EPA814-B-96-002
April 1996
DBP/ICR Analytical Methods Manual
Technical Support Division
Office of Ground Water and Drinking Water
U.S. Environmental Protection Agency
Cincinnati, OH 45268
Printed on Recycled Paper
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Foreword
The Information Collection Rule (ICR) for Public Water Systems [Subpart M of the National
Primary Drinking Water Regulations, ง141.141(e)] requires public water systems that meet
certain applicability criteria to collect specified information for a limited period of time. The ICR
establishes data collection requirements and specifies the manner of collecting data and
transmitting these data to the United States Environmental Protection Agency (EPA). Four
technical manuals serve as supporting documents for implementing the rule requirements. They
are:
ICR Sampling Manual, EPA 814-B-96-001, NTIS # PB96-157508
DBP/ICR Analytical Methods Manual, EPA 814-B-96-002, NTIS # PB96-157516
ICR Manual for Bench- and Pilot-Scale Treatment Studies, EPA 814-B-96-003,
NTIS#PB96-157524
ICR Microbial Laboratory Manual, EPA/600/R-95/178, NTIS # PB96-157557
These technical manuals serve as "rule by reference" documents, and have two main objectives:
(1) to complement the ICR by further specifying the details of the rule requirements; and (2) to
provide guidance on how to comply with the ICR requirements. Copies of the manuals are
available for a fee from the National Technical Information Service (NTIS), U.S. Department of
Commerce, 5285 Port Royal Road, Springfield, VA 22161. The toll free number for NTIS is
(800)-336-4700.
The purpose of the DBP/ICR Analytical Methods Manual is to provide detailed information to the
laboratory community that will be analyzing the samples collected by the Public Water Systems to
meet the ICR requirements. The manual is intended to:
Describe the laboratory approval process ;
Describe the procedures that EPA will use to assess a laboratory's ability to produce
data of known accuracy and precision
Describe laboratory data quality control requirements for ICR analyses
Specify how ICR data are to be reported back to the utilities and to" EPA
Clarify specific analytical procedures that are not adequately described in some
methods that are referenced in this manual or that are unique to the ICR
This document was prepared by EPA's Office of Ground Water and Drinking Water, Technical
Support Division, Cincinnati, Ohio. Principal contributors to this document were Patricia Snyder
Fair, Caroline A. Madding, David J. Munch, and R. Kent Sorrell.
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Disclaimer
Mention of trade names or commercial products does not constitute endorsement or
recommendation for use.
in
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Acknowledgements
The following persons are gratefully acknowledged for their contributions in the preparation of
this manual:
Steven C. Allgeier, Oak Ridge Institute for Science and Education
John Ban, American Water Works Service Co., Inc.
Daniel Bender, Ph.D., USEPA, NERL
Herbert J. Brass, Ph.D., USEPA, OGWDW
Paul Britton, USEPA, NERL
Sanwat Chaudhuri, Ph.D., Utah Department of Health Laboratory Services
Zaid K.Chowdhury, Malcolm Pirnie, Inc
Hilda Cox, Montgomery Watson Laboratories.
Michael D. Cummins, USEPA, OGWDW
Steve Dickson, Utah Department of Health Laboratory Services
Andrew Eaton, Ph.D., Montgomery Watson Laboratories
Mary Ann Feige, USEPA, OGWDW
Charles R. Feldmann, USEPA, OGWDW
Bradford R. Fisher, Washington Suburban Sanitary Commission
Debbie Frank, Montgomery Water Laboratories
Don Gentry, Utah Department of Health Laboratory Services
Robert Graves, USEPA, NERL
Daniel P. Hautman, International Consultants, Inc.
Steve Jenniss, Ph.D., State of New Jersey, Department of Health
Stuart W. Krasner, Metropolitan Water District of Southern California
Sharon K. Laycock, Oak Ridge Institute for Science and Education
Richard J. Miltner, USEPA, NMRL
Jean W. Munch, USEPA, NERL
Jack Oman, Utah Department of Health Laboratory Services
Douglas M. Owen, Malcolm Pirnie, Inc.
John Pfaff, USEPA, NERL
Esperanza Renard, USEPA, QAMS
Alan Roberson, American Water Works Association
Mary Roughen, Montgomery Watson Laboratories
Hfiba M. Shukairy, Ph.D., Oak Ridge Institute for Science and Education
Kenneth E. Smith, Ph.D., NSF International
R. Scott Summers, Ph.D., University of Cincinnati
Judy Suzurikawa, Cincinnati Water Works
Richard Tomaskovic, Senior Environmental Employment Program
Ronald E.Twillman, St. Louis County Water Company
Yuefeng Xie, Ph.D., Perm State University at Harrisburg
IV
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Contents
Foreword ii
Disclaimer iii
Acknowledgements iv
List of Tables vi
Section Title Page
1. Introduction 1
2. Laboratory Quality Assurance Plan and ICR Quality Assurance Manual 5
3. Laboratory Registration for DBP/ICR Analyses 9
4. Laboratory Approval Process 11
5. Approved Methods for ICR DBP Monitoring 17
6. Initial Demonstration of a Laboratory's Ability to Perform DBP/ICR Analyses
not Covered under Current Drinking Water Regulations 35
7. Minimum Reporting Levels 39
8. Performance Evaluation (PE) Studies 41
9. Quality Control Requirements 45
10. Reporting Quality Control Data 73
11. Laboratory Evaluation During DBP/ICR Monitoring 77
12. Reinstatement of Laboratory Approval 81
Appendices
A. Laboratory Registration Form 83
B. Verification of State Certification/Approval Form 87
C. Laboratory Approval Forms 91
D. Determination of the Method Detection Limit-Revision 1.11
(CFRPt. 136, App. B) 139
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Tables
Number Title Page
5.1 Analytical Methods Approved for DBF Monitoring 29-33
6.1 Laboratory Performance Assessment Requirements 37
7.1 Minimum Reporting Levels (MRLs) 40
8.1 Acceptance Criteria for ICR Chemistry PE Studies 43
8.2 PE Acceptance Criteria for ICR General Water Quality Parameters 44
9.1 Frequency Requirements for Verifying Calibration 49
9.2 Low-Level Calibration Check Standard Concentrations & Acceptance Criteria 50
9.3 Mid-Level Calibration Check Standard Concentrations & Acceptance Criteria .... 51
9.4 High-Level Calibration Check Standard Concentrations & Acceptance Criteria ... 52
9.5 Frequency Requirements for Analyzing Laboratory Reagent (Method) Blanks .... 55
9.6 Acceptance Criteria for Laboratory Reagent (Method) Blanks 56
9.7 Requirements for Analyzing Field Reagent Blanks (Shipping Blanks) 58
9.8 Requirements for Performing Laboratory Duplicate Analyses 61
9.9 Requirements for Performing Fortified Sample Analyses \ 64
9.10 Concentrations for Fortifying Samples 65
9.11 Requirements for Internal Standard Analyses 67
9.12 Requirements for Surrogate Standard Analyses 69
9.13 ICR Sample pH Acceptance Criteria 70
9.14 Maximum Holding Times (in Days) for Samples and Extracts 71
10.1 QC Data to be Submitted to the ICR Federal Database by the Water System 75
10.2 QC Data to be Submitted to the ICR Federal Database by the Laboratory 76
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Section 1. Introduction
Background on the Information Collection Rule (ICR)
The U.S. Environmental Protection Agency (EPA) instituted a formal regulation negotiation
process in 1992 to develop the Disinfectant/Disinfection Byproduct (D/DBP) Rule. The Advisory
Committee that was established to negotiate the regulation included representatives from the
water industry, State health agencies, environmental groups, consumer groups, and EPA. During
negotiations, the Advisory Committee realized that setting strict limits on the levels of
disinfectants and disinfection byproducts (D/DBPs) in drinking water could result in an increasing
risk of waterborne disease from pathogens. To balance the risks between pathogens and
chemicals, the Advisory Committee made several recommendations. These recommendations
were developed into three new drinking water regulations.
Disinfectant/Disinfection Byproduct (D/DBP) Rule
Enhanced Surface Water Treatment Rule (ESWTR)
Information Collection Rule (ICR)
The D/DBP Rule was the primary rule negotiated, with the Advisory Committee recommending a
two stage approach to regulating D/DBPs. The first stage of the Rule introduces specific limits
for certain disinfectants and disinfection byproducts in drinking water. As proposed, it:
Sets limits on the amount of disinfectants allowed in drinking water.
Reduces the limits on total trihalomethanes (TTHMs) from 0.10 mg/L to 0.080 mg/L.
Sets limits on additional DBPs [sum of five haloacetic acids (HAAS), chlorite, and
bromatej.
Requires the use of enhanced coagulation by utilities treating surface water containing
total organic carbon (TOG) concentrations above a certain level.
Applies to all community and nontransient noncommunity water systems.
In the second stage of this rule, the acceptability limits of disinfectants and disinfection byproducts
in drinking water will be refined. Data collected in the Information Collection Rule (see below)
and in concurrent health effects investigations will be used to justify any modifications to the stage
one limits.
The second rule developed during the negotiation process is the Enhanced Surface Water
Treatment Rule (ESWTR). This rule specifies levels of treatment to control pathogens in
drinking water based on the microbial quality of the source water. This rule will be initially
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introduced as an "interim" rule that will include a range of regulatory alternatives affecting only
systems serving more than 10,000 people. The "interim" Enhanced Surface Water Treatment Rule
will become effective at the same time as the Stage 1 D/DBP Rule.
The third rule that was recommended by the Advisory Committee is the Information Collection
Rule (ICR). This rule addresses data needs in three areas, or elements. The most critical element
involves the collection of data on the concentrations of specific microbes (including
Cryptosporidium, Giardia konblia, and total culturable viruses) in surface water that is treated to
produce drinking water. (Monitoring for microbes in the drinking water may also be required, in
certain situations, for very large water systems.) Information concerning treatment processes
which are used to control pathogens will be collected in conjunction with the microbial
monitoring data. The data from the ICR will be used in the development of the ESWTR.
The second data collection element of the ICR involves the monitoring of the source water and
drinking water for general water quality characteristics, DBFs, surrogates for DBFs, surrogates
for DBF precursors, and the collection of treatment plant operational data. Data from the
DBP/ICR will be used to characterize the source water parameters that influence DBF formation,
determine concentrations of DBFs in drinking water, refine models for predicting DBF formation,
and establish cost-effective monitoring techniques. Successful development of the Stage 2
Disinfectant/Disinfection Byproduct Rule will be dependent on analyses of these data.
(Note that in the preceding paragraph, the term DBP/ICR was used. There are two basic types of
analyses for the ICR, microbial analyses, and disinfectant/disinfection byproduct (D/DBP)
analyses. In this manual, for clarity, D/DBP analyses for the ICR are identified as DBP/ICR,
while microbial analyses, if referred to, will be identified as Micro/ICR. This distinction is
necessary to separate D/DBP lab approval procedures from microbial lab approval procedures.
This manual only addresses the approval of laboratories to perform D/DBP analyses.
The third element of the ICR involves a requirement for some systems to conduct bench or pilot
scale studies to more completely investigate the use of granular activated carbon or membrane
filtration in removing DBF precursors during water treatment operations. The systems must
conduct TOC monitoring in order to determine whether they are subject to performing the
precursor removal treatment studies. (This TOC monitoring is referred to as Treatment
Study/ICR applicability monitoring in this manual.) The Treatment Study/ICR is intended to:
Obtain more information regarding the cost effectiveness of using these technologies
to reduce DBF levels
Decrease the time water treatment facilities will need to install such technology should
such technology be required under the Stage 2 Disinfectant/Disinfection Byproduct
Rule
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Ensuring Data Quality for the DBP/ICR
One of the major issues discussed during development of the ICR concerned the quality of the
data that are to be generated during the monitoring period. The Advisory Committee recognized
that the data must meet specific accuracy and precision targets in order to meet the ICR
objectives. Since the data are to be generated by many laboratories, strict data quality controls
will be essential. Maintaining data comparability between laboratories will be necessary if the data
are to be successfully used in sophisticated correlational analyses which will reliably predict DBF
formation as a function of water quality conditions. The Advisory Committee felt that the only
way to ensure useable data is to define and maintain strict controls on the collection and analysis
of the data, and for EPA to assist the drinking water industry in identifying qualified laboratories
which can accurately and reliably perform the analyses required by the DBP/ICR.
In August of 1993, EPA convened a panel of technical experts to assist in the development of
guidelines and requirements for ensuring analytical data was of adequate quality. Representatives
from utility, state, university, and commercial laboratories, and a nonprofit certification
organization were present at the two-day meeting. Attendees were invited to this meeting based
on their expertise in one or more of the following areas:
Analyzing for DBFs
Day-to-day management of laboratory operations
Drinking water laboratory certification programs.
The technical experts made several general recommendations regarding approaches that could be
used to ensure data quality. EPA used information from the panel as a basis for developing the
first draft of a manual titled "DBP/ICR Analytical Methods Guidance Manual - Public Comment
Draft," and it was made available to the public when the ICR was proposed on February 10,
1994. EPA received comments on the manual content during the public comment period
following the ICR proposal. The comments were generally supportive of the procedures
described in the manual, but issues were raised concerning some of the specific QC and PE
acceptance criteria. Commenters also identified areas that needed clarification, and recommended
that additional information, concerning certain methods, be added.
The panel of experts was reconvened on April 28-29, 1994 to assist EPA in evaluating the
comments and recommendations that were received. This manual reflects EPA's finalization of
the document after considering the panels comments and recommendations. This manual is
intended to:
Describe the laboratory approval process
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Describe the data that EPA will use to assess a laboratory's ability to produce data of
known accuracy and precision for the DBP/ICR
Describe laboratory data quality control requirements for ICR analyses for both the
DBP/ICR and the Treatment Study/ICR
Specify how ICR data are to be reported back to the utilities and to EPA for the
DBP/ICR
Clarify specific analytical procedures that are not adequately described in some
methods that are referenced in this manual
Laboratories will be approved to perform analyses for the DBP/ICR and the TOC monitoring to
determine applicability for treatment study requirements under the ICR according to the
procedures outlined in this manual. To maintain approval, they are required to follow the
procedures outlined herein.
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Section 2. Laboratory Quality Assurance Plan and ICR Quality
Assurance Manual
Laboratory Quality Assurance Plan
To ensure that analytical data generated for the ICR are scientifically valid and are of known and
acceptable precision and accuracy, all laboratories analyzing samples for the ICR will be required
to adhere to defined quality assurance procedures. To facilitate the accomplishment of these
goals, each laboratory must have a written description of its quality assurance (QA) activities, a
QA Plan, which describes the QA management of day to day routine operations. The plan must
be available for review for ICR laboratory approval, and it must be kept current during the time
the laboratory is performing ICR measurements. A copy of the Laboratory QA Plan table of
contents must be submitted to EPA as part of the laboratory approval application for analyses not
covered under state certification/approval processes.
The Laboratory QA Plan should be a separately prepared text. However, certain sections in the
Plan can simply reference existing documented procedures, such as the laboratory's standard
operating procedures (SOPs), EPA Methods, or other literature (e.g., Standard Methods for the
Examination of Water and Wastewater). Since most drinking water laboratory certification
programs require the preparation of a Laboratory QA Plan in order to obtain/maintain
certification, EPA anticipates that many laboratories applying for ICR approval will already have a
Laboratory QA Plan in place.
The following items should be addressed in each Laboratory QA Plan:
1. Laboratory organization and responsibility
include a chart showing the laboratory organization and line authority, including QA
Managers
list the key individuals who are responsible for ensuring the production of valid
measurements and the routine assessment of quality control (QC) measurements
specify who is responsible for internal audits and reviews of the implementation of the
Laboratory QA plan and its requirements
describe training available to keep personnel up to date on regulations, methods, etc.
2. Field sampling procedures
who collects, how collected, preservation, containers, holding times, transport to
laboratory
documentation of procedures
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3. Laboratory sample handling procedures
bench sheets used
storage; temperature, how isolated from standards and highly contaminated samples
tracking; specify procedures used to maintain integrity of all samples, i.e., logging,
tracking samples from receipt by laboratory through analysis to disposal
4. Calibration procedures
type used for each method
frequency of calibration
standards; source, age, storage, labeling
comparability checks
5. Analytical procedures
reference method used ;
SOP availability
6, Data reduction, verification, validation and reporting
data reduction; conversion of raw data to mg/L, coliforms/100 mL, etc.
verification; includes ensuring accuracy of data transcription and calculations
validation
reporting; includes procedures and format for reporting data to clients
7. Types of quality control (QC) checks and frequency of their use
laboratory performance check standard
Method Detection Limit (MDL) generation; acceptable, frequency
internal standards and surrogate standards
blanks; field, method, frequency
replicate analyses; frequency
QC samples; source, frequency
Performance Evaluation (PE) samples
fortified sample analyses; frequency
initial demonstration of precision and accuracy and control charts
8. Preventive maintenance procedures and schedules
manuals available
spare parts inventory
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schedule
documentation
9. Corrective action contingencies
response to obtaining unacceptable results from analysis of PE samples and from
internal QC checks
who is responsible
documentation of actions taken and effectiveness of actions
10. Record Keeping
how are records maintained (electronically?)
how long are records kept
where are records stored
The Laboratory QA Plan should be concise but responsive to the above-listed items. Minimizing
paperwork while improving data dependability and quality are the intended goals.
ICR Quality Assurance Manual
All laboratories seeking approval to perform chemical analyses for the ICR will also be required
to prepare a Quality Assurance (QA) Manual, specific to the Information Collection Rule. The
goals of the Laboratory QA Plan in general are different from the goals of the ICR QA Manual.
The former describes QA management of day to day routine operations while the latter describes
goals, interactions and procedures for a specific project, in this case, the ICR. The ICR QA
Manual is intended to supplement the Laboratory QA Plan by documenting the specific changes in
sample handling, analytical methods, QC, and data reporting that the laboratory makes to address
ICR requirements. This Manual must be available for review, if requested.
"Preparation Aids for the Development of Category I Quality Assurance Plans, EPA/600/8-
91/003", is a document laboratories may find useful in preparing the ICR QA Manual. It can be
obtained by calling the Center for Environmental Research Information at 513-569-7562.
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Section 3. Laboratory Registration for DBP/ICR Analyses
Analyses for the ICR must be performed only by laboratories that are capable of producing data
meeting the ICR accuracy and precision criteria. All laboratories wishing to perform analyses for
the DBP/ICR or TOC analyses for Treatment Study/ICR applicability must register with EPA by
requesting a Laboratory Registration Form (see Appendix A) from EPA at the address noted
below:
ICR Laboratory Coordinator
Technical Support Division/USEPA
26 West Martin Luther King Jr. Drive
Cincinnati, OH 45268
After receiving the official Laboratory Registration Form from EPA, the laboratory is to identify,
on the form, the ICR parameters that the laboratory wishes to analyze. There are several reasons
why EPA is requiring laboratory registration:
To assist EPA in determining which analyses will be performed by each laboratory
To allow EPA to send the correct application packages to a laboratory that requests
approval
To assist EPA in tracking the progress of the laboratory approval process
To allow EPA to ensure that utilities are using only EPA approved laboratories for
their DBP/ICR monitoring and their TOC monitoring to determine treatment study
applicability requirements
Based on the information provided by a laboratory in its registration form, EPA will send the
laboratory a "Verification of State Certification/Approval" form and/or application packages for
specific methods for which the laboratory has requested approval. The process that EPA will use
to approve laboratories for ICR analyses is outlined in Section 4.
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Section 4. Laboratory Approval Process
Laboratories that register with EPA to perform DBP/ICR analyses or TOC analyses for
Treatment Study/ICR applicability will be approved to perform testing in one of two ways.
Laboratories can be approved to perform certain analyses by submitting
information to demonstrate that they have existing state certification/approval to
perform these analyses using the methods specified in the ICR. Analyses that can be
approved in this fashion are: alkalinity, ammonia, calcium hardness, disinfectant
residuals, pH, temperature, total hardness, trihalomethanes, and turbidity.
Laboratories requesting approval to perform analyses that are not currently required
under other drinking water regulations (or not listed above) must complete a detailed
evaluation process as outlined in the following pages.
Overview of the Laboratory Approval Process
Laboratories must notify EPA no later than six months after the ICR promulgation
date of their intent to perform ICR chemical analyses by writing to the following
address:
ICR Laboratory Coordinator
Technical Support Division/USEPA
26 West Martin Luther King Jr. Drive
Cincinnati, OH 45268
EPA will forward an ICR Registration Form to the laboratory.
The laboratory must complete the ICR Registration Form and return it to EPA at the
above address.
Based on the information in the registration form, EPA will forward appropriate
application forms.
For analyses currently required under existing water regulations, laboratories can
be approved by submitting information to demonstrate that they have state
certification/approval to perform those analyses using ICR specified methods. See
the paragraph "Approval via Existing State Certification/Approval," in the text that
follows.
For analyses currently not required under other drinking water regulations, the
approval process is more detailed. Laboratories, in general, are required to:
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- Conduct precision, accuracy and method detection limit (MDL) studies for the
analyses in question.
- Demonstrate their capability by participating in, and passing, one or more PE
studies.
- Provide Personnel and Quality Assurance information (including the Table of
Contents from their Quality Assurance Plan).
- Provide information regarding analytical equipment, and sample handling
procedures.
EPA will acknowledge receipt of the completed application forms. All application
forms must be received by EPA no later than nine months after the ICR promulgation
date in order for the laboratory to be considered for ICR Laboratory Approval.
After reviewing the submitted application forms, EPA will notify the laboratory, in
writing, of its approval, or identify the reasons why the laboratory is not approved and
advise the laboratory of necessary action.
Laboratories are not authorized to analyze ICR compliance monitoring samples until
the laboratory is formally approved by EPA.
Laboratories approved for ICR analyses are required to maintain their approval status
by performing the various Performance Evaluation and Quality Control testing
outlined in Sections 8 and 9 of this manual.
NOTE: Approval of laboratories to perform ICR analyses will apply only during
the ICR 18 month monitoring period. If similar analyses are required as a result
of the promulgation of new drinking water regulations, laboratories will then be
required to be certified through the certification process appropriate for their
State and/or Region.
The ICR approval process is not related to the laboratory certification process
for conducting compliance monitoring under other drinking water regulations.
Approval, or failure to obtain ICR laboratory approval, will have no impact on a
laboratory's certification to perform compliance monitoring under other
drinking water regulations.
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Approval via Existing State Certification/Approval
General Water Quality Analyses. Several of the analyses that are required for the ICR are
currently required under other water regulations. As a result, mechanisms for reviewing
laboratory qualifications are already in place for these measurements. Measurements for pH,
alkalinity, turbidity, temperature, calcium hardness and disinfectant residuals are required in order
to meet current drinking water regulations, while ammonia and total hardness are specified in
other water regulations. If a laboratory documents that it is currently approved by a state to
perform these analyses using one of the methods specified in the ICR, then it will be approved, by
EPA, to perform the same analyses for the ICR. (See relevant Note that follows.)
To obtain approval for these general water quality analyses and THM analyses (for most methods)
laboratories must complete the "Verification of State Certification/Approval" form (see Appendix
B). The completed form will be reviewed by EPA to ensure that all requested data were
provided. If the information is complete, the laboratory will be advised, in writing, of its approval
to perform the requested analyses.
NOTE: In some circumstances, a laboratory may be performing some of these analyses
and reporting data to a State Primacy Agency with only de facto, and not documented,
State approval. In such situations (where the laboratory does not have a formal State
document to forward to EPA), a letter explaining the State's de facto approval must be
written by the laboratory manager and forwarded, along with the "Verification of State
Certification/Approval" form, to EPA.
Trihalomethane (THM) Analyses. Trihalomethane (THM) analyses for compliance monitoring
with the existing THM Rule must be conducted by laboratories that are certified by a State
Primacy Agency for drinking water. To obtain certification, the laboratory must demonstrate the
ability to generate accurate data by passing at least one Performance Evaluation (PE) study
sample for THMs on an annual basis. (Many states also conduct periodic on-site audits of
laboratories they certify.) If a laboratory can demonstrate that it is currently certified by a state
for THM compliance monitoring (see "Verification of State Certification/Approval" form,
Appendix B), then EPA will not need to evaluate the laboratory's capability to measure these
analytes prior to allowing it to perform THM analyses for the ICR (as long as the laboratory uses
the same method for which it is certified).
All laboratories approved to perform THM analyses for the ICR, however, are required to
participate in the ICR Chemistry Performance Evaluation (PE) Studies (see Section 8) that will be
conducted on a quarterly basis during the monitoring period. They are also required to follow the
quality control requirements described in Section 9. Therefore, although laboratories are State
certified to perform THM analyses, if they wish to perform analyses for the ICR, they are required
to meet additional requirements during the ICR monitoring period. (These additional
requirements will be separate from the certification process.) This "approval via state
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certification" applies only for THM analyses using methods 502.2, 524.2, and 551. See text
below regarding methods 551 and 551.1.
Again, the approval of a laboratory to perform ICR testing, or the failure of a laboratory to obtain
ICR laboratory testing approval, has no impact on a laboratory's certification to perform
compliance monitoring under other drinking water regulations.
Approval for Analyses not Covered under Current Drinking Water
Regulations
Laboratories that register with EPA to perform ICR analyses not listed in the above subsection,
are required to pass a review process prior to being granted approval to perform those analyses
for the ICR. EPA will also evaluate laboratories that do not have state approval/certification to
perform ammonia or total hardness analyses or THM analyses by Method 551. EPA will request
information from the laboratory for each method for which the laboratory wants approval. On a
method by method basis, the laboratory must list the names and qualifications of all personnel
involved in each method, the equipment used for each analysis, and its general sample handling
protocols. Samples of the forms to be used in reporting the applicable information are included in
Appendix C. (Note: The appendix does not contain forms for aldehyde and cyanogen chloride
methods, because EPA is performing these measurements for the water utilities.)
Laboratories are required to meet specific precision, accuracy, and method detection limit (MDL)
requirements for most methods for which they are seeking approval (as specifically shown in the
ICR application forms). The procedures that must be used to demonstrate precision, accuracy,
and MDLs are described in Section 6. Data from these analyses must be reported as part of the
laboratory approval application. Laboratories are also required to pass at least one ICR
Chemistry PE study, or to provide satisfactory historical PE study data, prior to being approved.
(PE studies are discussed in Section 8 of this manual.)
All laboratories that are approved to perform analyses for the ICR will be assigned unique
identification (ID) numbers or codes. The laboratory ID must be reported with the monitoring
data to allow laboratory precision and accuracy data to be associated with specific monitoring
data in the ICR Federal Database.
To maintain approval during the DBP/ICR monitoring period, laboratories are required to
participate in quarterly PE studies and to submit, to EPA, selected QC data (see Section 11).
Analyses exempted from these requirements are ammonia and total hardness.
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Approval for Special Analyses
Additional Haloacetic Acids. Approval to perform haloacetic acid (HAA) analyses for the ICR
encompasses the six HAAs for which the water systems are required to monitor:
monochloroacetic acid (MCAA)
dichloroacetic acid (DCAA)
trichloroacetic acid (TCAA)
monobromoacetic acid (MBAA)
dibromoacetic acid (DBAA)
bromochloroacetic acid (BCAA).
Laboratories may analyze and report data for up to three additional HAAs:
bromodichloroacetic acid (BDCAA)
chlorodibromoacetic acid (CDBAA)
tribromoacetic acid (TBAA)
if they are approved for the six HAAs. EPA will only accept monitoring data for these additional
HAAs, if the QC criteria specified in Section 9 are met.
Standard Method 4500-C1B. Water systems are permitted to use this method when
determining free residual chlorine concentrations in hypochlorite stock solutions. This method is
not approved for drinking water compliance monitoring, so it is unlikely that a water system has
state approval/certification to perform this analysis. EPA will grant ICR laboratory approval to
perform this analysis to laboratories that are approved for other free residual chlorine methods
under the ICR.
Simulated Distribution System Test. This test involves storing a sample of disinfected water
for a set period of time at a known temperature and pH and then analyzing the sample for:
trihalomethanes (THMs), HAAs, haloacetonitriles (HANs), chloropicrin (CP), haloketones (HKs),
chloral hydrate (CH), total organic halide (TOX), pH, alkalinity, turbidity, temperature, calcium
and total hardness, and disinfectant residual. EPA recommends that the storage part of the test be
conducted at the individual water treatment plants. There is no laboratory approval requirement
for setting up and conducting the test. The specific analyses at the conclusion of the storage
period must be conducted by laboratories approved to perform those analyses for the ICR.
Chlorine Demand Test. There is no laboratory approval requirement specific to the chlorine
demand test. However, this test includes measurements of free residual chlorine, pH and
temperature and these analyses must be conducted by laboratories approved to perform them for
the ICR.
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Assimilable Organic Carbon (AOC) and Biodegradeable Organic Carbon (BDOC)
Analyses. There is no laboratory approval requirement for these analyses, but laboratories are
required to obtain an ICR Laboratory Identification (ID) Number. Laboratories can obtain this
ID number by writing to:
ICR Laboratory Coordinator
Technical Support Division/ USEPA
26 West Martin Luther King Jr. Drive
Cincinnati, OH 45268.
Laboratories must indicate in their letter to the Coordinator whether they are under consideration
for approval to perform other analyses for the ICR (either chemical pr microbial).
The ID number must be provided to the water system when monitoring data for AOC or BDOC
are reported. In addition, the laboratory must report specific quality control data to the water
system (see Section 10). Water systems are required to report laboratory ID numbers and
associated QC data to EPA when AOC or BDOC monitoring data are reported. This will provide
the users of the ICR Federal Database the ability to assess the quality of the AOC/BDOC data
when they analyze/use them.
16
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Section 5. Approved Methods for ICR DBF Monitoring
Laboratories must use the methods specified in ง141.142 (b)(l) to perform DBP/ICR analyses
during the 18-month monitoring period and during the treatment studies. (A list of methods, in
effect as of July 1, 1996, is summarized in Table 5.1) They must also follow all analytical (see
following text) and quality control procedures (see Section 9) outlined in this manual. With the
exception of analyses for chlorine demand, assimilable organic carbon (AOC), and biodegradeable
organic carbon (BDOC), analyses shall be conducted only by laboratories that have been formally
approved, by EPA, for ICR water sample analyses during the 18-month monitoring period. The
TOC monitoring to determine whether a water system is subject to the treatment study
requirements must also be performed by a laboratory approved for TOC analyses. It is
recommended that the THM, HAA or TOX monitoring to determine treatment study applicability
requirements be performed by a laboratory approved for those analyses; the laboratory must meet
the performance evaluation requirements described in Section 8 and the quality control
requirements in Section 9 of this manual. Water systems that are required to conduct treatment
studies are encouraged (but not required) to have the samples from these studies analyzed by
laboratories that were approved by EPA for the 18-month monitoring period.
The list of analytical methods promulgated in the ICR is not exactly the same as the list that was
included in the February 14, 1994 proposal. A brief discussion of the changes and the rationale
for making them is incuded in this section under the subsection titled "Proposed and Promulgated
Methods for ICR Monitoring" (see page 26).
Special Analytical Procedures
Chlorine Residual Analyses. The ICR requires water systems to monitor disinfectant residuals
using the methods specified at ง141.74(a)(2), and a summary of those methods is included in
Table 5.1. Section 141.74(a)(2) also states: "If approved by the State, residual disinfectant
concentrations for free chlorine and combined chlorine also may be measured by using DPD
colorimetric test kits." Therefore, water systems that are using these test kits to perform drinking
water compliance monitoring under approval from the State, may also use the test kits to perform
analyses for the ICR.
Haloacetic Acids. The ICR requires water systems to monitor for six haloacetic acids (HAA6)
(monochloroacetic, dichloroacetic, trichloroacetic, monobromoacetic, dibromoacetic, and
bromochloroacetic acids) [ง 141.142(a)] and therefore the ICR laboratory approval process only
pertains to these six compounds. Studies that were not available during negotiations for the ICR
17
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indicate that some drinking waters could contain significant concentrations of additional HAAs.1'2
As a result, EPA is encouraging, but not requiring, water systems to collect monitoring data for
these additional compounds (bromodichloroacetic, chlorodibromoacetic, and tribromoacetic
acids). [ง 141.142(a) Table Ib]
Only EPA Method 552.2 lists these three compounds as analytes and provides method
performance data. The data presented in the above references were generated using an expanded
version of SM 6251B, but the precision, accuracy and sensitivity achievable using SM 6251 B
was not documented. Laboratories that decide to provide analytical services for these additional
compounds are encouraged to use EPA Method 552.2. However, data from the other HAA
method will be accepted by EPA (i.e., entered into the ICR Federal Database) as long as the
laboratory is able to meet the quality control requirements for the compounds as specified in
Section 9. These QC requirements are based on criteria easily achievable using EPA Method
552.2 and may not be achievable using other methods.
Standard Method 6251B Errata/Clarification. Two corrections to this method were brought
to the attention of the Standard Methods Committee after the 19th edition was published. An
errata/clarification sheet was issued to address the corrections. The text changes to the method
and their explanations are described below:
The 19th edition version of this method implies that all extracts must be dried prior to the
derivatization step. This step may not be necessary if the analyst is careful to not transfer any of
the aqueous phase from the extraction vial. Therefore, section 5.d of the method is amended as
shown below.
The procedure to be used for preparing the acidified sodium sulfate that is used in the drying step
was inadvertently omitted from the method. Therefore section 4.b of the method is now divided
into two subsections (4.b.l and 4.b.2) and the original "4.b" is now 4.b.l.
4.b.J. Sodium sulfate, granular reagent grade,....
4.3.2. Acidified sodium sulfate (acidified Na^O4) After heating 100 g anhydrous sodium
sulfate to 400ฐC and cooling to room temperature, prepare the acidified sodium sulfate by
making a slurry in di-ethyl ether. The solid should be just covered. Add 0.1 mL
concentrated sulfuric acid and throughly mix. Remove the ether under low vacuum. Mix
^ourmoghaddas, H. et. al. Effect of Bromide Ion on Formation of HAAs During
Chlorination. Jour. AWWA, 85:1:82 (Jan. 1993)
2Cowman, G. & P.C. Singer. Effect of Pre-ozonation on Haloacetic Acid Speciation in
Chlorinated Waters Containing Bromide. AWWA Water Quality Technology Proceedings, Nov
1994.
18
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1 g of the acidified sodium sulfafe with 5 mL of reagent water and measure the pH of the
mix. The pH must be less than 4. Store at 130ฐC.
5.d. Separation and concentration: NOTE: Ensure that all items .... sulfuric acid.
The drying step included here may be used if excess diazomethane is required to
maintain the persistent yellow color of the sample (5.e). It has been found not to be
necessary in all cases and may be used at the discretion of the analyst. Plug a small
disposable pipet....
EPA Method 551.1 Analyses. This method can be used to determine the concentrations of
tnhalomethanes (THMs), haloacetonitriles (HANs), haloketones (HKs), chloropicrin (CP) and
chloral hydrate (CH) in water. Sodium sulfite must be used to dechlorinate samples for CH
analyses and ammonium chloride must be used when HAN, HK, or CP analyses are to be
performed. The THMs can be determined in samples that have been treated with either sodium
sulfite or ammonium chloride. In order to ensure that laboratories do not mistakenly analyze the
same sample for CH and HANs, laboratories are required to extract and analyze CH and HAN
samples in separate batches.
Oxyhalides and Bromide. EPA Method 300.0 is divided into two parts. Bromide is listed as an
analyte in Part A and the oxyhalides (bromate, chlorite, and chlorate) are listed in Part B. One of
the primary differences between the two parts is the analytical column. Part A specifies an AS4A
column while Part B specifies an AS9 column. Some analysts have found that they can analyze
for bromide ion using the AS9 column. This option is allowed according to Section 6.2 2 1 of the
method which states that "An optional column may be used if comparable resolution of peaks is
obtained, and the requirements of Section 9.2 can be met." Therefore, laboratories are permitted
to use an AS9 column to perform bromide analyses for the ICR as long as the necessary
performance criteria are met.
Chloride ion interferes with the measurement of bromate ion in some samples, because it is
present in much higher concentrations than bromate and it elutes from the chromatography
column close to the bromate peak. Analysts are allowed to pretreat the sample to remove the
chloride ion, but this should only be done after it is demonstrated that optimizing the performance
of the chromatographic system is not enough to resolve the chloride and bromate peaks. In some
cases, the purchase of a new chromatographic column may provide the necessary resolution
Some laboratories may find it necessary to use a weaker eluent in order to achieve the necessary
resolution between the bromate ion and chloride ion peaks. This is permitted (Sections 11 8-9 of
the method) as long as the QC performance criteria are met. The strength of the carbonate eluent
can be adjusted to provide additional resolution. A borate eluent has also been used successfully
to improve resolution.3
3Hautman, D.P. & M. Bolyard. Using Ion Chromatography to Analyze Inorganic
Disinfection By-Products, Jour. AWWA. 84:11:88 (Nov 1992).
19
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If chloride ion is still a problem after implementing the above measures, then pretreatment of the
sample to remove the chloride ion should be considered. (Samples with chloride concentrations
>30 mg/L are likely to require pretreatment.) This can be accomplished by passing the sample
through a silver cartridge or pretreatment guard column. If this procedure is used for samples, it
must also be used on blanks, calibration standards and QC samples even though they do not
contain significant concentrations of chloride ion. Analysts must be aware that some of the silver
will leach into the sample and become deposited on the analytical column, if additional
precautions are not taken. When this happens, the column CANNOT be used to determine
bromide ion concentrations.
In order to prevent the deposition of silver onto the analytical column, the sample may be passed
through a chelating cartridge or pretreatment guard column after the silver column but prior to
the analytical column in order to remove the silver. If a guard column is used, it must be
periodically regenerated according to the manufacturer's instructions to ensure continued
performance. The analyst must monitor the instrument's sensitivity for bromide ion to verify that
the chelating cartridge or guard column is removing the silver. A loss in sensitivity or a change in
the bromide ion peak shape indicates silver may have been deposited in the analytical system. As
stated above, if chelating cartridges or guard columns are used for samples, they must also be
used on blanks, calibration standards and QC samples.
Analysis for bromide ion must not be performed on samples that have been pretreated to remove
chloride ion, because the silver removes all halide ions, including bromide.
The method performance data listed in Method 300.0 were generated using a carbonate eluent
and a 50 yiL sample injection volume. A larger sample volume (e.g., 200 ^L) may also be
required in order to measure bromate ion concentrations as low as 5 /zg/L.
Total Organic Halide. The ICR requires water systems to monitor total organic halide (TOX)
concentrations in untreated water and in the finished drinking water. Particulates may cause
problems in the analysis of untreated water samples, because they clog the activated carbon
columns during the adsorption step. For the ICR, analysts must not use traditional filtration
techniques to remove gross particulates from the sample prior to the adsorption step, since that
would cause volatiles, such as trihalomethanes, to be lost from the sample. If the sample is
suspected to contain particulates which could prevent the free-flow of sample through the carbon
column, a small amount of quartz wool can be used as a prefilter during the adsorption process.
The quartz wool is inserted into a clean and empty glass column (or TOX-free holder) and placed
in series ahead of the two carbon columns. (Note that insertion of a Cerafelt plug, at the bottom
of the glass column, may be necessary to retain the quartz wool.) After sample adsorption, this
column is nitrate washed, then pyrolyzed. Prior to the use of a quartz wool column, a system
blank should be analyzed with the quartz wool column in place in order to ensure the column does
not introduce contamination to the sample.
20
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Total Organic Carbon. The ICR requires water systems to monitor total organic carbon (TOC)
concentrations on a monthly basis at several sampling points. [ง 141.142 (a)(l)] The methods
cited in the ICR are not clear concerning whether TOC includes the volatile fraction of organic
carbon. Many studies published in the literature4-5'6, which support the use of organic carbon as a
surrogate for disinfection byproduct (DBF) precursors, measured the non-purgeable fraction of
organic carbon. This was done by acidifying the samples to a pH s 2 to convert the inorganic
carbon (e.g., carbonates and bicarbonates) to carbon dioxide and then sparging the samples to
eliminate the carbon dioxide. The sparging process eliminated the volatile fraction of organic
carbon. Therefore, for the ICR, the term TOC refers to the non-purgeable fraction of the organic
carbon.
Several researchers have used dissolved organic carbon (DOC) instead of TOC as a surrogate for
precursors. However, TOC was chosen by the negotiators as the parameter to be measured
during the ICR. Therefore, samples must not be filtered prior to analyses for TOC. The methods
specify that samples containing particulates may be homogenized or mixed and diluted prior to
analysis. In some cases, the use of certain instruments may be precluded, if the sample
introduction system cannot accommodate particulates.
UV Absorbance at 254 nm. The Standard Method (5910) provides some procedural options
that are not applicable for the ICR. The absorbance must be measured at 254 nm for all ICR
samples. All samples must be filtered to remove particulates. Filtration is the only pretreatment
of the sample prior to measuring UV absorbance. There must not be any pH adjustment made to
the samples; nor should a buffer be used in the spectrophotometer check standards. The UV
absorbance reading must not be corrected for interferences. Samples should be analyzed as soon
as possible after collection; samples must be analyzed within two days of sample collection.
Absorbance must be reported on a cm'1 basis, which means that appropriate calculations must be
performed if a 5 or 10-cm cell path length is used to perform the measurements; e.g., The
absorbance reading should be divided by five when a 5-cm cell is used for the measurement. The
method indicates that the sample pH should be recorded; however, the laboratory is not required
to determine pH on UV samples for the ICR, because the pH is measured at the water treatment
plant when the UV sample is collected.
"Miller, R.E. et. al. Organic Carbon and THM Formation Potential in Kansas
Groundwaters, Jour. AWWA. 82:3:49 (Mar 1990).
5Symons, J.M. et. al. National Organics Reconnaissance Survey for Halogenated Oreanics
Jour. AWWA. 67:ll:634(Novl975).
6Reckhow, D.A. & P.C. Singer. Chlorination by-products in drinking waters: from
formation potentials to finished water concentrations, Jour. AWWA. 82:4:173 (Apr 1990).
21
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Simulated Distribution System (SDS) Test. This test involves storing a sample of disinfected
water for a set period of time at a known temperature and pH and then analyzing the sample for
certain parameters. The ICR specifies Standard Method 5710 C for the SDS test. This method
provides a general description of the test, but users are given many procedural options depending
upon the purpose of conducting the test. For the ICR, the DBF concentrations in the SDS sample
will be compared to the DBF concentrations measured in a sample from the distribution system.
Therefore, the conditions under which the SDS test is conducted for the ICR are specific to each
water treatment plant.
The SDS test conditions (i.e., storage time and temperature) are selected based on information
about the distribution system equivalent (DSE) sample which is collected from the distribution
system of each water treatment plant. The DSE sample's detention time (time the water has spent
traveling from the water treatment plant to the sampling point in the distribution system) is used
as the basis for establishing the SDS storage time. The SDS sample should be stored for a time
period comparable in length to the DSE sample's detention time. The storage temperature should
be comparable to the temperature of the water in the distribution system between the treatment
plant and the DSE sampling point. In order to accomplish-this, the SDS sample should be
maintained at the temperature measured at either the SDS sampling point or the DSE sampling
point. The goal should be to achieve a temperature within ฑ2ฐC of one of these temperatures.
The contact time of the SDS test begins when the sample is collected. Therefore the storage part
of the test is best conducted at the treatment plant where the sample is collected. If this is not
possible, then the sample should be transported to a nearby site for the test. The SDS sample
must not be iced or treated in any other manner and shipped to off-site laboratories until after the
storage part of the test is completed and the sample is divided into aliquots with the appropriate
dechlorinating agents for the individual analyses.
There are many techniques available to maintain the SDS sample at a constant temperature during
the storage period. Some examples include (but are not limited to):
using an incubator or constant temperature water bath set at the appropriate
temperature
placing the SDS sample containers) in an insulated container (e.g., an ice chest) and
allowing a constant flow of finished water to pass through the container to maintain
the sample at the finished water temperature
placing the SDS sample container(s) in a bucket in a sink and allowing a constant flow
of finished water to pass around the sample to maintain it at the finished water
temperature
suspending the SDS sample containers) in the treatment plant clearwell to maintain it
at the finished water temperature
22
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The goal should be to store the SDS sample for the same length of time as the detention time of
the DSE sample. Since the DSE detention time is estimated, the SDS storage time should
reasonably approximate (within ฑ25%) the DSE detention time.
At the conclusion of the storage time, the SDS sample must be analyzed for several parameters
The SDS sample must be divided by pouring it into sample bottles containing the appropriate
dechlonnatmg agents/preservatives. (This may be done at the storage site or at a nearby
laboratory, if the sample temperature is maintained during transport and the transport time is
factored into the storage time.) Care must be taken to not aerate the sample during this transfer
in order to prevent the loss of volatile compounds such as THMs. (The samples for THM, HAN
TOX, and CH analyses should be transferred first, because they contain volatile analytes which
can be easily lost during the pouring process.) The subsamples must be analyzed by ICR
approved laboratories using the appropriate analytical methods. Three analyses must be
conducted as soon as possible after the conclusion of the storage period: chlorine residual pH and
temperature. Holding times for the remainder of the analyses begin when the SDS sample is
divided for individual analyses.
Chlorine Demand Test. The method cited in the ICR is Standard Method 2350 B This method
describes how to perform the test, but it leaves the choice of chlorine dose, temperature PH and
contact time up to the discretion of the person performing the test. In order to meet the
objectives of determining the chlorine demand resulting from the presence of inorganics specific
guidelines are established which must be followed in order to comply with the ICR. The test is to
be conducted under conditions specific to each water treatment plant.
Chlorine Dose. If the first disinfectant (or oxidant) used in the treatment process is chlorine
and breakpoint chlorination is practiced, selection of an appropriate chlorine dose should be
based on what is used at this point in the treatment process to achieve a desired free chlorine
residual. Ideally, the same dose should be used, with the exception that the goal for this test is
to obtain a final free residual chlorine concentration (as measured in this test) between 0 5 and
1.0 mg/L. In order to consider the test results valid, the residual must be no less than 0 2
mg/L and no greater than 1.5 mg/L.
If breakpoint chlorination is not practiced at the first point of chlorine application, then the
dose used for the chlorine demand test must be based on a dosage that will result in a free
residual chlorine between 0.2 and 1.5 mg/L (goal is between 0.5 and 1.0 mg/L, as described
above). Selection of an appropriate dosage may require several iterations in the test. If the
water contains ammonia-nitrogen as the major contributor to inorganic chlorine demand then
the chlorine dose necessary for this test can be estimated by multiplying the ammonia
concentration (as mg nitrogen/L) by 7.6 and then adding an additional 1.0 mg/L. (This should
provide a free residual chlorine concentration near 1 mg/L.)
23
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If chlorine is not the first disinfectant (or oxidant) used in the treatment process, then the
chlorine dose must be determined using the same guidelines as for when breakpoint
chlorination is not practiced.
Contact Time. Free residual chlorine should be measured approximately 5 minutes after the
chlorine is added to the sample. If the residual cannot be measured in the dosed sample within
10 minutes, then the test must be repeated with a fresh sample. This short time period was
chosen because reactions with the inorganics are expected to occur quickly and it is physically
feasible to make the free residual chlorine measurement within the 10 minute time frame.
The free residual chlorine measurement must be made using the same method as is used to
make other free residual chlorine measurements for the ICR.
Temperature. The water sample must be at the same temperature as the process water. This
means that the test should be conducted on a freshly collected aliquot of water. The
temperature of the sample should be determined after the free residual chlorine measurement
is completed.
pH. The pH of the water must not be adjusted for this test. It should reflect the pH of the
water at the point of first disinfectant/oxidant addition in the treatment process. The pH of
the sample should be determined after the free residual chlorine measurement is completed.
Reporting Requirements. The following data must be reported for this test:
Chlorine dose (mg/L)
Contact time (min)
Analysis date
Chlorine residual (mg/L)
pH (after contact time)
Temperature (ฐC) (after contact time)
EPA will calculate the chlorine demand by subtracting the chlorine residual from the chlorine
dose.
Analyses of Hypochlorite Stock Solutions. Water systems that use hypochlorite solutions for
disinfection are required to measure the pH, temperature, free residual chlorine, and chlorate ion
concentrations in the feed stock solution. The chlorine and chlorate concentrations in
hypochlorite stock solutions are expected to be hundreds to thousands times greater than the
concentrations typically measured in drinking water samples. Therefore, the water systems are
required to report the concentrations of these two parameters in g/L units for this sample type.
All other analyses for free residual chlorine and chlorate ion must be reported as mg/L as C12 and
#g/L, respectively. Laboratories are encouraged to report the results of these analyses in the
same units as the water systems are required to report the data to EPA.
24
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EPA recommends that the hypochlorite stock solution sample for chlorate determination be
collected without a preservative in the sample bottle. The sample must be chilled upon collection
in order to minimize the formation of additional chlorate from the decomposition of the
hypochlorite solution. The sample will probably require significant dilution prior to analysis for
chlorate ion concentration. Enough ethylenediamine (EDA) should be added to the diluted
sample to eliminate the free residual chlorine before the sample is analyzed by ion
chromatography.
Five methods for determining free residual chlorine are listed in Table 5.1 and are approved for
use on the hypochlorite stock solution samples. These stock solution samples are expected to
contain free residual chlorine concentrations that are orders of magnitude above the normal
working range of approved methods, so users must exercise care in diluting the samples to
concentrations that are appropriate for the method in use. In order to minimize the magnitude of
the necessary dilution, EPA encourages the use of Standard Method 4500-C1B with the following
modifications (numbers refer to sections in the method as described in the 19th edition of
Standard Methods for the Examination of Water and Wastewater):
2.d. Standard sodium thiosulfate titrant, 0.01N or 0.025N: Do not prepare this
dilution. Use the 0. IN Na^Os standard solution prepared and standardized
according to l.c when performing the titration described in 3.c.
3 .a. Volume of sample: Prepare a dilution of the stock hypochlorite solution sample
by pipetting 20 mL of it into a 1 liter volumetric flask. Dilute to the mark with
chlorine-demand-free water (see 4500-C1 C.3.m.). Use an aliquot from this dilution
when performing the titration described in 3 .c. For hypochlorite stock solutions with
concentrations in the range of 5 - 15% chlorine by weight, use a 10-mL aliquot of the
diluted sample for the titration. (The goal is to select a sample volume that will
require between 1 and 10 mL of the 0.1N Na^A titrant to reach the starch-iodide
end point.)
3.b. Preparation for titration: Place 5 mL acetic acid, Pour sample (aliquot
from dilution made in 3.0.) in, add approximately 400 mL chlorine demand free
water, and mix with a stirring rod.
3.c. Titration: Titrate away from direct sunlight. Add 0. IN Na^Os from a buret
until
3.d Blank titration: Correct result of sample titration....
Take a volume of chlorine demand free water corresponding to the volume of
diluted sample used for the titration in 3.c and the volume of chlorine demand free
water added in 3.c, add 5 mL acetic acid, ....Perform blank titration as in 1) or 2)
below, whichever applies.
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1) If a blue color develops, titrate with (UNNa^C^ to disappearance of blue
color and record result. B (see f 4, below) is negative.
2) If no blue color occurs, titrate with 0.0282N iodine solution until a blue color
appears. Back-titrate with 0.1NNa2S2O3 and record the difference. B is positive.
Before calculating the chlorine concentration,
4. Calculation: For determining total available residual chlorine in a hypochlorite
stock solution sample, use the following equation:
g Cl as CIJL = (Aฑ B') x N x 35.45 x 1QQQ
Cx20
where:
A = mL titration for sample
B = mL titration for blank (positive or negative)
C =ป mL of diluted sample
N = normality of Na^C^ used as titrant (should be approximately 0. IN)
The above equation assumes:
20 mL of the hypochlorite stock solution sample is diluted to 1000 mL (hence the
correction factor of 1000/20) and the titration is performed on an aliquot from the
1000 mL dilution.
(mL of diluted sample) is the volume of the diluted sample which is used in the
titration. If the undiluted hypochlorite stock solution concentration is in the range of 5
- 15% chlorine by weight, and the sample is diluted according to 3.a., then this volume
is 10 mL.
35.45 is the equivalent weight of chlorine and is used to convert the concentration
from Normality to g/L as C12.
Concentration of hypochlorite stock solution is reported as: g Cl as CyL.
Proposed and Promulgated Methods for ICR Monitoring
The final ICR did not promulgate all the methods that were included in the February 1994
proposal. These method modifications to the ICR rule were made in response to public
comments, revisions in related EPA regulations, updates to Standard Methods and incorporation
of improved methodology.
In the interim between proposal and promulgation, EPA revised the list of methods approved for
drinking water compliance monitoring. [See National Primary and Secondary Drinking Water
Regulations: Analytical Methods for Regulated Drinking Water Contaminants; Final Rule, Federal
26
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Register 59(232) pg. 62456-62471, December 5, 1994.] Approval for several methods was
withdrawn effective July 1, 1996. Therefore, these methods are not listed in Table 5 1 and EPA
will not approve laboratories to perform analyses for the ICR using the withdrawn methods.
The 19th edition of Standard Methods for the Examination of Water and Wastewater was
published between proposal and promulgation. EPA proposed three draft methods from the 19th
edition (HAAs, UV254, and Aldehydes). The final ICR promulgated two of these (SM 6251 B
formerly 6233 B, for HAAs and SM 5910 for UV2S4). The third method (SM 6252 B) is being
used by EPA when aldehyde samples are analyzed for the water systems during the 18-month
monitoring period.
EPA also cited only the 19th (not 18th) edition of Standard Methods in the ICR for analyses that
were not previously required under other drinking water regulations. This necessitated dropping
one method for ammonia (nesslerization - SM 4500-NH3 D), because it was no longer supported
by Standard Methods due to the use of mercury. The ammonia method numbers were also
changed between the two editions, so the method numbers were changed between the ICR
proposal and promulgated rule. SM 4500-NH3 F in the proposal is listed as SM 4500-NH, D in
the final rule.
EPA received public comments from the proposal requesting the addition of automated methods
for ammonia analyses. EPA deemed three automated methods to be equivalent to the manual
methods included in the proposal. Therefore, EPA Method 350.1 SM 4500-NH, G and
Industrial Method 379-75 WE were added in the final rule.
EPA received many comments concerning the proposed methods for TOC analyses. EPA
evaluated the data that were submitted indicating that some combustion instruments based on SM
5310 B are sensitive and precise enough to meet ICR requirements and EPA concurred with the
commenters. Therefore, EPA added SM 5310 B to the list of methods approved for TOC
monitoring under the ICR.
The preamble to the proposed ICR rule discussed difficulties in the preservation of samples for
the determination of haloacetonitriles, haloketones, chloropicrin, and chloral hydrate
concentrations in drinking water. In the interim between proposal and promulgation, EPA was
able to develop a preservation technique for these samples and a revised method was published
Because the new version of the method (EPA Method 551.1) addresses a problem that was of
concern both to EPA and many commenters, EPA promulgated 551.1 instead of EPA Method
551 for the compounds listed above.
EPA was also able to develop a new method for measuring HAA concentrations in drinking water
during the period between proposal and promulgation. EPA Method 552.2 combines the positive
aspects of the two methods that were included in the proposal and eliminates some of the
concerns expressed by the laboratory community regarding the proposed methods. Therefore
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EPA decided to list Method 552.2 as an additional approved method for performing HAA
analyses.
Low Bromate
EPA Method 300.0 is not sensitive enough to meet all the ICR objectives. The routine method
can be used to determine whether a utility would be able to comply with the proposed 10 //g/L
Maximum Contaminant Level (MCL) proposed in the Stage 1 D/DBP Rule. However, the
variability in the data below 10 y^g/L prevents using the data to determine how changes in
treatment processes affect the formation of bromate. In order to obtain that type of information,
samples must be analyzed using methodology that can quantitate bromate at concentrations < 1
/^g/L. EPA's laboratory has the capability to measure down to approximately 0.2 //g bromate/L
using a technique that involves selectively concentrating the bromate prior to the ion
chromatographic analysis.7 EPA will be performing this analysis for the utilities during the 18-
month monitoring period. EPA's analyses will be in addition to the analyses that are performed
using Method 300.0 by laboratories commissioned by the water utilities. Many of the tables in
this manual refer to a "low BrO3"" analysis. It is included, in order to document the criteria that
EPA will follow when performing this analysis.
Aldehyde and Cyanogen Chloride Analyses
EPA will perform all the required aldehyde and cyanogen chloride analyses for the water utilities
during the 18-month monitoring period. EPA will use Standard Method 6252 B8 to perform the
aldehyde analyses. A modified version of EPA Method 524.2s will be used for the cyanogen
chloride analyses. Many of the tables in this manual refer to the aldehyde and cyanogen chloride
analyses. They are included, in order to document the criteria that EPA will follow when
performing these analyses.
'Hautman, D.P. Analysis of Trace Bromate in Drinking Water Using Selective Anion
Concentration and Ion Chromatography. AWWA Water Quality Technology Proceedings, Nov.
1992.
'Standard Methods for the Examination of Water and Wastewater. 19th edition, 1995,
American Public Health Association, 1015 Fifteenth Street NW, Washington, D.C. 20005.
'Flesch, JJ. and P.S. Fair. The Analysis of Cyanogen Chloride in Drinking Water.
AWWA Water Quality Technology Proceedings, Nov 1988.
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Table 5.1. Analytical Methods Approved for DBF Monitoring
Analyte
PH
Alkalinity
Calcium hardness
Turbidity
Temperature
Free Residual Chlorine
Total Residual Chlorine
Chlorine Dioxide Residual
Ozone Residual
Trihalomethanes (THMs):
Chloroform (CHC13)
Bromodichloromethane (BDCM)
Dibromochloromethane (DBCM)
Bromoform CCHBrS)
Methodology
EPA
Method
150. 12,
150.22
200.7s-6
180. 16-7
502.26'10,
524.26-11,
55 16-12,
551. 113
Standard
Method1
4500-ITB
2320 B
3111 B6,
3120B6,
3500-CaD
2130 B6
2550 B
4500-C1 B9,
4500-C1 D,
4500-C1 F,
4500-C1 G,
4500-C1 H
4500-C1 D,
4500-C1 E6,
4500-C1 F,
4500-C1 G6,
4500-C1 1
4500-C1O2 C,
4500-C1O2D,
4500-C1O, E
4500-O, B
Other
ASTMD1293-843
ASTMD1067-92B3,
I-1030-854
ASTMD511-93A3,
ASTMD511-93B3'6
GLI Method 26-8
29
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Analyte
^^^^!^=
Haloacetic acids (HAAs):
Monochloroacetic Acid (MCAA)
Dichloroacetic Acid (DCAA)
Trichloroacetic Acid (TCAA)
Monobromoacetic acid (MB AA)
Dibromoacetic acid (DB AA)
Bromochloroacetic acid (BCAA)
Optional analytes:
Bromodichloroacetic acid (BDCAA)
Chlorodibromoacetic acid (CDB AA)
Tribrornoacetic acid (TBAA)
Chloral Hydrate (CH)
Haloacetonitriles (HANs):
Trichloroacetonitrile (TCAN)
Dicnloroacetonitrile (DCAN)
Bromochloroacetonitrile (BCAN)
Dibromoacetonitrile (DBAN)
Haloketones (HKs):
1,1-Dichloropropanone (DCP)
LLl-Trichlorooropanone (TCP)
I Chloropicrin (CP)
1 Chlorite (CIO,')
I Chlorate (CIO,')
a Bromide QBr')
1 Bromate (BrO3')
1 Total Organic Halide (TOX)
Total Organic Carbon (TOC)
TJV absorbance at 254 nm fUV-254)
Methodology
EPA
Method
=====
552.1",
552.213
551.113
551.113
551.113
551. 113
300.07
300.07
300.07
300.07
Standard
Method1
=====
6251 B14
5320 B
5310B,
53 IOC,
5310D
591014
Other
======
1
30
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Analyte
Simulated Distribution System Test
(SDS)
Total Hardness
Ammonia
Chlorine Demand Test
Assimilable Organic Carbon (AOC)
(Optional analysis)
Biodegradeable Organic Carbon
(BDOC) (Optional analysis)
Methodology
EPA
Method
350.1
Standard
Method1
5710 C
2340 B1S,
2340 C
4500-NH3 D14,
4500-NH, G14
2350 B
9217 B
Other
379-75 WE16
See Footnote "
1 Except where noted, the 18th and 19th editions of Standard Methods for the Examination of
Water and Wastewater, 1992 and 1995, respectively, American Public Health Association,
1015 Fifteenth Street NW, Washington, D.C. 20005 are equivalent for the methods cited.
Therefore, either edition may be used.
2 Methods 150.1 and 150.2 are available from US EPA, NERL, Cincinnati, Ohio 45268. The
identical methods are also in "Methods for Chemical Analysis of Water and Wastes/' EPA-
600/4-79-020, March 1983, available from the National Technical Information Service
(NTIS), U.S. Department of Commerce, 5285 Port Royal Road, Springfield, Virginia 22161
PB84-128677. (Note: the NTIS toll-free number is 800-553-6847.)
3 Annual Book of ASTM Standards 1994, Volumes 11.01 and 11.02, American Society for
Testing and Materials, 1916 Race Street, Philadelphia, PA 19103.
4 Available from Books and Open-File Reports Section, US Geological Survey, Federal Center
Box 25425, Denver CO 80225-0425.
"Methods for the Determination of Metals in Environmental Samples - Supplement I"
EPA-600/R-94-111, May 1994. Available at NTIS, PB 94-184942.
Mandatory and recommended modifications to this approved procedure are identified in
"Technical Notes on Drinking Water," EPA-600/R-94-173, October 1994. Available at NTIS
PB95-104766.
31
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7 "Methods for the Determination of Inorganic Substances in Environmental Samples,"
EPA-600/R-93-100, August 1993. Available at NTIS, PB94-121811.
1 GLI Method 2, "Turbidity," November 2,1992, Great Lakes Instruments, Inc., 8855 North
55th Street, Milwaukee, Wisconsin 53223.
9 This method is only applicable for determining free residual chlorine in samples of
hypochlorite stock solutions. It is not approved for other types of samples required under the
ICR.
10 "Methods for the Determination of Organic Compounds in Drinking Water," EP A-600/4-88-
039, December 1988, Revised, July 1991. Available at NTIS, PB91-231480.
11 "Methods for the Determination of Organic Compounds in Drinking Water - Supplement II,"
EPA-600/R-92-129, August 1992. Available at NTIS, PB92-207703.
12 "Methods for the Determination of Organic Compounds in Drinking Water - Supplement I,"
EPA/600/4-90-020, July 1990. Available at NTIS, PB91-146027.
13 "Methods for the Determination of Organic Compounds in Drinking Water - Supplement HI,"
EPA-600/R-95-131, August 1995. Available at NTIS, PB95-261616.
14 This method is only found in the 19th edition of Standard Methods for the Examination of
Water and Wastewater.
15 The following methods can be used to determine both calcium and magnesium concentrations
for use in conjunction with Standard Method 2340 B: EPA Method 200.7, Standard Method
3111 B, Standard Method 3120 B, or ASTM method D511-93 B.
16 Ammonia, Automated Electrode Method, Industrial Method Number 379-75 WE, February
19,1976, is available from Bran & Luebbe Analyzing Technologies, Inc., Elmsford, NY.
10523.
17 When Public Water Systems request laboratories to perform optional Biodegradeable Organic
Carbon (BDOC) analyses, the laboratory must use one of the following methods to conduct
the analysis:
(i) Biodegradeable Organic Carbon (BDOC). Servais, P., Billen, G., and Hascoet, M.
Determination of the Biodegradable Fraction of Dissolved Organic Matter in Waters,
Water Research 21(4\ PP 445-450,1987.
(ii) Biodegradeable Organic Carbon (BDOC). Joret, J.C., Levi, Y., Dupin, T., Gibert, M.
and Recherche, A. Rapid Method for Estimating Bioeliminable Organic Carbon in Water,
Proceedings of AWWA Annual Conference, Orlando, FL, June, 1988.
32
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(iii) Biodegradeable Organic Carbon (BDOC). Summers, R.S. Biocharacterization of
Natural Organic Matter, Natural Organic Matter in Drinking Water, Origin,
Characterization, and Removal, Workshop Proceedings, Chamonix, France, Sponsored by
AWWA Research Foundation and Lyonnaise des Eaux-Dumez, September 19-22, 1993.
(iv) Biodegradeable Organic Carbon (BDOC). Mogren, E.M., Scarpino, P., and
Summers, R.S., Measurement of Biodegradable Dissolved Organic Carbon in Drinking
Water, Proc. of AWWA Annual Conference, Cincinnati, OH, June, 1990.
(v) Biodegradeable Organic Carbon (BDOC). Friar, J., Ribas, F., and Lucena, F., A
Method for the Measurement of Biodegradable Organic Carbon in Waters, Water
Research 26(2), pp255-258, 1992.
33
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-------
Section 6. Initial Demonstration of a Laboratory's Ability to
Perform DBP/ICR Analyses Not Covered Under Current
Drinking Water Regulations
An Initial Demonstration of a Laboratory's Ability to Perform the Method must be completed by
each laboratory desiring to be approved for analytes/methods not currently included in States'
certification or approval programs. EPA recognizes that a laboratory may use multiple
instruments and analysts (or groups of analysts) to perform analyses. If more than one analyst is
to perform ICR analyses, EPA recommends that each analyst perform each of the determinations
described in this section (Section 6) before they are allowed to perform ICR analyses. (Prior to
performing these determinations, the analyst must be thoroughly familiar with the method.)
Similar testing of each instrument that will be used in ICR analyses should also be conducted.
This will ensure that each operator and each instrument will be able to maintain minimum quality
standards. Data from each of these tests should be maintained in the laboratory for review, should
such review become necessary during the ICR monitoring and data analysis period.
Data from a representative set of the following determinations are to be reported to EPA as part
of the laboratory approval application package. This representative data is to be just one set of
data for each type of analysis, and it can represent any combination of operators/instruments. The
application form for each method (or set of analytes) provides the format for reporting these data.
(See Appendix C for examples of appropriate application forms.)
1. Initial Demonstration of Low System Background - Analyze a Laboratory Method
Blank to verify that no contamination exists above 1A the minimum reporting levels for the
analytes of interest (see Table 7.1).
2. Initial Demonstration of Precision - Analyze a total of five samples of reagent water
fortified at the "Precision Demonstration" concentration listed in Table 6.1, for each
analyte of interest, on five separate days (e.g., one per day for five days). The five days
need not be consecutive. Samples must not be batched with each other for extraction or
analysis. The relative standard deviation must be no greater than 20%.
3. Initial Demonstration of Accuracy - Calibrate the instrument as directed in the method.
a. Analyze a quality control sample obtained from either a commercial source, or one
made from chemicals not used in the preparation of the calibration standards.
Recovery must be within ฑ 20% of the true value.
b. Calculate the average recovery of the replicates in the Initial Demonstration of
Precision (see preceding paragraph). The average recovery must also be within
ฑ 20% of the expected amount.
35
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4. Method Detection Limit (MDL) Determination - Laboratories must calculate their
Method Detection Limits for each analysis (using the primary column) according the
procedure in CFR ง136 Appendix B, with the following additional requirements. (A copy
of the CFR procedure is included in Appendix D.)
a. All sample processing steps must be included in the determination. Extractions
and analyses must be conducted over at least three days.
b. Select a fortifying concentration which provides an instrument signal 2 to 5 times
above the noise level, but which does not exceed the concentration limits of Table
6.1. Analyze a total of seven replicates of reagent water fortified to a
concentration in the range of the estimated detection limit but no more than the
maximum MDL fortifying concentrations listed in Table 6.1.
NOTE: EPA recognizes that the bromate MDL fortifying level in Table 6.1.
may be below the estimated detection limit for some laboratories. For this
reason, bromate results are exempted from the 50% measurement accuracy
requirement in paragraph 4.d. below. However, this MDL fortifying
concentration is the maximum level which can be used by participants
applying for ICR testing approval.
c. Calculate the MDL for each analyte according to the formula listed in CFR ง 136
Appendix B. Do not subtract the blank value as suggested in the procedure.
d. From the data collected in 4.b, calculate measurement accuracy. Each data point
must be within ฑ 50% of the value of the fortified solution concentration. (See
NOTE in paragraph 4.b. for bromate accuracy requirements.)
36
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Table 6.1. Laboratory Performance Assessment Requirements
Method/Analyte(s)
551, 551.1/CHC13, BDCM, CDBM,
CHBr3
55 1. 1/TCAN, DCAN, BCAN, DBAN,
DCP, TCP, CP
551.1/CH
552.1, 552.2, 6251 B/DCAA, TCAA,
MBAA,DBAA,BCAA
552.1, 552.2, 6251 B/MCAA
300.0/C1O,-, ClO,"
300.0/BrO,-
300.0/Br
5310B, 5310 C, 5310D/TOC
5910 B/UV254
5320 B/TOX
6252 B/Formaldehyde**
6252 B/Acetaldehyde, Butanal, Glyoxal,
Methyl Glyoxal, Pentanal, Propanal
(Optional: Benzaldehyde, Decanal,
Hexanal, Heptanal, Nonanal, Octanal)
LowBrO,-**
modified 524.2/CNC1**
350.1, 4500-NH3 D, 4500-NH3 G, 379-
75 WE/Ammonia
Concentration of each Analyte
for Demonstrating Precision
20. Mg/L ฑ1.0 Mg/L
5.0 Mg/L ฑ0.5 Mg/L
10. Mg/L ฑ0.5 Mg/L
20. Mg/L ฑ1.0 Mg/L
20. Mg/L ฑ1.0 Mg/L
250 Mg/L ฑ10. Mg/L
10. Mg/L ฑ0.50 Mg/L
0.10mg/Lฑ0.010mg/L
4.0 mg/Lฑ 0.50 mg/L
6.5 mg/L* ฑ 0.50 mg/L (This
DOC concentration produces an
absorbance reading of 0.10 cm'1.)
250 Mg Cl'/L ฑ 10 Mg Cl'/L
20. Mg/L ฑ1.0 Mg/L
20. Mg/L ฑ1.0 Mg/L
1.0 Mg/L ฑ0.1 Mg/L
5.0 Mg/L ฑ0.5 Mg/L
1.0 mg/L ฑ0.1 mg/L
Maximum MDL
Fortifying Cone.
0.50 Mg/L
0.25 Mg/L
0.25 MS/L
0.50 Mg/L
1.0 Mg/L
lO.-Mg/L
5.0 Mg/L
0.0 10 mg/L
0.50 mg/L
0.50 mg/L* (This DOC
concentration produces
an absorbance reading
of 0.009 cm'1.)
25. Mg Cl'/L
1.0 Mg/L
0.50 Mg/L
0.20 Mg/L
0.50 Mg/L
Not Applicable ***
* Concentration as dissolved organic carbon (DOC) in potassium hydrogen phthalate (KHP) standards.
** The minimum reporting level (MRL) for this analyte must be as low as possible. Therefore, the
concentrations listed here are based on an estimate of the laboratory's capability to report quantitative
results at the MRL listed in Table 7.1. The final concentrations may change slightly based on the
laboratory's capabilities at the time DBP/ICR monitoring begins.
*** Laboratory is not required to perform an MDL study for this analyte.
37
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-------
Section 7. Minimum Reporting Levels
The method detection limit (MDL) is defined as the minimum concentration of a substance that
can be measured and reported with 99% confidence that the analyte concentration is greater than
zero. Usually, measurements at the MDL concentration are considered qualitative, because they
are not precise enough to meet the needs of the data user(s). If accurate and precise data are
required, concentrations are not reported below the level at which the necessary precision and
accuracy are achieved.
Based on recommendations from the panel of technical experts, minimum reporting levels (MRLs)
were established for the ICR. A list of MRLs is presented in Table 7.1. All laboratories
performing analyses for the ICR must be able to measure the analyte concentrations at these levels
with specified accuracy and precision. (A discussion of the accuracy and precision requirements
is included in Section 9.)
The MRLs were established based on two factors:
meeting the precision and accuracy criteria at the MRL concentrations was technically
feasible without placing undue burden on the laboratories.
based on current information concerning DBF occurrence, most of the samples
analyzed during the ICR are expected to contain concentrations greater than the
respective MRL.
Laboratories must demonstrate that they can achieve reliable data at the minimum reporting level
(MRL) for each analyte. Therefore, the calibration curve must encompass the MRL
concentration. The laboratory must verify the accuracy of the curve at the MRL by analyzing a
calibration check standard at the MRL concentration (see Section 9).
EPA recognizes that some laboratories are able to provide reliable data at concentrations lower
than those shown in Table 7.1. However, in order to achieve consistency in the ICR Federal
Database, laboratories are only required to report quantitative results for concentrations equal to
or greater than the MRLs. The laboratory may report lower concentrations to the water utility,
but only concentrations equal to or greater than the MRLs will be entered into the ICR Federal
Database.
When performing analyses during the treatment studies, laboratories are required to achieve the
specified accuracy and precision at lower concentrations for two analyses: TOC and TOX. This is
because determining precursor removal efficiencies depends on the capability to obtain
quantitative data for samples collected after application of the precursor removal technology. The
lower MRL reporting requirements for the treatment studies are listed in Table 7.1 and
subsequent tables in this manual.
39
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Table 7.1. Minimum Reporting Levels (MRLs)
Method/Analyte(s)
502.2, 524.2, & 551, 551.1/CHC13, BDCM, CDBM,
CHBrS
551.1/TCAN, DCAN, BCAN, DBAN, DCP, TCP,
CP,CH
552.1, 552.2, 6251 B/DCAA, TCAA, MBAA,
DBAA, BCAA
552. 1, 552.2, 625 1 B/MCAA
552.2/BDCAA (Optional)
552.2/CDBAA (Optional)
552.2/TBAA (Optional)
300.0/Br
300.0/CKV, CKV
300.0/BrO,-
5310 B, 5310 C, 5310 D/TOC
5910 B/UVซ4
5320 B/TOX
6252 B/Formaldehyde*
6252 B/Acetaldehyde, Butanal, Glyoxal, Methyl
Glyoxal, Pentanal, Propanal
Optional: Benzaldehyde, Decanal, Hexanal,
Heptanal, Nonanal, Octanal
Low BrO,"*
modified 524.2/CNC1*
MRL
1.0 //g/L for each analyte
0.50 //g/L for each analyte
1.0 (j.g/L for each analyte
2.0 Mg/L
1.0 Mg/L
2.0 Mg/L
4.0/zg/L
0.020 mg/L
20. fJ-g/L for each analyte
5.0 ftg/L
0.70 mg/L (0.50 mg/L during
treatment studies)
0.009 cm'1
50. //g C1VL (25. //g C1VL during
treatment studies)
2.0 Mg/L
1.0
0.20 Mg/L
0.50 Mg/L
* The minimum reporting level (MRL) for this analyte must be as low as possible. Therefore,
the concentration listed here is based on an estimate of the laboratory's capability to report
quantitative results at the MRL. The final concentrations may change slightly based on the
laboratory's capabilities at the time DBP/ICR monitoring begins.
40
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Section 8. Performance Evaluation (PE) Studies
Requirements for Initial Approval via Existing State Certification/Approval
Laboratories that apply for approval to perform ICR analyses based on current state certification
or approval status (see Section 4) are not required to participate in special PE studies prior to
receiving ICR Laboratory Approval for those analyses.
Requirements for Initial Approval - Analyses Not Covered by State
Certification/Approval
Laboratories that apply for approval to perform one of the ICR analyses not covered by state
certification or approval programs (see Section 4) are required to demonstrate their capabilities to
perform the analysis through successful participation in Performance Evaluation (PE) Studies.
This must be demonstrated in one of two ways for laboratories that submit completed application
packages no later than three months following the ICR promulgation date:
Successful analysis of an ICR Chemistry PE Study sample using the method for which
approval is desired. (If the laboratory participated in more than one of these studies
prior to applying for approval, then successful performance must be demonstrated in
the most recent study in which the laboratory participated.) EPA conducted two ICR
Chemistry PE Studies prior to promulgation of the ICR. Study 1 was completed in
August of 1994 and Study 2 was completed in March of 1995. Two additional ICR
Chemistry PE Studies (3 & 4) will be conducted prior to the start of the 18-month
monitoring period and laboratories can participate in one or more of these four studies
to demonstrate capability to successfully perform analyses for the ICR.
OR
Provide data from the three most recent Water Supply (WS) or Water Pollution (WP)
PE studies in which the laboratory participated using the method for which approval is
desired. All PE data must be from studies conducted after June 1993 with at least one
set of data from a study conducted after June 1994. (This ensures that at least some of
the data were generated in the same time frame as when the first two ICR Chemistry
PE Studies were conducted.) The laboratory must have successfully analyzed two
samples, including the most recent one, in these studies. (If a laboratory only
participated in two WS or WP studies and both were successfully completed, then the
laboratory has also met the PE requirements for approval.)
Laboratories that submit applications for approval more than three months after the ICR
promulgation date must successfully participate in an ICR Chemistry PE Study prior to receiving
approval. (Approval to perform ammonia analyses will be granted based on WP PE study data,
because this parameter is not included in the ICR Chemistry PE Studies.)
41
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Successful performance in the above-mentioned PE studies (ICR, WS, or WP) is defined as
meeting the acceptance criteria listed in Table 8.1. (Note that these criteria are different from the
acceptance criteria normally applied to data in WS or WP PE studies.)
Two analytical methods approved for use during the ICR were not available to laboratories when
ICR Chemistry PE Studies 1 and 2 were conducted. Because EPA Method 551.1 is very similar
to EPA Method 551, EPA will accept PE Study 1 and 2 data generated using 551 as the basis for
meeting the PE acceptance criteria for approval to perform Method 551.1. However, laboratories
must use 551.1 (not 551) in ICR Chemistry PE Studies conducted after the ICR promulgation
date and during the 18-month monitoring period.
EPA Method 552.2 was also not available during ICR Chemistry PE Studies 1 and 2.
Laboratories are required to successfully analyze a PE sample using Method 552.2 in order to
meet the PE acceptance criteria for laboratory approval, if they propose to use Method 552.2 to
analyze samples for the ICR.
ICR Chemistry PE Studies During Monitoring
EPA will conduct ICR Chemistry PE Studies on approximately a quarterly basis beginning shortly
prior to the 18-month monitoring period. All laboratories approved for the analyses listed in
Table 8.1 are required to participate in these studies in order to maintain ICR Laboratory
Approval. The first of these "required" studies (ICR Chemistry PE Study 4) will be conducted
close to the start of monitoring, in order to verify that previously approved laboratories are still
capable of acceptable performance. The acceptance criteria described in Table 8.1 will apply for
all ICR Chemistry PE Studies.
ICR Chemistry PE Studies 5 through 9 will be conducted during the 18-month monitoring period.
Further details on how these studies will be used to monitor laboratory performance are given in
Section 11.
Laboratories that perform general water quality analyses (pH, alkalinity, turbidity, calcium
hardness, total hardness, ammonia, and disinfectant residuals) are strongly encouraged to analyze
and pass a PE sample annually. Acceptance criteria for these analyses are listed in Table 8.2. PE
samples for these analytes can be obtained as part of the routine EPA Water Supply (WS) or
Water Pollution (WP) Series PE Studies. There is no requirement to report these WS or WP PE
studies to the ICR Laboratory Coordinator, but the results should be kept on file.
42
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Table 8.1. Acceptance Criteria for ICR Chemistry PE Studies
ICR Parameter
(#ofcpds)
Bromide
Chloral Hydrate
Haloacetic Acids (6)
Haloacetonitriles (4)
and Haloketones (2)
Inorganic DBPs (3)
Trihalomethanes (4)
TOC
TOX
UV Absorbance at 254nm
Pass Criteria
(% of True Value)
ฑ 35% (1)
ฑ40%(2)
ฑ 40% for each cpd (2)
ฑ 40% for each cpd (2)
ฑ 40% for each ion (2)
ฑ 20% for each cpd (3)
ฑ 25% (1)
ฑ 25% (1)
ฑ25%(4)
Minimum # of cpds passing
4 of 5 cpds (excluding MCAA)
4 of 5 cpds (excluding TCAN)
3 of 3 ions
3 of 4 cpds
(1) The listed value was derived from laboratory performance data given in the method, ASTM
laboratory studies and/or EPA PE studies
a) These values were established by recommendation of the expert panel.
(3) EPA criterion for TTHM drinking water laboratory certification.
(4) Determined from interlaboratory data given in SM 5910 B. The value given represents twice
the maximum percent relative standard deviation for absorbances >0.014 cm'1 at 254nm for
potassium acid phthalate concentrations from 0.93 to 100 mg/L (as Dissolved Organic
Carbon).
43
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Table 8.2. PE Acceptance Criteria for ICR General Water Quality Parameters
ICR Parameter
(# of cpds)
Alkalinity
Ammonia
Chlorine - Free
Chlorine - Total
Hardness - Calcium
Hardness - Total
PH
Turbidity
Pass Criteria
(% of True Value)
ฑ 15% (1) :
ฑ 30% (2)
ฑ 30% (1)
ฑ 30% (1)
ฑ 10% (1)
ฑ20%(1)
ฑ5%(1>
ฑ 20% (1)
(1) This criterion was determined based on the results from at least four EPA WS/WP PE studies.
The relative percent deviation was calculated for each study by dividing the concentration
represented by two standard deviations, around the study true value, by the true value, and
multiplying by 100%. The maximum relative percent deviation from the studies was used as
the basis for this criterion.
m The listed value was derived from laboratory performance data given in the method, ASTM
laboratory studies and/or EPAPE studies.
44
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Section 9. Quality Control Requirements
Laboratories that perform analyses for the DBP/ICR and Treatment Study/ICR are required to
use only the analytical methods specified in the ICR. (See Section 5 for a listing of the methods.)
These methods specify quality control (QC) procedures which must be followed to ensure
accurate and precise data.
QC procedures and the frequency of QC testing vary among the methods.. In an effort to
standardize these requirements and to obtain consistent application of QC protocols, a frequency
for performing QC analyses has been established for many of the methods specified in the ICR.
This standardization was necessary because much of the QC data for these analyses is being
reported to EPA and the water utilities in order to document the quality of the monitoring data.
Many of the methods specified in the ICR provide criteria to be used in evaluating and accepting
laboratory performance based on related QC data. These criteria were compared to what EPA
and technical experts believe are necessary to meet the objectives of the ICR. This comparison
indicated that some of the QC procedures required by the ICR are not specifically addressed in
some methods, and in other methods the QC acceptance criteria are different from those identified
as necessary for the ICR.
This section describes the various QC procedures required as part of the ICR and the rationale for
the ICR acceptance criteria The general water quality parameters (alkalinity, ammonia, calcium
hardness, disinfectant residuals, pH, temperature, total hardness, and turbidity) are not addressed
in this section, because there are no QC reporting requirements for them included in the ICR
Laboratory Quality Control (QC) Database System. Laboratories performing analyses for the
general water quality parameters must adhere to the QC protocols specified in the methods and
they are encouraged to take additional measures as appropriate.
Aldehydes, cyanogen chloride, and low-level BrO3" are discussed in this section even though these
ICR analyses are being conducted by EPA. They are included simply to document the QC criteria
that are applicable.
It is imperative that laboratories adhere to the QC described in this section, because monitoring
data will be deleted from the ICR Federal Database if the applicable ICR QC requirements are not
met. Loss of monitoring data due to failures in QC could result in loss of ICR laboratory
approval (see Section 11). The following will cause monitoring data to be invalidated and not
included in the database:
failure to use the correct calibration check standard concentration
failure to verify the calibration curve at the specified frequency
45
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failure to meet the acceptance criteria for verifying calibration
analytes detected in the laboratory reagent (method) blank at concentrations equal to
or more than one-half the minimum reporting level
for aldehydes, analytes detected at concentrations equal to or more than one-half the
minimum reporting level in the field reagent (shipping or travel) blank
for TOC and UV^,,, failure to meet the precision acceptance criteria for duplicate
analyses ,
when applicable, failure to meet the acceptance criteria for the internal standard
when applicable, failure to meet the acceptance criteria for the surrogate standard.
when applicable, failure to measure and report the pH of samples prior to analysis.
failure to analyze samples and/or extracts within the specified holding times.
for TOX, TOC, and \TV2S4, failure to analyze ICR samples in duplicate
Laboratories must also report the following QC data in order to maintain ICR laboratory
approval. Since these data are being collected to evaluate the quality of the monitoring data,
there are no acceptance criteria for them and the data will not impact laboratory approval:
duplicate analyses, except for TOC and UV254
laboratory fortified matrix (spiked) sample recoveries.
Calibration
Each method describes calibration procedures that are used to determine the concentrations of the
method analytes. Some methods allow several options:
a calibration curve based on either external standards or detector responses to the
analyte relative to an internal standard
an average response factor for each analyte
a single point calibration.
The laboratory must select and follow one of the calibration procedures outlined in the approved
method in order to meet the requirements of the ICR. In addition, the mass spectrometer method
has specific tuning criteria that must be met prior to performing the calibration procedure.
46
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All methods specified in the ICR require that calibration span the expected concentration range of
the samples being analyzed. The number of calibration standards necessary to do this varies from
one to five, depending upon the method. The ICR does not require laboratories to change
method calibration procedures, nor does it specify the concentrations of the standards to be used
in the calibration process. (Note: There is no calibration process for the UV2S4 analysis. The
method only requires that the spectrophotometer performance be checked using a standard.)
One of the techniques that EPA will use to assure that data generated in many laboratories are
consistent is to provide stock solutions of the method analytes to each laboratory that is approved
to perform the analysis. The laboratories are required to use these stock solutions in the
preparation of the standards that are used for calibration.
Verify Calibration
The analyst must periodically verify calibration during the analysis of samples in order to ensure
accuracy of the analytical results. The methods vary in the frequency at which calibration must be
checked. In order to meet the accuracy requirements of the ICR, EPA is defining specific
frequencies at which the instrument calibration must be verified. These frequencies are listed in
Table 9.1.
Most of the methods recommend checking the instrument calibration using a mid-level calibration
check standard. The method acceptance criteria for verifying calibration are based on this
standard. However, in order to meet the objectives of the ICR, calibration must be verified across
the range of analyte concentrations that are being measured. Based on the recommendations from
technical experts experienced with these methods, EPA is specifying three concentrations at
which the calibration must be verified for each method. These concentrations were chosen based
on the concentrations that are expected to be found in samples collected for the ICR.
Laboratories are required to prepare and use aqueous calibration check standards with
concentrations that are within ฑ 20% of the concentrations listed in Tables 9.2-9.4 when they
verify their calibration curves. The check standards must be processed through each step of the
sample preparation procedure prior to analysis.
The frequency of verifying calibration for ICR samples is based on the number of samples being
analyzed together in an analysis batch. For the ICR, an analysis batch is defined as samples
analyzed using the same instrument within a 24 hour period AND the maximum number of ICR
samples that can be included in one analysis batch is 30. The 24-hour period begins with the
analysis of the low-level calibration check standard and it ends with the analysis of the final
calibration check standard. The 24-hour period does not necessarily include the analysis time
used to generate the calibration curve. However, if a new curve is prepared each time samples are
analyzed, the 24-hour period still begins with the analysis of the low level calibration check
standard.
47
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Method blanks, shipping blanks, calibration check standards, duplicate samples, fortified samples,
and any independent QC samples [see Quality Control (QC) Sample Subsection] that are analyzed
with the ICR samples are not counted iff determining the 30 sample maximum.
Analysis of the low-level calibration check standard must be completed prior to analysis of any
samples and each analyte must meet the acceptance criteria given in Table 9.2. If the criteria
cannot be met, the source of the problem must be identified and eliminated. Then a new
instrument calibration must be performed according to the method calibration procedures.
After analyses of no more than ten ICR samples for all methods except TOX (no more than seven
TOX samples analyzed in duplicate), the calibration curve must be verified using either a mid- or
high-level calibration check standard and each analyte must meet the acceptance criteria listed in
Table 9.3 or 9.4. If the criteria are not met, then all samples or extracts that were analyzed
between this standard and the last one meeting the acceptance criteria must be reanalyzed for the
problem analyte(s) after the calibration problem is resolved. If the samples or extracts cannot be
reanalyzed, then the data for the problem analyte(s) are considered invalid for those samples and
the monitoring data should be flagged as not meeting QC criteria. If reported, these monitoring
data will be deleted from the ICR Federal Database.
After each additional ten ICR samples (or seven TOX samples analyzed in duplicate), the curve
must be verified by alternating between the mid- and high-level check standards. The final
analysis in an analysis batch MUST be a calibration check standard and all the analytes must meet
the acceptance criteria.
The interval between calibration check standards is smaller for TOX than the other analyses,
because each ICR TOX field sample must be analyzed in duplicate. Seven is approximately the
number of field samples that can be realistically analyzed in duplicate by an analyst during a
routine work shift.
The TOX, TOC and UV^ methods specify that each analysis should be performed in duplicate.
EPA will not require laboratories to analyze TOX calibration check standards in duplicate.
However, TOC and UV^ analyses of calibration check standards must be performed in duplicate
and the analyses must meet the precision acceptance criteria listed in Table 9.2, 9.3, or 9.4 in
addition to the accuracy requirements. The relative percent differences (RPDs) listed in Tables
9.2, 9.3 and 9.4 are calculated using the following formula:
RPD = [|r, - r2|/(( r, + r^/2)] x 100, where
RPD = Relative Percent Difference
1*1 = First analytical result
T2 = Duplicate analytical result
48
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rable9.1. Frequency Requirements for Verifying Calibration
Method
502.2 (THMs)
524.2
(THMs)
551
(THMs)
551.1
(THMs,HANs,
HKs, CP, & CH)
552.1(HAAs)
552.2
(HAAs)
6251B(HAAs)
300.0
(Br,Br03-,C102-,
CIO,')
53 10 B, 53 IOC,
5310D (TOC)
5910 B (UV,ซ)
5320 B
(TOX)
6252 B
Aldehydes
LowBrO3-
modified 524.2
(CNC1)
Method Specifications
Daily
Beginning each 8-hr work shift
External Standard Calibration: Check at
beginning and end of analysis day
Internal Standard Calibration: Check at
beginning of day plus monitor IS
response in all samples
Preceding each analysis set, after every
tenth sample analysis and after the final
sample analysis
Daily
Preceding each analysis set, after every
tenth sample analysis and after the final
sample analysis
With each sample batch
After every tenth sample plus at the
beginning of each 8 hour period and as
the last analysis run on the instrument
Daily
Daily
Perform several
microcoulometer/titration cell checks
with NaCl std soln at start of each day;
Analyze several nonvolatile TOX
calibration stds daily
Daily
Not specified
Beginning each 8-hr work shift
ICR Specifications
Use low-level calibration check
standard to verify calibration before
analysis of first sample. Verify
calibration after every tenth sample
and after last sample in analysis batch
by alternating between mid- and high-
level calibration check standards.
Perform 3 microcoulometer/
taxation cell checks with NaCl std
soln at beginning of each 8-10 hr
work shift; Use low-level calibration
check standard to verify calibration
before analysis of first sample. Verify
calibration after every seventh sample
(analyzed in duplicate) and after last
sample in analysis batch by
alternating between mid- and high-
level calibration check standards
Use low-level calibration check
standard to verify calibration before
analysis of first sample. Verify
calibration after every tenth sample
and after last sample in analysis batch
by alternating between mid- and high-
level calibration check standards.
49
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Table 9.2. Low-Level Calibration Check Standard Concentrations & Acceptance Criteria
Mcthod/Analyte(s)
502.2, 524.2, 551, 551.1/CHC13, BDCM, CDBM, CHBrS
55 1.1/TCAN, DCAN, BCAN, DBAN, DCP, TCP, CP,
CH
552.1, 552.2, 625 IB/
DCAA, TCAA, MBAA, DBAA, BCAA
552.1, 552.2, 6251 BMCAA
552.2/BDCAA (Optional)
552.2/CDBAA (Optional)
552.2/TBAA (Optional)
300.0/Br
300.0/C1CV. CIO,'
300.0/BrO,"
5310 B, 5310 C, 5310 D/TOC
5910B/UV2J4
5320B/TOX
6252 B/Formaldehyde**
6252 B/Acetaldehyde, Butanal, Glyoxal, Methyl Glyoxal,
Pentanal, Propanal
Optional: Benzaldehyde, Decanal, Hexanal, Heptanal,
Nonanal, Octanal
LowBrO,-**
modified 524.2/CNC1**
Low-Level Standard
1.0 Mg/L
0.50 Mg/L
1.0 Mg/L
2.0 M8/L
1.0 Mg/L
2.0 Mg/L
4.0 Mg/L
0.020 mg/L
20. Mg/L
5.0 Mg/L
0.70 mg/L (0.50 mg/L
during treatment
studies)
.009 cm"1 (prepared
using 0.50 mg/L as
DOC*)
50.MgClYL(25.Mg
C1YL durinjg treatment
studies)
2.0 Mg/L
1.0 Mg/L
0.20 Mg/L
0.50 Mg/L
Acceptance
Criteria
50 - 150%
50 - 150%
50 - 150%
50 - 150%
50 - 150%
50 - 150%
50 - 150%
50 - 150%
75 - 125%
50 - 150%
50 - 150%
(*20%RPD)
75 - 125%
(*20%RPD)
75 - 125%
50 - 150%
50 - 150%
75 - 125%
50 - 150%
* Concentration as dissolved organic carbon (DOC) in potassium hydrogen phthalate (KHP) standards.
** The minimum reporting level (MRL) for this analyte must be as low as possible. Therefore, the
concentrations listed here are based on an estimate of the laboratory's capability to report quantitative
results at the MRL listed in Table 7.1. The final concentrations may change slightly based on the
laboratory's capabilities at the time DBP/ICR monitoring begins.
50
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Table 9.3. Mid-Level Calibration Check Standard Concentrations & Acceotance Criteria
Method/Analyte(s)
502.2, 524.2, 551, 551.1/CHC13, BDCM, CDBM,
CHBrS
551.1/TCAN, DCAN, SCAN, DBAN, DCP, TCP,
CP
551.1/CH
552.1, 552.2, 6251 B/MCAA, DCAA, TCAA,
MBAA, DBAA, BCAA
552.2/BDCAA, CDBAA, TBAA (Optional)
300.0/Br'
300.0/C1O,; C1O,-
300.0/BKV
5310B, 53 IOC, 5310D/TOC
5910 B/UV2S4
5320B/TOX
6252 B/Formaldehyde, Acetaldehyde, Butanal,
Glyoxal, Methyl Glyoxal, Pentanal, Propanal
Optional: Benzaldehyde, Decanal, Hexanal,
Heptanal, Nonanal, Octanal
Low BrOV
modified 524.2/CNC1
Mid-Level
Standard
20. Mg/L
5.0Mg/L
10. Mg/L
20.fj.gfL
20. Aig/L
O.lOmg/L
250/JigfL
10. //g/L
4.0mg/L
.088 cm'1
(prepared using
6.0 mg/L as
DOC*)
200 //g C1YL
10. //g/L
1.0 Mg/L
5.0 //g/L
Acceptance
Criteria
80 - 120%
80 - 120%
80 - 120%
80 - 120%
80 - 120%
90-110%
90-110%
80 - 120%
90-110%
(<;10%RPD)
85-115%
(<;10%RPD)
85-115%
80 - 120%
80 - 120%
80 - 120%
* Concentration as dissolved organic carbon (DOC) in potassium hydrogen phthalate (KHP)
standards.
51
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Table 9.4. High-Level Calibration Check Standard Concentrations & Acceptance Criteria
Method/Analyte(s)
502.2, 524.2, 551, 551.1/CHC13, BDCM, CDBM,
CHBrS
551.1/TCAN, DCAN, BCAN, DBAN, DCP, TCP,
CP
551.1/CH
552.1, 552.2, 6251 B/MCAA, DCAA, TCAA,
MBAA, DBAA, BCAA
552.2/BDCAA, CDBAA, TBAA (Optional)
300.0/Bf
300.0/C1O,-, CIO,"
300.o/BrO,-
5310 B, 5310 C, 5310 D/TOC
5910 B/UVj*
5320BATOX
6252 B/Formaldehyde, Acetaldehyde, Butanal,
Glyoxal, Methyl Glyoxal, Pentanal, Propanal
Optional: Benzaldehyde, Decanal, Hexanal,
Heptanal, Nonanal, Octanal
LowBrO,'
modified 524.2/CNC1
High-Level
Standard
40. Mg/L
IS.pg/L
25. //g/L
40. A*g/L
40. //g/L
0.30 mg/L
750 //g/L
30.//g^L
10. mg/L
.87 cm"1 (prepared
using 60. mg/L as
DOC*)
500 //g Cl'/L
40. //g/L
5.0 //g/L
20. //g/L
Acceptance
Criteria
80 - 120%
80 - 120%
80 - 120%
80 - 120%
80 - 120%
90-110%
90-110%
90-110%
90-110%
(*10%RPD)
85-115%
(*10%RPD)
85-115%
80 - 120%
80 - 120%
80 - 120%
* Concentration as dissolved organic carbon (DOC) in potassium hydrogen phthalate (KHP)
standards.
52
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Laboratory Reagent (Method) Blank
All of the methods approved for DBP/ICR monitoring require periodic analysis of a laboratory
reagent (method) blank. For all the methods except TOX, this is defined as an aliquot of reagent
water that is treated exactly as a sample, including exposure to all glassware, equipment, solvents,
reagents, internal standards, and surrogates that are used with other samples. This blank is used
to determine if method analytes or other interferences are present in the laboratory environment,
the reagents, or the apparatus.
The frequency of the laboratory reagent (method) blank analysis depends upon the type of sample
manipulation required prior to the instrumental analysis. Methods that involve extraction of the
sample usually stipulate analysis of a laboratory reagent blank with each set of samples that are
extracted together. When the samples are analyzed directly, a blank is analyzed on a daily basis,
with the exception of UV2S4 and TOX analyses for which a blank is analyzed after the analysis of
every ten and seven samples, respectively.
The required frequencies for analyzing laboratory reagent (method) blanks for the ICR are listed
in Table 9.5. In order to meet the objectives of the ICR, the laboratory reagent (method) blank
must be analyzed as the first sample on the instrument (prior to the calibration check standard).
For methods that involve extractions, the laboratory reagent (method) blank must be carried
through the extraction process. Each extraction batch of samples must include a laboratory
reagent (method) blank. An extraction batch is defined as all samples prepared/extracted together
by the same person(s) during a work day (normally an 8-10 hour period for routine working
schedules). The same lot of extracting solvent, internal standard fortifying solution, and surrogate
standard fortifying solution must be used for all samples included in a batch. When applicable, all
samples in an extraction batch must be derivatized with the same batch of derivatizing agent. A
maximum of 20 ICR samples can be included in an extraction batch. Method blanks, shipping
blanks, calibration check standards, any independent QC samples [see Quality Control (QC)
Sample Subsection], duplicate samples, and fortified samples that are extracted with the ICR
samples are not counted as samples in determining the 20 sample maximum.
In the TOX method, several types of blanks are specified, and two of them will be required for the
DBP/ICR:
the laboratory reagent (method) blank - the analysis of 40 mg of nitrate-washed
carbon, which is used to correct for TOX found in the carbon.
the system blank - the analysis of a reagent water blank, which is used to assess
background TOX contributions from the equipment, reagents, and procedure.
The laboratory must analyze two laboratory reagent (method) blanks (nitrate-washed activated
carbon cartridges) at the beginning of each day and they must meet the acceptance criteria listed
in Table 9.6. Analyses must not begin until this criterion is met. The system blank (reagent
53
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water) is analyzed after the method blanks and this blank must meet the criteria listed in Table 9.6.
After the TOX analysis of seven ICR samples (analyzed in duplicate), the laboratory is required to
analyze another laboratory reagent (method) blank which is also subject to the acceptance criteria
listed in Table 9.6. If the acceptance criteria are not met for this method blank, then no further
TOX sample analyses should be performed until the source of carbon contamination is eliminated.
All samples that were analyzed between this blank and the last one meeting the acceptance criteria
must be reanalyzed after the contamination is eliminated. If the samples cannot be reanalyzed,
then the TOX data are considered invalid for those samples and the monitoring data should be
flagged as not meeting QC criteria. If reported, these TOX monitoring data will be deleted from
the ICR Federal Database.
While some methods state that background interferences should be below the minimum detection
limit, the general goal for all methods within the ICR is to ensure that the background levels are
low enough so that they do not interfere with an accurate measurement. If any of the method
analytes are detected at a concentration equal to or greater than half the minimum reporting levels
(see Table 9.6), then no further analyses should be performed until the source of the problem is
identified and eliminated. If the source is traced to any material that was used in the preparation
of the set of samples to be analyzed, then all these prepared samples (or extracts) must be
discarded and the preparation procedure repeated using another aliquot of each sample. If the
samples cannot be re-extracted, then all data for the problem analyte(s) are considered invalid for
all samples in the extraction or analysis batch, as appropriate and the monitoring data should be
flagged as not meeting QC criteria. If reported, these monitoring data will be deleted from the
ICR Federal Database.
Contamination problems in the extraction process cannot be detected until the analysis step. If a
problem is discovered, then the data for one or more analytes in all the samples in the extraction
batch are lost unless the laboratory has a back-up aliquot of each sample which can be extracted.
EPA limited the extraction batch to 20 ICR samples in order to minimize the number of samples
that could be potentially lost due to a contamination problem. More than one batch of samples
may be extracted within a day.
Laboratories should be aware of the potential for carryover between samples when highly
contaminated samples are analyzed. Li order to avoid this, laboratories may find that additional
blanks are needed to "rinse" the system after high concentration samples are analyzed. If blanks
are analyzed for this purpose, the laboratory is not required to report data from these analyses.
54
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Table 9.5. Frequency Requirements for Analyzing Laboratory Reagent (Method) Blanks
Method
502.2
(THMs)
524.2
(THMs)
551
(THMs)
551.1
(THMs,HANs,
HKs,CP,&CH)
552.1
(HAAs)
552.2
(HAAs)
625 IB
(HAAs)
300.0
(Br,Br03-,C102-,
cio,-)
53 10 B, 53 IOC,
5310D
(TOC)
5910 B
(UV,ซ)
5320 B
(TOX)
6252 B
(Aldehydes)
LowBrtV
modified 524.2
(CNC1)
Method Specifications
I/batch of samples processed as a group within a
work shift
Daily-shipping blank can be substituted for
method blank
I/set of samples
1 each time a set of samples is extracted or
reagents are changed
I/set of samples
1 each time a set of samples is extracted or
reagents are changed
I/set of samples
I/batch of samples
Daily
Initial zero; Check after each 10 samples
I/set of 8 samples - minimum of 2/day (nitrate-
washed activated carbon)
I/set of samples
Not Specified
Daily
ICR Specifications
1 per analysis batch
1 per analysis batch
(1 per extraction batch)
1 per analysis batch
Initial zero; Check after each
10 samples
2 nitrate-washed activated
carbon analyses at beginning
of each analysis batch, then 1
after every 7 samples
(analyzed in duplicate)
(minimum of 3/day); Analyze
1 system blank per analysis
batch
1 per analysis batch
(1 per extraction batch)
1 per analysis batch
1 per analysis batch
55
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Table 9.6. Acceptance Criteria for Laboratory Reagent (Method) Blanks
Method/Analyte(s)
502.2, 524.2, 551, 551.1/CHC13, BDCM, CDBM, CHBrS
551.1/TCAN, DCAN, SCAN, DBAN, DCP, TCP, CP, CH
552.1, 552.2, 6251 B/DCAA, TCAA, MBAA, DBAA, BCAA
552.1, 552.2, 6251 B/MCAA
552.2/BDCAA (Optional)
552.2/CDBAA (Optional)
552.2/TBAA (Optional)
300.0/Br
300.0/C1O,-, ClO,'
300.0/BrfV
5310 B.5310 C, 5310 D/TOC
5910 B/UV
5320B/TOX
6252 B/Formaldehyde*
6252 B/Acetaldehyde, Butanal, Glyoxal, Methyl Glyoxal, Pentanal,
Propanal
Optional: Benzaldehyde, Decanal, Hexanal, Heptanal, Nonanal,
Octanal
LowBrO,'*
modified 524.2/CNC1*
Maximum Allowable
Background Concentration
<0.50^g/L
< 0.25 Atg/L
< 0.50 yug/L
<1.0A42/L
< 0.50 ,ug/L
<1.0yWg/L
< 2.0 /ug/L
<0.010mg/L
< 10. ,ug/L
<2.5,ug/L
< 0.35 mg/L (< 0.25 mg/L
during treatment studies)
< 0.0045 cm'1
< 0.80 ^g C1V40 mg of
activated carbon for method
blank
< 25. //g C1YL for system blank
(< 12.5 vg C17L during
treatment studies)
< 1.0 yUg/L
< 0.50 Afg/L
<0.10//g/L
< 0.25 yUg/L
The minimum reporting level (MRL) for this analyte must be as low as possible. Therefore, the
concentrations listed here are based on an estimate of the laboratory's capability to report quantitative
results at the MRL listed in Table 7.1. The final concentrations may change slightly based on the
laboratory's capabilities at the time DBP/ICR monitoring begins. The value in this table will be set at
less than one-half the MRL.
56
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Field Reagent Blank (Shipping Blank or Travel Blank)
Five of the DBP/ICR methods require the preparation and analysis of a field reagent blank with
each group of samples collected from the same general sample site at approximately the same
time. This blank is an aliquot of reagent water or other blank matrix that is placed in a sample
container in the laboratory and treated as a sample in all respects, including shipment to the
sampling site, storage, preservation, and all analytical procedures. The purpose of this blank is to
determine if method analytes or other interferences are present in the field or shipping
environment.
If analyses using EPA Methods 502.2 or 524.2 are being performed only for the ICR, then field
reagent blanks will not be required. It is rare to find trihalomethane (THM) contamination as a
result of the shipping or storage conditions. (Field reagent blanks in Methods 502.2 and 524.2 are
primarily focused on the volatile organic compounds that are measured by these methods.)
However, laboratories may be required to include field reagent blanks in their sample's sets, if the
analyses are being conducted for compliance with non-ICR Rules.
Field reagent blanks are required for aldehyde analyses. Formaldehyde contamination can. result
from improper sample containers or shipping material, or as a result of atmospheric
contamination. A field reagent blank should be prepared in the laboratory using the same type of
sample bottle and dechlorinating agent used in the collection of the aldehyde samples. This blank
should accompany the sample bottles to the utility and it should be carried to each aldehyde
sampling point. The blank should NOT be opened during this process. At the conclusion of
sampling, the field reagent blank should be sent back to the laboratory with the group of samples
collected at the utility (defined as a shipping batch) and it should be stored with the samples until
processing. This blank should then be processed and analyzed with the samples from that utility.
If any of the analytes are detected at concentrations equal to or greater than half the minimum
reporting level, then all data for the problem analyte(s) are considered invalid for all samples in the
shipping batch and the monitoring data should be flagged as not meeting QC criteria. If reported,
these monitoring data will be deleted from the ICR Federal Database.
The requirements for field reagent blanks are listed in Table 9.7.
57
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Table 9.7. Requirements for Analyzing Field Reagent Blanks (Shipping Blanks)
Method
502.2, 524.2
(THMs)
6252 B
(Aldehydes)
Method
Specifications
I/set of field
samples
I/sampling
location
ICR Specifications
There will not be an
ICR requirement to
perform these
analyses.
I/shipping batch
ICR Acceptance Criteria
Methods do not set
acceptance criteria for these
analyses & no criteria are
necessary for the ICR
<1.0//g/Lfor
formaldehyde,
< 0.50 ^g/L for all other
aldehydes
Qualify Control (QC) Sample
Most of theDBP/ICR analytical methods recommend that the laboratory analyze a quality control
(QC) sample at least quarterly. A QC sample is a solution of method analytes of known
concentration which is used to fortify an aliquot of reagent water or sample matrix. The QC
sample is obtained from a source external to the laboratory, and different from the source of
calibration standards. It is used to check laboratory performance.
One of the major reasons for analyzing a QC sample is to check the accuracy of the standards
being used to calibrate the analytical instrumentation. Since EPA is providing the primary
analytical standards for the DBP/ICR methods discussed in this section, all DBP/ICR laboratories
will be using comparable standards of known quality. In addition, all of the DBP/ICR methods
require the use of aqueous standards that are processed in the same way as the samples. This
further minimizes the possibility of analytical errors.
Since EPA is providing the stock solutions for the preparation of calibration standards,
laboratories are not required to analyze and report results from QC samples as part of the ICR.
However, the use of QC samples is encouraged. Laboratories may wish to check their
performance using QC samples containing concentrations that are known to them. Laboratories
can prepare their own QC samples or purchase QC samples from one of several commercial
suppliers. Splitting samples with another laboratory is another mechanism for evaluating
performance. Use of either or both of these procedures is encouraged, especially when
laboratories (or analysts) are developing capabilities to perform new methods.
58
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Laboratory Duplicates
One technique that is useful in evaluating a laboratory's precision for a method is to determine the
precision of replicate analyses. The sample is divided into two or more aliquots in the laboratory
and the aliquots are processed and analyzed as separate samples. This technique is only useful
when the original sample contains background concentrations of the method analytes. Most
samples that are analyzed using the DBP/ICR methods discussed in this section are expected to
contain measurable concentrations of the majority of the analytes. Therefore, replicate analyses
will be a valuable tool for determining the precision of the DBP/ICR monitoring data.
The DBP/ICR approved methods vary in their requirements pertaining to duplicates. There are
generally two types of duplicate samples:
Field Duplicates - two separate samples collected at the same time and place under identical
circumstances and treated exactly the same throughout field and laboratory procedures
Laboratory Duplicates - one sample divided into two aliquots in the lab and analyzed as two
separate samples
Some methods specify the analysis of field duplicates, while other methods require laboratory
duplicate analyses for all samples, and field duplicate analyses for a percentage of the samples.
Several methods do not discuss any duplicate analyses. For the ICR, all duplicates will be
laboratory duplicates, with the exception of samples which are analyzed using EPA Methods
502.2, 551.1 and 524.2. These methods require the use of field duplicates, because the sample is
analyzed directly from the sample bottle. (The extraction is performed in the sample bottle in
551.1. Samples for 502.2 and 524.2 are usually collected in vials that contain only enough sample
for one analysis and the vials are loaded directly onto an autosampler.)
The required frequencies for analyzing duplicates for the ICR are listed in Table 9.8. With the
exception of TOX, TOC and UV254 analyses, laboratories are required to perform duplicate
analyses on a minimum of 5% of the ICR samples that are processed together. For methods that
involve extractions, this means that at least one sample from each extraction batch must be
divided into two aliquots prior to extraction. Both aliquots must be carried through the entire
extraction and analysis process. For methods that do not involve extractions, this means that for
analysis batches of 20 or less, one of the ICR samples in the batch must be analyzed in duplicate.
If the analysis batch contains more than 20 ICR samples, then two samples must be analyzed in
duplicate.
Note: As described earlier in this section under "Laboratory Reagent Blank," an extraction batch
is defined as all samples prepared/extracted together by the same person(s) during a work day.
The same lot of extracting solvent, internal standard fortifying, solution, and surrogate standard
fortifying solution must be used for all samples included in a batch. When applicable, all samples
in a batch must be derivatized with the same batch of derivatizing agent. A maximum of 20 ICR
59
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samples can be included in an extraction batch in order to minimize the potential for loss of data.
As described earlier in this section under "Verify Calibration," an analysis batch is defined as ;
samples analyzed within a 24-hour period AND the maximum number of samples that can be
included in one analysis batch is 30.
Since duplicate measurements are only required on 5% of the samples in a batch, the precision
data may not reflect the laboratory's performance on samples from a specific utility unless the
laboratory is analyzing samples from only one utility. The laboratory will randomly select one of
the samples being processed in the batch, unless it has an agreement with a specific utility to
provide duplicate analyses.
EPA plans to use the data from duplicate analyses to provide an estimate of the precision of
measurements made by individual laboratories. Subsets of the ICR monitoring data may be
selected for specific modeling or correlational analyses, based on laboratory precision for the
analytes of interest. The precision data from Methods 502.2, 551.1 and 524.2 will also provide an
estimate of the overall precision of the ICR data for those three analyses, because they are
generated using field duplicates.
With the exception of TOC and UV2S4, laboratories will not be required to meet specific precision
requirements for the duplicate analyses. TOC and UV2s4 duplicates must meet the requirements
listed in Table 9.8 in order to be considered valid. Failure to meet the precision requirements
indicates the instrument is not operating properly and the sample(s) should be reanalyzed. If this
cannot be done, the monitoring data should be flagged as not meeting QC criteria. These data
will not be entered into the ICR database.
60
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Table 9.8. Requirements for Performing Laboratory Duplicate Analyses
Method
502.2
(THMs)
524.2
(THMs)
551
(THMs)
551.1
(THMs, HANs,
HKs, CP, & CH)
552.1 (HAAs)
552.2 (HAAs)
625 IB (HAAs)
300.0 (Br,ClO2-,
CKV.&BiOr)
53 10 B, 53 IOC,
5310D
(TOC)
5910 B
(UV^)
5320 B (TOX)
6252 B (Aldehydes)
Low BKV
modified 524.2
(CNC1)
Method Specifications
No Requirement
No Requirement
No Requirement
(Field dups) 10% or 1 per
sample set, whichever is
greater
No Requirement
No Requirement
10% of Samples
No Requirement
No Requirement
All samples (plus 10% field
duplicates)
All Samples Analyzed in
Duplicate, with replicate of a
different dilution, so that the
concn. ratio is <0.7 or >1.4
10% of Samples
Not Specified
No Requirement
ICR Specifications
At least 5% of the samples in each analysis
batch (field duplicates)
At least 5% of the samples in each analysis
batch (field duplicates)
1 laboratory duplicate per extraction batch
1 field duplicate per extraction batch
1 laboratory duplicate per extraction batch
At least 5% of the samples in each analysis
batch (laboratory duplicates)
All samples analyzed in duplicate (laboratory
duplicates)
(RPD <; 20% for TOC concn <; 2.0 mg/L;
RPD <; 10% for TOC concn > 2.0 mg/L)
All samples analyzed in duplicate (laboratory
duplicates)
(RPD <: 20% for UV2S4 <; 0.045; RPD <; 10%
for UV,S4> 0.045)
All samples analyzed in duplicate (laboratory
duplicates)
1 laboratory duplicate per extraction batch
At least 5% of the samples in each analysis
batch (laboratory duplicates)
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Laboratory Fortified Matrix Sample (Spiked Sample)
A laboratory fortified matrix sample is an aliquot of an environmental sample to which known
quantities of the method analytes are added in the laboratory. This fortified sample is analyzed
exactly like a sample, and its purpose is to determine whether the sample matrix contributes bias
to the analytical results. The concentrations of the analytes in the unfortified sample matrix must
be determined in a separate aliquot.
Laboratories are required to fortify samples at the frequencies listed in Table 9.9. The stock
solutions of the analytical standards provided by EPA must be used as the basis for preparing the
fortified samples. With the exception of analyses for UV2S4, TOX and HAAs by EPA Method
552.1, laboratories are required to perform fortified sample analyses on a minimum of 5% of the
ICR samples that are processed together. For methods that involve extractions, this means that
one sample from each extraction batch must be fortified with a known concentration of the
analytes prior to extraction. Both the fortified and unfortified sample must be carried through the
entire extraction and analysis process. For methods that do not involve extractions, this means
that for analysis batches of 20 or less, one of the ICR samples in the batch must be fortified and
analyzed. If the analysis batch contains more than 20 ICR samples, then two samples must be
fortified and analyzed.
Note: As described earlier, an extraction batch is defined as all samples prepared/extracted
together by the same person(s) during a work day. The same lot of extracting solvent, internal
standard fortifying solution, and surrogate standard fortifying solution must be used for all
samples included in a batch. When applicable, all samples in a batch must be derivatized with the
same batch of derivatizing agent. A maximum of 20 ICR samples can be included in an extraction
batch. An analysis batch is defined as samples analyzed within a 24-hour period with 30 as the
maximum number of samples that can be included in one analysis batch.
Laboratories will not be required to fortify samples for UV2S4 analyses.
A minimum of 5% of all TOX field samples analyzed each quarter (three month period) must be
fortified, instead of a minimum of 5% of the field samples that are processed together. This
means at least one sample out of every 20 samples (excluding duplicates) must be fortified. This
requirement for TOX is less stringent than for the other ICR analyses due to the relative labor
intensity of the method. The fortified TOX sample must be analyzed in duplicate.
EPA Method 552.1 is subject to matrix interferences (see Section 4 of the method), so
laboratories must demonstrate that use of this method is appropriate for the samples they are
analyzing. At least one sample from each set of quarterly samples received from a water utility
must be fortified. This requirement may mean that laboratories analyzing samples from many
water utilities must fortify more than 5% of the samples that are processed together.
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The laboratory must choose a fortifying concentration from one of the three concentrations listed
in Table 9.10. The fortifying concentration should be within ฑ20% of one of the levels given in
the tablet In order to obtain reliable data from laboratory fortified samples, the fortifying
concentration should be equal to or greater than the background concentration of each analyte
present in the sample. If EPA required laboratories to meet this criterion on all fortified samples,
laboratories would have to analyze each sample prior to fortifying it. EPA does not consider this
a reasonable requirement for meeting the ICR objectives. When possible, EPA recommends that
the laboratory select a fortifying concentration based on information provided by the utility. If the
utility has information concerning the levels of the various analytes found in samples collected at a
previous time, then the laboratory should use these "historical" data to select appropriate
fortifying concentrations. If there are no data available to predict the levels of individual analytes,
then the laboratory should base the fortification level on the utility's "historical" total
trihalomethane (TTHM) levels. (If the utility's TTHMs are normally <; 20 //g/L, then the lowest
level concentration should be chosen; for TTHMs between 20 and 50 //g/L, the mid-level
concentration should be chosen; and for TTHMs > 50 ,ug/L, the highest level concentration
should be used.) EPA realizes that this system will result in analyses of some fortified samples
that are not fortified at appropriate concentrations for all the analytes. However, over the course
of the ICR monitoring period, EPA believes that enough data will be obtained to assess the bias of
the measurements for all analytes over the range of concentrations found in drinking water
samples.
EPA recognizes that for some laboratories, especially commercial laboratories, it may not be
feasible to fortify samples using historical information from water utilities. In those cases, the
laboratory should rotate the fortification concentrations (low, mid, and high) without regard to
the background concentration in the sample matrix.
Laboratories must report all fortified sample recovery data and all data from the batch of samples
processed/analyzed with the fortified sample. Data from samples fortified at appropriate
concentrations (fortified at concentrations ;> background concentrations), will be used by EPA to
evaluate the quality of the monitoring data. A comparison of recoveries in fortified samples and
fortified reagent water (calibration check standards) will indicate whether there is a bias in the
ICR monitoring data. Water systems and laboratories may also use these data to determine the
appropriateness of the methodology used to analyze the ICR samples.
Note: Laboratories do not report the calculated recoveries for fortified samples to EPA. (See
Table 10.2.) EPA will calculate recoveries using the data that are submitted by the laboratory
and the water system.
Monitoring data will not be rejected from the ICR Federal Database based on fortified sample
recovery data.
63
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Table 9.9. Requirements for Performing Fortified Sample Analyses
Method
502.2 CTHMs)
524.2 OHMs)
551
(THMs)
551.1
(THMs,HANs,
HKs, CP,&CH)
552.1
(HAAs)
552.2
(HAAs)
6251 B
(HAAs)
300.0
(Br-,CKV,C103-,
BrOT)
5310B, 53 IOC,
5310D
(TOG)
5910
(UV,ซ)
5320 B
(TOX)
6252 B (Aldehydes)
LowBrO,'
modified 524.2
(CNC1)
Method Specifications
No Requirement
No Requirement
10% of samples or I/set
(whichever is larger)
10% of samples or I/set
(whichever is larger)
10% of samples or I/set
10% of samples or I/set
(whichever is larger)
10% of samples or I/set
10% of samples
None Specified
None Specified
10% of samples
10% of samples or I/set
Not Specified
No Requirement
ICR Specifications
At least 5% of the ICR samples in each
analysis batch
At least 1 sample in each extraction
batch
At least 1 sample in each set of quarterly
samples from a water utility
At least 1 sample in each extraction
batch
At least 5% of the ICR samples in each
analysis batch
At least 5% of the ICR samples in each
analysis batch. (Fortified samples must
be analyzed in duplicate.)
No requirement
At least 5% of all ICR samples analyzed
each quarterly period. (Fortified
samples must be analyzed in duplicate.)
At least 1 sample in each extraction
batch
At least 5% of the ICR samples in each
analysis batch
64
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Table 9.10. Concentrations for Fortifying Samples
Method
502.2, 524.2, 551, 551.1/CHC13, BDCM,
CDBM, CHBrS
551.1/TCAN, DCAN, BCAN, DBAN,
DCP, TCP, CP
551.1/CH
552.1, 552.2, 6251 B/DCAA, TCAA,
MBAA, DBAA, BCAA
552.1, 552.2, 6251 B/MCAA
552.2/BDCAA (Optional)
552.2/CDBAA (Optional)
552.2/TBAA (Optional)
300.0/Br
300.0/C1O2% C1O3-
300.0/BrO3-
53 10 B, 53 10 C, 53 10 D/TOC
5320 B/TOX
6252 B/Formaldehyde *
6252 B/Acetaldehyde, Butanal, Glyoxal,
Methyl Glyoxal, Pentanal, Propanal
Optional: Benzaldehyde, Decanal,
Hexanal, Heptanal, Nonanal,Octanal
LowBrO3'*
modified 524.2/CNC1 *
Low- Level
l.OAtg/L
0.50 Mg/L
0.50A*g/L
l.OyUg/L
2.0 //g/L
1.0yUg/L
2.0A
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Internal Standard
i
Several of the DBF methods require or recommend the use of an internal standard (IS) for
calibration and quantitation purposes. An internal standard is a pure analyte that is added to a
sample or sample extract in a known amount. It is used to measure the relative responses of other
method analytes and surrogates that are components of the same solution. The IS must be an
analyte that is not a sample component. When used, the IS is added to all samples, standards, and
QC samples or their extracts.
The methods usually recommend specific compounds and concentrations for use as internal
standards. When the method provides flexibility in the selection of the IS or IS concentration,
EPA allows the same flexibility during analyses of ICR samples.
The methods vary in their specifications of when the IS is added during the sample processing
steps. Some methods require the addition of the IS to the sample prior to any processing, while
other methods stipulate the addition to the sample extract immediately prior to instrumental
analysis. Laboratories are required to follow the method directions when performing analyses for
the ICR.
The methods also vary in the criteria used to evaluate the IS recovery. In general, the detector
response to the IS should be monitored in each sample, and it should be relatively constant during
the period in which a batch of samples is analyzed. Specific criteria for evaluating the IS for ICR
analyses are presented hi Table 9.11. Each sample's IS detector response should be compared to
the average IS detector response obtained for the calibration curve. The acceptance criteria are
given as % Recovery which is determined using the following formula:
IS % Recovery = Sample IS detector response X 100
Calibration Curve Average IS detector response
If the IS in a specific sample does not meet the acceptance criteria, then data from that sample
analysis will not be considered valid. If possible, the laboratory should reanalyze the sample. If
this cannot be done, then the data for that sample are considered invalid for the analysis and the
monitoring data should be flagged as not meeting QC criteria. If reported, these monitoring data
will be deleted from the ICR Federal Database.
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Table 9.11. Req
Method
502.2
(THMs)
524.2
(THMs)
551
(THMs)
551.1
(THMs,
HANs, HKs,
CP, & CH)
552.1
(HAAs)
552.2
(HAAs)
6251 B
(HAAs)
6252 B
(Aldehydes)
modified
524.2
(CNC1)
uirements for Internal Standard Analyses
Method Specifications
2-Bromo- 1-chloropropane
Fluorobenzene in each sample
Method doesn't specify
compound, but recommends
use of appropriate IS in each
sample prior to processing
(EPA has successfully used
1,2,3-Trichloropropane as IS
for this method)
Bromofluorobenzene in each
extract (required when pentane
is extracting solvent; IS use is
optional for MTBE)
1,2,3-Trichloropropane in each
extract
1,2,3-Trichloropropane in each
extract
1,2-Dibromopropane OR
1,2,3-Trichloropropane in each
extract
1,2-Dibromopropane OR
Decafluorobiphenyl in each
extract
Fluorobenzene in each sample
ICR Specifications
IS use is optional -
depends upon the
calibration procedure
Follow method & add to
each sample as directed.
IS use is optional -
depends upon the
calibration procedure
Follow method & add to
each extract as directed.
IS use is optional if
MTBE is the extracting
solvent.
Follow method & add to
each extract as directed.
Follow method & add to
each sample as directed.
ICR
Acceptance
Criteria
70 - 130%
Recovery
67
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Surrogate Standard
Several of the DBF methods require the use of surrogate analytes. A surrogate is a pure analyte
which is extremely unlikely to be found in any sample. It is added to a sample aliquot in a known
amount before the sample is processed, and is measured with the same procedures used to
measure other sample components. The purpose of a surrogate analyte is to monitor method
performance with each sample. When used, the surrogate is added to all samples, standards, and
QC samples.
The methods usually recommend specific compounds and concentrations for use as surrogate
standards. When the method provides flexibility in the selection of the surrogate standard or its
concentration, EPA allows the same flexibility during analyses of ICR samples.
A list of the methods that require surrogates, and the recommended surrogate(s) for each method,
is included in Table 9.12. The criteria for evaluating surrogate recoveries are also listed in Table
9.12. Surrogate recovery must be monitored for each sample, standard and QC sample.
There are two techniques for monitoring the surrogate standard. If the method specifies that the
same concentration of surrogate standard must be added to all samples, standards and QC
samples, then the surrogate detector response in each analysis must be compared to the average
surrogate detector response obtained for the calibration curve. The acceptance criteria are given
as % Recovery which is determined using the following formula: :
Surrogate % Recovery = Sample Surrogate detector response X 100
Calibration Curve Average Surrogate Detector Response
Some methods recommend preparing a calibration curve for the surrogate standard similar to the
preparation of a curve for each of the method analytes. In those cases, the acceptance criteria are
given as % Recovery which is determined using the following formula:
Surrogate % Recovery = Measured Surrogate Concentration X 100
Expected Surrogate Concentration
If the surrogate in a specific sample does not meet the acceptance criteria, then if possible, the
laboratory should reanalyze the sample. If this cannot be done, then the data for that sample are
considered suspect for the analysis in question and the monitoring data should be flagged as not
meeting QC criteria. If reported, these monitoring data will be deleted from the ICR Federal
Database.
EPA recognizes that failure to meet the surrogate standard recovery criteria could be the result of
matrix interferences in a small number of instances. Even if this is the reason for failure, the data
are suspect for all the analytes in the analysis and entry of the monitoring data into the ICR
Federal Database would dilute the quality of the database.
68
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Table 9.12. Requirements for Surrogate Standard Analyses
Method
524.2
(THMs)
551.1
(THMs,
HANs, HKs,
CP, & CH)
552.1
(HAAs)
552.2
(HAAs)
6251 B
(HAAs)
6252 B
(Aldehydes)
Method Specifications
Bromofluorobenzene in each
sample
Decafluorobiphenyl in each
sample
2-bromopropionic acid in each
sample
2,3-dibromopropionic acid in
each sample
2,3-dibromopropionic acid OR
2,3,5,6-tetrafluorobenzoic acid
in each sample
2,3,5,6-tetrafluorobenzaldehyde
in each sample
ICR Specifications
Add to each sample
according to the
method
specifications
ICR Acceptance
Criteria
70 - 130%
Recovery
Additional QC
The laboratory has the responsibility to examine the samples when they arrive in the laboratory to
determine if the proper shipping conditions were used. Samples for which the methods specify
storage at 4ฐC should arrive at the laboratory packed in ice or frozen gel packs. If there is no
visible ice or the gel packs are completely thawed, the laboratory should report the conditions to
the utility. Samples should not be analyzed if they were not shipped properly. If resampling
cannot be performed, then the utility should indicate in the report to EPA that the samples were
invalidated due to a shipment problem and no data should be reported.
The laboratory also has the responsibility to invalidate samples that were collected in improper
sampling containers (e.g., plastic bottles instead of glass) or that were improperly filled (e.g.,
half-filled bottles for samples that are required to be head-space-free). If resampling cannot be
performed, then the utility should indicate in the report to EPA that the samples were invalidated
due to a sampling error and no data should be reported.
The stability of some samples is dependent upon proper preservation techniques. The laboratory
is required to check the pH of samples that are to be analyzed for haloacetonitriles, chloropicrin,
haloketones, chloral hydrate, TOC, or TOX in order to determine that the samples were properly
69
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preserved. The pH can be determined immediately prior to the analysis using narrow range pH
paper. If the pH is not within the required ranges (see Table 9.13), the samples should not be
analyzed. If resampling cannot be performed, then the utility should indicate in the report to EPA
that the samples were invalidated due to a sampling error and no data should be reported.
Table 9.13. ICR Sample pH Acceptance Criteria
Method
551.1 (THMs, HANs, HKs, CP, & CH)
5310 B, 5310 C, 5310 D (TOC)
5320B(TOX)
ICR Specification
pH ฃ 4.5 and pH <,
5.5
pH * 2.0
pH s 2.0
Finally, the laboratory has the responsibility to ensure each sample is analyzed within the required
holding time. A list of applicable holding times is presented in Table 9.14. When appropriate,
EPA standardized the holding times across analytical methods for the same analyte group. For
example, each HAA method specifies a different holding time for the samples prior to the
extraction procedure. Since all the HAA methods specify the same sample collection and storage
conditions, EPA believes it is reasonable to assume these samples have the same shelf life. EPA
has specified a 14 day holding time for HAA samples, because under standard storage conditions,
all nine HAAs are stable for this period of time. However, the extract holding times (Table 9.14)
cannot be standardized across the various HAA methods, because the extracts are not chemically
equivalent,
EPA also shortened the holding time for a few ICR analyses. Method 300.0 indicates that
bromate and chlorate samples may be stored up to 28 days, but chlorite samples must be analyzed
within 14 days. The computer programs, that EPA is using to validate the QC data in the ICR
Federal Database, check holding times based on the method/analyte group, not the analyte.
Therefore, EPA had to set the maximum holding time at the shortest time applicable for the three
inorganic DBPs covered by Method 300.0.
If an ICR sample is not extracted or analyzed within the times specified in Table 9.14, then the
data for the sample should not be reported. The laboratory should indicate to the utility that the
sample was invalidated due to a holding time problem. This information would then be reported
to EPA when the utility submits its report for that monthly sampling period.
The ICR Sampling Manual provides additional information concerning recommended sample
collection and holding procedures for ICR samples.
70
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Table 9.14. Maximum Holding Times (in Days) for Samples and Extracts
Method
502.2, 524.2 (THMs)
551 (THMs)
551.1 (THMs, HANs, HKs, CP & CH)
552.1 (HAAs)
552.2 (HAAs)
6251 B (HAAs)
300.0 (Bf)
300.0 (CIO/, C1CV, & Br(V)
5310 B, 53 10 C, 5310 D (TOC)
5910 B
5320 B
6252 B (Aldehydes)
Low BrO3'
modified 524.2 (CNC1)
Sample
14
14
14
14
14
14
28
14
28
ASAP*
Not to exceed 2 days
14
ASAP*
Not to exceed 2 days
28
ASAP*
Not to exceed 2 days
Extract
Not Applicable
7
14
2
7
7
Not Applicable
Not Applicable
Not Applicable
Not Applicable
Not Applicable
7
Not Applicable
Not Applicable
* This analysis should be performed "as soon as practical" after the sample is collected. The
sample is not considered valid if the analysis is not done within 2 days from sample collection.
(Note: Aldehyde samples must be extracted within 2 days.)
71
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Section 10. Reporting Quality Control Data
Laboratories that perform analyses for the DBP/ICR are required to comply with the quality
control requirements described in Section 9 of this manual. Laboratories must report a subset of
these data to the ICR Federal Database (see Tables 10.1 and 10.2.) to verify that the ICR
monitoring data are of sufficient accuracy and precision to meet ICR data objectives. [The ICR
Chemistry Performance Evaluation (PE) Studies are not included in these tables, because they are
not directly associated with the routine ICR samples. These PE data must also be reported, but
not through the same mechanisms that are used for the other ICR QC data. See Section 8 for a
discussion of ICR Chemistry PE Studies.]
EPA has developed two data entry software packages that are to be used in reporting ICR data.
The ICR Water Utility Database System is to be used by the utilities primarily to report treatment
plant design information, treatment plant operational data, and the analytical results from the
monthly sample collection. However, some of the ICR QC data will be reported to EPA using
this system, because the data are associated with specific samples rather than batches of samples.
QC data that must be reported by the water systems are listed in Table 10.1. Laboratories must
provide the client water systems with this QC information when they report their analytical results
for the ICR samples, because monitoring data that are reported to EPA without the appropriate
QC data will be deleted from the ICR Federal Database.
The majority of the ICR QC data must be reported to EPA by the laboratory using the ICR
Laboratory Quality Control (QC) Database System. This software, along with a user's guide, will
be provided to each laboratory that is approved to perform analyses for the ICR. The data that
will be collected using this software are summarized in Table 10.2.
The ICR Laboratory QC Database System is designed to be used after sample analyses are
completed, instead of as a sample tracking system. The data entry screens collect the data on a
method and batch basis, so laboratories that organize their QC data in this manner will be more
efficient in their data entry activities.
The QC data listed in Table 10.2 must be reported to EPA on a monthly basis by the laboratories.
The QC data from all batches that were completed during the month are included in the monthly
report and laboratories have up to two months from the month in question to submit their QC
data to EPA (e.g., QC data from all batches completed in January must be received by EPA no
later than the last day of the following March). It is imperative that laboratories submit their QC
data to EPA in a timely manner, because the monitoring data will be deleted from the ICR Federal
Database when the appropriate QC data are not present. Lack of QC data will cause monitoring
data to be invalidated. Water systems must submit their data reports, which include the
monitoring data, to EPA no later than the fourth month following sampling [ง141.142(c)(l)]. All
associated QC data from the laboratories must be entered into the ICR Federal Database before
these monitoring data are entered.
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The QC data are to be reported on a computer disk in accordance with the requirements of the
ICR data collection software. (Laboratories will not report internal standard responses and
surrogate recoveries to EPA, but will rather report these data directly to the utility, because these
data are associated with individual samples. These data are then to be reported, by the utility, to
EPA when the utility submits its verified and validated monitoring data. Similarly, duplicate data
for TOX, UV2S4, and TOC analyses will also be reported through the utility, because each sample
is analyzed in duplicate.)
Mail the QC data disks to:
USEPA(ICR4600)
ICR Data Center
Room 111 East Tower
401M Street, SW
Washington, DC 20460
Laboratories should provide a copy of the QC data to the utility when the monitoring data are
reported, but the utility will not report, to EPA, QC data already reported by the laboratories.
Exceptions to this, however, are the internal standard responses, the surrogate recoveries, and the
TOX, UV2S4, and TOC analyses which were not previously reported to EPA.
The water systems will report to EPA, the EPA assigned laboratory ICR identification number to
identify the laboratory that performed each analysis.
It is the utility's responsibility to report all ICR monitoring data, other than the QC data discussed
above, to the EPA ICR database in accordance with the requirements for reporting ICR data.
Laboratories can assist the water utilities by providing the results of their analyses in a format that
is similar to the data entry screens used by the ICR Water Utility Database System.
74
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Table 10.1. QC Data to be Submitted to the ICR Federal Database bv the Water System
Data
Internal Standard Recovery
Surrogate Standard
Recovery
ICR Sample pH
Laboratory Duplicates
AOC QC Data
BDOC QC Data
Lab ID Code
Comments
One data point for each ICR sample analyzed using the
applicable methods.
One data point for each ICR sample analyzed using the
applicable methods.
pH of each preserved ICR sample for the applicable methods.
All TOC, UV2S4, and TOX samples are analyzed in duplicate
and the results from both analyses are reported.
Semiannual report on AOC yield factors. Data are reported for
P17 and NOX growth controls, P17 and NOX yield controls,
and P 17 and NOX blank controls.
Quarterly report indicating average TOC blank concentration,
estimated TOC detection limit, and results from analysis of a
fortified reagent water sample.
ICR Laboratory Code for each laboratory performing analyses
of ICR samples
75
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Table 10.2. QC Data to be Submitted to the ICR Federal Database by the Laboratory
Data
Comments
Identification
of Shipping
Batches
Laboratory will report shipping batch ID number (laboratory generated) along with the
sample ID numbers for the ICR samples and the shipping blank associated with the
shipping batch. This requirement only applies to aldehyde analyses. ,
Identification
of Extraction
Batches
Laboratory will report the extraction batch ID number (laboratory generated) and date
of extraction along with a h'st of sample ID numbers for the ICR samples, duplicate
samples, fortified samples, the method blank, calibration check standards, and
shipping blanks (aldehydes only) extracted in the batch,
Identification
of Analysis
Batches
Laboratory will report the analysis batch ID number (laboratory generated) and the
beginning and ending date and time of analysis along with a list of sample ID numbers
for the ICR samples, duplicate samples, fortified samples, the method blank,
calibration check standards, and shipping blanks (aldehydes only) analyzed in the
batch.
Method Blank
If the method blank met all the ICR QC acceptance criteria (< Yt MRL for each
analyte, and the surrogate and internal standard recoveries are within the acceptance
range, if applicable), then the laboratory is only required to indicate that the method
blank was analyzed and met the QC criteria. If the criteria were not met for one or
more parameters, then the laboratory is required to report the concentrations of those
analytes which failed QC criteria and recovery data for the surrogate and internal
standards, if applicable. ______^^
Verification of
Calibration
At least two calibration standards will be associated with each analysis batch.
Laboratory will report expected and measured concentrations of each analyte in the
standards. Internal standard and surrogate standard recoveries will also be reported, if
applicable.
Laboratory
Duplicates
At least one duplicate analysies will be associated with each extraction or analysis
batch of samples except for TOC, UVjs^ and TOX which require duplicates of ALL
samples. Laboratory will report measured concentrations of each analyte in the
duplicate sample analysis except for TOC, UV^, and TOX which will be reported by
the water system.
Laboratory
Fortified
Samples
At least one fortified sample will be associated with each extraction or analysis batch
of samples for most of the DBF methods. Laboratory will report the concentration of
each analyte used to fortify the sample, the concentration of each analyte measured in
the fortified sample without correcting for original concentration, and internal and
surrogate standard recoveries, if applicable.
Lab ID Code
Each laboratory will be assigned a unique code for ICR reporting purposes.
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Section 11. Laboratory Evaluation During DBP/ICR Monitoring
Laboratories must be approved on a method by method basis prior to performing any chemical
analyses for the ICR. Approval is based on the criteria specified in Sections 4, 6, and 8. EPA
recognizes that demonstrating capability to perform a specific analysis does not necessarily
guarantee that a laboratory will operate at the required level of performance on a day to day basis
during the 18-month monitoring period. Therefore, EPA will also monitor laboratory
performance during the period in which the laboratory is generating data for the ICR Federal
Database. In order to maintain approval to perform analyses for trihalomethanes, the
haloacetonitriles, haloketones, and chloropicrin, chloral hydrate, haloacetic acids, oxyhalides,
bromide ion, total organic halide, total organic carbon and ultraviolet absorbance at 254 nm, the
laboratory must meet the following criteria during the time of approval:
Successful performance on periodic Performance Evaluation (PE) Studies
Timely and accurate submission of Quality Control (QC) data
Successfully meet the QC criteria for at least 80% of the ICR samples analyzed
EPA may also require submission of additional documentation and/or perform on-site audits
during the time of approval.
Performance Evaluation (PE) Studies
EPA will conduct ICR Chemistry PE Studies on approximately a quarterly basis during the 18-
month monitoring period and all approved laboratories will be required to participate in these
studies in order to maintain ICR Laboratory Approval. The first of these "required" studies (ICR
Chemistry PE Study 4) will be conducted close to the start of monitoring, in order to verify that
previously approved laboratories are still capable of acceptable performance. The acceptance
criteria described in Section 8 will apply for all ICR Chemistry PE Studies.
ICR Chemistry PE Studies 5 through 9 will be conducted during the 18-month monitoring period.
EPA recognizes that even good laboratories can occasionally fail a PE study for a particular
method. Therefore, laboratories that fail to meet the necessary criteria on one or more methods in
a specific PE study will be provided an additional PE sample for each method that was failed. The
PE sample(s) will be sent to the laboratory in the same time frame as the report of the PE study
results and the laboratory will have three weeks to analyze the sample(s) and report the data back
to EPA. A laboratory that fails the second sample (i.e., two consecutive PE samples for the same
method) will not be allowed to continue performing that analysis for ICR samples. No further
ICR samples should be analyzed by that method, because data from ICR samples analyzed using
the same method as the failed PE sample after the date that the second PE sample was analyzed
77
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will be deleted from the ICR Federal Database. The laboratory must meet the criteria specified in
Section 12 in order to have ICR Laboratory Approval reinstated for the method in question.
Submission of QC Data
EPA has developed computer programs to examine the QC data associated with the ICR samples.
The programs will automatically match each analytical result from an ICR sample reported by a
water system with the associated QC data for the extraction and analysis batch reported by a
laboratory. The QC data must meet the acceptance criteria in order for the monitoring data for
that analyte to be maintained in the ICR Federal Database.
Because the QC data must be available before the monitoring data from ICR samples can be
evaluated and in order to identify problems at the laboratory as quickly as possible, EPA will use
timeliness of data submission as one of the ongoing laboratory approval criteria. The QC data
must be reported to EPA within the time frame specified in Section 10. EPA will notify
laboratories when they have failed to submit data by the required date.
Laboratories also have the responsibility to fully review their data for accuracy prior to submitting
the monthly QC reports to EPA. The water systems are required to report their monitoring data
to EPA within four months from the sampling date. The water systems expect EPA to process
the data quickly and report back to them concerning the results of EPA's QC verification process.
Since laboratories are given almost three months to report the QC data, there is a limited time
between laboratory submission of QC data and water system submission of monitoring data.
There is not enough time for laboratories to submit "corrected" QC reports on a routine basis.
Therefore, EPA will consider resubmissions on a case-by-case basis. The ICR Chemistry
Laboratory Coordinator must authorize resubmissions and each resubmission will be considered
the same as failing the timeliness criteria, even if the resubmission occurs within the time frame
specified in Section 10. Laboratories must request approval to resubmit QC data by writing (or
faxing) to the ICR Chemistry Laboratory Coordinator.
Because it is critical that the QC data be received by EPA in a timely manner, laboratories that fail
to meet the timeliness criteria for three reporting periods over the course of the 18-month
monitoring period will not be allowed to continue performing any analyses of ICR samples. No
further ICR samples should be analyzed, because data from ICR samples analyzed after the date
on which the laboratory is notified of loss of laboratory approval will be deleted from the ICR
Federal Database. The laboratory must meet the criteria specified in Section 12 in order to have
ICR Laboratory Approval reinstated for the remainder of the ICR.
Completeness of Data
Because the data in the ICR Federal Database will be used as the basis for future regulations, EPA
has established QC criteria that must be met for much of the monitoring data. Analytical results
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from samples that do not meet the QC criteria will be deleted from the ICR Federal Database.
This means that some monitoring data will be lost due to failures in the laboratories' QC. (There
will also be losses outside the control of the laboratories for reasons such as sampling errors,
sample breakage during shipment, etc.) EPA has estimated that the data set must be 80%
complete in order to achieve all of the ICR objectives.
In order to ensure that enough monitoring data is maintained in the ICR Federal Database, EPA
will determine the percentage of each laboratory's ICR sample analyses that meet all the QC
requirements and are therefore kept in the ICR Federal Database (i.e., completeness rate). A
laboratory must maintain an 80% or greater data completeness rate for each analytical method
that is performed for the ICR during each reporting period in order to maintain laboratory
approval for each method.
Multi-analyte methods are also subject to completeness criteria for each analyte in order to guard
against bias in the data through the consistent loss of one analyte in a method. A laboratory must
maintain a 60% or greater data completeness rate for each analyte in a method. As an example,
analyses often trihalomethane samples will generate forty analytical results (4 analytes/sample X
10 samples). Of the forty results, thirty-two must be valid (meet all the QC requirements) in order
to meet the 80% completeness rate for the method. In addition at least six of the ten results for
each analyte (e.g., bromoform) must be valid in order to meet the 60% completeness criteria for
each analyte. Without the latter criteria, it would be possible to meet the 80% completeness rate
for the method and lose eight out often results for a single analyte.
Completeness will be determined for each reporting period that contains a minimum often ICR
sample analyses and EPA will notify a laboratory when it has failed to meet this criterion.
A laboratory that fails the completeness criteria three times during the 18-monitoring period for
the same method will not be allowed to continue performing that analysis for ICR samples. Data
from ICR samples analyzed using the problem method after the date on which the laboratory is
notified of loss of laboratory approval will be deleted from the ICR Federal Database, so no
further ICR samples should be analyzed by that method. The laboratory must meet the criteria
specified in Section 12 in order to have ICR Laboratory Approval reinstated for the method in
question.
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Section 12. Reinstatement of Laboratory Approval
Should review of laboratory QC or PE data indicate that a laboratory is not meeting the ICR data
requirements, EPA will notify the laboratory of the problem. EPA will identify those analyses
which seem to be suspect, and summarize the reasons why the data are suspect. If the problem(s)
cannot be resolved and the laboratory loses approval for one or more methods (see Section 11),
the laboratory can apply for reinstatement of laboratory approval subject to the following
requirements:
Loss of approval was not the result of fraud.
There are at least six months of DBP/ICR monitoring to be conducted after the month
in which EPA issues a letter of disapproval.
In order to have EPA consider reinstating ICR Laboratory Approval, the laboratory must submit a
new application package within two months of loss of approval for each method under
consideration. All data in the application must be generated after loss of laboratory approval.
EPA will provide the laboratory with the appropriate application forms to be used in applying for
reinstatement.
In addition to the application, the laboratory must pass the first available ICR Chemistry PE study
for each method under consideration. EPA may also require a laboratory audit or on-site
inspection prior to reinstating laboratory approval.
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Appendix A
83
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ICR REGISTRATION FORM
Instructions: Please complete the following form. For your convenience, the return address is
affixed to the back of this form.
Laboratory Type: _Utility _ Commercial _ State _ Other.
Lab Name:
Address:
Contact Person:
Telephone:
Please <
abqyeป
.the fo
meters that will be analyzed by the lab listed
AnaIyTOrwhich\edui^e)EPA evaluation prior to ICR Approval:
ide _ Chloral Hydrate _ Haloacetic Acids _ Total Organic Carbon
_ Total Organic Halide _ UV Absorbance _ Oxyhalides (bromate, chlorate, chlorite)
_ Total Hardness _ Haloacetonitriles, Haloketones and Chloropicrin _ THMs
(via 551/551.1)
The parameters listed below do not require EPA evaluation prior ICR Approval if state
approval or certification can be demonstrated:
_ Alkalinity _ Calcium Hardness _pH _ Temperature _THMs _ Turbidity
(via 502.2/524.2/551)
Disinfectant Residuals:
_ free-chlorine _ total-chlorine _ chlorine dioxide _ combined chlorine _ ozone
85
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If any of the unchecked analytes are to be analyzed by another lab (contracted by you),
please provide the name and address of the contracted laboratory in the space below. Also
list the parameter for which they are analyzing.
Laboratory Address Analyte
(fold here first)
ICR Laboratory Approval (Chemistry)
Technical Support Division / USEPA
26 W. Martin Luther King Jr. Drive
Cincinnati, OH 45268
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Appendix B
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VERIFICATION OF STATE
CERTIFICATION / APPROVAL
Laboratory Type: _Utility _ Commercial _ State _ Other.
Lab Name:
Address:
Contact Person:
Telephone:
Certification
The information re
ICR parameters list
D
to Odnonstrate certification/approval of the
ipletely, and supply all requested documentation.
for the ICR? _Yes _No
1 section.)
1 used in your lab for the determination of THMs.
'_501.2 _ 502.2 _ 524.2 _551 _ Other
Using the method you indicated above, is your laboratory currently certified to measure THMs in
drinking water? _Yes, _No
If "yes", please list: 1) the states in which the lab is certified and the certification #s, 2) indicate if
the certification was achieved via on-site inspection, reciprocity, or a paper evaluation, and 3) if
the certification is full or provisional, (e.g. NY. 11383 onsite Ml )
(1)
(2)
(3)
Please attach a copy of your certificate^)
Within the last three years, has your laboratory ever lost certification for THMs?
(If yes, attach an explanation of when and why.)
_Yes, _No
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State Approvals
If your laboratory intends to measure any of the parameters listed in the table below and is
approved by a State to perform analyses of water samples using one of the methods specified in
the ICR, then complete this section of the form. Please check the appropriate analyte, list one
State in which your lab is approved, and indicate the manner of approval (on-site inspection,
reciprocity, via a paper evaluation, or de facto), the method used for the analysis, and the type(s)
of samples for which you are approved (drinking water, ground water, wastewater, etc.). Please
ICR Parameter
(Indicate with a/)
( ) Alkalinity
( ) Ammonia
( ) Calcium hardness
n PH
( ) Temperature
( ) Total Hardness
( ) Turbidity
( ) Free-chlorine
( ) Chlorine dioxide
( ) Total-chlorine
( ) Combined-chlorine
( ) Ozone
State in Which Approved,
and Manner of Approval
(e.g. De Facto, etc.)
Method Used for
the Analysis
fee. SM2320 B)
Type of Sample
(e.g. Wastewater)
NOTE: In some circumstances, a laboratory may be performing some of these analyses and reporting data to a
State Primacy Agency with only de facto, and not documented, State approval. In such situations (where the
laboratory does not have a formal State document to forward to EPA), a letter explaining the State's de facto
approval is to be written by the laboratory manager and forwarded to EPA along with the completed
Verification of State Certification/Approval Form. This letter should indicate the nature of the data that are
being submitted, the name of the State Primacy Agency, the types of samples, method(s) of analysis, and
frequency of reporting.
Within the past three years, has your lab lost approval for the analysis of any parameter for which
you are applying for approval? _Yes _No (If yes, attach an explanation of when and
why.)
Lab Manager Signature:. Date:
This signature affirms that the information in the completed package is correct.
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Appendix C
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ICR LABORATORY APPROVAL FORM
(For Analyses Not Covered Under Existing Drinking Water Regulations)
INSTRUCTIONS: Please fill-in these forms as completely as possible. The cover letter sent with
this packet should address most of the questions you may have concerning the completion of
these forms. It also provides a telephone number that can be called to obtain additional
information.
Lab Name:
Address:
Contact Person:
Telephone:
What is
vr
lyses for which your laboratory is seeking
faloacetic Acids _ Total Organic Carbon _ Total Organic Halide
552. 1; EPA 552.2; (SM 53 10 B,C,D) (SM 5320 B)
SM6251 B)
. UV Absorbance _ Total Hardness
(SM5910) (SM2340B,C)
_ Ammonia
(SM 4500-NH3 D,G;
EPA 350. 1,379-75 WE)
Bromide
(EPA 300.0)
_ Haloacetonitriles, Haloketones and Chloropicrin _ Oxyhalides - bromate, chlorate & chlorite
(EPA 55 1.1) (EPA 300.0)
_THMs
(EPA 551, 551.1)
Lab Manager
Signature:
Date:
This signature affirms that the information in the completed package is correct.
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QUALITY ASSURANCE
Please provide the following quality assurance (QA) information:
1) QA Officer's name and telephone number
2) Her/his QA experience
3) An organizational chart (Be certain to show the position of the QA officer.)
4) The Table of Contents from your Laboratory QA Plan (After you receive ICR
approval, you must have an ICR QA Manual available for review.)
5) The date of the last revision of your Laboratory QA Plan
CERTIFICATION
Is your laboratory currently certified to perform drinking water analyses? Yes No
If Yes, please list in the table below, the following information:
- Methods for which your laboratory is certified (If lab is certified for many methods, limit
submission to methods that are similar to the ones for which the lab is seeking ICR
approval.)
- States in which your laboratory is certified, and the certification numbers (If certified by
multiple states, list should include home state, if applicable, and specify how many
additional states are applicable.)
- Indicate if the certification was achieved via on-site inspection, reciprocity, or a
paper evaluation (Focus on home state, if applicable.)
- Identify whether the certification is full or provisional (as of the date of this application)
Methods for Which
Lab is Certified
States in Which Certified -
and Certification Numbers
Manner of
Certification (on-
site, reciprocity,
paper)
Type of
Certification
(full or
provisional)
Please attach a copy of your certificate(s) for conducting these analyses.
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Laboratory Name:
ICR Lab No..-
Personnel Qualifications
Instructions:
Please complete a personnel qualification form for each employee who will be associated with the
ICR analyses which require EPA approval (see list on page 1 of this Laboratory Approval form).
Include those involved with ICR sample handling, analysis, data review and lab management.
Note that professional biographies may be substituted for this part of the ICR application if they
contain all the personnel information requested by this form.
NAME (Last, First, Middle) 1 i , ,
1 iFull-Time 1 IPart-Time
POSITION CURRENTLY HELD/ ICR ASSOCIATION
EDUCATION r - . ,
a. High School Graduate or Equivalent ' 'Yes 1 (No
b. Colleges & Universities
Name and address
of Institution
MAJOR
Degree, Diploma,
Certificate. Inc.
MO/YR Conferred
c. Special Schools, Short Courses and Programs of Instruction
Name and address
of Institution
PROGRAM
TITLE
Degree, Diploma,
Certificate. Inc.
MO/YR Conferred
(Verification of Degree, Diploma, Certificate and/or Transcript of grades may be requested.)
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PERSONNEL QUALIFICATIONS
LICENSE, CERTIFICATION, OR REGISTRATION
Last Name:
Name of Granting Agency
License, Certification or
Registration Title
Granted
MO/YR
License, Certification or
Registration #
Verification may be requested.
LABORATORY EXPERIENCE
Name and Address of Laboratory
or Institution. Begin with earliest
employment and continue
THROUGH PRESENT
EMPLOYMENT. Any gaps in
employment will be assumed to be
non-laboratory work periods.
PERIOD
EMPLOYED
FROM TO
MO/YR MO/YR
POSITION(S)
HELD
i
EXPERIENCE
e.g. Micro,Chem,etc.
(also include
experience with
specific analyses and
methods)
REMARKS (Add information pertinent to education, training, employment, etc., not included above.)
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Laboratory Name:
ICR Lab No.:
ICR Method Approval: Chloral Hydrate, Haloacetonitriles, Haloketones,
Chloropicrin, and Trihalomethanes
DESCRIPTION: This analysis determines the concentration of chloral hydrate (CHX 4
haloacetonitriles (HANs), 2 haloketones (HKs), chloropicrin (CP) and the 4 trihajprtlepianes in
water. The HANs include bromochloroacetonitrile (SCAN), dibromoacetopitrfl^OBAN),
dichloroacetonitrile (DCAN), and trichloroacetonitrile (TCAN). The
dichloropropanone (DCP) and 1,1,1-trichloropropanone (TCP). The trihaloY
chloroform (CHC13), bromodichloromethane (BDCM), dibrom^cl^oromethan^
bromoform (CHBr3).
For which analytes are you seeking approvaj?
_ CH _ HANs, HKs, CP
<
Which method is used in your 1
.EPA 551 _
or description of the method used.
Does your lab have a written SOP for this analysis? Yes No
Is your lab currently certified for 501.2 or 504 or similar methods? _Yes _ No
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EQUIPMENT
Please list the equipment used in the method for which you are seeking approval.
Gas Chromatograph
Detector(s)
Injector(s)
Analytical Column
Confirmation Column
Sample Storage Unit
Extract Storage Unit
Standard Storage Unit
Manufacturer
Model & Serial #
Type:
Type:
Type:
NOTE: In the following tables in this form, please provide information only
for those analytes for which you are seeking approval,
SAMPLE HANDLING INFORMATION
ANALYTE
CH
HANs,
HKs.CP
THMs
SAMPLE
STORAGE
TEMP(ฐC)
MAX.
HOLDING
TIME
(days)
PRESERVATIVE USED
Name
Cone, in
Sample
(mg/mL)
DECHLORINATING
AGENT
Name
>
Cone, in
Sample
(mg/mL)
What is the sample container made from?
bottles septa, liner, or cap (whichever contacts sample)
Sample bottle volume?
EXTRACT HANDLING INFORMATION
ANALYTE
CH
HANs,HKs,
CP
THMs
SOLVENT USED
EXTRACT STORAGE TEMP (ฐC)
1
'
MAX HOLDING TIME
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Laboratory Name:
ICR L,ab No.:
QC INFORMATION
Initial Demonstration of Capability: Using the procedure outlined in the DBP/ICR Analytical
Methods Manual, Section 6, paragraphs 2 and 3, enter in the table below, the data, and resultant
calculated values, for your initial determination of precision and accuracy
CHC13
TCAN
DCAN
BDCM
CH
DCP
CP
DBCM
BCAN
TCP
CHBr3
DBAN
Spike
Cone.
fcg/L)
Date of Analysis
of Replicate Sample
Concentration Determined in Replicate Samples
(MJ/L)
1
2
3
4
5
Mean %
Recovery
(accuracy)
%RSD
(precision)
j
NOTE: Please attach an example chromatogram from one of these determinations. Be sure
to label each analyte, giving its retention time, concentration, and detector attenuation.
99
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Internal Standard and Surrogate
If you used an internal standard and/or surrogate in the determination of precision and accuracy
(see preceding paragraph) please identify in the table below, the name of the chemical, the amount
used, and average recovery
Name of chemical
Amount added
Average recovery
Internal Standard
//g/mL
(cone, in extract)
Surrogate
(cone, in sample)
Method Blank (Reference Section 6, paragraph 1)
What was the average concentration in your method blanks during the determination of precision
and accuracy (reference paragraphs 2 and 3).
CHC13:_
TCAN:
DCAN:
BDCM:.
CH:
DCP:
CP:
DBCM:_
BCAN:
TCP:
CHBr3:_
DBAN:
NOTE: Please attach an example chromatogram of your method blank. (Be sure to
label the potential position of the method analytes and detector attenuation.)
What is your lab's normal (non-ICR) reporting limit
CHC13:_
TCAN:
DCAN:
BDCM:_
CH:
DCP:
CP:
DBCM:.
BCAN:
TCP:
CHBr3:_
DBAN:
Briefly describe how these reporting limits are established.
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Laboratory Name:
ICR Lab No.:
Primary Column MDL: Using the minimum detection limit procedure described in the DBP/ICR
Analytical Methods Manual, Section 6, paragraph 4., enter in the table below, the data and the
MDLs Q/g/L) for this analysis.
CHC13
TCAN
DCAN
BDCM
CH
DCP
CP
DBCM
BCAN
TCP
CHBr3
DBAN
Spike
Cone.
0
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CALIBRATION CURVE
!
List the approximate concentrations Og/L) of the calibration standards currently used to
establish the standard curve. (Note: The concentrations used to establish the calibration curve
may be revised for the ICR monitoring period.)
CHCl,
TCAN
DC AN
BDCM
CH
DCP
CP
DBCM
BCAN
TCP
CHBr,
DBAN
Std#l
Std#2
Std#3
Std#4
Std#5
Does this calibration provide you with a linear curve? Yes __ No
Was this curve generated by a data system or calibrated manually
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Laboratory Name:
ICR L,ab No.:
PERFORMANCE EVALUATION
Has your lab analyzed EPA WS PE samples using this method? _ Yes _ No. If yes, please
list in both tahtes helnw, the results, in //g/L, from the three most recent studies in which you
participated.
CHCl,
BDCM
OBCM
CHBr,
Study* Hate-
Studyl Date:
Stlldvtf Date-
CH
Study*.
.Date:
Study#_
.Date:
Study)? Date:
ADDITIONAL INFORMATION
Using this Analytical Method, how many samples can your laboratory analyze per week?
List the personnel who will be performing these analyses for the ICR and give their duties
(extraction, GC Analyst, etc.).
Name
Duties
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Laboratory Name: ICR Lab
ICR Method Approval: Haloacetic Acids
DESCRIPTION: This analysis determines the concentration of 6 haloacetic acids (HAAs) in
water, monochloroacetic acid (MCAA), dichloroacetic acid (DCAA), trichloroacetic acid
(TCAA), monobromoacetic acid (MBAA), dibromoacetic acid (DBAA), and
bromochloroacetic acid (BCAA).
Which HAA method is used in your laboratory? _ EPA 552.1 _ SM 6251 B
_ EPA 552.2 _ Other
If "Other", please give the name, number or description of the method used by yen
laboratory.
Does your lab have a written SOP for thi
Is your lab certified for chlo
other similar methods?
_Yes _No
EQUIPMENT
Please list the equi
InjecSgr^s) s
Analytical Column
Confirmation Column
Sample Storage Unit
Extract Storage Unit
Standard Storage Unit
Diazomethane Generator
Solid Phase Extraction
Apparatus
Temperature Bath
Type:
Type:
Type:
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SAMPLE HANDLING INFORMATION
What is the sample container made from? bottles
Sample bottle volume?
Storage Temp: ฐC Maximum Holding Time: Days
Are samples dechlorinated? _Yes _No; with
Are samples acidified? _Yes _No; with (_
septa, liner, or cap
(whichever contacts sample)
_mg/mL concn in sample)
_mg/mL concn in sample)
EXTRACT HANDLING INFORMATION
Storage Temp: ฐC Maximum Holding Time: Days ;
QC INFORMATION
Initial Demonstration of Capability: Using the procedure outlined in the DBP/ICR Analytical
Methods Manual, Section 6, paragraphs 2 and 3, enter in the table below, the data, and resultant
calculated values, for your initial determination of precision and accuracy.
MCAA
MBAA
DCAA
TCAA
BCAA
DBAA
Spike
Cone.
fcg/L)
Concentration Determined in Replicate Samples
teE/L)
1
Date of Analysis |
of Replicate Sample ||
2
3
4
5
Mean %
Recovery
(accuracy)
V.RSD
(precision)
I
NOTE: Please attach an example chromatogram from one of these determinations. Be sure
to label each analyte, giving its retention time, concentration, and detector attenuation. All
peaks should be "on scale."
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Laboratory Name:
Internal Standard and Surrogate
ICRLabNo.
If you used an internal standard and/or surrogate in the determination of precision and accuracy
(see preceding paragraph) please identify in the table below, the name of the chemical, the amount
used, and average recovery.
Name of chemical
Amount added
Internal Standard
//g/mL
(cone, in extract)
Surrogate
//g/mL
(cone, in sample)
Method Blank (Reference Section 6, paragraph 1)
What was the average concentration in your method blanks during the determination of precision
and accuracy (reference paragraphs 2 and 3).
MCAA:.
MBAA:
DCAA:
TCAA:
BCAA:
DBAA:
NOTE: Please attach an example chromatogram of your method blank. (Be sure to
label the potential position of the method analytes and detector attenuation.)
What is your lab's normal (non-ICR) reporting limit Qzg/L)?
MCAA:
MBAA:
DCAA:
TCAA:
BCAA:
DBAA:
Briefly describe how these reporting limits are established.
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Primary Column MDL: Using the minimum detection limit procedure described in the DBP/ICR
Analytical Methods Manual, Section 6, paragraph 4., enter in the table below, the data and the
MCAA
MBAA
DCAA
TCAA
BCAA
Spike
Cone.
-------
Laboratory Name:
PERFORMANCE EVALUATION
ICRLabNo.
Has your lab analyzed EPA WSPE samples using this method? _Yes_No. If yes please list
in the table below, the concentrations reported to EPA, in //g/L, from the three most recent
studies in which you participated.
MCAA
MBAA
DCAA
TCAA
BCAA
DBAA
ADDITIONAL INFORMATION
Using this Analytical Method, how many samples can your laboratory analyze per week?
List the personnel who will be performing these analyses for the ICR and give their duties
(extraction, GC Analyst, etc.).
Name
Duties
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laboratory Name: ICRLabNo.:
ICR Method Approval: Total Organic Carbon
DESCRIPTION This analysis determines the total organic carbon (TOC) concentration in
water.
Which TOC method is used in your laboratory?
SM5310B _SM5310C _SM5310D _ Other
If "Other", please give the name, number or description of the method used to
laboratory.
Does your lab have ajvritten
EQUIPMENT
bottles
SAMPLE HANDLING INFORMATION
What is the sample container made from?
Sample bottle volume?
Storage Temp: __ฐC Maximum Holding Time: Days
Are samples acidified? _ Yes _ No ; with
Preserved sample pH?
Ill
septa, liner, or cap
(whichever contacts sample)
-------
QC INFORMATION
Initial Demonstration of Capability: Using the procedure outlined in the DBP/ICR Analytical
Methods Manual, Section 6, paragraphs 2 and 3, enter in the table below, the data, and
resultant calculated values, for your initial determination of precision and accuracy.
Spike
Cone.
(mg/L)
Dote of Analysis
of Replicate Sample
Concentration Determined in Replicate Samples
(mg/L)
2
3
4
5
Mean%
Recovery
(accuracy)
%RSD
(precision)
Method Blank
What was the average concentration of TOC in your method blank during the determination of
precision and accuracy? (Reference above paragraph) mg/L
What i$ your normal (non-ICR) minimum reporting limit for TOC?
Briefly describe how the reporting limit was established.
-mg/L
112
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Laboratory Name:
ICR Lab No.:
MDL: Using the minimum detection limit procedure described in the DBP/ICR Analytical
Methods Manual, Section 6, paragraph 4, enter in the table below, the data and the MDL
(mg/L) for this analysis.
Spike
Cone.
(mg/L)
Concentration Determined in Replicate Samples
(mg/L)
Date of Analysis
of Replicate Sample
MDL
(mg/L)
Although not specifically required, has this MDL been confirmed by analysis of a
reagent water spiked near the MDL? _ Yes _ No
CALIBRATION CURVE
List the approximate concentrations (mg/L) of the calibration standards currently used to
establish the standard curve. (Note: The concentrations used to establish the calibration curve
be revised for the ICR monitorim
Does this calibration provide you with a linear curve? Yes No
Was this curve generated by a data system or calibrated manually ?
What compound is used to prepare your TOC standards?
PERFORMANCE EVALUATION
Has your lab analyzed EPA WP PE samples for TOC using this method? _ Yes _ No If
yes, please list in the table below, the concentrations reported to EPA, in mg/L, from the three
most recent studies in which you participated.
113
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ADDITIONAL INFORMATION
What types of quality control checks are performed for this analysis?
At what concentration is the quality control check analyzed?.
Using this analytical method, how many TOC samples per week can your laboratory analyze?
/wk
List the personnel who will be performing this analysis for the ICR and list their duties.
Duties
114
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ICR Method Approval: Total Organic Halfde
: This analysis clefenmines the total organic halideCTO:^ concentration M wafer.
Which TO>X method is used in your laboirataEy?
_ SM 532ฉ B _ Of&er
If "Other", please give the name, number or description! offfee met fed used fey yo
Does your lafo have a written SOP fe
EQIMPMEMT
Please fist the equipment used
Model & Serial #
diorptroni Module
What is the sample contamer made from?
Sample bottle volume?
- bottles septa, finer, or cap
(whichever contacts sample}
Storage Temp: ฐC Maximum Holding Time: Days
AresampIesdechIorinated?_Yes _Jfe ; with C-mg/mt concentration in sample)
Are samples acidified? _Tes _No> - with
Preserved sample pH:
115
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QC INFORMATION
i
Initial Demonstration of Capability: Using the procedure outlined in the DBP/ICR Analytical
Methods Manual, Section 6, paragraphs 2 and 3, enter in the table below, the data, and resultant
calculated values, for your initial determination of precision and accuracy
Concentration Determined in Replicate Samples
Mean%
Recovery
(accuracy)
%RSD
(precision)
Date of Analysis
of Replicate Sample
Method Blank
What was the average concentration of TOX in your method blank during the determination of
precision and accuracy? (Reference the above paragraph.) /zgClYL
What is your normal (non-ICR) minimum reporting limit for TOX? AtgClYL
Briefly describe how the reporting limits were established.
MDL: Using the minimum detection limit procedure described in the DBP/ICR Analytical
Methods Manual, Section 6, paragraph 4, enter in the table below, the data and the MDL
for this analysis.
Spike
Cone.
TOX
nB=E
Date of Analysis
of Replicate Sample
Concentration Determined in Replicate Samples
MDL
G/gcr/L)
Although not specifically required, has this MDL been confirmed by analysis of a reagent
water spiked near the MDL? _Yes _No
116
-------
laboratory Name:
CALIBRATION CURVE
ICR Lab No.:
List the approximate concentrations fcgCT/L) of the calibration standards currently used to
establish the standard curve. (Note: The concentrations used to establish the calibration curve may
be revised for the ICR monitoring period.) y
Does this calibration provide you with a linear curve? Yes No
Was this curve generated by a data system or calibrated manually
What compound is used to prepare your TOX standards?
ADDITIONAL INFORMATION
What types of quality control checks are performed for this analysis?
At what concentration is the quality control check analyzed?
Using this analytical method, how many TOX samples per week can your laboratory analyze?
/wk
List the personnel who will be performing this analysis for the ICR and list their duties.
Name
Duties
117
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Laboratory Name: ICR Lab No .
ICR Method Approval: UV Absorbing Organic Constituents
DESCRIPTION: This analysis determines the UV absorbing organic constituents in water.
Which UV method is used in your laboratory? _ SM 5910 _ Other
If "Other", please give the name, number or description of the method used by your laboratory.
Does your lab have a written SOP
EQUIPMENT
Please list an
SAMPLE HANDLING INFORMATION
What is the sample container made from?
Sample bottle volume?
Storage Temp: ฐC Maximum Holding Time:
Are samples dechlorinated? _Yes _J^o ; with
Are samples acidified? _Yes _No ; with
bottles septa, liner, or cap
(whichever contacts sample)
Days
( mg/mL cone, in sample)
119
-------
QC INFORMATION
Initial Demonstration of Capability: Using the procedure outlined in the DBP/ICR Analytical
Methods Manual, Section 6, paragraphs 2 and 3, enter in the table below, the data, and resultant
-
uv
.Vif^A YCUUWV, *^^*
ConcofKHP
(mg/Lus
DOC)
Dtte of Analysis
1
Analyzed Absorbance of Replicate Samples
(cm'1)
3
4
5
Mean
Absorbance at
254nm (cm'1)
%RSD
(precision)
Method Blank
What was the average measurement of UV absorbance in your method blank during ^ the
determination of precision and accuracy? (Reference the above paragraph) cm'
What is your normal (non-ICR) minimum reporting limit for UV absorbance?
Briefly describe how the reporting limits were established?
cm
120
-------
Laboratory Name:
ICR Lab No.:
MDL: Using the minimum detection limit procedure described in the DBP/ICR Analytical Methods
Manual, Section 6, paragraph 4, enter in the table below, the data and the MDLs for this analysis.
uv
Cone, of
KHP(mg/L
as DOC)
Date of Analysis
of Replicate Sample
Analyzed Absorbance of Replicate Samples
(cm'1)
MDL
(cmj)
Although not specifically required, has this MDL been confirmed by analysis of a reagent
water spiked near the MDL? _ Yes _No
ADDITIONAL INFORMATION
What types of quality control checks are performed for this analysis?
At what concentration is the quality control check analyzed?.
Using this analytical method, how many samples per week can your laboratory analyze? _
List the personnel who will be performing this analysis for the ICR and list their duties.
Namfi Duties
/wk
121
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laboratory Name: ICK Z,afe Wo,:
ICR Method Approval; Total Hardness
DESCRIPTION: TMs analysis determines the tola! hardness concentration in water.
Which Total Hardness method is used in your laboratory?
SM2340B SM2340C Other
If "Other",
Does your lab have a written SOP
STATE APPROVALS
Is your laboratory certified or
samples using one
Total Hardness analyses on water
Yes Mo
ory may be performing tills
State Primacy Agency with only de
late approval. For purposes of Hie ICE,
e above if this is your circumstance.
If you
Caldi
3 to the above question, is your laboratory approved fey a State to perform
Ea53nBgฃ analyses on water samples;
Yซes No
iff your laboratory is State approved fer Calcium Hardness, identify Ihe method(s) for which your
laboratory is approved.
.EPA 215.1
.SM3111B
.ASTMB511-93B
JEPA200.7
SM3120B
.ASTMB511-93A
NOTE: You must submit Hie ICR "Verification of State Certification/Approval" fram
to EPA if yon are State approved for either Total Hardness or Calcium Hardness.
123
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Laboratory Name: ICR Lab No.:
ICR Method Approval: Ammonia
DESCRIPTION: This analysis determines the concentration of ammonia in water.
Which ammonia method is used in your laboratory?
_SM4500-NH3D _SM4500-NH3G _ EPA 350.1 _ 379-75 WE _ Other
(19th edition) (19th edition)
If "Other", please give the name, number or description of the method used by your laboratory.
\<
Does your lab have a written SOP
STATE APPROVALS
Is your laboratory
of the methods spec;
form this analysis on water samples using one
3S No
NOTEtJn soUe/-ctrcum$tarfces a laboratory may be performing this
iorting data to a State Primacy Agency with only de
facto, anM ijo^dbcumented, State approval. For the purposes of the
i^R, cjj*tjj/"yes" to the above question if this is your circumstance.
~-^^^^^~
If you responded "yes" to the above question, you need only submit the "Verification of State
Certffication/Approval" form to EPA You do not need to submit the rest of the information requested
in this application. If you responded "no", you must complete the remainder of this application.
125
-------
EQUIPMENT
Please list the equipment used in this analysis.
Manufacturer
Model & Serial #
SAMPLE HANDLING INFORMATION
Storage Temp: ฐC Maximum Holding Time: Days
Are samples acidified? _Yes _No; with
QC INFORMATION
What is your normal (non-ICR) minimum reporting limit for ammonia? mg/L
CALIBRATION CURVE
List the approximate concentrations (mg/L) of the calibration standards currently used to establish the
standard curve.
Ammonia
Std#l
Std#2
Std#3
Std#4
Std#5
Does this calibration provide you with a linear curve? Yes No
Was this curve generated by a data system or calibrated manually ?
PERFORMANCE EVALUATION
Has your lab analyzed EPA WP PE samples? _ Yes _ No. If yes, please list in the table below, the
concentrations reported to EPA, in mg/L, from the three most recent studies in which you participated.
Study#_
Date-
Study#_
Date:
Study*.
Date:
126
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Laboratory Name:
ICR JLab No.:
Initial Demonstration of Capability: Using the procedure outlined in the DBP/ICR Analytical
Methods Manual, Section 6, paragraphs 2 and 3, enter in the table below, the data, and resultant
calculated values, for your initial determination of precision and accuracy
Ammonia
Spike
Cone.
(mg/L)
Date of Analysis
of Replicate Sample
Concentration Determined in Replicate Samples
(mg/L)
1
2
3
4
5
Mean %
Recovery
(accuracy)
%RSD
(precision)
Method Blank
What was the average concentration in your method blanks during the determination of precision
and accuracy? (Reference previous paragraph) mg/L
ADDITIONAL INFORMATION
What types of quality control checks are performed for this analysis?
At what concentration is the quality control check analyzed?.
List the personnel who will be performing your analyses for the ICR and list their duties.
Name Duties
127
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Laboratory Name-.
ICR Lab No.:
ICR Method Approval: Bromide
DESCRIPTION: This analysis determines the concentration of bromide (Bf).
Which method is used in your laboratory for the analysis of bromide?
EPA 300.0 Other
If "Other", please give the name, number or description of the method used by yoMf^boratory,
Does your lab have a
.nass? Yes No
^-Y>U
Ion ChjphTatggfaph
Guard Column
Sample Storage Unit
Analytical Column
Detector(s)
Suppressor
Manufacturer
Model & Serial #
Type:
Type:
129
-------
ELUENTAJMD
Eluent
Suppressor Regenerant
Concentration (mM)
Mowiate
(mL/min)
Frequency
prepared
SAMPLE HANDLING INFORMATION
bottles
j sepia, liner,
-------
laboratory Mame:
Internal Standard
If an internal standard as used, please list fhe name of fee chemical, fee amount used, and fee
average recovery.
Nameofitaieai
Amount added
Average recovery
Method Blank
What was fee average concentration of bromide in your method blanks during fee determination
of precision and accuracy ? (Reference earlier paragraph.) mg/L
NOTE: Please attach an example chromatpgram of your method blank. (Be sure to
label the potential position of fhe mefliod analytes and detector attenuation.)
What Is your normal (non-ICR) mimm&m bromide reporting limit?
Briefly describe how fee reporting lignite were established.
MDL: Using the minimum detection lirmt procedure described in fee DBP/ICR Analytical Mefeods
Br-
Spike
Cone.
Dale of Analysis of
Replicate Sample
1
Cmjj/L)
2
3
4
5
6
7
MDI,
(mj^L)
1
Alfeough not speeificaHy retired, has feis MDL been confirmed
water spiked near fee MDL? Yes Mo
: Mease attach an example ctiromatogram from one of Hie above
determmations. Be sme to label each analyte,^mig its jretentlon time, concentration,
and detector attenuation.
131
-------
CALIBRATION CURVE
List the approximate concentrations (mg/L) of the calibration standards currently used to establish
the standard curve. (Note: The concentrations used to establish the calibration curve may be revised
for the ICR monitoring period.)
Br'
Std#l
Std#2
Std#3
Std#4
StdffS
Does this calibration provide you with a linear curve? Yes No
Was this curve generated by a data system or calibrated manually
ADDITIONAL, INFORMATION
What types of quality control checks are performed for this analysis?
Using this analytical method, how many samples per week can your laboratory analyze? /wk
List the personnel who will be performing your bromide analyses for the ICR and give their duties.
Name ', Duties
132
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Laboratory Name:
ICR Lab No.:
ICR Method Approval: Oxyhalides
DESCRIPTION: This analysis determines the concentration of the three oxyhalides, bromate
(BrCy), chlorate (C1O3"), and chlorite (C1O2'). If bromate is determined separately from chlorate and
chlorite, please indicate the differences in analytical conditions between the two analyses.
Which method is used in your laboratory for the analysis of the oxyhalides?
_ EPA 300.0 _ Other
If "Other", please give the name, number or description of the method u
is\nalysi$7__Yes No
Ion ChrbmattSgraph
Guard Column(s)
Concentrator Column
Analytical Column
Detector(s)
Suppressor
Sample Storage Unit
Manufacturer
Model & Serial #
Type:
Type:
Type:
133
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ELTJENT AND SUPPRESSOR REGENERANT INFORMATION
Eluent
Suppressor
Regenerant
Concentration (mM)
(N)
Flow rate (mL/min)
Frequency prepared
SAMPLE HANDLING INFORMATION
What is the sample container made from?
bottles
. septa, liner, or cap
Sample bottle volume? _
Storage Temp: ฐC
Maximum Holding Time:
Are samples preserved? _Yes _No; with
Sample injection volume (loop size)
\ (whichever contacts sample)
. Days
_mg/mL concentration in sample)
Describe any sample pretreatment steps used prior to injection into the 1C.
QC INFORMATION
Initial Demonstration of Capability: Using the procedure outlined in the DBP/ICR Analytical
Methods Manual, Section 6, paragraphs 2 and 3, enter in the table below, the data, and resultant
calculated values, for your initial determination of precision and accuracy.
CIO,'
BrO,'
CKV
Spike
Cone.
fag/L)
Concentration Determined in Replicate Samples
(MJ/L)
1
ii
Dote of Analysis R
2
3
4
5
'
Mean %
Recovery
(accuracy)
%RSD
(precision)
NOTE: Please attach an example chromatogram from one of these determinations.
Be sure to label each analyte, giving its retention time, concentration, and detector
attenuation.
134
-------
Laboratory Name:
Internal Standard
ICR Lab No.:
If an internal standard is used, please list the name of the chemical, the amount used, and the
average recovery.
Name of chemical
Amount added
Average recovery
Method Blank
What was the average concentration in your method blanks (in Mg/L) during the determination of
precision and accuracy? (Reference earlier paragraph)
C102-:.
BrCV:.
C1O3-:.
NOTE: Please attach an example chromatogram of your method blank. (Be sure to
label the potential position of the method analytes and detector attenuation.)
What is your normal (non-ICR) minimum reporting limit? 0/g/L)
CIO/: BrO3': C1CV:
Briefly describe how the reporting limits were established.
135
-------
MDL: Using the minimum detection limit procedure described in the DBP/ICR Analytical Methods
Manual, Section 6, paragraph 4, enter in the table below, the data! and the MDLs (A*g/L) for this
analysis.
cio,-
BKV
CIO,'
Spike
Cone.
(pg/L)
Concentration Determined in Replicate Samples
(M5/L)
1
Date of Analysis |
of Replicate Sample ||
2
3
4
5
6
7
MDL
fag/L)
1
Although not specifically required, have these MDLs been confirmed by analysis of a
reagent water spiked near the MDL? Yes _ No
NOTE: Please attach an example chromatogram from one of the above
determinations. Be sure to label each analyte, giving its retention tune, concentration,
and detector attenuation.
CALIBRATION CURVE
List the approximate concentrations (A^g/L) of the calibration standards currently used to establish
the standard curve. (Note: The concentrations used to establish the calibration curve may be revised
for the ICR monitoring period.)
CIO,'
BrO,'
CIO,'
Std#l
Std#2
Std#3
Std#4
Std#5
Does this calibration provide you with a linear curve? Yes _ No
Was this curve generated by a data system or calibrated manually
136
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Laboratory Name:
PERFORMANCE EVALUATION
ICR Lab No.
Has your lab analyzed EPA WS PE samples? _ Yes _ No. If yes, please list in the table
below, the concentrations reported to EPA, in Mg/L, from the three most recent studies in which
you participated.
CIO,'
BiO,"
cio,
Study# Date:.
Study# Date:.
Study# Date:
ADDITIONAL INFORMATION
What types of quality control checks are performed for this analysis?
Using this analytical method, how many samples per week can your laboratory analyze?
/wk
List the personnel who will be performing your oxyhalide analyses for the ICR and give their
duties.
Name
Duties
137
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139
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Environmental Protection Agency
APPENDIX B TO PART 13&DEFINITION
AND PROCEDURE FOR THE DETER-
MINATION OF THE METHOD DETEC-
TION LIMITREVISION 1.11
Definition
The method detection limit (MDL) is de-
fined as the minimum' concentration of a
substance that can be measured and reported
with 99% confidence that the analyte con-
centration is greater than zero and is deter-
mined from analysis of a sample in a given
matrix containing the analyte.
Scope and Application
This procedure is designed for applicability
to a wide variety of sample types ranging
from reagent (blank) water containing
analyte to wastewater containing analyte.
The MDL for an analytical procedure may
vary as a function of sample type. The proce-
dure requires a complete, specific, and well
defined analytical method. It is essential
that all sample processing steps of the ana-
lytical method be included in the determina-
tion of the method detection limit.
The MDL obtained by this procedure is'
used to Judge the significance of a single
measurement of a future sample.
The MDL procedure was designed for appli-
cability to a broad variety of physical and
chemical methods. To accomplish this, the
procedure was made device- or instrument-
independent.
Procedure
1. Make an estimate of the detection limit
using one of the following:
(a) The concentration value that cor-
responds to an instrument signal/noise in the
range of 2.5 to 5.
(b) The concentration equivalent of three
times the standard deviation of replicate in-
strumental measurements of the analyte in
reagent water.
(c) That region of the standard curve where
there is a significant change in sensitivity,
i.e., a break in the slope of the standard
curve.
(d) Instrumental limitations.
It is recognized that the experience of the
analyst is important to this process. How-
ever, the analyst must include the above
considerations in the initial estimate of the
detection limit.
2. Prepare reagent (blank) water that is as
free of analyte as possible. Reagent or inter-
ference free water is defined as a water sam-
ple in which analyte and interferent con-
centrations are not detected at the method
detection limit of each analyte of interest.
Interferences are defined as systematic er-
rors in the measured analytical signal of an
established procedure caused by the presence
of interfering species (interferent). The
interferent concentration is presupposed to
Pi. 136, App. B
be normally distributed in representative
samples of a given matrix.
3. (a) If the MDL is to be determined in re-
agent (blank) water, prepare a laboratory
standard (analyte in reagent water) at a con-
centration which is at.least equal to or in
the same concentration range as the esti-
mated method detection limit. (Recommend
between 1 and 5 times the estimated method
detection limit.) Proceed to Step 4.
(b) If the MDL is to be determined In an-
other sample matrix, analyze the sample. If
the measured level of the analyte is in the
recommended range of one to five times the
estimated detection limit, proceed to Step 4.
If the measured level of analyte is less
than the estimated detection limit, add a
known amount of analyte to bring the level
of analyte between one and five times the es-
timated detection limit.
If the measured level of analyte is greater
than five times the estimated detection
limit, there are two options.
(1) Obtain another sample with a lower
level of analyte in the same matrix if pos-
sible.
(2) The sample may be used as is for deter-
mining the method detection limit if the
analyte level does not exceed 10 times the
MDL of the analyte in reagent water. The
variance of the analytical method changes as
the analyte concentration increases from the
MDL, hence the MDL determined under
these circumstances may not truly reflect
method variance at lower analyte concentra-
tions.
4. (a) Take a minimum of seven aliquots of
the sample to be used to calculate the meth-
od detection limit and process each through
the entire analytical method. Make all com-
putations according to the defined method
with final results in the method reporting
units. If a blank measurement is required to
calculate the measured level of analyte, ob-
tain a separate blank measurement for each
sample aliquot analyzed. The average blank
measurement is subtracted from the respec-
tive sample measurements.
(b) It may be economically and technically
desirable to evaluate the estimated method
detection limit before proceeding with 4a.
This will: (1) Prevent repeating this entire
procedure when the costs of analyses are
high and (2) insure that the procedure is
being conducted at the correct concentra-
tion. It is quite possible that an inflated
MDL will be calculated from data obtained
at many times the real MDL even though the
level of analyte is less than five times the
calculated method detection limit. To insure
that the estimate of the method detection
limit is a good estimate, it is necessary to
determine that a lower concentration of
analyte will not result in a significantly
lower method detection limit. Take two
aliquots of the sample to be used to calculate
the method detection limit and process each
141
-------
Pf. 136, App. B
through the entire method, including: blank
measurements as described above in 4a.
Evaluate these data:
(1) If these measurements indicate the
sample is in desirable range for determina-
tion of the MDL, take five additional
aliquots and proceed. Use all seven measure-
ments for calculation of the MDL.
(2) If these measurements indicate the
sample is not in correct range, reestimate
the MDL, obtain new sample as in 3 and re-
peat either 4a or 4b.
5. Calculate the variance (S2) and standard
deviation (S) of the replicate measurements,
as follows:
n-1
where:
Xt; i=l to n, are the analytical results in the
final method reporting units obtained
from the n sample aliquots and Z refers
to the sum of the X values from 1=1 to n.
6. (a) Compute the MDL as follows:
MDL
- o.ป)
(S)
where:
MDL = the method detection limit
t3.05, respike at the most recent
calculated MDL and process the samples
through the procedure starting with Step
4. If the most recent calculated MDL
does not permit qualitative identifica-
tion when samples are spiked at that
level, report the MDL as a concentration
between the current and previous MDL
which permits qualitative identification.
(c) Use the Spooled as calculated in 7b to
compute the final MDL according to the fol-
lowing equation:
MDL=2.681 (Spo,**)
where 2.681 is equal to tot i-a =.w).
(d) The 95% confidence limits for MDL de-
rived in 7c are computed according to the
following equations derived from precentiles
of the chi squared over degrees of freedom
distribution.
LCL=0.72 MDL
UCL=1.65 MDL
where LCL and UCL are the lower and upper
95% confidence limits respectively based on
14 aliquots.
TABLES OF STUDENTS' t VALUES AT THE 99
PERCENT CONFIDENCE LEVEL
Number of replicates
7
8 ,
9 .
10 , ..
11 . . ... .. .
16
21
26
31
61
00
Degrees
offree-
dom (n-1)
6
7
8
9
10
15
20
25
30
60
00
W .99)
3143
2.998
2.896
2.821
2.764
2602
2.528
2485
2.457
2.390
2.326
Reporting
The analytical method used must be spe-
cifically identified byinumber or title aid the
MDL for each analyte expressed in the ap-
propriate method reporting units. If the ana-
lytical method permits options which affect
the method detection limit, these conditions
must be specified with the MDL value. The
sample matrix used to determine the MDL
must also be identified with MDL value. Re-
port the mean analyte level with the MDL
and indicate if the MJDL procedure was iter-
142
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Environmental Protection Agency
ated. If a laboratory standard or a sample
that contained a known amount analyte was
used for this determination, also report the
mean recovery.
If the level of analyte in the sample was
below the determined MDL or exceeds 10
times the MDL of the analyte in reagent
water, do not report a value for the MDL.
[49 FR 43430, Oct. 26, 1964; SO FR 694. 696, Jan.
4, 1965, as amended at SI FR 23703, June 30,
1986]
U.S. Government Printing Office: 1996 - 752-090/49037
143
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