United States Office of
Washington, DC 20460
is>EPA NPDES Compliance
Monitoring Inspector
Training
Sampling Procedures
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NPDES COMPLIANCE MONITORING
INSPECTOR TRAINING MODULE
SAMPLING PROCEDURES
U.S. ENVIRONMENTAL PROTECTION AGENCY
ENFORCEMENT DIVISION
OFFICE OF WATER ENFORCEMENT AND PERMITS
COMPLIANCE BRANCH
JUNE 1980
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING
DISCLAIMER
This module has been reviewed by the Office of Water
Enforcement and Permits, U.S. Environmental Protection Agency, and
approved for publication. Mention of trade names or commercial
products does not constitute endorsement or recommendation for use,
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING
ACKNOWLEDGEMENT
These modules were developed by Barbara A. Schick,
Claire M. Gesalman, Duane Geuder, Edward Bender, and with contri-
butions by Dave Shedroff, all of whom are staff members of the
Enforcement Division, Office of Water Enforcement and Permits. The
Compliance Branch, Enforcement Division, Office of Water Enforcement
and Permits, wish to express their appreciation to the secretarial
staff for the assistance provided in the preparation of this module,
especially Mrs. Mary F. Rogers and Mrs. Wilma Haney.
II
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING
LIST OF HANDOUTS
1 . GLOSSARY
2. RECOMMENDATION FOR SAMPLING AND PRESERVATION
OF SAMPLES ACCORDING TO MEASUREMENT
3. STANDARD ANALYTICAL TEST METHODS
4. CRITERIA FOR SELECTING AUTOMATIC SAMPLERS
5. PROCEDURES FOR CALIBRATING FIELD EQUIPMENT
6. CHAIN-OF-CUSTODY RECORD
7. SAMPLE LABEL FORMATS
III
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING
FOREWORD
The National Pollutant Discharge Elimination System (NPDES)
Compliance Monitoring Inspector Training Modules were developed
by the Environmental Protection Agency (EPA), Office of Water
Enforcement and Permits (OWEP), to instruct NPDES inspectors in
various aspects of conducting NPDES Compliance Monitoring
Inspections.
The EPA Regions have identified a need for training materials
to instruct new employees in conducting NPDES inspections. Train-
ing seminars that are currently offered either do not address the
training needs of an NPDES inspector or are not available due to
limited resources or conflicting course schedules. These training
modules were developed to fill the Regions' need for in-house
inspector training.
The objectives of the training modules are:
1. To acquaint new inspectors with the NPDES Compliance
Inspection program;
2. To serve .as a refresher course for experienced NPDES
Inspectors;
3. To assure consistency in the NPDES Compliance Inspection
program; and
4. To inform and instruct inspectors concerning new inspection
procedures.
The modules were designed to be used as a self-taught course
or as the basis for a lecture course to supplement on-the-job
training. The modules should be presented by experienced and
knowledgeable Regional staff who can answer any questions, discuss
Regional policies regarding the topic being presented, and conduct
on-the-job training.
The module format was chosen for this training program because
of its flexibility. Each module covers a specific aspect of a com-
pliance inspection. Instructors for a particular module may be
selected according to their expertise, and training sessions could
be scheduled based on the needs, the resources, and the time avail-
able to the Region. The modules can be presented individually or
as a complete package.
An outline of information contained in the individual training
modules is listed below. There are currently five NPDES Compliance
Monitoring Inspector Training modules:
1. The Overview module gives the inspector an overview
of the compliance program and a brief summary of the
different types of compliance inspections.
IV
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COMPLIANCE MONITORING INSPECTOR TRAINING
FOREWORD (Continued)
2. The Legal Issues module outlines the legal issues which
must be addressed during an inspection and legal
information that will assist inspectors in performing
their duties.
3. The Biomonitoring module outlines the principles of bio-
monitoring and the role of biological testing in the
inspection program.
4. The Sampling module details the sampling procedures that
an inspector uses when conducting a sampling inspection.
5. The Laboratory Procedures module outlines the procedures
and information necessary for an inspector to perform an
effective evaluation of a permittee laboratory.
The layout of the text of each module is on a half page so that
students may include their notes with the text.
These training modules were developed for the Regions and are
designed to be used by the Regions for in-house training. If these
modules are to be a success, the Regions must participate in their
ongoing development. This can be accomplished by providing EPA
Headquarters with changes or information which Regional instructors
or managers believe would improve the modules. The format of the
modules can be updated and revised at OWEP as the need arises as
they were developed and produced at EPA Headquarters. Cooperation
and commitment to training by the Regions will promote the
development of a useful training document.
These training modules were developed primarily for Regional
NPDES Inspectors; but they are also available to other interested
parties such as State offices, attorneys, other program offices,
facility owners and operators, and members of the general public.
Comments, information, and suggestions to improve the modules
should be addressed to the:
Technical Evaluation and Support Section (EN-338)
Office of Water Enforcement and Permits
U.S. Environmental Protection Agency
401 M Street, SW
Washington, D.C. 20460
Modules covering new topics may be added to the existing ones as
the need arises. Subject suggestions for future modules should
be sent to the above address.
Requests for training modules will be handled at the above
address depending on available supplies.
V
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING
TABLE OF CONTENTS
DISCLAIMER p. I
ACKNOWLEDGEMENT p. ;Q
LIST OF HANDOUTS p.-
FOREWORD p. iv
TABLE OF CONTENTS P. VI
I. INTRODUCTION p. 1
A. Background P. i
B. Objectives of Sampling P. 2
C. Sampling Inspection Tasks . p. 3
D. Compliance Sampling Protocols p. 4
II. SAMPLE COLLECTION p. 4
A. Introduction p. 4
B. Monitoring Study Plan p. 5
C. Sampling Considerations p. 8
D. Sample Volume P. lo
E. Selection and Preparation
of Sample Containers p. 11
F. Sampling Techniques p. 12
G. Sample Preservation p. 14
H. Analytical Mehtods P. 16
III. MANUAL SAMPLING P. 17
IV. AUTOMATIC SAMPLERS p. 18
A. Subsystem.Components p. 18
B. Installation and Operation
of Automatic Sampling Equipment p. 22
VI
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COMPLIANCE MONITORING INSPECTOR TRAINING
V. QUALITY ASSURANCE P. 25
A. Purpose P. 25
B. Objectives p. 25
C. Elements of a Quality Assurance Program p. 26
D. Quality Assurance in Sample Collection p. 26
E. Analyzing the Special Parameters P.~ 28
VI. CHAIN-OF-CUSTODY PROCEDURES P. 28
A. Evidence p. 29
B. Transfer of Custody and Shipment P. 29
C. Sample Collection, Handling,
and Preparation p. 30
VII. SUMMARY P. 31
HANDOUTS
REFERENCES
VII
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE: SAMPLING
——_______________^ PP.OCEDU RES
NOTES
LESSON
I. INTRODUCTION
Background
Elements of a Permit
I. INTRODUCTION
A. Background
The Federal Water Pollution
Control Act Amendments of 1972
established the objectives of
restoring and maintaining the
chemical, physical, and biological
quality of the Nation's water. To
achieve those objectives, the Act
set a goal of eliminating the
discharge of pollutants into
navigable waters by 1985; and
Section 402 of the Act established
the National Pollutant Discharge
Elimination System (NPDES), under
the Environmental Protection Agency
(EPA), as the principal mechanism
for reducing the discharge of
pollutants.
NPDES discharge permits have
been issued to more than 50,000
municipal and industrial pollutant
dischargers. These permits contain
four primary elements:
1. Interim effluent limitations
governing effluent discharges
during treatment facility
construction activities;
2. Final effluent limitations
reflecting the required
treatment levels;
3. Schedules for the
construction and completion
of treatment facilities for
achieving final effluent
limitations; and
4. Reporting requirements
relating to compliance with
milestones contained in the
construction schedules and
with self-monitoring of the
effluent limitations. Self-
monitoring requirements
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COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
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LESSON
Handout 1: Glossary
Objectives of Sampling
specify which parameters are
to be monitored, the sample
type, and the monitoring and
reporting frequency.
Compliance with the NPDES
permit is assessed by EPA and the
States through a program of self-
monitoring report reviews and
facility inspections.
A glossary of terms associated
with sampling procedures and equip-
ment is shown in Handout 1.
B. Objectives of Sampling
A facility inspection encom-
passes many activities, from review
of self-monitoring and analytical
laboratory records to actual
sampling. This module deals with
sampling activities. Other
activites will be, or have been,
discussed in other modules.
Your sampling activities as
NPDES inspectors will be conducted
to accomplish one or more of the
following objectives:
1. Verify compliance with
effluent limitations
2. Verify self-monitoring
data
3. Verify that parameters
specified in the permit are
consistent with wastewater
characteristics
4. Support permit reissuance
and revision
5. Support enforcement
action.
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COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
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LESSON
Sampling Inspection
Tasks
C. Sampling Inspection Tasks
In order to achieve the sampling
objectives, you must perform one or
more of the following tasks:
1. Sample—at the location and
for the parameters specified
in the NPDES permit
2. Sample at locations and for
parameters not specified in
the NPDES permit, as requested
by enforcement personnel (this
may require informal consent
of the permittee)
3. Verify operation and
calibration of monitoring
equipment
4. Measure flow either by verify-
ing accuracy of in-plant
equipment or by actual
independent flow measurement
Your sampling inspection should
also verify that the:
1. Permittee's sampling loca-
tion^) includes all the
effluent from process and
nonprocess wastewater
system(s)
2. Sampling location specified
in the permit is adequate
for the collection of a
representative sample of the
wastewater
3. Permittee's sampling tech-
nique is adequate to ensure
the collection of a
representative sample
4. Permit sampling and monitoring
requirements will yield
representative samples
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COMPLIANCE MONITORING INSPECTOR TRAINING MODULE: PROCEDURES
NOTES
LESSON
Compliance Sampling
Protocols
II. SAMPLE COLLECTION
Introduction
5. Parameters specified in the
permit are adequate to cover
all pollutants of concern
that may be discharged by the
permittee
D. Compliance Sampling Protocols
You must exercise extreme care
to ensure that all sampling efforts
comply with quality assurance
practices and chain-of-custody
procedures discussed later in this
module. IN ADDITION, ALL COMPLIANCE
INSPECTION ACTIVITIES SHOULD BE
CONDUCTED ON THE PREMISE THAT THEY
MAY LEAD TO AN ENFORCEMENT ACTION.
II. SAMPLE COLLECTION
A.
Introduction
The actual sample collection
is an extremely important part of
any compliance sampling inspection.
Without the use of proper sample
collection techniques, the most
precise and accurate analytical
procedures are useless and the
results of the inspection may be
invalid. In addition, the flow
and composition of the waste
streams you will be sampling dur-
ing a compliance inspection will
vary. In a plant using continuous
processes or in a municipal treat-
ment facility, the period of
variation will be long. In plants
where production is seasonal or
batch processes are used, the period
of variation is much shorter, some-
times instantaneous.
In order to accommodate the
variety of conditions that exist
and to ensure that representative
samples are collected and properly
handled, you should perform a
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE: ^CEDUPES
NOTES
LESSON
Monitoring Study
Plan
Items to Address in
Sampling Plan
reconnaissance of the site, if
necessary, and prepare a sampling
study plan.
B. Monitoring Study Plan
To develop a monitoring study
plan, you will need:
1. EPA guideline materials;
2. A copy of the NPDES permit;
3. A knowledge of the waste
treatment processes
employed;
4. A knowledge of the
production processes
employed or, in a municipal
plant, a knowledge of the
raw waste; (For industrial
processes, the EPA
development documents are a
good source of information.
A plant flow diagram is also
useful.)
5. A knowledge of travel and
shipping schedules (airline
schedules) in the area of
the plant to be sampled; and
(The availability of dry ice
or chilling packs should be
ascertained.)
6. A thorough knowledge of the
Department of Transportation
(DOT) shipping regulations
as they apply to the con-
stituents contained in your
samples including the
preservatives.
Your sampling plan should
address the following items:
1. Pollutant parameters to be
measured. The pollutant
parameters that are speci-
fied in the NPDES permit
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COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
_. . _... __._ PROCEDUP.ES
NOTES
LESSON
4.
will provide the basis for
parameter selection. The per-
mit specifies the pollutant
parameters that must be moni-
itored by the permit holder,
and these parameters are given
as mass or concentration-based
discharge limitations, You
will select these same
parameters for compliance
sampling, but you may select
additional parameters if new
processes or products have
been incorporated in the plant
or new or added sources of
wastewater are in evidence.
If new processes or products
have been incorporated in the
plant, additional sampling
will help provide the basis
for the necessary permit
modifications.
Sampling sites. You should
select sampling sites that
correspond to the outfalls
that appear in the NPDES
permit. Additional sample
sites other than those speci-
fied in the NPDES permit, may
also need to be sampled.
Sample volume*. The volume
of samples you will collect
depends on the type of sample
collected, that is, grab or
composite, and the type and
number of analyses that are
needed as reflected in the
parameters to be measured.
Type of sample containers*.
Your selection and preparation
*All of these considerations must be
closely coordinated with the laboratory(s)
scheduled to perform the required analyses.
Contact the laboratory(s) in advance of any
sampling, go over your sampling plan, and
ensure that all laboratory requirements will
be met.
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COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
NOTES
LESSON
*
4
of sample containers will be
based on the parameters that
are to be measured.
5. Sample preservation
techniques*. In addition
to providing temperature
control as needed to
preserve samples, you must
also determine and provide
the appropriate chemicals
for sample preservation.
Preservation techniques and
prescribed holding times are
specified in 40 CFR 136.
6. Sample identification
format*. You must provide
an acceptable identification
label for each container so
that each sample can be
tracked accurately, and an
uninterrupted chain-of-
custody can be maintained.
7. Sample delivery schedules*.
Once it is collected, you
must arrange for the sample
to be delivered to the
laboratory for analysis
within the prescribed hold-
ing time period. This may
be dependent on the local
airline or ground transpor-
tation schedules.
8. Procedures for potentially
hazardous samples*. Sam-
ples of effluent or process
waste that are potentially
hazardous, samples with
extremely high or low pH,
and samples that may contain
extremely toxic, volatile,
or explosive substances will
require special handling.
9. Chain-of-custody
procedures*. You must
prepare chain-of-custody
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
NOTES
Considerations in
Sampling
LESSON
report forms that will be
necessary for evidentiary
purposes.
C. Sampling Considerations
Because varying conditions
cannot be predicted for different
sampling locations, you will have
to compensate for these differences
to collect representative samples.
However, there are basic considera-
tions that will guide you in the
collection of samples. First, you
should collect samples where the
wastewater flow is well mixed. The
most desirable sample collection
point is the area of greatest
turbulence; skimming of the water
surface or dragging the channel
bottom should be avoided unless you
are specifically sampling for oil and
grease or sediments. Stilled areas
should be avoided, particularly if the
wastewater contains immiscible liquids
or suspended solids. Second, you
should collect samples from the center
of the stream. Unless samples are to
be drawn from a wide conduit, collect
them from the center of the flow.
Ideally, the entire wastewater flow
should be captured, for example, for
6-inch or 8-inch pipes, into a
wide-mouthed sample container. Wide
conduits or paths of flow may require
dyeing to determine the most repre-
sentative sampling site. If dyeing
is not performed or is inconclusive,
consider cross-sectional sampling.
The most representative samples will
be drawn from a depth of 40 to 60% of
the total depth of the wastewater.
Grab samples for analysis of oil
and grease or other immiscible pollu-
tants should not be transferred from
the sampling container. These single-
dip samples must be analyzed separately
to avoid the loss of pollutants. Avoid
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U.S. EIMVIROIMMEIMTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE: SAKPLIHG
- PROCEDURES
NOTES
LESSON
Information
on Oil and Grease
Sample Locations
subdividing the sample in the labora-
tory. When information is required
about the average grease concentration
of a waste over an extended period,
examine individual portions collected
at prescribed time intervals to
eliminate losses of grease on sampling
equipment during collection of a
composite sample.
As mentioned earlier, samples
should be collected at the location
specified in the NPDES permit. How-
ever, in some instances this specified
location may not be adequate for the
collection of representative samples,
and you may determine that a better
and more representative sample loca-
tion exists. This judgment must be
based on your knowledge of the plant,
the production processes, and the
outfalls. If a conflict as to the
most representative site exists,
collect samples at both sites. The
reason for the conflict should be
thoroughly documented for later reso-
lution by the permitting authority.
You should sample the influent
to the wastewater treatment facility
when this is specified in the permit.
The preferred sample collection loca-
tions are those that provide the best
mixing. These include the:
1. Aerated grit chambers
2. Upflow siphon following a
comminutor in the absence
of a grit chamber
3. Upflow distribution box
following pumping from
the main plant wet well
4. Flume throat
5. Pump wet well
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COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
NOTES
LESSON
Sample Volume
Volume Requirements
Handout 2: List of
Minimum Volume
Requirements and
Preservation Methods
You should collect these samples
upstream of any sludge or supernatant
recirculation. Dechlorination of
wastewater should be done to avoid
prolonged, unrepresentative
disinfection.
If you are collecting wastewater
samples from a pond or lagoon, com-
posite samples should be taken.
Although ponds and lagoons may have
extremely long detention times, which
may reduce or eliminate concentration
fluctuations, the tendency of these
bodies to short circuit or to release
batches of algae makes composite
sampling advisable in the absence of
information to the contrary. Bodies
of water that have the inlet and
outlet located near'one another are
likely to short circuit. Grab
samples may be employed if past
experience or dye studies indicate
a homogeneous discharge.
D. Sample Volume
The volume of the collected and
properly preserved sample should be
sufficient to perform all the
analyses required in the sample
study. The minimum volume will have
been established through your coor-
dination with the laboratory
scheduled to perform the analyses.
Volume requirements for
individual analyses range from 25
milliliters for pH and organic carbon
determinations to 1,000 milliliters
or more for BOD, oil and grease,
settleable matter,, and temperature
determinations. Refer to Handout 2
for a list of minimum volume require-
ments, but the ultimate authority
is the receiving laboratory.
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NOTES
LESSON
Selections and
Preparation of
Sample Containers
Parameters which have identical
collection and preservation require-
ments should be grouped into the same
container(s) to minimize work and
number of contrainers.
E. Selection and Preparation
of Sample Containers
It is essential that the sample
containers be made of chemically
resistant material that do not
affect the concentrations of the
pollutants to be measured. The
sample containers that you will be
using will usually be either glass
or plastic (see CFR 136). For most
analyses, the option of using either
glass or plastic sample containers
is open, and the selection of the
sample container is based on whether
the container material will affect
pollutant concentrations of the
sample. The lids and liners for
the containers must be inert so
that they do not interfere with the
pollutant parameters to be measured.
If either type of sample container
is acceptable, plastic ones are pre-
ferred because they are less likely
to break. Plastic sample bottles
are usually made of polyethylene;
but Teflon bottoms that provide
added chemical resistance to strong
mineral acids or organic solvents
are available, although this added
chemical resistance is not normally
needed. Glass sample bottles are
required when collecting samples
for oil and grease, phenolics, or
odor determinations. Plastic sam-
ple bottles are required when silica
analysis is to be performed on the
sample. Strong acids used as
preservatives can react with
polyethylene containers and should
always be added to a comparatively
large sample (see CFR 136.3 for
required containers). As with the
sample volume, be sure to use the
sample container prescribed by the
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COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
PROCEDURES
NOTES
LESSON
Sampling Techniques
Grab Samples
receiving laboratory so long as it
does not conflict with CFR 136.3.
F. Sampling Techniques
The two types of sampling
techniques that you will be using are
grab and composite. Each technique
is used to provide different data and
to achieve different objectives.
A grab sample is an individual
sample collected over a period of
time not exceeding 15 minutes. Grab
samples are used to represent the
conditions that exist at the moment
of sampling and do not represent
conditions at any other time. You
will use grab samples to characterize
the wastewater stream at a particular
instant.
Grab samples may be dictated
by the NPDES permit. You should
use these samples to determine
consistency between the plant's
self-monitoring data and the terms
of the permit. In addition, other
objectives may be satisfied with grab
samples. For example, in cases where
composite samples are mandated, you
may also want to collect grab samples
to corroborate the results of the
composite samples.
In lieu of direct field
measurement, grab samples must
often be used for evaluating
parameters that are immediately
affected by biological, chemical,
or physical interactions. You
may often use grab samples when
analyzing for pH, temperature,
residual chlorine, or dissolved
oxygen, and these samples should
be analyzed immediately. Oil and
grease, and bacteriological samples
are always taken by individual grab
samples.
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PROCEDURES
LESSON
Composite Samples
Methods for Collecting
Composite Samples
A composite sample is composed
of a number of discrete samples taken
during the compositing period. These
samples may be collected individually
at equal time intervals if the flow
rate of the sample or stream does not
vary widely, for example, plus or
minus 15%, or they may be collected
proportional to the flow rate. Flow or
time proportioning may be dictated by
the permit.
You will use composite samples
to characterize wastewater streams
that are highly variable in pollutant
concentration or flow rate. The
analytical results of a composite
sample yield the average pollutant
parameter concentration in the waste-
water stream during the compositing
period. NPDES permits may be written
such that the limitations are based on
the average discharge concentration or
on mass-based limitations. In both
cases, a composite that meets the
permits conditions and that fairly
represents the wastewater should be
taken.
Various methods for collecting
composite samples are available.
One compositing method is continuous
sampling at a constant rate. This
method essentially collects a small
side stream, and is not widely used
because it yields excessively large
sample volumes and may not be repre-
sentative where variable flows are to
be sampled. A second compositing
method also involves continuous
sampling, but it differs from the
first method in that the sample
pumping rate varies proportionally to
the flow of the sampled stream. This
type of sample can be collected by a
variable speed positive displacement
pump. This compositing method yields
large representative sample volumes,
but is not widely used due to the
high cost of equipment.
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______—___»__^_^^-^—^^——____________________^______ PROCEDURE
NOTES
Sample Preservation
LESSON
The remaining methods involve
periodic collection and combination
of individual sample aliquots. One
such compositing method yields a
single sample composed of discrete
sample aliquots that are collected in
one container at constant time
intervals. This method is widely used
by both automatic and manual samplers.
It provides representative samples
when the flow of the sampled stream is
constant or when the sample volume is
manually adjusted for varying flow
prior to being added to the composite
sample container, Another compositing
method provides for the collection of
a constant sample volume at time
intervals that are proportional to
stream flow, (e.g., 200 ml of sample
collected for every 5,000 gallons of
stream flow). This compositing method
provides representative samples of all
waste streams when flow is measured
accurately. You will use this method
most frequently because it ensures
representative samples and allows
maximum utilization of the automatic
sampler.
Another method also allows for
collection of discrete samples at
constant time intervals. The volume
of these samples is proportional to
the total stream flow since the last
sample. This method is not widely
used because most automatic samplers
do not provide for it.
G. Sample Preservation
The majority of the pollutants
in the samples collected are unstable
to some extent. This instability
requires that either the sample be
analyzed immediately or that it be
preserved or fixed to prevent (or
minimize) changes in the pollutant
concentrations between the time of
collection and the time of analysis.
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SAMPLING
PROCEDURES
NOTES
LESSON
Sample Preservation
Techniques
4
Handout 2: Preservation-
Methods and List of
Minimum Volume
Requirements •
Because immediate analysis is not
always possible, most samples are
preserved regardless of the time of
analysis. Additional problems may
be encountered when 24-hour composite
samples are collected. Sample
deterioration can take place during
the compositing process, and you will
find it necessary to preserve or
stabilize the samples during com- -
positing in addition to preserving
aggregate samples before shipment
to the laboratory. Note that samples
are to be preserved immediately upon
sample collection unless precluded
by the use of certain automatic
samplers.
Preservation techniques vary
depending on the pollutant parameter
that is to be measured. When the
preservation techniques for one
parameter may affect the analytical
results of another parameter, you
should collect discrete samples
for each preservation technique.
Familiarity with 40 CFR 136, par-
ticularly the proposed revisions,
is essential to ensuring proper
preservation techniques.
Sample preservation techniques
include refrigeration, pH adjust-
ment, disinfection, and chemical
fixation. Refrigeration is the most
widely used method and requires that
the sample be quickly chilled to a
temperature of 4°C, which retards
bacterial action and suppresses the
volatilization of dissolved gases and
organic substances. The temperature
should be verified and recorded during
compositing. The temperature should
not go below 4°C.
A detailed list of the
preservation methods can be found
in Handout 2.
15
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U.S. ElMVIROIMMEIMTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
SAMPLING
PROCEDURES
NOTES
LESSON
Analytical Methods
Handout 3: Standard
Analytical Test Methods
Instantaneous
Measurements
Temperature
Dissolved Oxygen
H. Analytical Methods
The pollutant parameter values
must be determined by one of the
standard analytical methods shown in
Handout 3 or by an alternate test
procedure approved by the Regional
Administrator. The actual analysis
of the collected sample is not
usually a task that you will perform.
The exception to this is determining
parameters that cannot be preserved.
The most common parameters for which
you will have to test are tempera-
ture, dissolved oxygen, and pH.
Measurement of parameters that
cannot be preserved should be taken
at the beginning of the sampling
cycle so that if violations or
problems are identified, you have
the option of taking additional
measurements or collecting additional
information during the remainder of
the inspection.
Temperature determinations may
be made with any good grade mercury-
filled or dial-type centigrade
thermometer or thermistor. All
temperature measuring devices mercury
device must be calibrated periodi-
cally with a precision thermometer
certified by the National Bureau of
Standards.
Temperature measurements should
be taken in situ, if possible.
You will usually use the probe,
or electrode method for in-situ dis-
solved oxygen determinations. The
sample size for this type of deter-
mination is 300 milliliters. No
specific probe is recommended.
However, some types that are used
frequently and have been shown to be
reliable are the Weston and Stack DO
Analyzer Model 30, the Yellow
Springs Instrument (YSI) Model 54,
16
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U.S. EIMVIRONMEIMTAL PROTECTION AGENCY
•
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
NOTES
LESSON
PH
Chlorine
Sample Identification
III. MANUAL SAMPLING
and the Beckman Field Lab Oxygen
Analyzer. These dissolved oxygen
probes are temperature sensitive,
and temperature compensation is
usually built in. Make sure the
probe does not dry out.
pH determinations are always
conducted during a sampling
inspection. Arrangements must be
made to have an appropriate pH meter
available. A recording pH meter may
be required by the NPDES permit and
should be examined for accuracy.
In addition to temperature and
dissolved oxygen field determina-
tions, field chlorine determinations
are sometimes needed. When chlorine.
determinations are deemed necessary
in the planning stage, you must
arrange to have the necessary
analytical equipment at the sample
site. A field kit is available
for the amperometric technique of
chlorine determinations.
Each sample that is collected
for laboratory or field analysis
must be accurately and completely
identified. An important feature
of any label that you choose is
that it be moisture resistant and
properly fixed to the container.
The information that the label
should contain is discussed in
detail in the quality assurance
section of this module.
III. MANUAL SAMPLING
Widemouthed bottles with openings
at least 2 inches in diameter can_be help-
ful for collecting manual samples to allow
for rapid sample collection. These bottles
should have a capacity of 1 to 4 liters to
provide sufficient sample volume for
analysis.
17
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r
U.S. ElMVIRONMEIMTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE: SAMPLING
NOTES
LESSON
IV. AUTOMATIC SAMPLERS
Subsystem Components
Sample Intake
Subsystem
Stainless steel buckets attached to
a rope can be used for sampling in deep
manholes or other difficult areas.
Point samplers, weighted bottles
that can collect samples at a specific
depth, are also used for manual sampling.
You must cork the weighted bottle and
lower it into the waste stream to the
desired depth, remove the cork using
another line, and collect the sample.
This is typically used for dissolved
oxygen determinations.
Hand-operated pumps provide an
acceptable method for obtaining samples
from inaccessible locations, but possible
contamination by the pump and/or tubing
must be carefully controlled.
IV. AUTOMATIC SAMPLERS
A. Subsystem Components
The automatic samplers with
which you will be provided have five
interrelated subsystem components.
These components are:
1. Sample intake
2. Sample gathering
3. Sample transport
4. Sample storage
5. Controls and power.
The sample intake reliably
gathers representative sample from
the sampling stream. This intake
is usually the end of a plastic
suction tube. You may find it
necessary to fit the end of the
tubing with a manifold device for
drawing a sample at various depths
or locations across the flow channel
simultaneously. The tubing should
be at least 1/4 inch inside diameter,
18
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
NOTES
P ROC EDU P.E S
LESSON
Sample Gathering
Subsystem
Mechanical Subsystem
Forced-Flow
which is large enough to lessen
chances of clogging but small enough
to maintain velocity to avoid settling
of solids. It should be free from
plugging and clogging, and resistant to
physical damage from large objects in
the flow stream. Non-leaching tubing
is most often used and may be replaced
for each composite sample. The end of
this tubing should be fixed so that its
sampling location can be maintained
throughout the sampling period. The
automatic sampler should provide for
line purging after each sample is drawn
to prevent contamination of subsequent
samples.
Various commercial samplers
provide one of three basic sample
gathering methods: mechanical,
forced flow, and suction lift.
Mechanical gathering subsystems
are usually built into place and
include devices such as cups on cables,
calibrated scoops, and paddle wheels
with cups. Although these systems may
obstruct the stream flow, they also
take into account site specific
considerations such as very high
sampling lifts and wide or extremely
deep channel flows. Because of the
mechanical system employed, these units
require periodic inspection
and maintenance. You will probably
not use this type of sample gathering
subsystem in the field, but you should
evaluate these installations as part
of your inspection.
Forced-flow gathering subsystems
are often built into place as per-
manent sampling facilities; thus, like
the mechanical gathering subsystems,
they may obstruct the stream flow.
They also require periodic inspection
and maintenance. However, forced flow
subsystems have the advantage of being
able to sample at great depths. In
addition, because this gathering
19
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
NOTES
LESSON
Suction Lift
Subsystem
Sample Transport
Subsystem
system uses air pressure to
transport the sample, it may be
ideal for sample collection in.
potentially explosive environments.
The Air Lift Automatic Sampler
System is one type of forced-flow
gathering subsystem that you may
encounter during your sampling
inspection.
The suction lift gathering
subsystems are the most widely used
type of sample gathering subsystem
because they have greatest versa-
tility, and they only minimally
affect flow patterns.
Suction lifts are limited to
25 vertical feet or less because of
internal friction losses and
atmospheric pressure. With all
suction devices, when the pressure on
a liquid that contains dissolved
gases is reduced, the dissolved gases
tend to pass out of the solution.
Because the gases leaving the surface
have entrained suspended solids, the
surface layer of the liquid becomes
enhanced with suspended solids.
The first flow of any suction
lift sampler should be discarded to
avoid this problem. To minimize the
concentration effect, you should
collect at least 100 milliliters per
sampling unit.
The sample is transported from
the sample intake to the collection
bottle by a plastic tube. This tube
is referred to as the sample trans-
port subsystem. This tubing -Should
be at least 1/4 inch inside diameter
to maintain adequate flow and to
prevent plugging. The tubing should
not be too large so that a velocity
of at least 2 feet per second can be
maintained. Care should be exercised
20
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
NOTES
LESSON
Sample Storage
Subsystem
Controls and Power
Subsystem
to avoid sharp bends, kinks, and
twists in the transport line.
Automatic samplers usually provide
a line purge after each sample is
collected to ready the line for the
next sample transfer. You should
provide new transport tubing for each
new sample site to prevent sample
contamination.
The sample storage subsystem
can accommodate either a single large
collection bottle or a number of
smaller (400-milliliter) collection
bottles. The total sample volume
storage capability should be at
least 2 gallons (7.6 liters), and
some samplers have a capacity as
great as 5 gallons. For preserving
the samples, storage subsystems should
also be large enough to provide space
for ice to chill the sample after
collection. Samples with individual
bottles for discrete collection are
usually equipped with a cassette which
rotates to fill the bottle at the time
of sampling. As mentioned before,
whether large composite or discrete
samples are collected, it is necessary
to use collection bottles made of the
appropriate materials.
The automatic samplers that are
most widely used have solid state
controls that are encapsulated. This
minimizes the effects of the highly
unfavorable environments that may be
encountered in the field such as high
humidity and corrosiveness. These
units are also sealed so that they
may be used with minimum risks in
potentially explosive environments.
Sealed units also protect the con-
trols if the sampler is accidentally
submerged. The control units allow
you to select the time or flow
compositing method, or continuous
sampling method.
21
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE: SAMPLING
_^____________________^^______^ PROCEDURES
NOTES
LESSON
Handout 4: Criteria for
Selecting Automatic
Samplers
Installation and
Operation of Automatic
Sampling Equipment
Sampling Sites
Equipment Security
The power supply for most units
is either alternating or direct
(batteries) current. Alternating
current is the most desirable power
source because of its greater
reliability. However, batteries can
provide adequate power in remote
areas.
Automatic wastewater samplers
may be subjected to rough use during
the course of sampling, e.g., being
dropped and submerged. To ensure
reliable sampler operation, you
should inspect and maintain the
units at regular intervals.
If you are in a position to
select an automatic sampler, the
criteria listed in Handout 4 will
serve as a useful guide.
B. Installation and Operation of
Automatic Sampling Equipment
Sampling equipment should be
installed at sampling sites in
which the flow is well mixed. You
must select these sites with care
in order to reduce the chance of
injuries to sampling personnel. use
the buddy system when entering man-
holes or wet wells; do not enter
these areas alone. Manholes or wet
wells may flood or contain toxic or
oxygen-depleted atmospheres. In
addition, personnel entering poorly
ventilated areas must be provided
with proper clothing and protective
equipment, such as acid-resistant
boots, gloves, coats, and self-
contained breathing apparatus.
In exposed or unprotected areas
where constant surveillance is not
possible, you should lock or seal
the samples to deter tampering with
the samplers and sampling equipment
or to detect tampering if it
occurs.
22
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
....... PROCEDUP.ES
NOTES
LESSON
Power Source
Sample Preservation
During Compositing
Winter Operation
As mentioned before, most
automatic samplers are capable of
operating on both AC and DC. AC
operation should always be chosen
when it is available unless there
are known irregularities in the
power supply. AC operation is also
more suitable for winter operation.
Battery units are not reliable
enough at extremely low temeratures.
Battery operation should be reserved
for remote sampling locations.
When installing automatic
sampling equipment,, the following
should be considered;
1. All samples should be
kept at 4sC during the
compositing period.
(Freezing will destroy
microbiological samples
and alter nutrient
concentrations.)
2. Most portable automatic
samples contain ice
compartments for sample
chilling.
3. Separate sample chilling
chambers can be provided
for those samplers without
the ice compartment.
Cold weather can frustrate
your best sampling efforts due
to frozen transport lines, dead
batteries, and sampler malfunc-
tions. Recently, electrically
heated transport lines have been
used, but availability is poor
and they are expensive. Smaller,
more frequently collected samples
will aid in keeping the transport
lines open. Alternating current
should be used to eliminate the
effects of weak batteries. Heat
may be provided for the sampling
container by placing the sampler
in a thermostatically controlled,
23
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U.S. EIMVIROIMMEIMTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE- SAMPLING
*»•-•.. PROCEDURES
NOTES
LESSON
V. QUALITY ASSURANCE
Purpose
Objectives
electrically heated enclosure. In
the absence of special equipment,
freezing may be prevented by install-
ing the sampler in a manhole or wet
well or by wrapping the sampler with
8-9 inches of insulation and wind
protection. Also, position the
sampler well above the effluent
stream so the tubing runs in"-a taut,
straight line to prevent pooling of
liquid.
V. QUALITY ASSURANCE
A quality assurance program must be
included in all phases of the NPDES com-
pliance sampling prograim. First, the role
of quality assurance in. the program from
the time of sample collection through the
presentation of evidence in court cases -
will be discussed and then quality
assurance procedures in sample collection
will be covered.
A.
Purpose
The purpose of the NPDES
compliance sampling program is to
provide qualitative and quantitative
data to determine whether individual
permittees are in compliance with
the requirements set forth in their
permits.
Inaccurate or incomplete
sampling results can not be used as
evidence in court. If the Region
has established a quality assurance
program, these procedures should be
followed closely.
B. Objectives
1. Obtain sampling results
that are reproducible and
consistent
2. Produce data that are com-
plete, precise, accurate,
and representative
24
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U.S. EIMVIROIMMEIMTAL PROTECTION AGEIMCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
NOTES
PROCEDURES
LESSON
Elements of a
Quality Assurance
Program
Quality Assurance in
Sample Collection
C. Elements of a Quality
Assurance Program
To achieve these objectives,
the following elements will be
included in the quality assurance
program:
0 Training. All members of
the compliance sampling team
should be trained in quality
assurance procedures.
0 Sample collection quality
assurance. You should per-
form various control checks
during actual sample
collection.
0 Chain-of-custody procedures.
You and all members of your
compliance sampling team
should document completely
the transfer of a sample
from one person's custody
to the next.
0 Sample analysis quality
assurance. Laboratory
analysis equipment should
be calibrated and control
checks performed.
D. Quality Assurance in Sample
Collection
Most errors in a sampling
program can be traced to poor
sample collection, preservation,
and compositing techniques. For
this reason, procedures have been
developed that can be used as
control checks.
Duplicate samples provide a
proficiency check for precision.
You should bottle and seal duplicate
samples using field sampling equip-
ment installed at the sample site.
25
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U.S. ENVIRONMENTAL PROTECTION AGENCY
— SAMPLING
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE: PROCEDURES
NOTES
LESSON
Split Samples
Spiked Samples
Sample Preservation
Blanks
Calibration Plan
Handout 5: Procedures
for Calibrating Field
Equipment
When automatic sampling equipment is
not used, you should collect duplicate
grab samples.
Split samples provide a method
for comparing the laboratory
procedures of the permittee with EPA
laboratory procedures. Existing
samples are divided into two segments
for analysis in the separate labora-
tories. You can then evaluate
statistically significant discrepan-
cies in results and identify the
cause.
Spiked samples provide a profi-
ciency check for accuracy of the field
sampling procedures. Known amounts of
a particular constituent should be
added to an actual sample or blanks of
deionized water at concentrations
where the accuracy of the test method
is satisfactory. The amount added
should be coordinated with the
laboratory.
Sample preservation blanks pro-
vide a method for determining whether
sample preservatives contain contami-
nation. You should add a specified
quantity of preservative (equal to
that ordinarily added to a wastewater
sample) to a sample of deionized
water. After laboratory analysis, the
value for the blank is subtracted from
the sample value to obtain the actual
value. (In the case of automatic
sampling, run the deionized water
through the sampler and then add the
appropriate preservative.) A
calibration plan and documentation
record should be prepared for all
field analysis equipment. Refer to
Handout 5 for a summation of tire
procedures to use for calibrating
field equipment. You should keep a
complete documentation record in your
quality assurance logbook, including
equipment specifications, calibration
date, calibration expiration date, and
26
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U.S. EIMVIROIMMEIMTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE: SAMPLIHG
NOTES
LESSON
Quality Assurance
Precision Control
Checks
Reference: Handbook for
Analytical Quality
Control in Water and
Wastewater
Analyzing the Special
Parameters
VI.
CHAIN-OF-CUSTODY
PROCEDURES
maintenance due date. Automatic
samplers should be calibrated for
sample quantity, line purge, and
timing.
Quality precision and accuracy
control charts are graphic charts in
which the vertical scale is plotted
in units of the test result, and the
horizontal scale is plotted in units
of time or sequence of results. The
upper and lower limits on the control
chart are used for judging the
significance of variation between
duplicate samples. The central line
represents the average value of the
statistical measure being plotted.
You must use mathematical equations
to construct the control charts, and
appropriate techniques for doing so
can be found in EPA's Handbook for
Analytical Quality Control in Water
and Wastewater"
E. Analyzing the Special
Parameters
Certain parameters require
special precautions in sample collec-
tion, preservation, and handling to
maintain the integrity of the sample.
These parameters include organics,
acidity/alkalinity, dissolved para-
meters, mercury (total), phenolics,
cyanides, sulfides, and sulfites.
Handout 2 summarizes the special
procedures required to maintain
sample integrity for these
parameters.
VI. CHAIN-OF-CUSTODY PROCEDURES
In order to be able to use NPDES
compliance sampling data in litigation,
there must be accurate written records
that trace the possession of a sample
through all phases of the program.
Custody refers to the possession of a
sample. Chain-of-custody refers to the
27
-------
U.S. EIMVIROIMMEIMTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE: j"B£*£"G
________^_^_^_^_______^___^____ PROCEDURES
NOTES
LESSON
Evidence
Transfer of Custody
and Shipment
Handout 6: Chain-of-
Custody Record
documented account of changes in possession
that occur for a particular sample or set of
samples.
A.
Evidence
Recording chain-of-custody pro-
cedures facilitates their admission as
evidence under Rule 803(b) of the
Federal Rules of Evidence (P.L,
93-575). Written records of regularly
conducted business activities may be
introduced into evidence without the
testimony of the persons who made the
record. It is important that you
follow the chain-of-custody procedures
that will be discussed. Chain-of-
custody should allow for an accurate
and step-by-step recreation of the
sample path, from origin through
analysis.
B. Transfer of Custody and
Shipment
You will be responsible for
properly packaging and dispatching
samples to the appropriate labora-
tories for analysis. This includes
filling out, dating, and signing the
Chain-of-Custody Record. A recom-
mended format for this record is
shown in Handout 6.
When transferring the possession
of samples, you must sign and record
the date and time on the Chain-of-
Custody Record (a signature, not
initials is required). Although
custody transfers ordinarily involve a
group of samples, the record should
account for each individual sample. To
prevent undue proliferation of custody
records, you should try to keep trans-
fers to a minumum. You should include
the Chain-of-Custody Records with the
instructions for analyses when you ship
samples to the laboratory. You should
register them and request a return
receipt. You should retain all
receipts as part of the chain-of-
custody documentation.
28
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
PHOCEDUP.ES
NOTES
LESSON
Sample Transportation
Photographs
VII. SUMMARY
After the samples are properly
labeled, they should be placed in
the transportation case, (which
complies with DOT regulations and
related EPA guidance) along with
the Chain-of-Custody Record Form,
pertinent field record and the
Analysis Request Form. You should
then seal and label the transpor-
tation case. If you find that the
use of a transportation case is
inconvenient, you may place a
tamper-proof seal around the cap
of each sample. The samples should
be packed in a synthetic ice sub-
stitute that will maintain sample
temperature at 4°C. throughout
shipment.
For composite samples, you may
transfer unsealed containers from
one crew to the next. The receiving
crew will sign for the samples thus
verifying the list of samples that
you have compiled.
If you take photographs or
color slides of the sample out-
fall location, you should keep a
photograph log which includes the
following information:
1. Your signature
2. Time and date
3. Site location
4.
VII. SUMMARY
Brief description of
subject.
We have now covered various sampling
procedures required for conducting a
NPDES compliance sampling inspection.
Review the handouts provided and consult
you manuals before initiating an
inspection.
30
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U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING MODULE:
PROCEDURES
NOTES
LESSON
Sample Collection,
Handling and Preparation
Sample Label Information
Handout 7: Sample Label
Formats
C. Sample Collection, Handling,
and Preparation
It is important to keep a
precise record of sample collection
and handling data. You should sign
all field records containing these
data at the time of collection. You
should also document the following
information in the field records:
1. Unique sample or log number
2. Date and time
3. Source of sample, including
facility name, location and
sample type
4. Preservative used
5. Analyses required
6. Name of collector(s)
7. Pertinent field data (pH,
dissolved oxygen, chlorine
residual, etc.)
8. Serial number on seals and
transportation cases
Gummed labels or standardized
tags should be attached to each
sample. Each label should include
the following information:
1. Sample identification number
2. Date and time of sample
collection
3. Source of sample
4. Preservative used
5. Collector's initials
Refer to Handout 7 for examples
of sample label formats.
29
-------
HANDOUT 1
GLOSSARY
Chain of Custody—The written record of the possession and handling of the
wastewater sample, from collection through laboratory analysis and dis-
position of the analytical results and the unused sample remnants.
Comminutor—A sewage grinder, usually located at the beginning of the treat-
ment process.
Composite Sample—A sample that is composed of at least eight discrete samples.
The aggregate sample will reflect the average water quality over the
compositing or sampling period.
Grab Sample—A sample that is collected over a time period not exceeding 15
minutes.
Instantaneous Measurements—In situ or grab measurements for such parameters
as dissolved oxygen, pH, temperature, specific conductance, etc.
Quality Assurance—Refers to the procedures and practices used during sampling
and analysis that ensure or provide proof of accuracy, reproducibility,
and representativeness.
Spiked Samples—Effluent or blank samples to which a known quantity of another
substance has been added.
Split Samples—Oupl icate samples or samples that have been divided into two
containers for analysis by separate laboratories.
Supernatant—The upper level of water or the overflow from a clarifier in a
waste treatment plant.
-------
RECOMMENDATION FOR SAMPLING AND PRESERVATION
OF SAMPLES ACCORDING TO MEASUREMENT
HANDOUT 2
Vol.
Measurement
100 Physical Properties
Color
Conductance
Hardness
Odor
pH
Residue
Filterable
Non-
Filterable
Total
Volatile
Settleable Matter
Temperature
Turbidity
200 Metals
Dissolved
Suspended
Total
Req.
(ml)
50
100
100
200
25
100
100
• 100
100
1000
1000
100
200
200
100
Container
P.G
P,G
P.G
G only
P.G
P.G
P.G
P,G
P,G
P.G
P.G
P.G
P.G
P.G
Preservative
Cool, 4'C
CooL 4'C
Cool, 4'C
HNOj to pH<2
Cool, 4'C
Oet. on site
Cool, 4'C
Cool, 4'C
Cool, 4'C
Cool, 4'C
None Req.
Det. on site
Cool, 4'C
Filter on site
HNOj to pH<2
Filter on site
HNOj to pH<2
Holding
Time
24 Hrs.
24 Hrs.
6 Mos.
24 Hrs.
6 Hrs.
7 Days
7 Days
7 Days
7 Days
24 Hrs.
No Holding
7 Days
6 Mos.
6 Mos.
6 Mos.
-------
Measurement
Dissolved Oxygen
Probe
Winkler
Phosphorus
Ortho-
phosphate,
Dissolved
Hydrolyzable
Total
Total,
Dissolved
Silica
Sulfate
Sulfide
Sulfite
400 Organics
BOD
COD
Oil & Grease
Organic carbon
Phenolics
Vol.
Req.
(ml)
300
300
50
50
50
50
50
50
500
50
•
1000
50
1000
25
500
Container
G only
G only
P.G
P,G
P,G
P,G
P only
P,G
P,G
P.G
P,G
P,G
G only
P,G
G only
Preservative
Del. on site .
Fix on site
Filter on site
Cool, 4'C
Cool, 4'C
H2SO4 to pH<2
Cool, 4'C
H2S04 to pH<2
Filter on site
Cool, 4'C
HjSO4 to pH<2
Cool. 4'C
Cool, 4'C
2 ml zinc
acetate
Del. on site
Cool, 4'C
HjSO4 to pH<2
Cool, 4'C
H2S04 or HC1 to pH<2
Cool, 4'C
H2SO« or Hd to pH<2
Cool, 4'C
HANDOUT 2
(Continued)
Holding
Time
No Holding
4-8 Hours
24 Hrs.
24 Hrs.
24 Hrs.
24 Hrs.
7 Days
7 Days
24 Hrs.
No Holding
24 Hrs.
7 Days
24 Hrs.
24 Hrs. .
24 Hrs.
H3PO4 to pH<4
1.0 g CuSO*/!
MBAS
250
P.G
Cool, 4'C
24 Hrs.
-------
Vol.
Req.
Measurement (ml)
Mercury
Dissolved
Total
300 Inorganics, Non-Metallics
Acidity
Alkalinity
Bromide
Chloride
Chlorine
Cyanides
Fluoride
Iodide
Nitrogen
Ammonia
Kjddahl, Total
Nitrate plus Nitrite
Nitrate
Nitrite
100
100
100
100
100
50
200
500
300
100
400
500
100
100
50
Container
P.G
P.G
P.G
P.G
P.G
P.G
P.G
P.G
P.G
P.G
P.G
P,G
P.G
P.G
P.G
Preservative
Filter on site
HNOj to pH<2
HNOj to pH<2
None Req
Cool. 4'C
Cool, 4*C
None Req.
Del. on site
Cool, 4'C
NaOH to pH 12
None Req.
Cool, 4*C
Cool.4'C
H2SO4 to pH<2
Cool, 4*C
H2SO« to pH<2
Cool. 4'C
H2SO4 to pH<2
Cool. 4'C
Cool. 4'C.
HANDOUT 2
(Continued)
Holding
Time
38 Days
(Glass)
13 Days
(Hard
Plastic)
38 Days
(Glass)
13 Days
(Hard
Plastic)
24 Hrs.
24 Hrs.
24 Hrs.
7 Days
No Holding
24 Hrs.
7 Days
24 Hrs.
24 Hrs.
24 Hrs.
24 Hrs.
24 Hrs.
48 Hrs.
-------
HANDOUT 2
(Continued)
Vol.
Req. Holding
Measurement (ml) Container Preservative Time
NTA 50 P.G Cool. 4'C 24 Mrs.
1. More specific instructions for preservation and sampling are found with each procedure as
detailed in this manual. A general discussion on sampling water and industrial wastewater may
be found in ASTM, Part 31, p. 72-82 (1976) Method D-3370.
2. Plastic (P) or Glass (G). For metals, polyethylene with a polypropylene cap (no liner) is
preferred.
3, It should be pointed out that holding times listed above are recommended for properly
preserved samples based on currently available data- It is recognized that for some sample
types, extension of these times may be possible while for other types, these times may be too
long. Where shipping regulations prevent the use of the proper preservation technique or the
holding time is exceeded, such as the case of a 24-hour composite, the final reported data for
these samples should indicate the specific variance.
4. If the sample is stabilized by cooling, it should be warmed to 25*C for reading, or temperature
correction made and results reported at 25°C.
3. Where HNO3 cannot be used because of shipping restrictions, the sample may be initially
preserved by icing and immediately shipped to the laboratory. Upon receipt in the laboratory,
the sample must be acidified to a pH <2 with HNO3 (normally 3 ml 1:1 HNO3/liter is
sufficient). At the time of analysis, the sample container should be thoroughly rinsed with 1:1
HNO3 and the washings added to the sample (volume correction may be required).
6. Data obtained from National Enforcement Investigations Center-Denver, Colorado, support a
four-week holding time for this parameter in Sewerage Systems. (SIC 4952).
(EPA. Methods for Chemical Analysis of Water and Wastes. March 1979.)
-------
ANALYSIS PROTOCOL
(A) 40 CFR Part 136
rMIDOUT 3
PART 13G—GUIDELINES ESTABLISHING
TEST PROCEDURES FOR THE ANALY-
SIS CF POLLUTANTS .
See. •"••••' -:" ' •'•
116.1 Applicability. " ' ' •' ' •
M6.2 Dcfi.-Jtlons.
43G.3 Idcnt:Sc;tlon of test procedures.
13C.4 Application Icr alternate- test proce-
dures. •
138.5 Approval or alternate test procedures.
ACTBOHITT: Sec. 30i(g) o' Federal \7ater
Pollution Coatrol Ac* Axaenclsicats o£ 1072
86 Stat. 315. etaiq.. Tub. L. 32-500). ..- .--,;
§ IS6.1. Applicability. '"." "' ";
Tfc.9 procedures prescribed herein
shall, except as noted in I 13G.5, bs used
to perform the measurements indicated
whenever the waste constituent specified
Is required to be measured for:
(a) An application submitted to the.
Administrator, or to a Stats having an
approved NPDES projram. for e. permit
under section 402 of the Federal Water
Pollution Control Act as amended
CPV/PCA). and,
(ti) Reports required to be submitted
by dischargers under the NPDES
established by Parts 124 and 125 of this
chapter, and,
(c.) Certifications issued by States pur-
suant to section '101 of the FWPCA, as
amended.
[35 KR 28753, Oct. 15. 1073]
§ 126.2 Dcfiniiions.
A3 used In this part, the term:
(a) "Act" means the Federal Water
Pollution Control Act, as amended, 33
U.S.C. 1314. et seq.
(b) "Administrator" means the Ad-
ministrator of the U.S. Environmental
Protection Ajency.
(c) "Regional Administrator" means
one of the EPA Regional Administrators.
(d) "Director" means the Director of
the State Ascncy authorized to can?
out an approved National Pollutant Dis-
charge Elimination System Program
under section 402 of the Act.
(c) "National Pollutant Discharge
•Elimination System (OTDES)" means
the national system 'or the Issuance of
permits under section. 402 of the Act and
Includes any State or interstate proirrain
which has bcc:i approved by the Admin-
-------
IBNDOOT 3
(Continued)
Chapter !—Environmental Prelection Agency § 136.3
TJJSES L—ZXii of approved test procedure*J—Conttsned
Ptra=eter and unit*
Jlctbod.
1974 Hth cd.
EPA standard
Df.icdj netfcodi
Re.'ercnccJ
(p«Ct DOS.)
Pt.3l
19T3 :
ASTM
uses
icttods >
approved
mllll-
v ETAis—C anttnucd
71. Ar«.-.ic—Dissolved, milll-
£.-i=j per liter.
SO. 3arii:r.-To:sl,
per liter.
31. Miriii.T.—Dissolved,
IM.T.S pur liter.
S. BerrKJws-Tottl. =1111
per liter.
32. Bt.-ylliurr.—Dissolved,
in.-as per liter.
Zi. Ec.-on—Total, aiUitrana per Coiorirnctnc (Carcu=in)_
0.45 nlcron flllrallnn " fol-
lowed by refcrfnetd
fnc'.hod for tntsl arsenic.
Dilution" followRd by
niamic ali^nrptinn.1*
0.45 nirron nitratlnn '* fnl-
lowed by rrfi'rcncrd
mcl!:od .'or 'oil! hsriuin.
Dicn5ttouu folloTred by
norcic aS.io.-T)Uoa " or by
coiorinirthe (Alumlnon).
O.U micron miration ^ to I- ,
lowed by referenced
87
n
U
ISJ
ist .
177 .
Uoron—Dissolved,
per liter.
M.
37.
um— Toi»l, a
per liter.
Cadmium— Dissolved, miM-
i,Ta.T» per liter.
, Ctlcium—Toti!, Ell
per liter.
Calsian—Dissolved,
r iiter.
101
103
M.
il.
O.
mini-
Chreniua VT, nilL'f ranu per
liter.
Chrom-nn VI— Dissolved,
=!Uicra.Ti5 per liter.
Chromium— Total,
per tiler.
J9, 105 _.
43. Ciiro.-aiura—Dissolved, rollll-
per liter. •
44. Cobalt—Total, mlUisrams per
liter.
4S. Cobalt—Dissolved, milli-
grams per liter.
«. Copper—Toil!, ailUirtxa
per liter.
47. Copper—Dissolved, mllll-
cranis per liter.
4S. Gold—Totil, aillisrsmi per
litrr.
49. Irldium—Total, dUlitracos
per liter.
!0. Iror.—Total, mHUframs per
liter.
11. Ircn— Diisolvcd,
per li:cr.
it. Lrn-l— Tc'.ll, ?.ilU;riai per
U'.cr.
0.45 micron nitration " fol- .
lowc-1 by referenced raeib*
oil for total boron.
Digestion n followed by
atomic absorption » or by .
cnlor.mctric tOltfiljnr.e).
0.43 micron filtration u fol* .
lowed by referenced meth-
od for to til cadmium.
Diction» followed by
atomic ft'osorptioa; or .
EDT.V tltntlon.
O.^IS micron nitration « fcl- .
lowed by referenced ixiolt*-
bd for total cnlcium.
Eitracfion and atomic ab-
snrption:co!orimetric(Dl- .
phcnylcarbn^ltlr).
0.13 micron nitration " fo'.* .
lowed by referenced mctla-
- ori for chromium VI.
Digestion" followed by
atnmii: absorption " or by .
col.uiinctnc (Uiplicuyl-
cnrlmido).
0.4j micron nilrittlon « fol- .
lowed bv referenced racth-
pd for tofal chronttua.
Dicrstion» followed by
atomic absovptlon.'1
0.43 micron nitra'lon >' fol- _
lowed by referenced meth-
od for total cobalt.
Dicestloti" followed by
rumnic absorption ll or by _
CPlorimetric (Keocu-
liroino).
0.4S micron miration " fol- ..
lowed by refcrcncod acttl-
oil for toial copper.
DJECStion » followed by „
ntrrnic absorption."
Dicesiioii » followed by __„..__
14*
is:
MS
ISO
315
a <(6ip);»t3n
102
101
107
103
US 345
1U 345
14S
ICd
SO '• (37)
a (815) « (37)
ainr.uc abjorplicn."
Dicrstion " fnllowe.d by
niiunic nMorpiion " t> r by
c*»ionmeiric vrher^vr.'.hra-
line).
0.43 micron flllrattnn n (g|.
ml (or totAI iron.
Discjtlon" [oilowol liy
*:u:iiic absorption "or by
co!oriL:elhc (Uilbt:
110
i::
14S
102 I (019)
133 > «19
Ece Jootaotci it end of Uble.
-------
ffiNDOUT 3
(Continued)
Tills 40—Protection of Environment. •"
TABLE I.—Lift of approved test procedures'—Continued '
J*aran-.elcr and ur.itj
l!>74
Jkliiod Kl'A
mctliodj
Rrfrrriuws
Ulh etl. (pace nri«.) Oilier
mcliiodi I'l..lt USOS incll>oiU
l!>Vi :ncltiotti '
ASTJt
« LIAU— Continued
S3. I^ail— Dissolved, milligrams
per liter.
S». >:.«r.r«nm— Total, niilll-
P '
Crams per liter.
3d. Marianne— Total milligrams
I,«T liter.
57. V.inrn:i.vw— Dissolved iruUl-
(trams v-or liter.
;.J. M. .-rtir\— Total, milligrams
IHT !l:rr.
grains per liter.
cm:::.« ;vr liler.
ni:il:;r:iuis per iiicr.
R. Nick»l— Total, railUsrams
j.-jms per liter.
per Hifr.
.#. ra!'.3d:u:a— Total, =iiUi?ranU
t>er liter.
rrr iiter.
.67. I'n:.v»iarr.— Toti!, niillisnrrj
jrams per liter.
per liter.
TO. nulrrnmir.— Total, milli-
trains rx-r Iiicr.
p*r liler.
77. ."» I:-r.:iun — Dissolved, miill-
(ira:iu per liler.
73. Silirt— Dissolved, mi;'.i;rams
;.-r iiicr.
74. EiiTr— Total,=« xilHcranu
7i Stiver— 11i»»lv«il,a oliil-
c,:a:ai per liter.
jH-r liter.
O-JS n>irrnn fill ration >' fnl-
Inn'ril by I rfrrrncnl molll*
oy
crarimetric.
Jnwrt! liy ri-ferrnitry
ninntic aHsnrpt inn " ur by
ctilnrl'iirfnc (l'crr.u|fatoor
l>i-rif>i)atc).
Q.iS ir.icruu .Til ration" (D19)
K3, S7 __.__.._. .......
113 ISfl 33S "(31)
141 US 315 IIS _. —
°*>3
.»
:
143 134 >(OM)
231 403
143 133 ....... .__ .. _
J74 4S7 338 130
148 1 •:* 142 »(G10> "(37)
147 143 «(631)
„ „_ —0 403 _.--._--——.-...._
r?. ;r luff. low* il l>y t»-li rrnrril iitcLh*
tnl luf lutnl Mnliuiu.
Sec footnotes at cud of table.
-------
Chapter !—Environmental Prolcclion' Agency
EMDOUT 3
(Continued)
§136.3
Istir.tor, In whole or in part, pursuant to •
section 402 or the Act.
(O "Standard Methods" means Stand-
crd Methods for the Examination of
Water and Waste Water, Mth Edition,
1076. This publication is available frcrn
the American Public Health. Association.
1015 18th Street, N.W.. Washington, D.C.
20035.
(jr) "ASTM" means Annual 3ook of
Standards, Part 31. Water. 1375, This
publication is available from the Air.eri--
can Society for Testing and Materials,
1516 Race Street, Philadelphia, Pcnnsyl-
. vania 1C 103.
(h) "EPA Methods" means Methods
for Chemical Analysis of Water and.,
Wests, 1974. Methods Development and
Quality Assurance Research Laboratory,
National Environmental Research Cen-
ter, Cincinnati. Ohio 45233: U.S. Envi- -
rcnmintal Protection Agency, OSce of
.Technology Transfer. Industrial Envi-
ronmental Research Laboratory, Cincin-
nati, Ohio 4526S. This publication is
available from the Office of Technology
Transfer.
[33 7H 28733. Oct. 16. 1973. is acicntied at
41 PS 52701, Deo. 1. 1375J
g 13J5.3 Identification
il'urcs.
of test proce?
(a.) Every parameter or pollutant for
which an effluent limitation is now spec-
ified pursuant to sections 401 and 402
of the Act Is named together with test
descriptions and references la Table I.
The discharge parameter values for
which reports are required must be de-
termined by one of the standard ana-
lytical methods cited and described
In Table I, or under certain circum-
stances by other methods that may bo
more advantageous to use when such
other methods have b:en previously ap-
proved by the Regional Administrator of
the Recioti in which the discharge will
occur, and providing that the Director
of the State in which such discharge
will occur does not object to the use o'J
such alternate test procedures.
Co) Under certain circumstances tho
Regional Administrator or the Director
In the Region or State where the dis-
charge will occur may determine for a
particular discharge that additional pa-
rameters or pollutants must be reported.
Under such circumscanccs. additional
test procedures for analysis of pollutants
may be specified by the Regional Admin-
istrator, or the Director upon the recom-
mendation of the Director of the Envi-
ronmental Monitoring: and Support
Laboratory, Cincinnati.
(c) Under certain circumstances, the
Administrator may approve, upon rec-
ommendation by the Director. Environ-
mental Monitoring and Support Labora-
tory, Cincinnati, additional alternate test
procedures for nationwide use.
TABLE I.—I/lit of approved tat procedures1
rrj-iaotcr and unlU
Method
1071
Uth cd.
itnnd.ird -
.
c nos.)
methods -iiciliods Ft. 31 USCS u-.c
• 107' nclhodi1
AST:.:
Ollwr
approved
1.
2.
X
«.
f
r,
ArMilr. ss CaCO>, =IUl-
JC.-.MS per liter.
Alir.linitr. rjt CaCO», =Uli-
;raias per liter.
per liter.
O.VCTERIA.
Cnlironn (f.:etl)', r.umbcf por
100 ir.L
Elcctromrtric end point
(pit of 3.2) or phenol-
plitlinki.Tend point.
Elccuoinculc titrr.f.on
lor.iy ta pLI 1.5) inaiiu.il
or automated, or equiva-
lent auloir.Rtcd cicthodj.
0/i> lollownl hy ucislTi-
trodi. Autoi^Atcd pbc-
noUtc.
lirX:< -.cmbrtr.c alter
do ii .
1
3
5 .
ISO
1&3 .
• l&S
:730ld) IIS <0 '(TOT)
ITS 111 4\ IiM7)
419
412 37 UC HOUi
CIS .,
._-_- ...„........._.
0"S 337 — .. ... .. ....
018
ffX '(3J)
Sec footnutci at end oC table.
-------
HANDOUT 3
(Continued)
§136.3
' Title 40 — Protection of Environment
I. — TAst of approved lest procedures1' — Continued
PsiacclcrindunitJ Method EPA stanusrd
methods methods
SACTtsU— Continued
e.' 'ehiorir.o." nutsbcr per 100 «1t!» cnriehruenl. ....
S. ?e"«i s'.-cMococci,' nuiabu' MPX:« mrrabrano C'.ten
per 100 mL PW« count.
10. Eioci'P:nical oxvccn Cetnandi WiuUier (Az;ue iuudi>*>cA' ....
$< (UOOtl, Euliicwss per tloa) or eScctroJc r.;cthod. __
litrr.
11. Brorr.ii'a.iaiiUpaTr.spfrUtcr.. TUrircctne. lodhio-iodatt...
12. C'c.rinirai orvrcn itrt'and Ulcnrjniata rcfiUt_.«_.—
(COnt.n-.'.liicnmsperlitst. _—
12. Ci'.oriie. niiliijnrjj per !i'.cr_ Silver n'.lt»te; mercuric nl-
trafe: or cuiomuM coiori*
pnnr.tis I'ptcrnL p«Ucidcs)»
•i'.'.lzraius r>er liter.
li. Ch'.crir.e— ;ou;re5iiuil,cil!J- Io'lnmeirictitratior..«mpcr-
rrams per lil&r. omciric or starch-iodina
end-point; DPU eoiori- _..
1 r.ielric nr Tluimtule .-_
mriliod^ (H;csr last 2 ftro
lntr:im methods pcudlnf
'.alior.ilorv U'i'.mc).
•8. Color. plM'.r.ura cobalt units Co'.orimemc; j;>cctr<ien, roinitramj WIr.fclcr (Atldo nioiliftm-
rrf I'tcr. lion) cr electrode mellin«U
:0. Jluo'riilc, mllUsrams pc-r HU-r., Dlstilutlnti • foilnwptl hv
ion rirctrortn; SI'AllNS;
ornutuiLiaLcdconipU'Lone.
21. Dsrdr.csj— Total. U ClCQi. EDTA lltrMlon; nulo-
aiilicrams per liter. muted rolorimctrlc; or
&lo;nic absorption (sum «...
of Ca and Me ru their
rcspcctlvr carbonates).
75. rlvrfrrctr.Jon tpm, pn unlia. Kleeiromciric nie.tfureniimt.
:3. Ik'piOaiil niiroccn (aj N'), Discs'.inn and d:sli!!.Minn
nillicratzs per liter. followed br r.csstrntatlnn,
tllrr.tion, or "Icctrode;
l\:Unniali"l dlcrstlou autCr
rr.aLcd pticnolato.
^ ETA 14
21. .'.1'inv.nr.m— Total, ir.illlcramj Dlc^lion » followprl by
per lllcr. a'.oimc rvlTorvMion i* or ny — .
H
20
31
-1T
38
33
40
51
56
ID
70
WO
US
1M
IK
52
918
033
N-!
•>17
M3
303
2C-1
613
31S
J7-)
M
3GI
37C
•H3
4.V)
•"M
hid
201
437
171
Ktlcrer.ctS
(pa;c r 03.) Other
Pt. 31 1JSGS TT^rt-ftnriy
1&7S nii:tUcdx
ASTJI
EEZEEEE
i{30)
m '• • ss
473 !2t > (610)
_. " (17)
2r>3 ri~nnii~"~""'"(6ij)
— — .— » (-5G) _.___—_
• .-. ••
._
SOI .. 6i . i«(I2>
JOS
3CS • 121 - HOT)
307 53 ..._
305
101 01 HG17)
178, 123 K6CO)
121 H6U)
"(10)
a. Alurr.inu-..".—Ditsalrcd, .aillll-
STims per liter.
2S. Aui'.rnony—Total. nTllll(;ran»
prr litrr.
17. A:::."'''«y—Oiir-olted. mllll-
i::r liter.
. (Kiiociironio
Cynniiw ID.
0.-I5 micron miration " fnl-
lowr-1 by it Ir.miecU nielli-
fxls for trial r.:u;niiuim.
Dif'ti'in •» follnr.-fil liy
avenue a!3or|itin
-------
IftNDOOT 3
(Continued)
§136.3 Tifle 40—Protection of Environment--.
TATII.S I.—Lht of approved lest procedures1—Continued
Parnn;ot:r and unit*
JB74
El'A
=ictiiod»
Inferences '
i prl. ;;.-u;o HOJ.) Other
ilai-d — approved
:odj Pt. 31 USG5 Lie:hodi
l?7i methods'
ASTM
aciiDui
in. Tot.il. ni;i!rr-ms PT !!:rr.._
;OJ. To:il dL'snlrrd (f.lUiabiB),
r::!'.ifr^nxj prr lilcr.
10s. Tola! juivniied (nonAllcr-
ibieK uu!!:".in:* per liter.
107. Sf.t:r.\i>>.. rullililcn PIT liter
or rrU;::cn:ns prr liter.
10S. To:.-.', volatile, mUU;."uw P«r
iii^r.
ICO. Sr-.'ific conilnct-inrr. micro-
n-.iif.s per c^iili^notcr at 2j*
113. S\:::.nc (:LS SOO, ir.illisranu
PIT liter.
111. Sii:!"nl» (A.I S). niiU'cnnu pnr
r.rarirnetrir. 103 to 103* C—
C'.JiS fiber R!Ln^rri.i:i!s. ni::!;nn:i per
:i!rr.
1U. Tcuipmturo, cU-crccs C
H.V Turi'Mit)-. NTU
lninpinr.
TiLrtJiieLnr;, Jodinp-iodato.,.
Coioriinciric (MclSiylono
I'inc).
C.iiilir'v!'''! cLi-a or electro-
nic! ric 1in-iinnn»p.U'r.
N'rpliclolnolric «
Ma 5CS ^IS
157 600 431 o(l')
SO IIS "(31)
2>S ' 132 :S3 138
1 ?.rc"-:":r.Tiil:uifln3 for Minplinz anr*. prriofvi.!ion nf vxmplp.t ner.nrtlin; to p-'.rimcur n:crjnrc«l inly !)n found in
"M. ii-.oi!? Tor Chemical Analysis ol U'iicr ami Wr-sies. 107-1" U.S. Environment.il I'rotcc'-ion A;ci-.cy, —bio 2, pp.
nolrd. nrc to nrnwn. P,., 5>'• K:s.*.::i-'vn. M. J. and Hrown. Knrcnc. "Selected Mc'-bods of tho U.S. Geological Surrey for Analysis of Wastt-
-ri-f-rs." (1'Jo^ op*n-ft;<, report 70-1T7.
.. .
t c rrtr.in rrti- t:\ls tlironi:!i |if-Tt()!.nticn.
tcorotis treatment Ls n-co;r.meiulcd as
-------
rSNDOOT 3
(Continued )
Chapter I—environmental Prelection Agency
I.—List of approved test procedures1—Continued
§136.3
Parnnscter iuid units
Method
1071
KPA
Hth i-d.
standard -
Tlc^crcnces
(puce noj.) Oth;r
apprrvpil
methods inclUods IX 31 VnC.K
I07S mclliodj I
ASTM
>i ETAU—Continued
7S. ThnKium—Tolal, rnillljrjma Dici-s!!oi\u tollownt by " 140 _ ..
p-.T liter. r.'.oi-.iie xbjorpUnn.u
7J. Ttiallliiai—Dissolved, siilli- OAS mirr.iii IH'.r.iUnn'T M- ..
;r:uus ITU lilcr. Inwi-il liy r.-f<-rrurril niclh-
SO. T::i—Total, millitrr.ra per Dirrsiion '» tnllowctl l»y liO .................. " (63)
El. T!:i—Oifiolfcd, !uiUi;T7.:ns O.IJ r.vicrnii r.llmimn " tol-
I>er lilcr. lon'nl liy (rf.Tcnccxi mei.li-
Ott for tnlnl Hit.
S2. T:liniimi—ToL-.l, iiiilllcr.tiiu Do-surm <• fnllnwnl by III
PIT liu-r. ntminr. .il'Snriiiliiii."
S3. TUaiuniu—Oissnlvcd. snllli- 0.4". micrun lilirnilnii " fol- .„
un;.-ji per litrr. lowvl l>y r, (rrcnrcd nielli-
ml lor lol.nl liLnniiiin.
.M. Vnr.si'.inm—Total, r.ulllijriimj Di-r.-:!.m'» fullnuvl hy IS3 ISI
pi*r!.lrr. r.Lninn: a'^nrplion '* or t»y . .. 2X) vll, ll w7) .
r.ikirliui'ihc Ui.illU*. uriill.
55. V.ii::i:!ilini—ni^Uved, llulll- CM". a..rrn:i llllmli.ini' f"l-
pruuta par litrr. ImvrU [>y rr(.-rrurrd nn'tli-
nrt .'or loLU rnnntliutn,
SO. Zinc—Total, milll^amj per Di^'Siinii" [ollnwrrt by 154 in MS ISO '(C1'J)"(37)
liter. n(n::;ic .lit^rpiloti M or by ... .... 2G.1 ... .. .... ............
culuiiuirlnr (Uitiiiu.no).
S7. Zi;ic—Dissolved. nuUiira-tu 0.-lj i^.icron nitniliun'•' fol-
per liter. le"'cd by rrf.-rcucrd inclh-
ori for tot.il zinc.
S3. XI'.ra'.DtaNJ.r-.iUJjn'.sisper Ca-J-jam reduction; bru- 201 \23)
•': radiiuum or bydraziiie if ' 207 620 ......
Auction."
39. Nltrila (is JO, ^Uigracu per M.v.-.inl or automated colon- 213 O4 . 121
00. Oil and crciso, railliffrasis per Liquid-liquid cxtrrvc'.ion ' 223 513.... ... ...... ......
liter. with tnchloro-tri(luor>
rth.-une-^rari-.Tittrie.
Bl. Omnlc wrbon: tot.il (TOO, Combustion—lotir-d 235 S3: 467 3(1) „
Tii'.y.icrxns Per liter. . ir.^thod.*1
92. 0.-cir.icit;trr.;cn(nsNl,.T!iUl. SJflil.-.I'.l mlrreen siinus 173, ISO O7 123 »(«:, CM)
03. Ot1!ioi>liospli.itc (."J P), n\!lll- 2I.-,::u:l or autnnvi'.cd ascor- 2-19 4S1 3S1 131 ' tOil)
:rr.ii\s per liter. Ijir. ncid reduction. 2jS 021
01. rciiuidilnrnplirnol, milll- OM cluomatotrnpliy " .
zr.:::u per lilcr.
05. Pf5ttci.iesr irullivrams per do." ......—. ... S53 523 a (21),...........
liter.
05. Phenols, r.uilifnms per liter DiMill.itlnn foilowrtl br Colo- 2U 574 543 _ •
ninctric. (4AAP)
07. Phosphorus (rkmcntal),:nilU- C^i cSroaiflto;rnpbr "
"n\nis per liter.
OS. rr-.ospiiMiis; tot.il (a> P), Pcrsulfate diics'.ion tol- 24H 47B,-;$l 354 131 '(Gil)
ir.:lllgrjLjiis per liter. lowed by :njim:nl or auto- —G GT1 . .
inr.icd ascorbl- wrid reduc-
tion.
RADIOLOGICAL
M. Alpiia—Total, pCi per liter... Pmnnrilonil or scintillation —._.._ CIS J!)l"1!(73+73)........__
co'.nucr.
100. Alplm—Countinj error, pCl do -. 0-13 33\ "(TO) _
101. Tleia—Tjil, pCl per litrr ProportlonM counter—. _..-.-, 048 Ml»«(73+7S) __
10i- Lf..i—Countir.f error. ;iCl per da __-._-.___ &U 006 u (70) _
litrr.
"103. (&) it.-.tiUim—Total. pCl per do Gul 6U
(b) '•" 1U, pCl pcrlllcr SejiUIl'.itioncounter „ __ CC7 "(51) _
Sec footnotes at end of table.
-------
HttJDOOT 3
(Continued)
Chapter I—cnvironmenfai Projection Agency
§ 136.4
« As lha various furnicc devices (."juries' AA) ore e«snntWly .itomle absorption tcchninucj. t?icy ar» consMrrtJ
to lie r.ppro™! test mct!:o--'.j. M>".hc:!s i< 5!indarir pof-
Is sl-o M
.
r^iiiie SubsV.nccs lt\ \Vntcr": U.S. C'Calopicvl purvey Tocil-
;i:l.'i!c on.1 sodium hyijrniiric to a pit of 12. 7hcrf(o.-f, for lfrr',5 o! silvrr
ttiVdicd to '.00 m[ by od^ii\f -iO rr.[ c?.cii of 2>I XirSsOi n.r,tl 2.M XsO}!. .;>
zinn-r. For Icvri* of silfcr below I nij.l ;'.ie rccoiniacndr-t method is s-i
11 An :utoir.a:cci hvdrailr.c rr'Juc'ion nirthed 15 ar^ii.ihjo from the
L-iixiraiiry. U.S. £nTi.-ov..iicn'.al Proicc'.iori Acency. Cincinnacl, Ohio
= A r'.unihcr nf IUCM jyjJer.is ntAiiiifActurr-i by varitias i-ompniiiirs r.rn
f.-.rm.-.:icr. In i(i:r, I'vsnl on n'ni';n«':on-inotlianr
*- f lot-riitt. 13.. lirnu-n, K.( "Mrthnds fnf Anr'.Iv^is of
r.ii;u.-i>nf 'iViiUT-Ui'Miircv ••< l-.tf^ !'<«(; 5, rli. A.I (tDr:>.
a r.. V. A-!'li<.in nu-.l ii. (i. .^.clciiKi:!. "!)irc<-t n<*it'i".n!nr\titw nf Elrnu-niftl riiosolvp(l iioriini! u'hito iho ^ictltod on p. To nacc^urcs only sus*
pcnd^ti, 1'hiTpforo. Mif * ro.'ul'-S niu.?: lii» lirittivt Inrrt.lMT in ohiniii "tornl."
" s.-.-vrrf, II. 11.. I''!c^^. 1. c\, ^:i4i ^:m »M'. G. 1'.. "\\'A:IT TftinpfrrxLuro — fnflnrniir.1 Fnriirs, Tipht M.-a5iiroi»eat
liiul i>:-.:ft r^i-y^MLMiou: S'.S, GrniorJr^i Purvey Tcrlnnn;ir* of \Va;j*r ilrsnurt-ra luv.. hooU I (iur.*.)."
[33 FP. :S753. Oct. 18. 1D73. as a=scndci at 41 FR C278I, Dec. 1. 1376; 43 ?R 3303, Jaa. iS,
1977]
§ 13S.4 Ajiplifnlioa for allcm.ite tMt
procedures.
(a) Any person maj' apply to the Ro-
3:or.nl Administrator in the Region
whcrs the discharge occurs Tor approval
of r.r. nHerr.ativc test procedure.
(b) When the dischnrse Tor which in
e.;tern2t!ve test procedure is proponed
occurs within a State havlr.j ft permit
prccrarn approved pursuant to section
402 oi the Act. the applicant shall sub-
mit his application to the Rejional Ad-
ministritar-throush the Elrcctor ot ths
Stats agency hrtvins? responsibility for
lssuar,ce of NPDES permits -.vlthln such
State.
(c) Unless ind ur.til printed applica-
tion forms are made available, an appli-
cation for an alternate test procedure
:nr.y be made by letter In triplicate. Any
application for an alternate test proce-
dure under this paragraph (c> shall:
(1) Provide the name and address of
the responsible person or firm makin?
the al.-.chai-ge (if not the applicant) and
the applicable ID number of the existing-
or pending permit, issuing accncy, and
type of permit for which the alternate
test procedure is requested, and the dis-
charge serial number.
' (2) Identify the pollutant or parame-
ter for ^,-hlch approval of nn alternate
testing procedure is tetn? requested.
(3) Provide Justification .'or uslne
testing procedures other than those
specked in Table I.
(4) Provide a. detailed description of
the proposed alternate test procedure,
together with references to published
studies of the c.pplicafaillty of the alter-
nate test procedure to the e.Tluents in
question.
(d) An application for approval of an
alternate test procedure for nationr.-ide
use may be made by letter in triplicate
to the Director. Environmental Monitor-
ing and Support Laboratory, Cincinnati,
Ohio 45263. Any application for an alter-
nate test procedure under this paragraph
(d) shall:
(1) Provide the name and address of
the responsible person or firm n-.akins
the application.
(2) Identify the pollutantfs) or pa-
rameter(s) for which nationwide ap-
proval of an alternate testing procedure
is beinff requested.
(3) Provide a detailed description of
the proposed alternate procedure, to-
gether with references to published or
other studies confirming1 the general ap-
plicability of the alternate test proccduro
to the pollutontfs) or paramctcr(s) In
waste water discharges from representa-
tive and specified Industrial or other
categories.
(4) Provide comparability data for the
performance of the proposed alternate
test procedure compared to the perform-
ance of the approved test procedures.
|33 FR IG760. Oct. 1G. 1973, ts nsncndcct at
41 Fn 52735, DCQ. 1. 19701
-------
HVNDOUT 3
(Continued)
§ ^36.5
§ 135.5 Approval'of ollcrnalo test pro-
cedures.
ra) The Ifcsicnsl Administrator of
the recion In which the ^charce will
occur has final responsibility for ap-
- --o-al of any alternate test procedure
p.-opned by the responsible person or
firm mn!iir.sf the discharce.
TiHo 40—Protection of Environment
mcr.flalion*, to ins n-.-u'-">" -~
Istrator. Where the Director recommends
rejection of the application for scien-
tific and technical reasons which he pro-
vides, the Regional Administrator shall
•• - • -i--n fnrrjarrt
Ills decision v.o «^:c ju*iu\--w* «. — — _
Permit Trojrarr. and to the Director of
th; Er.vironmental Monitoring and Sup-
port Lr.boi--toi.-y, Cincinnati.
(c) Seiore approving any application
for nn altcrr.ai ?. test, procedure proposed
by the responsible person or firm mak-
ing the discharge, the Regional Admin-
istrator shall forward a copy of the ap-'
plication to the Director of the Environ-
ment?.! Mor.itorine and Support Labora-
tory, Cincinnati.
(d) V/lthin ninety days of receipt by
the Regional Administrator of an appli-
cation for an alternate test procedure,
proposed by the responsible person or
firm making the discharge, the Regional
Administrator shall notify the applicant
and the appropriate State r.gcncy of ap-
proval or rejection, or shall specify the
additional information which is required
to determine whether to approve the pro-
posed test procedure;. Prior to the expira-
tion of such ninety day period, a recom-
mendation' providing the scientific and
ether technical basis for acceptance or
rejection will be forwarded to the Re-
gional Administrator by the Director of
;::e Environmental Monitoring and Sup-
port Laboratory, Cincinnati. A copy of
all approval and rejection notifications
will be forwarded to the Director, Envi-
ronmental Monitoring and Support
Laboratory, Cincinnati, for the purposes
of national coordination.
(c) Within ninety days of the receipt
by the Director of the Environmental
Monitonns and Support Laboratory,
Cincinnati of an application for an
alternate test procedure for nationwide
use, the Director of the Environmental
Monitoring and Support Laboratory.
Cincinnati shall notify the applicant of
his recommendation to. the Adminis-
trator to approve or reject the applica-
tion, or shall specify additional informa-
tion which is required to determine
whether to approve the proposed tsst
procedure. After such notification, an
alternate method determined by the Ad-
ministrator to satisfy the applicable re-
quirements of this part shall be approved
for nationwide use to satisfy the require-
ments of this subchapter; alternate test
procedures determined by the Adminis-
trator not to meet the applicable require-
ments of this part shall be rejected.
Notice of these determinations shr.ll be
submitted for publication in the PrscRAL
REGISTER not later than 15 days after
such notification and determination is
made. "
[30 PR 207GO. Oct. 1G. 1D73. ;
41 Fn 02735, Dec. 1, 107S]
at
-------
HANDOUT 4
CRITERIA FOR SELECTION OF AUTOMATIC -SAMPLING EQUIPMENT
1. Capability for AC/DC operation with adequate dry battery energy
storage for 120-hour operation at 1-hour sampling intervals.
2. Suitability for suspension in a standard manhole while accessible
for inspection and sample removal.
3. Total weight, including batteries, under 18 kilograms (40 pounds).
4. Sample collection interval adjustable from 10 minutes to 4 hours.
5. Capability for flow-proportional and time-composite samples.
•Bi 6.. Capability for collecting a single 9.5-liter (2.5-gallon) sample
^^ and/or collecting 400-milliliter (0.11-gallon) discrete samples
in a minimum of 24 containers.
7. Capability for multiplexing repeated aliquots into discrete bottles,
8. One intake hose with a minimum inner diameter of 0.64 centimeters
(0.25 inches)..
9. Intake hose liquid velocity adjustable from 0.61 to 3 meters per
second (2.0 to 10 feet per second) with dial setting.
10. Minimum lift of 6.1 meters (20 feet).
11. Explosion-proof.
12. Watertight exterior case to protect components in the event of
rain or submersion.
-------
HANDOUT 4
(Continued)
13. Exterior case capable of being locked, including lugs for
attaching steel cable to prevent tampering and to provide
security.
14. No metal parts in contact with waste source or samples.
15. An integral sample container compartment capable of maintaining
samples at 4 to 6°C for a period of 24 hours at ambient tempera-
tures ranging from -30 to 50°C.
16. With the exception of the intake hose, capability of operating
in a temperature range from -30 to 50°C.
17. Purge cycle before and after each collection interval and
sensing mechanism to purge in event of plugging during sample
collection and then to collect complete sample.
18. Field repairability.
19. Interchangeability between glass and plastic bottles, particularly
in discrete samplers is desirable.
20. Sampler exterior surface painted a light color to reflect sunlight.
-------
HANDOUT 5
QUALITY ASSURANCE PROCEDURES FOR FIELD ANALYSIS AND EQUIPMENT
Parameter
General
Quarterly
Dissolved Oxygen
Membrane
Electrode
Enter the make,
model, serial,
and/or ID number
for each meter
in a logbook.
Calibrate meter using
manufacturer's in-
structions or Winkler-
Azide method.
Check instrument cali-
bration and linerarity
using a series of at
least three dissolved
oxygen standards.
Report data to
nearest 0.1 mg/1
Check membrane for
air bubbles and holes,
Change membrane and
KC1 if necessary.
Check leads, switch
contracts, etc. for
corrosion and shorts
if meter pointer
remains offscale.
Winkler-Azide
Met,u 3d
.Record data to
nearest 0.1 mg/1
Duplicate analysis
should be run as a
precision check.
Duplicate values
should agree within
+0.2 mg/1.
p_H_ - Electrode
Method
Enter the make,
model, serial,
and/or ID number
for each meter
in a logbook.
Calibrate the system
against standard
buffer solutions of
known pH value, e.g.
4, 7, and 9 at the
start of a sampling
run.
Take all meters to the
laboratory for main-
tenance, calibration,
and quality control
checks.
-------
HANDOUT 5
(Continued)
Parameter
General
Quarterly
(Continued)
Periodically check the
buffers during the
sample run and record
the data and in the
logbook.
Be on the alert for
erratic meter response
arising from weak
batteries, cracked
electrodes, fouling,
etc.
Check response and
linearity following
highly acidic or alka-
line samples. Allow
additional time for
equilibration.
Check against the
closest reference
solution each time a
violation is found.
Rinse electrodes
thoroughly between
samples and after
calibration.
Conductivity
Enter the make,
model, serial
and/or ID number
for each meter
in a logbook.
Standardize with KC1
standards having
similar specific con-
ductance values to
those anticipated in
the samples. Calcu-
late the cell constant
using two different
standards.
Take all meters
to lab for main-
tenance
bration
control
, cali-
and quality
checks.
-------
HANDOUT 5
(Continued)
Parameter
General
Quarterly
Temperature
Manual
(Continued)
All standard-
ization shall be
against an NBS or
NBS calibrated
thermometer.
Readings shall
agree within ;*10C.
If enforcement
action is antici-
pated, calibrate
the thermometer
before and after
analysis. All data
shall be read to
the nearest 1°C.
Report data between
10 and 99°C to two
significant figures.
Temperature readings
shall agree within
+1°C or the thermo-
meter shall be re-
placed or recalibrated.
Initially and Biannually:
Accuracy shall be
determined throughout
the expected working
range of 0 to 50°C.
A minimum of three
temperatures within
the range should be
used to verify accu-
racy. Preferable
ranges are: 5-10°,
15-25°, 35-45°C.
Thermistors,
Thermographs,
etc.
Enter the make,
model, serial,
and/or ID number
of the instrument
in a logbook. All
standardization
shall be against a
•NBS or NBS cali-
brated thermometer.
Reading should
agree within +1°C.
If enforcement
action is antici-
pated refer to the
procedure listed
above.
Check thermistor
or sensing device
for response and
operation according
to the manufacturer's
instructions. Record
actual vs. standard
temperature in
logbook.
Initially and Biannually:
Accuracy shall be
determined throughout
the expected working
range of 0 to 50°C.
A minimum of three
temperatures within
the range should be
used to verify accu-
racy. Preferable
ranges are: 5-10°,
15-25°, 35-45°C.
Flow Measurement
Enter the make,
model, serial,
and/or ID number
of each flow
measurement in-
strument in a
logbook.
Install the device
in accordance with
the manufacturer's
instructions and
with the procedures
given in your manual
Annually: Affix
record of calibration
NBS, manufacturer,
or other to the
instrument log.
-------
HANDOUT 5
(Continued)
Parameter
General
Quarterly
Conductivity
(Continued)
Cell Constant3
Standard Value/
Actual Value
Specific Conductance5
Reading X Cell
Constant
Check temperature
compensation.
Check date of last
platinizing and
replatinize, if
necessary.
Rinse cell after
sample to prevent
carryover.
Analyze N8S or EPA
reference standard
and record actual vs,
observed readings in
the logbook.
Residual Chlorine
Amperometric
Ti tration
Enter the make,
model, ID, and/or
serial number of
each titration
apparatus in a
logbook. Report
results to nearest
0.01 rag/1.
Refer to instrument
manufacturer's in-
structions for proper-
operation and cali-
bration procedures.
Biweekly: Return
instrument to lab for
maintenance and
addition of fresh,
standardized reagents.
,^-iperature
Manual
Enter the make,
model, serial,
and/or ID number
and temperature
range for each
thermometer.
Check for air spaces
of bubbles in the
column, cracks, etc.
Compare with a known
source if available.
Biweekly: Check at
two temperatures
against a NBS or
equivalent thermometer.
Enter data in logbook.
-------
HANDOUT 5
(Continued)
Parameter General Daily Quarterly
Automatic Samplers Enter the make, Check intake
model, serial, velocity vs. head
and/or ID number (minimum of three
of each sampler . samples), and clock
in a logbook. time setting vs.
actual time interval
-------
HANDOUT 6
CHAIN OF CUSTODY RECORD
SURVEY
STATION
NUMBER
1
STATION LOCATION
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Relinquished by: fs^noh,«/
Dispatched by: (s;9««
-------
0 U.S. E.P.A. REGION
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-------
U.S. ENVIRONMENTAL PROTECTION AGENCY
COMPLIANCE MONITORING INSPECTOR TRAINING
REFERENCES
American Society of Testing Materials. Standards Part 23; Water
and Atmosphere Analysis. 1973. o
Environmental Protection Agency. Basic Water Monitoring Program.
Washington, D.C.: EPA, 1977.
Environmental Protection Agency. Handbook for Analytical Quality
Control in Water and Wastewater Laboratories. Washington,
D.C.: EPA, 1972.
Environmental Protection Agency. Handbook for Monitoring
Industrial Wastewater. Washington, D.C.: EPA, 1973.
Environmental Protection Agency. Methods of Chemical Analysis of
Water and Wastes. Washington, D.C.: EPA, 197.4 and 1979.
Envrionmental Protection Agency. NPDES Compliance Sampling
Manual. Washington, D.C.: EPA, 1979.
Card, C.M. and Snavely, C.A. "An Automatic Waste Sampler," Water
and Sewage Works, p. 157, 1952.
j Laboratory Analysis for Treatment Plant Operators. Washington,
| D.C.: U.S. Department of the Interior, Federal Water
i Pollution Control Commission, April 1968.
! Planning and Making Industrial Waste Surveys. Ohio River Valley
i Water Sanitation Commission, April 1952.
• §tandard Methods for the Examination of Water and Wastewater.
I Washington, D.C.: American Public Health Association, 1976.
j
j Environmental Protection Agency. Handbook for Sampling and
I Sampling Preservation of Water and Wastewater (Draft) - EMSL,
I Cincinnati, December 1980.
i
i NEIC Policies and Procedures Manual - EPA, Office of Enforcement,
NEIC-Denver, EPA-330/9-78-001R, May 1978, Revised October
1979.
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