United States
Environmental Protection
Agency
Office of Water Enforcement and Permits
Office of Water
Washington, DC 20460 August 1990
vxEPA
NPDES Compliance
Monitoring Inspector
Training
Laboratory Analysis
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NPDES COMPLIANCE MONITORING INSPECTOR
TRAINING MODULE
LABORATORY ANALYSIS
U.S. ENVIRONMENTAL PROTECTION AGENCY
ENFORCEMENT DIVISION
OFFICE OF WATER ENFORCEMENT AND PERMITS
ENFORCEMENT SUPPORT BRANCH
APRIL 1990
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DISCLAIMER
This module has been reviewed by the Office of Water Enforcement and Permits, U.S.
Environmental Protection Agency, and approved for publication. This module represents EPA's
introductory training on selected topics relating to conducting NPDES compliance inspections. Failure
on the part of any duly authorized official, inspector, or agent to comply with its contents shall not be a
defense in any enforcement action, nor shall a failure to comply with this guidance alone constitute
grounds for rendering evidence obtained thereby inadmissible in a court of law. The mention of trade
names or commercial products constitutes neither endorsement nor recommendation for use.
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ACKNOWLEDGMENTS
This document represents an update of a module originally developed in June 1980 by the
Enforcement Division of the Office of Water Enforcement and Permits (OWEP). The module was
revised under the direction of Virginia Lathrop and Gary Polvi of OWEP with extensive input from the
NPDES Inspection Materials Work Group. In addition, the EPA Regions provided extensive reviews.
Many valuable comments were produced, most of which have been incorporated into this manual.
Science Applications International Corporation prepared this updated module under EPA Contract Nos.
68-01-7050, and 68-C8-0066, Work Assignment Nos. El-7, E2-1, E2-8, C-O-ll(E), C-1-2(E) and C-1-4(E).
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TABLE OF CONTENTS
Page
FOREWORD v
1. INTRODUCTION M
1.1 OVERVIEW OF THE NPDES PROGRAM 1-1
1.2 PURPOSE OF THE NPDES COMPLIANCE MONITORING
PROGRAM 1-2
2. PERFORMANCE AUDIT INSPECTION 2-1
2.1 PREINSPECTION PLANNING 2-1
2.2 INITIAL MEETING 2-6
2.3 SAMPLING TECHNIQUES 2-8
2.4 LABORATORY SAMPLE CONTROL 2-10
2.5 ANALYTICAL METHODS 2-13
2.6 EVALUATION OF LABORATORY QA/QC PROGRAMS 2-16
2.7 LABORATORY FACILITIES AND EQUIPMENT 2-31
2.8 RECORDS AND REPORTS REVIEW 2-50
2.9 EXIT MEETING AND FINAL REPORT 2-53
3. COMPLIANCE EVALUATION INSPECTION 3-1
3.1 RECORDS AND REPORTS REVIEW 3-1
3.2 REVIEW OF SELF-MONITORING DATA, PROCEDURES,
AND LABORATORY FACILITIES 3-2
4. SUMMARY 4-1
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APPENDICES
APPENDIX A - REFERENCES
APPENDIX B - GLOSSARY
APPENDIX C - APPROVED METHODS (EXCERPT FROM 40 CFR PART 136)
APPENDIX D - REQUIRED CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING TIMES
(EXCERPT FROM 40 CFR PART 136 TABLE II)
APPENDIX E - METHODS CHECKLISTS
APPENDIX F - SAMPLE CHAIN-OF-CUSTODY FORM
APPENDIX G - SAMPLE CONTROL FORM
APPENDIX H - POTENTIAL PROBLEM AREAS ASSOCIATED WITH POLLUTANT ANALYSIS
APPENDIX I - LABORATORY SERVICES
APPENDIX J - REVIEW QUESTIONS AND ANSWERS
LIST OF FIGURES AND TABLES
Figure Page
2-1 PRECISION AND ACCURACY 2-23
2-2 EXAMPLE CONTROL CHART 2-28
2-3 EPA DEFICIENCY NOTICE FORM 2-55
2-4 NPDES COMPLIANCE INSPECTION REPORT FORM 2-56
Table Page
2-1 QA QUESTIONS 2-18
2-2 ANALYSIS OF TOTAL PHOSPHATE-PHOSPHORUS STANDARDS 2-27
IV
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FOREWORD
This document is one of five training modules developed by the Office of Water Enforcement and
Permits, U.S. Environmental Protection Agency to introduce the National Pollutant Discharge
Elimination System (NPDES) program to new inspectors. Information in each module provides training
to an inspector unfamiliar with the NPDES program. The modules address the following topics:
1. Overview: presents an overview of the entire NPDES program and briefly summarizes
different types of inspections conducted under this program
2. Legal Issues: discusses the legal issues which must be addressed during an inspection and
provides legal information to assist inspectors in performing their duties
3. Biomonitoring: outlines the principles of biomonitoring and the role of biological testing in
the inspection program
4. Sampling Procedures: details procedures to be used when conducting a sampling inspection
5. Laboratory Analysis: outlines procedures and information necessary to perform an effective
evaluation of a permittee's laboratory.
The modules are best used in a classroom setting where there is a discussion between students and
instructors and where questions can be asked. Yet, they can also stand alone as reference sources. A
general discussion of the topics covered in these modules appears in the NPDES Compliance Inspection
Manual (May 1988).
These training modules were developed primarily for in-house training of Regional and State
NPDES inspectors. However, they are available as well to other interested parties such as attorneys,
other program offices, facility owners and operators, and members of the general public.
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Regional and State personnel are encouraged to provide EPA Headquarters with suggested changes
or information which instructors or managers believe would improve these modules. The content of the
modules will be updated and revised periodically. Comments, information, and suggestions to improve
the modules should be addressed to:
Enforcement Support Branch (EN-338)
Office of Water Enforcement and Permits
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
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1. INTRODUCTION
1.1 OVERVIEW OF THE NPDES PROGRAM
The Federal Water Pollution Control Act of 1972, as amended by the Clean Water Act of 1977
and the Water Quality Act of 1987, specifies the objectives of restoring and maintaining the chemical,
physical, and biological quality of the Nation's waters. The Act provides broad authority to the U.S.
Environmental Protection Agency (EPA):
To establish the National Pollutant Discharge Elimination System (NPDES) program and the
National Pretreatment Program
To establish effluent limitations based on pollution control technologies and/or water quality
standards
To obtain information through reports and compliance inspections
To take enforcement actions, both civil and criminal, when violations of the Act occur.
The NPDES program, mandated by Section 402 of the Act, regulates the discharge of pollutants from
point sources such as municipal treatment plants, industries, animal feedlots, aquatic animal production
facilities, and mining operations. In order to discharge, each point source is required to obtain a
NPDES permit which specifies effluent limits, monitoring and reporting requirements, and any other
terms and conditions necessary to protect water quality.
To determine whether these NPDES permit conditions are being met, Section 308 of the Act
authorizes inspection and monitoring of permittee facilities. Under the authority of Section 308, two
types of monitoring have been established: self-monitoring by the permittee and compliance monitoring
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by the permit-issuing agency. According to the Act, an inspection may be conducted where there is an
existing NPDES permit or where a discharge exists or is likely to exist and no permit has been issued.
Compliance with NPDES permit conditions is often monitored by States. Sections 308 and 402 of
the Act allow the transfer of Federal program authority to conduct NPDES permit compliance
monitoring to State agencies. Currently, over 75 percent of the States and territories are approved by
EPA to implement State NPDES programs.
1.2 PURPOSE OF THE NPDES COMPLIANCE MONITORING PROGRAM
As mentioned above, each NPDES permit contains specific, legally enforceable effluent limitations
and monitoring and reporting requirements. The purpose of the NPDES compliance monitoring
program is to verify the accuracy of self-monitoring data used in evaluating compliance with applicable
effluent limitations and monitoring and reporting requirements and to gather information that supports
enforcement of the Federal Water Pollution Control Act, as amended. This information collection
involves two aspects: 1) the collection of samples of a permittee's effluent by a NPDES inspector during
a Compliance Sampling Inspection (CSI), a Toxics Sampling Inspection (TSI), or a Compliance Bio-
monitoring Inspection (CBI); and 2) the evaluation of a permittee's self-monitoring procedures during a
Compliance Evaluation Inspection (CEI) and a Performance Audit Inspection (PAI). Under certain
circumstances, inspectors may also evaluate the industrial monitoring and enforcement efforts conducted
as part of a municipality's pretreatment program. This type of inspection is called a Pretreatment
Compliance Inspection (PCI).
An integral part of the NPDES compliance monitoring inspection is the evaluation of the
permittee's laboratory to determine if proper laboratory procedures are followed and if data are reported
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in a way that is proper and consistent with NPDES permit requirements. This evaluation is a primary
part of the PAJ and may be included (to a lesser degree) in a CEI, CSL, XSL. or CBL
The CEI, which usually requires less than one day on-site, provides the basic framework for all
other more resource-intensive types of NPDES inspections, The CEI does not include the collection of
samples; rather, it is intended to verify the accuracy of a permittee's self-monitoring program, as well as
other issues such as record keeping, flow monitoring, operation and maintenance, and status of progress
where there is a schedule for construction or upgrading of treatment facilities. The CEI also provides an
opportunity to gather information on the compliance status of a facility.
The PAJ includes the tasks and functions of the CEI. However, the PAI provides a more
resource-intensive review of the permittee's self-monitoring program, particularly the laboratory
operations. The PAI does not include the collection of samples by the NPDES inspector. However, the
permittee may be required by the inspector to analyze performance samples for laboratory evaluation
purposes.
This module has been organized to highlight the major components involved in a laboratory
evaluation conducted as part of a CEI, and in a more comprehensive laboratory evaluation conducted
during a PAI. The module discusses the following subjects for the two types of inspections:
Performance Audit Inspection
- Completing preinspection planning
- Conducting the initial meeting
- Observing sampling techniques
- Assessing the laboratory's sample control
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- Reviewing the laboratory's analytical methods
- Evaluating the laboratory's Quality Assurance/Quality Control (QA/QC) techniques
- Reviewing the laboratory's Discharge Monitoring Reports (DMR) QA lab data and records
- Conducting an audit of the laboratory's facilities and equipment
Conducting the exit meeting
- Preparing the final report
Compliance Evaluation Inspection
- Reviewing records and reports
- Completing a review of self-monitoring data and procedures
- Conducting a review of the laboratory facilities.
The objective of this module is to provide the inspector with background information necessary to
conduct an appropriate evaluation of the permittee's laboratory procedures for sample control, sample
analysis, and quality assurance, as well as to assess the adequacy of the laboratory facilities and
equipment Additional sources of information are provided in the references identified throughout the
text of this module and summarized in Appendix A. A glossary of terms used in this module appears as
Appendix B.
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2. PERFORMANCE AUDIT INSPECTION
The PAI examines the self-monitoring procedures of the permittee and includes all aspects of a
CEI. The PAI usually requires one or more days onsite in order to allow for a more intensive review of
the permittee's NPDES laboratory operations, including the observation of sample collection and
analysis. Of concern to the scope of this module, the laboratory inspection and examination of a
permittee's logs and records serves to support or refute the accuracy of analytical data provided by the
permittee's laboratory. The best way to conduct the laboratory tour during a PAI is to track a sample
through the laboratory process, from sample receipt through analysis and data validation to DMR
completion and sample disposal. If the permittee utilizes a contract laboratory for pan or all of the
analysis of permit parameters, the PAI should include the contract laboratory as well. The remainder of
this chapter describes elements of the inspection in detail.
2.1 PREINSPECTION PLANNING
2.1.1 Purpose
The purpose of the laboratory evaluation portion of the PAI is to determine whether the
laboratory is performing analyses and reporting analytical results in a manner consistent with NPDES
permit requirements and applicable regulations. A key component of the evaluation is proper
preparation and planning prior to the laboratory visit The inspector should approach the evaluation as
an audit, in which laboratory procedures are compared to standard procedures and deviations are noted,
evaluated, and reported. Typically, preparation time may range from 1 to 4 hours, depending on the
inspector's familiarity with the analytical techniques and the number of parameters to be evaluated
during the laboratory audit
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2.1.2 Approach
Prior to a site visit, the inspector may send a '308 letter* or notification letter to the permittee
advising that an inspection is to be scheduled within the next 6 months. Typically a "notification letter'
contains a legal citation of the inspector's legal authority to sample and inspect. Information on the
permittee's onsite safety regulations may be requested. The 'notification letter' may also set up the
subsequent contact, via a form letter or phone call, to determine a mutually convenient inspection date
and to ensure that the appropriate personnel will be available. Due to the varying monitoring
frequencies between permittees, the inspection should ensure that sampling and analytical testing are
being conducted the day of the scheduled inspection. The inspector must also determine which
analytical methods will be used in order to prepare and be familiar with those techniques. For example,
Dissolved Oxygen (DO) may be analyzed either by the DO probe method or by titrimetric analysis.
Appendix C is an excerpt of 40 CFR Part 136 which identifies the various parameters and their
respective approved analytical techniques. The inspector may also provide the permittee with a
performance evaluation sample (discussed in Section 2.1.3) 45 to 60 days in advance so that the
permittee's analytical results can be reviewed during the inspection. If the PAI includes an inspection of
a contract laboratory, arrangements should be made in advance, through the appropriate permittee, to
gain entrance for the inspection and to establish the date and time of the visit. The inspector may want
to consult the Legal Issues Training Module for information on notification procedures.
As pan of the preinspection planning process, the inspector should consult EPA or State permit
and inspection files for the facility being inspected, the DMR QA Program, and the Permit Compliance
System (PCS) for information about the permittee and its compliance status. The review of these
sources of information will be discussed in more detail in Section 2.1.3. Additionally, the inspector may
coordinate the preparation and conduct of the inspection with other offices from the Federal, State, and
local government
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2.1.3 Review of Information
The first step in preparing for a laboratory evaluation is to divide the laboratory requirements into
two categories: general and specific. General requirements are those that should be followed by all
laboratories, regardless of the terms of individual discharge permits. Sample control procedures fall into
this category. Specific requirements are those which apply only to the particular permit under
evaluation. Before visiting an onsite or contract laboratory, the inspector should become familiar with
both the general laboratory requirements, described later in this module, and the specific requirements
applicable to the laboratory in question.
As mentioned above, the main sources of information about the permittee, its laboratory
requirements, and its compliance status are the:
Permit file
Compliance file
DMR QA program
PCS.
The permit specifies the type and frequency of sampling required of the permittee and the
pollutant parameters to be analyzed. The permit file also contains information on any alternative
analytical procedures or deviations from existing procedures that have been approved by EPA. The
Inspector should ensure that the CODV of the permit being examined Is current fl.e, effective! and
up-to-date especially If enforcement activities are ongoing or completed. If enforcement action is
complete the inspector should review any enforceable orders or court decrees to assess compliance. The
permit should be reviewed to determine the types of samples the permittee is required to collect and
analyze. Once this has been determined, the inspector should review 40 CFR Part 136 for information
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on required sample containers, sample preservation techniques, maximum allowable holding times, and
approved analytical methods. For parameters that have multiple approved testing procedures it may be
helpful to confirm this method with the permittee so that the procedure may be reviewed. A table
summarizing this information for various pollutants has been provided as Appendix D. Thereafter, the
inspector should also review EPA's Methods for Chemical Analysis of Water and Wastes and NPDES
Compliance Inspection Manual; the American Society of Testing and Materials' Annual Book of
Standards. Pan 31, Water, the edition of Standard Methods for the Examination of Water and
Wastewater referenced by the current version of 40 CFR Part 136, and other sources referenced in 40
CFR Part 136 for descriptions of the appropriate analytical method for each pollutant parameter.
The inspector may find it helpful to prepare detailed checklists like those in Appendix E (discussed
in greater detail in Section 2.5.4 of this chapter). Although these checklists do not carry the weight of
the law, they can guide the inspector and serve as a memory aid. These checklists can be reviewed and
compared against the analytical methods studied in preparation for the inspection. In addition, the
inspector should be aware of any regional standard operating procedures applicable to the inspection.
Prior to an inspection, it is also useful to examine DMRs for the past 6 months as well as any
DMR QA study results. This information should be available during the inspection. The DMR QA
program is a tool used to assess and ensure the quality of NPDES self-monitoring data. Under the
DMR QA program, selected NPDES permittees are sent performance evaluation samples as part of an
annual study. These performance evaluation samples contain unknown quantities of pollutants normally
found in industrial and municipal wastewaters. The permittees are required to analyze the performance
samples for their permit parameters as a minimum, and provide the analytical results to DMR QA
coordinators at EPA Regional and State offices. The inspector should cross-check these study results
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prior to the onsite visit Analytical results noted to be outside the parameters' margin of error should
be carefully checked during the laboratory inspection.
SpeciGcally, when searching DMR QA records for information, the inspector should:
Look for general trends or problems in DMR QA performance (for example, a single
parameter that is routinely in error).
Determine if the concentration of a sample is significantly different than the permitted limit for
this pollutant If so, the DMR QA sample may have required a different analytical technique
than the laboratory normally performs.
Determine if the permittee passed its last performance evaluation sample test (i.e., did the
laboratory achieve acceptable levels for all parameters).
Contact the DMR QA coordinator and review the laboratory's justification for failing particular
parameters or not participating in the program.
Determine which laboratory performs each analysis.
2.1.4 Equipment
The inspector should gather the following items and information for use during the laboratory
inspection:
Notebook
Calculator
Measuring tape
Camera
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Safety equipment, including any required by the facility, as determined during the pre-inspection
planning process
Current permit, consent decrees, DMRs, or DMR QA performance evaluation results
Copies of 40 CFR Pan 136, Standard Methods for the Examination of Water and Wastewater.
Methods for Chemical Analysis of Water and Wastes, and other reference materials
DMR QA samples for the laboratory to analyze
Regional standard operating procedures, pertinent to the inspection where available.
2.2 INITIAL MEETING
2.2.1 Objective
There are three objectives of the initial meeting with representatives of the permittee:
To provide notice of the inspection and to receive consent to enter the facility. This notice
gives the facility an opportunity to deny access. For information on how to deal with denial of
access, the inspector should consult the companion module on Legal Issues.
To obtain the cooperation of the laboratory.
To obtain initial data for evaluating the laboratory.
This initial meeting usually lasts from IS minutes to an hour and plays a key pan in the actual
inspection. It brings the concerned parties together and sets the tone for the rest of the inspection.
Because the relationship between EPA and permittees can be adversarial from the beginning, it is
important to make every effort to generate trust on the pan of laboratory personnel. This can be
accomplished by candidly and succinctly presenting the purpose of the visit and the process by which it is
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to be conducted. The outcome of the initial meeting can determine whether conduct during the rest of
the inspection will be cordial and cooperative or difficult, and whether personnel of the laboratory to be
inspected will be honest or will attempt to conceal information. Therefore, it is very important that the
inspector set the tone of the initial meeting to his/her advantage.
2.2.2 Attendees
The initial meeting should include laboratory directors to answer questions on in-house policies
and laboratory personnel to answer questions on sample receipt, storage, analysis, and reporting proce-
dures. This mixture can ensure both maximum cooperation of personnel and release of data in a
minimum amount of meeting time. It should be noted that the laboratory analyst is an invaluable
source of information on whether the permittee's internal policies and procedures are actually
implemented on a regular basis. Entry-level laboratory staff need not be present during the initial
meeting but should be interviewed during the inspection to evaluate in-house procedures.
2.2.3 Opening Discussion
The opening discussion should include presentation of the inspector's credentials, a brief
description of the visit's purpose including timeframes of the inspections and how that purpose will be
achieved. The inspector should also explain the results that the laboratory can expect from the visit and
approximately when it will receive this information. Presenting business cards along with the EPA (or
State) credentials may make the display of credentials less formal and antagonistic. It is important to
allow time for laboratory personnel to ask questions about what will happen and why. Answers should
be as forthright and candid as possible. By this, the laboratory personnel can satisfy themselves that they
have learned all they need to know, consequently, their trust in EPA (or the State) will be increased.
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2.2.4 Organization of Laboratory Inspection
The laboratory inspection should be designed to evaluate the following programs or procedures:
Review the laboratory's QA/QC Manual
Observe sample collection, compositing, preservation, and transfer techniques, including field
chain-of-custody procedures
Observe sample receipt and documentation (including in-house chain-of-custody procedures) by
the laboratory as well as sample preparation and storage techniques
Inspect the analytical equipment used
Observe laboratory personnel's analytical procedures and techniques
Review the laboratory's equipment calibration and maintenance records
Evaluate field and laboratory records and reports
Evaluate date used to generate DMRs such as lab bench sheet and monthly summary sheet.
The activities listed above enable the inspector first to determine whether or not the permittee or
its contract laboratory has defined an effective sampling and analytical program and then to evaluate
whether that program has been implemented as defined. The remainder of this chapter discusses in
more detail the way in which the activities listed above should be conducted.
2.3 SAMPLING TECHNIQUES
During the PAI, the inspector should observe the way in which the permittee staff conducts the
sampling activities specified in the permit. During this observation, the inspector should evaluate the
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permittee's procedures against EPA methodologies and guidelines to assess sample validity and integrity.
The inspector should also ensure that the sampling location is correct and representative of the
discharge and meet the permit requirements.
The inspector should review the specific sampling and analytical procedures pertinent to the
permit In general, the quality of analytical data produced by a permittee's laboratory is dependent on
proper sampling procedures. The best analytical methods will be useless unless samples are collected
properly. As part of a PAJ, the inspector should ascertain that proper sampling procedures are used by
the permittee. This may be accomplished by discussing with the permittee, sampling procedures
including sample location and equipment, or by observing the permittee collect all samples specified in
the permit. Any deviations from approved methodology should be noted in the final report for action by
the enforcement staff. The inspector should refer to the module on Sampling Procedures for further
information.
2.3.1 Sample Validity
Samples should be representative of the wastestream, collected using proper sampling methods,
composited properly, sampled and delivered in appropriate containers, and preserved by approved
measures. Analytical checks (blanks) should be made of containers and preservatives. Appropriate
sample holding times must be observed at all times. The inspector should refer to the most current
copy of 40 CFR Part 136 to determine sample holding times and sample containers, and to the Sampling
Procedures Training Module for appropriate sampling techniques.
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2.3.2 Sample Integrity
Written procedures for all aspects of sample handling should be distributed to all appropriate
personnel. For field samples, adequate seals, labels, and records should be kept for each container.
Appropriate transport to the laboratory should be assured. The NPDES compliance monitoring in-
spector training module on Sampling Procedures describes transportation procedures in greater detail.
2.4 LABORATORY SAMPLE CONTROL
Appropriate storage conditions and holding times must be observed for all samples. The
laboratory should have formal systems for receiving samples, for distribution analyses, for storage or
discard of samples after analysis, and for chain-of-custody documentation. Incoming samples should be
received and signed for on the chain-of-custody form by a designated sample custodian. An example
chain-of-custody form is included in Appendix F. The laboratory should be secured and have restricted
access; samples should be stored in a secure area and handled by a minimum number of people. Sample
preparation (i.e., extraction or filtration) must be done in accordance with EPA-approved methods.
2.4.1 Documentation System
It is a good practice for laboratories to keep organized, complete and permanent records. Records
should be kept in bound logbooks with numbered pages whenever possible. Any procedures undertaken
as quality checks, the results of any quality checks, and any checks by outside service personnel should
be recorded, dated, and signed.
As mentioned earlier, one objective of the laboratory inspection is to evaluate general procedural
requirements that should be followed, regardless of specific permit terms. The laboratory's sample
control (chain-of-custody) procedures fall into this category. A laboratory sample control system is
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important legally when used in compliance tracking activities. It is also useful to maintain the quality of
analytical laboratory results. The importance of such a system should be emphasized to any permittee
who does not have one.
2.4.2 Record Keeping Requirements
The purpose of a laboratory sample control system is to provide sufficient information to
reconstruct the sample handling process after the sample has been analyzed. This reconstruction should
be able to:
Establish what preservatives were used in samples and what checks were made upon receipt in
the laboratory to ensure that samples were properly preserved
Establish that the analysis was performed
Trace the source of errors, correction, or unusual readings, should it become necessary to
conduct such an investigation. In making corrections in records it is important to only put
one line through a mistake (instead of making the incorrect entry unreadable by blocking it
out) and then initial and date the correction.
Establish (for later examination) that requirements of a given analysis procedure were met (e.g.,
sample holding times were followed).
A laboratory sample control system maintains records of:
Dates that samples were collected, transferred, received, prepared, and analyzed
Parameter analyses that were performed for each sample
Results of analyses
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Associated QA/QC results
Persons handling a sample received by the laboratory.
It is a good practice for a laboratory to use such a sample control system for all samples.
Pursuant to Section 308 of the Clean Water Act, permittees are required to establish and maintain
monitoring records, "typically, NPDES permits require that the following information be recorded for
routine samples:
Date, time, and location of sample collection or measurement
Name(s) of sampling and analysis personnel
Date and time of analyses
Results of analyses
Analytical techniques or methods used (including QA/QC).
Appendix G provides an example of a sample control form.
Permittees are required by regulation to Detain records (including computer disks) of all monitoring
information including the above data, all calibration and maintenance records, original strip charts from
continuous monitoring instruments, and copies of all reports and records of data used in the permit
application for at least 3 years. The permittee may be required to retain these for longer periods of
time in the event of unresolved litigation. In addition, the laboratory should maintain a file of all DMR
QA records for a minimum of 3 years. The inspector should verify that records have been documented
and maintained in accordance with these requirements.
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To test the laboratory's record keeping system, the inspector should request the laboratory to
provide several months (randomly picked) of self-monitoring data.
2.5 ANALYTICAL METHODS
Analytical methods used by a permittee's in-house or contract laboratory should be selected by
consulting the most recent 40 CFR Pan 136 and one of the referenced sources or by contacting the
appropriate EPA Regional Office for approval of alternate methods. The inspector should determine
which analytical methodology is used for each parameter measured during the inspection. Standardized
analytical test procedures that have been promulgated under 40 CFR Pan 136 appear in Appendix C
The methods identified as approved in 40 CFR Pan 136 are published primarily in the following sources:
Methods for Chemical Analysis of Water and Wastes (1979)
Standard Methods for the Examination of Water and Wastewater
ASTM Annual Book of Standards. Part 31, Water (1975)
Microbiological Methods for Maintaining the Environment
It should be noted that these sources are continuously being updated. However, the latest editions may
not contain approved techniques and therefore, approval should be verified prior to use. The inspector
should ensure that the laboratory has copies of necessary source materials.
2.5.1 Approval For Alternate Methods
If any deviation from the use of approved methods is observed, the inspector should determine
whether the permittee's laboratory has filed the proper application for alternate test procedures and has
received, in writing, the proper approval of alternate test procedures, as specified by 40 CFR 136.4 and
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40 CFR 136.5. Modifications of standardized analytical methods intended to provide specific
improvements may be used for permit monitoring only if the required written EPA approval has been
obtained. The permittee should obtain approval from EPA for alternative techniques during the public
notice period prior to permit issuance. Permittees with existing NPDES permits may wish to request a
permit modification to include alternative testing procedures. The inspector should ask to see the
written approval in question.
Some suppliers of analytical "test kits' advertise that they market "EPA-Approved" methods. While
this may be true in some cases (e.g., QIC Chemical Oxygen Demand Method and Hach Method 8000
Chemical Oxygen Demand Method), others, by the same manufacturer, may not have received similar
approval. In most cases, this lack of approval is due to a procedural variation, which may render the
results unsuitable for NPDES reporting. However, some "test kits* may use equivalent chemistry (i.e.,
the same reagents in smaller volumes or different detection limits), thereby eliminating them from
consideration as 'alternative methods.' If there is a question about the suitability of such a test kit, the
inspector should review the methods carefully to determine whether it is an "equivalent chemistry," not
requiring alternate method approval, or a nonapproved method. If the inspector is unable to determine
the suitability of a method, the questions should be referred to the Agency's QA staff.
2.5.2 Analytical Performance
The key to quality analytical performance is the skilled analyst who has had appropriate and
continuing training. The inspector should review the credentials of laboratory analysts to ensure that
each is:
Adequately trained (particularly for technical equipment such as AA or GC/MS)
Skilled in the manipulation of laboratory equipment and techniques required in analyses
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Knowledgeable and skilled at performing the analyses for which he/she is responsible
Precise and accurate in performing analytical tasks
Assigned clearly defined tasks and responsibilities.
2.5.3 QC of Analytical Methods
Just as every analytical method has a rigid protocol, QC associated with a specific test method
must include definite steps designed to monitor the test and ensure that its results are correct. For
example, in a titration, standardization of the titrant on a frequent basis is an essential element of QC
In any instrumental method of analysis, calibration and evaluation of instrument response are necessary
QC functions. The inspector should ascertain that variables affecting the results of the analytical
methods used by a permittee's laboratory are considered, evaluated, and controlled.
2.5.4 Potential Problem Areas
Appendix E provides an example of checklists available to evaluate of NPDES-approved test
methods. Each checklist briefly describes the method and contains a list of items to be considered while
observing each analysis. The checklists can be invaluable as reminders to the inspector during a PAL
They are available on an IBM PC compatible disk from the Enforcement Division of OWEP, EPA
Headquarters. A checklist is available for each NPDES test method. Again, the inspector should stress
parameters for which the facility has reported unacceptable or marginal DMR QA results.
Appendix H lists potential problem areas associated with various analytical methods published in
Methods for Chemical Analysis of Water and Wastes. A copy of the information provided in this
appendix should be available to the inspector when checking the laboratory's analytical methods. Use of
this list to evaluate a permittee's analytical methods is helpful because of the limited amount of time
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available for the inspection. If every procedure cannot be monitored, questions should be designed to
evaluate the analyst's knowledge of difficult or complex steps within specific analytical methods.
2.5.5 Microbiological Procedures
The emphasis of this module is on sampling and analysis of physical or chemical constituents since
the majority of required permit parameters are physical or chemical in nature. In addition to these
parameters, however, particular attention must be given to microbiological testing procedures. For
explanations of the unique requirements related to microbiology, inspectors should refer to Standard
Methods for the Examination of Water and Wastewater. and EPA's Procedure for the Evaluation of
Environmental Monitoring Laboratories.
2.6 EVALUATION OF LABORATORY QA/QC PROGRAMS
2.6.1 Introduction
Each NPDES permittee's laboratory should have a written QA/QC program that is known by all
personnel responsible for analyses. The QA/QC program manual should clearly state the laboratory's
objectives to produce data that meet user requirements in terms of specificity, completeness, precision,
accuracy, representativeness, and comparability. Approximately 10 to 20 percent of each laboratory's
resources should be devoted to its QA/QC program. The QA/QC manual should clearly identify the
individuals involved in the QA gram and their responsibilities and document the laboratory's standard
operating procedures. In small laboratories where it is less likely that a QA/QC program exists, all
individuals involved in the generation of data should be aware of QA and data quality objectives and
practices. The inspector may suggest the development of such a program if one does not exist.
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There are many factors that affect the precision and accuracy of analytical data. However, there
are many other sources of error independent of the analytical method, such as poor analyst techniques,
poorly maintained equipment, or bad or outdated reagents. Unfortunately, the effects of these other
sources cannot be predicted in advance. A QA/QC program is the only way to identify and correct these
and other sources of error, minimizing their effect on the overall precision and accuracy of reported
analytical results.
Laboratory data should be supported by adequate documentation that provides valid records of all
control measures that affect final analytical results. The inspector should review 40 CFR 122.41(e)
(conditions applicable to all permits) which states that the permittee shall maintain adequate laboratory
and process controls, including appropriate QA procedures.
The questions in Table 2-1 provide the focus of an inspector's review of the laboratory's QA
procedures. By obtaining and verifying the answers to these questions, the inspector should be able to
determine the laboratory's adequacies and any deficiencies. The inspector should keep in mind that any
plan is insufficient if it is not implemented by the analyst. Identification of deficiencies is important for
the inspector's exit meeting when he/she discusses findings with the permittee, as well as for preparation
of the final report.
2.6.2 Definitions and Techniques
Laboratory QA is an internal system for continually monitoring factors that impact data reliability.
As part of this internal system, methods and techniques are established to measure the accuracy and
precision of analytical data. Examples of such methods are the use of spiked, duplicate, and
performance evaluation samples.
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TABLE 2-1. QA QUESTIONS
Question
Rationale
Is there a Laboratory Methods Manual
Is there a Laboratory Quality Assurance
Manual?
Is there a Manager/Coordinator for
Quality Assurance?
Are EPA-approved analytical methods used?
If alternate methods are used, has Regional
approval been obtained for their use?
What procedures are used to calibrate each
type of analytical instrument in use?
Are the results of the calibration documented?
To determine if the laboratory has written
procedures for analysis.
To determine if the laboratory has written
procedures for quality control.
To determine if there is a person responsible for
enforcing these procedures.
To ascertain whether EPA-approved methods are
being used for chemical analysis
What are the laboratory's quality control
procedures?
What percent of the laboratory sample load is
duplicate samples?
What percent of the laboratory load is spiked?
Is the laboratory certified by the State or
by any other certifying entity?
To determine whether adequate quality control
procedures are being used
To determine if the laboratory is certified by the
State (or another entity)
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TABLE 2-1. QA QUESTIONS (Continued)
Question
Rationale
Are acceptable standard reference materials
used as a routine part of calibration and
quality control programs?
Are the standard reference materials verified
against EPA QC samples?
Are QC samples analyzed quarterly?
What happens to a sample after it enters
the laboratory?
How are quality control data used?
To indicate how important the laboratory regards
its standard and calibration reagents. Analysis of a
known standard is required to standardize analytical
methods. The known standards must be composed
of materials of unimpeachable purity and product
quality. An inspector should examine the standards
used in calibration to ensure that they are of
appropriate quality. Appropriate quality refers
to a standard that is traceable to. or is a standard
reference material (SRM) provided by the National
Bureau of Standards (NSB). Laboratories that use
any other reagents as calibration standards are
calibrating their methods against a standard of
poorer quality and greater variability.
To give a perspective of the laboratory's internal
sample control procedure. The inspector should
receive an explanation of the laboratory sample
control procedure and should also request a copy of
the written procedure. Lack of such a program
makes reconstructing a past analysis impossible and
is indicative of potentially deficient procedures in
other work areas.
To determine how criteria are established and used
for acceptance and rejection of quality control
samples. The inspector should also determine the
disposition of samples/data when quality control
results are rejected (i.e., are samples reanalyzed or
is data flagged and rejected).
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Spiked samples are used to evaluate accuracy by analyzing a sample before and after the addition
('spike") of a known amount of one or more constituents. Percent recovery of the spiked material is
calculated from the two data. The closer the percent recovery comes to 100 percent, the more accurate
the analysis.
Duplicate or replicate analyses of the same sample are used to evaluate the precision of the
analysis by comparing the results of the two or more analyses. These comparisons are often expressed as
the relative percent difference between the resulting data. The closer the relative percent difference
comes to zero, the more precise the analysis.
Performance evaluation samples are used to assess the accuracy and precision of analyses by
submitting samples for analysis where neither the analytes nor the concentrations are known to the
analyst. These samples are also known as "blind samples." the results of the analyses are compared to
the known analytes and concentrations. This evaluation may be made an internal QA procedure; it is
also used as an external QA procedure. An example of this type of external QA procedure is the
receipt and analysis of samples provided by EPA for submission of DMR QA data.
Laboratory QC is the routine application of procedures necessary for the measurement process to
meet prescribed standards of performance. All analysts practice QC, to some degree, in their laboratory
activities. Such exercises as choosing the appropriate glassware and performing quantitative transfers are
part of QC A formal QC program encompasses several steps, including:
Regular analysis of standards [traceable to National Bureau of Standards (NBS) or EPA
repository standard reference materials] for instrument calibration
Regular analysis of reference unknowns as a check on both identification and quantification
procedures.
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2.6.3 Elements of a QA/OC Plan
In evaluating the laboratory QA/QC plan, the inspector should ensure that it includes:
Provisions for the assurance of valid sampling
Use of EPA-approved methodology or approved alternative test procedure in all cases
Periodic calibrations and checks of services, instruments, equipment, lab pure water, and
supplies
Maintenance of quality analytical performance
Efficient data handling and reporting procedures
Provisions for adequate number of duplicate analyses (5 to 10 percent)
Provisions for adequate number of spiked analyses (5 to 10 percent)
Provisions for analyses of adequate number of standards.
Section 2.7 provides more discussion of these aspects of a laboratory's QA/QC program and of items to
evaluate during the QA part of an inspection. The inspector should also refer to the training module on
Sampling Procedures.
2.6.4 QA/QC Coordinator
The laboratory should have a QA/QC coordinator who has overall responsibility for the
development, implementation, and administration of the QA/QC program. The QA/QC coordinator
should assess the program continually, identify needs for QC training, and coordinate interlaboratory QC
programs.
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2.6.5 Control of T -ahoratorv Services. Instruments. Equipment, and Supplies
Elements of QC affected by laboratory services, equipment, supplies, or reagents should be
included in the overall QA plan. The inspector should determine whether the laboratory is conforming
with the recommendations or requirements provided in Section 2.7 of this chapter by evaluating and
determining generally the amount of time spent on each area. The inspector should devote extra time to
areas that look suspicious or that could present potential problems. This subject is pursued in more
depth in Section 2.7.
2.6.6 Precision and Accuracy
Precision refers to the reproducibility or degree of agreement among replicate measurements of the
same quantity. The closer the numerical values of the measurements come to each other, the more
precise are the measurements. In a laboratory QA program, precision is determined not by using
reference standards, but by the use of actual water samples covering a range of concentrations and a
variety of interfering materials usually encountered by the analyst Such data should not be collected
until the analyst is thoroughly familiar with the method and has obtained a reproducible standard curve.
Accuracy refers to the degree of difference between measured or calculated values and the true
value. The closer the numerical value of the measurement comes to the true value or actual
concentration, the more accurate the measurement is. Again, accuracy should be determined with actual
water samples representative of samples routinely analyzed. Preferably, accuracy should be determined
with the same series of samples used in the precision determinations. Figure 2-1 presents definitions
and diagrams of precision and accuracy.
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Imprecise and Inaccurate
Accuracy degree of
agreement between
measured value and true
value
Precise but Inaccurate
Accurate but Imprecise
Precision - degree of
agreement among results
obtained by repeated
measurements on a single
sample under a given set
of conditions
Precise and Accurate
FIGURE 2-1. PRECISION AND ACCURACY
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2.6.7 QA/QC in Sample Collection and Analysis
As stated in the NPDES compliance inspection guidelines, the inspector should check to ensure
that sampling has been property conducted by the permittee. Many common errors are caused by
improper sampling, poor or improper preservation, or lack of adequate mixing during compositing and
testing. The checks described below will help the inspector to determine when the permittee's sampling
and analysis system is outside the accepted typical deviations for laboratory analysis.
2.6.7.1 Duplicate Samples
Duplicate samples are identical portions of the same raw sample. The same analytical steps are
performed on each of the duplicate samples to provide a proficiency check for precision. Duplicate
analyses should be performed on at least one sample per group of samples analyzed, 5 to 10 percent of
all samples measured.
2.6.7.2 Replicate Samples
Replicate samples are identical portions of the same prepared sample. Analytical steps are
performed on the primary sample. The primary sample is then divided into replicates. The results of
the replicates analysis provides a check on the homogeneity of the sample. There are currently no
recommended guidelines for the analysis of replicates. However, the inspector should be familiar with
the preparation and use of replicates to ensure that they are not being substituted by the permittee's
laboratory for duplicate samples.
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2.6.7.3 Split Samples
Split samples allow the comparison of analytical techniques and procedures from separate
laboratories. Samples are divided into two or (preferably) three segments. They are then analyzed in
different laboratories using the same analytical techniques. Differences between EPA (or State) and
permittee results can then be evaluated.
2.6.7.4 Performance Samples
If the permittee analyzes performance samples of permit parameters, discrepancies in its analytical
techniques and procedures can be identified. It is preferable to have these performance samples
provided to the permittee for analysis and submission to EPA prior to the visit or use them during
inspections to observe analytical techniques so that problems can be discussed and corrected during the
inspection. The laboratory should be encouraged to analyze QC performance evaluation samples as pan
of its QC program.
2.6.7.5 Spiked Samples
Spiked samples provide a check on the accuracy of analytical procedures. Known amounts of a
particular constituent should be added to an actual sample at concentrations where the accuracy of the
test method is satisfactory.
2.6.7.6 Sample Blanks
Blank samples provide a check on contamination of acid and other chemicals and the bottle
cleaning procedure. A specified quantity of chemicals or preservative should be added to a sample of
distilled water as would normally be added to the wastewater sample. This blank is sent to the
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laboratory for analysis, and the concentration of constituents in the blank is sometimes subtracted from
the wastewater sample results. However, the analytical method determines if the blank is subtracted.
For example, blanks of distilled water analyzed during BOD5 analyses should not be subtracted from
sample analytical results. Batches of chemical preservatives should be changed as often as necessary to
prevent contamination of samples.
2.6.7.7 Acceptance Criteria and Control Charts
Acceptance criteria are statistically derived values that define the range of acceptability for QC
data. A control chart is a graphic display of data with the vertical scale plotted in units of the test
result and the horizontal scale in units of time or sequence of results. The upper and lower control
limits shown on the chart are used as criteria for action or to judge the significance of variations
between duplicate samples. The central line represents the average, or the standard value, of the
statistical measure being plotted. Figure 2-2 is an example control chart plotted from the data in Table
2-2.
The inspector should review EPA's Handbook for Analytical Quality Control in Water and
Wastewater Laboratories for derivation of acceptance criteria and for construction and use of control
charts. QC charts were originally developed for the control of production processes where large
numbers of items were being manufactured and inspected on a continuous basis.
Daily precision and accuracy data can be compared to calculated acceptance criteria or plotted by
means of QC charts to determine whether valid, questionable, or invalid data are being generated from
day to day. There are several techniques available for constructing QC charts and plotting subsequent
data. Two techniques currently used are the Shewhart technique and the CuSum technique (see EPA's
Handbook for Analytical Quality Control in Water and Wastewater Laboratories).
NOTES:
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Point
TABLE 2-2. ANALYSIS OF TOTAL PHOSPHATE-PHOSPHORUS STANDARDS
IN mg/l TOTAL PO4-P
Known Obtained
Difference
Percent
Recovery
P,1
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
0.34
0.34
0.40
0.49
0.49
0.49
0.50
0.50
0.50
0.52
0.66
0.66
0.67
0.68
0.83
0.98
1.3
1.3
1.6
2.3
2.3
3.3
4.9
033
034
0.40
0.49
0.49
0.63
0.47
0.53
0.56
0.59
0.70
0.60
0.65
0.65
0.80
0.75
1.2
1.3
1.7
2.3
2.4
3.3
4.6
0.01
0.00
0.00
0.00
0.00
-0.14
0.03
-0.03
-0.06
-0.07
-0.04
0.06
0.02
0.03
0.03
0.23
0.10
0.00
-0.10
0.00
-0.10
0.00
0.30
00001
0.0000
0.0000
0.0000
0.0000
0.0196
0.0009
0.0009
0.0036
0.0049
0.0016
0.0036
0.0004
0.0009
0.0009
0.0529
0.0100
0.0000
0.0100
0.0000
0.0100
0.0000
0.0900
97
100
100
100
100
129
94
106
112
113
106
91
97
96
96
77
92
100
106
100
104
100
94
9.409
10,000
10,000
10.000
10.000
16.641
8.836
11,236
12,544
12,769
11,236
8,281
9.409
9,216
9,216
5,929
8,464
10,000
11,236
10,000
10,816
10,000
8,836
Totals
2.310
234,074
1 Using a colorunetnc method with persulfate digestion.
Percent Recovery
/>=» 100
Average Percent
Recovery
100.4
observed- background
spike
The Standard Deviation
for Percent Recovery
a*
a>
22
.074-(2.310)2/23
22
> ^94.0751
Front
= 9.70
Handbook for Analytical Quality Control In Water
and Haetewater Laboratories (EPA.- 600/4-79-019)
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Based on the data and calculation in Table 2-2.,
the upper control limit becomes the following:
UCL = F+ 3Sf
= 100.4 + 3(9.70)
= 129.5
and the lower control limit becomes
LCL =100.4- 29.1
= 71.3
The completed control chart is shown below
140 r
_^ UCL
£ 120
8
S 100
UJ
60
.. P
80
LCL
5 10 15 20 25
SAMPLE NUMBER
Shewhart control chart for percent recovery data.
From: Handbook for Analytical Quality Control in Water
^nTwaatewater Laboratories (KPA-600/4-79-019)
FIGURE 2-2. EXAMPLE CONTROL CHART
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Precision control charts are developed by collecting data from a minimum of IS to 20 samples run
in duplicate under controlled conditions. These data should be generated over an extended period of
laboratory time (e.g., 10 to 20 days) and be representative of normal operating conditions.
Accuracy control charts are developed by collecting data from a minimum of IS to 20 samples
(preferably spiked samples although reference standards may be used) under controlled conditions.
Again, these data should be generated over an extended period of laboratory time and be representative
of normal operating conditions.
The determination of the control limits (acceptance criteria) depends on the accuracy and precision
of the procedure itself. It is common practice to set a warning limit at two standard deviations and an
action limit at three standard deviations of the accuracy and precision specified for the method.
2.6.7.8 Establishing Analyst Precision and Accuracy
The following analyses should be run to establish analyst accuracy (except for radiological
instrumentation):
One pair of duplicate samples per group of samples analyzed or at least 10 percent of all
analyses. The typically accepted range of percent difference between duplicates is zero to 10
percent However, the percent is method dependent
One spiked sample per group of samples analyzed or at least 10 percent of all analyses. The
typically accepted range of percent recovery of spikes is 90 to 100 percent
Sufficient standards analyzed to verify all calibration curves.
Performance samples, may be available from EPA-Environmental Monitoring and Support
Laboratory (EMSL), Cincinnati.
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Laboratory participation in round-robin split samples method, performance evaluation studies,
and laboratory evaluation programs.
2.6.8 Performance Evaluation to Assure Quality
The inspector's review should determine whether at least two standards with concentrations which
bracket those of the samples are analyzed dairy, with a blank, at comparable operating conditions to
verify an established standard curve. Many methods, such as atomic absorption, require daily preparation
of a standard curve. In general, it is good practice for the analyst to ensure that 1 of about every 10
samples is a duplicate in order to check precision, according to acceptable standard deviation or percent
relative standard deviation (as given in EPA's Handbook for Analytical Water Quality). One of every
ten samples should be a spiked sample to check accuracy according to acceptable percent recovery or
percent bias. If fewer than 10 samples are analyzed for a specific parameter, one duplicate sample and 1
spiked sample should be run with this group of samples. Acceptability of data is determined by
evaluation of the result of the QC analyses against the established acceptance criteria or control charts.
Data falling outside the upper or lower control limit (acceptance criteria) indicates a problem with the
analyses. The problem must be located and corrected, and these samples must be reanalyzed or the
results qualified.
2.6.9 Documentation of Daily Performance
After about 20 sets of duplicate data results or spiked sample results have been collected, the
laboratory analyst should construct control charts for precision and accuracy, respectively, to document
data reliability. These charts are used to show data which deviate from the upper and lower control
limits. Although control charts are not required in the NPDES program, the inspector should ascertain
whether such charts are prepared on a regular basis.
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2.6.10 Secondary Checks on Performance
QC samples for many commonly analyzed constituents are available from EPA; the concentrations
of each constituent are provided with the samples. Such QC samples should be run every quarter at the
time of sample collection, whether the sample is a grab sample or a composite of grab samples.
2.7 LABORATORY FACILITIES AND EQUIPMENT
An important factor in QA is the maintenance of the laboratory's fetilities and equipment. While
this has been touched on briefly in Section 2.6, the following section will provide greater detail with
regard to laboratory services, safety procedures, instruments, glassware, reagents and standard solutions,
solvents, and gases.
2.7.1 Reviewing Laboratory Services and Safety Procedures
Appendix I lists laboratory services and the potential problems in their supply. These services
include distilled water, compressed air, adequate electrical power (including voltage regulated sources for
delicate electronic instruments), adequate space, lighting, ventilation, temperature, and humidity control
where appropriate, and efficient fume hood systems. The lab pure water should be ammonia-free,
carbon dioxide-free, ion-free, have a low organic background, and must be available at all times. The
distilled water should be periodically checked to see if it meets these requirements and the results of
such testing should be documented. Dry, oil-free, uncontaminated compressed air should also be
available on a continuous basis. Further, written requirements for daily warm-up, standardization,
calibration, and/or optimization procedures should be provided for all analytical instruments. Since many
problems can be traced to poor services, the inspector should note any problems or deficiencies found.
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During the laboratory tour, the inspector should ensure that proper safety equipment (gloves,
goggles, and fume hoods) are being used if necessary for the analysis being performed. The laboratory
should also be equipped with a fire extinguisher, eye wash station, shower, and first aid kit. The
inspector should verify that any safety violations noted during the last inspection have been corrected.
The inspector should also determine if the laboratory disposes of hazardous wastes (spent solvents and
chemicals, highly concentrated standards, and samples) in an acceptable manner.
The inspector will also find it useful to query the laboratory staff about laboratory funding.
Determining if funds are available for training, instrument maintenance, and facility upkeep may be
useful to pinpoint problems in the laboratory and to make recommendations for modification in the final
report.
2.7.2 Examining Equipment
The analytical laboratory relies heavily on instrumentation to generate reported data. Most
analytical methods involve the use of one or more instruments. Therefore, a fundamental understanding
of how the instruments work will assist the inspector in evaluating their use. While this information is
available in any advanced analytical chemistry textbook, the major problems that may be encountered
when observing the analyst using modern, analytical equipment are presented here. Instruction manuals
for the daily operation of each instrument and piece of equipment should be provided and followed. In
addition, written troubleshooting procedures and written schedules for replacement, cleaning, checking
and adjustment by service personnel should be available. The following instruments are those most
commonly used in routine water and wastewater analysis:
Analytical balances
pH meters
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Dissolved oxygen meters
Conductivity meters
Turbidimeters
Spectrophotometers
Atomic spectroscopic instruments
Organic carbon analyzers
Selective ion analyzers
Gas-liquid chromatographs
Titrimetric analyses
Temperature controls.
Each of these instruments or systems is discussed below.
2.7.2.1 Analytical Balances
The analytical balance is one of the most important pieces of equipment in any analytical
laboratory. If the balance is not accurate, all gravimetric data, and data related to weight-prepared
standards, will be in error.
Most analytical balances currently used are "single-pan* balances. Since these instruments are
fragile (subject to shock, temperature, and humidity changes, and of course, mishandling), the inspector
should note any indications of misuse. Calibration should be checked and recorded dairy when the
instrument is in use, using a 1.0-g and 0.1-g Class 'S* weight or weights bracketing the anticipated
sample measurement range. The full scale vernier of a mechanical balance must be checked to verify the
balance's sensitivity. This is accomplished by dialing in one gram less than the actual weight and letting
the vernier scale roll to the end of its scale. A label or separate record indicating annual service checks
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by outside representatives should also be affixed to the balance. The high sensitivity of these balances
requires that they be isolated from sources of thermal fluctuation or vibrational disturbances, such as hot
air ovens, mechanical shakers, and flowhoods.
2.7.2.2 pH Meters
A pH meter is used to measure the standard units (S.IL) of the hydrogen ion concentration of a
solution. A glass electrode is used as the indicator and a calomel electrode as the reference (combined
electrodes are also available). Glass electrodes have a very Cast response time in well-buffered solutions.
However, in poorly buffered solutions, accurate readings are obtained slowly. This is particularly true
when changing from buffered to unbuffered samples, as after standardization.
The inspector should examine the electrode to make sure it is filled with electrolyte solution to a
level above the level of the sample and the wick not clogged. Glass electrodes should not be allowed to
become dry. When not in use, they should be immersed in distilled water or pH 7.0 buffer. The
inspector should observe the analyst's technique to ensure the meter is calibrated with standards which
bracket the anticipated range of the sample pH. Records of the calibration procedures and replacement
of electrodes should be maintained and should indicate daily calibration of the pH meter when in use.
Electrodes should be well rinsed with distilled water after each reading and rinsed or dipped
several times in the next test sample before the final reading is taken. The analyst should also stir
weakly buffered solutions during pH measurement and allow enough time for the pH meter to come to
equilibrium before pH is recorded.
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2.7.2.3 Dissolved Oxygen Meters
Dissolved oxygen meters are very common in laboratories. Dissolved oxygen meters rely on a
probe to measure the dissolved oxygen content in mg/1 of a solution.
Dissolved oxygen meters require a short warm-up time prior to being used. The meters should
also be red lined prior to calibration. Calibration can be conducted through the wet air, saturated water,
or titrimetric methods. Wet air and saturated water calibrations require good quality temperature and
barometric pressure readings. Certified mercury thermometers and barometers are recommended. If
such are unavailable, the permittee should have these instruments calibrated with certified mercury
thermometers and barometers periodically. Titrimetric analyses are described in Section 2.7.2.11.
2.7.2.4 Conductivity Meters
Conductivity meters measure the conductance of a solution expressed in mhos/cm. For natural
water samples, the reporting unit is micromhos/cm because of the small amount of current that can pass
through. The sensing element in this conductivity meter is the conductivity cell.
During the inspection, cells should be examined to ensure that the platinized coating is intact
The plates should not be coated with suspended matter, bent, distorted, or misaligned. The lead wires
should be properly spaced. The conductivity meter should be calibrated monthly using a standard
potassium chloride solution.
Temperature has a pronounced effect on solution conductance and must be corrected for when
results are reported. The specified temperature for reporting data used by most analytical groups and all
EPA laboratories is 25-C
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2.7.2.5 Turbidimeters
Turbidimeters compare the intensity of light scattered by sample particles under defined conditions
with the intensity of light scattered by a standard reference suspension. Reference standards are
commercially available to calibrate turbidimeters. In addition, correct use of the meter requires that
samples containing turbidities in excess of 40 Nephelometric Turbidity Units (NTU) be diluted to a
value below this level and the results multiplied by the dilution factor. The inspector should ensure that
the instrument is properly calibrated and check the condition of the sample cuvets to ensure that they
are not scratched, because scratches result in measurement errors. The cuvets should also be clean.
2.7.2.6 Spectrophotometers
In Spectrophotometers, the sample solution absorbs electromagnetic radiation; the amount absorbed
or emitted is related to the concentration of the chemical in the solution. Absorption
Spectrophotometers can be divided into three types: Ultraviolet (UV), Visible (VIS), and Infrared (IR).
The inspector should determine whether care is being taken to follow the manufacturer's
instructions when using Spectrophotometers. Colored solutions can be used for visible
spectrophotometry and organic compounds with known absorption curves can be used for UV and IR.
Filters, solutions, and standard reference materials, with standard absorption curves, are available for
calibration of these Spectrophotometers. Spectrophotometers must be calibrated with standards that have
concentrations which bracket those of the samples. A standard should also be run with each set of
samples to verify the existing curve. A constant power supply is required.
Care of absorption cells should be emphasized. All cells should be kept scrupulously clean and
free of scratches, fingerprints, smudges, and evaporated film residues. Matched cells should be checked
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to ensure that they are equivalent by placing portions of the same solution in both cells and by taking
several readings of the percent Transmittance (T) or Optical Density (OD) values. If a cell is mis-
matched, it should be discarded or reserved for rough work.
Generally speaking, trained technicians may successfully operate any spectrophotometer. Because
of the special techniques of sample presentation, instrument operation, and interpretation of absorption
curves, the competence of the operator is important Thus, the inspector should ascertain the
qualifications of the individual who interprets specirophotometric data.
2.7.2.7 Atomic Spectroscopic Instruments
Atomic spectroscopic instruments measure the absorption or emission of radiation by free atoms.
Atomic Absorption (AA) instruments are the most important in this group; they are used for metal
analysis. There are a number of accessories available for atomic absorption equipment:
Radiation source
Nebulizer
Burners
Graphite furnace
LVov platform
Cold vapor mercury cell
Optical systems
Readout devices
Mode conversion.
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For a program analyzing a wide variety of samples for a number of elements at varying concentrations,
an instrument with maximum versatility is required.
The inspector should verify metals digestion to ensure the metals fraction specified by the permit is
actually being measured. The inspector should also ensure that standards are run at appropriate
concentrations and frequencies. At a minimum, a calibration curve consisting of at least three standards
must be run prior to all sample batches, and at least one standard in the anticipated concentration range
of the samples should be run intermittently and upon completion of the sample batch. The analyst
should have a written check-out procedure for the AA instrument, and records showing when the
check-out was performed and what results were obtained.
Many analyses of metals suffer from potential interferences. This information should be readily
available to the analyst, on an anaryte-by-analyte basis, so that the sample can be correctly prepared.
2.7.2.8 Organic Carbon Analyzers
In the organic carbon analyzer, material containing carbon is combusted to convert the carbon to
carbon dioxide, which is then measured. The inspector should consult the permit to determine the type
of TOC analysis required (e.g. dissolved, purgable, etc) Injection of a representative sample should be
ensured by the inspector.
2.7.2.9 Selective Ion Analyzers
The selective ion analyzer develops an electrical potential in response to the activity of the ion for
which it is selective. For example, the probe designed to measure divalent cations does not respond to
precipitated calcium and magnesium and, therefore, does not accurately measure total hardness.
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Selective ion analyzers are specific for the ion in question but can respond to other ions in high
concentrations; therefore, care must be taken to eliminate interferences. The manufacturer's operating
instructions should be available in the laboratory, and should be referred to and followed by the analyst.
A calibration curve consisting of at least three standard concentrations of analyte should be
prepared independently. At least one standard should be run during each set of samples to verify the
curve. Newer models of selective ion analyzers generate an internal calibration curve from two
standards. In this case, a third standard should be run during each batch of sample to verify the
accuracy of the internal curve.
2.7.2.10 Gas-Liquid Chromatographs
The Gas-Liquid Chromatograph (GLC or GC) is one of the most useful instruments available in
an analytical laboratory. To obtain useful data from these instruments, special attention must be paid to
the following items:
Thermal Control
It is necessary to have accurate control of the column oven temperature. The temperature
should be reproducible to 1*C and have maximum thermal gradients of 2*C throughout the
oven. Most instruments on the available today meet these requirements, if the instrument
is properly maintained.
Column Bleed
The stationary phase may bleed off the column at high temperatures resulting in a drifting
baseline and changes in column efficiency (retention times and specificity). Keep the
column below the maximum temperature of the stationary phase.
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Thermal Cycle
- Before sample injection, the temperature of the column and injection port should be
allowed to equilibrate.
Inert Injector
- Many organic compounds decompose when they come into contact with hot stainless steel.
Therefore, the injection block should be capable of accepting a quartz or glass tube to
prevent the compounds from contacting hot metal.
Sample Carryover
- Memory peaks ("ghosting") can be eliminated or greatly reduced by using glass inserts for
injection.
Sample Introduction
- A precision, gas-tight, 10-microliter syringe that can be accurately filled, that will deliver
reproducible injections, and that can be easily and thoroughly cleaned is recommended for
packed column gas chromatographic use. A 1.0- or 0.5-microliter syringe is recommended
for capillary column gas chromatographic use. A teflon plunger seal to prevent backwash
and low dead volume are desirable features. A gas-tight syringe is not required for liquid
injections but is required for injections of vapors. Many GCs are fitted with automatic
samplers which may be programmed to introduce preset volumes of samples into the
chromatograph at preset time intervals. Because of design differences, separate automatic
samplers are required for liquid and vapor injections.
Injectors
- The injector septum should be changed at the end of each day's use. Changing the septum
at the end of the day allows overnight purging of any bleed-off contaminants from the new
septum. To avoid most of this bleed-off, the septa can be preconditioned by heating at
250* C in a vacuum oven for 2 hours. Some chromatographs are fitted with septumless
injectors. With these injectors, care should be taken to ensure that there is no leak of
sample or carrier gas.
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Electron Capture Detectors, Thermal Limits
- The tritium detector has an upper limit of 225*C because of radioactive leakage. This
temperature limitation makes the tritium detector susceptible to a buildup of high-boiling
contaminants (those that boil above 225-C), which reduce its sensitivity. The nickel
detector can be operated up to 400-C to prevent this buildup. The detector should be kept
at a higher temperature than the column to avoid contaminant buildup.
Detectors
- Many types of detectors are available for gas cbromatography, including Flame lonization
(FID), Electron Capture (ECD), flame photometric, electrolytic conductivity, and
microcoulometric titration detectors. Each of these detectors is best suited for a specific
type of analysis. Individual methods specify the type of detector to be used. The laboratory
should have the specified detectors available.
Gas Supplies
- Nitrogen, helium, argon, or hydrogen can be used as a carrier gas for the chromatographic
separation. Specific gases are required by some methods. To avoid the risk of system or
detector contamination from materials possibly present in the gas cylinder, the cylinder
should be replaced when the tank pressure reaches 200 pounds per square inch (psi). It is
also recommended that some type of gas purifier, composed of a molecular sieve, desiccant,
and filter, be used on all combustion gases and carrier gases used with electron capture
detectors.
Quality Control
. NPDES CC methods specify certain quality control procedures that must be performed.
2.7.2.11 Titrimetric Analyses
Titrimetric analyses are often used in the place of electronic analytical equipment Titrimetric
analyses involve the addition of chemical reagents, and a color indicator to a sample, and titration with a
chemical reagent until an end point is reached (color disappears).
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The most common titrimetric analyses are used to monitor for dissolved oxygen, ammonia nitrogen,
and total residual chlorine. Regardless of which titrimetric analysis is performed, the chemical reagents
and indicator used must be of high quality and purity. Section 2.7.3 of this chapter provides further
information to help the inspector in the evaluation of reagents.
2.7.2.12 Temperature Controls
Many of the analytical techniques used are temperature dependent In addition, the shelf life of
many reagents and chemicals is dependent on storage temperature. Common laboratory instruments and
the corresponding temperatures for accurate pollutant analytical testing are as follows:
Sample refrigerator temperature must be maintained at s4*C
BODs incubator temperature must be maintained at 20+1*C
TSS diving oven temperature must be maintained between 103-105
Fecal coliform bath temperatures must be maintained at 44.5+0.5'C
Daily logs should be maintained of these laboratory instruments' temperatures. Thermometers with
a temperature range from 0-110'C can be used to measure temperature during temperature monitoring
for all pollutant testing except fecal coliform. A speciGc fecal coliform bath thermometer must be used
to measure bath temperature. Standard thermometers which measure temperature should be calibrated
once per year with an NBS or equivalent certified thermometer. Instruments' temperature control
should not be relied upon because they can be inaccurate and unreliable. Temperature control should
be checked periodically with a thermometer.
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2.7.3 Evaluation of Equipment and Reagents
The inspector should verify that certified and standardized equipment and reagents are available in
the laboratory to perform daily check procedures, such as:
Standardized weights (class "S," at a minimum)
Certified thermometers (NBS or NBS traceable)
Filters or solutions for wavelength alignment checks
NBS, EPA Repository, or other standard reference materials with standard absorption curves
Standard resistors
Calibration solutions (buffers, conductivity standards and turbidity standards)
Analytical standards to establish or check calibration curves
Radioactive standards with date and count
The use of the above should be recorded in daily use logs or calibration logs.
The laboratory should use polyethylene bottles for solutions of boron, silica, and alkali; glass
containers for organics; and brown glass containers for light-sensitive solutions such as phenols.
Volumetric analyses should be performed only with Class "A" calibrated glassware. A standardized and
consistent program for cleaning glassware should be mandatory, with analytical checks on its effec-
tiveness. These checks include analysis of blanks, generated in random selections from batches of
cleaned glassware, for each method for which the glassware is to be used.
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The purity required of laboratory reagents depends on the analyte of interest, the sensitivity of the
method, and the specificity of the detection system. If purity of reagents is not specified in the method,
general inorganic analyses require:
Analytical Reagent (AR) grade chemicals (however, standardizing solutions must be made up
with primary standard grade reagents)
Distilled and deionized water and solvents that are free of the analyte of interest
Commercial grade gases.
Flame emission and atomic absorption analyses of metal compounds require:
Certified reagents
Distilled-in-glass acids
Deionized distilled water
Commercial-grade, laboratory-supplied gases.
Radiological analyses require:
Scintillation grade reagents and solvents
High-purity, extra dry gases with low radioactive background.
Organic analyses (e.g., gas chromatographic methods) require:
High purity solvents [e.g., pesticide grade or High Performance Liquid Chromatography
(HPLQ grade]
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Reference grade chemicals of highest purity
High purity gases.
Laboratory supplies with limited shelf lives should be marked by the laboratory with date of receipt
and date by which they should be disposed of. The inspector should check to see that shelf life
recommendations, including the disposal date on the container and storage requirements, are being
observed. The 'background' of reagents and solvents in use should be checked, and method blanks
should be run with every series of samples, or one for every nine samples (whichever is more frequent).
Purchasing high purity reagents with identical batch numbers will reduce the need to constantly monitor
these background solutions and may prove cost-effective. The Laboratory's QA/QC program should
include written procedures for reagents and solvents describing:
Tolerance units
Clean-up
Hazard response methods
Application of correction procedures. Gas cylinders should be replaced at a minimum of
100-200 psi.
Reagents and standard solutions should be prepared using:
Primary standard grade chemicals
Careful weighing
Class A volumetric glassware
Appropriate quality distilled water or solvent
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Dilute standards should be prepared at the time of use. Standard solutions should be prepared as
required by stability. Concentrations of stock solutions should be verified prior to being used to prepare
dilute or standard solutions and working standards should be standardized checked frequently to
determine if changes in concentration have occurred. The standard solutions and reagents should be
property labeled including the date of preparation and analyst's identification. Purchased solutions
should contain the chemicals specified by the method being used and they should be checked for accur-
acy. Clean containers of suitable composition with tight-fitting stoppers or caps should be used for
storage. Safeguards should be taken against evaporation of solvents, absorption of gases and water
vapor, and the effects of light or temperature. Reagents or solvents should be discarded when signs of
discoloration, formation of precipitates, or significant changes in concentration are observed.
2.7.4 Examining Glassware
The measurement of trace constituents in water demands methods capable of maximum sensitivity.
This requirement is especially true for metals and trace organics, such as pesticides. Acceptable accuracy
and precision in these methods cannot be attained unless special attention is given to glassware,
particularly to prevent contamination. The purpose of this section is to acquaint the inspector with the
kinds of glassware available, with the correct use of volumetric ware, and with various cleaning
requirements. The inspector should request a description of the glassware and the cleaning operations in
use. Where possible, he/she should observe these procedures being performed.
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2.7A.I Types of Glassware
There are many grades and types of glassware available, ranging from student grade to grades
possessing specific properties, such as resistance to thermal shock, resistance to alkali, low boron
content, and super strength. Examples of these include:
Kimax- or Pyrex-brand glass, which is a relatively inert, all-purpose borosilicate glass, with high
thermal stability
Vycor-brand glass, which is a silica glass (96 percent) made to withstand continuous
temperatures up to 900* C (can be down-shocked in ice water without breaking)
Coming-brand glass, which is claimed to be SO times more resistant to alkalies than
conventional ware and practically boron-free (maximum 0.2 percent)
Ray-Sorb- or Low-Actinic-brand glass, which is used with light sensitive material
Corex-brand labware, which is harder than conventional borosilicates and better able to resist
clouding and scratching.
2.7.4.2 Volumetric Glassware
Volumetric glassware, including volumetric flasks, volumetric pipets, and burets, are accurately
calibrated for precise measurements of volume. Other less accurate types of volumetric glassware, such
as graduated cylinders, are useful when exact volumes are not necessary. The volumetric apparatus must
be read correctly, that is, the bottom of the meniscus should be tangent to the calibration mark. In
order to reduce errors that might result from other sources such as temperature changes, Class A
borosilicate glassware should be used. Stock solutions, standards, and QC samples should be prepared
using volumetric glassware.
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Volumetric apparatus is calibrated 'to contain* or "to deliver* a definite volume of liquid. This
will be indicated on the apparatus with the letters TC* (To Contain) or TD* (To Deliver). For
example, volumetric flasks are calibrated to contain a given volume. They are available in various shapes
and sizes ranging from a 1 to a 2,000-milliliter capacity. Similarly, volumetric pipets are calibrated to
deliver or to contain a fixed volume of liquid. The usual capacities are 1 to 100 milliliters although
micro-pipets are also available. Volumetric pipets should be held in a vertical position when they are
being emptied, and the outflow should be unrestricted. The tip of the pipet is placed in contact with the
wall of the receiving vessel for a second or two after the free-flow has stopped. For "to deliver* pipets,
it is important that the liquid remaining in the tip of the pipet is not forced out
Burets are used to deliver definite volumes of liquid. The more common types that usually have a
25- or 50-milliliter capacity are graduated to tenths of a milliliter, and are provided with stopcocks.
(Ten milliliter burets are commonly used for DO titration.)
2.7.4.3 Federal Specifications for Volumetric Glassware
Circular 602 of the NBS Testing of Glass Volumetric Apparatus* describes the Federal
specifications for volumetric glassware. Manufacturers designate volumetric glass apparatus that meet the
Federal specifications as Class "A" and all such glassware is permanently marked (etched) with a large
"A.* In addition to the "A" marking and markings indicating the temperature at which the calibration
was made, other markings appear, such as type of glass (e.g., Pyrex, Corex, or Kirnax), stock number of
the particular item, and capacity of the vessel. If the vessel contains a ground-glass connection, this will
also be included along with the TD or TC symbol.
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2.7.4.4 Fritted Ware
Porosity of Gritted ware is controlled during manufacturing and the ware is individually tested and
graded into six classifications according to pore size. This ware is less resistant to thermal shock than
nonporous glassware. Strong alkalies, strong hydrofluoric acid and phosphoric acid, or scratching the
surface may weaken or damage fritted ware.
2.7.4.5 Qeaning Glassware
Cleaning methods for glassware and porcelain should be appropriate for the substances to be
removed and the determination to be performed and should not damage the glassware or porcelain (see
EPA's Handbook for Analytical Quality Control in Water and Wastewater ! ^boratoriesV Water-soluble
substances are simply washed out with hot or cold water, and the vessel is finally rinsed with successive
small amounts of distilled water. Other substances that are more difficult to remove may require the use
of a detergent, organic solvent, dichromate cleaning solution, nitric acid, or aqua regia. To dry glass a-
pparatus, the analyst should rinse with acetone and blow or draw air through it
Absorption cells used in spectrophotometers may be cleaned with detergent solutions to remove
organic residues, but should not be soaked for prolonged periods in caustic solutions because of the
possibility of etching. Organic solvents may be used to rinse cells in which organic materials have been
used. Nitric acid rinses are permissible, but dichromate solutions are not recommended because of the
absorptive properties of dichromate on glass. Rinsing and drying cells with alcohol or acetone before
storage is the preferred practice. Cells used for analyses in the parts per billion (ppb) range should be
soaked in a 1:1 solution of hydrochloric acid and alcohol
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For certain determinations, especially trace metals, glassware should also be rinsed with a 1:1 nitric
or hydrochloric acid-water mixture. This operation should be followed by thoroughly rinsing with
de-ionized water. This may require as many as 12 to IS rinses, especially if chromium is being
determined. The nitric acid rinse is also important if lead is being determined.
Glassware used for phosphate determinations should not be washed with detergents containing
phosphates. This glassware must be thoroughly rinsed with tap water and distilled water. For ammonia
and Kjeldahl nitrogen, glassware must be rinsed with ammonia-free water. Glassware used in deter-
mining trace organic constituents in water, such as chlorinated pesticides, should be as free of organic
contaminants as possible. A chromic acid wash for at least 15 minutes is necessary to destroy these
organic residues, followed by a thorough rinse with tap water and, finally, with distilled water. Glassware
for organics analysis can also be cleaned by heating in a muffle furnace for 30 minutes at 400* C
2.8 RECORDS AND REPORTS REVIEW
As pan of its QA program, the NPDES permittee's laboratory must have a program to
systematically and uniformly record data, and to process and report this data in the proper form for
interpretation and use. The inspector should verify that:
Data, records, and reports contain all necessary information as discussed in Section 2.8.1 of this
chapter
Significant figures and round-off rules as discussed in Section 2.8.2 are properly applied
Correct formulas and units are used to calculate final results
Provisions are made to cross check calculations.
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2.8.1 Data Storage. Processing, and Reporting
Raw data (data measured or observed before calculations were made), calculations, analyzed data,
and laboratory records must be kept readily available. Laboratory notebooks or preprinted data forms
should be permanently bound and include date of analysis performed, analyst, original value recorded,
blanks used, correction factors applied, reported values, and any abnormalities that occurred during the
testing procedure.
The laboratory should have report forms to provide complete data documentation and permanent
records to facilitate data processing. Computer data should be routinely backed up with duplicate
copies. To avoid data transcription errors, the number of forms should be minimal. Original data,
transcribed data, and calculations should be verified by other laboratory staft The inspector should
check these procedures by following randomly selected values from laboratory records through to
recording on the DMRs. The DMRs should be reviewed for accuracy and consistency with the analyst's
records/bench calculation sheets.
In some cases, municipalities and industries use contract laboratories to conduct analytical testing.
Regardless of the use of those labs, the permittee is still required to maintain monitoring records at the
facility site as per the NPDES permit All laboratory records have to be kept readily available to the
regulatory agency for a minimum of 3 years.
2.8.2 Handling Analytical Values
Forms should contain correct calculation formulas reduced to simplest factors for quick, correct
calculations. Provisions should be made for cross-checking calculations. Significant figures should be
established for each analysis and properly presented on the forms. Significant figures are all digits in a
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number that are known reasonably well with the last digit in the number having a greater uncertainty
than the other digits. This means that numbers resulting from calculations cannot be more precise than
the data used in the calculations. For example, if 256 and 0.98 are added, the answer of 256.98 implies
that the quantity is known reasonably well to the hundredths place. However, the number 256 is least
certain to the units place, so the number 0.98 has no meaning in the calculation. This is also true for
subtraction, multiplication, and division.
A zero may or may not be a significant figure, depending on its placement:
Final zeros after a decimal point are significant figures.
Final zeros before a decimal point may or may not be significant (e.g., 1,000 may have from
one to four significant figures). The best practice for such numbers is to express them
exponentially, with the numerical portion giving the significance of figures (e.g., 1.0 X 103 is
one thousand with two significant figures).
If a number is less than one, zeros following the decimal point are not significant, but any
zeros following the digits are significant (for example, in the number 0.002580, the first three
zeros are not significant while the zero following 258 is significant).
In mathematical operations, the numbers must be rounded off to ensure that all reported digits are
significant The rounding off rule for addition and subtraction is to round off the sum or difference to
the largest digit of uncertainty (e.g., 13.681 - 0.5 = 13.181 should be rounded off to the tenths place,
with a correct answer of 13.2). The rounding off rule for multiplication and division is to ensure that
the reported answer contains the same number of significant figures as the number having the least
number of significant figures that was used in the calculation (e.g., 1588 + 4.0 = 397 should be rounded
off to two significant figures, with a correct answer of 4.0 X 102). The inspector should ensure that all
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of these provisions are used and that the calculation and treatment of data are performed correctly and
accurately.
The inspector may wish to leave a copy of this procedure for establishing the significance of figures
and rounding off of figures with each laboratory inspected. It is important that all laboratories handle
analytical data correctly, especially for enforcement cases.
2.9 EXIT MEETING AND FINAL REPORT
2.9.1 Introduction
After the laboratory inspection has been completed, the inspector should hold a closing conference
with the appropriate laboratory staff. At this point, the inspector will have recorded much of the
information necessary to complete the evaluation. The exit meeting provides the inspector with an
opportunity to gather any additional information.
2.9.2 Purpose of Exit Meeting
The purpose of the exit meeting is to provide the inspector with an opportunity to ask specific
questions relating to the laboratory's QA practices and analysis methods, and to clarify any issues that
remain uncertain. The exit meeting should also provide the permittee with the following information:
Review of what the inspector has done
Description of obvious problems that need to be corrected immediately. EPA Form 3560-8,
shown in Figure 2-3, should be used for follow-up on all deficiencies. [Note: See the Overview
Training Module for use of the deficiency notice]
NOTES:
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Explanation of steps to be taken in reaching a supportable conclusion concerning the adequacy
of the laboratory
General content of the final report, so that there will be no surprises when the permittee reads
the report
Schedule of dates when the results of the evaluation will be provided.
2.9.3 Final Report
After the visit, the inspector will need to fill out the EPA Compliance Inspection Report (EPA
form 3560-3, shown in Figure 2-4) with a supplementary narrative documenting whether the subject
laboratory procedures were proper and consistent with NPDES permit requirements. This should be
done promptly. The inspector should also:
Compare the analytical methods observed with the standard approved procedures provided in
Appendix C of this module
Compare the QA procedures with those outlined in the Handbook for Analytical Quality
Control in Water and Wastewater Laboratories and in this module
Compare the inspector's observations on the state of the equipment with the information
provided in this module
Note in the report any discrepancies observed in the above comparisons.
The supplementary narrative should discuss problems noted by the inspector during the inspection and
any suggestions that the inspector may have to correct these problems or to improve the laboratory,
analytical procedures, and staff training. This narrative should also include any information that the
inspector may have on contract laboratories used by the permittee.
NOTES:
2-54
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
DEFICIENCY NOTICE
NATIONAL POLLUTANT DtSCHABCK
EUMDf ATtON SYSTEM (NPDB3)
fRoorf Inatraetiona am emeM al Imml omit baton coeflottnt)
PCHHITTBB
Dunns the
Additional
formation
-UBMTATWI n
TITUt
IHMWBPI
rha (tiifirwtncifli
areaa of deSoency may be brought to your attention following a complete review of the Inipw
on file with the REGULATORY AUTHORITY admuuaterma your NPDES PERMIT.
Deer*Nw>
noted below were found.
won Report and other in-
MONITOHIMO LOCATION fDMCMMJ
LOW MCASUHKM
AM-ll COLLtCTION/HOLOIMO TIMB ta»*mHmm>
-HKI«I»VATIO« rO'
TIST -MOCKOUHC*. ticrioN *e«. «o cwm
nicono KifpiNO ro»»c*i*»>
OTMIN »«Lr-MOMITO-INO OI-ICIIHCIIS (DMMM)
HiBHTS
mouuno Acnow.
to raqu
wnpi of t daulptlai of i>» <
Adml«l»aiir«» of Upl AcMom. Your IIMBO» li to bo <»«-»->
n IBMMI or (31 mmn^ntd t* dvoratf *y MU I
Mn row NPDU Pvnll.
Yo«r MtrnHMi 10 ib* camctKM of llw
! tfct d«nrmte«tk»« of IX Mod for faf
nitfirfirtift yomr -riff NfOfS U
rolle*Hi» MUM « b> anNrad by MM WCULATOHV AUTHORITY to «Mcb row OMRs m UnUtud
INtPBCTOirt IHTCO HAMB
IHSPBCTOIfi AOOmai/VNOMB MO.
fOULATOHY
PA
RGURE2-3. EPA DEFICIENCY NOTICE FORM
2-55
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
6 EPA
Wasmnqion 0 C 20460
NPDES Compliance Inspection Report
Section A National Oat» System Coding
Transaction Code
it a Si 3
NPOES
mo/aav
11 1Z
17
Inspection Type Inspector
a 19
Fac 7*
:o
Remarks
Reserved Fatuity evaluation aann
6* 69 7O
81
71
QA
72 ,
74
-Reserved
73
30
Section B Facility Data
Name and Location of Facility Inspected
Entry T,meQAM£] PM
Exit Time/ Date
Permit E'fective Date
Permit Expiration Date
Named) of On-5ite Representative!!)
Titlelsi
Pnone Nols)
Name Address ol Responsio'e Official
rule
Phone No
Contacted
D YesO No
Section C An»at Evaluated During Inspection
IS - Satisfactory M = Marginal U - Unsatisfactory. N - Not Evaluated!
Permit
Racords/Repons
Facility Site Review
Flow Measurement
' i Laboratory
I Effluent/Receiving Waters
Pretreatment
Compliance Schedule*
Self-Monitoring Program
I Operations & Maintenance
Sludge Disposal
Other
Section O Summary of Findmga/Commanta (Attach idOitiontl ina»fi rf ntetturyl
NameU) an«f Signaturals) of Inspenorls)
Agency/Off ica/Talaphonaj
Data
Signature of Reviewer
Agency/Office
Data
Ragulatoty OtHea Uaa Onty
Action Taken
Data
Noncompliance
Compliance
EPA Form 3S6O-3 (Rev 3-86) Previous editions are obsolete ^__^_._..
HGURE 2-4. NPDES COMPLIANCE INSPECTION REPORT FORM
2-56
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
INSTRUCTIONS
Section A: National Data System Coding (i.e.. PCS)
Column 1 : Transaction Code: Use N, C. or 0 for New, Change, or Delete All inspections will be new
unless there is an error in the data entered
Columns 3-11: NPDES Permit No. Enter the facility's NPOES permit number (Use the Remarks
columns to record the State permit number, if necessary )
Columns 12-17: Inspection Date. Insert the date entry was made into the facility Use the
year/month/day format (e g . 82/06/30 = June 30. 1982).
Column 1 8: Inspection Type. Use one of the codes listed below to describe the type of inspection
A Performance Audit E Corps of Engrs Inspection S Compliance Sampling
8 Biomonitoring L Enforcement Case Support X Toxic Sampling
C Compliance Evaluation P Pretreatment
D Diagnostic R Reconnaissance Inspection
Column 1 9: Inspector Code. Use one of the codes listed below to describe the lead agency in the
inspection.
C Contractor or Other Inspectors (Specify in N NEIC Inspectors
Remarks columns) R EPA Regional Inspector
E Corps of Engineers S State Inspector
J Joint EPA/State Inspectors EPA lead T Joint State/EPA Inspectors State lead
Column 2O: Facility Type. Use one of the codes below to describe the facility
1 Municipal. Publicly Owned Treatment Works (POTWs) with 1972 Standard Industrial Code
(SIC) 4952.
2 Industrial. Other than municipal, agricultural, and Federal facilities.
3 Agricultural. Facilities classified .with 1 972 SIC 01 1 1 to 0971 .
4 Federal. Facilities identified as Federal by the EPA Regional Office.
Columns 21 -66: Remarks. These columns are reserved for remarks at the discretion of the Region
Column 70: Facility Evaluation Rating. Use information gathered during the inspection (regardless
of inspection type) to evaluate the quality of the facility self -monitoring program. Grade the program
using a scale of 1 to 5 with a score of 5 being used for very reliable self-monitoring programs. 3 being
satisfactory, and 1 being used for very unreliable programs
Column 71 : Biomonitoring Information. Enter D for static testing. Enter F for flow through testing.
Enter N for no biomonitormg.
Column 72: Quality Assurance Data Inspection. Enter Q if the inspection was conducted as
followup on quality assurance sample results. Enter N otherwise.
Columns 73-80: These columns are reserved for regionally defined information.
Section B: Facility Data
This section is self-explanatory.
Section C: Areas Evaluated During Inspection
Indicate findings (S, M, U. or N) in the appropriate box. Use Section D and additional sheets as
necessary. Support the findings, as necessary, in a brief narrative report. Use the headings given on
the report form (e.g.. Permit. Records/ Reports) when discussing the areas evaluated during the
inspection. The heading marked "Other" may include activities such as SPCC, BMP's, and multime-
dia concerns.
Section D: Summary of Findings/ Comments
Briefly summarize the inspection findings. This summary should abstract the pertinent inspection
findings, not replace the narrative report. Reference a list of attachments, such as completed
checklists taken from the NPDES Compliance Inspection Manuals and pretreatment guidance
documents, including effluent data when sampling has been done. Use extra sheets as necessary
EPA Form 3BSO-3 (R«v 3-851 R
FIGURE 2-4. NPDES COMPLIANCE INSPECTION REPORT FORM (Continued)
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NPDES CompUance Monitoring Inspector Training: LABORATORY ANALYSIS
3. COMPLIANCE EVALUATION INSPECTION
The CEI is a nonsampling inspection intended to evaluate a permittee's wastewater treatment plant
operations and sludge disposal methods, as well as compliance with applicable NPDES permit self-
monitoring requirements and compliance schedule conditions. The CEI reviews the permittee's records
and reports, treatment facilities, compliance schedule status, and self-monitoring program, and allows for
site review by an inspector. It requires about 4 to 8 hours to complete, (shorter and less comprehensive
than the PAI discussed in Chapter 2). The following sections discuss the CEI in terms of activities
required for an appropriate laboratory evaluation.
3.1 RECORDS AND REPORTS REVIEW
The NPDES program requires permittees to maintain records and report periodically on the
amount and nature of waste constituents in their effluents. Section 308 of the Act authorizes inspections
of such required records and reports. The review of these records and reports is one element of the
CEI. During a review, the inspector will generally examine the permittee's files to determine if the
permittee:
Keeps and properly files the required records
Maintains records in an up-to-date manner
Retains all records for the time period required by the NPDES permit or by State regulations
Needs assistance on how to comply with the Agency's requirements on records and reports.
The laboratory portion of the CEI focuses primarily on records/reports of sample control (or
chain-of-custody) procedures and DMRs. A laboratory sample control system is important legally when
NOTES:
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
used in compliance tracking activities; it is also useful to maintain the quality of analytical laboratory
results. DMRs are used to notify EPA or the State of the results of analyses required by the permit and
must be maintained by the facility for at least 3 years. DMRs maintain information on the results of
measurements and analyses of parameters required by the permit Results reported on DMRs must be
consistent with laboratory analytical data. The inspector should review the DMRs for consistency and
accuracy and ensure that required data are being maintained for the requisite time period. Sections 2.3
and 2.4 of this module discussed sample control systems and the requirements for maintaining sampling
and analytical records in greater detail.
3.2 REVIEW OF SELF-MONITORING DATA, PROCEDURES, AND
LABORATORY FACILITIES
The inspector must be familiar with the monitoring requirements including sample collection
procedures and analytical methods contained in the facility's permit, including any nonroutine
requirements stated in the Special Conditions section, and with any correspondence or orders which may
have modified conditions or approved analytical procedures. The inspector should be thoroughly familiar
with approved test methods and specified sample holding times or, in the case of a complex list of
analyses, have available a reference list of the approved methods for those samples required by the
permit
3.2.1 Purpose
The objective of reviewing self-monitoring data and procedures is to verify that the analyses are
being performed with the proper equipment and by persons who have the requisite skills and to confirm
that the analytical test methods used for pollutants or parameters specified in NPDES permits conform
with the Agency's regulations specified in 40 CFR Pan 136.
NOTES:
3-2
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
3.2.2 Approach
Prior to the site visit, the inspector should consult the permit file, the inspection file, the DMR
QA Program, and PCS for information about the permittee and its compliance status. The DMR QA
program contains results of analyses of performance evaluation samples using methods normally
employed for the permittee's NPDES self-monitoring. The PCS is a computerized information
management system for tracking permit compliance and enforcement status. Section 2.1.3 of this module
discusses these sources of information in greater detail.
When conducting the review of the laboratory equipment, staff, and procedures, the inspector
should have enough knowledge or experience to:
Examine laboratory equipment to verify that the equipment is maintained, operated, and
calibrated correctly and that calibration logs are up-to-date
Verify that samples are properly preserved and analyzed within holding times specified in
40 CFR Pan 136 and analyzed according to approved test methods
Perform a detailed inspection of analytical methods for onsite analysis (temperature, dissolved
oxygen, pH, and residual chlorine)
Verify that QA is used in all self-monitoring programs.
Information about laboratory services and instrumentation may be gathered during an inspection of
the laboratory. Sufficient time should be devoted to satisfy the inspector that the laboratory has the
proper equipment and reagents necessary to conduct the analyses required by the permit. The inspector
should observe the housekeeping practices of the laboratory since dirty, poorly kept labs may not be
NOTES:
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
producing quality analyses. Section 2.7 of this module discusses laboratory facilities and equipment in
detail.
Information about analytical methods and holding times may be verified by asking the laboratory
supervisor the following questions:
What analytical methods are used?
Is there a Laboratory Methods Manual?
Does the laboratory have the references cited in 40 CFR Part 136 (that is, Methods for
Chemical Analysis of Water and Wastes. Standard Methods for the Examination of Water and
Wastewater. and ASTM Annual Book of Standards. Pan 31, Water)?
If analytical methods that are not EPA-approved are used, has approval been obtained for their
use?
What happens to a sample after it enters the laboratory?
How does the laboratory ensure that samples are analyzed within the appropriate holding
times?
Is a contract laboratory employed? If so, for what parameters? What analytical methods are
used by the contract laboratory?
Approved test methods, promulgated under 40 CFR Part 136, are listed in Appendix C
Information about the laboratory's QA program may be gathered by asking the laboratory
supervisor the following questions:
Is the Laboratory QC Manual up to date?
NOTES:
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Is there a Manager/Coordinator for QA?
What percent of the laboratory sample load is duplicate samples?
What percent of the laboratory sample load is spiked samples?
What is the laboratory's sample rejection policy?
Is the laboratory certified by the State or by any other certifying entity?
Are standard reference materials used as a routine pan of calibration and QC programs?
Does the laboratory participate in EPA's DMR QA program and/or privately operated QA
programs?
Does the laboratory which performs the DMR QA analyses routinely perform the
self-monitoring analysis?
Section 2.4, and 2.6 of this module discuss laboratory QA programs in more detail.
NOTES:
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
REFERENCES
American Society for Testing and Materials. ASTM Annual Book of Standards. Part 31, Water.
(American Society for Testing and Materials) Philadelphia, PA, 1975.
American Public Health Association, American Water Works Association, and Water Pollution Control
Federation. Standard Methods for the Examination of Water and Wastewater. Use the most
current version.
Federal Water Pollution Control Act. 33 U.S.C 1251 et seq. As amended by the Water Quality Act of
1987. P.L. 100-4 February 4, 1987.
Office of the Federal Register National Archives and Records Service General Services Administration.
"Guidelines Establishing Test Procedures for the Analysis of Pollutants." (40 CFR Pan 136).
Use most current version. U.S. Government Printing Office, Washington D.C, 1982.
U.S. Environmental Protection Agency. Handbook for Analytical Quality Control in Water and
Wastewater Laboratories. Environmental Monitoring and Support Laboratory, Cincinnati, Ohio,
March 1979.
U.S. Environmental Protection Agency. Manual for the Interim Certification of Laboratories Involved in
Analyzing Public Drinking Water Supplies.
U.S. Environmental Protection Agency. Methods for Chemical Analysis of Water and Wastes.
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio, 1979.
U.S. Environmental Protection Agency. NPDES Compliance Inspection Manual. May 1988.
U.S. Environmental Protection Agency. NPDES Compliance Monitoring Inspection Training Overview.
Office of Water Enforcement and Permits, Washington, D.C, 1988.
U.S. Environmental Protection Agency. NPDES Compliance Monitoring Inspection Training Sampling
Procedures. Office of Water Enforcement and Permits, Washington, D.C, 1988.
U.S. Environmental Protection Agency. Procedure for the Evaluation of Environmental Monitoring
Laboratories. Environmental Monitoring and Support Laboratory, Cincinnati, Ohio, March
1978.
A-l
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
APPENDIX A
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
4. SUMMARY
This module has presented the components to conduct an evaluation of a NPDES permittee's
laboratory. A key ingredient of the evaluation is advance preparation; namely, being familiar with chain-
of-custody and QC procedures and with EPA-approved analytical methods. By using the information
presented in this module, the inspector will be able to conclude whether the subject laboratory is, in
fact, providing results consistent with the NPDES permit requirements. To assess his/her understanding
of the information presented in this module, the inspector can use the review questions in Appendix J.
NOTES:
4-1
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NPDES CompUance Monitoring Inspector Training: LABORATORY ANALYSIS
APPENDIX B
GLOSSARY
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
GLOSSARY
Accuracy - The degree between a measured value or a value calculated from measurements, and an accepted
"true" value.
Aliquot - The portion of the sample to be analyzed.
Analyte - The constituent (i.e., pollutant or parameter) of the sample to be analyzed.
Buffer - A salt of a weak acid and a strong base, a salt of a strong acid and a weak base, or a combination
of such salts capable of maintaining a desired pH value of a solution when substances of differing pH
are added; pH buffers are resistant to change making them useful as pH references.
Chain-of-Custody - A procedure that is established to record data on the handling of a sample from its
generation to its final disposal
Compliance Evaluation Inspection (CEI) - An inspection conducted without sampling to determine
compliance with the Clean Water Act and NPDES permit requirements.
DMR QA - Discharge Monitoring Report Quality Assurance - program to evaluate and improve laboratory's
performance by sending sample containing known concentrations of pollutants which the laboratory
analyzes and submit the results.
Discharge Monitoring Report (DMR) - A report of effluent quality and quantity that is required to be
filed by companies and municipalities that release such effluent to surface waters. This requirement
arises from provisions of PL 92-500.
Effluent For the purposes of this module, an outflow from a point source with some of its physical,
chemical, and biological parameters regulated by a NPDES permit.
Infrared Light - The range of wavelengths of the electromagnetic spectrum that is beyond the red end of
the visible spectrum; from about 700 millimicrons to 25 microns.
Laboratory Quality Assurance - A procedure that is established to maintain a high standard of quality in
a given process or function.
pH - A numerical expression of the acidity or alkalinity of a solution; it is the negative of the logarithm
of the hydrogen ion concentration in moles per liter.
Performance Audit Inspection (PAI) - A nonsampling inspection which includes observation of all the
elements of a permittee's self-monitoring program, such as testing procedures and methodology, quality
assurance, data gathering and interpretation, files, and laboratory facilities.
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NPDES CompUancc Monitoring Inspector Training: LABORATORY ANALYSIS
Point-Source - Any discernible, confined, and discrete conveyance, including, but not limited to, any pipe,
ditch, channel, tunnel, conduit, well, discrete fissure, container, rolling stock, concentrated animal
feeding operation or vessel, or other floating craft from which pollutants are or may be discharged as
defined in the Act This term includes landfill leachate collection systems but does not include
agricultrual storm water discharges and return flow from irrigated agriculture.
Precision - The degree of agreement between two or more measurements of the same quantity.
Quality Assurance (QA) - The total program for ensuring data reliability by using administrative procedures
and policies to evaluate and maintain the desired quality of data.
Quality Control (QC) The routine application of procedures to control the accuracy and precision of
sampling and analytical measurement process (as a function of quality assurance). Quality control of
sampling procedures should include the use of duplicate, spike and/or split samples, and sample blanks.
Quality control of analytical procedures should include proper calibration of instruments and the use
of appropriate anlaytical procedures.
Reagent - A chemical of known purity used in laboratory work, of which quantities and identities of
impurities are known.
Self-Monitoring - Monitoring conducted by the permittee (or its representative) of its own effluent.
Spectrophotometer An instrument that measures the amount of light of chosen wavelengths or range of
wavelengths that a sample absorbs.
Standard - Reference material used for QA purposes. Its main function is to determine the reprodutibility
of test results.
Turbidity - The degree of opacity of a suspension due to the suspended particulates; proportional to the
degree of light scattered by a suspension.
Ultraviolet Light - The range of wavelengths of the electromagnetic spectrum that is beyond the violet end
of the visible range; from about 450 to 200 millimicrons.
Visible Light - The range of wavelengths of the electromagnetic spectrum that can be seen by humans;
about 450 to 700 millimicrons (violet through red).
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NPDES CompUance Monitoring Inspector Training: LABORATORY ANALYSIS
ACRONYMS
ACRONYMS - The Following Letter Abbreviations are Common to Laboratory Activities:
AA - Atomic Absorption
ASTM - American Society for Testing Materials
BOD Biochemical Oxygen Demand
CBI - Compliance Biomonitoring Inspection
CEI - Compliance Evaluation Inspection
CFR - Code of Federal Regulations
CSI - Compliance Sampling Inspection
DMR Discharge Monitoring Reports
DO - Dissolved Oxygen
ECD - Electron Capture Detectors
EMSL - Environmental Monitoring and Support Laboratory
EPA - Environmental Protection Agency
FID - Flame lonization Detector
GC/MS - Gas Chromatograph/Mass Spectrophotometer
HPLC - High Performance Liquid Chromatography
IR - Infrared
NBS National Bureau of Standards
NPDES - Nationa! Pollutant Discharge Elimination System
NTU - Nephelometric Turbidity Units
OD - Optical Density
PAI - Performance Audit Inspection
PCI - Pretreatment CompUance Inspection
PCS - Permit Compliance System
ppb - pans per billion
QA - Quality Assurance
QC - Quality Control
SRM - Standard Reference Material
B-3
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
T - Transmittance
TC - To Contain
TD - To Deliver
TOC - Total Organic Carbon
TSS - Total Suspended Solids
UV - Ultraviolet
XSI - Toxics Sampling Inspection
B-4
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
APPENDIX C
APPROVED METHODS
(EXCERPT FROM 40 CFR PART 136)
-------
NPDCS Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Environmental Protection Agency
PART 136GUIDELINES ESTABLISH-
ING TEST PROCEDURES FOR THE
ANALYSIS OF POLLUTANTS
Sec.
136 1 Applicability.
1362 Definitions.
136 3 Identification of test procedures.
Sec.
136.4 Application for alternate teat proce-
dures.
136.5 Approval of alternate test proce-
dures.
APPENDIX A TO PART 136 METHODS FOR OR-
GANIC CHEMICAL ANALYSIS or MUNICIPAL
AND INDUSTRIAL WASTEWATER
APPENDIX B TO PART 136DEPTNRION AND
PROCEDURE FOR THE DETERMINATION OP
THE METHOD DETECTION LIMITREVISION
1.11
APPENDIX C TO PART 136INDUCTIVELY COU-
PLED PLASMAATOMIC EMISSION SPBCTRO-
METRIC METHOD POR TBMX ELEMENT
ANALYSIS OP WATER AND WASTES METHOD
200.7
AUTHORITY: Sees. 301. 304. 307 and
SOl(a). Pub. L. 98-217. 91 Stat. 1560. ct seq.
(33 U.S.C. 1251. et seq.) (the Federal Water
Pollution Control Act Amendments of 1972
as amended by the Clean Water Act of
1977).
§136.1 Applicability.
The procedures prescribed herein
shall, except as noted In { 136.5. be
used to perform the measurements in-
dicated whenever the waste constitu-
ent specified Is required to be meas-
ured for.
(a) An application submitted to the
Administrator, or to a State having an
approved NFDES program for a
permit under section 402 of the Clean
Water Act of 1077. as amended (CWA).
and/or to reports required to be sub-
mitted under NPDES permits or other
requests for quantitative or qualitative
effluent data under Parts 122 to 125 of
Title 40. and.
(b) Reports required to be submitted
by discharges under the NPDES estab-
lished by Parts 124 and 125 of this
chapter, and.
(c) Certifications Issued by States
pursuant to section 401 of the CWA.
as amended.
(38 PR 28758. Oct. 16. 1973. as amended at
49 PR 43350. Oct. 26.1984]
§136.2
§ 136.2 Definitions.
As used In this part, the term:
(a) "Act" means the Clean Water
Act of 1977. Pub. L. 95-217. 91 Stat.
1566. et seq. (33 U.S.C. 1251 et seq.)
(The Federal Water Pollution Control
Act Amendments of 1972 as amended
by the Clean Water Act of 1977).
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
§1364
and described In Tables LA, IB. 1C. ID.
and IE. or by any alternate test proce-
dure which has been approved by the
Administrator under the provisions of
paragraph (d) of this section and
tl 136.4 and 136.5 of this Part 136.
Under certain circumstances (| 136.3
(b) or (c) or 40 CFR 401.13) other test
procedures may be used that may be
40 CFR Ch. I (7-148 Edition)
more advantageous when such other
test procedures have been previously
approved by the Regional Administra-
tor of the Region in which the dis-
charge will occur, and providing the
Director of the State in which such
discharge will occur does not object to
the use of such alternate test proce-
dure.
TABLE IALIST OF APPROVED BIOLOGICAL TEST PROCEDURES
EPA*
RMrano* (MMiod NUIMT or Pig*)
ism
ASTM
uses
1 CoMerm (t*c*i) number p*r
100 mt
i CoMom (tac*fl M pr***no*
of eMonn* numbor p*r 100
1 CoMorm (total ruiMr p*r
IQOfflL
4 GOMQRVI (lOtsY) sT) pfMMHOil
*r or oln*r por*_*g* miMMu by
* lRMrl*J* Mb. MV Wiwl infl
C-2
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Environmental Protection Agency
TABLE 1BUST OF APPROVED INORGANIC TEST PROCEDURES
I No. or pig*)
EPA 1979
ASTM
USGS1
i AodNy. M C«COinig/L EUcBomnox
nd pout of pnt
2. AMMy. H CoCO. mg/L
pH 4 8, mm*, or
3. Alwnrun-ToM mg/L
Iby-
l(ICP)..
Orael cwroM pMm (OCP). or .
CaKnwlnc (EfMram cymo R)..
4 Ammano (§ N). mg/L MmM dun-
K«ipM95)'tole»»OPr
309.1
3101 . ..
3101.
202.1
20U. ...
390.2-. ..
330.2.
402(4 )..
403 ...
087-42IE) .,
D10S7-42IB).
-103044..
303C
304 ..
330141
2007*
33
S. AMmonyToM ». mg/L Pgnnon '
a AMK-TOM*. mg/L OonMn*
oo««Md plama. or -
: (SDOCI .
7 town-Tow*. mg/L Ogwaon tot-
iby
oi"1 <"»"- D««aon
AAturraot.
ICP
OCP. or. ...
3M2...
3903- .
1 . .
2041 .
2042 .
JOB'S'""
2083.
20B.2..
208 i" '
11 ..
2W.2. .
2101 .
210A
417A
4178
41 TO
417EOTF
417Q
0142a-79(A)..
3920 M.
33.067"
01420-79(0)
D1426-79(Q.
303A
304 .
303E
304 .
3078
303C
304 ...
SOW .
304 ...
02972-84(8).
KXM2-M.
02972-84(A) .
200.7«
200.7'
2007'
D38S4-a4(A)
-3099-
9 Bmrnmca oqgon dommd (BOOt).
Ottatatit Oiygw Bullion
10. Boron-ToM. mg/L
907 ...
Oak
ICP. or.
OCP
2113
I-UTB-TB'
1-3112-84 .
mg/L Tta
Tow*, i
11
12. CtdrnunToM *. mg/L
loy
AAft*
3201
213.1
213i.
01248-82(0.
303 A or
304
a 03957-84 (A
a en.
M129-84
1-3139-84 or
200.7*
No* 33
31019*. p. 17
2007*
NOM33
p. 344."
«. p.37«
C-3
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
§ ia&3 40 Ot Ch. I (7-148 Edition)
TABLE 1BLIST OF APPROVED INORGANIC TEST PROCEDURESContinued
I No or MOV)
EPA 1979
tarn Ed.
ASTM
usos>
ICP .
DCP
3106
13. Criobm-Tottl*. mg/L OjiiHon'
219.1.
0911-04(8)-
1-3192-04 .
OCP.or..
(EDTA)..
14
I (C8OO.I. mg/L'
Oxygen OgiHon win inMnaon «v
(COO).
15.
mg/L.
219A.
4101. ......
311C
907(9*4)
0811-844A).. ..
200 7 «
33
200 7 «
33
01292-83.
4103
410 4
329 3...
LI. or
3292.
3301 .
3303
3302..
3304 ....
3309 ...
2184
1-3981-04
33.034 . p. 17
12 or 13
407A
407B.
4070
408C.
0912-81(8).. -.
O912-8KA) ..
0912-81(C) .
M183-84
1-1184-84
1-1187-84
1-2187-84
33.087
012S3-7WA).
01293-78IB)
Pan 18 3
19 CrnmwnToH *. mg/L. OOM-
2181
2183
218.2.
2191 .
40BE
3038
303A
NOM19
1-1232-04
M230-84
3038
304
0188744(0)
33.089'
200.7*
No* 33
3128
303 A or B
304 .....
01887-84(A).
(A
or 8)
1-3239-04 or.
1-3240-84 ..
1101
110.2.
110.3
204O.
P 37«
2007*
Net* 33
NOM17
204A..
2048-
1-1290 84 .
22. CappvTaM> mg/L Ogwoon* tot-
AAta
220.1..
220 A.
304.
I A or 8. 01688-04(0
orO.
KI270-84or
1-3271-84
SIMS', pi 37.*
C-4
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Environmental Protection Agency
TABLE 1BLIST OF APPROVED INORGANIC TEST PROCSO
§136J
Con*
EPA 1979
ten Ea
I No. or pigs)
ASTM
usas>
CP.
DCP, or.
(Btancft
(Nooowrorah or.
M).
313
01999 8«1A).
29i CVonrti To«a. mp.L
Mon vMh MojCh Moowd Dy
D2006-62(A).
200.7*
133
US.
0.22,'
02036-82(8)
01179-800)
432744 .
(SPAONS),.
340.1
340.3..
or
«
AAIU
ToW. mg/l_
231 1
231A-
413C-
413E-
303A.
O1179-tO|AI_
-Tot*
mo/L
TIMI»>IC (EDTA>. or C* Hut Mg §
(900
33.).
28. HyttBQBi on (pM). pM
130.1-
130.2-
3148-
01126-10
1-1338-64.
33
33.082.'
1S0.1.
O1293-84(A
orB)
LI.
238.2..
30 bon-ToMr*. ng/L:
303 A or B
01088-84 (C
at at
331080.*
OOP. or.
31.
L
or
TOM. us m. mg/
POM
351 X
381 X
351 X
351.1
351.2.
351 4 .....
315B
420 A or I
4170
4178
417EOTF
01088 ««(A).
200.7.*
NOM33
NOM21
OOSt
3X081'
OMBOIN
MSS1-78'.
03590-
TaW'. mg/L:
239.1..
239.2
303 A orB
304
3X080.'
or 8).
NO* 33
. or..
03969-85(0).
31fl
C-5
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
§ 136J 40 CF1 Ch. I (7-148 Edition)
TABLE 18UST OF APPROVED INORGANIC TEST PROCEDURESContinued
EPA 1979
IMlEd.
ASTM
USOS*
33. Magmun-Tout . mg/L
Oon'MMMdbr
242.1
303A.
0511-04(8).
1-344744..
33.088.*
|QP
OCPor
ToM*. mg/L 0*g*»
»
AAIW
tOP.~
243.1..
24&2_
3188 ...
303 A or B-.
304
S11-77JA)
(Ber
200.7
133
3188
200.7*
33
33.128*
39. MmyToM . mo/L.
CeMWI
38. MolyM«mm-ToM«. mg/L. Og**-
CP. or
OOP
37 MhMi TOM*. mg/L
2*8.1
248 A....
248.1..
248A.
303C..
4480-84
200.7*
No* 33
AAlt*
248 1 ....
2482.....
303 A or 8..
304
0118844(0
orO).
OOP. or.
38. NMM (« N). mg/L CofanmMC
(Bruom . or NauxMiH N
IfWB HBliB N |9fl9 pMflMMH 39
nd40V
38. M»«l» m»m (« N). mg/L C*dmk*n
3511.
3218
418C
418F
0982-71.
200.7*
NOM33
33083*. 4180'
p. 28."
4a NMM (M N). mg/L
393.1.
3941.
O3B8749IB)-
D3887-aS(A).
418.
01294-87.
n)..
494084.
41. OB and jriiii T<
mg/L Qji»»n«8lc (merjon).
42. Oravne eMen-ToM (TOO. mg/L
413.1 .
419.1..
909.
43.
(W N) mg/L- ToVJ
31) mnui im-
4).
(a* P). mg/L Awr-
02978 89 (A or
8).
NOM24
33.044 . p. 4 "
33.118.1
33.111
P 327
P 328
C-6
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Envlr
ital Protection Agoncy
§13t3
TABLE 18LIST OF APPROVED INORGANIC TEST PROCEDURESContinued
urna. M m**Kod
EPA 1979 .
i8V) Ed.
INaortngii
A8TM
USOS>
01783-80 (A
or 8)
DS1S-S2W.
D142B-82CA).
20.
27
33.111"
33118.*
133
33.100.'
200.7*
3178.'«
S3.
103-106%
54 niajui iKntMi mg/L-
Me. ierc __
QHMIUBK. 109-106% POM
SB. niij|>ii_ llBIMtH. HiQ/L.
nc» (knhofl cons) of or>win(nc.
57 niadui VoMfc. mg/L
MbSSOX.
SB Rhodkm-ToM*. mg/L Olgiittan«
180.1.
16
2098..
20BC-
K17SO-64 .
M790-94.
1-3780-84.
180.4...
(-3753-84.
AAHv
11.
28SJ-
303A.
SB. Runmm-ToM . mg/L
pnooaer
AAMi
induct
2871..
287A...
270.2
30*
200.7*
270J-
03859 B«(A).
-3887-84.
3701.
42SC.
08S9-BO(B)-
M700-84.
(-2700-64 .
200.7.'
TaM". mg/L
to
2711.
303 A or I
KI720-M.
«. p.37«
AA h
CP.er
318B."
200.7*
NOM33
88. SodUt>-ToM'. mg/L
273.1.
303A.
33.107*
200.7.*
Na»33
C-7
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
§1364
TABLE 1BLIST OF APPROVED INOROANIC
40 CR OS. I (7-1-M Edition)
TEST PROCEDURESContinued
EPA 1879
ten Ed.
I Ne orp*jgt)
ASTM
Ftaim pnotontMnc .....
84 SpaoAe oendueanea.
em « 2S'C WlwMMon* Mg*
65 SiMtt (H SO.). mg/L
120.1.
373.1
01426-42IA) .
33.002.*
*
89 Ttnvmtora. 'C. nmmo
70 ThMtumToM>. mg/U
i BIT
426 A or B
OS16-62IA).
DS16-62IB).
33124*
42OC."
4270.
427C..
-3840-M
22SA."
AAluman. w.
IIM
71 Tht-Tottf*. mg/L
279 1...
279J ..
262.1
AA IwniM.
72. TttmjmTew'
(OiOMdby
mg/L
AAfianan .
OCP
73 'fOOOt. NTU
74 .imaun. TeW*. mg/L
263.2...
iiio'i
2861
512B.
212 ..
303A
304 ..
303A
304 ..
303C
304 ..
214A.
01339-6*10).
02330-62IA).
Not* J1
200.7.«
1-78* _
0166941
OCP. of .... -..
Cetenmnnc (Gtfkc aod)
75 Zinc-ToW1. mg/L OtgwMn'
AAtwnao*
ICP _
OCP or.
2691 ..
269^....
304 . . ..
327B
303Aere
304
D3373-844A)-
O1691-44 (C
orOV
Nan 33
2007*
Not* 33
33069*.p.37*
200.7*
NOW 33
Cctonmwnc (OtJMen*)) or
(Zlnoon)
> "IMMdi far Aiwytj* ct upvitton or
tfW tOMOMHQ GnlBrtK
. m to* 000 «20)
C-8
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Environmental Protection Agency
wow frti
oalonaaa
Mhaturi
let 1 NTUorl
i percoptabMi odor, and
d a ol one tqud praea arvf tree al peracuMte or luetiriiliil metier leeavrnq audrtfcalMi.
The Ml ten of MMMd 200 7. "Inducovarf Coupled Plaema Atomc Emeaon SeecBememe MMMd lor Trace Element
Anaiyee of water and wanea." » grvan al Append* C ol m» Pan 139
' Manual Jaaunon net raquted it comparebety data en tapraeaiiiailia affluent lampiei are on company Be to anew met
Ova pietnvnary naMaaon BMP net naceiiery. however, manual anjalauuii ** be reqund to tieorm any con'
Ammona. Automated Elactrede Memod. induetnar Memod Number 379-79 WE. dated February 19. 1979.
AuMAnaiyier II. Tecnraeon MduMnal SyMeme Tarn/toMi. NY 10991 r«-r
'The emni»an mooted mat cried n "MetMda far Oatemnedon ot Inorganc "ifialanei n Water a
GaamentTTiSoS TWHI. Book 9. Chepter Al (1979) --«-- J«i.«w-
Amercan Nadonal Standard on Phntoqraprvc Prociemng Effluent*. Apr 2. 1979. ' ii'atili from ANSI. 1430 Broad***.
New vom. NY 10018
"Silieujd AnaTyecel MMMda Approved and Cried by ma United Statea Envnrmental Proteedon Agency." SuppHmem to
me FUteenm Edtapn ol SMncbrtf Uitnatfi tier mt Eamr»eon ol rtMar tna tViifinarei (1991>
'Ttie uae of normal and dmaremjal pmaa voltage rampa to «icreaaa lenertivay and feaMuban i
(CBOOt) muat not ba mntieed Mm me I
tow BOO." Tt» wtdnon ol ow
-,- -,__-_
t tfitt uiviQ tfw nAtflcrton
» OC Owmori OxygK Oon
SMIton. TX 77B40
The
"Onon
OxyoonOi
OOM637
nMontf CorporMon. 912 WM> Loop. PO Ban 2990. CoHgo
at Wuor Anolym 1979. HMI) erwim Componr. PO. Box
I Drive. Cambridge. MA 02139 __
j approved memed * mat cMd « SavMertf IHBiiBi «r Me
1 " NMtonal Couned ol ma Paper mduMry tar A* and SI
"Copper Bvoncfoneta MMMdi MMMd 9900. Keen i
Ba 399. LOMlena CO 90937
' Alter me manual
w vnptrfkvd by oonnBC
mo buiMr U «auu bo
or 4203. (phonok)
«Mmod3393.
"Iron.
2-117. t
orecay umei
r 78 found i
Memod. induMnal MMMd Number 379-7SWA. I
10991
1990. Hacn CMmcel Company. Pa BOB 399. LovMend. CO 00937
Memod 0034. Hacn Handbook ol WaaaMetar Anaiyee. 1979. pagea 2-113 and
17. Keen Chemcel Company. LunMand. CO 90937
"Goono. 0.. Brown. E. "MMMdt Mr Aneiyee ol Organc Subnancea n Water." US. Oaaloalral Survey Tearnquae ol
"K£2Z^^£^^££?C<^,. PO BP. >». L^M. CO .0537.
JuM pngr tp Jauiabnn. edkiM me mfune-eBd preierved lampM to pH 4 MOI 1 4- 9 NaOH __^_ _
memod «7tSB cried n Sttntna uunaa§ tar am fiiamnapan ol watr mtt Mtoejiidlar. 1401 EdHen. The
i 9 conducted at a pH ol tOO±Oi The eiMjiuiiid mamoda are gwen on pp. 979-61 ol me urn EdMorc
... . _ roeadure, or Memod 910C tar me manual
910A tor
Modiod S10B for a* manual tuiuni»u«.
" R F Addaon and R. a Acumen. "Direct OaeiiiBHiBn el Elemental PMepnorua by
i vot 47. No. 3. pp. 421-420, 1970.
> ol elver i
eMuH be prepared » me lame mat
el 1 mg/L and above ere
cfeonde are relaOveiy MMlubla In
end eBtfum liyumuue tp a pH ol
be dMad to 100 mL by adflna 40 mL aeon 012 M
For levee) of erver aakw 1 i
mg/L ma i
"the approved memed met oied n Senders' MeMek «r tne aamnaapri at WM* tnd
The approved memod mat oted « SttnOvti m»i»b *r M eojmneapn of
" Slevana. H H.. Ftaka. J. F. and Smoel a F. "Water Temgaiaua inltuenael Fi .-__
PraaontMon." U & Oeoloojeel Survey. Tecrnquae pi Water Haaoureea aillgaBon.. Book 1. OiaMar 01,1979.
-i znc. Zircon Memod. Mimed 9009. Keen Handbook ot Watar Anar/ee. 1979. pagae 2-391 end i
2-333.
Ctianatal
Company. Lovatand. CO 80937
i "Greet Currant Ptaarm E ORGANIC COMPOUNDS
ParanM
1 AcraiHi -
9 Boraatala/aniapana J
EPAIi
QC
910
010
909
909
910
002
1 9101
MMdNumbar>'
OC/MS
029. 029
924. 934
624. 624
624. 624
629. 629
629. 629
HPIC
010
010
010
009
910
fWw
Note 3. p. 1;
C-9
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
§1364
40 CHI Ch. I (7-1-tt Edition)
TABIC 1CLIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS
Continued
GO/MS
HPUC
629. 1825
829. 1629
829. 1625
629. 1629
610
610
610
610
3tt 3. p. 130:
NOM6.P
8102.
629. 1629
629. 1629
629. 1629
624. 1624
624. 1624
624.1624
629.1629
624. 1624
629. 1629
624. 1624
624. 1624
624. 1624
624. 1624
624. 1624
629, H
629. 1629
629. 1629
629. 1629
625.1625
624. 1624
624.629. 1629
824.629. 162S
629.1624. 1629
13. p. 130;
MOM 3. p. 130:
13. p. 130:
610
610
624. 1624
624. 1624
624. 1624
624. 1624
629. 1629
624. 1624
624.1624
624. 1624
629.1
629.1629
629. 1629
629.1629
629.1629
629.1629
629.1
NGW3.PL130E
NO* 6. p.
S102.
624.1624
624.
61
NOH3.P.130:
61
C-10
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Environmental Protection Agency
TABLE 1CLIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS
Contmu6d
629.1695
629. 1629
1
629. 1629
NOM3.P 43:
No* 3. p 43.
NMB3.P.43:
NMB3. p. 43:
NOM3. p. 43;
NOW 3. p. 43;
Mama. p. 4*
MOM X p. 14ft
79 PCB-1242..
60. PC8-1246
61 PC8-12S4.
61 PC8-1260
63 t
629. 1629
629. 1829
1
1
613
624. 1624
624. 1624
624.1624
629. 1629
624. 1624
624.1624
624.1624
624
1
624.1624
Net* 3. P 130:
Matt 3. p. 130S
NMB3.pl 130:
NMB3.P.130:
92. 1.1.1-TdcHanMa
93.
94. Trtd
FOR PESTICIDES
NOTV. ThBM
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
40cm oi. i (7-i-*t
TABLE toLIST OF APPROVED TEST PROCEDURES FOR PESTCDES >ContmiMd
14. C4
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
§13oJ
TABLE IDUST OF APPROVED TEST PROCEDURES FOR PESTICIDES 'Continued
EPA"
IMl
Ed
ASTM
58. PI
57
58.
SO. Prop*
83. s*
84. SMI
88. 2.43-T
87. 14.9-TP(S§»«)-
ea.
ao-Topm
oc
QC
QC
TIC
TIC
TIC
TIC
QC
QC
nc
oc
OC
OC
OC
NOH 3. p. st NOH
NOW a. p. 83: Net*
NoH3.p.83:NoH
NOH 3, p. 104. Noli
NOM 3. p. 94; NoH
NoH 3. p. Sk Nat*
New 3. p. 104; NOH
NM 3. p. 8* NoH
NOH3.P.7
NoH 3, p. 104. NOH
NOH 3. p. lit: NOH
NOH 3. p. 119.
NoH3.p.83:NoH
NOH 3. p. 7: NOH
p. see
p. sea.
p.saa.
. p. S84.
p. S80.
. PL 368.
, p. S64
p. S88.
«. p. S64.
4. p. 39.
O.p.Saa.
4. p. 30.
70.
NOH 3. p. 7
Of OtBHVC PGHUHn^Bi Ol
IMI IHOU Mr ttmt HOI
,- ._ - _
H MI uo*d H IIOHMIBM BH mMhod
~
CMorMMd Of«»nlc CompouM.
Agoney. I«PH»na»f. 1978. TN( EPA
» Moaipdi 80S tnd 929 ISw AppondhA <* Mo PonI13B> n oaciojneo <
VMM fnMhodiV AdoVtonoffyi MOD Bworitofy, on off^oiv^giTjQ boBs\ mutf vpsto
Moviod 600 of 5% of ol MfflpiH 9VMiVnd vMi Mvffod 625 to fnonstof end
TABLE IEOar OF APPROVED RAOKXOOICAL TEST PROCEDURES
EPA i
(nHMdNaor
ASTH
1. AHAtToM. pO par Mr
a.
X MfrToHJ. pO por 8Hr
9. () RMfun-ToHL 'pQ por
703
709
703
703
70S
70S
01943-81
01943-81
01890-81
Ol 880-81
02490-70
P- 70.
pp.79ond78.'
P- 79.
PL 81.
C-13
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
APPENDIX D
REQUIRED CONTAINERS, PRESERVATION TECHNIQUES,
AND HOLDING TIMES (EXCERPT FROM 40 CFR PART 136 TABLE
-------
Parameter
BACTERIAL TESTS
CoHform, fecal and total
Fecal streptococci
INORGANIC TESTS
Acidity
Alkalinity
Aonunia
Biochemical oxygen demand
Biochemical oxygen
demand carbonaceous
Bromide
Chemical oxygen demand
Chloride
Chlorine, total residual
REQUIRED CONTAINERS, PRESQWATKM TEOtQQ
Source: 49 FR 43260 Friday October 26,
Container' "
P,G
P,G
P,C
P,G
P,G
P,G
P,G
P,G
P,G
P,G
P,G
JES, AND Bourne TDfS
1984 40 CFR Part 136
Preservative121'131
Cool, 4«C
0.008* Na2S2Oj(51
Cool, 4°C
O-OOKNajSjO,151
COol, 4°C
Cool, 4%
Cool, 4«C
H2S04 to p«<2
Cool, 4%
Cool, 4«C
None required
Cool, 4%
H2SOt to pB<2
None required
None required
Maximo
Holding Time'41
6 hours
6 hours
14 days
14 days
28 days
48 hours
48 hours
28 days
28 days
28 days
Analyze imnediately
Z
a
p
o.
u
s
f
1
V9
B
.
3
a
a"
M
£
9
I
0
?
>
^
en
35
-------
REQURB) CCNIAD
Source:
Parameter
Color
Cyanide, total and amenable
to chlorination
Fluoride
Hardness
Hydrogen ion (pH)
Kjeldahl and organic nitrogen
HEELS'71
Chromiuni VI
Mercury
Metals except above
Nitrate
Nitrate-nitrite
Nitrite
12
0.6 ascorbic acid1"
None Required
BO, to plK2
None required
Cool, 4°C
H2S04 to pH<2
Cool, 4°C
HO, topB<2
no, to pH<2
Cool, 4"C
Cool, 4°C
H2904 to pnX2
Cool, 4°C
28 days
6 months
Analyze iomediately
28 days
24 hours
28 days
6 months
48 hours
28 days
48 hours
Z
HS
O-
1
o,
1
2
0
1
IN
1
H
3
9*
3
IN
E
o
i
£
1
C/l
So
-------
a
Ul
REQUIRE
Parameter
Oil and grease
Organic Carbon
Orthophosphate
Dissolved oxygen
Probe
Uinkler
Phenols
Phosphorus (elemental)
Phosphorus, total
Residue, total
Residue, filterable
Residue, nonfilterable (TSS)
Residue, settleable
Residue, volatile
DOCNLAJMRS, PRESERVATION TECUIIQ1E
Source: 49 FR 43260 Friday October
Container111
G
P,G
P,G
G bottle & top
G bottle & top
G
G
P,G
P,G
P,G
P,G
P,G
P,G
S, AN) BOUHtC HUES (Continued)
26, 1984 40 era Part 136
Preservative''1'111
Cool, 4°C
H SO to pfl<2
Cool, 4°C
H2S04 to pH<2
Filter immediately
Cool, 4%
None required
Fix onsite and
store in the dark
Cool, 4°C
H2S04 to phX2
Cool, 4°C
Cool, 4«C
B,SO to pH<2
0)014%
Cool 4°C
Cool4aC
00014%
06014%
Maxinun
Holding Time' 4>
28 days
28 days
48 hours
Analyze imnediately
8 hours
24 hours
48 hours
28 days
7 days
48 hours
7 days
48 hours
7 days
z
3
?
5
-3.
k»>
9
3*
5.
e
3.
"«
j»
o
3
i
to
i
cj
J
^
*<
en
on
-------
REQUIRED OON1M1IHS,
PRESERVATION TEcanauES, AND noumc TIMES (Continued)
Source: 49 FR 43260 Friday October 26,
Parameter
Silica
Specific conductance
Sulfate
Sulfide
Sulfite
Surfactants
Tanperature
TVirbidity
ORGANIC TESTS181
Purgeables Halocarbons
Purgeable Aranatics Hydrocarbons
Container111
P
P.G
P,G
P,G
P,G
P,G
P.G
P,G
G, teflon-lined
septum
G, teflon-lined
septun
1984 40 OR Part 136
Preservative'21'111
Cool4°C
Cool4°C
Cool4"C
Cool 4°C add
Zinc Acetate and
sodiun hydroxide
to pH>9
None required
Cdol4"C
None required
Cool, 4°C
Cool 4«C
O.OOKNaSO tsl
0.008Z
Cool 4«C
0.008Z Na2S2°i
HC1 topB2("
Haximm
Holding Tine141
28 days
28 days
28 days
7 days
Analyze immediately
48 hours
Analyze iimadiately
48 hours
14 days
14 days
9
D
En
I/I
n
o
o
A
2
zs
o
1
M
s
i
I
s
1
E
|
o
70
|
C/j
35
-------
a
On
REQUIRED OMADCRS, FRESERVATICN TECmiQUES, AM) HOLDING TIMES (Continued)
Source: 49 FR 43260 Friday October 26,
Parameter Container' l '
Acrolein and Acrylonitrite G, teflon-lined
septun
Extractables (phenols) G, teflon-lined
cap
Benzidenes'111 G, teflon-lined
cap
Fhthalate esters'111 G, teflon-lined
cap
Nitrosamines111"141 G, teflon-lined
cap
PCBs1111 Acrylonitrate G, teflon-lined
cap
Nitroaranatics and isophorone' u ' G, teflon-linad
cap
Polynudear aromatic hydrocarbons'111 G, teflon-lined
cap O.OOBZ(b2S20]ISI
1984 40 CTR Part 136
Preservative121 -(J>
00014^
O.OQK Na S 0
Adjust pH lo4.5UCI
Cool, 4°C
H29?4 tophX2
O.OOBZ Na2S20315 '
Cool, 4"C
O.OOK Na2S203' '
Cool, 4°C
Cool, 4°C
store in dark
O.OOK Na2S203
Cool, 4°C
Cool, 4«C
O.OOK Na2S20
store in the dark
Cool, 4°C
extraction, 40 days
store in the dark
Haxmin
Holding Time"1
14 days
7 days (until extraction)
30 days (after extraction)
7daysmtil
extraction ' '
7 days until
extraction, 40 days after
extraction1121
7 days until
extraction, 40 days after
extract ion( 12)
7 days until
extraction. 40 days after
extraction
7 days until
extraction. 40 days after
extraction' '
7 days until
after
extraction1121
i
o
o
3
T^
5*
3
i!
1
3.
00
if
f^
o
3
^
a
p
S
1
0
90
\
>
En
-------
REQUIRED GCNEADBS, RESERVATION THHHQUES, AN) BOUTOC TIMES (Continued)
Source: 49 F8 43260 Friday October 26, 1984 40 CTR Part 136
O
6\
Parameter
Haloethers
TEST
Pesticides
'111
RADIOLOGICAL TEST
Alpha, beta, and radiun
Maximm
Container111 Preservative121'111 Holding Time1''
G, teflon-lined Cool, 4%
cap
O.OOK
IS)
7 days until
extraction. 40 days after
extraction
Chlorinated hydrocarbons1111
TOD
G, teflon-lined
cap
G, teflon-lined
cap
Cool, 4°C
Cool, 4"C
O.OOEK Ma S 0
7 days until
extraction. 40 days after
extraction
7 days until
extraction. 40 days after
extraction
G, teflon-lined
cap
P,G
Cool, 4JC
pHS-91151
DO, to pH<2
7 days until
extraction. 40 days after
extraction 12>
6 months
(2)
'Polyethylene (P) or Glass (G).
Sample preservation should be performed imnediately upon sample collection.
For composite samples each aliquot should be preserved at the tine of
collection. When use of an automatic sampler makes it impossible to preserve
each aliquot, then samples may be preserved by maintaining at 4^C until
compositing and sample splitting is completed.
0
D
R
n
o
c.
5*
I
o
o
w
I
i1
5]
do
I
*
>
en
33
-------
REQUIRED OMADBIS, [RESERVATION TBOfffOiS, MO HDU2DG TIMES (Continued)
Source: 49 FR 43260 Friday October 26, 1984 40 OR Part 136
13 'when any sample is to be shipped by caiman carrier or sent through the United
States mails, it oust comply with the Department of Transportation Hazardous
Materials Regulations (49 OR Fart 172). The person offering such naterial
for transportation is responsible for ensuring such compliance. For the
preservation requirements of Table 5-1, the Office of Hazardous Materials,
Materials Transportation Bureau, Department of Transportation has determined
that the Bazardous Materials Regulations do not amply to the following
materials: Hydrochloric acid (HQ) in utter solutions at concentrations of
0.04Z by weight or less (pH about 1.% or greater); Nitric acid (HN)3) in
water solutions at concentrations of 0.15* by weight or less (pH about 1.62
or greater); Sulfuric acid (H.SO,) in water solutions at concentrations of
0.35Z by weight or less (pH about 1.15 or greater); and Sodium hydroxide
(teOH) in water solutions at concentrations of 0.808! by weight or less (pH
about 12.30 or less).
(4>Sanples should be analyzed as soon as possible after collection. The times
listed are the OBXUUI times that samples nay be held before analysis and
still considered valid. Samples may be held for longer periods only if the
permittee, or monitoring laboratory, has data on file to shou that the
specific types of samples under study are stable for the longer time. Sane
samples may not be stable for the maximm time period given in the table. A
permittee, or monitoring laboratory, is obligated to hold the sample for a
snorter time if knowledge exists to show this is necessary to maintain saqde
stability. ,
15'Should only be used in the presence of residual chlorine.
16'Maximum holding time is 24 hours when sulfide is present.
17'Samples should be filtered immediately onsite before adding preservative for
dissolved metals.
""Guidance applies to samples to be analyzed by QC, 1C, or GC/MS for specific
organic compounds.
-------
REQUIRED CONTAINERS, PRESHMOICN THHttQlES, AN) HOLDING TIMES (Continued)
Source: 49 FR 43260 Friday October 26, 1984 40 OR Part 136
"'Sample receiving no pH adjustment oust be analyzed within 7 days of sampling. z
110'Samples for acrolein receiving no pH adjustment oust be analyzed within 3 m
days of sampling. Optionally, all samples may be tested with lead acetate r
paper before pfl adjustnents in order to determine if sulfide is present. If o
sulfide is present, it can be removed by the addition of cadmium nitrate a
powder until a negative spot test is obtained. The sample is filtered, then
NaGH is added to pH 12.
=
(11(ghen the extractable analytes of concern fall within a single chemical
category, the specified preservation and maximm holding times should be
observed for option safeguard of sample integrity. Uhen the analytes of
concern fall within two or more chemical categories, the sample may be
preserved by cooling to 4%, reducing residual chlorine with O.ODK sodium
thiosulfate, storing in the dark, and adjusting the pH to 6-9; samples _
9 preserved in this manner may be held for 7 days before extraction and for 40 »
°° days after extraction. Exceptions to this optional preservation and holding »
time procedure are noted in footnote(5) (re: the requirement for thiosulfate e
reduction of residue chlorine and footnotes (12),(D) (re: the analysis of H
benzidine). 3
5*
11 "Extracts may be stored up to 7 days before analysis if storage is conducted
under an inert (oxidant-free) atmosphere.
113'if 1,2-diphenylhydrazine is Likely to be present, adjust the pU of the _
sample to 4.0 * 0.2 to prevent rearrangement to benzidine. O
114'For the analysis of diphenylnitrosamine, add O.OOK Na2S20, and adjust pfl to H
7-10 with NaOH within 24 hours of sampling. °
1 I5'lhe pH adjustment may be performed upon receipt at the laboratory and may be
omitted if the samples are extracted within 72 hours of collection. For the ^
analysis of aldrin, add 0.008* Na290,. h
CM
En
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
APPENDIX E
METHODS CHECKLISTS
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
METHODS CHECKLISTS
Attached is an example of a methods checklist which may be used to evaluate NPDES-approved
test methods. There is a checklist available for each NPDES test method. Each checklist gives a brief
description of the analytical method and contains a list of items to consider while observing each
analysis.
The checklists are available on an IBM PC compatible disk from the Enforcement Division of
OWEP, EPA Headquarters.
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
METHODS CHECKLIST: CHLORINE TOTAL RESIDUAL, ng/1, DPD COLORIMETRIC METHOD
EPA RequirementVCompany Practice
Holding Time: Immediately/
Preservation: None required/
Sample Container: Polyethylene, glass/
MO CFR Part 136, October 26, 1984, p. 43260.
Introduction;
The N,N-diethyl-p-phenylene diamlne (DPO) coloMmetrlc method Is applicable
to natural and treated waters at concentrations from 0.2-4 mg/1. Chlorine
(hypochlorlte Ion, hypochlorous acid) and chloramlnes stolchl(metrically liberate
Iodine from potassium Iodide at pH 4 or less.
The liberated Iodine reacts with OPD to produce a red colored solution.
The solution 1s spectrophotometrlcally compared to a series of standards,
using a graph or a regression analysis calculation. The results are read or
calculated Into mg/1 Cl.
Federal Register References:** 1979 US EPA Manual entitled "Methods for Chemical
Analysis of Water and Wastes." EPA 600/4-79-020
Revised 3/83 (p. 330.5-1) Method 330.5. "Standard
Methods for the Examination of Water and Wastewater,1
16th edition. 1985 (p. 309) Method 408E.
**40 CFR Part 136, June 30, 1986.
Company Reference:
Analyst's Name:
Required by the 1979 EPA Methods Manual and the 16th Edition of Standard Methods;
Yes No
3. Is the phosphate buffer solution preserved with HgCl2?
(p. 307)
4. Is the DPD Indicator solution made using either 1.5 g DPO
oxalate (Eastman Chemical No. 7102 or equivalent) or 1.5 g
OPO sulfate pentahydrate (available from Gallard-Schleslnger
Chemical Mfg Corp.. 584 Mlneola Avenue, :arle Place, NY.
11514. or equivalent)? (p. 307)
5. Is the DPD stored In a brown glass-stoppered bottle
1n the dark and discarded when discolored? (p. 307)
6. Is a solution blank periodically run on the DPO solution
(discarded when absorbence at 515 NN exceeds 0.002/cm)?
(p. 307)
E-I
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Yes No
7. Is the potassium Iodide solution stored 1n a brown
glass-stoppered bottle, preferably in a refrigerator, and
discarded when 1t turns yellow? (p. 308)
8. Is chlorine demand free water used? (p. 308)
9. If a spectrophotometer 1s used, 1s 1t set up for use at
515 nm and provide a light path of 1 cm or longer?
(P. 309)
10. If a filter photometer 1s used, 1s 1t equipped with a
filter having maximum transmission 1n the range of 490 to
530 run and provide a light path of 1 cm or longer?
(p. 309)
11. Is separate glassware used (Including separate
spectrophotometer cells) for free and combined (dlchlor-
amlne) measurements? (p. 309)
12. Is the photometer or colorimeter calibrated using either
the chlorine or potassium permanganate solutions?
(P. 309)
13. Are the chlorine standards 1n a range of 0.05 to
4 mg/1? (p. 309)
14. Does the potassium permanganate solution contain 891 mg
KMNOa/l? (p. 309)
15. Are the KMN04 standards 1n a range of 0.05 to 4 mg/1?
(P. 310)
16. If the total chlorine exceeds 4 mg/1, 1s the sample
diluted? (p. 310)
17. Are the reagent quantities adjusted to the volume of
sample used? (p. 310)
18. When analyzing sample, 1s the color read Immediately?
(P. 310)
19. When testing for d1chloram1ne, 1s the sample allowed to
stand for 2 minutes before analysis? (p. 310)
Calculations:
Readl ng
A
8
C -
N
2(N
C -
A
B
- A)
N
NCI? Absent
Free Cl
NH2C1
NHC12
_.
NCI 3 Prr;ent
Free Cl
NH2C1
NHC19 +
1/2RC13
Free Cl +
1/2 NCI 3
NCI 3
In the event that mono chloramlne 1s present with NCI3, 1t will be
Included In reading N. 1n which case obtain NCI3 from 2(N - B).
E-2
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
METHODS CHECKLIST: BIOCHEMICAL WREN DEMAND
EPA Requirementyrompany Practice
Holding Time: Aft hours/
Preservation: Cool. a°r./
Sample Container: Polyethylene, glass/
*40 CFR Part 136, October 26, 1984, p. 43260.
Introduction;
The Biochemical Oxygen Demand (ROD) determination is an empirical test in
which standardized laboratory procedures are used to determine the relative
oxygen requirements of wastewaters, effluents, and polluted waters. The test
measures the oxygen required for the biochemical degradation of organic material
(carbonaceous demand) and the oxygen used to oxidize inorganic materials, such as
sulfides and ferrous iron.
The method consists of placing a sample in a full, airtight bottle and
incubating the bottle under specified conditions for a specific time. Dissolved
Oxygen (00) 1s measured initially and after incubation. The BOO 1s computed
fron the difference between Initial and final DO.
Federal Register References:** 1979 US EPA Manual entitled "Methods for Chemical
Analysis of Water and Wastes," EPA 600/4-79-020,
Revised 3/83 (p. 405.1-1) Method 405.1. "Standard
Methods for the Examination of Water and Wastewater."
Iffth Edition, 19fl5 (p. 525) Method 507.
**40 CFR Part 136, June 30, 1986.
Company Reference: .
Analyst's Name:
Required by the 1979 EPA Methods Manual and the 16*h Edition of Standard Methods;
Yes No
1. Are the samples kept at or below 4°C and 'ncubation
begun within 24 hours? (p. 526)
2. Are the samples grab samples? (p. 526)
3. If the samples are grab samples. Is the analysis
started within 6 hours and If not Is the storage
length and temperature recorded? (p. 527)
4. If the samples are grab samples. Is the analysis
started 24 hours after grab collection? (p. 527)
E-3
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
5. If the samples are composite samples, is the
compositing period limited to ?& hours? (p. 527)
fi. Are the Incubation bottles 25D to 300 ml capacity
with ground glass stoppers? (p. 527)
7. Are incubation bottles cleaned well with detergent.
before use? (p. 527)
8. Is a water seal used? (p. 527)
9. Is a protective cover of foil or paper cup placed
over the flared end of the bottle to reduce evaporation
during Incubation? (p. 5?7)
10. Is the air incubator or water bath kept at a temperature
of 20°C +. 1°C? (p. 527)
11. Are the samples, while being Incubated, kept In the
dark to prevent possible photosynthetlc production
of 00? (p. 527)
12. Is the phosphate buffer solution maintained at
a Ph level of 7.2? (p. 527)
13. Is the sodium sulflte solution prepared dally? (p. 5?7)
14. Is the glucose glutamic acid solution prppared
immediately before use? (p. 527)
15. For the dilution water 1s 1 ml of each phosphate Miffer,
MgSOa, CaCi?, and FeCi3 solutions/liter of water added?
(p. 527)
16. Is a seed used?
If so, what kind?
Is the seeding enough to produce a nn uptake of
0.06 to 1.0 mg/1 In 5 days at 20°C? (p. ^28)
17. When dilution water Is brought back to room
temperature, 1s It aerated and the 00 lev°l
saturated? (p. 528)
18. Is the dilution water brought up to ?0°C -fore use?
(P. 528)
19. Is the dilution water quality checked?
(P. 528)
20. Is the standard check solution a mixture of 150 mg
glucose/1 and 150 mg glutanic ac1d/l? (p. 528)
21. Is the 5-day 20°C BOD value Inside the range of 200 *
37 mg/1? (p. 528)
Yes NO
E-4
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
VPS No
2?.. If the 5-day 20°C BOO value is outside the range of
200 * 37 ng/l. Is the nix of seed and dilution water
rejected? (p. 528)
73. Is the seed DO uptake determined? (p. 5?9)
24. Are the samples neutralized to a pH between 6.5 and 7.5
(P. 529)
25. Is residual chlorine destroyed? (p. 526)
26. Is the dilution water seeded? (p. 529)
27. Are the sample temperatures brought to 20°C * 1°C
before analysis? (p. 529) ~
28. If a sample Is supersaturated with DO, Is It
properly adjusted by aerating in a partially
filled container and agitated vigorously? (p. 529)
29. If used, 1s nitrogen inhibition reported In the results?
(P. 529)
(Inhibitor may only be used 1f permit specifies
CBOD.) (see footnote *1)
30. Hoes the dilution technique result 1n a residual
00 of at least 1 ng/l and a DO uptake of at
least 2 mg/1 after a 5-day incubation? (p. 529)
(It has been found that these parameters produce the
most reliable results.)
31. Are multiple sample dilutions prepared to
obtain a DO in this (question 34) range? (p. 530)
(It has been found helpful that the
following dilutions for respective sample
origins are used:
0.0% to 1.0% for strong Industrial wastes,
1.0% to 5.0% for raw and settled waste witer,
5.0% to 25.0% for biologically treated e -fluent,
25.0 % to 100% for polluted river waters )
32. Is the sample Initial DO determined 1mme > lately
after addition of the diluted sample to .he BOD
bottle? (p. 529)
(If the rapid Initial DO uptake Is insignificant, the
time period between preparing dilution and measuring
Initial DO Is not critical.)
33. Is a dilution water blank used? (p. 531)
34. Is an unseeded dilution blank measured with each
batch of samples, and an Initial and final
DO determined? (p. 531)
E-5
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Yes No
35. Is the DO uptake less than 0.2 mg/1? (p. 531)
(DO should not be nore than 0.? mg/1 and
preferably not more than 0.1 ng/1.)
Calculations:
When dilution water 1s not seeded:
BOP, ng/1 PI - P?
~~P
When dilution water Is seeded:
BOD. mg/L = f "i - Dy) - ( HI - R?) F
Where:
Bl
B2
00 of diluted sample Immediately after preparation, mg/1.
00 of diluted sample after 5-day Incubation at 20°C, mg/1.
decimal volumetric fraction of sample used.
DO of seed control before Incubation, mg/1.
no of seed control after Incubation, mg/1.
ratio of seed In sample to seed In control = (% seed 1n n)«
(% seed In B).
Required by Permit *
Yes No
1. Are the analyst's Initials analysis date,
and time recorded?
2. Are all raw data retained for 3 years?
"Carbonaceous Biochemical Oxygen Demand (CROOS) -mst not be confused with
the traditional BOP-s test which measures "Total 100." The addition of the
nitrification Inhibitor Is not a procedural opt on. but must be Included
to report the CBODs parameter. A discharger whose permit requires reporting
the traditional BODs nay not use a nitrification Inhibitor In the procedure
for reporting the results. Only when a discharger's permit specifically
states CBODj Is required, can the permittee report data using the nitrification
Inhibitor (40 CFR, Part 136, June 30, 1986, footnote 11).
E-6
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
APPENDIX F
SAMPLE CHAIN-OF-CUSTODY FORM
-------
T
ENVIRONMENTAL PROTECTION AGENCY
OHice ol Enforcement
CHAIN OF CUSTODY RECORD
REGION 9
216 Fremont Street
Sen Frencitco Celilornie 94106
PROJ NO f
ROJECT NAME
SAMPLERS l&giutunl
STA NO
DATE
TIME
|
0
Relinquished by IStgnttunl
Relinquished by ISigntiunl
Relinquished by ISigmivitl
Dttliibulion
STATION LOCATION
Date
Date
Dale
'Time
'Time
'Time
NO
OF
CON
TAINERS
.
Received by ISignttunl
Received by ISignmml
Received lor Laboratory by
ISigamlunl
/////// REMARKS
Relinquished by ISipit
/ Dale /Time Received by fSifwrur*;
Relinquished by lS
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
APPENDIX G
SAMPLE CONTROL FORM
-------
0:
FROM:
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
SAMPLE CONTROL FORM
SAMPLE STORAGE. RZ7E:.TICV a a£'-
Sample Description:
Project Code: D«ee Sample Received:_
Sample Mo. (s);
Sample to be retained by lab:.
Sample eo be returned to customer:_
Sample onrtion to be retained by lab, remainder to Cjssaaer:
Special precautions for handling (combustible? detrimental to health? etc.)
Sample delivered to lab by:.
Sample received at lab by:
Sample returned to Customer (date);
Signature of person picking up sanple:_
Signature of employee releasing sample:.
Source: "Industrial Hygiene Laboratory Quality Control Manual . Technical Report So.
78. Department of Health Education and Welfare, National Institute for Occupational
Safety and Health, rivision of Physical Sciences and £rgi.n*«riag, Cincinatti, Ohia (l
G-l
-------
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
APPENDIX H
POTENTIAL PROBLEM AREAS
ASSOCIATED WITH POLLUTANT ANALYSIS
-------
F/834-03-501-03a/#22
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
POTENTIAL PROBLEM AREAS ASSOCIATED
WITH POLLUTANT ANALYSIS
Pollutant Parameter
Analyzed
Acidity
Alkalinity
Alkalinity, automated
Ammonia As Nitrogen
Distillation procedure
Problem Areas
Check calibration of pH meter.
Check that samples are refrigerated at 4*C until they
are run.
Check that samples are refrigerated at 4*C until they
are run. Check that samples are filtered through
0.45 u membrane before analysis.
Check to see that residual chlorine has been
removed by pretreatment of the sample with sodium
thiosulfate.
Check to see that samples are preserved with H2SO4
and refrigerated at 4*C before analysis.
Check to ensure that distilled water is ammonia-
free. Distilled water should be passed through an
ion exchange column comprised of a mixture of both
strongly acidic cation and strongly basic anion
exchange resins.
Note that direct nesslerization without distillation
invalidates the method due to the fact that many
aromatic, alphatic, and other compounds, both
organic and inorganic, will cause turbidity upon the
addition of Nessler reagent However, 40 CFR
states that manual distillation may not be necessary
if comparability data is available.
Check to see that interfering volatile alkaline
compounds such as certain ketones, adlehydes, and
alcohols are eliminated by boiling off at pH 2-3
prior to distillation and nesslerization.
H-l
-------
C/834-03-501-03a/#22
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Pollutant Parameter
Analyzed
Problem Areas
Selective ion electrode
Automated colorimetric
phenate method
Biochemical Oxygen Demand (BOD)
Note that in the test for ammonia as nitrogen,
manual distillation of the sample (prior to analysis)
is not required if comparability data on repre-
sentative effluent samples are on a company file to
show that this preliminary distillation step is not
necessary. Also note that some States have
generated such comparability data on representative
effluent samples from various plants, and provided
this information to their wastewater treatment
facilities. Based on the EPA findings, this is
acceptable. Each individual WWTP within a certain
size category (usually <1.0 mgd flow rate) could use
this information and, therefore, not be required (by
the State) to generate such comparability data by
itself.
Note that samples must not be preserved with
mercuric chloride because mercury interferes by
forming a strong complex with ammonia.
Check that the selective ion analyzer has been
properly calibrated.
Check that calcium and magnesium precipitation
problems are eliminated for river water and
industrial waste samples by using 5 percent EDTA.
Check that sample turbidity is removed by filtration
prior to analysis.
Check that samples are cooled to 4*C
Check that cooled samples are warmed to 20* C
before initial DO analysis and that samples are
incubated at 20* C for 5 days.
Check that oxygen depletion of dilution water does
not exceed 0.2 mg/L
Check that the sample is dechlorinated with sodium
sulfite (NaSO3), not sodium thiosulfate
H-2
-------
C/834-03-501-03a/#22
NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
Pollutant Parameter
Analyzed
Problem Areas
Chemical Oxygen Demand (COD)
Chloride
Chlorine, total residual
Color
Cyanide, total
Check that pH of sample is between 6.5 and 7.5. If
necessary, adjust pH with sulfuric acid or sodium
hydroxide.
Check that DO depletes at least 2 mg/1 in 5 days
and that at least 1 mg/1 DO remains.
Check that the glucose and glutamic acid test results
in BOD; in the range of 200+37 mg/1.
Check that sample is preserved with H2SO4 to a PH
<. 2 s.u.
Check that flask is cooled during H2SO4 addition to
reduce loss of volatile organics.
Check that glassware used in test is conditioned by
running blanks to eliminate traces of organic
materials.
Check that samples suspected of containing sulfites
are treated by oxidizing with H2O2 to eliminate
interference.
Check to see that samples are not stored; chlorine
determinations must be started immediately after
sampling, avoiding light and agitation.
Check that determinations are for total residual
chlorine rather than free available chlorine.
Check that samples showing visible turbidity are
clarified by centrifugation.
Check that samples are refrigerated at 4*C
Check that samples are collected in .> 1 liter plastic
bottles that have been thoroughly cleansed and
rinsed.
Check that samples are dechlorinated with ascorbic
acid if chlorine is present
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Pollutant Parameter
Analyzed
Problem Areas
Dissolved oxygen
Fecal Coliform
Fluoride, total
Check that samples are tested for chlorine with
Kl-starch paper and treated with ascorbic acid if
blue color results.
Check that samples have been preserved with 2 ml
of ION NaOH/liter of sample (pH >. 12) at time of
collection.
Check that samples are refrigerated at 4*C and
analyzed as soon as possible.
Check calibration procedure of spectrophotometer
for colorimetric measurement
Check that special sampling techniques specified on
p. 360.2-2 of the '1979 EPA Methods' have been
observed.
Check to see that the DO meter is properly
calibrated.
Check to see that DO samples are analyzed
immediately.
Check that samples are dechlorinated with Na2S2O3.
Check that tests with EC medium are incubated at
44.5 * 0.5-C
Check that tests with A-l medium are incubated at
35 t 0.2«C for 3 hours before incubating at 44.5 t
0.2'C
Check that incubator water depth is sufficient to
immerse tubes to the upper level of the medium.
Check that a geometric mean is calculated, rather
than an arithmetic mean.
For SPADNS and electrode methods, distillation is
required unless data is on file which proves it is not
necessary.
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Pollutant Parameter
Analyzed
Problem Areas
Hardness, total
Kjeldahl Nitrogen, total auto-
mated phenate method
Check that addition of highly colored SPADNS
reagent is done with utmost accuracy because a small
error in reagent addition is the most prominent
source of error in this test
For automated complexone method, check that
8-hydroxyquinoline addition and subsequent
extraction is performed on samples suspected of
containing >. 0.2 mg aluminum per liter.
For selective ion electrode method, check calibration
of pH meter or selective ion meter having direct
concentration scale for fluoride. Also, check that
pH 5.0 buffer containing a strong chelating agent, is
added to samples to eliminate interferences due to
aluminum, iron, and silicon and other complexes
formed at extremes of pR
Check that routine addition of sodium cyanide
solution is done to prevent potential interferences
from heavy metals.
Check that samples have been preserved by addition
of 2 ml of concentrated H2SO4 per liter and stored
at 4-C
Check to ensure that distilled water is ammonia-
free. Distilled water should be passed through an
ion exchange column comprised of a mixture of both
strongly acidic cation and strongly basic anion
exchange resins.
Preserved samples should be analyzed as soon as
possible to avoid conversion of organic nitrogen to
ammonia.
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Pollutant Parameter
Analyzed
Problem Areas
Metals
Aluminum
Antimony
Check that distillation apparatus is presteamed
before use by distilling a 1:1 mixture of distilled
water and sodium hydroxide-sodium thiosulfate
solution until the distillate is ammonia-free. This
operation should be repeated each time the
apparatus is out of service long enough to
accumulate ammonia (usually 4 hours or more).
Check that samples have been preserved with HNO3
to a pH<. 2 s.u.
Check calibration of atomic absorption
spectrophotometer.
For determination of dissolved metals, check that
samples are filtered through a 0.45 u membrane
filter as soon as practical after collection and before
preservation with HNO3 to pH<2.
For determination of suspended metals, check that a
representative volume of unpreserved sample is
filtered through a 0.45 u membrane filter and the
insoluble material is digested with HNO3 and HC1
and diluted prior to analysis.
Check that calibration standards are prepared at the
time of analysis using the same type of acid (HC1 or
NHO3) and at the same concentration as the
samples for analysis.
Check that one mg potassium/ml solution is added
to both sample and standard solutions to control
ionization of aluminum in the nitrous oxide/
acetylene flame.
The use of halide acids and nitrogen purge gas
should be avoided in furnace analyses because of
signal suppression.
For analysis of samples that contain lead (1000 mg/I)
check that 231.1 nm antimony line is used.
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Pollutant Parameter
Analyzed
Problem Areas
Arsenic
Barium
Beryllium
Boron
Bromide
Cadmium
Because increase in acid concentration causes
decrease in antimony absorption, check that acid
concentration in samples and standards match.
Check that organic forms of arsenic are converted to
inorganic compounds and organic matter is oxidized
before beginning the analysis.
Check to see that sample is airtight during evolution
of arsine to avoid losses.
Check to see that potassium (1000 mg/I) is added to
samples and standard alike to control barium
ionization in nitrous oxide-acetylene flame.
Check to see that lanthanum (2000 mg/1) is added to
samples and standard alike to avoid depression of
barium absorbance by phosphate, silicon, and
aluminum in acetylene-air flame.
When performing analysis by the furnace technique,
the use of halide acides should be avoided.
When performing analysis by the direct aspiration
technique, check to see that samples are acidified to
pH 1.5 to eliminate interference of bicarbonate ion.
Nitrogen should not be used as the purge gas for
furnace analyses to avoid possible chemical
interaction.
Check to see that samples with total Ca and Mg
hardness > 100 mg/1 as CaCO3 are passed through
cation exchange resin before analysis.
Check to see that samples are stored at 4°C and
analyzed as soon as possible.
For cadmium concentration less than 20 ug/1,
samples should be analyzed by the furnace tech-
nique or by the direct asperation technique using the
extraction procedure.
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Pollutant Parameter
Analyzed
Problem Areas
Chromium
Cobalt
Copper
Iron
When analyzing samples with low concentrations of
cadmium, contamination from the work area is
critical. Use of pipet tips which are free of
cadmium is of particular importance.
Check that both standards and samples are prepared
in dilute HC1 solution.
The nitrous oxide-acetylene flame provides the
greatest freedom from chemical and matrix
interferences, when performing flame analyses.
Check that 1 percent ammonium bifluoride in 0.2
percent sodium sulfate is added to samples to
control the suppression of both Cr (III) and Cr (VI)
absorption by most interfering ions when a fuel rich
air-acetylene flame is used.
Check that the extraction procedure or the furnace
technique is used for chromium levels < SO mg/1 and
that an oxidation step is included to measure
trivalent chromium.
Nitrogen should not be used as a purge gas for
furnace analyses, due to possible CN interference.
Check that the furnace technique or the extraction
procedure is used for cobalt levels < 50 mg/1.
Check that the furnace technique or the extraction
procedure is used for copper levels < 20 mg/1.
Check that calibration standards are prepared at the
time of analysis using the same type of acid (HC1 or
HNO3) and at the same concentration as the
samples for analysis.
Better signal-to-noise ratio can be obtained from a
neon-filled hollow cathode lamp than an argon-filled
lamp.
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Pollutant Parameter
Analyzed
Problem Areas
Lead
Magnesium
Manganese
Mercury, manual cold
vapor technique
Since glassware contamination is a severe problem in
lead analysis, all glassware should be cleaned
immediately prior to use, and once cleaned, should
not be opened to the atmosphere except when
necessary.
Check that care is taken to position the light beam
in the most stable, center portion of the flame
because analysis for lead is very sensitive to
turbulence and absorption bands in the flame. The
burner should first be adjusted to maximize the
absorbance reading with a lead standard; then a
water blank should be aspirated and fine adjustments
made in the burner alignment to minimize the
signal.
Check to see that the extraction procedure or the
furnace technique is used for lead levels < 200 ug/1.
To suppress sulfate interference, lanthanum nitrate is
added to both samples and calibration standards for
furnace analyses.
Check that interferences caused by aluminum
concentrations > 2 mg/1 are masked by addition of
lanthanum.
Check that the furnace technique or extraction at
pH 4.5-5 is carried out for levels of manganese <
25 mg/1, and that analysis is made without delay to
prevent resolution of manganese chelate in aqueous
phase.
Check that the samples are preserved by acidification
with nitric acid to pH <. 2 immediately upon
collection. Check that dissolved mercury samples
are filtered through an all glass apparatus before the
acid is added.
Check that organomercury compounds are oxidized
to mercuric ion by potassium persulfate before
measurement
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Pollutant Parameter
Analyzed Problem Areas
Check that possible interference from sulfide has
been eliminated by the addition of potassium
permanganate.
Check that »25 ml excess permanganate solution has
been added to sea waters, brines, and industrial
effluents high in chlorides.
Check to make certain that dead air space in the
BOD bottle has been purged before addition of
stannous sulfate.
Check to see that a preliminary run without reagents
is made to identify possible interference from certain
volatile organic materials. If an interference is
found, the sample should be analyzed both by using
the regular procedure and again under oxidizing
conditions only (without the reducing agents). The
true mercury value is obtained by subtracting the
two values.
Check to see that laboratory follows directions for
disposal of mercury-containing wastes given in
ASTM Standards, Pan 23, Water and Atmospheric
Analysis, p. 352, Method D3223 (1973).
See above, Mercury, manual cold vapor technique
plus following:
Check to ensure that formation of a heavy
precipitate does not occur upon addition of
concentrated sulfuric acid to the technique sample; if
such a precipitate is encountered, the problem
sample cannot be analyzed by the automated
method.
Check to see that samples containing solids are
blended and then mixed while being sampled if total
mercury values are to be reported.
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Pollutant Parameter
Analyzed
Problem Areas
Molybdenum
Nickel
Potassium
Selenium
Silver
Check to see that with a nitrous oxide-acetylene
flame, interferences of calcium and other ions are
controlled by adding 1000 mg aluminum/liter of
solution.
The use of nitrogen is not recommended for analysis
of molybdenum by furnace.
Check to see that the furnace technique or the
extraction procedure is used for levels of nickel
below SO ug/1.
Check that samples are preserved at pH 2 with 1:1
nitric acid at the time of collection.
Check that any high-level sodium interference is
compensated for by adding excess sodium (1000
ug/ml) to both sample and standard solutions.
Check that possible enhancement effects of Na, Li,
and Cs, especially in a high temperature fuel rich
flame, are eliminated by setting the burner assembly
approximately O.OS cm below the optical light path
so that the optical light path is sliced at the bottom
by the burner head. To cover the range of
potassium values normally observed in surface waters
(0.1-20 mg/1), it is suggested that the burner be
rotated 75*.
Check that organic forms of selenium are converted
to an inorganic form and organic matter is oxidized
before beginning the analysis.
1 percent Ni should be added to samples suspected
to contain chloride >800mg/l and sulfates >200
mg/1.
Check that the furnace technique or the extraction
procedure is used for levels of silver < 30 ug/1.
The use of halide acids should be avoided when
analyzing by the furnace technique.
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Pollutant Parameter
Analyzed
Problem Areas
Sodium
Tin
Titanium
Vanadium
Zinc
pH
Note that low temperature flames increase sodium
sensitivity by reducing utilization. If a high
temperature flame is used, check that ionization is
controlled by adding potassium (1000 mg/1) to both
standards and samples.
For concentrations of tin below 2 mg/1, the furnace
technique is recommended.
Chloride interference may be prevented by the
addition of ammonium nitrate and alteration of the
ashing program.
Check that potassium (1000 mg/1) is added to
standards and samples alike to control enhancement
effects of many interfering elements.
Titanium concentrations below 1.0 mg/1 should be
analyzed by furnace.
Because of possible chemical interactions, nitrogen
should not be used as the purge gas.
Check that enhancement effects of aluminum and
titanium interferences are controlled by adding
excess aluminum (1000 ppm) to both samples and
standards.
Note that zinc sensitivity may be increased by the
use of low-temperature flames.
The analysis of zinc by graphite furnace is extremely
sensitive and subject to contamination from the work
area. It is recommended that zinc be analyzed by
flame technique whenever possible (>0.01 mg/1).
Check that unsealed reference electrodes are filled to
the proper level with the correct electrolyte, making
sure that the junction is properly wetted.
Always report temperature at which pH is measured.
If this is different from temperature at which meter
is standardized, report both temperatures.
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Pollutant Parameter
Analyzed
Problem Areas
Total Suspended Solids (TSS)
Check that electrodes are stored in solutions
according to manufacturer's specifications.
Check to see that meter is calibrated according to
manufacturer's specifications, using at least three
different buffers.
If pH of samples to be measured varies widely,
standardize for each sample with a buffer having a
pH within 1 to 2 pH units of the sample.
Check that filters are cooled in a desiccator after
oven drying. This will prevent rehydration of the
filter.
Check that filters are dried and cooled until a
constant weight is achieved (or less than 0.5 mg
difference between weighings)
Check that size of sample used yields of at least 0.5
mg and no more than 200 mg residue. This will
limit the formation of a water-entrapping crust on
the residue.
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
APPENDIX I
LABORATORY SERVICES
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LABORATORY SERVICES
Distilled Water
In metal stills, surfaces in contact with the distillate should be coated with tin to prevent
contamination.
Glass stills are preferable to metal but have limited capacity. They are often used to "finish"
water stored from metal stills, or to distill water that has been deionized.
All stills require periodic cleaning.
Pretreating the incoming feed water will improve the quality of distilled water. For example,
carbon filters will remove organic materials. A mixed-bed ion exchanger will remove ions.
If the distilled water is piped into the laboratory, it should not be contaminated by the pipes. The
pipes should be tin lines or chemically resistant glass.
Where the distilled water is stored in the laboratory, borosilicate-free glass containers should be
used to prevent contamination. These containers should be covered and have a filter in the air
vent to remove airborne dust, gases, and fumes.
Distilled water for certain analysis is required to be ammonia-free, organic-free, carbon dioxide-
free or ion-free. Ammonia-free water is used for analysis of ammonia. Ion-free water is suitable
for the same purpose as well as determining trace metals and low concentrations of most ions.
It is not suitable for some organic analysis because organic contaminants are added to the water
during its treatment Organic-free water is used for the analysis of organic compounds. This water
is best obtained by the use of activated carbon, after distillation, to remove any organic compounds
remaining in the water.
Compressed Air
Analytical laboratories usually require high quality compressed air. Oil, water, and din are
undesirable contaminants and should be removed by filtering the flow from the compressors.
High quality compressed air is available in cylinders.
Electric Services
An adequate electric system including both 115- and 230-volt sources in sufficient capacity for the
type of work that must be done, is indispensable to the analytical laboratory. If necessary for the
proper functioning of electronic equipment, a constant voltage source must be available. For
example, spectrophotometers, flame photometers, atomic absorption equipment, and gas
chromographs all need constant voltage to prevent drift
The lighting in a laboratory must be sufficient to accurately read glassware graduations, balance
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
The temperature and humidity must be adequately controlled for proper instrument operation.
Fume hoods must be adequate for proper ventilation.
The laboratory should have safety equipment including goggles, gloves, fire extinguisher, shower,
eye wash, and first aid kit.
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
APPENDIX J
REVIEW QUESTIONS AND ANSWERS
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NPDES Compliance Monitoring Inspector Training: LABORATORY ANALYSIS
REVIEW QUESTIONS
1. What is the purpose of the laboratory evaluation?
2. What are the primary sources of information about a permittee and its compliance with requirements
imposed?
3. Why is it important that a laboratory have adequate sample control procedures?
4. Why is it important that a laboratory use approved, standardized analytical methods?
5. What is the key to quality analytical performance?
6. What is Quality Assurance (QA)?
7. What is Quality Control (QC)?
8. What laboratory procedures are used to assure the quality of data?
9. What laboratory procedures are used to control the quality of data?
10. What is precision?
11. What is accuracy?
12. How is precision of laboratory analyses determined?
13. How is accuracy of laboratory analyses determined?
14. Why is a laboratory QA/QC program important?
IS. How extensive should a laboratory's QA/QC program be?
16. What is DMR QA?
17. What are the major steps in a PAI?
18. What is a CEI?
19. What is PCS?
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ANSWERS TO REVIEW QUESTIONS
1. The purpose of the laboratory evaluation is to determine whether the laboratory is performing analyses
and reporting analytical results in a manner consistent with NPDES permit requirements and
applicable regulations.
2. The primary sources of information are:
The permit file
The inspection file
DMRs and DMR QA results
The initial meeting
PCS.
3. A laboratory sample control system is important legally when used in enforcement activities, and is
useful for the maintenance of quality analytical laboratory results.
4. Standardized methods are necessary when comparing or using data from more than one laboratory.
The use of approved methods ensures that superior methods are being used.
5. The key to quality analytical performance is the skilled analyst who has had appropriate and continuing
training.
6. Quality assurance is a system for ensuring data reliability by using administrative procedures and
policies to evaluate and maintain the desired quality of data.
7. Quality control is the routine application of procedures to control the accuracy and precision of
sampling and analytical measurement process.
8. Laboratory checks for quality assurance include:
Duplicate samples
Split samples
Performance samples
Spiked samples
Sample preservative blanks.
9. The quality of laboratory data is controlled by the use of:
Quality control charts
Analytical grade reagents
Standardization of instruments.
10. Precision is the degree of agreement between two or more measurements of the same quantity.
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NPDES CompUance Monitoring Inspector Training: LABORATORY ANALYSIS
ANSWERS TO REVIEW QUESTIONS (Continued)
11. Accuracy is the degree of agreement between a measured or calculated value and the "true" value.
12. Precision of laboratory analyses is determined by analyzing duplicate samples.
13. Accuracy of laboratory analyses is determined by analyzing spiked samples before and after the addition
of a known amount of a compound ("spike").
14. A laboratory QA/QC program monitors and documents laboratory analyses and provides a vehicle for
detection and correction of problems in the analyses.
IS. Approximately 20 percent of each laboratory's resources should be devoted to its QA/QC program.
16. DMR QA (Discharge Monitoring Report Quality Assurance) is a program which evaluates and
improves the analytical ability of laboratories serving NPDES permittees. Major permittees are sent
samples containing constitutents normally found in wastewaters and are to analyze the samples using
the analytical methods normally used for self-monitoring data and report the results. In turn, they
receive a report showing evaluation of their reported data.
17. Major steps of a PAI include:
Preinspection planning
Conduct initial meeting
Conduct audit inspection including sampling and analytical techniques, analytical QA/QC
procedures, laboratory services and equipment, and data and records management
Conduct exit meeting
Prepare report.
18. CEI (Compliance Evaluation Inspection) is a nonsampling inspection to verify a permittee's compliance
with self-monitoring and compliance schedule requirements. Reviews permittee's records and reports,
treatment facilities, compliance schedule status and self-monitoring program.
19. Permit Compliance System - National computerized tracking of NPDES information.
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