United States
Environmental Protection
Agency
Office of
Solid Waste and
Emergency Response
9285.9-14B
EPA/540/R-95/067
PB95-963244
Superfund
vvEPA HAZARDOUS MATERIALS
INCIDENT RESPONSE OPERATIONS
-------
9285.9-14B
EPA540/R-95/067
PB95-963244
FOREWORD
This manual is for reference use of participants 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 discussion among the participants and the instructional staff.
Individual instructors may provide additional materials 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 improving content and format of the manual are welcome.
i
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HAZARDOUS MATERIALS INCIDENT RESPONSE OPERATIONS
(165.5)
This course is designed for personnel involved with the investigation and remediation of uncontrolled
hazardous waste sites and, to a lesser extent, response to an accident involving 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 or response
personnel.
Discuss regulations and action levels to ensure health and safety of the workers.
Discuss fundamentals needed to develop organizational structure and standard
operating procedures.
Select and use dermal and respiratory protective equipment.
Demonstrate the use, calibration, and limitations of direct-reading air monitoring
instruments.
After completing this course, participants will be more knowledgeable in hazardous waste operations,
team functions, personnel health and safety procedures, and operation of field monitoring equipment.
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Emergency and Remedial Response
Environmental Response Team
-------
CONTENTS
SECTION 1
SECTION 2
SECTION 3
SECTION 4
SECTION 5
Acronyms and Abbreviations
Day 1 Standard Orientation and Introduction
Introduction to 29 CFR 1910.120
Hazard Recognition
Air Monitoring Instruments I
Air Monitoring Instruments II
Day 2
Day 3
Toxicology and Exposure Guidelines
Respiratory Protection: Air-Purifying Respirators
Respiratory Protection: Supplied-Air Respirators
Levels of Protection and Chemical Protective Clothing
Site Entry and Reconnaissance
Radiation Survey Instruments
Decontamination
Day 4
Appendix A
Appendix B
Appendix C
Appendix D
Response Organization
29 CFR 1910.120 - Hazardous Waste
Operations and Emergency Response
Warning Concentrations of Various Chemicals
Hazardous Materials Identification Systems
Glossary and Bibliography
9/95
v
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ACGIH
AIHA
ANSI
APF
APR
ASR
ASTM
BEIs
BOD
Btu
C
CAG
CDC
CERCLA
CFR
CGI
CHEMTREC
CHRIS
CMA
CPC
CPE
CPM
CRC
9/95
ACRONYMS AND ABBREVIATIONS
American Conference of Governmental Industrial Hygienists
American Industrial Hygiene Association
American National Standards Institute
assigned protection factor
air-purifying respirator
atmosphere-supplying respirator
American Society for Testing and Materials
biological exposure indices
biological oxygen demand
British thermal unit
ceiling
Carcinogen Assessment Group
Centers for Disease Control
Comprehensive Environmental Response, Compensation and Liability Act
Code of Federal Regulations
combustible gas indicator
Chemical Transportation Emergency Center
Chemical Hazard Response Information System
Chemical Manufacturers' Association
chemical protective clothing
chlorinated polyethylene
counts per minute
(CRC Press) publisher of scientific reference books
1 Acronyms and Abbreviations
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CRP
community relations plan
DDT
dichlorodiphenyltrichloroethane
DECON
decontamination
DFM
diesel fuel marine
DHHS
U.S. Department of Health and Human Services
DOD
U.S. Department of Defense
DOI
U.S. Department of the Interior
DOL
U.S. Department of Labor
DOT
U.S. Department of Transportation
DRI
direct-reading instruments
EL
exposure limit
EPA
U.S. Environmental Protection Agency
ERT
Environmental Response Team
eV
electron volt
FEMA
Federal Emergency Management Agency
FES
fully encapsulating suit
FID
flame ionization detector
FM
Factory Mutual
GC
gas chromatograph or gas chromatography
GFCI
ground fault circuit interrupter
HASP
health and safety plan
HazCom
. federal hazard communications standard
HEPA
high efficiency particulate air filter
HMIS
Hazardous Materials Identification System
Acronyms and Abbreviations
2
9/95
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IDLH
immediately dangerous to life or health
IP
ionization potential
IR
infrared radiation
IUPAC
International Union of Pure and Applied Chemists
LCso
lethal concentration, 50%
LDjq
lethal dose, 50%
LQ.
lethal concentration lowest observed
LD^
lethal dose lowest observed
LEL
lower explosive limit
LFL
lower flammable limit
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
MSD
mass spectroscopy detector
MSDS
material safety data sheets
MSHA
Mine Safety and Health Administration
MUC
maximum use concentration
MUL
maximum use limits
NBR
nitrile-butadiene rubber (syn. Buna-N)
NCP
National Contingency Plan
NEC
National Electrical Code
9/95 3 Acronyms and Abbreviations
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NFPA National Fire Protection Association
NIOSH National Institute for Occupational Safety and Health
NOAA National Oceanic and Atmospheric Administration
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
PID photoionization detector
ppb parts per billion
PPE personal protective equipment
ppm parts per million
ppt parts per trillion
PVA polyvinyl alcohol
PVC polyvinyl chloride
Acronyms and Abbreviations
4
9/95
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QA/QC
Quality Assurance and Quality Control
RCRA
Resource Conservation and Recovery Act
REL
recommended exposure limits
RI/FS
remedial investigation/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
TC^,
toxic concentration, lowest observed
TCDD
tetrachlorodibenzo-p-dioxin
TCE
trichloroethylene
TD^
toxic dose, lowest observed
THR
toxic hazard rating
TLV
threshold limit value
TWA
time-weighted average
2,4,5-T
2,4,5-trichlorophenoxyacetic acid
UEL
upper explosive limit
9/95
5
Acronyms and Abbreviations
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UFL
upper flammable limit
UL
Underwriters Laboratories
UN
United Nations
USCG
U.S. Coast Guard
USGS
U.S. Geological Survey
WEEL
workplace environmental exposure levels
Acronyms and Abbreviations
6
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n?
CD
f)
C*
CJ
a
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Hazardous Materials Incident
Response Operations
(165.5)
Orientation and Introduction
Student Guide
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HAZARDOUS MATERIALS
INCIDENT RESPONSE
OPERATIONS
(165.5)
Presented by:
Halliburton NUS Corporation
EPA Contract No. 68-C2-0121
Orientation and Introduction
Agenda:
Environmental Response Training Program (ERTP) overview
Synopsis of ERTP courses
Course layout and agenda
Course materials
Facility information
Hazardous Matenats Incufont Response Operations
Orientation and Introduction
0/95
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Notes
Hazardout Materials Inodent Re*pcnta Operations 9/95
Onentation and introduction page 3
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ERTP OVERVIEW
Comprehensive Environmental Response, Compensation I
and Liability Act of 1980 I
(CERCLA) I
Superfund Amendments and Reauthorization Act of 1986
(SARA)
U.S. Environmental
(EF
Protection Agency
>A)
Environmental Response Training Program
(ERTP)
S-2
ERTP Overview
In 1980, the U S Congress passed the Comprehensive Environmental Response, Compensation and
Liability Act (CERCLA), also known as Superfund In 1986, the Superfund Amendments and
Reauthorization Act (SARA) was passed. This act reauthorized CERCLA. CERCLA provides for
liability, compensation, cleanup, and emergency response for hazardous substances released into the
environment and for the cleanup of inactive waste disposal sites. The U.S Environmental Protection
Agency (EPA) allocated a portion of Superfund money to training. EPA's Environmental Response Team
(ERT) developed the Environmental Response Training Program (ERTP) in response to the training
needs of individuals involved in Superfund activities.
Hazardous Material* Incident Response Operations
Onentation and Introduction
6/95
page 4
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Notes
Hazardous Materials Incident Response Operations e/05
Onentatton and Introduction .
page 5
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ERTP OVERVIEW
U.S. Environmental Protection Agency
(EPA)
Office of Solid Waste and Emergency Response 1
(OSWER) 1
Environmental F
(EF
Response Team 1
U) 1
Environmental Response Training Program
(ERTP)
S-3
ERTP Overview
ERTP is administered by ERT, which is part of the Office of Solid Waste and Emergency Response
(OSWER) ERT offices and training facilities are located in Cincinnati, Ohio, and Edison, New Jersey
ERT has contracted the development of ERTP courses to Halliburton NUS Corporation (EPA Contract
No. 68-C2-0121) The ERTP program provides education and training for environmental employees at
the federal, state, and local levels in all regions of the United States. Training courses cover areas such as
basic health and safety and more specialized topics such as air sampling and treatment technologies
Hazardous Materials Incident Response Operations
Onentabon and Introduction
9/95
paged
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Notes
Hazardous Materials Incident Response Operations e/95
Onentabon and Introduction
page 7
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Types of Credit Available
Continuing Education Units
(3.8 CEUs)
CEU Requirements
100% attendance at this course.
ฃ70% on the exam.
American Board of Industrial Hygiene
(4 5 Certification Maintenance [CM] points, ABIH approval #9630)
Hazardous Materials Incident Response Operation!
Orientation and Introduction
9/95
paged
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Notes
Hazardous Material# incident Response Operations
Onentabon and Introduction ฎ
paged
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ERTP Courses
S-4
S-5
S-6
S-7
Health and Safety Courses
Hazardous Materials Incident Response Operations (165.5)
Safety and Health Decision-Making for Managers (165.8)
Emergency Response to Hazardous Material Incidents (165.15)
Technical Courses
Treatment Technologies for Superfund (165.3)
Air Monitoring for Hazardous Materials (165.4)
Risk Assessment Guidance for Superfund (165.6)
Introduction to Groundwater Investigations (165.7)
Sampling for Hazardous Materials (165.9)
Radiation Safety at Superfund Sites (165.11)
Special Courses
Health and Safety Plan Workshop (165.12)
Design of Air Impact Assessments at Hazardous Waste Sites (165.16)
Removal Cost Management System (165.11)
Inland Oil Spills (165.18)
Courses Offered in Conjunction with Other EPA Offices
s Chemical Emergency Preparedness and Prevention Office (CEPPO)
Chemical Safety A udits (165.19)
S Site Assessment Branch
Preliminary Assessment
S-8 Site Investigation
Federal Facilities Preliminary Assessment/Site Investigation
Hazard Ranking System
Hazard Ranking System Documentation Record
Hazardous Matenats Incident Response Operations
Onentabon and Introduction
9/95
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Notes
Hazardous Materials Incident Response Operations 0/0S
Orientation and Introduction
page 11
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Course Goals
S-9
Identify methods and procedures for recognizing, evaluating, and
controlling hazardous substances.
Identify concepts, principles, and guidelines to properly protect site or
response personnel.
S-10
Discuss regulations and action levels to ensure health and safety of the
workers.
Discuss fundamentals needed to develop organizational structure and
standard operating procedures.
S-ll
Select and use dermal and respiratory protective equipment.
Demonstrate the use, calibration, and limitations of direct-reading air
monitoring instruments.
Hazardous Materials Incident Response Operations
Orientation and Introduction
9/95
P89612
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Notes
Hazardous Materials Incident Response Operations 0/96
Orientation and Introduction page
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Course Layout and Agenda
Key Points:
Agenda times are only approximate. Every effort is made to complete units, and to
finish the day, at the specified time.
Classes begin promptly at 8:00 am. Please arrive on time to minimize distractions to
fellow students.
Breaks are given between units.
Lunch is 1 hour.
Each student must take the examination given on Thursday.
Direct participation in field or laboratory exercises is optional. Roles are randomly
assigned to ensure fairness.
Attendance at each lecture and exercise is required in order to receive a certificate.
Hazardous Materials Incident Response Operations
Onentation and Introduction
9/95
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Notes
Hazardous Materials Incident Response Operations 9/95
Orientation and Introduction P&9*15
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CHEMICALS USED IN THIS COURSE
Toluene
Ammonia
Acetone
Alcohol
Methane
Isobutylene
Propane
Carbon dioxide
Hexane
Isoamyl acetate
S-12
A
For your safety, please speak with the Course Director regarding
any health concerns that may prohibit your direct participation in
exercises or labs involving use or close proximity to these
chemicals. Material Safety Data Sheets (MSDS) are available for
review.
Chemical Use and Health-Related Considerations
Using Air Monitoring Instruments I:
Using Air Monitoring Instruments II:
Air-Purifying Respirators:
SCBA Checkout:
Level B Dressout:
Level A Dressout:
Thursday and Friday Exercises:
(role dependent)
Methane, propane, toluene, carbon dioxide
Acetone, ammonia, alcohol, hexane, isobutylene,
toluene, methane
Must remove glasses; isoamyl acetate
Must remove glasses
Must remove glasses; acetone, toluene, alcohol,
wear light cotton sweats or coveralls
Wear light cotton sweats or coveralls; must remove
glasses
Must remove glasses; wear light cotton sweats or
coveralls
Hazardous Materials Incident Response Operations
Onentation and Introduction
9/65
page 16
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Notes
Hazardous Materials Incident Response Operations 9/05
Onentation and Introduction page 17
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Training Evaiuation
The Training Evaluation is a tool to collect valuable feedback from YOU
about this course.
We value YOUR comments!! Important modifications have been made to
this course based on comments of previous students.
DO DON'T
Write in your comments at the end of
each unit!
Tell us if you feel the content of the
course manual (and workbook) is clear
and complete!
Tell us if you feel the activities and
exercises were useful and helpful!
Tell us if you feel the course will help
you perform related duties back on the
job!
Complete the first page at the end of
the course before you leave!
Hold back!
Focus exclusively on the presentation
skills of the instructors.
Write your name on the evaluation, if
it will inhibit you from being direct
and honest.
Write comments in ink.
Hazardous Matenats Incident Response Opera Dons
Orientation and introduction
9/95
page 18
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Notes
Hazardous Materials Incident Response Operations QMS
Orientation and Introduction page 10
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Facility Information
Please put beepers in the vibrate mode and
turn off radios. Be courteous to fellow
students and minimize distractions.
Emergency
Telephone
Numbers
Emergency Exits
Alarms
Sirens
Hazardous Materials Incident Response Operations
Orientation and Introduction
0/05
P&06 2O
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Notes
Hazardous Matenats Incident Response Operations 0/05
Orientation and Introduction page 21
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INTRODUCTION TO
29 CFR 1910.120
STUDENT PERFORMANCE OBJECTIVES
At the conclusion of this unit, students will be able to:
1. List the types of hazardous waste site operations that this
regulation applies to
2. Identify which paragraphs of the regulation apply to each
type of hazardous waste site operation
3. Identify the paragraph of the regulation that requires their
attendance in this course
4. List at least 10 subject areas covered by the regulation.
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
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NOTES
INTRODUCTION TO
29 CFR 1910.120
Hazardous Waste Operations
and Emergency Response
paragraph (a);
Scope, application and definitions
Governmental body clean-up operations, (b)-(o)
RCRA corrective action clean-up operations,
(b) - (o)
Voluntary clean-up operations, (b)-(o)
TSD facility haz waste operations, (p)
Emergency response operations, (q)
3-2
-
paragraph (b);
Safety and health program
General requirements
Organizational structure
Comprehensive workplan
Site specific health and safety plan
S-3
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Introduction to 29 CFR 1910.120
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NOTES
paragraph (c);
Site characterization and analysis
< Preliminary evaluation
Hazard identification
Required information
Personal protective equipment
Monitoring
Risk identification
Employee notification
S-4
paragraph (d);
Site control
Written site control program
Minimum elements of site control program
SS
paragraph (e);
Training
General
Elements to be covered
Types and amount of training (i.e., initial,
supervisor, refresher, equivalent)
Employee certification/trainer qualification
S-6
Introduction to 29 CFR 1910.120
2
9/95
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NOTES
paragraph (f);
Medical surveillance
Employees who require medical surveillance
Frequency of examinations (uaoc,
Contents and cost of medical examinations
Information provided to the physician
Physician's written opinion
Recordkeeping requirements
paragraph (g); Engineering controls, work
practices and personal protective equipment
for employee protection
Hierarchy of controls ** l<
Objective Z.&xffltCfc'i
UcJiD, lerb.fyW'
paragraph (h);
Monitoring
Determine appropriate level of employee
protection
Types of monitoring
AO S
eft A-
9/95
S-9
Introduction tc
0^
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NOTES
paragraph (i);
Informational programs
Inform employees, contractors, subcontractors
(or their representatives)
Requirement under paragraph (b)
8-10
.i
paragraph 0);
Handling drums and containers
Procedures for handling, sampling, labeling,
transporting and disposing of hazardous
wastes, radioactive waste, shock-sensitive
waste, and laboratory waste packs
Tank and vault procedures
S-11
A
paragraph (k);
Decontamination
Procedures for decontamination of personnel
and equipment
Procedures for showers, change rooms,
commercial laundries and cleaning
establishmentsซ- /j , t
aw. -W ^
8-12
Introduction to 29 CFR 1910.120
4
9/95
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NOTES
paragraph (I); Emergency response by
employees at uncontrolled hazardous waste
sites
Elements of an emergency response plan
Procedures for handling emergency incidents
Exemption if complying with 29 CFR 1910.38(a)
8-13
paragraph (m);
Illumination
Minimum illumination intensity table
8-14
-L, %
paragraph (n);
Sanitation at temporary workplaces
Potable/non-potable water
Toilet facilities
Wash facilities
Showers
Change rooms
S-15
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Introduction to 29 CFR 1910.120
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NOTES
paragraph (o);
New technology programs
Evaluate for effectiveness
Available to OSHA upon request
3-10
paragraph (p); Certain operations conducted
under the Resource Conservation and
Recovery Act of 1976 (RCRA)
TSD facilities regulated under 40 CFR
Parts 264 and 265
Many sections refer to paragraphs (b)
through (o)
S-17
Introduction to 29 CFR 1910.120
paragraph (q); Emergency response to
hazardous substance releases
Emergency response personnel not
identified in paragraphs (a)(1)(i)
through (a)(1)(iv)
Exempt if covered under Emergency
Planning and Community Right-To-Know
Act of 1986
Elements of emergency response plan
Procedures of Incident Command System (ICS)
S-18
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HAZARD RECOGNITION
STUDENT PERFORMANCE OBJECTIVES
At the conclusion of this unit, students will be able to:
1. Identify and describe the three components of the Incident
Response Model
2. Identify and describe the following types of chemical hazards
that may be present or which may occur at an incident or a
site:
a. Toxic hazards
b. Combustion hazards
c. Hazards due to chemical reactivity
d. Oxidation hazards
e. Corrosion hazards
3. Identify and describe the following types of physical hazards
that may be present at an incident or site:
a. Drum/container handling
b. Kinetic
c. Thermal
d. Electrical
e. Acoustic
f. Heat and cold exposure
g. Confined space
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
-------
STUDENT PERFORMANCE OBJECTIVES (cont.)
4. Identify several key elements of a spill control plan
5. Identify references books and agencies available to assist in
identifying and evaluating chemical hazards.
9/95
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NOTES
HAZARD RECOGNITION
8-1
HAZARDOUS INCIDENT
RESPONSE
Recognition
Evaluation
Control
3-2
RECOGNITION
Identification of the substances involved,
the associated hazards, and the degree
of hazard
8-3
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1
Hazard Recognition
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NOTES
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
ss
CHEMICAL HAZARDS
Toxic
Combustion
Explosive
Chemical reactive
Corrosive
S-0
Hazard Recognition
2
9/95
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NOTES
Toxic Hazards
COMBUSTION HAZARDS
Fires
Explosions
COMBUSTION HAZARDS
Practical Considerations
Most dangerous substances:
Low ignition temperature
Low lower explosive limit (LEL)
Wide flammable range
8-0
9/95
3
Hazard Recognition
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NOTES
COMBUSTION HAZARDS
Practical Considerations (cont.)
Additional hazards:
Shockwave, heat, flying objects
Initiation of secondary fires
Releases of toxic and corrosive
compounds
S-10
Hazards due to
Chemical Reactivity
3-11
CHEMICAL INCOMPATIBILITY
The combination of two or more reactive
materials resulting in uncontrollable,
undesirable conditions
S-12
Hazard Recognition
4
9/95
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NOTES
SOME RESULTS OF
CHEMICAL REACTIONS
Heat generation
Fire
Explosion
Formation of toxic vapors
Volatilization of toxic or flammable substances
Violent polymerization
S-13
OXIDIZERS
Substances usually containing chemically
bound oxygen that reacts vigorously with
reducing materials at ambient conditions
3-14
EXAMPLES OF OXIDIZERS
Halogens
- Chlorine
- Fluorine
Peroxides
- Hydrogen peroxide
- Benzoyl peroxide
Ozone
Hypochlorites
9/95
5
Hazard Recognition
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NOTES
OXIDATION HAZARDS
Practical Considerations
Destruction of metals and organics
Ignition of combustible materials
Shock-sensitive organic peroxides
8-16
Corrosion Hazards
8-17
CORROSION
The electrochemical degradation of metals
or alloys due to reaction with their
environment, which is accelerated by the
presence of acids or bases
8-1#
Hazard Recognition
6
9/95
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pH SCALE
>0 ACID , BASE 14
< I I I I I | I I I I I I ~
7.0
Neutral
NOTES
8-10
EXAMPLES OF CORROSIVES
ACIDS
BASES (Caustics)
Acetic acid
Sodium hydroxide
A
Hydrochloric acid
Potassium hydroxide,
Sulfuric acid
Ammonia
s-20
/leftQj&tWud^ %
(j* ^/L'
CORROSIVE HAZARDS
Practical Considerations
What is the toxicity of the corrosive?
What structural damage can occur?
What other hazards can this lead to?-7
Can the corrosive be monitored?
S-21
9/95
7
Hazard Recognition
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NOTES
PHYSICAL PROPERTIES
Vapor pressure'^''
Solubility-
Physical form
S-22
ad.
PHYSICAL HAZARDS
Drum/Container Handling
Labels or placards?
Sound or undamaged?
Rusted or corroded?
Bulging or leaking?
CONTAINER HANDLING
PROCEDURES
ฃV
/ u\ฐ'
Assume all containers are hazardous
Inspect all containers BEFORE moving
them
Brief all personnel on potential hazards
Develop a spill prevention and cpntainment
pl?^ JLJD&silk ฃ$ (X*
)OsK
8-24
~ฅ
Hazard Recognition
9/95
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NOTES
SPILL CONTAINMENT
AND CONTROL
Reduces the spread of contamination
Minimizes cleanup efforts
Reduces exposure to hazardous materials
S-2S
SPILL CONTAINMENT
AND CONTROL PLAN
Define the hazards of materials onsite
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
S-27
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9
Hazard Recognition
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NOTES
OTHER PHYSICAL HAZARDS
Kinetic
Thermal
Electrical
Acoustic
S-26
OTHER PHYSICAL HAZARDS
(cont.)
Biological
Radiological
Heat stress/cold exposure
8-29
HEAT-RELATED ILLNESSES
AND EMERGENCIES
Heat rash
Heat cramps
Heat exhaustion
Heat stroke
S-30
Hazard Recognition
10
9/95
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NOTES
COLD EXPOSURE
Frostbite
Hypothermia
8-31
CONFINED SPACE HAZARDS
Atmospheric <=?
Safety ^ [0Ul otf/
CONFINED SPACE
A space which by design:
Is large enough for personnel to enter
and work
Has limited or restricted entry or exit
Is not meant for continuous occupancy
S-33
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11
Hazard Recognition
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NOTES
CONFINED SPACE HAZARDS
Atmospheric hazards:
ltd ft*
Oxygen deficient
Toxic
* 1
Flammable
Irritant (corrosive)
3-34
CONFINED SPACE HAZARDS
(cont.)
Safety hazards:
Slip/trip/fall
Mechanical/electrical
Limited entry/exit
Physiological stress
<&dr-
S-35
Reference Materials
and
Resources
8-36
Hazard Recognition
12
9/95
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HAZARD RECOGNITION
A hazardous material incident is a situation in which a hazardous material is or can 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 times 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, record -
keeping, 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 comes 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.
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INFORMATION
4 ~
CONTROL
RECOGNITION
EVALUATION
4*
i ~ I SAFETY
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.
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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) have 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 are 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 develops 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 involve 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
ecisions based upon: (1) receipt and evaluation of good information, and (2) development of a good
knowledge base concerning the situation.
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Safety
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 is both an input for consideration and
an outcome of each response activity (i.e., an outcome of identifying a specific chemical may e
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 to be 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 is 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 4- 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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HEAT
FUEL
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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Fuel -
(Reducing
Agent)
Oxidizing
Agent
Uninhibited
Chain Reactions
Temperature
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
Phosphorus
Ketones
Magnesium dust
Amines
Zirconium dust
Ethers
Titanium dust
Aliphatic hydrocarbons
Aluminum dust
Aromatic hydrocarbons
Zinc dust
Alcohols
Nitroaliphatics
Water-Reactive Flammable Solids
Pvrophoric Liquids
Potassium
Organometallic compounds
Sodium
Dimethyl zinc
Lithium
Tributyl aluminum
An explosive is a substance which 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 >
0 1 2 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
ACIDS
Bromine
Acetic acid
Chlorine
Hydrochloric acid
Fluorine
Hydrofluoric acid
Iodine
Nitric acid
Sulfuric acid
BASES (CAUSTICS)
Potassium hydroxide
Sodium hydroxide
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 flashpoint 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
Acid and Water
Fire
Hydrogen Sulfide and Calcium Hypochlorite
Explosion
Picric Acid and Sodium Hydroxide
Toxic Gas or Vapor Production
Sulfuric Acid and Plastic
Flammable Gas or Vapor Production
Acid and Metal
Formation of a Substance with Greater
Toxicity than the Reactants
Chlorine and Ammonia
Formation of Shock or Friction Sensitive
Compounds
Peroxides and Organics OR
Liquid Oxygen and Petroleum Products
Pressurization of Closed Vessels
Fire Extinguisher
Solubilization of Toxic Substances
Hydrochloric Acid and Chromium
Dispersal of Toxic Dusts and Mists
Sodium or Potassium Cyanide and Water or
Acid Vapor
Violent Polymerization
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 (4ฐC). Numerically, SpG is equal to the
density in g/cc, 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 (ฐC) or Fahrenheit (ฐF).
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
flashpoint. If the vapor does ignite, combustion can continue as long as the temperature remains
at or above the flashpoint. The relative flammability of a substance is based on its flashpoint. An
accepted relation between the two is:
Highly flammable: Flashpoint less than 100ฐF
Moderately flammable: Flashpoint greater than 100ฐF but
less than 200ฐF
Relatively inflammable: Flashpoint greater than 200ฐF
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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. Although electrical shock may cause
death, it can cause 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, cjr have a layer of insulating
material isolating the electrical components from a metal housing (used for more rugged
9/95
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Hazard Recognition
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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 ([~]).
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, high-pitched sounds being 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.
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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 Q/T, + C^/Tj .... 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 50 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 Environmental Protection Agency (EPA) recommends that, for an eight-hour work day, workers
should not be exposed to noise levels above an 85 dBA TWA. EPA's goal is to reduce that level
to 75 dBA. They also believe that individuals should not be exposed to a 70 dBA TWA for an entire
24-hour day.
BIOLOGICAL HAZARDS
Animal bites/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 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. Waterborne and foodborne
diseases can be a problem if adequate precautions are not taken. Examples of waterborne 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 bloodborne 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 bloodborne 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. Ionization 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.
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Gamma radiation is pure electromagnetic energy and is wave-like rather than particulate. 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 over-exposures (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
The Occupational Safety and Health Administration (OSHA) issued a final rule on Permit-Required
Confined Spaces for General Industry (29 CFR 1910.146) on January 14,1993, having an effective
date of April 15, 1993.
This rule requires the establishing of a permit-required confined space entry program, an entry
permit system, emergency procedures, and engineering and procedural controls to protect employees
performing work within confined spaces.
A confined space is any space which: (1) is large enough and so configured that an employee can
bodily enter and perform assigned work, (2) has limited or restricted means for entry and/or exit,
and (3) is not designed for continuous employee occupancy. A permit-required confined space
(PRCS) is a confined space that has one or more of the following hazards: (1) contains or has
known potential to contain a hazardous atmosphere, (2) contains a material with potential for
engulfment, (3) has an internal configuration such that an entrant could entrapped or asphyxiated by
inwardly converging walls or a floor which slopes downward and may taper to a smaller cross
section, or (4) contains any other recognized serious safety or health hazard (e.g., rotating
machinery, electrical hazards).
PRCSs are removed from service and completely protected against the release of energy or material
into the space by such means as: (1) blanks, blinds, misaligning, or removing sections of pipes; (2)
double-lock and bleed systems; (3) lockout or tagout of all energy sources; or (4) locking or
disconnecting mechanical linkages. Some methods of isolating hazards are shown in Figure 4. Not
only are these methods of hazard isolation used in conjunction with PRCS entry but any time
employees are working in an area where the sudden release of energy or material could result in
personnel injury.
To ensure adequate protection for worker safety and health while performing activities in PRCS, a
permitting program must be in place. Specific duties and responsibilities are assigned to the entry
supervisor, attendant, and all entry personnel.
Hazardous atmospheres within PRCS are defined as: (1) oxygen concentration below 19.5% or
above 23.5%; (2) flammable gases, vapors, or mist exceeding 10% of lower explosive limit (LEL);
(3) toxic substances in concentrations exceeding published exposure limits; (4) combustible dust
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concentrations that obscure vision at a distance of 5 feet or less; or (S) any condition recognized to
be immediately dangerous to life or health (IDLH).
*
-------
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.
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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.
The National Institute for Occupational Safety and Health (NIOSH), 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
sometimes felt early but subsides later (often there is no pain), and the affected part feels intensely
cold and numb.
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Standard first aid for frostbite includes getting the victim to a warm shelter. Put frozen parts in
warm water (100-105ฐF) 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.
Medical 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.
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.
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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.
FIGURE 5
COMBINATION DRENCH SHOWER AND EYEWASH
Source- U.S DHHS 1979
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REFERENCES
U.S. DHHS. 1979. Occupational Safety and Health in Vocational Education: A Guide for
Administrators, Faculty, and Staff. Publication No. 79-138 U.S. Department of Health and Human
Services, National Institute for Occupational Safety and Health, Cincinnati, OH.
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AIR MONITORING INSTRUMENTS I
STUDENT PERFORMANCE OBJECTIVES
At the conclusion of this unit, students will be able to:
1. State the reasons why portable air monitoring instruments are
used in hazardous materials response operations
2. List four basic characteristics of field air monitoring
instruments
3. Define inherent safety and explain why it is an important
feature for air monitoring instruments
4. Describe the National Electric Code (NEC) classification
system for electrical devices and explain how it applies to air
monitoring instruments
5. Define the following characteristics related to air monitoring
instruments as electrical devices and identify which NEC
class each refers to:
a. Intrinsically safe
b. Explosion proof
c. Purged system
d. Non-incendive
e. Dust-ignition proof
6. Explain why it is important to use oxygen meters and
monitor the oxygen level of an atmosphere
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
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STUDENT PERFORMANCE OBJECTIVES (cont.)
7. Identify and describe types of oxygen monitors based on the
following basic design features:
a. External sensor
b. Internal sensor
c. Manual pump
d. Automatic pump
e. Combination units
8. Explain how oxygen monitors operate
9. List several conditions that can interfere with the operation
of an oxygen meter
10. Explain why it is important to calibrate an oxygen meter at
the altitude at which it is used
11. Explain why it is important to use combustible gas indicators
(CGIs)
12. Identify and describe types of CGIs based on the following
basic design features:
a. External sensor
b. Internal sensor
c. Manual pump
d. Automatic pump
e. "Supersensitive" unit
f. Combination unit
13. Explain how CGIs operate
14. Define the following terms and identify the corresponding
needle response location on a CGI
a. UEL
15. List the conditions that may interfere with the operation of
a CGI
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
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STUDENT PERFORMANCE OBJECTIVES (cont.)
16. Define relative response and explain how it influences CGI
readings
17. Explain why it is important to use toxic monitors
18. Describe two types of detector tube systems
19. Explain how detector tubes operate
20. List the limitations that should be considered when using
detector tube systems
21. Describe other types of toxic atmosphere monitors.
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
-------
NOTES
AIR MONITORING
INSTRUMENTS
PARTI
.1
8-1
FIELD AIR MONITORING
INSTRUMENTS
Collection of "real time" data to aid
in decisions concerning:
Hazards and risks to public and personnel
Personal protective equipment selection
Site work zones
Effects on environment
Mitigative actions 82
FIELD INSTRUMENTS
Desired Characteristics
Portable and rugged
Easy to operate
Inherently safe
Reliable and useful results
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Air Monitoring Instruments I
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NOTES
RELIABLE AND USEFUL RESULTS
Response time
Sensitivity
Selectivity
Accuracy
Precision
HAZARDOUS ATMOSPHERES
Concentration between the lower
explosive limit and upper explosive
limit (LEL - UEL)
Presence of an ignition source
Exothermic reaction
s-s
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
s-e
Air Monitoring Instruments J
2
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NOTES
SAFETY STANDARDS
Inherent Safety
National Electrical Code (NEC) consensus
standard, presented by National Fire
Protection Association (NFPA), defining:
Hazardous locations
Approval criteria
S-7
HAZARDOUS LOCATIONS
Inherent Safety
class
I Combustible Gases and Vapors
II Combustible Dusts
III Combustible Fibers, Flyings
NFPA 1991 S-fl
HAZARDOUS LOCATIONS
Inherent Safety (cont.)
GROUP
A,B,C,D Gases & Vapors found in
Class I Atmosphere
E,F,G Dusts found in Class II
Atmosphere
NFPA 1901 S-9
ฆฆ
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NOTES
HAZARDOUS LOCATIONS
Inherent Safety (cont.)
DIVISION
1 Location in which hazardous
concentrations exist continuously,
intermittently, or periodically
under NORMAL operating conditions
HFPA 1001 8-10
HAZARDOUS LOCATIONS
Inherent Safety (cont.)
DIVISION
2 Location in which hazardous
concentrations do NOT normally
exist under normal operating
conditions
HFPA 1991 3-11
v
INSTRUMENT PROTECTION
CRITERIA
Class I, Division 1, Groups A,B,C,D
"Instrinsically Safe"
"Explosion-Proof
"Purged System"
NFPA 1901 8-12
Air Monitoring Instruments I
4
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INSTRUMENT PROTECTION
CRITERIA
Class I, Division 2, Groups A.B.C.D
"Non-lncendive"
Class II, Divisions 1 and 2, Groups E,F,G
"Dust-Ignition Proof
8-13
DEFINITIONS
Intrinsically safe
Designed so that parts are not exposed to
explosive atmosphere or, if so, there is
insufficient energy for ignition
3-14
NOTES
DEFINITIONS (cont.)
Explosion proof
Designed to contain an explosion and
cool gases to prevent spread
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Air Monitoring Instruments I
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NOTES
DEFINITIONS (cont.)
Purged system
Inert gas-filled system; positive pressure
to prevent explosive gases or vapors from
entering
OXYGEN INDICATORS
Used to determine:
Types of respirator protection
Combustion risk
Use of other instruments
Presence of contaminants
9-17
OXYGEN INDICATORS
Exterior sensor
Interior sensor
- Manual pump
- Automatic pump
Combination units
3-16
Air Monitoring Instruments I
6
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NOTES
OXYGEN INDICATORS
Theory of Operation
Oxygen diffusion into detector cell
Chemical reaction establishes current
proportional to oxygen concentration
s-ie
OXYGEN INDICATORS
Theory of Operation (cont.)
, * * + + + r
[l ! 1 1 1 1 1 -j
Protective disk
Membrane
Electrode
ฆ Electrolyte
' Electrode
$20
OXYGEN INDICATORS
Limitations/Precautions
Atmospheric pressure (altitude)
Interfering gases
Operating temperature
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NOTES
OXYGEN INDICATORS
Interpretation of Data
Instantaneous response
Specific, quantitative results
- 0-25% oxygen
- 0-100% oxygen
Calibrate to ambient oxygen (20.8%)
S-22
ALTITUDE/OXYGEN METER
READING
17.3%
5000 ft
19 3% /
2000 ft y
20 8%
Sea level
MM No dat*-a .......
8-23
ALTITUDE/OXYGEN INDICATION
AltltuHn
QwBBn Indication ft)
-1000 fปet
21.6
Sea level
20.6
1000
20.1
2000
103
3000
is e
4000
18.0
5000
173
8000
16.7
7000
16 1
8000
15 4
9000
14 9
10000
14 3
USA No date-e
S-24
Air Monitoring Instruments I
8
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NOTES
COMBUSTIBLE GAS INDICATORS
(CGIs)
Used to determine:
Risk of fire/explosion
Indication of contaminants
S-SB
CGIs (cont.)
Manual vs. automatic pumps
"Supersensitive" unit
Combination units (CGI-oxygen)
8-20
CGIs
Theory of Operation
In the presence of a combustible gas, a
heated catalytic filament (or bead) burns
the gas, increasing the filament's
temperature. An electrical resistance is
created, causing an imbalance in a
Wheatstone Bridge circuit.
837
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Air Monitoring Instruments I
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NOTES
CGIs
Theory of Operation (cont.)
Battery
Display
Gat sample
Compensating filament
WHEATSTONE BRIDGE CIRCUIT
8-26
CONCENTRATION
LEL
5%
UEL
15% (Methane)
I b
0 100%
METER READING
-
< LEL LEL UEL
> UEL
8-29
CGIs
Limitations/Precautions
Temperature
Oxygen requirements
Relative response
3-30
Air Monitoring Instruments I
10
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NOTES
CGIs
Limitations/Precautions (cont.)
Interfering gases
- Lead
- Sulfur
- Silicone
- Hydrogen chloride
- Hydrogen fluoride
S-31
CGIs
Relative Response Curve
100
Acetylene
/ / /
Pentane
00
Methane / /
60
/ / /
70
0>
c
/ //
Ethyl chlonde
S 60
/ / /
(0
ฉ
/ //
1,4-Dioxane
= 50
k.
/ /s
0
"0
/ /s
2
/ //
30
/
Xylene
20
10
0
10 20 30 40 50 60 70 80 90
100
MSA No dato-b
Percent LEL
(MSA 260) S"32.
CGIs
Relative Response
Chemical LEL
Concentration %LEL Meter Response %LEL
Methane (S 0%)
50
85
Acetylene (2 5%)
50
60
Pentane (1 5%)
50
53
Ethyl
chloride (3 8%)
50
37
1,4-Dioxane (2 0%)
50
37
Xylene (1 1%)
50
27
MSA No dale-b
8-33
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NOTES
TOXIC ATMOSPHERE MONITORS
Used to determine:
Health risks to workers/public
Personal protective equipment
Work zones/safety plans
8-34
TOXIC ATMOSPHERE MONITORS
Types
Detector tube system
Monitors for specific agents
(i.e., carbon monoxide, hydrogen sulfide)
Total vapor analyzers \
Gas chromatograph
(RID, FID)
8-35
DETECTOR TUBE SYSTEMS
Components
Pump
- Piston
- Bellows
Tubes
- Specific chemicals
- General chemicals
- Concentration ranges
8-33
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NOTES
DETECTOR TUBE SYSTEM
Theory of Operation
Glass tube with indicating chemical
Specific volume of air
Color change
Stain length = concentration
3-37
DETECTOR TUBE SYSTEMS
Limitations/Precautions
Accuracy
Temperature/humidity/pressure
Expiration date
Chemical group/specific
Lot number
DETECTOR TUBE SYSTEMS
Limitations/Precautions (cont.)
Color change/endpoint
Pump strokes/volume/time
Interferences
Reusable
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NOTES
DETECTOR TUBE SYSTEM
Plug
Glass tube
1iir
0 10 20 30
Prefilter
>
Plug
Indicating chemical
8-40
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AIR MONITORING INSTRUMENTS I
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 are useful for:
Assessing the health risks to the public and response workers.
Selecting personal protective equipment.
Defining work zones.
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 concentrations of contaminants as low as one part of
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. An instrument should not
be so heavy or bulky that it is difficult for a response worker to carry. 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.
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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.
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. Workers
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 reproducibility. These factors can be indicated by the error factor. For
example, some detector tubes may have an error factor of ฑ35% of the true value, which indicates
that 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.
Another consideration is that the instrument must give results that are immediately useful.
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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), which is 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, as well as 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 categorizes 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).
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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 those 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
ally! 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: NFPA 1991
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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, unconfined 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. For 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 flammable liquids are transferred at
the site, or if releases of flammable gases/vapors are 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, and
thermosetting and molding compounds.
Source: NFPA 1991
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
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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 NEC, 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). An arcing or flame-producing device 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 laboratories recognized by OSHA.
To ensure personnel safety, it is recommended that only approved instruments be used onsite 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.
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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
Class II, Division 1, Group E (combustible metal dust) would offer little protection
around a flammable vapor or gas.
Instruments Incorporated
TOXIC GAS MONITOR
Factory Mutual
Approved
Model 3750
Intrinsically safe for use in Class 1,
Division 1, Group ABCD hazardous
locations when used with Battery Pack
P/N 6473-4152.
Warning. Must be operated in accordance with manual instructions.
Parts substitution may Impair intrinsic safety.
FIGURE 1
CERTIFICATION LABEL FROM A TYPICAL AIR MONITORING INSTRUMENT
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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 ensure 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. For example, a CGI calibrated to pentane will give a higher instrument reading for
methane than the actual concentration. This variability is called relative response.
The relative response of an instrument to different chemicals can be calculated by dividing the
instrument reading by the actual concentration and expressing the value as a ratio or a percent. 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, 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 (0.27 x actual concentration = 100 ppm; then actual concentration =
100/0.27 = 370 ppm). If there are 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. Because
recalibration is time-consuming, it is usually done only if the instrument is going to be used for many
measurements of the special chemical.
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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, CGIs, 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 20.8% 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 of oxygen (by combustion or a reaction such as rusting) 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 that display the
oxygen concentration from 0-25%. There are also oxygen indicators available that measure
concentrations from 0-5% and 0-100%. The most useful range for response is the 0-25% oxygen
content readout because decisions involving air-supplying respirators and the use of CGIs 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
CGIs 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: 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. The
oxygen detector uses an electrochemical sensor to determine the oxygen concentration in air. A
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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. Although the
actual percentage of oxygen does not change with altitude, at sea level, the weight of the atmosphere
is greater, and more 02 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. With the advent of modern electronic
circuitry, this correction for changes in atmospheric pressure as it relates to converting the partial
pressure of oxygen to a percent concentration of oxygen is performed internally and is "transparent"
to the user of the instrument. When using older analog instruments, the correction is done manually
by recalibrating as atmospheric pressure changes.
High concentrations of carbon dioxide (C02) shorten the useful life of the oxygen sensor. As a
general rule, the unit can be used in atmospheres greater than 0.5 % C02 only with frequent replacing
or rejuvenating of the sensor. Lifetime in a normal atmosphere (0.04% COj) can be from 1 week
to 1 year depending on the manufacturer's design.
Temperature can affect the response of oxygen indicators. The normal operating range is between
32ฐ and 120ฐF. Between 0ฐ and 32ฐF, the response of the unit is slower. Below 0ฐF, the sensor may
be damaged by the solution freezing. The instrument should be calibrated at the temperature at
which it will be used.
Strong oxidizing chemicals, like ozone and chlorine, can cause increased readings and indicate high
or normal 02 content when the actual content is normal or even low.
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o2 o2 o2 o2 o2
Protective disk
Thermistor
Membrane
Electrode
Electrolyte
Electrode
V////////////A
FIGURE 2
SCHEMATIC OF OXYGEN SENSOR
Combustible Atmosphere Indicators
CGIs measure the concentration of a flammable vapor or gas in air, indicating the results as a
percentage of the 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. All 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.
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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 concentrations up to the LEL of the gas
(Figure 3a).
If a concentration greater than the 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. Optimum results are
obtained when the instrument is calibrated and zeroed 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 liquidlike
gasolinein a sewer system where methane may be present, the operator cannot tell if the reading
is the contaminant or the methane. A prefilter 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.
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100
% LEL
% LEL
% LEL
Lower than
the LEL
Between the
LEL and UEL
Above the
UEL
FIGURE 3
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 situation usually involves measurements at concentrations lower
than would be indicated by oxygen indicators or CGIs. There is a need to determine whether toxic
chemicals are present and identify them so the environmental concentration can be compared to
exposure guidelines. Toxic atmosphere monitoring is done to:
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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 and acrylonitrile tube for acrylonitrile gas. Some
manufacturers do produce tubes for groups of gases, e.g., aromatic hydrocarbons and 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 chemicai group such as acid gas or halogenated hydrocarbon. 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.
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 ฑ35% at concentrations at one-half the OSHA Permissible Exposure Limit (PEL) and
ฑ25 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, the tubes should 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.
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Plug
Glass tube
0 10
20 30
>
>
<
$
*
*
>
Prefilter Indicating
chemical
Plug
FIGURE 4
DIRECT-READING COLORIMETRIC
INDICATOR TUBE
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.
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, die manufacturers provide information with the tubes on interfering gases and vapors.
Interpretation of results can be a problem. Because 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.
9/95
29
Air Monitoring Instruments I
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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.
Whereas there are many limitations of 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.
REFERENCES
NFPA. 1991. National Fire Protection Association Fire Protection Guide, NFPA 497M,
Classification of Gases, Vapors, and Dusts for Electrical Equipment in Hazardous (classified)
Locations. National Fire Protection Association, Quincy, MA.
Air Monitoring Instruments I
30
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AIR MONITORING INSTRUMENTS II
STUDENT PERFORMANCE OBJECTIVES
At the conclusion of this unit, students will be able to:
1. Describe how a photoionization detector (PID) works
2. Identify general controls and functions for HNU PI-101
3. List several limitations of PIDs
4. Explain how a flame ionization detector (FID) works
5. List several limitations of FIDs
6. Explain the theory of supersensitive combustible gas
indicators (CGIs)
7. Compare the advantages and disadvantages of using PIDs,
FIDs, and CGIs for hazardous materials response operations.
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
9/95
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NOTES
9195
AIR MONITORING
INSTRUMENTS
PART II
PHOTOIONIZATION
rซ
Amplifier
Meter
k
s\*t.
Sample out
UV
lamp
Electrode V Electrode
S-1
8-2
J
ecfo oen^c-
V
Sample in
fl
-------
NOTES
PHOTOIONIZATION
R + hu ~ R+ + e'
R = chemical absorbing UV
h(nu) = photon with energy a ionization
potential (IP) of chemical
8-4
IONIZATION POTENTIALS
CHEMICAL
IP (eV)
CHEMICAL
IP faVl
Carbon monoxide
14 0
Hydrogen sulfide
105
HCN
is e
Hexana
102
Methane
13 0
Ammonia
10 1
Water
12 6
Acetone
9 7
HCI
12 7
Trichloroethylene
8 45
Oxygen
12 1
Benzene
9 2
Chlorine
11 5
Trlsthyl amine
7 5
Propane
11 1
~n
IF
HNU 1085
Examples of Lamp Energies
and Detectable Chemicals
11 7
Kalocarboro
Methanol
Other single C compounds
102
Lamp
Vinyl chloride
MEK
MIBK
TCE
Other 2-4 C compound*
A
ss
ArorrmtlcB
Large molecules
Air Monitoring Instruments II
9/95
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NOTES
SELECTIVE DETERMINATION OF VINYL
CHLORIDE
COMPOUND
Carbon dioxide
Propane
Vinyl chloride
Acetone
IE
13.8
11.1
10.0
9.7
PHOTOIONIZATION
Considerations
Lamp energy/chemical IP
Dust/humidity
High methane
Electromagnetic radiation
/
w
PHOTOIONIZATION
Considerations (cont.)
t crust
Lamp aging
Relative response'
High concentration
-l
Air Monitoring Instruments II
-------
NOTES
RELATIVE RESPONSES FOR HNU
PI-101 WITH 10.2-eV PROBE
CHEMICAL
RR
!ฃ
m-Xylene
1.12
8.56
Benzene
1.00
9.25
Phenol
0.78
8.69
Isobutylene
0.56
9.25
Acetone
0.63
9.69
Hexane
0.22
10.18
Ammonia
0.03
10.15
HNU 1 MS 8-10
ppm (by volume)
HNU 7985
Lamp powซ
tup0r
Bsttvy
I ton tfivnbtr I
_E_J
/
\
Pump
frปamp
| tamp |
8-12
Air Monitoring Instruments II
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FLAME IONIZATION
DETECTOR
A
Sample
(air)
s-13
FLAME IONIZATION
Considerations
Detects only organics
Sensitive to methane
Relative response
Hydrogen gas needed
Electromagnetic radiation
3-14
NOTES
9/95
5
Air Monitoring Instruments II
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AIR MONITORING INSTRUMENTS II
Photoionization Detectors (PIDs)
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.
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 1). 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. Because 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 1).
TABLE 1
IONIZATION POTENTIALS OF SELECTED CHEMICALS
Chemical
Ionization Potential (eV)
Hydrogen cyanide
13.9
Carbon dioxide
13.8
Methane
13.0
Hydrogen chloride
12.5
Water
12.6
Oxygen
12.1
Chlorine
11.5
Propane
11.1
Hydrogen sulfide
10.5
Hexane
10.2
Ammonia
10.1
Vinyl chloride
10.0
Acetone
9.7
Benzene
9.2
Phenol
8.5
Ethyl amine
8.0
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7
Air Monitoring Instruments II
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Amplifier
*
Meter
0"/
Sample out
Electrode
UV
Lamp
t
H
t
Sample in
Electrode
FIGURE 1
DIAGRAM OF PHOTOIONIZATION DETECTOR
LAMP AND COLLECTING ELECTRODES
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.
Air Monitoring Instruments II
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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 1, 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.
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 bum out.
Photoionization detectors are calibrated to a single chemical. The instrument's response to chemicals
other than the calibration gas/vapor can vary. Table 2 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.
HNU PI 101 Photoionization Detector
The HNU PI 101 consists of two modules connected via a single power cord (Figure 2):
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.
9/95
9
Air Monitoring Instruments II
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TABLE 2
RELATIVE RESPONSES FOR SELECTED CHEMICALS USING
THE HNU MODEL PI 101 WITH 10.2 eV PROBE CALIBRATED TO BENZENE
Chemical
Relative Response
m-Xylene
1.12
Benzene
1.00
Phenol
0.78
Vinyl chloride
0.63
Acetone
0.50
Hexane
0.22
Phosphine
0.20
Ammonia
0.03
Reprinted from Trace Gas Analyzer, HNU Model PI 101, 1985, with permission from HNU Systems,
Inc.
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.
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 lamps9.5, 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 II
10
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Meter
readout
Battery
Lamp power
supply
Ion Chamber
Bias
/
\
Ion chamber
Pump
Preamp
*
Lamp
Sample
Probe
FIGURE 2
PORTABLE PHOTOIONIZATION DETECTOR
Reprinted from Trace Gas Analyzer, HNU Model PI 101, 1985, with permission from HNU Systems,
Inc.
Flame Ionization Detectors fFID)
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 + O RHO+ + e- - C02 + H20
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
9/95
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Air Monitoring Instruments II
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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 (CI"), 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 3 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.
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 3).
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 and GC mode.
Air Monitoring Instruments II
12
9/95
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TABLE 3
RELATIVE RESPONSES FOR SELECTED CHEMICALS
USING THE OVA CALIBRATED TO METHANE
Percent Relative
Compound
Response
Methane
100
Ethane
90
Propane
64
n-Butane
61
n-Pentane
100
Ethylene
85
Acetylene
200
Benzene
150
Toluene
120
Acetone
100
Methyl ethyl ketone
80
Methyl isobutyl ketone
100
Methanol
15
Ethanol
25
Isopropyl alcohol
65
Carbon tetrachloride
10
Chloroform
70
Trichlorethylene
72
Vinyl chloride
35
Reprinted from Model OVA 128 Century Organic Vapor Analyzer MI611-132, 1985, with permission
of The Foxboro Company.
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. GC is a technique for separating components of a sample and
qualitatively and quantitatively identifying them. The sample 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
9/95
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Air Monitoring Instruments II
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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 Recordei
Compressed Gas
Column
_g^LJ Detector
Injeciion valve
/ Sample Pump
FIGURE 3
ORGANIC VAPOR ANALYZER SCHEMATIC
Reprinted from Model OVA 128 Century Organic Vapor Analyzer PSS6-1221F, 1985, 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.
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.
Air Monitoring Instruments II
14
9/95
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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 particulate and not the
type of particulate. 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
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
9/95
15
Air Monitoring Instruments II
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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 does not recognize, it cannot
identify. Most portable units have libraries for up to 100 chemicals. Also, the detection method
(e.g., PID, FID) used must be considered because that limits the number of chemicals that can be
identified.
REFERENCES
HNU. 1985. Trace Gas Analyzer, HNU Model PI 101: Instruction Manual. HNU Systems, Inc.,
Newton Highlands, MA. Used with permission of HNU Systems, Inc.
Air Monitoring Instruments II
16
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CO
-------
TOXICOLOGY AND EXPOSURE
GUIDELINES
STUDENT PERFORMANCE OBJECTIVES
At the conclusion of this unit, students will be able to:
1. Define toxicology and toxicity
2. List the conditions that influence toxicity
3. Briefly explain the "dose-response relationship" as it relates
to toxicity
4. Define the following terms:
a.
Adverse effect
b.
Local effect
c.
Systemic effect
d.
Asphyxiation
e.
Sensitization
f.
Teratogenic
g-
Mutagenic
h.
Carcinogenic
5. Define the term "routes of exposure" and list examples
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
9/95
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STUDENT PERFORMANCE OBJECTIVES (cont.)
6. List types of adverse effects
7. Define the terms:
a. Chemical interaction
b. Addition
c. Synergism
d. Potentiation
e. Antagonism
8. Name the organization identified under 29 CFR 1910.120
that develops exposure limits
9. Define the term exposure limit and list the types of exposure
limits
10. Explain the difference between "Permissible Exposure Limit"
and "Published Exposure Level" as defined in 29 CFR
1910.120
11. List the three uses for exposure limits as specified in 29
CFR 1910.120.
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
9/95
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NOTES
TOXICOLOGY AND
EXPOSURE GUIDELINES
WHICH CHEMICAL POSES THE
GREATEST RISK?
Chlorine
Hydrogen cyanide
Ammonia
Lead
Toluene
Mercury
Benzene
Asbestos
Methyl alcohol
Polychlorinated
biphenyls
8-2
RISK ASSESSMENT
FOR CHEMICALS
What is the toxicity of the compound?
What is the probability of exposure?
9/95
1 Toxicology and Exposure Guidelines
-------
NOTES
WHAT IS THE TOXICITY
OF THE COMPOUND?
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"
Toxicology and Exposure Guidelines 2 9/95
-------
NOTES
All substances are poisons; there is none
which is not a poison. The right
dose differentiates a poison and a
remedy.
PARACELSUS
(1493 - 1541)
Reproduced from KJaasson 9t af, Casarett and Ooutte
Totfcofoffr The Basio Sc fence 6tPolaomt 1086, with
permission from McQf&w-hW, Inc.
TYPES OF TOXICITY
INFORMATION
Epidemiologic data
Animal bioassays
Short-term studies
Comparisons to molecular structure
DOSE-RESPONSE CURVE
100
T3
ฉ
| 50-
C
o
-------
NOTES
EXAMPLES OF
DOSE-RESPONSE INDICES
ENDPOINT- L _ : Lethality
T : Toxicity
E : Effectiveness
_ q : Dose based on all routes
except inhalation
Q : Concentration based
on inhalation only
RESPONSE Percentage of experimental population
Lo - Lowest dose at which effect
was observed
s-10
LETHAL DOSE FIFTY
(LD50)
The dose of a substance that is
expected to cause the death of
50% of a defined experimental
animal population
8-11
RELATIONSHIP OF LD50 TO
DOSE-RESPONSE
100
Response
(%)
8
I
n
1
ID 90
Dose (mg/kg)
6-12
Toxicology and Exposure Guidelines 4
9/95
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NOTES
LIMITATIONS OF
DOSE-RESPONSE DATA
Species variation
Based on single dose
Statistical value
S-13
DOSE-RESPONSE CURVES FOR
TWO SUBSTANCES
100
ฉ
c
a* 50-
ot
a>
CC
yj
20
n
Dose
(mg/kg)
S-14
ADVERSE EFFECTS
Local effects
Systemic effects
Asphyxiation
- Simple
- Chemical
8-15
.
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NOTES
ADVERSE EFFECTS (cont.)
Sensitization
Teratogenic
Mutagenic
Carcinogenic
3-16
WHAT IS THE PROBABILITY
OF EXPOSURE
Route of exposure
Duration and frequency of exposure
Personal characteristics
Chemical interactions
8-17
ROUTES OF EXPOSURE
Inhalation
Absorption
- Skin
- Eyes
Injection
Ingestion
S-18
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NOTES
PERSONAL CHARACTERISTICS
Gender
Genetic factors,
Health status
7
Age
3-19
TYPES OF CHEMICAL
INTERACTIONS
Examples
Addition
(2 + 2 = 4)
Synergism
(2 + 2 = 6)
Potentiation
(0 + 2 = 4)
Antagonism
(2 + 2 = 2)
X ' 8-20
EXPOSURE GUIDELINES
Occupational Safety and Health
Administration (OSHA)
- Permissible exposure limits (PELs)
- Enforced standards
9-21
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NOTES
EXPOSURE GUIDELINES (cont.)
National Institute for Occupational Safety
and Health (NIOSH)
- Recommended exposure limits (RELs)
- Research agency; recommendations for
OSHA
8-22
EXPOSURE GUIDELINES (cont.)
American Conference of Governmental
Industrial Hygienists (ACGIH)
- ThresholcTLimit Values (TLV)
- Recommended workplace exposure
levels
EXPOSURE LIMITS
29 CFR Part 1910.120
Permissible Exposure Limits
- 29 CFR Part 1910.1000,
Subparts G and Z (OSHA)
"Published Exposure Levels"
- NIOSH Recommendations for
Occupational Health Standards, 1986
- ACGIH's TLVs and BEIs for 1987-1988
S-24
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NOTES
EXPOSURE LIMITS
Used io determine:
Site characterization
Medical surveillance
Exposure controls
- Engineered controls
- Work practices
- Personal protective equipment
selection
28 CFR 1010.110 S-iS
TIME-WEIGHTED AVERAGE (TWA)
Averages the concentrations of exposure
Based on duration of exposure
S-20
TWA (cont.)
Example
Acetone TLV-TWA 750 ppm (ACGIH)
1000 ppm for 3 hrs
500 ppm for 2 hrs
200 ppm for 3 hrs
For an 8-hr TWA:
= (3 hrsHIOOO) + (2 hrsHSOO) + f3 hrsH200)
8
= 575 ppm
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NOTES
TWA (cont.)
c 750
TWA-EL
o
"3
7 T ~r V
**
C
ฉ
f\J \ I \
c
J \ \
/ \J \
6 am 10 am 3 pm
Time
8-2B
SHORT-TERM EXPOSURE LIMIT
(STEL)
A 15-minute Time-Weighted Average (TWA)1
exposure concentration not to be exceeded
at any time during the workday even if the
8-hour exposure is within the TLV-TWA
ACQIH 1994 8-20
STEL (cont.)
Exposures up to the STEL should:
Not exceed 15 minutes
Not occur more than 4 times per workday
Not have less than 60 minutes between
successive STEL exposures
ACQIH 1994 S-30
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NOTES
STEL (cont.)
A STEL is intended to protect against:
Irritation
Chronic or irreversible tissue damage
Narcosis
AC QIH 1904 8-31
STEL (cont.)
6am 10am 3pm
Time g.32
CEILING
(C)
5
0
6 am
10 am
3 pm
Time 5.33
ฃ4 ai&^\
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NOTES
THRESHOLD LIMIT VALUES
Are not intended for use:
As a relative index of toxicity
As legal standards
In estimating the toxic potential of
continuous, uninterrupted exposures
or other extended work periods
ACQJH 1004
S-34
THRESHOLD LIMIT VALUES (cont.)
As proof or disproof of existing disease
or physical condition
In the evaluation or control of community
air pollution nuisances
" For adoption or use by countries whose
working conditions or cultures differ from
those in the United States of America and
where substances and processes differ
ACQIH 7904
S-35
\ " .1
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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
personal 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 harmfiilness 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).
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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/m1).
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.
Increasing Dose
a> a)
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 Effects of Chemical Substances
(NIOSH 1983, p. xxxii). A summary of these terms is listed in Table 1.
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TABLE 1
SUMMARY OF DOSE-RESPONSE TERMS
Category
Exposure
Time
Route of Exposure
Toxic Effects
Human
Animal
TDlo
Acute or chronic
All except inhalation
Any nonlethal
Reproductive,
Tumorigenic
TClq
Acute or chronic
Inhalation
Any nonlethal
Reproductive,
Tumorigenic
LDlo
Acute or chronic
All except inhalation
Death
Death
LDjq
Acute
All except inhalation
Not applicable
Death
(statistically
determined)
LClq
Acute or chronic
Inhalation
Death
Death
LCso
Acute
Inhalation
Not applicable
Death
(statistically
determined)
Source: U.S. DHHS 1982
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 (TClq): 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 LDS0, 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 (LD^): 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 (LClq): The lowest concentration of a substance in air,
other than LC50, which has been reported to have caused death in humans or animals.
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Lethal concentration Fifty (LCjq): A calculated concentration of a substance in air,
exposure to which for a specified length of time is expected to cause the death of 50
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 LDM or LCn 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 LDjq, but at lower doses the situation is
reversed. At LDM, Chemical B is more toxic than Chemical A.
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.
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 durationa minute to a few days. Chronic exposures involve
frequent doses at relatively low levels over a period of time ranging from months to
years.
100
A / B
/ s
c
/ f
T
o
m
od
-------
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.
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.
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, because 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 because of 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,
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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: 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:
(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 Toxicity 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.
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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.
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 LDso of chemicals in animals gives a relative ranking
of potency or toxicity of each. For example, DDT (LDjq for rats = 113 mg/kg) would be
considered more toxic than ethyl alcohol (LDjq for rats = 14,000 mg/kg). Using the LDy, (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 2 and 3).
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.
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TABLE 2
TOXICITY RATING
Toxicity Rating or
Class
Probable Lethal Oral Dose for Humans
Dosage
For Average Adult
Examples
1. Practically nontoxic
> 15 g/kg
More than 1 quart
Ethyl alcohol
2. Slightly toxic
5-15 g/kg
Between pint and quart
Sodium chloride
3. Moderately toxic
0.5-5 g/kg
Between ounce and pint
Ferrous sulfate
4. Very toxic
50-500 mg/kg
Between teaspoonful and
ounce
Phenobarbital
5. Extremely toxic
5-50 mg/kg
Between 7 drops and
teaspoonful
Picrotoxin
6. Supertoxic
<5 mg/kg
A taste (less than 7 drops)
Nicotine, dioxin
Source: Klaassen et al. 1986, p. 13; used with permission of McGraw-Hill, Inc.
TABLE 3
LD,o VALUES FOR RATS FOR A GROUP
OF WELL-KNOWN CHEMICALS
Chemical
LDjo (mg/kg)
Sucrose (table sugar)
29,700
Ethyl alcohol
14,000
Sodium chloride (common salt)
3,000
Vitamin A
2,000
Vanillin
1,580
Aspirin
1,000
Chloroform
800
Copper sulfate
300
Caffeine
192
Phenobarbital, sodium salt
162
DDT
113
Sodium nitrite
85
Nicotine
53
Aflatoxin B1
7
Sodium cyanide
6.4
Strychnine
2.5
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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.
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) Nasopharyngealextends 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-
bronchialconsists 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 acinusis 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.
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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
respiratory tract when they are inhaled (Table 4).
they affect the respiratory tract.
can produce acute or chronic diseases of the
The toxicants can be classified according to how
Asphyxiants: Gases that deprive the body tissues of oxygen
Simple asphyxiants: Physiologically inert gases that at high concentrations displace
air leading to suffocation. Examples: nitrogen, helium, methane, neon, argon.
Chemical asphyxiants: 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.
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.
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.
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.
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TABLE 4
EXAMPLES OF INDUSTRIAL TOXICANTS THAT PRODUCE
DISEASE OF THE RESPIRATORY TRACT
Toxicant
Site of Action
Acute Effect
Chronic Effect
Ammonia
Upper airways
Irritation, edema
Bronchitis
Arsenic
Upper airways
Bronchitis, irritation,
pharyngitis
Cancer, bronchitis,
laryngitis
Asbestos
Lung parenchyma
Fibrosis, cancer
Chlorine
Upper airways
Cough, irritation, asphyxiant
(by muscle cramps in larynx)
Isocyanates
Lower airways,
alveoli
Bronchitis, pulmonary edema,
asthma
Nickel Carbony
Alveoli
Edema (delayed symptoms)
Ozone
Bronchi, alveoli
Irritation, edema, hemorrhage
Emphysema, bronchitis
Phosgene
Alveoli
Edema
Bronchitis, fibrosis,
pneumonia
Toluene
Upper airways
Bronchitis, edema,
bronchospasm
Xylene
Lower airways
Edema, hemorrhage
Source: Klaassen et al., pp. 350-51; used with permission of McGraw-Hill, Inc.
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:
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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
chromium compounds, ethylene oxide, hydrogen chloride, iodine, methyl ethyl
ketone, mercury, phenol, phosgene, styrene, sulfur dioxide, picric acid, toluene,
xylene.
Photosensitizers: 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.
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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.
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.
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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.
Organophosphorus compounds: Often used as flame retardants (triorthocresyl
phosphate) and pesticides (Leptofor and Mipafox).
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.
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* 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.
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 (an herbicide), and ethylene dibromide (a fiimigant).
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.
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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
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 particulate 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:
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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.
Types 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.
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.
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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.
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.
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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.
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
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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.
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 (NIOSH 1983). 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
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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
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
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extracted from the 1968 TLVs, the ANSI standards, and other federal standards. Hie 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 13 carcinogens in which there
is no allowable inhalation exposure. The current PELs in 29 CFR 1910.1000 were issued in July
1993 and are the old 1971 values reinstated.
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). NIOSH was formed at the same
time as OSHA to act as a research 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 in 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 III 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:
1000ppm for 3 hours
500 ppm for 2 hours
200 ppm for 3 hours
would have an 8-hour, TWA exposure of:
(3 hrs)(100Q ppm) + (2 hrs)(500 ppm) + (3 hrs)(200 ppm)
8 hrs
3000 ppm + 1000 ppm + 600 ppm
8
= 575 ppm
This exposure would be compared to an 8-hour TWA exposure limit.
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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.
TIME-WEIGHTED AVERAGE
(TWA)
c 750
o
"ฆ+>
CO
-tป
c
d)
o
c
o
o
0
10 am
Time
TWA-EL
6 am
3 pm
GRAPH 3
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 15 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
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be limited to avoid exceeding the TWA. Graph 4 illustrates an exposure that exceeds the IS minute
limit for an STEL of 1000 ppm.
SHORT-TERM EXPOSURE LIMIT
(STEL)
STEL
1000
1 5 mm
TWA-EL
2 750
ฆ*->
CO
-4<
c
Q)
O
c
o
o
10 am
3 pm
6 am
Time
GRAPH 4
EXAMPLE OF AN EXPOSURE COMPARED TO AN STEL AND A TWA
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.
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.
Ceiling (C). 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.
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NIOSH also uses ceiling values. However, their ceiling values are more like an 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.
CEILING
(C)
Ceiling
JlM /\
6 am 10 am 3 pm
Time
GRAPHS
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 are limited. For example, ANSI allowed the
25 ppm ceiling value for benzene to be exceeded to 50 ppm, but only for 10 minutes during an
8-hour period. ANSI withdrew its exposure limit standards in 1982.
"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
C
o
(0
L_
ฃZ
CD
O
c
o
O
0
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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.
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." Where the IDLH concentration is based on the chemical's flammable
characteristics for safety considerations, that value will be 10 percent of the LEL when that value
is more limiting than the toxicological data indicate. Guidelines for potentially explosive, oxygen
deficient, or radioactive environments can be found in the U.S. EPA Standard Operating Safety
Guides (U.S. EPA 1992) and the NIOSH/OSHA/USCG/EPA Occupational Safety and Health
Guidance Manual for Hazardous Waste Site Activities (U.S. DHHS 1985).
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 = (C1Ll + C2~L2) + . . . (CnLJ
where:
Em is the equivalent exposure for the mixture.
C is the concentration of a particular contaminant.
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L is the exposure limit for that substance.
The value ofEm should not exceed unity (1).
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
Biobgical Exposure Indices.
Engineered Controls and Work Practices. 29 CFR 1910.120(g)(l)(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(f)(2)(i) requires a medical surveillance program for all
Toxicology and Exposure Guidelines
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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.
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 for Chemical Substances and Physical Agents and
Biological Exposure Indices (ACGIH 1994) states:
These values 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
or use by countries whose working conditions differ from those in the United States
of America and where substances and processes differ. These limits are not fme lines
between safe and dangerous concentration nor are they a relative index of toxicity.
They 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.
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REFERENCES
ACGIH. 1994. Threshold Limit Values for Chemical Substances and Physical Agents and
Biological Exposure Indices. American Conference of Governmental Industrial Hygienists,
Cincinnati, OH. Used with permission of ACGIH.
Klaassen, C.D., M.O. Amdur, and J. Doull. 1986. Casarett and Doull's Toxicology: The Basic
Science of Poisons. Third Edition. McGraw-Hill, Inc., New York. Used with permission of
McGraw-Hill, Inc.
U.S. DHHS. 1982. Registry of Toxic Effects of Chemical Substances. 1980 Edition - Volume
One. DHHS (NIOSH) Publication No. 81-116. Richard J. Lewis, Sr., and Rodger L. Tatken, eds.
U.S. Department of Health and Human Services, Public Health Service, National Institute for
Occupational Safety and Health, Washington, DC.
U.S. DHHS. 1985. Occupational Safety and Health Guidance Manual for Hazardous Waste Site
Activities. DHHS (NIOSH) Publication 85-115. Prepared by National Institute of Occupational
Safety and Health, Occupational Safety and Health Administration, and U.S. Environmental
Protection Agency for the U.S. Department of Health and Human Services, Washington, DC.
U.S. EPA. 1992. Standard Operating Safety Guides. Publication 9285.1-03; PB 92-3414. U.S.
Environmental Protection Agency, Office of Emergency and Remedial Response, Washington, DC.
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RESPIRATORY PROTECTION:
AIR-PURIFYING RESPIRATORS
STUDENT PERFORMANCE OBJECTIVES
At the conclusion of this unit, students will be able to:
1. Identify and explain the minimal acceptable requirements for
a respiratory program as required by the Occupational Safety
and Health Administration (OSHA) in 29 CFR 1910.134
2. Explain physiological and psychological limitations for
respirator use
3. Give the oxygen requirements for air-purifying respirator
(APR) use as written by the following organizations and
agencies: American Conference of Governmental Industrial
Hygienists (ACGIH) threshold limit values (TLVs),
American National Standards Institute (ANSI) standards,
OSHA, and U.S. Environmental Protection Agency (EPA)
4. Define immediately dangerous to life or health (IDLH)
5. Interpret the safety information as it is written on APR filters
6. List and describe the different types of airborne contaminants
for which APRs are designed
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
-------
STUDENT PERFORMANCE OBJECTIVES (cont.)
7. Identify and describe the types of National Institute of
Occupational Safety and Health (NIOSH)-approved
particulate filters
8. Identify and describe the types of vapor-removing and gas-
removing filters
9. Define "warning properties" and give an example for a
specific chemical
10. Define "breakthrough time" and give an example for a
specific chemical
11. Define "protection factor" and give examples
12. Define maximum use concentration (MUC)
13. Explain how the NIOSH decision logic is used to determine
whether a specific type of respirator can be worn in a
hazardous atmosphere.
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
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NOTES
RESPIRATORY PROTECTION:
AIR-PURIFYING RESPIRATOR!
Y^j/ctLs <4&^
-------
NOTES
fjX
&
M ***
u
APPROVED RESPIRATORS
Mine Safety and Health Administration
(MSHA): Establish testing criteria
National Institute of Occupational Safety
and Health (NIOSH): Conduct approval
testing
S-4
PHYSIOLOGICAL AND PSYCHOLOGICAL
LIMITATIONS FOR RESPIRATOR WEARERS
Respiratory impairment
Anemia
Epilepsy
Punctured eardrum
Facial hair _
as *2/r76t^&-e
ANSI Z88 2-1980
8-5
PHYSIOLOGICAL AND PSYCHOLOGICAL
LIMITATIONS FOR RESPIRATOR WEARERS
(cont.)
^^j^r^iovascular impairment
Diabetes
Claustrophobia
Comfort
Vision ฆ ^
ANSI Z88 2-1980
8-4
Respiratory Protection:
Air-Purifying Respirators
2
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OXYGEN REQUIREMENTS
ACGIHTLVs
ANSI standards
OSHA regulations
U.S. EPA guides
NOTES
19.5%
19.5%
19.5%
IMMEDIATELY DANGEROUS TO
LIFE OR HEALTH (IDLH)
An exposure 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."
/D<-
+1
US. DHHS 1087
s-e
AIRBORNE CONTAMINANTS
Gases
Vapors
Aerosols
- Dust
- Fumes
- Mist
0k
f[)<^
s-s
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Respiratory Protection:
Air-Purifying Respirators
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NOTES
F
yd ฆ
Jl
M 9ft
D/m mlf-
l#d%
WAMtJ
Ml
NIOSH-APPROVED
PARTICULATE FILTERS
Dust
Mist
Fume
HEPA
S-10
NIOSH-APPROVED
PARTICULATE FILTERS
Radionuclides
Asbestos
f{ฃPA
jZjt-.
Single use
Abrasive blasti.
5c
blasting
K.
8-11
l/M/f-'
ePfij
W HX&}
PARTICULATE CLASSIFICATION
Dust and mist
- 80-90% efficiency 0.6 /L/m
Fume
- 90-99% efficiency 0.6 jjm
High-efficiency particulate air (HEPA)
- 99.97% efficiency 0.3 fjm
- Exposure limit <0.05 mg/m3
30 C FRPsrt 11
S-12
Respiratory Protection:
Air-Purifying Respirators
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VAPOR AND GAS-REMOVING
RESPIRATORS
Organic vapors
Acid gases
Ammonia
Combinations (gases, vapors, and
particulates)
8-13
NOTES
VAPOR AND GAS-REMOVING
RESPIRATORS (cont.)
Specific conditions/approvals required
- Carbon monoxide
- Hydrogen sulfide
- Hydrogen cyanide
- Vinyl chloride
- Formaldehyde
S-14
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
US DHHS 1987 S-1S
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Air-Purifying Respirators
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NOTES
fjooDfprty
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
8-16
WARNING PROPERTIES
Warning
EL
Chemical
Concentration
Acetone
0.1-699
759
Butylamine
0.1-5
C - 5
Carbon monoxide
ODORLESS
35 I
Carbon tetrachloride
2-700
C - 2
Hydrogen sulfide
0.00001 -1.4 (fatigue)
C - 10
Sulfur dioxide
0.3-5 (taste)
2
Butyl mercaptan
0.0008-0.038
C-0.5
8-17
PROTECTION FACTORS
Gas and Vapor Exposures
Resoirator Tvoe
NIQ$H
Air-purifying
Quarter mask
5
Half mask
10
Full mask
50
U & DHHS 1087
3-10
Respiratory Protection:
Air-Purifying Respirators
6
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NOTES
PROTECTION FACTORS
Gas and Vapor Exposures (cont.)
Respirator Type NIOSH
Air-puwfymg
Demand
Half mask 10
Full mask 50
Pressure-Demand
Full mask airline 2,000
Full mask SCBA 10,000
US. DHHS 1997
S-10
cK? ST
"HVIUC = PF X EL
? =10x10 ppm
500 = ? x 5 ppm
RESPIRATOR SELECTION
Substanoo
IdontHlftd
I
| Oxygen oonient~
-ป| Carcinogen | ~ | SCBA
-ป| Intulllclont -+\ SCBA
J
Known
ooncartratton
fclDLH
->[ SCBA
Respirator protection
factor
>MUC
"M SCBA
J .
|
-------
NOTES
RESPIRATOR SELECTION
Nature of hazard
Characteristics of operation and worker
activity
Location of hazardous area
Duration of respirator use
Respirator capabilities and limitations
ANSI Z8B 2-1080 S-22
Respiratory Protection:
Air-Purifying Respirators
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RESPIRATORY PROTECTION: AIR-PURIFYING RESPIRATORS
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. 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.
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.
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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
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
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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, Z88.2-1992, was issued 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.
Section b of 29 CFR 1910.134, as well as Z88.2-1992, 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.
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Air-Purifying Respirators
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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 Z88.2-1992 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.
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 Z88.2-1992 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).
Respiratory Protection:
Air-Purifying Respirators
12
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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 1994, is entitled the NIOSH Certified Equipment List as of December 31,
1994. 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).
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Air-Purifying Respirators
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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) particulate 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 - 1992. 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 particulate 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
Respiratory Protection:
Air-Purifying Respirators
14
9195
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Maximum Use Concentration of a particular type and size cartridge or canister must
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-Purifving 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 particulate can be determined by its exposure
limit (EL). A nuisance particulate will have an EL of 10 mg/m3, while a toxic
particulate may have an EL well below 0.05 mg/m3.
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Respiratory Protection:
Air-Purifying Respirators
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Mechanical filters are classified according to the protection for which they are
approved under schedule 21C of 30 CFR Part 11. Most particulate filters are
approved only for dusts 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 1. 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
Respiratory Protection:
Air-Purifying Respirators
16
9/95
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several factors: the breathing rate of the wearer, contaminant concentration, and
sorption efficiency.
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 50 ppm.
Chemical sorbents vary in their ability to remove different specific chemicals within
a given chemical group. A cartridge designed to remove alcohols, for example, may
break through after only 10 seconds in a 1000 ppm concentration of methanol, but
last as long as 100 minutes in a 1000 ppm concentration of allyl alcohol. Cartridge
efficiencies need to be considered when selecting APRs.
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17
Respiratory Protection:
Air-Purifying Respirators
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TABLE 1
CHEMICAL CARTRIDGE TYPES AND COLOR CODING
29 CFR 1910.134
Atmospheric Contaminants to be
Protected Against
Colors Assigned1
Acid gases
White
Hydrocyanic acid gas
White with 1/2-inch green stripe completely around
the canister near the bottom
Chlorine gas
White with 1/2-inch yellow stripe completely around
the canister near the bottom
Organic vapors
Black
Ammonia gas
Green
Acid gases and ammonia gas
Green with 1/2-inch white stripe completely around
the canister near the bottom
Carbon monoxide
Blue
Acid gases and organic vapors
Yellow
Hydrocyanic acid gas and chloropicrin
vapor
Yellow with 1/2-inch blue stripe completely around
the canister near the bottom
Acid gases, organic vapors, and
ammonia gases
Brown
Radioactive materials, excepting
tritium and noble gases
Purple (Magenta)
Particulates (dusts, fumes, mists, fogs,
or smokes) in combination with any of
the above gases or vapors
Canister color for contaminant, as designated above,
with 1/2-inch gray stripe completely around the
canister near the top
All of the above atmospheric
contaminants
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.
Respiratory Protection:
Air-Purifying Respirators
18
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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 levelsthat is, greater than ELis 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.
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.
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19
Respiratory Protection:
Air-Purifying Respirators
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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:
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.
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:
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.
Concentration outside mask
APF = Concentration inside mask
MUL = APF X TLV
Respiratory Protection:
Air-Purifying Respirators
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RESPIRATORY PROTECTION:
SUPPLIED-AIR RESPIRATORS (SAR)
STUDENT PERFORMANCE OBJECTIVES
At the conclusion of this unit, students will be able to:
1. State the benefits of supplied-air respirators (SARs)
2. Identify three types of SARs in use today
3. Identify and explain the following as related to hose mask
SARs:
a. Components and basic operation
b. Uses and limitations
4. Identify and explain the following as related to air-line
SARs:
a. Components and basic operation
b. Emergency air supply requirements with air-line
systems
c. Breathing air sources available with air-line systems
d. Uses and limitations
5. Identify and explain the following as related to escape self-
contained breathing apparatus (SCBA):
a. Components and basic operation
b. Uses and limitations
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
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STUDENT PERFORMANCE OBJECTIVES (cont.)
6. Identify and explain the following as related to SCBA SARs:
a. Basic operation and differences between the open
circuit SCBA and closed circuit SCBA systems
b. The advantages and disadvantages of closed circuit
systems
c. The advantages and disadvantages of open circuit
systems
d. Positive pressure vs. negative pressure (demand)
SCBA units
e. Major components of an open circuit SCBA
f. Types of air cylinders and hydrostatic tests
g. Minimum breathing air standards.
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
9/95
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ฆe/icycLo^edi^
NOTES
RESPIRATORY PROTECTION:
SUPPLIED-AIR RESPIRATORS
SUPPLIED-AIR RESPIRATORS
Benefits
Provide breathing air
No filter/sorbent limitations
Better protection factors
S-2
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"
8-3
CGS-
i lAs
Must (]ottk.a~
C. -
cJ^c^xacjZ,
9/95
1
Respiratory Protection:
Supplied-Air Respirators
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NOTES
tP
6^
pe-c-ki ?
Respiratory
Supplied-Air
COMPARISON OF
RESPIRATOR PROTECTION FACTORS
TvDe of ResDirator
Assigned Protection
Factor (APF)
Negative Pressure
Full facepiece APR
Full faceDiece SAR
50
50
Positive Pressure
Full facepiece alr-line
(without SCBA)
Full facepiece SCBA
2,000
10,000
US DHHS 1087
8-4
pA
a
oJ
ection:
irators
SUPPLIED-AIR RESPIRATORS ^
Types
" Hose mask-f^
Airline-
Self-contained breathing apparatus (SCBA)
Combination airline/SCBA
Escape SCBA
3.5
TYPES OF SCBAs
Closed circuit
Open circuit
8-0
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NOTES
BREATHING AIR SPECIFICATIONS
Breathing air quality shall be at least
Grade D air as defined in the
Compressed Gas Association
Standard, ANSI/CGA G-7.1 Commodity
Specifications for Air
7
<2/
oc^cxcjfxrX- a&&~'
9/95
Respiratory Protection:
Supplied-Air Respirators
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RESPIRATORY PROTECTION: SUPPLIED-AIR RESPIRATORS
Supplied-air respirators (SARs) 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
>vearer by a portable breathing air source (self-contained breathing apparatus [SCBA]) or by a
stationary source such as an air line (an SAR).
Types of Supplied-Air Respirators
Respiratory apparatus must frequently be used during response to hazardous materials incidents. If
the contaminant is unknown, or the requirements for using APRs cannot be met, then am SAR is
required. Several types of SARs 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.
Air-line Respirator. The air-line 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 air line 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 C02 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 air line. 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:
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Respiratory Protection:
Supplied-Air Respirators
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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 1). 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 1
RELATIVE PRESSURE INSIDE AND OUTSIDE SCBA FACEPIECE
Pressure Demand
Action
Demand
(positive pressure)
Inhalation
_
+
Exhalation
+
+
Static (between breaths)
same
+
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.
Respiratory Protection: ^
Supplied-Air Respirators If" 6
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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
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
Source: Los Alamos Scientific Laboratory 1977
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 Pan 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
Hta4 Hirrull
fiuplttt
Chrct Viln
Eilulillon
SjIi*i lrip _ (
int Prcnuri j
Relief Vilrc
Irillhlnf
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FIGURE 1
CLOSED-CIRCUIT SCBA
9/95
7
Respiratory Protection:
Supplied-Air Respirators
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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."
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.
Respiratory Protection:
Supplied-Air Respirators
8
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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 ฑ5%.
Because the gauge is exposed and subject to abuse, it should be used only forjudging
if the cylinder is full, and not for monitoring air supply to the wearer.
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.
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9
Respiratory Protection:
Supplied-Air Respirators
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FIGURE 2
REGULATOR ASSEMBLY
Reprinted from MSA Data Sheet 01-00-11: Pressure Demand Air Mask and Air Club", no date-c, with
permission of Mine Safety Appliances Company.
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.
Respiratory Protection:
Supplied-Air Respirators
10
9/95
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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
DOT E - 7277-2216
ALT 59-32150
ELASTIC EXPANSION 96-106 ml
G
SCI
8-88
CONTENTS- AIR; 45 SCF AT 2216 PSIG
MINE SAFETY APPLIANCES CO.
PART NO 460320
FIGURE 3
INFORMATION ON TYPICAL SCBA CYLINDER LABEL
Reprinted from MSA cylinder label, 1994, with permission of Mine Safety Appliances Company.
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:
9/95
11
Respiratory Protection:
Supplied-Air Respirators
-------
That the units be NIOSH/MSHA certified positive-pressure
The maximum weight shall not exceed 35 pounds, in accordance with
NIOSH/MSHA certification
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
Respiratory Protection:
Supplied-Air Respirators
12
9/95
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apparatus is designed to properly function when exposed to dust conditions commonly
present during firefighting operations.
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.
REFERENCES
Los Alamos Scientific Laboratory. 1977. A Guide to Industrial Respiratory Protection. LA-6671-
M. Los Alamos Scientific Laboratory, Los Alamos, NM.
U.S. DHHS. 1987. NIOSH Respirator Decision Logic. DHHS Publication No. 87-108. U.S.
Department of Health and Human Services, Public Health Service, Centers for Disease Control,
National Institute for Occupational Safety and Health, Division of Standards Development and
Technology Transfer.
9/95
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Respiratory Protection:
SuppUed-Air Respirators
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LEVELS OF PROTECTION AND
CHEMICAL PROTECTIVE CLOTHING
STUDENT PERFORMANCE OBJECTIVES
At the conclusion of this unit, students will be able to:
1. List the factors that should be considered when selecting a
level of protection
2. Identify the major criteria used to select Level A, Level B,
Level C, and Level D
3. List the U.S. Environmental Protection Agency equipment
for Level A, Level B, Level C, and Level D
4. Identify and explain the performance qualities that should
be considered when selecting protective clothing
5. Identify and explain the chemical resistance properties that
are attributed to protective clothing
6. Explain the difference between nonelastomers and
elastomers as the construction materials used in protective
clothing
7. Give examples of nonelastomer and elastomer materials
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
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STUDENT PERFORMANCE OBJECTIVES (cont.)
8. Give examples of "proprietary materials" for protective
clothing
9. Explain the difference between disposable, limited-use,
and extended-use clothing
10. Describe the various types of suit configurations
11. List the various suit components
12. Explain how to inspect a suit and how to determine its
integrity
13. Briefly explain the chemical protective clothing regulatory
standards and guidance under Occupational Safety and
Health Administration (OSHA), National Fire Protection
Association, and American Society for Testing and
Materials
14. Briefly explain the personal protective clothing
requirements under OSHA 29 CFR 1910 General Industry
Standards: General Requirements, Eye and Face
Protection, Respiratory Protection, Head Protection, and
Foot Protection.
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
9/95
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NOTES
LEVELS OF PROTECTION
AND CHEMICAL
PROTECTIVE CLOTHING
8-1
SELECTING LEVELS OF
PROTECTION
Known
Chemical hazard recognition
Actual concentrations vs. exposure guidelines
Work function - ^ ^
Work location
Weather conditions
/ (J
US EPA 1X2
LEVEL D
Should not be worn on any site
with respiratory or skin hazards.
Level D is primarily a work uniform
providingIrriinimarprotection from
physical hazards.
U $ EPA 1992
8-3
c ffrlr Ms
77
f/laojU"
<0
jfjjl
9/95
1
Levels of Protection and
Chemical Protective Clothing
-------
NOTES
LEVEL D PROTECTION
IS USED WHEN:
Atmosphere contains no known hazard
Work function precludes the potential
for unexpected exposure to hazardous
levels of anv substances #3 - ^ 1
U.S. EPA 1092
8-4
LEVEL D EQUIPMENT
Coveralls
Gloves*
Safety boots/shoes
(leather or chemical
resistant)
Disposable boot covers-
US. EPA 1092
S-5
LEVEL D EQUIPMENT (cont.)
Safety glasses or chemical
splash goggles*
Hard hat (face shield*)
Escape mask*
'Optional
US. EPA 1992
8-0
Levels of Protection and
Chemical Protective Clothing
9/95
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NOTES
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
U & EPA 1992
8-7
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
U S. EPA 1992
LEVEL C EQUIPMENT
Air-purifying respirator
(full-face, canister)
Hooded chemical-resistant
clothing
Inner clothing
Chemical-resistant gloves
(inner and outer)
U S EPA 1992
8-9
9/95
3
Levels of Protection and
Chemical Protective Clothing
-------
NOTES
~j-ฃ>
TJjx^-
Jt
LEVEL C EQUIPMENT
Chemical-resistant safety boots
Disposable boot covers*
Hard hat (face shield*)
Escape mask*
Two-way radio
'Optional
US. EPA 1092
8-10
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.
US. EPA 1992
3-11
LEVEL B PROTECTION
IS USED WHEN:
9^* 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
rffe. Direct contact does not pose a severe
skin hazard
US. CPA 1092
8-12
Levels of Protection and
Chemical Protective Clothing
4
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LEVEL B EQUIPMENT
Supplied-air respirator
(pressure-demand)
Hooded chemical-resistant clothing/
Inner clothing
y
Chemical-resistant gloves
(inner and outer)
NOTES
U S. EPA 1002
S-13
LEVEL B EQUIPMENT
Chemical-resistant safety boots
Disposable boot covers*
Hard hat (face shield*)
Two-way radio
'Optional
US. EPA 1992
LEVEL A
Should be worn when the highest level
of respiratory, skin, and eye protection
is required
US EPA 1002
9/95
5
Levels of Protection and
Chemical Protective Clothing
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NOTES
Levels of Protection and
Chemical Protective Clothing
LEVEL A PROTECTION
IS USED WHEN:
Conditions are unknown
Substance has been identified and
requires highest level of protection
US EPA 1002
8-19
LEVEL A PROTECTION
IS USED WHEN: (cont.)
Operations are conducted in
confined, poorly ventilated areas
Work involves a high potential for
splash or exposure to skin hazards
US. EPA 1002
S-17
Level A Equipment
Supplied-air respirator
(pressure-demand)
fully encapsulating
chemical-resistant suit
Inner clothing
Chemical-resistant gloves
(inner and outer) u
pfcLwt ff! 0^'
U.S EPA 1092
3
8-18
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NOTES
Level A Equipment (cont.)
Chemical-resistant safety boots
Outer clothing (disposable protective
suit, gloves, and boot covers)*
Hard hat* (under suit) , ^
-cr^rCC^t
Two-way radio
ad
yU
A '
LtsO -A-
Cooling unit* - /w&f
Two-wav "*"* tT ^
1 xl
US. EPA 1902
'Optional
S-1Q
Levels of Protection
Chemical
Protective
Clothing
Respiratory
Protection
Level A
FES
SAR
Level B
Splash
Suit
LevelC
APR
Level D
None
None
8-20
Jhnffe ฆ O/ fl
'54^.
/3/ป/^ 1&P-
PERFORMANCE QUALITIES
/j/lL %L ML- iaUla^
Durability
Temperature resistance
Ma.
resistance
Aging resistance r
Design
f&e) 0
Flexibility
es
(color)
''f? i
pzt~- u'
9195 7
8-21
fKajf - Lia/ tO
6f protection an
Chemical Protective Clothing
-------
fNOTES
WW**
CHEMICAL RESISTANCE
Penetration
Degradation
Permeation
S-22
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
3-23
DEGRADATION
(A Chemical Process)
A deleterious change in one or more
physical properties of a protective
clothing material due to contact
. drcmiMl ff.
ASTM F739
ULfft,
' 8-24
O
Levels of Protection and
Chemical Protective Clothing
8
9/95
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PERMEATION
(A Chemical Process)
The process by which a chemical
moves through a protective clothing
material on a molecular level
ASTMF73B
8-25
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
3. Desorption of the molecules from the
opposite (inside) surface of the
material into the collectingjnediura-
ASTU F739
S-20
MEASURED PARAMETERS
Breakthrough time
Permeation rate (steady-state)
NOTES
A f/*-
-------
PERMEATION/DEGRADATION RESISTANCE GUIDE
NITRILE NBR
NEOPRENE
PVC
PR
PBT
DR
PR
PBT
DR
PR
PBT
DR
3 hr
Acetone
NR
NR
5 min
Cellosolve
acetate
NR
1.5 hr
VG
Hydrofluoric
acid (48%)
2 hr
Toluene
NR
NR
10 min
NR
NR
1.5 hr
Trichloroethane
DR = Degradation rating
PBT = Permeation breakthrough time
PR = Permeation rate
NR = Not recommended
Ansell Edmont 1990
S-28
0
Levels of Protection and
Chemical Protective Clothing
10
9/95
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NOTES
BLENDS AND LAYERS
Neoprene and latex rubber (gloves)
Vitonฎ/Neoprene (FES - MSA Vautex,
Draeger)
Vitonฎ/Butyl (FES - Trellborg)
PVC/Nitrile (boots)
PVC/Paracril (splash suit)
S-29
PROTECTIVE CLOTHING
REFERENCES
Manufacturers' data
Published studies
Guidelines for the Selection of
Chemical Protective Clothing
(Arthur D. Little, Inc.)
Field test kits
PROTECTIVE CLOTHING
REFERENCES
Personal Protective Equipment for
Hazardous Material Incidents:
A Selection Guide (NIOSH)
Quick Selection Guide to
Chemical Protective Clothing
(K. Forsberg/S.Z. Mansdorf)
Computer systems
9/95
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Levels of Protection and
Chemical Protective Clothing
-------
NOTES
PERSONAL PROTECTIVE
EQUIPMENT
OSHA REGULATION
29CFR 1010 132
General Requirements
41 CFR 50-204.7
29 CFR 1910.133
Eye and Face Protection
ANSI Z87.1-1068
(Rev. 1069)
20 CFR 1010 134
Respiratory Protection
ANSI Z88.2-1060
(Rev 1002)
20 CFR 1010 135
Head Protection
ANSI Z80.1-1069
(Rev 1080)
20 CFR 1010 136
Foot Protection
ANSI Z41.1-1067
(Rev 1083)
S-32
Levels of Protection and
Chemical Protective Clothing
12
9/95
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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 that have a detrimental
effect on the skin or that 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 chemical protective
clothing. 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 chemical protective clothing. Each
of these materials provides a degree of skin protection against a range of chemicals. Not one
materia] affords the maximum protection against all chemicals. The chemical protective clothing
selected must be made from a material which 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.
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Chemical Protective Clothing
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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 and oxidizing
agents 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 makes it easier to maintain visual contact
among personnel. Suits of darker colors (e.g., 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 that may have to be discarded after
limited use.
Chemical Protective Clothing
14
9/95
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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
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
because of design or garment imperfections. Stitched seams, buttonholes, 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 chemicals or generic classes of chemicals (Table 1) are 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
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 that involves the sorption of the chemical on the outside
surface, diffusion through the material, 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
9/95
15
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)
Generic Class
Butyl
Rubber
Polyvinyl
Chloride
Neoprene
Natural
Rubber
Alcohols
E
E
E
E
Aldehydes
E-G
G-F
E-G
E-F
Amines
E-F
G-F
E-G
G-F
Esters
G-F
P
G
F-P
Ethers
G-F
G
E-G
G-F
Halogenated hydrocarbons
G-P
G-P
G-F
F-P
Hydrocarbons
F-P
F
G-F
F-P
Inorganic acids
G-F
E
E-G
F-P
Inorganic bases and salts
E
E
E
E
Ketones
E
P
G-F
E-F
Natural fats and oils
G-F
G
E-G
G-F
Organic acids
E
E
E
E
E - Excellent F - Fair
G - Good P - Poor
Source: U.S. DOT 1974
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
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, available from manufacturers, give specific rates and times
(Table 2). A given manufacturer's recommendations serve as a relative guideline to properly
selecting their products. These data are obtained using the American Society for Testing and
Materials (ASTM) standard test method F739-81. Although ASTM has a standard method for
Chemical Protective Clothing
16
9/95
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TABLE 2
PERMEATION/DEGRADATION RESISTANCE FOR EDMONT GLOVES*
Nitrite NBR
Neoptcns
FVC
Permeation Rate
Permeation Breakthrough
Degradation Rating
Permeation Rate
Permeation Breakthrough
Degradation Rating
Permeation Rate
Permeation Breakthrough
Degradation Rating
Acetone
NR
-
-
B
5 min
F
NR
3 hr
-
Cellosolve acetate
F
1.5 hr
G
G
1.25 hr
VG
NR
-
-
Dimethyl sulfoxide
(DMSO)
E
<4 hr
VG
E
ND
E
NR
-
-
Hydrofluoric acid,
48%
E
2 hr
-
E
1 hr
-
G
40 min.
-
Propyl acetate
F
20 min.
G
P
-
-
NR
-
-
Toluene
F
10 min.
F
NR
-
-
NR
-
-
1,1,1-Trichloroethane
F
1.5 hr
P
NR
-
-
NR
-
-
KEY TO PERMEATION RATE
(Simply stated, drops per hour through a glove (eyedropper-size drop).
ND
None detected during 6-hour test (Equivalent to
NONE
Excellent)
E
Excellent; permeation rate of less than 0.09
0-1/2 drop
/xg/cm2/min.
VG
Very Good; permeation rate of less than 9
1-5 drops
/ig/cm2/min.
G
Good; permeation rate of less than 90
6-50 drops
/xg/cm2/min.
F
Fair; permeation rate of less than 900
51-500 drops
/ig/cm2/min.
P
Poor; permeation rate of less than 9000
501-5000 drops
/xg/cm2/min.
NR
Not recommended; permeation rate greater than
^5001 drops
9000 ^g/cm2/min.
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, "/ig/cm2/min."
Reprinted from Ansell, Edmont Chemical Resistance Guide, 5th Edition, 1990, with permission from
Ansell, Edmont Industrial.
9/95
17
Chemical Protective Clothing
-------
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 manufacturers' 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 that 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
reflect 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 (A.D. Little, Inc. 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. Further selection information is also available on
computer data bases.
Specific chemicals are rated against a variety of protective materials. The ratings (RR, it, 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 chemical protective clothing 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.
Classification of Chemical Protective Clothing
Style:
Fully Encapsulating Suit (FES). Fully encapsulating, chemical protective clothing
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 ensure integrity.
Respiratory protection and breathing air is provided to the wearer by a positive-
pressure, self-contained breathing apparatus worn under the suit, or by an air-line
respirator which 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.
Chemical Protective Clothing
18
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TABLE 3
GUIDELINES FOR THE SELECTION OF CHEMICAL PROTECTIVE CLOTHING (ACGIH)
4>
t-l
u
0>
3
73
In
3
n
2
Neoprene
'S
2
Nitrile
ฃ
Oh
PV Alcohc
PVC
Viton
1
2
s
PQ
Other
Materials
Inorganic Salts (34)
Ammonium fluoride
Neop+Nat Rub (r)
Ammonium fluoride, 30-70%
rr
rr
rr
rr
Ammonium sulfate
r
R
R
r
r
R
Polyurethane (R)
Arsenic trichloride
n
n
Bromine trifluoride
n
n
Calcium chloride
r
R
R
r
r
R
Polyurethane (r)
Calcium hypochlorite
r
R
R
r
r
R
Polyurethane (r)
Copper chloride
n
r
r
r
Polyurethane (r)
Copper sulfate
n
R
r
R
Polyurethane (r)
Cupric chloride
r
n
R
r
R
Polyurethane (r)
Cupric sulfate
r
n
R
r
r
R
Polyurethane (r)
Ferric chloride
r
r
R
r
R
Polvurethane
Source: A.D. Little, Inc. 1987
Note: For explanation of recommendation codes (e.g. r, it, R, n), refer to Arthur D. Little, Inc., 1987.
-------
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 chemical protective clothing (frequently
called splash suits) does not have a facepiece as an integral part of the suit. A
positive pressure self-contained breathing apparatus 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 chemical protective clothing is commonly considered to be less than
$25.00 per garment. In 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 (A.D. Little, Inc. 1985) and
manufacturer's literature.
Chemical Protective Clothing
20
9195
-------
Elastomers
Natural Rubber: (Polyisoprene)
Good for: alcohols, dilute acids and bases, flexibility
Poor for: organic chemicals, aging (affected by ozone)
Polyvinyl Alcohol (PVA):
Good for: almost all organics, ozone resistance
Poor for: esters, ethers, acids and bases, water and water solution's
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)
Nitrile 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 and halogenated hydrocarbons, amides, ketones,
esters, cold temperature
Note: The higher the acrylonitrile concentration, the better the chemical
resistance; but also increases stiffness.
Polyvinyl Chloride (PVC):
Good for: acids and bases, some organics, amines, peroxides
Poor for: most organic compounds, cut and heat resistance,
decontamination
Neoorene (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
21
Chemical Protective Clothing
-------
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:
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.
Polvurethane:
Good for: bases, aliphatic hydrocarbons, alcohols, abrasion resistance,
flexibility - especially at cold temperatures
Poor for: halogenated hydrocarbons
Blends/Lavers:
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
Tvvek (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 contamination of nondisposable items and under
suits to replace cotton.
Chemical Protective Cbthing
22
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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 for 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 mechanism. 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.
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.
9/95
23
Chemical Protective Clothing
-------
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.
-Tubing manifold
Perforated tubing
Adjusting valve
Supply air
FIGURE 1
FULLY ENCAPSULATING SUIT WITH AIR DISTRIBUTION SYSTEM
The air is delivered to the units comes 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
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
Chemical Protective Clothing
24
9/95
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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.
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
minute. Also, the hot air from the vortex tubeas hot as 162' Fcan add heat to the
environment or to the outside surface of the protective clothing.
<%>
Hot air
FIGURE 2
SCHEMATIC OF VORTEX TUBE
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 supplywhich can be
chilledor a portable chilling unit for recirculated water.
9/95
25
Chemical Protective Clothing
-------
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/jacket or in removable packets. The size and number
of packets vary form manufacturer to manufacturer. Some systems come with a
inner vest to prevent direct contact with the skin. Some have an outer vest to reduce
external heat effects on the ice.
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 (12-15 pounds) with no cooling benefit. If there is
no inner insulation, they may be too cold.
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. 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.
Chemical Protective Cbthing
26
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REFERENCES
A.D. Little, Inc. 1985. Guidelines for the Selection of Chemical Protective Clothing. Second
Edition. Prepared by Arthur D. Little, Inc., Cambridge, MA, under contract to Los Alamos
National Laboratory, for the U.S. Environmental Protection Agency, Washington, DC.
A.D. Little, Inc. 1987. Guidelines for the Selection of Chemical Protective Clothing. Third
Edition. Prepared by Arthur D. Little, Inc., Cambridge, MA, under contract to Los Alamos
National Laboratory, for the U.S. Environmental Protection Agency, Washington, DC.
Ansell, Edmont. 1990. Chemical Resistance Guide, 5th Edition. Ansell, Edmont Industrial,
Coshocton, OH. Used with permission.
ASTM. 1981. ASTM Standard Test Method F739-81. American Society for Testing and Materials,
Philadelphia, PA.
U.S. DOT. 1974. Survey of Personal Protective Clothing and Respiratory Apparatus. U.S.
Department of Transportation, Office of Research and Development, Washington, DC.
U.S. EPA. 1992. Standard Operating Safety Guides. U.S. Environmental Protection Agency,
Office of Emergency and Remedial Response, Emergency Response Division, Environmental
Response Team, Washington, DC.
9/95
27
Chemical Protective Clothing
-------
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(t>
o
o
CO
-------
SITE ENTRY AND RECONNAISSANCE
V
STUDENT PERFORMANCE OBJECTIVES
At the conclusion of this unit, students will be able to:
1. Explain the purpose of a health and safety plan
2. Identify the minimal acceptable requirements for a health and
safety plan
3. Define offsite characterization and give examples of the
types of information obtained in an offsite characterization
4. Define perimeter reconnaissance and give examples of what
to look for when conducting a perimeter reconnaissance
5. Define initial site survey and entry and explain what is
accomplished during an initial site survey and entry.
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
9/95
-------
NOTES
SITE ENTRY AND
RECONNAISSANCE
8-1
SITE SAFETY PLAN
REQUIREMENTS
At a minimum, the plan must cover:
Key personnel, alternates, and health and
safety personnel
Safety and health risk analysis
Employee training
Personal protective equipment
Air monitoring program
QiM.
'0'
- ui . Jpo- *
SITE SAFETY PLAN
REQUIREMENTS (cont.)
Site control measures
Decontamination procedures-^
Emergency response planning*^
Confined space procedures
9/95
o J
Site Entry and Reconnaissance
-------
NOTES
SITE SAFETY PLAN
REQUIREMENTS (cont.)
Medical surveillance program
Spill containment
S-4
THREE WORK ZONES J,
Support zone (cold) ^
- Command post
- No contamination
- Normal work clothes
Contamination reduction zone (warm)
- Decon line * n
- PPE required a1
Exclusion zone (hot)
- Hot line
- Contamination
- PPE required
Hot fine
EXCLUSION ZONE
Aeoati oontrol
polrm ~
Ptnoimtl
Decontamination
CoirMo'
Wind
CONTAMINATION
REDUCTION ZONE
Control
s-s
OWMnd
potl
SUPPORT ZONE
DIAGRAM OF SITE WORK ZONES
s-e
Site Entry and Reconnaissance
2
9/95
-------
NOTES
SITE CONTROL
Security/physical barriers
Minimize personnel/equipment
Work zones
Access control points
Control airborne dispersion
Decontamination procedures
OFFSITE CHARACTERIZATION
Interviews and Records Research
Habitation
Site location and size
Response activities/emergency
Duration of employee activity
Site topography
OFFSITE CHARACTERIZATION
Interviews and Records Research (cont.)
Geologic and hydrologic data
Accessibility by air/road
Hazardous substances involved
Pathways of dispersion
Previous surveying/sampling
9/95
3
Site Entry and Reconnaissance
-------
NOTES
PERIMETER RECONNAISSANCE
->v
&
Site maps
Historical/current photographs-
Container/vehicle markings
Condition of containers/vehicles
Biologic indicators
S-10
/ ,(P'
7
PERIMETER RECONNAISSANCE
(cont.)
Unusual conditions
Unusual odors
Air monitoring at site perimeter
Offsite samples
mpi
8-11
ONSITE SURVEY
Primary Entry Objective
Monitor air for IDLH atmospheres
- Combustibles or explosives
- Oxygen deficiency ซ
-------
NOTES
EPA ACTION GUIDELINE v
Combustible Gas Indicators
METER READING
ACTION
<10% LEL
Continue investigation
with caution
10-25%
Continue onsite monitoring
with extreme caution as
higher levels are encountered
>25%
Explosion hazard! Withdraw
from area immediately
U S EPA 1992
S-13
EPA ACTION GUIDELINE
Oxygen Indicators
METER READING
<19.5%
19.5-25%
ACTION
Monitor wearing SCQA
(Note: CGI readings may . ฆ )
not be valid
Continue investigation with
caution. SCBA not needed
based only on oxygen content.
>25%
Discontinue Investigation:
fire hazard potential
US EPA 1092
3-14
Sc>
EPA ACTION GUIDELINE
Radiation Survey
METER HEAPIMS
<1 mR/hr
al mR/hr
ACTION
l( levels are above background,
continue investigation with
caution. Perform thorough
monitoring. Consult health
physicist.
Potential radiation hazard.
Suspended site activities.
Continue monitoring only upon
advice of a health physicist
5
U S. EPA 1992
7U&3&
emd^^0
jjbdL^X-^
9/95
5
Site Entry and Reconnaissance
-------
NOTES
EPA ACTION GUIDELINE
Total Gas/Vapor Meters
MFTFR RFADINGS
ACTION
Unknowns
Background
Level D
0-5
Level C
5-500
Level B
500-1000
Level A
>1000
Consider explosive
Knowna
Compare to Exposure Quldes
IDLH/PEL/REL/TLV
U.S. EPA 1002
8-10
ONSITE SURVEY
Primary Entry Objective (cont.)
Visually observe for signs of IDLH
conditions
- Confined spaces
- Visible vapor clouds
- Biological indicators
8-17
ONSITE SURVEY
Entry Objective
Note types of containers
- Paper or wood packages
- Metal or plastic barrels/drums
- Underground tanks
- Aboveg round tanks
- Compressed gas cylinders
- Pits, ponds, or lagoons
8-1B
Site Entry and Reconnaissance
6
9/95
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NOTES
ONSITE SURVEY
Entry Objective (cont.)
Note condition of containers
and storage systems
- Sound (undamaged)
- Rusted or corroded
- Leaking
- Bulging
- Types and quantities of material
- Labels
ONSITE SURVEY
Entry Objective (cont.)
Note physical condition of materials
- Solid, liquid, or gas
- Color and turbidity
- Behavior (corroding, foaming,
or vaporizing)
- Conditions conducive to splash
or contact -*9toU?
S-20
ONSITE SURVEY
Entry Objective (cont.)
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
S-21
9/95
Site Entry and Reconnaissance
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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. TTiis 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 onsite
immediately, conduct an offsite reconnaissance by: (1) making visual observations; (2) monitoring
atmospheric hazards near the site; and (3) collecting offsite samples that may indicate onsite
conditions or migration from the incident.
An offsite 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.
9/95
9
Site Entry and Reconnaissance
-------
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.
Offsite 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
10
9/95
-------
- 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.
Onsite Survey
A more thorough evaluation of hazards generally requires personnel to enter the defined site. Before
going onsite, 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. Onsite 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.
9/95
11
Site Entry and Reconnaissance
-------
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
12
-------
REFERENCES
U.S. EPA. 1992. Standard Operating Safety Guides. U.S. Environmental Protection Agency,
Office of Emergency and Remedial Response, Emergency Response Division, Environmental
Response Team, Washington, DC.
9/95
13
Site Entry and Reconnaissance
-------
RADIATION SURVEY INSTRUMENTS
V
STUDENT PERFORMANCE OBJECTIVES
At the conclusion of this unit, students will be able to:
1. Briefly explain atomic structure
2. Define radioactivity
3. Describe radiation characteristics for alpha particles, beta
particles, and gamma rays
4. Describe radiation units of measurement: roentgen, rad,
rem, and quality factor
5. Describe the biological effects of ionizing radiation
6. Define background radiation
7. State the U.S. Environmental Protection Agency Action
Level for radiation
8. Define ALARA (as low as reasonably achievable)
9. List and explain the primary methods for reducing external
radiation dose
10. Explain the purpose of radiation monitoring
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
9/95
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STUDENT PERFORMANCE OBJECTIVES (cont.)
11. List the limitations and considerations when using radiation
detection instruments.
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
9/95
-------
NOTES
RADIATION SURVEY
INSTRUMENTS
RADIOACTIVITY
S-1
' f
The tendency of unstable atoms to
undergo radioactive decay.
Radioactive atoms are called
radionuclides.
3-2
A#ฃfz<~tCฃ^(U<7
sC*3 /If-
1*
Radioactive Decay
-/
}&ijWi/L d f) -r-f. a>~- *
effete
v
9/95
1
Radiation Survey Instruments
-------
NOTES
e&cL
RADIATION
Characterics of the Three Major Types
f
Source
Symbol
Form
Relative
Matt
(Charge)
0 of
Ionizations
/cm In Air
Path
Length
In Air
Hazard
Location
ot Source
ALPHA
a
Particle
4
(+2)
100,000*6
<1 inch
Internal
BETA
0
Part tela
0 00099
(+/-1)
100*8
1 meter
Internal/
External
GAMMA
y
Bactro-
magnetic
energy
0
(0)
1.^
Several
meters
to
kilometers
Internal/
External
S-4
DEFINITIONS
Roentgen (R) - 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 (QF) - 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 that represents
the risk associated with the radiation exposure
s-s
rad x
QF
= 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
S-6
Radiation Survey Instruments
2
9/95
-------
RADIATION SUBUNITS
1000 mrem = 1 rem
1000/irem = 1 mrem
NOTES
8-7
ACUTE EXPOSURE RISK
700 rem
^100^
fJo <
600 rem
= ">99
450 rem
= LDso
200 rem
* lDlo
100 rem
* TDlo
25 rem
2
Q
UJ
II
8-8
a/q cr>c&- />
CHRONIC EXPOSURE RISK
A normal U.S. citizen has a 25% risk
of cancer. 1 rem increases risk to 25.03%.
33%
100 rem increases risk to 28%.
S-8
9/95
3
Radiation Survey Instruments
-------
NOTES
1
AP'osi
V ^
ivy
BACKGROUND RADIATION
Is unavoidable
Comes from cosmic sources and earth
materials
Averages .01 -.02 mR/hr gamma in the
United States'" ~
U.S. EPA ACTION LEVEL
1 mR/hr gamma above background
1 mR/hr = 1000/iR/hr
$,4 e
U S EPA 1002
S-11
AS LOW AS REASONABLY
ACHIEVABLE
Maintain exposure ALARA
'&JM
Radiation Survey Instrume
S-12
9/95
-------
EXPOSURE REDUCTION
MECHANISMS
Time
Distance -
Shielding- pi c,JrX*4
S-13
NOTES
JluvjUL&e*'
4mu^rLUi^ .
JaeO^{jO-
7o oz ScฃLs.
&tju
INTERPRETATION OF
INSTRUMENT DATA
mR/hr (beta/gamma) - used to make
exposure estimates
cpm (alpha or beta) - used to determine
activity of the source
-------
NOTES
LIMITATIONS AND
CONSIDERATIONS
Annual calibration (minimum)
Instruments are calibrated for one type of
radiation (relative response)
8-10
Radiaxion Survey Instruments 6 9/95
-------
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. Beta particles 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 die 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. Tlie 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.
9/95
7
Radiation Survey Instruments
-------
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 QiR/hr).
Instruments reading out in mR/hr and ^R/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 ^R/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 Survey Instruments
8
9195
-------
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 fiR/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
/xR/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.
9/95
9
Radiation Survey Instruments
-------
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. Hie 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 Survey Instruments
10
9/95
-------
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 the 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 smaJl 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. Hie 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. 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.
9/95
11
Radiation Survey Instruments
-------
REFERENCES
U.S. EPA. 1992. Standard Operating Safety Guides. U.S. Environmental Protection Agency,
Office of Emergency and Remedial Response, Emergency Response Division, Environmental
Response Team, Washington, DC.
Radiation Survey Instruments
12
9/95
-------
DECONTAMINATION
STUDENT PERFORMANCE OBJECTIVES
At the conclusion of this unit, students will be able to:
1. List and describe the work zones established at a site
2. Identify the proper location of the contamination reduction
zone and state its purpose
3. Describe the proper procedures involved in implementing a
decontamination plan
4. Identify types of decontamination equipment and the setups
used for decontaminating workers
5. Given realistic site decontamination practices, identify good
and poor decontamination practices.
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
-------
/ \
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
Prevent inadvertent and unnecessary
contact with contaminated materials
NOTES
9/95
1
Decontamination
-------
I" Heavy 1
I equipment '
I decon '
J
T0-O'
ป O
" -6
= ฎ "K l3
= O C <0
g o o a.
< < O
EXCLUSION ZONE
U.S. EPA 1086
t
O
CONTAMINATION
REDUCTION ZONE
ฆ^-01o^-
Exit path
I
.1
2 c
<3 2 o
ฆE t> 2
p =ป t
o
3
XJ
C ^ o
o
o
Dressout I
"SUPPORT ZONE
Hot line
K/J Exit point
Q Entrance
point
CONTROL LINE
I Redress |
S-3
CONTAMINATION
_ REDUCTION
ZONE
DeconUrn
Command
- Ron
Level C
EXCLUSION ZONE
SUPPORT ZONE
ฆ Level B .
Access Control
S-4
U.S. EPA 1984
NOTES
Decontamination
2
9/95
-------
NOTES
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 decontamination methods
DECONTAMINATION PLAN (cont.)
Should provide for:
Program evaluation
Disposal of decontamination materials
Emergency decontamination procedures
Jป
Decontamination
-------
NOTES
zrrt*-
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 and ending
with the least contaminated
S-6
DECONTAMINATION
PROCEDURES (cont.)
Wash and rinse each piece of protective
clothing at least once
Separate each operation by a minimum of
3ft
Adapt original decontamination 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
8-10
Decontamination
4
9/95
-------
EXCLUSION
ZONE
/\
Tank Change
CONTAMINATION
REDUCTION
ZONE
Field Wash
SUPPORT ZONE
Outer Glove
Removal
Tape Removal
Boot Cover
& Glove Wash
Boot Cover
Removal
7 j Suit/Safety Boot
Wash
Suit/Safety Boot
Rinse
10
11
Safety Boot
Removal
\ Fully Encapsulating Suit
& Hard Hal Removal
12 I SCBA Backpack
Removal
13
14
I Inner Glove
Wash
I Inner Glove
Rinse
15 ] Face Piece
Removal
j Inner Glove
Removal
17
\ Inner Clothing
Removal
0 )@
Boot Cover
& Glove Rinse
Segregated
Equipment Drop
Redress
U.S. EPA 1992
HOTLINE
MAXIMUM
DECONTAMINATION LAYOUT
LEVEL A PROTECTION
CONTAMINATION
CONTROL LINE
S-11
NOTES
9/95
5
Decontamination
-------
EXCLUSION
ZONE
Outer Glove
Removal
Boot Cover
Glove Wash
Tape Removal 8
0ซG>-0<-
Boot Cover
& Glove Rinse
Segregated
Equipment Drop
Boot Cover
Removal
HOTLINE
Suit/Safety Boot
Wash
Sult/SCBA/Boot/Glove
Rinse
Tank Change
Safety Boot
Removal
SCBA Backpack
Removal
CONTAMINATION
REDUCTION
ZONE
Splash Suit
Removal
MAXIMUM
DECONTAMINATION LAYOUT
LEVEL B PROTECTION
Inner Glove
Wash
Inner Glove
Rinse
Face Piece
Removal
Inner Glove
Removal
Inner Clothing
Removal
CONTAMINATION
CONTROL LINE
Redress
Field Wash
SUPPORT ZONE
S-12
U.S. EPA 1992
NOTES
Decontamination
6
9/95
-------
EXCLUSION
ZONE
Boot Cover
& Glove Wash
Outer Glove
Removal
Tape Removal
Segregated
Equipment Orop
Boot Cover
& Glove Rinse
Boot Cover
Removal
HOTLINE
Suit/Safety Boot
Wash
Suit/Safety Boot
Rinse
Canister or
Mask Change
Safety Boot
Removal
Splash Suit
Removal
CONTAMINATION
REDUCTION
ZONE
Inner Glove
Wash
Inner Glove
Rinse
Face Piece
Removal
Inner Glove
Removal
Inner Clothing
Removal
CONTAMINATION
CONTROL LINE
Redress
Field Wash
MAXIMUM
DECONTAMINATION LAYOUT
LEVEL C PROTECTION
SUPPORT ZONE
U.S. EPA 1992
S-13
NOTES
9/95
7
Decontamination
-------
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 particulates 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 or 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.
9/95
9
Decontamination
-------
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 15 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 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.
Decontamination
10
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I HEAVY EQUIPMENT
I DECONTAMINATION
1 AREA
I
I
I J
EXCLUSION
ZONE
j-
x
>- <
CC (/> ฃL
-------
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
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
Decontamination
12
9/95
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NO
YES
NO
YES
NO
YES
NO
YES
NO
YES
Are the decontamination
materials compatible with the
materials to be decontaminated?
Are the decontamination
materials compatible with the
hazardous substances present?
Is the method effective for
removing contaminants?
Can appropriate protective
measures be instituted?
Do the decontamination materials
or process pose health or safety
hazards?
Method OK to use.
Take additional measures to
prevent contamination or find
another decontamination
method.
Consult specialists if necessary
FIGURE 2
DECISION AID FOR EVALUATING HEALTH AND SAFETY
ASPECTS OF DECONTAMINATION METHODS
Source: U.S. DHHS1985, p. 10-5
9/95
13
Decontamination
-------
TABLE 1
GENERAL GUIDE TO SOLUBILITY OF CONTAMINANTS
IN FOUR SOLVENT TYPES
Solvent
Soluble Contaminants
Water
Low-chain hydrocarbons
Inorganic compounds
Salts
Some organic acids & other polar compounds
Dilute Acids
Basic (caustic) compounds
Amines
Hydrazines
Dilute Bases
Acidic compounds
Detergent
Phenols
Soap
Thiols
Some nitro and sulfonic compounds
Organic Solvents'
Nonpolar compounds (e.g., some organic
compounds)
Alcohols
Ethers
Ketones
Aromatics
Straight-chain alkanes (e.g., hexane)
Common petroleum products (e.g.,
fuel oil, kerosene)
ฆ WARNING: Some organic solvents can permeate and/or degrade the protective clothing.
Source: U.S. DHHS1985.
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.
Decontamination
14
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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 worst-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.
9/95
15
Decontamination
-------
EXCLUSION
ZONE
Out
Tip* Removal
Segregated
_ . _ , Equipment
Bool Covซr & M _
and Redresi -
Boot Cover/
Outer Glovea
Glove With
Drop
ay*
i
I
Boot Cover
Removal
Boot Cover &
Glove Rlnaa
/p\ Sult/Salaty
\ / Boot Waah
Tank Chang*
Sult/Satety
Bool Rlnee
HOTLINE
10
Salety Boot
Removal
. \ Fully Encapaulatlng Suit
and Hard Hat Removal
j2 \ SCBA Backpack
Removal
CONTAMINATION
REDUCTION
ZONE
13
Innar Glova
Waah
\ Inner Glove
Rinse
\ Face Piece
Removal
16
inner Glove
Removal
j7 \ Inner Clothing
Removal
ฉ<ป>
Redreai
CONTAMINATION
CONTROL LINE
SUPPORT ZONE
FIGURE 3
MAXIMUM DECONTAMINATION LAYOUT: LEVEL A PROTECTION
Source: U.S. EPA 1992, p. 167
Decontamination
16
9/95
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EXCLUSION
ZONE
Tank Changa
and Radrasa --
Boot Covar/
Outer Glovaa
&
Tap* Removal
Boot Covar &
Glova With
Sagragitad
Eq Jlpmi nt
Drop
ฐrmฐr CD
Boot Covar
Ramoval
Boot Covar &
Glova Rlnaa
Sult/Safaty
Boot Waah
Sult/SCBA/Bool
/Qlova Rlnaa
HOTLINE
JO \ Salaty Boot
Ramoval
11
SCBA Backpack
Ramoval
12) Splaih Suit
Ramoval
CONTAMINATION
REDUCTION
ZONE
13
Innar Glova
Waah
14
Innar Glova
Rlnaa
IS
Faca Placa
Ramovil
16
Innar Glova
Ramovtl
^7 ^ Innai Clothing
Ramovil
Radraaa
CONTAMINATION
' CONTROL LINE
SUPPORT ZONE
FIGURE 4
MAXIMUM DECONTAMINATION LAYOUT: LEVEL B PROTECTION
Source: U.S. EPA 1992, p. 171
9/95
17
Decontamination
-------
EXCLUSION
ZONE
Tip* Ramoval
and Rปdrปsa
Boot Covar/
Oultr Glovas
Outar Glova / c \ ^
Removal \ / ~*
Boot Covar k
Glova Waah
Sagragatad
Equipment
Drop
-------
REFERENCES
U.S. DHHS. 1985. Occupational Safety and Health Guidance Manual for Hazardous Waste Site
Activities. U.S. Department of Health and Human Services, Public Health Service, Centers for
Disease Control, National Institute of Occupational Safety and Health, Washington, DC.
U.S. EPA. 1984. Standard Operating Safety Guides. U.S. Environmental Protection Agency,
Office of Emergency and Remedial Response, Emergency Response Division, Environmental
Response Team, Washington, DC.
U.S. EPA. 1988. Standard Operating Safety Guides. U.S. Environmental Protection Agency,
Office of Emergency and Remedial Response, Emergency Response Division, Environmental
Response Team, Washington, DC.
U.S. EPA. 1992. Standard Operating Safety Guides. U.S. Environmental Protection Agency,
Office of Emergency and Remedial Response, Emergency Response Division, Environmental
Response Team, Washington, DC.
9/95
19
Decomamination
-------
CO
(0
o
-------
RESPONSE ORGANIZATION
STUDENT PERFORMANCE OBJECTIVES
At the conclusion of this unit, students will be able to:
1. Identify key personnel and describe the responsibilities of the
key personnel involved in hazardous materials response
2. Create an organizational chart that will be used for the
response exercises in the course (Thursday and Friday
exercises).
NOTE: Unless otherwise stated, the conditions for
performance are using all references and materials
provided in the course, and the standards of
performance are without error.
-------
NOTES
RESPONSE
ORGANIZATION
US DHHS 1085
3-1
RESPONSE IMPLEMENTATION
Organize
Evaluate situation
Develop plan of action
- Make preliminaiy offsite survey
- Make initial onsite reconnaissance
Modify original plan of action
Complete planned cleanup and restoration
S>2
KEY REQUIREMENTS
Establish a chain of command
Assign job functions/duties
Develop personnel requirements
Establish internal communications
&
8-3
9/95
" rS^ I0*' S
^ Response Organization
-------
NOTES
// *,
Cltck, enVf^Mz-
osc
Safety
Field
Science
Officer
Officer
Advisor
1
Record-
PR and
keeper
Communications
X
Asst Science
Advisor
Entry
Team
~3/
Z Financial officer lM-
Logistics officer
Medical
ฆ Specified ty 20 Cffi 1910 120
officer^.
8-8
Response Organization
2
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NOTES
ONSITE PERSONNEL
PROJECT TEAM LEADER
Directs response operations
Prepares and organizes work plan, site
safety plan, and field team
Ensures that the, work plan is completed
and on schedule^
S-7
ONSITE PERSONNEL
SAFETY AND HEALTH OFFICER
Recommends stopping work when
conditions warrant
Selects personal protective equipment
and takes care of storage and
maintenance
Monitors onsite hazards and conditions
at
4
ONSITE PERSONNEL
SAFETY AND HEALTH OFFICER (cont.)
Confirms team members' suitability for
work based on physician's
recommendation
Coordinates emergency medical care
8-0
J
9/95
3
Response Organization
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NOTES
ONSITE PERSONNEL
FIELD TEAM LEADER
Responsible for field team operations
^ Executes work plan and schedule
Enforces site control and safety
<$> ฆ ,
^ ^0r
m
Documents field activities and sample
collection
8*10
ONSITE PERSONNEL
SCIENTIFIC ADVISOR
Advises team on:
- Field monitoring
- Sample collection and analysis
- Scientific studies
- Data interpretation
- Remedial plans
8-11
ONSITE PERSONNEL
PUBLIC INFORMATION OFFICER
Releases information to the news media
and public concerning site activities
8-12
-------
NOTES
ONSITE PERSONNEL
LOGISTICS/EQUIPMENT OFFICER
Plans and mobilizes facilities, materials,
and personnel required for response
Calibrates equipment
8-13
ONSITE PERSONNEL
RECORDKEEPER
Maintains official records of site
activities
ฆ
ONSITE PERSONNEL
DECONTAMINATION OFFICER
Sets up decon lines
Controls decon of all equipment,
personnel, and samples
Ensures that all required equipment
is available
3-15
9/95
5
Response Organization
-------
NOTES
ONSITE PERSONNEL
ENTRY TEAM/WORK PARTY
Safely completes the onsite tasks
Complies with site safety plan
Notifies safety officer of unsafe
conditions
ONSITE PERSONNEL
SECURITY OFFICER
Manages site security
8-17
AS-NEEDED PERSONNEL
Firefighters
Bomb squad/explosion experts
Environmental scientists
Hazardous chemical experts
Health physicists
Industrial hygienists
Toxicologists
8-18
Response Organization
6
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NOTES
EFFECTIVE ORGANIZATION
Designate leader
Determine objectives
Establish authority
Develop policy and procedures
- Assign duties
- Plan and direct operations
- Establish internal communications
- Manage resources
- Establish external communications
S-19
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7
Response Organization
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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.
9/95
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Response Organization
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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
10
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FIGURE 1
EXAMPLE OF A POSSIBLE
RESPONSE ORGANIZATION FLOWCHART
9/95
11
Response Organization
-------
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.
The Safety Officer (required under 29 CFR 1910.120) advises the project leader on all matters
related to the health and safety of those involved in site operations. This individual establishes and
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.
Response Organization
12
9/95
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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.
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 offsite 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 onsite reconnaissance. Determine level of
protection, if necessary, for offsite personnel. Establish boundaries for
contaminated areas.
Make initial onsite 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
9/95
13
Response Organization
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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 onsite 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 offsite studies.
The Project Leader, after review of intelligence gained from site reconnaissance, makes decisions
on the matters that follow:
Offsite measurements needed
The need to go onsite
Equipment available vs. 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 as 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
14
9/95
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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.
EXAMPLE LIST OF RESPONSE EQUIPMENT
Communication Eauipment
Field EquiDment
Hand-held radios
Combustible gas indicator
HNU photoionizer
Protective Clothing
Organic vapor analyzer (OVA)
Oxygen meters
Fully encapsulating suit
Colorimetric indicator pump/tubes
Chemical-resistant splash suit
Specific gas detectors
Chemical-resistant safety boots
Radiation detector
Work gloves
Metal detector
Rain suit
Pressure-demand SCBAs
Windbreaker
Extra air cylinders
Medium-weight jacket
Full-face APR (w/canisters)
Coveralls (work)
Photographic equipment
Coveralls (Nomex)
Film badges
Uniform pants and shirt
Dosimeters
Socks (regular)
Organic vapor badges
Socks (heavy)
Hand tool kit (Schedule A)
Underclothes
First Aid kit (Schedule B)
Earplugs
Reference materials (Schedule C)
Clipboard
Field support kit (Schedule D)
Hardhat (w/faceshield)
Soil sample set (Schedule E)
Hardhat for cold weather
Water sample set (Schedule F)
Safety goggles
Air sample set (Schedule G)
Safety glasses
Emergency oxygen inhaler
Portable wash unit
Fire extinguisher
Portable eyewash
SCHEDULE A: HAND TOOL KIT
Wood mallet
Rubber mallet
Ballpeen hammer
Claw hammer
Hand hammer (nonsparking)
Hacksaw
Lumberjack knife
Duckbill snip
Rod and bolt cutter
Cutting pliers
Lineman's pliers
Slipjoint pliers
Plier wrench
Pipe wrench
Screwdrivers
Stapler/staples
Pressure gauge
Measure tape
Reel tape
Electrical tape
Strapping tape
Duct tape
9/95
15
Response Organization
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SCHEDULE B: FIRST AID KIT
First Aid Guide
Scissors
Aspirin
Forceps
Pain aid
Tweezers
Cold tablets
Cotton swabs
Lozenges
Alcohol swabs
Antiseptic swabs
Antacid
Antiseptic spray
Burn spray
Syrup of ipecac
Spray-on bandage
Vaseline
Eye drops
Antibiotic ointment
Eye/skin neutral izer
Insect repellent
Eye wash
Sting relief
Adhesive tape
Chigger/tick remover
Cohesive tape
Poison ivy treatment
Snake bite kit
Band-Aids
Ammonia inhalants
Blood clotter
Finger tip bandages
Tourniquet
Knuckle bandages
Ice packs
Elastic strip bandages
Triangle bandages
Salt tablets
Gauze bandages
Finger splint
Blanket
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 (two 7 x 35-mm-wide angle) Rangefinder (2)
Spotting scope Stereoscopes
Compass (2) Hand level (2)
Hand calculator (2) Cassette recorder
SCHEDULE E:
SOIL SAMPLING SET
Soil auger
Auger extensions
Power head (electric)
Soil sample tubes
Replacement tips for tube samplers
Wet, heavy duty tips
Scoops for bottom sediments
Labels
Stainless steel pipe section
Logbooks for soil profiles
Electrical resistivity apparatus
Stainless steel spoons
Post hole digger
Pick-ax
Shovel
Stainless steel pans
Response Organization
16
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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
Teflonฎ bailer
Dissolved oxygen meter
Conductivity meter
SCHEDULE G: AIR SAMPLING SET
Colorimetric indicator tubes
Impinger tubes
Particulate samplers
Wind speed indicator
Barometric pressure indicator
Hi-vol sampler
Carbon adsorption tubes
Wind direction indicator
Temperature indicator
9/95
17
Response Organization
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REFERENCES
U.S. DHHS. 1985. Occupational Safety and Health Guidance Manual for Hazardous Waste Site
Activities. U.S. Department of Health and Human Services, Public Health Service, Centers for
Disease Control, National Institute of Occupational Safety and Health, Washington, DC.
Response Organization
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APPENDIX A
1910.120Hazardous Waste Operations
and Emergency Response
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Part Number: 1910
Standard Number: 1910.120
Title: Hazardous waste operations and emergency response
(a) Scope, application, and definitions.
(1) Scope. This section covers the following operations,
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 governmental
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 priority site lists, sites recommended for
the EPA NPL, and initial investigations of
government identified sites which are conducted
before the presence or absence of hazardous
substances has been ascertained;
(11) Corrective actions involving cleanup operations at
sites covered by the Resource Conservation and
Recovery Act of 1976 (RCRA) as amended (42
U.S.C. 6901 et seq);
(in) Voluntary cleanup operations at sites recognized
by federal, state, local, or other governmental bodies
as uncontrolled hazardous waste 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.
(l) All requirements of Part 1910 and Part 1926 of
Title 29 of the Code of Federal Regulations apply
pursuant to their terms to hazardous waste and
emergency response operations whether covered by
this section or not. If there is a conflict or overlap,
the provision more protective of employee safety and
health shall apply without regard to 29 CFR
1910.5(c)(1).
(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).
(111) Operations within the scope of paragraph (a)(l)(i)
of this section must comply only with the
requirements of paragraph (p) of this section.
Notes and Exceptions:
(A) All provisions of paragraph (p) of this
section cover any treatment, storage, or disposal
(TSD) operation regulated by 40 CFR parts 264
and 265 or by state law authorized under RCRA,
and required to have a permit or interim status
from EPA pursuant to 40 CFR 270.1 or from a
state agency pursuant to RCRA.
(B) Employers who are not required to have a
permit or interim status because they are
conditionally exempt small quantity generators
under 40 CFR 261.5 or are generators who
qualify under 40 CFR 262.34 for exemptions
from regulation under 40 CFR 262.34 for
exemptions from regulation under 40 CFR parts
264, 265, and 270 ("excepted employers") are
not covered by paragraphs (p)(l) through (p)(7)
of this section. Excepted employers who are
required by the EPA or state agency to have
their employees engage in emergency response
or who direct their employees to engage in
emergency response are covered by paragraph
(p)(8) of this section, and cannot be exempted by
(p)(8)(i) of this section.
(C) If an area is used primarily for treatment,
storage, or disposal, any emergency response
operations in that area shall comply with
paragraph (p) (8) of this section. In other areas
not used primarily for treatment, storage, or
disposal, any emergency response operations
shall comply with paragraph (q) of this section.
Compliance with the requirements of paragraph
(q) of this section shall be deemed to be in
compliance with the requirements of paragraph
(p)(8) of this section.
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29 CFR 1910.120
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(iv) Emergency response operations for releases of,
or substantial threats of releases of, hazardous
substances which are not covered 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 m the work
group. The purpose of the buddy system is to provide
rapid assistance to employees m the event of an
emergency.
"Clean-up operation" means an operation where
hazardous substances are removed, contained, 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 hazardous
substances from employees and their equipment to the
extent necessary to preclude the occurrence of foreseeable
adverse health effects.
"Emergency response" or "responding to
emergencies" means a response effort by employees from
outside the immediate release area or by other designated
responders (1 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 controlled at the time of release
by employees m 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 hazard (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 (including 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 otherwise
come to be located; but does not include any consumer
product in consumer use or any water-borne vessel.
"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 substance.
The team members perform responses to releases or potential
releases of hazardous substances 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
lire brigade or fire department.
"Hazardous substance" means any substance
designated or listed under (A) through (D) of this
definition, exposure to which results or may result in
adverse effects on the health or safety of employees:
(a) Any substance defined under section 101(14) of
CERCLA;
(b) Any biologic agent and other disease causing agent
which after release into the environment and upon
exposure, ingestion, inhalation, or assimilation into any
person, either directly from the environment or indirectly
by ingestion through food chains, will or may reasonably
be anticipated to cause death, disease, behavioral
abnormalities, cancer, genetic mutation, physiological
malfunctions (including malfunctions in reproduction) or
physical deformations in such persons or their offspring;
(c) Any substance listed by the U.S. Department of
Transportation as hazardous materials under 49 CFR
172.101; and
(d) Hazardous waste as herem defined.
"Hazardous waste" means
(a) A waste or combmation 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 operation
conducted within the scope of this standard.
"Hazardous waste site" or "Site" means any facility
or location within the scope of this standard at which
hazardous waste operations take place.
"Health hazard" means a chemical, mixture of
chemicals, or a pathogen for which there is statistically
significant evidence based on at least one study conducted
in accordance with established scientific principles that
acute or chrome health effects may occur in exposed
employees. The term "health hazard" includes chemicals
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29 CFR 1910.120
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which are carcinogens, toxic or highly toxic agents,
reproductive toxins, irritants, corrosives, sensitizers,
hepatotoxins, nephrotoxins, neurotoxins, agents which act on
the hematopoietic system, and agents which damage the lungs,
skin, eyes, or mucous membranes. It also mcludes stress due
to temperature 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 interfere with an individual's ability
to escape from a dangerous atmosphere.
"Oxygen deficiency" means that concentration of
oxygen by volume below which atmosphere supplying
respiratory protection must be provided. It exists m
atmospheres where the percentage of oxygen by volume
is less than 19.5 percent oxygen.
"Permissible exposure limit" means the exposure,
inhalation, or dermal permissible exposure limit specified
in 29 CFR Part 1910, Subparts G and Z.
"Published exposure level" means the exposure limits
published in "NIOSH recommendations for Occupational
Health Standards" dated 1986 incorporated by reference,
or if none is specified, the exposure limits published m
the standards specified by the American Conference of
Governmental Industrial Hygiemsts in their publication
"Threshold 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 (q)(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 compliance with applicable safety
and health requirements.
"Small quantity generator" means a generator of
hazardous wastes who in any calendar month generates 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 individuals or the environment
or both. Some sites are found on public lands, such as
those created by former municipal, county or state
landfills where illegal or poorly managed waste disposal
has taken place. Other sites are found on private property,
often belonging to generators or former generators of
hazardous waste. Examples of such sites include, but are
not limited to, surface impoundments, landfills, dumps,
and tank or drum farms. Normal operations at TSD sites
are not covered by this definition.
1910.120(b)
(b) Safety and health program.
Note to (b): Safety and health programs developed
and implemented to meet other federal, 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
paragraph.
(1) General.
(i) Employers shall develop and implement a
written safety and health program for their
employees involved in hazardous waste
operations. The program shall be designed to
identify, evaluate, and control safety and health
hazards, and provide for emergency response for
hazardous waste operations.
(u) 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
standard operating procedures required in
paragraph (b)(l)(ii)(F) of this section;
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29 CFR 1910.120
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(D) The safety and health training program;
1910.120(b)(l)(ii)(E)
(E) The medical surveillance program;
(F) The employer's standard operating
procedures for safety and health; and
(G) Any necessary interface between general
program and site specific activities.
(111) Site excavation. Site excavations created
during initial site preparation or during
hazardous waste operations shall be shored or
sloped as appropnate 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 contractors,
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's
information program.
(v) Program availability. The written safety and
health program shall be made available to any
contractor or subcontractor or their
representative who will be mvolved with the
hazardous waste operation; to employees; to
employee designated representatives; to OSHA
personnel, and to personnel of other federal,
state, or local agencies with regulatory authority
over the site.
1910.120(b)(2)
(2) Organizational structure part of the site program.
(1) The organizational structure part of the
program shall establish the specific cham of
command and specify the overall responsibilities
of supervisors and employees. It shall include, at
a minimum, the following elements:
(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
hazardous waste site operations and
emergency response and their general
functions and responsibilities.
(D) The lmes of authority, responsibility,
and communication.
(u) 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
program. 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 define
anticipated clean-up activities as well as normal
operating procedures which need not repeat the
employer's procedures available elsewhere.
1910.120(b)(3)(H)
(u) The comprehensive workplan shall define
work tasks and objectives and identify the
methods for accomplishing those tasks and
objectives.
(m) The comprehensive workplan shall establish
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
informational programs required m paragraph (l)
of this section.
(vi) The comprehensive workplan shall provide
for the implementation of the medical
surveillance program described in paragraph (f)
if this section.
(4) Site-specific safety and health plan part of the
program.
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29 CFR 1910.120
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(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.
(ii) Elements. The site safety and health plan, as
a minimum, shall address the following:
1910.120(b)(4)(n)(A)
(A) A safety and health risk or hazard
analysis for each site task and operation
found in the workplan.
(6) 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 program
m paragraph (g)(5) of this section.
(D) Medical surveillance requirements in
accordance with the program in paragraph
(f) 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
paragraph (d) of this section.
(G) Decontamination procedures in
accordance 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.
1910.120(b)(4)(ii)(I)
(I) Confined space entry procedures.
(J) A spill containment program meeting the
requirements of paragraph (j) of this section.
(m) 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 analysis 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 deficiencies 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 evaluated
in accordance with this paragraph to identify specific
site hazards and to determine the appropriate safety
and health control procedures needed to protect
employees from the identified hazards.
1910.120(c)(2)
(2) Preliminary evaluation. A preliminary evaluation
of a site's characteristics shall be performed prior to
site entry by a qualified person in order to aid in the
selection of appropnate employee protection methods
pnor to site entry. Immediately 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 m the selection of the
appropnate 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 hazards
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 vegetation are located.
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29 CFR 1910.120
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(4) Required information. The following
information to the extent available shall be obtained
by the employer prior to allowing employees to enter
a site:
1910.120(c)(4)(i)
(I) Location and approximate size of the site.
(II) Description of the response activity and/or
the job task to be performed.
(in) 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
dispersion.
(vn) Present status and capabilities of emergency
response teams that would provide assistance to
on-site employees at the time of an emergency.
(vin) Hazardous substances and health hazards
involved or expected at the site and their
chemical and physical properties.
(5) Personal protective 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 evaluation. If there is no
permissible exposure limit or published exposure
level, the employer may use other published studies
and information as a guide to appropriate personal
protective equipment.
1910.120(c)(5)(ii)
(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 identified during the preliminary site
evaluation, an escape self-contained breathing
apparatus of at least five minute's duration shall be
earned by employees during initial site entry.
(in) If the preliminary site evaluation does not
produce sufficient information to identify the hazards
or suspected hazards of the site an ensemble
providing 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
guidelines on Level B protective equipment.)
(iv) Once the hazards of the site have been identified,
the appropriate PPE shall be selected and used in
accordance with paragraph (g) of this section.
(6) Monitoring. The following monitoring shall be
conducted during initial site entry when the site evaluation
produces information which shows the potential for
ionizing radiation or IDLH conditions, or when the site
information is not sufficient reasonably to eliminate these
possible conditions:
1910.120(c)(6)(i)
(i) Monitoring with direct reading instruments for
hazardous levels of ionizing radiation.
(u) Monitoring the air with appropriate direct reading
test equipment for (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.)
(m) Visually observing for signs of actual or potential
IDLH or other dangerous conditions.
(iv) An ongoing air monitoring program in
accordance with paragraph (h) of this section shall be
implemented after site characterization has
determined the site is safe for the start-up 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 covered 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:
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29 CFR 1910.120
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[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.
1910.120(c)(8)
(8) Employee notification. Any information concerning
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 commencement 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 hazardous 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, mclude: 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, identification of the nearest
medical assistance. Where these requirements are
covered elsewhere they need not be repeated.
1910.120(e)
(e) Training.
(1) General.
(1) 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 hazardous 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
participate 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 responsible for
site safety and health;
(ii) Safety, health and other hazards present on the
site;
(lii) Use of PPE;
(iv) Work practices by which the employee can
minimize risks from hazards;
1910.120(e)(2)(v)
(v) Safe use of engineering controls and equipment on
the site;
(vi) Medical surveillance requirements including
recognition of symptoms and signs which might
indicate over exposure to hazards; and
(vn) The contents of paragraphs (G) through (I) of
the site safety and health plan set forth in paragraph
(b)(4)(ii) of this section.
(3) Initial training.
(1) 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 substances 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.
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29 CFR 1910.120
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(u) Workers on site only occasionally for a specific
limited task (such as, but not limited to, ground water
monitoring, land surveying, or geophysical
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 expenence under the direct supervision of
a trained, experienced supervisor.
1910.120(e)(3)(in)
(111) Workers regularly on site who work m areas
which have been monitored and fully characterized
indicating that exposures are under permissible
exposure limits and published exposure limits where
respirators are not necessary, and the characterization
indicates 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 (e)(3)(ii) and (e)(3)(in) of this
section, and who become general site workers or who
are required to wear respirators, 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 responsible for or
who supervise employees engaged m hazardous waste
operations shall receive 40 hours initial and three days of
supervised field expenence (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)(u) and (e)(3)(iii) and at least eight additional hours
of specialized training at the time of job assignment on
such topics as, but no limited to, the employer's safety
and health program, personal protective equipment
program, spill containment program, and health hazard
monitoring procedure and techniques.
1910.120(e)(5)
(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
experience necessary for teaching the subjects. Instructors
shall demonstrate competent instructional skills and
knowledge of the applicable subject matter.
(6) Training certification. Employees and supervisors
that have received and successfully completed the training
and field experience specified in paragraphs (e)(1) through
(e)(4) of this section shall be certified by their instructor
or the head instructor and trained supervisor as having
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
prohibited from engaging m hazardous waste operations.
(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 m how to respond
to such expected emergencies.
1910.120(e)(8)
(8)Refresher training. Employees specified in paragraph
(e)(1) of this section, and managers and supervisors
specified m paragraph (e)(4) of this section, shall receive
eight hours of refresher training annually on the items
specified in paragraph (e)(2) and/or (e)(4) of this section,
any critique of incidents that have occurred in the past
year that can serve as training examples 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)(1)
through (e)(4) of this section shall not be required to
provide the initial training requirements of those
paragraphs to such employees and shall provide a copy of
the certification or documentation to the employee upon
request. However, certified employees or employees with
equivalent training new to a site shall receive appropriate,
site specific training before site entry and have
appropnate supervised field experience at the new site.
Equivalent training includes any academic training or the
training that existing employees might have already
received from actual hazardous waste site experience.
(f) Medical surveillance
(1) General. Employees 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
(q)(9) shall institute a medical surveillance program
in accordance with this paragraph.
July 1994
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29 CFR 1910.120
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1910.120(0(2)
(2) Employees covered. The medical surveillance
program shall be instituted by the employer for the
following employees:
(1) All employees who are or may be exposed to
hazardous substances or health hazards at or
above the established permissible exposure limit,
above the published exposure levels for these
substances, without regard to the use of
respirators, for 30 days or more a year;
(a) All employees who wear a respirator for 30
days or more a year or as required by 1910.134;
(111) All employees who are injured, become ill
or develop signs or symptoms due to possible
overexposure involving hazardous substances or
health hazards from an emergency response or
hazardous waste operation; and
(iv) Members of HAZMAT teams.
(3) Frequency of medical examinations and
consultations.
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 (f)(2)(i),
(f)(2)(a), and (f)(2)(iv);
1910.120(f)(3)(i)(A)
(A) Prior to assignment;
(B) At least once every twelve months for each
employee covered unless the attending physician
believes a longer interval (not greater than
biennially) is appropriate;
(C) At termination of employment or
reassignment to an area where the employee
would not be covered if the employee has not
had an examination within the last six months
(D) As soon as possible upon notification by an
employee that the employee has developed signs
or symptoms indicating possible overexposure to
hazardous substances or health hazards, or that
the employee has been injured or exposed above
the permissible exposure limits or published
exposure levels in an emergency situation;
(E) At more frequent times, if the examining
physician determines that an increased frequency
of examination is medically necessary.
(11) For employees covered under paragraph (f)(2)(iii)
and for all employees including of employers covered
by paragraph (a)(l)(iv) who may have been injured,
received a health impairment, developed signs or
symptoms which may have resulted from exposure to
hazardous substances resulting from an emergency
incident, or exposed during an emergency incident to
hazardous substances at concentrations above the
permissible exposure limits or the published exposure
levels without the necessary personal protective
equipment being used:
1910.120(f)(3)(u)(A)
(A) As soon as possible following the emergency
incident or development of signs or symptoms;
(B) At additional times, if the examining
physician determines that follow-up examinations
or consultations are medically necessary.
(4) Content of medical examinations and consultations.
(i) Medical examinations required by paragraph (f)(3)
of this section shall mclude a medical and work
history (or updated history if one is in the employee's
file) with special emphasis on symptoms related to
the handling of hazardous substances and health
hazards, and to fitness for duty including the ability
to wear any required PPE under conditions (i.e.,
temperature extremes) that may be expected at the
work site.
(u) 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 U 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 knowledgeable in occupational medicine, and shall be
provided without cost to the employee, without loss of
pay, and at a reasonable time and place.
1910.120(0(6)
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29 CFR 1910.120
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(6) Information provided to the physician. The
employer shall provide one copy of this standard and its
appendices to the attending physician and in addition the
following for each employee:
(1) A description of the employee's duties as they
relate to the employee's exposures,
(ii) The employee's exposure levels or anticipated
exposure levels.
(iii) A description of any personal protective
equipment used or to be used.
(iv) Information from previous medical examinations
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
examining physician containing the following:
(A) The physician's opinion as to whether the
employee has any detected medical conditions
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 limitations
upon the employees assigned work.
1910.120(f)(7)(i)(C)
(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 examination or treatment.
(u) The written opinion obtained by the
employer shall not reveal specific findings
or diagnoses unrelated to occupational
exposure.
(8) Recordkeeping.
(i) An accurate record of the medical surveillance
required by paragraph (0 of this section 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 mclude at least the following
information:
(A) The name and social security number of the
employee;
(B) Physicians' written opinions, recommended
limitations and results of examinations and tests;
(C) Any employee medical complaints related to
exposure to hazardous substances;
(D) A copy of the information provided to the
examining physician by the employer, with the
exception of the standard and its appendices.
1910.120(g)
(g) Engineering controls, work practices, and personal
protective equipment for employee protection.
Engineering controls, work practices and PPE for
substances regulated in Subpart Z. (i) Engineering
controls, work practices, personal protective equipment,
or a combmation of these shall be implemented in
accordance with this paragraph to protect employees from
exposure to hazardous substances and safety and health
hazards.
(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 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.
Note to (g)(1) (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 handling equipment. Work practices
which may be feasible are removing all non-essential
employees from potential exposure during opening of
drums, wetting down dusty operations and locating
employees upwind of possible hazards.
1910.120(g)(l)(ii)
(n) Whenever engineering controls and work
July 1994
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29 CFR 1910.120
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practices are not feasible, or not required, any
reasonable combination of engineering controls, work
practices and PPE shall be used to reduce and
maintain to or below the permissible exposure limits
or dose limits for substances regulated by 29 CFR
Part 1910, Subpart Z.
(111) The employer shall ngt 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.
(2) Engineering controls, work practices, and PPE for
substances not regulated in Subparts G and Z.
An appropriate combination of engineering controls, 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 MSDS 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.
1910.120(g)(3)
(3) Personal protective equipment selection.
(I) Personal protective equipment (PPE) shall be
selected and used which will protect employees from
the hazards and potential hazards 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 performance
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
identified at the site.
(III) Positive pressure self-contained breathing
apparatus, or positive pressure air-line respirators
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 protection as
recommended in Appendix B) shall be used in
conditions where skin absorption of a hazardous
substance may result in a substantial 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 or site
conditions show 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 protection provided
may be decreased when additional information or site
conditions show that decreased protection will not result
in hazardous exposures to employees.
1910.120(g)(3)(vi)
(vi) Personal protective equipment shall be selected
and used to meet the requirements of 29 CFR Part
1910, Subpart I, and additional requirements
specified in this section.
(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.
(11) Totally encapsulating suits shall be capable of
maintaining positive air pressure. (See Appendix A
for a test method which may be used to evaluate this
requirement.)
(ni) Totally encapsulating suits shall be capable 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
personal protective equipment program, 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 established.
The PPE program shall address the elements 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
mto the plan as long as they adequately address the
July 1994
11
29 CFR 1910.120
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procedure or element.
1910.120(g)(5)(f)
(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,
(vn) PPE donning and doffing procedures,
(vin) PPE inspection procedures prior to, during, and
after use,
(ix) Evaluation of the effectiveness of the PPE
program, and
(x) Limitations during temperature extremes, heat
stress, and other appropnate medical considerations.
(h) Monitoring.
(1) General.
(1) Monitoring shall be performed m accordance
with this paragraph where there may be a
question of employee exposure to hazardous
concentrations of hazardous substances m order
to assure proper selection of engineering
controls, work practices and personal protective
equipment so that employees are not exposed to
levels which exceed permissible exposure limits,
or published exposure levels if there are no
permissible exposure limits, for hazardous
substances.
(li) Air monitoring shall be used to identify and
quantify airborne levels of hazardous substances
and safety and health hazards in order to
determine the appropriate level of employee
protection needed on site.
1910.120(h)(2)
(2) Initial entry. Upon initial entry, representative 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,
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 is
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 nsen are as
follows:
{1} When work begins on a different portion of the
site.
{u} When contaminants other than those previously
identified are being handled.
{111} When a different type of operation is initiated
(e.g., drum opening as opposed to exploratory well
drilling.)
{iv} When employees are handling leaking drums or
containers or working in areas with 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 operation
commences; for example, when soil, surface water or
containers are moved or disturbed; the employer shall
monitor those employees likely to have the highest
exposures to those 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. The employer may utilize a representative
sampling approach by documenting that the employees
and chemicals chosen for monitoring are based on the
criteria stated m the first sentence of this paragraph. 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 operations covered by
paragraph (c) of this section.
1910.120(0
(i) Informational programs.
July 1994
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29 CFR 1910.120
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Employers shall develop and implement a program 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 subcontractors
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,
liquids and other residues shall be handled,
transported, labeled, and disposed of in
accordance with this paragraph.
(II) Drums and containers used during the
clean-up shall meet the appropnate DOT,
OSHA, and EPA regulations for the wastes that
they contain.
(in) When practical, drums and containers shall
be inspected and their integrity shall be assured
pnor to being moved. Drums or containers that
cannot be inspected before being moved because
of storage conditions (i.e., buned 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.
1910.120(j)(l)(iv)
(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
minimize the amount of drum or container
movement.
(vi) Prior to movement of drums or containers,
all employees exposed to the transfer operation
shall be warned of the potential hazards
associated with the contents of the drums or
containers.
(vii)U.S. Department of Transportation specified
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.
(vin) 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 buried drums
or containers.
1910.120(j)(l)(xi)
(xi) Soil or covering material shall be removed
with caution to prevent drum or container
rupture.
(xu) Fire extinguishing equipment meeting the
requirements of 29 CFR Part 1910, Subpart L,
shall be on hand and ready for use to control
incipient fires.
(2) Opening drums and containers. The following
procedures shall be followed m areas where drums or
containers are being opened:
(i) Where an airlme 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 opening
drums or containers shall be kept a safe distance from
the drums or containers being opened.
(in) If employees must work near or adjacent to
drums or containers being opened, a suitable 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 accidental explosion.
(iv) Controls for drum or container opening
equipment, monitoring equipment, and fire
suppression equipment shall be located behind the
July 1994
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29 CFR 1910.120
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explosion-resistant barrier.
1910.120(j)(2)(v)
(v) When there is a reasonable possibility of
flammable atmospheres being present, material
handling equipment and hand tools shall be of the
type to prevent sources of ignition.
(vi) Drums and containers shall be opened m such a
manner that excess interior pressure will be safely
relieved. If pressure cannot 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.
(vn) Employees shall not stand upon or work from
drums or containers.
(3) Material handling equipment. Material handling
equipment used to transfer drums and containers 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 handled 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 suspected of containing
shock-sensitive wastes are handled:
1910.120(j)(5)(i)
(i) All non-essential employees shall be evacuated
from the area of transfer.
(u) Material handling equipment shall be provided
with explosive containment devices or protective
shields to protect equipment operators from exploding
containers.
(lii) 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 appropriate) shall
be maintained between the employee-in-charge of the
immediate handling area and both the site safety and
health supervisor and the command post until such
time as the handling operation is completed.
Communication equipment or methods that could
cause shock sensitive materials to explode shall not
be used.
(v) Drums and containers under pressure, as
evidenced by bulgmg or swelling, shall not be moved
until such time as the cause for excess pressure is
determined and appropriate containment procedures
have been implemented to protect employees from
explosive relief of the drum.
(vi) Drums and containers containing packaged
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.
1910.120(])(6)
(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):
(l) Lab packs shall be opened only when necessary
and then only by an individual knowledgeable in the
inspection, classification, and segregation of the
containers within the pack according to the hazards of
the wastes.
(u) If crystalline material is noted on any container,
the contents shall be handled as a shock-sensitive
waste until the contents are identified.
(7) Sampling of drum and container contents.
Sampling of containers and drums shall be done in
accordance with a sampling procedure which is part
of the site safety and health plan developed for and
available to employees and others at the specific
worksite.
(8) Shipping and transport.
(i) Drums and containers shall be identified and
classified prior to packaging for shipment.
(u) Drum or container staging areas shall be kept
to the minimum number necessary to safely
identify and classify materials and prepare them
for transport.
July 1994
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29 CFR 1910.120
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1910.120(j)(8)(iii)
(111) Staging areas shall be provided with
adequate access and egress routes.
(iv) Bulking of hazardous wastes shall be
permitted only after a thorough characterization
of the materials has been completed.
(9) Tank and vault procedures.
(1) Tanks and vaults containing hazardous substances
shall be handled in a manner similar to that for drums
and containers, taking into consideration the size of
the tank or vault.
(ii) Appropriate tank or vault entry procedures as
described in the employer's safety and health plan
shall be followed whenever employees must enter a
tank or vault.
(k) Decontamination
(1) General. Procedures for all phases of
decontamination shall be developed and implemented
in accordance with this paragraph.
(2) Decontamination procedures.
(i) A decontamination procedure shall be
developed, communicated to employees and
implemented before any employees or equipment
may enter areas on site where potential for
exposure to hazardous substances exists.
(u) Standard operating procedures shall be
developed to minimize employee contact with
hazardous substances or with equipment that has
contacted hazardous substances.
1910.120(k)(2)(iii)
(iii) All employees leaving a contaminated area
shall be appropriately decontaminated; all
contaminated clothing and equipment leaving a
contaminated area shall be appropriately disposed
of or decontaminated.
(iv) Decontamination procedures shall be
monitored by the site safety and health
supervisor to determine their effectiveness. When
such procedures are found to be ineffective,
appropriate steps shall be taken to correct any
deficiencies.
(3) Location. Decontamination shall be performed in
geographical areas that will minimize the exposure of
uncontaminated employees or equipment to contaminated
employees or equipment.
(4) Equipment and solvents. All equipment and solvents
used for decontamination shall be decontaminated or
disposed of properly.
(5) Personal protective clothing and equipment.
(i) Protective clothing and equipment shall be
decontaminated, cleaned, laundered, maintained or
replaced as needed to maintain their effectiveness.
(ii) Employees whose non-impermeable clothing
becomes wetted with hazardous substances shall
immediately remove that clothing and proceed to
shower. The clothing shall be disposed of or
decontaminated before it is removed from the work
zone.
1910.120(k)(6)
(6) Unauthorized employees shall not remove protective
clothing or equipment from change rooms.
(7) Commercial laundries or cleaning establishments.
Commercial laundries or cleaning establishments that
decontaminate protective clothing or equipment shall be
informed of the potentially harmful effects of exposures
to hazardous substances.
(8) Showers and change rooms. Wheie the
decontamination procedure indicates a need for regular
showers and change rooms outside of a 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
cleansing shall be provided and used.
(1) 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 paragraphs (a)(l)(i) through
(ii) of this section, section to handle anticipated
emergencies prior to the commencement 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
July 1994
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29 CFR 1910 120
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relevant responsibilities.
1910.120(l)(l)(n)
(11) Employers who will evacuate their employees
from the danger area 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 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.
(u) Personnel roles, lines of authority, training, and
communication.
(111) Emergency recognition and prevention.
(iv) Safe distances and places of refuge.
(v) Site security and control.
(vi) Evacuation routes and procedures.
(vu) Decontamination procedures which are not
covered by the site safety and health plan.
(vm) Emergency medical treatment and first aid.
(ix) Emergency alerting and response procedures.
(x) Critique of response and follow-up.
1910.120(l)(2)(xi)
(xi) PPE and emergency equipment.
(3) Procedures for handling emergency incidents.
(l) In addition to the elements for the emergency
response plan required m paragraph (1)(2) of this
section, the following elements 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 agencies.
(li) 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 1910.165 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.
1910.120(l)(3)(vn)
(vn) 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.
(m) Illumination.
Areas accessible to employees shall be lighted to not less
than the minimum illumination intensities listed m the
following Table H-120.1 while any work is in progress:
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29 CFR 1910 120
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TABLE H-120.1.MINIMUM ILLUMINATION INTENSITIES IN FOOT-CANDLES
Foot-Candles
Area or operations
5
3
5
5
10
30
General site areas.
Excavation and waste areas, accessways, active storage areas, loading platforms, refueling, and field
maintenance areas.
Indoors: Warehouses, corridors, hallways, and exitways.
Tunnels, shafts, and general underground work areas. (Exception: Minimum of 1 foot-candles is required
at tunnel and shaft heading during drilling, mucking, and scaling. Mine Safety and Health Administration
approved cap lights shall be acceptable for use in the tunnel heading.)
General shops (e.g., mechanical and electrical equipment rooms, active storerooms, barrracks or living
quarters, locker or dressing rooms, dining areas, and indoor toilets and workrooms).
First aid stations, infirmaries, and offices.
1910.120(n)
(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.
(in) Any container used to distribute dnnking
water shall be clearly marked as to the nature of
its contents and not used for any other purpose.
(2) Nonpotable water.
(i) Outlets for nonpotable water, such as water for
firefighting purposes shall be identified 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 potable water
and a system furnishing nonpotable water.
(3) Toilets facilities.
(i) Toilets shall be provided for employees according
to Table H-120.2.
(iv) Where single service cups (to be used but
once) are supplied, both a sanitary container for
the unused cups and a receptacle for disposing of
the used cups shall be provided.
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29 CFR 1910.120
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TABLE H-120.2.TOILET FACILITIES
Number of employees Minimum number of facilities
20 or fewer One.
More than 20, fewer than 200 One toilet seat and one unnal per 40 employees.
More than 200 One toilet seat and one urinal per 50 employees.
1910.120(n)(3)(n)
(n) Under temporary field conditions, provisions shall be
made to assure not less than one toilet facility is available.
(in) Hazardous waste sites, not provided with a sanitary
sewer, shall be provided with the following toilet facilities
unless prohibited by local codes:
(A) Chemical toilets;
(6) Recirculating 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.
(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 applicable laws,
ordinances, and regulations of the jurisdictions in which
they are located.
(5) Temporary sleeping quarters. When temporary
sleeping quarters are provided, they shall be heated,
ventilated, and lighted.
1910.120(n)(6)
(6) Washing facilities. The employer shall provide
adequate washing facilities for employees engaged in
operations where hazardous substances may be harmful to
employees. Such facilities shall be in near proximity to
the worksite; in areas where exposures are below
permissible exposure limits and which are under the
controls of the employer; and shall be so equipped as to
enable employees to remove hazardous 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
hazardous waste clean-up or removal operations.
(i) Showers shall be provided and shall meet the
requirements of 29 CFR 1910.141(d)(3).
(n) 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 an area where they can put on, remove and store
work clothing and personal protective equipment.
1910.120(n)(7)(iu)
(iu) 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 accomplished, 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
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29 CFR 1910.120
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available to the industry, such as the use of foams,
absorbents, absorbents, neutralizes, 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.
1910.120(p)
(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 shall provide and implement the programs
specified m this paragraph. See the "Notes and
Exceptions" to paragraph (a)(2)(in) of this section for
employers not covered.
(1) Safety and health program. The employer shall
develop and implement a written safety and health
program for employees mvolved in hazardous waste
operations that shall be available for inspection by
employees, their representatives and OSHA personnel.
The program shall be designed to identify, evaluate and
control safety and health hazards m their facilities for the
purpose of employee protection, to provide for emergency
response meeting the requirements of paragraph (p)(8) of
this section and to address as appropriate site analysis,
engineering controls, maximum exposure limits,
hazardous waste handling procedures and uses of new
technologies.
(2) Hazard communication program. The employer
shall implement a hazard communication program meeting
the requirements of 29 CFR 1910.1200 as part of the
employer's safety and program.
Note to 1910.120 - The exemption for hazardous waste
provided in 1910.1200 is applicable to this section.
1910.120(p)(3)
(3) Medical surveillance program. The employer shall
develop and implement a medical surveillance program
meeting the requirements of paragraph (f) of this section.
(4) Decontamination program. The employer shall
develop and implement a decontamination procedure
meeting the requirements of paragraph (k) of this section.
(5) New technology program. The employer shall
develop and implement procedures meeting the
requirements of paragraph (o) of this section for
introducing new and innovative equipment into the
workplace.
(6) Material handling program. Where employees will
be handling drums or containers, the employer shall
develop and implement procedures meeting the
requirements of paragraphs (])(l)(u) through (viii) and (xi)
of this section, as well as (j)(3) and 0(8) of this section
prior to starting such work.
(7) Training program
(i) New employees. The employer shall develop and
implement a training program which is part of the
employer's safety and health program, for employees
exposed to health hazards or hazardous substances at
TSD operations to enable the employees to perform
their assigned duties and functions in a safe and
healthful manner so as not to endanger themselves or
other employees. The initial training shall be for 24
hours and refresher training shall be for eight hours
annually. Employees who have received the initial
training required by this paragraph shall be given a
written certificate attesting that they have successfully
completed the necessary training.
1910.120(p)(7)(n)
(11) Current employees. Employers who can show by
an employee's previous work experience and/or
training that the employee has had training equivalent
to the initial training required by this paragraph, shall
be considered as meeting the initial training
requirements of this paragraph as to that employee.
Equivalent training includes the training that existing
employees might have already received from actual
site work experience. Current employees shall receive
eight hours of refresher training annually.
(m) Trainers. Trainers who teach initial training
shall have satisfactorily completed a training course
for teaching the subjects they are expected to teach or
they shall have the academic credentials and
instruction experience necessary to demonstrate a
good command of thee subject matter of the courses
and competent instructional skills.
(8) Emergency response program
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29 CFR 1910 120
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(i) Emergency response plan. An emergency
response plan shall be developed and implemented by
all employers. Such plans need not duplicate any of
the subjects fully addressed in the employer's
contingency planning required by permits, such as
those issued by the U.S. Environmental Protection
Agency, provided that the contingency plan is made
part of the emergency response plan. The emergency
response plan shall be a written portion of the
employers safety and health program required in
paragraph (p)(l) of this section. Employers who will
evacuate their employees from the worksite location
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
paragraph (p)(8) if they provide an emergency action
plan complying with section 1910.38(a) of this part.
1910 120(p)(8)(n)
(u) Elements of an emergency response plan. The
employer shall develop an emergency response plan
for emergencies which shall address, as a minimum,
the following areas to the extent that they are not
addressed in any specific program required m this
paragraph:
(A) Pre-emergency planning and coordination
with outside parties.
(B) Personnel roles, lines of authority, training,
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.
(I) Emergency alerting and response procedures.
(J) Critique of response and follow-up.
(K) PPE and emergency equipment.
(111) 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
m that case to summon the fully trained employees
and not attempt control activities for which they are
not trained.
Exception #2: An employer need not train all
employees to the degree specified if arrangements
have been made in advance for an outside
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 recognize that an emergency response
situation exists and they have been instructed to call
the designated outside fully-trained emergency
response team for assistance.
1910.120(p)(8){in)(B)
(B) Employee members of TSD facility emergency
response organizations shall be trained to a level of
competence in the recognition of health and safety hazards
to protect themselves and other employees. This would
include training in the methods used to minimize the risk
from safety and health hazards; in the safe use of control
equipment; in the selection and use of appropriate
personal protective equipment; in the safe operating
procedures to be used at the mcident scene; in the
techniques of coordination with other employees to
minimize risks; in the appropnate response to over
exposure from health hazards or injury to themselves and
other employees; and m the recognition of subsequent
symptoms which may result from over exposures.
(C) The employer shall certify that each covered
employee has attended and successfully completed the
training required m paragraph (p)(8)(iii) of this section, or
shall certify the employee's competency for certification
of training shall be recorded and maintained by the
employer.
(iv) Procedures for handling emergency incidents.
July 1994
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29 CFR 1910 120
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(A) la addition to the elements for the emergency
response plan required m paragraph (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 contained in the
emergency response plan:
191Q.120(p)(8)(iv)(A){l}
{1} Site topography, layout, and prevailing
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 disaster, 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 keep it current with new or changing site
conditions or information.
(E) An employee alarm system shall be installed m
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 appropriate steps to implement the site
emergency response plan.
1910.120(q)
(q) Emergency response program to hazardous
substance 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 section. Those emergency response
organizations who have developed and implemented
programs equivalent 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 implemented 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, OSHA personnel. Employers who
will evacuate their employees from the danger area
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
complying with section 1910.38(a) of this part.
1910.120(q)(2)
(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 areas to the extent that they are not
addressed in any specific program required in this
paragraph:
(i) Pre-emergency planning and coordination with
outside parties.
(ii) Personnel roles, lines of authority, training,
and communication.
(lii) Emergency recognition and prevention.
(iv) Safe distances and places of refuge.
(v) Site security and control.
(vi) Evacuation routes and procedures.
(vii) Decontamination.
(vui) Emergency medical treatment and first aid.
(ix) Emergency alerting and response
procedures.
(x) Critique of response and follow-up.
(xi) PPE and emergency equipment.
(xu) Emergency response organizations may use
the local emergency response plan or the state
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29 CFR 1910.120
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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 properly addressed by the SARA Title
TIT plans may be substituted into their emergency
plan or otherwise kept together for the employer
and employee's use.
1910.120(q)(3)
(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 individual in charge of the ICS assisted
by the senior official present for each employer.
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 controlling the operations at the site.
Initially it is the senior officer on the first-due piece of
responding emergency apparatus to arrive on the incident
scene. As more semor 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 established.
(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
procedures, and use of any new technologies.
1910.120(q)(3)(in)
(lii) Based on the hazardous substances and/or
conditions present, the individual m charge of the ICS
shall implement appropriate emergency operations,
and assure that the personal protective equipment
worn is appropnate 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 performing fire
fighting operations beyond the incipient stage for any
incident.
(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 protection will not
result m hazardous exposures to employees.
(v) The individual m charge of the ICS shall limit the
number of emergency response personnel at the
emergency site, in those areas of potential or actual
exposure to mcident or site hazards, to those who
are actively performing emergency operations.
However, operations m hazardous areas shall be
performed using the buddy system in groups of two
or more.
1910.120(q)(3)(vi)
(vi) Back-up personnel shall be standing by with
equipment ready to provide assistance or rescue.
Qualified basic life support personnel, as a minimum,
shall also be standing by with medical equipment and
transportation capability.
(vn) The individual m charge of the ICS shall
designate a safety officer, who is knowledgeable 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.
(via) When activities are judged by the safety officer
to be an IDLH and/or to mvolve an imminent danger
condition, the safety officer shall have the authority
to alter, suspend, or terminate those activities. The
safety official shall immediately inform the individual
m charge of the ICS of any actions needed to be
taken to correct these hazards at the emergency
scene.
(ix) After emergency operations have terminated, the
individual m charge of the ICS shall implement
appropriate decontamination procedures.
(x) When deemed necessary for meeting the tasks at
hand, approved self-contained compressed air
breathing apparatus may be used with approved
cylinders from other approved self-contained
compressed air breathing apparatus provided that such
cylinders are of the same capacity and pressure
rating. All compressed air cylinders used with
self-contained breathing apparatus shall meet U.S.
Department of Transportation and National Institute
for Occupational Safety and Health criteria.
1910.120(q)(4)
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29 CFR 1910.120
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(4) Skilled support personnel. Personnel, not necessarily
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
immediate emergency support work that cannot reasonably
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 m any emergency response. The initial
briefing shall 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 m
the hazards of specific hazardous substances, and who
will be called upon to provide technical advice or
assistance at a hazardous substance release incident to the
individual in charge, shall receive training or demonstrate
competency in the area of their specialization annually.
1910.120(q)(6)
(6) Training. Training shall be based on the duties and
function to be performed by each responder of an
emergency response organization. The skill and
knowledge levels required for all new responders, those
hired after the effective 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 individuals 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 authorities of the
release. First responders at the awareness level shall
have sufficient training or have had sufficient
experience to objectively demonstrate competency in
the following areas:
(A) An understanding of what hazardous
substances are, and the risks associated with
them in an incident.
(B) An understanding of the potential outcomes
associated with an emergency created when
hazardous substances are present.
1910.120(q)(6)(i)(C)
(C) The ability to recognize the presence of
hazardous substances in an emergency.
(D) The ability to identify the hazardous
substances, if possible.
(E) An understanding of the role of the first
responder awareness individual in the employer's
emergency response plan including site security
and control and the U.S. Department of
Transportation's Emergency Response
Guidebook.
(F) The ability to realize the need for additional
resources, and to make appropriate notifications
to the communication center.
(li) First responder operations level. First responders at
the operations level are individuals 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 awareness level and the employer shall so
certify:
1910.120(q)(6)(ii)(A)
(A) Knowledge of the basic hazard and risk
assessment techniques.
(B) Know how to select and use proper personal
protective equipment provided to the first responder
operational level.
(C) An understanding of basic hazardous materials
terms.
(D) Know how to perform basic control, containment
and/or confinement operations within the capabilities
of the resources and personal protective equipment
available with their unit.
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29 CFR 1910.120
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(E) Know how to implement basic decontamination
procedures.
(F) An understanding of the relevant standard
operating procedures and termination procedures.
(m) 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 training equal to the first responder
operations level and in addition have competency in the
following areas and the employer shall so certify:
1910.120(q)(6)(iii)(A)
(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 specialized
chemical personal protective equipment provided to
the hazardous materials technician.
(E) Understand hazard and nsk assessment
techniques.
(F) Be able to perform advance control, containment,
and/or confinement operations within the capabilities
of the resources and personal protective equipment
available with the unit.
(G) Understand and implement decontamination
procedures.
(H) Understand termination procedures.
(I) Understand basic chemical and toxicological
terminology and behavior.
(iv) Hazardous materials specialist. Hazardous materials
specialists are individuals who respond with and provide
support to hazardous materials technicians. Their duties
parallel those of the hazardous materials technician,
however, those duties require a more directed or specific
knowledge of the various substances they may be called
upon to contain. The hazardous materials specialist would
also act as the site liaison with federal, state, local and
other government authorities m regards to site activities.
Hazardous materials specialists shall have competency in
the following areas and the employer shall so certify :
1910.120(q)(6)(iv)(A)
(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 instruments and equipment.
(C) Know the state emergency response plan.
(D) Be able to select and use proper specialized
chemical personal protective equipment 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
toxicological 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
competency in the following areas and the employer shall
so certify:
1910.120(q)(6)(v)(A)
(A) Know and be able to implement the employer's
incident command system.
(B) Know how to implement the employer's
emergency response plan.
(C) Know and understand the hazards and risks
July 1994
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29 CFR 1910 120
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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 completed a
training course for tmrhing the subjects they are expected
to teach, such as the courses offered by the U.S. National
Fire Academy, or they shall have the training and/or
academic credentials 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 m accordance
' with paragraph (q)(6) of this section shall receive
annual refresher training of sufficient content and
duration to maintain their competencies, or shall
demonstrate competency m those areas at least
yearly.
1910.120(q)(8)(n)
(II) A statement shall be made of the training or
competency, and if a statement of competency is
made, the employer shall keep a record of the
methodology used to demonstrate competency.
(9) Medical surveillance and consultation.
(i) Members of an organized and designated
HAZMAT team and hazardous materials specialist
shall receive a baselme physical examination and be
provided with medical surveillance as required in
paragraph (f) of this section.
(11) Any emergency response employees who exhibit
signs or symptoms which may have resulted from
exposure to hazardous substances during the course
of an emergency incident either immediately or
subsequently, shall be provided with medical
consultation as required in paragraph (f)(3)(a) of this
section.
(10) Chemical protective clothing. Chemical protective
clothing and equipment to be used by organized and
designated HAZMAT team members, or to be used by
hazardous materials specialists, 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 hazardous substances, health
hazards and materials contaminated with them (such as
contaminated soil or other elements of the natural
environment) from the site of the incident, the employer
conducting the clean-up shall comply with one of the
following:
1910.120(q)(ll)(i)
(i) Meet all the requirements of paragraphs (b)
through (o) of this section; or
(li) Where the clean-up is done on plant property
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.
Part Number; 1910
Standard Number: 1910.120 Appendix A
Title: Personal protective equipment test methods
This appendix sets forth the non-mandatory examples of tests
which may be used to evaluate compliance with paragraphs
1910.120(g)(4) (11) and (111). Other tests and other challenge
agents may be used to evaluate
compliance.
A. Totally encapsulating chemical protective suit pressure test
1.0Scope
1.1 This practice measures the ability of a gas-tight, totally
encapsulating chemical protective suit material, seams, and
closures 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,
July 1994
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29 CFR 1910 120
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penetration, and degradation by specific hazardous substances
is not determined by this test method.
2.0Description of Terms
2.1 "Totally encapsulated chemical protective suit (TECP
suit)" means a full body garment which is constructed of
protective 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
purpose 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 the 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.
3.0Summary 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
inflation to the pre-test suit expansion pressure for removal of
suit wrinkles and creases. The pressure is lowered to the test
pressure 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.
4.0Required 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 1/4-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.
5.0Safety Precautions
5.1 Care shall be taken to provide the correct pressure safety
devices required for the source of compressed air used.
6.0Test Procedure
6.1 Prior to each test, the tester shall perform a visual
inspection of the suit. Check the suit for seam integrity by
visually examining the seams and gently pulling on the seams.
Ensure that all air supply lines, fittings, visor, zippers, and
valves 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
airline. 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
pressure test apparatus should be tested before and after each
test by closmg off the end of the tubing attached to the suit
and assuring a pressure of three inches water gauge for three
minutes 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 tests 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) = 3 mches water gauge
and (B) = 2 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
pressure (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
sufficient air to reduce the suit pressure to pressure (B), the
suit test pressure. Begin timing. At the end of three minutes,
record 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 penod, the
suit fails the test and shall be removed from service.
7.0Retest Procedure
7.1 If the suit fails the test check for leaks by inflating the
suit to pressure (A) and brushing or wipmg the entire suit
(including seams, closures, lens gaskets, glove-to-sleevejoints,
etc.) with a mild soap and water solution. Observe the suit for
the formation of soap bubbles, which is an indication of a
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29 CFR 1910.120
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leak. Repair all identified leaks.
7.2 Retest the TECP suit as outlined in Test Procedure 6.0.
8.0Report
8.1 Each TECP 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 fit
features; 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 80 percent of the test
pressure (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.
8.1.3 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
positioned 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 mside and
outside of the suit is completely dry before it is put into
storage.
B. Totally encapsulated chemical protective suit qualitative
leak test
1.0Scope
1.1 This practice semi-quahtatively 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,
penetration, 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.
2.0Description of Terms
2.1 "Totally encapsulated chemical protective suit (TECP
suit)" means a full body garment which is constructed of
protective 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
purpose 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 practice the
limited flow of a gas 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 test room challenge agent concentration by the
concentration of challenge agent found mside the suit. The
accuracy of the intrusion coefficient is dependent on the
challenge agent monitoring methods. The larger the intrusion
coefficient the greater the protection provided by the TECP
suit.
3.0Summary of recommended practice
3.1 The volume of concentrated aqueous ammonia solution
(ammonia hydroxide, NH(4) 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 appropriate
respiratory equipment (either a self-contained breathing
apparatus or a supplied air respirator) and worn mside 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 concentration 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 concentration is
measured again. The suited individual exits the test room and
his stand-by person measures the ammonia concentration
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
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29 CFR 1910.120
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doffing 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 colorunetnc indicator strip of bromophenol
blue 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 should leave the test room immediately.
4.0Required supplies
4.1 A supply of concentrated aqueous ammonium hydroxide
(58 percent by weight).
4.2 A supply ofbromophenol/blue indicating paper, sensitive
to 5-10 ppm ammonia or greater over a two-minute period 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
corresponding 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 plastic pan (PVC) at least 12":14":1" 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 milliliters in .volume with an accuracy of
at least ฑ1 milliliters. j *
5.0Safety precautions
5.1 Concentrated aqueous ammonium hydroxide, NH(4)OH,
is a corrosive volatile liquid requiring eye, skin, and
respiratory protection. The person conducting test shall review
the MSDS for aqueous ammonia.
5.2 Smce the established permissible exposure limit for
ammonia is 35 ppm as a 15 minute STEL, only persons
wearing a positive pressure self-contained breathing apparatus
or a supplied air respirator shall be in the chamber. Normally
only the person wearing the total-encapsulating suit will be
inside the chamber. A stand-by person shall have a positive
pressure self-contained breathing apparatus, or a 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 carried 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
respiratory protection and checked for allergies to ammonia
before participating m this test procedure.
6.0Test procedure
6.1.1 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.
6.1.2 Measure this volume from the supply of concentrated
ammonia and place it into a closed plastic container.
6.1.3 Place the container, several high range ammonia
detector 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.
6.2.1 In a non-contaminated atmosphere, open a pre-sealed
ammonia indicator strip and fasten one end of the strip to the
mside of 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.
6 2.2 If problems are encountered with this method of
attachment, the indicator strip can be attached to the outside
of the respirator face piece bemg used during the test.
6.3 Don the respiratory protective device normally used with
the suit, and then don the TECP suit to be tested. Check to be
sure all openings which are intended to be sealed (zippers,
gloves, etc.) are completely sealed. DO NOT, however, plug
off any venting valves.
6.4 Step into the enclosed test room such as a closet,
bathroom, or test booth, equipped with an exhaust fan. No air
should be exhausted from the chamber during the test because
this will dilute the ammonia challenge concentrations.
6.5 Open the container with the pre-measured volume of
concentrated aqueous ammonia within the enclosed test room,
and pour the liquid into the empty plastic test pan. Wait two
minutes to allow for adequate volatilization of the concentrated
aqueous ammonia. A small mixing fan can be used near the
evaporation pan to mcrease the evaporation rate of ammonia
solution.
6.6 After two minutes a determination of the ammonia
concentration within the chamber should be made using the
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29 CFR 1910.120
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high range colonmetnc detector tube. A concentration of 1000
ppm ammonia or greater shall be generated before the
exercises are started.
6.7 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 penod.
6.7.3 Touching the toes with a 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 colonmetnc indicating
paper should change colors, the test should be stopped and
section 6.10 and 6.12 initiated (See 4.2).
6.9 After completion of the test exercise, the test area
concentration should be measured agam using the high range
colonmetnc detector tube.
6.10 Exit the test area.
6.11 The opening created by the suit zipper or other
appropnate 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 intenor
ammonia concentration the test is concluded and the suit is
doffed and the respirator removed.
6.13 The ventilatmg fan for the test room should be turned
on and allowed to run for enough time to remove the ammonia
gas. The fan shall be vented to the outside of the building.
6.14 Any detectable ammonia in the suit interior (five ppm
(NH(3)) or more for the length of stain detector tube) indicates
the suit has failed the test. When other ammonia detectors are
used a lower level of detection is possible, and it should be
specified as the pass/fail critena.
6.15 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 coefficient is 200
or more, then the suit is suitable for emergency response and
field use.
7.0Retest procedures
7.1 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.
8.0Report
8.1 Each gas tight totally encapsulating chemical protective
suit tested by this practice shall have the following information
recorded.
8.1.1 Umque identification number identifying brand name,
date of purchase, matenal of construction, and unique suit
features; 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 date.
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 samplmg 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
concentrations, their average, the intenor 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
detectable ammonia (five ppm or greater for the length of stain
detector tube) in the suit intenor 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 cntena.
Caution
Visually inspect all parts of the suit to be sure they are
positioned 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
storage.
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29 CFR 1910.120
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Part Number: 1910
Standard Number: 1910.120 Appendix B
Title: General description and discussion of the levels of
protection and protective gear
This appendix sets forth information about personal
protective 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 during 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 m this process are identification of the hazards, or
suspected hazards; their routes of potential hazard to
employees (inhalation, skin absorption, ingestion, and eye 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.(end of sentence deleted - FR 14074, Apr 13.
1990)
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 m
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 the 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 levels (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
relation to the specific hazards at the job site, and that PPE
selection, evaluation and re-selection is an ongoing process
until sufficient information about the hazards and PPE
performance is obtained.
Part A. Personal protective equipment is 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 ATo be selected when the greatest level of skin,
respiratory, and eye protection is required.
The following consti^ite 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 (NIOSH).
2. Totally encapsulating chemical-protective suit.
3. Coveralls.(l)
4. Long underwear.(1)
5. Gloves, outer, chemical-resistant.
6. Gloves, inner, chemical-resistant.
7. Boots, chemical-resistant, steel toe and shank.
8. Hard hat (under suit).(l)
9. Disposable protective suit, gloves and boots (depending on
suit construction, may be worn over totally encapsulating suit).
[Footnote(l) Optional, as applicable.]
II. Level BThe 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).
July 1994
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29 CFR 1910.120
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3. Coveralls.(l)
4. Gloves, outer, chemical-resistant.
5. Gloves, inner, chemical-resistant.
6. Boots, outer, chemical-resistant steel toe and shank.
7. Boot-covers, outer, chemical-resistant (disposable).(l)
8. Hard hat.(l)
9. [Reserved]
10. Face shield.(1)
[Footnote(l) Optional, as applicable.]
HI. Level CThe concentration(s) and type(s) of airborne
substance(s) is known and the criteria for using air purifying
respirators are met.
The following constitute Level C equipment; it may be used
as appropriate.
1. Full-face or half-mask, air purifying respirators (NIOSH
approved)
2. Hooded chemical-resistant clothing (overalls; two-piece
chemical-splash suit; disposable chemical-resistant overalls).
3. Coveralls.(l)
4. Gloves, outer, chemical-resistant.
5. Gloves, inner, chemical-resistant.
6. Boots (outer), chemical-resistant steel toe and shank.(1)
7. Boot-covers, outer, chemical-resistant (disposable).(l)
8. Hard hat.(l)
9. Escape mask.(l)
10. Face shield.(l)
[Footnote(l) Optional, as applicable.]
IV. Level DA work uniform affording minimal protection:
used for nuisance contamination only.
The following constitute Level D equipment; it may be used
as appropriate:
1. Coveralls.
2. Gloves.(l)
3. Boots/shoes, chemical-resistant steel toe and shank.
4. Boots, outer, chemical-resistant (disposable).(1)
5. Safety glasses or chemical splash goggles.(l)
6. Hard hat.(l)
7. Escape mask.(l)
8. Face shield.(1)
[Footnote(l) Optional, as applicable.]
Part B. The types of hazards for which levels A, B, C, and
D protection are appropriate are described below:
I. Level ALevel 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 respiratory system
based on either the measured (or potential for) high
concentration of atmospheric vapors, gases, or particulates; or
the site operations and work functions involve a high potential
for splash, immersion, or exposure to unexpected vapors,
gases, or particulates of materials that are harmful to skin or
capable of being absorbed through the slan,
2. Substances with a high degree of hazard to the skin are
known or suspected to be present, and slan contact is possible;
or
3. Operations must be conducted in confined, poorly
ventilated areas, and the absence of conditions requiring Level
A have not yet been determined.
II. Level BLevel B protection should be used when:
1. The type and atmospheric concentration of substances
have been identified and require a high level of respiratory
protection, but less skin protection.
2. The atmosphere contains less than 19.5 percent oxygen;
or
3. The presence of incompletely identified vapors or gases
is indicated by a direct-reading organic vapor detection
instrument, but vapors and gases are not suspected of
containing high levels of chemicals harmful to skin or capable
of being absorbed through the slan.
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29 CFR 1910.120
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Note: This involves atmospheres with IDLH concentrations
of specific substances that present severe inhalation hazards
and that do not represent a severe skin hazard; or that do not
meet the criteria for use of air-purifying respirators.
IE. Level CLevel C protection should be used when:
1. The atmospheric contaminants, liquid splashes, or other
direct contact will not adversely affect or be absorbed through
any exposed skin;
2. The types of air contaminants have been identified,
concentrations measured, and an air-purifying respirator is
available that can remove the contaminants; and
3. All criteria for the use of air-punfying respirators are
met.
IV. Level DLevel D protection should be used when:
1. The atmosphere contains no known hazard; and
2. Work functions preclude splashes, immersion, or the
potential for unexpected inhalation of or contact with
hazardous levels of any chemicals.
Note: As stated 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 should 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:
NFPA 1991 - Standard on Vapor-Protective Suits for
Hazardous Chemical Emergencies (EPA Level A Protective
Clothing)
NFPA 1992 - 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-emergency. Non-flammable Hazardous Chemical
Situations (EPA Level B Protective Clothing)
These standards would apply documentation and performance
requirements to the manufacture of chemical protective suits.
Chemical protective suits meetmg these requirements would be
labeled as compliant with the appropriate standard. When
these standards are adopted by the National Fire Protection
Association, it is recommended that chemical protective suits
which meet these standards be used.
Part Number: 1910
Standard Number: 1910.120 Appendix C
Title: Compliance guidelines
1. Occupational Safety and Health Program. Each
hazardous waste site clean-up effort will require a site-specific
occupational safety and health program headed by the site
coordinator or the employer's representative. The purpose of
the program will be the protection of employees at the site and
will be an extension of the employer's overall safety and
health program work. The program will need to be developed
before work begins on the site and implemented as work
proceeds as stated in paragraph (b). The program is to
facilitate coordination and communication of safety and health
issues among personnel responsible for the various activities
which will take place at the site. It will provide the overall
means for planning and implementing the needed safety and
health training and job orientation of employees who will be
working at the site. The program will provide the means for
identifying and controlling worksite hazards and the means for
monitoring program effectiveness. The program will need to
cover the responsibilities and authority of the site coordinator
for the safety and health of employees at the site, and the
relationships with contractors or support services as to what
each employer's safety and health responsibilities are for their
employees on the site. Each contractor on the site needs to
have its own safety and health program so structured that it
will smoothly interface with the program of the site
coordinator or principal contractor.
Also those employers mvolved with treating, storing or
disposal of hazardous waste as covered in paragraph (p) must
have implemented a safety and health program for their
employees. This program is to mclude the hazard
communication program required in paragraph (p)(l) and the
training required in paragraphs (p)(7) and (p)(8) as parts of the
employers comprehensive overall safety and health program.
This program is to be in writing.
Each site safety and health program will need to mclude the
following: (1) Policy statements of the line of authority and
accountability for implementing the program, the objectives of
the program and the role of the site safety and health officer
or manager and staff; (2) means or methods for the
development of procedures for identifying and controlling
workplace hazards at the site; (3) means or methods for the
development and communication to employees of the various
plans, work rules, standard operating procedures and practices
that pertain to individual employees and supervisors; (4)
means for the training of supervisors and employees to
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29 CFR 1910.120
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develop the needed skills and knowledge to perform their work
in a safe and healthful manner; (5) means to anticipate and
prepare for emergency situations and; (6) means for obtaining
information feedback to aid in evaluating the program and for
improving the effectiveness of the program. The management
and employees should be trying continually to improve the
effectiveness of the program thereby enhancing the protection
being afforded those working on the site.
Accidents on the site or workplace should be mvestigated to
provide information on how such occurences can be avoided
in the future. When injuries or illnesses occur on the site or
workplace, they will need to be mvestigated to determine what
needs to be done to prevent this mcident from occurring agam.
Such information will need to be used as feedback on the
effectiveness of the program and the information turned mto
positive steps to prevent any reoccurrence. Receipt of
employee suggestions or complaints relating to safety and
health issues involved with site activities is also a feedback
mechanism that can be used effectively to improve the
program and may serve m part as an evaluative tool(s).
For the development and implementation of the program to
be the most effective, professional safety and health personnel
should be used. Certified Safety Professionals, Board Certified
Industrial Hygienists or Registered Professional Safety
Engineers are good examples of professional stature for safety
and health managers who will administer the employer's
program
2. Training. The training programs for employees subject to
the requirements of paragraph (e) of this standard should
address: the safety and health hazards employees should expect
to find on hazardous waste clean-up sites; what control
measures or techniques are effective for those hazards; what
monitoring procedures are effective m characterizing exposure
levels; what makes an effective employer's safety and health
program; what a site safety and health plan should mclude;
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
regulations. 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, the medical
surveillance program, the emergency response plan and other
areas.
The training programs for employees subject to the
requirements of paragraph (p) of this standard should address:
the employer's safety and health program elements impacting
employees; the hazard communication 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
requirements 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
persons; 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 mcident command system and other
subjects. Hands-on training should be stressed whenever
possible. Critiques done after an incident which include an
evaluation of what worked and what did not and how could the
mcident be better handled the next time may be counted as
training time.
For hazardous materials specialists (usually members of
hazardous 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
mcident command system. They should know where and how
to obtain additional assistance and be familiar with the local
district's emergency response plan and the state emergency
response plan.
Specialist employees such as technical experts, medical
experts or environmental experts that work with hazardous
materials in their regular jobs, who may be sent to the mcident
scene by the shipper, manufacturer or governmental agency to
advise and assist the person m charge of the incident should
have training on an annual basis. Their training should mclude
the care and use of personal protective equipment including
respirators; knowledge of the mcident command system and
how they are to relate to it; and those areas needed to keep
them current in their respective field as it relates to safety and
health involving specific hazardous substances.
Those skilled support personnel, such as employees who
work for public works departments or equipment operators
who operate bulldozers, sand trucks, backhoes, etc., who may
be called to the mcident 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
requirements, should be made aware of the hazards they face
July 1994
33
29 CFR 1910 120
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and should be provided all necessary protective clothing and
equipment required for their tasks. There are two National
Fire Protection Association standards. NFPA 472 - "Standard
for Professional Competence of Responders to Hazardous
Material Incidents" and NFPA 471 - "Recommended Practice
for Responding to Hazardous Material Incidents", which are
excellent resource documents to aid fire departments and other
emergency response organizations m developing their training
program materials. NFPA 472 provides guidance on the skills
and knowledge needed for first responder awareness level,
first responder operations level, hazmat technicians, and
hazmat specialist. It also offers guidance for the officer corp
who will be in charge of hazardous substance incidents.
3. Decontamination. Decontamination procedures should be
tailored to the specific hazards of the site and will vary in
complexity and number of steps, depending on the level of
hazard and the employee's exposure to the hazard.
Decontamination procedures and PPE decontamination
methods will vary depending upon the specific substance, since
one procedure or method will not work for all substances.
Evaluation of decontamination methods and procedures should
be performed, as necessary, to assure that employees are not
exposed to hazards by reusing PPE. References in Appendix
D may be used for guidance m establishing an effective
decontamination program. In addition, the U.S.Coast Guard's
Manual, "Policy Guidance for Response to Hazardous
Chemical Releases," U.S. Department of Transportation,
Washington, DC (COMDTINST M16465.30) 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 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 reference being used to aid m developing the
state and local district plans is the Hazardous Materials
Emergency Planning Guide, NRT-1. The current Emergency
Response Guidebook from the U.S. Department of
Transportation, CMA's CHEMTREC and the Fire Service
Emergency Management Handbook may also be used as
resources.
Employers involved with treatment, storage, and disposal
facilities for hazardous waste, which have the required
contingency plan called for by their permit, would not need to
duplicate the same planning elements. Those items of the
emergency response 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
protective 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
periodically.
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 any given
situation, equipment and clothing should be selected that
provide an adequate level of protection. However,
over-protection, as well as under-protection, can be hazardous
and should be avoided where possible. Two basic objectives
of any PPE program should be to protect the wearer from
safety and health hazards, and to prevent injury to the wearer
from incorrect use and/or malfunction of the PPE. To
accomplish these goals, a comprehensive PPE program 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 manuals, 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 mcident. 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.
During large complex fires involving several companies and
many pieces of apparatus, a command post would be
established. This enabled one individual to be in charge of
managing the mcident, rather than having several officers from
different companies making separate, 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
confusion. 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,
July 1994
34
29 CFR 1910.120
-------
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, m addition 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 designated as back-up personnel since the assistance needed
may mclude rescue.
To illustrate the operation of the ICS, the following scenario
might develop during a small incident, such as an overturned
tank truck with a small leak of flammable liquid.
The first responding semor officer would implement and take
command of the ICS. That person would size-up the mcident
and determine if additional personnel and apparatus were
necessary; 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 control the leak using the fewest number of personnel
that can effectively accomplish the tasks. The individual m
charge of the ICS then would designate himself as the safety
officer and two other employees as a back-up in case rescue
may become necessary. In this scenario, decontamination
procedures would not be necessary.
A large complex mcident may require many employees and
difficult, time-consuming efforts to control. In these situations,
the individual in charge of the ICS will want to delegate
different tasks to subordinates m order to maintain a span of
control that will keep the number of subordinates, that are
reporting, to a manageable level.
Delegation of task at large incidents may be by location,
where the incident scene is divided into sectors, and
subordinate officers coordinate activities within the sector that
they have been assigned.
Delegation of tasks can also be by function. Some of the
functions that the individual in charge of the ICS may want to
delegate at a large mcident are: medical services; evacuation;
water supply; resources (equipment, apparatus); media
relations; safety; and, site control (integrate activities with
police for crowd and traffic control). Also for a large mcident,
the individual 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 mcident
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
central 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 Flans. The safety and security
of response personnel and others in the area of an emergency
response mcident site should be of primary concern to the
mcident 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 mclude
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;
command 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
hazardous 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 m hazardous waste
operations and during the course of work; to provide
emergency and other treatment as needed; and to keep
accurate records for future reference.
The Occupational Safety and Health Guidance Manual for
Hazardous Waste Site Activities developed by the National
Institute for Occupational Safety and Health (NIOSH), the
Occupational Safety and Health Administration (OSHA), the
U.S. Coast Guard (USCG), and the Environmental Protection
Agency (EPA); October 1985 provides an excellent example
of the types of medical testing that should be done as part of
a medical surveillance program.
9. New Technology and Spill Containment Programs.
Where hazardous substances may be released by spilling from
a container that will expose employees to the hazards of the
materials, the employer will need to implement a program to
contain and control the spilled material. Diking and ditching,
as well as use of absorbents like diatomaceous earth, are
traditional techniques which have proven to be effective over
the years. However, in recent years new products have come
into the marketplace, the use of which complement and
mcrease the effectiveness of these traditional methods. These
July 1994
35
29 CFR 1910.120
-------
new products also provide emergency responders and others
with additional tools or agents to use to reduce the hazards of
spilled materials.
These agents can be rapidly applied over a large area and
can be uniformly applied or otherwise can be used to build a
small dam, thus improving the workers' ability to control
spilled material. These application techniques enhance the
intimate contact between the agent and the spilled material
allowing for the quickest effect by the agent or quickest
control of the spilled material. Agents are available to solidify
liquid spilled materials, to suppress vapor generation from
spilled materials, and to do both. Some special agents, which
when applied as recommended by the manufacturer, will react
in a controlled manner with the spilled material to neutralize
acids or caustics, or greatly reduce the level of hazard of the
spilled material.
There are several modern methods and devices for use by
emergency response personnel or others mvolved with spill
control efforts to safely apply spill control agents to control
spilled material hazards. These include portable pressurized
applicators similar to hand-held portable lire extinguishing
devices, and nozzle and hose systems similar to portable fire
fighting foam systems which allow the operator to apply the
agent without having to come into contact with the spilled
material. The operator is able to apply the agent to the spilled
material from a remote position.
The solidification of liquids provides for rapid containment
and isolation of hazardous substance spills. By directing the
agent at run-off points or at the edges of the spill, the reactant
solid will automatically create a barrier to slow or stop the
spread of the material. Clean-up of hazardous substances is
greatly improved when solidifying agents, acid or caustic
neutralizes, or activated carbon absorbents are used, properly
applied, these agents can totally solidify liquid hazardous
substances or neutralize or absorb them, which results m
materials which are less hazardous and easier to handle,
transport, and dispose of. The concept of spill treatment, to
create less hazardous substances, will improve the safety and
level of protection of employees working at spill clean-up
operations or emergency response operations to spills of
hazardous substances.
The use of vapor suppression agents for volatile hazardous
substances, such as flammable liquids and those substances,
such as flammable liquids and those substances which present
an inhalation hazard, is important for protecting workers. The
rapid and uniform distribution of the agent over the surface of
the spilled material can provide quick vapor knockdown.
There are temporary and long-term foam-type agents which
are effective on vapors and dusts, and activated carbon
adsorption agents which are effective for vapor control and
soaking-up of the liquid. The proper use of hose lines or
hand-held portable pressurized applicators provides good
mobility and permits the worker to deliver the agent from a
safe distance without having to step into the untreated spilled
material. Some of these systems can be recharged in the field
to provide coverage of larger spill areas than the design limits
of a single charged applicator unit. Some of the more effective
agents can solidify the liquid flammable hazardous substances
and at the same time elevate the flashpoint above 140 degrees
F so the resulting substance may be handled as a nonhazardous
waste material if it meets the U.S. Environmental Protection
Agency's 40 CFR part 261 requirements (See particularly
261.21). All workers performing hazardous substance spill
control work are
expected to wear the proper protective clothing and equipment
for the materials present and to follow the employer's
established standard operating procedures for spill control. All
mvolved workers need to be trained in the established
operating procedures; in the use and care of spill control
equipment; and m the associated hazards and control of such
hazards of spill containment work.
These new tools and agents are the things that employers
will want to evaluate as part of their new technology program.
The treatment of spills of hazardous substances or wastes at an
emergency incident as part of the immediate spill containment
and control efforts is sometimes acceptable to EPA and a
permit exception is described in 40 CFR 264.1(g)(8) and
265. l(c)(ll).
Part Number: 1910
Standard Number: 1910.120 Appendix D
Title: References
The following references may be consulted for further
information on the subject of this standard:
1. OSHA Instruction DFO CPL 2.70 - January 29, 1986,
Special Emphasis Program: Hazardous Waste Sites.
2. OSHA Instruction DFO CPL 2-2.37A - January 29,1986,
Technical Assistance and Guidelines for Superfund and Other
Hazardous Waste Site Activities.
3. OSHA Instruction DTS CPL 2.74 - January 29, 1986,
Hazardous Waste Activity Form, OSHA 175.
4. Hazardous Waste Inspections Reference Manual, U.S.
Department of Labor, Occupational Safety and Health
Administration, 1986.
5. Memorandum of Understanding Among the National
Institute for Occupational Safety and Health, the Occupational
July 1994
36
29 CFR 1910.120
-------
Safety and Health Administration, the United States Coast
Guard, and the United States Environmental Protection
Agency, Guidance for Worker Protection During Hazardous
Waste Site Investigations and Clean-up and Hazardous
Substance 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.
Environmental Protection Agency, Office of Emergency and
Remedial Response, Hazardous Response Support Division,
December 1984.
8. Preparation of a Site Safety Plan, Field Standard
Operating Procedures (F.S.O.P.) 9; U.S. Environmental
Protection Agency, Office of Emergency and Remedial
Response, Hazardous Response Support Division, April 1985.
9. Standard Operating Safety Guidelines; U.S.
Environmental Protection Agency, Office of Emergency and
Remedial Response, Hazardous Response Support Division,
Environmental 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);
October 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 Materials
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, Federal
Emergency Management Agency, Washington, DC, January
1985.
15. Emergency Response Guidebook, U.S. Department of
Transportation, Washington, DC, 1987.
16. Report to the Congress on Hazardous Materials
Training. Planning and Preparedness, Federal Emergency
Management Agency, Washington, DC, July 1986.
17. Workbook for Fire Command, Alan V. Brunacim and J.
David Beageron, National Fire Protection Association,
Batterymarch Park, Quincy, MA 02269, 1985.
18. Fire Command, Alan B. Brunacuu, National Fire
Protection Association, Batterymarch Park, Qumcy, MA
02269, 1985.
19. Incident Command System, Fire Protection Publications,
Oklahoma State University, Stillwater, OK 74078, 1983.
20. Site Emergency Response Planning, Chemical
Manufacturers 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 Matenals Transportation Safety. U.S. Department
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
information collection requirements in this section under
control number 1218-0139.)
[54 FR 9317, Mar. 6, 1898, as amended at 55 FR 14073,
Apr. 13, 1990; 56 FR 15832, Apr. 18, 1991]
July 1994
37
29 CFR 1910.120
-------
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. 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.
9/95
B-l
Warning Concentrations
-------
Chemical
Warning Concentratioif
Acetaldehyde
0 0001 - 2 3 (50)
Acetamide
"odorless when pure"
Acetic acid
0 1 - 24 (10-15)
Acetic anhydride
0.1 - 81 2(5)
Acetone
0 1 - 699
Acetonitrile
40- 170
Acetophenone
0 002 - 0 60
Acetyl bromide
5 0 x 104
Acetyl chloride
1
Acrolein
0 05 - 16 6(0 21-0 5)
Aery lam ide
"odorless"
Acrylic acid
0 1-1
Acrylonitrile
1 6 - 100, fatigue
Akrol
10
Aldrin
0 2536 - 0 4027 mg/m5
Allyl alcohol
0 08 - 7 2 (0 75-25)
Allylamine
6 3 - 28 7
Allyl chloride
0 1 - 10 (50-100)
Allyl chloroformate
1.4
Allyl disulfide
0 0012
Allyl glycidyl ether
<10
Allyl isocyanide
0 018
Ally isothiocyanate
0 15 - 0 42
Allyl mercaptan
0 00005 - 0 21
Ammonia
0.04 - 55 (55-140)
Ammonium hydroxide
50
Ammonium sulfanate
"odorless"
n-Amyl acetate
0 00090 - 10 (200)
sec-Amyl acetate
0 0017 - 0.082
tert-Amyl acetate
0 0017
n-Amyl alcohol (1-pentanol)
0 0065 - 35
Amylene (2-methyI-2-butene)
0 0022 - 2 3
Amyl isovalerate
0 11
Warning Concentrations
B-2
9/95
-------
Chemical
Warning Concentration
n-Amyl mcrcaptan
0 07
N-Amyl methyl ketone
0 0009 - 0.35
Amyl sulfide
0.0030 - 0.005
Anethole
0 003
Aniline
ฉ
1st
1
-J
O
Apiol
0.0063
Arsenic anhydride (arsenic pentoxide)
1
Arsine
0.21 - 0.63
Benzaldehyde
0.003 - 0.69 (4 6)
Benzene
1.4 - 120(2817)
Benzoyl peroxide
"odorless"
Benzyl alcohol
5 5
Benzyl chloride
0 01 -031 (8)
Benzyl mercaptan
0.00019 - 0.04 (4.5
Benzyl sulfide
0 0021 - 0 07
Bornyl acetate
0.0078
Boron oxide
"immediate irritation"
Boron trifluoride
1 - 1.5
Bromine
0 05 - 3 5 (0 6 intolerable)
Broraoacetone
0.090
Bromoacetophenone
0.015 - 0.17 (0 04)
Bromoform
1 3 - 530
1,3-Butadiene
0 16 - 1 8 (>8000)
n-Butanc
5 5 - 5000
2-Butoxyethanol
0 1 - 60 (100-195)
Butyl acetate
0 037 - 20 (300)
sec-Butyl acetate
3 - 7
tcrt-Butyl acetate
0 004 - 47
Butyl acrylate
0.04 - 0.9
Butyl alcohol
0 1 - 20 (25-100)
sec-Butyl alcohol
0.1 - 43
tert-Butyl alcohol
0.1 - 73 (100)
Butylamine
0.1-5 (10-15)
9/95
B-3
Warning Concentrations
-------
Chemical
Warning Concentration
sec-Butylamine
0 24 (as n-Butylamine)
tert-Butylamine
0 24 (as n-Butylamine)
Butyl cellosolve (see 2-Butylamine)
Butyl cellosolve acetate
0 20
n-Butyl chloride
0.9 - 13
1-Butylene (1-Butene)
0 07 - 26
2-Butylene (2-Butene)
0 57 - 22
Butylene oxide
071
Butyl ether
0 24 - 0 47
n-Butyl formate
17 - 20
n-Butyl lactate
1 - 7
n-Butyl mercaptan
0 00082 - 0.38
tert-Butyl mercaptan
0 00009 - 0 06
Butyl sulfide
0 015-0 18
p-tert-Butyltoluene
5 (5-8)
n-Butyraldehyde
0 0046 - 0 039
Butyric acid
0 00056 - 0 001
Cadmium dust
"inadequate"
Cadmium fume
"inadequate"
Calcium dodccylbcnzcnc sulfonate
Calcium hydroxide
"odorless"
Calcium hypochlorite
3 5 (as Chlorine)
Calcium phosphide
0 13 - 13 4
Camphor-synthetic
0 003- 200 (1.77)
Caprolactam
0 001 - 0 065
Carbaryl (Scvinฎ)
"essentially odorless"
Carbitol acetate
0 157 - 0 263
Carbon dioxide
"odorless"
Carbon disulfide
0 0011 - 7 7
Carbon monoxide
"odorless"
Carbon tetrachloride
2 - 700
Cavacrol
0 0023
Chloral
0.047
Warning Concentrations
B-4
9/95
-------
Chemical
Warning Concentration
Chlordane
'odorless*
Chlorine
0 01 - 5 (1-6)
Chlorine dioxide
0.1 (5.0)
Chloroacetaldehyde
0 93 (0 01-1)
Chloracetic acid
0 045
Chloroacetophenone (CN, Tear Gas)
0 01 - 1 35 (0.024-0 063)
Chlorobenzene
0 1 - 60
o-chlorobenzylidene malononitrile
(0 2)
Chlorobromomethane
100 - 400
Chloroform
50 - 307, fatigue (> 4096)
Chloromethane (see Methyl chloride)
Chlorophenol
0 034
o-Chlorophenol
0 0036
p-Chlorophenol
1 2-30
Chloropicrin
0 8 - 1 1 (0 3-0 37)
B-Chloroprene
o
OP
Chlorosulfonic acid
1 - 5 (from HC1 produced)
o-Chlorotoluene
0 32
Chlorovinyl arsine
1 6
Cinnam aldehyde
0.0026
Citric acid
"odorless"
Cobalt, Metal Fume & Dust
(> 1 mg/m!)
Coumarin (Coumaphos, Baymix)
0 0033 - 0 2
Crag* Herbicide
"none"
m-Cresol
0 25 - 0 68
o-Cresol
0 26 - 0 68
p-Cresol
0 00047 - 0 0455
Crotonaldehyde
0 01 - 7 35 (45)
Crotyl mercaptan
0 00016 - 0 0099
Crude-heavy (Loganillas-Crude)
ฉ
o
l/l
Crude-light (Louisiana-Crude)
0 1-05
Crude-medium (Barbados-Crude)
0 1-05
Cumene
004- 1 2
9/95
B-5
Warning Concentrations
-------
Chemical
Warning Concentratioif
Cyanogen chloride (CNCL)
1
Cyclohexane
0 1 - 300 (300)
Cyclohexanol
0.06 - 160 (100)
Cyclohexamone
0 01-4
Cyclohexene
0 18 - 300
Cyclohexylamine
2.6
Cyclopentadiene
0.01 - 250
2,4-D esters
0.02-0.1
DDT (Dichlorodiphenyl trichloroethane)
2 9 mg/mฎ
Decaborane
0.0S - 0 35 (fatigue)
Decanoic acid
0.0020 - 0 35
Decanal
0 0064 - 0 168
1-Decylene
0.12
Diacetone alcohol
0 1-17
Diacctyl
0 025
Diallyl ketone
90
Diazomelhane
"inadequate*
Diborane
18-4, 'not reliable'
Di-N-Butyl amine
0 08 - 0 48
Dibutyl phosphate
"inadequate'
Dichlorobenzene
0 005
o-Dichlorobenzene
0.3 - 50 (20-30)
p-Dichlorobenzene
0.18 - 30 (80-160)
Dichlorodiethyl sulfide (Mustard Gas)
0 0023 - 0.19
Dichlorodifluoromelhane
"odorless"
1,3-Dichloro-5,5-dimcthy 1 hydatoin
"adequate," 0 01 (1 14)
1, 1-Dichloroethane
50 - 1350, "adequate"
1,2-Dichloroethylene
0.085 - 500
Dichloroethyl ether
0 0005 - 35 (100-200)
bis-a-Dichloroethyl sulfide
0 0023
Dichloroisopropyl ether
0 32
Dichloromethane (see Methylene chloride)
dichloromonofluoromethane
"nearly odorless'
Warning Concentrations
B-6
9/95
-------
Chemical
Warning Concentration
2,4-Dichlorophenol
0.21 - 0 008
1,2-Dichloropropanc
o
-J
o
2,2-Dichloropropiomcacid (Dalapon)
428
Dichlorotetrafluoroethane
"nearly odorless"
Dieyelopentadiene
0 003 - 0 020
Dieldrm
0 041
Diesel Fuel No 1-D
025
Diesel Fuel No 2-D
0 08
Diesel Fuel No 4-D
0 01
Diethanolamine
0 011-0 27
Diethylamine
0 01 - 38 (SO, animals)
Diethylaminoethanol
0 01 -025
Diethylene glycol
"almost odorless"
Diethylene triamine
10
Diethyl ketone
1 - 10
Diethyl selenide
0 00014
Diethyl succinate
0 021
Difluorodibromomethane
"inadequate"
Diglycidyl ether
5
Diisobutyl carbinol
0 048 - 0 160
Diisobutyl ketone
0.11 -0 31 (25.8)
Diisopropylamine
0.1 - 4 (25-50, injury)
Dimethyl acetamide
21-47
Dimethylamine
0.01 - 6 (97-183, animals)
Dimethylaminoethanol
0.015 0.045
Dimethylaniline
0.001 - 0.2
Dimethyl ether
0.3-9
Dimethyl formam ide
0 1 - 100
1, 1-Dimethylhydrazine
1 - 14
Dimethyl sulfate
"nearly odorless'
dimethyl sulfide
0.001 - 0 020
Dimethyl sulfoxide
"practically no odor*
Dimethyl trichiocarbonate
0.0058 - 0 18 mg/m5
9/95
B-7
Warning Concentrations
-------
Chemical
Warning Concentration
Dinitro-o-cresol
'odorless'
2,6-Dimtrophenol
0.21 (as phenol)
Dinitrocoluene
"inadequate'
Dioxane
0 003 - 278 (200-300)
Dioxolane
64- 128
Diphenyl (Biphenyl)
0.0008 - 0 06 (3-4)
Diphenyl chloroarsine
0.030
Diphenylcyanoarsine
0.3
Diphenyl ether (see Phenyl ether)
Diphenyl sulfide
0.00034 - 0.0047
Diphosgene (Tnchloromethyl chloroformate)
1.2
Dipropylamine
0 02 - 55
Dipropylene glycol
"practically odorless"
Dipropylene glycol methyl ether
34 7 - 1000 (74.3)
dithioethylene glycol
0.031
Dodecanol
0 0064
Dodecycibenzene sulfonic acid
00
ฆ**
o
Epichlorohydrin
0 1 - 16 (100)
EPN
"inadequate"
Ethane
150 - 899
1,2-Ethanedithiol
0 0042
Ethanol
1 - 5100(5041)
Ethanolamine
2-4
2-Ethyoxy-3,4-dihydro-1,2-py ran
0 10-0 60
2-Elhoxyethanol (Cellosolve acetate)
0 55-50
2-Ethoxyethyl acetate (Cellosolve acetate)
0 056 - 50 (600, animals)
Ethyl acetate
0.01 - 50 (200-400)
Ethyl acrylate
0 00024 - 1 (75)
Ethylamine
0 01 - 1 (100, delayed)
Ethyl benzene
0 1 - 200 (200)
Ethyl bromide
3 1 - 200 (6500)
2-Ethylbutanol
0 07 - 0 77
Ethyl butyl ketone
0 1 - 10
Warning Concentrations
B-8
9/95
-------
Chemical
Warning Concentration
Ethyl butyrate
0.0082 - 0 015
Ethyl chloride (Chloroethanc)
4.2
Ethyl disulfide
0 0028
Ethylene
261 - 4010
Ethylene bromide (see Ethylene dibromide)
Ethylene chloride (see Ethylene dichloride)
Ethylene chlorohydrin
"odorless," 0.4
Ethylene diamine
1 - 11.2(100)
Ethylene dibromide
10-25
Ethylene dichloride
6.2 - 185
Ethylene glycol
0.08 - 40
Ethylene imine
"inadequate" 1 - 100+
Ethylene oxide
0 1 - 700
Ethyl ether
0 1 -9 (200)
Ethyl formate
18 - 33 (330)
Ethyl glycol
25
Ethyl hexanol
0.075 - 0.138
Ethyl hexanoate
0 0056
Ethyl hexyl acetate
0 18
Ethyl hexyl acrylate
0.007 - 0 073
Ethyl isothiocyanate
16 - 10.7
Ethyl mercaptan
0 00051 -0 075
Ethyl methacrylate
0 0067
n-Elhylmorpholine
0 1 - 25, fatigue (40 - 100)
Ethyl pelargonate
0.0014
Ethyl phthalate
"odorless"
Ethyl selenide
0 0003 - 0 014 mg/m5
Ethyl selenamercaptan
0 0003
Ethyl silicate
17 - 85 (250)
Ethyl sulfide
0.00060 - 0 068
Ethyl isovalerate
0.12
Ethyl decanoate
0 00017
Ethyldichlorarsine
0.14 - 1 4
9/95
B-9
Warning Concentrations
-------
Chemical
Warning Concentration
Ethyl n-valerate
0 060
Ethyl undecanoate
0.00054
Eugenol
0 0046
Fluoride dust
(5.0 mg/m')
Fluorine
0.035 - 3 (25-100)
Fluorotrichloromethane
5 - 100, 'odorless*
Formaldehyde
0.01 - 60 (0 25-2)
Formic acid
0 024 - 340(15)
Fuel Oil H\ (Kerosene, Jet Fuel)
0.082 - 1
Fuel Oil tfl (Diesel Oil)
0 082
Fuel Oil #4
05
Fuel Oil #6 (Bunker-C)
0 - 13
Furfural
0 006 - 5 (12 2-50)
Furfuryl alcohol
8
Fumaric Acid (trans-Butenedioic)
"odorless"
Gasoline
0 005 - 10
Glutaraldehyde
0 04
Glycol diacetate
0 077 - 0.312
Halothane
33
n-Heptal chloride
0 060
Heptachlor
0.306 mg/m1
Heptaldehyde
0.050
n-Heptane
0.5 - 329
Heptanol
0 057 - 20
HETP (see TEPP)
Hexachlorocyclopentadiene
0.03 - 0 33
Hexachloroethane
0.13
Hexamethylenediamine
0.0009
n-Hexane
65 - 248 (1400-1500)
Hexanoic acid
0 0061
Hexanol
0 0050 - 0 09
Hexanone (see Methyl Butyl Ketone)
sec-Hexyl acetate
0.1 - 100(100)
Warning Concentrations
B-10
9/95
-------
Chemical
Warning Concentration
Hexylene glycol
SO
Hydrazine
3 -4
Hydrocinnamyl alcohol
0 00027
Hydrogen bromide
2 (3-6)
Hydrogen chloride
1 - 10 (35)
Hydrogen cyanide
0 00027 - 5, fatigue
Hydrogen fluoride
0 04 - 0.163
Hydrogen peroxide
"odorless" (100)
Hydrogen selemde
0 0005 - 3 6, fades fast (1 5)
Hydrogen sulfide
0.00001 - 1 4 (50-100)
(fatigue at high concentration)
2-Hydroxpropyl acrylate
0 05
Indene
0 02
Iodine
1 73 (1.63 -
disappears within 2 minutes)
Iodoform
0.0004 - 0 5
Ionone
5.9 x 104 -73
Isoamyl acetate
0 001-1
Isoamyl alcohol
0 01 - 35 (100-150)
Isoamyl mercaptan
0 0043 - 0 7
Isobutyl acetate
0 002 - 7 (< 150)
Isobutyl acrylate
0 009 - 0 012
Isobutyl cellosolvc
0 114-0.191
Isobutyl mercaptan
0 00054 - 0 00097
Isobutylraldehyde
0 047 - 0 336
Isobutyric acid
0.001
Isocyanochloride
0 98
Isodecanol
0 31 - 0 042
Isopentanoic acid
0 005 - 0 026
Isopentyl acetate (see Isoamyl acetate)
Isophorone
0 18 - 8 85 (8 85)
Isoprene (2-methylbutadiene)
0 005
Isopropanolamine dodecylbenzene sulfate
0.3
9/95
B-ll
Warning Concentrations
-------
Chemical
Warning Concentration
Isopropyl acetate
0 5 - 400 (200)
Isopropyl alcohol
7 5 - 300 (400)
Isopiopylamine
0 1 - 10 (10-20)
Isopropyl ether
0 02 - 300 (800)
Isopropyl glycidyl ether
300
Isopropyl Mercaptan
0 00025
Kerosene
0 082-1
Ketene
(23)
Kuwait-Crude
0 1-05
Lactic acid
4 x 107
Laurie acid
0 0034
Lauryl mercaptan
4 mg/m5
Light Gasoline
800
Lindane
"practically odorless"
3 9 mg/m' - 21 3 mg/m'
Linoleyl acetate
0.0016
Lithium hydride
(0.1 mg/m')
LPG
20000 (propane)
Magnesium dodecyl sulfate
0 2
Malathion
10 13 5 mg/m'
Maleic anhydride
0 1 - 0 5 (0 25-1 83)
Menthol
1.5
2-Mercaptoelhanol
0 12 - 0 65
Mercury, Inorganic (except Mercury
pernitrate)
"odorless"
Mercury, vapor
"odorless"
Mesitylcne (sec Trimethylbenzene)
Mesityl oxide
0 017-25
Methoxy naphthal ene
0 00012
3-Methoxypropylamine
0 2 - 42
Methyl acetate
0 2 - 300 (10000)
Methyl acetylene- Propadiene Mixture
100
Methyl acrylate
0 0005 - 20 (75)
Warning Concentrations
B-12
9/95
-------
Chemical
Warning Concentration
Methylacrylomtrile
2 - 14 (fatigue)
Methyl alcohol
10 - 20482 (7500 - 69000)
Methylamine
0 001 - 10 (fatigue) (20-100)
Methyl amyl acetate
0 002 - 1048 (1048)
Methyl amyl alcohol (Methyl isobutyl
carbinol)
0 01 - 50 (24-50)
n-Methylaniline
16-2
Methyl anthranilate
0 00066 - 0 06
Methyl bromide
20 6 - 1030
2-Methyl-2-butanol (tert-Amyl alcohol)
0 23 - 2 3
Methyl n-butyl ketone
0 07 - 0 09
Methyl n-butyrate
0 0026
Methyl cellosolve
0 0925 - 92 5 (118)
Nethyl cellosolve acetate
0 64 - 50
Methyl chloride
10 - 250, "no odor" (500-1000)
Methyl chloroform
20 - 714 (500-1000)
Methyl 2-cyanoacrylate
1-3
Methylcyclohexane
500 - 630
Methyl dichloroarsine
0 11
Methyl biphenyl isocyanate (MDI)
(Dichloromethane)
"can adapt to odor"
25 - 227 (5000)
Methyl ethanol amine
3,4
Methyl ethyl ketone (MEK)
0 25 - 85 (200)
Methylethyl pyridine
0 006-19
Methyl formate
204 - 3000, (fatigue (3563))
Methyl glycol (1,2-propylene glycol)
60-90
5-Methyl-3-heptanone(Ethyl amyl ketone)
6(50)
Methyl hydrazine
1 - 3
Methyl iodide
(4300)
Methyl i so amyl alcohol
0 20
Methyl i so amyl ketone
0 01 - 0 28
Methyl isobutyl ketone
0 01 - 47 (100)
Methyl isocyanate
2 0 (2)
9/95
B-13
Warning Concentrations
-------
Chemical
Warning Concentratiorf
Methyl ispropyl ketone
0.1 - 4 8
Methyl mercaptan
0.0001 - 1.1
Methyl methacrylate
0 01 - 1 (170-250)
2-Methylpentaldehyde
0 09-0.136
2-Methyl- 1-pentanol
0 024 - 0 082
2-Methylpropene (isobutylene)
0.57 - 20
Methyl salicylate
0 1 - 0 14
a-Methyl styrene
0 1 - 200 (200)
Methyl sulfide (see Dimethyl Sulfide)
Methyl thiocyanate
0 25 - 3 2
Methyltrichlorosilane
1
Methyl vinyl ketone
0.2
Methylvinyl pyridine
0040
Mineral spirits
30
Morpholine
001 - 0.14
Musk (Synthetic)
4 0 x 107
Naphtha - coal tar
4 68 - 100 (200-300)
Naphtha - petroleum (rubber solvent)
<500
Naphthalene
0 001 - 0 8 (15)
2-Naphthol
1 3
Nickel carbonyl
1 - 3
Nitric acid
0 3 - 1 0 (62)
Nitric oxide
"odorless," 0 3-1, "poor"
p-Nilroaniline
"odorless"
Nitrobenzene
0 001 - 6
o-Nitrochlorobenzene
0.002
Nitroethane
2 1 - 200 (100-500)
Nitrogen dioxide
0 1 - 5 3 (5-20)
Nitrogen tetroxide
5
Nitrogen Irtfluoride
"no odor-warning properties at potentially
dangerous levels"
Nitromethane
3 5 - 100 (200-500)
1-Nilropropane
11 -300 (99-150)
Warning Concentrations
B-14
9/95
-------
Chemical
Warning Concentration
2-Nitropropane
48 - 300
Nitrotoluene(m, o, p isomers)
Nitrous oxide
"poor"
Nonane
0 1 - 47
n-Octane
05- 235
Octanoic Acid
0 0014
1-Octanol
0 0021 -0 31
2-Octanol
0 0026
Oenanthic acid (Hept&noic acid)
0 015
Oxygen difluoride
0 1-05, (fatigue)
Ozone
0 0005 - 0 5 (1-3 7)
Parathion
0 48 mg/m'
Pelargonic acid (Nonyl Alcohol)
0 00086
Pentaborane
0.8(1)
Pentachlorphenol
9.3 mg/m'
(0 3 - 10.9 mg/m')
n-Pentane
2 2- 1100
2,4-Pentanedione
0 01 - 0 024
2-Pentanone (Methyl propyl ketone)
3 - 14
Pentanol (see amyl alcohol)
Pentene (n-Amylene)
2.2
n-Pentyl acetate (see n-Amyl acetate)
1-Pentyl mercaptan
0 00021
Perchloroethylene (see Tetrachloroethylene)
Perchloromethyl mercaptan
0.001
Perchloryl fluoride
10 (but not reliable)
Pro-Klean-No-818
0.005
Petroleum distillates (Petroleum naphtha)
<500
Phenol
0 005 - 5 (48)
Phenyl ether
0 001 - 0 10 (3-4)
Phenyl ether-biphenyl mixture
0.1-1 (3-4)
Phenyl isocyanide
0 029 mg/m5
Phenyl isothiocyanate
0 43
9/95
B-15
Warning Concentrations
-------
Chemical
Warning Concentration
Phosgene
0 125 - 6 (dulls senses) (1-2)
Phosphine
0 01 - 5 (7 7)
Phosphorous pentasulfide
"fatigue," 0 0047
(as H'S)
Phosphorous trichloride
0 7 (2-4)
Phthalic anhydride
0.05 - 0 12 (30 mg/m5)
2-Picohne
0.023 - 0 046
Propane
1000 - 20000
Propionaldehyde
0.04-1
Propionic acid
0 001 - 20
n-Propyl acetate
0.05 - 200
Propyl alcohol
0 01 - 200 (5500)
Propylene
23 - 67 6
Propylene diamine
0 014 - 0 067
Propylene dichlonde
0 25 - 130
Propylene glycol
"odorless"
Propylene glycol dinitrate
0 24
Propylene glycol monomethyl ether
10
Propylene oxide
10 - 210 (457-473, animals)
Propyl mercaptan
0 00075 - 0.02
n-Propyl nitrate
50-90
Propyl sulfide
0011-0 17
Pyridine
0 001 - 5 (fatigue at 5,
but taste remains)
Pyrolgallo (1,2,3-trihydroxybenzene)
20
Quinoline
0 16- 71
Quinone
0 08 - 0 5, fatigue (0 1-0 5)
Resorchinol (1,3-dihydroxylbenzene)
40
Rotenone
"odorless," 222 mg/m'
Safrole
0 0032
Selenium oxide
0 0002 mg/m'
Silver Cyanide
"odorless"
Skatole (3-Methyl indole)
7.5 x 10* - 1 68
Warning Concentrations
B-16
9/95
-------
Chemical
Warning Concentration
Sodium Butyldiphenol sulfonate
0 5 (as alky aryl sulfonate)
Sodium butylphenylphcnol sulfonate
0 5 (as alky aryl sulfonate)
Sodium hydroxide
"odorless"
Sodium mtrochlorobenzene sulfonate
0 5 (as alky aryl sulfonate)
Sodium octyl sulfate
0 2
Sodium sulfate
"odorless"
Sorbitol
"odorless"
Stoddard solvent
1 - 30 (400)
Strychnine
"odorless"
Styrene
0 001 - 200 (200-400)
Styrene oxide
0 40
Sulfoxide
91
Sulfur dichlonde (SCI,)
0 001
Sulfur dioxide
0 2- 5 (6-20), 0 3-taste
Sulfuric acid
0 6- 2 4 mg/m5
Sulfur monochloride (Sulfur chloride, SjCl2)
0 001 (2-9)
Sulfuryl fluoride
"odorless"
Tannic acid
2 - 4
TEPP (HETP, Bladex, Vaportone)
"odorless"
Terphenyls
>1
1,1,2,2-Tetrachloroethane
02-8
Tetrachlorethylene (Perchloroethylene)
2 - 50 (106-690)
Tetraethyl-o-sihcate
5 0-72
Tetrahydrofuran
0 1 - 60
Tetramelhylbenzene
0 0029
Tetranilromethane
(0 40)
Thiocresol (Toluenethiol)
0 0027 - 0 02
Thiophenol (Phenyl mercaptan)
0 001 - 85
Thymol
0 00086
Toluene
0 02 - 70, fatigue (300-400)
Toluene dnsocyanate (TDI)
0 2 - 2 14
Toxaphene (Phenatox)
2 4 mg/m3
1,2,4-Trichlorobenzene
14-3
9/95
B-17
Warning Concentrations
-------
Chemical
Warning Concentration
1,1,2-Trichloroethane
0 5 - 167
o-Tolidine
0 0048 - 20
1,1,1-Tnchloroethane (Methyl chloroform)
20 - 400(500-1000)
Trichloroethylene
0 2 - 400 (160)
Trichlorofluoromethane
5 - 209
Trichlorophenol
0 1 - 0 667
1,2,3-T richloropropane
100 (100)
1,1,2-trichloro-1,2,2-tnfluoroethane
05 - 200
Triethanolamine dodecylbenzene sulfonate
0.3
Tnethylamine
0 009 - 2.8 (50)
Tnethylene glycol
"practically odorless"
Trimethylamme
0 0001- 1.7
Trimethylbenzene (Mesitylene)
0 006 - 2 4
Trimethyl phosphite
0 001
Trinitrobutylxylene
6 5 X 10* - 0 0008
Triphenyl phosphate
"odorless"
Turpentine
50 - 200 (100-200)
n-Undecane
0 12
D-Valeraldehyde
0.001 - 8.2
Valeric acid
0.00060
io8 Valeric acid
0.0018
Vandium pentoxide - Dust/Fume
(0.5 - 2.2 mg/m')
Vanillin
3.2 x 10*
Vinyl acetate
0.1 - 1
Vinyl chloride
260 - 3000
Vinyl toluene
10 - 50 (50)
Warfarin
"odorless"
Xylene
0.05 - 200, fatigue (100-200)
m-Xylene
0 08- 40
o-Xylene
0.08 - 40
p-Xylene
0 08- 40
Xyhdine
0.0048 - 0.06
Vinylidene chloride (1,1-Dichloroethylene)
190
Warning Concentrations
B-18
9/95
-------
Chemical
Warning Concentratiorf
V M & P Naphtha
10
Fatigue - Indicates that the chemical can cause olfactory fatigue.
Animal - Irritation concentration based on animal studies.
9/95
B-19
Warning Concentrations
-------
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.
9/95
C-l
Appendix C
-------
(RED)
Hazard
(BLUE)
Health
Hazard
(YELLOW)
Reactivity
Hazard
(WHITE) N
Special
nformation
FIGURE 1
NFPA 704 M HAZARD IDENTIFICATION SYSTEM
704 M Hazard Ranking System
HEALTH HAZARD (BLUE):
Rank Description
Materials that on very short exposure could cause death or major
residual injury even though prompt medical treatment was given.
Materials that on short exposure could cause serious temporary
or residual injury even though prompt medical treatment was given
Materials that on intense or continued exposure could cause
temporary incapacitation or possible residual injury unless
prompt medical treatment was given
Examples
Acrylomtnle,
Parathion, Bromine
Aniline, Sodium
Hydroxide, Sulfuric Acid
Bromobenzene,
Pyridine, Styrene
Materials that on exposure would cause irritation but only
minor injury even if no hazard beyond that of ordinary
combustible material.
Acetone, Methanol
0 Material that on exposure under fire conditions would offer
no hazard beyond that ordinary combustible material.
Reprinted with permission from NFPA 704, Identification of the Fire Hazards of Materials, Copyright
e 1990, National Fire Protection Association, Quincy, MA 02269. This reprinted material is not the
complete and official position of the National Fire Protection Association, on the referenced subject
which is represented only by the standard in its entirety.
Appendix C
C-2
9/95
-------
FLAMMABILITY HAZARD (RED):
Rank Descnption
4
1
0
Materials that (1) rapidly or completely vaporize at atmospheric
pressure and normal ambient temperatures and burn rapidly or
(2) are readily dispersed m air and burn readily.
Liquids and solids that can be ignited under almost all ambient
temperature conditions.
Examples
1,3-Butadiene, Propane,
Ethylene
Phosphorous, Acrylonitrile
Materials that must be moderately heated or exposed to relatively 2-Butanone, Kerosene
high ambient temperatures before ignition can occur.
Materials that must be preheated before ignition can occur.
Materials that will not burn.
Sodium, Red Phosphorous
REACTIVITY HAZARD (YELLOW):
Rank Description
Materials that m themselves are readily capable of detonation
or of explosive decomposition or reaction at normal temperatures
and pressures.
Matenals 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.
Matenals that (1) m 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.
Matenals 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.
Matenals that in themselves are normally stable, even when exposed
to lire, 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.
9/95
C-3
Appendix C
-------
TABLE 1
SPECIAL INFORMATION DESIGNATORS
Designator
Special Hazard
y
Water reactive
OXY
Oxidizer or oxidizing properties
COR
Corrosive
V
Radioactive
Reprinted with permission from NFPA 704, Identification of the Fire Hazards of Materials, Copyright
9 1990, National Fire Protection Association, Quincy, MA 02269. This reprinted material is not the
complete and official position of the National Fire Protection Association, on the referenced subject
which is represented only by the standard in its entirety.
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
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TABLE 2
UN HAZARD CLASS SYSTEM
United Nations
Hazard
Class Number
Description
1
Explosives
2
Nonflammable/flammable/poison compressed gases
3
Flammable/combustible liquids
4
Flammable solids, spontaneously combustible substances, and water-
reactive substances
5
Oxidizing materials, including organic peroxides
6
Class B poisons, irritants, and etiologic (disease-causing) materials
7
Radioactive materials
8
Corrosive materials (acids, alkaline liquids, and certain corrosive liquids
and solids)
9
Miscellaneous hazardous materials not covered by any of the other
classes
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.
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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
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
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TABLE 3
HAZARDOUS MATERIALS DEFINITIONS
(49 CFR Part 173)
Hazard Class
Definitions
An Explosive - Anv chemical comoound. 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).
CLASS A EXPLOSIVE
Detonating or otherwise of maximum hazard The nine types of Class A explosives are
defined in Sec 173 S3.
CLASS B EXPLOSIVE
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)
BLASTING AGENT
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))
COMBUSTIBLE
LIQUID
Any liquid having a flash point above lOCF and below 200ฐF as determined by tests listed
in Sec 173 115(d). Exceptions are found in Sec 173.115(b)
CORROSIVE
MATERIAL
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.)
FLAMMABLE LIQUID
Any liquid having a flash point below 100ฐF as determined by tests listed in Sec
173 115(d) For exceptions, see Sec 173 115(a)
Pvrofonc Liauid - Anv liauid that lenites srxmtaneouslv in drv or moist air at or helnw
130ฐF. (Sec 173 115(c))
Compressed Gas - Any material or mixture having in the container a pressure exceeding 40
psia at 70ฐF, or a pressure exceeding 104 psia at 130ฐF, or any liquid flammable material
having a vapor pressure exceeding 40 psia at 100ฐF (Sec 173.300(a))
FLAMMABLE GAS
Any compressed gas meeting the requirements for lower flammabihty limit, flammability
limit range, flame projection, or flame propagation criteria as specified in Sec 173 300(b)
NONFLAMMABLE
GAS
Any compressed gas other than a flammable compressed gas
FLAMMABLE 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 senous transportation hazard.
(Sec 173 150)
ORGANIC PEROXIDE
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)
OXIDIZER
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)
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TABLE 3 (Continued)
HAZARDOUS MATERIALS DEFINITIONS
(49 CFR Part 173)
Hazard Class
Definitions
POISON A
Extremely Dangerous Poisons - Poisonous eases or liauids of such nature that a verv small
amount of the gas. or vapor of the liauid. mixed with air is daneerous to life. (Sec
173 326)
POISON B
Less Daneerous Poisons - Substances, liauids. or solids fincluding pastes and semi-solids),
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 toxicitv. are o resumed to be toxic to man (Sec 173 3431
IRRITATING
MATERIAL
A liquid or solid substance which upon contact with fire or when exposed to air gives off
daneerous or intensely irritating fumes, but not including any poisonous material. Class A
(Sec 173.381)
ETIOLOGIC AGENT
An "etiologic agent" means a viable micro-organism, or its toxin which causes or may
cause human disease (Sec 173 386)
RADIOACTIVE
MATERIAL
Any material, or combination of materials, that spontaneously emits ionizing radiation, and
having a specific activity greater than 0 002 microcunes per gram (Sec. 173.389) Note.
See Sec 173 389(a) and (1) for details.
ORM-OTHER
REGULATION
MATERIALS
(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 100ฐF 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 110 gallons
ORM-A
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 173 500(l))
ORM-B
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 7075-T6) at a
test temperature of 130ฐF An acceptable test is described in NACE Standard TM-01-69,
and (u) specifically designated by name in Sec 172 101 (Sec 173 50(Jb,(2))
ORM-C
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
173.500^(3))
ORM-D
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 173.500fb>(4))
Appendix C
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TABLE 3 (Continued)
HAZARDOUS MATERIALS DEFINITIONS
(49 CFR Part 173)
Hazard Class
Definitions
ORM-E
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 (1) 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)
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)
FLASHPOINT
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
FORBIDDEN
Means that the material is prohibited from being offered or accepted for transportation
Note This prohibition does not aDDlv 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)(1))
HAZARDOUS
SUBSTANCES
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
HAZARDOUS
WASTES
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
LIMITED QUANTITY
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.
REPORTABLE
QUANTITY
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)
SPONTANEOUSLY
COMBUSTIBLE
MATERIAL (SOLID)
Means a solid substance (including sludges and pastes) which may undergo spontaneous
heating or self-igmtion under conditions normally incident to transportation or which may,
upon contact with the atmosphere, undergo an increase in temperature and ignite (Sec
171 8)
WATER REACTIVE
MATERIAL (SOLID)
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)
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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-li
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
ExDlosives
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Explosives with a mass explosion hazard
Explosives with a projection hazard
Explosives with predominantly a fire hazard
Explosives with no significant blast hazard
Very insensitive explosives
Class 2
Gases
Division 2.1
Division 2.2
Division 2.3
Flammable gases
Nonflammable gases
Poison gases
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Class 3
Flammable liquids
Division 3.1 Flashpoint below -18ฐC (0ฐF)
Division 3.2 Flashpoint -18ฐC and above but less than 23ฐC (73ฐF)
Division 3.3 Flashpoint of 23ฐC and up to 61 ฐC (141 ฐF)
Class 4
Division 4.1
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 5
Division 5.1
Division 5.2
Oxidizers and Organic peroxides
Oxidizers
Organic peroxides
Class 6
Poisonous and Etiologic (infectious) materials
Division 6.1
Division 6.2
Poisonous materials
Etiologic (infectious) materials
Class 7
Radioactive materials
Class 8
Corrosives
Class 9
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 Table 4, the placarding rules apply to My quantity transported in a motor
vehicle. Freight container or rail car must be placarded as illustrated.
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TABLE 4
DOT TABLE 1 PLACARDING TITLE 49 CFR 172.504
Category of Material
(Hazard or Division Number)
Placard to be Utilized
Reference Number for
Placard Design
1.1
Explosives 1.1
172.522
1.2
Explosives 1.2
172.522
1.3
Explosives 1.3
171.522
2.3
Poison Gas
172.540
4.3
Dangerous When Wet
172.542
6.1 (PGI, Inhalation
Hazard Only)
Poison
172.554
7 RAD (Yellow III
Labeling)
Radioactive
172.556
For the materials illustrated in Table 5, 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 5 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.
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TABLE 5
DOT TABLE 2 PLACARDING TITLE 49 CFR 172.504
United Nations
Hazard Class Number
Hazardous Material Described as
Placards
1.4
Explosives 1.4
172.523
1.5
Explosives 1.5
172.524
1.6
Explosives 1.6
172.525
2.1
Flammable gas
172.532
2.2
Nonflammable gas
172.528
3
Flammable
172.542
Combustible Liquid
Combustible
172.544
4.1
Flammable Solid
172.546
4.2
Spontaneously Combustible
172.547
5.1
Oxidizer
172.550
5.2
Organic Peroxide
172.552
6.1 (PGIor II
other than PGI
Inhalation
Hazard)
Poison
172.554
6.1 (PGIII)
Keep Away From Food
172.553
6.2
(NONE)
8
Corrosive
172.558
9
Class 9
172.560
ORM-D
(NONE)
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.
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Appendix C
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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 persdn 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 reduce the radiation level at the surface of the container.
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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.
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Appendix C
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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 bums; 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.
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:
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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 corroding a piece of
metal and 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.
Appendix C C-18 9/95
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HAZARDOUS MATERIALS LABELING CHART
CLASS 1
Explosive
EXPLOSIVE
Include appropriate division number
and compatibility group
CLASS 1
Explosive l 4 CLASS 1
EXPLOSIVE
Include appropriate compatibility
group
Explosive 1 5 CLASS 1
BUSTING AGENT
*
1
Include appropriate compatibility
group
Explosive 1 6 CLASS 1
EXPLOSIVE
Include appropriate compatibility
group
Subsidiary
No compatibility group letter or
Class/Division number may be
displayed
CLASS 2
Flammable gas
CLASS 2
CLASS 2
CLASS 2
CLASS 3
MMtMWNaiUS
OXYGEN
m
CLASS 4
Division 4 \
FlAI ll IAB E
CLASS 4
m
Non flammable gas
Oxygen
Poison gas
Flammable liquid
Flammable solid
Spontaneously combustible
CLASS 4
CLASS 5
CLASS 5
CLASS 6
ORGANIC PEROXIDE
Division 6 1
Pactang Groups IA
Inhalation
Hazard
CLASS 6
Division 6 1
Packing Groups IS
(not Inhalation
Hazard)
CLASS 6
Division 6 1
PacUtg Group
Dangerous when wet
Organic peroxide
Poison inhalation hazard
Poison
The word "TOXIC* may be used in place
of the word "POISON"
Keep away from lood
A POISON label may be used in place
oJ a KEEP AWAY FROM FOOD label
INFECTIOUS SUBSTANCE
CLASS 6
CLASS 7
CLASS 7
CLASS 7
CLASS 8
i---i I BIOMEDICAL
^ MATERIAL
Inleclious substance
The Etiologic Ageni label may be
required (42 CFR 72 3)
CLASS 9
SUBSIDIARY RISK
EMPTY
FOR AIRCRAFT
PTY
The hazard class or division number
may not be displayed on a subsidiary
label
For Class 7 packagings that meet the
requirements in ง173 428
DANGER
MAGNETIZED
MATERIAL
KEEPWft FBOU MOWFTCCWSSCenrTCfllMI
Cargo aircraft only
Magnetized material
GENERAL GUIDELINES ON USE OF HAZMAT LABELS
1 The shipper must attach the appropriate label(s) to each package of hazardous material offered for shipment unless excepted from
labeling requirements (ง172 400)
2 If the material in a package has more than one hazard classification, the package must be labeled for each hazard (ง172 402)
3 When two or more hazardous materials of different classes are packed within the same packaging or outer enclosure, the outside ol the
package or enclosure must be labeled for each class of hazardous material involved (ง172 404)
. 4 Radioactive materials requiring labeling, must be labeled on two opposite sides of the package (ง172 403)
5 A label should only be applied to a package containing a hazardous material if it represents the hazard inside (ง172 401)
6 No one may offer or transport a package bearing any marking or label which by its color, design, or shape could be confused with a
hazardous materials label This does not prohibit the use of labels in conformance with U N recommendations, IMO requirements, ICAO
Technical Instructions, orTDG Regulations (ง172 401)
ฉ Copyright 1997 J J KELLER & ASSOCIATES, INC , Neenah, Wl USA (800) 327-6868 Printed in the United States
38-FB (Rev 9/97)
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HAZARDOUS MATERIALS LABELING CHART
H72.400 General labeling requirements.
(a) Except as specified in 4} 172 400a, each person
who offers for transportation or transports a
hazardous material in any of the following packages
or containment devices, shall label the package or
containment device with labels specified for the
material in the 172 101 Table and in this subpart
(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 m1(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
subpart F of this part,
(4) A DOT Specification 106 or 110 multi-unit tank
car tank, unless placarded in accordance with
subpart F of this part, and
(5) An overpack, freight container or unit load
device, of less than 18 ni3(640 cubic feet), which
contains a package for which labels are required,
unless placarded or marked in accordance with
4(172 512 or this part
(b) Labeling is required for a hazardous material
which meeLs one or more hazard class definitions, in
accordance with Column 6 of the 4)172 101 Table and
the following table
Hazard class or
division
Label name
Label design
or section
reference
1 1
EXPLOSIVES l l
172411
1 2
EXPLOSIVES 1 2
172411
1 3
EXPLOSIVES 1 3
172411
1 4
EXPLOSIVES 1 4
172411
1 5
EXPLOSIVES 1 5
172411
1 6
EXPLOSIVES 1 6
172411
2 \
FLAMMABLE GAS
172417
22
NONFLAMMABLE GAS
172415
23
POISON GAS
172416
3 (flammable liquid)
FLAMMABLE LIQUID
172419
Combustible liquid
(none)
4 1
FLAMMABLE SOLID
172 420
42
SPONTANEOUSLY
172 422
COMBUSTIBLE
43
DANGEROUS WHEN WET
172 423
5 1
OXIDIZER
172 426
52
ORGANIC PEROXIDE
172 427
6 1 (inhalation
POISON INHALATION
172 429
hazard Zone A
HAZARD
or B)
6 1 (PG 1 or II other
POISON
172 430
than Zone A or B
inhalation
hazard)
6 1 (PG III)
KEEP AWAY FROM FOOD
172 431
62
INFECTIOUS SUBSTANCE
172 432
7 (see ง172 403)
RADIOACTIVE WHITE-I
172 436
7
RADIOACTIVE YELLOW-II
172 438
7
RADIOACTIVE YELLOW-HI
172 440
7 (empty packoges
EMPTY
172 450
see ง173 427)
8
CORROSIVE
172 442
9
CLASS 9
172 446
Uhe ETIOIOGIC 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
M72 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
(1) Not poisonous,
(u) Carried by a private or contract motor carrier,
(in) Not overpacked, and
(iv) Durably and legibly marked in accordance with
CGA Pamphlet C-7, appendix A
(2) A package or unit of military explosives
(including ammunition) shipped by or on behalf of
the DOD when in
(1) Freight containerload, carload oi truckload
shipments, if loaded and unloaded by the shipper or
DOD, or
(n) 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
palletized load
(3) A package containing a hazardous material other
than ammunition that is
(i) Loaded and unloaded under the supervision of
DOD personnel, and
(11) Escorted by DOD personnel in a separate vehicle
(4) A compressed gas cylinder permanently mounted
in or on a transport vehicle
(5) A freight container, aircraft unit load device or
portable tank, which
(0 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 173 425(b) of this
subchapter
(b) Certain exceptions to labeling requnements aic
provided for small quantities and limited quantities
in applicable sections in part 173 of this subchapter
(c) Notwithstanding the provisions of *?172 402(a), a
subsidiary hazard label is not requned on a package
containing a Class 8 (corrosive) matenal which has a
subsidiary hazard of Division 6 1 (poisonous) if the
toxicity of the material is based solely on the
corrosive destruction of tissue rather than systemic
poisoning
(d) For Division 6 1 Packing Group 111 materials, a
POISON label may be used in place of a KEEP
AWAY FROM FOOD label
<)172 401 Prohibited labeling.
(a) Except as provided in paragraph (c) of this
section, no person may offer for transpoi tation or no
carrier may transport any package bearing a label
specified in this subpart unless
(1) The package contains a matenal that is a
hazardous material, and
(2) The label represents a hazard of the hazardous
material in the package
(b) No person may offei for transportation and no
carrier may transport a package bearing any
marking or label which by its color, design, oi shape
could be confused with or conflict with a label
prescribed by this part
(c) The restrictions in paragraphs (a) and (b) of this
section, do not apply to packages labeled in
conformance with
(1) Any United Nations recommendation, including
the class number (sec 4}172 407), in the document
entitled "Transport of Dangerous Goods ",
(2) The International Maritime Organization (IMO)
requirements, including the class numbei (see
172 407), in the document entitled "International
Maritime Dangerous Goods Code",
(3) The ICAO Technical Instructions, or
(4) The TDG Regulations
til72.402 Additional Labeling requirements.
(a) Subsidiary hazard labels Each package
containing a hazardous material
(1) Shall be labeled with primary and subsidiary
hazard labels as specified in Column 6 of the
H72 101 Table (unless excepted in paragraph (a)(2)
of this section), and
(2) For other than Class 2 or Class 1 materials (for
subsidiary labeling requirements for Class 1
materials see paragraph (e) of this section), if not
already labeled under paragraph (a)(1) of this
section, shall be labeled with subsidiary hazaid
labels in accordance with the following table
SUBSIDIARY HAZARD LABELS
Subsidiary
hazard level
(packing
group)
Subsidiary Hazard (Class or Division)
3
4 1 4 2
43
5 161 8
1
X
X
X ,
II
X
X X
X
X
III
X X
X
XXX
X Required for all modes
If the flashpoint of a material is at or above
38'C (100'F), required for transport by air or vessel
only
Impossible as subsidiary hazard
(b) Display of hazard cla,ss on labels The nppiopnate
hazard class or, for Division 5 1 or 5 2 the division
number, shall be displayed in the lower corner of a
piimary hazard label and may not be displayed on a
subsidiary label
(c) Cargo Aircraft Only label Each person who ofTers
foi transportation or transports by aircraft a
package containing a hazaidous matenal which is
authorized on cargo airciaft only shall label the
package with a CARGO AIRCRAFT ONLY label
specified in U72 448 of this subpart
(d) Class 7 (Radioactive) Materials Except as
otherwise provided m this paiagiaph, each package
containing a Class 7 matenal that also meets the
definition of one or more additional hazard classes
must be labeled as a Class 7 material as requued by
t)172 403 of this subpart and foi each additional
hazard A subsidiary hazard label is not requued on
a package containing a Class 7 mateiinl that
conforms to criteria specified in 4)173 4 of this
subchapter, except 4}173 4(a)( 1)(iv) of this subchapter
(e) Class 1 (explosive) Materials In addition to the
label specified in Column 6 of the 4f 172 101 Table,
each package of Class 1 material that also meets the
definition for
(1) Division 6 1, Packing Groups I or 11, a
labeled POISON, or
(2) Class 7, shall be labeled in accordance with
4)172 403 of this subpart
(0 Division 2 2 materials In addition to the label
specified in Column 6 of the 1>172 101 Table, each
package of Division 2 2 material that also meets the
definition for an oxidizing gas (see 4)171 8 of this
subchapter) must be labeled OXIDIZER
(g) Division 2 3 materials In addition to the label
specified in Column 6 of the 4)172 101 Table, each
package of Division 2 3 matenal that also meets the
definition for
(1) Division 2 1, must be labeled Flammable Gas,
(2) Division 5 1, must be labeled Oxidizer, and
(3) Class 8, must be labeled Corrosive
H72.403 Contains special requirements for
RADIOACTIVE materials Sec regulations.
4)172.405 Authorized label modifications.
(a) For Classes 1, 2, 3, 4, 5, 6, and 8, text indicating a
hazaid (for example FLAMMABLE LIQUID) is not
required on a primary oi subsidiaiy label when
(1) The label otherwise conforms to the provisions of
this subpart, and
(2) The hazard class or, for Division 5 1 oi 5 2 the
division number, is displayed in the lower corner of
the label, if the label corresponds to the primary
hazard class of the hazardous material
(b) For a package containing Oxygen, compiessed, or
Oxygen, refrigerated liquid, the OXIDIZER label
specified in 4(172 426 of this subpart, moriifunL to.
display the word "OXYGEN" instead of"OX
-------
HAZARDOUS MATERIALS PLACARDING CHART
CLASS 1
EXPLOSIVES
EXPLOSIVES 1 1, 1 2, A 1 3
Tho Division number 11 1 2 or 1 3 and
compatibility group ate in black ink
Placard any quantity of Division number 1112
Or 1 3 matanal
CLASS 1
EXPLOSIVE
EXPLOSIVES 1 4
The compatibility group o in black ink
Placard 454 kg (1001 lbs ) or more of 1 4
Explosives
CLASS 1
BLASTING
AGENTS
*
v1,
EXPLOSIVES 1 5
The compatibility group is in black ink
Placard 454 kg (1001 lbs ) or more of 1 5
Blasting Agents
CLASS 1
EXPLOSIVE
EXPLOSIVES 1 6
The compatibility group is in black tnk
Placard 454 kg (1001 lbs ) or more of 1 <
Explosives
CLASS 2
0
OXYGEN
Placard 454 kg (1001 lbs ) or more oggregato
gross weight of either oxygon comprossod and
oxygen refrigerated liquid Soo 172 504(f)(7)
CLASS 2
Division 2 1
CLASS 2
CLASS 2
CLASS 3
CLASS 3
INHALATION
HAZARD
2
FLAMMABLE GAS
Placard 454 kg (1001 lbs ) or more of flammable
gas See DANGEROUS
NON-FLAMMABLE GAS
Placard 454 kg (1001 lbs) or more aggregate
gross weight of non llammable gas Seo
DANGEROUS
POISON GAS
Placard any quantity ol Drvtsion 2 3 matanal
FLAMMABLE
Placard 454 kg (1001 lbs) or more gross weight
of flammable bqurf See DANGEROUS
GASOLINE
May be used in the place of FLAMMABLE on a
placard (fcsptayed on a cargo tank or a portoblo tank
being used to transport gasobno by taghway Sฉo
172 542(c)
CLASS 3
CLASS 3
CLASS 4
CLASS 4
CLASS 4
Division 4 3
COMBUSTIBLE
placard a combustible liquid when transported in
bulk A FLAMMABLE placard may be used in
place of a Combustible placard on a cargo tank
or portable tank or a compartmented tank car
contains both llammable and combustible
.See 172 504(f)(2)
FUEL OIL
May be used in place ot COMBUSTIBLE on a
placard displayed on a cargo tank or portable tank
being used to transport by highway fuel oil not
dassed as a flammable liquid See 172 544(c)
FLAMMABLE SOLID
Placard 454 kg (1001 lbs) or more gross weight
of flammable solid See DANGEROUS
SPONTANEOUSLY COMBUSTIBLE
Placatd 454 kg (1001 lbs ) or more gross
weight of spontaneously combustible matenal
See DANGEROUS
DANGEROUS WHEN WET MATERIAL
Placard any quantity of Division 4 3 matenal
oS 5
Dtvtston 5 1
CLASS 5
Division 5 2
CLASS 6
OXIDIZER
Placard 454 kg (1001 lbs ) or more gross weight
of oxidizing matenal See DANGEROUS
ORGANIC PEROXIDE
Placard 454 kg (1001 lbs ) or moro gross woigtit
ol organic peroxtde Soe DANGEROUS
Placard any quantity of 5 2 ORGANIC
PEROXIDE TYPE B LIQUID OR SOLID
TEMPERATURE CONTROLLED
Division 6 1
Packing Group I
Zone A and B
CLASS 6
D vis on 6 1
Packing Groups I & II
(other than
inhalation
hazard)
CLASS 6
Division 8 1
Pocking Group III
POISON INHALATION HAZARO
Placard any quantity of 6 1 PGI Zone A and B
POISON
Placard 454 kg (1001 lbs) or more gross weight
of Packing Groups I & II See DANGEROUS
The word TOXIC' may be used in lieu ol the
word "POISON"
KEEP AWAY FROM FOOD
Placard 454 kg (1001 lbs) or more gross werght
of Packing Group II) See DANGEROUS
A POISON placard may bo usod in placo of a
KEEP AWAY FROM FOOD placard
CLASS 7
CLASS 6
CLASS 9
DANGEROUS
RADIOACTIVE
Placard any quantity of packages bearing the
RADIOACTIVE YELLOW III label Certain low
specific activity radioactive materials in
'exclusive use* will not bear the label but the
RAOIOACTIVE placard a required
CORROSIVE
Placard 454 kg (1001 lbs ) or moro gross weight
ol corrosive matenal See DANGEROUS
MISCELLANEOUS
A Class 9 placard is nol required Howovor you
may placard 454 kg (1001 lbs ) or more gross
weight ol a malenal which presents a hazard
during transport but which is not included in any
other hazard class See DANGEROUS
Placard 454 kg (1001 lbs) gross woight of two or
more categories of hazardous matonals Icstod in
Table 2
A freight containoi unit load device transport
vehicle or rail car which contains nonbulk
packages with two or moie categories of
hazardous materials that lequiro difforont
placards as specified in Tab'o 2 may bo
ptacardod with a DANGEROUS placard instoad
of the separato placarding specified lor each of
the materials in Table 2 However when 1 000 kg
(2 205 pounds) aggregate gross weight or more
of one category of material is loaded therein at
one loading facility on a froight container unit
load device transport vehiclo or rail car the
placard specified in Table 2 for that category must
be applied
SUBSIDIARY RISK
PLACARD
SQUARE BACKGROUND
DISPLAY OF IDENTIFICATION NUMBER
Class or division numbers do not appear on
subsidiary risk placards
The white squaro background ts roquired for the
fodowirtg placards when on rail cars
EXPLOSIVES 1 1 or 1 2 POISON GAS (Division
2 3 Hazard Zone A) POISON INHALATION
HAZARD (Dtvtsnn 6 1 PGt Hazard Zone A) and
for DOT 113 tank cars FLAMMABLE GAS
The white square background is required for
placards on motor vehicles transporting highway
route controlled quantities of Class 7 materials
The display of an identification number on a
placard is allowed except for Class 1 Class 7
DANGEROUS or subsidiary hazard placards
For a COMBUSTIBLE placard used to display
an identification number tho ontiro background
below the identification number must be whilo
lor transportation by rail and may bo whito for
transportation by highway
ฉ Copyright 1997 J J KELLER & ASSOCIATES, INC , Neenah, Wl USA (800) 327-6868 Printed in the United States
39-FB (Rev 3/97)
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HAZARDOUS MATERIALS PLACARDING CHART
ง172 502 Prohibited and permissive placatding
(a) Prohibited placarding Except as provided in paragraph (b) of this section no person may affix or display on a packaging freight container uml load device motor vehicle or rail car
(1) Any placard described in this subpart unless
(0 The material being offered or transported is a hazardous material
Cn) The placard represents a hazard of the hazardous material being offered or transported and
(in) Any placarding conforms to the requirements of this subpart
(2) Anysgn advertisement slogan (such as "Drive Safely") or device that by its color design shape or content could be confused with any placard prescribed m this subpart
(b) Exceptions (I) The restrictions in paragraph (a) of this section do not apply to a bulk packaging freight container unit load device transport vehicle oi rail car which Is placard
conformance with the TDG 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-point configuration m accordance with ง 172 336(b) of this pa*
(3) The restrictions in paragraph (a)(2) of this section do not appty until October 1 2001 to a safety sign or safety slogan (e g "Drive Safely" or "Drive Carefully*) which was permanently marked
on or before October 1 1996 on a transport vehicle bulk packaging or freight container
(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
ง 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 งง172 519 through 172 558
(b) DANGEROUS placard A freight container unit load device transport vehicle or rail car which contains nonbulk packages with two or more categories of hazardous materials that require
different placards specified m Table 2 of paragraph (e) of this section may be placarded with a DANGEROUS placard instead of the separate placarding specified for each of the materials In Table 2
of paragraph (e) of this section However when \ 000 kg (2 205 pounds) aggregate gross weight or more of one category of material is loaded therein at one loading facility on a freight container
unit load device transport vehicle or rail car 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 (J 001 pounds) Except for bulk packagmgs and hazardous materials subject to ง172 505 when hazardous materials covered by Table 2 of this 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 cor 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 m the manner prescribed in this subpart if not otherwise prohibited (see ง 172 502) on transport
vehicles or freight containers which are not required to be placarded
(d) Exception for 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) Ptacarding tables Placards are specified for hazardous materials in accordance with the following tables
TABLE 1
Category of material (Hazard class or division number and
DlrirnrH nnmfl
Placard design section
additional description as appropriate)
r lUl^lJIU MUM It?
reference (ง)
1 1
EXPLOSIVES t 1
172 552
1 2
EXPLOSIVES 1 2
172 522
1 3
EXPLOSIVES 1 3
172 522
23
POISON GAS
172 540
43
DANGEROUS WHEN WET
172 548
5 2 (Organic peroxide Type B liquid or solid temperature controlled)
ORGANIC PEROXIDE
172 552
6 t (PG 1 inhalation hazard Zone A and B)
POISON INHALATION HAZARD
172 555
7 (Radioactive Yellow III label only)
RADIOACTIVE '
172 556
1 RADIOACTIVE placard also required lor exclusive use shipments of low specific activity material and surface contaminated objects transported in accordance with ง 173 427(b)(3) or (c) of this
subchapter
TABLE 2
Category of material (Hazard class or division number and
DlnrnrH nnmo
Placard design section
additional description as appropriate)
reference (ง)
1 4
EXPLOSIVES 1 4
172 523
1 5
EXPLOSIVES 1 5
172 524
1 6
EXPLOSIVES 1 6
172 525
2 1
FLAMMABLE GAS
172 532
22
NON-FLAMMABLE GAS
172 528
3
FLAMMABLE
172 542
Combustible liquid
COMBUSTIBLE
172 544
4 1
FLAMMABLE SOLID
172 546
42
SPONTANEOUSLY COMBUSTIBLE
172 547
5 1
OXIDIZER
172 550
5 2 (Other than organic peroxide. Type B. liquid or solid, temperature controlled)
ORGANIC PEROXIDE
172 552
6 1 (PG 1 or II other than PG 1 inhalation hazard)
POISON
172 554
6 1 (PG III)
KEEP AWAY FROM FOOD
172 553
62
(None)
8
CORROSIVE
172 558
9
CLASS 9
172 560
ORM-D
(None)
(0 Additional piacordmg 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 onfy the placard
representing the lowest division number must be displayed
(2) A FLAMMABLE placard may be used in place of a COMBUSTIBLE placard on
(0 A cargo tank oi portable tank
(iO 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 FLAMMABLE GAS or OXYGEN placards as required
(4) OXIDIZER placards are not required for Division 5 1 materials on freight containers unil load devices transport vehicles or rail cars which also contain Divston 1 1 or 1 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 rail car or freight container which also contains Division
1 5 explosives and is placarded with EXPLOSIVES 1 5 placards as required
(6) The EXPLOSIVE I 4 placard is not required for those Division 1 4 Compatibility Group S (1 4S) materials that ore not required to be labeled 1 4S
(7) For domestic transportation of oxygen compressed or oxygen refrigerated liquid the OXYGEN placard in ง 172 530 of this subpart may be used m 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 Wquid
when transported in a non-bulk packaging
(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 on an orange panel or a white-square-on-pcnnt display configuration are required by subpart D of this part
(10) For domestic transportation of Division 6 1 PG 111 materials a POISON placard may be used in place of a KEEP AWAY FROM FOOD placard
(11) For domestic transportation a POISON placard Is not required on a transport vehicle or freight container required to display a POISON INHALATION HAZARD or POISON GAS placard
(g) For shipments of Class 1 (explosive) materials by aircraft or vessel the applicable compatibility group lettei must be displayed on the placards required by this section
ง172 505 Placarding for subsidiary hazards
(a) Each transport vehicle freight container portable tank unit load device or rail car that contains a poisonous material subject to the "Poison-lnhalatlon Hazard" shipping descrr
ง172 203(m)(3) must be placarded with a POISON INHALATION HAZARD or POISON GAS placard as appropriate on each side and each end in addition to any other placard requlrec
material In ง 172 504 Duplication of the POISON INHALATION HAZARD or POISON GAS placard is not required *
(b) in addition to the RADIOACTIVE placard which may be required by ง172 504(e) of this subpart each transport vehicle portable tonk or freight container that contains 454 kg (1001 pounds) or
more gross weight of fissile or tow 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 ง 173 124 of this
subchapter shall be placarded with DANGEROUS WHEN WET placards on each side and each end in addition to the placards required by ง 172 504
(d) Hazardous materials that possess secondary hazards may exhibit subsidiary placards that correspond to the placards described in this part even when not required by this part (see also
ง 172 519(bX4) of this subpart)
ฉ Copyright 1997 J J KELLER & ASSOCIATES, INC , Neenah, Wl USA (800) 327-6868 Printed in the United Slates 39-FB (Rev 3/97)
Backer
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APPENDIX D
Glossary and Bibliography
-------
GLOSSARY
Accident
Action Level
Acute Exposure
Air Surveillance
Aquifer
Chronic Exposure
Confinement
Containment
Contaminant/
Contamination
Control
Decontamination
An unexpected event generally resulting in injury, loss of property, or
disruption of service.
A quantitative limit of a chemical, biological, or radiological agent at which
actions are taken to prevent or reduce exposure or contact.
A dose that is delivered to a receptor in a single event or in a short period of
time.
Use of air monitoring and air sampling during a response to identify and
quantify airborne contaminants on and offsite, and monitor changes in air
contaminants that occur over the lifetime of the incidents.
A water-bearing formation of permeable rock, sand, or gravel capable of
yielding water to a well or spring.
Low doses repeatedly delivered to a receptor over a long period of time.
Control methods used to limit the physical area or size of a released material.
Examples: dams, dikes, and absorption processes.
Control methods used keep the material in its container. Examples: Plugging
and patching.
An unwanted and nonbeneficial substance.
Chemical or physical methods used to prevent or reduce the hazards
associated with a material. Example: Neutralizing an acid spill.
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
Emergency
Emergency Removal
A portable device that rapidly measures and displays the concentration of a
contaminant in the environment.
A sudden and unexpected event calling for immediate action.
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).
9/95
1
Appendix D: Glossary
-------
Environmental
Assessment
Environmental
Emergencies
Environmental
Hazard
Environmental
Sample
Episode
First Responder
Groundwater
The measurement or prediction of the concentration, transport, dispersion,
and final fate of a released hazardous substance in the environment.
Incidents involving the release (or potential release) of hazardous materials
into the environment which require immediate action.
A condition capable of posing an unreasonable risk to air, water, or soil
quality, and to plants or wildlife.
Samples that are considered to contain no contaminants or low concentrations
of contaminants as compared to hazardous samples.
Incident.
The first personnel to arrive on the scene of a hazardous materials incident
(usually officials from local emergency services, firefighters, and police).
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 (U.S. Department
of Transportation). Capable of doing harm.
Hazardous Material A substance or material which has been determined by the U.S. 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 (U.S. Department of Transportation.)
Appendix D: Glossary
2
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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, 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 U.S. 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.
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Appendix D: Glossary
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Intelligence Information obtained from existing records or documentation, placards,
labels, signs, special configuration of containers, visual observations,
technical records, eye witnesses, and others.
Investigation Onsite and offsite 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.
National Contingency Policies and procedures that the Federal Government follows in implementing
Plan responses to hazardous substances.
Offsite Presence outside of the worksite.
Onsite Presence within the boundaries of the worksite.
Pathways of The environmental medium (water, groundwater, soil, and air) through which
Dispersion 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.
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
nonimmediate time period. Under CERCLA: actions intended to minimize
increases in exposure such that time and cost commitments are limited to 12
months and/or 2 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.
Planned Removal
("Non-Time-CriticaO
Appendix D: Glossary
4
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Qualified Individual
Regulated Material
Release
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.
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.
Any spilling, leaking, pumping, pouring, emitting, emptying, discharging,
injecting, escaping, leaching, dumping, or disposing of hazardous substances
into the environment.
Remedial Actions
Removal Actions
Reportable Quantity
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.
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.
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
Risk Management
The use of factual base to define the health effects of exposure of individuals
or populations to hazardous materials and situations.
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.
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Appendix D: Glossary
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Sampling
SfiXSES
Site
Site Safety Plan
Toxicity
Work Plan
The collection of representative portion of the universe. Example: the
collection of a water sample from a contaminated stream.
A relative term used to describe the degree to which hazardous material
releases can cause adverse effects to human health and the environment.
Location.
Written, site-specific safety criteria that establish requirements for protecting
the health and safety of responders during all activities conducted at an
incident.
The ability of a substance to produce injury once it reaches a susceptible site
in or on the body.
Written directives that specifically describe all work activities that are to take
place at a work site.
Appendix D: Glossary
6
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BIBLIOGRAPHY
Hazard Recognition
American Red Cross. 1979. Standard Safety First Aid and Personal Safety. Doubleday and Co.,
Inc., Garden City, NY.
Doull, J. et. al. 1980. Toxicology: The Basic Science of Poisons. MacMillan Publishing Co.,
Inc., New York.
Dreisbach, R.H. 1980. Handbook of Poisoning. Lange Medical Publications, Los Altos, CA.
Guthrie, R.K. 1972. Food Sanitation. Avi Publishing Co., Inc., Westport, CT.
ICO. 1974. Safety in the Manual Handling of Materials. Industrial Commission of Ohio, Division
of Safety and Hygiene, Columbus, OH.
Justrite Mfg. Co. 1977. How to Handle Flammable Liquids Safely. Justrite Manufacturing
Company, Des Plaines, IL.
NFPA. 1981. National Electrical Code. National Fire Protection Association, Boston, MA.
NSC. 1974. Accident Prevention Manual for Industrial Operations. Seventh Edition. National
Safety Council, Chicago, IL.
Proctor, N.H., and J.P. Hughes. 1978. Chemical Hazards of the Workplace. J. B. Lippincott Co.,
Philadelphia, PA.
Smith, A.L. 1973. Principles of Microbiology. C.V. Mosby Co., St. Louis, MO.
U.S. DHEW. 1978. Working Safely with Flammable and Combustible Liquids. Publication No.
78-206. U.S. Department of Health, Education, and Welfare, National Institute of Occupational
Safety and Health, Cincinnati, OH.
U.S. DHEW. 1979. Criteria for a Recommended Standard ..Working in Confined Spaces.
Publication No. 80-106. U.S. Department of Health, Education, and Welfare, National Institute for
Occupational Safety and Health, Washington, DC.
U S. DHHS. 1979. Occupational Safety and Health in Vocational Education: A Guide for
Administrators, Faculty, and Staff. Publication No. 79-138. U.S. Department of Health and Human
Services, National Institute for Occupational Safety and Health, Cincinnati, OH.
U.S. DHHS. 1986. Alert - Request for Assistance in Preventing Occupational Fatalities in Confined
Spaces. Publication No. 86-110. U.S. Department of Health and Human Services, National Institute
for Occupational Safety and Health, Cincinnati, OH.
U.S. DHHS. 1987. A Guide to Safety in Confined Spaces. Publication No. 87-113. U.S.
9/95
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Appendix D: Bibliography
-------
Department of Health and Human Services, National Institute for Occupational Safety and Health,
Morgantown, WV.
U.S. DOL. 1973. The Principles and Techniques of Mechanical Guarding. OSHA Publication No.
2057. U.S. Department of Labor, Occupational Safety and Health Administration, Washington, DC.
U.S. DOL. 1977. General Industry Standards 29 CFR 1910. U.S. Department of Labor,
Occupational Safety and Health Administration, Washington, DC.
U.S. DOL. 1980. Construction Industry Standards 29 CFR 1926. U.S. Department of Labor,
Occupational Safety and Health Administration, Washington, DC.
U.S. DOL. 1980. Noise Control - A Guide for Workers and Employers. OSHA Publication No.
3048. U.S. Department of Labor, Occupational Safety and Health Administration, Washington, DC.
Air Monitoring Instruments
ACGIH. 1989. Air Sampling Instruments for Evaluation of Atmospheric Contaminants. Sixth
Edition. American Conference of Governmental Industrial Hygienists, Cincinnati, OH.
Cee, R.J., et al. 1987. An Evaluation of Commercial Detector Tube Systems. Presentation at the
American Industrial Hygiene Conference, Montreal, Canada, June 1987.
Clayton, G.D., and F.E. Clayton (eds). 1978. Patty's Industrial Hygiene and Toxicology. Third
Review Edition, Volume I: General Principles. John Wiley and Sons, New York.
Clayton, G.D. (ed). 1973. The Industrial Environment - Its Evaluation and Control. Third.
Edition. U.S. Public Health Services Publication.
Conley, R. 1972. Infrared Spectroscopy. Second Edition. Allyn and Bacon, Inc., Boston, MA.
Klinsky, J. (ed). Manual of Recommended Practice for Combustible Gas Indicators and Portable
Direct-Reading Hydrocarbon Detectors. First Edition. American Industrial Hygiene Association,
Akron, OH.
NFPA. 1986. National Electrical Code, Volume 70. National Fire Protection Association, Boston,
MA.
Toxicology and Exposure Guidelines
ACGIH. 1994. Threshold Limit Values for Chemical Substances and Physical Agents and
Biological Exposure Indices. American Conference of Governmental Industrial Hygienists,
Cincinnati, OH.
Ariens, E., A.M. Simonis, and J. Offermeir. 1976. Introduction to General Toxicology. Academic
Press, New York.
Appendix D: Bibliography
2
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Klaassen, C.D., M.O. Amdur, and J. Doull, eds. 1986. Casarett and Doull's Toxicology: The
Basic Science of Poisons. Third Edition. Macmillan Publishing Company, New York.
Loomis, T.A. 1970. Essentials of Toxicology. Lea and Febiger, Philadelphia, PA.
NIOSH. 1973. The Industrial Environment: Its Evaluation and Control. National Institute for
Occupational Safety and Health, Washington, DC.
NIOSH. 1977. Occupational Diseases: A Guide to Their Recognition. National Institute for
Occupational Safety and Health, Washington, DC.
Proctor, N.H., and J.P. Hughes. 1978. Chemical Hazards of the Workplace. J.B. Lippincott Co.,
Philadelphia, PA.
U.S. DHHS. 1983. Registry of Toxic Effects of Chemical Substances. DHHS (NIOSH)
Publication No. 83-107, Volumes 1-3. U.S. Department of Health and Human Services, National
Institute of Occupational Safety and Health, Washington, DC.
U.S. DOL. 1981. Occupational Safety and Health Toxicology Training Course 100-124-9.
December 8-16, 1981, Chicago, IL. U.S. Department of Labor.
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Appendix D: Bibliography
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HAZARDOUS MATERIALS INCIDENT RESPONSE OPERATIONS
WORKBOOK
CONTENTS
Exercise Page
Using Air Monitoring Instruments I 1
Using Air Monitoring Instruments II 7
Air-Purifying Respirators 15
Handout: APR Communications Exercise: Team 1 APR-1
Handout: APR Communications Exercise: Team 2 APR-2
Self-Contained Breathing Apparatus 21
Radiation Survey Instruments 27
Level B Dressout 33
Level A Dressout 37
Decontamination 41
Site Safety and Work Plan Development 49
Appendices
Appendix A: Abandoned Warehouse Scenario A-l
Appendix B: HMIRO Superfund Site Scenario B-l
-------
USING AIR MONITORING INSTRUMENTS I
I. OBJECTIVES
Given a combustible gas indicator (CGI), a combination CGI and oxygen indicator, an oxygen
indicator, and colorimetric indicator tubes and pumps, the student will:
Calibrate the instruments or prepare tubes
Sample test atmospheres
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, gas sampling bags, and instructions. Each team (consisting of at
least two students) must complete the tasks at the appropriate station.
Instructions for Combustible Gas Indicators (CGIs) and Oxygen Indicators
Instruments should always be checked in a contaminant-free, open-air environment.
Furthermore, units incorporating air-drawing devices should be checked for leaks prior to
use.
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.*
*Note: 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.
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Using Air Monitoring Instruments I
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Station A: Combustible Gas Indicators (CGIs)
Three gas sampling bags contain mixtures of flammable gas/vapor in air at each of the
following concentrations:
Below the LEL
Between the LEL and the UEL
Above the UEL
Measure the concentration in each bag using both CGIs. Record concentrations on the
answer sheet below. In Column 4, identify the mixture in each bag.
ANSWER SHEET
Concentrations
MSA Model 2A
(% LEL)
Bag A jo
Bag B 7
ID 0^
Bag C
Combination Unit -J n
26.0
(% LEL)
ytoo
(% Oxygen)
JO. 87.
-?77(P0% 7'7/00% 14%
Mixture
(check one)
\S<
LEL
LEL - UEL
>UEL
UEL
UEL
Using Air Monitoring Instruments I
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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.
ANSWER SHEET
% Oxygen
MSA Model 245
(% Oxygen)
Combination Unit
(% Oxygen)
SiฐฅQ~2_
(% LEL)
Bag 1
/z %
/,?. y %
Bag 2
*/7.
2^0 . ฐl 7'
n r>
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Using Air Monitoring Instruments I
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Instructions for Colorimetric Indicator Tubes and Pumps
All colorimetric indicator tubes and pumps should be field checked prior to use:
Insert unbroken tube into pump's tube holder.
If using a bellows-tvpe pump, squeeze bellows. Bellows should not regain
its original shape. Start this test and move to piston pump (returning to
bellows after using the piston pump).
If using a piston-tvpe pump, align red arrow on handle with red line on cap
of pump. Pull back and lock handle. After 60 seconds rotate handle 1/4
turn. Handle should return to within 1/4 inch of zero cc mark.
If a pump fails these tests, contact an instructor.
Station C: Colorimetric Indicator Tubes and Pumps
Two gas sampling bags contain mixtures of toluene in air and carbon dioxide in air. Measure
the concentration in each bag using the colorimetric indicator tubes and pumps and following
the manufacturer's instructions provided. Record type of gas and concentrations on answer
sheet below.
A
ANSWER SHEET
Concentration
Gas Sensidyne/Gastec Draeger
(P^Bagl ^0-2/ 0. ^ D* lo
"A
/^y^Bag 2 ฃ~&> jofynQ
Using Air Monitoring Instruments I
4
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NOTES
Using Air Monitoring Instruments I
-------
USING AIR MONITORING INSTRUMENTS II
I. OBJECTIVES
Given an HNU PI-101 Photoionization Detector (PID), the student will:
Calibrate the instruments
Sample gases present
Record the data gathered from the PID.
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 Photo ionizer 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 die 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
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Using Air Monitoring Instruments II
-------
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.
Using Air Monitoring Instruments II
8
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STEP 1
With the assistance of the instructor and/or the technician, calibrate the instrument using
isobutylene.
To calibrate the HNU PI-101:
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 counterclockwise.
Adjust the "Span Control" until 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 A J-/
STEP 2
Record the following. The EPA sticker number can be used if no serial number is found.
HNU Serial Number:
HNU Probe Number: 47/p74L
HNU Lamp Energy:
9
Using Air Monitoring Instruments II
-------
STEP 3
With the instruments at the same span settings from Step 1, make and record readings for
the following gas bags.
Actual
PID
Concentration
Reading
Toluene
100 ppm
Acetone
100 ppm
Hexane
50 ppm
Methane
100 ppm
f)
Calculate the relative response for each of the chemicals. Relative response = 100% times
INSTRUMENT READING divided by ACTUAL CONCENTRATION.
% Relative Response
Toluene
3 (, ^
Acetone
qo/
Hexane
I/O
/) V
Methane
0 (6
STEP 4
Calibrate the instrument to toluene using the 100-ppm toluene bag. Adjust the span setting
until the instrument reads 100. Record the span setting.
PED span setting
.JLa^p
Using Air Monitoring Instruments II 10 9/95
-------
STEP 5
Take a reading of the atmosphere in and around the container of solvent. Take care that the
probe does not come in contact with the liquid. Record your results below.
LOCATION
1 foot from opening
6 inches from opening
over opening
inside container
REAPING
r>
D
(*{)&
oฐ
O
, Z
STEP 6
Conduct a room survey and record your readings at each of the containers.
READING
led
Container
Container HI
Container #3
Container M
J[L
Jfv
After obtaining the readings, the instructor will then reveal the contents of each container.
STEP 7
The instructor will demonstrate the effects of electromagnetic radiation on the instruments.
Iftle U
\
a-
-------
STEP 8
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?
Using Air Monitoring Instruments II
12
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NOTES
13 Using Air Monitoring Instruments II
-------
AIR-PURIFYING RESPIRATORS
I. OBJECTIVES
Given a full-face air-purifying respirator (APR), a Motorola HT600 radio, and an escape
mask, the student will:
Select the proper style and size of APR for their face
Communicate wearing an APR
Describe the proper method for donning and doffing escape masks.
II. PROCEDURE
A. The instructor will demonstrate fit-testing methods using 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.)
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Air-Purifying Respirators
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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-Purijying Respirators
16
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FIT-TEST RECORD
Name.
Location-
Date:
Isoamyl
Acetate
Type of mask: (pas^/fail
Manufacturer: 3^ '
Model/Size: /
Type of mask: pass/fail
Manufacturer:
Model/Size:
Type of mask: pass/fail
Manufacturer:
Model/Size:
Type of mask: pass/fail
Manufacturer:
Model/Size:
Type of mask: pass/fail
Manufacturer:
Model/Size:
Comments:
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Air-Purifying Respirators
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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 5 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. 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."
6. Turn the radio off when exercise is complete.
Air-Purifying Respirators
18
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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.
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Air-Purifying Respirators
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Air-Purifying Respirators
NOTES
20
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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.
9/95
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."
20. "COME BACK TO THE CLASSROOM."
9/95
APR-2
Handout
-------
SELF-CONTAINED BREATHING APPARATUS
I. OBJECTIVES
Given an MSA Ultralight II self-contained breathing apparatus (SCBA) unit, the student will:
Identify components of the SCBA
Demonstrate the correct procedure for inspecting and checking out the
components
Activate the emergency by-pass system
Select from and demonstrate one of the methods for donning the SCBA
Demonstrate the correct method for doffing the SCBA
Demonstrate the proper method for storing the SCBA after each use
Demonstrate necessary hand signals.
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 procedure until they have successfully completed the
checkout.
9/95
21
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 CHECKOUT PROCEDURES
Preliminary Checks
1. High-pressure hose connector is tight on cylinder fitting.
2. Cylinder, bypass, and mainline valves are shut.
3. Regulator outlet is covered.
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.
3. Check high-pressure hose assembly for damage or leaks.
Self-Contained Breathing Apparatus 22
9/95
-------
Regulator
1.
Cover regulator outlet.
2.
Open mainline valve.
3.
Note pressure reading on regulator gauge.
4.
Close cylinder valve while keeping regulator outlet covered.
5.
Slowly uncover the outlet to allow air to escape.
6.
Note pressure when low-pressure warning alarm sounds; it should alarm.
7.
Close mainline valve.
8.
Open cylinder valve.
9.
Quickly open, then close, bypass valve to check operation.
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.
9/95
23
Self-Contained Breathing Apparatus
-------
Storage of SCBA 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 (at least 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
24
9/95
-------
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."
9/95
25
Self-Contained Breathing Apparatus
-------
NOTES
Self-Contained Breathing Apparatus 26
-------
RADIATION SURVEY INSTRUMENTS
I. OBJECTIVES
Given a Ludlum Model 19 Micro R Meter and under controlled conditions, the student will:
List the steps of an operability check for the instrument being used
Describe the behavior of the instruments in various conditions of use
Describe 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.
Ludlum 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.
9/95
27
Radiation Survey Instruments
-------
"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.
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.
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. Remember that the Model 19 gives readings in micro-Roentgens (micro R). 1000
micro R = 1 milli R.
Radiation Survey Instruments
28
9/95
-------
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.
Station 4: Locate the hidden radiation sources.
9/95
29
Radiation Survey Instruments
-------
ANSWER SHEET
Serial Number:
y to f/
Station 1: Background 'J micro R/hr
Station 2: Source ^ micro R/hr
6 inches (15.2 cm) yUc^A.
1 foot (30.5 cm) ^ jJ .tIII micro R/hr
2 feet (61 cm) D b bonify- 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 between radiation monitoring procedures for unknown vs. known situations.
4. What type of protection is adequate to perform a survey at a site that may have radioactive
materials? . * ^
LeM
-------
NOTES
m R./hr
^ 0 ahou*. boud^roxjuiL^
I (yJort) JL \qcx_j1/1^ (^fouutk^
f J^OL^pjiMjLA/ S~2-7 ^
oJb bf~&
C^J*>7A_ & J ^
-<
'&?K T
9/95
31
Radiation Survey Instruments
-------
LEVEL B DRESSOUT
I. OBJECTIVES
Given Level B dressout protective equipment, an HNU combustible gas indicator, an oxygen
indicator, and detector tubes and pumps, in a simulated site entry, die student will:
Identify Level B equipment
Don and doff Level B equipment
Sample drum contents with instruments
Record and interpret the readings from the instruments.
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.
9/95
33
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
34
9/95
-------
SAMPLING RESULTS
Instrument Concentration Mixture
ฃ
Combustible Gas Indicator / IX ^
-------
Level B Dressout
NOTES
36
9/95
-------
LEVEL A DRESSOUT
I. OBJECTIVES
Given Level A protective equipment and varied tasks and activities, the student will:
Identify Level A equipment and dress out
Demonstrate proper procedure for donning and doffing Level A
Identify the physical limitations while wearing a fully encapsulating suit
Review emergency hand signals.
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 gloves (lineman's gloves)
4. Boots
B. Wipe the inside and outside of the SCBA facepiece lens and the inside of the suit lerts
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).
9/95 37 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 suit gloves and fit elastic band around suit cuff.
12. Put on outer gloves.
13. Place hood on head.
14. Connect breathing tube to regulator.
15. Secure suit by closing all fasteners.
Level A Dressout
38
9/95
-------
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 arms from suit sleeves (one at a time).
3. Open suit.
4. Raise hood over head and place on air cylinder.
5. Lower suit to waist.
6. Remove boots.
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.
9/95
39
Level A Dressout
-------
Level A Dressout
NOTES
40
-------
DECONTAMINATION
I. OBJECTIVES
Given Level B and Level C protective equipment, decontamination equipment, and an
assigned level of protection and scenario, the student will operate in teams to:
Construct and set up a decontamination line
Justify steps used or not used in procedure
Conduct a simulation of a decontamination of a person entering the
decontamination line
Describe how methods and procedures differ for Levels B, C, and A.
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 Bl or Level C2
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.
1 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.
2 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.
9/95,
41
Decontamination
-------
E. Don appropriate level of protection (i.e., PVC splash gear and air-purifying
respirators [APRsJ) 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.
Decontamination
42
9/95
-------
MAXIMUM DECONTAMINATION LAYOUT FOR LEVEL A PROTECTION
EXCLUSION
ZONE
Taps Removal
and Redress -
Boot Cover/
Outer Gloves
Segregated
Boot Cover & Equipment
Glove Wash D,op
Outer Glove
Removal
04
0<__0<--0*0ซ_0-'0
i
i
Boot Cover Boot Cover &
Removal Glove Rinse
i\ Sult/Salety
/ Boot Wash
Tank Change
Sult/Salety
Boot Rinse
HOTLINE
10
Salety Boot
Removal
11
Fully Encapaulallng Suit
and Hard Hat Removal
12 \ SCBA Backpack
Removal
CONTAMINATION
REDUCTION
ZONE
13
Inner Glove
Wash
14
Inner Glove
Rinse
15
Face Piece
Removal
16
Inner Glove
Removal
17
Inner Clothing
Removal
Field
Wash
18
Redress
CONTAMINATION
' CONTROL LINE
SUPPORT ZONE
Source: U.S. EPA 1992, p. 167
9/95 43 Decontamination
-------
MINIMUM DECONTAMINATION LAYOUT FOR LEVELS A & B PROTECTION
HOTLINE
EXCLUSION
ZONE
Equipment
Drop
Plastic
Sheet
Decon Outer
Garments
Remove
Boot Covers
& Outer Gloves
Redress.
Boot Covers
and Outer
Gloves
Decon
Solution
10
Gallon
Can
Water
Tank Change-
Over Point
Remove Boots,
Gloves and Outer
Garments (for
disposal and
olf-site
decontamination)
32 Gallon
Can
CONTAMINATION
REDUCTION
ZONE
Remove SCBA
SUPPORT ZONE
20
Wind
Direction
Source: U.S. EPA 1992, p. 169
Decontamination
44
9/95
-------
MAXIMUM DECONTAMINATION LAYOIF FOR LEVEL B PROTECTION
EXCLUSION
ZONE
Tap* Removal
Segregated
Boot Cover i. Equlpm.nl
and Redress
Boot Covar/
Outer Gloves
Glova Wash
Drop
Outer Glove
Removal
G>
(D
i
Bool Covar Boot Cover &
Removal Glove Rinse
^ Suit/Safety
/ Boot Wash
Tank Change
B \ Sult/SCB A/Boot
/Glova Rlnar
HOTLINE
10
Safety Boot
Removal
^ \ SCBA Backpack
Removal
12
Splash Suit
Removal
CONTAMINATION
REDUCTION
ZONE
13
Inner Glove
Wash
14
Inner Glove
Rinse
IS
Face Piece
Removal
16 \ Inner Glove
Removal
57 \ Innsr Clothing
Removal
Field
Wash
18
-------
MAXIMUM DECONTAMINATION LAYOUT FOR LEVEL C PROTECTION
EXCLUSION
ZONE
Tap* FUmoval
Sogrcgatod
Boot Cov.r & Equipment
Tank Change
and Redress -
Boot Cover/
Outer Gloves
Glove Wash
Drop
Outer Glove
Removal
0q
0
Boot Cover
Removal
Boot Cover &
Glove Rinse
7 ^ Suit/Safety
Boot Wash
Sult/SCB A/Boot
/Glove Rinse
Safety Boot
Removal
HOTLINE
Splash Suit
Removal
CONTAMINATION
REDUCTION
ZONE
j2 \ Inner Glove
Wash
Inner Glove
Rinse
Face Piece
Removal
Inner Glove
Removal
\ Inner Clothing
Removal
0
Redress
CONTAMINATION
' CONTROL LINE
SUPPORT ZONE
Source: U.S. EPA 1992, p. 175
Decontamination
46
9/95
-------
NOTES
9/95
47
Decontamination
-------
SITE SAFETY AND WORK PLAN DEVELOPMENT
OBJECTIVES
Given an exercise scenario and generic site safety plan forms, the student will operate in
teams to:
Develop a site safety plan
Submit plan to instructor for review before implementation.
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.
49
Site Safety and Work Plan Development
-------
$
%
^ Itvfl cgtfc-
" ^ B$S"
m
Generic Site Safety Plan*
SITE DESCRIPTION
Date
Location
Hazards 4Odiuyisd-fltjza cu1 r raided
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
Publio Info i Officer
Security-Offirpr .
Recordkeeper
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 198S.
Ai'4
Site Safety and Work Plan Development 50 5/95
MM M
isr Tฐ.r5 tum D-es~4 k.
K*S1A
"Phil HpuI kir k
-------
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
Zonell
9/95
51
Site Safety and Work Plan Development
-------
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 substances) 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
i 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
5/95
-------
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 tvpel , 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
9/95
53
Site Safety and Work Plan Development
-------
COMMUNICATION PROCEDURES
Generic Site Safety Plan
Channel I 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.
" AlouJ _ 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 so6n as possible. The phone number is
/23-45^7 .
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:
1. 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.1 will be used as the
decontamination solution.
Site Safety and Work Plan Development
54
5/95
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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 personnell 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 bnefed 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
9/95
55
Site Safety and Work Plan Development
-------
Generic Site Safety Plan
SITE SAFETY AND HEALTH FLAN (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/hourlyVdaily/other
HNU/OVA continuously/hourly/daily/other
Colorimetnc 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. All 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 untd 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 stated 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 mvolved 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
5/95
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Generic Site Safety Plan
SITE SAFETY AND HEALTH FLAN (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 evacuationl
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 m the Site Safety Plan.
Personal Monitoring
The following personal monitoring will be in effect onsite:
Personal exposure sampling: fuse of personal sampling pumps, air monitors etc.. worn bv personnel to monitor
exposure')
Medical monitoring: 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
9/95
57
Site Safety and Work Plan Development
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NOTES
Site Safety and Work Plan Development 58 5/95
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APPENDIX A
Abandoned Warehouse Scenario
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HAZARDOUS MATERIALS INCIDENT RESPONSE OPERATIONS
Abandoned Warehouse Scenario
I. OBJECTIVES
Given an exercise scenario, the site safety plan from the previous exercise, personal
protective equipment, monitoring instruments, communication radios, and decontamination
equipment, the student will operate in teams to:
Organize lines of authority with roles and responsibilities
Obtain information
Perform tasks necessary to evaluate, identify, and control the hazards at the
site
II. 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 in the 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 objectives of the Toxic Waste Investigation Team are to:
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.
9/95 A-l Appendix A
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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.
III. 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 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. Any additional equipment may be requested through an instructor. The instructor
will determine whether the equipment will be made available to the team.
6. Nothing may be simulated without the approval of an instructor. Simulations should
be recorded in the logbook.
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 hypochlorite
hp*
Appendix A
A-2
9/95
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APPENDIX B
Superfund Site Scenario
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HAZARDOUS MATERIALS INCIDENT RESPONSE OPERATIONS
Superfund Site Scenario
I. OBJECTIVES
Given an exercise scenario, personal protective equipment, monitoring instruments,
communication radios and decontamination equipment, students will operate as one team to:
Characterize the site to determine whether any harmful concentrations are
present
Identify the hazards that exist and protect the people who live and work in the
immediate area
Provide recommendations on how the waste site should be remediated.
II. SUPERFUND SITE SCENARIO
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!
III. GROUND RULES
I. 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.
9/95
B-l
Appendix B
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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.
Appendix B
B-2
ซU9 GOVERNMENT PRINTING OFFICE 1996 - 722 - 958 / 83291
9/95
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Draft 4/29/98
PRIORITY NEEDS IDENTIFIED
at the
U.S. EPA/ORIA-ASTSWMO
State Needs Assessment Meeting
April 22,1998, Kansas City, MO
~ Solve the Superfiind funding issue, so that states can do risk assessment for non-NPL
sites
~ Resolve the RAD methodology (risk management) issue at the national level
~ Provide training on MARSIM and other guidances
~ Provide health and safety training
~ Provide financial assistance for cleaning up orphan sites
~ Form/fund a DOE-RAD Task Force
GROUP 1 REPORT
Health and Safety
Training
Find out what is available (EPA videos, state/federal agenciesDOE, NRC)
EPA takes lead, check with other agencies
Safety
Site access
Spill response/emergency
Sampling/collection
Lab handling^)
Equipment training
Who Needs It?
State
RPMs
Rad folks
Emergency response
SEMA
Drinking water
* EPA conduct needs assessment to find out what type of training neededfor each
group
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