immediate control measures are implemented, actions can start to restore the area to
environmentally acceptable conditions. If there is no emergency, time can be spent to: (1) evaluate
hazards; (2) design cleanup plans; and (3) establish safety requirements for response personnel.
Also, information to characterize the hazards can be obtained from intelligence (records, placards,
eye witnesses, etc.), direct-reading instruments, and sampling. Various combinations of these
information gathering techniques can be used depending on the nature of the incident and the time
available.
The outline that follows lists the types data necessary to evaluate the impact of a hazardous materials
incident. Not every incident requires all items to be obtained. However, the list does provide a
guide that can be adapted to meet site-specific conditions.
Data Gathering and Preliminary Assessment. Upon notification or discovery of an incident, obtain
the following information:
Brief description.
Exact location.
Date and time of occurrence.
Hazardous materials involved and their physical/chemical properties.
Present status of incident.
Site Entry and Reconnaissance 2 6/93
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Potential pathways of dispersion.
Habitation - population at risk.
Environmentally sensitive areas - endangered species, delicate ecosystems.
Economically sensitive areas - industrial, agricultural.
- Accessibility by air and roads.
Waterways.
Current weather and forecast.
- Terrain - include topographic map.
Geology and hydrology - include appropriate maps.
Aerial photographs.
Communications.
Any other related background information.
Information about an incident, especially abandoned waste sites, may also be available from:
Other federal agencies.
State and local health or environmental agencies.
Company records.
Court records.
Water departments, sewage districts.
State and local authorities.
On-Site Survey
A more thorough evaluation of hazards generally requires personnel to enter the defined site. Before
going on-site, an entry plan is developed to: (1) address what will be initially accomplished and
(2) give the procedures to protect the health and safety of response personnel. On-site inspection
and information gathering includes:
• Monitoring ambient air with direct-reading instruments for: oxygen deficiency,
combustible gases, radiation, organic vapors and gases, inorganic vapors and gases,
particulates, and specific materials if known.
• Types of containers, impoundments, and their storage systems: numbers, types, and
quantities of material.
• Condition of storage systems (such as state of repair or deterioration).
• Leaks or discharges from containers, tanks, ponds, vehicles, etc.
• Potential pathways of dispersion: air, surface water, groundwater, land surface,
biological routes.
• Placards, labels, markings, identification tags, or indicators of material.
• Container configuration, shape of tank cars or trailers.
6/93 3 Site Entry and Reconnaissance
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• Standing water or liquids.
• Condition of soil.
• Wells, storage containers, drainage ditches, or streams and ponds.
Comprehensive Characterization
The second phase, comprehensive characterization (which may not be needed in all responses), is
a more methodical investigation to enhance, refine, and enlarge the information base obtained during
the preliminary inspection. This phase provides more complete information to characterize the
hazards associated with an incident. As a continuously operating program, the second phase also
reflects environmental changes resulting from response activities.
Available information and information obtained through initial site entries may be sufficient to
thoroughly identify and assess the human and environmental effects of an incident. If not, an
environmental surveillance program needs to be implemented. Much of the same type of information
as collected during the preliminary inspection is needed. However, it may be much more extensive.
Instead of one or two groundwater samples being collected, an extensive groundwater survey may
be needed over a long period of time. Results from the preliminary inspection provide a screening
mechanism for a more complete environmental surveillance program to determine the extent of
contamination. Also, since mitigation and remedial measures may cause changes in the original
conditions, a continual surveillance program must be maintained to identify any changes.
Evaluating the hazards associated with an incident involves various degrees of complexity. The
release of a single, known chemical compound may represent a relatively simple problem. It
becomes progressively more difficult to determine harmful effects as the number of compounds
increase. Evaluation of the imminent, or potential hazards, associated with an abandoned waste site,
storage tanks, or lagoons holding vast amounts of known, or unknown, chemical substances is far
more complex than a single release of an identifiable substance.
The major responsibility of response personnel is the protection of public health and the environment.
The effective accomplishment of this goal is dependent upon a thorough characterization of the
chemical compounds involved, their dispersion pathways, concentrations in the environment, and
deleterious effects. A base of information is developed over the lifetime of the incident to assess the
harmful effects and ensure that effective actions are taken to mitigate the release.
Site Entry and Reconnaissance 4 6/93
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RADIATION
There are three primary categories of radiation that might be encountered in a field survey: (1)
alpha, (2) beta, and (3) gamma. Each of these has unique properties that must be considered in
selecting an instrument for use. Alpha particles are simply energetic helium ions (i.e., atoms that
have lost their electrons). Because of their large size (compared to other forms of radiation) and
high charge, they will not penetrate through much matter. They will penetrate through more material
than alphas, but generally can be stopped by a thin piece of metal. Gamma radiation is simply high
energy light and is the most penetrating of the radiation types. Very high energy gammas can
penetrate through several centimeters of lead.
There are hazards associated with exposure of humans to radiation, but if the exposure is limited to
low levels, that hazard is not very serious. In fact, humans are exposed to natural background
radiation every day. Naturally occurring radioactive materials can be found in the soil, building
materials, certain foods, and even the human body. The unit used to quantify the radiation dose
received by an individual is the roentgen equivalent man (rem). The average dose, due to natural
background radiation and natural radioactive materials in the environment, to an individual in the
United States is about 0.2 rem/year.
The actual health risk from low-levels of radiation is quite small. There is no direct evidence that
low doses of radiation can injure the health of humans. All of the estimates of the health risks
associated with radiation have been extrapolated from studies of people who have received doses
equivalent to hundreds of rem. It has been assumed that very low levels of radiation would affect
the body in the same way as these very high doses, only with proportionately less damage. As
radiation passes through matter, it may interact and lose energy. The damage done by radiation as
it interacts with the body results from the way it affects molecules essential to the normal functioning
of human cells. One of four things may happen when radiation strikes a cell: (1) the radiation may
pass through the cell without doing any damage, (2) the cell may be damaged but repairs itself, (3)
the cell may be damaged so that it not only fails to repair itself, but reproduces in damaged form
over a period of years, or (4) the cell may be killed. The death of a single cell may not be harmful
because the body can readily replace most cells, but problems will occur if so many cells are killed
that the body cannot properly function. Incompletely or imperfectly repaired cells can lead to
delayed health effects such as cancer, genetic mutations, or birth defects. Again, it is important to
recognize that the risks from radiation are small. For example, the statistical risk of a cancer death
from 7 mrem of radiation is equivalent to that associated with smoking a single cigarette.
Radiation cannot be detected by any of the human senses. We cannot taste, smell, feel, see or hear
it. Because of this, we must rely upon instruments that respond to an interaction between the
radiation and the instrument itself. Radiation is nothing more than energetic particles or photons.
As the radiation passes through matter, it interacts with the material's electrons to lose some of the
energy. This energy results in either excitation or ionization of atoms. Depending upon the type
of detector, either the excitation or the ionization is sensed, quantified, and the instrument produces
a response that is proportional to the total amount of radiation that is present in the area being
monitored or surveyed.
6193 \ Radiation
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Portable survey instruments are calibrated to read out in either counts per minute (CPM), in direct
units or radiation intensity, such as milli-Roentgen/hour (mR/hr) or micro-Roentgen/hour (jiR/hr).
Instruments reading out in mR/hr and /zR/hr are used to measure extended radiation fields such as
that experienced in the vicinity of radioactive materials' storage or disposal sites. Instruments that
read out in CPM are usually used to monitor for low-level surface contamination, particularly on
hard, nonporous surfaces.
One of the difficulties in measuring radiation is that there is always some background level of
radiation present. This background will vary with location; some regions of the country will have
higher background than others, brick buildings will have higher backgrounds than wooden buildings,
etc. Because of this variation, when any survey instrument is used, a determination of local
background must be made in an area that is not believed to contain any radioactive materials. Any
reading significantly above the background (two to three times background) is indicative of the
presence of radioactive materials. Background levels throughout the United States will typically
range between 5 and 100 jtR/hr. The United States Environmental Protection Agency limits the
radiation exposure to workers to 1 mR/hr above background. This action level is specified in the
EPA's Standard Operating Safety Guides.
The detectors used in most portable survey instruments are gas-filled or scintillation devices. The
gas-filled detectors measure the amount of ionization in the gas that is caused by radiation entering
the detectors. This is accomplished by establishing a voltage potential across a volume of gas.
When the gas is ionized, the current that flows between the electrodes producing the potential can
be measured. The amount of current is directly proportional to the amount of radiation that enters
the detector. Scintillation detectors depend upon light that is produced in a crystal plastic, of certain
compounds, when the material's atoms are excited by interactions with radiation. The amount of
light produced is measured and converted to an easily monitored electrical signal by a photomultiplier
tube. There are gas-filled and scintillation detectors designed to detect all three of the radiation types
of interest in field surveys.
The most obvious difference in detectors used for different radiation types is the manner in which
radiation can enter the sensitive volume of the detector. Many gamma survey instruments will not
appear to have a detector, but only an electronics box. This is because the gammas can easily
penetrate the metal electronics enclosure and the detector is placed inside where it is protected from
damage. The Ludlum Model 19 Micro R meter is an example of such a detector. Alpha and beta
detectors must have thin entrance windows so that these particles can enter the sensitive volume.
some gas filled detectors are designed with a thick metal shield so they can discriminate between
betas and gammas; with the shield open, the detector is sensitive to both betas and gammas; with it
closed, it will detect only gammas, since the shield absorbs the betas before they can interact with
the detector.
A good survey meter should be portable, rugged, sensitive, simple in construction, and reliable.
Portability implies lightness and compactness with a suitable handle or strap for carrying.
Ruggedness requires that an instrument be capable of withstanding mild shock without damage.
Sensitivity demands an instrument which will respond to the type of energy level of the radiation
being measured. Rarely does one find an instrument capable of measuring all types and energies of
radiation that are encountered in practice. Simplicity in construction necessitates convenient
arrangement of components and simple circuitry comprised of parts which may be replaced easily.
Reliability is that attribute which implies ability to duplicate response under similar circumstances.
Radiation 2 6/93
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Ludlum Model 19 Micro R Meter
The Ludlum Model 19 Micro R Meter is designed to monitor low-level gamma radiation. The
instrument utilizes an internally mounted sodium iodide scintillator crystal. The meter face has two
scales, one in black representing 0-50 /iR/hr and one in red representing 0-25 /xR/hr. The meter
range is controlled with a six position switch: OFF, 5000, 500, 250, 50 and 25. The full scale
reading of the meter is equal to the switch setting; the red scale corresponds to the 25 and 250
position and the black scale to the other three positions. As an example, if the switch is in the 500
position and the meter pointer is aligned with the "30" scale marking, the radiation field is 300
pR/hr.
The Ludlum Model 19 is equipped with five additional switches or buttons. One button, labeled L,
lights the meter face while depressed. This allows accurate readings in poor lighting conditions.
The BAT button tests the battery condition. If the batteries are good, the meter pointer will deflect
to the "batt OK" portion of the scale. The audio switch controls the audible signal; in the ON
position, a "beeping" signal accompanies each radiation event that is detected. The switch marked
with the F and S controls the meter response; the S (slow) position is used for most applications,
although in conditions where the radiation level is changing rapidly, the F (fast) position will
provide a better representation of the radiation level. The remaining button resets the detector
operating high voltage should a transient pulse cause it to be disabled.
Detector Probes
Detector probes will fall into two major categories: gas-filled detectors and scintillation detectors.
These have been briefly discussed in the introduction section. This section will describe a few of
the most commonly used probes.
The Geiger-Mueller (GM) pancake probe is very common and is most valuable for monitoring for
surface activity on equipment, benchtops, soil surface and personnel. The probe may be used to
monitor alpha, beta or gamma radiation. The sensitive volume of the detector is covered with a thin
mica window of about 1.75 inch diameter. This window allows detection of alphas and low energy
betas. The fragile window is protected by a metal screen, and care must be taken to avoid
puncturing it.
End-window GM probes may also be used for alpha, beta, and gamma monitoring. These tubes are
generally cylindrical, about 6-8 inches long and have mica entrance windows about 1 inch in
diameter. The window often does not have a protective screen and is easily punctured. Because of
its configuration, this tube is not as convenient as a pancake probe for surface monitoring. Also,
because of the smaller entrance window, it is less efficient for detecting alphas and betas.
Thin-walled GM probes are used for beta and gamma detection. The tube is constructed within steel
walls through which beta rays can pass. The tube is housed in a protective cage fitted with a
movable steel shield. With the shield in place, betas are absorbed and only gammas can be detected.
When the shield is moved away from the cage opening, the detector is sensitive to both betas and
gammas.
6/93 3 Radiation
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Scintillation probes are available for alphas, betas, and gammas. They differ in the type of
scintillator used and the detector housing. Alpha detectors are made of thin activated zinc sulfide
crystals. The beta detectors generally use thin scintillation plastic crystals. Gamma probes use thick
crystals of activated sodium iodide. Beta and alpha probes have entrance windows of thin aluminized
mylar. This window protects the detector from light which would be sensed by the photomultiplier
as if it were a high radiation field. Care must be taken not to puncture the window.
The alpha probes often have large surface areas (50-100 cm2) to allow efficient detection of low
levels of alpha contamination. The gamma detectors are usually housed in an aluminum shell. This
shell is not easy to puncture and is quite rugged, although dropping or banging it against a hard
object may break the crystal or the photomultiplier.
Personnel Dosimeters
The amount of radiation dose received by an individual working in a radiation field is measured by
the use of personnel dosimeters. Two types that are frequently used are the direct-reading dosimeter
and the thermoluminescent dosimeter (TLD).
The direct-reading dosimeter provides an immediate indication of the gamma radiation dose the
wearer has received. By checking his dosimeter periodically, the wearer can get an up-to-the-minute
estimate of the total gamma dose he/she has received. Only gamma radiation is measured. There
is no way that beta radiation can penetrate the walls of the dosimeter to cause ionization.
Inside the detection chamber of the dosimeter is a stationary metal electrode with a movable quartz
fiber attached to it. The dosimeter is charged so that both the electrode and the fiber are positively
charged. Because both are positively charged, they repel each other, and the movable fiber moves
as far away from the electrode as it can. When gamma radiation causes ionization in the detection
chamber, the negative ions move to the positively charged electrode or fiber. This action reduces
the positive charge and allows the fiber to move a little closer to the stationary electrode. The
movement of the fiber, then, is a measure of the amount of gamma radiation absorbed by the
detector.
In direct-reading pocket dosimeters, a scale is placed so that the hairline on the scale is the movable
fiber. As the fiber moves, the scale indicates the total amount of gamma radiation absorbed by the
dosimeter. A magnifying glass inside the dosimeter enables the scale to be read. This provides an
immediate estimate of an individual's total gamma exposure.
Anyone who is instructed to wear a direct-reading dosimeter should make sure that it is properly
charged. When a dosimeter is properly charged, there is sufficient potential between the electrode
and the fiber that the fiber is significantly displaced and the hairline on the scale reads near zero.
In general, a dosimeter is considered adequately charged if it reads below 10 mR.
If a dosimeter is not properly charged, a charger must be used to charge it before it can be worn.
The dosimeter is pushed into the charger, and the charger control is turned until the dosimeter is
zeroed. The dosimeter must be checked again after it is taken out of the charger. Sometimes the
hairline shifts when the dosimeter is removed from the charger, and the dosimeter will have to be
readjusted so that the hairline will end up at or near zero.
Radiation 4 6/93
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Because the direct-reading dosimeter measures the whole-body gamma radiation dose, it should be
worn on the trunk of the body. When using a dosimeter, care must be taken not to bang or drop it.
Rough treatment may cause die electrode to discharge completely, sending the hairline all the way
upscale.
Thermoluminescent dosimeters (TLDs) are often used for beta and gamma whole-body
measurements. Inside the TLD is a very small quantity of crystalline material called a detector chip
that is used to measure beta and gamma exposure. A typical detector chip is approximately 1/8 inch
across and 1/32 inch thick.
To understand how a detector chip measures radiation, we first need to go through a short review
of electron energy levels. As we know, electrons in a solid material prefer to be in their ground
energy state. This is especially true for a crystalline material. If radiation imparts enough energy
to one of these electrons, the electron will jump up to a higher, instable energy level. However,
since the electron prefers to be in the ground state, it will drop to the ground state and emit the extra
energy in the form of heat, x-rays, or light.
In TLD material, there is an in-between state called a metastable state, which acts as an electron
trap. When radiation strikes the ground state electron, the electron jumps up and is trapped in the
metastable state, It remains there until it gets enough energy to move it up to the unstable state.
This energy is supplied when the TLD chip is heated to a high enough temperature. Then the
electron will drop back down to the ground state and, because the TLD chip is a luminescent
material, it will release its extra energy in the form of light. The total quantity of light emitted by
electrons returning to the ground state is proportional to the number of electrons that were trapped
in the metastable state. The number of electrons trapped in the metastable state is proportional to
the amount of beta and gamma radiation that interacts with the material. This means the amount of
light emitted when the TLD is heated is proportional to the total amount of beta and gamma radiation
interacting with the material.
In the photomultiplier tube, electrons are produced in the photocathode, multiplied across the
dynodes, and finally collected on the anode. This then produces a pulse in the circuit that is
proportional to the total amount of beta and gamma radiation absorbed by the TLD material.
There are several reasons for using TLDs instead of film badges. One reason is size - TLD chips
are so small that they can be taped to the fingers to measure exposure to the extremities without
interfering with work. A second reason is sensitivity. The TLD is generally more sensitive than
a film badge, more accurate in the low mR range, and able to provide a better overall indication of
the total beta/gamma dose received. A third reason is that the TLD chip can be reused after it is
read.
As with the direct-reading dosimeter, TLD is normally worn on the trunk of the body to give the
best indication of whole-body dose. There are times, however, when these devices might be worn
on other parts of the body. For example, a TLD might be moved to an arm or a leg if these portions
of the body might receive more radiation than the trunk area. An additional device such as a finger
ring might also be used to measure an extremity dose. A finger ring contains a TLD chip to
measure absorbed dose from beta and gamma radiation.
6/93 5 Radiation
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DECONTAMINATION
There are a number of ways that hazardous waste site workers and emergency responders may
become contaminated such as:
• Contact with gases, mists, vapors or participates in the air.
• Splash from materials while sampling or working.
• Walking, sitting, touching, or handling contaminated liquids, soils, or equipment.
Protective clothing and respirators help prevent the worker from coming in contact with
contaminants, while proper work practices help to reduce the contact and spread of contaminants.
Care must be taken to prevent the transfer of contaminants to clean areas and to prevent exposing
unprotected personnel. In order to prevent such events, contamination reduction and decontamination
procedures must be developed and implemented as part of the health and safety plan before any
activity begins. These procedures should include: the number of decontamination stations, equipment
needed, methods to minimize overall contamination, and disposal methods.
Decontamination has four primary goals:
• To protect workers from hazardous substances that may contaminate and eventually
permeate the protective clothing, respiratory equipment, tools, and vehicles used on-
site.
• To protect all site personnel by reducing/minimizing the transfer of contaminants to
clean areas.
• To prevent the mixing/contact of incompatible substances.
• To protect the community from the migration of contaminants off-site.
Initial Planning
Some considerations must be given when developing a decontamination plan:
• Stress work practices that minimize contact with contaminants (e.g., do not work in
puddles, do not set equipment down in obvious contamination).
• Use remote sampling, handling, and container opening techniques.
• Protect monitoring and sampling instruments by bagging (making openings in the
bags for sample ports, probes, sensors, etc.,)
• Wear disposable outer garments and use disposable equipment where appropriate.
6/93 1 Decontamination
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• Cover equipment and tools with strippable coating which can be removed during
decontamination.
• Encase the source of contaminants (e.g., plastic or overpacks).
• Use protective liner when setting equipment on the ground.
Zone Layout
An area within the Contamination Reduction Zone, or CRZ, (Figure 1) is designated as the
Contamination Reduction Corridor, or CRC. The CRC controls access into and out of the
Exclusion Zone and confines personnel decontamination activities to a limited area. The size of the
corridor depends on the number of stations in the decontamination procedure, the overall dimensions
of work control zones, and the amount of space available. A corridor of 75 x IS feet should be
adequate for full decontamination. Whenever possible, it should be a straight path.
The CRC boundaries should be conspicuously marked with entry and exit restricted. The far end
is the hotline, the boundary between the Exclusion Zone and the Contamination Reduction Zone.
Personnel exiting the Exclusion Zone must go through the CRC. Anyone in the CRC should be
wearing the level of protection designated for the decontamination crew. Another corridor may be
required for the entrance and exit of heavy equipment needing decontamination. Within the CRC,
distinct areas are set aside for the decontamination of personnel, portable field equipment, removed
clothing, etc., These areas should be marked and restricted to those personnel wearing the
appropriate level of protection. All activities within the corridor are confined to decontamination.
Protective clothing, respirators, monitoring equipment, sampling supplies, and other equipment are
all maintained outside the CRC. Personnel don their protective equipment away from the CRC and
enter the Exclusion Zone through a separate access control point at the hotline.
Decontamination 2 6/93
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HEAVY EQUIPMENT
DECONTAMINATION
AREA
EXCLUSION
ZONE
-
Is!
o
EXIT
PATH
CONTAMINATION
REDUCTION
ZONE
•K II K-
LEGEND
., HOTLINE
CONTAMINATION
CONTROL LINE
ACCESS CONTROL
POINT - EXTRANCE
ACCESS CONTROL
POINT - EXIT
I DRESSOUT i
I AREA j
SUPPORT
ZONE
*, REDRESS I
J AREA |
u 1
ENTRY
PATH
FIGURE 1
CONTAMINATION REDUCTION ZONE LAYOUT
Source: Standard Operating Safety Guides. U.S. Environmental Protection Agency, Office of
Emergency and Remedial Response, Emergency Response Division, Environmental Response Team
(July 1988).
6/93
Decontamination
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Decontamination Worker Protection
Generally, decontamination workers will either don the same level of protection that is worn by
workers in the Exclusion Zone or downgrade one level of protection. In any case, the level of
protection for decontamination workers is relative to the site in question and the worker's position
in the decontamination line.
The level of protection worn by decontamination workers is determined by:
• Expected or visible contamination on workers.
• Type(s) of contaminant(s) and associated respiratory and skin hazards.
• Total vapor/gas concentrations in the CRC.
• Particulates and specific inorganic or organic vapors in the CRC.
• Results of swipe tests.
• The presence (or suspected presence) of highly toxic or skin-destructive materials.
Effectiveness of Decontamination
There is no method of determining immediately how effective decontamination is in removing
contaminants. Discolorations, stains, corrosion, and residues on objects may indicate that
contaminants have not been removed. However, observable effects only indicate surface
contamination and not permeation (absorption) into clothing. Many contaminants are not easily
observed.
One method for determining the effectiveness of surface decontamination is swipe testing. Cloth
or paper patches (swipes) are wiped over predetermined surfaces of the suspect contaminated clothing
and later analyzed in a laboratory. Both the inner and outer surfaces of protective clothing should
be swipe tested. Positive results for both sets of swipes would indicate that surface contamination
has not been removed and substances have penetrated or permeated the garment. Swipe tests can
also be performed on skin or inside clothing. Another way to test the effectiveness of
decontamination procedures is to analyze for contaminants left in the cleaning solutions. Elevated
levels of contaminants in the final rinse solution may suggest that additional cleaning and rinsing are
needed. As noted, laboratory analysis is required for the aforementioned test methods. As can be
seen, lab testing provides after-the-fact information. However, along with visual observations,
results of these tests can help in ascertaining the effectiveness of decontamination. In addition, the
decision-making chart can aid in evaluating the health and safety aspects of decontamination methods
(Figure 2).
Decontamination Solutions
Protective equipment, sampling tools, and other equipment are usually decontaminated by scrubbing
with detergent water using a soft-bristle brush, followed by rinsing with copious amounts of water.
While this process may not be fully effective in removing some contaminants (in some cases, the
contaminants may react with water), it is a relatively safe option compared to the use of other
decontamination solutions. The contaminant must be identified before a decontamination chemical
Decontamination
-------
is used, and reactions of such a chemical with unidentified substances or mixtures and personal
protective equipment could be especially troublesome. A decontamination solution must always be
selected in consultation with an experienced chemist and an industrial hygienist.
Although it is recommended that water be used for decontamination as much as possible, Table 1
provides a general guide toward developing decontamination solutions.
Disposal of Contaminated Materials
All materials and equipment used for decontamination must be disposed of properly. Clothing, tools,
buckets, brushes, and all other equipment that are contaminated must be secured in drums or other
containers and labeled. Clothing not completely contaminated on the site should be secured in plastic
bags pending further decontamination and/or disposal.
Contaminated wash and rinse solutions can be kept temporarily in a step-in container (for example
a child's wading pool) or in a plastic-lined trench about 4 inches deep. Such solutions are ultimately
transferred to labeled drums and disposed of with other substances on the site. Generally, hazardous
waste or industrial haulers are called upon to handle the ultimate disposal of decontamination
equipment and drums.
Figures 3-5, describe basic decontamination procedures for workers wearing levels A, B, or C
protection. Bear in mind that these decontamination lines are designated by theory for a worse-case
situation. Field modifications will and can occur as necessary.
Medical Emergency Decontamination
When outlining decontamination procedures in the health and safety plan, provisions must be made
for decontaminating personnel with medical problems and injuries. There is the possibility that
decontamination may aggravate a health problem or cause more serious problems. For example life-
saving care should be instituted immediately without considering decontamination. The outside
garments can be removed (depending on the weather) if this does not cause delays, interfere with
treatment, or aggravate the problem. Respiratory masks and backpack assemblies must always be
removed. Fully encapsulating suits or chemical-resistant clothing can be cut away. If the outer
contaminated garments cannot be safely removed, the individual should be wrapped in plastic
rubber, or blankets to help prevent contaminating medical personnel and/or the inside of ambulances'
Outside garments are then removed at the medical facility. Whenever possible, response personnel
should accompany contaminated victims to the medical facility to advise on matters involving
decontamination. No attempt should be made to wash or rinse the victim unless it is known that the
victim has been contaminated with an extremely toxic or corrosive material that could also cause
severe injury or loss of life. For minor medical problems or injuries, the normal decontamination
procedures should be followed.
5 Decontamination
-------
NO
NO
NO
Take additional measures to
prevent contamination or find
another decontamination
method.
Consult specialists if necessary.
NO
Is the method effective for
removing contaminants?
YES
Are the decontamination
materials compatible with the
hazardous substances present?
YES
Are the decontamination
materials compatible with the
materials to be decontaminated?
YES
Do the decontamination materials
or process pose health or safety
hazards?
NO
YES
Can appropriate protective
measures be instituted?
YES
Method OK to use.
FIGURE 2
DECISION AID FOR EVALUATING HEALTH AND SAFETY
ASPECTS OF DECONTAMINATION METHODS
Source: NIOSH/OSHA/USCG/EPA nrrunational Safety and Health Guidance Manual for
Waste Site Activities (1985).
Decontamination
6/93
-------
TABLE 1
GENERAL GUIDE TO SOLUBILITY OF CONTAMINANTS
IN FOUR SOLVENT TYPES
Solvent
Water
Dilute Acids
Dilute Bases
Detergent
Soap
Organic Solvents8
Alcohols
Ethers
Ketones
Aromatics
Straight-chain alkanes (e.g., hexane)
Common petroleum products (e.g.,
fuel oil, kerosene)
Soluble Contaminants
Low-chain hydrocarbons
Inorganic compounds
Salts
Some organic acids & other polar compounds
Basic (caustic) compounds
Amines
Hydrazines
Acidic compounds
Phenols
Thiols
Some nitro and sulfonic compounds
Nonpolar compounds (e.g., some organic
compounds)
WARNING: Some organic solvents can permeate and/or degrade the protective clothing.
Source: NIOSH/OSHA/USCG/EPA Occupational Safety and Health Guidance Manual for Hazardous
Waste Site Activities (1985).
6/93
Decontamination
-------
EXCLUSION
ZONE
Tap* Removal
Boot Cover &
Glove Wash
Segregated
Equipment
Drop
Outer Glove
Removal
I
k Changt _
. 1 Boot Covar
' 1 Removal
Boot Cover &
Glova Rinse
/ 7 \ Sult/Salaty
\ / Boot Waah
and Redress -
Boot Cover/
Outer Glovea
CONTAMINATION
REDUCTION
ZONE
Fully Encapsulating Suit
•nd Hard Hat Removal
SCBA Backpack
Removal
Redreaa
CONTAMINATION
CONTROL LINE
SUPPORT ZONE
FIGURES
DECONTAMINATION LAYOUT: LEVEL A PROTECTION
Source: Standard Operating Saferv Guides. U.S. Environmental Protection Agency, Office of
Emergency and Remedial Response, Emergency Response Division, Environmental Response Team
(June 1992).
Decontamination
6/93
-------
EXCLUSION
ZONE
Tip* Removal
Boot Cover &
Glove Wash
Segregsted
Equipment
Drop
Outer Glove
Removal
Tank Chang*
and Redresa -
Boot Cover/
Outer Gloves
CONTAMINATION
REDUCTION
ZONE
Boot Cover &
Glove Rinse
Sult/SCB A/Boot
/Glove Rinse
SCBA Backpack
Remove!
Field
Wash
Redress
CONTAMINATION
CONTROL LINE
SUPPORT ZONE
FIGURE 4
DECONTAMINATION LAYOUT: LEVEL B PROTECTION
Source: Standard Operating Safety Guides. U.S. Environmental Protection Agency, Office of
Emergency and Remedial Response, Emergency Response Division, Environmental Response Team
(June 1992).
6/93
Decontamination
-------
EXCLUSION
ZONE
Tip* Removal
Boot Cover &
Glove Waah
Segregated
Equipment
Drop
-------
RESPONSE ORGANIZATION
The number of people needed to respond to an incident involving the release or potential release of
hazardous substances can vary greatly. To successfully accomplish the primary response goal, of
protecting public health and the environment, requires the coordinated, cooperative effort of these
people.
Every incident is unique. The hazardous materials involved, their impact on public health and the
environment, and the activities required to remedy the event are incident specific. Each incident
tends to establish its own operational and organizational requirements. However, common to all
incidents are planning, organizational considerations, personnel, and the implementation of
operations.
Hazardous Materials Contingency Plans
Many of the problems encountered by responders can be reduced if a hazardous materials
contingency plan exists. When an incident (involving chemicals or other kinds of man-made or
natural disasters) occurs, local government reacts. An organization, comprised of all who are
available, will naturally evolve. Its capability, however, to efficiently manage the situation may be
severely restricted. Expertise, equipment, and funds needed to prevent or reduce the impact of the
event may not be readily available. Necessary actions to ameliorate the situation may be delayed.
A more effective response occurs when a contingency plan exists. In general, contingency plans
anticipate the myriad of problems faced by responders and through the planning process solves them.
A response organization is established, resources are identified, and prior arrangements made to
obtain assistance. A good plan minimizes the delays frequently encountered in a no-plan response,
thus permitting more prompt remedial actions. It also reduces the risk to the health of both the
responders and public by establishing, in advance, procedures for protecting their safety.
A contingency plan can lessen many of the problems encountered in a response. However, even a
good plan cannot anticipate and address all the circumstances created by a release of chemicals.
Even with a plan, modifications may be needed in the response organization to accommodate
unforeseen situations. A well-written plan acknowledges that adaptations are necessary and provides
the framework for doing so without impeding the progress of implementation.
Without a plan the ability to effectively manage the incident is diminished. Time is wasted
attempting to define the problem, get organized, locate resources, and implement response activities.
These organizational difficulties can cause delays in the response actions, thus creating additional
problems that prompt action would have avoided. For hazardous materials contingency plans to be
effective they must be: well-written, agreed upon by all involved, current, flexible, reviewed and
modified and tested.
Response Organization
-------
Organization
The responders needed for an incident may range from a few to hundreds. They represent many
government agencies and private industries. Functions and responsibilities of each responders group
differ. These diverse elements must be organized into a cohesive unit capable of managing and
directing response activities toward a successful conclusion (Figure 1).
Relatively few well-trained response teams exist. Most response teams are associated with
metropolitan fire services or with industry, but are small and may have limited capability or
responsibility. In an incident of any magnitude, where more personnel and resources are needed,
a team is assembled from the various responding government agencies or private contractors. An
organization is then established according to an existing contingency plan. Without a plan, an ad hoc
organization is created to manage that specific incident.
The contingency plan or ad hoc organization established, to function effectively must:
• Designate a leader
• Determine objectives
• Establish authority
• Develop policies and procedures
• Assign responsibilities
• Plan and direct operations
• Establish internal communications
• Manage resources (money, equipment, and personnel)
• Establish external communications
In any incident involving more than a few responders, it is generally necessary to develop an
organizational chart. This chart depicts the organization's structure. It links personnel and
functions, defines lines of responsibility, and establishes internal communication channels. To a
large degree, the form and complexity of the organizational chart depends on the magnitude of the
incident, the activities needed, the number of people and agencies involved, and the project leader's
mode of operation. The key requirements are:
• Establish a chain-of-command
• Assign responsibilities and functions
• Develop personnel requirements
• Establish internal communications
Response Organization
-------
OFF-SITE
Multldlacipllnary
Advisor*
ON-SITE
OFF-SITE
& ON-SITE
AS NEEDED
Government Agency
Oversight
JL
Lead Organization
Senior-Level
Management
Medical Support
Project
Team Leader
Command Post
Supervisor
Decontamination
Station Olllcer*
Rescue
Team
Q.
O
• Scientific Advlior
• Logistics Officer
• Financial Officer
• Photographer
• Security Officer
• Recordkeeper
• Public Information
Officer
Bomb Squad Experts • Firefighters
Communication Personnel • Hazardous Chemical
Experts
Health Physicists
Toxlcologlsts
Environmental Scientists
Evacuation Personnel
Industrial Hyglenlsts
Meteorologist*
Public Safety
Officer
FIGURE 1
EXAMPLE OF A POSSIBLE RESPONSE ORGANIZATION
FLOWCHART
Personnel
To manage and direct the various operations, personnel or responding agencies must be assigned the
responsibility for certain activities. The positions, functions, and responsibilities that follow represent
personnel requirements for a major response effort. They should be tailored to fit a particular
chemical incident. A person must not be assigned responsibility for more than one function.
The Project Leader/On-Scene Coordinator/Incident Manager (required under 29 CFR 1910 120)
has clearly defined authority and responsibility to manage and direct all response personnel and
operations while ensuring protection of the health and safety of site personnel and the public.
9 CFR 1910'120) advises the Pr°J'ect leader °n all matters
related to the health and safety of those involved in site operations. This individual establishes and
6/93
Response Organization
-------
directs the safety program and coordinates these activities with the scientific advisor. The Safety
Officer can halt operations if unsafe conditions exist.
The Scientific Advisor directs, coordinates, and prioritizes scientific studies, sample collection, field
monitoring, analysis of samples, and the interpretation of results. The science advisor may also
recommend remedial plans and/or actions and may provide technical guidance to the project leader
in those areas.
The Field Team Leader directs activities related to cleanup contractors and others involved in
emergency and long term restoration measures.
The Public Information Officer (PIO) disseminates information to news media and the public
concerning site activities. This individual establishes internal communications to keep all team
members informed. All media questions are referred to the PIO.
The Security Officer manages general site security and controls site access. The security officer
provides a liaison with local law enforcement and fire departments.
The Recordkeeper documents and maintains the official records of site activities. The recordkeeper
assures that the written record is sufficiently clear, detailed and accurate for presentations in courts
of law.
The Field/Operations Officer directs the activities of team leaders. This individual coordinates
these operations with the scientific advisor and safety officer.
The Team Leaders manage specific assigned tasks such as: entry team(s), decontamination,
sampling teams, monitoring, equipment, photography, and communications.
The Financial Officer provides financial and contractual support.
The Logistics Officer provides necessary equipment and other resources.
The Medical Officer provides medical support and acts as liaison with the medical community.
Implementing Response Operations
The release or potential release of hazardous materials requires operations (or activities) that will
eventually restore the situation to normal, or as near as possible to pre-incident conditions. Although
each incident establishes its own operational requirements, there is a general sequence of events for
all responses. Planning and implementing a response involves, as a minimum, the following:
• Organize: Select key personnel. Establish an organization. Assign responsibilities.
Modify operations as needed. Institute emergency actions.
• Evaluate situation: Based on available information, make preliminary hazard
evaluation.
Response Organization
-------
Develop plan of action: Develop preliminary operations plan for gathering and
disseminating information; taking immediate counter measures; and implementing
emergency and remedial actions. Reevaluate the situation as supplemental
information becomes available.
Make preliminary off-site survey. Collect additional data to evaluate
situation (monitor using direct-reading instruments, sample, make visual
observations). Establish emergency actions to protect public health and
environment. Identify requirements for on-site reconnaissance. Determine
level of protection, if necessary, for off-site personnel. Establish boundaries
for contaminated areas.
Make initial on-site reconnaissance. Collect data (monitor, sample, make
visual observations) to determine or verify hazardous conditions and make an
overall assessment of the incident. Modify initial entry safety procedures as
more data is obtained. Determine levels of protection for initial entry team(s)
and subsequent operations. Plan and implement site control and
decontamination procedures.
Modify original plan of action: Modify or adapt original plan based on additional
information obtained during initial entries. Revise immediate emergency measures.
Plan long-term actions including:
Additional monitoring and sampling
Resource requirements
Site safety plan
Cleanup and restoration measures
Legal implications and litigation
Site activity documentation
Complete planned cleanup and restoration
Personnel and Site Reconnaissance
The greatest risk to the safety of responders occurs close to the release. The health and safety of
those responders is of paramount importance. Therefore, projected on-site operations must be
carefully thought out, well-planned, and properly executed. To accomplish this, a site
reconnaissance must be completed prior to entering the hazardous substance release area. During
this reconnaissance, it is necessary to collect as much information as possible in the time available,
on the types and degrees of hazards, as well as risks that may exist. This information can be
obtained from shipping manifests, transportation placards, existing records, container labels,
sampling results, monitoring data, or off-site studies.
Response Organization
-------
The Project Leader, after review of intelligence gained from site reconnaissance, makes decisions
on the matters that follow:
• Off-site measurements needed
• The need to go on-site
• Equipment available versus equipment needed
• Type of data needed to evaluate hazards such as: organic vapors/gases,
inorganic vapors/gases, particulates, oxygen concentration, radiation,
• Samples needed for laboratory analysis
• Levels of protection needed by entry team(s)
• Number and size of entry team(s) needed
• Briefing/Debriefing of response team
• Site control procedures which include: designation of work zones, access
control, and physical barriers
• Decontamination procedures required
• Medical backup resources available versus needed
• Emergency actions/countermeasures to be taken
• Priority for collecting data and samples
To effectively prevent or reduce the impact of a hazardous materials incident on people or the
environment, the personnel responding must be organized into a structured operating unit - a
response organization. For the response organization to be effective it must be developed in
advance, be tested, and be an integral part of a Hazardous Materials Contingency Plan. To a large
degree, the success of the response is dependent upon how well the response personnel are
organized. The more organized, the more rapidly the organization can begin to function. A
response organization, once established (whether specified in a contingency plan or as an "ad hoc"
incident specific-group) must be flexible enough to adapt to the ever changing conditions created as
the incident progresses.
Response Organization
-------
EXAMPLE LIST OF RESPONSE EQUIPMENT
Communication Equipment Field Equipment
Hand-held radios
Protective Clothing
Fully encapsulating suit
Chemical-resistant splash suit
Chemical-resistant safety boots
Work gloves
Rain suit
Windbreaker
Medium-weight jacket
Coveralls (work)
Coveralls (Nomex)
Uniform pants and shirt
Socks (regular)
Socks (heavy)
Underclothes
Earplugs
Clipboard
Hardhat (w/faceshield)
Hardhat for cold weather
Safety goggles
Safety glasses
Combustible gas indicator
HNU photoionizer
Organic vapor analyzer (OVA)
Oxygen meters
Colorimetric indicator pump/tubes
Specific gas detectors
Radiation detector
Metal detector
Pressure-demand SCBAs
Extra air cylinders
Full-face APR (w/canisters)
Photographic equipment
Film badges
Dosimeters
Organic vapor badges
Hand tool kit (Schedule A)
First Aid kit (Schedule B)
Reference materials (Schedule C)
Field support kit (Schedule D)
Soil sample set (Schedule E)
Water sample set (Schedule F)
Air sample set (Schedule G)
Emergency oxygen inhaler
Portable wash unit
Fire extinguisher
Portable eyewash
Wood mallet
Claw hammer
Lumberjack knife
Cutting pliers
Plier wrench
Stapler/staples
Reel tape
Duct tape
SCHEDULE A: HAND TOOL
Rubber mallet
Hand hammer (nonsparking)
Duckbill snip
Lineman's pliers
Pipe wrench
Pressure gauge
Electrical tape
KIT
Ballpeen hammer
Hacksaw
Rod and bolt cutter
Slipjoint pliers
Screwdrivers
Measure tape
Strapping tape
6/93
Response Organization
-------
First Aid Guide
Forceps
Cold tablets
Alcohol swabs
Antiseptic spray
Spray-on bandage
Antibiotic ointment
Eye wash
Chigger/tick remover
Snake bite kit
Blood clotter
Knuckle bandages
Triangle bandages
Finger splint
SCHEDULE B: FIRST AID KIT
Scissors
Pain aid
Cotton swabs
Antiseptic swabs
Burn spray
Vaseline
Eye/skin neutral izer
Sting relief
Cohesive tape
Band-Aids
Finger tip bandages
Ice packs
Salt tablets
Blanket
Aspirin
Tweezers
Lozenges
Antacid
Syrup of ipecac
Eye drops
Insect repellent
Adhesive tape
Poison ivy treatment
Ammonia inhalants
Tourniquet
Elastic strip bandages
Gauze bandages
Stretcher
SCHEDULE C: REFERENCE MATERIALS
NFPA Guide on Hazardous Materials
CHRIS Condensed Guide to Chemical Hazards
Dangerous Properties of Industrial Materials (Sax)
NIOSH Pocket Guide to Chemical Hazards
TLVs for Chemical Substances & Physical Agents in the Work Environment
SCHEDULE D: FIELD SUPPORT KIT
Binoculars (2, 7 x 35-mm-wide angle)
Spotting scope
Compass (2)
Hand calculator (2)
Rangefinder (2)
Stereoscopes
Hand level (2)
Cassette recorder
SCHEDULE E: SOIL SAMPLING SET
Soil auger
Power head (electric)
Replacement tips for tube samplers
Scoops for bottom sediments
Stainless steel pipe section
Electrical resistivity apparatus
Post hole digger
Shovel
Auger extensions
Soil sample tubes
Wet, heavy duty tips
Labels
Logbooks for soil profiles
Stainless steel spoons
Pick-ax
Stainless steel pans
Response Organization
6/93
-------
SCHEDULE F: WATER SAMPLING SET
Weighted bottle sampler Pond sampler
Glass and polyethylene containers Scoops and dippers
Suction devices (hand pumps) Water level indicator
Cased thermometers/thermistors Teflon® bailer
Dissolved oxygen meter Conductivity meter
SCHEDULE G: AIR SAMPLING SET
Colorimetric indicator tubes Hi-vol sampler
Impinger tubes Carbon adsorption tubes
Paniculate samplers Wind direction indicator
Wind speed indicator Temperature indicator
Barometric pressure indicator
6/93 9 Response Organization
-------
Section 6
-------
APPENDIX A
1910.120 —Hazardous Waste Operations
and Emergency Response
-------
I !M I). I join)
OCCUPATIONAL SAFETY AND HEALTH
.STANDARDS AND INTERPRETATIONS
1910.120-HAZARDOUS WASTE OPERATIONS
AND EMERGENCY RESPONSE
(a) Scope, application, and definitions.
(1) Scope. This section covers the following oper-
ations, unless the employer can demonstrate
that the operation does not involve employee
exposure or the reasonable possibility for
employee exposure to safety or health hazards:
(i) Clean-up operations required by a govern-
mental body, whether Federal, state, local or
other involving hazardous substances that are
conducted at uncontrolled hazardous waste
sites (including, but not limited to, the EPA's
National Priority Site List (NPL), state pri-
ority site lists, sites recommended for the
EPA NPL, and initial investigations of gov-
ernment identified sites which are conducted
before the presence or absence of hazardous
substances has been ascertained);
(ii) Corrective actions involving cleanup oper-
ations at sites covered by the Resource Con-
servation and Recovery Act of 1976 (RCRA)
us amended (42 U.S.C. 6901 et seq.);
(iii) Voluntary clean-up operations at sites rec-
ognized by Federal, state, local or other gov-
ernmental bodies as uncontrolled hazardous
u aste sites;
(iv) Operations involving hazardous wastes
that are conducted at treatment, storage, and
disposal (TSD) facilities regulated by 40 CFR
Parts 264 and 265 pursuant to RCRA; or by
agencies under agreement with U.S.E.P.A. to
implement RCRA regulations; and
(v) Emergency response operations for
releases of. or substantial threats of releases
of. hazardous substances without regard to
the location of the hazard.
(2) Application.
(i) All requirements of Part 1910 and Part
192(5 of Title 29 of the Code of Federal Reg-
ulations apply pursuant to their terms to haz-
ardous waste and emergency response
operations whether covered by this section or
not. If there is a conflict or overlap, the provi-
sion more protective of employee safety and
health shall apply without regard to 29 CFR
(ii) Hazardous substance clean-up operations
within the scope of paragraphs (a)(l)(i)
through (a)(l)(iii) of this section must comply
with all paragraphs of this section except
paragraphs (p) and (q).
(iii) Operations within the scope of paragraph
(a)(l)(iv) of this section must comply only with
the requirements of paragraph (p) of this sec-
tion.
Exceptions: For large quantity generators
of hazardous waste who store those wastes
less than 90 days and for small quantity gen-
erators of hazardous wastes, who have
emergency response teams that respond to
releases of, or substantial threats of releases
of, hazardous substances, for their RCRA
workplaces only paragraph (p)(8) of this sec-
tion is applicable. Such generators of haz-
ardous wastes who do not have emergency
response teams that respond to releases of, or
substantial threats of releases of, hazardous
substances are exempt from the requirements
of this section.
(iv) Emergency response operations for
releases of, or substantial threats of releases
of, hazardous substances which are not cov-
ered by paragraphs (a)(l)(i) through (a)(l)(iv)
of this section must only comply with the
requirements of paragraph (q) of this section.
(3) Definitions."Buddy system" means a system
of organizing employees into work groups in
such a manner that each employee of the work
group is designated to be observed by at least
one other employee in the work group. The pur-
pose of the buddy system is to provide rapid
assistance to employees in the event of an
emergency.
•'Clean-up operation" means an operation
where hazardous substances are removed, con-
I'MII. ll'
330
Change 51
-------
OCCUPATIONAL SAFETY AND HEALTH
1910.120(a)(3)
tained, incinerated, neutralized, stabilized,
cleared-up, or in any other manner processed or
handled with the ultimate goal of making the
site safer for people or the environment.
"Decontamination" means the removal of haz-
ardous substances from employees and their
equipment to the extent necessary to preclude
the occurrence of foreseeable adverse health
affects.
"Emergency response" or "responding to
emergencies" means a response effort by
employees from outside the immediate release
area or by other designated responders (i.e.,
mutual-aid groups, local fire departments, etc.)
to an occurrence which results or is likely to
result, in an uncontrolled release of a hazardous
substance. Responses to incidental releases of
hazardous substances where the substance can
be absorbed, neutralized, or otherwise con-
trolled at the time of release by employees in
the immediate release area, or by maintenance
personnel are not considered to be emergency
responses within the scope of this standard.
Responses to releases of hazardous substances
where there is no potential safety or health haz-
ard (i.e., fire, explosion, or chemical exposure)
are not considered to be emergency responses.
"Facility" means (A) any building, structure,
installation, equipment, pipe or pipeline (includ-
ing any pipe into a sewer or publicly owned
treatment works), well, pit, pond, lagoon,
impoundment, ditch, storage container, motor
vehicle, rolling stock, or aircraft, or (B) any site
or area where a hazardous substance has been
deposited, stored, disposed of, or placed, or oth-
erwise come to be located; but does not include
any consumer product in consumer use or any
water-borne vessel.
(3) "Hazardous materials response (HAZMAT)
team" means an organized group of employees,
designated by the employer, who are expected
to perform work to handle and control actual or
potential leaks or spills of hazardous substances
requiring possible close approach to the sub-
stance. The team members perform responses to
releases or potential releases of hazardous sub-
stances for the purpose of control or stabilization
of the incident. A HAZMAT team is not a fire
brigade nor is a typical fire brigade a HAZMAT
team. A HAZMAT team, however, may be a
separate component of a fire brigade or fire
department.
STANDARDS AND INTERPRETATIONS
"Hazardous substance" means any substance
designated or listed under paragraphs (A)
through (D) of this definition, exposure to which
results or may result in adverse affects on the
health or safety of employees:
(a) Any substance defined under section 101(14)
of CERCLA;
(b) Any biological agent and other disease-
causing agent as defined in section 101(33) of
CERCLA;
(c) Any substance listed by the U.S. Depart-
ment of Transportation as hazardous materials
under 49 CFR 172.101 and appendices; and
(d) Hazardous waste as herein defined.
"Hazardous waste" means
(a) A waste or combination of wastes as defined
in 40 CFR 261.3, or
(b) Those substances defined as hazardous
wastes in 49 CFR 171.8.
"Hazardous waste operation" means any opera-
tion conducted within the scope of this standard.
"Hazardous waste site" or "Site" means any
facility or location within the scope of this stand-
ard at which hazardous waste operations take
place.
"Health hazard" means a chemical, mixture of
chemicals or a pathogen for which there is statis-
tically significant evidence based on at least one
study conducted in accordance with established
scientific principles that acute or chronic health
effects may occur in exposed employees, the term
"health hazard" includes chemicals which are car-
cinogens, toxic or highly toxic agents, reproduc-
tive toxins, irritants, corrosives, sensitizers,
heptaotoxins, nephrotoxins, neurotoxins, agents
which act on the hematopoietic system, and agents
which damage the lungs, skin, eyes, or mucous
membranes. It also includes stress due to tem-
perature extremes. Further definition of the terms
used above can be found in Appendix A to 29 CFR
1910.1200.
"IDLH" or "Immediately dangerous to life or
health" means an atmospheric concentration of any
toxic, corrosive or asphyxiant substance that poses
an immediate threat to life or would cause irrever-
Change 51
330.1
I910.120(a)<3)
-------
OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
sible or delayed adverse health effects or would
interfere with an individual's ability to escape from
a dangerous atmosphere.
"Oxygen deficiency" means that concentration of
oxygen by volume below which atmosphere sup-
plying respiratory protection must be provided. It
exists in atmospheres where the percentage of
oxygen by volume is less than 19.5 percent oxy-
gen.
"Permissible exposure limit" means the
exposure, inhalation or dermal permissible
exposure limit specified in 29 CFR Part 1910, Sub-
parts G and Z.
"Published exposure level" means the exposure
limits published in "NIOSH Recommendations for
Occupational Health Standards" dated 1986 incor-
porated by reference, or if none is specified, the
exposure limits published in the standards spec-
ified by the American Conference of Governmental
Industrial Hygienists in their publication "Thresh-
old Limit Values and Biological Exposure Indices
for 1987-88" dated 1987 incorporated by reference.
"Post emergency response" means that portion
of an emergency response performed after the
immediate threat of a release has been stabilized
or eliminated and clean-up of the site has begun. If
post emergency response is performed by an
employer's own employees who were part of the
initial emergency response, it is considered to be
part of the initial response and not post emergency
response. However, if a group of an employer's
own employees, separate from the group providing
initial response, performs the clean-up operation,
then the separate group of employees would be
considered to be performing post-emergency
response and subject to paragraph (g)(ll) of this
section.
"Qualified person" means a person with specific
training, knowledge and experience in the area for
which the person has the responsibility and the
authority to control.
"Site safety and health supervisor (or official)"
means the individual located on a hazardous waste
site who is responsible to the employer and has the
authority and knowledge necessary to implement
the site safety and health plan and verify com-
pliance with applicable safety and health require-
ments.
"Small quantity generator" means a generator of
hazardous wastes \\ ho in any calendar month gen-
erates no more than 1.000 kilograms (2.205
pounds) of hazardous waste in that month.
"Uncontrolled hazardous waste site" means an
area where an accumulation of hazardous waste
creates a threat to the health and safety of individ-
uals or the environment or both. Some sites are
found on public lands, such as those created by for-
mer municipal, county or state landfills where ille-
gal or poorly managed waste disposal has taken
place. Other sites are found on private property,
often belonging to generators or former genera-
tors of hazardous waste. Examples of such sites
include, but are not limited to, surface impound-
ments, landfills, dumps, and tank or drum farms.
Normal operations at TSD sites are not covered by
this definition.
(b) Safety and health program.
Note to (b): Safety and health programs
developed and implemented to meet other Fed-
eral, state, or local regulations are considered
acceptable in meeting this requirement if they
cover or are modified to cover the topics required
in this paragraph. An additional or separate safety
and health program is not required by this para-
graph.
(1) General.
(i) Employers shall develop and implement a
written safety and health program for their
employees involved in hazardous waste opera-
tions. The program shall be designed to iden-
tify, evaluate, and control safety and health
hazards, and provide for emergency response
for hazardous waste operations.
(ii) The written safety and health program
shall incorporate the following:
(a) An organizational structure:
(b) A comprehensive workplan:
(c) A site-specific safety and health plan
which need not repeat the employer's stand-
ard operating procedures required in para-
graph (b)(l)(ii)(F) of this section:
(d) The safety and health training program:
330.2
Change .~>l
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OCCUPATIONAL SAFETY AND HEALTH
mo. lint i)t< iitii iu-1
STANDARDS AND INTERPRETATIONS
(e) The medical surveillance program:
(f) The employer's standard operating pro-
cedures for safety and health: and
(g) Any necessary interface between gen-
eral program and site specific activities.
(Hi) Site excavation. Site excavations created
during initial site preparation or during haz-
ardous waste operations shall be shored or
sloped as appropriate to prevent accidental
collapse in accordance with Subpart P of 29
CFR Part 1926.
(iv) Contractors and sub-contractors. An
employer who retains contractor or sub-
contractor services for work in hazardous
waste operations shall inform those contrac-
tors, sub-contractors, or their representatives
of the site emergency response procedures
and any potential fire, explosion, health,
safety or other hazards of the hazardous
waste operation that have been identified by
the employer, including those identified in the
employer's information program.
(v) Program availability. The written safety
and health program shall be made available to
any contractor or subcontractor or their rep-
resentative who will be involved with the haz-
ardous waste operation; to employees; to
employee designated representatives; to
OSHA personnel, and to personnel of other
Federal, state, or local agencies with regula-
tory authority over the site.
(2) Organizational structure part of the site pro-
gram.
(i) The organizational structure part of the
program shall establish the specific chain of
command and specify the overall respon-
sibilities of supervisors and employees. It
shall include, at a minimum, the following ele-
ments:
(a) A general supervisor who has the
responsibility and authority to direct all
hazardous waste operations.
(b) A site safety and health supervisor who
has the responsibility and authority to
develop and implement the site safety and
health plan and verify compliance.
(c) All other personnel needed for haz-
ardous waste site operations and emergency
response and their general functions and
responsibilities.
(d) The lines of authority, responsibility.
and communication.
(ii) The organizational structure shall be
reviewed and updated as necessary to reflect
the current status of waste site operations.
(3) Comprehensive workplan part of the site pro-
gram. The comprehensive workplan part of the
program shall address the tasks and objectives
of the site operations and the logistics and
resources required to reach those tasks and
objectives.
(i) The comprehensive workplan shall address
anticipated clean-up activities as well as nor-
mal operating procedures which need not
repeat the employer's procedures available
elsewhere.
(ii) The comprehensive workplan shall define
work tasks and objectives and identify the
methods for accomplishing those tasks and
objectives.
(iii) The comprehensive workplan shall estab-
lish personnel requirements for implementing
the plan.
(iv) The comprehensive workplan shall
provide for the implementation of the training
required in paragraph (e) of this section.
(v) The comprehensive workplan shall provide
for the implementation of the required infor-
mational programs required in paragraph (i)
of this section.
(vi) The comprehensive workplan shall
provide for the implementation of the medical
surveillance program described in paragraph
(f) of this section.
(4) Site-specific safety and health plan part of the
program.
(i) General. The site safety and health plan.
which must be kept on site, shall address the
safety and health hazards of each phase of site
operation and include the requirements and
procedures for employee protection.
Chance 51
330.3
I910.120(b)(4)(i)
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OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
(ii) Elements. The site safety and health plan,
as a minimum, shall address the following:
(a) A safety and health risk or hazard anal-
ysis for each site task and operation found
in the workplan.
(b) Employee training assignments to
assure compliance with paragraph (e) of this
section.
(c) Personal protective equipment to be
used by employees for each of the site tasks
and operations being conducted as required
by the personal protective equipment pro-
gram in paragraph (g)(5) of this section.
(d) Medical surveillance requirements in
accordance with the program in paragraph
(0 of this section.
(e) Frequency and types of air monitoring,
personnel monitoring, and environmental
sampling techniques and instrumentation to
be used, including methods of maintenance
and calibration of monitoring and sampling
equipment to be used.
(f) Site control measures in accordance with
the site control program required in para-
graph (d) of this section.
(g) Decontamination procedures in accord-
ance with paragraph (k) of this section.
(h) An emergency response plan meeting
the requirements of paragraph (1) of this
section for safe and effective responses to
emergencies, including the necessary PPE
and other equipment.
(i) Confined space entry procedures.
(j) A spill containment program meeting the
requirements of paragraph (j) of this sec-
tion.
(iii) Pre-entry briefing. The site specific safety
and health plan shall provide for pre-entry
briefings to be held prior to initiating any site
activity, and at such other times as necessary
to ensure that employees are apprised of the
site safety and health plan and that this plan
is being followed. The information and data
obtained from site characterization and anal-
ysis work required in paragraph (c) of this
section shall be used to prepare and update
the site safety and health plan.
(iv) Effectiveness of site safety and health plan.
Inspections shall be conducted by the site
safety and health supervisor or, in the
absence of that individual, another individual
who is knowledgeable in occupational safety
and health, acting on behalf of the employer
as necessary to determine the effectiveness of
the site safety and health plan. Any deficien-
cies in the effectiveness of the site safety and
health plan shall be corrected by the
employer.
(c) Site characterization and analysis.
(1) General. Hazardous waste sites shall be eval-
uated in accordance with this paragraph to iden-
tify specific site hazards and to determine the
appropriate safety and health control procedures
needed to protect employees from the identified
hazards.
(2) Preliminary evaluation. A preliminary evalua-
tion of a site's characteristics shall be performed
prior to site entry by a qualified person in order
to aid in the selection of appropriate employee
protection methods prior to site entry. Imme-
diately after initial site entry, a more detailed
evaluation of the site's specific characteristics
shall be performed by a qualified person in order
to further identify existing site hazards and to
further aid in the selection of the appropriate
engineering controls and personal protective
equipment for the tasks to be performed.
(3) Hazard identification. All suspected conditions
that may pose inhalation or skin absorption haz-
ards that are immediately dangerous to life or
health (IDLH). or other conditions that may
cause death or serious harm, shall be identified
during the preliminary survey and evaluated
during the detailed survey. Examples of such
hazards include, but are not limited to. confined
space entry, potentially explosive or flammable
situations, visible vapor clouds, or areas where
biological indicators such as dead animals or veg-
etation are located.
(4) Required information. The following informa-
tion to the extent available shall be obtained by
the employer prior to allowing employees to
enter a site:
(i) Location and approximate size of the site.
1910.120(c)(4)(i)
330.4
Change 51
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OCCUPATIONAL SAFETY AND HEALTH
mil.l2tMcK.IMii)
STANDARDS AND INTERPRETATIONS
(ii) Description of the response activity and/or
the job task to be performed.
(iii) Duration of the planned employee
activity.
(iv) Site topography and accessibility by air
and roads.
(v) Safety and health hazards expected at the
site.
(vi) Pathways for hazardous substance disper-
sion.
(vii) Present status and capabilities of
emergency response teams that would provide
assistance to hazardous waste clean-up site
employees at the time of an emergency.
(viii) Hazardous substances and health haz-
ards involved or expected at the site, and
their chemical and physical properties.
(5) Personal protective equipment. Personal pro-
tective equipment (PPE) shall be provided and
used during initial site entry in accordance with
the following requirements:
(i) Based upon the results of the preliminary
site evaluation, an ensemble of PPE shall be
selected and used during initial site entry
which will provide protection to a level of
exposure below permissible exposure limits
and published exposure levels for known or
suspected hazardous substances and health
hazards, and which will provide protection
against other known and suspected hazards
identified during the preliminary site evalua-
tion. If there is no permissible exposure limit
or published exposure level, the employer
may use other published studies and informa-
tion as a guide to appropriate personal protec-
tive equipment.
(ii) If positive-pressure self-contained
breathing apparatus is not used as part of the
entry ensemble, and if respiratory protection
is warranted by the potential hazards identi-
fied during the preliminary site evaluation, an
escape self-contained breathing apparatus of
at least five minute's duration shall be carried
by employees during initial site entry.
(iii) If the preliminary site evaluation does not
produce sufficient information to identify the
hazards or suspected hazards of the site, an
ensemble providing protection equivalent to
Level B PPE shall be provided as minimum
protection, and direct reading instruments
shall be used as appropriate for identifying
IDLH conditions. (See Appendix B for a
description of Level B hazards and the recom-
mendations for Level B protective equip-
ment.)
(iv) Once the hazards of the site have been
identified, the appropriate PPE shall be
selected and used in accordance with para-
graph (g) of this section.
(6) Monitoring. The following monitoring shall be
conducted during initial site entry when the site
evaluation produces information that shows the
potential for ionizing radiation or IDLH condi-
tions, or'when the site information is not suffi-
cient reasonably to eliminate these possible
conditions:
(i) Monitoring with direct reading instruments
for hazardous levels of ionizing radiation.
(ii) Monitoring the air with appropriate direct
reading test equipment (i.e., combustible gas
meters, detector tubes) for IDLH and other
conditions that may cause death or serious
harm (combustible or explosive atmospheres.
oxygen deficiency, toxic substances).
(iii) Visually observing for signs of actual or
potential IDLH or other dangerous condi-
tions.
(iv) An ongoing air monitoring program in
accordance with paragraph (h) of this section
shall be implemented after site characteriza-
tion has determined the site is safe for the
startup of operations.
(7) Risk identification. Once the presence and
concentrations of specific hazardous substances
and health hazards have been established, the
risks associated with these substances shall be
identified. Employees who will be working on
the site shall be informed of any risks that have
been identified. In situations coxered by the
Hazard Communication Standard. 29 CFR
1910.1200, training required by that standard
need not be duplicated.
Note to (c)(7).—Risks to consider include, but
are not limited to:
Change 51
330.5
-------
OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
(a) Exposures exceeding the permissible
exposure limits and published exposure levels.
(b) IDLH concentrations.
(c) Potential skin absorption and irritation
sources.
(d) Potential eye irritation sources.
(e) Explosion sensitivity and flammability
ranges.
(f) Oxygen deficiency.
(8) Employee notification. Any information con-
cerning the chemical, physical, and toxicologic
properties of each substance known or expected
to be present on site that is available to the
employer and relevant to the duties an employee
is expected to perform shall be made available to
the affected employees prior to the commence-
ment of their work activities. The employer may
utilize information developed for the hazard
communication standard for this purpose.
(d) Site control.
(1) General. Appropriate site control procedures
shall be implemented to control employee
exposure to hazardous substances before clean-
up work begins.
(2) Site control program. A site control program
for protecting employees which is part of the
employer's site safety and health program
required in paragraph (b) of this section shall be
developed during the planning stages of a haz-
ardous waste clean-up operation and modified as
necessary as new information becomes available.
(3) Elements of the site control program. The site
control program shall, as a minimum, include: A
site map: site work zones: the use of a "buddy
system": site communications including alerting
means for emergencies: the standard operating
procedures or safe work practices: and. identi-
fication of the nearest medical assistance. Where
these requirements are covered elsewhere they
need not be repeated.
(e) Training.
(1) General.
(i) All employees working on site (such as but
not limited to equipment operators, general
laborers and others) exposed to hazardous
substances, health hazards, or safety hazards
and their supervisors and management
responsible for the site shall receive training
meeting the requirements of this paragraph
before they are permitted to engage in haz-
ardous waste operations that could expose
them to hazardous substances, safety, or
health hazards, and they shall receive review
training as specified in this paragraph.
(ii) Employees shall not be permitted to par-
ticipate in or supervise field activities until
they have been trained to a level required by
their job function and responsibility.
(2) Elements to be covered. The training shall
thoroughly cover the following:
(i) Names of personnel and alternates respon-
sible for site safety and health;
(ii) Safety, health and other hazards present
on the site;
(iii) Use of personal protective equipment:
(iv) Work practices by which the employee can
minimize risks from hazards:
(v) Safe use of engineering controls and equip-
ment on the site:
(vi) Medical surveillance requirements, includ-
ing recognition of symptoms and signs which
might indicate overexposure to hazards: and
(vii) The contents of paragraphs (g) through
(j) of the site safety and health plan set forth
in paragraph (b)(4Xii) of this section.
(3) Initial training.
(i) General site workers (such as equipment
operators, general laborers and supervisory
personnel) engaged in hazardous substance
removal or other activities which expose or
potentially expose workers to hazardous sub-
stances and health hazards shall receive a
minimum of 40 hours of instruction off the
site, and a minimum of three days actual field
experience under the direct supervision of a
trained, experienced supervisor.
330.6
(.'hiingc ol
-------
iK'CITATIONAL SAFETY AND HEALTH
m(U2l)(e)(3Mii)
STANDARDS AND INTERPRETATIONS
(ii) Workers on site only occasionally for a spe-
cific limited task (such as, but not limited to.
ground water monitoring, land surveying, or
geo-physical surveying) and who are unlikely
to be exposed over permissible exposure
limits and published exposure limits shall
receive a minimum of 24 hours of instruction
off the site, and the minimum of one day
actual field experience under the direct super-
vision of a trained, experienced supervisor.
(iii) Workers regularly on site who work in
areas which have been monitored and fully
characterized indicating that exposures are
under permissible exposure limits and pub-
lished exposure limits where respirators are
not necessary, and the characterization indi-
cates that there are no health hazards or the
possibility of an emergency developing, shall
receive a minimum of 24 hours of instruction
off the site and the minimum of one day actual
field experience under the direct supervision
of a trained, experienced supervisor.
(iv) Workers with 24 hours of training who are
covered by paragraphs (a)(3)(ii)and (a)(3)(iii)
of this section, and who become general site
workers or who are required to wear respira-
tors, shall have the additional 16 hours and
two days of training necessary to total the
training specified in paragraph (e)(3)(i).
(4) Management and supervisor training. On-site
management and supervisors directly respon-
sible for. or who supervise employees engaged
in, hazardous waste operations shall receive 40
hours initial training, and three days of super-
vised field experience (the training may be
reduced to 24 hours and one day if the only area
of their responsibility is employees covered by
paragraphs (e)(3)(ii) and (e)(3)(iii) and at least
eight additional hours of specialized training at
the time of job assignment on such topics as. but
not limited to. the employer's safety and health
program and the associated employee training
projrram. personal protective equipment pro-
m-am, spill containment program, and health
hazard monitoring procedure and techniques.
(5) Qualifications for trainers. Trainers shall be
qualified to instruct employees about the subject
matter that is being presented in training. Such
trainers shall have satisfactorily completed a
training program for teaching the subjects they
are expected to teach, or they shall have the
academic credentials and instructional experi-
ence necessary for teaching the subjects.
Instructors shall demonstrate competent
instructional skills and knowledge of the applica-
ble subject matter.
(6) Training certification. Employees and super-
visors that have received and successfully com-
pleted the training and field experience specified
in paragraphs (e)(l) through (e)(4) of this section
shall be certified by their instructor or the head
instructor and trained supervisor as having suc-
cessfully completed the necessary training. A
written certificate shall be given to each person
so certified. Any person who has not been so
certified or who does not meet the requirements
of paragraph (e)(9) of this section shall be pro-
hibited from engaging in hazardous waste opera-
tions.
(7) Emergency response. Employees who are
engaged in responding to hazardous emergency
situations at hazardous waste clean-up sites that
may expose them to hazardous substances shall
be trained in how to respond to such expected
emergencies.
(8) Refresher training. Employees specified in
paragraph (e)(l) of this section, and managers
and supervisors specified in paragraph (e)(4) of
this section, shall receive eight hours of
refresher training annually on the items spec-
ified in paragraph (e)(2) and/or (e)(4) of this sec-
tion, any critique of incidents that have occurred
in the past year that can serve as training exam-
ples of related work, and other relevant topics.
(9) Equivalent training. Employers who can show
by documentation or certification that an
employee's work experience and/or training has
resulted in training equivalent to that training
required in paragraphs (e)(l) through (e)(4) of
this section shall not be required to provide the
initial training requirements of those paragraphs
to such employees. However, certified
employees new to a site shall receive appropri-
ate, site specific training before site entry and
have appropriate supervised field experience at
the new site. Equivalent training includes any
Chanel1 *>l
330.7
1910.120(61(9)
-------
19111.120(e><9)
OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
academic training or the training that existing
employees might have already received from
actual hazardous waste site work experience.
(f) Medical surveillance.
(1) General. Employers engaged in operations
specified in paragraphs (a)(l)(i) through
(a)(l)(iv) of this section and not covered by
(a)(2)(iii) exceptions and employers of employees
specified in paragraph (g)(9) shall institute a
medical surveillance program in accordance with
this paragraph.
(2) Employees covered. The medical surveillance
program shall be instituted by the employer for
the following employees:
(i) All employees who are or may be exposed
to hazardous substances or health hazards at
or above the permissible exposure limits or. if
there is no permissible exposure limit, above
the published exposure levels for these sub-
stances, without regard to the use of respira-
tors, for 30 days or more a year;
(ii) All employees who wear a respirator for 30
days or more a year or as required by §
1910.134;
(iii) All employees who are injured due to
overexposure from an emergency incident
involving hazardous substances or health haz-
ards; or
(iv) Members of HAZMAT teams.
(3) Frequency of medical examinations and con-
sultations.
Medical examinations and consultations shall be
made available by the employer to each
employee covered under paragraph (f)(2) of this
section on the following schedules:
(i) For employees covered under paragraphs
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OCCUPATIONAL SAFETY AND HEALTH
1910.1201 f)(4)(ii)
STANDARDS AND INTERPRETATIONS
(ii) The content of medical examinations or
consultations made available to employees
pursuant to paragraph (f) shall be determined
by the attending physician. The guidelines in
the Occupational Safety and Health Guidance
Manual for Hazardous Waste Site Activities
(See Appendix D, Reference #10) should be
consulted.
(5) Examination by a physician and costs. All
medical examinations and procedures shall be
performed by or under the supervision of a
licensed physician, preferably one knowledge-
able in occupational medicine, and shall be
provided without cost to the employee, without
loss of pay, and at a reasonable time and place.
(6) Information provided to the phyiieian. The
employer shall provide one copy of this standard
and its appendices to the attending physician,
and in addition the following for each employee:
(i) A description of the employee's duties as
they relate to the employee's exposures.
(ii) The employee's exposure levels or antici-
pated exposure levels.
(iii) A description of any personal protective
equipment used or to be used.
(iv) Information from previous medical exam-
inations of the employee which is not readily
available to the examining physician.
(v) Information required by §1910.134.
(7) Physician's written opinion.
(i) The employer shall obtain and furnish the
employee with a copy of a written opinion
from the attending physician containing the
following:
(a) The physician's opinion as to whether
the employee has any detected medical con-
ditions which would place the employee at
increased risk of material impairment of the
employee's health from work in hazardous
waste operations or emergency response, or
from respirator use.
(b) The physician's recommended limita-
tions upon the employee's assigned work.
(c) The results of the medical examination
and tests if requested by the employee.
(d) A statement that the employee has been
informed by the physician of the results of
the medical examination and any medical
conditions which require further examina-
tion or treatment.
(ii) The written opinion obtained by the
employer shall not reveal specific findings or
diagnoses unrelated to occupational ex-
posures.
(8) Recordkeeping.
(i) An accurate record of the medical sur-
veillance required by paragraph (f) of this sec-
tion shall be retained. This record shall be
retained for the period specified and meet the
criteria of 29 CFR 1910.20.
(ii) The record required in paragraph (f)(8)(i)
of this section shall include at least the follow-
ing information:
(a) The name and social security number of
the employee;
(b) Physician's written opinions, recom-
mended limitations, and results of examina-
tions and tests;
(c) Any employee medical complaints
related to exposure to hazardous sub-
stances;
(d) A copy of the information provided to
the examining physician by the employer,
with the exception of the standard and its
appendices.
(g) Engineering controls, work practices, and
personal protective equipment for employee
protection.
Engineering controls, work practices, personal
protective equipment, or a combination of these
shall be implemented in accordance with this para-
graph to protect employees from exposure to haz-
ardous substances and safety and health hazards.
Change 51
330.9
1910.120(g)
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OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
(1) Engineering controls, work practices and PPE
for substances regulated in Subparts G and Z.
(i) Engineering controls and work practices
shall be instituted to reduce and maintain
employee exposure to or below the permissi-
ble exposure limits for substances regulated
by 29 CFR Part 1910. to the extent required
by Subpart Z, except to the extent that such
controls and practices are not feasible.
Note to (g)(l)(i): Engineering controls which
may be feasible include the use of pressurized
cabs or control booths on equipment, and/or
the use of remotely operated material hand-
ling equipment. Work practices which may be
feasible are removing all non-essential
employees from potential exposure during
opening of drums, wetting down dusty opera-
tions and locating employees upwind of possi-
ble hazards.
(ii) Whenever engineering controls and work
practices are not feasible, PPE shall be used
to reduced and maintain employee exposures
to or below the permissible exposure limits or
dose limits for substances regulated by 29
CFR Part 1910, Subpart Z.
(iii) The employer shall not implement a
schedule of employee rotation as a means of
compliance with permissible exposure limits
or dose limits except when there is no other
feasible way of complying with the airborne or
dermal dose limits for ionizing radiation.
(iv) The provisions of 29 CFR, Subpart G,
shall be followed.
(2) Engineering controls, work practices, and PPE
for substances not regulated in Subparts G and Z.
An appropriate combination of engineering con-
trols, work practices and personal protective
equipment shall be used to reduce and maintain
employee exposure to or below published
exposure levels for hazardous substances and
health hazards not regulated by 29 CFR Part
1910. Subparts G and Z. The employer may use
the published literature and MSOS as a guide in
making the employer's determination as to what
level of protection the employer believes is
appropriate for hazardous substances and health
hazards for which there is no permissible
exposure limit or published exposure limit.
(3) Personal protective equipment selection.
(i) Personal protective equipment (PPE) shall
be selected and used which will protect
employees from the hazards and potential haz-
ards they are likely to encounter as identified
during the site characterization and analysis.
(ii) Personal protective equipment selection
shall be based on an evaluation of the per-
formance characteristics of the PPE relative
to the requirements and limitations of the
site, the task-specific conditions and duration.
and the hazards and potential hazards identi-
fied at the site.
(iii) Positive pressure self-contained breathing
apparatus, or positive pressure air-line respi-
rators equipped with an escape air supply,
shall be used when chemical exposure levels
present will create a substantial possibility of
immediate death, immediate serious illness or
injury, or impair the ability to escape.
(iv) Totally-encapsulating chemical protective
suits (protection equivalent to Level A protec-
tion as recommended in Appendix B) shall be
used in conditions where skin absorption of a
hazardous substance may result in a substan-
tial possibility of immediate death, immediate
serious illness or injury, or impair the ability
to escape.
(v) The level of protection provided by PPE
selection shall be increased when additional
information on site conditions indicates that
increased protection is necessary to reduce
employee exposures below permissible
exposure limits and published exposure levels
for hazardous substances and health hazards.
(See Appendix B for guidance on selecting
PPE ensembles.)
Note to (g)(3): The level of employee protec-
tion provided may be decreased when addi-
tional information or site conditions show that
decreased protection will not result in haz-
ardous exposures to employees.
(vi) Personal protective equipment shall be
selected and used to meet the requirements of
29 CFR Part 1910, Subpart 1. and additional
requirements specified in this section.
m0.r.!0(RM3)(vi)
330.10
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OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
(4) Totally-encapsulating chemical protective
suits.
(i) Totally-encapsulating suits shall protect
employees from the particular hazards which
are identified during site characterization and
analysis.
(ii) Totally-encapsulating suits shall be capable
of maintaining positive air pressure. (See
Appendix A for1 a test method which may be
used to evaluate this requirement.)
(iii) Totally-encapsulating suits shall be capa-
ble of preventing inward test gas leakage of
more than 0.5 percent. (See Appendix A for a
test method which may be used to evaluate
this requirement.)
(5) Personal protective equipment (PPE) program.
A written personal protective equipment pro-
gram, which is part of the employer's safety and
health program required in paragraph (b) of this
section or required in paragraph (p)(l) of this
section and which is also a part of the site-
specific safety and health plan shall be estab-
lished. The PPE program shall address the ele-
ments listed below. When elements, such as
donning and doffing procedures, are provided by
the manufacturer of a piece of equipment and
are attached to the plan, they need not be
rewritten into the plan as long as they ade-
quately address the procedure or element.
(i) PPE selection based upon site hazards.
(ii) PPE use and limitations of the equipment,
(iii) Work mission duration.
(iv) PPE maintenance and storage,
(v) PPE decontamination and disposal.
(vi) PPE training and proper fitting,
(vii) PPE donning and doffing procedures.
(viii) PPE inspection procedures prior to. dur-
ing, and after use.
(ix) Evaluation of the effecti\ eness of the PPE
program, and
(x) Limitations during temperature extremes,
heat stress, and other appropriate medical
considerations.
(h) Monitoring.
(1) General.
(i) Monitoring shall be performed in accord-
ance with this paragraph where there may be
a question of employee exposure to hazardous
concentrations of hazardous substances in
order to assure proper selection of engineer-
ing controls, work practices and personal pro-
tective equipment so that employees are not
exposed to levels which exceed permissible
exposure limits or published exposure levels
for hazardous substances.
(ii) Air monitoring shall be used to identify
and quantify airborne levels of hazardous sub-
stances and safety and health hazards in order
to determine the appropriate level of
employee protection needed on site.
(2) Initial entry. Upon initial entry, representa-
tive air monitoring shall be conducted to identify
any IDLH condition, exposure over permissible
exposure limits or published exposure levels,
exposure over a radioactive material's dose
limits or other dangerous condition such as the
presence of flammable atmospheres or oxygen-
deficient environments.
(3) Periodic monitoring. Periodic monitoring shall
be conducted when the possibility of an IDLH
condition or flammable atmosphere has
developed or when there if indication that
exposures may have risen over permissible
exposure limits or published exposure levels
since prior monitoring. Situations where it shall
be considered whether the possibility that
exposures have risen are as follows:
(i) When work begins on a different portion of
the site.
(ii) When contaminants other than those pre-
viously identified are being handled.
(iii) When a different type of operation is initi-
ated (e.g., drum opening as opposed to explor-
atory well drilling).
(iv) When employees are handling leaking
drums or containers or working in areas \\ ith
obvious liquid contamination (e.g.. a spill or
lagoon).
(4) Monitoring of high-risk employees. After the
actual clean-up phase of any hazardous waste
330.11 I»li).l2i)(h)i4i
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1910.120(h)(4)
OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
operation commences; for example, when soil.
surface water or containers are moved or dis-
turbed: the employer shall monitor those
employees likely to have the highest exposure to
hazardous substances and health hazards likely
to be present above permissible exposure limits
or published exposure levels by using personal
sampling frequently enough to characterize
employee exposures. If the employees likely to
have the highest exposure are over permissible
exposure limits or published exposure limits,
then monitoring shall continue to determine all
employees likely to be above those limits. The
employer may utilize a representative sampling
approach by documenting that the employees
and chemicals chosen for monitoring are based
on the criteria stated above.
Note to (h): It is not required to monitor
employees engaged in site characterization oper-
ations covered by paragraph (c) of this section.
(i) Informational programs.
Employers shall develop and implement a pro-
gram, which is part of the employer's safety and
health program required in paragraph (b) of this
section, to inform employees, contractors, and
subcontractors (or their representative) actually
engaged in hazardous waste operations of the
nature, level and degree of exposure likely as a
result of participation in such hazardous waste
operations. Employees, contractors and sub-
contractors working outside of the operations part
of a site are not covered by this standard.
(j) Handling drums and containers.
(1) General.
(i) Hazardous substances and contaminated
soils, liquids, and other residues shall be han-
dled, transported, labeled, and disposed of in
accordance with this paragraph.
(ii) Drums and containers used during the
clean-up shall meet the appropriate DOT,
OSHA. and EPA regulations for the wastes
that they contain.
(iii) When practical, drums and containers
shall be inspected and their integrity shall be
assured prior to being moved. Drums or con-
tainers that cannot be inspected before being
moved because of storage conditions (i.e.. bur-
ied beneath the earth, stacked behind other
drums, stacked several tiers high in a pile,
etc.) shall be moved to an accessible location
and inspected prior to further handling.
(iv) Unlabeled drums and containers shall be
considered to contain hazardous substances
and handled accordingly until the contents are
positively identified and labeled.
(v) Site operations shall be organized to mini-
mize the amount of drum or container move-
ment.
(vi) Prior to movement of drums or con-
tainers, all employees exposed to the transfer
operation shall be warned of the potential haz-
ards associated with the contents of the drums
or containers.
(vii) U.S. Department of Transportation spec-
ified salvage drums or containers and suitable
quantities of proper absorbent shall be kept
available and used in areas where spills, leaks,
or ruptures may occur.
(viii) Where major spills may occur, a spill
containment program, which is part of the
employer's safety and health program
required in paragraph (b) of this section, shall
be implemented to contain and isolate the
entire volume of the hazardous substance
being transferred.
(ix) Drums and containers that cannot be
moved without rupture, leakage, or spillage
shall be emptied into a sound container using
a device classified for the material being
transferred.
(x) A ground-penetrating system or other
type of detection system or device shall be
used to estimate the location and depth of bur-
ied drums or containers.
(xi) Soil or covering material shall be removed
with caution to prevent drum or container
rupture.
(xii) Fire extinguishing equipment meeting
the requirements of 29 CFR Part 1910, Sub-
part L. shall be on hand and ready for use to
control incipient Tires.
(2) Opening drums and containers. The following
procedures shall be followed in areas where
drums or containers are being opened:
1910.120(j)<2)
330.12
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OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
(i) Where an airline respirator system is used,
connections to the source of air supply shall be
protected from contamination and the entire
system shall be protected from physical
damage.
(ii) Employees not actually involved in open-
ing drums or containers shall be kept a safe
distance from the drums or containers being
opened.
(iii) If employees must work near or adjacent
to drums or containers being opened, a suita-
ble shield that does not interfere with the
work operation shall be placed between the
employee and the drums or containers being
opened to protect the employee in case of acci-
dental explosion.
(iv) Controls for drum or container opening
equipment, monitoring equipment, and fire
suppression equipment shall be located behind
the explosion-resistant barrier.
(v) When there is a reasonable possibility of
flammable atmospheres being present, mate-
rial handling equipment and hand tools shall
be of the type to prevent sources of ignition.
(vi) Drums and containers shall be opened in
such a manner that excess interior pressure
will be safety relieved. If pressure can not be
relieved from a remote location, appropriate
shielding shall be placed between the
employee and the drums or containers to
reduce the risk of employee injury.
(vii) Employees shall not stand upon or work
from drums or containers.
(3) Material handling equipment. Material hand-
ling equipment used to transfer drums and con-
tainers shall be selected, positioned and
operated to minimize sources of ignition related
to the equipment from igniting vapors released
from ruptured drums or containers.
(4) Radioactive wastes. Drums and containers
containing radioactive wastes shall not be han-
dled until such time as their hazard to
employees is properly assessed.
(5) Shock sensitive wastes. As a minimum, the
following special precautions shall be taken
when drums and containers containing or sus-
pected of containing shock-sensitive wastes are
handled:
(i) All non-essential employees shall be evacu-
ated from the area of transfer.
(ii) Material handling equipment shall be
provided with explosive containment devices
or protective shields to protect equipment
operators from exploding containers.
(iii) An employee alarm system capable of
being perceived above surrounding light and
noise conditions shall be used to signal the
commencement and completion of explosive
waste handling activities.
(iv) Continuous communications (i.e., portable
radios, hand signals, telephones, as appropri-
ate) shall be maintained between the
employee-in-charge of the immediate handling
area and both the site safety and health super-
visor and the command post until such time as
the handling operation is completed. Com-
munication equipment or methods that could
cause shock sensitive materials to explode
shall not be used.
(v) Drums and containers under pressure, as
evidenced by bulging or swelling, shall not be
moved until such time as the cause for excess
pressure is determined and appropriate con-
tainment procedures have been implemented
to protect employees from explosive relief of
the drum.
(vi) Drums and containers containing pack-
aged laboratory wastes shall be considered to
contain shock-sensitive or explosive materials
until they have been characterized.
Caution: Shipping of shock sensitive wastes
may be prohibited under U.S. Department of
Transportation regulations. Employers and
their shippers should refer to 49 CFR 173.21
and 173.50.
(6) Laboratory waste packs. In addition to the
requirements of paragraph (j)(5) of this section.
the following precautions shall be taken, as a
minimum, in handling laboratory waste packs
(lab packs):
(i) Lab packs shall be opened only when neces-
sary and then only by an individual knowl-
edgeable in the inspection, classification, and
segregation of the containers within the pack
according to the hazards of the wastes.
(ii) If crystalline material is noted on any con-
330.13
1'JIO.r.iOij 1(6)1 ii)
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lSUU20!
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OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
contaminated area, they shall be provided and
meet the requirements of 29 CFR 1910.141. If
temperature conditions prevent the effective use
of water, then other effective means for cleans-
ing shall be provided and used.
(I) Emergency response by employees at
uncontrolled hazardous waste sites.
(1) Emergency response plan.
(i) An emergency response plan shall be
developed and implemented by all employers
within the scope of this section to handle
anticipated emergencies prior to the com-
mencement of hazardous waste operations.
The plan shall be in writing and available for
inspection and copying by employees, their
representatives, OSHA personnel and other
governmental agencies with relevant respon-
sibilities.
(ii) Employers who will evacuate their
employees from the workplace when an
emergency occurs, and who do not permit any
of their employees to assist in handling the
emergency, are exempt from the require-
ments of this paragraph if they provide an
emergency action plan complying with section
1910.38(a) of this part.
(2) Elements of an emergency response plan. The
employer shall develop an emergency response
plan for emergencies which shall address, as a
minimum the following:
(i) Pre-emergency planning.
(ii) Personnel roles, lines of authority, and
communication.
(iii) Emergency recognition and prevention.
(iv) Safe distances and places of refuge.
(v) Site security and control.
(vi) Evacuation routes and procedures.
(vii) Decontamination procedures which are
not covered by the site safety and health plan.
(viii) Emergency medical treatment and first
aid.
(ix) Emergency alerting and response proce-
dures.
(x) Critique of response and follow-up.
(xi) PPE and emergency equipment.
(3) Procedures for handling emergency incidents.
(i) In addition to the elements for the
emergency response plan required in para-
graph (1)(2) of this section, the following ele-
ments shall be included for emergency
response plans:
(a) Site topography, layout, and prevailing
weather conditions.
(b) Procedures for reporting incidents to
local, state, and federal governmental agen-
cies.
(ii) The emergency response plan shall be a
separate section of the Site Safety and Health
Plan.
(iii) The emergency response plan shall be
compatible and integrated with the disaster.
fire and/or emergency response plans of local,
state, and federal agencies.
(iv) The emergency response plan shall be
rehearsed regularly as part of the overall
training program for site operations.
(v) The site emergency response plan shall be
reviewed periodically and, as necessary, be
amended to keep it current with new or
changing site conditions or information.
(vi) An employee alarm system shall be
installed in accordance with 29 CFR 1910.1(55
to notify employees of an emergency situation:
to stop work activities if necessary: to lower
background noise in order to speed communi-
cation: and to begin emergency procedures.
(vii) Based upon the information available at
time of the emergency, the employer shall
evaluate the incident and the site response
capabilities and proceed with the appropriate
steps to implement the site emergency
response plan.
( h.ingv 51
330.15
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l!M0.120(m>
OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
(m) Illumination.
Areas accessible to employees shall be lighted to
not less than the minimum illumination inten-
sities listed in the following Table H-120.1 while
any work is in progress:
TABLE H-120.1—MINIMUM ILLUMINATION
INTENSITIES IN FOOT-CANDLES
Foot-
candles
Area or operations
o
•3
General site areas.
Excavation and waste areas, access-
ways, active storage areas, loading
platforms, refueling, and field main-
tenance areas.
Indoors: Warehouses, corridors, hall-
ways, and exitways.
Tunnels, shafts, and general under-
ground work areas. (Exception:
Minimum of 10 foot-candles is
required at tunnel and shaft heading
during drilling mucking, and scaling.
Mine Safety and Health Administra-
tion approved cap lights shall be
acceptable for use in the tunnel head-
ing).
General shops (e.g., mechanical and
electrical equipment rooms, active
storerooms, barracks or living quar-
ters, locker or dressing rooms,
(lining areas, and indoor toilets and
workrooms.)
First aid stations, infirmaries, and
offices.
10
30.
(n) Sanitation at temporary workplaces.
(1) Potable water.
(i) An adequate supply of potable water shall
be provided on the site.
(ii) Portable containers used to dispense
drinking water shall be capable of being
tightly closed, and equipped with a tap. Water
shall not be dipped from containers.
(Mi) Any container used to distribute drinking
water shall be clearly marked as to the nature
of its contents and not used for any other pur-
pose.
(iv) Where single service cups (to be used but
once) are supplied, both a sanitary container
for the unused cups and a receptacle for dis-
posing of the used cups shall be provided.
(2) Nonpotable water.
(i) Outlets for nonpotable water, such as
water for firefighting purposes, shall be iden-
tified to indicate clearly that the water is
unsafe and is not to be used for drinking,
washing, or cooking purposes.
(ii) There shall be no cross-connection, open or
potential, between a system furnishing pota-
ble water and a system furnishing nonpotable
water.
(3) Toilet facilities.
(i) Toilets shall be provided for employees
according to the following Table H-120.2.
TABLE H-120.2—TOILET FACILITIES
Number of employees
Minimum number of
facilities
20 or fewer One.
More than 20, fewer One toilet seat and one
than 200. urinal per 40
employees.
More than 200 One toilet seat and one
urinal per 50
employees.
(ii) Under temporary field conditions, provi-
sions shall be made to assure that at least one
toilet facility is available.
(iii) Hazardous waste sites not provided with a
sanitary sewer shall be provided with the fol-
lowing toilet facilities unless prohibited by
local codes:
(a) Chemical toilets:
(b) Recirculatmg toilets:
(c) Combustion toilets: or
(d) Flush toilets.
(iv) The requirements of this paragraph for
sanitation facilities shall not apply to mobile
crews having transportation readily available
to nearby toilet facilities.
330.16
Chance ~>1
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OCCUPATIONAL SAFETY AND HEALTH
I910.120(n)(3)(v)
STANDARDS AND INTERPRETATIONS
(v) Doors entering toilet facilities shall be
provided with entrance locks controlled from
inside the facility.
(4) Food handling. All food service facilities and
operations for employees shall meet the applica-
ble laws, ordinances, and regulations of the
jurisdictions in which they are located.
(5) Temporary sleeping quarters. When tempo-
rary sleeping quarters are provided, they shall
be heated, ventilated, and lighted.
(6) Washing facilities. The employer shall
provide adequate washing facilities for
employees engaged in operations where haz-
ardous substances may be harmful to
employees. Such facilities shall be in near prox-
imity to the worksite: in areas where exposures
are below permissible exposure limits and pub-
lished exposure levels and which are under the
controls of the employer; and shall be so
equipped as to enable employees to remove haz-
ardous substances from themselves.
(7) Showers and change rooms. When hazardous
waste clean-up or removal operations commence
on a site and the duration of the work will
require six months or greater time to complete,
the employer shall provide showers and change
rooms for all employees exposed to hazardous
substances and health hazards involved in haz-
ardous waste clean-up or removal operations.
(i) Showers shall be provided and shall be
provided and shall meet the requirements of
29CFRl910.141(d){3).
(ii) Change rooms shall be provided and shall
meet the requirements of 29 CFR 1910.141(e).
Change rooms shall consist of two separate
change areas separated by the shower area
required in paragraph (n)(7)(i) of this section.
One change area, with an exit leading off the
worksite, shall provide employees with a clean
area where they can remove, store, and put
on street clothing. The second area, with an
exit to the worksite, shall provide employees
with an area where they can put on. remove
and store work clothing and personal protec-
tive equipment.
(iii) Showers and change rooms shall be
located in areas where exposures are below
the permissible exposure limits and published
exposure levels. If this cannot be accom-
plished, then a ventilation system shall be
provided that will supply air that is below the
permissible exposure limits and published
exposure levels.
(iv) Employers shall assure that employees
shower at the end of their work shift and
when leaving the hazardous waste site.
(o) New technology programs.
(1) The employer shall develop and implement
procedures for the introduction of effective new
technologies and equipment developed for the
improved protection of employees working with
hazardous waste clean-up operations, and the
same shall be implemented as part of the site
safety and health program to assure that
employee protection is being maintained.
(2) New technologies, equipment or control
measures available to the industry, such as the
use of foams, absorbents, adsorbents, neu-
tralizers, or other means to suppress the level of
air contaminants while excavating the site or for
spill control, shall be evaluated by employers or
their representatives. Such an evaluation shall
be done to determine the effectiveness of the
new methods, materials, or equipment before
implementing their use on a large scale for
enhancing employee protection. Information and
data from manufacturers or suppliers may be
used as part of the employer's evaluation effort.
Such evaluations shall be made available to
OSHA upon request.
(p) Certain Operations Conducted Under the
Resource Conservation and Recovery Act of
1976 (RCRA).
Employers conducting operations at treatment,
storage, and disposal (TSD) facilities specified in
paragraph (a)(l)(iv) of this section not exempted
by paragraph (a)(2)(iii) of this section shall
provide and implement the programs specified
in this paragraph.
(1) Safety and health program. The employer
shall develop and implement a written safety
and health program for employees involved in
hazardous waste operations that shall be avail-
able for inspection by employees, their repre-
sentatives and OSHA personnel. The program
shall be designed to identify, evaluate and con-
trol safety and health hazards in their facilities
Change 51
330.17
I910.120(p)
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I9io.i2o
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OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
(a) Pre-emergency planning and coordina-
tion with outside parties.
(b) Personnel roles, lines of authority, and
communication.
(c) Emergency recognition and prevention.
(d) Safe distances and places of refuge.
(e) Site security and control.
(f) Evacuation routes and procedures.
(g) Decontamination procedures.
(h) Emergency medical treatment and first
aid.
(!) Emergency alerting and response proce-
dures.
(j) Critique of response and follow-up.
(k) PPE and emergency equipment.
(iii) Training.
(a) Training for emergency response
employees shall be completed before they are
called upon to perform in real emergencies.
Such training shall include the elements of the
emergency response plan, standard operating
procedures the employer has established for
the job, the personal protective equipment to
be worn and procedures for handling
emergency incidents.
Exception #1: An employer need not train all
employees to the degree specified if the
employer divides the work force in a manner
such that a sufficient number of employees
who have responsibility to control emergencies
have the training specified, and all other
employees, who may first respond to an
emergency incident, have sufficient awareness
training to recognize that an emergency
response situation exists and that they are
instructed in that case to summon the fully
trained employees and not attempt control
activities for which they are not trained.
Exception #1: An employer need not train all
employees to the degree specified if arrange-
ments have been made in advance for an out-
side fully-trained emergency response team to
respond in a reasonable period and all
employees, who may come to the incident
first, have sufficient awareness training to rec-
ognize that an emergency response situation
exists and they have been instructed to call
the designated outside fully-trained
emergency response team for assistance.
(b) Employee members of TSD facility
emergency response organizations shall be
trained to a level of competence in the recogni-
tion of health and safety hazards to protect
themselves and other employees. This would
include training in the methods used to mini-
mize the risk from safety and health hazards;
in the safe use of control equipment; in the
selection and use of appropriate personal pro-
tective equipment; in the safe operating proce-
dures to be used at the incident scene; in the
techniques of coordination with other
employees to minimize risks; in the appropri-
ate response to over exposure from health haz-
ards or injury to themselves and other
employees; and in the recognition of subse-
quent symptoms which may result from over
exposures.
(e) The employer shall certify that each cov-
ered employee has attended and successfully
completed the training required in paragraph
(p)(8)(iii) of this section, or shall certify the
employee's competency at least yearly. The
method used to demonstrate competency for
certification of training shall be recorded and
maintained by the employer.
(iv) Procedures for handling emergency inci-
dents.
(a) In addition to the elements for the
emergency response plan required in para-
graph (p)(8)(ii) of this section, the following
elements shall be included for emergency
response plans to the extent that they do
not repeat any information already con-
tained in the emergency response plan:
(1) Site topography, layout, and prevail-
ing weather conditions.
(2) Procedures for reporting incidents to
local, state, and federal governmental
agencies.
(b) The emergency response plan shall be
compatible and integrated with the disas-
Change 51
330.19
iyi0.120(p)(8)(iv)(b)
-------
I910.120(p)(8)(iv)(b)
OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
ter, fire and/or emergency response plans of
local, state, and federal agencies.
(c) The emergency response plan shall be
rehearsed regularly as part of the overall
training program for site operations.
(d) The site emergency response plan shall
be reviewed periodically and, as necessary,
be amended to l^eep it current with new or
changing site conditions or information.
(e) An employee alarm system shall be
installed in accordance with 29 CFR
1910.165 to notify employees of an
emergency situation; to stop work activities
if necessary; to lower background noise in
order to speed communication; and to begin
emergency procedures.
(f) Based upon the information available at
time of the emergency, the employer shall
evaluate the incident and the site response
capabilities and proceed with the appropri-
ate steps to implement the site emergency
response plan.
(q) Emergency response to hazardous sub-
stance releases.
This paragraph covers employers whose
employees are engaged in emergency response no
matter where it occurs except that it does not
cover employees engaged in operations specified in
paragraphs (a)(l)(i) through (a)(l)(iv) of this sec-
tion. Those emergency response organizations who
have developed and implemented programs equiv-
alent to this paragraph for handling releases of
hazardous substances pursuant to section 303 of
the Superfund Amendments and Reauthorization
Act of 1986 (Emergency Planning and Community
Right-to-Know Act of 1986, 42 U.S.C. 11003) shall
be deemed to have met the requirements of this
paragraph.
(1) Emergency response plan. An emergency
response plan shall be developed and imple-
mented to handle anticipated emergencies prior
to the commencement of emergency response
operations. The plan shall be in writing and
available for inspection and copying by
employees, their representatives and OSHA
personnel. Employers who will evacuate their
employees from the workplace when an
emergency occurs, and who do not permit any of
their employees to assist in handling the
emergency, are exempt from the requirements
of this paragraph if they provide an emergency
action plan in accordance with §1910.38(a) of this
part.
(2) Elements of an emergency response plan. The
employer shall develop an emergency response
plan for emergencies which shall address, as a
minimum, the following to the extent that they
are not addressed elsewhere:
(i) Pre-emergency planning and coordination
with outside parties.
(ii) Personnel roles, lines of authority, train-
ing, and communication.
(iii) Emergency recognition and prevention.
(iv) Safe distances and places of refuse.
(v) Site security and control.
(vi) Evacuation routes and procedures.
(vii) Decontamination.
(viii) Emergency medical treatment and first
aid.
(ix) Emergency alerting and response proce-
dures.
(x) Critique of response and follow-up.
(xi) PPE and Emergency equipment.
(xii) Emergency response organizations may
use the local emergency response plan or the
state emergency response plan or both, as
part of their emergency response plan to
avoid duplication. Those items of the
emergency response plan that are being prop-
erly addressed by the SARA Title III plans
may be substituted into their emergency plan
or otherwise kept together for the employer
and employee's use.
(3) Procedures for handling emergency response.
(i) The senior emergency response official
responding to an emergency shall become the
individual in charge of a site-specific Incident
Command System (ICS). All emergency
responders and their communications shall be
coordinated and controlled through the indi-
vidual in charge of the ICS assisted by the
senior official present for each employer.
1910.120(q)(3)d)
330.20
Change 51
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OCCUPATIONAL SAFETY AND HEALTH
mo.l20(q)CM(i)
STANDARDS AND INTERPRETATIONS
Note to (q)(3)(i).—The "senior official" at an
emergency response is the most senior official
on the site who has the responsibility for con-
trolling the operations at the site. Initially it
is the senior officer on the first-due piece of
responding emergency apparatus to arrived
on the incident scene. As more senior officers
arrive (i.e., battalion chief, fire chief, state
law enforcement official, site coordinator,
etc.) the position is passed up the line of
authority which has been previously estab-
lished.
(ii) The individual in charge of the ICS shall
identify, to the extent possible, all hazardous
substances or conditions present and shall
address as appropriate site analysis, use of
engineering controls, maximum exposure
limits, hazardous substance handling proce-
dures, and use of any new technologies.
(iii) Based on the hazardous substances and/or
conditions present, the individual in charge of
the ICS shall implement appropriate
emergency operations, and assure that the
personal protective equipment worn is appro-
priate for the hazards to be encountered.
However, personal protective equipment shall
meet, at a minimum, the criteria contained in
29 CFR 1910.156(e) when worn while per-
forming fire fighting operations beyond the
incipient stage for any incident or site.
(iv) Employees engaged in emergency
response and exposed to hazardous substances
presenting an inhalation hazard or potential
inhalation hazard shall wear positive pressure
self-contained breathing apparatus while
engaged in emergency response, until such
time that the individual in charge of the ICS
determines through the use of air monitoring
that a decreased level of respiratory protec-
tion will not result in hazardous exposures to
employees.
(v) The individual in charge of the ICS shall
limit the number of emergency response per-
sonnel at the emergency site, in those areas of
potential or actual exposure to incident or site
hazards, to those who are actively performing
emergency operations. However, operations
in hazardous areas shall be performed using
the buddy system in groups of two or more.
(vi) Back-up personnel shall stand by with
equipment ready to provide assistance or res-
cue. Advance first aid support personnel, as a
minimum, shall also stand by with medical
equipment and transportation capability.
(vii) The individual in charge of the ICS shall
designate a safety official, who is knowledge-
able in the operations being implemented at
the emergency response site, with specific
responsibility to identify and evaluate hazards
and to provide direction with respect to the
safety of operations for the emergency at
hand.
(viii) When activities are judged by the safety
official to be an IDLH condition and/or to
involve an imminent danger condition, the
safety official shall have the authority to alter.
suspend, or terminate those activities. The
safety-official shall immediately inform the
individual in charge of the ICS of any actions
needed to be taken to correct these hazards at
an emergency scene.
(ix) After emergency operations have termi-
nated, the individual in charge of the ICS
shall implement appropriate decontamination
procedures.
(x) When deemed necessary for meeting the
tasks at hand, approved self-contained com-
pressed air breathing apparatus may be used
with approved cylinders from other approved
self-contained compressed air breathing appa-
ratus provided that such cylinders are of the
same capacity and pressure rating. All com-
pressed air cylinders used with self-contained
breathing apparatus shall meet U.S. Depart-
ment of Transportation and National Institute
for Occupational Safety and Health criteria.
(4) Skilled support personnel. Personnel, not nec-
essarily an employer's own employees, who are
skilled in the operation of certain equipment.
such as mechanized earth moving or digging
equipment or crane and hoisting equipment, and
who are needed temporarily to perform immedi-
ate emergency support work that cannot reason-
ably be performed in a timely fashion by an
employer's own employees, and who will be or
may be exposed to the hazards at an emergency
response scene, are not required to meet the
training required in this paragraph for the
employer's regular employees. However, these
personnel shall be given an initial briefing at the
site prior to their participation in any
emergency response. The initial briefing shall
C'htingc 51
330.21
H»10.120(q)<4)
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OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
include instruction in the wearing of appropriate
personal protective equipment, what chemical
hazards are involved, and what duties are to be
performed. All other appropriate safety and
health precautions provided to the employer's
own employees shall be used to assure the
safety and health of these personnel.
(5) Specialist employees. Employees who, in the
course of their regular job duties, work with and
are trained in the Hazards of specific hazardous
substances, and who will be called upon to
provide technical advice or assistance at a haz-
ardous substance release incident to the individ-
ual in charge, shall receive training or
demonstrate competency in the area of their
specialization annually.
(6) Training. Training shall be based on the
duties and function to be performed by each
responder of an emergency response organiza-
tion. The skill and knowledge levels required for
all new responders, those hired after the effec-
tive date of this standard, shall be conveyed to
them through training before they are permitted
to take part in actual emergency operations on
an incident. Employees who participate, or are
expected to participate, in emergency response,
shall be given training in accordance with the
following paragraphs:
(i) First responder awareness level. First
responders at the awareness level are individ-
uals who are likely to witness or discover a
hazardous substance release and who have
been trained to initiate an emergency
response sequence by notifying the proper
authorities of the release. They would take no
further action beyond notifying the authorities
of the release. First responders at the aware-
ness level shall have sufficient training to
have had sufficient experience to objectively
demonstrate competency in the following
areas.
(a) An understanding of what hazardous
materials are. and the risks associated with
them in an incident.
(b) An understanding of the potential out-
comes associated with an emergency cre-
ated when hazardous materials are present.
(c) The ability to recognize the presence of
hazardous materials in an emergency.
(d) The ability to identify the hazardous
materials, if possible.
(e) An understanding of the role of the first
responder awareness individual in the
employer's emergency response plan includ-
ing the site security and control and the
U.S. Department of Transportation's
Emergency Response Guidebook.
(f) The ability to realize the need for addi-
tional resources, and to make appropriate
notifications to the communication center.
(ii) First responder operations level. First
responders at the operations level are individ-
uals who respond to releases or potential
releases of hazardous substances as part of
the initial response to the site for the purpose
of protecting nearby persons, property, or the
environment from the effects of the release.
They are trained to respond in a defensive
fashion without actually trying to stop the
release. Their function is to contain the
release from a safe distance, keep it from
spreading, and prevent exposures. First
responders at the operational level shall have
received at least eight hours of training or
have had sufficient experience to objectively
demonstrate competency in the following
areas in addition to those listed for the aware-
ness level and the employer shall so certify:
(a) Knowledge of the basic hazard and risk
assessment techniques.
(b) Know how to select and use proper per-
sonal protective equipment provided to the
first responder operational level.
(c) An understanding of basic hazardous
materials terms.
(d) Know how to perform basic control, con-
tainment and/or confinement operations
within the capabilities of the resources and
personal protective equipment available
with their unit.
(e) Know how to implement basic decon-
tamination procedures.
(f) An understanding of the relevant stand-
ard operating procedures and termination
procedures.
330.22
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OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
(iii) Hazardous materials technician. Hazardous
materials technicians are individuals who
respond to releases or potential releases for
the purpose of stopping the release. They
assume a more aggressive role than a first
responder at the operations level in that they
will approach the point of release in order to
plug, patch or otherwise stop the release of a
hazardous substance. Hazardous materials
technicians shall have received at least 24
hours of trainirlg equal to the first responder
operations level and in addition have compe-
tency in the following areas and the employer
shall so certify:
(a) Know how to implement the employer's
emergency response plan.
(b) Know the classification, identification
and verification of known and unknown
materials by using field survey instruments
and equipment.
(c) Be able to function within an assigned
role in the Incident Command System.
(d) Know how to select and use proper spe-
cialized chemical personal protective equip-
ment provided to the hazardous materials
technician.
(e) Understand hazard and risk assessment
techniques.
(f) Be able to perform advance control, con-
tainment, and/or confinement operations
within the capabilities of the resources and
personal protective equipment available
with the unit.
(g) Understand and implement decon-
tamination procedures.
(h) Understand termination procedures.
(i) Understand basic chemical and tox-
icological terminology and behavior.
(iv) Hazardous materials specialist. Hazardous
materials specialists are individuals who
respond with and provide support to haz-
ardous materials technicians. Their duties
parallel those of the hazardous materials tech-
nician, however, those duties require a more
directed or specific knowledge of the various
substances they may be called upon to con-
tain. The hazardous materials specialist would
also act as the site liaison with Federal, state.
local and other government authorities in
regards to site activities. Hazardous materials
specialists shall have received at least 24
hours of training equal to the technician level
and in addition have competency in the follow-
ing areas and the employer shall so certify:
(a) Know how to implement the local
emergency response plan.
(b) Understand classification, identification
and verification of known and unknown
materials by using advanced survey instru-
ments and equipment.
(c) Know of the state emergency response
plan.
(d) Be able to select and use roper spe-
cialized chemical personal protective equip-
ment provided to the hazardous materials
specialist.
(e) Understand in-depth hazard and risk
techniques.
(f) Be able to perform specialized control.
containment, and/or confinement operations
within the capabilities of the resources and
personal protective equipment available.
(g) Be able to determine and implement
decontamination procedures.
(h) Have the ability to develop a site safety
and control plan.
(i) Understand chemical, radiological and
lexicological terminology and behavior.
(v) On scene incident commander. Incident
commanders, who will assume control of the
incident scene beyond the first responder
awareness level, shall receive at least 24
hours of training equal to the first responder
operations level and in addition have compe-
tency in the following areas and the employer
shall so certify:
(a) Know and be able to implement the
employer's incident command system.
(b) Know how to implement the employer's
emergency response plan.
51
330.23
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l91U.12U(q)(6)(v)(c)
OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
(c) Know and understand the hazards and
risks associated with employees working in
chemical protective clothing.
(d) Know how to implement the local
emergency response plan.
(e) Know of the state emergency response
plan and of the Federal Regional Response
Team.
(f) Know and understand the importance of
decontamination procedures.
(7) Trainers. Trainers who teach any of the above
training subjects shall have satisfactorily com-
pleted a training course for teaching the sub-
jects they are expected to teach, such as the
courses offered by the U.S. Fire Academy, or
they shall have the training and/or academic cre-
dentials and instructional experience necessary
to demonstrate competent instructional skills
and a good command of the subject matter of the
courses they are to teach.
(8) Refresher training.
(i) Those employees who are trained in accord-
ance with paragraph (q)(6) of this section shall
receive annual refresher training of sufficient
content and duration to maintain their compe-
tencies, or shall demonstrate competency in
those areas at least yearly.
(ii) A statement shall be made of the training
or competency, and if a statement of compe-
tency is made, the employer shall keep a rec-
ord of the methodology used to demonstrate
competency.
(9) Medical surveillance and consultation.
(i) Members of an organized and designated
HAZMAT team and hazardous materials spe-
cialists shall receive a baseline physical exam-
ination and be provided with medical
surveillance as required in paragraph (0 of
this section.
(ii) Any emergency response employees who
exhibits signs or symptoms which may have
resulted from exposure to hazardous sub-
stances during the course of an emergency
incident, either immediately or subsequently,
shall be provided with medical consultation as
required in paragraph (f)(3)(ii) of this section.
(10) Chemical protective clothing. Chemical pro-
tective clothing and equipment to be used by
organized and designated HAZMAT team mem-
bers, or to be used by hazardous materials spe-
cialists, shall meet the requirements of
paragraphs (g)(3) through (5) of this section.
(11) Post-emergency response operations. Upon
completion of the emergency response, if it is
determined that it is necessary to remove haz-
ardous substances, health hazards, and mate-
rials contaminated with them (such as
contaminated soil or other elements of the natu-
ral environment) from the site of the incident.
the employer conducting the clean-up shall com-
ply with one of the following:
(i) Meet all of the requirements of paragraphs
(b) through (o) of this section; or
(ii) Where the clean-up is done on plant prop-
erty using plant or workplace employees, such
employees shall have completed the training
requirements of the following: 29 CFR
1910.38(a); 1910.134; 1910.1200, and other
appropriate safety and health training made
necessary by the tasks that they are expected
to be performed such as personal protective
equipment and decontamination procedures.
All equipment to be used in the performance
of the clean-up work shall be in serviceable
condition and shall have been inspected prior
to use.
APPENDICES TO 1910.120—HAZARDOUS WASTE OPER-
ATIONS AND EMERGENCY RESPONSE
Note: The following appendices serve as non-mandatory
guidelines to assist employees and employers in complying with
the appropriate requirements of this section However para-
graph 1910.120(g) makes mandatory in certain circumstances
the use of Level A and Level B PPE protection.
Appendix A—Personal Protective Equipment Test Methods
This appendix sets forth the nonmandaton examples of tests
which may be used to evaluate compliance with * 1910.120
(g)(4)(ii) and dii). Other tests and other challenge agents mas-
be used to evaluate compliance.
A. Totally-encapsulating chemical protective suit pressure
test.
1.0—Scope
1.1 This practice measures the ability of a pas tight totally-
1910.121) Appendix A
330.24
Change 51
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OCCUPATIONAL SAFETY AND HEALTH
1910.120 Appendix A
STANDARDS AND INTERPRETATIONS
encapsulating chemical protective suit material, seams, and clo-
sures to maintain a fixed positive pressure. The results of this
practice allow the gas tight integrity of a totally-encapsulating
chemical protective suit to be evaluated.
1.2 Resistance of the suit materials to permeation, penetra-
tion, and degradation by specific hazardous substances is not
determined by this test method.
2.0—Definition of terms
2.1 "Totally-encapsulated chemical protective suit (TECP
suit)" means a full body garment which is constructed of protec-
tive clothing materials; covers the wearer's torso, head, arms,
legs and respirator; may cover the wearer's hands and feet with
tightly attached gloves and boots; completely encloses the
wearer and respirator by itself or in combination with the
wearer's gloves and boots.
2.2 "Protective clothing material" means any material or
combination of materials used in an item of clothing for the pur-
pose of isolating parts of the body from direct contact with a
potentially hazardous liquid or gaseous chemicals.
2.3 "Gas tight" means, for the purpose of this test method,
the limited flow of a gas under pressure from the inside of a
TECP suit to atmosphere at a prescribed pressure and time
interval.
3.0—Summary of test method
3.1 The TECP suit is visually inspected and modified for the
test. The test apparatus is attached to the suit to permit infla-
tion to the pre-test suit expansion pressure for removal of suit
wrinkles and creases. The pressure is lowered to the test pres-
sure and monitored for three minutes. If the pressure drop is
excessive, the TECP suit fails the test and is removed from
service. The test is repeated after leak location and repair.
4.0—Required Supplies
4.1 Source of compressed air.
4.2 Test apparatus for suit testing, including a pressure
measurement device with a sensitivity of at least 1* inch water
gauge.
4.3 Vent valve closure plugs or sealing tape.
4.4 Soapy water solution and soft brush.
4.5 Stop watch or appropriate timing device.
5.0—Safety Precautions
5.1 Care shall be taken to provide the correct pressure safety
devices required for the source of compressed air used.
ri.O—Test Procedure
H.I Prior to each test, the tester shall perform a visual
inspection of the suit. Check the suit for .seam integrity by vis-
ually examining the seams and gently pulling on the seams.
Ensure that all air supply lines, fittings, visor, zippers, and
valies are secure and show no signs of deterioration.
6.1.1 Seal off the vent valves along with any other normal
inlet or exhaust points (such as umbilical air line fittings or face
piece opening) with tape or other appropriate means (caps.
plugs, fixture, etc.). Care should be exercised in the sealing
process not to damage any of the suit components.
6.1.2 Close all closure assemblies.
6.1.3 Prepare the suit for inflation by providing an
improvised connection point on the suit for connecting an air-
line. Attach the pressure test apparatus to the suit to permit
suit inflation from a compressed air source equipped with a
pressure indicating regulator. The leak tightness of the pres-
sure test apparatus should be tested before and after each test
by closing off the end of the tubing attached to the suit and
assuring a pressure of three inches water gauge for three min-
utes can be maintained. If a component is removed for the test,
that component shall be replaced and a second test conducted
with another component removed to permit a complete test of
the ensemble.
6.1.4 The pre-test expansion pressure (A) and the suit test
pressure (B) shall be supplied by the suit manufacturer, but in
no case shall they be less than: (A)=three inches water gauge;
and (B) = two inches water gauge. The ending suit pressure (C)
shall be no less than 80 percent of the test pressure (B); i.e..
the pressure drop shall not exceed 20 percent of the test pres-
sure (B).
6.1.5 Inflate the suit until the pressure inside is equal to
pressure (A), the pre-test expansion suit pressure. Allow at
least one minute to fill out the wrinkles in the suit. Release suf-
ficient air to reduce the suit pressure to pressure (B), the suit
test pressure. Begin timing. At the end of three minutes, rec-
ord the suit pressure as pressure (C), the ending suit pressure.
The difference between the suit test pressure and the ending
suit test pressure (B-C) shall be defined as the suit pressure
drop.
6.1.6 If the suit pressure drop is more than 20 percent of the
suit test pressure (B) during the three-minute test period, the
suit flails the test and shall be removed from service.
7.0—Retest Procedure
7.1 If the suit fails the test check for leaks by inflating the
suit to pressure (A) and brushing or wiping the entire suit
(including seams, closures, lens gaskets, glove-to-sleeve joints,
etc.) with a mild soap and water solution. Observe the suit for
the formation of soap bubbles, which is an indication of a leak.
Repair all identified leaks.
7.2 Retest the TECP suit as outlined in Test procedure 6.0.
8.0—Report
8.1 Each TECP sun tested by this practice shall have the fol-
lowing information recorded:
8.1.1 Unique identification number, identifying brand name.
date of purchase, material of construction, and unique fit fea-
tures, e.g.. special breathing apparatus.
8.1.2 The actual values for test pressures (A). (B), and (C)
shall be recorded along with the specific observation times. If
the ending pressure (C) is less than 30 percent of the test pres-
Change 51
330.25
1910.120 Appendix A
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1910.120 Appendix A
OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
sure (B). the suit shall be identified as failing the test. When
possible, the specific leak location shall be identified in the test
records. Retest pressure data shall be recorded as an additional
test.
M.I. 3 The source of the test apparatus used shall be identified
and the sensitivity of the pressure gauge shall be recorded.
8.1.4 Records shall be kept for each pressure test even if
repairs are being made at the test location.
Caution
Visually inspect all parts of the suit to be sure they are posi-
tioned correctly and secured tightly before putting the suit
back into service. Special care should be taken to examine each
exhaust valve to make sure it is not blocked.
Care should also be exercised to assure that the inside and
outside of the suit is completely dry before it is put into stor-
B. Totally-encapsulating chemical protective suit qualitative
leak test.
1.0-Scope
1.1 This practice semi-qualitatively tests gas tight totally-
encapsulating chemical protective suit integrity by detecting
inward leakage of ammonia vapor. Since no modifications are
made to the suit to carry out this test, the results from this
practice provide a realistic test for the integrity of the entire
suit.
1.2 Resistance of the suit materials to permeation, penetra-
tion, and degradation is not determined by this test method.
ASTM test methods are available to test suit materials for
these characteristics and the tests are usually conducted by the
manufacturers of the suits.
2.0—Definition of terms
2.1 "Totally-encapsulated chemical protective suit (TECP
suit) means a full body garment which is constructed of protec-
tive clothing materials: covers the wearer's torso, head, arms,
legs and respirator; may cover the wearer's hands and feet with
tightly attached gloves and boots: completely encloses the
wearer and respirator by itself or in combination with the
wearer's gloves, and boots.
2.2 "Protective clothing material" means any material or
combination of materials used in an item of clothing for the pur-
pose of isolating parts of the body from direct contact with a
potentially hazardous liquid or gaseous chemicals.
2.3 "Gas tight" means, for the purpose of this test method.
the limited flow of a pas under pressure from the inside of a
TECP suit to atmosphere at a prescribed pressure and time
interval.
2.4 "Intrusion Coefficient" means a number expressing the
level of protection provided by a gas tight totally-encapsulating
chemical protective suit The intrusion coefficient is calculated
by dividing the lest room challenge agent concentration by the
concentration of challenge agent found inside the suit. The
accuracy of the intrusion coefficient is dependent on the chal-
lenge agent monitoring methods. The larger the intrusion
coefficient the greater the protection provided by the TECP
suit.
3.0—Summary of recommended practice
3.1 The volume of concentrated aqueous ammonia solution
(ammonia hydroxide NH,OH) required to generate the test
atmosphere is determined using the directions outlined in 6.1.
The suit is donned by a person wearing the appropnate respira-
tory equipment (either a positive pressure self-contained
breathing apparatus or a positive pressure supplied air respira-
tor) and worn inside the enclosed test room. The concentrated
aqueous ammonia solution is taken by the suited individual into
the test room and poured into an open plastic pan A two-
minute evaporation period is observed before the test room
concentration is measured, using a high range ammonia length
of stain detector tube. When the ammonia vapor reaches a con-
centration of between 1000 and 1200 ppm, the suited individual
starts a standardized exercise protocol to stress and flex the
suit. After this protocol is completed, the test room concentra-
tion is measured again. The suited individual exits the test
room and his stand-by person measures the ammonia con-
centration inside the suit using a low range ammonia length of
stain detector tube or other more sensitive ammonia detector.
A stand-by person is required to observe the test individual
during the test procedure: aid the person in donning and doff-
ing the TECP suit; and monitor the suit interior. The intrusion
coefficient of the suit can be calculated by dividing the average
test area concentration by the interior suit concentration. A
colorimetric ammonia indicator strip of bromophenol blue or
equivalent is placed on the inside of the suit face piece lens so
that the suited individual is able to detect a color change and
know if the suit has a significant leak. If a color change is
observed the individual shall leave the test room immediately.
4.0—Required supplies
4.1 A supply of concentrated aqueous (58 percent ammonium
hydroxide by weight).
4.2 A supply of b-omophenol/blue indicating paper or equiv-
alent, sensitive to 5-10 ppm ammonia or greater over a two-
minute penod of exposure. [pH 3.0 (yellow) to pH 4.6 (blue)]
4.3 A supply of high range (0.5-10 volume percent) and low
range (5-700 ppm) detector tubes for ammonia and the corre-
sponding sampling pump. More sensitive ammonia detectors
can be substituted for the low range detector tubes to improve
the sensitivity of this practice.
4.4 A shallow plastic pan (PVC) at least 12" M'-l" and a half
pint plastic container (PVC) with tightly closing lid
4.5 A graduated cylinder or other volumetric measuring
device of at least 50 milhliters in volume with an aecuraev of at
least = 1 milliliters.
5.0—Safety precautions
5.1 Concentrated aqueous ammonium hydioMcle. NH,OH. is
a corrosive volatile liquid requiring eye. skin, and respiratory
protection. The person conducting the test shall review the
MSDS for aqueous ammonia.
1910.120 Appendix A
330.26
Change 51
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OCCUPATIONAL SAFETY AND HEALTH
1910.120 Appendix A
STANDARDS AND INTERPRETATIONS
5.2 Since the established permissible exposure limit for
ammonia is 50 ppm. only persons wearing a positive pressure
-elf-contained breathing apparatus or a positive pressure sup-
plied air respirator shall be in the chamber. Normally only the
person wearing the totally-encapsulating suit will be inside the
ihamber A stand-by person shall have a positive pressure self-
contained breathing apparatus, or a positive pressure supplied
air respirator available to enter the test area should the suited
individual need assistance.
5.3 A method to monitor the suited individual must be used
during this test. Visual contact is the simplest but other
methods using communication devices are acceptable.
5.4 The test room shall be large enough to allow the exercise
protocol to be earned out and then to be ventilated to allow for
easy exhaust of the ammonia test atmosphere after the test(s)
are completed.
5.5 Individuals shall be medically screened for the use of res-
pirator}' protection and checked for allergies to ammonia before
participating in this test procedure.
6.0—Test procedure
fi.1.1 Measure the test area to the nearest foot and calculate
its volume in cubic feet. Multiply the test area volume by 0.2
milliliters of concentrated aqueous ammonia solution per cubic
foot of test area volume to determine the approximate volume
of concentrated aqueous ammonia required to generate 1000
ppm in the test area.
K.I.2 Measure this volume from the supply of concentrated
aqueous ammonia and place it into a closed plastic container.
K.I.:) Place the container, several high range ammonia detec-
tor tubes, and the pump in the clean test pan and locate it near
the test area entry door so that the suited individual has easy
access to these supplies.
K.2.1 In a non-contaminated atmosphere, open a pre-sealed
ammonia indicator strip and fasten one end of the strip to the
inside of the suit face shield lens where it can be seen by the
wearer. Moisten the indicator strip with distilled water. "Care
shall be taken not to contaminate the detector part of the
indicator paper by touching it. A small piece of masking tape or
equivalent should be used to attach the indicator strip to the
interior of the suit face shield.
K.2.2 If problems are encountered with this method of attach-
ment, the indicator strip can be attached to the outside of the
respirator face piece lens being used rlrnnjr the test
K.3 Don the respiratory protective device normallv used with
the .Milt, and then don the TECP suit to be tested. Check to be
-ure all openings which are intended to be sealed uippers.
dove;., etc ) are completely sealed. DO NOT. however, plug olf
•my venline valves.
b.-l Step into the enclosed test room such as a closet, bath-
loom, or test booth, equipped with an exhaust fan No air
-huuld be exhausted from the chamber during the te.-t becau>e
this will dilute the ammonia challenge concentrations
K.5 Open the container with the premeasured volume of con-
1 entrated aqueous ammonia \uthin the enclosed lest room, and
|M>ur the liquid into the empty plastic test pan. Wait two min-
utes to allow for adequate volatilization of the concentrated
aqueous ammonia. A small mixing fan can be used near the
evaporation pan to increase the evaporation rate of the
ammonia solution.
6.6 After two minutes a determination of the ammonia con-
centration within the chamber should be made using the high
range colonmetric detector tube. A concentration of 1000 ppm
ammonia or greater shall be generated before the exercises are
started.
K.7 To test the integrity of the suit the following four minute
exercise protocol should be followed:
6.7.1 Raising the arms above the head with at least 15 raising
motions completed in one minute.
6.7.2 Walking in place for one minute with at least 15 raising
motions of each leg in a one-minute period.
6.7.3 Touching the toes with at least 10 complete motions of
the arms from above the head to touching of the toes in a one-
minute period.
6.7.4 Knee bends with at least 10 complete standing and
squatting motions in a one-minute penod.
6.8 If at any time during the test the colonmetric indicating
paper should change colors, the test should be stopped and sec-
tion 6.10 and 6.12 initiated (See 14.2).
6.9 After completion of the test exercise, the test area con-
centration should be measured again using the high range col-
onmetric detector tube.
6.10 Exit the test area.
6.11 The opening created by the suit zipper or other appro-
priate suit penetration should be used to determine the
ammonia concentration in the suit with the low range length of
stain detector tube or other ammonia monitor. The internal
TECP suit air should be sampled far enough from the enclosed
test area to prevent a false ammonia reading
6.12 After completion of the measurement of the suit interior
ammonia concentration the test is concluded and the suit is
doffed and the respirator removed.
6.13 The ventilating fan for the test room should be turned
on and allowed to run for enough time to remov e the ammonia
gas The fan shall be vented to the outside of the building
8.14 Any detectable ammonia in the suit interior (five ppm
ammonia (NH,) or more tor the length of stain detector tube)
indicates that the suit has tailed the test. When other ammonia
detectors are used a lower level of detection L< possible, and it
i-hould be specified as the pass/fail cntena
K.15 By following this test method, an intrusion coefficient of
approximately 200 or more can be measured with the suit in a
completely operational condition. If the intrusion coefficient is
200 or more, then the suit is suitable for emertrcncy response
and field use.
Change 51
330.27
1910.120 Appendix A
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1910.120 Appendix A
OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
7.0—Retest procedures
T.I If the suit fails this test, check for leaks by following the
pressure test in test A above.
7.2 Retest the TECP suit as outlined in the test procedure
6.0.
8.0—Report
8.1 Each gas tight totally-encapsulating chemical protective
suit tested by this practice^ shall have the following information
recorded.
8.1.1 Unique identification number, identifying brand name,
date of purchase, material of construction, and unique suit fea-
tures; e.g., special breathing apparatus.
8.1.2 General description of test room used for test.
8.1.3 Brand name and purchase date of ammonia detector
stnps and color change data.
8.1.4 Brand name, sampling range, and expiration date of the
length of stain ammonia detector tubes. The brand name and
model of the sampling pump should also be recorded. If another
type of ammonia detector is used, it should be identified along
with its minimum detection limit for ammonia.
8.1.5 Actual test results shall list the two test area con-
centrations, their average, the interior suit concentration, and
the calculated intrusion coefficient. Retest data shall be
recorded as an additional test.
8.2 The evaluation of the data shall be specified as "suit
passed" or "suit failed," and the date of the test. Any detect-
able ammonia (five ppm or greater for the length of stain detec-
tor tube) in the suit interior indicates the suit has failed this
test. When other ammonia detectors are used, a lower level of
detection is possible and it should be specified as the pass fail
criteria.
Caution
Visually inspect all parts of the suit to be sure they are posi-
tioned correctly and secured tightly before putting the suit
back into service. Special care should be taken to examine each
exhaust valve to make sure it is not blocked.
Care should also be exercised to assure that the inside and
outside of the suit is completely dry before it is put into stor-
age.
Appendix B—General Description and Discussion of the
Levels of Protection and Protective Gear
This appendix sets forth information about personal protec-
tive equipment (PPE) protection levels which may be used to
assist employers in complying with the PPE requirements of
this section.
As required by the standard. PPE must be selected which
will protect employees from the specific hazards which they are
likely to encounter dunng their work on-site
Selection of the appropriate PPE is a complex process which
should take into consideration a variety of factors. Key factors
involved in this process are identification of ;.ie hazards, or sus-
pected hazards; their routes of potential hazard to employees
(inhalation, skin absorption, ingestion. and e>e or skin contact).
and the performance of the PPE materials (and seams) in
providing a barrier to these hazards. The amount of protection
provided by PPE is material-hazard specific. That is. protective
equipment materials will protect well against some hazardous
substances and poorly, or not at all. against others. In many
instances, protective equipment materials cannot be found
which will provide continuous protection from the particular
hazardous substance. In these cases the breakthrough time of
the protective material should exceed the work durations, or
the exposure after breakthrough may not pose a hazardous
level.
Other factors in this selection process to be considered are
matching the PPE to the employee's work requirements and
task-specific conditions. The durability of PPE materials, such
as tear strength and seam strength, should be considered in
relation to the employee's tasks. The effects of PPE in relation
to heat stress and task duration are a factor in selecting and
using PPE. In some cases layers of PPE may be necessary to
provide sufficient protection, or to protect expensive PPE
inner garments, suits or equipment.
The more that is known about the hazards at the site, the
easier the job of PPE selection becomes. As more information
about the hazards and conditions at the site becomes available,
the site supervisor can make decisions to up-grade or down-
grade the level of PPE protection to match :he tasks at hand.
The following are guidelines which an employer can use to
begin the selection of the appropriate PPE. As noted above.
the site information may suggest the use of combinations of
PPE selected from the different protection ie\els (i.e . A. B. C,
or D) as being more suitable to the hazards of the work. It
should be cautioned that the listing below does not fully
address the performance of the specific PPE material in rela-
tion to the specific hazards at the job site, and that PPE selec-
tion, evaluation and re-selection is an ongoing process until
sufficient information about the hazards and PPE performance
is obtained.
Part A. Personal protective equipment :s divided into four
categories based on the degree of protection afforded. (See
Part B of this appendix for further explanation of Levels A. B.
C. and D hazards.)
I. Level A—To be selected when the greatest level of skin.
respiratory, and eye protection is required
The following constitute Level A equipment: it may be used
as appropriate;
1. Positive pressure, full face-piece self-contained breathing
apparatus (SCBA). or positive pressure supplied air respirator
with escape SCBA. approved by the National Institute for
Occupational Safety and Health (NI05H).
2. Totally-encapsulating chemical-protec'.\e suit.
1910.120 Appendix B
330.28
Change 51
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OCCUPATIONAL SAFETY AND HEALTH
1910.120 Appendix li
STANDARDS AND INTERPRETATIONS
:t. Coveralls '
4. Long underwear '
5. Gloves, outer, chemical-resistant.
H. Gloves, inner, chemical-resistant.
7. Boots, chemical-resistant, steel toe and shank.
8. Hard hat (under suit).1
9. Disposable protective suit, gloves and boots (depending on
suit construction, may be worn over totally-encapsulating suit).
II. Level B—The highest level of respiratory protection is
necessary but a lesser level of skin protection is needed
The following constitute Level B equipment: it may be used
as appropriate
1. Positive pressure, full-facepiece self-contained breathing
apparatus (SCBA). or positive pressure supplied air respirator
with escape SCBA (NIOSH approved).
2. Hooded chemical-resistant clothing (overalls and long-
sleeved jacket; coveralls; one or two-piece chemical-splash suit,
disposable chemical-resistant overalls).
3. Coveralls.1
4. Gloves, outer, chemical-resistant
5. Gloves, inner, chemical-resistant.
B. Boots, outer, chemical-resistant steel toe and shank
7. Boot-covers, outer, chemical-resistant (disposable).1
A. Hard hat.1
9. [Reserved]
10. Face shield '
111. Level C—The concentration(s) and type(s) of airborne
•substance(s) is known and the criteria for using air purifying
i espirators are met
The following constitute Level C equipment, it may be used
as appropriate
1. Full-face or half-mask, air purifying respirators (NIOSH
approver!)
•1. Hooded chemical-resistant clothing (overalls, two-piece
chemical-splash suit, disposable chemical-resisitant overalls)
.'!. Coveralls '
4. Gloves, outer, chemical-resistant
'Optional, as applicable
Change 51
5. Gloves, inner, chemical-resistant
ft. Boots (outer), chemical-resistant steel toe and shank '
7. Boot-covers, outer. chemical-reMslanl i disposable I.1
X. Hard hat.1
9. Escape mask.1
10. Face shield.1
IV. Level D—A work uniform affording minimal piotection.
used for nuisance contamination only.
The following constitute Level D equipment, it may be used
as appropriate:
1. Coveralls.
2. Gloves.'
3. Boots/shoes, chemical-resistant steel toe and shank.
4. Boots, outer, chemical-resistant (disposable).1
5. Safety glasses or chemical splash goggles*
6. Hard hat.1
7. Escape mask.1
8. Face shield.1
Part B. The types of hazards for which levels A. B. C. and D
protection are appropriate are described below
I. Level A—Level A protection should be used when:
1. The hazardous substance has been identified and requires
the highest level of protection for skin, eyes, and the respira-
tory system based on either the measured (or potential for)
high concentration of atmospheric vapor; eases, or particu-
lates; or the site operations and work functions involve a high
potential for splash, immersion, or exposure to unexpected
\apors. gases, or participates of materials ihat are harmful to
skin or capable of being absorbed through the skin.
2. Substances with a high degree of hazard to the skin are
known or suspected to be present, and skin contact is possible.
or
3. Operations are being conducted in confined, poorlv venti-
lated areas, and the absence of conditions requiring Level A
have not yet been determined
II. Level B—Level B protection should be used when
I. The type and atmospheiic concent ration nf substance*
have been identified and require a high lc\ el of respirators pro-
tection, but less skin piotection.
2. The atmosphere contains less than lit i percent oxvgen, 01
3. The presence of incompletely identified vapors or jrase.- i*
indicated by a direct-reading organic vapor detection in.stru-
ment. but vapors and gases are not inspected of containing
high levels of chemicals harmful to skin or capable of bcmc
absorbed through the skin.
330.29
1910.1211 Appendix H
-------
mil. 120 Appendix K
OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
Vote: This invokes atmospheres \mh IDLH concentration-.
nl -pecitic substances thai present severe inh.il.ition hazards
.ind th.it do not represent a severe skin hazard: or that do not
meet the criteria lor use of air-puiif\ing respnatois
III. Level C—Level C protection should be used when:
I The atmospheric contaminants, liquid splashes, or other
direct contact will not adversely affect or be absorbed through
.ins exposed skin.
2. The types of air contaminants h.ue been identified, con-
ccmraiions measured, and'an air-purifying respirator is avail-
able that can remove the contaminants: and
.'!. All criteria for the use of air-purifying respirators are met
IV. Level I)—Level D protection should be used \\hen.
1. The atmosphere contains no know n hazard, and
1. Work functions preclude splashes, immersion, or the
potenti.il for unexpected inhalation of or contact with hazardous
lev els of any chemicals.
Note: As slated before, combinations of personal protective
equipment other than those described for Levels A. B. C. and
D protection may be more appropriate and may be used to
provide the proper level of protection.
As an aid in selecting suitable chemical protective clothing, it
.>hould be noted that the National Fire Protection Association is
developing standards on chemical protective clothing. These
standards are currently undergoing public review prior to
adoption, including
XFPA 1991—Standard on Vapor-Protective Suits for Haz-
ardous Chemical Emergencies (EPA Level A Protective
Clothing)
NFPA 1991—Standard on Liquid Splash-Protective Suits for
Hazardous Chemical Emergencies (EPA Level B Protective
Clothing.)
NFPA 1993—Standard on Liquid Splash-Protective Suits for
Non-emergencv. Non-flammable Hazardous Chemical Situa-
tions (EPA Level B Protective Clothing)
These standards would apply documentation and perform-
ance requirements to the manufacture of chemical protective
-nils Chemical protective suns meeting these requirements
would be labelled as compliant with the appropriate standard
When these standards are adopted by the National Fire Protec-
tion Association, it is recommended that chemical protective
-nits w hich meet these standards be used
Appendix C—Compliance Guidelines
1. Occupational Safetv and Health Program. Each haz-
ardous waste site clean-up effort will require an occupational
>alet\ and health program headed bv the site coordinator or
the employer's representative The purpose of the pioirram will
lie the pioteclion of employees al the site and will be an e\ten-
-lon of the employer's overall safetv and health pingrum The
program will need to be developed before \voik begins on the
-ite and implemented as work proceeds as stated in paragraph
-------
OCCUPATIONAL SAFETY AND HEALTH
1910.120 Appendix C
STANDARDS AND INTERPRETATIONS
to find on hazardous waste clean-up sites: what control meas-
ures or techniques are effective for those hazards; what
monitoring procedures are effective in characterizing exposure
levels, what makes an effective employer's safety and health
program: what a site safety and health plan should include:
hands on training with personal protective equipment and
clothing they may be expected to use: the contents of the
OSHA standard relevant to the employee's duties and function;
and. employee's responsibilities under OSHA and other regula-
tions. Supervisors will need training in their responsibilities
under the safety and health program and its subject areas such
as the spill containment program, the personal protective
equipment program. th.e medical surveillance program, the
emergency response plan and other areas.
The training programs for employees subject to the require-
ments of paragraph (p) of this standard should address: the
employers safety and health program elements impacting
employees, the hazard communication program: the medical
surveillance program: the hazards and the controls for such
hazards that employees need to know for their job duties and
functions. All require annual refresher training.
The training programs for employees covered by the require-
ments of paragraph (q) of this standard should address those
competencies required for the various levels of response such
as. the hazards associated with hazardous substances; hazard
identification and awareness, notification of appropriate per-
sons; the need for and use of personal protective equipment
including respirators; the decontamination procedures to be
used: preplanning activities for hazardous substance incidents
including the emergency response plan; company standard
operating procedures for hazardous substance emergency
responses; the use of the incident command system and other
subjects. Hands-on training should be stressed whenever possi-
ble. Critiques done after an incident which include an evalua-
tion of what worked and what did not and how could the
incident be better handled the next time may be counted as
training time.
For hazardous materials specialists (usually members of haz-
ardous materials teams), the training should address the care.
use and/or testing of chemical protective clothing including
totally encapsulating suits, the medical surveillance program.
the standard operating procedures for the hazardous materials
team including the use of plugging and patching equipment and
other subject areas.
Officers and leaders who may be expected to be in charge at
an incident should be fully knowledgeable of their company's
incident command system. They should know where and how to
obtain additional assistance and be familiar with the local dis-
trict's emergency response plan and the state emergency
response plan
Specialist employees such as technical experts, medical
experts or en\ ironmental experts that work with hazardous
materials in their regular jobs, who may be sent to the incident
scene by the shipper, manufacturer or governmental agency to
:i
be called to the incident scene to provide emergency support
assistance, should have at least a safety and health briefing
before entering the area of potential or actual exposure These
.•skilled support personnel, who have not been a part of the
emergency response plan and do not meet the training require-
ments, should be made aware of the hazards they face and
should be provided all necessary protective clothing and equip-
ment required for their tasks.
3. Decontamination. Decontamination procedures should be
tailored to the specific hazards of the site, and may vary in
complexity and number of steps, depending on the level of haz-
ard and the employee's exposure to the hazard. Decontamina-
tion procedures and PPE decontamination methods will vary
depending upon the specific substance, since one procedure or
method may not work for all substances. Evaluation of decon-
tamination methods and procedures should be performed, as
necessary, to assure that employees are not exposed to hazards
by re-using PPE. References in Appendix F may be used for
guidance in establishing an effective decontamination program
In addition, the U.S. Coast Guard's Manual. "Policy Guidance
for Response to Hazardous Chemical Releases." U.S Depart-
ment of Transportation. Washington. DC (COMDTINST
M 16465.30) is a good reference for establishing an effective
decontamination program.
4. Emergency response plans. States, along with designated
districts within the states, will be developing or have developed
local emergency response plans. These state and district plans
should be utilized in the emergency response plans called for in
the standard. Each employer should assure that its emergency
response plan is compatible with the local plan. The major ref-
erence being used to aid in developing the state and local dis-
trict plans is the Hazardous Materials Emergency Planning
Guide, NRT—1. The current Emergency Response Guidebook
from the U.S. Department of Transportation. CMA's CHEM-
TREC and the Fire Service Emergency Management Hand-
book may also be used as resources.
Employers involved with treatment, storage, and disposal
facilities for hazardous waste, which have the required con-
tingency plan called for by their permit, would not need to
duplicate the same planning elements. Those items of the
emergency response plan that are properly addressed in the
contingency plan may be substituted into the emergency
response plan required in 1910.120 or otherwise kept together
for employer and employee use.
5. Personal protective equipment programs. The purpose of
personal protective clothing and equipment (PPE) is to shield
or isolate individuals from the chemical, physical, and biologic
hazards that may be encountered at a hazardous substance site
As discussed in Appendix B. no single combination of protec-
tive equipment and clothing is capable of protecting against all
hazards. Thus PPE should be used in conjunction with other
protective methods and its effectiveness evaluated penodicalh
The use of PPE can itself create significant worker hazards.
such as heat stress, physical and psychological stress, and
impaired vision, mobility, and communication. For anv given
situation, equipment and clothing should be -elected that
provide an adequate level of protection However, over-
protection, as well as under-protection. can be hazardous and
should be avoided \\ here possible.
Two basic objectives of any PPE program .should be to pro-
tect the wearer from safety and health hazards, and to prexent
Change 51
330.31
1910.120 Appendix C
-------
1910.120 Appendix C
OCCUPATIONAL SAFETY AND HEALTH
STANDARDS AND INTERPRETATIONS
injury to the wearer from incorrect use and/or malfunction of
the PPE. To accomplish these goals, a comprehensive PPE pro-
gram should include hazard identification, medical monitoring.
environmental surveillance, selection, use. maintenance, and
decontamination of PPE and its associated training
The written PPE program should include policy statements.
procedures, and guidelines. Copies should be made available to
all employees, and a reference copy should be made available at
the worksite. Technical data on equipment, maintenance man-
uals, relevant regulations, and other essential information
should also be collected and maintained.
6. Incident command system (ICS). Paragraph
1910.120(q)(3)(ii) requires the implementation of an ICS. The
ICS is an organized approach to effectively control and manage
operations at an emergency incident. The individual in charge
of the ICS is the senior official responding to the incident. The
ICS is not much different than the "command post" approach
used for many years by the fire service. Dunng large complex
fires involving several companies and many pieces of appa-
ratus, a command post would be established. This enabled one
individual to be in charge of managing the incident, rather than
having several officers from different companies making sepa-
rate, and sometimes conflicting, decisions. The individual in
charge of the command post would delegate responsibility for
performing various tasks to subordinate officers. Additionally.
all communications were routed through the command post to
reduce the number of radio transmissions and eliminate confu-
sion However, strategy, tactics, and all decisions were made
by one individual.
The ICS is a very similar system, except it is implemented
for emergency response to all incidents, both large and small,
that involve hazardous substances.
For a small incident, the individual in charge of the ICS may
perform many tasks of the ICS. There may not be any, or little,
delegation of tasks to subordinates. For example, in response
to a small incident, the individual in charge of the ICS. in addi-
tion to normal command activities, may become the safety
officer and may designate only one employee (with proper
equipment) as a backup to provide assistance if needed. OSHA
does recommend, however, that at least two employees be des-
ignated as back-up personnel since the assistance needed may
include rescue.
To illustrate the operation of the ICS, the following scenario
might develop during a small incident, such as an overturned
lank truck u ith a small leak of flammable liquid.
The first responding senior officer would implement and take
command of the ICS. That person would size-up the incident
and determine if additional personnel and apparatus were nec-
essary: would determine what actions to take to control the
leak. and. determine the proper level of personal protective
equipment. If additional assistance is not needed, the individual
in charge of the ICS would implement actions to stop and con-
trol the leak using the fewest number of personnel that can
effectively accomplish the tasks. The mdmdual in charge of the
ICS then would designate himself as the safety officer and two
other emplovees as a back-up in case rescue may become neces-
»ar\ In this scenario, decontamination procedures would not
be necessan.
A large complex incident mav require many employees and
difficult, time-consuming efforts to control In these situations.
the individual in charge of the ICS will want to delegate dif-
ferent tasks to subordinates in order to maintain a span of con-
trol that \iill keep the number of subordinates, that are
reporting, to a manageable level
Delegation oi task at large incidents may be by location,
\\ here the incident .-.cene is divided into sectors, and subordi-
nate officers coordinate activities w ithin the sector that they
hat e been assigned
Delegation of tasks can also be by function. Some of the func-
tions that the individual in charge of the ICS may want to dele-
gate at a large incident are: medical services; evacuation, water
supply, resources (equipment, apparatus): media relations;
safety, and. site control (integrate activities with police for
croud and traffic control). Also for a large incident, the individ-
ual in charge of the ICS will designate several employees as
back-up personnel: and a number of safety officers to monitor
conditions and recommend safety precautions.
Therefore, no matter what size or complexity an incident
may be. by implementing an ICS there will be one individual
in charge who makes the decisions and gives directions, and, all
actions, and communications are coordinated through one cen-
tral point of command Such a system should reduce confusion,
improve safety, organize and coordinate actions, and should
facilitate effective management of the incident.
7. Site Safety and Control Plans. The safety and security of
response personnel and others in the area of an emergency
response incident site should be of primary concern to the inci-
dent commander. The use of a site safety and control plan could
greatly assist those in charge of assuring the safety and health
of employees on the site.
A comprehensive site safety and control plan should include
the following: summary analysis of hazards on the site and a
risk analysis of those hazards: site map or sketch: site work
zones (clean zone, transition or decontamination zone, work or
hot zone); use of the buddy system, site communications; com-
mand post or command center: standard operating procedures
and safe work practices: medical assistance and triage area;
hazard monitoring plan (air contaminate monitoring, etc.);
decontamination procedures and area, and other relevant areas.
This plan should be a part of the employer's emergency
response plan or an extension of it to the specific site.
8. Medical surveillance programs. Workers handling haz-
ardous substances may be exposed to toxic chemicals, safety
hazards, biologic hazards, and radiation. Therefore, a medical
surveillance program is essential to assess and monitor
workers' health and fitness for employment in hazardous waste
operations and during the course of work to provide
emergency and other treatment as needed: and to keep accu-
rate records for future reference
The Occupational Safety and Health Guidance Manual for
Hazardous Waste Site Actnities developed by the National
Institute for Occupational Safen and Health (N'lOSH). the
Occupational Safet\ and Health Administration (OSHA). the
I' S Coast Guard (L'SCG). and the Environmental Protection
Agency (EPA). October 1985 provides an excellent example of
the tvpes of medical testing that should be done as part of a
medical surveillance program
Appendix D—References
The following references mav be consulted for further infor-
mation on the subject of this .-tamlard
1910.120 Appendix D
I. OSHA Instruction DFO CPL > 70-Januarv 29. 19St>. Spa-
inl Kmplia.'iii I'lix/rnni Hozuntnnt \Vn\le ifi'i'-
330.32 Change 51
-------
OCCUPATIONAL SAFETY AND HEALTH
191U.120 Appendix D
STANDARDS AND INTERPRETATIONS
2. OSHA Instruction DFO CPL 2-2 37A-January 29. 1986.
Technical Assistance and Guidelines for Super]und and Other
Hazardous Waste Site Activities
3. OSHA Instruction DTS CPL 2.7-1-January 29. 1986. Haz-
ardous Waste Activity form. OSHA 175.
4. Hazardous Waste Inspections Reference Manual. U.S
Department of Labor. Occupational Safety and Health Admin-
istration, 1986.
5. Memorandum of Understanding Among the National
Institute for Occupational Safety and Health, the Occupational
Safety and Health Administration, the United States Coast
Guard, and the United States Environmental Protection
Agency, Guidance for Worker Protection Dunng Hazardous
Waste Site Investigations and Clean-up and Hazardous Sub-
stance Emergencies. December 18, 1980.
6. National Priorities List, 1st Edition, October 1984; U.S.
Environmental Protection Agency, Revised periodically.
7. The Decontamination of Response Personnel, Field
Standard Operating Procedures (F.S.O.P.) 7; U.S. Environ-
mental Protection Agency, Office of Emergency and Remedial
Response, Hazardous Response Support Division, December
1984.
8. Preparation of a Site Safety Plan, Field Standard Oper-
ating Procedures (F.S.O.P.) 9; U.S. Environmental Protection
Agency, Office of Emergency and Remedial Response, Haz-
ardous Response Support Division, April 1985.
9. Standard Operating Safety Guidelines; U.S. Environ-
mental Protection Agency, Office of Emergency and Remedial
Response, Hazardous Response Support Division, Environ-
mental Response Team; November 1984.
10. Occupational Safety and Health Guidance Manual for
Hazardous Waste Site Activities, National Institute for
Occupational Safety and Health (NIOSH), Occupational Safety
and Health Administration (OSHA), U.S. Coast Guard
(USCG), and Environmental Protection Agency (EPA); Octo-
ber 1985.
11. Protecting Health and Safety at Hazardous Waste
Sites; An Overview, U.S. Environmental Protection Agency,
EPA/625/9—85/006; September 1985.
12. Hazardous Waste Sites and Hazardous Substance
Emergencies, NIOSH Worker Bulletin, U.S. Department of
Health and Human Services. Public Health Service, Centers
for Disease Control. National Institute for Occupational Safety
and Health; December 1982.
13. Personal Protective Equipment for Hazardous Mate-
rials Incidents: A Selection Guide; U.S. Department of
Health and Human Services. Public Health Service, Centers
for Disease Control, National Institute for Occupational Safety
and Health; October 1984.
14. Fire Service Emergency Management Handbook,
International Association of Fire Chiefs Foundation, 101 East
Holly Avenue, Unit 10B, Sterling. VA 22170, January 1985.
IS. Emergency Response Guidebook, U.S. Department of
Transportation, Washington, DC, 1987.
16. Report to the Congress on Hazardous Materials Train-
ing, Planning and Preparedness, Federal Emergency Man-
agement Agency, Washington. DC, July 1986.
17. Workbook for Fire Command, Alan V. Brunacini and J.
David Beagerbn, National Fire Protection Association, Bat-
terymarch Park, Quincy, MA 02269, 1985.
18. Fire Command, Alan V. Brunacini, National Fire Pro-
tection, Batterymarch Park, Quincy, MA 02269,1985.
19. Incident Command System, Fire Protection Publica-
tions, Oklahoma State University, Stillwater, OK 74078, 1983.
20. Site Emergency Response Planning, Chemical Manufac-
turers Association. Washington, DC 20037, 1986.
21. Hazardous Materials Emergency Planning Guide,
NRT-1, Environmental Protection Agency, Washington, DC,
March 1987.
22. Community Teamwork: Working Together to Promote
Hazardous Materials Transportation Safety. U.S. Depart-
ment of Transportation, Washington, DC, May 1983.
23. Disaster Planning Guide for Business and Industry,
Federal Emergency Management Agency, Publication No.
FEMA 141, August 1987.
(The Office of Management and Budget has approved the infor-
mation collection requirements in this section under control
number 1218-0139)
Change 51
Appendix A
330.33
1910.120 Appendix D
-------
APPENDIX B
Warning Concentrations of Various Chemicals
-------
WARNING CONCENTRATIONS OF VARIOUS CHEMICALS
The following table is a compilation of warning concentrations of various chemicals taken from
several sources. A warning concentration is that concentration in air at which a person can detect
the material either by its odor, by its taste, or by it causing irritation. Exposure limits, where they
exist, are included so that a comparison can be made to determine whether a chemical has adequate
warning properties. A material has adequate warning properties if the effects (e.g., odor, taste, or
irritation) are detectable and persistent at concentrations "at" or "below" the exposure limit. Note
that some sources give a statement like "adequate" or "inadequate" for the warning properties.
Because the statement may be used in conjunction with a different exposure limit than is used in this
table, it should be used with caution. Some of the chemicals have a range of concentrations because
the different sources have different values. This can be due to the variability of human perceptions
or different test methods. The sources may have used different endpoints for their testing. This
value could be when the first person detected the odor, when everyone could smell it, or when 50%
of the test subjects could detect it. Because of these variations, the full range of warning
concentrations is given so that the user can decide which value to use.
The warning concentrations given are generally odor thresholds with irritation thresholds given in
parentheses. Taste thresholds are noted as special cases. The concentration units used in the table
are parts per million unless otherwise noted.
B-l Warning Concentrations
-------
0\
58
a
Chemical
Acetaldehyde
Acetamide
Acetic acid
Acetic anhydride
Acetone
Acetonitrile
Acetophenone
Acetyl bromide
Acetyl chloride
Acrolein
Aery lam ide
Acrylic acid
Acrylonitrile
Akrol
Aldrin
Allyl alcohol
Allylamine
Allyl chloride
Allyl chloroformate
Allyl disulfide
Allyl glycidyl ether
Allyl isocyanide
Warning Concentration1
0.0001 - 2.3 (SO)
"odorless when pure"
0.1-24(10-15)
O.I -81.2(5)
0.1-699
40- 170
0.002 - 0.60
5.0 X 10*
1
0.05 - 16.6 (0.21-0.5)
"odorless"
0.1- 1
1 6 - 100, fatigue
10
0.2536 - 0.4027 mg/mj
0.08 - 7.2, (0.75-25)
6.3 - 28.7
0.1- 10(50-100)
1.4
0.0012
<10
0.018
PEL/TWA/STEL
100/150
10
10
C-5
750/1000
40/60
WEEL - 10
0.1/0.3
0.3 mg/m5
10
2
C-10
0.2S mg/m1
2/4
1/2
5/10
Exposure Limits'
REL TLV IDLH
250
20
0.3 mg/m1
1
C-10
D
1
C-3
C-9.6
100/150
10/15
C-5
750/1000
40/60
0.1/0.3
0.3 mg/m',A2
10
2.A2
0.25 mg/m1
2/4
1/2
5/10
10000
1000
1000
20000
4000
5
N.A.
Ca
Ca
ISO
300
270
<*>
I
-------
I
3'
1
Chemical
Ally isothiocyanate
Allyl mercaptan
Ammonia
Ammonium hydroxide
Ammonium sulfanate
n-Amyl acetale
sec-Amyl acetate
ten- Amy 1 acetate
n-Amyl alcohol (1-pentanol)
Amylene (2-methyl-2-butene)
Amyl isovalerate
n-Amyl mercaptan
N-Amyl methyl ketone
Amyl sulfide
Anethole
Aniline
Apiol
Arsenic anhydride (arsenic
pentoxide)
Arsine
Benzaldehyde
Benzene
Benzoyl peroxide
Warning Concentration*
0. IS -0.42
0.00005 - 0.21
0.04 - 55 (55-140)
50
"odorless"
0 00090 - 10 (200)
0.0017 - 0.082
0.0017
00065-35
0 0022 - 2 3
0.11
0.07
0.0009 - 0 35
0.0030 - 0.005
0.003
0.5 - 70
0.0063
1
021 -0.63
0 003 - 0 69 (4 6)
1 4- 120(2817)
"odorless"
PEL/TWA/STEL
WEEL -/I
-/35
10 mg/m3 (Total dust)
5 mg/m' (Respirable fraction)
100
125
2
0 01 mg/m1
0.05
WEEL - 2/4
1/5
5 mg/m3
Exposure Limits'
REL
C-50
C-0.002
mg/m3
(as As)
C-0.002
mg/m3
(as As)
0 1
C-l
5 mg/m1
TLV IDLH
25/35
10 mg/m3
100
125
2
0.2 mg/m3
(as As)
005
10.A2
5 mg/m1
500
5000 mg/m1
4000
9000
4000
100
Ca
(as As)
Ca
Ca
7000 mg/m1
I
-------
1
00
61
I
'
S
I
Chemical
Benzyl alcohol
Benzyl chloride
Benzyl mercaptan
Benzyl sulflde
Bornyl acetate
Boron oxide
Boron trifluoride
Bromine
Bromoacetone
Bromoacetophenone
Bromoform
1 ,3-Butadiene
n-Butane
2-Butoxyethanol
Butyl acetate
sec-Bulyl acetate
tert-Butyl acetate
Butyl acrylate
Butyl alcohol
sec-Butyl alcohol
tert-Butyl alcohol
Butylamme
sec-Butylamme
tert-Butylamme
Warning Concentration1
5.5
0.01 -0.31 (8)
0.00019-004(45
0.0021 - 0 07
0.0078
"immediate irritation*
1 - 1.5
0.05 - 3.5 (0.6 intolerable)
0.090
0.015-0.17(004)
1.3-530
0.16- I.8(>8000)
55-5000
0 1 -60(100-195)
0 037 - 20 (300)
3-7
0004-47
004-09
0.1 -20(25-100)
0.1-43
0 1 - 73 (100)
0.1 -5(10-15)
0.24 (as n-Butylamine)
0.24 (as n-Butylamme)
PEL/TWA/STEL
1
10 mg/m' (Total dust)
5 mg/m3 (Respirable fraction)
C-l
0.1/03
0.5
1000
800
25
150/200
200
200
10
C-5
100
100/150
C-5
C-5
C-5
Exposure Limits'
REL TLV IDLH
C-5 mg/mj
0.1
NE
LL
1
10 mg/m1
C-l
0.1/0.3
0.5
10.A2
800
25
150/200
200
200
10
C-50
100/150
100/150
C-5
C-5
C-5
10
N.A
100
10
N.A.
700
10000
10000
10000
8000
10000
8000
2000
-------
\
CD
ON
o\
Chemical
Butyl cellosolve (see
2-Butylene (2-Butene)
Butyl ether
Butyl sulfide
Cadmium dust
Cadmium fume
Calcium dodecylbenzene
Warning Concentration'
020
09-13
0 07 - 26
0.57 - 22
0.71
0.24 - 0.47
17-20
1-7
0.00082 - 0.38
0.00009 - 0.06
0.015-0.18
5 (5-8)
0.0046 - 0.039
0 00056 - 0.001
"inadequate"
"inadequate"
'odorless*
3.5 (as Chlorine)
0 13- 13.4
0.003 - 200 (1 77)
PEL/TWA/STEL
5
0.5
10/20
0.2 mg/m'
C-0.6 mg/m1
0 1 mg/m'
C-0.3 mg/m9
03
2 mg/tnj
Exposure Limits'
REL TLV IDLH
C-05
LL
LL
5
0.5
10/20
0.05 mg/m1
C-0.05 mg/m1
5 mg/m1
12/18 mg/m1
2500
1000
Ca
Ca
200 mg/m1
-------
1
CO
Chemical
Caprolactam
Carbaryl (Sevin*)
Carbitol acetate
Carbon dioxide
Carbon disulfide
Carbon monoxide
Carbon tetrachloride
Cavacrol
Chloral
Chlordane
Chlorine
Chlorine dioxide
Chloroacetaldehyde
Chloracetic acid
Chloroacetophenone(CN, Tear
Gas)
Chlorobenzene
o-chlorobenzy 1 idene
malononitrile
Chlorobromomethane
Chloroform
Chloromethane (see Methyl
chloride)
Chlorophenol
o-Chlorophenol
Warning Concentration1
0.001 - 0.065
'essentially odorless"
0.157- 0.263
'odorless"
0.001 1 - 7.7
•odorless"
2-700
0.0023
0.047
'odorless*
0.01 - 5 (1-6)
0.1(5.0)
0.93 (0.01-1)
0.045
001- 1.35(0.024-0.063)
0.1-60
(0.2)
100-400
50-307. fatigue (> 4096)
0.034
0.0036
PEL/TWA/STEL
Dust- 1/3 mg/m'
Vapor 5/10
5 mg/m3
10000/30000
4/12
35
2
0.5 mg/m'
0.5/1
0.1/03
C-l
WEEL - 0.3/1
0.05
75
C-0.05
200
2
Exposure Limits'
REL TLV IDLH
5 mg/m1
10000
C-30000
,
35
C-200
C-2
C-0.5
C-2
Dust 1/3 mg/m1
Vapor 5/10
5 mg/m1
5000/30000
10
50/400
5.A2
0 5/2.0 mg/m1
1/3
0.1/0.3
C-l
0.05
75
C-0.05
200/250
10.A2
600 mg/m1
50000
500
1500
Ca
30
10
250
100 mg/m1
2400
2 mg/m1
5000
Ca
t
-------
I
CO
00
Chemical
p-Chlorophenol
Chloropicrin
B-Chloroprene
Chlorosulfonic acid
o-Chlorotoluene
Chlorovinyl arsine
Cinnamaldehyde
Citric acid
Cobalt, Metal Fume & Dust
Coumarin (Coumaphos,
Baymix)
Crag* Herbicide
m-Cresol
o-Cresol
p-Cresol
Crotonaldehyde
Crotyl mercaptan
Crude-heavy (Loganillas-Crude)
Crude-light (Louisiana-Crude)
Crude-medium (Barbados-
Crude)
Cumene
Cyanogen chloride (CNCL)
Cyclohexane
Cyclohexanol
Warning Concentration1
1.2 - 30
0.8- 1.1(0.34.37)
0.1 - 138
1 - 5 (from HC1 produced)
0.32
1.6
0.0026
•odorless*
(>1 mg/m1)
0.0033 - 0.2
"none*
0.25 - 0.68
0.26 - 0.68
0.00047 - 0.0455
0.01 - 7.35 (45)
0.00016-0.0099
0.1 -0.5
0.1-0.5
0.1-0.5
0.04- 1.2
1
0.1 -300(300)
0.06 - 160 (100)
PEL/TWA/STEL
0.1
10
WEEL - 0.3
50
0.05 mg/in1
10 mg/m1 (Total dust)
5 mg/m1 (Respirable fraction)
5
5
5
2
50
C-0.3
300
50
Exposure Limits'
REL TLV IDLH
C-l
0.05 mg/m1
2.3
2.3
2.3
0.1/0.3
10
50/75
20 mg/m1
5
5
5
2
50
C-0.3
300
50
4
Ca
5000 mg/m1
250
250
250
400
8000
50 mg/m1
(asCN)
1000
3500
-------
0\
CO
a
OQ
I
I
5
Chemical
Cyclohcxamone
Cyclohexene
Cyclohexylamine
Cyclopentadiene
2,4-D esters
DDT (Dichlorodiphenyl
trichloroethane)
Decaboranc
Decanoic acid
Decanal
1-Decylene
Diacetone alcohol
Diacetyl
Diallyl ketone
Diazomethane
Diborane
Di-N-Butyl amme
Dibutyl phosphate
Dichlorobenzene
o-Dichlorobenzcne
p-Dichlorobenzene
Dichlorodiethyl sulfide
(Mustard Gas)
Dichlorodifluoromelhane
1 ,3-Dichloro-S.S-dimethyl
hydatom
Warning Concentration1
001-4
0 18 - 300
2.6
0 01 - 250
0 02 - 0 1
2.9 mg/rn'
0.05 - 0.35 (fatigue)
0 0020 - 0 35
0 0064 - 0 168
0 12
01-1.7
0025
9.0
'inadequate*
18-4, "not reliable1
0.08 - 0 48
"inadequate*
0005
0 3 - 50 (20-30)
0.18-30(80-160)
00023-0.19
•odorless*
•adequate", 0.01 (1.14)
PEL/TWA/STEL
25
300
10
75
10 mg/m5
1 mg/m3
005/0.15
50
02
0.1
1/2
(see o-, p-)
C-50
75/110
1000
0.2/0 4 mg/m1
Exposure Limits'
REL TLV IDLH
25
LD
50
25
300
10
75
10 mg/m3
1 mg/m1
00/0.15
50
0.2
0.1
1/2
C-50
75/110
1000
0.2/0 4 mg/m1
5000
10000
2000
500 mg/m1
Ca
20
2100
10
40
125
1700
1000
50000
5 mg/m1
-------
I
cs'
g
DO
H-»
o
I
Chemical
1,1-Dichloroethane
1 ,2-Dichloroethylene
Dichloroethyl ether
bis-a-Dichloroethyl sulflde
Dichloroisopropyl ether
Dichloromethane (see
Methylene chloride)
dichloromonofluoromethane
2,4-Dichlorophenol
1 ,2-Dichloropropane
2,2-Dichloropropionic acid
(Dalapon)
Dichlorotetrafluoroelhane
Dicyclopentadiene
Dieldrin
Diesel Fuel No. 1-D
Diesel Fuel No. 2-D
Diesel Fuel No. 4-D
Diethanolamine
Diethylamine
Diethylammoethanol
Diethylene glycol
Diethylene iriomine
Diethyl ketone
Diethyl selenide
Warning Concentration*
SO - 1350, 'adequate'
0 085 - 500
0 0005 - 35 (100-200)
0.0023
032
"nearly odorless"
0.21 - 0 008
0 1 -70
428
'nearly odorless"
0 003 - 0 020
0041
0.25
0.08
0.01
0.01 1 - 0.27
0.01 - 38 (50, animals)
0 01 - 0.25
'almost odorless"
10
1 - 10
0.00014
PEL/TWA/STEL
100
200
5/10
10
75/1 10
1
1000
5
0.25 mg/m'
3
10/25
10
WF.EL - 50 ppm. Total -
10 mg/m1. Aerosol only
1
200
0.2 mg/m3
(asSe)
Exposure Limits1
REL TLV
HWC
200
LD
0.2 mg/m3
(asSe)
200/250
200
5/10
10
75/110
1
1000
5
0 25 mg/m3
3
10/25
10
1
200
0.2 mg/m1
(asSe)
IDLH
4000
250
50000
50000
Ca
2000
500
-------
I
I
a
i
I
1
Chemical
Diethyl succmate
Difluorodibromomelhane
Diglycidyl ether
Diisobutyl carbinol
Diisobutyl ketone
Diisopropylamine
Dimethyl acetamide
Dimethylamine
Dimethylaminoethanol
Dimethylaniline
Dimethyl ether
Dimethylformamide
1 , 1-Dimethylhydrazme
Dimethyl sulfate
dimethyl sulfide
Dimethyl sulfoxide
Dimethyl tnchiocarbonate
Dinitro-o-cresol
2 ,6- Dinitrophenol
Dmitrotoluene
Dioxane
Dioxolane
Diphenyl (Biphenyl)
Diphenyl chloroarsine
Diphenylcyanoarsine
Warning Concentration1
0021
'inadequate"
5
0 048 - 0 160
0 II -031 (25 8)
0. 1 - 4 (25-50. injury)
21 -47
001 -6 (97- 183. animals)
0015-0045
0.001 - 0.2
03-9
0 1 - 100
1 - 14
"nearly odorless"
0 001 - 0 020
"practically no odor"
0.0058 -0.1 8 mg/mj
"odorless"
0.21 (as phenol)
"inadequate"
0.003 - 278 (200-300)
64- 128
0.0008 - 0.06 (3-4)
0030
0.3
PEL/TWA/STEL
100
0.1
25
5
10
10
5/10
WEEL - 500
10
0.5
0 1
0.2 mg/m3
1 5 mg/m'
25
0.2
Exposure Limits'
REL TLV IDLH
25
006
0.2 mg/m1
LL
C-l
100
0.1
25
5
10
10
5/10
10
0.5 ,A2
0 1.A2
0 2 mg/m1
1 5 mg/m3
25
02
2500
Ca
2000
1000
400
2000
100
3500
Ca
10
5 mg/m1
Ca
Ca
300 mg/m1
-------
I
I
ro
Chemical
Diphenyl ether (see Phenyl
ether)
Diphenyl sulfide
Diphosgene (Trichloromethyl
chlororormaie)
Dipropylamine
Dipropylene glycol
Dipropylene glycol methyl ether
dithioethylene glycol
Dodecanol
Dodecycibenzene sulfonic acid
Epichlorohydrin
EPN
Ethane
1,2-Ethanedithiol
Ethanol
Ethanolamine
2-Ethyoxy-3,4-dihydro-l ,2-
pyran
2-Ethoxyethonol (Cellosolve
acetate)
2-Elhoxyethyl acetate
(Cellosolve acetate)
Ethyl acetate
Ethyl acrylate
Elhylamine
Ethyl benzene
Warning Concentration1
0.00034 - 0.0047
1.2
0.02 - 55
'practically odorless"
34.7 - 1000 (74.3)
0.031
0.0064
0.4-8
0.1 - 16(100)
"inadequate"
150 - 899
0.0042
1 - 5100(5041)
2-4
0.10-0.60
0.55-50
0.056 - 50 (600, animals)
001 -50(200-400)
0.00024 - 1 (75)
0.01 - 1 (100, delayed)
0.1 -200(200)
PEL/TWA/STEL
100/150
2
0 5 mg/m1
1000
3/6
200
100
400
5/10
10
100/125
Exposure Limits'
REL TLV IDLH
ME
LL
5
100
2
0.5 mg/m1
(a)
0.5
1000
3/6
5
2500
400
5/25
10
100/125
N.A.
Ca
50 mg/m1
1000
NN
1000
2000
4000
2000
-------
1
eo
3
I
I.
Chemical
Ethyl bromide
2-Elhylbutanol
Ethyl butyl ketone
Ethyl butyrate
Ethyl chloride (Chloroethane)
Ethyl disulfide
Ethylene
Ethylene bromide (see Ethylene
dibromide)
Ethylene chloride (see Ethylene
dichloride)
Ethylene chlorohydrin
Ethylene diamine
Ethylene dibromide
Ethylene dichloride
Ethylene glycol
Ethylene imine
Ethylene oxide
Ethyl ether
Ethyl formate
Ethyl glycol
Ethyl hexanol
Ethyl hexanoate
Ethyl hexyl acetate
Warning Concentration*
3.1 -200(6500)
0 07 - 0.77
0.1 - 10
0.0082 -0.015
42
0.0028
261 - 4010
'odorless1, 0.4
1 - 11.2(100)
10-25
6.2 - 185
0 08 - 40
'inadequate* 1 - 100+
0. 1 - 700
0.1-9(200)
18-33 (330)
25
0075-0.138
0.0056
0.18
PEL/TWA/STEL
200/250
50
1000
C-l
10
20
C-30
P-50
1/2
C-50
LL
1
400/500
100
Exposure Limits'
REL TLV IDLH
HWC
0.045
C-0.13
1
C-2
LL
0.1
C-5
200/250
50
1000
(a)
C-l
10
A2
10
C-50
0.5
1.A2
400/500
100
3500
3000
20000
10
2000
Ca
Ca
Ca
Ca
19000
8000
-------
i
5
a
i—»
•t*.
Chemical
Ethyl hexyl acrylate
Ethyl isothiocyanate
Bhyl mercaptan
Ethyl methacrylate
n-Ethylmorpholine
Ethyl pelargonate
Ethyl phthalate
Ethyl selenide
Ethyl selenamercaptan
Ethyl silicate
Ethyl sulfide
Ethyl isovalerate
Ethyl decanoate
Ethy Id ichlorarsine
Ethyl n-valerate
Ethyl undecanoate
Eugenol
Fluoride dust
Fluorine
Fluorotrichloromethane
Formaldehyde
Formic acid
Warning Concentration1
0 007 - 0.073
1.6- 10.7
0.00051-0.075
0.0067
0 1-25 .fatigue (40- 100)
0.0014
"odorless"
0 0003 - 0.014 mg/m3
00003
17-85 (250)
0.00060 - 0.068
0.12
0.00017
0.14- 1.4
0.060
0.00054
0.0046
(5.0 mg/m1)
0035-3(25-100)
5 - 100. "odorless"
001 -60(025-2)
0.024 - 340 (15)
PEL/TWA/STEL
C-5
0.5
5
0.2 mg/m9
(asSe)
0.2 mg/m1
(asSe)
100
2.5 mg/m1
0.1
C-1000
3
C-IO
5
Exposure Limits'
REL TLV IDLH
C-05
0 02 mg/m9
(asSe)
0.2 mg/m1
(asSe)
2.5 mg/m1
(asF)
0.016
C-0.1
C-5
0.5
5
0.2 mg/m9
(asSe)
0.2 mg/m1
(asSe)
10
2.5 mg/m1
1/2
C-1000
1/2.A2
5
25000
2000
1000
500 mg/m'
25
10000
Ca
100
-------
oo
I
!
Chemical
Fuel Oil #1 (Kerosene, Jet
Fuel)
Fuel Oil #2 (Diesel Oil)
Fuel Oil #4
Fuel Oil #6 (Bunker-C)
Furfural
Furfuryl alcohol
Fumaric Acid (trans-
Butenedioic)
Gasoline
Glutaraldehyde
Glycol diacelatc
Halothane
n-Heptal chloride
Heptachlor
Heptaldehyde
n- Heptane
Heptanol
HETP (see TEPP)
Hexachlorocyclopentadiene
Hexachloroethane
Hexamethylenediamme
n-Hexane
Hexanoic acid
Hexanol
Warning Concentration'
0.0X2 - 1
0.082
O.S
0- 13
0.006-5(122-50)
8
"odorless*
0.005- 10
0.04
0.077-0.312
33
0.060
0.306 mg/m'
0.050
0 5 - 329
0.057 - 20
0.03 - 0.33
0.13
0.0009
65-248(1400-1500)
0.0061
0.0050 - 0.09
PEL/TWA/STEL
2
10/15
300/500
C-0.2
0.5 mg/m3
400/500
0.1
1
WEEL - 5mg/m3
500/100
Exposure Limits'
REL TLV IDLH
50
85
C-440
LL
100
C-510
2
10/15
300/500
C-0.2
50
0.5 mg/m3
400/500
0.01
10
50
250
250
100 mg/m1
5000
Ca
5000
-------
I
3
s-
00
I
I
e
00
Chemical
Hexanone (see Methyl Butyl
Ketone)
sec-Hexyl acetate
Hexylene glycol
Hydrazine
Hydrocinnamyl alcohol
Hydrogen bromide
Hydrogen chloride
Hydrogen cyanide
Hydrogen fluoride
Hydrogen peroxide
Hydrogen selenide
Hydrogen sulfide
2-Hydroxpropyl acrylate
Indene
Iodine
lodoform
lonone
Isoamyl acetate
Isoamyl alcohol
Isoamyl mercaptan
Isobutyl acetate
Isobutyl acrylate
Isobutyl cellosolve
Warning Concentration1
0.1 - 100(100)
50
3-4
0.00027
2 (3-6)
1 - 10 (35)
0.00027 - 5. fatigue
0.04-0.163
•odorless" (100)
00005-3.6, fades fast (1.5)
0.00001- 1.4(50-100)
(fatigue at high concentration)
0.05
0.02
1.73(1 63-
disappears within 2 minutes)
0 0004 - 0.5
5.9 x 10' -73
0.001 - 1
0.01 - 35 (100-150)
0 0043 - 0 7
0.002- 7 (< 150)
0.009-0012
0.114-0.191
PEL/TWA/STEL
50
C-25
O.I
C-3
C-5
-/4.7
3/6
1
0.05
10/15
0.5
10
C-0.1
0.6
100
100/125
150
Exposure Limits'
REL TLV IDLH
C-003
C-4.7
3
C-6
C-10
C-0.1
50
C-25
0.1, A2
C-3
C-5
C-10
C-3
1
0.05
10/15
0.5
10
10
0.6
100
100/125
150/187
400
Ca
50
100
50
30
75
2
300
3000
8000
7500
-------
1
CO
Chemical
Isobutyl mercaptan
Isobutylraldehyde
Isobutyric acid
Isocyanochloride
Isodecanol
Isopentanoic acid
Isopentyl acetate (see Isoamyl
acetate)
Isophorone
Isoprene (2-methylbutadiene)
Isopropanolamine
dodecylbenzene sulfate
Isopropyl acetate
Isopropyl alcohol
Isopropylamine
Isopropyl ether
Isopropyl glycidyl ether
Isopropyl Mercaptan
Kerosene
Ketene
Kuwait-Crude
Lactic acid
Laurie acid
Lauryl mercaptan
Light Gasoline
Warning Concentration1
0.00054 - 0.00097
0.047 - 0.336
0.001
0.98
0.31-0.042
0.005 - 0.026
0.18-8.85(8.85)
0.005
0.3
0.5 - 400 (200)
7 5 - 300 (400)
0.1- 10(10-20)
0.02 - 300 (800)
300
0.00025
0.082-1
(23)
0.1-0.5
4x ia7
0.0034
4 mg/m5
800
PEL/TWA/STEL
4
WEEL-50
250/310
400/500
5/10
500
50/75
0.5/1.5
300/500
Exposure Limits1
REL TLV IDLH
4
500
C-800
C-50
100 mg/rn1
C-5
250/310
500/500
5/10
250/310
50/75
0.5/1.5
800
16000
12000
4000
10000
1500
50
-------
i
00
K—*
OO
1
Chemical
Lindane
Linoleyl acetate
Lithium hydride
LPG
Magnesium dodecyl sulfate
Malathion
Maleic anhydride
Menthol
2-Mercaptoelhanol
Mercury, Inorganic (except
Mercury pern it rate)
Mercury, vapor
Mesitylene (see
Trimethylbenzene)
Mesityl oxide
Methoxynaphthalene
3-Methoxypropylamine
Methyl acetate
Methyl acetylene- Propadiene
Mixture
Methyl acrylate
Methylacrylonitrile
Methyl alcohol
Methylamine
Methyl amyl acetate
Warning Concentration*
"practically odorless'
3.9 mg/m' - 21.3 mg/m'
0.0016
(0.1 mg/m9)
20000 (propane)
0.2
10 13.5 mg/m1
0.1-0.5(0.25-1.83)
1.5
0.12-0.65
•odorless'
•odorless*
0.017 - 25
000012
02-42
0.2-300(10000)
100
0.0005 - 20 (75)
2-14 (fatigue)
10 - 20482 (7500 - 69000)
0.001 - 10 (fatigue) (20- 100)
0.002- 1048(1048)
PEL/TWA/STEL
0.5 mg/m'
0.025 mg/m1
1000
10 mg/m3 (Total dust)
5 mg/m5 (respirable fraction)
0.25
C-0.1 mg/m'
(asHg)
0.05 mg/m3
15/25
WEEL - 10
200/250
1000/1250
10
1
200/250
C-800
10
Exposure Limits'
REL TLV IDLH
15 mg/m'
0.05 mg/m3
(asHg)
10
200
0.5 mg/m'
0.025 mg/m'
1000
10 mg/m'
0.25
0.1 mg/m'
0.05 mg/m'
15/25
200/250
1000/1250
10
1
200/250
10
1000 mg/m'
55 mg/m1
19000
5000 mg/m'
500
28 mg/m'
28 mg/m'
5000
10000
20000
1000
25000
100
-------
1
td
a
I
Chemical
Methyl amyl alcohol (Methyl
2-Methyl-2-butanol (tert-Amyl
Methyl biphenyl isocyanate
(MDI) (Dichloromethane)
Methyl ethyl ketone (MEK)
Methyl glycol (1.2-propyIene
S-Methy 1-3-heptanone (Ethyl
Warning Concentration1
001 -50(24-50)
1.6-2
0.00066-006
20 6 - 1030
0.23 - 2.3
0.07 - 0.09
0.0026
0.0925-92.5(118)
0.64-50
10 - 250, 'no odor- (500-1000)
20-714(500-1000)
1 -3
500 - 630
0 11
"can adapt to odor"
25 - 227 (5000)
3,4
0.25 - 85 (200)
0006-19
204 - 3000, (fatigue (3563))
60-90
6(50)
1 - 3
PEL/TWA7STEL
25/40
0.5
5
5
25
25
50/100
350/450
2/4
400
500
C-1000
P-2000
C-0.7
100/150
25
C-02
Exposure Limits'
REL TLV
0.5
LL
I
LL
LL
LL
200
C-0.04
25/40
100
5
5
5
5
50/100
350/450
2/4
400
50/175.A2
200/300
100/150
25
C-02.A2
IDLH
2000
Ca
5000
NN
4000
Ca
1000
10000
Ca
3000
5000
3000
Ca
-------
I
e
a
00
Chemical
Methyl iodide
Methyl isoamyl alcohol
Methyl isoamyl ketone
Methyl isobutyl ketone
Methyl isocyanate
Methyl ispropyl ketone
Methyl mercaptan
Methyl methacrylaie
2-Methylpcntaldehyde
2-Methy 1- 1 -pcntanol
2-Methylpropene (isobutylene)
Methyl sal icy late
a-Methyl styrene
Methyl sulfide (see Dimethyl
Sulfide)
Methyl thiocyanate
Methyltrichlorosilane
Methyl vinyl ketone
Meihylvinyl pyridine
Mineral spirits
Morpholine
Musk (Synthetic)
Naphtha - coal tar
Naphtha - petroleum (rubber
solvent)
Naphthalene
Warning Concentration1
(4300)
0.20
0.01 - 0.28
0.01 - 47 (100)
2.0 (2)
0.1-4.8
0.0001- 1.1
0.01-1 (1 70-250)
0.09-0.136
0 024 - 0.082
0.57 - 20
0.1 -0.14
0.1-200(200)
0.25 - 3.2
1
0.2
0.040
30
0.01 -0.14
4 0 x 10-7
4.68 - 100 (200-300)
<500
0.001 - 0.8 (15)
PEL/TWA/STEL
2
SO
50/175
0.02
200
0.5
100
50/100
20/30
100
10/15
Exposure Limits'
REL TLV IDLH
LL
100
50
0.5
2.A2
50
50/75
0.02
0.5
100
50/100
20/30
10/15
Ca
3000
20
400
5000
8000
10000
500
-------
1
03
f
I
e
Chemical
2-Naphthol
Nickel carbonyl
Nitrogen irifluoride
n-Octane
Warning Concentration*
1.3
1 -3
0.3- 1.0(62)
"odorless*
0001-6
0.002
2 1 -200(100-500)
0.1 -53(5-20)
5
'no odor-warning properties at
3 5 - 100 (200-500)
11 -300(99-150)
48-300
0 1-47
0 5 - 235
0.0014
00021 -0.31
0.0026
0015
0.1 - 0 5, (fatigue)
PEL/TWA/STEL
0.001
2/4
25
3 mg/m'
1
100
-/I
10
100
25
10
0.05- 1.74
200
300/375
WEEL - 50
C-0.05
Exposure Limits'
REL TLV
0.001
2
C-l
LL
2
25
75
C-385
C-0.5
0.05
(asNi)
2/4
25
3 mg/m'
1
100
3/5
10
100
25
C-10.A2
200
300/375
C-O.05
IDLH
Ca
100
100
300 mg/m'
200
10000
50
2000
1000
2300
Ca
2200
5000
0.5
-------
Chemical
Ozone
Parathion
Pelargonic acid (Nonyl Alcohol)
Pentaborane
Pentachlorphenol
n-Penlane
2,4-Pentanedione
2-Pentanone (Methyl propyl
ketone)
Pentanol (see amyl alcohol)
Pentene (n-Amylene)
n-Pentyl acetate (see n-Amyl
acetate)
1-Pentyl mercaptan
Perchloroethylene (see
Tetrachloroethylene)
Perchlorotnethyl mercaptan
Perchloryl fluoride
Pro-Klean-No-818
Petroleum distillates (Petroleum
naphtha)
Phenol
Phenyl ether
Phenyl ether-biphenyl mixture
Phenyl isocyanide
Warning Concentration1
0.0005 - 0.5 (1-3.7)
0.48 mg/tn1
000086
0.8(1)
9.3 mg/m3
(0.3 - 10.9 mg/m5)
2.2 - 1 100
0 01 - 0.024
3- 14
22
0.00021
0001
10 (but not reliable)
0.005
<500
0.005 - 5 (48)
0.001 -0.10(3-4)
0. 1 - 1 (3-4)
0.029 mg/m1
PEL/TWA/STEL
0 1/0.3
0.1 mg/m1
0.005/0.015
0.5 mg/m1
600/750
200
0.1
3/6
400
5
,
1
Exposure Limits'
REL TLV IDLH
0.15 mg/m1
120
C-610
ISO
52
C-15.6
0.1/0.3
0 1 mg/m1
0.005/0.015
0.5 mg/m1
600/750
200/250
0 1
3/6
5
1/2
10
20 mg/m1
3
150 mg/m1
15000
5000
10
385
1000
250
N.A.
N.A
-------
1
03
Chemical
Phenyl isothiocyanate
Phosgene
Phosphine
Phosphorous pentasulfide
Phosphorous trichloride
Phthalic anhydride
2-Picoline
Propane
Propionaldehyde
Propionic acid
n-Propyl acetate
Propyl alcohol
Propylene
Propylenediamine
Propylene dichloride
Propylene glycol
Propylene glycol dmitrate
Propylene glycol monomethyl
ether
Propylene oxide
Propyl mercaplan
n-Propyl nitrate
Propyl sulfide
Pyridine
Warning Concentration*
0.43
0 125 - 6 (dulls senses) (1-2)
0.01 - 5 (7.7)
•fatigue1. 0.0047
(asH'S)
0.7 (2-4)
0.05 - 0. 12 (30 mg/mj)
0.023 - 0.046
1000- 20000
0.04-1
0.001 - 20
0 05 - 200
0.01 - 200 (5500)
23 - 67 6
0.014- 0.067
0.25 - 130
•odorless'
024
10
10-210 (457-473, animals)
0.00075 - 0 02
50-90
0.011-0.17
0.001 - 5 (fatigue at 5,
PEL/TWA/STEL
O.I
0.3/1
1 mg/m'
0 2/0.5
1
WEEL - 2/5
1000
10
200/250
200/250
75/110
WEEL - 500 ppm, Total
0.05
100/150
100
25/40
5
REL
0.1
Exposure Limits'
TLV
0.1
0.3/1
1/3 Rig/Hi'
0.2/0.5
1
(a)
10/15
200/250
200/250
(a)
75/110
100/150
20
25/40
5
IDLH
2
200
750 mg/rn1
50
16700
20000
—
8000
4000
2000
0.05
2000
2000
3600
I
3
1
o'
8
-------
i
I
i
03
fe
I
Chemical
Pyrolgallo (1.2.3-
trihydroxybenzene)
Quinoline
Quinone
Resorchmol(l,3-
dihydroxylbenzene)
Rotenone
Safrole
Selenium oxide
Silver Cyanide
Skatole (3-Melhyl indole)
Sodium Butyldiphenol sulfonate
Sodium butylphenylphenol
sulfonate
Sodium hydroxide
Sodium nilrochlorobenzene
sulfonate
Sodium octyl sulfate
Sodium sulfate
Sorbitol
Stoddard solvent
Strychnine
Styrene
Styrene oxide
Sulfoxide
Warning Concentration*
20
0.16-71
0.08 -0.5. fatigue (0.1-0.5)
40
•odorless'. 222 mg/m1
0.0032
0.0002 mg/m3
'odorless*
7.5 x 10*- 1.68
0.5 (as alky aryl sulfonate)
0.5 (as alky aryl sulfonate)
"odorless*
0.5 (as alky aryl sulfonate)
0.2
"odorless"
•odorless*
1 - 30 (400)
•odorless'
0.001-200 (200-400)
0.40
91
PEL/TWA/STEL
WEEL-0.1
0.1
10/20
5 mg/m1
0.2 mg/m'
(asSe)
0 01 mg/m1
(asSe)
C-l mg/m1
100
100
50/100
Exposure Limits1
REL TLV IDLH
C-2 mg/m1
350 mg/m1
350 mg/m1
50
C-IOO
0.1
10/20
5 mg/m1
0.2 mg/m1
(asSe)
0.01 mg/m1
(asAg)
C-2 mg/m1
100
100
50/100
75
5000 mg/m1
100 mg/m1
50 mg/m1
(CN)
250 mg/m1
5000
100
5000
-------
1
09
Chemical
Sulfur dichloride (SCI,)
Sulfur monochloride (Sulfur
chloride. S2C I2)
TEPP (HETP, Bladex,
Tetrachlorethylene
Tetraethyl-o-silicate
Thymol
Toluene
Toluene diisocyanate (TDI)
Warning Concentration1
0.001
0.2 - S (6-20) 0.3-uste
0.6 - 2.4 mg/m'
0.001 (2-9)
"odorless"
2-4
"odorless"
>1
0.2-8
2 - SO (106-690)
5.0-7.2
0.1-60
0.0029
(0.40)
0.0027 - 0 02
0 001 - 85
0.00086
0.02 - 70, fatigue (300-400)
0.2-2.14
2.4 mg/m'
1.4-3
0.5 - 167
PEL/TWA/STEL
2/5
1 mg/m1
C-l
5/10
O.OS mg/m1
C-0.5
1
25
200/250
1
0.5
100/150
0 005/0.02
0.5/1 mg/m1
C-5
10
Exposure Limits'
REL TLV
0.5
1 mg/m'
LL
ME
100
C-200
0.005
C-200
LL
2/5
1 mg/m1
C-l
5/10
0.004 mg/m1
C-05
1
50/200
200/250
1
05
100/150
100/150
0.5/1 mg/m1
C-5
10
IDLH
100
80 mg/m'
10
1000
10 mg/m1
3500 mg/m1
Ca
Ca
20000
5
2000
C-200
2000
C-200
200 mg/m1
Ca
-------
f
s
o'
g
DO
to
ON
I
Chemical
o-Tolidine
1,1, l-Trichloroelhane (Methyl
chloroform)
Trichloroethylene
Trichlorofluoromethane
Trichlorophenol
1 ,2,3-Trichloropropane
1,1,2-trichloro- 1,2,2-
trifluoroethane
Triethanolamine dodecylbenzene
sulfonate
Triethylamine
Triethylene glycol
Trimelhylamme
Trimethylbenzene (Mesitylene)
Trimethyl phosphite
Tnnilrobutylxylene
Triphenyl phosphate
Turpentine
n-Undecane
n-Valeraldehyde
Valeric acid
ios Valeric acid
Vandium pentoxide -
Dust/Fume
Vanillin
Warning Concentration1
0.0048 - 20
20 - 400 (500-1000)
0.2-400(160)
5-209
0.1 -0.667
100(100)
0.5 - 200
0.3
0.009 - 2.8 (50)
"practically odorless"
0.0001 - 1 7
0006-24
0.001
6.5 x 10" - 0 0008
"odorless"
SO - 200 (100-200)
0 12
0001-82
0.00060
0.0018
(05-22 mg/mj)
32x 10'
PEL/TWA/STEL
5
350/450
50/200
C-1000
10
1000/1250
10/15
10/15
WEEL- 1
25
2
100
50
0.05 mg/m'
0.05 mg/m1
Exposure Limits'
REL TLV IDLH
C-0.02 mg/m1
C-350
25
C-0.05 mg/m'
0.1 mg/m1
(asVa)
2.A2
350/450
50/200
C-1000
10
1000/1250
10/15
10/15
25
2
3 mg
100
50
0.05 mg/m1
0.05 mg/m1
100
1000
Ca
1000
4500
1000
N.A.
1900
70 mg/m1
-------
1
CO
to
-j
Chemical
Warfarin
Xylene
Vinyhdene chloride (1,1-
Warning Concentration*
0.1 - 1
260-3000
10 - SO (SO)
"odorless"
O.OS - 200. fatigue (100-200)
0.08 - 40
0.08 - 40
0 08 - 40
0.0048 - 0.06
190
10
PEL/TWA/STEL
10/20
,
100
0.1 mg/m'
100/150
100/1 50
100/150
100/1 SO
2
1
300/400
Exposure Limits'
REL TLV
C-4
LD
100. C-200
100. C-200
100, C-200
100. C-200
300
10/20
S.A1
SO/100
0.1 mg/m1
100/1 SO
100/1 SO
100/1 SO
100/lSO
2
5/20
IDLH
Ca
5000
200 mg/m1
1000
1000
1000
1000
150
I
i
1 The exposure limits are 8-hour time-weighted averages (TWA) unless otherwise noted.
1 Fatigue - Indicates that the chemical can cause olfactory fatigue.
(a) Simple asphyxiant Check oxygen concentration.
A1 Confirmed human carcinogen (ACGIH)
A2 Suspected human carcinogen (ACGIH).
animal Irritation concentration based on animal studies
C Ceiling limit Ceiling limits for REL may be limited to 10 minutes, 15 minutes or not to be exceeded for any lime Check individual value.
Ca National Institute for Occupational Safety and Health (NIOSH) has recommended that the substance be treated as a potential human carcinogen; IDLH s are not listed for those
substances.
HWC 'To be handled in the workplace with caution" (NIOSH)
IDLH Immediately Dangerous to Life or Health, NIOSH Pocket Guide to Chemical Hazards, September 1985
LD 'Reduce exposure to lowest reliably detectable level" (NIOSH)
LL " Reduce exposure to lowest feasible level * (NIOSH).
ME "Minimize occupational exposure" (NIOSH)
N.A. NIOSH has not assigned an IDLH.
NN Not appl icable because of NIOSH REL
NE "No exposure limit recommended due to absence of a reliable monitoring method" (NIOSH).
P "Acceptable maximum peak above the acceptable ceiling concentration for an 8-hour shift " Each has a specific time limit
PEL Permissible Exposure Limits, "29 CFR 1910 Subpart Z," Occupational Safety and Health Administration (OSHA).
REL Recommended Exposure Limits, NIOSH Recommendations for Occupational Safety and HeallH Standards, NIOSH. 1988. /A__IUV
TLV Threshold Limit Value, Threshold Limit Values and Biological Exposure Indices for 1988-1989, American Conference of Governmental Industrial Hygienists (ACGIH)
STEL Short-term exposure limit. . . . . _
WEEL American Industrial Hygiene Association Workplace Environmental Exposure Level Guides. 1988. This is not a PEL but is placed in that column due to space limitations. The
first number is an 8-hour TWA The second number is a short-term TWA The time varies from 1-15 minutes. Check individual values.
-------
APPENDIX C
Hazardous Materials Identification Systems
-------
HAZARDOUS MATERIALS IDENTIFICATION SYSTEMS
Hazardous materials are frequently stored and transported in large quantities. An accidental release
of these materials presents a potential hazard to the public and environment. Such an incident is
managed more expeditiously when the hazardous material is specifically identified and characterized.
Unfortunately, the contents of storage tanks or trucks may not be specifically or properly identified.
Records or shipping papers may be inaccessible. Even with such information, an experienced person
must define the hazards and their seriousness.
The immediate need for information concerning a hazardous material, required two systems for
hazardous material identification. Both help responders to deal with a hazardous material incident
quickly and safely, and both were devised for persons untrained in chemistry.
The first is the National Fire Protection Association (NFPA) 704 M System, which is used on
storage tanks and smaller containers (fixed facility). The second system is used exclusively on
containers and tanks transported in interstate commerce. The U.S. Department of Transportation
(DOT) is responsible for this system. Its use, by way of placards and labels, is required under DOT
regulations found in the Code of Federal Regulations 49 (49 CFR).
NFPA 704 M HAZARD IDENTIFICATION SYSTEM
NFPA 704 M is a standardized system which uses numbers and colors on a sign to define the basic
hazards of a specific material. Health, Flammability, and Reactivity are identified and rated on a
scale of 0 to 4 depending on the degree of hazard presented (Figure 1).
The ratings for individual chemicals can be found in the NFPA Guide to Hazardous Materials.
Other references such as the U.S. Coast Guard Manual, CHRIS Volume 2, and the National Safety
Council's Fundamentals of Industrial Hygiene contain the NFPA ratings for specific chemicals. Such
information can be useful not only in emergencies but also during long-term remedial activities when
extensive evaluation must be completed.
6/93 C-l Appendix C
-------
(RED)
Flammability
Hazard
(BLUE)
Health
Hazard
(YELLOW)
Reactivity
Special
Information
FIGURE 1
NFPA 704 M HAZARD IDENTIFICATION SYSTEM
704 M Hazard Ranking System
HEALTH HAZARD (BLUE):
Rank Description
4 Materials that on very short exposure could cause death or major
residual injury even though prompt medical treatment was given.
Examples
Acrylonitrile,
Parathion, Bromine
Materials that on short exposure could cause serious temporary Aniline, Sodium
or residual injury even though prompt medical treatment was given. Hydroxide, Sulfuric Acid
Matenals that on intense or continued exposure could cause
temporary incapacitation or possible residual injury unless
prompt medical treatment was given.
Materials that on exposure would cause irritation but only
minor injury even if no hazard beyond that of ordinary
combustible material.
Material that on exposure under fire conditions would offer
no hazard beyond that ordinary combustible material.
Bromobenzene,
Pyridine, Styrene
Acetone, Methanol
Appendix C
C-2
6/93
-------
FLAMMABILITY HAZARD (RED):
Rank Description
4 Materials that (1) rapidly or completely vaporize at atmospheric
pressure and normal ambient temperatures and burn rapidly or
(2) are readily dispersed in air and burn readily.
1
0
Examples
1,3-Butadiene, Propane,
Ethylene
Liquids and solids that can be ignited under almost all ambient
temperature conditions.
Phosphorous, Acrylomtrile
Materials that must be moderately heated or exposed to relatively 2-Butanone, Kerosene
Sodium, Red Phosphorous
high ambient temperatures before ignition can occur.
Materials that must be preheated before ignition can occur.
Materials that will not burn.
REACTIVITY HAZARD (YELLOW):
Rank Description
4 Materials that in themselves are readily capable of detonation
or of explosive decomposition or reaction at normal temperatures
and pressures.
3 Materials that (1) in themselves are capable of detonation or
explosive reaction but require a strong initiating source or
(2) must be heated under confinement before initiation or
(3) react explosively with water.
2 Materials that (1) in themselves are normally unstable and
readily undergo violent chemical change but do not detonate
or (2) may react violently with water or (3) may form potentially
explosive mixtures with water.
1 Materials that in themselves are normally stable but which can
(1) become unstable at elevated temperatures or (2) react with
water with some release of energy but not violently.
0 Materials that in themselves are normally stable, even when exposed
to fire, and that do not react with water.
Examples
Benzoyl Peroxide, Picric
Acid
Diborane, Ethylene Oxide,
2-Nitropropadene
Acetaldehyde, Potassium
Ethyl Ether, Sulfuric Acid
SPECIAL INFORMATION (WHITE):
The white block is designated for special information about the chemical. For example, it
may indicate that the material is radioactive by displaying the standard radioactive symbol,
or unusually water-reactive by displaying a large W with a slash through it 0#). For more
complete information of these various hazards, consult Table 1, Special Information
Designators.
6/93
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Appendix C
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TABLE 1
SPECIAL INFORMATION DESIGNATORS
Designator
K
OXY
COR
V
EXP
TOX
IGN
Special Hazard
Water reactive
Oxidizer or
oxidizing properties
Corrosive
Radioactive
Explosive
Toxic
Ignitible
DOT HAZARD IDENTIFICATION SYSTEM
DOT's Hazardous Materials Transportation Administration regulates over 1,400 hazardous materials.
The regulations require labels on small containers and placards on tanks and trailers. These placards
and labels indicate the nature of the hazard presented by the cargo. The classification used for the
placards and labels is based on the United Nations Hazard Classes (Table 2). The UN hazard class
number is found in the bottom corner of a DOT placard or label. The various hazards are defined
in Table 3.
Appendix C
C-4
6/93
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TABLE 2
UN HAZARD CLASS SYSTEM
United Nations
Hazard
Class Number
1
2
3
4
5
6
7
8
9
Description
Explosives
Nonflammable/flammable/poison compressed gases
Flammable/combustible liquids
Flammable solids, spontaneously combustible substances,
reactive substances
and water-
Oxidizing materials, including organic peroxides
Class B poisons, irritants, and etiologic (disease-causing)
materials
Radioactive materials
Corrosive materials (acids, alkaline liquids, and certain corrosive liquids
and solids)
Miscellaneous hazardous materials not covered by any of
classes
the other
To facilitate handling a hazardous material incident some placards are being altered to accept a
4-digit identification number (Figure 2). This number comes from the Hazardous Material Table
in the DOT regulations, 49 CFR 172.101. This ID number also must be written on the shipping
papers or manifest. In the event of an incident, the ID number on the placard will be much easier
to obtain than the shipping papers. Once the number is obtained, the DOT's Emergency Response
Guide Book can be consulted. This book describes the proper methods and precautions for
responding to a release of each hazardous material with an ID number. The DOT system goes one
step further in aiding response personnel than the NFPA system. However, using both systems when
responding to hazardous material incidents will help to identify properly and characterize the
materials involved.
6/93
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Appendix C
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HAZARD SYMBOL
ID NUMBER
UN HAZARD CLASS NUMBER
FIGURE 2
MODIFICATION OF DOT PLACARD
HAZARDOUS MATERIAL TABLE
49 CFR 172.101
The following definitions have been abstracted from the Code of Federal Regulations, Title 49-
Transportation, Parts 100-177. Refer to referenced sections for complete details.
Note: Rulemaking proposals are outstanding or are contemplated concerning some of these
definitions.
HAZARDOUS MATERIAL - A substance or material which has been determined by the
Secretary of Transportation to be capable of posing an unreasonable risk to health, safety,
and property when transported in commerce, and which has been so designated. (Sec. 171.8)
MULTIPLE HAZARDS - A material meeting the definition of more than one hazard class
is classed according to the sequence given in Sec. 173.2.
Appendix C
C-6
6/93
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TABLE 3
HAZARDOUS MATERIALS DEFINITIONS
Hazard Class
CLASS A EXPLOSIVE
CLASS B EXPLOSIVE
BLASTING AGENT
COMBUSTIBLE
LIQUID
CORROSIVE
MATERIAL
FLAMMABLE LIQUID
FLAMMABLE GAS
NONFLAMMABLE
GAS
FLAMMABLE GAS
ORGANIC PEROXIDE
OXIDIZER
Definitions
An Explosive - Any chemical compound, mixture, or device, the primary or common
purpose of which is to function by explosion, i.e., with substantially instantaneous release
of gas and heat, unless such compound, mixture, or device is otherwise specifically
classified in Parts 170-177 (Sec. 173.50).
Detonating or otherwise of maximum hazard. The nine types of Class A explosives are
defined in Sec. 173.53.
In general, function by rapid combustion rather than detonation and include some explosive
devices such as special fireworks, flash powders, etc. Flammable Hazard. (Sec. 173 88)
A material designed for blasting which has been tested in accordance with Sec. 173.114a(b)
and found to be so insensitive that there is very little probability of accidental initiation to
explosion or of transition from deflagration to detonation. (Sec. 173.144a(a))
Any liquid having a flash point above 100°F and below 200°F as determined by tests listed
in Sec. 173.115(d). Exceptions are found in Sec. 173.115(b).
Any liquid or solid that causes visible destruction of human skin tissue or a liquid that has a
severe corrosion rate on steel. (See Sec. 173.240(a) and (b) for details.)
Any liquid having a flash point below 100°F as determined by tests listed in Sec
173.115(d). For exceptions, see Sec. 173.115(a).
Pvroforic Liquid - Any liquid that ignites spontaneously in dry or moist air at or below
130°F. (Sec. 173.1 15(c))
Compressed Gas - Any material or mixture having in the container a pressure exceeding 40
psia at 70°F, or a pressure exceeding 104 psia at 130°F; or any liquid flammable material
having a vapor pressure exceeding 40 psia at 100°F. (Sec. 173.300(a))
Any compressed gas meeting the requirements for lower flammability limit, flammability
limit range, flame projection, or flame propagation criteria as specified in Sec. 173.300(b).
Any compressed gas other than a flammable compressed gas.
Any solid material, other than an explosive, which is liable to cause fires through friction,
retained heat from manufacturing or processing, or which can be ignited readily and when
ignited bums so vigorously and persistently as to create a serious transportation hazard.
(Sec. 173.150)
An organic compound containing the bivalent -0-0 structure and which may be considered a
derivative of hydrogen peroxide where one or more of the hydrogen atoms have been
replaced by organic radicals must be classed as an organic peroxide unless - (see Sec.
173.151(a) for details).
A substance such as chlorate, permanganate, inorganic peroxide, or a nitrate that yields
oxygen to readily stimulate the combustion of organic matter (see Sec. 173.151).
6/93
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Appendix C
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TABLE 3 (Continued)
HAZARDOUS MATERIALS DEFINITIONS
Hazard Gass
POISON A
POISON B
IRRITATING
MATERIAL
ETIOLOGIC AGENT
RADIOACTIVE
MATERIAL
ORM-OTHER
REGULATION
MATERIALS
ORM-A
ORM-B
ORM-C
ORM-D
Definitions
Extremely Dangerous Poisons - Poisonous gases or liquids of such nature that a very small
amount of the gas, or vapor of the liquid, mixed with air is dangerous to life. (Sec.
173.326)
other than Class A or Irritating materials, which are known to be so toxic to man as to
afford a hazard to health during transportation; or which, in the absence of adequate data
on human toxicity, are presumed to be toxic to man. (Sec. 173.343)
A liquid or solid substance which upon contact with Tire or when exposed to air gives off
dangerous or intensely irritating fumes, but not including anv poisonous material. Class A.
(Sec. 173.381)
An "etiologic agent" means a viable micro-organism, or its toxin which causes or may
cause human disease. (Sec. 173.386)
Any material, or combination of materials, that spontaneously emits ionizing radiation, and
having a specific activity greater than 0.002 microcuries per gram. (Sec. 173 389) Note.
See Sec. 173.389(a) and (1) for details.
(1) Any material that may pose an unreasonable risk to health and safety or property when
transported in commerce; and (2) does not meet any of the definitions of the other hazard
classes specified; or (3) has been reclassed an ORM (specifically or permissively) according
to this subchapter (Sec. 173.500(a)). Note: A material with a flashpoint of 100°F may not
be classed as an ORM if it is a hazardous waste or is offered in a packaging having a rated
capacity of more than 1 10 gallons.
A material which has an anesthetic, irritating, noxious, toxic, or other similar property and
which can cause extreme annoyance or discomfort to passengers and crew in the event of
leakage during transportation. (Sec. 173.5000>)(1))
A material (including a solid when wet with water) capable of causing significant damage
to a transport vehicle or vessel from leakage during transportation. Materials meeting one
or both of the following criteria are ORM-B materials: (i) A liquid substance that has a
corrosion rate exceeding 0.250 inch per year (IPY) on aluminum (nonclad 707S-T6) at a
test temperature of 130°F. An acceptable test is described in NACE Standard TM-01-69,
and (u) specifically designated by name in Sec. 172.101. (Sec. 173.500*>(2))
A material which has other inherent characteristics not described as an ORM-A or ORM-B
but which makes it unsuitable for shipment, unless properly identified and prepared for
transportation. Each ORM-C material is specifically named in Sec. 172.101. (Sec.
173.500W(3))
A material such as a consumer commodity which, though otherwise subject to the
regulations of this subchapter, presents a limited hazard during transportation due to its
form, quantity and packaging. They must be materials for which exceptions are provided
in Sec. 172.101. A shipping description applicable to each ORM-D material or category of
ORM-D materials is found in Sec. 172.101. (Sec. 173.500*>(4))
Appendix C
C-8
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TABLE 3 (Continued)
HAZARDOUS MATERIALS DEFINITIONS
Hazard Class
ORM-E
Definitions
A material that is not included in any other hazard class, but is subject to the requirements
of this subchapter. Materials in this class include (i) Hazardous waste and (ii) Hazardous
substances as defined in Sec. 171.8. (Sec. 173.500">(5))
THE FOLLOWING ARE OFFERED TO EXPLAIN ADDITIONAL TERMS USED IN
PREPARATION OF HAZARDOUS MATERIALS FOR SHIPMENT. (SEC. 171.8)
CONSUMER
COMMODITY (See
ORM-D)
FLASHPOINT
FORBIDDEN
HAZARDOUS
SUBSTANCES
HAZARDOUS
WASTES
LIMITED QUANTITY
REPORTABLE
QUANTITY
SPONTANEOUSLY
COMBUSTIBLE
MATERIAL (SOLID)
WATER REACTIVE
MATERIAL (SOLID)
Means a material that is packaged or distributed in a form intended and suitable for sale
through retail sales agencies or instrumentalities for consumption by individuals for
purposes of personal care or household use This term also includes drugs and medicines.
(Sec. 171.8)
Means the minimum temperature at which a substance gives off flammable vapors which in
contact with a spark or flame will ignite. For liquids, see Sec 173.115, for solids, see
Sec. 173.150.
Means that the material is prohibited from being offered or accepted for transportation.
Note: This prohibition does not apply if these materials are diluted, stabilized, or
incorporated in devices and they are classed in accordance with the definitions of hazardous
materials. (Sec. 172.101(d)(l))
For transportation purposes, means a material, and its mixtures or solutions, that is
identified by the letter "E" in Column 2 of the Hazardous Materials Table to Sec. 172.101
when offered for transportation in one package, or in one transport vehicle if not packaged,
and when the quantity of the material therein equals or exceeds the reportable quantity
(RQ). For details, refer to Sec. 171.8 and Sec. 172 101, Hazardous Materials Table
For transportation purposes, means any material that is subject to the hazardous waste
manifest requirements of the Environmental Protection Agency in CFR, Title 40, Part 123,
Chapter F. (Sec. 171.8) For details on the Hazardous Waste and Consolidated Permit
Regulations, refer to CFR, Title 40, Parts 260-267 and Parts 122-125. Questions regarding
these regulations, call Toll Free: 800/424-9346 or 202/554-1404.
Means the maximum amount of a hazardous material; as specified in those sections
applicable to the particular hazard class, for which there are specific exceptions from the
requirements of this subchapter. See Sec. 173.118, 173 118(a), 173.153, 173.244,
173.306, 173.345 and 173.364.
For transportation purposes, means the quantity of hazardous substance and/or hazardous
waste specified in the Hazardous Material Table, Column 2 and identified by the letter "E"
in Column 1. (Sec. 171.8)
Means a solid substance (including sludges and pastes) which may undergo spontaneous
heating or self-ignition under conditions normally incident to transportation or which may,
upon contact with the atmosphere, undergo an increase in temperature and ignite (Sec.
171.8)
Means any solid substance (including sludges and pastes) which, by interaction with water,
is likely to become spontaneously flammable or to give off flammable or toxic gases in
dangerous quantities. (Sec 171.8)
6/93
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Appendix C
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U.S. DEPARTMENT OF TRANSPORTATION
Research and Special Programs Administration
This handout (revised 1981) is designed as a training aid for all interested parties who may become
involved with hazardous materials. It does not relieve persons from complying with the Department
of Transportation Hazardous Materials Regulations. Final authority for use of these hazard classes
and definitions is found in CFR, Title 49, Parts 100-177.
Information Services Division, DMT-11
Office of Operations and Enforcement
Materials Transportation Bureau
Research and Special Programs Administration
Department of Transportation
Washington, DC 20590
Note: This material may be reproduced without special permission from this Bureau and any
questions or comments concerning this handout should be directed to the address above.
Each hazardous material is assigned an identification number. Those numbers that are preceded by
a "UN" (United Nations Class) are associated with descriptions considered appropriate for
international shipments as well as domestic shipments. Those hazardous materials that are preceded
by an "NA" are associated with descriptions that are not recognized for international shipment except
to and from Canada. Each label, placard or shipping paper must contain the UN and IMO
(International Maritime Organization) hazard class number and, when appropriate, the division
number. The number must be Black or another authorized color, located in the lower corner of the
placard or label or in the hazardous materials description on shipping papers. The number must be
one-half inch (12.7 mm.) or less in height. In certain cases, the Class or Division number may
replace the written name of the hazard class in the shipping paper description. The United Nations
Class and Division numbers have the following meanings:
Class 1 Explosives
Division 1.1 Explosives with a mass explosion hazard
Division 1.2 Explosives with a projection hazard
Division 1.3 Explosives with predominantly a fire hazard
Division 1.4 Explosives with no significant blast hazard
Division 1.5 Very insensitive explosives
Class 2 Gases
Division 2.1 Flammable gases
Division 2.2 Nonflammable gases
Division 2.3 Poison gases
Appendix C C-10 6/93
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Division 3.1
Division 3.2
Division 3.3
Flammable liquids
Flashpoint below -18°C (0°F)
Flashpoint -18°C and above but less than 23°C (73°F)
Flashpoint of 238C and up to 61 °C (141°F)
Divisional
Division 4.2
Division 4.3
Flammable solids: Spontaneously combustible materials; and.
Materials dangerous when wet
Flammable solids
Spontaneously combustible materials
Materials that are dangerous when wet
Class S
Division S.I
Division 5.2
Oxidizers and Organic peroxides
Oxidizers
Organic peroxides
Class 6
Division 6.1
Division 6.2
Poisonous and Etiologic (infectious) materials
Poisonous materials
Etiologic (infectious) materials
Class 7
Class 8
Class 9
Radioactive materials
Corrosives
Miscellaneous hazardous materials
Placarding
Under DOT's requirements, each end and each side of a motor vehicle, rail car, freight container,
or portable tank containing hazardous materials must have a diamond-shape placard for the hazardous
materials that are transported.
For materials illustrated in Tables 4a and 4b, the placarding rules apply to any quantity transported
in a motor vehicle. Freight container or rail car must be placarded as illustrated.
6/93
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Appendix C
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TABLE 4A
DOT TABLE 1 PLACARDING TABLE 49 CFR 172.504
United Nations
Hazard Class Number
1
1
2
4
7
Hazardous Material Described As
Class A explosives
Class B explosives
Poison A
Flammable solid
Radioactive material:
Uranium hexafluoride, fissile
(containing more than 0.7% U235)
Uranium hexafluoride, low specific
activity (containing 0.7% or less U235)
Placards
EXPLOSIVES
EXPLOSIVES B
POISON GAS
FLAMMABLE SOLID
(DANGEROUS WHEN
WET label only)
RADIOACTIVE AND
CORROSIVE
RADIOACTIVE AND
CORROSIVE
The placarding shown in Table 4a was in effect as of January 1, 1991. If it is used, all
DOT hazard communications must be in compliance with it.
TABLE 4A
DOT TABLE 1 PLACARDING TABLE 49 CFR 172.504
Category of Material
(Hazard or Division Number)
1.1
1.2
1.3
2.3
4.3
6.1 (PGI, Inhalation
Hazard Only)
7 RAD (Yellow III
Labeling)
Placard to be Utilized
Explosives 1.1
Explosives 1.2
Explosives 1.3
Poison Gas
Dangerous When Wet
Poison
Radioactive
Reference Number for
Placard Design
172.522
172.522
171.522
172.540
172.542
172.554
172.556
Appendix C
C-12
6/93
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For the materials illustrated in Tables 5a and 5b, motor vehicles, freight containers, or rail cars are
not required to be placarded until the aggregate total weight of the hazardous materials reaches a
weight of 1000 pounds or more. If 5000 pounds or more of any materials illustrated in Table 5a
or 5b are loaded in a motor vehicle, freight container, or rail car at one facility, then the appropriate
placard for that material must be attached to the container, regardless of what placards may already
be on the units.
The placarding shown in Table 5a is in effect as of January 1, 1991. If it is used, all DOT hazard
communications must be in compliance with it.
TABLE 5A
DOT TABLE 2 PLACARDING TABLE 49 CFR 172.504
United Nations
Hazard Class Number
3
1.5
2
2
2
2
2
2
3
3
4
5
5
6
8
9
Hazardous Material Described as
Class C explosives
Blasting agent
Nonflammable gas
Nonflammable gas
Nonflammable gas (chlorine)
Nonflammable gas (fluorine)
Nonflammable gas (oxygen),
pressurized liquid)
Flammable gas
Combustible Liquid
Flammable liquid
Flammable solid
Oxidizer
Organic peroxide
Poison B
Corrosive material
Irritating material
Placards
DANGEROUS
BLASTING AGENT
NONFLAMMABLE GAS
NONFLAMMABLE GAS
CHLORINE
POISON
OXYGEN
FLAMMABLE GAS
COMBUSTIBLE
FLAMMABLE
FLAMMABLE SOLID
OXIDIZER
ORGANIC PEROXIDE
POISON
CORROSIVE
DANGEROUS
6/93
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Appendix C
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TABLE 5B
DOT TABLE 2 PLACARDING TABLE 49 CFR 172.504
United Nations
Hazard Class Number
1.4
1.5
1.6
2.1
2.2
3
Combustible Liquid
4.1
4.2
5.1
5.2
6.1(PGIorII
other than PGI
Inhalation
Hazard)
6.1 (PGIII)
6.2
8
9
ORM-D
Hazardous Material Described as
Explosives 1.4
Explosives 1.5
Explosives 1.6
Flammable gas
Nonflammable gas
Flammable
Combustible
Flammable Solid
Spontaneously Combustible
Oxidizer
Organic Peroxide
Poison
Keep Away From Food
(NONE)
Corrosive
Class 9
(NONE)
Placards
172.523
172.524
172.525
172.532
172.528
172.542
172.544
172.546
172.547
172.550
172.552
172.554
172.553
172.558
172.560
In many instances, a placard will contain a 4-digit identification number rather than a descriptive
term. This 4-digit number comes from the Hazardous Material Table in the DOT regulations, 49
CFR 172.101. This ID number must also be written on the shipping papers or manifest. To identify
the hazardous material, responders should look for the ID number in DOT'S Emergency Response
Guide Book. This book provides basic response guidelines and precautions that should be used
during an initial response to a release of hazardous materials.
Appendix C
C-14
6/93
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Labeling
DOT also requires the labeling of individual packages containing hazardous materials. When
labeling is required, each label must be affixed to or printed on the surface of the package near the
marked proper shipping name. Also, each label must either be affixed to a background of
contrasting color or have a dotted or solid line outer border. For hazardous materials that meet the
definition of one or more hazards, warning labels representing each hazard are required and must
be displayed next to each other. For example, a material classed as a flammable solid, that also
meets the definition of a water reactive material, must have both FLAMMABLE SOLID and
DANGEROUS WHEN WET labels affixed to the package. When two or more packages containing
hazardous materials are packaged within the same overpack, the outside container must be labelled
as required with each hazardous material that is contained within the overpack. Reference Label
Chart, following page.
In addition, each label that is affixed to or printed on a package must be durable and weather
resistant. The colors on a label must be able to withstand without substantial change: (1) a 72-hour
fadeometer test or (2) a 30-day exposure to conditions incident to transportation that reasonably could
be expected to be encountered by the labeled package (e.g., differing weather conditions, temperature
changes, and handling by numerous persons).
Package Identification
Packages or containers that are used for the shipment of hazardous materials must be manufactured,
assembled, and marked in accordance with the DOT requirements. Each package or container must
identify the DOT specification in effect on the date that the package or container was manufactured.
In addition, each specification container must be marked in an unobstructed area with letters and
numerals identifying the container specification (e.g., DOT-1A, DOT-17E-304HT, DOT-23G40).
The name and address or symbol of the person making this mark must be registered with the
Director, OHMT. These markings must be at least one-half inch high and should be stamped,
embossed, burned, or printed on the package to ensure that the markings can be seen and are
understood. Tank cars and appurtenances may only be used for the transportation of hazardous
materials where the tank cars have been approved by the Association of American Railroads'
Committee on Tank Cars for use in transporting hazardous materials. Each tank car that has been
approved by the Committee on Tank Cars can be identified by a DOT specification number that has
been embossed or marked in the tank car by the manufacturer. Likewise, packages may be identified
by numbers which are printed on the package by the manufacturer. For example, the EPA
regulations required that all pesticides be registered with the EPA. This pesticide registration
number is useful for identifying the particular pesticide and the manufacturer.
Containers of Radioactive Material
Radioactive materials may be packaged in drums, tanks, or other suitable packages. A container of
gamma radioactive material generally includes some additional "shielding" material such as lead or
iron to prevent the radiation from being emitted through the container.
6193 C-15 Appendix C
-------
Alpha and beta radioactive material may be packaged in containers that are of sufficient quality to
hold a hazardous material.
Containers of radioactive material must be clearly labelled. Each label must be durable, clearly
visible, bear the radiation caution symbol, and the words: "CAUTION, RADIOACTIVE
MATERIAL" or "DANGER, RADIOACTIVE MATERIAL." In addition, the label should provide
sufficient information to permit individuals handling the containers to take adequate precautions to
avoid or minimize exposures.
Shipping Papers
When hazardous materials are transported, the materials must be specifically identified on the
shipping paper. A shipping paper should describe the shipping name of the hazardous material, its
classification and its ID number. With certain exceptions, shipping papers identifying hazardous
materials are required to be:
• in the cab of the motor vehicle
• in the possession of a train crew member
• kept in a holder on the bridge of a vessel
• in an aircraft pilot's possession.
The DOT regulations require that a (shipping) description on the shipping paper include:
• the shipper's name and address
• the consignee's name and address
• the proper shipping name as shown in the commodity list
• the proper hazard classification of the shipment (e.g., oxidizing material, flammable
liquid)
• the identification number (preceded by "UN" or "NA") that has been assigned to the
hazardous material
• the total quantity by weight or volume
• a certification by the shipper that the shipment has been properly prepared
• emergency response information (Material Safety Data Sheets [MSDS] or ERG or
equivalent) and 24-hour emergency response telephone number.
Typically, the shipping paper that accompanies a shipment of hazardous materials that is transported
by highway is called a Bill of Lading. A Bill of Lading is a receipt that is issued by the trucker that
lists all materials of shipment as well as the hazardous materials that are being transported. A Bill
of Lading must be prepared in accordance with DOT requirements for shipping papers that are
described above. The driver of the motor vehicle or truck containing the hazardous material must
clearly make this shipping distinctive and recognizable from other shipping papers by tabbing it or
having it appear first. Also, the driver of the motor vehicle at the vehicle's controls must be certain
that the shipping paper is either within his immediate reach or visible to a person entering the
driver's cab. When the driver is not at the controls, the shipping paper may be either in a holder
which is mounted to the inside of the door on the driver's side of the vehicle, or on the driver's seat.
Appendix C C-16 6/93
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FEDERAL HAZARD COMMUNICATION STANDARD (HazCom)
In 1983, the Occupational Safety and Health Administration (OSHA) announced its Federal Hazard
Communications Standard, 29 CFR 1910.1200, referred to as HazCom. The law guarantees the
right to information about hazardous chemicals in the workplace. This law is referred to as the
"Right to Know" law.
The Federal Hazard Communication Standard, HazCom, establishes requirements in the following
four areas:
• Determining the chemical hazards in a workplace
• Labeling chemicals that are hazardous
• Maintaining MSDS that provide information about the hazardous chemicals
• Providing a written hazardous chemical training program.
Determining Chemical Hazards in a Workplace
There are many different hazardous chemicals. HazCom groups hazardous chemicals into two (2)
types: physical hazards and health hazards.
Chemicals that are physical hazards are flammable, corrosive, or reactive. Flammable chemicals can
cause fires; corrosive chemicals can cause chemical burns; and reactive chemicals can cause
explosions or release toxic fumes.
Chemicals that are health hazards are toxic chemical poisons. Overexposure to these chemicals can
cause acute, or immediate, effects such as nausea or vomiting. Overexposure to some of these
chemicals can cause chronic, or long-term, effects such as liver damage or cancer.
Labeling Requirements
HazCom requires that all containers of hazardous chemicals entering or leaving the workplace must
be labeled. The label must show the identity of the hazardous chemical, appropriate hazard warnings
(i.e., flammable, corrosive), and the name and address of the manufacturer, distributor, or importer.
The label may also include picture symbols that help to identify the hazard and show the proper
personal safety equipment to use when working with the chemical.
Labeling is also required for portable containers filled with chemicals from other containers. Tanks
and other nonmovable containers may be labeled by using the National Fire Protection Association
(NFPA) fire diamonds or the Hazardous Materials Identification System (HMIS) labels.
6/93 C-17 Appendix C
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Material Safety Data Sheets
MSDS required by HazCom must contain the following information:
The identity of the material
An emergency telephone number
A list of hazardous ingredients
Fire and explosion data
Health hazard data
Precautions for safe handling and use
Proper employee protection measures
Written Training Program
Written training programs are required by HazCom. The training program details how a company
intends to implement HazCom, and the type and kinds of training the company intends to conduct.
HazCom Identification Systems
Labeling for hazardous chemicals entering or leaving the workplace are governed by federal
regulations. HazCom and Department of Transportation (DOT) regulations govern labels, placards,
and warning signs for shipping hazardous chemicals.
Each of the different types of signs and labels serves a purpose. One type of chemical labeling are
written warnings such as:
Corrosive - Chemicals that cause chemical burns
Flammable - Chemicals that can cause fires
Toxic - Poisonous chemicals
Oxidizer - Chemicals that support combustion
Dangerous when wet - Chemicals that react with water and explode or produce toxic
fumes
Another type of labeling is color coding. Three systems that are used in color coding are the
National Fire Protection Association's 704 M Hazard Identification System (see above), the
Hazardous Materials Identification System (HMIS) and Department of Transportation (DOT).
The Hazardous Materials Identification System (HMIS) labels also use the colors red, blue, yellow
and white and number 0 through 4. HMIS labels are rectangular, with the colors in horizontal
stripes. As with the NFPA system, the red, blue, and yellow stripes indicate fire, health, and
reactivity respectively, and higher numbers show more severe hazards. The white section is used
to show the proper personal protection gear to be used when working with the hazardous chemical.
DOT labels are similar to the picture symbols discussed earlier. DOT labels are color-coded squares
or diamonds that are attached to hazardous chemicals being shipped. Some examples of DOT labels
are:
Appendix C C-18 6/93
-------
• Red Flammable liquid or gas Flame
• Yellow Oxygen or oxidizer Flame circled at base
• Orange Explosive Explosion
• Green Compressed gas Gas cylinder
• Black & White Corrosive Drops eating a hole in a
person's hand
• Blue Dangerous when wet Flame
DOT placards are fixed to the outside of the vehicles that carry hazardous chemicals. They are
similar to the warning labels, but they may not carry a written warning. Instead, they may contain
a 4-digit number that is the United Nations identification code for that material being shipped.
6/93 C-19 Appendix C
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HM 181 HAZARDOUS MATERIALS PLACARDING CHART
CLASS 1
EXPLOSIVES 1.1, 1.2. » 1.3
'The Division number 1 1. 1 2 or 1 3 and
compatibility group are in black ink
Placard any quantity ol Division number 11,12
n5 1
CLASS 5
Division 52
CLASS 6
Division 6 1
. • Packing Groups I & II
CLASS 6
OXIDIZED,
ORGANIC
.PEROXIDE,
POISON;
6,
DIVISKXI 6 1
Packing Group III
CLASS 7
.RADIOACTIVE;
7,
OXIMZER
Placard 454 kg (1001 Ibs I or more gross weight
of oxidizing matenal See DANGEROUS
ORGANIC PEROXIDE
Placard 454 kg |1001 Ibs ) or more gross weighl
of organ* peroxide See DANGEROUS
POISON
Placard 454 kg (1001 Ibs I or more gross weight
of Packing Groups I & II See DANGEROUS
Placard any quantity of Inhalation Hazard 6 1
PQI
KEEP AWAY FROM FOOD
Placard 454 kg (1001 Ibs ) or more gross weight
ol Packing Group III See DANGEROUS
A POISON placard may be used in place ol a
KEEP AWAY FROM FOOD placard
RADIOACTIVE
Placard any quantity ol packages bearing the
RADIOACTIVE YELLOW III label Certain low
specific activity radioactive materials in
"exclusive use' will not bear the label, bul the
RADIOACTIVE placard is required
CLASS 8
CLASS 9
CORROSIVE
Placard 454 kg (1001 Ibs.) or more gross weight
of corrosive matenal See DANGEROUS
MISCELLANEOUS
A Class 9 placard is not required However, you
may placard 454 kg (1001 Ibs.) or more gross
weight of a material which presents a hazard
during transport, but which is not included in any
other hazard class See DANGEROUS
DANGEROUS
DANGEROUS
Placard 454 kg (1001 Ibs.) gross weight ol two or
more categories ol hazardous materials listed in Table
2 A Freight container, unit load device, transport
vehicle tx rail car which contain non-bulk packagmgs
with two or more categories ol hazardous materials
that require different placards specified >n Table 2 may
be placarded with DANGEROUS placards instead of
the separate placarding specified for each ol the
materials in Table 2 However, when 2,266 kg (5000
ibs I or more of one category ol material is loaded
therein at one loading facility, the placard specified in
Table 2 for that category must be applied
Division 1 4 lexptostves)
Division 1 5 (blasting agents)
Division 1.6 (explosives)
Division 2 1 (flammable gas)
Division 2.2 (non-flammable gas)
Class 3 (flammable liquid)
Combustible liquid
Division 4 1 (flammable sow)
Division 4 2 (spontaneously combustotel
Dtviston 5 1 (oxidizef)
Division 5 2 (organic peroxide)
Dmsion 6 1, PG I i II. other than
PG I INHALATION HAZARD (poison)
Division 6 1. PG III (keep away from food)
Class 8 (corrosive)
Class 9 (miscellaneous)
SUBSIDIARY RISK
PLACARD
Class or division numbers do not appear on
subsidiary nsk placards
Fl'MIGATED
IKI ATH>
FUMIGATED
Placard motor vehicle, freight container or rail
car on or near each door when fumigated with
Division 6.1 (Poison) or Division 2.3 (Poison
gas)
Placard empty tank cars for residue ol matenal
last contained
The square background is required lor the following
placards when on rail cars. EXPLOSIVES 1 1 or 1 2.
POISON GAS or POISON GAS-RESIDUE (Division
2 3, Hazard Zone A): POISON or POISON-RE SI DUE
(Division 6 1, PGI. Hazard Zone A) The square
background is required for placards on molor
vehicles transporting highway route controlled
quantities of radioactive materials (Class 7}
DISPLAY OF IDENTIFICATION NUMBER WHEN TRANSPORTING HAZARDOUS
MATERIALS IN PORTABLE TANKS. CARGO TANKS AND TANK CARS.
1075
ORANGE PANEL
PLACARD
© Copyright 1993 & Published by J. J. KELLER & ASSOCIATES, INC., Neenah. Wl 54957-0368 • USA • (800)327-6868
39-FBREV. 10/93
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HM 181 HAZARDOUS MATERIALS PLACARDING CHART
§172 502 Prohibited and permissive placarding
(a) Prohibited placarding Except as provided In paragraph (b) of this section, no person may affix or display on a packaging, freight container, unit load device, motor vehicle or roil car—
(1) Any placard described In this subpart unless —
(I) The material being offered or transported Is a hazardous material.
(«) The placard represents a hazard of the hazardous material being offered or transported; and
(Hi) Any placarding conforms to the requirements of this subpart
(2) Any sign or other device that, by Its color, design, shape or content, could be confused with any placard prescribed In this subpart
(b) Exceptions (1) The restrictions In paragraph (a) of this section do not apply to a bulk packaging, freight container, unit load device, transport vehicle or rail car which 1s placarded In
conformance with the TOG Regulations the IMDG Code or the UN Recommendations.
(2) The restrictions of paragraph (a) of this section do not apply to the display of an Identification number on a white square-on-polnt configuration In accordance with § 172 33Mb) of this part.
(c) Permissive placarding Placards may be displayed for a hazardous material, even when not required. If the placarding otherwise conforms to the requirements of this subpart
§172.504 General placarding requirements
(a) General. Except as otherwise provided In this subchapter, each bulk packaging, freight container, unit load device, transport vehicle or rail car containing any quantity of a hazardous material
must be placarded on each side and each end with the type of placards specified In Tables 1 and 2 of this section and In accordance with other placarding requirements of this subpart, Including
the specifications for the placards named In the tables and described In detail In §§172 519 through 172 558
(b) DANGEROUS placard A freight container, unit load device, transport vehicle or rail car which contains non-bulk packaging! with two or more categories of hazardous materials that require
different placards specified In Table 2 may be placarded with DANGEROUS placards Instead of the separate placarding specified for each of the materials In Table 2. However, when 2268 kg (5,000
pounds) or more of one category of material Is loaded therein at one loading faculty, the placard specified in Table 2 of paragraph (e) of this section for that category must be applied
(c) Exception for less than 454 kg (1.001 pounds) Except for bulk packaglngs and hazardous materials subject to §172505. when hazardous materials covered by Table 2 ol thb section are
transported by highway or rail, placards are not required on—
(1) A transport vehicle or freight container which contains less than 454 kg (1001 pounds) aggregate gross weight of hazardous materials covered by Table 2 of paragraph (e) of this section, or
(2) A rail car loaded with transport vehicles or freight containers, none of which Is required to be placarded
The exceptions provided In paragraph (c) of this section do not prohibit the display of placards In the manner prescribed In this subpart If not otherwise prohibited (see § 172.502) on transport
vehicles or freight containers which are not required to be placarded
(d) Exception far empty non-bulk packages A non-bulk packaging that contains only the residue of a hazardous material covered by Table 2 of paragraph (e) of this section need not be
Included In determining placarding requirements
(e) Placarding tables Placards are specified for hazardous materials In accordance with the following tables
Table 1
Category of material (Hazard class or division number and
additional description as appropriate)
1 1
1 2
1 3
2.3.
43
6 1 (PG 1 Inhalation hazard only)
7 (Radioactive Yellow III label only)
Placard name
EXPLOSIVES 11
EXPLOSIVES 1 2
EXPLOSIVES 1 3 ...
POISON GAS
DANGEROUS WHEN WET
POISON
RADIOACTIVE1. .
Placard design section
reference (§)
172.552
172.522
172.522
172540
172.548
172.554
172556
1 RADIOACTIVE placard also required for exclusive use shipments of low specific activity material In accordance with § 173 425(b) or (c) of this subchapter
Table 2
Category of material (Hazard class or division number and
additional description, as appropriate)
1 4
15
16
2 i
22
3
Combustible liquid
4.1
42
5 1
5.2
6 1 (PG 1 or II. other than PG 1 Inhalation hazard)
6 1 (PGIII)
62
8
9.. ...
ORM-D
Placard name
EXPLOSIVES 1 4
EXPLOSIVES 1 5
EXPLOSIVES 1 6
FLAMMABLE GAS
NON-FLAMMABLE GAS
FLAMMABLE
COMBUSTIBLE
FLAMMABLE SOLID ...
SPONTANEOUSLY COMBUSTIBLE
OXIDIZER
ORGANIC PEROXIDE
POISON
KEEP AWAY FROM FOOD .
(None)
CORROSIVE
CLASS 9
(None)
Placard design section
reference (§)
172.523
172.524
172.525
172.532
172.528
172.542
172.544
172.546
172.547
172.550
172552
172.554
172.553
172.558
172.560
(0 Additional placarding exceptions (1) When more than one division placard Is required for Class 1 materials on a transport vehicle, rail car. freight container or unit load device, only the
placard representing the lowest division number must be displayed
(2) A FLAMMABLE placard may be used in place of a COMBUSTIBLE placard on —
(D A cargo tank or portable tank.
(ID A compartmented tank car which contains both flammable and combustible liquids
(3) A NON-FLAMMABLE GAS placard Is not required on a transport vehicle which contains non-flammable gas If the transport vehicle also contains flammable gas or oxygen and It Is placarded
with FLAMMABU GAS or OXYGEN placards, as required
(4) OXIDIZER placards are not required for Division 5 1 materials on freight containers, unit load devices, transport vehicles or ran cars which aba contain Division 1 1 011 2 materials and which are
placarded with EXPLOSIVES 1 1 or 1 2 placards, as required
(5) For transportation by transport vehicle or rail car only, an OXIDIZER placard Is not required for Division 5 1 materials on a transport vehicle, ran car or freight container which also contains Division
1 5 explosives and b placarded with EXPLOSIVES 1 5 placards, as required
(6) The EXPLOSIVE 1 4 placard b not required for those Division 1 4 Compatibility Group S (14S) materials that are not required to be labeled 1 45
(7) For domestic transportation of oxygen, compressed or oxygen, refrigerated liquid, the OXYGEN placard In § 172 530 of thb subpart may be used In place of a NON-FLAMMABLE GAS placard
(8) Except for a material classed as a combustible liquid that also meets the definition of a Class 9 material, a COMBUSTIBLE placard Is not required for a material classed as a combustible liquid
when transported In a non-bulk packaging For a material In a non-bulk packaging classed as a combustible liquid that also meets the definition of a Class 9 material, the CLASS 9 placard may be
substituted for the COMBUSTIBLE placard
(9) For domestic transportation, a Class 9 placard b not required. A bulk packaging containing a Class 9 material must be marked on each side and each end with the appropriate Identification
number displayed an an orange panel or a whlte-square-on-polnt display configuration are required by subpart D of this part.
(10) For domestic transportation of Division 6 1. PG III materials, a POISON placard may be used In place of a KEEP AWAY FROM FOOD placard
S172 505 Placarding for subsidiary hazards
(a) Each transport vehicle, freight container, portable tank and unit load device that contains a poisonous material subject to the 'Poison-Inhalation Hazard' shipping description of § 172.: ^
must be placarded with a POISON or POISON GAS placard, as appropriate, on each side and each end. In addition to any other placard required for that material In S172 504. Duollcaj '
POISON of POISON GAS placard b not required _
(b) In addition to the RADIOACTIVE placard which may be required by § 172 504(e) of thb subpart each transport vehicle, portable tank or freight container that contains 454 kg (1001 poo- J;r>x
more gross weight of fissile or low specific activity uranium hexafluoride shall be placarded with a CORROSIVE placard on each side and each end
(c) Each transport vehicle, portable tank, freight container or unit load device that contains a material which as a subsidiary hazard of being dangerous when wet. as defined In §173.124 of thb
subchapter. shall be placarded with DANGEROUS WHEN WET placards, on each side and each end. In addition to the placards required by § 172 504
(d) Hazardous materials that possess secondary hazards may exhibit subsidiary placards that correspond to the placards described In thb part, even when not required by thb part (see also
§172 519(b)(4) of this subpart)
© Copyright 1993 & Published by J J KELLER & ASSOCIATES. INC. Neenah, Wl 54957-0368 • USA • (800)327-6868
39-FB(REV 10/93)
Backer
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HM 181 HAZARDOUS MATERIALS LABELING CHART
CLASS 1
1.4
'Include appropriate division number
and compatibility group
EXPLOSIVE
'Include appropriate compatibility
CLASS 1
Explosive
'include appropriate compatibility
group
CLASS 1 Explosive
'include appropriate compatibility
group
CLASS 2 0'v.s
FLAMMABLE
Flammable gas
CLASS 2
Non-flammable gas
CLASS 2 Division
22
Oxygen
CLASS 2 D,V»
CLASS 3
CLASS 4
CLASS 4
UAMMABLE LIQUID
in
^r
CLASS 5
CLASS 5
Poison gas
Flammable liquid
Flammable solid
Spomaneously combustible
Dangerous when wel
Organic peroxide
CLASS 6 Division
CLASS 6
CLASS 6
CLASS 7
CLASS 7
CLASS 7
Posoo-Packing Groups I and II
Poison - Packing Group N
infectious substance
The Etioiogrc Agent label may be
required (42 CFR 72 3)
CLASS 8
CLASS 9
SUBSIDIARY RISK LABELS
Explosives
Flammable Gas
Flammable Liquid
Flammable Solid
^^ Corrosive
^F Oxidizer
* Poison
Sponlaneously Combustible
Dangerous When Wet
The hazard class or division number may nol be displayed on
a subsidiary label
FOR AIRCRAFT
D.O.T. GENERAL GUIDELINES ON USE OF WARNING LABELS
1. Shipper must furnish and attach appropriate label(s) to each package of hazardous material offered for shipment unless exempted from
labeling requirements.
2 If the material in a package has more than one hazard classification, the package must be labeled for each hazard. (Ref. Title 49, CFR,
Sec. 172.402).
3 When two or more hazardous materials of different classes are packed within the same packaging or outer enclosure, the outside of the
package must be labeled for each material involved. (Ref. Title 49, CFR, Sec. 172.404).
4. Radioactive materials requiring labeling, must be labeled on two opposite sides of the package. (Ref. Title 49, CFR, Sec. 172.403(f)).
Labels must not be applied to a package containing only material which is not subject to Parts 170 - 189 of this subchapter or which is
exempted therefrom. This does not prohibit the use of labels in conformance with U.N. recommendations ("Transport of Dangerous
Goods"), or with the IMO requirements ("International Maritime Dangerous Goods Code"), ICAO Technical Instructions, or TDG
Regulations (Ref. Title 49, CFR, Sec. 172.401).
5
HAZARDOUS MATERIALS PACKAGE MARKINGS
SAMPLE PACKAGING MARKING
Proper Shipping Name. ACETONE
UN I D Nu'*«..... UN 1090
T -i
WNING LABEL
lUUHiMU LHKJID
<•-) Copyright 1993 & Published by J. J. KELLER & ASSOCIATES, INC.. Neenah, Wl 54957-0368 • USA • (800)327-6868
38-FBREV 12/93
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HM 181 HAZARDOUS MATERIALS LABELING CHART
§172.400 General labeling requirements.
(a) Except as specified in §172 400a, each person
who offers for transportation or transports a haz-
ardous material in any of the following packages or
containment devices, shall label the package or con-
tainment device with labels specified for the material
in the 172.101 Table and in this subpait
(1) A non-bulk package;
(2) A bulk packaging, other than a cargo tank,
portable tank, or tank car, with a volumetric capacity
of less than 18 m3 (640 cubic feet), unless placarded
in accordance with subpart F of this part,
(3) A portable tank of less than 3785 L (1000 gallons)
capacity, unless placarded in accordance with sub-
part F of this part;
(4) A DOT Specification 106 or 110 multi-unit tank
car tank, unless placarded in accordance with sub-
part F of this part; and
(5) An overpack, freight container or unit load
device, of less than 18 m3 (640 cubic feet), which
contains a package for which labels are required,
unless placarded or marked in accordance with
§172.512 of this part
(b) Labeling is required for a hazardous material
which meets one or more hazard class definitions, in
accordance with Column 6 of the §172.101 Table and
the following table.
Hazard class or
division
1 1
12
13
14
15
16
21
22
23 .
3 (flammable liquid)
Combustible liquid
41.
42
43
51
52
6 1 (Packing Groups
land II)
6 1 (Pocking Group
110
62
7 (see §172 403)
7
7
7 (empty packages.
see §173 427)
8
9
Label name
EXPLOSIVE 1 1
EXPLOSIVE 12
EXPLOSIVE 1 3
EXPLOSIVE 1 4
EXPLOSIVE 1 5
EXPLOSIVE 1 6
FLAMMABLE GAS .
NON-FLAMMABLE GAS
POISON GAS
FLAMMABLE LIQUID
(none)
FLAMMABLE SOLID
SPONTANEOUSLY
COMBUSTIBLE
DANGEROUS WHEN WET
OXIDIZER
ORGANIC PEROXIDE
POISON
KEEP AWAY FROM FOOD
INFECTIOUS SUBSTANCE!
RADIOACTIVE WHITE-I
RADIOACTIVE YELLOW-II
RADIOACTIVE YELLOW-IN
EMPTY
CORROSIVE
CLASS 9
Label design
or section
reference (§)
172411
172411
172411
172411
172411
172411
172417
172415
172416
172419
172.420
172422
172423
172426
172427
172430
172431
172432
172436
172438
172440
172450
172442
172446
'The ETIOLOGIC AGENT label specified In regulations of the
Department of Health and Human Services at 42 CFR 72 3 may
apply to packages of Infectious substances
§172.400a Exceptions from labeling.
(a) Notwithstanding the provisions of §172.400, a
label is not required on -
(1) A cylinder containing a Division 2 1 or Division
2.2 gas that is
CO Not poisonous;
(ii) Carried by a private or contract motor earner
(iii) Not over-packed; and
(iv) Durably and legibly marked in accordance with
CGA Pamphlet C-7, appendix A.
(2) A package or unit of military explosives (includ-
ing ammunition) shipped by or on behalf of the DOD
when in —
(i) Freight containerload, carload or truckload ship-
ments, if loaded and unloaded by the shipper or
DOD, or
(ii) Unitized or palletized break-bulk shipments by
cargo vessel under charter to DOD if at least one
required label is displayed on each unitized or pal-
letized load
(3) A package containing a hazardous material other
than ammunition that is—
(i) Loaded and unloaded under the supervision of
DOD personnel, and
(ii) Escorted by DOD personnel in a separate vehi-
cle.
(4) A compressed gas cylinder permanently mounted
in or on a transport vehicle.
(5) A freight container, aircraft unit load device or
portable lank, which —
(i) Is placarded in accordance with Subpart F of this
part, or
(ii) Conforms to paragraph (a) (3) or (b)(3) of
§172.512
(6) An overpack or unit load device in or on which
labels representative of each hazardous material in
the overpack or unit load device are visible.
(7) A package of low specific activity radioactive
material, when transported under §173.4250)) of this
subchapter.
(b) Certain exceptions to labeling requirements are
provided for small quantities and limited quantities in
applicable sections in part 173 of this subchapter
§172.401 Prohibited labeling.
(a) Except as provided in paragraph (c) of this sec-
tion, no person may offer for transportation or no ear-
ner may transport any package bearing a label speci-
fied in this subpart unless —
(1) The package contains a material that is a haz-
ardous material, and
(2) The label represents a hazard of the hazardous
material in the package
(b) No person may offer for transportation and no
carrier may transport a package bearing any marking
or label which by its color, design, or shape could be
confused with or conflict with a label prescribed by
this part
(c) The restrictions m paragraphs (a) and (b) of this
section, do not apply to packages labeled in confor-
mance with —
(1) Any United Nations recommendation, including
the class number (see §172.407), in the document
entitled Transport of Dangerous Goods °,
(2) The International Maritime Organization OMO)
requirements, including the class number (see
§172407), in the document entitled "International
Maritime Dangerous Goods Code";
(3) The ICAO Technical Instructions, or
(4) The TDG Regulations.
§172.402 Additional Labeling requirements.
(a) Subsidiary hazard labels. Each package contain-
ing a hazardous material —
(1) Shall be labeled with primary and subsidiary haz-
ard labels as specified in Column 6 of the §172.101
Table; and
(2) For other than Class 2 or Class 1 materials (for
subsidiary labeling requirements for Class 1 materi-
als see paragraph (e) of this section), if not already
labeled under paragraph (a) (1) of this section, shall
be labeled with subsidiary hazard labels in accor-
dance with the following table.
SUBSIDIARY HAZARD LABELS
Subsidiary
hazard level
(packing
group)
I
II
III
Subsidiary Hazard (Class or Division)
3
X
X
•
41 42 43 5.1 6.1
X X X X X X
N X X N N ..
X — Required for all modes.
«— Required for transport by vessel only
•«— Required for transport by aircraft and vessel only.
...— Impossible as subsidiary hazard
N — None required
(b) Display of hazard class on labels. The appropriate
hazard class or, for Division 5.1 or 5.2 the division
number, shall be displayed in the lower corner of a
primary hazard label and may not be displayed on a
subsidiary label
(c) Cargo Aircraft Only label. Each person who
offers for transportation or transports by aircraft a
package containing a hazardous material which is
authorized on cargo aircraft only shall label the pack-
age with a CARGO AIRCRAFT ONLY label specified
in §172 448 of this subpart.
(d) Radioactive Materials. Each package containing a
radioactive material that also meets the definition of
one or more additional hazards, except Class 9, shall
be labeled as a radioactive material as required by
§172 403 of this subpart and for each additional haz-
ard
(e) Class 1 (explosive) Materials. In addition
label specified in Column 6 of the §172.1011 .._,<,
each package of Class 1 material that also meets the
definition for
(1) Division 6 1, Packing Groups I or II, shall be
labeled POISON; or
(2) Class 7, shall be labeled in accordance with
§172 403 of this subpart.
§172.403 Contains special requirements for
RADIOACTIVE materials. See regulations.
§172.405 Authorized label modifications.
(a) For Classes 1, 2, 3, 4, 5, 6, and 8, text indicating a
hazard (for example FLAMMABLE LIQUID) is not
required on a primary or subsidiary label when —
(1) The label otherwise conforms to the provisions of
this subpart, and
(2) The hazard class or, for Division 5.1 or 5.2 the
division number, is displayed in the lower comer of
the label, if the label corresponds to the primary haz-
ard class of the hazardous material.
(b) For a package containing Oxygen, compressed,
or Oxygen, refrigerated liquid, the OXIDIZER label
specified in §172 426 of this subpart, modified to dis-
play the word "OXYGEN" instead of "OXIDIZER",
and the class number "2" instead of "5.r,-m?iv_be
used in place of the NON-FLAMMABL1;
OXIDIZER labels. Notwithstanding the proN _
paragraph (a) of this section, the word "OXYGEN"
must appear on the label.
© Copyright 1993 & Published by J J KELLER & ASSOCIATES. INC . Neenah. Wl 54957-0368 • USA • (800)327-6868
38-FBREV 12/93
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APPENDIX D
Glossary and Acronym List
-------
GLOSSARY
Accident - An unexpected event generally resulting in injury, loss of property, or disruption of
service.
Action Level - A quantitative limit of a chemical, biological, or radiological agent at which actions
are taken to prevent or reduce exposure or contact.
Acute Exposure - A dose that is delivered to a receptor in a single event or in a short period of time.
Air Surveillance - Use of air monitoring and air sampling during a response to identify and quantify
airborne contaminants on and off-site, and monitor changes in air contaminants that occur over the
lifetime of the incidents
Aquifer - A water bearing formation of permeable rock, sand, or gravel capable of yielding water
to a well or spring.
Chronic Exposure - Low doses repeatedly delivered to a receptor over a long period of time.
Confinement - Control methods used to limit the physical area or size of a released material.
Examples: dams, dikes, and absorption processes.
Containment - Control methods used keep the material in its container. Examples: Plugging and
patching.
Contaminant/Contamination - An unwanted and non-beneficial substance.
Control - Chemical or physical methods used to prevent or reduce the hazards associated with a
material. Example: Neutralizing an acid spill.
Decontamination - The process of physically removing contaminants from individuals and equipment
or changing their chemical nature to innocuous substances
Degree of Hazard - A relative measure of how much harm a substance can do.
Direct-Reading Instruments - A portable device that rapidly measures and displays the concentration
of a contaminant in the environment.
Emergency - A sudden and unexpected event calling for immediate action.
Emergency Removal - Action or actions undertaken, in a time-critical situation, to prevent,
minimize, or mitigate a release that poses an immediate and/or significant threat(s) to human health
or welfare or to the environment. (See also Removal Action)
Environmental Assessment - The measurement or prediction of the concentration, transport,
dispersion, and final fate of a released hazardous substance in the environment.
6/93 D-l Appendix D
-------
Environmental Emergencies - Incidents involving the release (or potential release) of hazardous
materials into the environment which require immediate action.
Environmental Hazard - A condition capable of posing an unreasonable risk to air, water, or soil
quality, and to plants or wildlife.
Environmental Sample - Samples that are considered to contain no contaminants or low
concentrations of contaminants as compared to hazardous samples.
Episode - Incident.
First Responder - The first personnel to arrive on the scene of a hazardous materials incident.
Usually officials from local emergency services, firefighters, and police.
Groundwater - Water found in the saturated portions of geologic formations beneath the surface of
land or water.
Hazard - A circumstance or condition that can do harm. Hazards are categorized into four groups:
biological, chemical, radiation, and physical.
Hazard Classes - A series of nine descriptive terms that have been established by the UN Committee
of Experts to categorize the hazardous nature of chemical, physical, and biological materials. These
categories are:
1. Explosives
2. Nonflammable and flammable gases
3. Flammable liquids
4. Flammable solids
5. Oxidizing materials
6. Poisons, irritants, and disease-causing materials
7. Radioactive materials
8. Corrosive materials
9. Dangerous materials
Hazard Evaluation - The impact or risk the hazardous substance poses to public health and the
environment.
Hazardous - Capable of posing an unreasonable risk to health and safety (Department of
Transportation). Capable of doing harm.
Hazardous Material - A substance or material which has been determined by the Secretary of
Transportation to be capable of posing an unreasonable risk to health, safety, and property when
transported in commerce, and which has been so designated. (Department of Transportation)
Hazardous Sample - Samples that are considered to contain high concentrations of contaminants.
Hazardous Substance - 1) A material and its mixtures or solutions that are listed in the Appendix
to the Hazardous Materials Table, 49 CFR 172.101, when offered for transportation in one package,
Appendix D D-2 6/93
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or in one transport vehicle if not packaged, and when the quantity of the material therein equals or
exceeds the reportable quantity. 2) Any substance designated pursuant to Section 311(b)(2) (A) of
the Federal Water Pollution Control Act, (B) any element, compound, mixture solution, or substance
designated pursuant to Section 102 of this Act, (C) any hazardous waste having the characteristics
identified under or listed pursuant to Section 3001 of the Solid Waste Disposal Act (but not including
any waste of the regulation of which under the Solid Waste Disposal Act has been suspended by Act
of Congress), (D) any toxic pollutant listed under Section 307(a) of the Federal Water Pollution
Control Act, (E) any hazardous air pollutant listed under Section 112 of the Clean Air Act, and (F)
any imminently hazardous chemical substance or mixture with respect to which the Administrator
has taken action pursuant to Section 7 of the Toxic Substances Control Act. The term does not
include petroleum, including crude oil or any fraction thereof which is not otherwise specifically
listed or designated as a hazardous substance under subparagraphs (A) through (F) of this paragraph,
and the term does not include natural gas, natural gas liquids, liquified natural gas, or synthetic gas
usable for fuel (of mixtures of natural gas and such synthetic gas).
Hazardous Waste - Any material that is subject to the hazardous waste manifest requirements of the
Environmental Protection Agency specified in 40 CFR, Part 262 or would be subject to these
requirements in the absence of an interim authorization to a State under 40 CFR Part 123, Subpart F.
Incident - The release or potential release of a hazardous substance or material into the environment.
Incident Characterization - The process of identifying the substance(s) involved in an incident,
determining exposure pathways and projecting the effect it will have on people, property, wildlife
and plants, and the disruption of services.
Incident Evaluation - The process of assessing the impact released or potentially released substances
pose to public health and the environment.
Information - Knowledge acquired concerning the conditions or circumstances particular to an
incident.
Inspection - Same as investigation.
Intelligence - Information obtained from existing records or documentation, placards, labels, signs,
special configuration of containers, visual observations, technical records, eye witnesses, and others.
Investigation - On-site and off-site survey(s) conducted to provide a qualitative and quantitative
assessment of hazards associated with a site.
Limited Quantity - With the exception of Poison B materials, the maximum amount of a hazardous
material for which there is a specific labeling and packaging exception.
Mitigation - Actions taken to prevent or reduce the severity of threats to human health and the
environment.
Monitoring - The process of sampling and measuring certain environmental parameters on a real-time
basis for spatial and time variations. For example, air monitoring may be conducted with direct-
reading instruments to indicate relative changes in air contaminant concentrations at various times.
6/93 D-3 Appendix D
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National Contingency Plan - Policies and procedures that the Federal Government follows in
implementing responses to hazardous substances.
Off-Site - Presence outside of the worksite.
Qn-Site - Presence within the boundaries of the worksite.
Pathways of Dispersion - The environmental medium (water, groundwater, soil, and air) through
which a chemical is transported.
Persistent Chemicals - A substance which resists biodegradation and/or chemical transformation when
released into the environment and tends to accumulate on land, in air, in water, or in organic matter.
Planned Removal (Non-Time-Critical Removal) - The removal of released hazardous substances that
pose a threat or potential threat to human health or welfare or to the environment from a site within
a non-immediate time period. Under CERCLA: Actions intended to minimize increases in exposure
such that time and cost commitments are limited to 12 months and/or two million dollars. (See also
Emergency Removal.)
Pollutant - A substance or mixture which after release into the environment and upon exposure to
any organism will or may reasonably be anticipated to cause adverse effects in such organisms or
their offspring.
Pollutant Transport - An array of mechanisms by which a substance may migrate outside the
immediate location of the release or discharge of the substance. For example, pollution of
groundwater by hazardous waste leachate migrating from a landfill.
Qualified Individual - A person who through education, experience, or professional accreditation is
competent to make judgements concerning a particular subject matter. A Certified Industrial
Hygienist may be a qualified individual for preparing a site safety plan.
Regulated Material - A substance or material that is subject to regulations set forth by the
Environmental Protection Agency, the Department of Transportation, or any other federal agency.
Release - Any spilling, leaking, pumping, pouring, emitting, emptying, discharging, injecting,
escaping, leaching, dumping, or disposing of hazardous substances into the environment.
Remedial Actions - As in the National Contingency Plan, responses to releases on a National Priority
List that are consistent with treatment-oriented remedy that is protective of human health and the
environment and that permanently and significantly reduces toxicity, mobility, or volume of
hazardous substances.
Removal Actions - Any appropriate actions(s) taken to abate, minimize, stabilize, mitigate, or
eliminate the release or threat of release that poses a threat to human health or welfare or to the
environment. As set forth in the National Contingency Plan, these actions shall be terminated after
$2 million has been obligated or 12 months have elapsed from the date of initial response.
Appendix D D-4 6/93
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Reportable Quantity - As set forth in the Clean Water Act, the minimum amount (pounds or
kilograms) of a hazardous substance that may be discharged in a 24 hour period that requires
notification of the appropriate government agency.
Response Actions - Actions taken to recognize, evaluate, and control an incident.
Response Operations - Same as Response Actions.
Risk - The probability that harm will occur.
Risk Assessment - The use of factual base to define the health effects of exposure of individuals or
populations to hazardous materials and situations.
Risk Management - The process of weighing policy alternatives and selecting the most appropriate
regulatory action integrating the results of risk assessment with engineering data and with social and
economic concerns to reach a decision.
Routes of Exposure - The manner in which a contaminant enters the body through inhalation,
ingestion, skin absorption, and injection.
Safety - Freedom from man, equipment, material, and environmental interactions that result in injury
or illness.
Sampling - The collection of representative portion of the universe. Example: the collection of a
water sample from a contaminated stream.
Severe - A relative term used to describe the degree to which hazardous material releases can cause
adverse effects to human health and the environment.
Site - Location.
Site Safety Plan - Written, site-specific safety criteria that establishes requirements for protecting the
health and safety of responders during all activities conducted at an incident.
Toxicity - The ability of a substance to produce injury once it reaches a susceptible site in or on the
body.
Work Plan - Written directives that specifically describe all work activities that are to take place at
a work site.
6/93 D-5 Appendix D
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ACRONYMS
ACGIH - American Conference of Governmental Industrial Hygienists
AIHA - American Industrial Hygiene Association
ANSI - American National Standards Institute
APF - assigned protection factor
APR - air-purifying respirator
ASR - atmosphere-supplying respirator
ASTM - American Society for Testing and Materials
BEIs - biological exposure indices
BOD - biological oxygen demand
B of M - Bureau of Mines
Btu - British Thermal Unit
£ - Ceiling
CAG - Carcinogen Assessment Group
CDC - Centers for Disease Control
CERCLA - Comprehensive Environmental Response, Compensation and Liability Act (1980)
CFR - Code of Federal Regulations
CGI - combustible gas indicator
CHEMTREC - Chemical Transportation Emergency Center
CHRIS - Chemical Hazard Response Information System
CMA - Chemical Manufacturers' Association
CPC - chemical protective clothing
CPE - chlorinated polyethylene
CPM - counts per minute
Appendix D D-6 6/93
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CRC - CRC Press - A publisher of scientific reference books
CRP - community relations plan
DDT - Dichlorodiphenyltrichloroethane
DECON - decontamination
DFM - diesel fuel marine
DHHS - U.S. Department of Health and Human Services
POD - U.S. Department of Defense
DPI - U.S. Department of the Interior
POL - U.S. Department of Labor
DOT - U.S. Department of Transportation
DRI - direct-reading instruments
EERU - Environmental Emergency Response Unit
EL - exposure limit
EPA - U.S. Environmental Protection Agency
ERGS - Emergency Response Cleanup Services (under EPA contract)
ERT - Environmental Response Team
eV - electron volt
FEMA - Federal Emergency Management Agency
FES - fully encapsulating suit
FID - flame ionization detector
FIT - Field Investigation Team (under contract to EPA)
FM - factory mutual
GC - gas chromatograph or gas chromatography
GFCI - ground-fault circuit interrupter
6/93 D-7 Appendix D
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HASP - health and safety plan
HazCom - Federal Hazard Communications Standard
HEPA - high-efficiency paniculate air filter (common use: "HEPA filter")
HMIS - Hazardous Materials Identification System
IDLH - immediately dangerous to life or health
IP - ionization potential
1R - infrared radiation
IUPAC - International Union of Pure and Applied Chemists
LC50 - lethal concentration, 50%
LD50 - lethal dose, 50%
LCLo - lethal concentration - low
LDLo - lethal dose - low
LEL - lower explosive limit
LFL - lower flammable imit
MACs - maximum allowable concentrations
mg/L - milligrams per liter
mg/m3 - milligrams per cubic meter
MIRAN - Trade name for series of Foxboro Miniature Infrared Analyzers
MOS - metal oxide semiconductor
Mr/hr - milliroentgens per hour
MSP - mass spectroscopy detector
MSDS - material safety data sheets
MSHA - Mine Safety and Health Administration
MUG - maximum use concentration
Appendix D D-8 6/93
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MUL - maximum use limits
NBR - nitrile-butadiene rubber (synonym. Buna-N)
NCP - National Contingency Plan
NEC - National Electrical Code
NFPA - National Fire Protection Association
NIOSH - National Institute for Occupational Safety and Health
NOAA - National Oceanic and Atmospheric Administration
NOS or n.o.s. - not otherwise specified
NPL - National Priorities List
NRC - Nuclear Regulatory Commission
NRR - noise reduction rating
NRT - National Response Team
OHMTADS - Oil and Hazardous Materials Technical Assistance Data System
ORM - other regulated material (specific classes such as ORM-A, ORM-E, etc.)
OSC - on-scene coordinator
OSHA- Occupational Safety and Health Administration
OVA - organic vapor analyzer
OVM - organic vapor meter
PCB - polychlorinated biphenyl
PEL - permissible exposure limit
PF- protection factor
PIP - photoionization detector
ppb - parts per billion
PPE - personal protective equipment
6/93 D-9 Appendix D
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ppm - parts per million
ppt - parts per trillion
PVA- polyvinyl alcohol
PVC - polyvinyl chloride
OA/OC - quality assurance and quality control
RCRA - Resource Conservation and Recovery Act
REL - recommended exposure limits
REMFIT - Field Investigation Team for remedial actions (under contract to EPA)
RI/FS - remedial investigation and feasibility study
RPF - required protection factor
RRP - regional response plan
RRT - Regional Response Team
SAR - supplied-air respirator
SBR - styrene-butadiene rubber
SCBA - self-contained breathing apparatus
SOPs - standard operating procedures
SOSGs - standard operating safety guides
SpG - specific gravity
STEL - short-term exposure limit
TAT - Technical Assistance Team (under contract to EPA)
TCLo - toxic concentration - low
TCDD - tetrachlorodibenzo-p-dioxin
TCE - trichloroethylene
T.DLO - toxic dose - low
Appendix D D-10 6/93
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THR - toxic hazard rating
TLVs - threshold limit values
TWA - time-weighted average
2. 4. 5-T - 2,4,5-trichlorophenoxyacetic acid
UEL - upper explosive limit
UFL - upper flammable limit
y_L - Underwriters Laboratories
UN - United Nations
USCG - United States Coast Guard
USGS- United States Geological Survey
WEEL - Workplace Environmental Exposure Levels
6/93 D-ll Appendix D
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Workbook
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HAZARDOUS MATERIALS INCIDENT RESPONSE OPERATIONS
WORKBOOK
CONTENTS
Exercise
Using Air Monitoring Instruments I !
Using Air Monitoring Instruments II 13
Air-Purifying Respirators ^
Handout: APR Communications Exercise: Team 1 APR-1
Handout: APR Communications Exercise: Team 2 APR-2
Self-Contained Breathing Apparatus 25
Radiation Survey Instruments 31
Level B Dressout 35
Level A Dressout 39
Decontamination 43
Site Safety and Work Plan Development 49
Appendices
Appendix A: Abandoned Warehouse Scenario A-l
Appendix B: HMIRO Superfund Site Scenario B-l
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USING AIR MONITORING INSTRUMENTS I
I. OBJECTIVE
In this exercise, students will operate air monitoring instruments including: Combustible Gas
Indicators, Oxygen Indicators, and Colorimetric Indicator Tubes and Pumps. Students will
analyze and interpret the data gathered from the instruments.
II. PROCEDURE
The exercise has been divided into three stations. Each station will be equipped with air
monitoring instruments and gas sampling bags. Each team (consisting of at least two
students) must complete the following tasks at the appropriate station.
Station A Combustible Gas Indicators (CGIs)
Three gas sampling bags contain mixtures of flammable gas/vapors in air, one
each at concentrations:
• below the LEL
• between the LEL and UEL
• above the UEL
Measure each bag using both CGIs. Record concentrations on the answer
sheet at the end of this exercise. In Column 4, identify the mixture in each
bag.
Station B Oxygen Indicators
Two gas sampling bags contain different concentrations of oxygen. Sample
each bag with each of the two instruments. Record results on the answer
sheet.
Station C Colorimetric Indicator Tubes and Pumps
Two gas sampling bags contain mixtures of toluene in air and carbon dioxide
in air. Using the Colorimetric indicator tubes and pumps, measure each bag
according to manufacturer's instructions (see end of this exercise). Record
type of gas and concentrations on answer sheet.
III. GENERAL OPERATING INSTRUCTIONS
General operating instructions for combustible gas indicators, oxygen indicators, and
Colorimetric indicator tubes and pumps are as follows. Specific air monitoring instrument
instructions are also given for all equipment used in this exercise. When performing the
6/93
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Using Air Monitoring Instruments I
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exercise procedures at each station, use these instructions as a guide to proper instrument
use. The following instructions have been rewritten for brevity and clarity. In actual use,
instruments should be operated and calibrated according to the manufacturer's instructions.
Combustible Gas Indicators (CGIs) & Oxygen Indicators (O2Is)
In addition to the following instructions, the instruments should be checked prior to use in
a noncontaminated, fresh air environment. Furthermore, units incorporating an aspirator
bulb or other air-drawing device should be checked for leaks in the following manner:
• Attach all hoses, probes, and other air-drawing devices.
• If instrument has a battery-operated pump, turn instrument on. Place a finger over
probe or hose end.*
• If instrument is equipped with an aspirator bulb, place a finger over probe or hose
end. Squeeze the bulb.*
* In a leak-free system, the bulb remains collapsed or pump labors. In a
leaking system, the bulb regains its shape or pump does not labor. If the
instrument does not pass a leak test, notify an instructor.
Colorimetric Indicator Tubes and Pumps
In addition to the following instructions, all colorimetric indicator tubes and pumps should
be field checked prior to use. This check tests for leaks in the following manner:
• Insert unbroken tube into pump's tube holder.
• If using a bellows-type pump, squeeze bellows. After 30 minutes (per Draeger),
bellows should not regain its original shape nor should chain be taut. Start this test
and move to piston pump (returning to bellows after using the piston pump).
• If using a piston-type pump, align index marks on handle and cap of pump. Pull
back and lock handle. After 60 seconds rotate handle 1/4 turn. Handle should return
within 1/4 inch of zero cc mark.
If a pump fails these tests, it should be serviced according to manufacturer's instructions.
Using Air Monitoring Instruments I 2 6/93
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MSA Model 2A Exolosimeter Combustible Gas Indicator
1. Turn the explosimeter on by lifting the end of the "locking" bar on the "Rheostat"
knob and rotating the "Rheostat" knob clockwise 1/4 turn. The bar stays up while
the instrument is in use. Do not attempt to depress the bar.
2. Flush the instrument with fresh air by squeezing and releasing the aspirator bulb at
least 10 times.
3. Rotate the "Rheostat" knob until the meter needle rests at zero. (Avoid large
clockwise rotation which sends large current through the filament, perhaps shortening
its useful life.)
4. To sample, place the hose or probe end in the atmosphere to be measured and operate
the aspirator bulb at least ten times.
5. While squeezing the bulb, read the percent of Lower Explosive Limit (% LEL) as
the meter needle reaches the maximum level.
6. Before sampling the next bag, purge the instrument with clean air by aspirating the
bulb 5 times or until the needle drops back to zero.
7. Turn the explosimeter "Off" by rotating the "Rheostat" knob counterclockwise until
it "clicks." The locking bar will then retract into the "Rheostat" knob.
Using Air Monitoring Instruments I
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Bacharach Model GPK Oxygen/Combustible Gas Indicator
1. Rotate the "Function" switch clockwise to the "Volt Test" position. The motor starts
and the "% Oxygen" and "Sniffer" needles move up scale.
2. Lift and rotate the "Volt Adj" knob to bring the "Gas Detector" needle over the green
arrow. The knob is supplied with a clutch to prevent accidental decalibration).
3. Turn the "Function" switch clockwise to "On". The "% Oxygen" needle should be
at about 20.8% and the "Gas Detector" needle should drop to about zero.
4. Lift and rotate the "Oxy Cal" knob to adjust the "% Oxygen" needle to black
"Calibrate" line.
5. Lift and rotate the "Zero Adj" knob to adjust the "Gas Detector" needle to zero.
6. Momentarily place finger over hose or thread "Air Intake" nipple and observe the
pump laboring.
7. To sample, place hose end or probe in atmosphere to be measured. Within 30
seconds, steady-state readings are indicated on "% Oxygen" and "Gas Detector"
scales.
8. Before sampling the next bag, allow the instrument to purge itself by pulling in clean
air until the "Gas Detector" needle drops to zero and the "% Oxygen" returns to
normal. If they do not, repeat steps 4 and 5.
9. After readings have been taken, allow instrument to purge, then rotate "Function"
switch counterclockwise to "Off."
Using Air Monitoring Instruments I 4 6/93
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MSA Model 245 Oxygen Indicator
1. To calibrate the instrument in normal air, remove the "Remote Sampling Adaptor"
or draw clean air into the sampler by squeezing the aspirator bulb 6-7 times.
2. Press the "Read" switch. The meter needle should indicate 21 % oxygen, represented
by the hash mark on "Meter Scale."
3. If the needle does not indicate 21%, adjust by rotating the "Calibration
Potentiometer" (on top of instrument) clockwise to increase reading or
counterclockwise to decrease it. Use the screwdriver provided.
4. Connect the "Remote Sampling Adaptor" to the face of the sensor.
5. To sample, place the hose or probe in the atmosphere to be sampled, press the
"Read" button and squeeze aspirator at least 6 or 7 times.
6. Read the meter needle once it has stabilized. Reading can be done while aspirator
bulb is being squeezed.
7. After taking a reading, clean the unit by flushing fresh air through it until the meter
returns to normal. If the meter does not return to normal, repeat step 3.
8. Turn the instrument off by releasing "Read" switch.
5/pj 5 Using Air Monitoring Instruments I
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MSA Model 260 Oxygen/Combustible Gas Indicator
1. Turn the center "On-Off" control clockwise to the far right "Horn-Off" position.
Both meter needles will move, one or both lights may light.
2. Adjust the meter needle on the % oxygen meter by pulling up and turning the "02
Calibrate" knob. (The knob is supplied with a clutch to prevent accidental field
decalibration). Adjust the needle to read 20.8% 02 represented by the hash mark
located directly below the 21% mark.
3. Adjust the meter needle on the % LEL meter by pulling up and turning the "LEL
Zero" knob. Adjust the needle to read 0% on the meter face.
4. Press the red alarm "Reset" button to deactivate the alarm circuit. If either of the
alarm lamps located in the upper corners of the control panel were lit, they will
extinguish upon depressing this button.
5. Press the black check button and observe the needle movement on the % LEL meter.
The needle should fall within the black battery arc on the meter face. If it fails to
reach this level, the battery needs recharging.
6. Momentarily hold finger over the threaded "Air Intake" nipple or over the end of the
hose (if attached) and listen and watch the "Flow" indicator for signs of pump
laboring.
7. Turn the "02 Calibrate" knob counterclockwise while observing the % oxygen meter.
At the 19.5% reading, the left alarm lamp will illuminate. Return the needle to the
20.8% 02. Depress the red "Reset" button to reactivate the alarm circuit.
8. Turn the "LEL Zero" knob clockwise until the needle reads 25%. The right alarm
lamp will illuminate. Return the needle to zero % LEL. Depress the red "Reset"
button to reactivate the alarm circuit.
9. To operate the "Combo" unit, place the hose or probe end in the atmosphere to be
sampled and wait for the needle deflection to stabilize on the 02 and % LEL meter.
10. If the unit senses an oxygen deficient (< 19.5 % O2) or a combustible (> 25 % LEL)
atmosphere, the alarm circuit will activate and remain so until the atmosphere
concentrations return to normal levels. When back at normal levels, the red reset
button must be pushed to silence and reactivate the alarm.
11. After all readings are at baseline, turn the unit off by turning the function knob
counterclockwise to "Off".
Using Air Monitoring Instruments I g tf/pj
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MSA Model 261 Oxygen/Combustible Gas Indicator
1. Turn the center "On-Off" control clockwise to the far right "Horn-Off" position.
Both meter needles will move, one or both lights may light.
2. Adjust the meter needle on the % oxygen meter by pulling up and turning the "02
Calibrate" knob. (The knob is supplied with a clutch to prevent accidental field
decalibration). Adjust the needle to read 20.8% 02 represented by the hash mark
located directly below the 21% mark.
3. Adjust the meter needle on the % LEL meter by pulling up and turning the "LEL
Zero" knob. Adjust the needle to read 0% on the meter face.
4. Press the red alarm "Reset" button to deactivate the alarm circuit. If either of the
alarm lamps located in the upper corners of the control panel were lit, they will
extinguish upon depressing this button, and the center green lamp will periodically
illuminate. If the red lights continue to flash and/or the green lamp is not
illuminated, do not use the unit. Consult an instructor.
5. Press the black check button and observe the needle movement on the % LEL meter.
The needle should fall within the black battery arc on the meter face. If it fails to
reach this level, the battery needs recharging.
6. Return the center function knob to the "On" position while observing the green
"Horn-Off" lamp. The lamp will change from a flashing state to a continuous
illuminated state when the knob is placed in the "on" position. This indicates the
pump is operating and the audible alarm is activated.
7. Turn the "02 Calibrate" knob counterclockwise while observing the % oxygen meter.
At the 19.5% reading, the left alarm lamp will illuminate and the horn will sound.
Return the needle to the 20.8% reading. Depress the red "Reset" button to reactivate
the alarm circuit.
8. Turn the "LEL Zero" knob clockwise until the needle reads 25%. The right alarm
lamp will illuminate and the horn will sound. Return the needle to zero % LEL.
Depress the red reset button to reactivate the alarm circuit.
9. To operate the "Combo" unit, place the hose or probe end in the atmosphere to be
sampled and wait for the needle deflection to stabilize on the 02 and % LEL meter.
10. If the unit senses an 02 deficient (< 19.5% Oz) or a combustible (> 25% LEL)
atmosphere, the alarm circuit will activate and remain so until the atmosphere
concentrations return to normal levels. When back at normal levels, the red reset
button must be pushed to silence and reactivate the alarm.
11. The Model 261 is equipped with a locking mechanism that locks the needle if the
LEL meter reaches 100% or higher. The needle will stay at 100 even if subsequent
67P3 7 Using Air Monitoring Instruments I
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concentrations are greater than the UEL or drop below the LEL. To unlock, the unit
must be turned off and then on.
12. When finished sampling and all readings return to normal, turn the unit off by
rotating the function knob counterclockwise to "Off."
Using Air Monitoring Instruments I g 6/93
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Sensidyne/Gastec Gas Sampling System
1. Break off both tips of a fresh colorimetric indicator tube in the tube breaker hole in
the side of the pump head.
2. Insert the tube into the tube holder with the arrow on the tube pointing towards the
pump. Insert the other end of the tube in the test atmosphere.
3. Align the index marks on the handle and the cap of the pump.
4. Pull the handle straight back to the desired volume of 1/2 (SO cc), or 1 pump stroke
(100 cc's) as specified in the tube's instruction. The handle automatically locks at
these volumes.
5. Wait for the time specified in the tube's instructions, or wait until the red button pops
up to the blue line on the "Flow Finish Indicator" if the pump is equipped with one.
6. Rotate the handle 90° to unlock it and push the handle in.
7. Realign the index marks for next stroke or test. Refer to the tube's instructions for
required number of strokes.
8. Read the concentration of the chemical in air at the stained-unstained interface.
6/93 9 Using Air Monitoring Instruments I
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Draeger Indicator Tube Pump
1. Break off both tips of a fresh colorimetric indicator tube in the break-off eyelet on
the front cover plate or in break-off husk (an accessory).
2. Insert the tube into the pump head with the arrow on the tube pointing towards the
pump.
3. Hold the pump between your thumb and the base of your index finger with the front
cover plate contacting your finger.
4. Insert the end of the tube into the sample atmosphere.
5. Compress the bellows completely with a squeezing motion assuring that the total
volume of the bellows is used.
6. Release your grip and allow the chain to become taut, signifying that 100 cc of air
have been pulled through the tube. Be sure to keep the tube end in the sample
atmosphere during the specified time.
7. Complete steps 4 and 5 as many times as the tube's instructions state.
8. Read the concentration of the material in air at stained-unstained interface.
Using Air Monitoring Instruments I 10 6/93
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ANSWER SHEET
STATION A: Combustible Gas Indicators
Concentrations
MSA Model 2A Bacharach Model GPK Mixture (check one)
%LEL % LEL % Oxygen
Bag A < LEL
LEL-UEL
> UEL
Bag B <
LEL-UEL
> UEL
Bag C < LEL
LEL-UEL
> UEL
STATION B: Oxygen Meters
% Oxygen
MSA Model 245 MSA Model 260/261
Bag 1 % LEL:.
2 % LEL:
STATION C: Colorimetric Indicator Tubes and Pumps
Concentrations
Sensidyne/Gastec Draeger
Gas:
6/93 11 Using Air Monitoring Instruments I
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NOTES
Using Air Monitoring Instruments I \i 6/93
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USING AIR MONITORING INSTRUMENTS II
I. OBJECTIVE
The students will calibrate an HNU PI-101 and measure concentrations of various gas
samples. The students will learn how to operate the instrument and record pertinent data
gathered.
II. PROCEDURE
A. Students will divide into groups as directed by the instructor.
B. Each station contains an HNU PI-101 and four gas bags. The gas bags contain:
• 100 ppm toluene
• 100 ppm acetone
• 50 ppm hexane
• 100 ppm methane
If the actual concentrations differ from above, the instructor will inform you of the
changes.
C. Read the following instructions for the instrument. The instructor will demonstrate
the check-out of the instrument and explain the function of the controls.
HNU PI-101 Photoionizer Operating Instructions
1. Turn the six position "Function Switch" to the BATTERY CHECK position. The
needle on the meter should read within or above the green "Battery Check" on the
scale. If not, recharge the battery. If the red battery indicator light comes on, the
battery must be recharged. Inform the instructor if the battery is not at optimum
charge.
2. Turn the "Function Switch" to any "Range Setting" (i.e. 0-20, 0-200, or 0-2000).
The lamp can be checked by holding the exposed tip of a solvent-based marking pen
next to the end of the probe. The meter will show a deflection.
3. Turn the "Function Switch" to the STANDBY position and rotate the "Zero
Adjustment" until the meter reads zero. Note: No zero gas is needed since this is
an electronic zero adjustment. If the span adjustment setting is changed after the zero
is set, the zero should be rechecked and adjusted, if necessary. Wait 15 to 20
seconds to ensure that the zero reading is stable. If necessary, readjust the zero.
The instrument is ready for operation.
6/93 13 Using Air Monitoring Instruments If
-------
STEP1
Record the following. The EPA sticker number can be used if no serial number is found.
HNU Serial Number:
HNU Probe Number:
HNU Lamp Energy:
STEP 2
With the assistance of the instructor and/or the technician, calibrate the instrument using
isobutylene.
To calibrate the HNU PM01, connect the probe inlet to the calibration gas source. Set the
"Function Switch" to the correct range setting for the concentration of the test gas. Unlock
the "Span Control" by moving the black lever counter clockwise. Adjust the "Span Control"
the desired reading is obtained. Turning the "Span Control" knob clockwise increases the
numbers on the span. The span will not turn past 0 or 10 (window number). The number
on the "Span Control" is the calibration setting for the test gas. The setting is read with the
number in the "window" as the integer and the number on the dial as a decimal.
HNU span setting
Using Air Monitoring Instruments II 14 6/93
-------
STEP 3
With the instruments at the same span settings from Step 1, make and record readings for
the following gas bags.
Actual HNU
Concentration Reading
Toluene 100 ppm
Acetone 100 ppm
Hexane 50 ppm
Methane 100 ppm
Calculate the relative response for each of the chemicals. Relative response = 100% times
INSTRUMENT READING divided by ACTUAL CONCENTRATION.
HNU
Toluene
Acetone
Hexane
Methane
STEP 4
Calibrate the instrument to acetone using the 100 ppm acetone bag. Adjust the span setting
until the instrument reads 100. Record the span setting.
HNU span setting
6/93 15 Using Air Monitoring Instruments II
-------
STEPS
Take a reading of the atmosphere in and around the container of solvent at the front of the
room. Take care that the probe does not come in contact with the liquid. Record your
results below.
LOCATION READING
1 foot from opening
6 inches from opening
over opening
inside container
STEP 6
Conduct a room survey and record your readings at each of the containers.
READING
Container ffl
Container #2
Container #3
Container #4
After obtaining the readings, the instructor will then reveal the contents of each container.
From what you learned in steps three and four, obtain the actual concentration of acetone in
container #4.
Actual Concentration
Acetone (Container #4)
STEP 7
The instructor will demonstrate the effects of electromagnetic radiation on the instruments.
Using Air Monitoring Instruments II 16 6/93
-------
STEPS
Answer the following questions.
1. Does the instrument respond the same for all chemicals?
2. Is it important to know what energy lamp you are using? Why?
3. What is the span control used for? Why would you change the span from its original
setting for benzene (isobutylene) calibration.
4. Your instrument is calibrated to benzene. You read 200 on your meter during an
investigation of a hazardous waste site. How do you report your findings? What
additional information is needed?
6/93 17 Using Air Monitoring Instruments II
-------
NOTES
Using Air Monitoring Instruments II 18 6193
-------
AIR-PURIFYING RESPIRATORS
I. OBJECTIVE
Students will be able to perform a qualitative fit test for a full-face air-purifying respirator.
While wearing full-face, air-purifying respirators, students will operate communication
devices (Motorola HT600 radios).
In this exercise, students will also demonstrate proper donning and doffing of escape masks.
II. PROCEDURE
A. The instructor demonstrates fit-testing methods using the isoamyl acetate.
B. Select at least two styles of full-face APRs. With the assistance of another student,
fit test each APR using the isoamyl acetate.
Select the proper cartridge for the particular testing method:
• Isoamyl Acetate - Organic Vapor Cartridge
C. Check radios for proper operation (see following instructions).
D. Don air-purifying respirators and separate into two groups (group number indicated
at bottom of handout).
E. Transmit messages given on handouts and write down messages received. Speak
slowly and clearly. Verify that a message has been received before proceeding to the
next one. You may need to repeat a message several times. (If there is more than
one person per radio, take turns transmitting and receiving.)
6/93 19 Air-Purifying Respirators
-------
Respirator Fit-Testing Instructions
1. Place head into the test atmosphere and breath normally for about ten seconds. If no
odor is detected proceed to the next step.
2. Breath deeply for 10 seconds. If no odor is detected, proceed to the next step.
3. Move head from side to side pausing at each extreme to inhale once. If no odor is
detected, proceed to next step.
4. Move head up and down, hold head up and inhale deeply at least once. If no odor
is detected, proceed to next step.
5. Speak loudly and slowly while counting backwards from 100 to 75. Recite name,
address or other script (i.e. the rainbow passage). If no odor is detected, proceed to
next step.
6. Make an exaggerated face or expression. If no odor is detected, proceed to next
step.
7. Bend at the waist and move head around. If no odor is detected, proceed to next
step.
8. Jog in place for 10 seconds. If no odor has been detected, the fit test has passed.
Air-Purifying Respirators 20
-------
Comments:
FIT-TEST RECORD
Name:
Location:
Date:
Type of mask:
Manufacturer:
Model/Size:
Isoamyl
Acetate
pass/fail
Type of mask:
Manufacturer:
Model/Size:
pass/fail
Type of mask:
Manufacturer:
Model/Size:
pass/fail
Type of mask:
Manufacturer:
Model/Size:
pass/fail
Type of mask:
Manufacturer:
Model/Size:
pass/fail
6/93
21
Air-Purifying Respirators
-------
Motorola HT600 Radio Operating Instructions
To check radio controls:
1. Turn on radio by rotating the on-off/volume control clockwise 1/2 turn. A
power-up alert tone is generated for approximately one half second. If this
short alert tone is not heard or if a continuous alert tone is generated, inform
the instructor.
2. Select channel 1, 2, 3, or 4 using the channel selector switch. For this
exercise, the instructor will assign channels. Channels S and 6 are not
usable.
3. Push one of the monitor buttons (small buttons on side near top of unit) and
adjust the volume.
4. Place toggle switch (squelch select switch) to the left position (speaker with
a slash symbol). This helps to eliminate interference from other users on
these channels.
5. The bi-color, light-emitting diode (LED) indicates normal transmission
(continuous red), low battery (flashing red), or channel busy (flashing green).
To transmit message:
1. To transmit, hold radio approximately 2 inches from your mouth and speak
slowly and clearly while depressing the push-to-talk button on the left side.
If the green LED on top is flashing, or other persons are heard, do not
transmit until they are finished. If the radio beeps when you attempt to
transmit, there is another user on the channel.
2. When finished transmitting, release the push-to-talk button.
3. Do not transmit unnecessarily. Do not use profanity. These are not CB
radios. They are business band radios that operate on shared channels with
other businesses.
4. When reading chemical names or other difficult words it is best to spell the
words. Many chemicals may differ by only one or two letters or numbers.
For example, potassium chloride (salt substitute) and potassium chlorate
(shock sensitive oxidizer used in explosives).
5. Answer a question by using "affirmative" or "negative" for yes or no.
6. When you are finished transmitting and expect a reply, say "over." When
you are finished and do not expect a reply say "out" or "clear."
7. Turn the radio off when exercise is complete.
Air-Purifying Respirators 22 6/93
-------
Radio safety:
1. Avoid physical abuse of the radio such as carrying it by the antenna.
2. DO NOT hold the radio such that the antenna is very close to, or touching,
exposed parts of the body, especially the face or eyes, while transmitting.
The radio will perform best if the microphone is two or three inches away
from the lips and the radio is vertical.
3. DO NOT hold the transmit switch on when not actually desiring to transmit.
4. DO NOT operate a portable transmitter near unshielded electrical blasting
caps or in an explosive atmosphere unless it is a type especially qualified for
such use.
6/93 23 Air-Purifying Respirators
-------
Escape Mask Donning and Doffing
Donning Procedures:
1. Choose an escape mask to don.
2. Don the North 845, Scott Scat-Pak, or ISI ELS A.
3. Lift flap and remove hood.
4. Turn valve ON by turning knob counterclockwise.
5. Slip hood over head making sure that the hose outlet is in front of the face.
Doffing Procedures:
1. Remove hood.
2. Turn valve OFF by turning clockwise.
Air-Purifying Respirators 24 6/93
-------
APR COMMUNICATIONS EXERCISE: TEAM 1
After going through the check-out procedure in the classroom, don your air-purifying respirator.
Each group of partners is issued two radios on matched frequencies. Partners numbered 1 leave the
classroom with a radio; partners numbered 2 remain in the classroom with a radio. The teams take
turns transmitting the following messages (Team 1 members transmit first). The teams write the
messages they receive in the blank spaces. Repeat or verify messages as necessary.
1. "ARE YOU RECEIVING MY TRANSMISSION?"
2. "FOUND ONE DRUM OF ACETONE."
3. "THE PINT BOTTLES CONTAIN A BLUE LIQUID."
4. "26 BOTTLES, 16 DRUMS, 60 VIALS, 70 BOXES."
5. "THE CHEMICAL IS TOLUENE DIISOCYANATE. YOUR TURN TO
TRANSMIT."
6.
7.
8.
9.
10.
11. "A BARREL CONTAINING CALCIUM HYPOCHLORITE."
12. "THE PLACARD IS RED WITH THE NUMBER 1203."
13. "THE CGI READS 10% AND THE 02 IS 20.5%."
14. "THE HNU IS READING 15."
15. "THE SHIPPER'S ADDRESS IS 22 TWAIN, CHATTANOOGA, TENNESSEE.
YOUR TURN TO TRANSMIT."
16.
17.
18.
19.
20.
6/93 APR-1 Handout
-------
APR COMMUNICATIONS EXERCISE: TEAM 2
After going through the check-out procedure in the classroom, don your air-purifying respirator.
Each group of partners is issued two radios on matched frequencies. Partners numbered 1 leave the
classroom with a radio; partners numbered 2 remain in the classroom with a radio. The teams take
turns transmitting the following messages (Team 1 members transmit first). The teams write the
messages they receive in the blank spaces. Repeat or verify messages as necessary.
1.
2.
3.
4.
5.
6. "THIS DRUM CONTAINS A SOLID MATERIAL."
7. "THE CHEMICAL IS LISTED AS A CARCINOGEN, A TERATOGEN, AND A
MUTAGEN."
8. "I GET A pH OF 1."
9. "THE WALKWAY LOOKS UNSTABLE."
10. "THERE ARE TWO CHEMICALS: TOLUENE AND METHYL ETHYL
KETONE." YOUR TURN TO TRANSMIT."
11.
12.
13.
14.
15.
16. "THE OVA IS READING 100."
17. "WE HAVE A RADIATION READING OF 200 micro/R."
18. "MY MASK IS FOGGING UP."
19. "THEY SAY THE ROAD IS COVERED WITH DEAD OXEN.1
20. "COME BACK TO THE CLASSROOM. "
6193 APR-2 Handout
-------
SELF-CONTAINED BREATHING APPARATUS
I. OBJECTIVE
Given an MSA self-contained breathing apparatus (SCBA) unit, the student will be able to
conduct a regular SCBA inspection and check-out.
II. PROCEDURE
A. The instructor will review monthly SCBA inspection procedures and demonstrate the
regular SCBA inspection and check-out procedures for the class.
B. Using the following instructions, each student will perform a regular SCBA check-
out. Students should repeat the check-out until they have successfully completed the
checkout.
6/93 25 Self-Contained Breathing Apparatus
-------
MONTHLY SCBA INSPECTION
1. Check cylinder label for current hydrostatic test date.
2. Inspect cylinder for large dents or gouges in metal or fiberglass.
3. Inspect cylinder gauge for damage.
4. Perform a complete SCBA checkout.
5. Fill out appropriate records with results and recommendations.
REGULAR SCBA CHECK-OUT PROCEDURES
Preliminary Checks
1. High-pressure hose connector is tight on cylinder fitting.
2. By-pass valve is closed.
3. Mainline valve is closed.
4. Regulator outlet is not covered or obstructed.
Backpack/Harness Assembly
1. Inspect straps for wear, damage, and completeness.
2. Inspect buckle for wear and proper functioning.
3. Inspect backplate for damage and proper fastening to cylinder.
Cylinder and High Pressure Hose Assembly
1. Check cylinder to ensure that it is firmly fastened to backplate.
2. Open cylinder valve. Listen or feel for leakage around packing and hose
connection.
3. Check high pressure hose assembly for damage or leaks.
Self-Contained Breathing Apparatus 26 6/93
-------
Regulator
1. Cover regulator outlet with palm of hand.
2. Open mainline valve.
3. Note stoppage of air flow after positive pressure builds.
4. Close mainline valve.
5. Remove hand from regulator outlet.
6. Open by-pass valve slowly to assure proper function.
7. Close by-pass valve.
8. Cover regulator outlet again with palm of hand.
9. Open mainline valve.
10. Note pressure reading on regulator gauge.
11. Close cylinder valve while keeping hand over regulator outlet.
12. Slowly move hand on the outlet to allow air to flow slowly.
13. Note pressure when low-pressure warning alarm sounds; it should read
between 550-650 psi.
14. Remove hand from regulator outlet.
15. Close mainline valve.
6/93 27 Self-Contained Breathing Apparatus
-------
Facepiece and Breathing Tube
1. Inspect head harness and facepiece for damage, serrations, and deteriorated
rubber.
2. Inspect lens for damage and proper seal in facepiece.
3. Inspect exhalation valve for damage and dirt build-up.
4. Stretch breathing tube and inspect for holes and deterioration.
5. Inspect connector for damage and presence of washer.
6. Perform negative pressure test with facepiece donned.
Storage ofSCBA Unit
1. Fully extend all straps.
2. Close cylinder valve.
3. Bleed pressure from high pressure hose by opening mainline valve.
4. Disconnect high pressure hose from cylinder.
5. Remove empty cylinder and replace with a full cylinder (approximately
1500 psi).
6. Reconnect high pressure hose to cylinder.
7. Close by-pass valve.
8. Close mainline valve.
9. Store facepiece and breathing tube.
Self-Contained Breathing Apparatus 28 6/93
-------
Emergency Hand Signals
1. Hand Gripping Throat:
"Out of air, can't breathe!"
2. Gripping partner's wrist or placing both hands around waist:
"Leave area immediately, no debating!"
3. Hands on top of head:
"Need assistance."
4. Thumbs up:
"Yes," "affirmative," "I understand."
5. Thumbs down:
"No," "negative," "I do not understand.
6/93 29 Self-Contained Breathing Apparatus
-------
NOTES
Self-Contained Breathing Apparatus 30 6/93
-------
RADIATION SURVEY INSTRUMENTS
I. OBJECTIVE
This exercise familiarizes students with the operation of radiation survey instruments.
Students will operate instruments under controlled conditions to determine the type of
radiation being emitted, interpret instrument readings, and learn radiation survey techniques.
II. INSTRUMENT OPERATING PROCEDURES
A wide variety of monitoring instruments are available for radiation surveys. Although each
instrument is unique in its uses and limitations, in general, many features are common to all
instruments. Therefore, familiarity with the operation of one instrument should transfer over
to other instruments.
This exercise features a Ludlum Model 19 Micro R Meter. The instrument uses an internally
mounted, 1 inch x 1 inch Nal(Tl) scintillator.
Model 19 Controls
The following controls are essential to operation of the Model 19:
• "AUDIO ON-OFF" Toggle Switch: In the ON position, operates the unimorph
speaker, located on the left side of the instrument. The frequency of the clicks is
relative to the rate of the incoming pulses. The higher the rate is, the higher the
audio frequency. The audio should be turned OFF when not required to reduce
battery drain.
• "F/S": Fast-Slow Toggle Switch provides meter response. Selecting the "F"
position of the toggle switch provides 90% of full scale meter deflection in 3 seconds.
In "S" position, 90% of full scale meter deflection takes 11 seconds. In "F" position,
there is fast response and large meter deviation. "S" position should be used for
slow response and damped, meter deviation.
"BAT" : BATTERY Pushbutton Switch, when depressed, indicates the battery charge
status on the meter. The range selector switch must be out of the OFF position.
"RES" Button: when depressed, provides a rapid means to drive the meter to zero.
"L": Light Pushbutton Switch, when depressed, lights the meter face.
"Range Selector Switch" is a six-position switch marked OFF, 5000, 500, 250, 50,
and 25. Moving the range selector switch to one of the range positions provides the
operator with an overall range of 0-5000 micro R/hr.
31 Radiation Survey Instruments
•
-------
The meter face is made up of two scales, 0-50 and 0-25, plus battery test. The 0-50
scale corresponds to the 50, 500, and 5000 positions on the range selector switch.
The 0-25 scale corresponds to the 25 and 250 positions on the range selector switch.
Note that range positions 5000, 500, and 50 are printed in black and correspond to
the meter scale, printed in black. The range positions 250 and 25 are printed in red
and correspond to the meter scale, printed in red.
Ludlum Model 19 Operation
1. Range Selector Switch: Select the 0-5000 range.
2. BAT TEST Button: Depress. Check the BAT test on the appropriate scale. Replace
the batteries if the meter pointer is below the battery CHK line.
3. Light Button: Depress. Check for light on the meter face.
4. Meter Response Switch: Check the response in the "F" and "S" positions.
i
5. Audio ON-OFF Switch: Check for audio indication.
6. Check the instrument for the proper scale indication with a known source. Check all
the ranges for the appropriate scale indication.
7. Reset Button: Depress. Check to see that the meter pointer returns to the zero
position.
8. The instrument is ready for monitoring.
9. During monitoring, use the lowest range scale that will still provide an on-scale
reading.
10. Please remember that the Model 19 gives readings in micro-Roentgens (micro R)
1000 micro R = 1 milli R.
Radiation Survey Instruments 32
6/93
-------
III. EXERCISE PROCEDURES
A. Using the Model 19, perform the requested operations at the following stations.
Record results on the following answer sheet.
Station 1: Record a background reading for the room.
Station 2: Measure the exposure rate due to the source at the three distances, as
marked.
Station 3: Screen the "samples" for the presence of radiation and record the
reading for radiation present (if any).
Station 4: Locate the "contamination" and record reading.
6193
33
Radiation Survey Instruments
-------
ANSWER SHEET
Serial Number:
Station 1: Background micro R/HR
Station!: Source micro R/HR
1 foot (30.5 cm) micro R/HR
2 feet (61 cm) micro R/HR
Station 3: Radioactive Sample(s) (letter)
Reading at surface of container micro R/HR
Station 4: Location of contamination:
Answer the following:
1. How does distance between the source of radiation and probe affect the reading?
2. If an instrument indicates an exposure of 50 mR/hr and a person worked in that area for 5
hours, what would be the total exposure?
3. Differentiate radiation monitoring procedures for unknown versus known situations.
4. What type of protection is adequate to perform a survey at a site that may have radioactive
materials7
Radiation Survey Instruments 34 5/03
-------
LEVEL B DRESSOUT
I. OBJECTIVE
In this exercise, students will don and doff level B protection and operate air monitoring in
a drum sampling exercise.
II. PROCEDURE
A. Level B dressout will be demonstrated.
B. Don level B.
1. Gather rain suit, gloves (inner gloves and outer gloves), boots, hard hat and
SCBA.
2. Inspect and check out SCBA.
3. Put on rain suit.
4. Put on boots.
5. Put on SCBA (with a buddy's assistance).
6. Put on SCBA facepiece (with breathing tube connected).
7. Put on gloves (when taping, tuck glove inside sleeve and tape sleeve to glove
leaving a pull tab).
8. When instructed, connect breathing tube to SCBA regulator outlet and go on
air.
C. When instructed, use air monitoring instruments to sample drums and write down
results.
6/93 35
Level B Dressout
-------
D. Doff level B protection.
1. Remove outer gloves (remove tape if used).
2. Remove hard hat and boots.
3. Remove SCBA.
4. Remove rain suit.
5. Remove facepiece.
6. Remove inner gloves.
7. Store SCBA.
Level B Dressout
35
-------
INSTRUMENT
Sampling Results
CONCENTRATION
MIXTURE
Combustible Gas Indicator
Oxygen Indicator
< LEL
LEL to UEL
> LEL
Colorimetric Indicator
Tubes and Pumps
Acetone
Alcohol
Toluene
HNU (Span = 9.8)
6/93
37
Level B Dressout
-------
NOTES
Level B Dressout 38
-------
LEVEL A DRESSOUT
I. OBJECTIVE
Following the level A demonstration, students will don and doff level A protection. Students
will perform tasks and activities while dressed in level A in order to experience the physical
limitations associated with wearing level A protection.
II. PROCEDURE
A. Collect and lay out level A protective equipment:
1. SCBA
2. Fully encapsulating suit
3. Three pairs of gloves
• inner gloves
• suit gloves
• outer (line man's gloves) gloves
4. Boots
B. Wipe the inside and outside of the SCBA facepiece lens and the inside of the suit lens
with anti-fog solution.
C. Follow the level A donning procedures as demonstrated (see following procedures).
D. Follow instructions for specific tasks and activities to be performed.
E. After completing the exercise, doff equipment and properly store it (see following
procedures).
39 Level A Dressout
-------
Donning Level A
Prior to wearing a fully encapsulating suit, inspect it thoroughly for damage and potential
malfunction.
1. While sitting, step into legs, place feet properly, and gather suit around waist.
2. Put on steel toe/shank boots over feet of suit.
3. Put on disposable boot covers (optional).
4. Don SCBA with assistance of partner.
5. Don SCBA facepiece and perform negative pressure check.
6. Put on hard hat if one is to be worn with suit. If suit has built-in headband or hard
hat see step 10.
7. Put on inner gloves.
8. Put arms into sleeves of suit.
9. Pull suit up and over SCBA, placing hood on top of air cylinder.
10. Adjust headband of suit or of hard hat if suit in suit by reaching up inside suit behind
head or having partner adjust it (this adjustment may be made prior to donning the
suit).
11. Put on outer gloves.
12. Place hood on head.
13. Connect breathing tube to regulator.
14. Secure suit by closing all fasteners.
Level A Dressout 40 0703
-------
Doffing Level A
During removal, protect wearer's air supply and prevent transfer of contaminants from suit
to wearer.
1. Remove disposable outer clothing such as gloves, boot covers, etc.
2. Remove boots.
3. Open suit.
4. Raise hood over head and place on air cylinder.
5. Remove arms from suit (one at a time).
6. Lower suit to waist.
7. While sitting (preferably) remove both legs from suit.
8. Remove SCBA.
9. Roll off inner gloves.
10. Store SCBA.
11. Dry suit, properly fold, and store.
5/pj 41 Level A Dressout
-------
NOTES
Level A Dressout 42
-------
DECONTAMINATION
I. OBJECTIVE
In this exercise, personnel decontamination methods and techniques are demonstrated and
practiced. Students gain practical experience in setting up decontamination lines and
practicing decontamination procedures.
II. PROCEDURE
A. The instructor gives a brief review of the decontamination procedure for Levels B
and C protection.
B. The instructor divides students into two groups: Level B Decontamination and Level
C Decontamination. One volunteer from each group dons Level B" or Level Cb
protection as appropriate for their respective group.
C. Students construct a decontamination line applicable for the assigned level of
protection and scenario given by the instructor. Decontamination equipment provided
for each group includes:
• 3 wash tubs • 7 garbage cans
• 6 Hudson sprayers • 2 buckets
• 6 brushes • 3 sponges
• 6 step stools
D. Justify any decisions to add, combine, or eliminate steps or procedures. A set of
decontamination equipment will be made available to each subgroup in the exercise
area.
E. Don appropriate level of protection (i.e., PVC splash gear and air-purifying
respirators [APRs]) and decontaminate the volunteer entering the line from the
"Exclusion Zone."
F. Discuss each group's decontamination line.
G. Disassemble the decontamination lines and properly store the equipment.
Level B equipment: SCBA, two-piece splash suit, inner gloves, outer gloves, boots,
disposable boot covers, hard hat, and taped joints at outer gloves and boots.
Level C equipment: full-face APR, two-piece splash suit, inner gloves, outer gloves, boots,
disposable boot covers, hard hat, and taped joints at outer gloves and boots.
5/93 43 Decontamination
-------
MAXIMUM DECONTAMINATION LAYOUT FOR LEVEL A PROTECTION
EXCLUSION
ZONE
Tap* Removal
Segregated
Boot Cov.r & Equlpm.nl
Clove Wash Drop
Tank Chang*
and Redress -
Boot Cover/
Outer Cloves
CONTAMINATION
REDUCTION
ZONE
Boot Cov*r &
Clove Rlns*
Fully Encapsulating Suit
and Hard Hat Removal
Field
Wash
Redress
CONTAMINATION
CONTROL LINE
SUPPORT ZONE
Source: U.S. EPA. 1992. Standard Operating Safer* Guides. Publication No. 9285.1-03. U.S.
Environmental Protection Agency, Washington, DC. p. 167.
Decontamination
44
6/93
-------
MINIMUM DECONTAMINATION LAYOUT FOR LEVELS A & B PROTECTION
EXCLUSION
ZONE
Plastic
Sheet
Equipment
Drop
Decon Outer
Garments
Remove
Boot Covers
& Outer Gloves
Decon
Solution
Mr "»r'
HOTLINE
Remove Boots.
Gloves and Outer
Garments (for
disposal and
off-site
decontamination)
{CONTAMINATION
REDUCTION
ZONE
i
•*•-••••••••••* • • 9^
»••»•••••»••*•» */
.....*...*»* - * - */
xSxixSixxXiX \
• ••••* ••••••••* • \
.*A... ..*->***- -V
. . •»»•_•• ••••_•_•. *-^*
ixxXiX SUPPORT ZONE >-:-:-x-x-:::xi:
LA * • *
> * * • '
' •' i
\ /
A
Wind
Direction
Source: U.S. EPA. 1992. Standard Operating Safety Guides. Publication No. 9285.1-03. U.S.
Environmental Protection Agency, Washington, DC. p. 169.
6/93
45
Decontamination
-------
MAXIMUM DECONTAMINATION LAYOUT FOR LEVEL B PROTECTION
EXCLUSION
ZONE
Tape Removal
Segregated
Boot Cover & Equipment
Glove Wash
Drop
Tink Change
and Redreee -
Boot Cover/
Outer Gloves
CONTAMINATION
REDUCTION
ZONE
Field
Wash
Redreee
CONTAMINATION
CONTROL LINE
SUPPORT ZONE
Source: U.S. EPA. 1992. Standard Operating Safety Guides. Publication No. 9285.1-03. U.S.
Environmental Protection Agency, Washington, DC. p. 171.
Decontamination
46
6/93
-------
MAXIMUM DECONTAMINATION LAYOUT FOR LEVEL C PROTECTION
EXCLUSION
ZONE
Tip* Removal
Beet Cover &
Qlove Waah
Segregated
Equlpmant
Drop
Outer Glova
Ramoval
i
k Chang* _
i
/•
J
Boot Covar
Ramoval
p
TV Sult/Safaty
_J Boot Waah
Boot Covar ft
Qlova Rlnaa
and Radraaa -
Boot Covar/
Outar Qlovaa
11
Sult/SCBA/Boot
/Qlova Rlnaa
Salaty Boot
Ramoval
Splash Suit
Ramoval
HOTLINE
CONTAMINATION
REDUCTION
ZONE
Innar Qlov*
Waah
Innar Olova
Rlnaa
Fae* Plaea
Ramoval
15\ Innar Qlova
Ramoval
,6\ Innar Clothing
Ramoval
nald
Waah
18 Radraaa
CONTAMINATION
1 CONTROL LINE
SUPPORT ZONE
Source: U.S. EPA. 1992. Standard Operating Saferv Guides. Publication No. 9285.1-03. U.S.
Environmental Protection Agency, Washington, DC. p. 175.
6/93
47
Decontamination
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NOTES
Decontamination 48 6/93
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SITE SAFETY AND WORK PLAN DEVELOPMENT
I. OBJECTIVE
Students will plan and develop a site safety plan and work plan for the given exercise
scenario.
II. PROCEDURE
A. Given the exercise scenario, each team of students will plan and develop a site safety
plan using the following generic site safety plan.
B. Each team submits one site safety plan and work plan to the instructor for review
before implementation.
6/93 49 Site Safety and Work Plan Development
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Generic Site Safety Plan'
SITE DESCRIPTION
Date Location
Hazards
Area affected
Surrounding population
Topography
Weather conditions
Additional information
ENTRY OBJECTIVES (actions, tasks to be accomplished, etc.)
ONSITE ORGANIZATION/COORDINATION
Team Leader
Scientific Advisor
Site Safety Officer
Public Info. Officer
Security Officer
Recordkeeper
Financial Officer
Field Team Leader
Field Team Members
Generic site safety plan based on a plan developed from the U.S. Coast Guard. It is not all inclusive and should
only be used as a guide, not a standard. From Occupational Safety and Health Guidance Manual for Hazardous
Waste Site Activities, NIOSH/OSHA/USCG/EPA, U.S. Department of Health and Human Services, Public Health
Service, Centers for Disease Control, National Institute for Occupational Safety and Health, October 1985.
Site Safety and Work Plan Development 50 6/93
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Generic Site Safety Plan
ONSITE ORGANIZATION/COORDINATION (continued)
Federal agency representatives __
State agency representatives
Local agency representatives
Contractors)
ONSITE CONTROL
has been designated to coordinate access control and security onsite. A safe
perimeter has been established at (distance and description of controlled areas)
.. No authorized person should be within this area.
The onsite Command Post and staging area have been established at.
The prevailing wind conditions are . This location is upwind from the
Exclusion Zone.
Control boundaries have been established, and the Exclusion Zone, hot line, Contamination Reduction Zone, and
Support Zone have been identified and designated as follows:
These boundaries are identified by: (marking of zones fe.g.. red boundary tape - hot line: traffic cones - Support
Zone!)
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Generic Site Safety Plan
HAZARD EVALUATION
Hazards known or suspected to be onsite. The primary hazards of each are identified.
Substances Involved Concentrations (if known) Primary Hazard (e.g., toxic, inhalation)
Additional hazards found onsite include: (e.g.. slippery ground, uneven terrain)
Hazardous substance information form(s) for the involved substance(s) have been completed and are attached.
PERSONAL PROTECTIVE EQUIPMENT
Based on the evaluation of potential hazards, the following levels of personal protection have been designated for
the applicable work areas or tasks:
Work Area/Zone
Job Function/Task
Level of Protection
A B C D Other
A B C D Other
A B C D Other
A B C D Other
A B C D Other
A B C D Other
Specific protective equipment for each level of protection is as follows:
Level A Level C
Level B
Level D
Other:
Site Safety and Work Plan Development
52
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Generic Site Safety Plan
PERSONAL PROTECTIVE EQUIPMENT (continued)
The following protective clothing materials are required for the involved substances:
Substance Material Type (i.e., PVC, Viton)
If air-purifying respirators are used, (filter type) , is the appropriate
canister for use with the involved substances and concentrations. A competent individual has determined that all
criteria for using this type of respiratory protection have been met.
NO CHANGES TO THE SPECIFIED LEVELS OF PROTECTION SHALL BE MADE WITHOUT THE
APPROVAL OF THE SITE SAFETY OFFICER AND THE TEAM LEADER.
ONSITE WORK PLANS
Work parties consisting of persons will perform the following tasks:
Project Team Leader (name) (function)
Work Party #1
Work Party #2
Rescue Team
Decon. Team
The work parties were briefed on the contents of this plan at.
6/93 53 Site Safety and Work Plan Development
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Generic Site Safety Plan
COMMUNICATION PROCEDURES
Channel has been designated as the radio frequency for personnel in the exclusion zone. All other
onsite communications will use channel .
Personnel in the Exclusion Zone should remain in constant radio communication or within site of the Project Team
Leader. Any failure of radio communication requires an evaluation of whether personnel should leave the Exclusion
Zone.
is the emergency signal to indicate that all personnel should leave the Exclusion
Zone.
The following standard hand signals will be used in case of failure of radio communications:
- hand gripping throat: "Out of air, can't breathe"
- gripping partner's wrist or
both hands around waist: "Leave area immediately"
- hands on top of head: "Need assistance"
- thumbs up: "OK, I am alright, I understand"
- thumbs down: "No, negative"
Telephone communication to the Command Post should be established as soon as possible. The phone number is
DECONTAMINATION PROCEDURES
Personnel and equipment leaving the Exclusion Zone shall be thoroughly decontaminated. The standard level
decontamination protocol shall be used with the following decontamination stations:
I. 5. 9.
2. 6. 10.
3. 7. Other
4. 8.
Emergency decontamination will include the following stations:
The following decontamination equipment is required:
(Detergent & water, etc.) will be used as the
decontamination solution.
Site Safety and Work Plan Development 54 6/93
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Generic Site Safety Plan
SITE SAFETY AND HEALTH PLAN
Site Safety Officer
is the designated Site Safety Officer and is directly responsible
to the Project Team Leader for safety recommendations onsite.
Emergency Medical Care
(Names of qualified personnel) are the qualified EMTs onsite.
(Medical facility, address, and telephone number) __
is located within minutes of this location, (name of person')
was contacted at (time) and briefed on the situation, the potential hazards, and the substances
involved. A map of alternative routes to this medical facility is available at (command post, etc.)
First aid equipment is available onsite at the following locations:
Equipment Location
(i.e., first-aid kit, emergency eye wash, shower)
Emergency medical information for substance present:
Substance Exposure Symptoms First-Aid Instructions
List of Emergency Phone Numbers:
Police
Fire
Hospital
Airport
Public Health Advisor
6/93 55 Site Safety and Work Plan Development
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Generic Site Safety Plan
SITE SAFETY AND HEALTH PLAN (continued)
Environmental Monitoring
The following monitoring instruments shall be used onsite at the specified intervals:
Combustible Gas Indicator continuously/hourly/daily/other
Oxygen Meters continuously/hourly/daily/other
HNU/OVA continuously/hourly/daily/other
Colorimetric Tubes (type) continuously/hourly/daily/other
Other
continuously/hourly/daily/other
continuously/hourly/daily/other
Emergency Procedures (modified as required for site)
The following standard procedures will be used by onsite personnel. The Site Safety Officer shall be notified of
any onsite emergencies and shall be responsible for ensuring that the appropriate procedures are followed.
Personnel Injury in the Exclusion Zone: Upon notification of an injury in the Exclusion Zone, the designated
emergency signal shall be sounded. AH site personnel shall assemble at
the decontamination line. The rescue team will enter the Exclusion Zone (if required) to remove the injured person
to the hot line. The Site Safety Officer and Project Team Leader should evaluated the nature of the injury and the
affected person should be decontaminated to the extent possible prior to movement to the Support Zone. The onsite
EMT shall initiate the appropriate first aid, and contact should be made with an ambulance and the designated
medical facility. No persons shall reenter the Exclusion Zone until the cause of the injury (or symptoms) is
determined.
Personnel Injury in the Support Zone: Upon notification of an injury in the Support Zone, the Project Team Leader
and Site Safety Officer will assess the nature of the injury. If the cause of the injury or loss of the injured person
does not affect the performance of site personnel, operations may continue, with the onsite EMT initiating the
appropriate first aid and necessary follow-up as slated above. If the injury increases the risk to others, the
designated emergence signal shall be sounded and all site personnel shall
move to the decontamination line for further instructions. Onsite activities will stop until the added nsk is removed
or minimized.
Fire/Explosion: Upon notification of a fire or explosion onsite, the designated emergency signal
shall be sounded and all site personnel assembled at the decontamination line. The
fire department shall be alerted and all personnel moved to safe distance from the involved area.
Personal Protective Equipment Failure: If any site worker experiences a failure or alteration of protective equipment
that affects the protection factor, that person and his/her buddy shall immediately leave the Exclusion Zone.
Reentry shall not be permitted until the equipment has been repaired or replaced.
Site Safety and Work Plan Development 56 6/93
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Generic Site Safety Plan
SITE SAFETY AND HEALTH PLAN (continued)
Other Equipment Failure: If any other equipment onsite fails to operate properly, the Project Team Leader and Site
Safety Officer shall be notified and then determine the effect of this failure on continuing operations onsite. If the
failure affects the safety of personnel or prevents completion of the Work Plan tasks, all personnel shall leave the
Exclusion Zone until the situation is evaluated and appropriate actions taken.
The following emergency escape routes are designated for use in those situations where escape from the Exclusion
Zone cannot occur through the decontamination line: (describe alternate routes for evacuation)
In all situations, when an onsite emergency results in evacuation of the Exclusion Zone, personnel shall not reenter
until:
1. The conditions resulting in the emergency have been corrected.
2. The hazards have been reassessed.
3. The Site Safety Plan has been reviewed.
4. Site Personnel have been briefed on any changes in the Site Safety Plan.
Personal Monitoring
The following personal monitoring will be in effect onsite:
Personal exposure sampling: (use of personal sampling pumps, air monitors etc.. worn by personnel to monitor
exposure)
Medical momtonng: The expected air temperature will be *F. If it is determined that heat stress monitoring
is required (mandatory if over 70'F), the following procedures shall be followed:
All site personnel have read the above plan and are familiar with its provisions.
(name) (signature)
Site Safety Officer
Project Team Leader
Other Site Personnel
6/93 57 Site Safety and Work Plan Development
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NOTES
Site Safety and Work Plan Development 58 6/93
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APPENDIX A
Abandoned Warehouse Scenario
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HAZARDOUS MATERIALS INCIDENT RESPONSE OPERATIONS
Abandoned Warehouse Scenario
Five days ago, police received a report that drums of chemicals were found at a vacant warehouse.
Two children discovered the drums while playing inside an abandoned, unsecured warehouse.
The police department informed the fire department of the situation. The fire department
investigated the scene. They discovered about 40 drums in the old warehouse. During their
investigation, they did not find any leaking containers and did not detect combustible levels of gases
or vapors while using their combustible gas indicator. The fire department determined that there was
no emergency or threat of fire. Thus, further investigation has been turned over to your team, the
Toxic Waste Investigation Team.
The owner of the building, a land developer, stated that he had no knowledge of the drums prior to
this time. The building has been abandoned for 10 years. He said he wants any information that
you can provide concerning this situation. He also said that a blueprint of the building is not
available. He knows that all of the utilities were disconnected in the warehouse.
The police department stated that they will provide security if it becomes an emergency situation.
They will assist in evacuating nearby residents and will control nearby traffic if needed. (If police
assistance is requested, they will be controlling the outside of the area; therefore, you will not see
them.)
The fire department will provide emergency medical service and will be on stand-by in the event of
fire. They will not be present at the warehouse during the investigation, so they must be called if
their assistance is needed. (If they are called to assist, simply note them as being present.)
The fire department produced a rough map (from memory) and wrote a list of information that they
could read from the drum labels in the warehouse. This is the only information that they have.
6/93 A-l Handout
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Warehouse Information Noted by Fire Department
At least one drum of each of the following chemicals was noted in the warehouse:
Toluene
Methylene chloride
Sodium hydroxide
Acetone
Amyl alcohol
Butyl alcohol
Isopropyl alcohol
Ammonium hydroxide
Muriatic acid
Aluminum arsenide
Calcium hydrochloride
Parking Lot
L
Drums
11 i 11
Drums
Handout
A-2
6/93
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APPENDIX B
Superfund Site Scenario (Road)
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HAZARDOUS MATERIALS INCIDENT RESPONSE OPERATIONS
Superfund Site Scenario (Road)
The city police department has requested that you, the state's Toxic Waste Investigation Team,
investigate a suspect illegal waste site. The site was reported to the police by Mr. Edward Haney,
a real estate appraiser who found several drums while conducting a property appraisal. Mr. Haney
reported to the police that he felt physically ill and went to an emergency room after leaving the
property. He reported that his eyes and skin felt irritated and that he felt nauseous and short of
breath.
The objectives of the Toxic Waste Investigation Team are:
1. Characterize the site, using air monitoring instruments, to determine whether any
harmful concentrations are present.
2. Identify the contents of the drums and determine what hazards they may pose to
people who live or work in the immediate area.
3. Provide a recommendation on how the site should be remediated.
Mr. Haney wants to know what's on that property!
GROUND RULES
1. Instrument readings will be provided by the instructor accompanying the entry team. The
entry team members will be expected to calibrate and operate the instruments in the proper
manner.
2. No entries into the site will be allowed without an instructor accompanying the entry team.
3. The instructors will be "invisible," but will answer justifiable questions.
4. Mock telephone calls may be made through an available instructor. All telephone calls
should be logged, listing the time the call was made and the information that was obtained.
5. Nothing may be simulated without the approval of an instructor. Simulations should be
recorded in the logbook.
6. Security and other team members should refrain from using any actions of a physical nature.
7. Any additional equipment may be requested through an instructor. The instructor will
determine whether the equipment will be made available to the team.
6/93 B-l *U'S- G.P.O.:1993-341-932:82680 Handout
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