AIR MONITORING FOR HAZARDOUS MATERIALS
(165.4)
5 Days
This course instructs participants in the practices and procedures for monitoring and sampling
airborne hazardous materials. It is designed for personnel who evaluate releases of airborne
hazardous materials at hazardous waste sites or accidental hazardous material releases.
Topics that are discussed include air monitoring and sampling programs, air monitoring and sampling
techniques, air monitoring and sampling equipment, instrument calibration, exposure guidelines, air
dispersion modeling, and health and safety considerations. The course will include operating
procedures for specific air monitoring and sampling equipment, as well as strategies for air
monitoring and sampling at abandoned hazardous waste sites and for accidental releases of hazardous
chemicals.
Instructional methods include a combination of lectures, group discussions, problem-solving sessions,
and laboratory and field exercises with hands-on use of instruments.
After completing the course, participants will be able to:
• Properly use the following types of air monitoring and sampling equipment:
Combustible gas indicators
Oxygen monitors
Detector tubes
Toxic gas monitors
Photoionization detectors
Flame ionization detectors
Gas chromatographs
Sampling pumps
Direct-reading aerosol monitors.
• Identify the operational parameters, limitations, and data interpretation requirements
for the instruments listed above.
• Identify the factors to be considered in the development of air monitoring and
sampling plans.
• Discuss the use of air monitoring data for the establishment of personnel and
operations health and safety requirements.
U.S. Environmental Protection Agency
Office of Emergency and Remedial Response
Environmental Response Team
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CONTENTS
Section
Acronyms and Abbreviations
Air Monitoring Plans and Strategies 1
Exposure Limits and Action Levels ; 2
Oxygen Monitors, Combustible Gas Indicators, and
Specific Chemical Monitors 3
Total Vapor Survey Instruments 4
Air Sample Collection 5
Introduction to Gas Chromatography 6
Air Dispersion Modeling During Emergency Response 7
References 8
Manufacturers and Suppliers of Air Monitoring Equipment 9
Workbook: Air Monitoring for Hazardous Materials 10
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ACRONYMS AND ABBREVIATIONS
ACGIH American Conference of Governmental Industrial Hygienists
AID argon ionization detector
AIHA American Industrial Hygiene Association
ALOHA areal locations of hazardous atmospheres
ANSI American National Standards Institute
ASTM American Society for Testing and Materials
BEI biological exposure indices
C ceiling (precedes exposure limit)
cc/min cubic centimeters per minute
cfrn cubic feet per minute
CFR Code of Federal Regulations
CGI combustible gas indicator
Cl chlorine
CO carbon monoxide
DNPH 2,4-dinitrophenylhydrazine
DQO data quality objective
BCD electron capture detector
EPA U.S. Environmental Protection Agency
ERT Environmental Response Team (EPA)
eV electron volt
FID flame ionization detector
FM Factory Mutual Research Corporation
GC gas chromatography
HC1 hydrogen chloride
ICS incident command system
IDLH immediately dangerous to life or health
IP ionization potential
KOH potassium hydroxide
LCD liquid crystal display
LED light-emitting diode
LEL lower explosive limit
LFL lower flammable limit
1pm liters per minute
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MACs maximum allowable concentrations
MAKs maximum concentrations at the workplace (Federal Republic of Germany)
MCE mixed cellulose ester
mg/m3 milligrams per cubic meter
ml milliliter
mm millimeter
MOS metal-oxide semiconductor
MSDS material safety data sheets
MSHA Mine Safety and Health Administration
NaOH sodium hydroxide
NEC National Electrical Code
NFPA National Fire Protection Association
NIOSH National Institute for Occupational Safety and Health
NRC Nuclear Regulatory Commission
OH hydroxide
OSHA Occupational Safety and Health Administration
OVA organic vapor analyzer (Foxboro®)
OVM organic vapor meter
PAH polycyclic (or polynuclear) aromatic hydrocarbon
PBK playback
PCS polychlorinated biphenyl
PEL permissible exposure limit
PID photoionization detector
ppb parts per billion
PPE personal protective equipment
ppm parts per million
ppt parts per trillion
PDF polyurethane foam
PVC polyvinyl chloride
REL recommended exposure limits
SA shift average
SCBA self-contained breathing apparatus
SEI Safety Equipment Institute
SOP standard operating procedure
SOSG Standard Operating Safety Guides
SS chemical-specific sensor
STEL short-term exposure limit
TCD thermal conductivity detector
TLV threshold limit values
TWA time-weighted average
Acronyms and Abbreviations 2 10/93
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UEL upper explosive limit
UL Underwriters' Laboratory, Inc.
UV ultraviolet light
VDC volts DC
WEEL® workplace environmental exposure level
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AIR MONITORING PLANS
AND STRATEGIES
PERFORMANCE OBJECTIVES
At the end of this lesson, participants will be able to:
• List six objectives of air monitoring specified by the EPA
Standard Operating Safety Guides
• Identify the OSHA standard and EPA standard that cover
hazardous waste site operations and emergency response
• List four situations that initial entry monitoring is designed
to detect
• Differentiate between "personal monitoring" and "area
monitoring"
• Define, per 1910.120, when personnel monitoring is
required
• List documents that EPA has developed as guidance for
compliance with 1910.120
• Given the Personal Air Sampling and Air Monitoring
Requirements Under 29 CFR 1910.120 fact sheet, define air
monitoring and air sampling
• List three uses of meteorological data.
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NOTES
AIR MONITORING PLANS
AND STRATEGIES
AIR MONITORING
EPA Objectives
• Identify and quantify airborne
contaminants onsite and offsite
• Track changes in air contaminants that
occur over the lifetime of the incident
• Ensure proper selection of work practices
and engineering controls
Source: EPASOSGs
AIR MONITORING
EPA Objectives
• Determine the level of worker protection
needed
• Assist in defining work zones
• Identify additional medical monitoring
needs in any given area of the site.
Source: EPA SOSGs
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NOTES
WORKER PROTECTION
STANDARDS (OSHA)
29 CFR 1910.120 (HAZWOPER)
Applies to
- Federal employees
- Private industry employees
- State and local employees in
OSHA states
WORKER PROTECTION
STANDARDS (EPA)
40 CFR Part 311
Applies to state and local employees
in non-OSHA states
Wording same as 1910.120
MONITORING
REQUIREMENTS
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NOTES
INITIAL ENTRY
Monitoring for:
• Immediately dangerous to life or
health (IDLH) conditions
• Exposures over permissible
exposure limits (PELs) or published
exposure levels
INITIAL ENTRY
Monitoring for:
• Exposure over a radioactive
material's dose limits
• Other dangerous conditions
- Flammable atmospheres
- Oxygen-deficient environments
PERIODIC MONITORING
"Periodic monitoring (shall) be done
when the possibility of a dangerous
condition has developed or when there
is reason to believe that exposures
may have risen above PELs since prior
monitoring was conducted."
Source: EPA SOSGs
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Air Monitoring Plans and Strategies
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NOTES
PERSONAL MONITORING
Required
• During actual cleanup phase
• To evaluate high-risk employees
(i.e., employees likely to have
highest exposures)
• Evaluation of other employees
needed if high-risk employees exceed
exposure limits
Source: 19W.120(h)(4)
PERSONAL MONITORING
AREA MONITORING
S = Area samplers
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NOTES
SITE SAFETY AND
HEALTH PLAN
Minimum requirement
"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."
Source: 1910.120(b)(4)(ii)(E)
GUIDANCE DOCUMENTS
OSHA
• Technical manual
• Analytical methods manual
GUIDANCE DOCUMENTS
EPA
EPA-ERT Standard Operating Safety
Guides (SOSGs), Publication
9285.1-03, June 1992
Personal Air Sampling and Air
Monitoring Requirements (PASAMR)
Under 29 CFR 1910.120 fact sheet,
Publication 9360.8-17FS, May 1993
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NOTES
AIR MONITORING vs.
AIR SAMPLING
Air monitoring refers to the use of
direct-reading instruments producing
instantaneous data
Air sampling refers to the use of a
sampling pump and collection media
that produce samples that must be
sent to a laboratory for analysis
AIR MONITORING
Features
"Real time" (direct reading)
Rapid response
Generally not compound specific
Limited detection levels
May not detect certain classes of
compounds
AIR SAMPLING
Features
Compound or class specific
Greater accuracy
Requires more time for results
Requires additional pumps, media,
and analytical support
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NOTES
PERSONNEL AIR SAMPLING
Elements in Sampling Strategy
• Employee sampled
• Tasks performed
• Duration
• Hazardous substances
• Equipment to be used
Source: PASAMR fact sheet
AREA SAMPLING
Locations
Upwind
- Establish background
Support zone
- Ensure support area is clean
and remains clean
Source; EPASOSGs
AREA SAMPLING
Locations
• Contamination reduction zone
- Ensure that personnel in zone are
properly protected
- Ensure that onsite workers are not
removing PPE in a contaminated area
Source: EPA SOSGs
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NOTES
AREA SAMPLING
Locations
• Exclusion zone
- Represents greatest risk of exposure
- Requires most sampling
- Use data to set boundaries
- Use data to select proper levels of
PPE
- Provide a record of air contaminants
Source: EPA SOSGs
AREA SAMPLING
Locations
Fenceline/downwind
- Determine whether air contaminants
are migrating from site
Source: EPASOSGs
AREA SAMPLING
Elements in Sampling Strategy
• Locations where air sampling will be
performed
• Hazardous substances that will be
sampled during the task
• Duration of the sample
Source: PASAMR fact sheet
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NOTES
AREA SAMPLING
Elements in Sampling Strategy
Equipment that will be used to sample
for the different hazardous substances
Collection of meteorological data
Source; PASAMR fact sheet
METEOROLOGICAL
CONSIDERATIONS
• Data needed
- Wind speed and direction
- Temperature
- Barometric pressure
- Humidity
METEOROLOGICAL
CONSIDERATIONS
• Data uses
- Placement of samplers
- Input for air models
- Calibration adjustments
• Data sources
- Onsite meteorological stations
- Government or private
organizations
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NOTES
AIR DISPERSION MODELS
Public exposure assessment
Air monitoring and air modeling
should interact
LONG-TERM AIR MONITORING
PROGRAMS
Considerations
Type of equipment
Cost
Personnel
Accuracy of analysis
Time to obtain results
Availability of analytical
laboratories
Source: EPA SOSGs
LONG-TERM AIR MONITORING
PROGRAMS
ERT Approach
• Use total vapor survey instruments
for organic vapors and gases
- Initial detection
- Periodic site surveys
- Area monitors to track changes
Source: EPA SOSGs
Air Monitoring Plans and Strategies
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NOTES
LONG-TERM AIR MONITORING
PROGRAMS
ERT Approach
• Collect air samples
- Analyze with field gas
chromatographs
- Send selected samples to
laboratories
• Use survey instruments or gas
chromatographs to screen samples
for laboratory analysis
Source: EPASOSGs
LONG-TERM AIR MONITORING
PROGRAMS
ERT Approach
• When they are known to be present
or when there are indications that
they may be a problem, sample for
- Particulates
- Inorganic acids
- Aromatic amines
- Halogenated pesticides
Source: EPASOSGs
ADDITIONAL READING
Air/Superfund Technical Guidance Study
Series
- Volume IV - Guidance for Ambient Air
Monitoring at Superfund Sites (revised),
EPA-451/R-93-007, May 1993
- Compilation of Information on Real-Time
Monitoring for Use at Superfund Sites,
EPA-451/R-93-008, May 1993
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NOTES
INSTRUMENT
CHARACTERISTICS
SELECTIVITY
• Selectivity is an instrument's ability to
differentiate a chemical from others in
a mixture
• Chemicals that affect an instrument's
selectivity are called interferences
SENSITIVITY
Sensitivity is the least change in
concentration that will register an
altered reading of the instrument
Source: Air Sampling and Analysis for Contaminants: An
Overview
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NOTES
ACCURACY AND PRECISION
• Accuracy refers to the difference
between the instrument reading and
the true or correct value.
• Precision is the grouping of the data
points around a calculated average.
Precision measures the repeatability
of data.
ACCURACY AND PRECISION
Accurate and Precise
©
Precise but Inaccurate
x
©
Accurate but Imprecise Inaccurate and Imprecise
Source: The Industrial Environment • Its Evaluation and Control
RELATIVE RESPONSE
Relative response is the relationship
between an instrument's reading and
the actual concentration
Calculation
Relative Response =
Instrument Reading
Actual Concentration
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NOTES
CALIBRATION
Process of checking an instrument to
see if it gives the proper response
and making any necessary
adjustments.
Direct-reading instruments generally
are calibrated to one chemical (the
standard).
RESPONSE TIME
• Response time is the time between
initial sample contact and readout
of the full chemical concentration
(usually seconds to minutes)
• Turnaround time is the time from
sample collection to receipt of
results (days to weeks)
MOBILITY
• Portable
- Handheld
- No external power supply
• Fieldable
- Particularly rugged
- Easily transported by vehicle
- Limited external power supply
• Mobile
- Small enough to carry in a mobile lab
Source: Field Screening Methods Catalog, EPAI540/2-88I005,
September 1888
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NOTES
EASE OF OPERATION
• How easy is it to operate the
controls?
• How easy is it to learn to operate?
• How many steps must be performed
before an answer is obtained?
• How easy is it to repair?
INHERENT SAFETY
32L6
LISTED
APPROVED
INTRINSICALLY SAFE COMBINATION
COMBUSTIBLE GAS AND OXYGEN INDICATING
DETECTOR FOR HAZARDOUS LOCATIONS
CLASS I, DIVISION 1, GROUPS A, B, C & D
Source; Scott Model S-105 Certification Label
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AIR MONITORING PLANS AND STRATEGIES
INTRODUCTION
Airborne contaminants present at a hazardous waste site or a hazardous materials release can present
a risk to human health and the environment. One way to assess that risk is to identify and quantify
these contaminants by air monitoring. The U.S. Environmental Protection Agency's (EPA) Standard
Operating Safety Guides (SOSGs) state that the objectives of air monitoring during response
operations are to:
• Identify and quantify airborne contaminants onsite and offsite
• Track changes in air contaminants that occur over the lifetime of the incident
• Ensure proper selection of work practices and engineering controls
• Determine the level of worker protection needed
• Assist in defining work zones
• Identify additional medical monitoring needs in any given area of the site.
Several questions should be addressed when you develop an air monitoring plan. Why is the air
monitoring being done? How will the monitoring be done? Who will do the monitoring? When and
where will the air monitoring be done? What equipment will be used?
The above list gives several reasons why air monitoring is done. Some organizations have developed
guidelines on the why, how, who, where, when, and what of air monitoring. Some organizations
have procedures that are legal requirements. These organizations will be discussed. Also, general
equipment characteristics will be covered in the latter part of this section.
STANDARDS AND GUIDELINES
U.S. Department of Labor - Occupational Safety and Health Administration (OSHA)
Since 1971, OSHA has regulated exposure to chemicals in industry. 29 CFR Part 1910.1000
specifies limits on exposure to airborne concentrations of chemicals. See the section on Exposure
Limits and Action Levels for further information.
On March 6, 1990, OSHA's Hazardous Waste Operations and Emergency Response standard (29
CFR Part 1910.120) went into effect. This standard addressed the legal requirements for protecting
workers involved with hazardous waste or emergency responses to hazardous materials. Air
monitoring is one of the many activities regulated by this standard.
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The standard requires the site- specific safety and health plan to address:
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.
Under section (c) Site characterization and analysis is:
(6) Monitoring. The following monitoring shall be conducted during initial site entry
when the site evaluation produces information that shows the potential for ionizing
radiation or IDLH (Immediately Dangerous to Life or Health) conditions, or when
the site information is not sufficient reasonably to eliminate these possible conditions:
(i) Monitoring with direct-reading instruments for hazardous levels
of radiation.
(ii) Monitoring the air with appropriate direct-reading test equipment
(e.g., combustible gas meter, detector tubes) for IDLH and other
conditions that may cause death or serious harm (combustible or
explosive atmospheres, oxygen deficiency, toxic substances).
(Hi) 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 startup of
operations.
This section states when monitoring should be done (site entry), why it is done (to identify IDLH
conditions), and what kind of equipment to use. Additional requirements are found under (h)
Monitoring.
(1) General
(i) Monitoring shall be performed in accordance with this paragraph
where there may be a question of employee exposure to hazardous
concentrations of hazardous substances in order to assure proper
selection of 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
for hazardous substances.
(ii) 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.
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Here the purpose (why) is to identify and quantify hazardous substances so that proper exposure
controls are used. The substances are identified and quantified so that the concentrations can be
compared to an exposure limit. See the Exposure Limits and Action Levels section for further
information on exposure limits.
(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 or oxygen-
deficient environments.
This paragraph expands on site characterization and analysis paragraph (c)(6) by including exposure
limits along with IDLH conditions to monitor.
(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 risen are as follows:
ft) When work begins on a different portion of the site.
(ii) When contaminants other than those previously identified are
being handled.
(in) 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).
Again, where, when, and why are covered.
(4) Monitoring of high-risk employees. After the actual cleanup 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 exposure to hazardous substances and health hazards likely to be
present above permissible exposure limits or published exposure levels by using
personal sampling frequently enough to characterize employee exposures. If the
employees likely to have the highest exposure are over permissible exposure limits
or published exposure limits, then monitoring shall continue to determine all
employees likely to be above those limits. The employer may utilize a representative
sampling approach by documenting that the employees and chemical 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.
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These paragraphs state that personal monitoring (how) must be done on high-risk employees (who)
during cleanup activities (when).
Section (q) of 1910.120 addresses emergency responses to hazardous substance releases. It states
in (q)(3)(ii) that
the individual in charge of the ICS (Incident Command System) 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 substances handling procedures, and use of any new technologies.
Air monitoring is not specifically mentioned in section (q), but would be a useful, if not necessary,
tool for assessment.
29 CFR 1910.120 is a federal regulation. In states where there is an approved state OSHA (state-
plan state), requirements at least as stringent as 1910.120 must be developed. Thus, in some states
the air monitoring requirements may be more detailed.
U.S. Environmental Protection Agency (EPA)
On June 23, 1989, EPA adopted 40 CFR Part 311, Worker Protection Standards for Hazardous
Waste Operations and Emergency Response. This standard is a duplicate of 1910.120. The
difference in the standards is to whom they apply. The OSHA standard applies to federal agencies,
private industries, and public employees in OSHA state-plan states. The EPA standard applies to
public employees in states that have no OSHA state-plan.
As noted in the previous paragraph, EPA has regulations for monitoring for worker protection.
There are also requirements for monitoring for public protection. However, this subject will not be
discussed here in detail. Additional information is mentioned in this manual in the Exposure Limits
and Action Levels section.
EPA has published guidelines for hazardous material operations which include air monitoring
procedures. General guidelines can be found in the SOSGs. The following topics are discussed in
the SOSGs:
1. Objectives of air monitoring
2. Identifying airborne contaminants
3, Air sampling equipment and media
4. Sample collection and analysis
5. General monitoring practices
6. Meteorological considerations
7. Long-term air monitoring programs
8. Variables in hazardous waste site air monitoring
9. Using vapor/gas concentrations to determine level of protection.
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Other EPA guidance documents are:
• Personal Air Sampling and Air Monitoring Requirements Under 29 CFR 1910.120 fact sheet
• Guidance for Ambient Air Monitoring at Superfund Sites, Volume IV in the Air/Superfund
National Technical Guidance Series
• Compilation of Information on Real-Time Monitoring for use at Superfund Sites
• Removal Program Representative Sampling: Air
• A Compendium of Superfund Field Operations Methods.
EPA's Environmental Response Team (ERT) has developed standard operating procedures for their
air monitoring equipment and strategies. These documents provide information on the why, how,
when, where, and what of air monitoring. Because EPA is concerned with offsite migration and
public exposure along with worker protection, their sampling requirements are broader than OSHA's.
Air monitoring is done onsite to determine the type and quantity of chemicals being released.
Downwind monitoring is done to determine offsite migration. Upwind sampling is done to determine
what background concentrations may be contributing to the downwind and onsite measurements.
This helps determine what the site is contributing to the environment.
Some of the methods use air monitoring equipment to monitor for the presence of chemicals in media
other than air (e.g., soil gas sampling and water headspace).
Other Organizations
The National Institute for Occupational Safety and Health (NIOSH), the American Conference of
Governmental Industrial Hygienists (ACGIH), the American Industrial Hygiene Association (AIHA),
and the American Society for Testing and Materials (ASTM) have publications about air monitoring
strategies. See the References section of this manual for more information.
CHARACTERISTICS OF AIR MONITORING INSTRUMENTS
The selection of equipment to be used must be part of the air monitoring plan. There are many
factors to consider when determining the proper equipment to use. Specific instrument characteristics
related to the following factors can be found in later sections of this manual.
Hazard
The proper equipment must be selected to monitor the hazard or chemical at hand.
Selectivity
Selectivity is the ability of an instrument to detect and measure a specific chemical. If other
chemicals are detected, they are called interferences. Interferences can affect the accuracy of the
instrument reading. In some situations, an instrument (like the combustible gas indicator [CGI]) that
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responds to more than one chemical is desired. Again, the purpose of the monitoring must be
considered.
Sensitivity
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. Therefore, 'sensitive"
instruments can detect small changes in concentration.
Accuracy
Accuracy is the measure of how close readings are to true values. It is expressed as % bias. For
example, if an instrument is tested and the average results are 15% higher than the true
concentration, ihen the instrument is said to have a bias of +15%. NIOSH recommends that a
portable direct-reading instrument be within 25% of the true value 95% of the time.
Precision
Precision is the grouping of the data points. It is a quantitative measure of the variability of a group
of measurements compared to their average value. It is defined by the standard deviation. This
value is a ± qualifier when a value is reported (e.g., 10+1 ppm).
Accuracy and precision are affected by factors such as the instrument's calibration and relative
response,
Calibration
An instrument must be properly calibrated, prior to use, in order to function properly in the field.
Calibration is the process of adjusting the instrument readout so that it corresponds to an actual
concentration. Calibration involves checking the instrument results with a known concentration of
a gas or vapor to see that the instrument gives the proper response. For example, if a combustible
gas meter is checked with a calibration 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 an accurate reading is 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 is usually different (see Relative Response below).
If the calibration is changed for an instrument, its relative responses will also change. Also, the
instrument may not give a one-to-one response to the chemical for the full range of detection (see
detection range).
Instruments come from the manufacturer calibrated to a specific chemical. The manufacturer
supplies information about how to maintain that calibration. If the user wants to change the
calibration gas, the manufacturer can supply information on how to do so.
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Relative Response
Whereas some instruments may detect more than one chemical, equal concentrations may not give
equal response. The relationship between the instrument's response and the actual concentration of
the chemical is termed the "relative response." Relative response can be calculated by using the
following formula:
Relative Response = Instrument ^ading (x m% far % ^^ Response)
Actual Concentration
For example, if an instrument reading for a 100 ppm concentration of acetone is 63, then the relative
response for that instrument and acetone is 0.63 or 63%. Table 1 gives relative response
information for a particular CGI.
TABLE 1. RELATIVE RESPONSE OF SELECTED CHEMICALS
FOR A CGI CALIBRATED TO PENTANE
Concentration
Chemical {% LED
Methane
Acetylene
Pentane
1,4-Dioxane
Xylene
50
50
50
50
50
Meter Response
(% LEU
85
60
50
37
27
Relative Response
(%)
170
120
100
74
54
Source: Portable Gas Indicator, Model 250 and 260, Response Curves,
Mine Safety Appliances Company, Pittsburgh, PA.
Relative responses vary with chemical and instrument. The same chemical may have a relative
response of 63% for one instrument and 120% response for another. Calibration also affects relative
response.
Instruments come from the manufacturer calibrated to a specific chemical. If the instrument is being
used for a chemical that is not the calibration standard, then it may be possible to look at the
manufacturer's information to get the relative response of that instrument for the chemical. Then
the actual concentration can be calculated. For example, if the instrument's relative response for
xylene is 0.27 (27%) and the reading is 100 ppm (parts per million), then the actual concentration
is 370 ppm (0.27 x actual concentration = 100 ppm; actual concentration = 100/0.27 = 370 ppm).
If there is no relative response data for the chemical in question, it may be possible to recalibrate
the instrument. If the instrument has adjustable settings and a known concentration is available, the
instrument may be adjusted to read directly for the chemical. Because recalibration takes time, this
is usually done only if the instrument is going to be used for many measurements of the special
chemical.
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Detection Range
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. The lower detection limit
is the lowest concentration to which an instrument will respond. It is important to use an instrument
with an operating range that will accurately measure the concentration in the range of concern. For
example, a CGI could be used to monitor for methane because methane is combustible. However,
the upper limit of the CGI is the lower explosive limit (LEL) of the chemical. LEL is the lowest
concentration of gas or vapor (in air) that will burn or explode if an ignition source is present at
ambient temperatures. In this case, that would be 5% methane. If higher concentrations of methane
need to be quantified, another type of instrument would be needed. Also, most CGIs are not
sensitive to ppm concentrations. A different instrument would be needed to measure that range.
Some instruments may respond to the chemical for a range of concentrations but not give a consistent
response throughout the range. The linear range is the range of concentrations over which the
instrument gives response proportional to the chemical concentration.
Response Time
Response time is the time between initial sample contact and readout of the full chemical
concentration. In direct-reading instruments, a rapid response time is desired. Response time for
direct-reading instruments can be from seconds to minutes. The HNU PI-101 gives 90% of full-scale
concentration in 3 seconds. Some hydrogen cyanide detectors may take 90 seconds to give a full
concentration reading. Factors that affect response time are temperature, type of detector, and
sample hose length.
For methods that require air sample collection and analysis, the response time is referred to as the
turnaround time. In other words, how long was the period of time between collection of the sample
and receipt of results from the laboratory?
Mobility
EPA's Field Screening Methods Catalog uses the following terms:
• Portable—Hand-held devices that can be easily carried by one person and require no
external power source.
• Fieldable—Easily transported in a van, pick-up, or four-wheel drive. Particularly
rugged and limited external power required.
• Mobile—Small enough to carry in a mobile lab. Power consideration may limit the
use of many instruments in mobile laboratories. (Size, durability, and power supply
are the main considerations in determining the mobility of an instrument.)
Air Monitoring Plans and Strategies 8 10/93
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Ease of Operation
Because many of these instruments were designed for industrial use, allowances may not have been
made for using the instrument while wearing protective equipment. One must consider how easy it
is to use the instrument while wearing gloves or how difficult it is to read the meter while wearing
a respirator. Also, how quickly a user 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.
Direct-Reading vs. Sample Analysis
Direct-reading instruments are those that give a response to a chemical within seconds or minutes
of contact. They are also meant to be taken to the location that is to be evaluated. Sample analysis,
however, involves collecting an air sample on a media or in a container and then sending it to an
analytical laboratory. This type of analysis involves much more time—sometimes days longer—than
using a direct-reading instrument.
Personal vs. Area Monitor/Sampler
A personal monitor/sampler is one that can be worn by the worker with the intent of obtaining the
exposure for the wearer. An area monitor/sampler obtains information for the area in which it is
placed. A personal monitor/sampler must be small enough to be worn by the worker and also must
have a battery supply if it is electronic. A personal monitor/sampler is the ultimate in portability.
They range in size from pocket size to a size that can be clipped to a belt without hindering the
wearer. Area samplers can be much larger and can use AC power. Many of the personal monitors
are equipped with warning alarms and with dataloggers to store and calculate exposures.
Inherent Safety
Many of the instruments used for air monitoring will be used in the atmosphere being monitored.
Therefore, they must be safe to use in that environment. Electrical devices, including instruments,
must be constructed 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. The National Fire Protection Association (NFPA)
publishes the National Electrical Code (NEC), which spells out types of areas in which hazardous
atmospheres can be generated and the types of materials that generate these atmospheres. It also lists
design safeguards acceptable for use in hazardous atmospheres.
10/93 9 Air Monitoring Plans and Strategies
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Hazardous Atmospheres
The term "hazardous atmosphere" causes response workers, depending on their backgrounds, to
imagine 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 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 2).
• Class II consists of combustible dusts like coal or grain and is divided into groups E, F,
and G (Table 3).
• Class III is ignitable fibers such as those produced by cotton milling.
TABLE 2. SELECTED CLASS I CHEMICALS BY GROUP
Group
Examples of Chemicals Within Group
Group A Atmospheres acetylene
Group B Atmospheres 1,3-butadiene
Group C Atmospheres carbon monoxide
diethyl ether
dicyclopentadiene
ethyl mercaptan
ethylene oxide
ethylene
hydrazine
hydrogen sulfide
methyl ether
hydrogen
nitropropane
tetrahydrofuran
tetramethyl lead
triethylamine
Group D Atmospheres
acetone
ammonia
benzene
ethanol
fuel oils
gasoline
liquified petroleum gas
methane
methyl ethyl ketone
propane
vinyl chloride
xylenes
Source: NFPA. 1991. Classification of Gases, Vapors, and Dusts for Electrical Equipment in
Hazardous (classified) Locations. National Fire Protection Association, ANSI/NFPA 497M.
Air Monitoring Plans and Strategies
10
10/93
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TABLE 3. SELECTED CLASS II CHEMICALS BY GROUP
Group Characteristics of Group
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 carbon black, coal, or coke dust
with more than 8% volatile material
Group G Nonconductive Dusts Atmospheres containing flour, starch, grain, carbonaceous,
chemical thermoplastic, thermosetting and molding
compounds.
Source: NFPA. 1991. Classification of Gases, Vapors, and Dusts for Electrical Equipment
in Hazardous (classified) Locations. National Fire Protection Association, ANSI/NFPA
497M.
Division is the term describing the "location" of generation and release of the flammable material.
• Division 1 is a location where the generation and release are continuous, intermittent,
or periodic into an open, unconfmed area under normal conditions. Instruments
certified for Division 1 locations are also called "intrinsically safe."
• Division 2 is a location where the generation and release are only from ruptures,
leaks, or other failures from closed systems or containers.
Using this system, a hazardous atmosphere can be routinely and adequately defined. As an example,
an abandoned waste site containing intact closed drums of methyl ethyl ketone, toluene and xylene
would be considered a Class I, Division 2, Group D environment. However, when transfer of the
flammable liquids takes place at the site, or if releases of flammable gases/vapors are considered
normal, those areas would be considered Class I, Division 1.
Certification
If a device is certified for a given class, division, and group, and it is used, maintained, and serviced
according to the manufacturer's instructions, it 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 recognized 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 and certification is done by such organizations as Underwriters' Laboratory, Inc.
(UL) or Factory Mutual Research Corporation (FM).
10/93 n Air Monitoring Plans and Strategies
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32L6
LISTED
APPROVED
INTRINSICALLY SAFE COMBINATION
COMBUSTIBLE GAS AND OXYGEN INDICATING
DETECTOR FOR HAZARDOUS LOCATIONS
CLASS I, DIVISION 1, GROUPS A, B, C & D
FIGURE 1. CERTIFICATION LABEL FROM SCOTT® MODEL S-105
COMBUSTIBLE GAS AND 02 INDICATOR
To ensure personnel safety, only approved instruments can 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.
• Some organizations test and certify instruments for locations different from the NEC
classifications. 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 1 (vapors and
gases), Division 1 (areas of ignitable concentrations), Groups A, B, C, and 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 may not be possible to certify
an all-inclusive instrument. Therefore, select a certified device based on the
chemicals and conditions most likely to be encountered. For example, a device
certified for a Class II, Division 1, Group E (combustible metal dust) would offer
little protection around a flammable vapor or gas.
Air Monitoring Plans and Strategies
12
10/93
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Accessories or Options
Many manufacturers offer accessories or options for their instruments. A useful option is an alarm
to alert the user that a concentration level has been exceeded. This is a common feature on CGIs
and oxygen meters.
A recent addition to instruments are microprocessors/dataloggers. This combination can help the
operator calibrate the instrument, store calibration information, make adjustments to the instrument,
store readings so that a readout of concentrations at specific locations or times can be made at the
end of a monitoring period, and report the data. Some units may even do time-weighted averaging
of the concentrations. Some instruments can transfer this information into an external computer for
storage and data manipulation.
Other accessories and options include special sample probes, special carrying cases, and the ability
to change detectors in an instrument.
DATA QUALITY
The Characteristics of Air Monitoring Instruments section discussed instrument characteristics (e.g.,
accuracy, selectivity, and sensitivity) that affect the quality of the data from the air monitoring
instruments. Data quality is a concern and EPA has published a document entitled Data Quality
Objectives for Remedial Response Activities (U.S. EPA 1987) that discusses how to address this
concern.
The data quality objectives (DQOs) basically state that the desired quality of data determines the
amount of time and effort needed to produce the result. There are different levels of data quality.
Table 4 illustrates this point. The higher the analytical level, the better the quality of data.
However, higher analytical levels usually require more time and money.
CONCLUSION
The desired air monitoring instrument is one that is portable, direct-reading, easy to use, and
accurate and precise. The instrument should also respond quickly, be capable of detecting ppb and
% concentrations, be inherently safe, identify and give concentrations of all the chemicals and
hazards in an atmosphere, and do its job while the operator is sitting at a safe distance from the
hazardous material site or spill. Unfortunately, no instrument meets these criteria. Thus, a variety
of instruments are needed depending on the air monitoring plan.
When preparing an air monitoring plan, the operator must determine why, how, when, and where
the monitoring is to be done and what equipment is necessary. In addition, there are legal
requirements to comply with. Guidance documents are available to assist in complying with these
requirements. Other factors must also be considered when selecting the monitoring equipment.
Additional information on why to sample, or what to sample for, will be covered in the Exposure
Limits and Action Levels section of the course. Characteristics of the various types of equipment will
also be discussed in later sections.
JO/93 13 Air Monitoring Plans and Strategies
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Air Monitoring Plans and Strategies
14
10/93
-------
EXPOSURE LIMITS AND
ACTION LEVELS
PERFORMANCE OBJECTIVES
At the end of this lesson, participants will be able to:
• Identify the three sources of exposure limits specified in
OSHA's 29 CFR 1910.120 Hazardous Waste Operations and
Emergency Response standard
• Define the terms "time-weighted average (TWA) limit,"
"short-term exposure limit," and "ceiling limit"
• Given the identity and concentration of a chemical exposure,
determine whether an exposure limit is exceeded
• Calculate an 8-hour TWA exposure when given a chemical's
exposure concentration and the duration of the exposure
• List the three uses mentioned in 1910.120 for exposure
limits
• List three of the five applications for which the American
Conference of Governmental Industrial Hygienists states the
threshold limit values should not be used
• List EPA's action levels for oxygen, combustible gas, and
radiation and the actions associated with each level.
-------
NOTES
EXPOSURE LIMITS AND
ACTION LEVELS
EXPOSURE LIMITS
(29 CFR Part 1910.120)
Permissible Exposure Limits (PELs)
- 29CFRPart1910,SubpartsG
and Z, Occupational Safety and
Health Administration (OSHA)
EXPOSURE LIMITS
(29 CFR Part 1910.120)
Published Exposure Levels
- NIOSH Recommendations for
Occupational Health Standards,
1986
- American Conference of
Governmental Industrial Hygienists1
(ACGIH) Threshold Limit values
(TLVs) and Biological Exposure
Indices (BEIs) for 1987-1988
10/93
Exposure Limits and Action Levels
-------
NOTES
EXPOSURE LIMITS
Sources
OSHA
- PELs
- Legal requirements
- 1968 TLVs and American National
Standards Institute (ANSI)
- 29 CFR 1910.1000 (tables)
- Specific standards - benzene
EXPOSURE LIMITS
Sources
National Institute for Occupational
Safety and Health (NIOSH)
- Recommended exposure limits
(RELs)
- May be legal (1910.120)
- Rationale in criteria documents
- Immediately dangerous to life or
health (IDLH)
EXPOSURE LIMITS
Sources
ACGIH
- TLVs
- Recommendations
- May be legal (1910.120)
- Yearly booklet
- Documentation
Exposure Limits and Action Levels
10/93
-------
NOTES
EXPOSURE GUIDELINES
Sources
American Industrial Hygiene
Association (AIHA)
- Workplace environmental
exposure levels (WEELs)
- Recommendations
- Yearly updates
- Documentation
EXPOSURE GUIDELINES
Sources
Other
- U.S. Army and U.S. Air Force
- Mine Safety and Health
Administration (MSHA)
- Other countries (e.g., Federal
Republic of Germany maximum
concentration values in the
workplace (MAKs))
TIME-WEIGHTED AVERAGE
(TWA)
c
o
Q)
O
C
o
O
750
TWA-EL
6AM
10AM
Time
3PM
10/93
Exposure Limits and Action Levels
-------
NOTES
TIME-WEIGHTED AVERAGE CALCULATION
Exposures: 1500 ppm for 1 hour
500 ppm for 3 hours
200 ppm for 4 hours
(1 hr)(1500 ppm) + (3 hrs)(500 ppm) + (4 hrs)(200 ppm)
8hrs
1500 ppm -I- 1500 ppm + 800 ppm
8
475 ppm
SHORT-TERM EXPOSURE LIMIT
(STEL)
c
o
w
2
-*-»
0)
o
c
0
O
1000
750 -
STEL
TWA-EL
6AM
3PM
STEL
Excursions to the STEL
• Should not be longer than 15
minutes in duration (OSHA, NIOSH,
ACGIH)
• Should be at least 60 minutes
apart (ACGIH)
• Should not be repeated more than
4 times per day (ACGIH)
• Supplement TWA
Exposure Limits and Action Levels
10/93
-------
NOTES
CEILING
(C)
Ceiling
3PM
CEILING
The exposure that shall not be exceeded
during any part of the work day. If
instantaneous monitoring is not feasible,
the ceiling shall be assessed as a 15-minute
TWA exposure (unless otherwise specified)
that shall not be exceeded at any time
during a work day
Source: NIOSH Recommendations for Occupational Safety and Health. 1092.
COMPARISON OF EXPOSURE LIMITS
Chemical
Acetone
Benzene
Lead (mg/m8)
Benzaldehyde
OSHA NIOSH
1000* 250
1/5 0.1 /C1
0.05 <0.1
NA NA
ACGIH
750/1000
10 (0.1)
0.15 (0.05)
NA
Note: * units are ppm; TWA/STH
( ) indicates intended change
4/94
Exposure Limits and Action Levels
-------
NOTES
IDLH
"...means an atmospheric concentration
of any toxic, corrosive, or asphyxiant
substance that poses an immediate threat
to life or would cause irreversible or
delayed adverse health effects or would
interfere with an individual's ability to
escape from a dangerous atmosphere."
Source' 29 CFR 1910 120(e)
IDLH
IDLH concentrations represent the maximum
concentration from which, in the event of
respirator failure, one could escape within
30 minutes without a respirator and without
experiencing any escape-impairing or
irreversible health effects.
Note: IDLH level defined by the Standards
Completion Program - NIOSH/OSHA -
only for purposes of respirator selection
IDLH VALUES
Examples
Chemical
IDLH
Acetone
Benzene
Lead
Tetraethyl lead
Benzaldehyde
Source: NIOSH Pocket Guide to Chemical Hazards. 1990.
20,000 ppm (LEL?)
Ca (3000 ppm)
700 mg/m3
40 mg/m3
Not available
Exposure Limits and Action Levels
10/93
-------
EVALUATION OF A MIXTURE
= C/L1+C2/L2 +... Cn/Ln
Em = the equivalent exposure for the mixture
C = the concentration of a particular contaminant
L = the exposure limit for that contaminant
EVALUATION OF A MIXTURE
Example
Chemical A C = 500 ppm L = 750 ppm (TWA)
Chemical B C = 200 ppm L = 500 ppm (TWA)
Chemical C C = 50 ppm L = 200 ppm (TWA)
Em = (500/750) + (200/500) + (50/200)
Em = 0.67 + 0.40 + 0.25
EVALUATION OF A MIXTURE
Em should not exceed 1
•m
The calculation applies to chemicals
where the effects are the same and
are additive
Do not mix TWAs, STELs, or ceilings
NOTES
10/93
Exposure Limits and Action Levels
-------
NOTES
EXPOSURE LIMITS
Used to determine:
• Site characterization
• Medical surveillance
• Exposure controls
- Engineered controls
- Work practices
- Personal protective equipment
(PPE)
Source: 29 CFR 1910.120
THRESHOLD LIMIT VALUES
Not intended for use:
• As a relative index of toxicity
• In the evaluation or control of
community air pollution nuisances
• In estimating the toxic potential of
continuous, uninterrupted exposures
or other extended work periods
Source: ACGIH TLVs and BEIs for 1993-1994
THRESHOLD LIMIT VALUES
Not intended for use:
• As proof or disproof of an existing
disease or condition
• For adoption by countries whose
working conditions differ from those
in the United States of America and
where substances and processes differ
Source: ACGIH TLVs and BEIs for 1993-1994
Exposure Limits and Action Levels
10/93
-------
NOTES
ENVIRONMENTAL
EXPOSURE LIMITS
U.S. EPA
- National Ambient Air Quality
Standards Program (NAAQS)
State/Local
- NAAQS
- Modified TLVs
- Risk assessment
ACTION GUIDE
• The chemical concentration or instrument
reading at which a specific action should
be taken
• Sources:
- EPA Standard Operating Safety
Guides (SOSGs)
- OSHA standards for specific chemicals
may require an action (e.g., medical
monitoring) if one-half the PEL is
reached (action level)
EPA ACTION GUIDES
Combustible Gas Indicator
Level
Action
<10%LEL
<<5*)*
10-25% LEL
>25% LEL
Continue monitoring
with caution
Continue monitoring,
but with extreme
caution
Explosion hazard!
Withdraw from area
immediately.
Confined space
4/94
Exposure Limits and Action Levels
-------
NOTES
EPA ACTION GUIDES
Oxygen Concentration
Level
Action
<1fi.5% Monitor wearing SCBA.
10.5-25% Continue monitoring
with caution. SCBA
not needed based only
on oxygen content
>25% Discontinue monitoring.
Fire potential!
Consult specialist
Exposure Limits and Action Levels
4/94
-------
EXPOSURE LIMITS AND ACTION LEVELS
INTRODUCTION
It is necessary, for response activities involving hazardous materials, to acknowledge and plan that
response personnel may become exposed. Most hazardous materials have levels of exposure that can
be tolerated without adverse health effects. However, it is imperative to determine:
• The identity of materials involved
• The type and extent of exposure
• The possible health effects from overexposure
• The exposure limits and/or action levels considered safe for each hazardous material
encountered.
SOURCES FOR EXPOSURE LIMITS FOR AIRBORNE CONTAMINANTS
Several organizations have proposed exposure limits for chemicals and other hazards. The
Occupational Safety and Health Administration (OSHA) is one such organization. It is charged with
protecting the health and safety of workers. In 29 CFR 1910.120, the Hazardous Waste Operations
and Emergency Response standard, OSHA specifies the use of certain exposure limits. The exposure
limits that are 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 "N1OSH Recommendations for Occupational Health
Standards" dated 1986 incorporated by reference. If none is specified, the exposure
limits published in the standards specified by the American Conference of
Governmental Industrial Hygienists in their publication "Threshold Limit Values and
Biological Exposure Indices for 1987-88" dated 1987 incorporated by reference. (29
CFR 1910.120 (a)(3))
Organizations that have developed exposure limits are discussed below. Not all of these groups are
specifically mentioned in 1910.120. Many of the following organizations have exposure guidelines
for exposures to hazards other than airborne contaminants (e.g. heat stress, noise, radiation). This
part will deal only with airborne chemical exposures.
Occupational Safety and Health Administration
In 1971, the OSHA promulgated PELs. These limits were extracted from the 1968 American
Conference of Governmental Industrial Hygienists' (ACGIH) threshold limit values (TLVs), the
American National Standards Institute (ANSI) standards, and other federal standards. The PELs are
found in 29 CFR 1910.1000. Since then, additional PELs have been adopted and a few of the
10/93 \ Exposure Limits and Action Levels
-------
originals have been changed. These initial changes have been incorporated into specific standards
for chemicals (e.g., 29 CFR 1910.1028 - benzene). There are also standards for 13 carcinogens for
which there is no allowable inhalation exposure.
OSHA is a regulatory agency. Therefore, its PELs are legally enforceable standards and apply to
all private industries and federal agencies. Depending on state or local laws, the PELs may also
apply to state and local employees.
National Institute for Occupational Safety and Health
NIOSH was formed at the same time as OSHA. NIOSH conducts scientific research and
recommends occupational safety and health standards. The exposure levels NIOSH has researched
have been used to develop new OSHA standards. However, many recommended exposure limits
(RELs) have not been adopted by OSHA. Unless OSHA adopts NIOSH RELs into a standard (like
1910.120), they are only recommendations. The RELs are found in the NIOSH Recommendations
for Occupational Health Standards.
NIOSH also publishes criteria documents that provide information on handling specific chemicals.
These documents also provide rationale for the chemical's exposure limit. Additionally, NIOSH
publishes immediately dangerous to life or health (IDLH) values in its Pocket Guide to Chemical
Hazards. IDLHs will be discussed later.
American Conference of Governmental Industrial Hygienists
One of the first groups to develop exposure limits was 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 TLVs.
"Threshold Limit Values (TLVs) refer to airborne concentrations of substances and represent
conditions under which it is believed that nearly all workers may be repeatedly exposed day after day
without adverse health effects." (Threshold Limit Values for Chemical Substances and Physical
Agents and Biological Exposure Indices, ACGIH). The publication further states that the TLVs "are
developed as guidelines to assist in the control of health hazards. These recommendations or
guidelines are intended for use in the practice of industrial hygiene, to be interpreted and applied
only by a person trained in this discipline." (Policy Statement on the Uses of TLVs and BEIs).
Along with the TLVs, ACGIH publishes biological exposure indices (BEIs). BEIs are to be used
as guides for evaluation of exposure where inhalation is not the only possible route of exposure.
Because the TLVs are for inhalation only, they may not be protective if the chemical is ingested or
absorbed through the skin. Biological monitoring (e.g., urine samples and breath analysis) can be
used to assess the overall exposure. This procedure 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.
Exposure Limits and Action Levels 2 10/93
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The TLVs are reviewed yearly and are published in ACGIH's Threshold Limit Values for Chemical
Substances and Physical Agents and Biological Exposure Indices.
American Industrial Hygiene Association (AIHA)
The AIHA 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. Although the list is not as large as others,
AIHA has chosen chemicals for which other groups have not developed exposure limits. Thus, they
are providing information to fill the gaps in information sources.
Other Organizations
In the United States, the Army and Air Force have also developed exposure limits for their purposes.
The Mine Safety and Health Administration (MSHA) has health standards for air contaminants that
may be encountered during mining activities.
Other countries have also developed exposure limits. An example are the Federal Republic of
Germany's maximum concentrations at the workplace (MAKs). They can be found in ACGIH's
Guide to Occupational Exposure Values along with PELs, RELs, and TLVs.
Even though the other organizations are not part of the list of published exposure limits in 1910.120,
they are sources that may be useful. 1910.120 (g) suggests looking at published literature and
material safety data sheets (MSDS) if PELs or published exposure limits do not exist.
TYPES OF EXPOSURE GUIDELINES
Although there are different organizations that develop exposure guidelines, the types of guidelines
they produce are similar.
Time-Weighted Average (TWA)
A TWA exposure limit is the average concentration of a chemical most workers can be exposed to
during a 40-hour work week and a normal 8-hour work day without showing any toxic effects.
Some TWA exposure limits (e.g., NIOSH) can also be used to evaluate exposures up to 10 hours.
The TWA permits exposure to concentrations above the limit, provided these excursions are
compensated by equivalent exposure below the TWA. Figure 1 shows an example that illustrates
this point for a chemical (e.g., acetone) with a TWA exposure limit of 750 ppm.
A TWA exposure is determined by averaging the concentrations during the different exposure periods
over an 8-hour period with each concentration weighted based on the duration of exposure. For
example, an exposure to acetone at the following concentrations and durations would have an 8-hour
TWA exposure of:
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1500 ppm for 1 hour
500 ppm for 3 hours
200 ppm for 4 hours
(1 ftr)(1500 ppm) + (3 M(500 ppm) * (4 hrs)(2W ppm)
8 hrs
1500
+ 1500 /y?m + 800 ppm _
8
This exposure would be compared to an 8-hour TWA exposure limit.
c
o
•J5 750
CD
o
c
O
O
TWA-EL
3PM
FIGURE 1. EXAMPLE OF AN EXPOSURE COMPARED TO A TWA EXPOSURE LIMIT
Short-Term Exposure Limit (STEL)
The excursions allowed by the TWA exposure could involve very high concentrations. This might
cause an adverse effect but still be within the allowable average. Therefore, some organizations felt
there was a need to limit these excursions. OSHA, NIOSH, and ACGIH define the STEL as a 15-
minute TWA exposure limit. ACGIH has the additional stipulation that excursions to the STEL
should not be longer than 15 minutes in duration, should be at least 60 minutes apart, and should not
be repeated more than 4 times per day. Figure 2 illustrates an exposure that does not exceed the
Exposure Limits and Action Levels
10/93
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15-minute limit for an STEL of 1000 ppm (note that in the previous example of an 8-hour TWA
calculation, the acetone STEL was exceeded but the TWA was not).
The STEL supplements the TWA and does not replace it. Both exposure limits should be used. The
STEL reflects an exposure limit protecting 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.
AIHA has some short-term TWAs that are 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.
c
o
'•§
•f-1
0
o
c
o
o
STEL
TWA-EL
6AM
3PM
FIGURE 2. EXAMPLE OF AN EXPOSURE COMPARED TO AN STEL AND A TWA
Ceiling (C)
Ceiling values exist for substances for which exposure could result in a rapid and specific response.
The ceiling is that concentration that should not be exceeded during any part of the work day. If
instantaneous monitoring is not feasible, the ceiling shall be assessed as a 15-minute TWA exposure
(unless otherwise specified) that shall not be excluded at any time during a work day. A ceiling
value is denoted by a "C" preceding the exposure limit.
Figure 3 illustrates an exposure that exceeds a ceiling value of 5 ppm.
10/93
Exposure Limits and Action Levels
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c
o
'2
•4—•
c
CD
O
C
o
O
0
Ceiling
6AM
10AM
Time
3PM
FIGURE 3. EXAMPLE OF AN EXPOSURE COMPARED TO A CEILING EXPOSURE LIMIT
Peaks
"Acceptable maximum peak" concentrations can be found in OSHA's 1910.1000 Table 7.-1.
Table ~L-1 contains exposure limits that OSHA had adopted from ANSI. This peak exposure is an
allowable excursion above the ceiling values for the chemicals. The duration and number of
exposures at this peak value is limited. For example, for those industries not incorporated in
1910.1028, OSHA allows the 25-ppm ceiling value for benzene to be exceeded to 50 ppm, but only
for 10 minutes during an 8-hour period.
Skin Notation
Whereas these exposure guidelines are based on exposure to airborne concentrations of chemicals,
the organizations 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 are few data available that quantify the amount of
allowable skin contact.
Some organizations provide qualitative information about skin-absorbable chemicals. When a
chemical has the potential to contribute to the overall exposure by direct contact with the skin,
mucous membranes, or eyes, it is given a "skin" notation.
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 limit for inhalation may not provide adequate
Exposure Limits and Action Levels
10/93
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protection. The inhalation exposure limit is designed for exposures only from inhalation. If
additional routes of exposure are added, there can be detrimental effects even if the inhalation
exposure limit is not exceeded.
Immediately Dangerous to Life or Health (IDLH)
As defined in the NIOSH Pocket Guide to Chemical Hazards, "IDLH concentrations represent the
maximum concentration from which, in the event of respirator failure, one could escape within 30
minutes without a respirator and without experiencing any escape-impairing or irreversible health
effects." Although 30 minutes is stated in the definition, this is not a 30 minute allowable exposure
limit. NIOSH's purpose in developing this IDLH was for respirator selection.
Other organizations, such as ANSI, OSHA, and MSHA, have similar definitions for IDLH, but not
always the same application. It is accepted by all of these groups that IDLH conditions include 1)
toxic concentrations of contaminants, 2) oxygen-deficient atmospheres, and 3) explosive, or near-
explosive (above, at, or near the lower explosive limits), environments.
Guidelines for potentially explosive, oxygen-deficient, or radioactive environments can be found in
the EPA's Standard Operating Safety Guides and the NIOSH/OSHA/USCG/EPA publication entitled
Occupational Safety and Health Guidance Manual for Hazardous Waste Site Activities.
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 concentration values for many substances can be found in the NIOSH Pocket Guide
to Chemical Hazards. For some chemicals, NIOSH gives a "Ca" designation along with a
concentration for IDLH. Ca denotes those chemicals that NIOSH considers to be potential human
carcinogens. NIOSH recommends the highest level of respiratory protection for exposure to these
substances, even below IDLH. However, carcinogenic effects were not considered when developing
the IDLH concentrations.
MIXTURES
The exposure limits that have been discussed are based on exposure to single chemicals. Because
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 following calculation is used:
Em = (C,-L,) + (C^l^) + . . . (Cn-Ln)
where:
Em = the equivalent exposure for the mixture
C = the concentration of a particular contaminant
L = the exposure limit for that substance.
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The value of Em should not exceed unity (1).
An example using this calculation would be as follows:
Chemical A C = 500 ppm; L = 750 ppm (TWA)
Chemical B C = 200 ppm; L = 500 ppm (TWA)
Chemical C C = 50 ppm; L = 200 ppm (TWA)
Em = (500+750) + (200+500) + (50+200)
Em = 0.67 + 0.40 + 0.25
Em = 1.3
Because Em exceeds unity, the exposure combination may be a problem. The next step should be
to determine whether exposure limits are based on similar effects. 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. Also, mixing TWA, STEL, and ceiling limits in this equation is not
appropriate.
APPLICATION OF EXPOSURE GUIDELINES
OSHA's Hazardous Waste Operations and Emergency Response standard specifies uses for exposure
limits.
Site Characterization
29 CFR 1910.120 (c) (3) requires identification of IDLH conditions during site characterization.
29 CFR 1910.120 (h) (3) requires air monitoring upon initial entry to identify IDLH conditions,
other dangerous conditions, and exposures over the exposure limits.
Medical Surveillance
29 CFR 1910.120 (0 (2) (i) requires a medical surveillance program for all employees exposed to
substances or hazards above the PEL for 30 or more days per year. If there is no PEL, then the
published exposure levels are used for evaluation. The exposures are considered even if a respirator
was being used at the time of exposure.
Exposure Controls
Engineered Controls and Work Practices
29 CFR 1910.120 (g) (1) (i) states "Engineering controls and work practices shall be instituted to
reduce and maintain employee exposure to or below the permissible exposure limits for substances
regulated by 29 CFR Part 1910, to the extent required by Subpart Z, except to the extent that such
Exposure Limits and Action Levels 8 10/93
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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 are used. If
there are no PELs or published exposure limits, published literature and MSDS may be used for
evaluation. In these circumstances, a combination of engineering controls, work practices, and
personal protective equipment (PPE) shall be used to reduce and maintain exposures.
Personal Protective Equipment
Because the selection of PPE must be based on the hazards present at the site, the exposure limits
are used to evaluate the appropriate PPE. Comparing the actual or expected exposure to the PEL
or other exposure limits gives the wearer information on selection of the proper PPE.
LIMITATIONS AND RESTRICTIONS OF USE
The exposure guidelines discussed in this section are based on industrial experience, experimental
human studies, experimental animal studies, or a combination of the three. The guidelines were
developed for workers in the industrial environment. Thus, they are not meant to be used for other
purposes. ACGIH in its Threshold Limit Values and Biological Exposure Indices states:
These limits are intended for use in the practice of industrial hygiene as guidelines
or recommendations in the control of potential health hazards and for no other use,
e.g., in the evaluation or control of community air pollution nuisances; in estimating
the toxic potential of continuous, uninterrupted exposures or other extended work
periods; as proof or disproof of an existing disease or physical condition; or adoption
by countries whose working conditions differ from those in the United States of
America and where substances and processes differ. These limits are not fine lines
between safe and dangerous concentration nor are they a relative index of toxicity.
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 to 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, consult the documentation for the exposure limit along with other toxicological data.
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NON-OCCUPATIONAL EXPOSURE LIMITS
As mentioned earlier, the occupational exposure limits are not intended for use in evaluating public
health hazards. However, they are often used because there may not be anything else available. In
other situations, a group may feel that the exposure may be for a short duration and the occupational
exposure limits are adequate. For example, many computer air dispersion models for emergency
response use the TLVs as action levels.
Some agencies have applied modifiers to the occupational exposure limits to adjust them for public
health use. These modifiers may include adjustments for exposure time (168 hours for the public
compared to 40 hours for occupational situations) and safety factors for sensitive populations
(dividing the exposure limit by 10). While groups like ACGIH discourage this application of their
data, the users argue that modification of human data is preferred to extrapolation of animal data.
In some cases, ambient air quality standards or guidelines have been developed for application to
public exposure. The federal government and many states have developed them. They are based
on modification of occupational exposure limits, risk assessment data, or both. EPA has developed
national ambient air quality standards in response to the Clean Air Act. The current list is very
limited and only some chemicals (e.g., lead and particulates) are applicable to waste sites.
In the risk assessment approach for chemical exposure, it is recognized that the public exposure to
a chemical may involve more than one route of exposure. With this approach, it is not appropriate
to use just an inhalation exposure limit. Results from air sampling are combined with other sample
results (e.g., drinking water and soil) to determine total exposure and risk.
ACTION LEVELS
Action levels can be developed for specific chemicals, hazards, or situations. The concept of an
action level is that if the action level is not exceeded, then there is little probability that a hazardous
exposure will occur.
In some of its specific standards, OSHA uses an action level that is one-half of the PEL. For
example, the action level for benzene is 0.5 ppm calculated as an 8-hour TWA. If this level is
exceeded, continual air monitoring and medical surveillance can be required.
EPA in its Standard Operating Safety Guides gives actions to take if certain instrument readings
(levels) are obtained during monitoring. These are listed in Table 1.
In some situations, site-specific action levels for direct-reading instruments may be developed. This
is done by using knowledge about what chemicals are present on the site and the instrument's
response to the chemicals. Whereas this may not be as accurate as using special monitoring
equipment and laboratory analysis, it allows rapid response to a potentially hazardous situation.
Exposure Limits and Action Levels 10 10/93
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CONCLUSION
There are many sources for exposure limits and action levels. Some of these are legal requirements;
some are guidelines. The goal is to use these numbers to protect personnel working with hazardous
materials.
10/93 11 Exposure Limits and Action Levels
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TABLE 1. ATMOSPHERIC HAZARD ACTION GUIDES
Monitoring
Equipment
Atmospheric
Hazard'
Level
Action
Combustible gas
indicator
Explosive <10%LEL Continue monitoring with caution.
10-25% LEL Continue monitoring, but with
extreme caution, especially as higher
levels are encountered.
>25% LEL Explosion hazard! Withdraw from
area immediately.
<19.5% Monitor wearing SCBA. Note:
Combustible gas readings not valid in
atmospheres with less than 19.5%
oxygen.
19.5-25% Continue monitoring with caution.
SCBA not needed based only on
oxygen content.
>25% Discontinue monitoring. Fire
potential! Consult specialist.
Oxygen
concentration
Radiation survey
instrument
Gamma
radiation
Above
background:
<1mR/hr
Continue monitoring. Consult a
Health Physicist.
Colorimetric
tubes
Photoionization
detector
Flame ionization
detector
Organic and
inorganic
vapors/gases
Organic
vapors/gases
Organic
vapors/gases
>1 mR/hr
Depends on
chemical
Depends on
chemical
Depends on
chemical
Withdraw. Continue monitoring only
upon the advice of a Health Physicist.
Consult reference manuals for air
concentration vs. PEL/TLV and
toxicity data.
Consult reference manuals for air
concentration vs. PEL/TLV and
toxicity data.
Consult reference manuals for air
concentration vs. PEL/TLV and
toxicity data.
• Hazard classes are general and not all compounds in these classes can be measured by realtime
instruments.
Note: The correct interpretation of any instrument readout is difficult. If the instrument operator
is uncertain of the significance of a reading, especially if conditions could be unsafe, a technical
specialist should immediately be consulted. Consideration should be given to withdrawing personnel
from the area until approval by the safety officer is given to continue operations.
Exposure Limits and Action Levels
12
10/93
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3. Role of Audit Team Members
3.1 Audit Team Composition
An EPA audit team consists primarily of EPA employees, and other designated
representatives, including contractors and the American Association of Retired Persons
(AARP) enrollees. The participation of other federal, state, and local government
personnel, particularly SERC and LEPC representatives, is encouraged, but they should
be made aware that they will be entering and accessing information from a facility under
their own authorities. Section 3.3 of this Manual further discusses the participation of
non-EPA audit team personnel.
The audit team can vary in size, depending upon the level of detail of the audit
(e.g., number of chemicals and/or processes under investigation; national significance).
At a minimum, however, there must be two technical experts on a team for collection
and verification of technical findings and observations. [Required Activity]
The following list represents suggested roles, responsibilities, associated
disciplinary backgrounds, and other parameters for composing a team. This list is
provided as guidance and in no way is a required format for forming an audit team. In
many cases, your team composition may require you to combine or divide roles.
Team Leader
Must be EPA employee; [Required Activity]
Coordinates audit logistics, makes team assignments, coordinates initial
liaison with facility personnel, and coordinates preparation and distribution
of final site visit report; and
Provides any needed follow-up information.
Deputy Team Leader
Must be EPA employee or designated representative; [Required Activity]
Provides logistical support, as directed by Team Leader; and
Assumes other responsibilities delegated by Team Leader.
Chemical Process Hazards Reviewer
Must be EPA employee or designated representative;
Responsible for collection and verification of process-related information;
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Primary liaison with facility technical personnel; and
Requires technical knowledge of chemical hazards, process engineering,
and maintenance procedures.
Chemical Accident Prevention Reviewer
Must be EPA employee or designated representative;
Responsible for collection and verification of facility information;
Liaison with appropriate facility technical personnel;
Requires technical knowledge of chemical accident prevention, including
hazard evaluation and modeling techniques and release
prevention/mitigation systems.
Safety and Training Reviewer
Must be EPA employee or designated representative;
Responsible for collection and verification of facility information;
Primary liaison with facility health and safety personnel; .
Requires knowledge of operator, safety, and worker right-to-know training
programs.
Emergency Planning and Response Reviewer
Must be EPA employee or designated representative;
Responsible for collection and verification of facility information;
Primary liaison with appropriate facility personnel responsible for planning
and response;
Requires knowledge of emergency planning and response requirements.
Technical expertise for the chemical safety audit program refers to knowledge,
experience, and disciplinary training in plant process design, engineering, operations,
training, and emergency planning. Example disciplines include:
Chemical, civil, industrial/safety, and environmental engineering,
Plant process experience,
Environmental science, ^
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Industrial hygiene,
Geology, and
Environmental and emergency management and planning.
Personnel with the appropriate expertise can be found in the following regional program
offices: media (e.g., air, water, radiation); RCRA; TSCA; Superfund (e.g., emergency
preparedness and response, removal, health, and safety); and Research and
Development.
In selecting team members, the skill base of the team must accommodate the
need for coverage of the major audit elements:
Process and safety system technologies;
Operating procedures;
Training programs;
Emergency planning activities; and
Management activities.
Specific tasks should be assigned to each team member. Each member should know
his/her respective role in all facets of the facility audit. Certain members may be
assigned the lead on one or more facets of the audit, and the other team members,
because of their individual skills and experiences, should be prepared to contribute to the
completion of that facet of the audit.
In summary, an EPA audit team can consist of EPA employees, EPA contractors
(e.g., Technical Assistance Team), AARP enrollees, and representatives from federal,
state, and local governments. Two basic restrictions apply to the "team;" one, the Team
Leader must be an EPA employee, and two, the Chemical Process Hazards Reviewer
must be an EPA employee or designated representative (i.e., EPA employee, contractor,
or AARP enrollee). [Required Activity] This last restriction is required to ensure
continuity in communicating the audit scope and intent.
The following provides an overview of the anticipated roles and responsibilities for
EPA employees, contractors/TAT personnel, and AARP enrollees:
EPA employees coordinate audit program and lead the audit team.
Contractors/TAT personnel provide technical support as defined by EPA.
AARP enrollees:
Provide support role in audits;
Apply professional expertise and experience in chemical engineering
or other technical or industrial fields for reviewing process safety
technologies at facilities;
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Apply other expertise in such areas as safety management or
training for involvement in other aspects of the audit (i.e., reviewing
emergency plans, training manuals, and emergency notification
procedures and/or systems);
Participate in report preparation, including observations and
recommendations from the audit;
Identify facilities for potential audits, using information sources such
as Accidental Release Information Program (ARIP) data, and
coordinate with regional response centers; and
Are limited to field activities that do not stress physical limitations.
3.2 Training and Safety Requirements
Field activities for EPA employees are subject to the training requirements
embodied in EPA Order 1440.2, Health and Safety Requirements for Employees
Engaged in Field Activities. The Order establishes policies, responsibilities, and
mandatory requirements for occupational health and safety training and certification, and
occupational medical monitoring.
EPA Order 1440.2 requires that a Site Safety Plan be developed for EPA
employees conducting a chemical safety audit at a facility handling hazardous substances.
EPA regional offices can either use the model site safety plan (see Attachment 3), or
develop their own program that complies with EPA Order 1440 and the Occupational
Safety and Health Administration's worker protection standards codified at 29 CFR 1910
and 1926. The plan should include a description of the proposed audit scope, facility
health hazards, necessary protective equipment, contractor participation, and
decontamination procedures, and must be completed and approved by the EPA project
coordinator, branch chief, on-scene supervisor, and health and safety manager. Under
certain circumstances, a more extensive plan may also be required. For more
information, contact the safety and health office in your region.
Audit team members should dress appropriately, including steel-toed boots, safety
glasses, and hard hats. Team members should provide their own safety equipment, and
should not rely on the facility.
Prior to participating in an audit, all EPA team members, which include EPA
employees, contractors, and AARP enrollees, must have completed the following training
courses:
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Training in occupational health and safety procedures under EPA Order
1440.2. Attending a 24-hour or 40-hour health and safety course that is
approved and sponsored by EPA and conducted by EPA or its contracted
agents fulfills the requirement of this Order; [Required Activity] and
EPA Chemical Safety Audit Training Course. (Course attendance
flexibility is discussed below.)
In addition to the listed training, annual medical monitoring is required. [Required
Activity]
In some audits, a specialized technical expert (i.e., contractor or other EPA
program personnel) who normally does not participate in CSA program activities will
assist in conducting the audit. Under these circumstances, it will be difficult for such an
individual to have taken the EPA CSA course. Consequently, the requirement for the
CSA course is flexible depending upon the situation. The health and safety training
requirements and medical monitoring, however, are not flexible. [Required Activity]
This requirement should not pose any problems, since it would be rare for a technically
qualified contractor or EPA employee not to have had this training.
Suggested topics for additional, but not required, training include:
Handling of confidential business information;
Interviewing techniques;
Hazard evaluation techniques;
Chemical processing techniques;
Negotiating techniques; and
Technical writing.
3.3 Non-EPA Personnel Participation on Audit Team
Non-EPA team members may include representatives of other federal agencies
and departments, states/SERCs, local officials/LEPCs, and any other group not previously
identified as an EPA team member. The regions are encouraged to invite participation
by non-EPA personnel in audits, but entry into the facility must be authorized pursuant
to authorities other than CERCLA. Participation of non-EPA personnel must be in a
support role as defined by the Team Leader. In addition, non-EPA personnel cannot
serve in the capacity of Team Leader or Chemical Process Hazards Reviewer. [Required
Activity]
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SERC and LEPC participation is encouraged to enhance their knowledge of
chemical hazards and process safety for use in planning activities under SARA Title III
and in future Clean Air Act Amendments Risk Management Program activities. SERCs,
LEPCs, and other federal agencies also serve as a valuable source of information in
preparing for the audit.
It is important to inform these representatives of the required health and safety
training that EPA employees and representatives undergo prior to audit participation.
As discussed in the next section, non-EPA participants require their own liability
coverage.
3.4 Liability
Liability associated with conducting audits is described in the following sections for
each group potentially represented on an audit team.
3.4.1 Federal Employees
Under the Federal Employees Liability Reform and Tort Compensation Act of
1988, a suit can no longer be maintained against a Federal employee in his or her
individual capacity for any act (discretionary or non-discretionary) performed within the
scope of the employee's employment. All such suits must now be brought against the
United States government. If named in a suit in his or her individual capacity, employees
should promptly notify the Office of Regional Counsel and the Office of General
Counsel.
The legislation does not change the potential liability of a Federal employee in his
or her individual capacity for grossly negligent actions (usually taking the action out from
under the scope of the employee's employment), for Constitutional violations, and for a
violation of a statute "for which a claim is otherwise authorized." All audit participants
should have audit responsibilities clearly delineated in their job description.
3.4.2 AARP Enrollees
There are no provisions for indemnifying AARP enrollees from personal liability
under the cooperative agreement between AARP and EPA. Since AARP enrollees serve
only in support roles in all aspects of CSA program implementation, the Regional
Chemical Emergency Preparedness and Prevention Coordinators and their staff are
responsible for ensuring that enrollees are not placed in situations that could result in
job-related personal liability.
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3.4.3 Technical Assistance Team Contractors
The Federal Employees Liability Reform and Tort Compensation Act of 1988
only covers TAT contractors when responding to a CERCLA hazardous substance
release or performing a clean-up/removal related to such release. Audit activities for
TAT contractors are not covered under this Act, since the contractor is not specifically
handling hazardous substances, pollutants, or contaminants. TAT contractors must
investigate liability coverage with their respective employer.
3.4.4 Federal, State/SERC and Local/LEPC Government Personnel
All non-EPA personnel will be entering a facility under their own authorities and
would require their own liability coverage.
3.5 Conflict of Interest
Conflict of interest refers to any person (i.e., EPA employee, contractor, AARP
enrollee, non-EPA personnel) who has a financial interest associated with the facility
being audited, has been previously employed with the facility, or a facility subsidiary,
and/or has been a consultant for the facility. Persons with conflict of interest should not
participate in any activities, either on-site or off-site, associated with the facility audit.
[Required Activity] In addition, such persons must identify themselves to the Team
Leader and excuse themselves from the audit of that facility. [Required Activity]
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4. Preparing for the Audit
4,1 Facility Selection
At present, there are no established procedures for selecting a facility for an audit.
Each region has flexibility in identifying facilities. A variety of options useful to
identifying a facility are discussed below. Although there is substantial flexibility in
facility selection, there are two important requirements:
A release of a CERCLA hazardous substance, pollutant, or contaminant
must have occurred, or there must be "reason to believe" that a threat of
such a release exists at the facility; [Required Activity] and
The Office of Regional Counsel and the SERC of the state where the
audited facility is located must be consulted to identify any legal actions
currently being pursued or anticipated. [Required Activity] It is advised
that regional media programs also be consulted.
The following list provides a variety of options to consider when selecting a
facility. Information sources to be used in evaluating these options include federal, state,
and local release notification reports and follow-up reports, OSC reports, Regional
Response Centers, ARIP, ERNS, and other sources (see Attachment 4 and chart in
section 4.3).
Previous release history of the facility;
SERC and/or LEPC referral;
Proximity to sensitive population(s);
Public sensitivity;
Opportunity for sharing new technology;
Population density; and
Concentration of industry in the area.
In addition, the region may wish to select facilities for a chemical safety audit as
part of a larger regional initiative, such as an evaluation of facilities using a specific
chemical or located near a particularly sensitive environment. For example, during fiscal
year 1992 a number of facilities that produce and use hydrogen fluoride were examined
by audit teams nationally, while Region 5 conducted all of its audits in coordination with
its Great Lakes Basin pollution prevention initiative.
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4.2 Facility Notification
Once a facility has been selected, the process of notifying the facility and (
scheduling the audit can be initiated. Although each region will invariably establish its
own procedures for notifying a facility and coordinating the audit, the following
suggestions and tools should be integrated into that process. These suggestions are
designed to help establish a constructive rapport with the facility and to ensure the
correct use of statutory authorities and other legal requirements.
The Team Leader should make an initial phone call to the facility owner/operator.
The purpose of this call is to identify a "contact" at the facility for all correspondences, to
communicate/explain the purpose and intent of the audit, and to schedule dates for
conducting the audit. In some instances, it may be useful to schedule a pre-audit meeting
with the facility to obtain further information.
The phone call should be followed by a letter to the facility contact that
summarizes the initial conversation and confirms any decisions made during the call. In
addition, the letter serves to confirm audit statutory authority, provide the facility an
opportunity to claim confidential information, and to identify the contractor, if a
contractor is participating. As previously stated in section 2.2.3 of this Manual, the
contractor must be identified by contractor name and contract number in order to have
access to confidential information.
Attachment 5 is a sample letter designed to fulfill the above goals. While
language may be added to the letter, such as a summary of a phone conversation, the A
legal aspects of the letter as contained in the attachment should not be materially "
altered. [Required Activity] It is suggested that all correspondence with the facility be
reviewed by the Office of Regional Counsel (ORC).
Unfortunately, not all efforts to schedule and coordinate an audit based upon the
voluntary consent of the facility will be successful. After receiving either the facility's
written or verbal denial of EPA's request to conduct the audit, a letter must be sent to
the facility (1) confirming this denial; and (2) invoking use of the CERCLA 104(b) and
104(e) authorities for entry. [Required Activity] Attachment 6 contains a sample letter
specifically designed for this situation. Preparation of this letter must be coordinated
with your Office of Regional Counsel. [Required Activity] The suggested letter states
that continued refusal of facility access can result in EPA issuing an order requesting
entry and/or initiating an enforcement action. Any further activities and contact with the
facility should be pursued in coordination with the Office of Regional Counsel.
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4.3 Facility Background Information
Preliminary preparation is an important factor in conducting an organized audit.
The team may find it useful to collect the facility background information several weeks
in advance of the audit. This will require contact with the facility and state and local
officials to arrange delivery of these materials. The audit team can then review this
information and become more familiar with the facility prior to the audit. Using this
technique, the team will be able to prepare a detailed list of topics and questions to help
organize their activities during the facility visit. The following list is a sampling of the
types and sources of information that will assist a team in preparing for the audit:
Type of Information
Release History
Regulatory History
Hazardous Chemicals
(Hazards, Amounts,
and Locations)
Chemical Processes
Community Involvement
Sources of Information
OSC reports; ARIP questionnaires; ERNS; SARA
Title III sections 304 and 305(b) reports; state
release files
Local, state, and federal air, water, and waste
permits; SARA Title III sections 302, 304, 311, 312,
and 313 submissions
SARA Title III sections 311 and 312 submissions;
OSHA hazard communication and process safety
management standard documents; hazards analysis;
NIOSH Pocket Guide to Chemical Hazards
Industry standards and processing techniques from
trade and professional groups (e.g., AIChE, ASSE,
and the Chlorine Institute); process flow diagrams
and piping and instrumentation diagrams
CAER; LEPC; and SERC
The "Audit Protocol/Report Preparation Guidance" as presented in section 6.0 of
this Manual provides further detail on the types of information that may be requested
from the facility prior to conducting the audit. Attachment 4 contains further
information on these listed sources.
4.4 Preparing for the Site Visit
Prior to conducting the on-site audit, a pre-visit meeting should be conducted with
the entire audit team, including any non-EPA personnel who will be visiting the facility.
This meeting should be held as close to the date of the site visit as possible to keep the
important points being emphasized fresh in everyone's mind. By this time, the audit
team should already be operating as a unit; all team members should be familiar with the
audit protocol, the information previously collected by the team should have been
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reviewed, additional information to be obtained at the facility should have been
identified, and the team members should have developed individual agendas. The pre-
visit meeting serves to reinforce what already is in place and should cover the following
items:
Clearly establish the responsibility and authority of the team leader;
Review highlights of the audit's objectives and note any specific team
member responsibilities;
Review any personal health and safety issues that may be present at the
site for the team to prepare for and avoid (see section 3.2);
Review information about key personnel and operations at the site;
Establish objectives and an agenda for each day of the site visit;
Caver logistical matters such as a nightly team meeting to discuss results
and plan the next day's activity; and
Cover any other topics that the Team Leader identifies.
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5. Conducting the Audit
The on-site chemical safety audit will consist of the following four phases:
Entry;
Opening Meeting;
On-site Activities; and
Exit Briefing.
5.1 Entry
The audit team should arrive at the facility during normal working hours at a time
and date pre-determined with the facility. At the facility entrance office, the facility may
provide a blank sign-in sheet, log, or visitor register. It is acceptable for the audit team
members to sign it. EPA employees and authorized representatives, however, must not
sign any type of "waiver" or "visitor release" which would relieve the facility of
responsibility for injury, or which would limit the rights of the Agency to use the data
obtained from the facility. [Required Activity] When such a waiver or release is
presented, the Team Leader should politely explain that such a document cannot be
signed, and a blank sign-in sheet should be requested. If the team is refused entry
because they do not sign such a release, the Team Leader must report all pertinent facts
to the ORC, and leave the facility if the matter cannot be resolved. [Required Activity]
All events surrounding the refused entry must be fully documented including the name of
the person(s) refusing entry. [Required Activity] Procedures described in section 4.2 of
this Manual concerning refusal of entry must then be followed. [Required Activity]
5.2 Opening Meeting
The entire audit team will meet with the plant manager and his/her key staff, and
will likely discuss the entire audit. The staff of the plant manager could include
superintendents of safety and operations, a lawyer, and corporate representation. The
team should be very clear about its purpose and should be prepared to discuss the audit
starting with an explanation of the CSA program, facility selection, the audit purpose and
scope, the background research performed, the specific objectives for the site visit, and
the report that will be written.
During the meeting, the audit team should outline its specific on-site agenda and
the cooperation needed to accomplish that agenda. In addition, the meeting provides a
good opportunity for the facility to provide the audit team with an overview of its
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operations and safety programs and may include a general tour of the whole facility (as
appropriate). This meeting typically requires at least a half day.
5.3 On-Site Activities
Once past the opening meeting, the audit team may split up into smaller groups to
take a plant tour and interview other operations and management personnel. The plant
tour should include specific tours of the chemical handling and process areas. The team
should interview personnel involved in such areas as process safety, process operations,
technical support, personnel, emergency planning and response, and environmental
management.
During these tours and interviews, individual team members should be obtaining
information and making observations that fulfill the needs of their individual
responsibilities. The questions and prompts for discussion contained in the annotated
audit protocol can be helpful.
During this or any other part of the site visit, it is possible that an observation will
be made or that information will be obtained that should be of significance to the audit
team, but that is beyond the scope of the facility audit. In this event, the Team Leader
should be notified.
5.4 Exit Briefing 4
In this final meeting, the entire audit team will meet with the plant manager and
his/her key staff to discuss the results of the audit as it presently stands. The plant
manager may be accompanied by the same people who attended the opening meeting.
The facility will want to know about all significant team findings and, more importantly,
about the conclusions that have been drawn and the recommendations that will be made.
Prior to the exit briefing, the audit team should have a private meeting to
establish an agenda for this meeting. Significant observations and findings should be
listed for discussion with the facility. The team should identify conclusions based on this
information only to the extent that a consensus among team members can be reached. A
team consensus is also necessary for identifying any recommendations to the facility at
this time. In the absence of team consensus, it is inappropriate to offer conclusions or
recommendations to the facility during the exit briefing. This does not, however,
preclude drawing such conclusions or making any recommendations in the audit report
that will be written later.
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6. Audit Protocol/Report Preparation Guidance
6.1 Purpose and Structure
This protocol/report preparation guidance (see Exhibits 1 and 2) provides a
detailed topic outline to direct the scope and content of the audit and a structure for
preparation of the audit report. The protocol and report format have been integrated to
accomplish the following goals:
Provide detailed guidance on the types of information that should be
reviewed during the audit and discussed in the report;
Ensure continuity in report preparation; and
Provide an organized and detailed report format for easy access to specific
lessons learned on chemical process safety management practices.
Because of the scope of the audit or the resources and expertise of the audit
team, it may not need, or be able, to address all areas of the protocol. However, all
areas of the protocol should be addressed in the audit report (e.g., state that the audit
team did not review the facility's hazard evaluation and modeling capabilities).
By providing this Manual to facility personnel prior to conducting the audit, the
facility will also have a more thorough understanding of the audit scope and intent. The
facility can prepare for the audit by assembling information and identifying personnel
with the required expertise to assist the audit team.
This guidance is structured to address each of the major elements of chemical
process safety management at the facility being audited. These include:
Facility Background Information;
Chemical Hazards;
Process Hazard Information;
Chemical Accident Prevention;
Accidental Release/Incident Investigation;
Facility Emergency Preparedness and Planning Activities;
Community Emergency Planning and Response Activities; and
Public Alert and Notification Procedures.
Preceding each of these sections in the annotated protocol/report guidance
(Exhibit 2) is a brief overview of the purpose of this section with respect to the audit
scope.
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Exhibit 1
Outline of Protocol/Report Preparation Guidance
1.0 INTRODUCTION
2.0 SUMMARY OF FINDINGS/CONCLUSIONS
3.0 BACKGROUND
3.1 General Facility and Audit Information
3.2 Purpose of the Audit and Facility Selection Process
3.3 Audit Methodology
4.0 FACILITY BACKGROUND INFORMATION
4.1 Site and Surrounding Area Description
4.1.1 Facility Profile
4.1.2 Site Topography and Meteorological Conditions
4.1.3 Site Access
4.1.4 Special/Sensitive Populations and Environments
4.1.5 Regional Demographics
4.1.6 Identification of Vulnerable Zones A
5.0 CHEMICAL HAZARDS
5.1 Overview of Hazards for Chemical(s) Being Audited
5.2 Facility Management of Chemical Hazard Data
6.0 PROCESS INFORMATION FOR HAZARDOUS CHEMICALS
6.1 Storage and Handling
6.1.1 Storage Systems
6.1.2 Shipping/Receiving
6.1.3 Material Transfer
6.2 Process Description
6.2.1 Overview of Processing Steps and Operating Procedures
6.2.2 General Description of Process Equipment Capacity
6.2.3 Back-ups and Redundancy
6.2.4 Process Parameter Monitoring
6.2.5 Environmental Monitoring
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6.3 Process Hazards
7.0 CHEMICAL ACCIDENT PREVENTION
7.1 Management Activities
7.1.1 Corporate Role in Facility Process Safety Management
7.1.2 Facility Role in Process Safety Management
7.1.3 Audit Activities and Procedures
7.2 Process Operation and Maintenance
7.2.1 Standard Operating Procedures
7.2.2 Training Practices
7.2.3 Equipment Maintenance Procedures
7.2.4 Instrument Maintenance
7.3 Hazard Evaluation and Modeling
7.3.1 Hazard Evaluation
7.3.2 Modeling
7.4 Release Prevention Systems
7.5 Mitigation Systems
8.0 ACCIDENT RELEASE INCIDENT INVESTIGATION
8.1 History of Accidental Releases/Incidents
8.2 Facility Investigation Procedures
9.0 FACILITY EMERGENCY PREPAREDNESS AND PLANNING ACTIVITIES
9.1 Facility Emergency Response Plan
9.2 Emergency Response Exercises and Simulations
9.3 Fire, Evacuation, and Rescue Corridors
9.4 Emergency Equipment Provisions
9.5 Emergency Response Chain of Authority
9.6 Emergency Response Management Procedures
9.7 Emergency Communication Network within the Facility
9.8 Emergency Response Personnel Training Requirements
9.9 Follow-up Release Procedures
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10.0 COMMUNITY AND FACILITY EMERGENCY RESPONSE PLANNING
ACTIVITIES
10.1 Facility Planning and Outreach Activities with Community
10.2 Local/Community Emergency Response Planning
11.0 PUBLIC ALERT AND NOTIFICATION PROCEDURES
11.1 Procedures for Public Notification of Releases
11.2 Schedule for Testing Procedures
11.3 History of Notification Procedures and Evaluation
11.4 Community and Facility Contacts
11.5 Facility and Media Interaction
12.0 CONCLUSIONS
13.0 RECOMMENDATIONS
APPENDICES
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Exhibit 2
Annotated Protocol/Report Preparation Guidance
STANDARD DISCLAIMER (see Attachment 7)
1.0 INTRODUCTION
Purpose and scope of the audit program (Attachment 8 contains standard
language to describe the purpose and scope of the program); and
Paragraphs identifying facility name and location and why audited
2.0 SUMMARY OF FINDINGS/CONCLUSIONS
Briefly summarize audit findings (both positive and negative)
3.0 BACKGROUND
3.1 GENERAL FACILITY AND AUDIT INFORMATION
Facility name, location, principal activities;
Dates audit conducted; and
Listing of team members and their affiliation, areas of responsibility,
and expertise.
3.2 PURPOSE OF THE AUDIT AND FACILITY SELECTION PROCESS
Briefly explain why facility was selected. Audit could be conducted
for a number of reasons such as:
To follow up on an accidental release or series of releases
(include description of triggering incident);
To focus on particular technologies, processes, operations, or
chemicals;
Regional or headquarters initiatives;
At request of state and/or local officials; or
At facility invitation.
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3.3 AUDIT METHODOLOGY
Summary of the process areas and other locations that were
investigated and why they were selected; and
Important audit limitations (e.g., no comparison of safety systems
across several similar operations was performed).
4.0 FACILITY BACKGROUND INFORMATION
A history of site activities and a description of the surrounding area provides
information on the potential risk that facility activities may pose to the surrounding
community and the environment in the event of an accidental chemical release.
4.1 SITE AND SURROUNDING AREA DESCRIPTION
4.1.1 Facility Profile
Facility history and principal activities (i.e., date built,
modifications and improvements, releases, etc.), size and
layout, and ancillary operations (e.g., power generation,
warehouse, distribution center, laboratory, waste treatment,
etc.); and
Reference maps in appendix or use simple maps in text.
4.1.2 Site Topography and Meteorological Conditions
Natural disaster potential (e.g., earthquake, flood);
Geology; and
Climate.
4.1.3 Site Access
Transportation routes, including railroad and waterways; and
Site security (e.g., fencing and gates, security guards, and
access by non-authorized persons).
4.1.4 Special/Sensitive Populations and Environments
Hospitals, schools, and nursing homes; and
Wetlands, drinking water supply, etc.
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4.1.5 Regional Demographics
Economy, population, industrial and growth patterns
4.1.6 Identification of Vulnerable Zones
5.0 CHEMICAL HAZARDS
This section serves to not only focus briefly on the hazards associated with
particular substances, but to provide pertinent facts on the facility's understanding of
what are the chemical hazards for each substance.
5.1 OVERVIEW OF HAZARDS FOR CHEMICAL(S) BEING AUDITED
Brief description of hazards; and
Reference detailed information in appendix (i.e., MSDS, etc.) -- do
not rewrite MSDS information.
5.2 FACILITY MANAGEMENT OF CHEMICAL HAZARD DATA
What the facility recognizes as the hazards associated with the
chemical(s);
Documentation available on hazards associated with chemical(s)
(e.g., MSDS, corrosion rates, reactivity data, etc.);
Availability of such data to employees (e.g., OSHA Hazard
Communication Standard training);
Mechanism for reviewing and updating information;
Mechanism for documenting suspected acute and chronic toxic
effects (e.g., medical and industrial hygiene personnel); and
On-site availability of emergency medical care.
6.0 PROCESS INFORMATION FOR HAZARDOUS CHEMICALS
A review of facility operations associated with the processing of the chemical(s)
being examined can reveal facility practices and techniques for handling process hazards,
as well as reveal facility understanding of the process hazards. (Within each subsection,
the report should address every chemical and process examined during the audit for
which observations, conclusions, and/or recommendations were noted.)
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6.1 STORAGE AND HANDLING
6.1.1 Storage Systems
Storage methods;
Capacity;
Location, including compatibility and spacing;
Hazard identification (placards and labelling);
Maintenance and housekeeping of area; and
Block diagrams to illustrate major process flows.
6.1.2 Shipping/Receiving
Method(s) of receiving and shipping (e.g., tank trucks, rail
cars, pipelines, cylinders, barges, etc.);
Schedules and quantities of shipments;
Responsible personnel and level of training;
Coordination of transportation issues with the community
contingency plan; and
Transportation corridors used.
6.1.3 Material Transfer
Transfer method(s) from storage to processing areas and
between different stages of process;
Pipe coding/labelling for flow direction and contents;
Other transfer systems (e.g., compressors, ejectors, pumps,
blowers, etc.);
Housing of transfer systems; and
Off-site accessibility.
6.2 PROCESS DESCRIPTION
6.2.1 Overview of Processing Steps and Operating
Procedures
Listing different operations and process steps in chronological
order for hazardous chemical; can use block-type flow
diagram to illustrate steps;
Chemical production or use rates;
Chemical reaction(s) description (e.g., catalysts, activators,
inhibitors, exothermic, etc.);
Blending or separation steps;
Material incompatibilities;
Pressure and temperature variations; and
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Consequences of deviation: what happens to chemicals
spilled, leaked, vented, etc.
6.2.2 General Description of Process Equipment
Capacity and design conditions;
Construction material;
Flow rates;
Parameters monitored, controlled, and recorded (at
equipment or in control room);
Production or use rates for chemical; and
Comparison of design limits and operating parameters.
Note: Attachment 9 contains further guidance on reviewing process operations.
6.2.3 Back-ups and Redundancy
List systems with back-ups or automatic shutdowns;
Description of back-ups and how and why used;
Availability of back-up power systems;
Method of detecting inoperative control equipment and
availability of back-ups; and
For facility with scrubbers or flares, their capacity for
handling accidental releases.
6.2.4 Process Parameter Monitoring
Description of process parameters for operations and
processes and why used;
Performance history at facility;
Monitoring and recording procedures; and
Procedures for addressing unsafe parameter levels.
6.2.5 Environmental Monitoring
Description of system(s) used to monitor hazardous chemical
levels within work areas and in the surrounding environment
(e.g., types, location, etc.);
Connection to alarm and communication systems; and
Performance history at facility.
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6.3 PROCESS HAZARDS
Hazards facility has identified for the process and determined to
present a significant risk to the facility and/or the surrounding
community (e.g., storage tank failure, pipeline leak, process vessel
overpressurization)
7.0 CHEMICAL ACCIDENT PREVENTION
Practices and technological systems for controlling the process hazards presented
in section 6.0 of this protocol/report outline, are an important part of chemical process
safety management. This section is intended to describe mechanisms for implementing
and maintaining safe process systems. Management directives are reviewed in this
section to identify goals and implemented activities, such as training and equipment
maintenance procedures, that present the facility's perspective and commitment to safe
management of process hazards.
7.1 MANAGEMENT ACTIVITIES
7.1.1 Corporate Role in Facility Process Safety Management
Corporate safety policy, guidance, and directives; and
Technical and financial assistance (e.g., process modifications,
information exchanges, and capital improvements).
7.1.2 Facility Role in Process Safety Management
Policy and directives;
Goals and objectives; and
Employee safety committees and incentive programs.
7.1.3 Audit Activities and Procedures
Frequency of facility audits;
Responsible department and involvement of external
personnel (e.g., corporate and private consultants);
Audit scope;
Audit procedures and time frame; and
Implementation of audit recommendations (e.g., policy and
procedures).
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7.2 PROCESS OPERATION AND MAINTENANCE
7.2.1 Standard Operating Procedures
SOP manuals available (e.g., operating procedures manual,
supervisory operating manual, safety manual, accident and
fire prevention manual);
How procedures/manuals reviewed and approved;
Listing of personnel roles and responsibilities;
Applicability of manuals to tasks conducted during normal
and emergency situations;
Other process guides: operating logs, shift turnover
procedures, overtime procedures, call out procedures during
emergencies, reporting procedures for unusual circumstances
or process deviations;
Experimental operating conditions for process changes, and
management of change; and
Startup, shutdown, and routine operation checklists.
Note: Attachment 10 contains a summary of the types of documentation and other
materials that the audit team may want to review for more information on facility SOPs.
7.2.2 Training Practices
Types of training available for operations and maintenance
personnel;
Methods and frequency of training;
Who performs training and qualifications;
Frequency and procedures for revising training;
Refresher courses and retraining;
Upset simulations and drills;
Use of process simulators;
Job duty qualifications/prerequisites;
Types and frequency of job qualification evaluations (e.g.,
performance reviews, tests);
Employee turnover rate; and
Master qualification list.
7.2.3 Equipment Maintenance Procedures
Work order systems;
Maintenance and testing scheduling;
Preventive and predictive maintenance;
Equipment history records;
System for spare parts control;
Level of training;
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Frequency and method of communication between
maintenance and operations personnel;
Prioritization of maintenance and inspections;
Securing equipment during shift breaks;
Assuring proper repairs replacement; and
Management of change for equipment (e.g., appropriateness
of materials of construction).
7.2.4 Instrument Maintenance
Work order systems;
Frequency and testing of instrument calibration, sensor
inspections, and alarm and interlock inspections;
Instrument history records;
System for spare parts control;
Frequency and method of communication between
maintenance and operations personnel;
Number of employees and shift coverage;
Level of training;
Management of change for instruments (e.g., appropriateness
of calibration settings); and
Error checking.
7.3 Hazard Evaluation and Modeling A
7.3.1 Hazard Evaluation
Type(s) or method(s) used at facility (e.g., What If, Hazop,
etc.) and why selected;
Processes and operations evaluated;
Procedures for targeting/scheduling evaluation (e.g., new
procedures, process modification, incidents);
Frequency and basis for updating methods;
Who participates in and reviews evaluation(s) and the
qualifications of such personnel;
Use of results and methods of documentation;
Performance of consequence analysis to understand impacts
of any potential release;
Implementation of results and recommendations; and
How is process change managed.
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7.3.2 Modeling
Uses and types of models for tracking releases into air,
surface water, and groundwater;
Processes, chemicals, and operations to which models have
been applied;
Goals of modeling activities (e.g. support for emergency
planning and emergency response);
Assumptions built in to the models (both by user and
developer) and facility perceptions of strengths and
limitations (e.g. dense gas releases, terrain effects, single-
phase versus multi-phase modeling capability);
Parameters covered by surface and groundwater models (e.g.
degradation, photolysis, volatization, geochemical processes,
local hydrology, adsorption, desorption);
Validate model against experimental measurements; and
Use during incidents and the results (e.g., improvements in
emergency response or planning).
7.4 Release Prevention Systems
Facility activities related to preventing a release
Description of type(s) of systems in place;
Why used;
Performance history at facility;
Testing and inspections; and
Modifications performed.
Examples of activities to prevent chemical releases:
Improvements in process and equipment design;
Reduction of inventories;
Changes in siting of particular equipment;
Increased training and safety reviews;
Improved process controls;
Installation of interlocks; and
Failsafe design.
7.5 MITIGATION SYSTEMS
Description of type(s) of system(s) in place;
Why used;
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Performance history at facility; and
Frequency of testing and inspections.
Examples of release mitigation systems include:
Water sprays and sprinkler systems;
Foams;
Physical separation of buildings and equipment; and
Physical barriers, including dikes, curbing, raised doorways,
and containment walls).
8.0 ACCIDENTAL RELEASE INCIDENT INVESTIGATION
Facility procedures for identifying the underlying causes of unplanned incidents,
including fires, explosions, or releases of hazardous chemicals, and for preventing similar
incidents from recurring serve as an important step toward the actual prevention of
future incidents.
8.1 HISTORY OF ACCIDENTAL RELEASES/INCIDENTS
Types (e.g., reportable, near miss);
Chronicle of releases; 1
Reporting history; and
Community response and interaction.
8.2 FACILITY INVESTIGATION PROCEDURES
Written procedures (e.g., guidelines, time frames);
Types of releases to be investigated (e.g., near misses; or those
reportable under federal, state, or local law);
Personnel responsible for investigations;
Management involvement;
Actions taken resulting from investigation; and
Use of reports to share results (e.g., through training programs and
lessons learned) and distribution scheme.
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9.0 FACILITY EMERGENCY PREPAREDNESS AND PLANNING ACTIVITIES
Emergency activities in preparing for and responding to accidental releases
illustrate facility knowledge, dedication, and practices for mitigating incidents.
9.1 Facility Emergency Response Plan
Type and coverage of facility response plans (e.g., OSHA emergency
action plan, SPCC plan, corporate plan);
Update schedule and procedures (i.e., how often revised and by
whom); and
Key procedural areas covered (e.g., release notification, evacuation,
response and mitigation activities).
9.2 Emergency Response Exercises and Simulations
Types, frequency, and groups involved; and
Uses of findings.
9.3 Fire, Evacuation, and Rescue Corridors
Procedures for conducting evacuations;
Condition and accessibility of fire and rescue corridors; and
Detail and location of facility and community maps (Maps should be
referenced in appendix.).
9.4 Emergency Equipment Provisions
Types;
Locations;
Inspection and maintenance policies, including testing; and
Sources of equipment (off-site versus on-site).
9.5 Emergency Response Chain of Authority
Chain of command (e.g., designation of control during an
emergency); and
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Coordination with off-site response personnel.
9.6 Emergency Response Management Procedures
Management's role in response incident situations.
9.7 Emergency Communication Network within the Facility
Types and accessibility of communication system(s) and backups,
including sirens, walkie-talkies, and phones;
Testing of communication system; and
Ability of personnel to interpret warning signals.
9.8 Emergency Response Personnel Training Requirements
Categories of facility emergency response personnel;
Type of training available and frequency;
Who performs training; and
Refresher courses.
9.9 Follow-up Release Procedures
Incident clean-up (e.g., self, private contractors); and
After-action review of response with all involved parties (e.g., public
and private organizations).
10.0 COMMUNITY AND FACILITY EMERGENCY RESPONSE PLANNING
ACTIVITIES
Communication to the community about facility activities and coordination with
the community in developing emergency response plans indicate a level of facility
commitment to safety, as well as revealing unique outreach activities.
10.1 Facility Planning and Outreach Activities with Community
Awareness and participation in LEPC activities;
Participation in CAER activities; and
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Outreach activities, scholarship programs, open houses, joint
training, education, etc.
10.2 Local/Community Emergency Response Planning
Community plan status;
Coordination between facility and community in plan preparation
and exercise;
Coordination with hospitals and emergency medical services on
treatment of chemical exposure victims;
Coordination with community response structures and procedures;
and
Mutual aid efforts and facility involvement in non-facility-related
community responses.
11.0 PUBLIC ALERT AND NOTIFICATION PROCEDURES
Public alert and notification procedures identify unique procedures and facility
commitment to safety for the community.
11.1 Procedures for Public Notification of Releases
Alarm systems (e.g. sirens, air horns, whistles);
Communication networks (e.g., radio, television, phone); and
Back-up systems.
11.2 Schedule for Testing Procedures
Frequency of tests; and
Number and type of individuals notified.
11.3 History of Notification Procedures and Evaluation
Type of incident;
Timeliness of public notification; and
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Number of individuals notified and methods of public and private
emergency notification.
I
11.4 Community and Facility Contacts
Alternate contacts; and
Telephone number update procedures.
11.5 Facility and Media Interaction
Direct communication links; and
History of past interaction.
12.0 CONCLUSIONS
The conclusions highlight safety practices observed at the facility. As described in
section 6.2.2, Tips for Writing the Report, the information should be presented in a factual
manner and should refrain from judgments of adequacy or inadequacy. This section
summarizes facility practices that reflect the facility's understanding of and commitment
to chemical process safety management.
13.0 RECOMMENDATIONS
If applicable, the audit team may wish to make one or more recommendations
regarding observed processes, practices, technologies, and so forth. Any such
recommendations should be stated clearly, and be practical and technologically feasible at
the facility. Recommendations are not required or mandatory actions that must be taken
by the facility. They should be presented as options that the facility may consider to
enhance their knowledge of and practices in chemical process safety management.
APPENDICES
During the audit process, the team will gather a variety of materials relating to the
operations of the facility. Most of this material, however, while very helpful in
conducting the audit and preparing the audit report, does not belong in the main body of
the audit report and should instead be placed in appendices or maintained in the files of
the regional office for future use. Examples of the types of material that might be
included as appendices are:
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Sample facility memoranda, guidelines, SOPs, policy statements;
Correspondence between the facility and the regional office; and
Graphics such as photographs, maps, charts.
All materials should be labeled with the:
Name of the facility;
Date of the audit; and
Other necessary identifying information.
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6.2 Writing the Report
6.2.1 Post-Visit Meeting I
The entire audit team should reassemble as soon as possible after completion of
the site visit. This is important because the details of the site visit can become confused
and fade rapidly. Certain items should be covered in this meeting:
Require that team members immediately review and edit their notes from
the site visit to obtain clarity and completeness;
Begin using the audit report outline as a basis for organizing all audit
information;
Consider the major audit elements during the review and analysis process,
the initial stage in to the completion of the audit report:
Facility Background Information;
Chemical Hazards;
Process Hazard Information;
Chemical Accident Prevention;
Accidental Release/Incident Investigation;
Facility Emergency Preparedness and Planning Activities;
Community and Facility Emergency Response Planning Activities;
and m
Public Alert and Notification.
Review all important observations and findings identified to this point in
the audit; and
Determine whether or not any particular conclusions can be drawn or
recommendations made for inclusion in the report.
6.2.2 Tips for Writing the Report
There are two main areas of consideration when preparing a report:
Writing style; and
Report format flexibility
Writing style
In many instances during report preparation, several individuals will be working on
separate sections pertaining to his/her role in conducting the audit. Although several
different writing styles may be presented in the report, it is very important that they all —
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have one common element of presentation style -- information is factual, relevant,
complete, objective, and clear. The entire report, including the Conclusions and
Recommendations sections, should be presented in a factual manner and refrain from
judgments of adequacy or inadequacy.
The Conclusions section should highlight facility safety practices observed during
the audit, identifying unique facility practices that should be shared as well as areas for
improvement. This summary should reflect the facility's understanding of, and
commitment to, chemical process safety management, and should refrain from judgments
of adequacy or inadequacy. As an example of how to present conclusions, consider the
following pair of statements:
Incorrect. "The facility has adequate procedures to investigate and respond to the
cause(s) of accidental chemical releases."
Correct. "The facility prepares follow-up reports for accidental releases of
hazardous chemicals that occur both on- and off-site. The report addresses the
cause of the incident, recommended actions to prevent the release from
reoccurring, and a schedule and list of responsible individuals for implementing
these actions." [If the facility uses a form for this practice, it could be referenced
in an appendix.]
The first statement does not provide any information on the facility's follow-up
procedures; in addition, a judgement is made on the procedures, which may or may not
be valid. The latter illustrates procedures that the facility takes following an accidental
release of hazardous chemicals both on- and off-site. Its style of presentation is factual
and provides clear information on what the facility does without commenting on the
adequacy or inadequacy of the procedures.
The Recommendations section should provide clearly stated suggestions and
include the factual basis for each recommendation. The recommendations should be
both practically and technologically feasible for the audited facility — they are neither
mandatory nor required, and are simply being presented for consideration by the audit
team to the facility to enhance its chemical process safety management. As an example
of how to present recommendations, consider the following pair of statements:
Incorrect. "The facility should implement a preventive maintenance program."
Correct. "The facility should evaluate the appropriateness of its use of the
periodic maintenance system for maintaining pressure relief valves. This
evaluation could include, among other aspects, a review of alternative schemes,
such as preventive maintenance and predictive maintenance."
The first statement does not provide any information on the facility's existing
maintenance program and it does not specify the particular application for the
recommended preventive maintenance. The latter clearly describes the current status of
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the element in question and provides alternatives for consideration. In addition, the style
of presentation is appropriate for the cooperative nature of the audit program. In both
the Conclusions and Recommendations sections, all statements must address observations
that are presented in detail in the main body of the report.
Report format flexibility
The introduction to this section of the Manual addresses the purpose and uses of
the report protocol/outline. One important purpose is to ensure consistency in report
preparation. This consistency will help to facilitate analysis of conclusions and
recommendations and will assist CEPPO in effectively identifying successful and
problematic practices and technologies, and in sharing information with the regions, other
program offices, other federal agencies, state and local governments, facilities, and other
involved parties.
There are 13 major report sections (i.e., 1.0, 2.0, etc.), and when preparing the
report, each of these must be addressed. [Required Activity] For some facilities,
however, information relevant to a major section may not exist, or the audit team may
not have been able to examine materials relevant to this element. For example, the
facility may not have any system for alerting/warning the public that a release has
occurred (section 11.0), or this element may not have been reviewed by the audit team.
Rather than skip that section of the report, it should be stated that the facility does not
have a public alert/warning system, or that this element was not examined in the audit.
6.2.3 Follow-up Information
With almost any audit, there is usually a need to contact the facility after the site
visit has occurred to clarify a point or to obtain more complete information. A chemical
safety audit is no different. The preferred way to handle follow-up inquiries is for the
Team Leader to designate a person or persons to serve as the contact with the facility;
the facility may take a similar approach in making any further responses to EPA. This
minimizes the opportunity for miscommunication and lends a credible appearance to the
conclusion of the audit.
6.2.4 Standard Report Disclaimer
A standard report disclaimer accompanies all audit reports and is located after the
cover page. [Required Activity] Attachment 7 contains a sample disclaimer. The report
disclaimer serves to describe the scope and limitations of the audit report contents by
identifying the time frame in which the audit was conducted, and by clarifying the
facility's role in adopting or implementing any of the report contents.
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6.3 Review and Finalization Procedures
In preparing the final audit report, there are two considerations to keep in mind:
Access of draft report information through the Freedom of Information Act
(FOIA); and
Report inclusion of facility confidential information.
6.3.1 Access of Draft Information
In order to ensure that draft report information is not available to the public
through FOIA prior to report finalization, the EPA regional office can designate an EPA
official (e.g., Section, Division, or Branch Chief) to approve the report as "final." This
procedure is not mandatory, but highly recommended, since this process is cited under
the Deliberate Process Privilege Section, exemption 5 of FOIA [5 USC 552(b)5].
Additional actions can be taken to prevent draft information from being accessible
under FOIA. For example, all draft materials can be stamped "DRAFT." Draft
materials can include the following citation at the bottom of each page or on a cover
sheet:
"Pre-decisional Document, Not Disclosable Under FOIA"
" - Do Not Cite or Quote - "
Please note that these actions do not have legislative or regulatory authority, as
compared to the finalization process described above.
6.3.2 Facility Confidential Information
Another suggested activity during the report finalization process is submission of
the draft report to the facility to identify any confidential information. The facility should
be contacted to establish a deadline (e.g., two weeks) to avoid lengthy delays. Any
information identified as confidential should be treated as such. Comments on the report
that are provided by the facility can, but do not have to be taken into consideration as
the report is finalized.
6.4 Report Distribution
When the audit report is final, standard distribution by the Regional Chemical
Emergency Preparedness and Prevention (CEPP) Coordinator is required to the
following groups and organizations: [Required Activity]
SERC and LEPC in which the facility is located;
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Facility owner/operator;
Facility CEO;
EPA Headquarters, Chemical Emergency Preparedness and Prevention
Office; and
Any other federal, state, and local agencies or departments that assisted in
conducting the audit.
The region should ensure that at least one unbound copy of the report suitable for
photocopying is provided to CEPPO.
The Regional CEPP Coordinators should also consider distributing final audit
reports to other EPA offices; other federal, state, and local agencies or departments; and
other private and public sector organizations. Sharing the report with regional media
offices is encouraged. EPA Headquarters will also circulate copies to interested
headquarters media offices, the Prevention Work Group, and other federal programs.
Press releases of audit activities (e.g., facility visit, report finalization, etc.) are also
discretionary for the Regional CEPP Coordinators and EPA Headquarters CEPPO staff.
To help professionals conducting audits, EPA Headquarters is developing a
computerized database that contains profiles of all of the chemical safety audit reports.
The profiles are summaries of the audit reports organized in a uniform format consistent
with the CSA protocol. The database has search capabilities that allow the user to m
identify report profiles based on SIC code, specific chemical hazards, etc. The
information contained in the database will be useful to the regions for a variety of
purposes, such as learning how a particular industry operates (e.g., the types of chemicals
and kinds of processes in use and the typical problems encountered), as well as
identifying field experts and comparing processes at different facilities for the same
chemical. CEPPO will also be able to use the database to assemble and distribute
information on chemical process safety management and chemical accident prevention
issues and to assess the implementation of the CSA program.
6.5 Preparing the Report Profile
An audit report profile should be submitted to headquarters in conjunction with
the submission of the audit report for inclusion into the database. The profile (see
Attachments 11 and 12) organizes the key information contained in the report, including
information on the facility and the audit team as well as report conclusions and
recommendations, in a format suitable for direct entry into the CSA database. In
addition to providing the basis for the continued development of the CSA database, the
profile format can also assist the audit team during the audit process. The profile can
serve as a method of organizing issues of interest and assigning areas of responsibility to
team members prior to the audit, monitoring the progress of the team during the audit
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visit, and organizing the collected information during report writing. The specific
information that should be included in the CSA report profile is described in the
annotated profile in Attachment 12. A hardcopy and an electronic version of the profile
should accompany the audit report when it is submitted to EPA headquarters to facilitate
entering the profile information into the database.
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7. Audit Follow-Up Activities
As a supplement to the chemical safety audit and CSA report preparation, each
regional office should establish an audit follow-up program. The follow-up program will
support EPA's efforts to evaluate the effectiveness of the CSA program in improving, as
well as heightening awareness of the need for, chemical process safety among chemical
producers, distributors, and users. In addition, it is hoped that the analysis of audit
results will provide a basis for amending the focus and direction of the CSA program to
better achieve its stated goals at the regional and headquarters level.
Although the specific nature of the follow-up activities has been left to the
discretion of the regional offices, at a minimum the program should be designed to track
audited facilities' implementation of CSA report recommendations. This will allow
Headquarters to analyze trends in the implementation of CSA recommendations as a
function of issue (e.g., employee training or instrument maintenance), level of effort (e.g.,
fixing a relief valve or replacing a storage tank), and type and size of facility. Within this
framework, the regional offices are free to examine other audit issues (e.g., format,
relationship with state and local officials) at their own discretion and to communicate
with the facility in writing or in person.
Optionally, some of the regions also may wish to develop a method to verify
whether the information received from the facility is accurate, to the extent that regional
resources permit. This may involve the continued participation of state and/or local
officials in the audit process or another facility visit by EPA or Technical Assistance
Team members.
7.1 Follow-Up Approaches
Currently, some regional offices have already developed follow-up programs.
They have approached the follow-up process from a variety of angles, ranging from
mailing worksheets to returning to the facilities for a post-audit review. For example:
• Region 6 conducted a comprehensive follow-up effort in FY 92 in which
representatives from the region revisited 14 facilities that had been audited
since 1989 to evaluate the implementation of audit team recommendations.
Issues studied included the most effective audit format; facility attitudes
toward the audit process; the role of facility size in implementing
recommendations; and the level of expertise of the audit team. Region 6
used the follow-up information to compile quantitative regional data, which
was summarized in charts and graphs to highlight key trends and issues.
The data indicated that 68 percent of the 173 recommendations were
implemented at the facilities involved in the project, with a notably lower
rate for the five facilities with greater than 1,000 employees (56%) and for
recommendations that involved changes in process design (40%), and a
notably higher rate for compliance-related recommendations (100%)
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• Region 8 has sent questionnaires to facilities six and 12 months after the
audits to check on the facility's progress in implementing the
recommendations of the audit team. The questionnaire lists each of the
audit team's recommendation, and the facility indicates its response to the
recommendations, including their future plans for implementing the
recommendations. For the questionnaires completed by facilities in 1991,
the region identified an 80-85 percent response rate for facilities in
implementing audit recommendations.
Another possible follow-up option suggested by one regional office is to present audited
facilities with an evaluation form at the same time as the final audit report is distributed
to the facility.
7.2 Specific Information Required
The follow-up program should begin with the facilities at which an audit has been
conducted in fiscal year 1993. Regions also have the option of performing follow-up
efforts at facilities audited in previous years. For each audit, the regional office should
provide EPA Headquarters with the following information:
• Full name and address of audited facility;
• List of recommendations made by the audit team as organized in the CSA
report profile prepared by the region;
• Indication of how each recommendation has been or is planned to be
implemented and/or addressed by the facility with the date completed or a
schedule for implementation, as appropriate;
• Rationale for any recommendations that have not been implemented
and/or addressed by the facility; and
• Audit implementation issues, including:
Facility attitude toward chemical safety audit, and
Successful and problematic audit practices.
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Attachments
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Attachment 1
Chemical Safety Audit Program Fact Sheet
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FACT SHEET
MARCH 1993
CHEMICAL SAFETY AUDIT PROGRAM
BACKGROUND
The Chemical Safety Audit (CSA) program has evolved
from the efforts of the U.S. Environmental
Protection Agency (EPA) under the Chemical Accident
Prevention (CAP) program. The CAP program emerged
from concerns raised by the release of methyl
isocyanate at Bhopal, India, and of aldicarb oxime
at Institute, West Virginia. Awareness of the
critical threat to public safety posed by similar
incidents led to an emphasis on preparedness and
planning for response to chemical accidents.
Simultaneous with the development of preparedness
activities by EPA was the passage and
implementation of the Emergency Planning and
Community Right-to-Know Act -- Title III of the
Superfund Amendments and Reauthorization Act (SARA)
by Congress in 1986. Because prevention is the
most effective form of preparedness, the CAP
program promotes an effort to enhance prevention
activities. The primary objectives of the CAP
program are to identify the causes of accidental
releases of hazardous substances and the means to
prevent them from occurring, to promote industry
initiatives in these areas, and to share activities
with the community, industry, and other groups.
Many of the key concerns of the CAP program arise
from the SARA Title III section 305(b) study
entitled Review of Emergency Systems. As part of
the information gathering efforts to prepare this
study, EPA personnel conducted a number of facility
site visits to learn about chemical process safety
management practices. The study covers
technologies, techniques, and practices for
preventing, detecting, and monitoring releases of
extremely hazardous substances, and for alerting
the public to such releases. One of the key
recommendations resulting from the study was the
continuation and expansion of the audit program.
As a follow-up to this national prevention study,
EPA has undertaken cooperative initiatives with
federal agencies, states, industry groups,
professional organizations, and trade associations,
as well as environmental groups and academia.
These joint efforts will serve to determine and
implement a means to share information on release
prevention technology and practices, and to enhance
the state of practice in the chemical process
safety arena.
PROGRAM GOALS
The CSA program is part of this broad initiative
and has been designed to accomplish the following
chemical accident prevention goals:
• Visit facilities handling hazardous substances
to gather information on and learn about safety
practices and technologies;
• Heighten awareness of the need for, and promote,
chemical safety among facilities handling
hazardous substances, as well as in communities
where chemicals are located;
• Build cooperation among facilities, EPA, and
other authorized parties by coordinating joint
audits; and
• Establish a database for the assembly and
distribution of chemical process safety
management information obtained from the
facility audits.
PROGRAM AUTHORITY
The Comprehensive, Environmental Response,
Compensation and Liability Act (CERCLA or
Superfund) was enacted December 11, 1980, and
amended by SARA on October 17, 1986. CERCLA
authorizes the federal government to respond where
there is a release or a substantial threat of a
release into the environment of any hazardous
substance, pollutant, or contaminant that may
present danger to the public health or welfare or
to the environment.
CERCLA Sections 104(b) and 104(e), as amended by
SARA in 1986, provide authorities for entering a
facility and accessing information to conduct a
chemical safety audit by EPA. While CERCLA
provides authority for states to use statutory
authorities for entry and information gathering,
such authorities may only be accessed pursuant to a
contract or cooperative agreement with the federal
government. Since there is no such arrangement,
states, as well as local governments, must use
their own authorities for audit participation.
As a matter of EPA policy under the CSA program,
all facilities that will receive an audit should
have experienced a release of a hazardous
substance, pollutant, or contaminant, or there
should be reaion to believe that there exists a
threat of such a release. The audits are intended
to be nonconfrontational and positive, such that
information on safety practices, techniques, and
technologies can be identified and shared between
EPA and the facility. Involvement in the CSA
program by Local Emergency Planning Committees
(LEPCs) and State Emergency Response Commissions
(SERCs) formed under SARA Title III is encouraged
to enhance the goals of both of these programs.
However, as stated above, state and local
government participation in the audit, itself, must
be performed under state and local authorities.
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AUDIT SCOPE
REPORT DISTRIBUTION
The audit consists of interviews with facility
personnel, and on-site review of various aspects of
facility operations related to the prevention of
accidental chemical releases. Specific topics
addressed include:
• Awareness of chemical and process hazards;
• Process characteristics;
• Emergency planning and preparedness;
• Hazard evaluation and release detection
techniques;
• Operations and emergency response training;
• Facility/corporate management structure;
• Preventive maintenance and inspection programs;
and
• Community notification mechanisms and
techniques.
Observations and conclusions from audits are
detailed in a report prepared by the audit team.
The report identifies and characterizes the
strengths of specific Chemical Accident Prevention
program areas to allow the elements of particularly
effective programs to be recognized. Copies of the
report are provided to the facility so that weak
and strong program areas may be recognized. The
audit is conducted following the Guidance Manual
for EPA Chemical Safety Audit Team Members, issued
by EPA Headquarters. This guidance contains
recommended actions, as well as mandatory
procedures that must be followed to ensure the
health and safety of program auditors and program
integrity. Each member of the audit team should
have a copy of the manual, and a copy of the manual
is transmitted to the audited facility.
AUDIT TEAM COMPOSITION
An EPA audit team primarily consists of EPA
employees, and other designated representatives
including contractors and the American Association
of Retired Persons (AARP) enrol lees. Other
federal, state, and local government personnel may
also be team members. The audit team can vary in
size, depending upon the level of detail of the
audit (e.g., number of chemicals and/or processes
under investigation; national significance).
FACILITY SELECTION
At present, there are no established procedures for
selecting a facility for an audit. Each EPA region
has flexibility in identifying facilities. Options
to consider in selecting a facility include:
Previous history of the facility;
SERC and/or LEPC referral;
Proximity to sensitive population(s);
Public sensitivity;
Regional accident prevention initiatives;
Opportunity for sharing new technology;
Population density; and
Concentration of industry in the area.
Standard distribution by EPA regional offices of
the audit report will be at a minimum to:
• SERC and LEPC in which the facility is located;
• Facility owner/operator and facility CEO;
• EPA Headquarters; and
• Any othe^ federal, state, and local agencies or
departments that assisted in conducting the
audit.
Distribution is available to other EPA offices,
other federal, state, and local agencies or
departments, and other private and public sector
organizations.
ACCOMPLISHMENTS
During the first four years of the CSA program, the
regions have conducted audits at over 150
facilities in 46 states and Puerto Rico. EPA has
analyzed the conclusions and recommendations listed
in the audit reports to identify trends within and
across industries, processes, and chemicals to
assist in the further development of the CSA and
CAP programs, particularly in light of the
accidental release provisions of section 112(r) of
the Clean Air Act. At the same time, follow-up
activities performed by several of the regional
offices indicate that the majority of the
recommendations to improve chemical process safety
practices suggested by the audit teams have been
implemented or are scheduled to be implemented at
audited facilities.
CSA PROGRAM BENEFITS
• Identification of effective, field-proven
chemical accident prevention technologies and
practices.
• Better understanding of the causes of chemical
releases.
• Greater awareness by facilities of chemical
safety and understanding of available
techniques, and specific suggestions for
improved programs.
• Identification of problem areas in industry
where more attention is needed.
• Cooperation and coordination of chemical safety
programs with other federal and state agencies
through joint audits and training.
For more information on the Chemical Safety Audit
program, contact the Chemical Emergency
Preparedness Program (CEPP) office in your EPA
regional office.
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Attachment 2
CERCLA Provisions Overview and CERCLA Statute
Section 104(a) Removal and Other Remedial Actions
This section provides the federal government with the authority to respond to releases or
threatened releases of hazardous substances, pollutants, or contaminants in certain situations.
Section 104(a) authorizes the EPA Administrator "to act, consistent with the national
contingency plan, to remove or arrange for the removal of, and provide for remedial action relating
to such hazardous substances, pollutants, or contaminants at any time, or take any other response
measure consistent with the national contingency plan which the Administrator deems necessary to
protect public health or welfare or the environment," where:
Any hazardous substance is released;
There is a substantial threat that a hazardous substance will be released into the
environment;
Any pollutant or contaminant is released into the environment "which may present
an imminent and substantial danger to the public health or welfare;" or
There is a substantial threat that a pollutant or contaminant may be released into the
environment "which may present an imminent and substantial danger to the public
health or welfare."
Section 104(b) Investigatory Response
Under Section 104(b), the Administrator is authorized to "undertake such investigations,
monitoring, surveys, testing, and other information gathering" that may be needed "to identify the
existence and extent of the release or threat thereof, the source and nature of the hazardous
substances, pollutants or contaminants involved, and the extent of danger to the public health or
welfare or to the environment." This investigatory response can be initiated whenever the
Administrator can act under Section 104(a) when he has "reason to believe" that:
A release has occurred;
A release is about to occur; or
"Illness, disease, or complaints thereof may be attributed to exposure to a hazardous
substance, pollutant, or contaminant and that a release may have occurred or be
occurring."
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Section 104(e) Information Gathering and Access
Under Section 104(e), a designated representative of the President or a state or political
subdivision under a contract or cooperative agreement is authorized to obtain information and gain
access to sites and adjacent property "for the purposes of determining the need for response, or
choosing or taking" a response, or to enforce any provision of CERCLA. The authority to enter a
site and to inspect and take samples from a site may only be exercised where "there is a reasonable
basis to believe there may be a release or threat of release of a hazardous substance or pollutant or
contaminant."
Access to Information. Section 104(e) authorizes any designated official, upon reasonable
notice, to require persons to provide relevant information or documents concerning:
"Identification, nature and quantity of materials which have been or are generated,
treated, stored, or disposed of at the facility;
"The nature or extent of a release or threatened release of a hazardous substance or
pollutant or contaminant at" the facility; and
"Information relating to the ability of a person to pay or perform a cleanup."
In addition, upon reasonable notice, Section 104(e) requires persons to grant access to a
facility to inspect and copy all documents or records, or at their option to provide copies.
Entry. Designated representatives are authorized to enter at reasonable times, any vessel,
facility, establishment, or other place or property:
"Where any hazardous substance, pollutant, or contaminant may be or has been
generated, stored, treated, disposed of, or transported from;"
"From which or to which a hazardous substance, pollutant, or contaminant has been
or may have been released;" and
"Where entry is needed to determine the need for response or the appropriate
response or to effectuate a response action."
Compliance Orders. If consent is not granted for access to information, entry onto the
facility, and inspection or sampling, Section 104(e)(5) authorizes EPA to:
"Issue an order directing compliance with the request," after such notice and
opportunity for consultation;
Ask the Attorney General to commence a civil action to compel compliance with a
request or order; and
Assess civil penalties up to $25,000/day for failure to comply with the order.
Section 104(e) also provides for the right to obtain access or information in any other lawful manner,
which includes warrants.
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Confidentiality of Information. Section 104(e)(7) provides that no person required to provide
information under CERCLA may claim that such information is entitled to protection unless such
person shows each of the following:
The "person has not described the information to any other person, other than a
member of a local emergency planning committee under Title III of SARA," an
officer or employee of the U.S. or a state or local government, an employee of such
person, or a person who is bound by a confidentiality agreement, and such person has
taken reasonable measures to protect the confidentiality of such information and
intends to continue to take such measures;"
"The information is not required to be disclosed, or otherwise made available, to the
public under any other federal or state law;"
"Disclosure of the information is likely to cause substantial harm to the competitive
position of such person;" and
"The specific chemical identity, if sought to be protected, is not readily discoverable
through reverse engineering."
The following information on hazardous substances is not entitled to protection:
Trade name, common name, or generic class or category;
Physical properties;
Hazards to health and the environment, including physical hazards (e.g., explosion)
and potential acute and chronic health hazards;
Potential routes of human exposure;
Disposal location of any waste stream;
Monitoring data or analysis on disposal activities;
Hydrogeologic or geologic data; and
Groundwater monitoring data.
Section 106(a) Abatement Action
This section of CERCLA provides the federal government with the authority to pursue
administrative and judicial action to require responsible parties to respond to actual or threatened
releases of hazardous substances. If the Administrator "determines that there may be an imminent
and substantial endangerment to the public health or welfare or the environment," he has two options
under 106(a):
Request the Attorney General to seek the necessary relief in the federal district court
where the threat occurs. The district court is given jurisdiction to grant relief as the
public interest and the equities of the case may require; or
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After providing notice to the affected state, he may take other action, including, but
not limited to the issuance of orders that may be necessary to protect public health
and welfare and the environment.
Note: Statutory texts of these reviewed CERCLA sections follows.
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COMPREHENSIVE ENVIRONMENTAL RESPONSE,
COMPENSATION AND LIABILITY
(42 U.S.C.A. §§ 9601 to 9675)
CHAPTER 103—COMPREHENSIVE ENVI-
RONMENTAL RESPONSE,
COMPENSATION, AND LIABILITY
SUBCHAPTER I—HAZARDOUS SUBSTANCES
RELEASES, LIABILITY, COMPENSATION
Sec.
9601. Definitions.
9602. Designation of additional hazardous substances
and establishment of reportable released quanti-
ties; regulations.
9603. Notification requirements respecting released sub-
stances.
(a) Notice to National Response Center upon re-
lease from vessel or offshore or onshore
facility by person in charge; conveyance of
notice by Center.
(b) Penalties for failure to notify; use of notice
or information pursuant to notice in crimi-
nal case.
(c) Notice to Administrator of EPA of existence
of storage, etc., facility by owner or opera-
tor; exceptions; time, manner, and form of
notice; penalties for failure to notify; use
of notice or information pursuant to notice
in criminal case.
(d) Recordkeeping requirements; promulgation
of rules and regulations by Administrator
of EPA; penalties for violations; waiver of
retention requirements.
(e) Applicability to registered pesticide product.
(f) Exemptions from notice and penalty provi-
sions for substances reported under other
Federal law or is in continuous release, etc.
9604. Response authorities.
(a) Removal and other remedial action by Presi-
dent; applicability of national contingency
plan; response by potentially responsible
parties; public health threats; limitations
on response; exception.
(b) Investigations, monitoring, etc., by President.
(c) Criteria for continuance of obligations from
Fund over specified amount for response
actions; consultation by President with af-
fected States; contracts or cooperative
agreements by States with President prior
to remedial actions; cost-sharing agree-
ments; selection by President of remedial
actions; State credits: granting of credit,
expenses before listing or agreement, re-
sponse actions between 1978 and 1980,
State expenses after December 11, 1980, in
excess of 10 percent of costs, item-by-item
approval, use of credits; operation and
Sec.
9604. Response authorities—Cont'd
maintenance; limitation on source of funds
for 0 & M; recontracting; siting.
(d) Contracts or cooperative agreements by Presi-
dent with States or political subdivisions or
Indian tribes; State applications, terms and
conditions; reimbursements; cost-sharing
provisions; enforcement requirements and
procedures.
(e) Information gathering and access; action au-
thorized, access to information, entry, in-
spection and samples; authority and sam-
ples, compliance orders; issuance and com-
pliance, other authority, confidentiality of
information; basis for withholding.
(f) Contracts for response action; compliance
with Federal health and safety standards.
(g) Rates for wages and labor standards applica-
ble to covered work.
(h) Emergency procurement powers; exercise by
President.
(i) Agency for Toxic Substances and Disease
Registry; establishment, functions, etc.
(j) Acquisition of property.
9605. National contingency plan; preparation, contents,
etc.
(a) Revision and republication.
(b) Revision of plan.
(c) Hazard ranking system.
(1) Revision.
(2) Health assessment of water contamina-
tion risks.
(3) Reevaluation not required.
(4) New information.
(d) Petition for assessment of release.
(e) Releases from earlier sites.
(f) Minority contractors.
(g) Special study wastes.
(1) Application.
(2) Considerations in adding facilities to
NPL.
(3) Savings provisions.
(4) Information gathering and analysis.
9606. Abatement actions.
(a) Maintenance, jurisdiction, etc.
(b) Fines; reimbursement.
(c) Guidelines for using imminent hazard, en-
forcement, and emergency response author-
ities; promulgation by Administrator of
EPA, scope, etc.
9607. Liability.
(a) Covered persons; scope; recoverable costs
and damages; interest rate; "comparable
maturity" date.
(b) Defenses.
(c) Determination of amounts.
467
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42 § 9601
FEDERAL ENVIRONMENTAL LAW
SUBCHAPTER IV—POLLUTION INSURANCE
Sec.
9671. Definitions.
(1) Insurance.
(2) Pollution liability.
(3) Risk retention group.
(4) Purchasing group.
(5) State.
9672. State laws; scope of subchapter.
(a) State laws.
(b) Scope of title.
9673. Risk retention groups.
(a) Exemption.
(b) Exceptions.
(1) State laws generally applicable.
(2) State regulations not subject to exemp-
tion.
(c) Application of exemptions.
(d) Agents or brokers.
9674. Purchasing groups.
(a) Exemption.
(b) Application of exemptions.
(c) Agents or brokers.
9675. Applicability of securities laws.
(a) Ownership interests.
(b) Investment Company Act.
(c) Blue sky law.
West's Federal Forms
Administrative agency decisions and orders, enforcement and re-
view, see § 851 et seq.
Administrative subpoenas, enforcement, see § 6004 et seq.
Depositions and discovery, see §§ 3271 et seq., 3681 et seq.
Intervention, motion for leave, see § 3111 et seq.
Jurisdiction and venue in district courts, see § 1003 et seq.
Production of documents, motions and orders pertaining to, see
§ 3551 et seq.
Sentence and fine, see § 7531 et seq.
Subpoenas, see § 3981 et seq.
WESTLAW Electronic Research
See WESTLAW guide following the Explanation pages of this
pamphlet
SUBCHAPTER I—HAZARDOUS SUBSTANCES
RELEASES, LIABILITY, COMPENSATION
§ 9601. Definitions
For purpose of this subchapter—
(1) The term "act of God" means an unantic-
ipated grave natural disaster or other natural
phenomenon of an exceptional, inevitable, and ir-
resistible character, the effects of which could not
have been prevented or avoided by the exercise of
due care or foresight.
(2) The term "Administrator" means the Ad-
ministrator of the United States Environmental
Protection Agency.
(3) The term "barrel" means forty-two United
States gallons at sixty degrees Fahrenheit.
(4) The_term "claim" means a demand in writ-
ing for a sum certain.
(5) The term "claimant" means any person who
presents a claim for compensation under this
chapter.
(6) The term "damages" means damages for
injury or loss of natural resources as set forth in
section 9607(a) or 9611(b) of this title.
(7) The term "drinking water supply" means
any raw or finished water source that is or may
be used by a public water system (as defined in
the Safe Drinking Water Act [42 U.S.C. 300f et
seq.]) or as drinking water by one or more indi-
viduals.
(8) The term "environment" means (A) the nav-
igable waters, the waters of the contiguous zone,
and the ocean waters for which the natural re-
sources are under the exclusive management au-
thority of the United States under the Magnuson
Fishery Conservation and Management Act [16
U.S.C. 1801 et seq.], and (B) any other surface
water, ground water, drinking water supply, land
surface or subsurface strata, or ambient air with-
in the United States or under the jurisdiction of
the United States.
(9) The term "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, im-
poundment, ditch, landfill, storage container, mo-
tor 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 in-
clude any consumer product in consumer use or
any vessel.
(10) The term "federally permitted release"
means (A) discharges in compliance with a permit
under section 1342 of Title 33, (B) discharges
resulting from circumstances identified and re-
viewed and made part of the public record with
respect to a permit issued or modified under
section 1342 of Title 33 and subject to a condition
of such permit, (C) continuous or anticipated inter-
mittent discharges from a point source, identified
in a permit or permit application under section
1342 of Title 33, which are caused by events
occurring within the scope of relevant operating
or treatment systems, (D) discharges in compli-
ance with a legally enforceable permit under sec-
tion 1344 of Title 33, (E) releases in compliance
with a legally enforceable final permit issued
pursuant to section 3005(a) through (d) of the
Solid Waste Disposal Act [42 U.S.C. 6925(a) to (d)]
from a hazardous waste treatment, storage, or
disposal facility when such permit specifically
472
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ENVIRONMENTAL RESPONSE, ETC.
42 § 9601
identifies the hazardous substances and makes
such substances subject to a standard of practice,
control procedure or bioassay limitation or condi-
tion, or other control on the hazardous substances
in such releases, (F) any release in compliance
with a legally enforceable permit issued under
section 1412 of Title 33 of1 section 1413 of Title
33, (G) any injection of fluids authorized under
Federal underground injection control programs
or State programs submitted for Federal approval
(and not disapproved by the Administrator of the
Environmental Protection Agency) pursuant to
part C of the Safe Drinking Water Act [42 U.S.C.
300h et seq.], (H) any emission into the air subject
to a permit or control regulation under section
111 [42 U.S.C. 7411], section 112 [42 U.S.C. 7412],
Title I part C [42 U.S.C. 7470 et seq.], Title I part
D [42 U.S.C. 7501 et seq.], or State implementa-
tion plans submitted in accordance with section
110 of the Clean Air Act [42 U.S.C. 7410] (and not
disapproved by the administrator of the Environ-
mental Protection Agency), including any sched-
ule or waiver granted, promulgated, or approved
under these sections, (I) any injection of fluids or
other materials authorized under applicable State
law (i) for the purpose of stimulating or treating
wells for the production of crude oil, natural gas,
or water, (ii) for the purpose of secondary, terti-
ary, or other enhanced recovery of crude oil or
natural gas, or (iii) which are brought to the
surface in conjunction with the production of
crude oil or natural gas and which are reinjected,
(J) the introduction of any pollutant into a public-
ly owned treatment works when such pollutant is
specified in and in compliance with applicable
pretreatment standards of section 1317(b) or (c) of
Title 33 and enforceable requirements in a pre-
treatment program submitted by a State or mu-
nicipality for Federal approval under section 1342
of Title 33, and (K) any release of source, special
nuclear, or byproduct material, as those terms are
defined in the Atomic Energy Act of 1954 [42
U.S.C. 2011 et seq.], in compliance with a legally
enforceable license, permit, regulation, or order
issued pursuant to the Atomic Energy Act of
1954.
(11) The term "Fund" or "Trust Fund" means
the Hazardous Substance Super-fund established
by section 9507 of Title 26.
(12) The term "ground water" means water in
a saturated zone or stratum beneath the surface
of land or water.
(13) The term "guarantor" means any person,
other than the owner or operator, who provides
evidence of financial responsibility for an owner
or operator under this chapter.
(14) The term "hazardous substance" means
(A)^any substance designated pursuant to section
1321(b)(2)(A) of Title 33, (B) any element, com-
pound, mixture, solution, or substance designated
pursuant to section 9602 of this title, (C) any
hazardous waste having the characteristics identi-
fied under or listed pursuant to section 3001 of
the Solid Waste Disposal Act [42 U.S.C. 6921] (but
not including any waste the regulation of which
under the Solid Waste Disposal Act [42 U.S.C.
6901 et seq.] has been suspended by Act of Con-
gress), (D) any toxic pollutant listed under section
1317(a) of Title 33, (E) any hazardous air pollutant
listed under section 112 of the Clean Air Act [42
U.S.C. 7412], and (F) any imminently hazardous
chemical substance or mixture with respect to
which the Administrator has taken action pursu-
ant to section 2606 of Title 15. The term does not
include petroleum, including crude oil or any frac-
tion thereof which is not otherwise specifically
listed or designated as a hazardous substance
under subparagraphs (A) through (F) of this para-
graph, and the term does not include natural gas,
natural gas liquids, liquefied natural gas, or syn-
thetic gas usable for fuel (or mixtures of natural
gas and such synthetic gas).
(15) The term "navigable waters" or "naviga-
ble waters of the United States" means the wa-
ters of the United States, including the territorial
seas.
(16) The term "natural resources" means land,
fish, wildlife, biota, air, water, ground water,
drinking water supplies, and other such resources
belonging to, managed by, held in trust by, apper-
taining to, or otherwise controlled by the United
States (including the resources of the fishery con-
servation zone established by the Magnuson Fish-
ery Conservation and Management Act [16 U.S.C.
1801 et seq.]) any State or local government, any
foreign government, any Indian tribe, or, if such
resources are subject to a trust restriction on
alienation, any member of an Indian tribe.
(17) The term "offshore facility" means any
facility of any kind located in, on, or under, any of
the navigable waters of the United States, and
any facility of any kind which is subject to the
jurisdiction of the United States and is located in,
on, or under any other waters, other than a vessel
or a public vessel.
(18) The term "onshore facility" means any
facility (including, but not limited to, motor ve-
hicles and rolling stock) of any kind located in, on,
or under, any land or nonnavigable waters within
the United States.
(19) The term "otherwise subject to the juris-
diction of the United States" means subject to the
Ssl.Env.Uw Stats. '87 Ed.—16
473
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42 § 9601
FEDERAL ENVIRONMENTAL LAW
jurisdiction of the United States by virtue of
United States citizenship, United States vessel
documentation or numbering, or as provided by
international agreement to which the United
States is a party.
(20XA) The term "owner or operator" means
(i) in the case of a vessel, any person owning,
operating, or chartering by demise, such vessel,
(ii) in the case of an onshore facility or an off-
shore facility, any person owning or operating
such facility, and (iii) in the case of any facility,
title or control of which was conveyed due to
bankruptcy, foreclosure, tax delinquency, aban-
donment, or similar means to a unit of State or
local government, any person who owned, operat-
ed or otherwise controlled activities at such facili-
ty immediately beforehand. Such term does not
include a person, who, without participating in the
management of a vessel or facility, holds indicia of
ownership primarily to protect his security interest
in the vessel or facility.
(B) In the case of a hazardous substance which
has been accepted for transportation by a com-
mon or contract carrier and except as provided in
section 9607(a)(3) or (4) of this title, (i) the term
"owner or operator" shall mean such common
carrier or other bona fide for hire carrier acting
as an independent contractor during such trans-
portation, (ii) the shipper of such hazardous sub-
stance shall not be considered to have caused or
contributed to any release during such transpor-
tation which resulted solely from circumstances
or conditions beyond his control.
(C) In the case of a hazardous substance which
has been delivered by a common or contract carri-
er to a disposal or treatment facility and except as
provided in section 9607(a)(3) or (4) of this title (i)
the term "owner or operator" shall not include
such common or contract carrier, and (ii) such
common or contract carrier shall not be con-
sidered to have caused or contributed to any
release at such disposal or treatment facility re-
sulting from circumstances or conditions beyond
its control.
(D) The term "owner or operator" does not
include a unit of State or local government which
acquired ownership or control involuntarily
through bankruptcy, tax delinquency, abandon-
ment, or other circumstances in which the govern-
ment involuntarily acquires title by virtue of its
function as sovereign. The exclusion provided
under this paragraph shall not apply to any State
or local government which has caused or contrib-
uted to the release or threatened release of a
hazardous substance from the facility, and such a
State or local government shall be subject to the
provisions of this chapter in the same manner and
to the same extent, both procedurally and sub-
stantively, as any nongovernmental entity, includ-
ing liability under section 9607 of this title.
(21) The term "person" means an individual,
firm, corporation, association, partnership, consor-
tium, joint venture, commercial entity, United
States Government, State, municipality, commis-
sion, political subdivision of a State, or any inter-
state body.
(22) The term "release" means any spilling,
leaking, pumping, pouring, emitting, emptying,
discharging, injecting, escaping, leaching, dump-
ing, or disposing into the environment (including
the abandonment or discarding of barrels, con-
tainers, and other closed receptacles containing
any hazardous substance or pollutant or contami-
nant), but excludes (A) any release which results
in exposure to persons solely within a workplace,
with respect to a claim which such persons may
assert against the employer of such persons, (B)
emissions from the engine exhaust of a motor
vehicle, rolling stock, aircraft, vessel, or pipeline
pumping station engine, (C) release of source,
byproduct, or special nuclear material from a
nuclear incident, as those terms are defined in the
Atomic Energy Act of 1954 [42 U.S.C. 2011 et
seq.], if such release is subject to requirements
with respect to financial protection established by
the Nuclear Regulatory Commission under sec-
tion 170 of such Act [42 U.S.C. 2210], or, for the
purposes of section 9604 of this title or any other
response action, any release of source byproduct,
or special nuclear material from any processing
site designated under section 7912(a)(l) or 7942(a)
of this title, and (D) the normal application of
fertilizer.
(23) The term "remove" or "removal" means
the cleanup or removal of released hazardous
substances from the environment, such actions as
may be necessary2 taken in the event of the
threat of release of hazardous substances into the
environment, such actions as may be necessary to
monitor, assess, and evaluate the release or
threat or release of hazardous substances, the
disposal of removed material, or the taking of
such other actions as may be necessary to pre-
vent, minimize, or mitigate damage to the public
health or welfare or to the environment, which
may otherwise result from a release or threat of
release. The term includes, in addition, without
being limited to, security fencing or other mea-
sures to limit access, provision of alternative wa-
ter supplies, temporary evacuation and housing of
threatened individuals not otherwise provided for,
action taken under section 9604(b) of this title,
and any emergency assistance which may be pro-
vided under the Disaster Relief Ace of 1974 [42
U.S.C. 5121 et seq.].
(24) The term "remedy" or "remedial action"
means those actions consistent with permanent
474
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ENVIRONMENTAL RESPONSE, ETC.
42 § 9601
remedy taken instead of or in addition to removal
actions in the event of a release or threatened
release of a hazardous substance into ihe euvuon-
ment, to prevent or minimize the release of haz-
ardous substances so that they do not migrate to
cause substantial danger to present or future
public health or welfare or the environment. The
term includes, but is not limited to, such actions
at the location of the release as storage, confine-
ment, perimeter protection using dikes, trenches,
or ditches, clay cover, neutralization, cleanup of
released hazardous substances or contaminated
materials, recycling or reuse, diversion, destruc-
tion, segregation of reactive wastes, dredging or
excavations, repair or replacement of leaking con-
tainers, collection of leachate and runoff, onsite
treatment or incineration, provision of alternative
water supplies, and any monitoring reasonably
required to assure that such actions protect the
public health and welfare and the environment.
The term includes the costs of permanent reloca-
tion of residents and businesses and community
facilities where the President determines that,
alone or in combination with other measures, such
relocation is more cost-effective than and environ-
mentally preferable to the transportation, stor-
age, treatment, destruction, or secure disposition
offsite of hazardous substances, or may other-
wise be necessary to protect the public health or
welfare; the term includes offsite transport and
offsite storage, treatment, destruction, or secure
disposition of hazardous substances and associat-
ed contaminated materials.
(25) The term "respond" or "response" means
remove, removal, remedy, and remedial action, all
such terms (including the terms "removal" and
"remedial action") include enforcement activities
related thereto.
(26) The term "transport" or "transportation"
means the movement of a hazardous substance by
any mode, including pipeline (as defined in the
Pipeline Safety Act), and in the case of a hazard-
ous substance which has been accepted for trans-
portation by a common or contract carrier, the
term "transport" or "transportation" shall include
any stoppage in transit which is temporary, inci-
dental to the transportation movement, and at the
ordinary operating convenience of a common or
contract carrier, and any such stoppage shall be
considered as a continuity of movement and not
as the storage of a hazardous substance.
(27) The terms "United States" and "State"
include the several States of the Unites States,
the District of Columbia, the Commonwealth of
Puerto Rico, Guam, American Samoa, the United
States Virgin Islands, the Commonwealth of the
Northern Marianas, and any other territory or
possession over which the United States has juris-
diction.
(28) The term "vessel" means every description
of watercraft or other artificial contrivance used,
or capable of being used, as a means of transpor-
tation on water.
(29) The terms "disposal", "hazardous waste",
and "treatment" shall have the meaning provided
in section 1004 of the Solid Waste Disposal Act
[42 U.S.C. 6903].
(30) The terms "territorial sea" and "contig-
uous zone" shall have the meaning provided in
section 1362 of Title 33.
(31) The term "national contingency plan"
means the national contingency plan published
under section 1321(c) of Title 33 or revised pursu-
ant to section 9605 of this title.
(32) The term "liable" or "liability" under this
subchapter shall be construed to be the standard
of liability which obtains under section 1321 of
Title 33.
(33) The term "pollutant or contaminant" shall
include, but not be limited to, any'element, sub-
stance, compound, or mixture, including disease-
causing agents, which after release into the envi-
ronment and upon exposure, ingestion, inhalation;
or assimilation into any organism, 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, physio-
logical malfunctions (including malfunctions in re-
production) or physical deformations, in such or-
ganisms or their offspring; except that the term
"pollutant or contaminant" shall not include pe-
troleum, including crude oil or any fraction there-
of which is not otherwise specifically listed or
designated as a hazardous substance under sub-
paragraphs (A) through (F) of paragraph (14) and
shall not include natural gas, liquefied natural
gas, or synthetic gas of pipeline quality (or mix-
tures of natural gas and such synthetic gas).
(34) The.term "alternative water supplies" in-
cludes, but is not limited to, drinking water and
household water supplies.
(35HA) The term "contractual relationship",
for the purpose of section 9607(b)(3) of this title
includes, but is not limited to, land contracts,
deeds or other instruments transferring title or
possession, unless the real property on which the
facility concerned is located was acquired by the
defendant after the disposal or placement of the
hazardous substance on, in, or at the facility, and
one or more of the circumstances described in
clause (i), (ii), or (iii) is also established uy the
defendant by a preponderance of the evidence:
475
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42 § 9601
FEDERAL ENVIRONMENTAL iAW
(i) At the time the defendant acquired the
facility the defendant did not know and had no
reason to know that any hazardous substance
which is the subject of the release or threat-
ened release was disposed of on, in, or at the
facility.
(ii) The defendant is a government entity
which acquired the facility by escheat, or
through any other involuntary transfer or ac-
quisition, or through the exercise of eminent
domain authority by purchase or condemnation.
(iii) The defendant acquired the facility by
inheritance or bequest.
In addition to establishing the foregoing, the de-
fendant must establish that he has satisfied the
requirements of section 9607(b)(3)(a) and (b) of this
title.
(B) To establish that the defendant had no
reason to know, as provided in clause (i) of sub-
paragraph (A) of this paragraph, the defendant
must have undertaken, at the time of acquisition,
all appropriate inquiry into the previous owner-
ship and uses of the property consistent with
good commercial or customary practice in an ef-
fort to minimize liability. For purposes of the
preceding sentence the court shall take into ac-
count any specialized knowledge or experience on
the part of the defendant, the relationship of the
purchase price to the value of the property if
uncontaminated, commonly known or reasonably
ascertainable information about the property, the
obviousness of the presence or likely presence of
contamination at the property, and the ability to
detect such contamination by appropriate inspec-
tion.
(C) Nothing in this paragraph or in section
9607(b)(3) of this title shall diminish the liability of
any previous owner or operator of such facility
who would otherwise be liable under this chapter.
Notwithstanding this paragraph, if the defendant
obtained actual knowledge of the release or
threatened release of a hazardous substance at
such facility when the defendant owned the real
property and then subsequently transferred own-
ership of the property to another person without
disclosing such knowledge, such defendant shall
be treated as liable under section 9607(a)(l) of this
title and no defense under section 9607(b)(3) of
this title shall be available to such defendant.
(D) Nothing in this paragraph shall affect the
liability under this chapter of a defendant who, by
any act or omission, caused or contributed to the
release or threatened release of a hazardous sub-
stance which is the subject of the action relating
to the facility.
(36) The term "Indian tribe" means any Indian
tribe, band, nation, or other organized group or
community, including any Alaska Native village
but not including any Alaska Native regional or
village corporation, which is recognized as eligible
for the special programs and services provided by
the United States to Indians because of their
status as Indians.
(37XA) The term "service station dealer"
means any person—
(i) who owns or operates a motor vehicle
service station, filling station, garage, or sim-
ilar retail establishment engaged in the busi-
ness of selling, repairing, or servicing motor
vehicles, where a significant percentage of the
gross revenue of the establishment is derived
from the fueling, repairing, or servicing of mo-
tor vehicles, and
(ii) who accepts for collection, accumulation,
and delivery to an oil recycling facility, recycled
oil that (I) has been removed from the engine of
a light duty motor vehicle or household appli-
ances by the owner of such vehicle or appli-
ances, and (II) is presented, by such owner, to
such person for collection, accumulation, and
delivery to an oil recycling facility.
(B) For purposes of section 9614(c) of this title
the term "service station dealer" shall, notwith-
standing the provisions of subparagraph (A), in-
clude any government agency that establishes a
facility solely for the purpose of accepting recy-
cled oil that satisfies the criteria set forth in
subclauses (I) and (II) of subparagraph (A)(ii),
and, with respect to recycled oil that satisfies the
criteria set forth in subclauses (I) and (II), owners
or operators of refuse collection services who are
compelled by State law to collect, accumulate, and
deliver such oil to an oil recycling facility.
(C) The President shall promulgate regulations
regarding the determination of what constitutes a
significant percentage of the gross revenues of
an establishment for purposes of this paragraph.
(38) The term "incineration vessel" means any
vessel which carries hazardous substances for the
purpose of incineration of such substances, so
long as such substances or residues of such sub-
stances are on board.
(Dec. 11, 1980, Pub.L. 96-510, Title I, § 101, 94 Stat. 2767;
Dec. 22, 1980, Pub.L. 96-561, Title II, § 238(b), 94 Stat.
3300: as amended Oct. 17, 1986, Pub.L. 99-499, Title I,
§§ 101, 114(b), 127(a), Title V, § 517(c)(2), 100 Stat. 1615,
1652, 1692, 1774.)
l So in original. Probably should be "or".
2 So in original. Probably should be "necessarily"
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ENVIRONMENTAL RESPONSE, ETC.
42 §9604
(e) Applicability to registered pesticide product
This section shall not apply to the application of a
pesticide product registered under the Federal In-
secticide, Fungicide, and Rodenticide Act [7 U.S.C.
136 et seq.] or to the handling and storage of such a
pesticide product by an agricultural producer.
(f) Exemptions from notice and penalty provisions for
substances reported under other Federal law or is
in continuous release, etc.
No notification shall be required under subsection
(a) or (b) of this section for any release of a hazard-
ous substance—
(1) which is required to be reported (or specifi-
cally exempted from a requirement for reporting)
under subtitle C of the Solid Waste Disposal Act
[42 U.S.C. 6921 et seq.] or regulations thereunder
and which has been reported to the National
Response Center, or
(2) which is a continuous release, stable in
quantity and rate, and is—
(A) from a facility for which notification has
been given under subsection (c) of this section,
or
(B) a release of which notification has been
given under subsections (a) and (b) of this sec-
tion for a period sufficient to establish the
continuity, quantity, and regularity of such re-
lease:
Provided, That notification in accordance with
subsections (a) and (b) of this paragraph shall be
given for releases subject to this paragraph annu-
ally, or at such time as there is any statistically
significant increase in the quantity of any hazard-
ous substance or constituent thereof released,
above that previously reported or occurring.
(Dec. 11, 1980, Pub.L. 96-510, Title I, § 103, 94 Stat. 2772;
Dec. 22, 1980, Pub.L. 96-561, Title II, § 238(b), 94 Stat.
3300; as amended Oct. 17, 1986, Pub.L. 99-499, Title I,
§§ 103, 109(aXD, (2), 100 Stat. 1617, 1632, 1633.)
Library References
Health and Environment «=25.5(10), 25.6(3), (9), 25.7(3), (24).
C.J.S. Health and Environment §§ 92, 103 et seq., 106, 113 et
seq.
§ 9604. Response authorities
(a) Removal and other remedial action by President;
applicability of national contingency plan; re-
sponse by potentially responsible parties; public
health threats; limitations on response: exception
(1) Whenever (A) any hazardous substance is re-
leased or there is a substantial threat of such a
release into the environment, or (B) there is a re-
lease or substantial threat of release into the envi-
ronment of any pollutant or contaminant which may
present an imminent and substantial danger to the
public health or welfare, the President is authorized
to act, consistent with the national contingency
plan, to remove or arrange for the removal of, and
provide for remedial action relating to such hazard-
ous substance, pollutant, or contaminant at any
time (including its removal from any contaminated
natural resource), or take any other response mea-
sure consistent with the national contingency plan
which the President deems necessary to protect the
public health or welfare or the environment. When
the President determines that such action will be
done properly and promptly by the owner or opera-
tor of the facility or vessel or by any other respon-
sible party, the President may allow such person to
carry out the action, conduct the remedial investiga-
tion, or conduct the feasibility study in accordance
with section 9622 of this title. No remedial investi-
gation or feasibility study (RI/FS) shall be autho-
rized except on a determination by the President
that the party is qualified to conduct the RI/FS and
only if the President contracts with or arranges for
a qualified person to assist the President in oversee-
ing and reviewing the conduct of such RI/FS and if
the responsible party agrees to reimburse the Fund
for any cost incurred by the President under, or in
connection with, the oversight contract or arrange-
ment. In no event shall a potentially responsible
party be subject to a lesser standard of liability,
receive preferential treatment, or in any other way,
whether direct or indirect, benefit from any such
arrangements as a response action contractor, or as
a person hired or retained by such a response action
contractor, with respect to the release or facility in
question. The President shall give primary atten-
tion to those releases which the President deems
may present a public health threat.
(2) Removal action
Any removal action undertaken by the Presi-
dent under this subsection (or by any other per-
son referred to in section 9622 of this title)
should, to the extent the President deems practi-
cable, contribute to the efficient performance of
any long term remedial action with respect to the
release or threatened release concerned.
(3) Limitations on response
The President shall not provide for a removal or
remedial action under this section in response to a
release or threat of release—
(A) of a naturally occurring substance in its
unaltered form, or altered solely through natural-
ly occurring processes or phenomena, from a loca-
tion where it is naturally found;
(B) from products which are part of the struc-
ture of, and result in exposure within, residential
buildings or business or community structures;
479
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42 § 9604
FEDERAL ENVIRONMENTAL LAW
(C) into public or private drinking water sup-
plies due to deterioration of the system through
ordinary use.
(4) Exception to limitations
Notwithstanding paragraph (3) of this subsec-
tion, to the extent authorized by this section, the
President may respond to any release or threat of
release if in the President's discretion, it consti-
tutes a public health or environmental emergency
and no other person with the authority and capa-
bility to respond to the emergency will do so in a
timely manner.
(b) Investigations, monitoring, etc., by President
(1) Information; studies and investigations
Whenever the President is authorized to act
pursuant to subsection (a) of this section, or
whenever the President has reason to believe that
a release has occurred or is about to occur, or
that illness, disease, or complaints thereof may be
attributable to exposure to a hazardous sub-
stance, pollutant, or contaminant and that a re-
lease may have occurred or be occurring, he may
undertake such investigations, monitoring, sur-
veys, testing, and other information gathering as
he may deem necessary or appropriate to identify
the existence and extent of the release or threat
thereof, the source and nature of the hazardous
substances, pollutants or contaminants involved,
and the extent of danger to the public health or
welfare or to the environment. In addition, the
President may undertake such planning, legal,
fiscal, economic, engineering, architectural, and
Other studies or investigations as he may deem
necessary or appropriate to plan and direct re-
sponse actions, to recover the costs thereof, and
to enforce the provisions of this chapter.
(2) Coordination of investigations
The President shall promptly notify the appro-
priate Federal and State natural resource trustees
of potential damages to natural resources result-
ing from releases under investigation pursuant to
this section and shall seek to coordinate the as-
sessments, investigations, and planning under
this section with such Federal and State trustees.
(c) Criteria for continuance of obligations from Fund
over specified amount for response actions; con-
sultation by President with affected States; con-
tracts or cooperative agreements by States with
President prior to remedial actions; cost-sharing
agreements; selection by President of remedial
actions; State credits: granting of credit, expenses
before listing or agreement, response actions be-
tween 1978 and 1980. State expenses after Decem-
ber 11, 1980, in excess of 10 percent of costs,
item-by-item approval, use of credits; operation
and maintenance; limitation on source of funds
for O&M; recontracting; siting
(I) Unless (A) the President finds that (i) contin-
ued response actions are immediately required to
prevent, limit, or mitigate an emergency, (ii) there is
an immediate risk to public health or welfare or the
environment, and (iii) such assistance will not other-
wise be provided on a timely basis, or (B) the
President has determined the appropriate remedial
actions pursuant to paragraph (2) of this subsection
and the State or States in which the source of the
release is located have complied with the require-
ments of paragraph (3) of this subsection, or (C)
continued response action is otherwise appropriate
and consistent with the remedial action to be taken l
obligations from the Fund, other than those autho-
rized by subsection (b) of this section, shall not
continue after $2,000,000 has been obligated for
response actions or 12 months has elapsed from the
date of initial response to a release or threatened
release of hazardous substances.
(2) The President shall consult with the affected
State or States before determining any appropriate
remedial action to be taken pursuant to the authori-
ty granted under subsection (a) of this section.
(3) The President shall not provide any remedial
actions pursuant to this section unless the State in
which the release occurs first enters into a contract
or cooperative agreement with the President provid-
ing assurances deemed adequate by the President
that (A) the State will assure all future maintenance
of the removal and remedial actions provided for the
expected life of such actions as determined by the
President; (B) the State will assure the availability
of a hazardous waste disposal facility acceptable to
the President and in compliance with the require-
ments of subtitle C of the Solid Waste Disposal Act
[42 U.S.C.A. § 6921 et seq.] for any necessary off-
site storage, destruction, treatment, or secure dispo-
sition of the hazardous substances; and (C) the
State will pay or assure payment of (i) 10 per
centum of the costs of the remedial action, including
all future maintenance, or (ii) 50 percent (or such
greater amount as the President may determine
appropriate, taking into account the degree of re-
sponsibility of the State or political subdivision for
the release) of any sums expended in response to a
release at a facility, that was operated by the State
or a political subdivision thereof, either directly or
through a contractual relationship or otherwise, at
the time of any disposal of hazardous substances
therein. For the purpose of clause (ii) of this sub-
paragraph, the term "facility" does not include navi-
gable waters or the beds underlying those waters.
The President shall grant the State a credit against
the share of the costs for which it is responsible
under this paragraph for any documented direct
out-of-pocket non-Federal funds expended or obli-
gated by the State or a political subdivision thereof
after January 1, 1978, and before December 11,
1980, for cost-eligible response actions and claims
480
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ENVIRONMENTAL RESPONSE, ETC.
42 § 9604
vene in any civi] action involving the enforcement of
such contract or subcontract.
(4) Where iwo or more noncontiguous facilities
are reasonably related on the basis of geography, or
on the basis of the threat, or potential threat to the
public health or welfare or the environment, the
President may, in his discretion, treat these related
facilities as one for purposes of this section.
(eV-Information gathering and access; action autho-
rized, access to information, entry, inspection and
samples; authority and samples, compliance or-
ders; issuance and compliance, other authority,
confidentiality of information; basis for withhold-
ing
(1) Action authorized
Any officer, employee, or representative of the
President, duly designated by the President, is
authorized to take action under paragraph (2), (3),
or (4) (or any combination thereof) at a vessel,
facility, establishment, place, property, or location
or, in the case of paragraph (3) or (4), at any
vessel, facility, establishment, place, property, or
location which is adjacent to the vessel, facility,
establishment, place, property, or location re-
ferred to in such paragraph (3) or (4). Any duly
designated officer, employee, or representative of
a State or political subdivision under a contract or
cooperative agreement under subsection (d)(l) of
this section is also authorized to take such action.
The authority of paragraphs (3) and (4) may be
exercised only if there is a reasonable basis to
believe there may be a release or threat of release
of a hazardous substance or pollutant or contami-
nant. The authority of this subsection may be
exercised only for the purposes of determining
the need for response, or choosing or taking any
response action under this subchapter, or other-
wise enforcing the provisions of this subchapter.
(2) Access to information
Any officer, employee, or representative de-
scribed in paragraph (1) may require any person
who has or may have information relevant to any
of the following to furnish, upon reasonable no-
tice, information or documents relating to such
matter:
(A) The identification, nature, and quantity
of materials which have been or are generated,
treated, stored, or disposed of at a vessel or
facility or transported to a vessel or facility.
(B) The nature or extent of a release or
threatened release of a hazardous substance or
pollutant or contaminant at or from a vessel or
facility.
(C) Information relating to the ability of a
person to pay for or to perform a cleanup.
In addition, upon reasonable notice, such person
either (i) shall grant any such officer, employee, or
representative access at all reasonable times to any
vessel, facility, establishment, place, property, or
location to inspect and copy all documents or
records relating to such matters or (ii) shall copy
and furnish to the officer, employee, or representa-
tive all such documents or records, at the option and
expense of such person.
(3) Entry
Any officer, employee, or representative de-
scribed in paragraph (1) is authorized to enter at
reasonable times any of the following:
(A) Any vessel, facility, establishment, or
other place or property where any hazardous
substance or pollutant or contaminant may be
or has been generated, stored, treated, disposed
of, or transported from.
(B) Any vessel, facility, establishment, or
other place or property from which or to which
a hazardous substance or pollutant or contami-
nant has been or may have been released.
(C) Any vessel, facility, establishment, or
other place or property where such release is or
may be threatened.
(D) Any vessel, facility, establishment, or
other place or property where entry is needed
to determine the need for response or the ap-
propriate response or to effectuate a response
action under this subchapter.
(4) Inspection and samples
(A) Authority
Any officer, employee or representative de-
scribed in paragraph (1) is authorized to inspect
and obtain samples from any vessel, facility,
establishment, or other place or property re-
ferred to in paragraph (3) or from any location
of any suspected hazardous substance or pollu-
tant or contaminant. Any such officer, employ-
ee, or representative is authorized to inspect
and obtain samples of any containers or label-
ing for suspected hazardous substances or pol-
lutants or contaminants. Each such inspection
shall be completed with reasonable promptness.
(B) Samples
If the officer, employee, or representative
obtains any samples, before leaving the premis-
es he shall give to the owner, operator, tenant,
or other person in charge of the place from
which the samples were obtained a receipt de-
scribing the sample obtained and, if requested,
a portion of each such sample. A copy of the
results of any analysis made of such samples
shall be furnished promptly to the owner, oper-
483
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42 §9604
FEDERAL ENVIRONMENTAL LAW
ator, tenant, or other person in charge, if such
person can be located.
(5) Compliance orders
(A) Issuance
If consent is not granted regarding any re-
quest made by an officer, employee, or repre-
sentative under paragraph (2), (3), or (4), the
President may issue an order directing compli-
ance with the request. The order may be is-
sued after such notice and opportunity for con-
sultation as is reasonably appropriate under the
circumstances.
(B) Compliance
The President may ask the Attorney General
to commence a civil action to compel compliance
with a request or order referred to in subpara-
graph (A). Where there is a reasonable basis
to believe there may be a release or threat of a
release of a hazardous substance or pollutant
or contaminant, the court shall take the follow-
ing actions:
(i) In the case of interference with entry
or inspection, the court shall enjoin such in-
terference or direct compliance with orders to
prohibit interference with entry or inspection
unless under the circumstances of the case
the demand for entry or inspection is arbi-
trary and capricious, an abuse of discretion,
or otherwise not in accordance with law.
(ii) In the case of information or document
requests or orders, the court shall enjoin in-
terference with such information or doc-
ument requests or orders or direct compli-
ance with the requests or orders to provide
such information or documents unless under
the circumstances of the case the demand for
information or documents is arbitrary and
capricious, an abuse of discretion, or other-
wise not in accordance with law.
The court may assess a civil penalty not to exceed
$25,000 for each day of noncompliance against any
person who unreasonably fails to comply with the
provisions of paragraph (2), (3), or (4) or an order
issued pursuant to subparagraph (A) of this para-
graph.
(6) Other authority
Nothing in this subsection shall preclude the
President from securing access or obtaining infor-
mation in any other lawful manner.
(7) Confidentiality of information
(A) Any records, reports, or information ob-
tained from any person under this section (includ-
ing records, reports, or information obtained by
representatives of the President) shall be avail-
able to the public, except that upon a showing
satisfactory to the President (or the State, as the
case may be) by any person that records, reports,
or information, or particular part thereof (other
than health or safety effects data), to which the
President (or the State, as the case may be) or
any officer, employee, or representative has ac-
cess under this section if made public would di-
vulge information entitled to protection under sec-
tion 1905 of Title 18, such information or particu-
lar portion thereof shall be considered confiden-
tial in accordance with the purposes of that sec-
tion, except that such record, report, document or
information may be disclosed to other officers,
employees, or authorized representatives of the
United States concerned with carrying out this
chapter, or when relevant in any proceeding un-
der this chapter.
(B) Any person not subject to the provisions of
section 1905 of Title 18 who knowingly and will-
fully divulges or discloses any information enti-
tled to protection under this subsection shall,
upon conviction, be subject to a fine of not more
than $5,000 or to imprisonment not to exceed one
year, or both.
(C) In submitting data under this chapter, a
person required to provide such data may (i) des-
ignate the data which such person believes is
entitled to protection under this subsection and (ii)
submit such designated data separately from oth-
er data submitted under this chapter. A designa-
tion under this paragraph shall be made in writ-
ing and in such manner as the President may
prescribe by regulation.
(D) Notwithstanding any limitation contained
in this section or any other provision of law, all
information reported to or otherwise obtained by
the President (or any representative of the Presi-
dent) under this chapter shall be made available,
upon written request of any duly authorized com-
mittee of the Congress, to such committee.
(E) No person required to provide information
under this chapter may claim that the information
is entitled to protection under this paragraph un-
less such person shows each of the following:
(i) Such person has not disclosed the infor-
mation to any other person, other than a mem-
ber of a local emergency planning committee
established under title III of the Amendments
and Reauthorization Act of 1986 [42 U.S.C.A.
§ 11001 et seq.], an officer or employee of the
United States or a State or local government,
an employee of such person, or a person who is
bound by a confidentiality agreement, and such
484
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ENVIRONMENTAL RESPONSE, ETC.
42 § 9604
person has taken reasonable measures to pro-
tect the confidentiality of such information and
intends to continue to take such measures.
(ii) The information is not required to be
disclosed, or otherwise made available, to the
public under any other Federal or State law.
(iii) Disclosure of the information is likely to
cause substantial harm to the competitive posi-
tion of such person.
(iv) The specific chemical identity, if sought
to be protected, is not readily discoverable
through reverse engineering.
(F) The following information with respect to
any hazardous substance at the facility or vessel
shall not be entitled to protection under this para-
graph:
(i) The trade name, common name, or gener-
ic class or category of the hazardous substance.
(ii) The physical properties of the substance,
including its boiling point, melting point, flash
point, specific gravity, vapor density, solubility
in water, and vapor pressure at 20 degrees
Celsius.
(iii) The hazards to health and the environ-
ment posed by the substance, including physical
hazards (such as explosion) and potential acute
and chronic health hazards.
(iv) The potential routes of human exposure
to the substance at the facility, establishment,
place, or property being investigated, entered,
or inspected under this subsection.
(v) The location of disposal of any waste
stream.
(vi) Any monitoring data or analysis of moni-
toring data pertaining to disposal activities.
(vii) Any hydrogeologic or geologic data.
(viii) Any groundwater monitoring data.
(f) Contracts for response action; compliance with Fed-
eral health and safety standards
In awarding contracts to any person engaged in
response actions, the President or the State, in any
case where it is awarding contracts pursuant to a
contract entered into under subsection (d) of this
section, shall require compliance with Federal
health and safety standards established under sec-
tion 9651(f) of this title by contractors and subcon-
tractors as a condition of such contracts.
(g) Rates for wages and labor standards applicable to
covered work
(1) All laborers and mechanics employed by con-
tractors or subcontractors in the performance of
construction, repair, or alteration work funded in
whole or in part under this section shall be paid
wages at rates not less than those prevailing on
projects of a character similar in the locality as
determined by the Secretary of Labor in accordance
with the Davis-Bacon Act [40 U.S.C. 276a et seq.].
The President shall not approve any such funding
without first obtaining adequate assurance that re-
quired labor standards will be maintained upon the
construction work.
(2) The Secretary of Labor shall have, with re-
spect to the labor standards specified in paragraph
(1), the authority and functions set forth in Reorga-
nization Plan Numbered 14 of 1950 (15 F.R. 3176;
64 Stat. 1267) and section 276c of Title 40.
(h) Emergency procurement powers; exercise by Presi-
dent
Notwithstanding any other provision of law, sub-
ject to the provisions of section 9611 of this title, the
President may authorize the use of such emergency
procurement powers as he deems necessary to ef-
fect the purpose of this chapter. Upon determina-
tion that such procedures are necessary, the Presi-
dent shall promulgate regulations prescribing the
circumstances under which such authority shall be
used and the procedures governing the use of such
authority.
(i) Agency for Toxic Substances and Disease Registry;
establishment, functions, etc.
(1) There is hereby established within the Public
Health Service an agency, to be known as the
Agency for Toxic Substances and Disease Registry,
which shall report directly to the Surgeon General
of the United States. The Administrator of said
Agency shall, with the cooperation of the Adminis-
trator of the Environmental Protection Agency, the
Commissioner of the Food and Drug Administra-
tion, the Directors of the National Institute of Medi-
cine, National Institute of Environmental Health
Sciences, National Institute of Occupational Safety
and Health, Centers for Disease Control, the Admin-
istrator of the Occupational Safety and Health Ad-
ministration, the Administrator of the Social Securi-
ty Administration, the Secretary of Transportation,
and appropriate State and local health officials, ef-
fectuate and implement the health related authori-
ties of this chapter. In addition, said Administrator
shall—
(A) in cooperation with the States, establish
and maintain a national registry of serious dis-
eases and illnesses and a national registry of
persons exposed to toxic substances;
(B) establish and maintain inventory of litera-
ture, research, and studies on the health effects
of toxic substances;
(C) in cooperation with the States, and other
agencies of the Federal Government, establish
485
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ENVIRONMENTAL RESPONSE, ETC.
42 §9606
health or the environment posed by the release
of such hazardous constituents at such facility.
This subparagraph refers only to available in-
formation on actual concentrations of hazard-
ous substances and not on the total quantity of
special study waste at such facility.
(3) Savings provisions
Nothing in this subsection shall be construed to
limit the authority of the President to remove any
facility which as of October 17, 1986 is included
on the National Priorities List from such list, or
not to list any facility which as of such date is
proposed for inclusion on such list.
(4) Information Catherine and analysis
Nothing in this chapter shall be construed to
preclude the expenditure of monies from the
Fund for gathering and analysis of information
which will enable the Presidentr*to consider the
specific factors required by paragraph (2).
(Dec. 11. 1980. Pub.L 96-510. Title I, § 105, 94 Sue 2779,
as amended Oct. 17, 1986, Pub.L 99-499, Title I, § 105,
100 Sue 1625.)
Code of Federal Refutations
Oil and hazardous lubttuiec* pollution contingency plan, M« iO
CFR 300.1 et icq.
Library Reference*
Health and Environment «"25.6, 25.7.
CJ.S. Health and Environment H 91 *t **q.. 106 *t MK).
§ 9606. Abatement action*
(a) Maintenance, jurisdiction, etc.
In addition to any other action taken by a State or
local government, when the President determines
that there may be an imminent and substantial
endangerment to the public health or welfare or the
environment because of an actual or threatened
release of a hazardous subatance from a facility, he
may require the Attorney General of the United
States to secure such relief as may be necessary to
abate such danger or threat, and the district court
of the United States in the district in which the
threat occurs shall have jurisdiction to grant such
relief as the public interest and the equities of the
case may require. The President may also, after
notice to the affected StXte, take other action under
this section including, but not limited to, issuing
such orders as may be necessary to protect public
health and welfare and the environment
order, be fined not more than $25,000 for each day
in which such violation occurs or such failure to
comply continues.
(2)(A) Any person who receives and complies
with the terms of any order issued under subsection
(a) of this section may, within 60 days after comple-
tion of the required action, petition the President
for reimbursement from the Fund for the reason-
able costs of such action, plus interest Any inter-
est payable under this paragraph shall accrue on
the amounts expended from the date of expenditure
at the same rate as specified for interest on invest-
ments of the Hazardous Substance Superfund es-
tablished under subchapter A of chapter 98 of Title
26.
(B) If the President refuses to grant all or part
of a petition made under this paragraph, the peti-
tioner may within 30 days of receipt of such refusal
file an action against the President in the appropri-
ate United States district court seeking reimburse-
ment from the Fund.
(C) Except as provided in subparagraph (D), to
obtain reimbursement the petitioner shall establish
by a preponderance of the evidence that it is not
liable for response costs under section 9€07(a) of
this title and that costs for which it seeks reim-
bursement are reasonable in light of the action
required by the relevant order.
(D) A petitioner who is liable for response costs
under section 9€07(a) of this title may also recover
its reasonable costs of response to the extent that it
can demonstrate, on the administrative record, that
the President's decision in selecting the response
action ordered was arbitrary and capricious or was
otherwise not in accordance with law. Reimburse-
ment awarded under this subparagraph shall in-
clude all reasonable response costs incurred by the
petitioner pursuant to the portions of the order
found to be arbitrary and capricious or otherwise
not in accordance with law.
(E) Reimbursement awarded by a court under
subparagraph (Q or (D) may include appropriate
costs, fees, and other expense* in accordance with
subsections (a) and (d) of section 2412 of Title 28.
(b) Fine*:
(1) Any person who, without sufficient cause,
willfully violates, or fails or refuses to comply with,
any order of the President under subsection (a) of
this section may, in an action brought in the appro-
priate United States district court to enforce such
(c) Guideline* for using Imminent hazard, ea/orecawat,
and emergency raponc* authoriti**; proaa mi-
ration far Administrator of EPA. teosw. etc.
Within one hundred and eighty days after Decem-
ber 11, 1980, the Administrator of the Environmen-
tal Protection Agency shall, after consultation with
die Attorney General, establish and publish guide-
lines for using the imminent hazard, enforcement
and emergency response authorities of this section
and other existing statutes administered by the
Administrator of the Environmental Protection
Agency to effectuate the responsibilities and pow-
493
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Attachment 3
Model Site Safety Plan for Chemical Safety Audits
-------
SITE SAFETY PLAN FOR
CHEMICAL SAFETY AUDITS
The OSHA Hazardous Waste Site Worker Standards (29 CFR 1910.120), the
EPA Safety Manual, Chapter 9, and other EPA protocols require certain safety
planning efforts prior to field activities. The following format is aligned with
these requirements. Extensive training and certifications, and further planning
in the form of a more extensive Site Safety Plan, may be required in addition to
the following plan.
PROJECT:
Project Coordinator: Date:
Branch Chief: Date:
On Scene Coordinator or
Supervisor: Date:
Health and Safety Manager
Approval: Date:
DESCRIPTION OF ACTIVITY
If any of the following information is unavailable, mark "UA"; if covered in
project plan, mark "PP."
Site Name:
Location and approximate size:
Description of the response activity and/or the job tasks to be performed:
Duration of the Planned Employee Activity:
Proposed Date of Beginning the Investigation:
Site Topography:
Site Accessibility by Air and Roads:
-------
HAZARDOUS SUBSTANCES AND HEALTH HAZARDS INVOLVED OR
SUSPECTED AT THE SITE
Fill in any information that is known or suspected
Chemical and Identity of Substance
Areas of Concern Physical Properties and Precautions
Explosivity:
Radioactivity:
Oxygen Deficiency:
(e.g., Confined Spaces)
Toxic Gases:
Skin/Eye Contact
Hazards:
Heat Stress:
Pathways from site for hazardous substance dispersion: _
WORK PLAN INSTRUCTIONS
A. Recommended Level of Protection: A B
Cartridge Type, if Level C:
-------
Additional Safety Clothing/Equipment:
Monitoring Equipment to be Used:
CONTRACTOR PERSONNEL:
Number of Skills:
CONTRACTOR SAFETY CLOTHING/EQUIPMENT REQUIRED:
Have contractors received OSHA required training and certification?
(29CFR 1910.120)
(If "yes," copy of training certificate(s) must be obtained from contractor)
B. Field Investigation and Decontamination Procedures:
Decontamination Procedures (contaminated protective clothing, instruments,
equipment, etc.):
-------
Disposal Procedures (contaminated equipment, supplies, disposal items, wash-
water, etc.):
EMERGENCY CONTACTS
Hospital Phone No.:
Hospital Location:
EMT/Ambulance Phone No.:
Police Phone No.:
Fire Assistance Phone No.:
Regional Health and Safety Manager:
-------
Attachment 4
Sources of Information
Concerning Hazardous Substance Releases
The Accidental Release Information Program (ARIP). EPA established ARIP to promote safety
initiatives by industry and to develop a national database on the causes of chemical accidents, but
more importantly, to identify methods used to prevent recurrences. The data collected in ARIP are
derived from questionnaires completed by selected facilities that have reported releases to the
National Response Center (NRC), as required by law.
Facilities selected to receive an ARIP questionnaire have experienced a "triggered" release
exhibiting one or more of the following characteristics:
Release quantities in excess of a multiple of the CERCLA reportable quantity for the
chemical involved;
Releases resulting in deaths or injuries;
Releases that are part of a trend of frequent releases from the same facility; or
Releases involving extremely hazardous substances designated under SARA Title III.
State Emergency Response Commissions (SERCs) and Local Emergency Planning Committees
(LEPCs). SERCs and LEPCs established under SARA Title III receive Section 304 reports detailing
accidental releases of hazardous chemicals (those listed under the OSHA Hazard Communication
Standard and CERCLA) and SERCs also received Section 313 reports recording annual releases,
routine and accidental, of hazardous substances by manufacturing facilities.
The National Response Center (NRC). The NRC receives notifications on accidental releases that
are subject to Reportable Quantity requirements of CERCLA. The NRC has been notified of
thousands of hazardous substance releases since 1978.
The Emergency Response Notification System (ERNS). ERNS is a recent effort of the Agency to
channel the state, regional, and NRC reports on releases of oil and hazardous substances into one
central database. ERNS is used by EPA for enforcement tracking and program management
purposes.
The Environmental Protection Agency (EPA). Both the national and regional offices of EPA receive
reports and notifications on accidental releases.
The Acute Hazardous Events Data Base (AHE/DB). Designed by EPA, AHE/DB collects a
representative sample of event reports from the above and other sources into a form that is more
convenient for gaining perspective on accidental releases and drawing policy conclusions. Developed
in 1985, it was recently updated and expanded to 6,300 records.
The Section 305(b) Report to Congress on Emergency Systems. Mandated by SARA Title III, the
report was a three-stage process. Information on certain facilities with completed questionnaires is
available. The report and backup information provide a good technical understanding for detecting,
monitoring and preventing releases, as well as for public alert.
-------
The Federal Emergency Management Agency (FEMA). FEMA keeps a record of all incidents
involving the participation of emergency management personnel.
The Occupation Safety and Health Administration (OSHA) and the National Institute of
Occupational Safety and Health (NIOSH). OSHA and NIOSH have records of accidents in the
workplace.
U.S. Coast Guard Marine Safety Offices (MSO). Local MSOs regularly conduct inspections of
waterfront facilities. These inspection reports are available from the respective MSO, and can
provide useful facility information.
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Attachment 5
Sample First Letter to Facility Owner/Operator
Dear (Facility Owner/Operator):
Through the records retained by the National Response Center pursuant to Section 103(a)
of the Comprehensive Environmental Response, Compensation, and Liability Act of 1980, as
amended (CERCLA), the U.S. Environmental Protection Agency has identified your facility as a site
where a reportable release of a CERCLA hazardous substance occurred. The EPA is currently
conducting chemical safety audits of particular facilities identified through the Section 103(a)
reporting system for the purpose of identifying technological and managerial mechanisms that might
be implemented to prevent future threatened releases harmful to human health and the environment.
The audit includes an on-site visit during which a review of equipment, procedures, training, and
management techniques is conducted to learn about prevention of accidental chemical releases.
Due to a report filed by the (facility name) under Section 103(a) of CERCLA, (facility name)
has been chosen as a potential candidate for an EPA chemical safety audit. The Agency is requesting
your cooperation in an audit of your facility under the authorities of Sections 104(b) and 104(e)
CERCLA, by (names and affiliation of audit team) on (date), or on a date convenient to you. Please
be assured that the audit team will make every effort to minimize any interference with your plant
operations during the actual safety audit.
If you wish to assert a business confidentiality claim for part or all of the information
collected, such a claim must accompany the information when it is received by EPA, or it may be
made available to the public without further notice to you. Information covered by a confidentiality
claim will be disclosed by EPA only to the extent, and by means of the procedures, set forth in EPA
regulations at 40 CFR Part 2. EPA has contracted with (contractor name and contract number) to
obtain information pertinent to conducting the safety audit. (Contractor name) has been designated
as an authorized representative of the Agency. Therefore, (contractor name) is subject to the
provisions of Section 104(e) of CERCLA respecting confidentiality of methods or processes entitled
to protection as trade secrets.
EPA would like to conduct this audit in a constructive and positive manner. The EPA solicits
your prompt response to the above request. If you have any questions about the audit or the
Chemical Safety Audit program, please contact (regional contact) for further information.
Sincerely,
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Attachment 6
Sample Letter to Facility Owner/Operator who has not Responded
or Consented to the Audit
Dear (Facility Owner/Operator):
Through the records retained by the National Response Center pursuant to Section 103(a)
of the Comprehensive Environmental Response, Compensation and Liability Act of 1980, as amended
(CERCLA), the U.S. Environmental Protection Agency has identified your facility as a site where
a reportable release of a CERCLA hazardous substance occurred. The EPA is currently conducting
chemical safety audits of particular facilities identified through the Section 103(a) reporting system
for the purpose of identifying technological and managerial mechanisms that might be implemented
to prevent future threatened releases harmful to human health and the environment. The (facility
name) has been chosen for a chemical safety audit due to its reportable release(s) of (CERCLA
hazardous substance(s)) on (date of release). The audit includes an on-site visit in which a review of
equipment, procedures, training and management techniques is conducted to learn about prevention
of accidental chemical releases. We wish to assure you that we will make every effort to minimize
any interference with your plant operations during the course of the audit.
On (date) EPA sent you a letter requesting your voluntary cooperation in a chemical safety
audit of your facility. [The Agency has not received a reply to that request.] [(By letter dated
,) (/Through a telephone conversation on ,) you indicated that you will not
extend your voluntary cooperation to an audit of your facility.] You should be aware that Sections
104(b) and 104(e)(4)(A) of CERCLA specifically give EPA the right to access private property where
there is a reasonable basis to believe that there has been or may be a release or threat of release of
a hazardous substance or pollutant or contaminant. Failure to grant such access within days
of receipt of this letter, or adequately to justify such failure to grant such access, can result in EPA
enforcing an order requesting entry pursuant to Section 104(e)(5) by seeking a warrant and/or
penalties for noncompliance with the entry order. Section 104(e)(5)(B) of CERCLA permits EPA
to seek the imposition of up to twenty-five thousand dollars ($25,000) for each day that you fail to
grant access to EPA. Please be further advised that provision of false, fictitious, or fraudulent
statements or representations may subject you to criminal penalties under 18 U.S.C. Section 1001.
If you wish to assert a business confidentiality claim for part or all of the information
collected, such a claim must accompany the information when it is received by EPA, or it may be
made available to the public without further notice to you. Information covered by a
confidentiality claim will be disclosed by EPA only to the extent and by means of the procedures set
forth in EPA regulations at 40 CFR Part 2. EPA has contracted with (contractor name and contract
number) to obtain information pertinent to conducting the safety audit. (Contractor name) has been
designated as an authorized representative of the Agency. Therefore, (contractor name) is subject
to the provisions of Section 104(e) of CERCLA respecting confidentiality of methods or processes
entitled to protection as trade secrets.
-------
Due to the legal ramifications of your failure to grant access, EPA strongly encourages you
to give this matter your immediate attention and further consideration within the time specified. If
you have any legal or technical questions relating to this matter, you may consult with the EPA prior
to the time specified above. Please direct legal questions to (Name of ORC Person) of the Office of
Regional Counsel at . Technical questions should be directed to (Name of Program
Person), at the above address, or at .
Sincerely,
-------
Attachment 7
Standard Report Disclaimer
The contents of this report reflect information concerning the (facility name) facility obtained
during a U.S. Environmental Protection Agency chemical safety audit and from records provided by
the (facility name) facility. The audit was conducted from (audit dates), and observations as presented
in this report provide a snapshot of conditions existing at the facility during the audit time frame.
They do not represent planned or anticipated changes proposed or on-going at the facility. The
recommendations and other report observations contained in this report are not mandatory actions
that the facility must implement. In addition, EPA makes no assurances that if implemented, the
recommendations and other report observations contained in this report will prevent future chemical
accidents, equipment failures, or unsafe management practices, and/or provide protection from a
future enforcement action under any applicable law or regulation.
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Attachment 8
Standard Language for Audit Report Introduction
The Chemical Safety Audit (CSA) program has evolved from the efforts of the U.S.
Environmental Protection Agency (EPA) under the Chemical Accident Prevention (CAP) program.
The primary objectives of the CAP program are to learn about the causes of accidental releases of
hazardous substances and the means to prevent such releases from occurring, to promote industry
initiatives in these areas, and to share activities with the community.
The Chemical Safety Audit program is part of this broad initiative, and has been designed to
accomplish the following chemical accident prevention goals:
Visit facilities handling hazardous substances to gather information on safety practices
and technologies;
Heighten awareness of the need for, and promote, chemical safety among facilities
handling hazardous substances, as well as in communities where chemicals are located;
Build cooperation among facilities, EPA, and other authorized parties by coordinating
joint audits; and
Establish a database for the assembly and distribution of chemical process safety
management information obtained from the facility audits.
The audit consists of interviews with facility personnel, and on-site review of various aspects
of facility operations related to the prevention of accidental chemical releases. CERCLA sections
104(b) and 104(e), as amended by SARA in 1986, provide authorities for entering a facility and
accessing information. Specific topics addressed include:
Awareness of chemical and process hazards;
Process characteristics;
Emergency planning and preparedness activities;
Hazard evaluation and release modelling efforts;
Release detection and monitoring techniques;
Training of operators and emergency response personnel;
Facility and corporate management structure;
Preventive maintenance and inspection programs; and
Community notification mechanisms and techniques.
-------
This report contains observations and conclusions and recommendations from an audit
conducted at (facility name, city, and state) from (audit dates). This report identifies and characterizes
the strengths of specific chemical accident prevention program areas to allow the elements of
particularly effective programs to be recognized. Copies of the report are provided to the facility so
that weak and strong program areas may be recognized.
i
-------
Attachment 9
Documentation Pertaining to the Processes and
Operations Using Hazardous Substances
The issues contained in sections 6.2.1 and 6.2.2 of the CSA protocol, Overview of Processing
Steps and Operating Procedures and General Description of Process Equipment, will require members
of the audit team to review processing and operating information. The team should review facility
documentation on the equipment and operating procedures relevant to the audit. Before examining
current practices, the audit team may want to review available technical documentation supporting
the original selection of technology, process chemistry, equipment, and operating parameters for the
process(es) under study. Typical documentation available for current operations include Process Flow
Diagrams (PFDs) and Piping and Instrumentation Diagrams (PIDs). The following questions can
provide a framework for your evaluation of these documents:
Does the facility have documentation on the design and operating parameters of the
equipment and processes using the substance(s) of interest?
Is the documentation for the process(es) complete, accurate, and legible?
Are symbols used uniformly?
Are items such as the location and sizes of nozzles for connection of process lines,
utility tie-ins, relief devices, controls, drains, vents, and blinds included?
Do pieces of equipment have assigned numbers and are descriptions provided?
Are the equipment specifications and operating parameters (e.g., dimensions, capacity,
surface area, temperatures, pressures) specified?
Are equipment spares shown?
For piping, are the items such as rating, diameter, fluid flow direction, insulation and
tracing requirements, and sloping requirements for expansion shown?
For instrumentation, are items such as control parameter, indicating and recording
functions, transmitter, signal type, control valve size, and actuator type shown?
Other issues to keep in mind when examining process documentation include materials of
construction; electrical area classification; design of relief, safety, and ventilation systems; relevant
design codes and standards; and material and energy balances.
PIDs indicate whether or not the crucial operating parameters are being monitored in order
for the operator to be able to respond to upsets in a timely manner. Therefore, the team should
review a PID for the following concerns: monitoring of operating parameters, provisions for
automatic shutdown, presence of alarm systems, interlock systems, overpressure protection, disposal
method of relief stream, and similar information. The audit team may want to compare a portion of
the PID to the systems and equipment in existence at the facility to verify their accuracy.
-------
Attachment 10
Descriptions of Standard Operating Procedure Manuals
Section 7.2.1 of the CSA protocol, Standard Operating Procedures, lists several types of SOP
manuals that should be reviewed, as relevant, by the audit team. In general, the audit team should
consider whether existing facility SOPs are complete - do they address initial and post-shutdown
startups, normal operations, temporary and emergency operations, normal and emergency shutdowns,
and maintenance. The following descriptions provide a summary of the type of information that
facility SOP manuals typically contain.
Supervisory Operating Manual
• Feed and product specifications;
PFDs; PIDs; MSDSs;
• Process parameters;
• Intermediate stream normal operating guidelines;
• List of alarms and interlocks;
• Equipment and instrumentation settings;
• Narrative description of start-up;
• Testing practices;
• Shutdown; and
• Emergency situations.
Operating Procedures Manual
• Detailed valve-by-valve procedures for all operating tasks;
• Schematic drawings;
• Safety instructions; and
• Equipment and systems.
Safety Procedures Manual
• Safety systems and equipment;
• Safety procedures; and
• Instructions.
In addition to comprehensiveness, the audit team should determine whether the SOP manuals
accurately reflect current equipment and current practices and whether they are understood and
implemented by operations personnel. Finally, the audit team should determine whether the manuals
are formally evaluated on a regular basis, whether both operations and management personnel
participate in the review and revision of SOPs, and how information on such changes is provided to
operations and supervisory personnel through training and drills.
Beyond the manuals listed above, there are a variety of other procedural documents (e.g.,
operating logs, shift turnover procedures, and maintenance guidelines) that the audit team may want
to examine, depending on the focus of the audit. Safety, health, and accident prevention topics that
can be investigated through these sources include overtime practices, emergency callout procedures,
procedures for reporting unusual occurrences, and consistency of equipment handling procedures for
maintenance and operations personnel.
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Attachment 11
Blank CSA Report Profile
-------
CHEMICAL SAFETY AUDIT PROFILE
Facility Name:
Facility Location:
Date(s) Audit Conducted:
Description of Facility:
SIC Code(s):
Location:
Products manufactured,
produced, or distributed:
Proximity to
sensitive populations:
Reason for Facility Selection:
ARIP Reports:
Focus of Audit:
Hazardous Substances(s)
Examined:
Physical Area(s) Examined:
Storage and Handling
• Storage Systems
• Shipping/Receiving
• Material Transfer
Process Area(s)
-------
Summary of Audit Findings and Recommendations:
Conclusions:
Facility Background Information
Chemical Hazards
Process Information
Chemical Accident Prevention
Accidental Release Incident Investigation
Facility Emergency Preparedness and Planning Activities
Community and Facility Emergency Response Planning Activities
-------
Public Alert and Notification Procedures
Recommendations:
Facility Background Information
Chemical Hazards
Process Information
Chemical Accident Prevention
Accidental Release Incident Investigation
Facility Emergency Preparedness and Planning Activities
-------
Community and Facility Emergency Response Planning Activities
Public Alert and Notification Procedures
Audit Team Member Composition:
Name and Title
Affiliation
Area of Responsibility
Expertise
Name and Title
Affiliation
Area of Responsibility
Expertise
Name and Title |
Affiliation "
Area of Responsibility
Expertise
Name and Title
Affiliation
Area of Responsibility
Expertise
Name and Title
Affiliation
Area of Responsibility
Expertise
Name and Title
Affiliation
Area of Responsibility
Expertise
Name and Title
Affiliation
Area of Responsibility
Expertise
-------
Follow-up Activities:
By the facility:
By the Regional office:
By State and local authorities;
Regional Contact:
Date:
-------
Attachment 12
Annotated CSA Report Profile
-------
CHEMICAL SAFETY AUDIT PROFILE
Facility Name:
[provide full name of facility
as well as any corporate
affiliation]
Facility Location:
[list city, state, and region]
Date(s) Audit Conducted:
[list actual days audit team
was on site at facility]
Description of Facility:
SIC Code(s):
Location:
Products manufactured,
produced, or distributed:
Proximity to
sensitive populations:
[provide four-digit SIC code]
[describe nature of surrounding
area (e.g., commercial,
industrial, rural, residential,
urban) and indicate direction
and distance to nearest major
city]
[list final
intended uses]
products and
[indicate direction and
distance to schools, hospitals,
day care centers, senior
centers, parks, lakes,
wetlands, and other sensitive
envi ronmen t s]
Reason for Facility Selection:
ARIP Reports:
[list all reasons, including
past releases, ARIP
questionnaires, requests from
state and local officials,
regional initiatives, interest
from facility, public concern,
chemical(s), process(es), or
system(s) of interest]
[list release date
substance released]
and
-------
Focus of Audit:
Hazardous Substances(s)
Examined: [list only CERCLA hazardous
substances or Title III
extremely hazardous substances
examined and provide Chemical
Abstract Service (CAS) number]
Physical Area(s) Examined:
Storage and Handling
• Storage Systems
[describe all storage systems examined (e.g., rail cars,
tanks, containers, cylinders) , including design,
capacity, material of construction, and length of
storage]
• Shipping/Receiving
[describe all shipping and receiving systems examined
(e.g., rail car, tank truck, and barge loading/unloading
areas, pipelines), including frequency of
delivery/shipment, design, capacity, and general
loading/unloading procedures]
• Material Transfer
[describe all material transfer systems examined (e.g.,
pipelines, conveyor belts, fork lifts, manual), including
design, material of construction, capacity, and general
transfer procedures]
Process Area(s)
[describe each stage in all process(es) examined
involving the hazardous substances (e.g., primary and
secondary manufacturing, recycling and reuse, waste and
waste water treatment and disposal, power generation),
including substances and equipment involved and a general
description of each step in the process]
-------
Summary of Audit Findings and Recommendations:
Conclusions:
[state observations and concerns on facility policies and
practices in a factual manner that refrains from judgments of
adequacy or inadequacy, and ensure that any concerns have been
addressed appropriately in the recommendations section.]
Facility Background Information
Chemical Hazards
Process Information
Chemical Accident Prevention
Accidental Release Incident Investigation
Facility Emergency Preparedness and Planning Activities
-------
Community and Facility Emergency Response Planning Activities
Public Alert and Notification Procedures
Recommendations:
[clearly state recommendations for facility policies and
practices (that are both practical and technologically
feasible at the facility) in a manner that reflects their non-
mandatory nature, as well as the observations and concerns
outlined in the conclusions section.]
Facility Background Information
*
•
Chemical Hazards
Process Information
Chemical Accident Prevention
-------
Accidental Release Incident Investigation
Facility Emergency Preparedness and Planning Activities
Community and Facility Emergency Response Planning Activities
Public Alert and Notification Procedures
Audit Team Member Composition:
[list audit team members in the following order: US EPA team
leader, other US EPA personnel, AARP enrollees, TAT members,
representatives from other federal agencies; and then state,
tribal, and local officials]
Name and Title
Affiliation
Area of Responsibility
[list the full name and title of the
auditor]
[indicate the federal, state, tribal, or
local government organization that the
auditor is representing (e.g., US EPA
regional office; Technical Assistance
Team -- company name; state department of
environmental protection; county health
department)]
[indicate the general subject matter(s)
with which the auditor was involved
(e.g., equipment and process(es),
training, off-site impacts, occupational
health, security, emergency planning,
observer)]
-------
Expertise [characterize the education, training,
and/or professional background of the
auditor (e.g., chemical engineer, public ,
health officer, hazardous waste
specialist, emergency responder,
emergency planner)]
Name and Title
Affiliation
Area of Responsibility
Expertise
Name and Title
Affiliation
Area of Responsibility
Expertise
Name and Title
Affiliation
Area of Responsibility
Expertise
Name and Title
Affiliation
Area of Responsibility
Expertise
Name and Title
Affiliation I
Area of Responsibility
Expertise
Name and Title
Affiliation
Area of Responsibility
Expertise
Follow-up Activities:
By the facility:
[as appropriate, discuss short and long term plans of facility
to address issues/implement recommendations raised during the
audit]
By the Regional office:
[as appropriate, discuss short and long term plans to follow
up with facility on issues and recommendations raised during
the audit]
-------
By State and local authorities:
[as appropriate, discuss follow up activities related to
issues and recommendations raised during the audit]
Regional Contact: [list contact for further
information]
Date: [indicate date that profile was
submitted]
-------
OXYGEN MONITORS,
COMBUSTIBLE GAS INDICATORS, AND
SPECIFIC CHEMICAL MONITORS
PERFORMANCE OBJECTIVES
At the end of this lesson, participants will be able to:
• Identify the purpose for oxygen monitoring
• List the four factors that can affect oxygen monitor response
• Identify the purpose for combustible gas monitoring
• List the four factors that can affect combustible gas indicator
response
• Identify the purpose of toxic atmosphere monitoring
• List three types of toxic atmosphere monitors
• List four types of specific chemical monitors
• List four factors that can affect the response of specific
chemical monitors.
-------
NOTES
OXYGEN MONITORS,
COMBUSTIBLE GAS INDICATORS,
AND
SPECIFIC CHEMICAL MONITORS
HAZARDS
Oxygen-deficient atmospheres
Combustible/explosive atmospheres
Toxic atmospheres
Radiation
OXYGEN MONITORING
Aid in determining:
• Type of respirator needed
• Flammability risk
• Sufficient oxygen for combustible
gas indicators (CGIs)
• Presence of contaminants
10/93
Oxygen Monitors, CGIs, and
Specific Chemical Monitors
-------
NOTES
OXYGEN SENSOR
4 ill8
Membrane / Cover
Electrode
OXYGEN MONITORS
Considerations
• Life span
• Operating temperature
• Interfering gases
• Atmospheric pressure
ALTITUDE/OXYGEN
METER READING
Instrument calibrated
at sea level
Oxygen Monitors, CG/s, and
Specific Chemical Monitors
10/93
-------
NOTES
FLAMMABLE
ATMOSPHERE MONITORING
• Used to determine risk of fire or
explosion
• CGI readings are indicative of
relatively high concentrations of
contaminants
COMBUSTIBLE GAS INDICATORS
Catalytic Sensors
KMM
Filament
Bead
COMBUSTIBLE GAS INDICATORS
Wheatstone Bridge Circuit
Sensor
Compensating
Filament
10/93
Oxygen Monitors, CGIs, and
Specific Chemical Monitors
-------
NOTES
COMBUSTIBLE GAS INDICATORS
Instrument Reading vs Concentration
Concentration
0%
LEL UEL
5%* 15%*
100%
0% 100%
Meter Reading (% LEL)
Note: * = methane
LEL = lower explosive limit
UEL = upper explosive limit
COMBUSTIBLE GAS INDICATORS
Readouts
UEL
120
COMPARISON OF LEL READINGS
WITH ACTUAL CONCENTRATIONS
HexaneLEL= 1.1%
For an instrument calibrated to hexane measuring hexane:
100% =1.1% (11,000ppm)
50% =0.55% (5,500 ppm)
25% = 0.275% (2,750 ppm)
10% =0.11% (1,100 ppm)
1% =0.011% (110 ppm)
Oxygen Monitors, CGls, and
Specific Chemical Monitors
10/93
-------
NOTES
COMBUSTIBLE GAS INDICATORS
Readout Ranges
"Normal" units
- 0-100%LEL
- 0-10%LEL
"Supersensitive" units
- Parts per million (ppm)
- Example: TLV Sniffer,
Gastech Model 1314
COMBUSTIBLE GAS INDICATORS
Considerations
• Oxygen requirements
• Contaminants that foul sensor
Temperature
Relative response
COMBUSTIBLE GAS INDICATORS
Relative Response Curves
100,
Methane
PvnUne
o>
3
3
"Z
50
Styrenc
Source: MSA 260
50 100
Percent LEL
JO/93
Oxygen Monitors, CGIs, and
Specific Chemical Monitors
-------
NOTES
TOXIC ATMOSPHERE
MONITORING
The purpose of monitoring is to:
• Identify chemicals and their
concentrations
• Evaluate worker/public exposures
• Evaluate protective equipment
selection
• Help develop exposure controls
TOXIC ATMOSPHERE
MONITORS
• Specific chemical monitors
• Total vapor survey monitors
• Gas chromatographs
• Aerosol monitors
SPECIFIC CHEMICAL
MONITORS
Designed to respond to a specific
chemical
Common types include
- Electrochemical
- Metal-oxide semiconductor (MOS)
- Colorimetric indicators
- Mercury detectors
Oxygen Monitors, CGIs, and
Specific Chemical Monitors
4194
-------
NOTES
METAL-OXIDE
SEMICONDUCTOR (MOS)
• Metal-oxide coating on a ceramic substrate
wrapped around a wire
• Contaminant alters conductivity by
removing oxygen
• Change in current is proportional to the
amount of contaminant present
• Also called "solid-state" sensor
MOS
Considerations
• Interferences
• Saturation
Temperature
Minimum oxygen requirements
COLORIMETRIC INDICATORS
Contaminant reacts with a chemical on
a tape, badge, or tube and causes a
color change
10/93
Oxygen Monitors, CGIs, and
Specific Chemical Monitors
-------
NOTES
COLORIMETRIC INDICATORS
Considerations
• Interferences
• Humidity
• Temperature
MERCURY DETECTORS
Ultraviolet light absorption
- Mercury vapor absorbs a specific
wavelength of light
Gold film
- Mercury reacts with film and
changes the electrical resistance
of the film
MERCURY DETECTORS
Considerations
• Ultraviolet light
- Interferences
- Humidity
• Gold film
- Factory calibration
- AC power needed to "clean"
Oxygen Monitors, CGIs, and
Specific Chemical Monitors
10/93
-------
OXYGEN MONITORS, COMBUSTIBLE GAS INDICATORS,
AND SPECIFIC CHEMICAL MONITORS
INTRODUCTION
Many hazards may be present when responding to hazardous materials spills or uncontrolled waste
sites. These include oxygen-deficient atmospheres, combustible/explosive atmospheres, toxic
atmospheres, and radiation. There are several types of instrumentation for detecting hazardous
atmospheres. This section will discuss oxygen monitors, combustible gas indicators (CGIs), and
monitors for specific chemicals.
OXYGEN MONITORS
Oxygen monitors are used to evaluate an atmosphere for:
• Oxygen content for respiratory purposes. Normal air contains 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, CGIs 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.
• The presence of contaminants. A decrease in oxygen content can be due to the
consumption (by combustion or a reaction such as rusting) of oxygen or the
displacement of air by a chemical. If it is due to consumption, then the concern is
the lack of oxygen. If it is due to displacement, then there is something present that
could be flammable or toxic. Because oxygen makes up only 20.8% of air, a 1%
drop in oxygen means that about 5% air (air being 1 part oxygen and 4 parts
nitrogen) has been displaced. This means that 5% or 50,000 ppm (1% = 10,000
ppm) of "something" could be there.
Most indicators have meters that display the oxygen concentration from 0 to 25%. There are also
oxygen monitors available that measure concentrations from 0 to 5% and from 0 to 100%. The most
useful range for hazardous material response is the 0-25 % oxygen content readout because decisions
involving air-supplying respirators and the use of CGIs fall into this range.
The oxygen sensor can be on the outside (external) or inside (internal) of the instrument. Internal
sensors need a pump—battery operated or hand operated—to draw a sample to it. Units that combine
O2 meters and CGIs into one instrument are available from many manufacturers. Also, flashing and
audible alarms can be found on many instruments. These alarms go off at a preset oxygen
Oxygen Monitors, CGIs, and
10/93 i Specific Chemical Monitors
-------
concentration to alert the users even if they are not watching the meter. A list of manufacturers of
oxygen monitors is found in this manual under Manufacturers and Suppliers of Air Monitoring
Equipment.
Principle of Operation
Oxygen monitors use an electrochemical sensor to determine the oxygen concentration in air. A
typical sensor consists of two electrodes, a housing containing a basic electrolytic solution, and a
semipermeable Teflon* membrane (Figure 1).
Display
Membrane / Cover
Electrode
Electrode
Electrolyte
FIGURE 1. SCHEMATIC OF OXYGEN SENSOR
Source: Atmospheric Monitoring for Employee Safety, BioMarine Industries Inc.
Oxygen molecules (O2) diffuse through the membrane into the solution. Reactions between the
oxygen, the solution, and the electrodes produce a minute electrical current proportional to the
oxygen content. The current passes through an electronic circuit which amplifies the signal. The
resulting signal is shown as a needle deflection on a meter or as a digital reading.
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.
Oxygen Monitors, CGIs, and
Specific Chemical Monitors
10/93
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Limitations and Considerations
The operation of oxygen monitors depends on the absolute atmospheric pressure. The concentration
of atmospheric oxygen is a function of the atmospheric pressure at a given altitude. Whereas the
actual percentage of oxygen does not change with altitude, at sea level the weight of the atmosphere
above is greater, and more O2 molecules (and the other components of air) are compressed into a
given volume than at higher elevations. As elevation increases, this compression decreases, resulting
in fewer air molecules being "squeezed" into a given volume. Consequently, an O2 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.
The reaction that produces the current in the sensor is nonreversible. Thus, once the sensor is
exposed to oxygen, it begins to wear out. The normal life span of a sensor is 6 months to 1 year.
Sensors are shipped in sealed packages that have been purged with nitrogen. The packet should not
be opened until the sensor is to be used. Storing the sensor in an oxygen absent atmosphere after
opening the package can prolong the sensor life, but may not be practical.
High concentrations of carbon dioxide (CO2) may shorten the useful life of the oxygen sensor. As
a general rule, the unit can be used in atmospheres greater than 0.5% CO2 only with frequent
replacing or rejuvenating of the sensor. Lifetime in a normal atmosphere (0.04% CC^) can be from
6 months to 1 year depending on the manufacturer's design. The service life of one sensor is 100
days in 1% CO2 and 50 days in 5% CO2.
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.
Temperature can affect the response of oxygen indicators. The normal operating range for them is
between 32°F and 120°F. Between O°F and 32°F the response of the unit is slower. Below O°F
the solution may freeze and damage the sensor. High temperature can also shorten the sensor life.
The instrument should be calibrated at the temperature at which it will be used.
COMBUSTIBLE GAS INDICATORS
CGIs measure the concentration of a flammable vapor or gas in air, indicating the results as a
percentage of the lower explosive limit (LEL) of the calibration gas. The LEL (or LFL - lower
flammable limit) of a combustible gas or vapor is the minimum concentration of the material in air
which will propagate flame on contact with an ignition source. The upper explosive limit (UEL) is
the maximum concentration. Below the LEL there is insufficient fuel to support combustion. Above
the UEL, the mixture is too "rich" to support combustion, so ignition is not possible. Concentrations
between the LEL and UEL are considered flammable.
CGIs are available in many styles and configurations. The combustible gas sensor can be on the
outside (external) or inside (internal) of the instrument. Internal sensors need a pump—battery
operated or hand operated—to draw a sample to it. Many units are "combination meters." This
means they have an O2 meter and a CGI (and sometimes one or two specific gas indicators)
Oxygen Monitors, CGIs, and
JO/93 3 Specific Chemical Monitors
-------
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 longer sampling lines, moisture traps, and dust filters are also
available. Manufacturers of CGIs are listed in Manufacturers and Suppliers of Air Monitoring
Equipment.
Principle of Operation
CGIs 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 (Figure 2). 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 50% (or 0.5, 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 would be indicating that a 2.5% concentration is present. Thus, the
typical meter indicates concentration up to the LEL of the gas (Figure 3a).
Sensor
Compensating
Filament
FIGURE 2. WHEATSTONE BRIDGE CIRCUIT
Source; Atmospheric Monitoring for Employee Safety, BioMarine Industries Inc.
Oxygen Monitors, CGIs, and
Specific Chemical Monitors
10/93
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If a concentration greater than the LEL and lower than the UEL is present, then the meter needle
will stay beyond the 100% (1.0) 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 may rise above the 100% (1.0) 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%.
This mechanism must be reset in an atmosphere below the LEL.
< LEL
LEL - UEL
> UEL
OVER
n
(a)
(b)
(c)
FIGURE 3. COMPARISON OF METER READINGS TO
COMBUSTIBLE GAS CONCENTRATIONS
Limitations and Considerations
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., leaded gasoline), 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.
10/93
Oxygen Monitors, CGIs, and
Specific Chemical Monitors
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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. The instrument should be calibrated and zeroed at the same
temperature that a reading will be taken. Some instruments have a compensating filament
(Figure 2). This filament is similar to the sensor and is exposed to the same atmosphere, but it does
not combust the atmosphere. It compensates for any temperature changes not caused by the
combustible gas.
There is no differentiation between petroleum vapors and combustible gases. If the flammability of
the combined vapors and gases in an atmosphere is the concern, this is not a problem. However,
if the instrument is being used to detect the presence of a released flammable liquid—like
gasoline—in a sewer system where methane may be present, the operator cannot tell whether the
reading is the contaminant or the methane. A prefilter can be used to remove the vapors, but it 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.
Relative response is also a concern. If the CGI is used to monitor a gas/vapor that the unit is not
calibrated to, it can give inaccurate results. Figure 4 illustrates the effect of relative response.
TOXIC ATMOSPHERE MONITORS
Along with oxygen concentration and flammable gases or vapors, there is also a concern about
chemicals present at toxic concentrations. This usually involves measurements at concentrations
lower than what 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:
• Identify airborne chemicals and their concentrations
• Evaluate the exposure of workers and the public
• Evaluate the need for and type of personal protective equipment
• Develop controls for exposure in the form of engineered safeguards, work practices,
safety plans, and work zones.
Several different groups of instruments can be used for these functions. In this manual the following
types will be discussed:
• Specific chemical monitors are instruments designed to respond to a specific chemical.
Common types include instruments that use electrochemical cells or metal-oxide
semiconductors (MOS), colorimetric indicators, and mercury detectors.
Oxygen Monitors, CGIs, and
Specific Chemical Monitors 5 10/93
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Total vapor survey meters have detectors (e.g., photoionization detector [PID] or
flame ionization detector [FID]) that respond to a variety of chemicals. Additional
information can be found in Total Vapor Survey Instruments.
Gas chromatographs are used to help identify what chemicals are present in the
atmosphere. Additional information is available in Introduction to Gas
Chromatography.
100
Methane
D)
c
T3
(0
0)
DC
h_
Q)
50
7
7
Pentane
Styrene
0
50 100
Percent LEL
FIGURE 4. EXAMPLES OF RELATIVE RESPONSE CURVES FOR MSA MODEL 260
Source: Portable Gas Indicator, Model 250 and 260, Response Curves, Mine Safety Appliances
Company, Pittsburgh, PA.
SPECIFIC CHEMICAL MONITORS
Electrochemical Cells
Electrochemical cells (Figure 1) contain a chemical solution and two or more electrodes. The
chemical reacts with the solution or the electrodes. The reaction can be a generation of electrical
current or a change in conductivity of the solution. The change in signal is expressed as a needle
10/93
Oxygen Monitors, CGIs, and
Specific Chemical Monitors
-------
movement or a digital response on a meter. The selectivity of the sensor depends on the selection
of the chemical solution and the electrodes.
In addition to the previously mentioned oxygen monitors (Figure 1), there are electrochemical
sensors for ammonia, carbon monoxide, carbon dioxide, chlorine, hydrogen chloride, hydrogen
cyanide, and hydrogen sulfide. Examples of these instruments are Compur's Monitox® Personal
Monitor Alarms, MDA's MSTox 8600 series, and National Draeger's PAC series of personal
monitors.
Limitations and Considerations
Like the oxygen sensor, these e'sctrochemical sensors also can wear out and are affected by
temperature and humidity.
Electrochemical cells are also affected by interferences. For example, many of the carbon monoxide
sensors will also respond to hydrogen sulfide. In fact, one manufacturer uses the same sensor for
both carbon monoxide and hydrogen sulfide detectors. The user must inform the instrument which
chemical is being monitored so the readout is in the proper units.
Metal-Oxide Semiconductors
MOS detectors, also called solid-state sensors, consist of a metal-oxide film coating on heated
ceramic substrate fused or wrapped around a platinum wire coil. When a gas comes in contact with
the metal oxide, it replaces oxygen in the oxide and alters the conductivity of the semiconductor.
The change in conductivity can be expressed in a meter readout. The substrate is heated to give a
constant baseline as oxygen in the air can combine with the oxide. Selectivity can be determined by
selecting specific metal oxides and/or using specific temperatures from the heater to prevent
chemicals from reacting.
There are MOS detectors for ammonia, carbon monoxide, hydrogen chloride, hydrogen cyanide,
hydrogen sulfide, methyl chloride, nitrogen oxides, and sulfur dioxide. Examples of instruments that
use an MOS to detect specific toxic compounds are the Enmet Tritechtor® and Biosystem's Model
100 series.
Even though the choice of metal oxide and sensor temperature can make the detector somewhat
selective, interferences are a major problem.
Because the sensor reaction is based on presence (or absence) of oxygen in the metal-oxide film,
factors that affect oxygen concentration affect meter response. The sensor needs a minimum 14%
ambient oxygen for operation. High concentrations can saturate the sensor, causing a slow recovery.
A minimum of 10% humidity is need for some sensors (check the manufacturer's specifications).
Oxygen Monitors, CGIs, and
Specific Chemical Monitors g 10/93
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Colorimetric Indicators
Colorimetric indicators use a chemical to react with the contaminant to produce a color change. The
chemical can be impregnated on a tape or a badge or put inside a glass tube. The color change can
be read by the human eye or by a spectrophotometer to determine the concentration of the
contaminant.
The chemicals are not always specific and can be affected by interfering chemicals. Humidity can
act as an interference by producing a reaction. Cold temperatures can slow the chemical reaction.
Hot temperatures may also cause the chemicals to indicate a reaction.
Examples of Colorimetric indicators are the Envirometrics, Inc. ACT™ cards (badges), MDA
Scientific's 7100 Series (tape), a ' Draeger detector tubes.
Mercury Detectors
Mercury detectors use either ultraviolet light absorption or a gold film detector. Mercury vapor
absorbs a certain wavelength of ultraviolet light. The instrument draws a sample into a chamber and
exposes it to the ultraviolet light source. The concentration of mercury vapor is measured by the
amount of light absorbed.
Some organic chemicals can absorb the ultraviolet light and act as an interference. Water vapor also
absorbs ultraviolet light, but can be adjusted for if the instrument is zeroed in the same humidity as
the sample area.
The gold film detector has a gold film as part of a circuit. Mercury reacts with the gold and changes
the resistance of the film. The change in resistance is used to determine concentration.
Because most operators do not have a mercury vapor standard, the gold film detector must be factory
calibrated. After long exposures or high concentrations, the film needs to be "cleaned." This
requires heating the film and using an AC power source.
An example of an ultraviolet absorption instrument is the Bacharach Model MV-2. An example of
a gold film instrument is the Jerome Instruments Model 411.
CONCLUSION
Many hazards can be present at a hazardous materials operation. Instruments are available for
determining the presence of hazardous situations like combustible atmospheres, oxygen-deficient
atmospheres, and toxic atmospheres. The instruments discussed in this section can only identify
certain hazardous situations and should be selected and used accordingly. Additional information
on identifying and evaluating toxic atmospheres will be discussed in the following sections.
Oxygen Monitors, CGIs, and
10/93 9 Specific Chemical Monitors
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TOTAL VAPOR SURVEY INSTRUMENTS
PERFORMANCE OBJECTIVES
At the end of this lesson, participants will be able to:
• Explain the principle of detection for the PID, FID,
supersensitive CGI, and metal-oxide semiconductor (MOS)
• Determine whether a chemical can be detected by
photoionization, given the ionization potential of the
chemical and the lamp energy of the photoionization detector
• Identify three considerations when using a PID
• Identify three considerations when using a FID
• Identify three consideration when using a supersensitive CGI
• Explain the difference between a CGI and a supersensitive
CGI.
-------
TOTAL VAPOR
SURVEY INSTRUMENTS
TOTAL VAPOR SURVEY
INSTRUMENTS
Instruments using detectors that
respond to a wide variety of chemicals
and give readings in the parts per
million range
WHAT ARE TOTAL VAPOR SURVEY
INSTRUMENTS USED FOR?
Site characterization
Exposure monitoring
Soil and water sample screening
Soil gas monitoring
NOTES
10/93
Total Vapor Survey Instruments
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NOTES
TYPES OF TOTAL VAPOR
SURVEY INSTRUMENTS
• Photoionization detector (PID)
• Flame ionization detector (FID)
• Supersensitive CGI
• Metal-oxide semiconductor (MOS)
PHOTOIONIZATION
U A
••'8
' \
o
> ionizatic
(IP) of che
++ e" — > R
orbing UV
th energy
)n potential
mical
Total Vapor Survey Instruments
10/93
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NOTES
PHOTOIONIZATION DETECTOR
Amplifier
Meter
Sample Out
Electrode
UV
Lamp
t
Electrode
Sample In
10/93
Total Vapor Survey Instruments
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IONIZATION
POTENTIAL
Chemical
Carbon monoxide
Hydrogen cyanide
Methane
Hydrogen chloride
Water
Oxygen
Chlorine
Propane
Hydrogen sulfide
Hexane
Ammonia
Acetone
Trichloroethylene
Benzene
Triethylamine
^
IP (eV)
14.0
13.9
13.0
12.7
12.6
12.1
11.5
11.1
10.5
10.2
10.1
9.7
9.45
9.2
7.5
NOTES
Total Vapor Survey Instruments . 10/93
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NOTES
EXAMPLES OF LAMP ENERGIES
AND DETECTABLE CHEMICALS
Hilocvbons
Wethanol
Other single C compounds
Vinyl Ohio-ids
MEK
MIBK
TCE
Other 2-4 C compounds
Aromfttics
Large molecules
Lamp
SELECTIVE DETERMINATION
OF VINYL CHLORIDE
Compound
IP
Carbon dioxide 13.8
Propane 11.1
Vinyl chloride 10.0
Acetone 9.7
PHOTOIONIZATION DETECTOR
11.7 vs. 10.2 Lamp
• 11.7 wears out faster than 10.2
• 11.7 is more susceptible to humidity
• 10.2 provides better response to
chemicals it can detect
10/93
Total Vapor Survey Instruments
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NOTES
PHOTOIONIZATION DETECTOR
Considerations
• Lamp energy/chemical IP
• Dust/humidity
• Interferences
• Electromagnetic interferences
• Lamp aging
• Relative response
• High concentrations
PHOTOIONIZATION DETECTOR
Relative Response
Chemical
m-Xylene
Benzene
Phenol
Acetone
Isobutylene
Hexane
Ammonia
Relative
Response*
1.12
1.00
0.78
0.63
0.55
0.22
0.03
IP
8.56
9.25
8.69
9.69
9.25
10.18
10.15
* HNU PI-101 with 10.2 eV lamp calibrated to benzene
PHOTOIONIZATION DETECTOR
High Concentration Effects
O>
C 600 •
Benzene
(gain = 9.8)
100 300 300 700 800
ppm (by volume)
Total Vapor Survey Instruments
10/93
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FLAME IONIZATION DETECTOR
Exhaust Vent
Igniter and
Electrode
Hydrogen Inlet
Collector
Electrode
Sample (air) Inlet
FLAME IONIZATION
RH
H20
Note: This ionization process is destructive.
COMPOUNDS GIVING LITTLE OR
NO RESPONSE IN THE FID
He
Ar
02
H20
H2S
S02
N2
NO
N02
N20
NH3
HCN
HCHO (formaldehyde)
CO
C02
CS2
Ethanolamine
NOTES
10/93
Total Vapor Survey Instruments
-------
NOTES
FLAME lONIZATION
Considerations
• Detects only organics
• Detects methane
• Hydrogen gas needed
• Flame out
• Electromagnetic interferences
• Relative response
FLAME lONIZATION
Relative Response
Chemical
% Relative Response*
Benzene 185
Toluene 126
Methane 100
Acetone 82
Trichloroethylene 54
Freon-12 13
Carbon tetrachloride 8
* OVA-128 calibrated to methane
SUPERSENSITIVE CGI
Detects combustible gases and
vapors
Detector is the same as a regular CGI,
but an amplifier is used to obtain ppm
readings
Total Vapor Survey Instruments
10/93
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NOTES
SUPERSENSITIVE CGI
Considerations
• Detects only combustibles
• Detects methane
• Temperature
• Chemicals that foul sensor
• Minimum oxygen
• Electromagnetic interference
• Relative response
METAL-OXIDE
SEMICONDUCTOR (MOS)
• Metal-oxide coating on a ceramic substrate
wrapped around a wire
• Contaminant alters conductivity by
removing oxygen
• Change in current is proportional to the
amount of contaminant present
• Also called "solid-state" sensor
MOS
Considerations
• Saturation
• Temperature
• Minimum oxygen requirements
• Relative response
10/93
Total Vapor Survey Instruments
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NOTES
CONCLUSION
Considerations
• What the instrument can detect
• Survey, not identification
• Logistical factors
• Environmental factors
• Special features
Total Vapor Survey Instruments
10/93
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TOTAL VAPOR SURVEY INSTRUMENTS
INTRODUCTION
Total vapor survey instruments are designed to respond to a wide range of gases and vapors.
Although they lack selectivity, this broad response allows the operator to detect the presence of
chemicals with one instrument. This allows the instrument to be used as a warning device during
survey operations.
If the identity of a chemical is known, the instruments can be calibrated to give a one-to-one response
for that chemical. If there is a mixture present, the instrument gives a total vapor reading. The
detectors themselves cannot identify the components of an atmosphere. The detectors can be used
in instruments, like the gas chromatograph (see Introduction to Gas Chromatography that are used
for identification.
This section will focus on total vapor survey instruments that are used for parts per million (ppm)
concentrations. It will discuss four types of toxic vapor survey instruments: photoionization
detectors (PIDs), flame ionization detectors (FIDs), supersensitive combustible gas indicators (CGIs),
and metal oxide semiconductors.
APPLICATIONS
Because of their ability to detect a wide range of chemicals, total vapor survey instruments are used
in site survey and characterization. Although they cannot identify what chemicals are present, they
can indicate what areas may have higher concentrations (hot spots) than others and delineate work
areas based on levels of concentrations.
If the identities of the contaminants are known, the instruments can also be used in exposure
assessment. The readings can give an approximate concentration and the information can be used
in selecting exposure controls.
The instruments are also used to screen water and soil samples to determine whether further, and
more complicated and expensive, analysis is needed. Usually specific reading (or any response) is
used to determine which samples need further analysis.
Total vapor survey instruments are also used in soil gas sampling as a screening tool to indicate
"hits" and hot spots that need further sampling.
PHOTOIONIZATION DETECTORS
These instruments detect concentrations of gases and vapors in air by using 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.
10/93 1 Total Vapor Survey Instruments
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Principle of Operation
The photoionization process can be illustrated as:
R + hv -» R+ + e"
R
where R is an organic or inorganic molecule and hp represents a photon of ultraviolet (UV) light with
energy equal to or greater than the ionization potential (IP) of that particular chemical species. R+
is the ionized molecule.
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. The R in the above equation
indicates that photoionization is nondestructive and the chemical exits the detector unchanged.
PIDs use a fan or a pump to draw air into the instrument's detector. There the contaminants are
exposed to UV light and the resulting negatively charged particles (ions) are collected and measured
(Figure 1).
Amplifier
Sample Out
Electrode
A Electrode
Sample In
FIGURE 1. DIAGRAM OF PHOTOIONIZATION DETECTOR LAMP
AND COLLECTING ELECTRODES
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).
Total Vapor Survey Instruments
10/93
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The ultraviolet light used to ionize the chemicals is emitted by a gaseous discharge lamp. The lamps
contain low-pressure gas through which a high-potential current is passed. A variety of lamps with
different ionization energies are made by varying the composition of the lamp gas. The energy of
lamps available are 8.4, 9.5, 10.0, 10.2, 10.6, and 11.7 eV. Not all lamps are available from a
single manufacturer.
The lamp energy designation is for the predominant UV wavelength emitted by the lamp. The
spectra from the lamp may have other wavelengths. Wavelengths of less energy do not have a major
impact because chemicals ionized by those wavelengths will also be ionized by the predominant
wavelength. The higher energy (but less photons) wavelengths will ionize the higher IP chemicals
but the response will be low. Thus, a 10.2 lamp may give a response (although a small one) for a
chemical with an IP of 10.9.
Photoionization Detector 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
discussed earlier, it may be possible to detect a chemical even if the chemical's IP is slightly greater
than the lamp energy. However, the response will be poor.
TABLE 1. IONIZATION POTENTIALS OF SELECTED CHEMICALS
Ionization Potential
Chemical
Carbon monoxide
Hydrogen cyanide
Methane
Hydrogen chloride
Water
Oxygen
Chlorine
Propane
Hydrogen sulfide
Hexane
Ammonia
Acetone
Trichloroethylene
Benzene
Triethyl amine
(eV)
14.0
13.9
13.0
12.7
12.6
12.1
11.5
11.1
10.5
10.2
10.1
9.7
9.45
9.2
8.0
10/93 3 Total Vapor Survey Instruments
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One use for 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 the chemicals can 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 (like a 11.7).
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 lamp window also affects response. The two types of windows are magnesium fluoride and
lithium fluoride. The former is used for the lower energy lamps and the latter is for the 11.7 eV
lamp. The lithium fluoride is used to permit the higher energy photons to be emitted. Lithium
fluoride has two disadvantages. The first is that humidity and the high-energy photons degrade the
window. This reduces the life span of the lamp. The 11.7 eV lamps are expected to have a life
expectancy one-tenth of that of 10.2 or 10.6 lamps. The second disadvantage is that lithium fluoride
also limits the amount of photons being emitted. Thus, if both a 10.2 and an 11.7 lamp have enough
energy to ionize a chemical (e.g., a chemical with an IP of 9.7), the 10.2 may give a higher response
because it is emitting more light.
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. The lamp should be cleaned regularly. Newer models of PIDs have dust filters.
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 can also reduce the readings. It is thought that the water molecules collide with the ionized
chemical and deactivate them. This reduction in response has been reported to be as much as 50%
for a relative humidity of 90%. As mentioned earlier, the 11.7 lamp window is especially sensitive
to moisture.
Because an electric field is generated in the sample chamber of the instrument, radio-frequency
interference from pulsed DC or AC power lines, transformers, generators, and radio wave
transmission may produce an error in response.
As the lamp ages, the intensity of the light decreases. It will still have the same ionization energy,
but the response will decline. This will be detected during calibration and adjustments can be made.
However, the lamp will eventually burn out.
Methane can act as an interference by absorbing the UV energy without ionization. This reduces
the ionization of other chemicals present. The net effect is a reading lower than the true
concentration.
Although oxygen is not needed for photoionization, a change in oxygen will affect the response.
Thus, there are oxygen limits for their use. The instruments are calibrated and used in normal
oxygen atmospheres. The HNU PI-101 requires a minimum of 10% oxygen for reliable results.
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.
Total Vapor Survey Instruments 4 10/93
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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 400 ppm for an instrument, a concentration of 900 ppm
may only give a meter response of 700 (Figure 2). Some instruments use a microprocessor to
compensate for this effect by storing calibration information for the high concentrations.
Manufacturers who make photoionization detectors can be found in this manual in the Manufacturers
and Suppliers of Air Monitoring Equipment section.
TABLE 2. RELATIVE RESPONSES FOR SELECTED
CHEMICALS USING THE HNU MODEL PI 101
WITH 10.2 eV PROBE CALIBRATED TO BENZENE
Chemical
m-Xylene
Benzene
Acetone
Isobutylene
Vinyl chloride
Hexane
Phosphine
Ammonia
Relative Response
1.12
1.00
0.63
0.55
0.50
0.22
0.20
0.03
Source: Instruction Manual for Model PI 101, Portable
Photoionization Analyzer, HNU Systems, Inc., Newton,
MA, 1986.
Examples of Photoionization Detector Instruments
HNU Systems, Inc.
HNU Systems, Inc., manufactures four models of photoionization detector survey instruments:
PI-101, IS-101, HW-101, and the DL-101.
All four consist of two modules connected via a single power cord (Figure 3):
• A readout unit having an analog meter or digital display, a rechargeable battery, and
power supplies for operation of the amplifier and the UV lamp
• A sensor unit consisting of the UV light source, pump, ionization chamber, and a
preamplifier.
10/93 5 Total Vapor Survey Instruments
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The PI-101 has a fan instead of a pump and cannot draw a sample through a resistance (like a piece
of long tubing). The PI-101 is rated for Class I, Division 2, Group A, B, C, and D locations.
The IS-101 is similar to the PI-101 except it is intrinsically safe for Division 1 locations.
The HW-101 has a pump instead of a fan, so it can be used to draw a sample through tubing or
through a probe used for soil gas sampling. The HW-101 also has a dust filter and is more moisture
resistant than the other models. It also has a light-emitting diode (LED) display on the handle that
indicates concentration changes.
The DL-101 has a pump and dust filter like the HW-101. However, it has many different fixtures
than other units. It has a pistol grip for holding the probe. There is a LED display on the handle.
The instrument has a datalogger to store calibration information and to record time and location of
readings. Information from the datalogger can be transferred to a computer. It has a digital readout
instead of an analog meter.
These units have a separate sensor unit because the lamps available - 9.5, 10.2 (standard), and 11.7
eV - require separate electronic circuits. To change the energy of ionization, the whole sensor or
O)
c
TJ
(C
0)
tr
H-*
0)
600 -
400 -
200 -
Benzene
(gain = 9.8)
100
300
500
700
900
ppm (by volume)
FIGURE 2. TYPICAL CALIBRATION CURVE FOR PHOTOIONIZATION ANALYZER
Source: Instruction Manual for Model PI-101 Photoionization Detecwr, copyright 1975, HNU
Systems, Inc.; reprinted with permission of publisher.
Total Vapor Survey Instruments
10/93
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probe has to be switched, not just the lamp. The exception is the DL-101. With the DL-101, lamps
can be interchanged and the datalogger/microprocessor makes the proper adjustments. In all models
the lamps are replaceable.
Lamp Power
Supply
Ion Chamber
Bias
Ion Chamber
£ + SAMPLE
PROBE
FIGURE 3. PORTABLE PHOTOIONIZATION DETECTOR
Source: Instruction Manual for Model PI-101 Photoionization Detector, copyright 1975, HNU
Systems, Inc.; reprinted with permission of publisher.
Photo vac. Inc.
Photovac has three versions of its MicroTIP®. All three have a microprocessor that is used to
calibrate the instrument and a datalogger to store data. Information from the datalogger can be
transferred to a computer. The standard lamp is 10.6 eV, but it can be easily replaced with a 8.4,
9.5, 10.2 or 11.7 eV lamp. The readout is digital with a range of 0 to 2000. They all have a dust
filter. The MP-1000 does not have a inherent safety approval. The HL-2000 is approved for Class
I, Division 2, Groups A, B, C, and D locations. The IS-3000 is intrinsically safe.
10/93
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Thermo Environmental Instruments
The Organic Vapor Meter (OVM) Model 580B is 5" by 5" by 10" with a handle in the center on
top. It can use any of four different lamps - 9.6, 10.0, 10.6 and 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 lock-out 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 OVM-580S is similar to the 580B, but is intrinsically safe.
Both have connections and software for interfacing the unit with a personal computer. They also
have a datalogger for recording readings at coded locations so that the readings can be looked at later
or downloaded into a computer.
Photoionization detectors are also used in gas chromatographs made by Photovac, HNU and Thermo
Environmental Instruments. Gas chromatography will be discussed in a later section.
FLAME IONIZATION DETECTOR
These units use a flame to ionize airborne contaminants. Once they are ionized, they can be detected
and measured.
Principle of Operation
FIDs use a hydrogen flame as the means to ionize organic vapors. FIDs respond to virtually all
organic compounds; that is, compounds that contain carbon-hydrogen or carbon-carbon bonds. FIDs
will not respond to inorganic compounds.
Inside the detector chamber, the sample is exposed to a hydrogen flame which ionizes the organic
vapors (Figure 4):
RH + O2 -* RH+ + e~ - CO2 -I- H2O
When most organic vapors burn, positively charged carbon-containing ions are produced. These can
be collected by a negatively charged collecting electrode in the detector 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
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 detector
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
Total Vapor Survey Instruments g , 10/93
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difference should be noted between the detectors. PID detection is dependent upon the ionization
potential (in 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. FIDs are the most sensitive for saturated hydrocarbons
(alkanes), unsaturated hydrocarbons (alkenes and alkynes), and aromatic hydrocarbons. Substances
that contain substituted functional groups, such as hydroxide (OH) and chloride (Cl), tend to reduce
the detector's sensitivity.
Companies that manufacture FIDs are listed in the Manufacturers and Suppliers of Air Monitoring
Equipment section. The Foxboro Century Organic Vapor Analyzer (OVA) will be discussed as an
example latef.
Exhaust vent
Igniter and
electrode
Hydrogen inlet
Collector
electrode
Sample (air) inlet
FIGURE 4. EXAMPLE OF A FLAME IONIZATION DETECTOR SCHEMATIC
Flame Ionization Detector Considerations
Flame ionization detectors respond only to organic compounds. Thus, they do not detect inorganic
compounds like chlorine, hydrogen cyanide, or ammonia. There are some carbon containing
chemicals for which the FID gives little or no response also. Table 3 illustrates this situation.
70/95
Total Vapor Survey Instruments
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TABLE 3. CHEMICALS GIVING LITTLE OR NO RESPONSE
WITH FLAME IONIZATION DETECTORS
He N2 HCHO (formaldehyde)
Ar NO CO
02 N02 C02
H20 N20 CS2
H2S NH3 TDI
S02 HCN ethanol amine
Source: Relative Response Data Sheet for Organic Vapor Analyzer,
January 16, 1989. The Foxboro Company.
Flame ionization, unlike photoionization, is a destructive form of monitoring. Typically, the
combustion products are carbon monoxide and water. However, substituted hydrocarbons (e.g.
chlorinated compounds) may produce toxic or corrosive byproducts.
The FID responds very well to methane. Methane is used as a calibration gas for many FIDs.
However, if monitoring is being done near a landfill or in a sewer system, the methane can mask
the response to low concentrations of other organics.
Hydrogen gas is used as fuel for the flame. This requires the extra logistics of maintaining a
hydrogen gas supply and recharging the instrument. It also involves working with a flammable
compressed gas.
Inadequate oxygen can cause the flame to go out. High concentrations of organics can also cause
a flame out. Without the flame, there is no detection.
Cold weather can also cause the flame to extinguish or inhibit startup (ignition) of the instrument.
Because an amplifier is used to enhance the signal from the detector, radio-frequency interference
from pulsed DC or AC power lines, transformers, generators, and radio wave transmission may
produce an error in response.
As with all instruments, flame ionization detectors respond differently to different compounds.
Table 4 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%.
Total Vapor Survey Instruments \Q 10/93
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TABLE 4. RELATIVE RESPONSES FOR SELECTED
CHEMICALS USING THE OVA CALIBRATED TO METHANE
Compound
Methane
Ethane
Propane
Acetylene
Benzene
Toluene
Acetone
Methanol
Isopropyl alcohol
Carbon tetrachloride
Freon-12
Trichloroethylene
Relative Response
(%)
100
77
70
225
185
126
82
12
65
8
13
54
Source: Product Literature, The Foxboro Company; used
with permission of The Foxboro Company.
Examples of Flame lonization Detector Instruments
Foxboro CENTURY Organic Vapor Analyzer (OVA)
One of the more common FID instruments is the Foxboro CENTURY OVA. There are two models:
the OVA-128 and the OVA-108. Both consist of two major parts (Figure 5):
• 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.
• A hand-held meter/sampling probe assembly.
10/93 11 Total Vapor Survey Instruments
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INTERNAL HYDROGEN
CYLINDEP
SIGNAL PROCESSOR
SAMPLE
FIGURE 5. ORGANIC VAPOR ANALYZER SCHEMATIC
Source: Product Literature, The Foxboro Company; used with permission of The Foxboro
Company.
The OVA-128 has a range of 0-1000 ppm. The OVA-108 reads from 0-10,000. Both are
intrinsically safe for Class 1, Division 1, Groups A, B, C and D. Both models are factory calibrated
to methane, but can be calibrated to other chemicals.
Other FID units are the Sensidyne Portable FID, Heath Consultants Porta-FID II, and Summit
Industries SIP-1000. The Portable FID and the SIP-1000 have gas chromatograph options.
Combination P/D and FID
Foxboro also manufactures the TVA-1000. The instrument can use a PID, an FID, or both. The
instrument has datalogging capabilities and digital readouts on a probe and side pack,
Total Vapor Survey Instruments
12
10/93
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SUPERSENSITIVE COMBUSTIBLE GAS INDICATORS
The CGI is a type of total vapor survey monitor. However, the normal range for a CGI is in the
percent LEL concentration. This range is too high for toxic concentration monitoring. Super-
sensitive combustible gas indicators use the combustible gas sensor with circuitry to amplify the
signal. Instead of measuring per cent of the LEL, the readout is in part per million. Because the
detection is based on combustion, the instruments can detect both organic and inorganic combustible
gases/vapors.
Some units—like the Bacharach TLV Sniffer—only measure in the ppm range. Other units (e.g.,
the Gas Tech Model 1314) can be switched from percent LEL to ppm readout.
These units have the same limitations and considerations as the regular combustible gas indicators.
In some cases, like sensitivity io temperature changes, the effects are a bigger problem because of
the amplifier circuit. Because of the amplifier, they are more sensitive to electromagnetic radiation
than standard combustible gas indicators.
METAL-OXIDE SEMICONDUCTORS (MOS)
MOS, also called solid-state sensors, consist of a metal oxide film coating on a heated ceramic
substrate fused or wrapped around a platinum wire coil. When a gas comes in contact with the metal
oxide, it replaces oxygen in the oxide and alters the conductivity of the semiconductor. The change
in conductivity can be expressed in a meter readout. The bead is heated to give a constant baseline
as oxygen in the air can combine with the oxide. Oxygen can combine with the sensor to cause an
instrument response.
Selectivity can be determined by selecting specific metal oxides and/or using specific temperatures
from the heater to prevent chemicals reacting. To use as a toxic atmosphere survey monitor, the
sensor should respond to a wide variety of chemicals. Thus, the sensor should be designed to be
nonselective.
Examples of instruments using a MOS for a total vapor sensor are the AIM 2000/3000 and the
Dynamation Model CGM™.
CONCLUSION
This section has described several types of detectors used for monitoring the presence of a wide
range of gases and vapors. While these are not the only types of detectors or monitors available,
they are the more commonly used devices for field surveys.
10/93 13 Total Vapor Survey Instruments
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AIR SAMPLE COLLECTION
PERFORMANCE OBJECTIVES
At the end of this lesson, participants will be able to:
• List four advantages to using air sample collection
• List three sources of sampling and analysis methods
• List three considerations when using liquid sorbent samplers
• List three considerations when using solid sorbent samplers
• List three considerations when using whole air samplers
• Describe two methods of collecting whole air samplers.
-------
NOTES
AIR SAMPLE
COLLECTION
DIRECT-READING INSTRUMENTS (DRI)
vs. AIR SAMPLE COLLECTION
Features
Response time
Quantitative
Identification
Detection range
Cost
cai
Seconds to minutes
Yes
No
Parts per million (ppm)
to percent
Inexpensive
Air Sample Collection
Hours to days
Yes
Yes
Parts per trillion (ppt)
to parts per million (ppm)
Expensive
AIR SAMPLE COLLECTION
Uses
• Identify and quantify airborne
chemicals onsite
• Evaluate personal exposures
• Evaluate releases from site
• Data for public health/ecological risk
assessment
10/93
Air Sample Collection
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NOTES
AIR SAMPLE COLLECTION
Components
Laboratory
analysis
Contaminant
Pump
COLLECTION AND
ANALYTICAL METHODS
EPA
- Compendium of Methods for
Determination of Toxic Organic
Compounds in Ambient Air
- Compendium of Methods for
Determination of Air Pollutants in
Indoor Air
- Compendium of Methods for
Determination of Toxic Inorganic
Compounds in Ambient Air
COLLECTION AND
ANALYTICAL METHODS
• NIOSH Manual of Analytical Methods
• OSHA Analytical Methods Manual
• American Society for Testing and
Materials
• Specialty methods
Air Sample Collection
10/93
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NOTES
COLLECTION AND
ANALYTICAL METHODS
Air Methods Database
- Combines previous methods into
a database
- Free from EPA
- See fact sheet
COLLECTION MEDIA
Types of Contaminants
Aerosols/particulates (nonvolatile)
Gases and vapors (volatile)
Combination (semivolatile)
FILTER MEDIA
Examples
Filter Media
0.8-micron (p)
mixed cellulose ester (MCE)
Glass fiber
Polyvinyl chloride (PVC)
Polytetrafluoroethylene
Application
Metals; asbestos
Pesticides
Total particulates;
hexavalent chromium
Alkaline dusts
10/93
Air Sample Collection
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NOTES
AEROSOLS/PARTICULATES
Size Selection Terminology
• Total suspended paniculate (TSP)
• Particulate matter - 10jL/ (PM-10)
• Total
• Respirable
AEROSOL SIZE SELECTION
Inertial Impactor
Air flow
Filter
Pump
AEROSOL SIZE SELECTION
Cascade Impactor
Collector
Air flow
\\
A
Pump
Plates
Air Sample Collection
10/93
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NOTES
GASES AND VAPORS
Examples
Organic vapors
- Benzene
- Trichloroethylene
- Ethyl alcohol
Inorganic gases
- Ammonia
- Hydrogen cyanide
- Hydrogen chloride
SOLID SORBENT MEDIA
Examples
Solid Sorbent
Activated carbon
Tenax®
Carbon molecular sieve
Silica gel
Compound
Nonpolar organics (NIOSH)
Volatile, nonpolar organics (EPA)
Highly volatile, nonpolar organics (EPA)
Polar organics (NIOSH)
SOLID SORBENT TUBE
Example
t t t
Dividers
A = Solid sorbent
B = Solid sorbent (backup or different sorbent)
10/93
Air Sample Collection
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NOTES
SOLID SORBENT
CONSIDERATIONS
Breakthrough
Sorption efficiency
No universal media
Stability/handling
Desorption
- Thermal
- Solvent
LIQUID SORBENT MEDIA
Examples
Media
O.INNaOH
Aniline
DNPH reagent + isooctane
0.1MHCI
Compound
Cresol/phenol (EPA)
Phenol (NIOSH)
Phosgene (EPA)
Aldehydes/ketones (EPA)
Hydrazine (NIOSH)
LIQUID SORBENT
CONSIDERATIONS
Spillage
Fragile holders
Hazardous liquids?
Stability
Evaporation
Air Sample Collection
10/93
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NOTES
WHOLE AIR COLLECTION
"Sampling Lung"
Sample flow
Air flow
Source: 'Sampling and Analysis of Emissions from Stationary Sourcse,' Schuatzle •(
>!., Joumfl ol tht Air Pollution Control Attodftion, Volum. 25, No. 8, S*pt 1875.
BAG SAMPLING vs. CANISTER
SAMPLING
Baa
Grab
Need field pump
Less stable sample
Cannot clean
Disposable
Cannot pressurize
Canister
Integrated
Need lab pump
More stable sample
Clean to reuse
Reusable
Can pressurize
COMBINATION MEDIA
Examples
Media Compound
Quartz filter PCBs/pesticides (EPA)
•f- polyurethane foam (PUF) PAHs (EPA)
Quartz filter + XAD-2 PAHs (EPA)
Glass filter + Florisil® PCBs (NIOSH)
MCE filter + 0.1 N KOH Cyanides (NIOSH)
4/94
Air Sample Collection
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NOTES
SAMPLING PUMPS
Most collection methods require a
pump to pull air through medium
Exceptions
- Evacuated canister
- Passive dosimeter
PASSIVE DOSIMETER
Example
Contaminant
Sorbent
Chemical permeates membrane and/or difluses into
sampler
PASSIVE DOSIMETERS
Considerations
• No pump
• Sorbent limits
- Breakthrough
- Humidity
- Temperature
• Early and late exposure problems
• Gases and vapors only
Air Sample Collection
JO/93
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NOTES
SAMPLE PUMPS
High Flow Rates
Greater than 10 cubic feet per minute
Ambient air sampling
SAMPLE PUMPS
Medium/High Flow Rates
1 to 6 liters per minute
Personal sampling
Aerosol sampling
SAMPLE PUMPS
Low Flow Rates
• 10 to 750 cubic centimeters
(milliliters) per minute
• Personal sampling
• Gas and vapor sampling
10/93
Air Sample Collection
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NOTES
SUMMARY
• Collect sample for laboratory analysis
• Determine whether air sampling is
appropriate
• Identify appropriate air sampling
method
Air Sample Collection
10/93
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AIR SAMPLE COLLECTION
INTRODUCTION
The types of equipment discussed in this section are media (filters and sorbents), containers (gas bags
and canisters) and pumps for collecting air samples. Unlike direct-reading instruments that give
immediate results, these samples must be analyzed by instruments that are not usually taken onsite.
The analysis may be done in the support area of a site or at a laboratory many miles away. This
causes a delay in receiving information. However, there are advantages to their use.
• The chemicals in the atmosphere can be concentrated so that the detection limit can
be lower than for a direct-reading instrument, even when the same type of detector
is used.
• Specialized detectors can be used. Some detectors (e.g., PID and FID) are used in
both direct-reading instruments and analytical instruments. However, some detectors
are only found in analytical instruments (e.g., electron capture detector). For specific
analysis of aerosols (e.g., lead), there are no direct-reading instruments. A sample
must be collected and then analyzed by a nonportable instrument.
• The analytical instruments used generally allow identification and quantification of
the chemicals. Instead of a total vapor reading, it may be possible to get an
identification and concentration of the components.
• The collection devices allow long duration (hours to days) and unattended sampling.
SAMPLE COLLECTION COMPONENTS
General
The basic components of a sample collection system are:
• A collection media for separating the contaminants from the atmosphere or a
collection container for holding part of the atmosphere.
• A pump to pull air through the media to push the sample into a container. When a
pump is used, the method is called "active" sampling. Some methods do not require
a pump and are called "passive" samplers.
• A method to analyze the collected sample. This part will not cover the analysis of
a sample. A limited discussion of analyses and detector types is found in Total Vapor
Survey Instruments and Introduction to Gas Chromatography.
10/93 1 Air Sample Collection
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Selection of Components
Several factors affect the selection of the components for a sample collection system. These include
1) the chemical and physical properties of the chemical to be collected, 2) the purpose of the sample,
3) the analytical method used by the laboratory, 4) the laboratory's capability to do a specific
procedure and their experience with the method, and 5) equipment characteristics. The following
elaborate on these factors:
• Chemical and physical properties of the chemical—The chemical/physical properties
of the chemical to be collected affect the type of media used. Volatile chemicals pass
readily through a filter. Therefore, some kind of sorbent is needed. In some cases,
a reaction, like an acid gas with an alkaline solution, may be used instead of sorption.
• Purpose of the sample—Two types of samples are the "personal" sample and the
"area" sample:
Personal sample—A personal sample requires a pump that can be worn by the
person being sampled. This means the pump must be compact and battery
operated. A personal sample is used to evaluate the exposure level of the
person being sampled. The sample results are usually compared to an
exposure limit (see Exposure Limits and Action Levels). A personal sample
collects the contaminants in the "breathing zone," a 12-inch-radius
hemisphere in front of the wearer's nose.
Area sample—An area sample, to determine chemicals and concentrations in
a specific area, can use the same type of pump. However, area samples
generally are for checking lower concentrations than personal samples. This
is because they are used for identification or evaluation of public exposure.
The lower concentrations require a larger volume of air to concentrate the
sample. This can be done by using a higher flow rate, by sampling longer,
or both. Longer sampling times are used because public exposure can be 24
hours each day compared to a site worker's exposure of 8 to 10 hours each
day. A long sampling time and a high flow rate require a pump that is AC
powered. Battery pumps are only rated for 8 to 10 hours of use.
• Analytical method used by the laboratory—The analytical method used by the
laboratory also affects the collection devices used. There are commonly used
methods developed by the U.S. Environmental Protection Agency (EPA), National
Institute of Occupational Safety and Health (NIOSH), and Occupational Safety and
Health Administration (OSHA) that specify sampling and analysis procedures. These
methods are found in EPA's Compendium of Methods for the Determination of Toxic
Organic Compounds in Ambient Air, NIOSH's Manual of Analytical Methods, and
OSHA's Analytical Methods Manual.
Air Sample Collection 2 10/93
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Although these methods were developed for similar chemicals, there are differences
in the procedures. The laboratory being used may also have different requirements.
The laboratory should be consulted prior to sampling.
EPA's Environmental Response Team (EPA-ERT) has developed an Air Methods
Database so that the user can determine what methods are available for sampling a
chemical. The database includes EPA, NIOSH, OSHA, and American Society for
Testing and Materials (ASTM) methods. Further information is found in a technical
bulletin (Appendix A).
Capability of the laboratory—When you choose a laboratory for analysis, make sure
you consider its capability to do a specific procedure and its experience with the
desired method. For NIOSH and OSHA methods, use an American Industrial
Hygiene Association (AIHA) accredited laboratory.
Equipment characteristics—This is an important consideration. For example, some
pumps have timers that may be useful or even necessary. Some collection devices
are fragile and may not be desirable under certain operating conditions.
AEROSOL (NONVOLATILE CHEMICALS) SAMPLERS
Media
Airborne aerosols include both dispersed liquids (mists and fogs) and solids (dusts, fumes, and
smoke). The most common method of sampling aerosols, especially the solids or particulates, is to
trap them on filters using active systems. Impingers (see Liquid Sorbents in the Gas and Vapor
(Volatiles) Samplers section) have been used, but filters are more convenient. Two types of filters
are used.
• Fiber filters are composed of irregular meshes of fibers forming openings or pores
of 20 ftm in diameter or less. As particulate-laden air is drawn through such filters,
it is forced to change direction. Particulates then impinge against the filter fibers and
are retained. A number of fiber filters are available (Table 1). The two with the
greatest application to hazardous materials operations are cellulose and glass. Filters
of these materials typically consist of thick masses of fine fibers and have low mass-
to-surface area ratios. Of the two, cellulose is the least expensive, is relatively low
in ash, has high tensile strength, and is available in a variety of sizes. Its greatest
disadvantage is its tendency to absorb water, thus creating problems in weighing.
• Membrane filters are microporous plastic films formed by precipitating a resin. Pore
sizes of 0.01-10 /xm can be formed during manufacture. Membrane filters act as a
sieve with collection of most particulates on the surface. This can be useful for
visual examination of the sample. This group of filters includes such materials as
cellulose ester, polyvinyl chloride, and polytetrafluoroethylene (Table 1). These
filters have an extremely low mass and ash content. Some are completely soluble in
10/93 3 Air Sample Collection
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organic solvents. This allows participates to be concentrated into a smaller volume
for analysis.
TABLE 1. FILTER MEDIA FOR AIRBORNE PARTICULATES
Filter Medium Representative Application/Analysis
Mixed cellulose ester (MCE), Metals/atomic adsorption; asbestos/phase
0.8-//m pore contrast microscopy
Glass fiber Pesticides/various
Polyvinyl chloride (PVC) Total particulates/gravimetric; hexavalent
chromium/visible spectrophotometry
Polycarbonate Fibers
Polytetrafluoroethylene Alkaline dusts/acid-base titration
Source: NIOSH Manual of Analytical Methods, Third Edition, Volume 1,
February 1984 and supplements.
Filter sizes range from 13 mm in diameter to 40 by 40 inches. Small sizes (25 mm and 37 mm
diameter) are generally used for personal samples and the larger sizes are normally used for Hi-Vol
sampling. Selection of the size and type of filter depends on the user application and analysis.
Table 1 gives examples of different filters and their applications.
The common filter holder used for personal samples is the polystyrene plastic cassette (Figure 1).
It consists of two or three stacked sections, the number depending on the contaminant and the
collection method. The sections of a cassette are molded to fit tightly when stacked and to tightly
grip the outer edge of the filter. Each cassette has end plugs to seal the inlet and tubing connector
part once the sample collection is completed.
Other materials than polystyrene can be used. Metal is used in large samplers with high flow rates.
Carbon-filled polypropylene is used for asbestos sampling because it prevents an accumulation of a
static charge, which would result in the attraction of the asbestos fibers to the cassette walls.
Air Sample Collection 4 10/93
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Ring piece
Filter paper
Backup pad
FIGURE 1. ASSEMBLY OF A THREE-PIECE FILTER CASSETTE
Source: OSHA Technical Manual, U.S. Department of Labor, OSHA, 1990.
Size Selection
Unlike gases and vapors, not all aerosols reach the deeper portions of the respiratory system. The
nose and bronchioles remove the larger sizes. Environmental or public health samples are usually
classified as total suspended particulates (TSP) or paniculate matter - 10 ^ (PM10). PM,0 samples
collect particulates that are 10 /* and smaller. This represents the fraction of airborne particles that
would be inhaled. PMi0 samples are used to assess the inhalation route of exposure. TSP is used
to assess exposure to contaminants that may be deposited downwind and available through ingestion.
Occupational samples are classified as total or respirable. Total samples are equivalent to TSP.
Respirable samplers are designed to collect particles that would reach farther into the respiratory
system. Most occupational exposure limits for particles are based on total samples. A few, silicon
dust, coal dust, and nuisance dust, are based on respirable samples.
The most common devices used for aerosol size separation are the inertial impactor, the centrifugal
separator, and the cascade impactor.
10/93
Air Sample Collection
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The inertial impactors rely on a sudden change in velocity and direction to separate
the sizes of particles. Figure 2 illustrates the principle. The example shows that the
larger particles (having more inertia) cannot follow the change in air direction and
impact in the separator. The smaller particles can make the turns and are collected
at the filter.
The centrifugal separator or cyclone is similar to the inertial impactors. Cyclones
commonly are conical or cylindrical in shape, with an opening through which
particulate-laden air is drawn along a concentrically curved channel. Larger particles
impact against the interior walls of the unit due to their inertia and drop into the base
of the separator. The lighter particles continue on through and are drawn up through
the separator and collected on a filter. Cyclones can be very compact and thus are
often used for personal sampling.
Air flow
Filter
Pump
FIGURE 2. ILLUSTRATION OF AN INERTIAL IMPACTOR
Cascade impactors (Figure 3) are composed of a number of stacked perforated
collection beds or plates, each with openings narrower than the one before it. The
cascade impactor separates particulates in an airstream by directing them toward a
dry or coated flat surface. As the particulate-laden air moves through the plates,
larger particles are deposited near the top and smaller near the bottom.
Air Sample Collection
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One major difference between the cascade impactor and other separators is that it can
be used to collect each separate fraction for analysis. The other separators are used
to separate the "respirable" fraction for analysis from the "total" mass of particulates.
With all preselectors, the separation efficiency is dependent on flow rate control. A specific flow
rate is needed for the device to do proper separation.
Air flow
Collector
Plates
Pump
FIGURE 3. CASCADE IMPACTOR
GAS AND VAPOR (VOLATILES) SAMPLERS
Gases and vapors have different physical properties than aerosols and thus would pass through
untreated filters without being collected. For gas and vapor collection, a sorbent is needed to
separate the contaminant from the atmosphere or a container is needed to collect a whole air sample.
The sorbents may be solid or liquid and the containers can be glass, plastic, or metal.
10/93
Air Sample Collection
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Solid Sorbents
Solid sorbents are a class of media widely used in hazardous materials sampling operations. Table 2
gives some examples and their applications. These materials collect by sorption and are often the
media of choice for insoluble or nonreactive gases or vapors. Their advantages include high
collection efficiencies, indefinite shelf lives while unopened, ease of use and specific analytical
procedures.
TABLE 2. COMMONLY USED SOLID SORBENTS
Solid Sorbent Representative Gas or Vapor Adsorbed
Activated charcoal Nonpolar organics (NIOSH)
Tenax® Volatile, nonpolar organics (EPA)
Carbon molecular sieve Highly volatile, nonpolar organics (EPA)
Silica gel Polar organics (NIOSH)
Sources: NIOSH Manual of Analytical Methods, Third Edition,
Volume 1, February 1984 and Supplements; EPA's Compendium of
Methods for the Determination of Toxic Organic Compounds in
Ambient Air, EPA/600/4-89/017, June 1988.
There are several considerations when using solid sorbents. One of the major concerns with the use
of solid sorbents is the potential for "breakthrough." Breakthrough occurs when the sorptive capacity
of the media is exceeded. There is a limit to the amount of chemical that the sorbent can hold.
Most methods limit the volume of air pulled through the sorbent to prevent this problem; hence, the
use of low flow pumps for sorbent tube sampling. A way to check for breakthrough is to use a
double section tube (Figure 4) and analyze each section separately. If a excessive amount of the
total sample—one agency uses 25%—is found in the "back-up" section, then the sample is considered
incomplete. Breakthrough is affected by humidity, temperature, total amount of chemicals in air,
and the type and amount of sorbent. The problem of breakthrough can be reduced by reducing the
air sample volume, increasing the amount of sorbent (e.g., use a 750 mg tube instead of a 150 mg
tube) or using tubes in series. For example, the NIOSH methods for vinyl chloride and methylene
chloride use two tubes in series.
A sorbent may not be able to collect all of a chemical. The efficiency will vary with sorbent and
chemical. That is why there is no universal collection media. The sampling method usually selects
the sorbent that will get the highest sorption efficiency (the closer to 100% the better).
Storage and handling of the sorbent samples can also be a problem. They cannot be stored
indefinitely. Analysis usually must be done within 2 weeks. Some sorbents require special handling.
The EPA method that uses Tenax® tubes for sampling requires the operator to wear cotton gloves
so as not to contaminate the media with skin oils. The method requires storage away from sunlight.
Air Sample Collection 8 10/93
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B
t
t t
Dividers
A = Solid sorbent
B = Solid sorbent (backup or different sorbent)
FIGURE 4. TYPICAL 150 MG SOLID SORBENT TUBE
When the samples are analyzed, the chemicals must be desorbed from the media. This can be done
with solvents (e.g., carbon disulfide) or with heat (thermal desorption). Solvent desorption can
involve hazardous liquids and needs a controlled laboratory environment. Thermal desorption can
be done with automated equipment and does not need hazardous chemicals. However, the elevated
temperatures may cause a change in some unstable chemicals.
Once the sample is desorbed, it can be analyzed by a variety of detectors.
Liquid Sorbents
Liquid sorbents are used to collect soluble or reactive gases and vapors (Table 3). Only a relatively
few analytical methods use liquid sorbents. Further, most of the common liquid absorbers tend to
be contaminant-specific and have limited shelf lives.
The liquid sorbents need a sampler to hold the liquid during sampling. These samplers ensure that
contaminants in the sampled air are completely absorbed by the liquid sampling medium. There are
several varieties of samplers. Differences in design are due to the efficiency needed for absorption.
• Impingers, or simple gas washers (Figure 5a), are a basic liquid holding sampler.
This device consists of an inlet tube connected to a stopper fitted into a graduated vial
such that the inlet tube rests slightly above the vial bottom. A measured volume of
liquid is placed into the vial, the stopper inlet is put in place, and the unit is then
connected to the pump by flexible tubing. When the pump is turned on, the
contaminated air is channeled down through the liquid at a right angle to the bottom
of the vial. The air stream then impinges against the vial bottom, mixing the air with
the liquid and the necessary air-to-liquid contact achieved by agitation. The
10/93
Air Sample Collection
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TABLE 3. COMMONLY USED LIQUID ABSORBERS
Absorbing Liquid
Gas/Vapor Absorbed
0.1 /VNaOH
0.1 /WHCI
Aniline
DNPH reagent and isooctane
Cresol/phenol (EPA); phenol (NIOSH)
Hydrazine (NIOSH)
Phosgene (EPA)
Aldehydes/ketones (EPA)
Sources: NIOSH Manual of Analytical Methods, Third Edition,
Volume 1, February 1984 and supplements; EPA Compendium of
Methods for the Determination of Toxic Organic Compounds in
Ambient Air, EPA/600/4-89/017, June 1988.
popularity of impingers rests on such qualities as simple construction, ease of cleaning, the
small quantity of liquid used (typically less than 25 to 30 milliliters), and a size suitable for
use as a personal monitor.
B
FIGURE 5. A - IMPINGER; B - FRITTED BUBBLER
Source: The Industrial Environment - Its Evaluation and Control, NIOSH, 1973.
Air Sample Collection
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• Fritted bubblers (Figure 5b) are generally used when a high degree of air-liquid
mixing is desired. They are similar in construction to the impinger, but have a mass
of porous glass, called frits, at the end of the submerged air tube. The frits break
the air stream into numerous small bubbles. The frits are categorized as fine, coarse,
or extra coarse, depending on the number of openings per unit area. By producing
smaller sized bubbles, a greater surface area of the air sample is in contact with the
liquid medium.
One of the major disadvantages with liquid sorbent sampling is that the samplers are generally made
of glass and, thus, are fragile. Other disadvantages are the need for low, controlled flow rates to
prevent overflow of liquid; spillage of liquid if the sampler is worn as a personal sampler; extra
handling and storage of liquids; possible evaporation of liquid sorbent during sampling and thus loss
of sample; and a need for a safety device (extra impinger, for example) between sampler and pump
to prevent liquid contamination of the pump.
Passive Dosimeters
Passive dosimeters now available apply to gas and vapor contaminants only. These devices primarily
function as personal exposure monitors, although they have some usefulness in area monitoring.
Passive dosimeters are commonly divided into two groups, primarily on how they are designed and
operated.
• Diffusion samplers (Figure 6) function by the passive movement of contaminant
molecules through a concentration gradient created within a stagnant layer of air
between the contaminated atmosphere and the collection material.
• Permeation dosimeters rely on natural permeation of a contaminant through a
membrane. The efficiency of these devices depends on finding a membrane that is
easily permeated by the contaminant of interest and not by other contaminants.
Permeation dosimeters are therefore useful in picking out a single contaminant from
a mixture of possibly interfering contaminants.
There are liquid and solid sorbents available for passive dosimeters. However, solid sorbents are
the most common.
JO/93 11 Air Sample Collection
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Contaminant
Sorbent
Chemical permeates membrane and/or diffuses into
sampler
FIGURE 6. DIFFUSION TYPE PASSIVE DOSIMETER
Quantitative passive dosimeters have become available only since the early 1970s, though a
semiquantitative passive monitor for carbon monoxide was patented as early as 1927. The key
advantage of dosimeters is their simplicity (Figure 6). These small, lightweight devices do not
require a mechanical pump to move a contaminant through the collection media. Thus, calibration
and maintenance of sampling pumps are not needed. However, the sampling period must still be
accurately measured. Like active systems, these devices can be affected by temperature and
humidity. Sources of error unique to passive dosimeters arise from the need for minimum face
velocities and the determination of contaminant diffusion or permeation coefficients.
Container Sampling
Because of the problems associated with sorbent sampling (breakthrough, sorbent efficiency, etc.),
methods have been used to collect a whole air sample in a container. Several types of containers
have been used.
Glass bonks have been used because of the relative inertness of glass. The procedure can be done
several ways. The glass container can be evacuated to produce a vacuum and then opened in the
sampling area. While this technique does not use a sampling pump, some way of evacuating the
container is needed. Another method uses a pump to pull air through the container. When the air
sample has replaced the air in the container, the container is closed. Another device uses a container
Air Sample Collection
12
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filled with water. When the water is drained, the air sample fills the space left by the departing
water. This method is undesirable if water vapor is a problem in the analysis.
The devices have two problems. The containers are fragile and only give a sample at ambient
pressure. To get a sample out, a vacuum needs to be pulled on the container or air added to equalize
pressure as a sample is taken out. As more and more samples are removed, it becomes harder and
harder to get the sample out. This also requires a pressure correction when calculating the
contaminant concentration. If air is added to equalize pressure, the sample becomes diluted.
Sample collection bags can be constructed of a number of synthetic materials, including polyethylene,
Saran™, Mylar™, Teflon™. They are square or rectangular with heat-sealed seams, hose valve
fittings, inlet valves, and septums for syringe extraction of samples. They come in a variety of
volumes. The selection of a bag should be based on a number of characteristics, including resistance
to adsorption and permeation, tensile strength, performance under temperature extremes, construction
features (seams, eyelets, and fittings), and intended service life.
Bag sampling can be done by connecting the bag inlet valve with flexible tubing to the exhaust outlet
of a sampling pump. The bag inlet valve is opened, the pump turned on, and the .sample collected.
Once sampling is completed, the pump is turned off, the bag valve closed and the bag disconnected.
The bag contents may be analyzed by connecting the bag to a direct-reading instrument; or a portion
of the contents can be taken from the bag by a syringe and injected into a gas chromatograph.
In situations where there is concern about sample contamination due to passing through a pump, an
alternate sampling apparatus can be constructed. This apparatus involves using the pump to evacuate
a chamber (a desiccator or a scalable box) in which the sample bag is installed (Figure 7). As the
pump creates a partial vacuum, the sample bag expands and draws the sample in through a sample
tube.
The major disadvantage of gas sample bags is sample stability. Chemicals in the sample may sorb
to the bag material or permeate through the bag walls. This would cause a decrease in sample
concentration. The sample can also be affected by contaminants outside the bag by permeation
through the bag walls. If a bag is reused, sorbed chemicals may desorb into the new sample and
cause contamination. Because of these problems, bags are seldom reused, and samples are analyzed
as quickly as possible (usually within 24 hours).
Chemicals in the bag can degrade with exposure to sunlight. The bags should be stored in a
container (e.g., a cooler or garbage bag) to prevent exposure to sunlight.
Recently, metal canisters have gained popularity. Until recently, there have been problems with
reactions occurring with the metal on the insides of the container. New polishing techniques have
greatly reduced the problem. Metal canisters are used similarly to glass containers. They are
evacuated to produce a vacuum. Unlike glass containers, metal canisters can be filled several ways.
The valve can be opened to get a instantaneous, or grab, sample. The canister can also be connected
to a controlled flow orifice so that the sample fills the canister at a fixed rate. This gives a long term
sample.
A pump can also be used to pressurize the canister so that a sample volume greater than the canister
size is obtained. This latter capability is not available for glass containers or gas bags.
JO/93 13 Air Sample Collection
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Sample flow
Air flow
Source: "Sampling and Analysis of Emissions from Stationary Sources," Schuetzle et
al., Journal of the Air Pollution Control Association, Volume 25, No. 9, Sept. 1975.
FIGURE 7. NEGATIVE PRESSURE BAG SAMPLING APPARATUS
Metal canisters are more durable than glass containers. They have better sample stability than gas
bags. There are special cleaning procedures that allow the canister to be reused.
Metal canisters have a problem with recovery of polar compounds (e.g., alcohols).
Syringes can also be used to take a sample. Although 1-liter syringes are available, most are rather
small and there may be a problem with having an adequate amount of sample.
Container sampling allows whole atmosphere sampling. This type of sampler eliminates the
problems associated with sorbent media. It also allows the use of more than one analytical method
per sample. Glass containers are fairly inert but are fragile. They also are limited in size. Gas bags
are more durable and have a variety of sizes, but have sample stability problems. Metal canisters
are durable, have good sample stability and can get a larger sample than their actual size (but only
if special equipment is used). There are systems for taking personal samples with a gas bag. Gas
bags and metal canisters can also obtain long term samples with controlled flow pumps.
SEMIVOLATILE SAMPLERS
Some chemicals, because of their physical properties, may be present in both solid and vapor form.
There are also chemicals that are not very volatile, but will vaporize gradually if air is passed over
them. This could happen is the chemical was captured on a filter. Because of these situations, some
methods use more than one type of media. Usually a filter (for the aerosol phase) is followed by
a sorbent (for the vapor phase). Table 4 gives examples of chemicals that are in this category and
the methods used to collect them.
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14
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Because two separate media are used, both will probably be analyzed by different methods. It will
also take more time and be more expensive for the analysis.
TABLE 4. COMMON MULTIMEDIA SAMPLERS
Media Used Chemical Being Sampled
Q.8-jjm MCE filter + 0.1 N KOH Cyanides (NIOSH)
13-mm glass fiber filter and Florisil Polychlorinated biphenyls
(PCBs) (NIOSH)
Quartz filter and polyurethane foam (PUF) PCBs/pesticides (EPA)
Polycyclic aromatic
hydrocarbons - PAHs (EPA)
Quartz filter + XAD-2 PAHs (EPA)
Sources: NIOSH Manual of Analytical Methods, Third Edition, Volume
1, February 1984 and supplements; EPA Compendium of Methods for the
Determination of Toxic Organic Compounds in Ambient Air, EPA/600/4-
89/017, June 1988.
SAMPLING PUMPS
Pump Characteristics
Air sample collection systems, with the exception of evacuated canisters and passive dosimeters, rely
on electrically powered pumps to mechanically induce air movement. The power source may be
batteries or an AC source. Battery-powered pumps can operate for 6-10 hours. AC-powered pumps
can operate longer, but are not usable as personal samplers.
Generally, sampling pumps incorporate several of the following features:
• A diaphragm or a piston-type pumping mechanism
• A flow regulator to control the sampling flow rate
• A rotameter or stroke counter to indicate flow rate or sample volume
• A pulsation dampener to maintain a set flow rate
• A programmable timer to start the pump at a set time and/or to stop the pump after
a set sampling period
• An inherent safety approval for gas/vapor and dust atmospheres
10/93 15 Air Sample Collection
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Other than differences in features mentioned above, the main difference in pumps is their
flow rate. Low flow pumps have a flow rate range from 10 cubic centimeters per minute
(cc/min) to about 750 cc/min. Medium flow pumps have a flow rate of about 1-6 liters per
minute (1pm). High volume (Hi-Vol) pumps are AC powered and can achieve up to 40 cubic
feet per minute (cfm). That is equivalent to 1130 1pm.
The choice of flow rate depends on the type of sampling done. Sorbent media, like carbon
tubes, cannot be used with a high flow rate. The capacity of the sorbent would be exceeded
and there would be a loss of sample (breakthrough). Also, the Hi-Vol pumps are not used
as personal samplers. Some pumps have the ability to do both low and medium flow
sampling, but not Hi-Vol.
Calibration
All pumps must be calibrated. The flow rate must be known so that a sample concentration can be
calculated. Calibration is also necessary to ensure the constant flow rate needed for some methods.
The flow rate stability of a pump should be accurate to within ±5% of its set flow rate.
An active sampling system must be calibrated prior to and after sampling. The overall frequency
of calibration depends upon the general handling and use a system received and the quality control
considerations of the user. Pump mechanisms must be recalibrated after they have been repaired,
when newly purchased, and following any suspected abuse. The sampling system as a whole must
be calibrated to the desired flow rate rather than the pump alone. The sampling system should be
calibrated prior to and after each use. The system can be adequately examined under field-like
conditions only with all components connected.
There are several devices for calibrating sampling pumps:
• The soap bubble meter represents a basic method of calibration and is a primary
standard. This device typically consists of an inverted graduated burette connected
by flexible tubing to the sampling train. Figure 8 shows one example.
Do the calibration as follows:
Start the system's pump to create airflow into the burette
Dip the open end of the burette into a soap solution to create a soap film
bubble across the opening
Remove the solution and allow the bubble to rise up through the burette
Measure the travel time of the bubble between two graduated points on the
burette; vary the flow rate by adjusting the pump flow regulator.
The general formula used for the calculation of the flow rate is:
,,, volumetric distance traveled by bubble (roQ
Flow rate - -—-
travel time of bubble (sec)
Air Sample Collection \6 10/93
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Inverted
buret
250
Filter
cassette
Soap bubble trap
Pump
Beaker
Soap solution
FIGURE 8. CALIBRATION SETUP FOR FILTER SAMPLER
USING A SOAP BUBBLE METER
Source: OSHA Technical Manual, U.S. Department of Labor, OSHA, 1990.
If the desired flow rate is 1pm, then the units need to be converted by multiplying the previous
equation by the following:
60 secondslminute
1000 mill
• There are electronic bubble meters that use sensors to detect the soap bubble and start
and stop an electronic timer. The calibrator then automatically calculates and
displays the pump flow rate.
10/93
17
Air Sample Collection
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The precision rotameter consists of a vertically mounted tapered tube with a float
inside the tube. When attached to an operating pump, the float rises until the rate of
flow is sufficient to hold the float stationary. The flow rate is read from markings
on the tube at the point the float is stationary. Figure 9 illustrates a precision
rotameter.
«- »
•
1
3500
=_. 3000
~ 2500
I_ 2000
Z_ 1500
E_ 1000
5_ 500
cc/min
| i" !• p rump
I -4— Air Flow
FIGURE 9. EXAMPLE OF A PRECISION ROTAMETER
Whereas the precision rotameter usually is more compact and portable than the soap bubbler meter,
it is considered a secondary standard. This means that the rotameter must be checked occasionally
with a primary standard such as a bubble meter.
• A manometer is sometimes used to calibrate Hi-Vol samplers because of the high
flow rates. A manometer is a tube filled with a liquid. The level of the liquid
changes due to pressure changes at the end attached to the sampling pump. A
calibration chart is used to convert the change in liquid level to flow rate.
CONCLUSION
When taking air samples for laboratory analysis, several factors need to be considered. Sampling
and analytical methods have been developed for many chemicals by several agencies that have looked
at these considerations. The References section provides a list of references on air monitoring and
sampling.
Air Sample Collection
18
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APPENDIX A
Air Sampling Methods Database
-------
United States
Environmental Protection
Agency
Office of
Solid Waste and
Emergency Response
January 1993
Air Sampling Methods
Database
Offioa of Emergency and Remedial Response
Emergency Response Division
Technical Bulletin
Volume 1, Number 1
What is the Air Sampling Methods
Database?
The Air Sampling Methods Database is a PC-based
software package which allows its users to access sum-
marized standard methods for chemical analysis. The
program, which was designed to be used in conjunction
with the Representative Air Sampling Guidance for the
Removal Program document, formulate sampling plans
to give the best possible site characterization. This al-
lows users to make quick determinations about which
methods are most appropriate to use and which best
suit their informational needs in order to plan a sam-
pling event that most aptly depicts the objectives of a
particular site investigation.
The user can search the software by method name and
number, chemical name, or Chemical Abstracts Num-
ber (CAS # ). The method summary can be viewed and
the method marked for printing. Furthermore, the soft-
ware can be tailored to its users since they have the ca-
pacity to input their own user-developed methods into
the database without affecting the established stand-
ardized methods. Users can submit supporting docu-
mentation for their methods to the United States
Environmental Protection Agency's Environmental Re-
sponse Team (U.S. EPA/ERT) for possible permanent
inclusion to the database.
Who Are the Anticipated Users?
On-Scene Coordinators (OSC), Technical Assistance
Team (TAT) members, Emergency Response Contrac-
tors (ERCs), site Health and Safety air personnel, and
U.S. EPA air plan reviewers are the primary users of
the Air Sampling Methods Database. By using the pro-
gram, these individuals gain access to the sampling ob-
jectives which best characterize a site. Then, users can
assimilate this information into an acceptable repre-
sentative sampling program. The Air Sampling Methods
Database also can aid any U.S. EPA personnel or
agency that performs air monitoring at hazardous waste
sites.
Why Was the Air Sampling
Methods Database Designed?
The Air Sampling Methods Database was created to ex-
pand the knowledge base during remedial emergency
response actions. It gives insight to two major criteria
for preparation of a representative air sampling plan:
selecting the appropriate air sampling approach and
choosing the proper equipment to collect and analyze a
sample. Timely decisions regarding health and safety
and acute health risks can be made by utilizing these
summarized methodologies:
• National Institute of Occupational Safety and
Health (NIOSH) 2nd and 3rd Edition Methods.
• Occupational Safety and Health Administration
(OSHA) Methods.
• Selected American Society of Testing and Materi-
als (ASTM) Methods. Volume 11.03 Atmospheric
Analysis; Occupational Health and Safety.
• EPA Toxic Organic Compounds Methods.
• Contract Laboratory Program - Statement of Work
Methods.
• Indoor Air Compendium Methods.
• Code of Federal Regulations (CFR) Methods.
This facilitates a greater variety of options for the users,
who then can select the appropriate air sampling objec-
tives and plans that best suit the needs of a particular
assignment.
-------
Features of the Air Sampling
Methods Database
• Is user friendly.
• Requires no other software for support (self-con-
tained).
• Adds, deletes, and edits methods added by a user.
• Traces information by on-line references.
• Provides single point of update.
• Gives semi-annually updates.
• Allows access to update information available via
Environmental Response Center (ERC), Office of
Solid Waste and Emergency Response (OSWER),
U.S. EPA/ERT, and Dataport bulletin boards by
modem.
• Generates hard copy.
Future Features:
• Hot-Key on-line help.
• Hot-Key on-line glossary of terms.
• 50-100 word text summaries discussing sampling
trains, flow rates, interferences, detection limits,
analysis information, etc.
• Synonym searching of chemical names.
Requirements
To run the Air Sampling Database, you must have the
following:
• An IBM PC or IBM-compatible computer
• A hard drive
• 640K RAM
• A printer (for hard copy output)
Formore information about the Air Sampling Database,
contact:
Mr. Thomas Pritchett, Phone: (908) 321-6738
U.S. Environmental Response Team
2890WoodbridgeAve
Building 18, MS-J01
Edison, New Jersey 08837-3679
4
-------
INTRODUCTION TO GAS
CHROMATOGRAPHY
PERFORMANCE OBJECTIVES
At the end of this lesson, participants will be able to:
• List the components of a gas chromatograph
• Define retention time
• List the factors that affect retention time
• Name the two types of columns and describe their
differences.
-------
NOTES
INTRODUCTION TO GAS
CHROMATOGRAPHY
GAS CHROMATOGRAPHY
Definition
A technique for separating
volatile substances in a mixture
by percolating a gas stream
over a stationary phase
Source: Basic Gas Chromatography
SEPARATION OF A MIXTURE
BY GAS CHROMATOGRAPHY
B
tol
Camponmt A
Cwnpon.ntB
4194
Introduction to Gas Chromatography
-------
NOTES
RETENTION TIME
Definition
Retention time is the time
from sample injection to peak
maxima (signal maxima)
Infection
RETENTION TIME
Application
Used for qualitative identification of
chemicals by comparing the retention
time of an unknown chemical with
retention times of known (standard)
chemicals
RETENTION TIME
Peak Comparisons
Injection
Standard
Unknown
s
Tim*
Introduction to Gas Chromatography
4/94
-------
NOTES
FACTORS AFFECTING
RETENTION TIME
• Column
- Type
- Temperature
- Length
• Carrier gas flow rate
EFFECT OF COLUMN TYPE
AND TEMPERATURE
Chemical
Temperature Retention Time
CO (min.)
G-8 Column T-8 Column
Benzene 0 1:19 1:43
40 0:25 0:32
Carbon tetrachloride 0 1:24 0:37
40 0:25 0:17
Source The Foxboro Company Chromatographic Column Guide lor the
Century OVA, 1966
PEAK RESOLUTION
Problems
A
I
Overlapping peaks
ri
\ fv\
V\A
4/94
Introduction to Gas Chromatography
-------
NOTES
PEAK AREA
Application
Peak area is used to quantify chemical
'Sampl«N
Concentration Sample
Concentration Standard
Area Standard
GAS CHROMATOGRAPH
Components
Flow
control
Inaction port
V I Column
Output
CARRIER GAS
Characteristics
• Suitable for detector
• High purity
• Does not interfere with sample
Introduction to Gas Chromatography
4/94
-------
NOTES
GAS CHROMATOGRAPH
Columns
Packed
Liqud stationary phase
coated on solid stationary
support
Capillary
Liquid stationary phase
coated on wall
COLUMN TEMPERATURE
• Ambient
- Variable
• Isothermal
- Constant temperature
• Temperature programming
- Temperature increases over time
DETECTORS USED IN
PORTABLE GCs
Common detectors
- Flame ionization detector (FID)
- Photoionization detector (PID)
Specialized detectors
- Thermal conductivity detector (TCD)
- Argon ionization detector (AID)
- Electron capture detector (BCD)
4/94
Introduction to Gas Chromatography
-------
NOTES
SPECIALIZED DETECTORS
Why Are They Used?
One detector may be more sensitive
than another for certain compounds.
e.g. The ECD is best detector for
halogenated compounds.
MASS SPECTROMETER
Chemical exposed to electrons
Molecule or fragments are ionized
Ions separated by magnetic field
Separation based on speed and
mass-to-charge ratio
Only detector capable of providing
additional compound identification beyond
retention time
MASS SPECTRUM
Benzene
1001
50-
Relative
abundance
78
I
«0 M> 100 110 120
Mass-to-charge ratio
Introduction to Gas Chromatography
4/94
-------
NOTES
MASS SPECTRUM
Toluene
1001
50-
Relative
abundance
3, a, —
I «s . . I
ll I I I 70 77 Mi
lllLlll Jll .Illll .... ul
40 SO 80 70 BO BO 100 110 120
Mass-to-charge ratio
GAS CHROMATOGRAPHY
Field Applications
• Air analysis
• Field screening
• Soil gas
SUMMARY
Gas chromatography is used to
identify and quantity chemicals
Qualified operators are needed
Right tool for the job?
4/94
Introduction to Gas Chromatography
-------
INTRODUCTION TO GAS CHROMATOGRAPHY
INTRODUCTION
Gas chromatography is a separation technique wherein components of a sample are separated by
differential distribution between a gaseous mobile phase (carrier gas) and a solid (gas solid
chromatography) or liquid (gas liquid chromatography) stationary phase held in a column. The
sample is injected into the carrier gas as a sharp plug and individual components are detected as they
come out ("elute") of the column at characteristic "retention times" after injection. Figure 1
illustrates this concept with a two component mixture.
A + B
Gas
Flow
Column
Component A
in Detector
Component A
Component B
FIGURE 1. SEPARATION OF A TWO COMPONENT MIXTURE
BY GAS CHROMATOGRAPHY
As different components elute from the column, they pass through a detector which generates a
response (or "peak") based upon the amount of each compound present and upon the sensitivity of
the detector. The signal vs. time plot is called the "chromatogram."
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Introducrion to Gas Chromatography
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QUALITATIVE ANALYSIS
If the temperature of the column and the flow rate of the carrier gas are constant, compounds will
elute from the column at a characteristic time (retention time). The retention is characteristic of the
compound and the type of column used. Retention time is the time from injection of the sample to
peak response of the detector to the eluted compound (Figure 2).
Retention time
Injection
8 9
Time
FIGURE 2. CHROMATOGRAM ILLUSTRATING RETENTION TIME
Qualitative analysis can be done by comparing the retention times of the compounds in an unknown
sample with the retention times of known compounds in a standard analyzed under identical
conditions. Figure 3 shows a comparison of a sample with a standard.
Retention Time
Retention times are governed by several factors:
1. The type of column used. Different packings and liquid coatings change retention
time.
2. The column temperature. As the column temperature increases, the retention time
decreases. This is why temperature controls are used to keep the column temperature
constant.
Introduction to Gas Chromatography
10/93
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3. The column length. Double the column length and double the retention time.
4. The carrier gas flowrate. Double the flowrate and halve the retention time.
Injection
Standard
Unknown
Time
FIGURE 3. EXAMPLE OF A GC CHROMATOGRAM AND THE USE OF
RETENTION TIMES TO IDENTIFY COMPOUNDS
Resolution
Resolution, or relative peak width, governs the number of discrete, detectable components of a
sample that can be identified and quantified during the GC run. Resolution is governed by:
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Introduction to Gas Chromatography
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1. The type of column. Capillary columns have much greater resolution (narrower peak
widths) than a packed column.
2. Column length. The longer the column, the narrower the peak weak width at a given
retention time. However, with ambient temperature GCs, increasing the column
length will increase the retention times.
3. The carrier gas flowrate. There exists an optimum value for peak resolution.
Increasing or decreasing the flowrate from this optimum will widen the peaks.
A problem with poor resolution is co-eluting and overlapping. If two chemicals elute at the same
time—co-elute—identification is hindered. If peaks overlap, quantitation of the compounds is
difficult. Figure 4 illustrates overlapping peaks.
Overlapping peaks
FIGURE 4. EXAMPLES OF OVERLAPPING PEAKS
QUANTITATIVE ANALYSIS
Signal Output
The size of the chromatogram peak for a specific compound is proportional to the amount of
chemical in the detector. Quantitative analysis is done by comparing the peak size of the sample
compound with the peak size of a known amount of the compound (the standard). The peak size can
be quantified in several ways.
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Planimetering
Planimetering uses a planimeter to trace the peak. A planimeter is a mechanical device that
measures area by tracing the perimeter of the peak. The area is presented digitally on a dial. This
method is considered tedious, time-consuming, and less precise than other methods.
Peak Height
Peak height compares the height of the sample compound with the height of the standard. This is
a quick and simple method for quantitation. However, peak heights and widths are dependent on
sample size and sample feed rate.
Height x Width at Half-Height
The height x width at half-height uses the height of the peak times the width of the peak at the half-
height of the peak. The normal peak base is not used because large deviations may be caused by
peak tailing.
Triangulation
Triangulation (Figure 5) transforms the peak into a triangle using the sides of the peak to form the
triangle and the baseline to form the base of the triangle. The area of the peak is calculated using
Area = 1/2 Base x Height.
Integrators
Peak height, height x width at half-height, and triangulation are done manually using the
chromatogram and a pencil and straight edge. Integrators calculate the peak size electronically and
record the output. Because of ease of operation, integrators are most frequently used in portable
GCs.
When a microprocessor is used, the retention times of the compounds in the sample are compared
to the compounds in the standard and the readout identifies the compounds in the sample.
Quantitative analysis is done by an integrator. If a compound has been identified, the peak size in
the sample is compared to the peak size of the compound in the standard and a sample concentration
is given. Thus, the sample is evaluated both qualitatively and quantitatively.
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*\
Area = 1/2 x base x height
Area = 1/2 b h
FIGURE 5. MEASUREMENT OF AREA BY TRIANGULATION
Source: An Introduction to Gas Chromatography, National Training Center, Water Program
Operations, U.S. Environmental Protection Agency, Cincinnati, OH.
COMPONENTS OF A GAS CHROMATOGRAPH
A gas chromatograph (GC) consists of (Figure 6):
• A carrier gas
• A flow control for the carrier gas
• A sample inlet or injector
• A column
• A temperature control for the column
• A detector
• A recorder.
Carrier Gas
A high pressure gas cylinder serves as the source of the carrier gas. The carrier gas should be:
1. Inert to avoid interaction with the sample or solvent
2. Able to provide a minimum of gaseous diffusion
3. Readily available and of high purity
4. Inexpensive
5. Suitable for the detector used.
Commonly used gases are helium, nitrogen, and hydrogen.
Introduction to Gas Chromatography 5 10/93
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Flow
control
Injection port
I
Output
Detector
Carrier gas
FIGURE 6. COMPONENTS OF A GAS CHROMATOGRAPH
Source: The Industrial Environment - Its Evaluation & Control, 1973, National Institute for
Occupational Safety and Health.
Portable gas chromatographs (GCs) have internal cylinders that usually have an 8- to 10-hour gas
supply. Many of these also have connections for external cylinders to provide longer duration
analysis.
Flow Control
Because compounds elute at a characteristic time (retention time) based on a given temperature and
a constant flow rate, carrier gas flow control and column temperature are important. A flow
controller is necessary to maintain a constant flow rate.
Sample Injection System
Samples are introduced into the column as a single sharp plug. The sample injection system allows
introduction of the sample rapidly and in a reproducible manner. Samples can be manually injected
by a syringe. Syringe injection allows the operator to control the sample volume. Some GCs have
a built-in sample loop that injects a known and consistent volume by manual operation or automatic
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programming. Sample volume is important in that the quantitative evaluation of a chromatogram is
affected by the sample volume. Also, some columns are limited by the size of sample that can be
injected onto them.
Column
The column is a tube made of stainless steel, glass, aluminum, or Teflon®. Packed columns contain
a solid adsorbent (gas-solid chromatography) or an inert solid support coated with liquid stationary
phase (gas-liquid chromatography). Capillary columns consist of a liquid stationary phase coated to
the inside wall of a thin tube. Gas-liquid chromatography columns and capillary columns are the
more common types for the portable GCs.
Tube sizes range from 0.5- to 6-mm outside diameter and from 20 cm to 50 m in length. Capillary
columns are usually longer than packed columns. Portable GC columns are typically 4 m in length.
Columns can be coiled to fit inside portable units.
Capillary columns give better resolution than packed columns. However, they require smaller
injection volumes than packed columns and thus need sample inlets and detectors that can handle
small volumes.
Temperature Control
Column temperature affects the retention time of a chemical. A constant temperature is desired to
ensure comparison of sample and standards. Temperature control can be:
• Ambient temperature control—The column temperature is the same as ambient air.
As ambient temperature changes, the retention times change. Consequently, frequent
calibration checks are needed. Ambient temperature limits use to volatile
compounds. The time to run a sample is longer and thus limits the number of
samples that can be run per day.
• Isothermal temperature control—The column temperature is maintained at constant
temperature by an oven. Retention times are much more stable. Temperatures can
be adjusted to reduce analysis time or expand the range of compounds that can be
analyzed. Retention times are halved for every 30'C increase in temperature.
Isothermal temperature control consumes more electricity than ambient.
• Temperature programming—Column temperature is slowly increased under very
controlled conditions. This allows simultaneous analysis of compounds with a wide
range of boiling points. A lower temperature is used for the volatile components.
The temperature is raised to elute the less volatile compounds. More electrical power
is needed for this operation.
Temperature control can also be used on the injector and the detector. Heating the injector prevents
condensation of the sample (if a vapor) or can ensure vaporization of a liquid sample. The detector
may need to be heated to prevent chemical condensation.
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Detector
There are a variety of detectors available for GCs. Flame ionization detectors (FID) and
photoionization detectors (PID) are frequently used. Characteristics of these two detectors are
discussed in the Total Vapor Survey Instruments section. Other detectors include:
• Thermal conductivity detector (TCD)—This detector is based on the principle that a
hot object will lose heat at a rate that is dependent on the composition of the
surrounding gas. When a compound enters the detector, there is a change in the
thermal conductivity of the carrier gas. Its advantage is that it is a universal detector
for noninert gases and all organics. Its drawback is limited sensitivity—ppm levels.
Preconcentration of samples has been used to offset this limitation.
• Electron capture detector (ECD)-A radioactive source is used to ionize the carrier
gas. Secondary electrons are produced and an electrical current flows between the
electrodes in the detector. When a separated compound which has an affinity for the
slow electrons enters the detector, electrons are captured with a resultant decrease in
electrical current in the detector. This decrease of current is a function of the
concentration of the electron capturing compound.
The detector is especially selective for polyhalogenated (e.g., pesticides) and nitro
compounds. It has a high sensitivity—mid ppb to high ppt. Sensitivity is a direct
function of halogen atoms per molecule.
Its main limitation is that a radioactive source (tritium or nickel-63) is needed, which
requires a Nuclear Regulatory Commission (NRC) license.
• Argon ionization detector (AID)—Argon ionization detector depends upon two
reactions: the excitation of argon to its metastable state by electron bombardment and
the ionization of vapor molecules by the transfer of energy from the metastable
atoms. When an ionization chamber contains argon and a source of free electrons,
the addition of vapor causes an increase in current flow. The current flow change
is detected and used as the signal for the presence of the compound in the sample.
Ionization is caused by a radioactive source. As with the ECD, an NRC license is
required for use of the radioactive source.
The reaction of the metastable argon atoms with the vapor molecules applies to all
molecules with an ionization potential equal to, or less than, the stored energy of the
metastable atoms, which is 11.7 eV.
• Mass Spectrometer (MS)—In an MS, the chemical is first exposed to a source of
electrons. The molecules or fragments are ionized. The ions are passed through a
magnetic field. The magnetic field separates the ions based on their speed and mass-
to-charge ratio. The ions are collected and a mass spectrum is produced showing the
relative abundance of each type of ion. Each chemical has a distinctive mass
spectrum. Thus, this detector is the only one listed here that is capable of providing
additional compound identification beyond retention time.
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Recording Devices
A device is needed to record when a signal is produced in the detector and to record the strength of
that signal. A plot of signal vs. time is called a chromatogram. The chromatogram is used for
qualitative and quantitative analysis of the sample. Integrators and microprocessors can be used to
electronically evaluate the chromatogram.
Power Supply
A power supply is needed to operate the detector, recorder, oven, and additional electronics of the
gas chromatograph. To make them portable, field portable GCs usually have a built-in rechargeable
battery supply. If only using the battery, time of operation is limited to 8-10 hours. These units
are also designed to operate off AC power sources. A few field GCs only operate on AC power.
APPLICATIONS
Portable gas chromatographs allow analysis in the field. Although the results may not be as accurate
and precise as a laboratory GC analysis, they can be used for screening purposes. This can reduce
the number of samples that need to be handled by a more sophisticated (and more expensive)
analysis.
Ambient Air Analysis
Portable GCs can analyze ambient air samples through several methods. Some units can be taken
to the area where the sampling is required and an analysis can be performed on the spot. Some units
can be programmed to do periodic sampling and store the chromatograms for later retrieval. Newer
units can do continual total vapor monitoring and run a sample if the total vapor reading exceeds a
designated level. The GC can also be set up in a more stable environment, and grab samples (e.g.,
a Tedlar bag of ambient air) can be brought to the GC for analysis.
Sample Screening
Soil and water samples can be screened for further analysis by doing headspace sampling.
Headspace sampling involves drawing a sample from above the surface of a liquid or soil in a
container. The sample is usually drawn with a small syringe which is also used to inject the sample
into the GC.
Soil Gas
Gas chromatography can be used to screen soil gas samples. Dissolved volatile organic compounds
have a tendency to partition into the atmosphere between the soil particles. By sampling this
atmosphere, underground contamination can be tracked.
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EXAMPLES OF PORTABLE GAS CHROMATOGRAPHS
The Foxboro Company
The Foxboro Century organic vapor analyzer (OVA) is the instrument described in the Total Vapor
Survey Instruments section. The OVA-128GC is equipped with a column. The detector used is an
FID. The column is at ambient temperature unless an optional temperature pack is used. The
portable isothermal pack allows column temperatures of O'C, 40'C and 100'C. The unit can be
purchased with an external recorder/plotter. The company does not supply an integrator, but there
are models from other suppliers that can be used.
Photovac International, Inc.
The Photovac series of GCs use photoionization detection. The temperature of the column is
controlled by an oven. The currently available models (10S50, 10S70, 10S Plus, Snapshot) have a
built-in microprocessor that aids in calibration and handles compound identification and quantitation.
These units can be programmed for automatic sampling. The 10S Plus can be programmed to do
total vapor monitoring and to do an analysis if an action level is reached. Options include a
telephone connection for transferring data from the instrument to a computer and for notifying the
user of unusual results during remote monitoring.
Sentex Sensing Technology, Inc.
The Sentex Scentograph is capable of using an AID or an BCD. One of the most notable features
of the Scentograph is that a lap-top computer is used for handling the data. This gives a more
graphic visual display of the chromatogram and makes operator use easier because of the normal size
keyboard. The GC can do automatic functions. It has a temperature controlled column. There is
the capability of concentrating the sample before injection. The air sample is pulled through and
collected on a sorbent. The sample is then desorbed and injected using a smaller volume than was
pulled through the sorbent. A primary consideration with the Scentograph is that, if an AID or an
BCD is used, a radioactive source is needed and thus an NRC license is required. A PID and TCD
are also available.
The Sentex Scentoscreen is similar to the Scentograph except it uses a PID and can also do total
hydrocarbon analysis. It can be switched to an AID/ECD, but can not do total hydrocarbon readout
with those detectors.
HNU Systems, Inc.
The HNU Systems' Model 311 is available with a PID or an ECD for its dete.ctor. The unit has a
microprocessor for data handling. The instrument does not have a battery supply and thus, needs
a line power or a portable generator.
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Microsensor Technology, Inc.
Microsensor Technology's M200 Microsensor Gas Analyzer uses a TCD. Although this is a more
universal detector, it suffers from poor sensitivity. A preconcentrator has been developed and used
to reduce this limitation. The more notable characteristic of the M200 is that it sends a sample
through two columns at the same time. This gives a better chance of correctly identifying the
compounds present.
Thermo Environmental Instruments
Thermo Environmental Instruments manufactures the Model 511 Portable Gas Chromatograph. The
main features of this GC is the variety of available detectors (FID, PID, ECD, TCD) and their easy
changeability. The unit does not have a built-in data handler, so an external integrator or
microprocessor is needed.
SUMMARY
Gas chromatography is a separation technique that can be used for identification of the components
of a mixture. Portable GCs can be used in the field for a variety of applications. This process of
identification can be affected by many factors that must be considered to ensure quality of data.
Because the equipment is more complicated to operate than most direct-reading instruments,
operators require more training and experience.
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DISPERSION MODELING
DURING
EMERGENCY RESPONSE
-------
Dispersion Modeling During Emergency Response
Objectives: . \_\s^ fjve major atmospheric dispersion considerations
• Describe the concept of stability as it applies to air
modeling
Given a set of environmental conditions, choose the
relevant stability class
Dispersion Modeling During Emergency Response
Objectives: • Describe the concept of Gaussian plume distribution
• Define near-field meandering and its effects to onsite
receptors
• Given an air dispersion model, list the data inputs needed
to run the model for an emergency response
• Given an emergency response scenario, list the elements
of the modeling plan
Notes:
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Collect site data
^
r
Collect source data
Collect contamination data
Collect meteorological data
^
r
Choose appropriate accidental release model
i
r
Input collected data to model and run model
i
T
Compare output to air action limits
i
>XDo the
<^ require «
\. proce
^
r
results ^^ M0 ,
?vcicuci uo n ? r iNt) ctoiioii ne6u6u
dures /"
Yes
r
Evacuate affected onsite/offsite populations as necessary
Figure ~\. Dispersion modeling during emergency removal.
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Dispersion Model Classes
Physical Models
Small-scale, laboratory
representations of the overall
process (e.g., wind tunnel, water
tank)
Mathematical Models
A set of analytical or mathematical
algorithms that describe the
physical and chemical aspects of
the problem (e.g., ALOHA, ISC,
and PAL)
Dispersion Model Classes
Mathematical models are primarily used because physical models (especially in an emergency response)
are much less practical for most Superfimd applications.
Mathematical models can be:
• Deterministic models, based on fundamental mathematical descriptions of atmosphere processes,
in which effects (i.e., air pollution) are generated by causes (i.e., emissions).
• Statistical models, based on semi-empirical statistical relationships among available data and
measurements.
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Notes:
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Diffusion Model Footprint
750
250
w
750
500
500
Yards
1000
1500
Reproduced with permission from The National Safety Council
Diffusion Model
An example of a deterministic model is a diffusion model from which the output (the concentration field
or footprint) is computed from mathematical manipulations of specified inputs (emission rates and
atmospheric parameters).
A statistical model is given by the forecast, in a certain region, of the concentration levels in the next
few hours as a statistical function of:
1. The current available measurements
2. The past correlation between these measurements and the concentration trends.
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Notes:
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Source-Receptor Relationship
Wind Direction
Receptor Location
Transport Medium
(Air)
Release
Mechanism
(Volatilization)
Waste Pile
(Source)
Source-Receptor Relationship
The source-receptor relationship is the goal of studies aimed either at improving ambient air quality
(usually the Superfund site goal) or preserving the existing concentration levels from future urban and
industrial development. Only a deterministic model can provide an unambiguous assessment of the
fraction of the responsibility of each pollutant source to each receptor area. This information then allows
the definition and implementation of appropriate emission control strategies.
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Notes:
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Dispersion Modeling Applications
The two major dispersion modeling applications for Superfund are:
• To design an air monitoring program
• To estimate concentrations at receptors of interest
Dispersion Modeling Applications
Dispersion models can be used when designing an air monitoring program to see how offsite areas of
high concentration relate to actual receptor locations. Places where high concentration areas correspond
to actual receptors are priority locations for air monitoring stations.
Dispersion models can also be used to provide seasonal dispersion concentration patterns based on
available representative historical meteorological data (either onsite or offsite). These dispersion patterns
can be used to evaluate the representativeness of any air monitoring data collection period. Data
representativeness is determined by comparing the dispersion concentration patterns for the air
monitoring period with historical seasonal dispersion concentration patterns.
It is often not practical to place air monitoring stations at actual offsite receptor locations of interest.
It will be necessary, however, to characterize concentrations at these locations to conduct a health and
environmental assessment. In these cases, dispersion patterns based on modeling results can be used to
extrapolate concentrations monitored at the site to offsite receptor locations.
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Notes:
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Atmospheric Dispersion Considerations
Stability
Inversions
Wind speed and direction
Air temperature
Terrain effects
Atmospheric Dispersion Considerations
There are many different types of dispersion models, ranging from simple models that only require a
few basic calculations to three-dimensional models that require massive amounts of input data and
intense computational platforms to handle the complexity. Choosing the model to use depends on the
scale of the problem, the level of detail available for input, the required output, the background of the
user, and the turnaround time needed for an answer.
The five atmospheric dispersion considerations (i.e., stability, inversions, wind speed and direction, air
temperature, and terrain effects) must all be considered throughout the modeling process.
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Notes:
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Stability Class
B
\ \
Weak Winds
Sunshine
Strong Heating
Strong Winds
E
\ \
\ \
Weak Winds
Night Cooling
(Ground
Trapping)
The Relationship Between Stability Class, Heating, and Wind Speed
Stability Class
Atmospheric stability is the extent of physical stirring and mixing on the vertical plane. When an
atmosphere is stable, there will be little mixing, which results in a persistent concentration. Stable
conditions will also generally result in longer, narrower plume shapes.
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Notes:
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Inversions
Inversions
Inversions limit upward movement of air masses due to temperature differentials. The inversion height
a modeler is concerned with is generally less than 100 feet. Inversions are generally an evening/night-
time phenomenon and their presence results in increased stability.
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Notes:
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Effects of Wind Speed and Direction
CD
c^S _*>
Weak Winds
CD
High Winds
CD
Moderate Winds
CD CD
CD
CD
o
-------
Notes:
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Ground Roughness - Terrain Steering Effects
Ground Roughness - Terrain Steering Effects
Areas with hills or valleys may experience wind shifts where the wind actually flows between hills or
down into the valleys, turning where these features turn.
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Notes:
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Gaussian Dispersion
Source of Spill
Crosswind
Gaussian Dispersion
In a Gaussian dispersion model, a curve is used to describe how a contaminant will be dispersed in the
air after it leaves the source. At the source, the concentration of the contaminant is very high and the
Gaussian distribution looks like a spike or a tall column. As the contaminant drifts farther downwind,
it spreads out and the "bell shape" gets continually wider and flatter.
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Notes:
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Near-Field Meandering
Near-Field Meandering
Near-field meandering is caused by individual drifting eddies in the wind that push the plume from side
to side. These eddies, or small gusts, are also responsible for much of the mixing that makes the plume
spread out. As the plume drifts downward from the spill source, these eddies shift and spread the
plume until it takes on the form of a Gaussian distribution.
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Notes:
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Emission Rates
APA Guidelines
Volumes II & III
EPA Modeling
Guidelines
Yes
COLLECT AND REVIEW INFORMATION
• Source data
• Urban/rural classification data and
receptor data
• Environmental characteristics
Available
Monitoring Data
SELECT MODEL CLASS AND
SOPHISTICATION LEVEL
• Screened
• Refined
DEVELOP MODELING PLAN
Select model
Select constituents to be modeled
Define model input requirements (emissions,
meteorology, receptors)
Select receptors
Select modeling period
Evaluate modeling uncertainty
EPA
Review/Approval
CONDUCT MODELING
Develop emission inventory
Process meteorological data
Develop receptor grid
Run model test cases
Verify input files
Perform calculation for averaging times under
consideration
SUMMARIZE/EVALUATE RESULTS
• Determine concentrations
• Prepare meteorological summaries
• Consider modeling uncertainty
No
ADDITIONAL ANALYSES NEEDED?
Reproduced from NTGS Volume IV
Input to EPA
Remedial/Removal
Decision-Making
Figure 2. Superfund air impact assessment dispersion modeling protocol.
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Superfund Air Impact Assessment Dispersion Modeling Protocol
Associated guidance documents:
• National Technical Guidance Study (NTGS) Volumes II and III
• Air quality modeling at Superfund sites factsheet
• Guidelines on air quality models (revised).
Notes:
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Dispersion Modeling Protocol
Emission Rates
APA Guidelines
Volumes II & III
COLLECT AND REVIEW
INFORMATION
• Source data
• Urban/rural classification
data and receptor data
• Environmental characteristics
Available
Monitoring Data
Reproduced from NTGS Volume IV
Step 1:
Step 1 involves collecting and compiling existing information pertinent to air dispersion modeling. This
information is obtained during a literature survey. Information that should be collected and compiled
includes source data, receptor data, and environmental data (e.g., land use classification, demography,
topography, and meteorology). Once the existing data have been collected and compiled, a thorough
evaluation will define the data gaps. A coherent dispersion modeling plan can then be developed using
site-specific parameters and requirements.
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Dispersion Modeling Protocol
SELECT MODEL CLASS AND
SOPHISTICATION LEVEL
• Screened
• Refined
Reproduced from NTGS Volume IV
Step 2:
Step 2 involves the selection of the dispersion modeling sophistication level and screening and refined
modeling techniques. The selection process depends on program objectives as well as available resource
and technical constraints. Screening models generally use limited and simplified input information to
produce a conservative estimate of exposure. Screening models assist in the initial determination of
whether the Superfund site, or site activity, will present an air impact problem. The emission source(s)
should then be evaluated with either a more sophisticated screening technique or a refined model. When
selecting a more sophisticated modeling technique or approach, the following aspects should be
considered: availability of appropriate modeling techniques for the Superfund list of toxic constituents;
site-specific factors, including source configuration and characteristics; applicability; limitations;
performance for similar applications; and comparison of advantages and disadvantages of alternative
modeling techniques and approaches.
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Dispersion Modeling Protocol
EPA Modeling
Guidelines
DEVELOP MODELING PLAN
• Select model
• Select constituents to be modeled
• Define model input requirements
(emissions, meteorology, receptors)
• Select receptors
• Select modeling period
• Evaluate modeling uncertainty
EPA Review/
Approval
Reproduced from NTGS Volume IV
Step 3:
Step 3 involves preparing a dispersion modeling plan. Elements that should be addressed in the plan
include overview of the Superfund site area, selection of constituents to be modeled, modeling
methodology (emission inventory, meteorology, receptor grid, rural/urban classification, models to be
used, concentration averaging time, and special situations such as wake effects), and documentation of
the air modeling plan.
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Notes:
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Dispersion Modeling Protocol
CONDUCT MODELING
Develop emission inventory
Process meteorological data
Develop receptor grid
Run model test cases
Verify input files
Perform calculation for averaging
times under consideration
Reproduced from NTGS Volume IV
Step 4:
Step 4 specifies the actual activities involved in conducting air dispersion modeling for a Superfund site.
Activities that are performed include developing an emission inventory, preprocessing and verifying
modeling, setting model switches, running model test cases, performing dispersion calculations, and
obtaining a printout of modeling input and output.
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Notes:
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Dispersion Modeling Protocol
SUMMARIZE/EVALUATE RESULTS
• Determine concentrations
• Prepare meteorological summaries
• Consider modeling uncertainty
Yes
No
ADDITIONAL ANALYSES NEEDED?
Input to EPA
Remedial/Removal
Decision Making
• > Return to Select Model Class and Sophistication Level
Reproduced from NTGS Volume IV
Step 5:
Step 5 involves the review and assessment of the dispersion modeling results.
Additional components of this step include preparation of data summaries, concentration mapping (i.e.,
isopleths), estimation of uncertainties, and assessment.
AMFHM
10/83
page 36
-------
Notes:
AMFHM
10/93
page 37
-------
Accidental Release Modeling
• Provides worst-case results
• Results used to determine evacuation of shelter-in-place options
• Cannot account for near-field patchiness
• Examples: ALOHA ™ ARCHIE, CHARM ™, TRACE, and TSCREEN
Accidental Release Modeling
Accidental release modeling is performed when results are needed immediately. Accidental release
models that assist in making source-term calculations, or provide probability warnings, are best when
real-time solutions are essential.
ALOHA™, ARCHIE, CHARM™, TRACE, and TSCREEN are examples of accidental release models.
Each model is a relatively simple estimation technique that provides conservative estimates of air quality
impact(s).
AMFHM
10/93
page 38
-------
Notes:
AMFHM
10/93
page 39
-------
Accidental Release Models
ALOHA™ (NOAA/EPA)
Areal
Locations
Of
Hazardous
Atmospheres
ALOHA
TM
The Areal Locations of Hazardous Atmospheres (ALOHA) model was developed through a joint venture
between the National Oceanic and Atmospheric Administration (NOAA) and EPA. It is an emission
estimation and air quality dispersion model for estimating the emission rate, movement, and dispersion
of gases released into the atmosphere. The model estimates pollutant concentrations downwind from
the source of a release, taking into account the toxicological and physical characteristics of the material.
ALOHA considers the physical characteristics of the release site, the atmospheric conditions, and the
initial source conditions.
The model has a built-in database of chemical names and properties that the model uses to calculate
emission rates. The program performs buoyant gas dispersion based on Gaussian dispersion equations
and heavier-than-air dispersion based on algorithms in the DEnse GAs Dispersion (DEGADIS) model.
Emission estimations can be made for puddles, tanks, and pipe releases or for direct input of material
into the atmosphere. The model uses hourly meteorological data that can be entered by the user or
obtained from real-time measurements. The results of the model can be displayed as concentration
plots or in text summary screens. The concentration outputs are limited to a 1-hour (or less) exposure.
AMFHM
10/93
page 40
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Notes:
AMFHM
10/93
page 41
-------
Accidental Release Models
ARCHIE (FEMA/DOT/EPA)
Automated
Resource for
Chemical
Hazard
Incident
Evaluation
ARCHIE
The Automated Resource for Chemical Hazard Incident Evaluation (ARCHIE) model was developed
through a joint effort by the Federal Emergency Management Agency (FEMA), the U.S. Department
of Transportation (DOT), and EPA. It is an emission estimation and atmospheric dispersion model that
can be used to assess the vapor dispersion, fire, and explosion impacts associated with episodic
discharges of hazardous materials into the environment. The model can estimate the emissions and
duration of liquid/gas releases from tanks, pipelines, and liquid pools, as well as the associated ambient
concentrations downwind of these releases. ARCHIE can also evaluate the thermal hazards resulting
from the ignition of a flammable release and the consequences of an explosion caused by a flammable
gas, tank overpressurization, or ignition of an explosive material. In addition, it can estimate the size
of the downwind hazard zone that may require evacuation or other public protection because of the
release of a toxic gas or vapor into the atmosphere.
To estimate downwind concentrations, simulated meteorological conditions are input to the model. The
user must input chemical properties of the material released from information contained in the material
safety data sheets.
AMFHM
10/93
p«ge 42
-------
Notes:
AMFHM
10/93
page 43
-------
Accidental Release Models
TM
CHARM (Radian Corporation))
Complex
HAzardous
Release
Model
CHARM
TM
The Complex Hazardous Release Model (CHARM™) is a proprietary Gaussian puff model for
continuous and instantaneous releases of gases or liquids. The model is configured to handle chemicals
that are buoyant, neutrally buoyant, or heavier-than-air. CHARM™ can estimate the emission rates of
chemicals using a modification of the SHELL spill model and a multiphase pressurized gas release
model. CHARM™ contains a database of chemical information that is used in calculating emission
estimates. The program is menu driven and can accept simulated meteorological data for up to 24
hours. The CHARM™ model can simulate the transport of chemicals in spatially and temporally
varying wind fields. The results from the program may be displayed graphically on a screen or output
to a printer.
AMFHM
10/93
page 44
-------
Notes:
AMFHM
10/93
page 45
-------
Accidental Release Models
TRACE (E.I. Dupont de Nemours)
Toxic
Release
Analysis of
Chemical
Emissions
TRACE
The SAFER System TRACE model is an engineering analysis tool for dispersion modeling. It models
accidental toxic releases, including those caused by pipe/flange leaks, aqueous spills, hydrogen fluoride
spills, fuming acid spills, stack emissions, or elevated dense gas emissions. The program is menu
driven and contains several modules to estimate the evaporation and dispersion of chemicals and analyze
the effect of certain parameters on downwind concentrations. The program has a built-in database of
chemicals and their properties and various source-term modules. The model uses real-time or simulated
meteorological data for atmospheric dispersion calculations. These data can vary with time during the
release. The results of the modeling analysis can be displayed visually on graphs or stored in tables.
AMFHM
10/93
page 46
-------
Notes:
AMFHM
10/93
page 47
-------
Accidental Release Models
TSCREEN (EPA)
• Model for screening toxic air pollutant concentrations
TSCREEN
TSCREEN, a model for screening toxic air pollutant concentrations, is an air quality dispersion model
that implements the procedures in A Workbook of Screening Techniques for Assessing Impacts of Toxic
Air Pollutants (EPA-450-88-009). The TSCREEN model is an atmospheric dispersion model that uses
the dispersion algorithms of SCREEN, Release Valve Discharge (RVD), and PUFF models. It
automatically selects the worst-case simulated meteorological conditions based on the criteria presented
in the workbook. The model contains a data table of chemicals and their associated parameters (limited
to two chemicals at this time) that TSCREEN can access. It can calculate the source term for dust
particles within a pile of a specified dimension. The model can also simulate the dispersion of gaseous,
liquid, and paniculate matter releases. TSCREEN outputs graphical and tabular summaries of predicted
pollutant concentrations.
AMFHM
10/93
page 48
-------
Notes:
AMFHM
10/83
paae 49
-------
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AMFHM
10/93
page SO
-------
Notes:
AMFHM
10/93
page 51
-------
REFERENCES
The following list represents a partial list of background references on the subject of air monitoring
and sampling. Although other sources may be available, it is believed that these will provide the
reader with a good understanding of the subject.
The references are listed alphabetically by title and include author, publisher, and place of
publication. The year of publication is given for governmental sources only. For the remainder,
the reader should attempt to obtain the most recent edition. An * after the title indicates that a copy
of the document is part of the course library and is available for review.
1. Advances in Air Sampling'
Lewis Publishers, Inc.
121 South Main Street
P.O. Drawer 519
Chelsea, MI 48118
(Also available through ACGIH. See #4.)
2. Air Methods Database
Available on the Cleanup Information electronic bulletin board (CLU-IN), formerly OSWER
BBS. For further information, call 301 589-8366.
3. Air Monitoring For Toxic Exposures: An Integrated Approach', 1991
Shirley A. Ness
Van Nostrand Reinhold
115 Fifth Avenue
New York, NY 10003
4. Air Monitoring Instrumentation: A Manual for Emergency, Investigatory, and Remedial
Responders', 1993
C. Maslonsky and S. Maslonsky
Van Nostrand Reinhold
115 Fifth Avenue
New York, NY 10003
5. Air Sampling Instruments'
American Conference of Governmental Industrial Hygienists
6500 Glenway Avenue, Building D-E
Cincinnati, OH 45211
513 661-7881
6. Air/Superfund National Technical Guidance Series:
• Volume IV—Guidance for Ambient Air Monitoring at Superfund Sites (revised). EPA-
451/R-93-007, May 1993
10/93 1 References
-------
• Compilation of Information on Real-Time Air Monitoring for Use at Superfund Sites.
EPA-451/R-93-008, May 1993
7. Atmospheric Analysis: Occupational Health and Safety, ASTM Standards, Volume 11.03
American Society for Testing and Materials
1916 Race Street
Philadelphia, PA 19103-1187
215 299-5400
8. Basic Gas Chromatography
H.M. McNair and E.J. Bonelli
Varian Instrument Division
Purchase from Supelco, Inc.
Supelco Park
Bellefonte, PA 16823-0048
9. Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air,
EPA/600/4-89/017, June 1988
Atmospheric Research and Exposure Assessment Laboratory
U.S. Environmental Protection Agency
Office of Research and Development
Research Triangle Park, NC 27711
10. A Compendium of Superfund Field Operations Methods*, EPA/540/P-87/001, December 1987
U.S.Environmental Protection Agency
Office of Emergency and Remedial Response
Office of Waste Programs Enforcement
Washington, DC 20460
11. Data Quality Objectives for Remedial Response Activities: Development Process,
EPA/540/G-87/003, March 1987
U.S. Environmental Protection Agency
Office of Emergency and Remedial Response
Office of Waste Programs Enforcement
Washington, DC 20460
12. Fundamentals of Industrial Hygiene
National Safety Council
444 North Michigan Avenue
Chicago, IL60611
13. Guidance on Applying the Data Quality Objectives Process for Ambient Air Monitoring
Around Superfund Sites (Stages I & II), EPA-450/4-89-015; (Stage III), EPA-450/4/90-005
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Research Triangle Park, NC 27711
References 2 10/93
-------
14. Guide to Occupational Exposure Values'
American Conference of Governmental Hygienists
6500 Glenway Avenue, Building D-E
Cincinnati, OH 45211
513 661-7881
15. Guide to Portable Instruments for Assessing Airborne Pollutants Arising from Hazardous
Wastes
International Organization of Legal Metrology
Paris, France
(Available through ACGIH)
16. The Industrial Environmental - Its Evaluation and Control, 1973
National Institute for Occupational Safety and Health
Rockville, MD
(Available from the Superintendent of Documents, U.S. Government Printing Office,
Washington, DC 20402 [202 783-3238])
17. Industrial Hygiene and Toxicology, Volumes I and III
Frank A. Patty
John Wiley and Sons, Inc.
New York, NY
18. Manual of Recommendation Practice for Combustible Gas Indicators and Portable Direct
Reading Hydrocarbon Detectors, 1980, 1st edition
John Klinsky (ed)
American Industrial Hygiene Association
Akron, OH
19. Methods of Air Sampling and Analysis'
Lewis Publishers, Inc.
121 South Main Street
P.O. Drawer 519
Chelsea, MI 48118
(Also available through ACGIH)
20. NIOSH Manual of Analytical Methods, Editions 1, 2, and 3'
National Institute for Occupational Safety and Health
Rockville, MD
(Available from the Superintendent of Documents, U.S. Government Printing Office,
Washington, DC 20402 [202 783-3238])
21. OSHA Analytical Methods Manuaf
Superintendent of Documents
U.S. Government Printing Office
Washington, DC 20402
202 783-3238
10/93 3 References
-------
22. OSHA Technical Manual"', 1990
(See ACGIH)
23. Removal Program Representative Sampling Guidance: Air
U.S. Environmental Protection Agency
Office of Emergency and Remedial Response
Emergency Response Division
Environmental Response Branch
Washington, DC
24. Standard Operating Safety Guides, June 1992
U.S. Environmental Protection Agency
Environmental Response Team
2890 Woodbridge Avenue
Building 18 (MS-101)
Edison, NJ 08837-3697
908 321-6740
25. Standard Operating Guide for the Use of Air Monitoring Equipment for Emergency Response
(See #21)
26. Standard Operating Guide for Air Sampling and Monitoring at Emergency Responses
(See #21)
27. Technical Assistance Document for Sampling and Analysis of Toxic Organic Compounds in
Ambient Air, EPA-600/4-83-027
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Research Triangle Park, NC 27711
References 4 10/93
-------
MANUFACTURERS AND SUPPLIERS OF
AIR MONITORING EQUIPMENT
AIR MONITORING EQUIPMENT
Aerosol/Particulate Direct-Reading Monitors:
Air Techniques Incorporated
HUND Corporation
Met One, Inc.
MIE, Inc.
MST Measurement Systems, Inc.
Pacific Scientific (HIAC/ROYCO Instrument Division)
Particle Measuring Systems, Inc.
PPM Enterprises
TSI Incorporated
Calibration Gases: (most manufacturers of instruments provide calibration gases for
use with their instruments; these companies provide a variety of calibration gases)
Airco Industrial Gases
Alphagaz
Bryne Specialty Gases
Digicolor
Environics, Inc.
GC Industries
Kin-Tek laboratories, Inc.
Liquid Air Corporation
National Specialty Gases
Norco, Inc.
Scott Specialty Gases
VICI Metronics
Calibrators, Pump:
Accura Flow Products Co., Inc.
Air Systems International
AMETEK
BGI Incorporated
BIOS International Corp
DuPont
Gillian Instrument Co.
Sensidyne
10/93 i Manufacturers and Suppliers
-------
SKC, Inc.
Spectrex Corporation
Canister Samplers:
Andersen Samplers Incorporated
Nutech Corporation
Scientific Instrumentation Specialists
Wedding & Associates, Inc.
Xontech, Inc.
Collection Media:
Ace Glass Incorporated
BGI Incorporated
DACO Products
Gelman Sciences
Gilian Instrument Corporation
Hi-Q Environmental Products Company
LaMotte Chemical Products Company
Micro Filtration Systems
Millipore Corporation
Mine Safety Appliances Company
Nuclepore Corporation
Omega Specialty Instruments Company
Paliflex, Inc.
Poretics Corporation
Schleicher & Schuell
Sipin, Anatole, J., Co., Inc.
SKC, Inc.
Supelco, Inc.
Colorimetric Detectors: (B = badges or dosimeters; DT = regular detector tubes; LT = long term
detector tubes)
American Gas & Chemical Co., Ltd. (B)
Analytical Accessories International (B)
Bacharach, Inc. (B)
Chemsense (B)
Crystal Diagnostics (B)
Enmet Corporation (DT, LT)
GMD Systems, Inc. (B)
Matheson Safety Products (DT, LT)
MDA Scientific (B)
Mine Safety Appliances Co. (B, DT, LT)
Manufacturers and Suppliers 2 10/93
-------
National Draeger, Inc. (B, DT, LT)
PPM Enterprises (B)
Sensidyne (DT), Inc.
SKC, Inc. (B, LT)
VICI Metronics (B)
Willson Safety Products (B)
Combustible Gas Meters:
A.I.M. Safety Company, Inc.
Astro International Corp.
Bacharach Instruments
Biosystems, Inc.
Chestec, Inc.
Control Instruments Corp.
Dynamation Incorporated
Energy Efficiency Systems,Inc.
Enmet Corporation
Gas Tech, Inc.
GfG America Gas Detection Ltd.
Grace Industries, Inc.
Heath Consultants Incorporated
Industrial Scientific Corporation
J and N Enterprises, Inc.
Lumidor Safety Products e.s.p., Inc.
Mine Safety Appliances Co.
National Draeger, Inc.
Neotronics N.A., Inc.
Quatrosense Environmental Ltd.
Scott Aviation
Sieger Gas Detection
Sierra Monitor Corporation
Texas Analytical Controls, Inc.
TIP Instruments, Inc.
Gas Bags:
AeroVironment, Inc.
The Anspec Company, Inc.
BGI Incorporated
Calibrated Instruments, Inc.
Digicolor
Jensen Inert
KVA Analytical Systems
Norton Performance Plastics
Nutech Corporation
10/93 3 Manufacturers and Suppliers
-------
Plastic Film Enterprises
Pollution Measurement Corporation
Science Pump Corporation
SKC, Inc.
Gas Chromatographs: (types of detectors available: AID = argon ionization; ECD
electron capture; FID = flame ionization; MS = mass spectroscopy; PID
photoionization; SS = chemical specific sensor; TCD = thermal conductivity)
Bruker Instruments (MS)
Canaan Scientific Products
CMS Research Corporation (SS)
The Foxboro Company (FID)
GOW-MAC (FID, TCD)
HNU Systems, Inc. (PID, FID)
Microsensor Systems Inc.
Microsensor Technology, Inc. (TCD)
Photovac Incorporated (PID, FID)
S-Cubed (ECD)
Sensidyne (FID)
Sentex Sensing Technology, Inc. (ECD, PID, PID, TCD)
Summit Interests (FID, PID, TCD)
Thermo Environmental Instruments, Inc. (ECD, FID, PID, TCD)
Viking Instruments (MS)
XonTech, Inc. (AID, ECD)
Oxygen Meters:
A.I.M. Safety Company, Inc.
Bacharach, Inc.
Biosystems, Inc.
Dynamation Incorporated
Energy Efficiency Systems, Inc.
Enmet Corporation
GasTech, Inc.
GC Industries
GfG America Gas Detection Ltd.
Industrial Scientific Corporation
Lumidor Safety Products e.s.p., Inc.
MDA Scientific, Inc.
Metrosonics, Inc.
Mine Safety Appliances Co.
National Draeger, Inc.
Neotronics N.A., Inc.
Rexnord Safety Products
Scott Aviation
Manufacturers and Suppliers 4 10/93
-------
Sensidyne
Sieger Gas Detection
Sierra Monitor Corporation
Teledyne Analytical Instruments
Passive Dosimeters: (these devices require laboratory analysis; for direct-reading
dosimeters see G. Colorimetric Detections)
Advanced Chemical Sensors
Air Technology Labs, Inc.
Assay Technology
EnSys, Inc.
Gilian Instrument Corporation
Landauer, R.S. Jr. & Company
Mine Safety Appliances Co.
National Draeger, Inc.
Pro-Tek Systems, Inc.
Sensidyne
SKC, Inc.
3M
Sampling Pumps and Accessories: (letters denote primary function of pumps and
apparatus: P = Personal; A = Area; B = Bag filling)
AeroVironment, Inc. (B)
Air Systems International, Inc. (A)
AMETFK (P)
Analytical Accessories International (A,P)
Andersen Samplers Incorporated (A)
Arjay Equipment Corporation (A)
Barnant Company (A)
BGI Incorporated (P, A)
BIOS International Corp
Calibrated Instruments, Inc. (B)
California Measurements, Inc. (A)
DuPont (P)
Environmetrics, Inc. (A)
General Metal Works, Inc. (A)
Gillian Instrument Corp. (P)
LaMotte Chemical Products Company (A)
Midwest Environics, Inc. (A)
Mine Safety Appliances Co. (P)
Omega Specialty Instrument Co. (A)
Wedding & Associates, Inc. (A)
Sensidyne (P)
Sipin, Anatole J., Co., Inc. (P)
JO/93 5 Manufacturers and Suppliers
-------
SKC, Inc. (P)
Spectrex Corporation (P)
Staplex Air Sampler Division (A)
Supelco, Inc. (P)
Thermedics, Inc. (P)
Wedding & Associates (A)
Toxic Monitors: (direct-reading instruments for low concentrations of contaminants;
letters denote types of detectors available; PID = photoionization; FID = flame
ionization; IR = infrared spectroscopy; TCD = thermal conductivity; GS = general
sensor, e.g., MOS or super-sensitive CGI; SS = sensor for specific chemical, e.g.,
CO, H2S)
A.I.M. Safety Company, Inc.(GS, SS)
Anacon Detection Technology (SS)
Analect Instruments (IR)
Arizona Instrument, Jerome Division (SS)
Astro International Corp. (SS)
Bacharach, Inc. (GS, SS)
Biosystems, Inc. (SS)
Bruel & Kjaer (IR)
CEA Instruments, Inc. (GS, SS)
Dynamation Incorporated (GS, SS)
Enmet Corporation (SS)
Environmental Technologies Group (GS)
The Foxboro Company (FID, IR)
GasTech, Inc. (GS, SS)
GfG America Gas Detection Ltd. (SS)
GMD Systems, Inc. (colorimetric)
GOW-MAC (TCD)
Grace Industries, Inc. (GS)
Graesby Ionics Ltd. (Ion Mobility Spectrometry)
Heath Consultants Incorporated (FID)
HNU Systems, Inc. (PID)
Industrial Scientific Corporation (SS)
International Gas Detectors, Inc.
InterScan Corporation (SS)
J and N Enterprises, Inc. (GS)
MDA Scientific, Inc. (SS)
Macurco, Inc. (GS, SS)
Mast Development Corporation (SS)
Matheson Safety Products (TCD)
Metrosonics, Inc. (SS)
Microsensor Systems, Inc. (SS)
Mine Safety Appliances Co. (PID, FID, SS)
National Draeger (SS)
Neotronics N.A., Inc. (SS)
Manufacturers and Suppliers 5 10/93
-------
Nicolet Instrument Corp. (IR)
Photovac Incorporated (PID)
Quatrosense Environmental Ltd. (SS)
Scott Aviation (SS)
Sensidyne (SS, FID)
Sentex Sensing Technology, Inc. (FID)
Servomax Company (IR)
Sieger Gas Detection (SS, IR)
Sierra Monitor Corporation (SS)
Spectrex Corporation (SS)
Summit Interests (FID, PID, TCD)
Tekmar Company (TCD)
Texas Analytical Controls, Inc. (SS)
Thermo Environmental Instruments, Inc. (FID, PID, TCD)
TIF Instruments, Inc. (GS)
Transducer Research, Inc. (SS)
MANUFACTURERS' AND SUPPLIERS' ADDRESSES
AccuRa Flow Products Co., Inc.
P.O. Drawer 100
Warminster, PA 18974
214 674-4782
Ace Glass Company
P.O. Box 688
Vineland, NJ
609 692-3333
Advanced Chemical Sensors
350 Oak Lane
Pompano Beach, FL 33069
305 979-0958
Advanced Calibration Designs, Inc.
7960 S. Kolb Rd.
Tucson, AZ 85705
602 574-9509
AeroVironment, Inc.
145 Vista Avenue
Pasadena, CA91107
818 357-9983
A.I.M. Safety Company, Inc.
P.O. Box 720540
Houston, TX 77272-0540
713 240-5020
1-800-ASK-4AIM
Air Systems International
814-P Greenbrier Circle
Chesapeake, VA 23320
1-800-866-8100
Air Techniques Incorporated
1801 Whitehead Road
Air Techniques Incorporated
1801 Whitehead Road
Baltimore, MD 21207
301 944-6037
Airco Industrial Gases
Division of Airco, Inc.
575 Mountain Avenue
Murry Hill, NJ 07974
201 464-8100
10/93
Manufacturers and Suppliers
-------
Alphagaz
Specialty Gases Division
Liquid Air Corporation
2121 N. California Blvd.
Walnut Creek, CA 94596
415 977-6506
AMETEK
Mansfield & Green Division
8600 Somerset Drive
Largo, FL 34643
813 536-7831
American Gas & Chemical Co., Ltd.
220 Pegasus Avenue
Northvale, NJ 07647
201 767-7300
1-800-288-3647
Anacon Detection Technology
117 South Street
Hopkinton, MA 01748
508 435-6973
Analect Instruments
Division of Laser Precision Corp.
1231 Hart Street
Utica, NY 13502
315 797-4449
Analytical Accessories International
P.O. Box 922085
Atlanta, GA 30092
1-800-282-0073
Anderson Instruments, Inc.
4801 Fulton Industrial Blvd.
Atlanta, GA 30336
404 691-1910
The Anspec Company, Inc.
122 Enterprise Drive
Ann Arbor, MI 48107
313 665-9666
1-800-521-1720
Arizonia Instrument Corp.
P.O. Box 1930
Tempe, AZ 85280
602 731-3400
1-800-528-7411
Arjay Equipment Corp.
P.O. Box 2959
Winston-Salem, NC 27102
919 741-3582
Assay Technology
1070 E. Meadow Cir.
Palo Alto, CA 94303
1-800-833-1258
Astro International Corp.
100 Park Avenue
League City, TX 77573
713 332-2484
BGI, Inc.
58 Guinan Street
Waltham, MA 02154
617 891-9380
BIOS International Corporation
756 Hamburg Turnpike
Pompton Lakes, NJ 07442
201 839-6908
Bacharach, Inc.
625 Alpha Drive
Pittsburgh, PA 15238
412 963-2000
Barnant Company
28W092 Commercial Avenue
Barrington, IL 60010
312 381-7050
Biosystems, Inc.
P.O. Box 158
Rockfall, CT 06481
203 344-1079
Manufacturers and Suppliers
10/93
-------
Bruel & Kjaer Instruments, Inc.
185 Forest Street
Marlborough, MA 01752
508 481-7000
Bruker Instruments, Inc.
Manning Park
Billerica, MA 01821
617 667-9580
Byrne Specialty Gases, Inc.
118 S. Mead Street
Seattle, WA 98108
206 764-4633
Calibrated Instruments, Inc.
200 Saw Mill River Road
Hawthorne, NY 10502
914 741-5700
CEA Instruments, Inc.
16 Chestnut Street
Emerson, NJ 07630
201 967-5660
CMS Research Corporation
100 Chase Park, Suite 100
Birmingham, AL 35244
205 733-6900
California Measurements, Inc.
150 E. Montecito Avenue
Sierra Madre, CA 91024
818 355-3361
Canaan Scientific Products
P.O. Box 50527
Indianapolis, IN 46250
317 842/1088
1-800-842-8578
ChemSense
3909 Beryl Rd.
Raleigh, NC 27607
919 821-2929
Chestec, Inc.
P.O. Box 10362
Santa Ana, CA 92705
714 730-9405
Compur Monitors
7015 West Tidwell
Suite Gill-A
Houston, TX 77092
713939-1103
Control Instruments Corp.
25 Law Drive
Fairfield, NJ 07006
201 575-9114
Costar/Nucleopore
One Alewife Center
Cambridge, MA 02140
617 868-6200
Crystal Diagnostics, Inc.
600 West Cummings Park
Woburn, MA 01801
617933-4114
DACO Products, Inc.
12 S. Mountain Avenue
Montclair, NJ 07042
201 744-2453
Digicolor
2770 East Main Street
P.O. Box 09763
Columbus, OH 43209
614236-1213
Dynamation Incorporated
3784 Plaza Drive
Ann Arbor, MI 48104
313 769-0573
Enmet Corporation
P.O. Box 979
2308 S. Industrial Highway
Ann Arbor, MI 48106-0979
313 761-1270
10/93
Manufacturers and Suppliers
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Energy Efficiency System, Inc.
1300 Shames Drive
Westbury, NY 11590
516 997-2100
1-800-645-7490
EnSys, Inc.
P.O. Box 14063
Research Triangle Park, NC
919 941-5509
Envirometrics, Inc.
1019 Bankton Dr.
Charleston, SC 29406
1-800-255-8740
Environics, Inc.
33 Boston Post Road West
Marlborough, MA 01752
617 481-3600
Environmental Technologies Group
1400 Taylor Avenue
Baltimore, MD 21284-9840
301 635-4598
The Foxboro Company (EMO)
P.O. Box 500
600 N. Bedford St.
East Bridgewater, MA 02333
508 378-5556
GasTech, Inc.
8445 Central Avenue
Newark, CA 94560
415 745-8700
GC Industries, Inc.
8976 Oso Ave., Unit C
Chatsworth, CA 91311
818 882-7852
GfG Gas Electronics, Inc.
6617 Clayton Rd., Suite 209
St. Louis, MO 63144
314 725-9050
GMD Systems, Inc.
Old Route 519
Hendersonville, PA 15339
412 746-3600
Gelman Sciences, Inc.
600 South Wagner Road
Ann Arbor, MI 48106
313 665-0651
General Metal Works, Inc.
145 South Miami
Village of Cleves, OH 45002
513 941-2229
Gilian Instrument Corporation
35 Fairfield Place
West Caldwell, NJ 07006
201 808-3355
GOW-MAC
P.O. Box 32
Bound Brook, NJ 08805
201 560-0600
Grace Industries, Inc.
P.O. Box 167
Transfer, PA 16154
412 962-9231
Graseby Ionics Ltd.
Analytical Division
Park Avenue, Bushey
Watford Herts Wb2 2BW
England
0923 816166
Heath Consultants, Inc.
100 Tosca Drive
P.O. Box CS-200
Stoughton, MA 02072-1591
617 344-1400
Hi-Q Filter Environmental Products
7386 Trade Street
San Diego, CA 92121
619 549-2820
Manufacturers and Suppliers
10
10/93
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HNU Systems, Inc.
160 Charlemont Street
Newton Highlands, MA 02161
617 964-6690
1-800-527-4566
HUND Corporation
777 Passaic Ave.
Clifton, NY 07012-1804
202 473-5009
Industrial Scientific Corporation
355 Steubenville Pike
Oakdale, PA 15071-1093
412 788-4353
1-800-338-3287
International Gas Detectors, Inc.
11221 Richmond Ave., Suite C-109
Houston, TX 77082
713 558-4099
InterScan Corporation
P.O. Box 2496
21700 Nordoff Street
Chatsworth, CA 91313-2496
1-800-458-6153
J and N Enterprises, Inc.
P.O. Box 108
Wheeler, IN 46393
219759-1142
Jensen Inert
P.O. Box 660824
Miami, FL 33266-0824
305 871-8839
1-800-446-3781
Kin-Tele Laboratories
2395 Palmer Highway
Texas City, TX 77590
409 945-3627
KVA Analytical Systems
281 Main St.
P.O. Box 574
Galmouth, MA 02541-99811
508 540-0561
LaMotte Chemical Products Co.
P.O. Box 329
Chesteitown, MD 21620
301 778-3100
1-800-344-3100
Lumidor Safety Products/E.S.P., Inc.
5364 NW 167th Street
Miami, FL 33014
305 625-6511
Macurco, Inc.
3946 S. Mariposa Street
Englewood, CO 80110
303 781-4062
Mast Development Company
Air Monitoring Division
2212 East 12th Street
Davenport, IA 52803
319 326-1041
Mateson Chemical Corporation
1025 E. Montgomery Avenue
Philadelphia, PA 19125
215 423-3200
Matheson Gas Products, Inc.
30 Seaview Drive
Secaucus, NJ 07096-1587
215 641-2700
MDA Scientific, Inc.
405 Barclay Blvd.
Lincolnshire, IL 60069
312 634-2800
1-800-323-2000
MG Industries
175 Meister Avenue
North Branch, NJ 08876
201/231-9595
10/93
11
Manufacturers and Suppliers
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MIE, Inc.
213 Burlington Road
Bedford, MA 01730
617 275-5444
MST Measurement Systems, Inc.
327 Messner Drive
Wheeling, IL 60090
708 808-2500
Met One, Inc.
481 California Avenue
Grants Pass, OR 97526
503 479-1248
Metrosonics, Inc.
P.O. Box 23075
Rochester, NY 14692-3075
716 334-7300
Micro Filtration Systems
6800 Sierra Court
Dublin, CA 94568
415 828-6010
Microsensor Systems, Inc.
6800 Versar Center
Springfield, VA 22151
703 642-6919
Microsensor Technology, Inc.
47747 Warm Springs Blvd.
Fremont, CA 94539
415 490-0900
Midwest Environics, Inc.
10 Oak Glen Court
Madison, WI 53717
608 833-0158
Millipore Corporation
Lab Products Division
80 Ashby Road
Bedford, MA 01730
617 275-9200
Mine Safety Appliances
P.O. Box 427
Pittsburgh, PA 15230
412 967-3000
1-800-MSA-INST
National Draeger, Inc.
P.O. Box 120
101 Technology Drive
Pittsburgh, PA 15230-0120
412 787-8383
National Specialty Gases
630 United Drive
Durham, NC 27713-9985
Neotronics N.A., Inc.
P.O. Box 370
411 North Bradford Street
Gainesville, GA 30503
404 535-0600
1-800-535-0606
Nicolet Instrument Corp.
5225 Verona Rd.
Madison, WI 53711
608 271-3333
Norco, Inc.
1121 W. Amity
Boise, ID 83705
208 336-1643
North Performance Plastics
150 Dey Road
Wayne, NJ 07470-4699
1-800-526-7844
Nutech Corporation
2806 Cheek Road
Durham, NC 27704
919 682-0402
Omega Specialty Instruments Company
4 Kidder Road, Unit 5
Chelmsford, MA 01842
508 256-5450
Manufacturers and Suppliers
12
10/93
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Pacific Scientific
HAIC-ROYCO Instruments Division
141 Jefferson Drive
Menlo Park, CA 94025
Paliflex, Inc.
125 Kennedy Drive
Putnam, CT 06260
203 929-7761
Particle Measuring Systems
1855 South 57th Court
Boulder, CO 80301-2886
303 443-7100
Photovac International, Inc.
25-B Jefryn Blvd. W.
Deer Park, NY 11729
516 254-4199
Plastic Film Enterprises
2011 Bellaire Avenue
Royal Oak, MI 48067
313 399-0450
Pollution Measurement Corporation
P.O. Box 6182
Chicago, IL 60680
708 383-7794
Poretics Corporation
151 I Lindbergh Avenue
Livermore, CA 94550-9412
415 373-0500
1-800-922-6090
PPM Enterprises
11428 Kingston Pike
Knoxville, TN 37922
615 966-8796
Pro-Tek Systems, Inc.
64 Genung Street
Middletown, NY 10940
914344-4711
Quatrosense Environmental Ltd.
5935 Ottawa Street
P.O. Box 749
Richmond, Ontario, Canada KOA 2ZO
613/838-4005
S-Cubed
P.O. Box 1620
La Jolla, CA 92038-1620
619/453-0060
Schleicher & Schuell, Inc.
10 Optical Street
Kenne, NH 03431
603/352-3810
800/245-4024
Scientific Instrumentation Specialists
P.O. Box 8941
Moscow, ID 83843
208/882-3860
Science Pump Corporation
1431 Ferry Avenue
Camden, NJ 08104
609/963-7700
Scott Aviation
225 Erie Street
Lancaster, NY 14086
716/683-5100
Scott Specialty Gases
Route 161 North
Plumsteadville, PA 18949
215/766-8861
Sensidyne, Inc.
16333 Bay Vista Dr.
Clearwater, FL 34620
813/530-3602
800/451-9444
Sentex Sensing Technology, Inc.
553 Broad Avenue
Ridgefield, NJ 07657
201/945-3694
10/93
13
Manufacturers and Suppliers
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Servomax Company
90 Kerry Place
Norwood, MA 02062
617 769-7710
Sieger Gas Detection
405 Barclay Blvd.
P.O. Box 1405
Lincolnshire, IL 60069-1405
1-800-221-1039
Sierra Monitor Corporation
1991 Tarob Court
Milipitas, CA 95035
408262-6611
Anatole J. Sipin Co., Inc.
505 Eighth Avenue
New York, NY 10018
212 695-5706
SKC, Inc.
334 Valley View Road
Eighty Four, PA 15330-9614
412 941-9701
1-800-752-8472
Spectrex Corporation
3580 Haven Avenue
Redwood City, CA 94063
415 365-6567
Staplex Company
Air Sampler Division
777 Fifth Avenue
Brooklyn, NY 11232-1695
212 768-3333
1-800-221-0822
Summit Interests
P.O. Box 1128
Lyons, CO 80540
303 444-8009
Supelco, Inc.
Supelco Park
Bellefonte, PA 16823-0048
814 359-3441
3M OH & ESD
3M Center
Building 220-3E-04
St. Paul, MN 55144-1000
612 733-5608
TIF Instruments Inc.
9101 NW 7th Avenue
Miami, FL 33150
305757-8811
TSI Incorporated
500 Cardigan Road
P.O. Box 43394
St. Paul, MN 55164
612 483-0900
Tekmar Company
P.O. Box 371856
Cincinnati, OH 45222
1-800-543-4461
Teledyne Analytical Instruments
16830 Chestnut Street
City of Industry, CA 91749
213 283-7181
Texas Analytical Controls, Inc.
P.O. Box 42520
Houston, TX 77242
713 240-4160
Thermedics, Inc.
470 Wildwood Street
Woburn, MA 01888
617 938-3786
Thermo Environmental Instruments, Inc.
8 West Forge Parkway
Franklin, MA 02038
508 520-0430
Transducer Research, Inc.
999 Chicago Ave.
Naperville, IL 60540
708 357-0004
Manufacturers and Suppliers
14
10/93
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VICI Metronics
2991 Corvin Drive
Santa Clara, CA 95051
408 737-0550
Viking Instruments Corp.
12007 Sunrise Valley Drive
Reston, VA 22091-3406
703 758-9339
Wedding & Associates, Inc.
P.O. Box 1756
Fort Collins, CO 80522
303 221-0678
Whatman Paper Division
9 Bridewell Place
Clifton, NJ 07014
201 773-5800
Wheaton Scientific
1000 North 10th Street
Millville, NJ 08332
609 825-1400
Willson Safety Products
P.O. Box 622
Reading, PA 19603-0622
215 376-6161
Xetex, Inc.
600 National Avenue
Mountain View, CA 94043
415 964-3261
XonTech Inc.
6862 Hayvenhurst Avenue
Van Nuys, CA 91406 .
818 787-7380
10/93
15
Manufacturers and Suppliers
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AIR MONITORING FOR HAZARDOUS MATERIALS
WORKBOOK
CONTENTS
Exercise Page
1 Oxygen Monitor, Combustible Gas Indicators,
and Specific Chemical Monitors 1
2 Photoionization Detectors - Survey 13
3 Flame lonization Detectors - Survey . . . 21
4 Gas Chromatography - Organic Vapor Analyzer 29
5 Detector Tubes '. 39
6 Direct-Reading Aerosol Monitors 53
7 Gas Chromatography - Photoionization Detector 63
8 Sampling Pumps and Collection Media 71
9 Field Exercise 87
10/93 \ Contents
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EXERCISE 1
Oxygen Monitors, Combustible Gas Indicators,
and Specific Chemical Monitors
OBJECTIVE
In this exercise, students will calibrate or check the calibration of a variety of combustible gas
indicators (CGIs), combination CGI/O2 monitors, and combination CGI/O2/toxic monitors. The
instruments will then be used to sample a variety of test atmospheres and the results will be
interpreted.
PROCEDURE
The exercise is divided into three different stations. Each station is equipped with an air monitoring
instrument or group of instruments.
Station 1: MSA Model 260/261 combination CGI/02 monitor
Station 2: MSA Model 360 combination CGI/O2/carbon monoxide monitor
Station 3: GasTech Model 1314 combination CGI/O2/toxic monitor
There may be more than one of each numbered station to reduce crowding. Follow the instructions
given for each instrument. Sample the indicated gas bags and record your results. At the end of
the exercise, answer the questions. The instructor will then hold a brief discussion.
The instructions given for each instrument are based on the manufacturers' operating manuals.
However, some steps may have been added for illustration purposes and some may have been
shortened for purposes of time or space. As with any instrument, consult the operator's manual
before using in the field.
10/93 1 Exercise 1
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STATION 1
MSA Model 260/261 Combination CGI/O, Monitor
The MSA Model 260/261 is a combination combustible gas and oxygen monitor. There are meter
displays for both indicators. Visual and audible alarms for a % LEL reading and a low oxygen
reading are included. The Model 261 also has a high oxygen reading alarm. The audible alarm can
be deactivated. Air is drawn into the instrument by a battery-operated pump.
SETUP
1. Record the instrument serial number or ID number on the data sheet.
2. Attach the sampling hose to the instrument. Make sure that the connection is hand tight.
STARTUP
3. Turn the center "ON-OFF" control clockwise to the "HORN-OFF" position. Both meter
pointers will move, both alarm lights will light, and the center green lamp will blink on and
off. (Note: On the Model 261, the light will not turn on until after the reset button is
pushed.) The green light indicates alarms status. When it glows continuously, the audible
alarm is operable. When it blinks on and off, it indicates that the audible alarm has been
deactivated.
4. Adjust the meter pointer on the % oxygen monitor by pulling and turning the "O2
CALIBRATE KNOB." The knob is supplied with a clutch to prevent accidental field
decalibration. Adjust the pointer to read 20.8%, which is the hatch mark below the 21%
mark.
5. Adjust the meter pointer on the %LEL meter by pulling and turning the "LEL ZERO
KNOB." Adjust the pointer to read 0%.
6. Press the red alarm "RESET" button to reset the alarms. Both red lights should stop
flashing. (Note: The "RESET" button will not reset the alarms if the meter pointers exceed
the alarm levels.)
7. Press the black "CHECK" button and observe the pointer on the %LEL meter. The pointer
should move above 80% LEL into the BATTERY zone of the meter. This indicates that the
battery is okay. If it does not reach the BATTERY zone, inform an instructor/technician.
LEAK TEST
8. Momentarily hold a finger over the sample inlet or end of sample probe. Observe that the
flow indicator float (lower right hand corner of instrument face) drops out of sight, indicating
Exercise 1 1 10/93
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no flow. If the float does not drop out of sight, check the system for leaks. If the
instrument does not pass the leak test, inform an instructor/technician.
ALARM CHECK
The purpose of these steps is to check the meter readings at which the alarms will sound.
9. Turn the O2 CALIBRATE knob counterclockwise (decreasing the % oxygen reading) while
watching the % oxygen meter and the oxygen alarm light. Note the reading at which the
alarm sounds and the light starts flashing. Adjust the reading back to 20.8% and press the
reset button. Record the reading on the data sheet. The lower alarm reading should be
19.5%.
10. (MSA 261 only) Turn the O2 CALIBRATE knob clockwise (increasing the % oxygen
reading) while watching the % oxygen meter and the oxygen alarm light. Note the reading
at which the alarm sounds and the light starts flashing. Adjust the reading back to 20.8%
and press the reset button. Record the alarm reading on the data sheet. . The upper alarm
reading should be 25%.
11. Turn the zero LEL knob clockwise until the alarm is activated. Record this reading. Return
the meter pointer to zero and press the reset button. The alarm should have activated at 25 %
LEL.
12. If any of the alarm points are not what they should be, inform an instructor/technician.
13. The instrument is ready for calibration.
CALIBRATION
14. Open the clamp to the gas bag labeled "PENTANE 0.75%" and attach the sample line to the
bag. Draw a sample into the instrument until a constant reading is obtained.
15. Record your reading on the data sheet. The instrument should give a reading of 50% LEL.
Inform the instructor if it does not.
16. Disconnect the sample line and clamp the bag. Allow fresh air to flow through the
instrument until the reading returns to zero. Rezero the instrument, if needed.
SAMPLING
17. Please note that the Model 261 has a latching mechanism that engages the %LEL meter
pointer if it reaches or exceeds 100. To disengage the lock, the instrument must be turned
10/93 3 Exercise 1
-------
off and then turned back on in an area where the LEL readings are less than 100%. Room
air will do.
18. For field monitoring, the alarm should be in the operable mode. For this exercise, you may
keep the audible alarm deactivated to reduce noise levels.
19. Sample each of the gas bags listed on the data sheet. Record the readings.
SHUTDOWN
20. When sampling is complete, flush fresh air through the instrument. Turn the instrument
OFF.
Exercise 1 4 10/93 '
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STATION 2
MSA Model 360 Combination CGI/CL/CO Monitor
The MSA Model 360 is a combination combustible, oxygen, and carbon monoxide (CO) monitor.
It has a digital display that shows only one reading. It has alarms for a specific % LEL reading, low
and high oxygen, and a specific carbon monoxide reading. If the alarm levels are reached for any
of these responses, there will be a visual and audible indication. This will occur no matter what
function is being displayed at the time. The audible alarm can be deactivated. Air is drawn into the
instrument by a battery-powered pump.
SETUP
1. Record the instrument serial number or ID number on the data sheet.
2. Attach the sampling hose to the instrument. Make sure the connection is- hand tight.
STARTUP
3. Turn the FUNCTION control to the "HORN-OFF" position. Alarm signals will flash for
all three chemicals, the "HORN OFF" green/yellow lamp will be off and % LEL will show
in the readout.
4. A low battery condition is indicated by a BATT sign in the readout or by a steady horn.
Inform an instructor/technician if this occurs.
5. Set the readout to zero (00) by lifting and turning the LEL ZERO knob. This must be done
within 30 seconds of turning ON to prevent the possibility of activating the off-scale, LEL
latching alarm.
6. Press the SELECT button firmly to obtain % OXY on the readout. Then set the readout to
20.8% by adjusting the OXY CALIBRATE knob.
7. Press the SELECT button firmly to obtain PPM TOX on the readout. Then set the readout
to zero (00) by adjusting the TOX ZERO knob.
8. Press the RESET button. (Note: The "RESET" button will not reset the alarms if the
exceed the alarm levels.) The "HORN OFF" green/yellow lamp will start flashing. The
light indicates alarm status. When it glows continuously, the audible alarm is operable.
When it blinks on and off, as it does now, it indicates that the audible alarm has been
deactivated.
10/93 5 Exercise 1
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LEAK TEST
9. Momentarily hold a finger over the sample inlet or end of sample probe. Observe that the
flow indicator float (lower right hand corner of instrument face) drops out of sight, indicating
no flow. If the float does not drop out of sight, check the system for leaks. If the
instrument does not pass the leak test, inform an instructor/technician.
ALARM CHECK
The purpose of these steps is to check the meter readings at which the alarms will sound.
10. Press the SELECT button until % LEL is displayed. Adjust the LEL ZERO knob until the
alarm sounds. Record the % LEL reading. Set the reading back to zero and press the
RESET button. The alarm should activate at 25%.
11. Press the SELECT button until OXY is displayed. Turn the OXY CALIBRATE knob
counterclockwise (decreasing the % oxygen reading) until the alarm sounds. Record the %
OXY reading. Adjust the reading back to 20.8% and press the RESET button. The lower
alarm reading should be 19.5%.
12. Turn the OXY CALIBRATE knob clockwise (increasing the % oxygen reading) until the
alarm sounds. Record the % OXY. Adjust the reading back to 20.8% and press the RESET
button. The upper alarm reading should be 25%.
13. Press the SELECT button until TOX is displayed. Turn the TOX ZERO knob clockwise
until the alarm is activated. Record this reading. Adjust the reading back to zero and press
the RESET button. The alarm should have activated at 35 ppm.
14. If any of the alarm points are not what they should be, inform an instructor/technician.
15. Turn the FUNCTION control to MANUAL for continuous readout of any one gas or to
SCAN for automatic scanning of the three gas readings. Note: All alarm functions operate
in either position.
16. The instrument is ready for sampling.
CALIBRATION
17. Open the clamp to the gas bag labeled "PENTANE 0.75%" and attach the sample line to the
bag. Draw a sample into the instrument until a constant reading is obtained.
18. Record your readings on the data sheet. The instrument should give a reading of 50% LEL.
Consult the instructor for proper oxygen and carbon monoxide readings.
19. Disconnect the sample line and clamp the bag. Allow fresh air to flow through the
instrument until the reading returns to zero. Rezero the instrument, if needed.
Exercise 1 6 10/93
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SAMPLING
20. For field monitoring, the alarm should be in the operable mode (SCAN or MANUAL
setting). For this exercise, you may keep the audible alarm deactivated to reduce noise
levels.
21. Note: The Model 360 has a latching mechanism that engages if the % LEL exceeds 100.
To disengage the lock, the instrument must be turned off and then turned back on in an area
where the LEL readings are less than 100%. Room air will do.
22. Sample each of the gas bags listed on the data sheet. Record the readings.
SHUTDOWN
23. When done sampling, flush fresh air through the instrument. Turn the instrument OFF.
10/93 7 Exercise 1
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STATION 3
Gastech Model 1314 Gastechtor
The GasTech Model 1314 is a combination combustible, oxygen, and toxic monitor. There is no
separate toxic sensor. The "toxic" response is provided by an amplification of the combustible
sensor (supersensitive CGI). Thus the toxic response is actually ppm combustible. The readout is
an analog meter that only displays one reading. The readout being displayed depends on the position
of the buttons on the side of the instrument. It has a specific % LEL, low and high oxygen, and
toxic level alarms. The oxygen alarm will sound even if % LEL is being displayed and vice versa.
The toxic alarm, however, will only sound if in the "PPM" mode. The unit has a battery-powered
pump for drawing air.
STARTUP
1. Attach the hose to instrument by means of the quick release fitting.
2. Put the PPM/LEL switch in the LEL (out) position, with the black indicator showing, and
OXY/LEL switch also in the LEL (out) position.
3. Press the POWER switch to turn the instrument on, with orange indicator dot showing. The
meter will normally rise upscale and a pulsing or steady alarm signal may sound. Audible
hum of pump will be noticed. The cause of the alarm condition (combustibles, oxygen, or
both) can be identified by the blinking lights.
4. Press the BATT CK button and note the meter reading. If reading is close to or below the
BATT CHECK mark on the meter, consult an instructor/technician.
5. Allow the instrument to warm up until the meter stabilizes (about a minute). If a pulsed
oxygen alarm continues to sound, turn the OXY CAL potentiometer clockwise to stop it.
If the sound is steady, turn the potentiometer counterclockwise.
6. With the hose inlet in a clean air location, turn the ZERO LEL potentiometer to bring the
meter to "0" indication. If this is not possible, consult an instructor/technician.
7. Put the OXY/LEL switch in the OXY (in) position, so that the orange indicator shows. Turn
the OXY CAL potentiometer to bring the meter to the 02 CAL mark (21 %).
8. As a quick check, gently breathe into hose inlet and allow instrument to sample exhaled air.
Reading should come down to about 16%, and alarm should sound at 19.5%. Allow it to
return to 21%, then put switch back in LEL position.
9. These particular units have a high oxygen alarm that will sound in a steady tone and the
amber alarm lights will blink when reading reaches or exceeds 25%.
Exercise 1 8 10/93
-------
10. The instrument will automatically test for oxygen whenever it is used, and will give a pulsed
audible and an amber light alarm if oxygen content drops to 19.5%. It is not necessary to
use the instrument with the switch in the OXY position unless oxygen measurements are of
primary interest. If both abnormal gas conditions exist simultaneously, both lights will blink
in their normal pattern, but alarm will sound continuously.
11. For readings in the 0-100% LEL range, hold inlet at point to be tested. Watch meter and
observe maximum reading as taken from the upper set of graduations, 0-100% scale. If
reading rises above the alarm setting (20% LEL), a pulsed red light and an audible alarm will
commence, and will continue as long as reading remains above alarm point.
12. If the reading on the 0-100% range is imperceptible or very small, use the sensitive range,
0-500 ppm. First allow to warm up in the LEL range, and then push range switch to put
circuit in PPM range (colored indicator showing). Rezero carefully with the ZERO LEL
potentiometer.
Because of the very high sensitivity of this range, the meter will tend to drift until instrument
is thoroughly warmed up. Always let it run for 5 minutes or more, whenever possible,
before operating on the PPM range. Take the reading immediately after zeroing, and
observe maximum deflection as taken from the middle set of graduations, 0-500 PPM scale.
The alarm will sound whenever the reading rises above the preset alarm level - 100 ppm.
CALIBRATION
13. Put the PPM/LEL switch in the LEL (out) position.
14. Unclamp the bag labeled "HEXANE 0.55%" and attach it to the sample inlet. Record the
reading when it has stabilized. The reading should be 50%. If not, please inform the
instructor.
SAMPLING
15. Sample each of the gas bags listed on the data sheet. Record the readings. DO NOT USE
THE PPM SETTING UNLESS THE LEL RESPONSE IS VERY LOW.
SHUTDOWN
16. When sampling is complete, flush fresh air through the instrument. Turn the instrument
OFF.
JO/93
Exercise 1
-------
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Exercise 1
10
-------
QUESTIONS
1. Did the alarms activate at the appropriate readings? Which instruments did not?
2. Why do the different instruments give different responses to similar combustible gases?
3. What are the hazards (if any) associated with each unknown bag?
10/93 11 Exercise 1
-------
4. List the limitations and advantages of each instrument for monitoring an unknown
atmosphere.
MSA 260/261:
MSA 360:
GasTech 1314:
Exercise 1 12 10/93 ™
-------
EXERCISE #2
Photoionization Detectors - Survey
OBJECTIVE
Participants will learn how to calibrate and operate the HNU Model PI-101 Photoionization Detector.
PROCEDURE
Students will divide into groups as directed by the laboratory instructor. Each group will have an
HNU PI-101 Photoionization Detector with either a 10.2 eV or 11.7 eV lamp, and eight gas bags.
Also, five containers with unknown chemicals will be placed around the room.
STATION 1: Bag A 100 parts per million (ppm) toluene
Bag B 100 ppm acetone
oag B luu ppm acetone
Bag C 100 ppm toluene/100 ppm acetone
Bag D 800 ppm acetone
Bag E 250 ppm acetone
Bag F 50 ppm acetone
Bag G 50 ppm hexane
Bag CH4 100 ppm methane
STATION 2: Five containers with unknowns
By following the instructions, sample each station and record your results. A discussion of your
findings will be held at the end of the exercise.
10/93 13 Exercise 2
-------
SETUP
1. Record the instrument serial number or ID number on the data sheet.
2. Record the lamp energy.
STARTUP
Refer to Figure 1 for location of instrument controls.
3. Connect the probe.
4. Turn the FUNCTION SWITCH to the BATTERY CHECK position. The needle should
deflect within or above the green arc. If not, inform the instructor. If the red indicator light
(low battery) comes on, do not use the instrument.
5. To ensure that the lamp will light, turn the FUNCTION switch to any RANGE setting and
place a solvent based marker near the sample intake on the probe. A needle deflection
should occur, thus indicating that the lamp is on.
6. There are two methods of zeroing an instrument. For this lab, use METHOD 1.
• METHOD 1 - Turn the FUNCTION SWITCH to the STANDBY
position and zero the instrument using the ZERO knob. This
procedure is used to zero the instrument electronically. If the SPAN
setting is altered, the zero should be rechecked and adjusted. Wait
fifteen to twenty seconds to ensure that the zero reading is stable. If
necessary, readjust the zero.
• METHOD 2 - Turn the FUNCTION SWITCH to the range being
used and rotate the ZERO knob until the meter reads zero. Now you
have zeroed out background. If the SPAN setting is changed after the
zero is set, the zero should be rechecked and adjusted.
You are now ready to calibrate your instrument.
CALIBRATION
7. The instructor will assist the students in the calibration procedure. A compressed gas
cylinder containing isobutylene will be used to calibrate the instrument. Set the FUNCTION
SWITCH to the 0-200 RANGE setting.
8. Connect the probe to the tubing from the ISOBUTYLENE cyclinder. Unlock the SPAN
knob by moving the black lock handle counter clockwise. By adjusting the SPAN setting
between 0-100, obtain the appropriate instrument reading. The instructor will tell you the
Exercise 2 14 10/93
-------
appropriate reading. Do not lock the SPAN knob at all during this lab exercise. Record the
SPAN setting at calibration on the data sheet.
SAMPLING
9. When taking readings, adjust the FUNCTION SWITCH to get the maximum on scale needle
deflection. If the reading exceeds the meter range, adjust the FUNCTION SWITCH.
10. Measure for contaminants in BAGS A, B, C, G, and CH4 and record the results.
11. Take readings over the openings of each of the unknown containers. Record the readings.
CALIBRATION CHANGE
12. By adjusting the SPAN, calibrate the instrument to BAG B (acetone). Measure the
concentration of BAGS C, D, E, and F and record your results. Then plot the instrument
readings vs. actual concentration from BAGS B, D, E, and F on Graph 1.
SHUTDOWN
13. Turn the FUNCTION SWITCH to the OFF position.
10/93 15 Exercise 2
-------
Low Battery Indicator
Light (LED)
Power Off
Sensitivity
Adjustment
Hi-Vbltage
Interlock
Battery Check
Position
Ranges (ppm)
Function
Switch
12 Pin Interface Connector
between readout unit and
seosor.
Zero Adjustment
Recorder Output
(-5V DC)
FIGURE 1. HNU PI 101 CONTROLS
Source: Instruction Manual for Model PI 101 Photoionization Analyzer, 1975, HNU Systems, Inc.
Used with permission of HNU Systems, Inc.
Exercise 2
16
10/93
-------
DATA SHEET
TABLE 1
INSTRUMENT MODEL
I.D. NUMBER
LAMP ENERGY
GAS
CONCENTRATION
INSTRUMENT READING
SPAN SETTING
TABLE 2
BAG
CONCENTRATION
INSTRUMENT
READING
RELATIVE
RESPONSE*
A - TOLUENE
100 ppm
B - ACETONE
C - TOLUENE/
ACETONE
G-HEXANE
100 ppm
100/100
50 ppm
CH, - METHANE
100 ppm
* Relative Response = Instrument Reading -r Actual Concentration. Multiply by 100% to get
% Relative Response.
10/93
17
Exercise 2
-------
DATA SHEET
TABLE 3
SAMPLE LOCATION*
1
2
3
4
5
READING
*Add information about location of probe when taking the reading.
TABLE 4
ACETONE CALIBRATION
BAG
ACTUAL
CONCENTRATION
INSTRUMENT
READING
100 ppm
100/100
800 ppm
250 ppm
50 ppm
Exercise 2
18
10/93
-------
GRAPH 1. INSTRUMENT READING VS. TRUE CONCENTRATION
yuu
800
700
O)
600
05
0
rr 500
|400
D
"oo 30°
_c
200
100
n
10/93
0 100 200 300 400 500 600 700 800 900
True Concentration (ppm)
19
Exercise 2
-------
QUESTIONS
1. Calculate and record the relative response for each of the chemicals in Table 2.
2. Why is the reading for Bag C in Table 2 different from the reading in Table 4?
3. From Graph 1, does the instrument accurately measure all four concentrations? If you were
going to measure acetone vapors at concentrations of 0-10 ppm, would this calibration curve
be of value to you?
4. Unknown 2 is found to be acetone. Develop a method(s) using the HNU to determine the
concentration of acetone at the location.
5. You are using an HNU to survey a site and obtain a reading of 200. How do you report
your findings and what additional information would you like recorded?
Exercise 2 20 10/93
-------
EXERCISE #3
Flame lonization Detectors - Survey
OBJECTIVE
Participants will learn how to calibrate and operate the Foxboro Organic Vapor Analyzer OVA-128
in the survey mode.
PROCEDURE
Students will divide into groups as directed by the laboratory instructor. Each group will have an
Foxboro OVA-128 plus eight gas bags. Also, five containers with unknown chemicals will be placed
around the room.
Station 1: Bag A 100 parts per million (ppm) toluene
Bag B 100 ppm acetone
Bag C 100 ppm acetone/100 ppm toluene
Bag D 800 ppm acetone
Bag E 250 ppm acetone
Bag F 50 ppm acetone
Bag G 50 ppm hexane
Bag CH4 100 ppm methane
Station 2: Five sampling containers
By following the instructions, sample each station and record your results. A discussion of your
findings will be held at the end of the exercise.
10/93 21 ExerdseS
-------
Please read each paragraph completely before following the directions and proceeding to the next
paragraph.
SETUP
1. Record the instrument serial number or ID number on the data sheet.
STARTUP
2. Turn off the charger and disconnect the charger cable from the instrument.
3. Unlock the GAS SELECT dial and adjust it to 300 (i.e., a 3 in the window and 00 on the
dial).
4. Turn the VOLUME knob fully counter clockwise.
5. Ensure that the SAMPLE INJECT VALVE and BACK FLUSH VALVE are in the full syl
position.
6. The toggle switches on this instrument have a lock to prevent accidental changes. To move
the toggle switch, lift and then move the lever.
7. Move the INSTRUMENT switch to ON and allow 5 minutes for warm-up.
8. Move the PUMP switch to ON. You should hear the pump running. Place the instrument
in a vertical position and look at the SAMPLE FLOW RATE (rotameter at lower left of
panel). The flow rate (read at center of ball) should be 2.0 (liters/minute). A reading
between 1.5 and 2.5 is considered adequate.
9. Set the CALIBRATE switch to XI0. Adjust the CALIBRATE knob until the meter reads
0.
10. Open the H2 TANK VALVE and H2 SUPPLY VALVE one and one-half turns counter
clockwise. The TANK gauge should be 500 psi or higher. The SUPPLY gauge should read
between 10 and 12 psi. If they do not, inform the instructor.
11. Wait about 1 minute. Depress the red IGNITER BUTTON (on the side of the pack) until
the flame ignites or until 6 seconds have passed. Flame ignition is indicated by a sharp
meter needle deflection towards 10 along with a small "pop" sound. Also, the meter needle
should return to a reading above 0 instead of 0. Do not depress the button longer than 6
seconds. If the flame does not ignite on the first try, wait a minute, and try again. If it does
not ignite on a second try, check that steps 1 through 10 have been completed. Then consult
an instructor or technician for assistance.
12. Use the CALIBRATE knob to adjust the meter reading to zero. Move the CALIBRATE
switch to XI and rezero.
Exercise 3 22 10193
-------
CALIBRATION
13. Set the CALIBRATE switch to X10.
14. Locate the METHANE calibration gas bag. Methane is the normal calibration gas for the
OVA.
15. Open the bag clamp and attach the methane bag to the probe inlet. It is important that the
bag be open before attaching it so that a "flame out" does not occur from oxygen starvation.
16. Unlock and adjust the GAS SELECT knob so that the meter reading is equal to the bag
concentration divided by the CALIBRATE switch setting. For example, if the bag
concentration is 90 ppm, then the reading should be 9 (90 divided by 10).
17. Disconnect the gas bag and close the clamp.
18. The GAS SELECT setting should be about 300. 300 is the "ideal" setting, but your
instrument may have a different reading. If the setting must be adjusted above 400 or below
200, internal calibration may be advisable.
19. The instrument is now calibrated to methane and ready for survey purposes.
SAMPLING
20. During the next two steps, change the CALIBRATE switch setting as necessary to get the
maximum on-scale reading. If the meter reads above 10 on the X100 setting, report the
reading as greater than 1000.
21. Take readings of bags A, B, C and G. Record the data.
22. Take readings at the five containers. Record the readings and locations.
CALIBRATION
23. Change the CALIBRATE switch to X10.
24. Open and connect Bag B to the probe inlet. Adjust the GAS SELECT knob until the
instrument reads 10 on the XI0 range.
25. Disconnect and close the bag. Use the CALIBRATE ADJUST knob to rezero, if needed.
26. Take readings of bags C, D, E, and F. Record the readings. Plot the readings from bags
B, D, E, and F on GRAPH 1.
10/93 23 Exercise 3
-------
SHUTDOWN
27. Close the H2 SUPPLY valve, then the H2 TANK valve.
28. Move the INSTRUMENT switch to OFF.
29. When the SUPPLY pressure gauge falls to zero, move the PUMP switch to OFF.
Exercise 3 24 10/93
-------
DATA SHEET
TABLE 1
INSTRUMENT MODEL
I.D. NUMBER
CALIBRATION
GAS
CONCENTRATION
INSTRUMENT READING
GAS SELECT SETTING
TABLE 2
BAG
CONCENTRATION
INSTRUMENT
READING
RELATIVE
RESPONSE*
A - TOLUENE
100 ppm
B - ACETONE
C - TOLUENE/
ACETONE
G-HEXANE
100 ppm
100/100
50 ppm
*Relative Response = Instrument Reading -*• Actual Concentration. Multiply by 100% to get
% Relative Response.
10/93
25
Exercise 3
-------
DATA SHEET
TABLE 3
SAMPLE LOCATION*
1
2
3
4
5
READING
* Add information about location of probe when taking the reading.
TABLE 4
ACETONE CALIBRATION
BAG
ACTUAL
CONCENTRATION
INSTRUMENT
READING
GAS SELECT
SETTING
D
100 ppm
100/100
800 ppm
250 ppm
50 ppm
Exercise 3
26
10/93
-------
GRAPH 1. INSTRUMENT READING VS. ACTUAL CONCENTRATION (from Table 4)
auu
800
700
O)
600
05
0
rr 500
•+-»
c
92 400
"GO 30°
_c
200
100
n
0 100 200 300 400 500 600 700 800 900
True Concentration (ppm)
10/93
27
Exercise 3
-------
QUESTIONS
1. Calculate the relative response for each of the chemicals in Table 2.
2. Why is the reading for Bag C in Table 2 different from the reading in Table 4?
3. From Graph 1, does the instrument accurately measure all four concentrations? If you were
going to measure acetone vapors at concentrations of 0-10 ppm, would this calibration curve
be of value to you?
4. Unknown 2 is found to be acetone. Develop a method(s) using the OVA to determine the
concentration of acetone at the location.
5. You are using an OVA to survey a site and obtain a reading of 200. How do you report
your findings and what additional information would you like recorded?
Exercise 3 28 10/93
-------
EXERCISE #4
Gas Chromatography - Organic Vapor Analyzer
OBJECTIVE
Participants will learn how to operate the Foxboro OVA-128 with gas chromatograph option as a
portable gas chromatograph.
PROCEDURE
The students will divide into groups as directed by the laboratory instructor. Each group will have
a Foxboro OVA-128 with gas chromatograph option and three gas bags.
Bag CH4: Calibration gas
Bag C: Standard of 100 ppm toluene and 100 ppm acetone
Unknown #1
By following the instructions of the lab manual and instructor, each group will produce a gas
chromatograph for each bag. By comparing the results from the standard to the unknown, the group
will try to determine what chemicals are present and at what concentrations. The results will be
recorded and discussed at the end of the exercise.
10/93 29 Exercise 4
-------
Please read each paragraph completely before following the directions and proceeding to the next
paragraph.
SETUP
1. Record the instrument serial number or ID number on the data sheet.
STARTUP
2. For gas chromatograph use, the charger can remain on and connected to the OVA.
3. Unlock the GAS SELECT dial and adjust it to 300 (i.e., a 3 in the window and 00 on the
dial).
4. Turn the VOLUME knob fully counter clockwise.
5. Ensure that the SAMPLE INJECT VALVE and BACK FLUSH VALVE are in the full out
position.
6. The toggle switches on this instrument have a lock to prevent accidental changes. To move
the toggle switch, lift and then move the lever.
7. Move the INSTRUMENT switch to ON and allow 5 minutes for warm-up.
8. Move the PUMP switch to ON. You should hear the pump running. Place the instrument
in a vertical position and look at the SAMPLE FLOW RATE (rotameter at lower left of
panel). The flow rate (read at center of ball) should be 2.0 (liters/minute). A reading
between 1.5 and 2.5 is considered adequate.
9. Set the CALIBRATE switch to X10. Adjust the CALIBRATE knob until the meter reads
0.
10. Open the H2 TANK VALVE and H2 SUPPLY VALVE one and one-half turns counter
clockwise. The TANK gauge should be 500 psi or higher. The SUPPLY gauge should read
between 10 and 12 psi. If they do not, inform the instructor.
11. Wait about 1 minute. Depress the red IGNITER BUTTON (on the side of the pack) until
the flame ignites or until 6 seconds have passed. Flame ignition is indicated by a sharp
meter needle deflection toward 10 along with a small "pop" sound. Also, the meter needle
should return to a reading above 0 instead of 0. Do not depress the button longer than 6
seconds. If the flame does not ignite on the first try, wait a minute, and try again. If it does
not ignite on a second try, check that steps 1 through 10 have been completed. Then consult
an instructor or technician for assistance.
12. Use the CALIBRATE knob to adjust the meter reading to zero. Move the CALIBRATE
switch to XI and rezero.
Exercise 4 30 10/93
-------
CALIBRATION
13. Set the CALIBRATE switch to XI0.
14. Locate the METHANE calibration gas bag. Methane is the normal calibration gas for the
OVA.
15. Open the bag clamp and attach the methane bag to the probe inlet. It is important that the
bag be open before attaching it so that a "flame out" does not occur from oxygen starvation.
16. Unlock and adjust the GAS SELECT knob so that the meter reading is equal to the bag
concentration divided by the CALIBRATE switch setting. For example, if the bag
concentration is 90 ppm, then the reading should be 9 (90 divided by 10).
17. Disconnect the gas bag and close the clamp.
18. The GAS SELECT setting should be about 300. 300 is the "ideal" setting, but your
instrument may have a different reading. If the setting must be adjusted above 400 or below
200, internal calibration may be advisable.
GAS CHROMATOGRAPH SETUP
19. Connect the strip chart recorder to the OVA. Move the HI/LO switch (on the side of the
recorder) to the LO position. The chart paper should start moving and you should hear a
clicking sound. If the chart does not operate, check the cable connections. Inform the
instructor if the chart doesn't work.
20. Turn the ZERO knob on the recorder (next to HI/LO switch) completely clockwise.
21. Turn the OVA CALIBRATE knob to adjust the baseline (black line produced by the pin) on
the chart. Do not use the ZERO knob on the recorder. The baseline should be about 1/4
inch (two thin brown lines) above the thick brown line next to the sprocket holes.
22.
Locate the stopwatch. Practice with the stopwatch until you can do lap counting. The
instructor will demonstrate. Lap counting involves stopping the readout without stopping the
stopwatch timing. This is useful for timing more than one peak.
STANDARD CHROMATOGRAM
23. Open and connect the STANDARD (Bag C: Acetone/Toluene) bag to the probe inlet.
Watch the meter needle. When the needle has deflected to its highest point, depress the
SAMPLE INJECT VALVE and start the stopwatch. Disconnect and close the gas bag. If
the needle passes 10, wait 3 seconds, then depress the INJECT VALVE.
Keep the SAMPLE INJECT VALVE depressed until the end of the chromatogram. The
instructor will discuss how to determine when the chromatogram is done.
10/93 31 Exercise 4
-------
24. Strike a line across the chart with a pen or pencil to indicate the start of a chromatogram.
Write the OVA CALIBRATE SWITCH setting (XI, X10, X100) and the recorder HI/LO
setting on the chart paper.
25. Watch the chart paper or meter face for an upward needle deflection. When the needle
reaches a maximum reading and starts to drop, note the time. This is the top of the peak and
the time is the retention time for the peak. Do this for each peak. Record the retention
times for each peak.
26. If a peak is too small or goes off scale, you will need to rerun the standard at a different
CALIBRATE SWITCH setting and/or different HI/LO setting. Table 1 shows the
relationship between peak size and instrument settings. For example, if a peak is off scale
on a HIX10 setting, changing the settings to LOX10 or HIX100 would make the peaks 1/2
or 1/10 the size of the original peaks.
TABLE 1
RECORDER RANGE
FACTOR
HI
LO
HI
LO
HI
LO
OVA SCALE
X1
XI
X10
X10
X100
X100
RELATIVE
PEAK SIZE
1
1/2
1/10
1/20
1/100
1/200
27. When a chromatogram is done (i.e, the last peak is out and the baseline is back to normal),
lift the SAMPLE INJECT VALVE. The instrument is ready for another run.
SAMPLE CHROMATOGRAM
28. Repeat steps 22 through 26 using the UNKNOWN sample bag.
SHUTDOWN
29. Close the H2 SUPPLY valve, then the H2 TANK valve.
30. Move the INSTRUMENT switch to OFF.
Exercise 4
32
10/93
-------
31. Move the RECORDER RANGE SETTING switch to OFF.
32. When the SUPPLY pressure gauge falls to zero, move the PUMP switch to OFF.
CALCULATIONS FOR QUALITATIVE EVALUATION
27. (Optional) Tear off the strip chart and measure the distance from the injection point to the
middle of the peak in mm (see Figure 1 below).
Retention time
i
Injection
Time
FIGURE 1. RETENTION TIME (DISTANCE) ILLUSTRATION
28. Compare the retention times of the known standard and the unknown. If the retention times
are relatively close, then the unknown can possibly be identified through comparison to the
known. For example, if a standard of acetone released at 144 seconds and a peak on our
unknown was at 136 seconds, then we can assume that the peak was acetone.
QUANTITATIVE ANALYSIS
29. To find the concentration of a chemical that has been identified with a standard, you will
need a ruler, a calculator, and a pencil.
30. Draw a triangle that approximates the area of the curve similar to the example (Figure 2)
below.
10/93
33
Exercise 4
-------
Area = 1/2 x base x height
Area = 1/2 b h
31.
32.
33.
FIGURE 2. PEAK AREA ILLUSTRATION
Calculate the area of the triangle for the standards and unknowns by using the following
formula:
Area = Vi(b)(h)
To compensate for the different instrument settings a corrected area formula must be used:
Corrected Area = OVA Setting x Recorder Range Factor x Area of Triangle
X100
X10
XI
HI = .5
LO = 1.0
To obtain the actual concentration of the unknown, divide the corrected area of the unknown
by the corrected area of the standard and multiply by the standard concentration.
Concentration of unknown =
Corrected Area
Corrected Area
x Standard concentration
'standard
Exercise 4
34
10/93
-------
TABLE 2
CONCENTRATION
RETENTION TIME
RETENTION
DISTANCE (mm)
PEAK BASE (mm)
PEAK HEIGHT (mm)
PEAK AREA (mm2)
OVA SCALE
SETTING
RECORDER
SETTING
CORRECTED AREA
(mm2)
STANDARD BAG C
ACETONE
TOLUENE
UNKNOWN #1
PEAK 1
PEAK 2
PEAKS
10/93
35
Exercise 4
-------
CALCULATIONS
Exercise 4 36 JO/93
-------
QUESTIONS
1. Identify the peaks in Unknown #1. For the peaks that can not be positively identified, list
the possible candidates.
2. What are the concentrations of the identified peaks? Compare your numbers with the actual
concentrations (from the instructor). Give reasons why your results may vary from the actual
concentrations.
10/93 37 Exercise 4
-------
CHROMATOGRAPHY AND SURVEY GUIDE
FOXBORO CENTURY ORGANIC VAPOR ANALYZERS
COMPOUND
ACETONE
ACETONtTRILE
ACRYLONFTRILE
ALLYL ALCOHOL
ALLYL CHLORIDE
BENZENE
BROMOETHANE
BROMOMETHANE
BROMOPROPANE
BUTADIENE. 1,3-
BUTANE
BUTANOL
BUTANOL.2-
BUTANONE.2-
BUTENE
BUTYL ACETATE
BUTYL ACRYLATE
BUTYL ACRYLATE.cert-
BUTYL FORMATE
BUTYL FORMATE.teit-
BUTYL METHACRYLATE
BUTYL METHYL ETHER.tert-
CAR3ON TETRACHLORDDE
CHLOROBENZENE
CHLOROFORM
CHLOROMETHANE
CHLOROPROPANE
CHLOROPROPANE.2-
CUMENE
CYCLOHEXANE
CYCLOHEXANONE
DECANE
DIACETONE ALCOHOL
DIBROMOETHANE.1.2-
DtCHLOROBENZENE, 1.2-
DICHLOROETH ANE. 1.1-
DICHLOROETHANE.1,2-
DICHLOROETH YLENE. 1,1-
DICHLOROETHYLENE.traiu-l
DICHLOROMETHANE
DICHLOROPROPANE.1.2-
DtCHLOROPROPANE.1.3-
DIOXANE.p-
TWA .
ppm
750
40
2
2
1
1
200
5
*
1000
300
100
100
200
*
150
10
*
*
*
*
*
10
75
2
50
•
*
50
300
25
*
50
20
50
100
1
1
200
100
75
*
25
T-ll COLUMN
RR
*
82
64
98
27
45
185
72
23
73
36
58
46
55
75
43
67
60
75
48
64
60
57
8
179
57
56
79
55
18
92
43
69
56
56
119
70
89
49
40
84
96
76
23
tR'
sec
118
384
252
623
36
116
23
13
51
3
12
725
340
203
5
572
1099
293
338
111
1600
21
41
713
122
4
25
13
690
16
225
950
1168
4060
66
239
11
37
73
258
677
760
&
2.23
7.25
4.75
11.75
0.68
2.19
0.43
0.25
0.96
0.06
0.23
13.68
6.42
3.83
0.09
10.79
20.74
5.53
6.38
2.09
30.19
0.40
0.77
13.45
2.30
0.08
0.47
0.25
13.02
0.30
0.00
4.25
17.92
22.04
76.60
1.25
5.45
0.21
0.70
1.38
4.87
12.77
14.34
G-7A COLUMN . :: .;.•'•' ' .., ;: ; ' life-.
tR'
SfC
36
39
45
98
38
142
35
14
100
7
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243
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397
242
• • • ..;•• .-'•'. *•'• ••' *';-SS£:.
a.
0.29
0.32
0.37
0.80
0.31
1.15
0.28
0.11
0.81
0.06
0.02
1.98
1.07
0.76
0.10
6.36
12.82
4.61
2.59
0.91
32.11
0.57
1.16
7.04
0.74
0.04
0.39
0.21
15.53
1.31
10.21
0.00
8.27
4.36
0.00
0.54
1.01
0.29
0.45
0.35
1.65
3.23
1.97
."•••• - •:::•"••: •*!&:.
SYNONYM ..:...•;.:/..
• '-.•:-•-- .
. .. : .-..:• -
-PROPANONE
VLN'YL CYANIDE
ETHYL BROMIDE
METHYL BROMIDE
PROPYL BROMIDE
BUTADIENE
BUTYL ALCOHOL
sec-BUTYL ALCOHOL
METHYL ETHYL KETONE
2-BUTYL ACRYLATE / PROPYLENE
2-BUTYL FORMATE
MONOCHLOROBENZENE
TRICHLOROMETHANE
METHYL CHLORIDE
PROPYL CHLORIDE
ISOPROPYL CHLORIDE
ISOPROPYL BENZENE
HEXAMETHYLENE
4-HYDROXY-4-METHYL-2-PENTANON"
ETHYLENE DIBROMIDE
-------
COMPOUND
ENFLURANE
ETHANE
ETHANETHIOL
ETHANOL
ETHENE
ETHER
ETHYL ACETATE
ETHYL ACRYLATE
ETHYL BENZENE
ETHYL BUTYRATE
ETHYL FORMATE
ETHYL METHACRYLATE
ETHYL PROPIONATE
ETHYLENE OXIDE
FREON-11
FREON-113
FREON-114
FREON-123
FREON-12
FREON-21
FREON-22
HALOTHANE
HEPTANE
HEXADECANE
HEXAFLUOROPROPENE
HEXANE
1SOBUTANE
ISOBUTENE
ISOPRENE
ISOPROPYL ACETATE
METHANE
METHANOL
METHYL ACETATE
METHYL ACRYLATE
METHYL CYCLOHEXANE
METHYL CYCLOPENTANE
METHYL ISOBUTYL KETONE
METHYL METHACRYLATE
METHYL SULFIDE
NITROMETHANE
NITROPROPANE
NITROPROPANE.2-
NONANE
OCTANE
PENTANE
PENTANOL
PENTANONE.2-
TWA
ppm
'
*
0.5
1000
*
400
400
5
100
*
100
*
•
1
1000
1000
1000
100
1000
10
1000
*
400
•
*
50
*
*
*
250
*
200
200
10
400
*
50
100
*
100
25
10
200
300
600
•
200
T-12. COLUMN
RJR
*
146
77
28
20
47
47
67
71
111
91
44
73
83
49
7
91
110
36
13
71
67
49
80
52
31
70
70
64
59
71
100
10
46
39
67
81
82
54
20
35
60
7
8
87
6
3
7
tR'
IOC
79
1
24
178
1
13
143
263
495
398
78
375
241
31
4
8
3
19
3
20
5
53
16
1764
1
7
3
2
9
155
1
139
93
197
20
9
468
291
27
1053
1893
1030
103
44
3
1771
365
a.
1.49
0.02
0.45
3.36
0.02
0.25
2.70
4.96
9.34
7.51
1.47
7.08
4.55
0.58
0.08
0.15
0.06
0.36
0.06
0.38
0.09
1. 00
0.30
33.28
0.02
0.13
0.06
0.04
0.17
2.92
0.02
2.62
1.75
3.72
0.38
0.17
8.33
5.49
0.5
19.37
35.72
19.43
1.94
0.83
0.06
33.42
6.3
C-24 COLUMN
tR'
sec
29
1
31
45
I
38
108
254
1054
588
43
514
274
35
24
43
3
22
5
17
3
51
232
2
88
14
10
32
180
1
64
49
107
230
114
353
266
35
73
285
191
1939
748
29
728
227
a.
" 0.24
0.0 1
0.25
0.37
0.01
0.31
0.38
2.07
8.57
4.73
0.35
4.18
2.23
0.23
0.20
0.35
0.07
0.13
0.04
0.14
0.02
0.41
1.89
0.00
0.02
0.72
0.11
0.08
0.26
1.46
0.01
0.52
0.40
0.37
2.23
0.93
2.37
2.16
0.23
0.59
2.32
1.55
15.76
6.08
0.24
5.92
1.85
-<
ET
ET
ET
Dl
EP
FL
TR
DI
Dt
CI
1-
P£
i_
IS
2-
M
4-
D
P
b
SYNONYM
-CHLORO-1,1,2rTRIFLUOROETHYL-Dl
FLUOROMETHYL ETHER/ETHRAN1
ETHYL MERCAPTAN
ETHYL ALCOHOL
ETHYLENE
IETHYL ETHER
EPOXYETHANE
FLUOROTRICHLOROMETHANE
RICHLOROTRIFLUOROETHANE
.2-DtCHLORO-l 122-TETRAFLUOROET
.2-DICHLORO-1.1.1-TRIFLUOROETH A
DICHLORODIFLUOROMETHANE
DtCHLOROFLUOROMETHANE
CHLORODtFLUOROMETHANE
2-BROMO-2CHLORO-11ITRIFLUOROET
ERFLUOROPROPENE
2-BUTANE / 2-METHYL PROPANE
SOBUTYLENE / 2-METHYL PROPENE
2-METHYL-1,3-BUT AD fENE
METHYL ALCOHOL
7 4-METHYL-2-PENTANONE / HEXONE
DIMETHYL SULFIDE
PENTYL ALCOHOL
METHYL PROPYL KETONE
-------
COMPOUND
PENTANONE.3-
PROPANE
PROPANOL
PROPANOL.2-
PROPYL ACETATE
PROPYL ETHER
PROPYL FORMATE
PROPYLENE
FROPYLENE OXIDE
PYRIDINE
5TYRENE
TETRACHLOROETHANE, 1.1.1,
TETRACHLOROETHYLENE
TETRAHYDROFURAN
TOLUENE
TRICHLOROETH ANE, 1,1,1-
TRICHLOROETHANE, 1,1.2-
TRICHLOROETHYLENE
TRIETHYLAMINE
TRIMETHYLPENTANE.2,2.4-
VINYL ACETATE
VINYL CHLORIDE
XYLENE.m-
XYLENE.o-
XYLENE.p-
KEY:
• No TWA levels available.
TWA 8 Hour Time Weighted Average for
Maximum allowable exposure.
RR Relative Response to METHANE in Percent =
(Measured Response / Prepared Concentration) x 100.
tR data not available
TWA.
ppm
'200...
1000
200
400
200
•
•
•
20
5
50
•
25
200
100
350
10
50
10
•
10
1
100
100
100
T-12 COLUMN
RR
%
.61
70
35
60
60
56
S3
36
66
109
92
31
67
47
126
101
95
54
59
91
40
38
107
106
106
tR'
. sec
355
1
351
153
283
36
157
2
46
1334
956
141
106
262
53
1158
104
14
116
5
563
804
545
a.
6.70
0.02
6.62
2.S9
5.34
0.68
2.96
0.04
0.87
0.00
26.11
18.04
2.66
2.00
4.94
1. 00
21.85
1.96
0.00
0.26
2.19
0.09
10.62
15.17
10.28
G-24 COLUMN
tR'
sec
257
5
102
57
286
217
111
4
40
1355
810
603
125
391
123
378
222
34
221
77
9
1135
1366
1140
A
2.09
0.04
0.83
0.46
2.33
1.76
0.90
0.03
0.33
0.00
11.02
6.59
4.90
1.02
3.18
1.00
3.07
1.30
0.28
1.30
0.63
0.07
9.23
11.11
9.27
SYNONYM
DIETHYL KETONE
PROPYL ALCOHOL
SOPROPANOL
1.2-EPOXYPROPANE
PERCHLOROETHYLENE
METHYL BENZENE '
METHYL CHLOROFORM
ISOOCTANE
1.3-D1METHYL BENZENE
1.2-DIMETHYL BENZENE
1,4-DIMETHYL BENZENE
tR
Solute Retention Time from point of injection
tR'3 Adjusted Retention Time in seconds
tM = Gas Hotd-Up. or Dead Time
tR' = tR - CM
a = Relative Retention as compared to a Reference
Reference Compound is 1,1,1-Trichloroechaae
Data collected at a chart speed - 1 cm/min. at
concentrations of 50 or 100 ppm, and at ambient
temperature
-------
HOW TO USE THIS CHART FOR IDENTIFICATION OF UNKNOWNS BY <3C
1. Calculate the Adjusted Retention time of Che Unknown solutes and of the Reference compound for Che selected
column. This can be accomplished by either running the reference compound separately, under similar conditions
as the unknown will be run. or along with the questioned sample by introducing it into the sample scream via
direct injection, dilator accessory, or other like means. The tR' for any solute is equal to (he time elapsed
from the point of injection to the projection of the peak maximum, minus the gas hold-up time of the column.
The gas hold-up time is the time elapsed from the point of injection to the maximum deflection of the air peak.
(NOTE: approximate hold-up times are 5 sees for a T-I2 column and 10 sees for a G-24 column.)
2. In order to minimise the effects of minor variation in operating conditions and in the stationary phase
loading of the columns, the parameter of Relative Retention (a) is used. To calculate a. for a particular
solute on a given column, divide the tR' of the solute by the cR' of the reference compound. If the value of a
fails within */- 10% of the chart value, Chen the chances are good that the questioned solute is one of the
compounds in this range.
3. To increase the probability of identifying an unknown solute, this chart provides the user with Che option
of Two-Column dimensional chromatography. By utilizing a second type column, one can calculate a second a value
for the questioned solute. If this value of a falls within •>•/- 10% of Che chart value, and the value of a for
(he previous columnn falls within +/- 10% of that chart value, Chen there is a high probability that the unknown
has been identified. •
•i. Laboratory GC analysis and standard preparation may be required for confirmation, depending upon the
application.
-------
EXERCISE #5
Detector Tubes
OBJECTIVE
During this exercise, participants will learn how to do a leak check and a volume check of both a
Draeger and a Sensidyne detector tube pump and how to use detector tubes quantitatively and
qualitatively.
INTRODUCTION
There are chemical indicators that use the reaction of a chemical reagent with the airborne chemical
of interest to produce a color change. The intensity of the color change or the length of color change
is used to determine the amount of airborne chemical present. The chemical reagent may be
impregnated on a piece of paper or tape and the color change read by eye or by an electronic device.
The chemical could also be placed in a glass tube called a colorimetric indicator tube or detector
tube.
PRINCIPLE OF OPERATION
Colorimetric indicator tubes or detector tubes (Figure 1) consist of glass tube impregnated with an
indicating chemical. A known volume of contaminated air passes through or into the tube. The
contaminant reacts with the indicator chemical in the tube, producing a change in color whose length
or intensity is proportional to the contaminant concentration.
The tubes may have a preconditioning filter preceding 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.
TYPES OF TUBES
Detector tubes can be classified by the way air is drawn into the tube:
• Short-term tubes use a hand pump to draw air through the tube for a sample duration
of a few seconds to a few minutes. This is used to give an instantaneous sample.
The hand pump may be a piston or bellows type pump. This exercise will use both
types. A piston pump has a handle that is pulled to evacuate a cylinder of known
volume. Air is pulled through the tube to equalize the pressure in the cylinder.
10/93 39 Exercise 5
-------
MSA, Sensidyne, Enmet, and Matheson manufacture piston pumps. In a bellows
pump, the bellows is squeezed and released. Air is pulled through the tube as the
bellows expands. Draeger and MSA manufacture bellows-type pumps.
Plug
Glass
vial
Plug
10
20
30
40
SO
n m 5
Prefilter
or reagent
Indicating
chemical
on silica gel
FIGURE 1. DETECTOR TUBE EXAMPLE
Long-term tubes (pump) use a battery-operated pump to draw air through the tube
over a longer period of time, usually 8 hours. These are used to determine 8-hour,
time-weighted average exposures.
Long-term tubes (dosimeter) do not use a pump. Contaminants diffuse into the tube
over a long period of time, usually 8 hours. These also are used for 8-hour, time-
weighted average exposure determination. However, a pump is not required for
operation.
The three types of tubes are not interchangeable. They are calibrated for their specific applications.
There are many more short-term tubes than there are long-term tubes.
Exercise 5
40
10/93
-------
Detector tubes can also be classified by the information generated the results:
• Chemical groups—Some tubes will react to a class of chemicals (e.g., alcohols or
hydrocarbons). They will only indicate that a chemical of a certain class is present.
• Specific chemicals—There are a few tubes that only react to that specific chemical.
Most tubes have a specific chemical listed for the tube, but can react to other
chemicals (interferences).
• Concentration ranges—There may also be different concentration ranges for the same
chemical. For example, there are tubes for carbon monoxide with concentration
ranges of 5-150 ppm, 10-300 ppm, 0.1-1.2% and 0.3-7%.
DETECTOR TUBE CONSIDERATIONS
There are several factors that determine the effective use of detector tubes. These factors can be
found in the instructions issued with each box of tubes.
Chemical Group: Some tubes are for a specific chemical and some are for a group of chemicals.
Lot #: The instructions for the tubes may change with different model numbers or different lots.
Thus, the instructions should be matched with the proper tubes.
Expiration Date: The chemicals used in the tubes deteriorate over time. Because of this, the tubes
are assigned a shelf life and the expiration date is printed on the box. This varies from 1 to 3 years.
Pump Strokes/Volume/Time: The total volume of air to be drawn through the tube varies with the
type of tube. 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.
Color Change: The instructions will give the appropriate color change for indicating the chemical
of concern. Other color changes may be noted for interferences. This information can be used to
check for the presence of other chemicals.
Interferences: As mentioned previously, not every tube is specific. For example, an acetone tube
will also respond to other ketones. Thus, methyl ethyl ketone would be considered an interference
if one were checking for acetone. The instructions will give known interferences or color changes
that are not for the chemical of interest.
Temperature/Humidity/Pressure: The length of color change (stain) can be affected by temperature,
humidity and barometric pressure. If this is a problem, the instructions will note it and may give
correction factors. Cold weather slows the chemical reaction in the tube and reduces the reading.
Hot temperatures increase the reaction and can cause a problem by discoloring the indicator even
JO/93 41 Exercise 5
-------
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 be refrigerated during storage.
Reusable?: Most tubes can only be used once, even if there is a negative result. There are some
tubes, however, that can be reused the same day until a positive result is obtained.
Accuracy: The accuracy of detector tubes vary. Some studies have reported error factors of 50%
and higher for some uncertified tubes. Some tubes are certified to be ±25% accurate at readings
from 1 to 5 times the OSHA Permissible Exposure Limit (PEL) and ±35% at concentrations one-
half the PEL. Only a few tubes are presently certified. Certification of detector tubes is being done
by a private organization - Safety Equipment Institute (SEI).
One factor that affects accuracy is the interpretation of the end of the color change. Some color
changes are diffused and the endpoint is not definite; others may have an uneven endpoint
(Figure 2). When in doubt, use the highest value that would be obtained from reading the different
aspects of the tube.
APPLICATIONS
Although there are many limitations and considerations for using detector tubes, detector tubes allow
the versatility of being able to measure a wide range of chemicals with a single pump. Also, there
are some chemicals for which detector tubes are the only direct-reading indicators.
They can be used to get a reading for a specific chemical in an atmosphere where a total vapor
survey instrument would response to all the chemicals in the atmosphere. They also give an
immediate response. Laboratory analysis (see the Air Sample Collection section) that can identify
and quantify a chemical in a mixture takes time.
Manufacturers use general tubes for identification in their HazMat kits. These kits identify or
classify the contaminants as a member of a chemical group such as acid gas, halogenated
hydrocarbon, etc. This is done by sampling with certain combinations of tubes at the same time by
using a special multiple tube holder or by using tubes in a specific sampling sequence. All
manufacturers of detector tubes have some kind of system for hazard categorization. Detector tube
manufacturers are listed in the Manufacturers and Suppliers of Air Monitoring Equipment section of
this manual.
SAFETY
Do not directly inhale the contents of the bags and keep the bags closed when not in use. The
contents of the gas bags, if released into the room, will not pose a hazard to the occupants.
Breaking the tips off the detector tubes can create a hazard. Please ensure that the glass tips are
discarded into the containers provided and not onto the table or floor. The tube breakers built into
the pumps can propel bits of glass. Direct the glass into the container provided. The instructor will
demonstrate proper procedures. The ends of the detector tubes are also sharp, so handle them
carefully.
Exercise 5 42 10/93
-------
Eating or drinking is not allowed during this exercise because it is nearly impossible to prevent small
shards of glass from being deposited on the desk, table, or floor. Also, check the work area so that
you do not pick up glass on your hands or arms.
PUMP CHECK - DRAEGER
Leak Test
The purpose of this test is to ensure that air is going through the tube and not around it or through
a leaky valve.
1. Insert an unopened tube into the socket of the pump. Do not use your finger to seal the
orifice. The instructor will demonstrate why not. .
2. Squeeze the pump completely and release. If the indicator mark has not appeared in 15
minutes, the pump passes the test. You may want to go to the Sensidyne pump check while
this is taking place.
3. If the pump fails the test, inform the instructor.
4. Remove tube from the socket.
5. (New model pump) Press counter reset button with a ball point pen or end of unopened tube
to set at zero.
Volume Check
The purpose of this step is make sure that the pump is drawing the specified volume (100 cubic
centimeters or milliliters). The tubes are calibrated for this volume. If the volume is not within
limits, the tubes can not be used quantitatively.
6. Break off the tips of a tube or use a previously opened tube.
7. Connect the detector tube and pump to the apparatus as shown in Figure 2.
10/93 43 Exercise 5
-------
Flexible tubing
Buret
Soap
solution^
Detector tube
Detector tube
•"" pump
FIGURE 2. DETECTOR TUBE PUMP VOLUME CHECK APPARATUS
8. Start a bubble at the mouth of the inverted buret by just touching the soap solution to the
mouth of the buret.
9. Squeeze the bellows pump in order to pull the bubble up the buret. Continue to squeeze and
release the pump until the bubble stops above the "0" mark on the buret. This maneuver
may require disconnecting the flexible tubing after the bubble passes the "0" mark.
10. Start with the bellows fully expanded. Reconnect the detector tube to the tubing. Record
the start point (ml) in Table 1.
11. Squeeze and release the pump.
12. When the bubble stops, record the stopping point (ml).
13. The difference in the two points (the travel volume) is the volume pulled by one stroke of
that pump. This volume should be between 95 and 105 ml (100 ml ±_ 5%).
14. You may repeat the test to see whether the results are consistent.
Exercise 5 44
10/93
-------
PUMP CHECK - SENSIDYNE
Leak Test
1. Insert an unbroken tube into the orifice of the pump.
2. Align the index marks on the pump handle and the pump cap. Pull the handle straight out
as far as it will go. It should lock in place.
3. Wait 1 minute. Turn the handle 1/4 turn and release the handle. Hold the pump barrel
firmly as the handle will pop back rapidly if the pump does not leak. The handle should
return to within 1/4 inch of the cap. If the pump is equipped with a "Flow Finish Indicator,"
the red button will remain down if there is no leak.
4. If the pump fails the test, inform the instructor.
Volume Check
5. Break off the tips of a tube or use a previously opened tube.
6. Connect the detector tube and pump to the apparatus as shown in Figure 2. An adapter may
be needed because of the small diameter of the tube.
7. Start a bubble at the mouth of the inverted buret by just touching the soap solution to the
mouth of the buret.
8. Pull the handle back in order to pull the bubble up the buret. Continue to pull the handle
until the bubble stops above the "0" mark on the buret. This maneuver may require
disconnecting the flexible tubing after the bubble passes the "0" mark.
9. Start with the piston empty (handle fully in). Reconnect the detector tube to the tubing.
Record the start point (ml) in Table 1.
10. Pull back the pump handle all the way.
11. When the bubble stops, stop the stopwatch. Record the time and the stopping point (ml).
12. The difference in the two points (the travel volume) is the volume pulled by one stroke of
that pump. This volume should be between 95 and 105 ml (100 ml + 5%).
13. You may repeat the test to see if the results are consistent.
10/93 45 Exercise 5
-------
QUANTITATIVE RESULTS - DRAEGER AND SENSIDYNE
The pumps and detector tubes will be used to determine the concentration of two chemicals. The
Draeger pump and tube will be used to determine the concentration of carbon dioxide in the gas bag.
The Sensidyne pump and tube will be used to determine the concentration of isopropyl alcohol in the
air above a beaker of liquid.
1. Read the instructions for the detector tube.
2. Determine the number of pump strokes needed; the color change expected; and any
adjustments to the reading.
3. Use a fresh tube. Break off both ends of the tube. Insert the opened tube into the pump
orifice with the arrow on the tube pointing towards the pump. Sample the bag (carbon
dioxide) and the air above the liquid (isopropyl alcohol). Do not pull liquid into the tube.
(This is air, not water, monitoring.) Liquid drawn into the tube can produce a change even
if the chemical is not present.
4. Record your results on Table 1.
CHEMICAL CLASSIFICATION - DRAEGER
In this step, a series of Draeger tubes will be used to determine the types of chemicals in an
unknown mixture. The flow chart on the next page will be used to determine the mixture's
components. The chart was provided by National Draeger, Inc. Other manufacturers have similar
systems for chemical classification.
This sample taking schedule refers to a selection of substances which occur frequently in practice.
Other situations may necessitate another sequence of measurements and, the case being, the use of
additional detector tubes, or measurements according to other procedures must be carried out. (from
National Draeger, Inc.)
The information on the next two pages has been reprinted with the permission of National Draeger,
Inc., Pittsburgh, PA. This information can also be found in their Haz Mat Kit. Similar flow
charts/decision logics have also been developed by MSA and Sensidyne for use with their detector
tubes.
1. Read the instructions for the tubes.
2. Use the tubes to sample the unknown atmosphere.
3. Record the result in the appropriate space in Table 2.
4. Repeat process with all the tubes provided.
5. Extra space is provided should any special tubes be used.
Exercise 5 46 10/93
-------
Safety Tips
The POLYTEST and HYDROCARBON tubes use sulftiric acid as a reagent. When the bellows is
squeezed, an aerosol (smoke-like) containing the acid will be emitted. Avoid breathing the "smoke."
If you think you may have some problems with the aerosol, please inform your instructor. You
should not have any problems unless you are more sensitive than the average person.
10/93 47 Exercise 5
-------
Detection of unknown substances by means of DRAEGER detector tubes*
Detection of various organic and some inorganic substances:
Polytest
e.g.. Acetone Gasoline (engine fuels) Liquid gases Perchloroethylene
Acetylene Benzene (propane, butane) Catbon disuKide
Arsenic hydride Ethylene Carbon monoxide, Monoslyrene Hydrogen sulfide
Municipal gas (with more tharr 2 vol. % of CO)
Nitrogen monoxide (NO)
Toluene, xylene. trichloroethylene
positive
Detection of various organic substances:
Ethyl acetate 200/a
positive
I
Detection of some
halogenated hydrocarbons:
Methyl bromide 5/b
e.g., esters of acetic acid, alcohols, ketones, benzene,
toluene, benzine hydrocarbons
e.g.. methyl bromide UN N°
1062 (chloroform, dichlo-
roethylene, dichloroethane,
dichloropropane), trichlo-
>.
'
>.
>,
'
Detection of important
aromatic hydrocarbons:
Benzene 0.05
e.g., benzene UN N* 1114
(ethyl benzene, toluene
and xylene in small
quantities discolor the
prelayer)
.
Detection of ketones:
Acetone 100/b
e.g.. acetone UN N° 1090
methylisobutyl ketone,
methylethyl ketone
•
Detection of alcohols:
Alcohol 100/a
Detection of
propane butane:
Hydrocarbon 0.1 %/b
e.g., propane UN N" 1978
Detection of CO:
Carbon monoxide 10/b
e.g., CO UN N° 1016
of other substances may be
4
4
4
e.g., alcohol UN N° 1096
butanol. methanol,
propanol
Detection of amines:
Hydrazine 0.25/a
e.g.. triethylamine UN N° 1296
(ethylene diamine,
hydrazine. ammonia)
Detection of acid-
reacting substances:
Formic acid 1 /a
e.g.. hydrochloric acid UN N°
1789, HNO,, Cl,, NO,,SO2
Further detection
e.g., methane, ethane, H2,
CO] and other substances
may be necessary
negative
'Important: This sample taking schedule refers to a selection of substances which occur frequently in practice. Other situations may
necessitate another sequence of measurements and, the case being, the use of additional detector tubes, or measurements
according to other procedures must be carried out.
©\ National Draeger, Inc.
101 Technology Drive (Shipping) • P.O. Box 120 (Mailing) • Pittsburgh. PA 15230 • 412/787-8383 • Telex: 86-6704
Exercise 5
48
10/93
-------
Examples for the (qualitative) indication response of the DRAEGER Polytest tubes
The results were obtained under the following test conditions:
Temperature 20°C; Humidity 50% relative; All tests carried out with pure substances
Substance '
Acetone
Acetone
Acetylene
Acetylene
Ursine
Arsine
Benzine (Gasoline)
Benzine (Gasoline)
Benzene
Benzene
Butane
Butane
Carbon disulfide
Carbon disulfide
Carbon monoxide
Carbon monoxide
Ethylene (ethene)
Ethylene (ethene)
Nitrogen monoxide (NO)
Nitrogen monoxide (NO)
Perchloroethylene
Perchloroethylene
Propane
Propane
Styrene (monostyrene)
Styrene (monostyrene)
Toluene
Toluene
Trichloroethylene
Trichloroethylene
Xylene
Xylene
Concentration
50OO ppm
above liquid
200 ppm
high cone.
(over 1 %)
10 ppm
high cone.
(over 1 %)
50 ppm
above liquid
100 ppm
above liquid
100 ppm
high cone.
(over 1%)
10 ppm
above liquid
100 pprn
high cone.
(over 1 %)
500 ppm
high cone.
(over 1 %)
50 ppm
high cone.
(over 1 %)
50 ppm
above liquid
500 ppm
high cone.
(over 1%)
500 ppm
above liquid
200 ppm
above liquid
50 ppm
above liquid
500 ppm
above liquid
Number
of strokes
of the bel-
lows pump
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
Length of Discoloration
approx. 10 mm
completely colored
approx. 10 mm
completely colored
approx. 10 mm
completely colored
approx. 10 mm
completely colored
approx. 10 mm
approx. 10 mm
approx. 10 mm
completely colored
approx. 10 mm
completely colored
approx. 10 mm
completely colored
approx. 10 mm
completely colored
approx. 10 mm
completely colored
approx. 10 mm
completely colored
approx. 10 mm
completely colored
approx. 1 0 mm
approx. 10 mm
approx. 10 mm
approx. 10 mm
approx. 10 mm
completely colored
approx. 10 mm
approx. 10 mm
Notes on the indication
brownish green
brownish
brownish green
brownish
brownish green
brownish
brownish green
brownish
brownish
brownish
faded green (spotty)
brownish green
greenish
brownish green
brownish green
brownish
brownish green
brownish
brownish green
brownish with
bleaching effect
greenish
brownish green
faded green (spotty)
brownish green
brownish
• brownish
brownish
brownish
brownish green
faded yellow
brownish
brownish
Examples for the (qualitative) indication response of the DRAEGER tubes for ethyl acetate 200/a
The results were obtained under the following test conditions:
Temperature 20°C; Humidity 50% relative; All tests carried out with pure substances
Substance
Acetone
Acetone
Benzene
Benzene
Ethyl alcohol
Ethyl alcohol
Octane
Octane
Toluene
Toluene
Xylene
Xylene
Concentration
3000 ppm
above liquid
500 ppm
above liquid
2000 ppm
above liquid
100 ppm
above liquid
500 ppm
above liquid
500 ppm
above liquid
Number
of strokes
of the bel-
lows pump
5
5
5
5
5
5
5
5
5
5
5
5
Length of Discoloration
approx. 10 mm
completely colored
completely colored
completely colored
approx. 5 mm
approx. 20 mm
approx. 10 mm
completely colored
approx. 10 mm
completely colored
approx. 10 mm
completely colored
Notes on the indication
greenish
greenish
very pale grey
greenish grey
greenish
greenish
grey-brown-greenish
greenish
greenish grey
greenish grey
greenish brown
greenish brown
10/93
National Draeger, Inc.
101 Technology Drive (Shipping) • P.O. Box 120 (Mailing) • Pittsburgh. PA 15230 • 412/787-8383 • Telex- 86-6704
49 Exercise 5
-------
SENSIDYNE
ID NUMBER
PASS FAIL
LEAK CHECK
PASS FAIL
VOLUME CHECK
BURET STOP POINT (ml)
BURET START POINT (ml)
TOTAL VOLUME
SAMPLE TIME
ACCEPTABLE VOLUME?
PASS FAIL
PASS FAIL
ISOPROPYL ALCOHOL
CARBON DIOXIDE
UNADJUSTED READING
READING ADJUSTED FOR
TEMPERATURE
READING ADJUSTED FOR
BAROMETRIC PRESSURE"
a The acceptable volume for a full pump stroke is 100 ml ± 5% (i.e., between 95 and 105 ml).
b Assume the sampling conditions were 30'C and 720 mm barometric pressure.
Exercise 5
50
10/93
-------
TABLE 2
NAME OF TUBE
POLYTEST
METHYL BROMIDE
ETHYL ACETATE
BENZENE
ACETONE
ALCOHOL
HYDROCARBON
CARBON MONOXIDE
HYDRAZINE
FORMIC ACID
READING/INDICATION
What types of chemicals are present in the mixture?
10/93
51
Exercise 5
-------
QUESTIONS
1. Based on your test results, how long should you wait between pump strokes for the MSA?
2. What factors could affect the detector tube results?
3. Does the CO2 concentration exceed the PEL? REL? TLV? IDLH?
4. Does the isopropyl alcohol concentration exceed the PEL? REL? TLV? IDLH?
Exercise 5 52 10/93
-------
EXERCISE #6
Direct-Reading Aerosol Monitors
OBJECTIVE
Participants will learn how to operate the MIE Real-Time Aerosol Monitor Model RAM-1 and the
MIE MINIRAM Personal Monitor Model PDM-3.
DESCRIPTION OF EQUIPMENT
The RAM-1 and the MINIRAM are portable, self-contained aerosol monitors. Their detection
system is based on the detection of near-forward, scattered, near-infrared radiation.
The RAM-1 uses a pump to draw air into the unit to the sensors. It uses an air screen to prevent
contamination of the sensors. The MINIRAM does not require a pump. Air passes through the
sensing volume by convection, circulation, ventilation and personnel motion. The sensors are also
in direct contact with the environment. Thus, there is a chance the sensors may get covered with
dust. The MINIRAM sensors require cleaning on a regular basis.
Both units indicate the aerosol concentration in milligrams per cubic meter (mg/m3). Both use a
digital display. The MINIRAM's displayed reading is updated every 10 seconds. The RAM-1 has
a variable time display.
The RAM-1 has a range of 0.000-200.0 mg/m3. The readout range is selected by the operator. The
MINIRAM normally operates in the 0.00 to 9.99 mg/m3 range. Whenever a 10-second concentration
exceeds 9.99 mg/m3, the MINIRAM automatically switches to the 0.0 to 99.9 mg/m$ range and
remains in that range as long as the measured 10-second concentration exceeds 9.99 mg/m3.
Otherwise the MINIRAM reverts to its lower range display.
The RAM-1 only displays real-time concentrations. A output device can be connected to record
data. The MINIRAM can store data for later output and for TWA calculations. Thus, it can be used
as a direct-reading monitor and a dosimeter.
Both instruments can be powered by internal batteries or an external AC source.
It is important to remember that these instrument only give total or respirable quantities of aerosols.
They do not give the composition of the aerosol. To determine the composition of the aerosol, a
sample must be taken and analyzed. Refer to the Air Sample Collection section of the course
manual.
10/93 53 Exercise 6
-------
MIE MINIRAM PERSONAL MONITOR MODEL PDM-3
Before using the instrument without the charger, charge the MINIRAM for a minimum of 8 hours.
Initial Condition
• Blank display—Indicates that the MINIRAM has not been in the measurement mode
for 48 hours or more, and is in the minimum power off mode.
• "OFF" display—MINIRAM has been in the off mode for less than 48 hours.
• Concentration display that changes or "blinks" once every 10 seconds: the
MINIRAM is in the measurement mode.
Controls (refer to Figure 1)
"MEAS'
"ZERO"
"TIME"
When this button is pressed, the measurement mode will start. Once the MEAS
mode has been entered, this sequence can only be interrupted by pressing OFF.
Pressing ZERO, TWA, SA, TIME, or ID# only affects the display during the time
the keys are pressed.
The readout will first display "GO" (or "CGO" if TIME is also pressed) followed by
the last concentration reading or " .00."
Approximately 36 seconds later, the first new 10-second-averaged concentration
reading is displayed. The reading will be updated and displayed every 10 seconds.
The MINIRAM will now run in the measurement mode for 500 minutes (8 hours and
20 minutes), after which time it will stop, displaying the OFF reading. It will retain
in storage the concentration average and elapsed time information.
If both MEAS and TIME are pressed at the same time (press TIME first and while
depressing it actuate MEAS) the MINIRAM will display "CGO," and will then
operate as above (i.e., pressing MEAS only), except that after the first 8.3-hour run,
it will restart automatically and continue to measure for an indefinite number of
8.3-hour runs, (with the battery charger) until the OFF key is pressed, or until the
batteries are exhausted. Concentration averages and timing information for the last
seven 8.3-hour runs will remain in storage at any give time.
When instrument displays "OFF," pressing this button initiates the ZERO procedure.
During the measurement mode, if TIME is pressed, the display will show the elapsed
time, in minutes, from the start to the last measurement run. The MINIRAM will
automatically return to concentration display after the TIME key is released.
Exercise 6
54
10/93
-------
1.85 -
OVR
ID
BAT
\/_
'\
.— MIE
_^ MINIRAM
AEROSOL
MONITOR
MOOEL PDM-»
(CLIP)
"TWA"
"SA"
"PBK"
"OFF"
FIGURE 1. FRONT PANEL OF MINIRAM
During the measurement mode, if the time-weighted average (TWA) is pressed, the
display will indicate the average concentration in milligrams per cubic meter (mg/m3)
up to that instant, from the start of the last run. The value of TWA is updated every
10 seconds. After releasing the TWA key, the MINIRAM display returns to the 10-
second concentration display.
During the measurement mode, pressing SA (Shift-Average) will provide a display
of the aerosol concentration, up to that moment, averaged over an 8-hour shift
period.
With the MINIRAM in the off mode, the stored information can be played back by
pressing PBK (Play Back). Pressing the PBK key for more than 1 second will cause
stored data to be automatically played back through the MINIRAM display: First,
the identification number is displayed with the ID indicator bar on; next the shift or
run number (i.e., 7 through 1, starting with the last run) is shown (with the OVR
indicator bar on as identification); followed by the sampling time in minutes, for that
run; followed by the off-time between the last and next run (in tens of minutes:;
finally, the average in mg/m3. This sequence is repeated seven times. An average
reading of 9.99 indicates that a significant overload condition occurred during that
run. The total time required for the complete automatic playback on the MINIRAM
display is approximately 70 seconds.
When this key is pressed, the MINIRAM will discontinue whatever mode is
underway displaying "GCA" followed by the display segments check ("8.8.8=") and
finally "OFF." The MINIRAM will then remain in this reduced power condition
(displaying "OFF").
10/93
55
Exercise 6
-------
Display
During the measurement mode, the display indicates the present concentration in mg/m3. If one of
the function buttons is pushed, the information indicated in CONTROLS is displayed. If a bar
appears in the display, the bar's location indicates one or more of the following:
"OVR" The concentration exceeds the range of the instrument or there is an overload due to
reflected line (e.g., sunlight).
"ID" This indicates that the ID number is being displayed and not a concentration.
"BAT" This indicates a low battery.
Zero Procedure
1. Zeroing must be performed in a clean-air environment. This can be done by using a clean
room or clean-bench, flowing clean air through the sensing chamber, or using an air-
conditioned office (without smokers).
2. Press OFF and wait until the display indicates "OFF."
3. Depress the ZERO button. Wait until the display again indicates "OFF." The average of
four consecutive 10-second zero level measurements will then be stored by the MINIRAM
as the new ZERO reference value. The ZERO reference value will be subtracted from
subsequent readings. When operating the MINIRAM is high particle concentration
environments (>5 mg/m3) the zero value should be updated approximately every 8 hours.
At aerosol concentrations below approximately 1 mg/m3 this update may only be required
once a week.
Start Measurement Cycle
4. Place the MINIRAM in the area to be monitored. The instrument should be placed vertically
(i.e., display/control panel facing upwards) by clipping it to a belt, shoulder strap, etc.
5. If the MINIRAM shows a blanked display, press OFF and wait until the display reads "OFF"
(approximately 5 seconds after pressing OFF) before pressing MEAS to initiate measurement
cycle.
6. If the MINIRAM shows "OFF," press MEAS directly to initiate measurement cycle (there
is no need to press OFF first, in this case).
7. Press MEAS.
8. Observe the readings for 1 minute to verify that the levels change every 10 seconds and that
the OVR bar is not displayed.
Exercise 6 56 10/93
-------
9. Avoid objects being placed in the sensing chamber. Also avoid direct sunlight scattering in
the sensing chamber.
10. At the end of the sampling period, press "TIME." Record the sample duration in Table 1.
11. Press the TWA button. Record the reading in Table 1.
12. Press OFF.
TABLE 1
INFORMATION
INSTRUMENT SERIAL #
START TIME
TWA
SHIFT AVERAGE (SA)
OFF TIME
RESULTS
MIE REAL-TIME AEROSOL MONITOR MODEL RAM-1
In the following procedure, the numbered buttons, displays, and switches refer to the illustration of
the RAM-1 in Figures 2 and 3.
Startup
1. Lift up protective cover of control panel.
2. Place selector switch (1) in battery (BATT) position.
3. Place inlet valve (2) in CLEAR position (horizontal).
4. Replace sealed cap on inlet valve with the restrictor orifice.
5. Switch instrument on (3) and check battery voltage. The digital readout (4) should indicate
between 6.0 and 6.6 volts. If not, inform the instructor. The reading should be identified
by a display of VDC (volts DC). Low battery voltage is indicated by a flashing "VDC" on
the right-hand side of the display, whenever the selector switch is not in the BAT position.
10/93 57 Exercise 6
-------
Zeroing
6. Check that the inlet valve is in the CLEAR position (horizontal). Place the selector switch
in the 0-200 position. The letter "m" should appear to the right of the display reading,
indicating that the instrument is set to read concentration measurements.
7. Place the time constant switch (5) in the 2-second position.
8. Allow 1 minute for instrument to stabilize (warm-up). IMPORTANT!
9. If necessary, lift the cover over the ZERO control (6) and adjust the control until a reading
of 00.0 is obtained.
10. Switch the selector to the 0-20 position and repeat step #9.
11. Switch the selector to the 0-2 position and repeat step #9. Readings may fluctuate. Try to
obtain an average reading of 0±0.005.
Secondary Calibration
12. Keep inlet valve in its CLEAR position.
13. Set the range selector to the 0-20 position.
14. Unlock the hinged flow chamber cover and place in the horizontal position.
Exercise 6
CLEAR
MIE
«VDC CHARGE
8 6
FIGURE 2. RAM-1 TOP VIEW
58
10/93
-------
Filters
Desiccant
12 11
FIGURE 3. RAM-1 SIDE VIEW
15. Push the reference scatterer knob (REF SCAT) (9) inward until a positive stop is detected.
The pump will automatically shut off. The letter "K" should be flashing in the upper right
side of the display. Allow the reading to stabilize for 30 seconds.
16. See if the instrument reading corresponds with the factory calibration label (10) by the (REF
SCAT).
17. If the indicated readings differ by more than 5%, adjust the CAL control (7) as required.
The CAL control has a lock that must be disengaged before attempting to turn the knob.
Allow to stabilize and repeat if required. Relock the CAL control.
18. Pull the REF SCAT back out.
19. Close the flow chamber cover and tighten thumb-screws.
Measurement Procedures
20. Switch RAM on.
21. Select measurement range (usually the 0-20 position).
22. Select desired time constant (usually 2 seconds).
23. Place inlet valve in SAMPLE position (vertical downwards).
24. Check the flow meters. The TOTAL (11) should read about 2 and the PURGE (12) should
read about 0.2 (or 10% of TOTAL). Adjust the total flow rate with the flow adjust screw
10/93
59
Exercise 6
-------
(8). Adjust the purge flow with the black valve on the rotameter. If the rotameter is pegged,
check that the inlet valve is in the SAMPLE position.
25. Measure the aerosol concentrations in the areas designated by the instructor.
26. If the aerosol concentration exceeds the maximum selected range, the RAM-1 will indicate
1 with all zeros blanked out. If this occurs, change the range selection to higher ranges as
needed.
27. Check and update zero periodically.
28. BEFORE SHUTTING OFF THE RAM-1, CLOSE THE INLET VALVE (CLEAR
POSITION) AND OPERATE FOR 3 MINUTES TO ALLOW PURGING OF THE
DUSTS INSIDE THE OPTICAL CAVITY.
29. When sampling and purging is complete, turn the instrument OFF.
Exercise 6 60 10/93
-------
QUESTIONS
1. Discuss the advantages and disadvantages of these instruments.
2. Analysis of the site soil or analysis of a filter sample shows the soil composition to be 5%
lead. You obtain a reading of 1.35 mg/m3 with the RAM-1. Determine (approximately) the
airborne lead concentration based on your reading.
3. The action level for lead at your site has been determined to be 1.5 jig/m3. The soil on the
site is 5 % lead, a) What instrument reading would be equivalent to your lead action level?
b) What reading would you be concerned about if your action level was 50 /ig/m3?
a)
b)
10/93 61 Exercise 6
-------
-------
EXERCISE #7
Gas Chromatography - PID
OBJECTIVE
The student will learn the basic operation of the Photovac 10S50 portable gas chromatograph and
analyze several air samples.
PROCEDURE
The instructor will describe and illustrate the different parts of the Photovac 10S50 and their
functions. Since the 10S50 needs a certain amount of warm-up time, the student will not be able to
go through start-up of the instrument. After the introduction, students will run a calibration standard
and an unknown sample. Students will also collect an air bag sample and analyze it.
OPERATING INSTRUCTIONS FOR THE PHOTOVAC 10S50 (CAPILLARY COLUMN
OPERATION)
Preparation for Use
Refer to the Photovac 10S50 instrument panel and Figure 1.
Recharge the Carrier Gas
1. Connect the fill line for the Photovac 10S50 to a cylinder of "Ultra-Zero Air" (contents < 0.1
ppm hydrocarbon).
2. Attach the "Quick-Connect" from the fill line to the REFILL receptacle on the upper right-
hand corner of the Photovac 10S50.
3. Turn on the cylinder and rotate the valve for the fill line so that the pointed end points
toward the cylinder. Be sure not to stand directly in front of the regulator.
4. The reservoir in the instrument will be filled to the maximum pressure of the supply cylinder.
The pressure is indicated on the CONTENTS gauge on the upper left of the instrument panel.
(The maximum pressure at which the instrument can be filled is 1750 psi.) The delivery
pressure is indicated on the DELIVERY gauge. This pressure should be 40 psi. When the
reservoir is filled, the excess air will be expelled at the fritted outlet on the supply cylinder
regulator. This will be indicated by a "hissing" sound. Turn off the supply cylinder valve
and then turn off the valve on the fill line.
5. Disconnect the fill line.
10/93 63 Exercise 7
-------
X)
4)
LU O
ZfJ
c
Q- o
•- >
?. o
co
o
in
to
o
r-
O
o
o
UJ
cc
§
1
a-
1
o
§
o
Exercise 7
64
6/94
-------
Set the Carrier Gas Flow Rate
6. The pieces of tubing to the flow meter are attached to the ports on the instrument panel.
7. Attach the line on the left side of the meter to the DETECTOR OUT port.
8. Attach the line on the right side of the meter to the needle valve marked AUX OUT.
9. Connections should be secured with a 7/16 inch open-ended wrench (1/4 turn past tight).
10. Adjust the flow rates on the meter.
a. If the instrument is being set up to stabilize overnight, set the DETECTOR OUT
FLOW using the red FLOW adjustment knob on the left side of the panel to 5
ml/min. Note: Turn knob clockwise to decrease the flow or counterclockwise to
increase the flow. Set AUX OUT flow using the needle valve to 0 ml/min. Allow
to stabilize overnight.
b. If the instrument is being set up for analysis, set the DETECTOR OUT flow using
the red FLOW adjustment knob to 10 ml/min. Set AUX OUT flow using the needle
valve to 10 ml/min.
Activate the Power Source
11. When the instrument is ready for use, attach the power cord for the instrument to the 3-prong
socket in the upper left-hand corner of the instrument. The cord is then plugged into an AC
outlet.
12. Press the ON key. The instrument will respond with "LAMP NOT READY, PLEASE
WAIT."
13. Wait until the display reads "READY ENTER COMMAND."
Set Instrument Parameters
14. Locate the LIBRARY block and press the USE key. The instrument will respond with
"LIBRARY IN USE?" There are four libraries numbered 1 to 4. Library #1 is the default.
We will use #1 for this exercise. Press the 1 key and then the ENTER key.
15. The instrument will prompt for "DAY" (1-31). Press the appropriate value for the day of
the month and then press the ENTER key.
10/93 65 Exercise 7
-------
16. The following information is entered in the same manner:
a. MONTH (1-12), then press ENTER
b. YEAR (e.g., 1993), then press ENTER
c. HOUR (0-23), then press ENTER
d. MINUTE (0-59), then press ENTER.
17. The instrument will read: "READY ENTER COMMAND."
Obtain a Status Report
18. Locate the STATUS block and press the TEST key. The instrument will respond with
"FUNCTION, USE < >, STATUS REPORT." Respond by pressing the ENTER key.
19. The instrument will print a status report containing the following information:
a. Current field date and time.
b. Field: The # represents the detector field in volts/10.
c. Power: The # indicates the current lamp consumption at mA/10.
d. EVENT settings show the ON and OFF times of the 10S50 sample pump and
solenoid valves. The instructors will have set the following EVENT values:
SAMPLE
CAL
EVENT #3
EVENT #4
EVENT #5
EVENT #6
EVENT #7
EVENT #8
(EVENT #1)
(EVENT #2)
0
0
10
0
13
0
0
0
10
0
60*
10
60*
0
0
0
* Some units may have a longer time (e.g., 80) instead.
20. Allow the instrument to stabilize for approximately 45 minutes. The instrument has been
stabilizing prior to the exercise so we may continue.
Select the Analytical Parameters
21. Locate the SETUP block on the instrument panel.
Exercise 7 66 10/93
-------
22. Press the GAIN key. The gain controls the amplification from the detector. The default
value is "2" For higher values, press the UP ARROW key until the desire value appears.
For this exercise, choose a gain setting of "5" and then press ENTER.
23. Press the CHART key. The instrument will respond with "CHART ON" or some other
readout. "CHART ON" means the chromatogram will be displayed along with identification
information and some instrument settings (e.g., GAIN). "CHART OFF" means that the
chromatogram will not be displayed, but identification information and some instrument
settings will be displayed. "CHART ON WITH BASELINE" prints out the same information
as "CHART ON," but also shows the baseline the instrument uses to calculate peak area.
"CHART ON WITH SETUP" prints out the same information as "CHART ON WITH
BASELINE" but also includes the setup information (e.g., SENS, WINDO). Use the UP
ARROW or DOWN ARROW key until "CHART ON WITH SETUP" is displayed. Press
ENTER. The next display is the chart speed. The default is 0.1 cm/min. Press the UP
ARROW key until 0.5 appears. Press ENTER.
24. Press the SENS key. The key controls the instrument integrator. The following settings
specify the minimum response that will be recognized as a peak on the chromatogram.
SLOPE UP; Use the arrow keys to display 18 mv. Then ENTER.
SLOPE DOWN; Use the arrow keys to display 16 mv. Then ENTER.
PW (Peak Width) at 4 minutes; Use the arrow keys to display 6 (sec). Then
ENTER.
25. Press the WINDO key. This key adjusts the 10S50's tolerance to retention time drift. A
peak, must be within a specified percentage of a stored retention to be identified as that
chemical by the instrument. Choose a value of "10" (i.e., 10%) and press ENTER.
26. Press the AREA key. This key sets a peak size threshold. All peaks smaller than the AREA
setting are deleted from the "PEAK INFORMATION" listing at the end of the analysis.
(However, these peaks will still be numbered on the chromatogram.) Set the minimum area
at "50" and ENTER.
27. Locate the PROGRAM block and press the CYCLE key. The instrument will prompt for
the following information:
a. "TIMER DELAY." This setting determines the delay in time from when the
START/STOP key is pressed and when the instrument will start looking for peaks.
Choose "10" seconds and ENTER.
b. "ANALYSIS TIME." The duration of the analysis is dependent upon the types of
compounds that are being considered for analysis. Select an analysis time of 600
seconds for this exercise. Press ENTER.
c. "CYCLE TIME." These times refer to the mode for continuous monitoring. This
mode will not be used in this exercise. Choose "0" min and ENTER. The
instrument will respond with "CYCLING DISABLED, COUNTERS RESET."
JO/93 67 Exercise 7
-------
Establish a Baseline for the Chromatogram
28. The baseline will be established by analyzing a bag of ultrazero air (a BLANK sample).
Connect the "zero" bag to the PROBE IN CONNECTION. Open the bag. To initiate the
analysis, locate the ANALYSIS block and press the START/STOP key. The instrument will
respond: "PROBE IN?" Press ENTER.
29. As soon as the ENTER key is pressed, the pump should start and run 10 seconds. If the
pump does not start, inform the instructor.
30. Allow the chromatogram to be generated. Examine the baseline for significant drift or
extraneous peaks. The baseline should be flat and smooth. Repeat this procedure until a
stable (zero slope) baseline is obtained or until the instructor informs you to stop.
Analyze the Standard Gas Bag
31. For this exercise, we will use the chemicals in Library 1 as the standard. The "standard gas
bag" will be used to check retention times and allow you to see a chromatogram.
32. Connect the "sample bag" bag to the PROBE IN CONNECTION. Open the bag. To initiate
the analysis, locate the ANALYSIS block and press the START/STOP key. The instrument
will respond: "PROBE IN?" Press ENTER.
33. Allow the chromatogram to be generated. This will take 600 seconds (the analysis time we
selected).
34. At the end of the chromatogram, the printout will print the peak numbers that exceed the area
setting, the identity of the peaks (if they match the retention times in the library) and the
concentration of identified peaks. Consult the instructor for the expected results. If the
peaks are not properly identified, a update adjustment or calibration run will be necessary.
See Updating the Library and Creating a Library before analyzing any samples.
Updating the Library
35. If library does not recognize all of chemicals in the standard, the library should be updated.
36. Select a peak (one that you can identify) as a reference point. Press the CAL key. The
instrument will request a plotter peak number. Enter the peak number you have selected.
Press ENTER.
37. The instrument will request an ID number. Look at the previous printout of the library.
Enter the number for the chemical that matches the peak. Press ENTER.
38. The instrument will request a concentration. Enter the concentration of the compound
corresponding to the plotter peak used. Press ENTER.
Exercise 7 68 10/93
-------
39. The plotter will print out a listing of the peaks from the recent analysis and hopefully identify
the peaks using retention times and peak areas adjusted by the reference peak.
Creating a Library
40. Connect the "sample bag" bag to the PROBE IN CONNECTION. Open the bag. To initiate
the analysis, locate the ANALYSIS block and press the START/STOP key. The instrument
will respond: "PROBE IN?" Press ENTER.
41. Allow the chromatogram to be generated.
42. The information from the chromatogram must be stored in the library IMMEDIATELY
FOLLOWING completion of the analysis. IF ANY OTHER KEY IS PRESSED BEFORE
STEP #43, THE STANDARD CHROMATOGRAM WILL NEED TO BE GENERATED
AGAIN TO UTILIZE ITS INFORMATION.
43. Locate the LIBRARY block and press the STORE key. The instrument will prompt for:
a. PLOTTER PEAK #: Select the number of the first peak of interest on the
chromatogram and press ENTER.
b. CHEMICAL NAME: Select the name of the compound using the alpha-numeric
keys on the key pad. After the name is complete press ENTER. (To change to
numbers, press the CAL (NUM) key. This key must also be pressed again to return
to letters.)
c. CONCENTRATION (in ppm): Select the actual concentration of the compound in
ppm. Press ENTER.
d. LIMIT VALUE: The limit value is the concentration, which if exceeded, causes the
plotter to print the concentration value in red instead of green. This "flags" the
compound. Press ENTER. This will instruct the instrument to use 0 as the limit, so
all concentrations will be in red.
e. This procedure is repeated for subsequent compounds in the chromatogram by
pressing the STORE key and following steps a through d.
f. To check the contents of the library, press CAL. The instrument prompts with
"PLOTTER PEAK #?" ENTER TO RELIST. Press ENTER. The plotter will print
out the added compounds and their concentrations.
Note: DO NOT enter a value here or the instrument will prompt for recalibration.
10/93 69 Exercise 7
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Editing the Library
44. A compound can be added to the library after any analysis. A compound can be added to
the library even if it is already in the library. However, the new entry will not replace the
old entry. There will be two listings for the compound.
45. To remove a compound from the library, first press EDIT.
46. The instrument will prompt with "ID NUMBER." Enter the ID number for the compound
in the library. The instrument will list the name of the compound.
47. Press CLEAR, then press ENTER. The instrument will respond with "COMPOUND
REMOVED FROM LIBRARY."
48. Repeat for any additional compounds.
Analyse the Samples
49. Using steps 31 through 34, analyze the unknown samples provided.
50. IMPORTANT! DO NOT USE ANY GAS BAGS, other than those provided by the
instructors, WITHOUT THE PERMISSION OF THE INSTRUCTORS. High concentrations
can contaminate the column.
Exercise Shutdown
51. When sample analysis is complete, do not turn the instrument off.
Shutdown (Overnight)
52. Generate a chromatogram of the baseline to ensure that there are no residual materials in the
column.
53. Locate the POWER block and press the OFF key. The instrument will respond with
"ENTER=OFF." Press ENTER.
54. Adjust the flow rate for the DETECTOR OUT to 5 ml/min. Make sure the air supply is
adequate for overnight operation.
Shutdown (Long Term)
55. Follow the same steps as in Shutdown (Overnight).
56. Disconnect the power cord from the AC source.
57. Before shipping, drain the carrier gas supply reservoir.
Exercise 7 70 10/93
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EXERCISE #8
Sampling Pumps and Collection Media
OBJECTIVE
Participants will assemble a variety of sampling trains and calibrate them using an electronic
bubble meter. They will also check the pump's flow compensator. The students will review
sample results and evaluate exposure levels.
PROCEDURE
The class will be divided into teams. Each team will be given a Gilian* HFS 113UT air
sampling pump.
The instructor will explain the operation of the Gilian* HFS 113UT sampling pump.
The students will calibrate the Gilian* sampling pump using different media and an electronic
bubble meter.
Demonstration: Calibration of Gilian* pump with filter media using a bubble-meter
(page 82).
Station 1: Calibration of Gilian® pump with filter media and with sorbent tube
media using an electronic bubble-meter (page 85).
Station 2: Check flow compensator of Gilian* pump using Gilian* Calibrator
Pack (page 92).
Note: The procedures shown here apply only to this specific sampling pump. The actual
procedures for other pumps may vary. Consult the manufacturer's instructions for
the pump you use in the field.
After calibrating their sampling pump, the students will look at sampling results and calculate
concentration levels (page 94).
10/93 71 Exercise 8
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OPERATION AND CONTROLS OF GILIAN® HFS 113UT SAMPLER
The Gilian® HFS 113UT sampler is a lightweight, battery-powered air sampling pump. It has a
high flow range—0.5-3.5 liters per minute (1pm) and a low flow range—1-500 cubic centimeters
per minute (cc/min). It has a built-in timer to shut off the pump after a preset time. The pump
is equipped with a flow compensation control that provides for constant air flow from the pump
at any preset flow within its performance limits.
The following is a brief description of the controls for operating the pump.
1. ON - OFF Switch. This turns pump on and off.
2. PRESS TO TEST Button. When the pump is on, pressing this button gives battery power
indication and also gives an elapsed time indication in TIME MIN window. If the pump
has stopped because of end of time or fault, pressing this button before turning the pump
off gives the pump run time.
3. PROGRAMMABLE TIMER. Allows operator to set sample time from 10 minutes to 990
minutes in ten minute increments. Note: The pump will not start if the timer is set at
00. When setting the timer, the dials should be turned clockwise past the zero point
several times.
4. BAT CK - Battery Check. Turn on pump and press the test button. If the BAT CK
illuminates, then the battery is fully charged.
5. FAULT. This light illuminates and the pump shuts down, if the pump is unable to
maintain the preset flow rate.
6. TIME OUT. This illuminates when the pump stops at the programmed time.
7. FLOW ADJUST. Turning clockwise increases flowing; turning counterclockwise
decreases flow.
8. PUMP INLET. Inlet to pump. Point where tubing and sampling media are connected.
9. DISCHARGE AIR CAP SCREW. Removing this screw provides access to discharge
port. Inserting adapter allows pump to be used to fill gas bag.
10. REGULATOR SHUTOFF CAP SCREW. Removing screw provides access to the
regulator shutoff valve. The valve is used to switch the pump from high to low flow.
11. FLOW METER. Rotameter used to show flow. Read center of flow meter ball.
Reading is ±2096 of true flow.
Exercise 8 72 10/93
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DEMONSTRATION: CALIBRATING GILIAN® PUMP
USING A BUBBLE METER
During this demonstration, the Gilian® pump will be calibrated for lead paniculate sampling.
The NIOSH analytical method for lead sampling (Method 7802) uses a 0.8-^ cellulose ester
membrane filter. The appropriate filter is provided with the calibration setup. The
recommended flow rate is between 1 and 4 liters per minute. For this exercise, calibrate the
pump to about 2 liters per minute (between 1.8 and 2.2 is okay). The important thing is to
know the actual flow rate of your pump. Step 4 explains how to convert the pump to the high
flow range.
BUBBLE METER PREPARATION
During this step, the Gilian0 pump will be calibrated using an inverted buret and soap bubbles
(bubble meter). This method is considered a primary calibration method because the buret
volume and the stopwatch time can be traced to an original standard.
1. Check the calibration set-up (Figure 1). It should contain all the parts shown in the
figure. If not, inform the instructor.
2. Wet the buret by pouring a small amount of soap solution into it, and tilting it up and
down while rotating. Seal the outlet end to prevent soap from getting into the tubing.
3. Reassemble the calibration setup.
PUMP PREPARATION
4. Remove the Pump Regulator Shutoff Protective Cap. Turn the exposed screw clockwise
until closed - DO NOT OVERTIGHTEN. Replace the protective cap.
5. Using the small screwdriver provided, set the programmable tinier to 240 minutes. Turn
each dial clockwise past zero several times before setting the time.
6. Turn the pump on.
7. Press the test button. The BAT CK light should illuminate or flicker.
10/93 73 Exercise 8
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Inverted
buret
250
Filter
cassette
Soap bubble trap
Pump
Beaker
Soap solution
FIGURE 1. BUBBLE METER CALIBRATION SETUP
8. Connect the tubing and filter to the pump. The filter pad should be nearest to the pump.
Connect the filter to the tubing attached to the bubble meter.
9. Start a bubble in the buret by briefly touching the surface of the soap solution to the open
end of the buret. When the bubble passes the "0" mark, start the stopwatch. Stop the
stopwatch when the bubble passes the "250" mark.
10. Flow rate is calculated using the following formula:
FLOW RATE (L/min) =
v '
VOLUME ^^LED (ml) 60 sec/min
TIME (sec) BUBBLE TRAVELED 1000 ml/L
11. Use Data Sheet 1 to record your calibration data.
Exercise 8
74
10/93
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DATA SHEET 1
1. PUMP MFG. AND MODEL:
2. PUMP IDENTIFICATION ti:
3. BATTERY CHECK YES NO
4. LOCATION/TEMP & BAROMETRIC PRESSURE:
5. CALIBRATION METHOD:
6. FLOW RATE CALCULATIONS
VOLUME
FLOW RATE (Z/min)=
TIME (seconds) 1000 w//L
VOLUME TRAVELED TIME FLOW RATE AVERAGE
(Continue calibration until three consecutive flow rates are within ± 5% of the average.)
7. FLOW RATE:
8. ROTAMETER SETTING:
9. SIGNATURE:
10. DATE/TIME:
10/93 75 Exercise 8
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STATION 1: CALIBRATING THE GILIAN® PUMP USING
AN ELECTRONIC BUBBLE METER
The Gilibrator™ is an example of an electronic bubble meter. It is a primary calibration method.
A fixed volume is located in the center tube of the flow cell. A quartz-controlled timer is used to
measure the travel time for a bubble between two sensors. A microprocessor calculates the
volume per unit time. The flow rate is displayed in cc/min for this model.
The control unit will display the actual flow for each sample and will accumulate and average
each successive reading.
AVERAGE - To display average and number of samples, depress and hold 1he
AVERAGE BUTTON. Releasing the button will display the last flow reading. Pressing
the button again and the number of reading made will be displayed. Release and the
display returns to the last flow reading.
DELETE - To delete obvious false readings, push the DELETE BUTTON. This will
delete the false information from the average and reset the average and sample number
back to the previous reading.
RESET - To reinitiate the sequence, hit the RESET BUTTON. This will zero out all
sample and average registers within the Control Unit. The Reset Button is also used if a
malformed bubble is generated and has not been subtracted from the average by use of
the DELETE Function.
GILIBRATOR™ PREPARATION
1. Remove the storage tubing between the air inlet and air outlet of the Gilibrator™. Pour a
small amount of soap through the BOTTOM AIR INLET of the Gilibrator1* to thoroughly
cover the bottom of the flow cell. Skip this step if already done.
2. Connect a pump to the UPPER AIR OUTLET using the piece of tubing provided.
3. Turn the regulator shutoff valve on the Gilian® pump (the screw under the brass cap on
•, top of the pump) fully clockwise. DO NOT OVERTIGHTEN. Turn on the pump.
Initiate soap film up the flow tube by rapidly pressing the CALIBRATOR BUTTON
down and releasing. Repeat this procedure until a bubble travels the length of the tube
without breaking.
4. After the Flow Tube walls have been "primed" (Step 3), turn on the Power switch of the
Control Unit. Wait approximately 10 seconds while the system runs through its check
sequence. The RUN LED will light at this time as well and a LO Battery indication and
a series of five dashes will be displayed on the LCD Readout. Do not operate the
Gilibrator until the RUN LED signal extinguishes. Ready operation is indicated by a
series of 4 dashes.
5. Calibrate the pump using the following steps.
Exercise 8 76 10/93
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Exercise 8
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HIGH-FLOW CALIBRATION (1 to 4 liters/min)
6. Insert a filter cassette and tubing between the pump and the tubing attached to the
calibrator.
7. Turn on the pump.
8. Depress the BUBBLE INITIATE BUTTON and hold to initiate 1 bubble up the Flow
Tube. Release the button to initiate a second bubble up the flow tube. At low flow rates,
the button can be depressed and released quickly for a single bubble.
9. After a bubble completes passage up the FLOW TUBE, a flow reading will appear on the
LCD display.
10. Adjust the flow rate (pump adjustment) and repeat Steps 8 and 9 until you have a flow
rate of about 2 litcr/min.
11. RESET the calibrator.
12. Repeat Steps 8 and 9 until you have three consecutive readings that are within 5% of their
average.
13. If the first set of 3 readings are not within the 5% allowable range, press the RESET
Button. Then repeat step 15 for 3 more readings. The Reset Button is used because the
Gilibrator™ averages all readings and not just the last 3. If the first reading was outside
the 5% limits, you wouldn't know till readings 2 and 3 were made. Readings 2, 3, and 4
may be within the limits, but you would not be able to check because reading 1 would
still be in the average.
14. If a bubble breaks before completing the timing sequence, timing will continue until
another bubble is generated to trip the second sensor. This will cause an erroneous
reading and should be subtracted from the average by hitting the Delete Button.
15. Record each run, the average, and other pertinent information on Data Sheet 2
LOW-FLOW CALIBRATION (20-500 cc/min)
16. Connect the pump to the Gilibrator™ with a piece of tubing.
17. Turn on the pump.
18. Using the steps above, adjust the pump to about 1 liter/min.
19. Open the regulator shutoff valve (located under the brass cap on top of the pump) by
turning it counterclockwise at least 5 turns.
Exercise 8 78 10/93
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20. Put a carbon tube in the sorbent tube holder. Connect the inlet side of the holder to the
upper outlet of the calibrator (Figure 2). Connect the outlet side of the holder to the
pump inlet.
21. Depress the Bubble Initiate Button to initiate a bubble up the Flow Tube. After the
bubble completes passage up the Flow Tube, a flow reading will appear on the LCD
display.
22. Remove the knurled cap from the end of the tube holder. Repeat Step 21 and adjust the
variable flow controller screw to get the desired flow rate. For this exercise, try to
obtain about 50 cc/min.
23. RESET the calibrator after each run if not at the desired flowrate. Reset after each flow
adjustment. Do three runs at the desired flow rate. Record your results on Data Sheet 3.
SHUTDOWN
24. Turn off the pump.
25. Turn off the calibrator.
26. Remove the air sampler from the Gilibrator™. Replace the Storage Tubing between the
upper and lower cell chambers.
27. Disconnect the pump from the tube holder.
28. Replace the cap on the tube holder.
10/93 79 Exercise 8
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DATA SHEET 2
1. PUMP MFG. AND MODEL:
PUMP IDENTIFICATION #:
BATTERY CHECK PASS FAIL
2. CALIBRATOR MFG. AND MODEL:
CALIBRATOR IDENTIFICATION #:
3. COLLECTION MEDIA:
4. LOCATION/TEMP & BAROMETRIC PRESSURE:
5. FLOW RATES: (Continue calibration until three consecutive flow rates are within ±5%
of average.)
FLOW RATE AVERAGE FLOW RATE AVERAGE
6. ROTAMETER SETTING:
7. FLOW RATE:
8. SIGNATURE:
9. DATE/TIME:
Exercises 80 10/93
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DATA SHEET 3
1. PUMP MFG. AND MODEL:
PUMP IDENTIFICATION #:
BATTERY CHECK
PASS
FAIL
2. CALIBRATOR MFG. AND MODEL:
CALIBRATOR IDENTIFICATION #:
3. COLLECTION MEDIA:
4. LOCATION/TEMP & BAROMETRIC PRESSURE:
5. FLOW RATES: (Continue calibration until three consecutive flow rates are within ±5%
of average.)
FLOW RATE
AVERAGE
FLOW RATE
AVERAGE
6. FLOW RATE:
7. SIGNATURE:
8. DATE/TIME:
JO/93
81
Exercise 8
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STATION 2: CHECKING GILIAN® PUMP WITH CALIBRATOR PACK
The Gilian* Calibrator Pack has precision rotameters that can be used to calibrate a pump. A t
rotameter is considered a secondary calibration standard since it needs to be calibrated or checked
with a primary calibration method periodically. The pack also has a magnehelic to produce a
pressure drop along the flow of a pump. This, in combination with the rotameters, can be used
to check the constant flow compensator on the Gilian* pump.
In this step, the precision rotameter will be used to check the constant flow compensator.
COMPENSATOR CHECK
1. Remove the Regulator Shutoff Protective Cap on the pump. Turn the exposed screw
clockwise until closed - DO NOT OVERTIGHTEN. Replace the protective cap.
2. On the Calibrator pack, move the BYPASS/CAL switch to the BYPASS position.
3. Move the CAL SELECT (V2) switch to the upward position (3 liters/minute).
4. Connect the pump to the PUMP SUCTION (Bl) outlet on the calibrator pack.
5. Turn on the pump.
6. Adjust (on the pump) the flow rate so that precision rotameter on the calibrator (not the
pump rotameter) reads "3.0" (3 liters/min or 3000 cc/min). The flow rate is read at the
center of the rotameter ball.
7. Move the CAL/BYPASS switch to the CAL position.
8. Turn the V3 knob until the magnehelic dial reads 10 inches of back pressure.
9. Read the flow rate on the rotameter. If the difference in flow rates with and without back
pressure is more than ±5% (i.e., if the flow rate is not between 2850 and 3150), the
pump needs adjustment. Consult the instructor.
10. Move the BYPASS/CAL switch to the BYPASS position.
11. Move the CAL SELECT (V2) switch to the downward position (1 liter/minute).
12. Adjust the flow rate to "1.0" (1 liter/min or 1000 cc/min) - reading the precision
rotameter on the calibrator.
13. Move the BYPASS/CAL switch to the CAL position.
14. Turn the V4 knob until the magnehelic dial reads 20 inches of back pressure.
Exercise 8 82 10/93
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15. Read the flow rate on the rotameter. If the difference in flow rates with and without the
back pressure is more than ±5% (i.e., if the flow rate is not between 950 and 1050), the
pump needs adjustment. Consult the instructor.
SHUTDOWN
16. When completed with the compensator check, turn off the pump and disconnect the pump
from the pack.
10/93 83 Exercise 8
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QUESTIONS AND CALCULATIONS
1. Calculate the concentrations in the sampled atmospheres based on the following
information.
Units: 1000 liter = 1 m3
1000 ml = 1000 cc = 1 liter
1 mg = 1000 micrograms
(A) Lead samples. Pump flow rate = 2.0 liters per minute.
SAMPLE DURATION
4HR
2HR
2HR
LAB ANALYSIS
0.041 mg
0.029 mg
0.008 mg
AVERAGE
CONCENTRATION
To calculate the Average Concentration (for each sample):
m chemical
C
sample volume (m3)
where:
1 m3
sample volume (/»3) = pump flow rate (liters/minute) x sample time (minutes) x
1000 liters
To calculate an 8-hour TWA:
8 hour TWA
8 hours
where T is sample time in hours. Minutes can be used for T if 480 minutes is used
instead of 8 hours in equation.
Exercise 8 84 10/93
-------
(B) Solvent vapor sampling. Flow rate = 50.0 cc/min.
SAMPLE
TIME
1 HR
2 HR
1 HR
15 MIN
15 MIN
15 MIN
30 MIN
15 MIN
30 MIN
2HR
CONCENTRATION (ppm)
TOLUENE
10
32
21
175
140
100
93
85
54
10
XYLENE
5
11
8
70
50
67
40
30
10
NO
ACETONE
ND
ND
100
300
1000
820
1000
50
45
30
Calculate an 8-hour TWA exposure for the three chemicals.
Calculate an 8-hour TWA exposure for the mixture. Is this calculation valid?
10/93
85
Exercise 8
-------
(C) Do any of the concentrations in (A) and (B) exceed an exposure limit?
2, Calibration of a pump prior to sampling gave a flow rate of 2.0 liters/minute. Calibration
after sampling gives a flow rate of 1.8 liters/minute. What do you do?
Exercise 8 86 JO/93
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EXERCISE #9
Field Exercise
OBJECTIVE
Using the instruments and information provided, participants will:
1. Perform a survey of the zones on the "hazardous waste site."
2. Characterize the "hazards" present at each "zone" on the site.
3. Identify as completely as possible the materials present on the site.
4. Quantify the airborne concentrations in each "zone" and evaluate the risk associated with
these concentrations.
PROCEDURE
The class will be divided into teams. Each team will select a leader/spokesperson. Each team will
receive the same equipment. The equipment available is the same equipment used earlier in the
week. Before each entry, the team must submit plan of action for that entry to an instructor.
The "site" simulates a much larger site. It is divided into six zones. A description of each zone is
on the next page. A "map" of the site also follows. Treat the readings obtained with the instruments
taken inside the containers as representing the average airborne concentrations in the "zone."
10/93 87 Exercise 9
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DESCRIPTION OF EXERCISE AREA
ZONE 1:
100 to 200 drums. Some with "FLAMMABLE" labels.
ZONE 2:
About 100 drums. Some with "CORROSIVE" labels.
ZONE 3:
Box trailer containing drums. Records indicate that the following chemicals were in the load. (Note:
This zone can be treated as a transportation incident separate from the site.)
Acetone
Methyl ethyl ketone
Methyl isobutyl ketone
Ethyl alcohol
Butyl alcohol
Toluene
Benzene
Xylenes
1,1,1 -Trichloroethane
Trichloroethylene
Tetrachloroethylene
Readings taken in the drum represent readings at the trailer.
ZONE 4:
About 50 drums with "Waste Cleaner" labels.
ZONE 5:
Opening to underground vault. The vault could contain many drums. Readings inside container are
equivalent to readings taken inside vault (using extended probes).
ZONE 6:
50 to 100 drums. Some with hand-painted labels reading "Paint Waste."
Exercise 9 88 10/93
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89
Exercise 9
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U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
-------
United States
Environmental Protection
Agency
Office of
Solid Waste and
Emergency Response
Publication 9360.B-17FS
August 1993
Personal Air Sampling and
Air Monitoring Requirements
Under 29 CFR 1910.120
Office of Emergency and Remedial Response
Emergency Response Division MS-101
Quick Reference Fact Sheet
Background and Purpose
Under the authority of Section 126
of the Superfund Amendments and
Reauthorization Act of 1986
(SARA Title I), the U.S. Environ-
mental Proteciion Agency (EPA)
and the U.S. Occupational Safety
and Health Administration
(OSHA) issued identical health and safety standards to
protect workers engaged in hazardous waste operations
and emergency response. The OSHA regulations,
codified at 29 CFR 1910.120, became effective on
March 6, 1990 (54 FR 9294). On April 13, 1990,
corrections to these regulations were published (55 FR
14072) to clarify certain medical surveillance
requirements and to identify which employers must
comply with 29 CFR 19l0.120(p). The EPA
regulations, published on June 23, 1989, at 54 FR
26654, incorporate the OSHA standards by reference
and are codified ai 40 CFR Part 311.
Although the two sets of standards contain
identical substantive provisions, the EPA and OSHA
standards address different audiences. In states that do
no_i have an OSHA-approved program, federal OSHA
standards protect all private and federal employees
engaged in hazardous waste operations and emergency
response; EPA worker protection standards protect all
state and local government employees. In states that
do have an OSHA-approved program, the state
program covers all private, state, and local government
employees; OSHA covers federal employees. The
OSWER Fact Sheet, Hazardous Waste Operations and
Emergency Response (HAZWOPER): Uncontrolled
Hazardous Waste Sites and RCRA Corrective Action
(OSWER Publication 9285.2-08FS, 1991), provides a
general overview of the worker protection standards as
they apply to operations conducted at uncontrolled
hazardous waste sites.
OSHA requirements for monitoring at uncon-
trolled hazardous waste sites are codified at 29 CFR
1910.120(h). While the provisions outlined in this
section may be interpreted to include the collection c
samples (i.e., surface wipes in the support area on
lead-contaminated site), the purpose of this Fact Shee
is to summarize the HAZWOPER air monitoring am
sampling aspects of these requirements. The Fac
Sheet is composed of five parts: (1) Introduction K
Air Monitoring and Air Sampling; (2) Air Monitoring
Requirements Upon Initial Entry; (3) Air Monitoring
Requirements After Initial Entry; (4) Conducting Air
Monitoring and Sampling; and (5) Information Sources
and Contacts.
Introduction to Air Monitoring and Air
Sampling
The presence of hazardous mater-
ials at a site, as well as actions
taken to address these materials,
can result in the release of hazar-
dous substances into the air.
Chemical fires, transportation
accidents, open or leaking con-
tainers, wind-blown dust, and site
cleanup activities all produce
emissions that can rapidly affect
the health and safety of response
personnel (site workers or
emergency response) and the public. Hazardous
atmospheres may be:
• Explosive (characterized by the presence of
ignitable or explosive vapors, gases, aerosols, and
dusts);
• Toxic/hazardous (characterized by the presence
of vapors, gases, particulars, and aerosols);
Oxygen-deficient (characterized by the
consumption or displacement of oxygen in
ambient air); or
• Radioactive (Characterized by the presence of
radioactive materials).
Recycled/Recyclable
Printed with Soy/duiola Ink on pecwr fhai
contains at toast 50* racyctod Itow
-------
The presence of one or more of these hazards is an
important factor in determining subsequent actions
that should be taken to protect workers, the
community, and the environment. Their presence may
dictate operations that arc necessary to mitigate the
likelihood of an incident, and will dictate safety
considerations for response personnel.
OSHA requirements for air monitoring are set
forth in the HAZWOPER standards at 29 CFR
1910.120(h). Specifically, §1910.120(h)(l)(i) states thai
monitoring must be performed "where there may be a
question of employee exposure to hazardous
concentrations of hazardous substances in order to
assure proper selection of engineering controls, work
practices and personal protective equipment [PPEj so
that employees are not exposed to levels which exceed
permissible exposure limits fPELs], or other published
exposure levels...." The regulations also require air
monitoring for use in identifying health hazards in
order to determine appropriate level of PPE. Once the
appropriate PPE is selected, personal air sampling
should be continued in order to ensure that personnel
exposures are not exceeding these limitations.
«3P NOTE: OSHA does not define the term
"air monitoring." Rather, OSHA uses this term
to refer 10 both monitoring using direct reading
instrumentation and to air sampling using
personal sampling pumps or. other quantitative
methods. However, in this Fact Sheet, the term
"air monitoring" refers to the use of direct
reading instruments producing instantaneous
data, while the term "air sampling" refers to the
use of a sampling pump and collection media
that produce samples thai must be sent to a
laboratory for analysis. The specific distinctive
features of each are:
Air monitoring:
• Provides "real-time" ijesults; , ,
• Provides rapid response;
Has limited detection levels; and-
May not- detect certain classes of
compounds.
Air sampling:
Can be compound- or ciass-sp^cifit-;
Provides greater accuracy of detection;
Requires more time for results; and
Requires additional pumps, medw*
analytical support.
One example of the difference between air moni-
toring and air sampling is thai air monitoring can be
performed to identify the exisiencc of a hazardous
atmosphere during initial site entry, while air sampling
is performed to identify and quantify an employee's
personal exposure to a hazardous chemical or range of
hazardous chemicals. Further, air monitoring data arc
instantaneous and are useful in comparing conservative
action guidelines to determine an appropnale level of
protection relative to the work activity Air sampling
data are information used to compare an employee's
exposure to OSHA 1971 time-weighted average PELs
(PEL-TWA), PEL-ceilmg (PEL-C), the American
Conference of Governmental Industrial Hygiemsts
time-weighted average Threshold Limit Values
(TLV-TWA), and associated values (STEL.C).
In addition to the requirements at 29 CFR
]910.120(h), OSHA mandates air sampling for specific
chemical contaminants under 29 CFR 1910.] 000, which
lists approximately 428 substances in Tables Z-l-A,
Z-2, and Z-3. OSHA also has comprehensive health
standards that have additional PELs and other
requirements (see Highlight I). Consult individual
standards for specifics.
«S" NOTE: The U.S. Court of Appeals. Eleventh
Circuit, issued a decision on July 7, 1992, vacating the
"Final Rule" of the Air Contaminants Standard. A
decision was made on March 22, 1993, not to appeal
to the Supreme Court, and the Eleventh Circuit
Court's decision stands. Employers and Employees
can find the 1971 permissible exposure limits thai are
now in effect listed in the Air Comaminams Standard,
in the columns headed "Transitional Limits" in Table
Z-l-A and in Tables Z-2 and Z-3 in 29 CFR
1910.1000 (1989 or later).
Air, Monitoring Requirements Upon InitiaJ
Entry
During the initial "Site entry, •
information is gathered to evaluate
site-specific risks and hazards. This •
information is used to select and
develop site-specific engineering/
administrative- controls, PRE, '
medical monitoring, and air
sampling requirements. Highlight 2 identifies some'of •
the contaminant and hazard risks that may 'be
encountered during initial site entry. , . •
-------
Highlight 1
SUBPART Z, TOXIC AND HAZARDOUS
SUBSTANCES
29 CFR 1910.1001
29 CFR 1910.1002
29 CFR 1910.1003
29 CFR 19)0.1004
29 CFR 1910.1006
29 CFR 1910.1007
29 CFR
29 CFR
29 CFR
29 CFR
29 CFR
29 CFR
29 CFR
29 CFR.
29 CFR
29 CFR
29 CFR
29 CFR
29 CFR
29 CFR
29 CFR
29 CFR
29 CFR
29 CFR
29 CFR
29 CFR
29 CFR
1910 1008
1910.1009
1910 1010
1910 1011
1910.1012
19)0.1013
1910.1014
1910.1015
1910.1016
1910.1017
1910.1018
1910.1025
1910.1027
1910.102S
1910.1029
1910.1043
1910.1044
1910.1045
1910.1047
1910.1048
1910.1101
Asbestos, tremolne,
anthophyllne, and actmoliie
Coal tar pitch volatiles
(interpretation of term)
4-Nitrobipheriyl
alpha-Naphtnylamine
Methyl chloromethyl ether
3,3'-Dichlorobenzidme (and
its salts)
bis-Chloromethy! ether
beta-Naphthylarnine
Benzidme
4-Ammodiphenyl
Ethyleneimme
beta-Propiolactone
2-Acetylaminafluorene
4-Dimethylaminoazobenzene
N-Nitrosodimethylamine
Vinyl chloride
Inorganic arsenic
Lead
Cadmium
Benzene
Coke oven emissions
Cotton dust
1,2-dibromo-3-chioropropane
Acrylonitnle
Ethylene oxide
Formaldehyde
Asbestos (Applies in lieu of
revised standards governing
occupational exposure to
asbestos, tremohte,
anthophyllne, and actmolite)
Air monitoring techniques are used to assess the
risks that may be present during initial site entry. As
specified at 29 CFR I910.120(h)(2), air monitoring
mtetfte fifa&ietetf Iftfing* Winhia'Psite'' e"mW' to^
identify: -
. conditions; . •' .- .» ,'7I_r '~
!- •• - -r •" 1 '.: "~.t
-rSxposwre over permissible exposure /limit*.- -or
exposure, levels;- *
/..Exposure, over.radioaciive marerials
• ;,;EjXposure to other 'idangerousi conditions (fe;g. --
^presence of na.mmable' atmospheres o* -oxygtn- '
deficient environrnenis). . , ,! : •
Highlight 2
CONTAMINANT AND HAZARD RISKS DURING
INITIAL SITE ENTRY
• Exposure exceeding the OSHA PELs or other
published exposure levels:
• Exposure to immediately dangerous to life and
health (JDLH) concentrations,
• Exposure through skin absorption and irritation
(chemical or biological),
• Eye irritation;
• Explosions resulting from shock-sensitive
substances and flammable atmospheres-
• Confined space-entry,
• Injury from physical hazards, and
Exposure to radioactive (ionizing radiation)
materials,
I3r NOTE: While required in 29 CFR 1910.120
(h)(2), monitoring for radioactive materials under
initial entry conditions is not an "air" monitoring
technique. If the main concern is to identify
exposure over radioactive material dose limns, the
contaminant of interesi is gammy radiation. Gamma
radiation is not air-matrix dependent.
Air sampling is not usually performed during the
initial entry. Instead, information about the potential
chemical hazards is gathered during the initial entry
and used to make decisions about air sampling needs.
For any contaminants discovered during the initial
entry that are regulated by 29 CFR 1910.1000 or
Subpart Z (see Highlight 1) or that could be
considered hazardous, the air sampling needs must be
assessed according i-cr-She requirements.
.-"c ( **'
Air Monitoring Requirements After Initial
Entry - Periodic Monitoring
Site conditions and atmospheric
chemical conditions may change
^.following .the " initial site
"characterization.' f/vs stated at 29
CF& 1910.'l'2\)(;V)(3), periodic
monitoring mustT (he conducted
when "the pps,sibiUi/,af an IDLH
con-dition or flammable atmosphere has developed or
wh$n there is yidicay^n th^j exposuresHRiajfebavfoiEiseB-
over permissible exposure limits or published exposure
- 3 •
-------
levels since prior monitoring." Highlight 3 identifies
situations that call for periodic monitoring required at
29 CFR 1910.120(h)(3)(i-iv).
Highlight 3
SITUATIONS THAT REQUIRE
PERIODIC MONITORING
When work begins on a different portion of the
site;
When contaminants other than those previously
identified are being handled,
When a different type of operation is initiated
(e.g., drum opening as opposed to exploratory
well drilling); or
When employees are handling leaking drums or
containers, or working in areas with obvious
liquid contamination (e.g., a spill or a lagoon).
Once cleanup activities begin on-site, 29 CFR
19J0.120(h)(4) requires employers to "monitor those
employees likely to have the highest exposures to
hazardous substances and health hazards likely to be
present above permissible exposure limits or published
exposure levels by using personal sampling frequently
enough to characterize employee exposures." Air
sampling for high-risk employees is performed to
identify the "worst-case exposure." If the worst-case
exposure is above the PEL, then monitoring should be
conducted to identify all employees likely to be above
those limits. (Note: It is not required to monitor
employees engaged in site characterization operations
covered under 29 CFR 1910.120(c). Appropriate PPE
based upon the preliminary evaluation is required.)
Post-initial entry situations that require periodic
monitoring also should be characierized by air
sampling, as appropriate, and should be determined by
a competent health and safety professional. Air
sampling information can be compared to the air
monitoring data for the same period of time to: (1)
illustrate trends in the accuracy of the air monitoring
data; (2) develop a correlation to the air monitoring
readings; and (3) develop better air monitoring action
guidelines. Air monitoring data may also be used to
determine when further sampling is needed (i.e., if site
conditions have changed).
Personal .sampling generally is not used to
characterize overall sue air quality. However, air
sampling conducted in areas of high concentration may
assist in determining whether personal sampling is
necessan Air sampling may also assist On-Scenc
Coordinators (OSCs), Remedial Project Managers
(RPMs), or other site managers in determining whether
chemical contaminants covered under 29 CFR
1930.1000, Subpart Z, need to be monitored.
An air sampling strategy outlined in the
site-specific health and safety plan must address
frequency and type of air monitoring, personal
monitoring, and environmental sampling (29 CFR
1910.120(b)(4)(ii)(E)). Highlight 4 identifies additional
information that should be provided in area and
personnel air sampling strategies.
Highlight 4
EXAMPLES OF ELEMENTS TO INCLUDE IN
AN AREA AIR SAMPLING STRATEGY
The locations where air sampling will be
performed;
The hazardous substances that will be sampled
during the task;
The duration of the sample;
The equipment that will be used to sample for
the different hazardous substances; and
Collection of meteorological data.
EXAMPLES OF ELEMENTS TO INCLUDE IN
A PERSONNEL AIR SAMPLING STRATEGY
Employee sampled;
Tasks performed,
Duration;
Hazardous substances; and
Equipment to be used.
4 •
-------
Conducting Air Monitoring
Table ] at the end of this Faci
Sheet, "Summary of Direct-
Reading Air Monitoring Instru-
ments," lists the direct-reading
instruments (DRIs) used during air
monitoring to characterize
hazardous atmospheres. DRIs may
he used to rapidly detect flammable or explosive
atmospheres, oxygen deficiency, certain gases and
vapors, and ionizing radiation. DRIs are the primary
tools of initial site characterization The information
provided by DRIs can be used to: select appropriate
protective measures such as personal protective
equipment, evacuation, and other similar measures;
determine the most appropriate equipment for further
monitoring; and assist in developing optimum sampling
and analytical protocols.
DRIs have limitations. For example, the Flame
ionization Detector (FID) and Photoionization
Detector (PID) are commonly used at hazardous waste
sites to monitor for a broad range of organics and
some inorganics. However, they do not detect some
particularly toxic agents such as hydrogen cyanide and
hydrogen sulfide. Thus, these devices must be
supplemented with other methods of detection (e.g.,
electrochemical sensors or colorometric indicator
tubes). Many DRIs designed to detect one particular
substance may also detect other (cross sensitive)
substances, thus rendering a "false positive." All DRI
information should be interpreted with a certain degree
of caution.
To characterize personal exposure, air monitoring
should be performed in the breathing zone of the
individual. Emission sources may be characterized
through head-space monitoring (e.g. drums) or close-
range monitoring, if this can be done safely. Emission
source measurements are not representative of
personal exposure.
1
ca
an
pe
B
CO
Ca
Air monitoring
brated on a daily
„
instruments should be field-
basis prior to the initial entry
I/or any field activity. Calibration must be
formed according
10 manuf^cturer'S'-.instructions.
Id calibration should take place in field atmospheric
ditions in a "clean"
irjraTion8<*rnust be'
a/^?w«l£& as tne c°JBPiancU?'fifiI-
documented, either in a site
logbook, or a logbook designated for instrument
calibration records as required in the site safety plan
(29 CFR 19l0.120(b)(4)(ii)(E)).
Air monitoring data should be documented in the
individual's field or the site logbook. Observations
pertaining to the monitoring data (i.e., weather
conditions, drum label information, activity performed
during monitoring, number/names of individuals bei
monitored, etc.) should be recorded with t,
monitoring data.
Conducting Air Sampling
Table 2 at the end of this Fat
Sheet, "Common Air Samplmj
Methods and Media Used by tht
EPA/ERT," summarizes some
sampling methods commonly used
on hazardous waste sues. Personal
air sampling is generally performed
using a personal sampling pump capable of both low-
flow (20-750 cc/min) and high-flow (1-4 L/min)
operation. Low-flow operation with various media-
packed tubes is used to sample volatile organic
materials and acid gas mists. High-flow operation with
various filter media or bubbler/impinger solutions is
generally used to sample panicles, paniculate aerosols,
and inorganic gases. Personal air sampling is
performed for the duration of the workshifi.
Employees with the highest exposure potential wear
the sampling pumps with the sample media positioned
on their shoulders and the inlet of the filter or tube
facing down toward the chest. (Applying protective
"covers" often eases'decontamination of the pumps.)
Personal air sampling results are generally compared to
the 8-hour PEL-TWA.
Sampling for comparison to the PEL-Short-Term
Exposure (PEL-STEL) will require collecting a
15-minute sample at higher flow rates. PEL-STEL and
PEL-C sampling may be run throughout the workshift
alongside the PEL-TWA sampling. PEL-STEL and
PEL-C sampling may be performed once every hour
throughout the workshift, at the times of highest
potential exposure. Judgment should be used when
identifying times of highest potential exposure and
performing a PEL-STEL and/or PEL-C sampling event
simultaneously during this high-risk exposure period.
There are a number'of references that list standard
methods for performing personal air sampling. OSHA
and the National Institute for Occupational Safety and
Health (NIOSH) publish two "sets of the most widely
used personal air sampling methods. Both NIOSH and
OSHA methods are "recipe's""for.performing both air
sampling and "chemical analysis. The methods outline
the sampling device, collection meaia, and flow rate at
which to set the sampling device. OSHA and NIOSH
usually include in the methods any interferences that
may bias the sampling. The EPA/Environmental
Response Team (EPA/ERT) has developed standard
sampling methods that incorporate existing NIOSH and
OSHA methods. The "Information Sources" section of
5 --
-------
this Fact Sheet identifies sources to obtain more
information on these methods.
Before a sampling method is chosen, the laboratory
should be contacted to determine whether ji can
perform the desired analysis. The EPA/ERT
recommends using laboratories accredited by the
American Industrial Hygiene Association (AIHA) for
performing analysis on personal air samples. A list of
AJHA-accredited laboratories may be obtained by
contacting the AIHA (see the "Contacts" section of this
Fact Sheet for AIHA's address and phone number).
As with DRIs, sampling pumps must be calibrated
prior to use. The goal of calibrating the personal
sampling pump is to set, and ensure that the pump can
maintain, a known flow rate. Calibration requires a
pump, a sampling train (including the sample media
and all connecting tubing), and a primary standard-flow
indicator, such as a bubble meter (Buck calibrator/
Gillibrator), or an inverted buret with bubble mixture.
A secondary standard flow indicator, such as a
rotameter, may be used to calibrate the pump as long
as the secondary standard has been previously
calibrated to a primary standard. Highlight 5 illustrates
several different methods of calibration.
Highlight 5
EXAMPLES OF CALIBRATION METHODS
Calibrating a Rotametef with a
Bubble Meter
Sampttng
Pump
Calibrating a Personal Sampling
Pump with a Bubble Meter
Calibrating a Personal Sampling
Pump with a Rotameter
•CD
* •*
• • •
°l
D1
Pump
1-UMr
Bur*}
Calibration Apparatus
TUWng
WMV
S<**on
• NOM: uMd tor Sttndwri TwmM^ir*
Sourta: U**u* rt Amtyteal »«nodi (Volum> 1.3rd EdMon)
(NOSH, 1M4, PU> NO. 64-100)
-------
Highlight 6
EXAMPLES OF PERTINENT INFORMATION
FOR AIR SAMPLING DOCUMENTATION
Name of employee sampled
Task performed during sampling period
Suspected hazardous substances.
Level of PPL
Type of collection media.
Flow rate of the calibrated pump (pre- and
post-sampling event),
Duration of the sample;
Date of sampling event,
Location of sampling event,
Environmental conditions during sampling event
(e.g., temperature, Rh, wind speed, etc.);
Unique sample number,
Volume of air sampled during event;
Any special handling requirements; and
Analytical holding times
Documentation of all aspects of the sam
monitoring event is critical for hoth air momionn
air sampling. Documentation provides informane
data interpretation and, in the case of air sample.
tracking the sample from the sample taker to
laboratory. Ajr sampling documentation is i
formalized than documentation for air moniio
Highlight 6 identifies pertinent information thai i
he documented for air sampling.
If sampling media (tubes or filters) are chan
throughout the da\ to prevent overloading, sarr
duration for that media must he noted Judgment IT
be used in deciding how to document such a sampl
event. Each tube/filter may be designated a unu
number and treated as a single sample, or each tu
filter may be designated the sample number wiir
different consecutive letter of the alphabet attacln
The tubes or filters are unique, but together iri
represent one complete workshilt sample. Setting
and performing personal air sampling genera
requires more preparation time than air momtonn
however, in both cases, the correct instrument <
sampling tram must be chosen, the instrument c
sampling train must be calibrated, and the momionn
or sampling event must be observed.
-------
TABLE 1
SUMMARY OF DIRECT-READING AIR MONITORING INSTRUMENTS
Principle of
Detection
and Monitoring
Need
Instrument
Features
Limitation!.
Wheatsione
Bridge Filament
Monitoring
Need:
Combustible
Gas
Combustible
Gas.
Indicator
* Calibrated to pentane, hexane. or methane
* Nonspecific deiecior (or combustible gasej,
measures gas concentrations as a percentage of
lower explosive limit (LEL)
* Lighlweighi, portable, and easy to use
4 Visual and audible alarms
(some models)
4 Probe provides remote sensing capabilities
4 8- to 12-hour batlery operating life (or roost
models
* Accuracy vanes depending upon the model,
accuracies of t 2 lo 3 percent are attainable*
* Potential interference* or filament damage from
leaded gasoline, silicones and silicates, which
are more strongly adsorbed on catalyst than
oxygen or gas in question Membranes are
available to minimize these eftects
* Most models do not measure specific gases
* May not function properly in oxygen-deficient
atmospheres (< 10 percent)
Chemical Cell
Monitoring
Need.
Oxygen
Deficiency
Oxygen
Meter
* Direct readout in percent oxygen
4 Visual and audible alarms
4 Lightweight, portable, and easy to use
4 Probe provides remote sensing capabilities
* Accuracies of i 1 percent are attainable, but
depend on the particular model
4 Generally 8- to 10-hour battery life
4 High humidity may cause interference
4 Strong oxidanls may cause artificially high
readout
4 Oxygen calibrations are dependent on altitude
and barometric pressure
4 CO2 "poisons" detector cell
Chemical Sensor
Wheatstone
Bridge Filament
Moniiomg
Need:
Combustible
Gas/Oxygen
Deficiency
Combination
Oxygen
Meter and
Combustible
Gas
Indicator
4 Calibrated to pentane, hexane, or methane
4 Measure percent oxygen and gas concentration as
a percentage of LEL
4 Both visual and audible alarms (some models)
4 Remote sensing capabilities
4 Lightweight, portable, and easy lo use
4 Accuracies of i 2 percent are attainable'
4 Same limitation as oxygen meters and
combustible gas detectors
4 In certain units, acid gases and high CO,
concentrations shorten the life of oxygen
sensor/cells
4 Certain units require a conversion factor for
true specific compound response readings
4 In certain units, oxygen calibration is altitude
dependent
Optical, Electrical,
Piezoelectric
Monitoring
Need.
Aerosol/
Particulate
Aerosol/
Paniculate
Monitor
4 Selectable ranges
4 Panicle size differentiation available
4 Certain units have data logging capabilities
4 Factory recalibration required on certain units
4 Values represent total paniculalcs: dust. mist.
aerosols are all inclusive with no differentiation
4 Cold weather may have adverse effect on
detector
4 High humidity and precipitation negatively
affect meter response
Manufacturer specifications. Actual field use may yield greater variations.
8
-------
TABLE 1 (CONTD)
SUMMARY OF DIRECT-READING AIR MONITORING INSTRUMENTS
Principle of
Detection
and Monitoring
Need
instrument
Features
Limitations
Phoioiontzation
Ultraviolet Light
Monitoring
Need
Toxic Gas/
Vapors
Photo-
lonization
Detector
(FID)"
4 Nonspecific gas and vapor detection for orgamcs
and some inorganics
4 Noi recommended for permanent pase.-.
4 Lightweight (4 to 9 Ibs) and portable
4 Sensitive to 0.1 ppm benzene Sensitivity is
related to lonization potential of compound
4 Remote sensing capabilities
4 Response time of 90 percent in less than 3
seconds
4 More sensitive to aromatics and unsaturated
compounds that the (lame iontzation detector
(FID)
4 8-hour battery operating life; certain units with
external interchangeable battery packs
4 Audible alarm is available
4 Certain units have data logging/computer interface
capabilities
4 Certain units available with calibration libraries
4 Certain units available with interchangeable lamps
4 Does not monitor for specific gases or vapon-
4 Cannot detect hydrogen cyanide or methane
4 Cannot detect some chlorinated orgamcs
4 High humidity and precipitation negatively
affect meter response
4 Readings relative to calibration standard
Hydrogen Flame
ionization
Monitoring
Need:
Toxic Gas/
Vapors
Flame
lonization
Detector
(FID)
4 In the survey mode, it functions as a nonspecific
total hydrocarbon analyzer, in the gas
chromalograph mode, it provides tentative
qualitative/quantitative identification (OVA-
specific)
4 Mosi sensitive to saturated hydrocarbons, alkanes,
and unsaturated hydrocarbon alkanes
4 Lightweight (12 Ibs) and portable
4 Remote sensing probe is available
4 Response time is 90 percent in
2 seconds
4 8-hour battery operating life
4 Sounds audible alarm when predetermined levels
are exceeded
4 Not suitable for inorganic gases (e.g , Ci,, HCN,
NH3)
4 Less sensitive to aromatics and unsaturated
compounds than PID
4 Requires skilled technicians to operate the
equipment m the GC mode and to analyze the
results (OVA-specific)
4 Requires changes of columns and gas supply
when operated in the GC (gas chromatography)
mode in certain units (OVA-specific)
4 Because specific chemical standards and
calibration columns are needed, the operator
must have some idea of the identification of the
gas/vapor (OVA-specific)
4 Substances that contain substituted functional
groups (e.g., hydroxide (OH-) or (CI-) chloride
groups) reduce the detector's sensitivity
'UV sources vary in strength among available units (10.2cv, I0.6ev, 11.7ev). Each source has a range of compounds it cannot detect based upon
ionizaiion potentials. See manufacturer's literature for specifics.
-------
TABLE 1 (CONPD)
SUMMARY OF DIRECT-READING AIR MONITORING INSTRUMENTS
Principle of
Detection
and Monitoring
Need
Instrument
Feature.*.
Limitations
infrared Radiation
Monnonrig
Need
Toxic Gas/
Vapors
Infrared
Analvzer
Overcomes the limns of mosi infrared
analyzers by use of a variable filler, can be used to
scan through a portion of the spectrum lo
measure concentration of several gases or can he
set at a particular wavelength to measure a
specific fas
Detects both organic and inorganic gases
Portable but not as lightweight
(32 Ibs ) as the PIDs or FIDs
Less portable than other methods of ga
detection
4 Requires skilled technicians to operate and •
analyze results when positive identification i'
needed
* Interference by water vapor and carbon dioxide
4 Most require AC power source
* Positive identification requires comparison of
spectrum from stnp chart recorder with
published adsorption spectrum, infrared
spectrum not available for all compounds
4 Intrinsic safety is unit dependent, set ' :
manufacturer's literature
Chemical
Reaction
Producing a Color
Change
Monitoring
Need
Toxic Gas./
Vapors
Indicator
Tubes
4 Quantitative accuracies are variable
4 Simple to use, and relatively inexpensive
4 Real ume/semi-real lime results
4 Low accuracy .:•
4 Subject to leakage during pumping
4 Requires previous knowledge of gases/vaporS'm
order lo select the appropriate detector tube
4 Some chemicals interfere with color reaction lo
read false positive
4 Temperature and humidity may affect readings
Electrochemical
Cell
Monitoring
Need:
Toxic Gas/
Vapors
Specific
Atmospheres
Toxic
Atmosphere
Monitor
4 Ease of operation
4 Small, compact, lightweight
4 Audible alarm upon exceeding pre-set action level
or Threshold Limit Value (TLV)
4 Certain units have digital readout
4 Generally compound-specific
4 Certain units interface with data logger
4 Cross sensitivity ,
4 Slow response/recover,' after exposure to high
contamination levels
4 Limited number of chemicals detected
Metal-Oxide
Semiconductor
Monitoring
Need:
Toxic Gas/
Vapors
Toxic
Atmosphere
Monitor
4 Ease of operation
4 Small, compact, lightweight
4 Audible alarm upon exceeding present action level
or TLV
4 Certain umis have digital readout
4 Certain units interface with data logger
4 Nonspecific gas and vapor detection [or some
organics and inorganics
4 Cross sensitivity
4 Slow response/recovery after exposure 10 high
contamination levels
- 10
-------
TABLE 1 (CONTD)
SUMMARY OF DIRECT-READING AIR MONITORING INSTRUMENTS
Principle of
Detection
and Jvlomlonng
Need
Instrument
Features
Limitations
Scintillation
Detector
Moniiormg
Need-
Radiation
Radiation
Meters
* Measures radiation in R/tir or fractions thereof
(gamma)
(battery operated)
* Probe provides remote sensing capabilities
* Accuracy and sensitivity vanes considerably with
manufacturer and type of meter
* A variety of meters are available. Some measure
total ionizing radiation; others are specific for
gamma, alpha, or a combination of two or more
types
Some meters do not determine type of radiation
NOTE: Initial entry surveys should focus on the
presence of gamma radiation If alpha or
beta are suspected, consult your health
physicist.
Gold Film Sensor
Monitoring
Need-
Mercury
Vapor,,
Mercury
Vapor
Analyzer
4 Compound specific; has survey and sample modes
4 0.001 mg/nr1 detection limit
* Provides sensor saturation readout; saturated
sensor cleaning capabilities
4 Can be used with dosimeters for on-site dosimctry
4 Microprocessor serves reading; automatically re-
zeros
4 Certain units have data logging capabilities
4 5-hour batterv life
* Requires yearly factory recahbration
* Short batiery life
* Requires AC power for Heat Cleaning Cycle
Sources: Mathamel, 1981; Spittler, 1980; McEnery, 1982; National Mine Service Company, 1980; Gas-Tech, 1980; Enmet Corporation,
1979; Foxboro Analytical, 1982; HNU Systems, 1982, 1991; Photovac International, Inc., 1989; Jerome, 1990; MIE, 1990.
11
-------
TABLE 2
COMMON AIR SAMPLING METHODS AND MEDIA USED BY EPA/EKT'
CONTAMINANT
i Hydrocarbons.
BP 36-126 Deg C
| Aromatic
Halogenaied
Inorganic Acids
Alcohols
Acetic Acid
Acetaldehyde
Aliphatic Amines
Aromalic Amines
Volatile Organic
Compounds
Volatile Organic
Compounds
Polynuclear Aromatic
Hydrocarbons (PAH)
PAH
Pesticide/PCBs
Dioxin-
Meials
Formaldehyde
Formaldehyde
AIR SAMPLING
METHODS
NIOSH 1500
NIOSH 1501
NIOSH 100?
NIOSH 7903
NIOSH 1402
NIOSH 1603
NiOSH 2538
NIOSH 2010
NIOSH 2002
EPA TO1 and TO2
EPA TO 14
NIOSH 5515
NIOSH 5506
Lewis and McCleod,
Modified v
EPA TO4
EPA TO9
NIOSH 7300
NIOSH 3500
NIOSH 2541
FLOW RATE
1 L/m
1 L/m
1 L/m
1 L/m
0.5 L/m
1 L/m
1 L/m
1 L/m
1 L/m
20 cc/m
Grab 10-50 cc/m
2.5 L/m or 5 L/m
260 L/m
- 3.5 L/m
260 L/m
3 L/m
1 L/m
0.] L/m
COLLECTION MEDIA
Charcoal
Silica Gel
Charcoal
Charcoal
2-Hydroxymelhyl (2-HMP)
Pipendmc on XAD-2 Resin
Silica Gel
Silica Gel
Tenax/Carbon Molecular Sieve
(CMS)
Summa Canister
Summa Canister with Critical
Onficc
XAD-2 Resin Tube with 37 mm
2 um TeflonR Filter with
Polytetranuoroethylene (PTFE) O-
Rmg Support
2" x 1" Polyurethane Foam (PUP;
with 50 grams XAD Resin
2" x 3" PUF wuh Glass Fiber Filter
2" x 3" PUF and Glass Fiber Filter
0.8 um Mixed Cellulose Ester
Filler (MCEF)
1 um PTFE Filler and 2 Impingers.,
Each wuh 20 ml of 1 percent
Sodium Bisulfite Solution
10 percent 2-HMP on XAD-2
Resin
SAMPLE
DURATION
(HOURS) _..
2-8
2-8
2-8
2-8
2-8
8
if :-•
1-2
Grab. 4-12
2-R . •.,.,
8-12 ' - '
2-8
72 .., ".
2-8 " J
2-8
(\i-~,t
4-8 • .., :
1 This table is to be considered a guideline only NIOSH methods were developed for indoor industrial use. Most NIOSH me,t!)od.s cited Jiere
have modified flow rates for use m outdoor ambient conditions Sample duration should reflect extent of work shifi when iised in personaf,
monitoring. If area sampling is being conducted for sue characterization, sample durations may need to be modified 10 achieve desired
detection Iimils
• For dioxin, method is for area sampling only
Nole: OSHA analytical methods should also be evaluated for appropriate, applicable use Most are available on OSHA's Camp\A-efize& •?'_'.'-
Information System (OC1S)
12
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, ' ' n\
Information Sources
Federal Regulations
The OSHA HAZWOPER regulations are codified at 29 CFR 1910.120 (54 FR 9294 and 55 FR 14072). Subpan
Z, Toxic and Hazardous Substances, can be found at 29 CFR 1910.1000.
The EPA HAZWOPER regulations are codified at 40 CFR 311 (54 FR 26654).
Computer Software
Air Methods Database (EPA/Environmental Response Team, Edison, NJ).
',. Available on the Cleanup Information electronic bulletin board (CLU-IN), formerly OSWER BBS. For
further information, call (301) 589-8366. Communications: No Parity, 8 Databits, I Stopbit, F Duplex.
I
EPA Heaith and Safety Planner: Software and User's Guide (EPA, OSWER Publication 9285.8-01, 1990).
Fact Sheets
Hazardous Waste Operations and Emergency Response: General Information and Comparison (EPA, OSWER
PuWieation 9285.2-09FS, 1991).
; Explains the scope and purpose of the HAZWOPER standards, and distinguishes the SARA Title 1 standards
', __from regulations and consensus standards covering the same or similar subject matter.
Hazardous Waste Operations and Emergency Response: Uncontrolled Hazardous Waste Sites and RCRA
Corrective Action (EPA, OSWER Publication 9285.2-08FS, 1991).
i
__Explains the principle HAZWOPER requirements as they apply to employees engaged in hazardous waste
operations and emergency response at uncontrolled hazardous waste sites, including employees who perform
> corrective actions at RCRA TSD facilities. _ ,
I '- -
Hazardous Waste Operations and Emergency Response: RCRA TSD and Emergency Response Without Regard
to_Location (EPA, OSWER Publication 9285.2-07FS, 1991). ____
^Describes the HAZWOPER planning, training, and medical-surveillance -requirements as they apply to
emergency responders regardless of location, and employees who perform routine hazardous waste operations
at RCRA TSD facilities. ______
i
Establishing Work Zones at Uncontrolled Hazardous Waste Sites (EPA, OSWER Publication 9285.2-06FS,
1&91).
Defines the different work zones usually found at a hazardous waste site (i.e., Exclusion, Contamination
_Rjeductipn, and Support) and. provides, information on selecting and maintaining-w&cfc-zones.
Hazardous Waste Operations and Emergency Response: Available Guidance (EPA, OSWER Publication 9285.2-
' '
Provides a list and description of computer software, fact sheets, guidance documents, and ERT training
programs that pertain to the worker protection standards.
General Hearth and Safety Guidance Documents
Standard Operating Safety Guides (EPA, OSWER Publication 9285.1-03, 1992).
Provide guidelines for use by any organization in developing specific operation safety procedures. These
Guides should be adapted to address the safety criteria required for protection of response personnel from
the hazards created by a specific operation or incident.
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Standard Operating Procedures for Air Sampling and Monitoring at Emergency Responses (EPA, OSWER
Publication 9285.2-03A, draft).
Describes the types and methods of air surveillance, procedures and equipment for air monitoring, and'a-t.. »IC
method for analyzing organic solvents by gas chromatography.
Standard Operating Procedures for Site Safety Planning (EPA, OSWER Publication 9285.2-05, being updated).
Describes the general requirements for a site safety plan, discusses development and implementation of a site
safety plan, and provides sample plans and a checklist.
Occupational Safety and Health Guidance Manual for Hazardous Waste Site Activities (N1OSH/OSHA/
USCG/EPA, N1OSH Publication 85-115, GPO No. 017-033-00419-6, 1985).
Draft International Document on Guide to Portable Instruments for Assessing Airborne Pollutants Arising from
Hazardous Wastes (U.S. .National Working Group (NWG-4 OIML) Pilot Secretariat PS-17: "Measuremeni of
Pollution." Reporting Secretariat RS-5: "Measuremeni of Hazardous Waste Pollution." ISBN: 0-936712-75-9).
Provides guidance for using portable instruments to assess airborne pollutants arising from hazardous waste.
Procedures for Conducting Air Pathway Analyses for Superfund Applications addresses a variety of issues
relevant to the air impacts at Superfund siies in four volumes entitled:
Volume 1: Application of Air Pathway Analyses for Superfund Applications (EPA, EPA-450/1-89-001, NT1S , -
PB90 113374/AS, 1989). , '
Volume II: Estimation of Baseline Air Emissions at Superfund Sites (EPA, EPA-450/1-89-002, NTIS PB89 ;
18053/AS, 1989).
' i;
Volume HI: Estimation of Air Emissions from Clcan-up Activities at Superfund Sites (EPA, EPA-450/1-89-003,
NTIS PB89 180061/AS, 1989). . , 5r
"Volume TV: Procedures for Dispersion Modeling and Air Monitoring for Superfund Air Pathway Analysis (EPA^ -''
fEPA-450/l-89-004, NTIS PB90 113382/AS,'1989). - ' ''"'":
Standard Air Sampling Method Documentation ' '•' '-''-' l
~ V
OSHA Analytical Methods. The OSHA Technical Center maintains an updated data base of analytical testing
methods. Printouts of analytical methods for individual chemicals are available by request. For more ; ' " :
information about the data base, contact: '' -'-.--
" i ' * }
l r-'
OSHA Technical Center • ,; ,c
1781 South 300 West • ':~"v;
Sal! Lake City, UT 84115
(801)487-0521 ,,; ., ,v;
Occupational Exposure Sampling Strategy Manual (Leidel, N.A., K.A. Busch, and J.R. Lynch. U.S: Department-'
of Health, Education, and Welfare, Publ.(NIOSH) pp. 77-173, 1979). , -.~ -;:
Manual of Analytical Methods (Volumes 1-3, 3rd Ed., with supplements) (NIOSH Publication 89-127, 1989). ;• '•
Recommended Exposure Limit Documentation ..-•, :- '.
1991-1992 Threshold Limit Values for Chemical Substances and Physical Agents and Biological Exposure ••:•-'•
Indices (American Conference of Governmental Industrial Hygienists, 1991). ,. ,'•;.::
Guide to Occupational Exposure Values-1992 (American Conference of Governmental Industrial Hygienists,
1QQ1\ , . *»-.»>... . •;:tf-u
J ""* )• , ,;«•«,"<»s.
NIOSH Pocket Guide to Chemical Hazards (NIOSH Publication 90-117, updated annually).
• 14
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Contacts
The following contacts can provide additional information on air monitoring and air sampling at uncontrolled
hazardous waste sites:
American Industrial Hygiene
Association (AIHA)
Washington. D.C.
2700 Prosperity Avenue
Suite 250
Fairfax, Virginia 22031
(703,) 8,49-88S8. % , .
U.S. EPA - ' -, .
Environmental Response Team
2890 Woodbridge Avenue,
Building-18 (MS-101)
Edison, NJ 08837-3679
(908) 321-6740
,24,Hour Hotline: (908) 321-6660
OSHA
U.S Department of Labor
200 Constitution Avenue, NW
Room N-3647
Washington DC 20210
(202) 219-8036
OSHA ratification Service
(Complaint Hotline) fof'Emergency
Situations: 1-800-321-6*742
EPA REGIONAL OFFICES
EPA Region' 1 ' ''
Emergency Planning and Response Branch
60 Westview Street ,, <,'.-.
Lexington, MA 02173
(617) 860-4367
EPA Region 2
Response and Prevention Branch, ,.
2890 Woodbridge Avenue, Raritan Depot
Building 209
Edison, NJ 08837
(908) 321-6656
EPA Region 3
Superfund Removal Branch
841 Chestnut Street, 9th Floor
Philadelphia, PA 19107
(215) 597-0992
EPA Region 4
Emergency Response and Removal Branch
345-iCotmiand Street, NE - ' - -
1st Floor
Atlanta, GA 30365
(404) 347-3931 ' <;
EPA Region 5
Emergency and Enforcement Response Branch
77 West Jackson Boulevard
Chicago, IL 60604
(312) 353-9295
lvEPA Region 6
Emergency Response Branch
1145 Ross-Avenue, 9th Floor
Dallas, TX 75202-2733
(214) 655-2270
EPA Region 7
Emergency^Planning and Response Branch
25 Funston Road, 2nd Floor
Kansas City, KS 66115
(913) 55
EPA Region .$•
Emergency Response Branch
999 18th Street, Suite 500
Denver, CO 80202-2405
(303) 924-7129
EPA Region 9
Field Operations Branch
75 Hawthorne Street
San Francisco, CA 94105'"'™
"(415)744-2353
EPA Region 10
Superfund Branch
1200 6th Avenue, llth Floor
Seattle, WA 98101
(206) 553-1677
15
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OSHA REGIONAL OFFICES
Region 1 (CT, MA, ME, NH, Rl, VT)
133 Portland Street, 1st Floor
Boston, MA 12114
(617) 565-7164
Region 2 (NJ, NY, PR, VI)
201 Vanck Street, Room 670
New York, NY 10014
(212) 337-2378
Region 3 (DC, DE, MD, PA, VA, WV)
Gateway building. Suite 2100
3535 Market Street
Philadelphia, PA 19104
(215) 596-1201
Region 4 (AL, FL, GA, KY, MS, NC, SC, TN)
1375 Peachtree Street, N.E.
Suite 587
Atlanta, GA 30367
(404) 347-3573
Region 5 (IL, IN, MI, MN, OH, WI)
230 South Dearborn Street, Room 3244
Chicago, IL 60604
(312) 353-2220
Region 6 (AR, LA, NM, OK, TX)
525 Griffin Street, Room 602
Dallas, TX 75202
(214) 767-4731
Region 7 (IA, KS, MO, NE)
911 Walnut Street, Room 406
Kansas City, MO 64106
(816) 426-5861
Region 8 (CO, MT, ND, SD, UT, WY)
Federal Building, Room 1576
1961 Stout Street
Denver, CO 80294
(303) 844-3061
Region 9 (American Samoa, AZ, CA, Guam,
HI, NV, Trust Territories of the Pacific)
71 Stevenson Street, Room 415
San Francisco, CA 94105
(415) 744-6670
Region 10(AK, ID, OR, WA)
1111 Third Avenue, Suite 715
Seattle, WA 98101-3212
(206) 553-5930
&EPA
United States
Environmental Protection
Agency
Washington. DC 20460
Official Business
Penalty for Private Use
S300
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