United States
Environmental Protection Office of Water EPA 814/P-94-001
Agency 4601 January 1994
DBP/ICR ANALYTICAL
METHODS GUIDANCE MANUAL
PUBLIC COMMENT DRAFT
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DBP/ICR Analytical Methods Guidance Manual
Table of Contents
Section Title Page
I. Introduction 2
II. Laboratory Quality Assurance Plan 5
III. Registration of Laboratories Performing
Analyses for the DBP/ICR 8
IV. Laboratory "Approval" Process 10
V. Approved Methods for DBP/ICR Monitoring . . 11
VI. Initial Demonstration of Laboratory's
Ability to Perform DBP/ICR Analyses that
Require EPA "Approval" 16
VII. Minimum Reporting Levels 19
VIII. Performance Evaluation (PE) Studies .... 21
IX. Quality Control Requirements 24
X. Quality Control Reporting Requirements. . . 42
XI. Laboratory Evaluation During DBP/ICR
Monitoring Period 45
Appendices
A. Draft Laboratory Registration Form
and Approval Verification Form 46
B. Draft Application Forms for Laboratory
Approval 50
C. Proposed Method for Measuring UV
Absorbing Organic Constituents 86
D. Proposed Method for Measuring Aldehydes . . 99
E. Definition and Procedure for the
Determination of the Method Detection
Limit-Revision 1.11 (CFR Pt. 136, App. B) . 115
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Section Z. Introduction
Background on the Information Collection Rule (ICR)
The Environmental Protection Agency (EPA) instituted a
formal regulation negotiation process in 1992 to develop the
Disinfectant/Disinfection By-Product (D/DBP) Rule.1 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 by-
products (D/DBPs) in drinking water could result in increasing
risk of waterborne disease from pathogens. In order to balance
the risks from pathogens and chemicals, the Advisory Committee
made several recommendations and the final result was the
development of three new drinking water regulations.
The D/DBP Rule was the primary rule negotiated. The
Advisory Committee recommended a two step approach to regulating
the D/DBPs with the first stage of the regulation coinciding with
a regulation to ensure microbial safety of the water. The
Stage 1 D/DBP Rule: 1) sets limits on the amount of
disinfectants allowed in drinking water; 2) reduces the limits
on total trihalomethanes (TTHMs) from 100 pg/L to 80 ng/L; 3)
sets limits on additional DBFs (sum of five haloacetic acids
[HAAS], chlorite, and brornate); 4) requires the use of enhanced
coagulation by utilities treating surface water containing total
organic carbon (TOC) concentrations above certain levels; and 5)
applies to all community and nontransient noncommunity water
systems.
The second rule developed during the negotiation process is
the Enhanced Surface Water Treatment Rule (ESWTR). It specifies
levels of treatment to control for pathogens in drinking water
based on microbial quality of the source water. This rule would
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 Requirements (ICR) rule.
This rule addresses data needs in three areas. The most critical
element of the ICR involves the collection of data on the
concentrations of specific microbes (including Cryptosporidium,
Giardia Iambila, and total culturable viruses) in surface water
that is treated to produce drinking water. Monitoring for
microbes in the drinking water is also being required of certain
systems. Information concerning treatment processes being used
to control for pathogens will be collected in conjunction with
the microbial monitoring data. The data from this Micro/ICR will
be used in the development of the ESWTR.
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The second element of the ICR involves the collection of
treatment plant operational data and monitoring of the source
water and drinking water for general water quality
characteristics, DBFs, and surrogates for DBFs and DBF
precursors. These data from the DBF/ICR will be used to: 1)
characterize the source water parameters that influence DBF
formation; 2) determine concentrations of DBFs in drinking
water; 3) refine models for predicting DBF formation; and 4)
establish cost-effective monitoring techniques. Development of
the Stage 2 D/DBP rule is dependent upon analyses of these data.
The third element of the ICR involves a requirement for some
systems to conduct bench or pilot scale studies on DBF precursor
removal using either granular activated carbon or membrane
filtration. The purposes of these Precursor Removal/ICR studies
are: 1) to obtain more information on the cost effectiveness of
these technologies for reducing DBF levels; and 2) to decrease
the time systems would need in order to install such technology,
if it was required under a Stage 2 D/DBP rule.
Ensuring Data Quality for the DBF/ICR
One of the major issues during development of the DBF/ICR
concerned the quality of the data that would be generated during
the monitoring period. The Advisory Committee recognized that
the data must be both accurate and precise in order to meet the
DBP/ICR objectives. Everyone realized the difficulty in ensuring
data quality considering that the data are to be generated by
many laboratories. Maintaining data comparability between
laboratories would be necessary in order to use the data for
sophisticated correlational analyses and to have data that are
useful for predicting DBF formation as a function of water
quality conditions. The Advisory Committee felt that the only
way to ensure useable data is for EPA to assist the drinking
water industry in identifying qualified laboratories for
performing the analyses required by the DBP/ICR.
In August of 1993, EPA convened a technical workgroup to
assist in developing approaches for ensuring analytical data
quality. Representatives from utility, state and commercial
laboratories were present at the two day meeting. Persons were
invited to this meeting based on their expertise in one or more
of the following areas: 1) analyzing for DBFs; 2) day-to-day
management of laboratory operations; and 3) drinking water
laboratory certification programs.
The technical workgroup made several general recommendations
on approaches to ensure data quality. EPA used the workgroup's
recommendations as a basis for developing this manual. However,
the workgroup has not yet had the opportunity to review the
specifics that are outlined in this document. Therefore,
although EPA used the workgroup discussions as a starting point,
some of the details may deviate from the initial workgroup
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discussion as a result of follow-up discussions within EPA. The
workgroup will have the opportunity to assist EPA in revising
this manual to ensure it meets the goal of providing practical
criteria for establishing and maintaining a group of laboratories
capable of providing accurate and precise data for the DBP/ICR.
The public also has the opportunity to assist in this process by
providing public comments directly to EPA at the following
address:
ESWTR/DBPR Monitoring Docket Clerk
Water Docket (MC-4101)
U.S. Environmental Protection Agency
401 M Street, SW
Washington, DC 20460
Duplicate copies of public comments on this manual can also
be sent to the address listed below:
U.S. Environmental Protection Agency
Office of Ground Water and Drinking Water
Technical Support Division
Attn: DBP/ICR Analytical Methods Guidance Manual
26 West Martin Luther King Drive
Cincinnati, OH 45268
1. 57 FR 53866, November 13, 1992,
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Section ZZ. Laboratory Quality Assurance Plan
All laboratories analyzing samples for the ICR will be
required to adhere to defined quality assurance procedures to
ensure that generated analytical data are scientifically valid
and are of known and acceptable precision and accuracy. To
facilitate the accomplishment of these goals, each laboratory
must have a written description of its quality assurance
activities, a QA plan, describing the QA management of day to day
routine operations. The plan must be available for inspection
for ICR laboratory approval and during the time which the
laboratory is performing ICR measurements.
The laboratory's QA plan should be a separately prepared
text. However, documentation for some of the listed QA plan
items can be made by reference to appropriate documents, such as
the laboratory's SOPs, EPA Methods, or to other literature (e.g.,
Standard Methods for the Examination of Water and Wastewater).
For the ICR data, the laboratory may use its current QA Plan with
items pertinent only to the ICR in an addendum. This addendum
must contain all the QC criteria for activities relating to ICR
measurements.
The following items should be addressed in each 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 QC measurements
specify who is responsible for internal audits and
reviews of the implementation of the QA plan and
its requirements.
describe training available to keep personnel up
to date on regulations, methods and/or TQM.
2. Field sampling procedures
— who collects, how collected, preservation,
containers, holding times, transport to lab
— documentation
3. Laboratory sample handling procedures
bench sheets used
storage; temperature, isolated from standards and
highly contaminated samples
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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
standards; source, age, storage, labeling
comparability checks
5. Analytical procedures
reference method used
consistent with ICR Reg
SOP available
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; ICR QC requirements have been met
reporting; includes procedures and format for
reporting data to utilities/EPA
7. Types of quality control (QC) checks and frequency of
their use
laboratory performance check standard
MDL generation; acceptable, frequency
internal standards and surrogate standards
blanks; field, method, frequency
replicate analyses; frequency
QC samples external to ICR; source, frequency
PE samples
spikes
IDC and control charts
8. Preventive maintenance procedures and schedules
manuals available
spare parts inventory
schedule
documentation
9. Corrective action contingencies
response to obtaining unacceptable results from
analysis of PE samples and from internal QC
checks.
who is responsible
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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
A laboratory QA plan should be concise but responsive to the
above-listed items. Minimizing paperwork while improving
dependability and quality of data are the intended goals.
"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 a QA plan for the ICR. It can be
obtained by calling the Center for Environmental Research
Information at 513-569-7562. Not all of the above sections are
described in the project plan guidance (i.e. laboratory sample
handling and record keeping) and the goals of a lab QA Plan in
general are differrent from the goals of a QAPP. The former
describes QA Management of day to day routine operations and the
latter describes goals, interactions and procedures for a
specific project. By adding to the QA lab plan what will be done
to meet ICR criteria the lab will develop a Project Plan for the
ICR responsibilities.
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Section III. Registration of Laboratories Performing Analyses
for the DBP/ICR
Analyses for the DBP/ICR must be performed by laboratories
that are capable of producing accurate and precise data. EPA
will use two approaches for ensuring that only qualified
laboratories conduct measurements for this monitoring rule. The
first approach involves the registration of all laboratories that
plan to perform analyses for the DBP/ICR. (A draft registration
form is included in Appendix A. A final version will be
available prior to the initiation of the registration procedure.)
The second approach involves a special approval process for
laboratories that will be performing analyses that are not
currently required under other drinking water regulations.
Several of the analyses that are required for the DBP/ICR
are currently required under other drinking water regulations.
As a result, mechanisms for reviewing laboratory qualifications
are already in place for these measurements.
Trihalomethane (THM) analyses for monitoring compliance with
the THM Rule must be conducted by laboratories that are certified
by a State Primacy Agency for drinking water. In order 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, 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
DBP/ICR as long as the laboratory uses the same method for which
it is certified.
All laboratories that perform THM analyses for the DBP/ICR
will be required to participate in the special DBP/ICR
Performance Evaluation (PE) Studies (see Section VIII) that are
planned on a quarterly basis during the monitoring period. They
will also be required to follow the quality control requirements
described in Section IX. Therefore, even though laboratories are
certified to perform THM analyses, they will be required to meet
additional requirements during the DBP/ICR monitoring period, if
they perform analyses for the DBP/ICR. (These additional
requirements will be separate from the certification process.)
Measurements for pH, alkalinity, turbidity, temperature,
calcium hardness and disinfectant residuals are also required in
order to meet current drinking water regulations. These analyses
must be performed by parties that have been approved by a State.
If a laboratory demonstrates it is currently approved by a State
to perform these analyses, then it will be allowed to perform the
same analyses for the DBP/ICR.
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Laboratories will be required to document their State
Certification or Approval by completing a Certification and/or
State Approval Form. (A draft version is included in
Appendix A.)
Analyses for the remainder of the DBP/ICR analytes will be
made by laboratories that have passed an EPA evaluation process
and are thereby "approved" to perform these analyses. The
"approval" process is discussed in Section IV of this manual.
Laboratories that plan to analyze for THNs using EPA Method 551
are required to receive "approval" from EPA prior to the DBP/ICR
monitoring.
All laboratories that perform analyses for the DBP/ICR will
be assigned unique identification (ID) numbers or codes. The
laboratory ID will be reported with the monitoring data so that
laboratory precision and accuracy data can be associated with the
monitoring data in the ICR database.
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Section IV. Laboratory Approval Process
Laboratories that register with EPA to perform DBP/ICR
analyses that are not covered under other drinking water
regulations, will be required to pass a review process prior to
being given "approval" to perform analyses for the DBP/ICR. EPA
will request information from the laboratory concerning each
method for which they want "approval." On a method by method
basis, the laboratory will list all personnel involved in the
analysis and their qualifications. The laboratory will also
specify the equipment used for the analysis and the general
sample handling protocols. Draft versions of the forms to be
used in reporting the applicable information are included in
Appendix B. (Final versions of these forms will be available
prior to-initiation of the "approval" process. Note: The
appendix does not contain forms for aldehyde and cyanogen
chloride methods, because EPA is proposing to conduct those
measurements for the water utilities.)
Laboratories will be required to meet specific precision and
accuracy requirements for each method for which they are seeking
"approval." Data from method detection limit (MDL) and initial
demonstration of capability (IDC) determinations will be
submitted to EPA in conjunction with the "approval" application
forms. Laboratories will also report historical Performance
Evaluation (PE) study data for each DBP/ICR method and study in
which they participated.
Laboratories that have met the necessary precision and
accuracy requirements as demonstrated by their MDL, IDC, and
historical PE study data, will be included in a special DBP/ICR
PE study prior to the initiation of the monitoring period. This
study will be separate from the routine Water Supply PE Studies
conducted by EPA. Laboratories will be required to pass at least
one PE study prior to being "approved." (MDLs, IDCs, and PE
studies are discussed in Sections VI and VIII of this manual.)
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Section V. Approved Methods for DBP/ICR Monitoring
The technical workgroup that EPA convened to assist in
developing approaches for ensuring analytical data quality for
the DBP/ICR strongly recommended that EPA require the use of
specific methods for the analysis of the DBP/ICR analytes. These
methods are summarized in Table V.I of this section.
The protocols for two analyses that are being required as
part of the DBP/ICR have not been published yet. In fact, when
DBP/ICR monitoring was first proposed by the Negotiating Advisory
Committee, no written methods were available for measuring
ultraviolet absorbance at 254 ran (UV^) and aldehydes. However,
two Joint Task Groups (JTGs), one for UV absorbing organic
constituents and one for ozonation byproducts: aldehydes, were
developing proposed methods for inclusion in the 19th Edition of
Standard Methods for the Analysis of Water and Wastewater. Their
methods were based on the experience of several laboratories
around the country.
During the last few months, both JTGs have been successful
in obtaining consensus within their groups on the UV and aldehyde
methods. Neither of these methods have been balloted by the full
Standard Methods Committee, so they are subject to further
revision prior to their inclusion in Standard Methods.
EPA has reviewed the draft methods for.UV absorbing organic
constituents (proposed Standard Method 5910) and for aldehydes
(proposed Standard Method 6252) and is recommending their use for
monitoring under the DBP/ICR. Draft versions of these methods
are included in Appendices C and D of this manual. Public
comments on either of these methods will be shared with the JTGs
who were responsible for their development.
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Table V.I Analytical Methods Approved for Monitoring Rule
Analyte
pH
Alkalinity
Turbidity
Temperature
Calcium Hardness
Free Residual Chlorine
Total Residual Chlorine
Chlorine Dioxide
Residual
Ozone Residual
Chloroform
Bromodichloromethane
Dibromochloromethane
Methodology
40 CFR
Reference1
141.74(a)(7),
141.89(a)
141.89(a)
141.22(a) ,
141.74(3) (4)
141.74(a)(6),
141.89(a)
141.89(a)
141.74(a) (5)
141.74(a)(5)
141.74(a)(5)
141.74(a) (5)
141 Subpt C,
App. C (EPA
Methods 501.1
& 501.2)
141 Subpt C,
App. C (EPA
Methods 501.1
& 501.2)
141 Subpt C,
App. C (EPA
Methods 501.1
& 501.2)
EPA
Method
180. 13
200. 74
502.2s,
52 4. 2s'6,
5517-8
502.2s,
524. 2s-6,
5517-'
502.2s,
524.2s-6,
5517-'
Standard
Method2
4500-H+
2320 B
2130 B
2550 B
3111 B,
3120 B,
3500-Ca D
4500-C1 D,
4500-C1 F,
4500-C1 G,
4500-C1 H
4500-C1 0,
4500-C1 E,
4500-C1 F,
4500-C1 G,
4500-C1 I
4500-ClOj
C, 4500-
C1O2 D,
4500-C102 E
4500-O, B
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Analyte
Bromoform
Monochloroacetic Acid
Dichloroacetic Acid
Trichloroacetic Acid
Monobromoacetic Acid
Dibromoacetic Acid
Bromochloroacetic Acid
Chloral Hydrate
Trichloroacetonitrile
Dichloroacetonitrile
Br omoch lor oacet on i tr i le
Dibromoacetonitrile
1, 1-Dichloropropanone
1,1,1-
Tr ichloropropanone
Chloropicrin
Chlorite
Chlorate
Bromide
Bromate
Cyanogen Chloride
Aldehydes
Total Organic Halide
(TOX)
Methodology
40 CFR
Reference1
141 Subpt C,
App. C (EPA
Methods 501.1
& 501.2)
EPA
Method
502.2s,
524.2s-6,
5517-»
552. 16
552.1*
552. 16
552. 16
552 . 16
552. 16
5517
5517-8
5517-»
5517-'
5517-«
5517-"
5517-'
5517-8
3 00. OB10
3 00. OB10
300.0A10
3 00. OB10
modified
524.2"
Standard
Method2
6233 B
6233 B
6233 B
6233 B
6233 B
6233 B9
6252 (draft
method
submitted
to 19th
Edition)
5320 B
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13
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Analyte
Total Organic Carbon
UV absorbance at 254 nm
(UV2S4)
Simulated Distribution
System Test (SDS)
Total Hardness
Ammonia
Oxidant
Demand/ Requirement
(optional)
AOC/BDOC (optional)
« Methodology
40 CFR
Reference1
EPA
Method
Standard
Method2
5310 C,
5310 D
5910 (draft
method
submitted
to 19th
Edition)
5710 E
2340 B,
2340 C
4500-NHj D,
4500-NH, F
2350 B,
2350 C,
2350 D
9217 B/
Currently approved methodology for drinking water compliance
monitoring is listed in Title 40 of the Code of Federal
Regulations in the sections referenced in this column.
Standard Methods for the Examination of Water and
Wastewater, 18th ed., American Public Health Association,
American Water Works Association, Water Pollution Control
Federation, 1992.
"Methods of Chemical Analysis of Water and Wastes," EPA
Environmental Monitoring Systems Laboratory, Cincinnati, OH
EPA-600/4-79-020, Revised March 1983.
Methods tor the Determination of Metals in Environmental
Samples. Available from National Technical Information
Service (NTIS), U.S. Department of Commerce, Springfield,
Virginia, PB91-231498, June 1991.
USEPA, "Methods for the Determination of Organic Compounds
in Drinking Water," EPA/600/4-88/039, PB91-231480, NTIS,
December 1988 (revised July 1991).
USEPA, "Methods for the Determination of Organic Compounds
in Drinking Water - Supplement II," EPA/600/R-92/129, PB92-
207703, NTIS, August 1992.
USEPA, "Methods for the Determination of Organic Compounds
in Drinking Water - Supplement I," EPA/600/4-90-020, PB91-
146027, NTIS, July 1990.
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8 Pentane may be used as the extraction solvent for this
analyte, if the quality control criteria of the. method are
met.
9 This analyte is not currently included in the method. The
method is being revised for the 19th edition of Standard
Methods and it will include this analyte. Data
demonstrating that it can be added to the method are
presented in Barth, R.C. & P.S. Fair, "Comparison of the
Microextraction Procedure and Method 552 for the Analysis of
HAAs and Chlorophenols," Journ. JWWA, 84:11:94 (Nov. 1992).
10 USEPA, "Methods for the Determination of Inorganic
Substances in Environmental Samples," EPA/600/R/93/100,
PB94-121811, NTIS, August 1993.
11 Flesch, J.J. & P.S. Fair, "The Analysis of Cyanogen Chloride
in Drinking Water," Proceedings of AWWA Water Quality
Technology Conference, Nov 1988.
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Section VI. Initial Demonstration of Laboratory's Ability to
Perform DBP/ZCR Analyses That Require EPA "Approval11
This 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 program. These determinations
are unique to the operator/instrument and must be done for each
operator/instrument to be used in the ICR. Prior to doing these
determinations, the analyst must be thoroughly familiar with the
method.
Data from these determinations will be reported to EPA as
part of the laboratory approval application package. The
approval form for each method (or set of analytes) provides the
format for reporting.these data. (See Appendix B for draft
versions of the approval forms.)
l. Initial Demonstration of Low System Background - Analysis of
a Laboratory Reagent Blank should verify that no
contamination exists above ^ the minimum reporting levels
(Table VI.1) for the analytes of interest.
2. Initial Demonstration of Accuracy - Calibrate the instrument
as directed in the method. Analyze a quality control sample
obtained from an outside source. Recovery should be within
± 20% of the true value. Average recovery of the replicates
in step 3 should also be within i 20% of the expected
amount.
3. Initial Demonstration of Precision - Analyze a total of five
replicates of reagent water fortified at the concentration
listed in Table VI.1 for each analyte of interest on five
separate days (i.e. one per day for five days). Each
replicate should be processed (e.g., extracted) and analyzed
on the same day. The relative standard deviation should be
no greater than 20%. (EPA is evaluating whether precision
criteria should be specified on a method by method basis.)
4. Method Detection Limit (HDL) Determination - Laboratories
must calculate their Method Detection Limits for each
analyte according the procedure in CFR S136 Appendix B once
per year (a copy of the procedure is included in Appendix E)
a. All sample processing steps should be included in
the determination. Analyses should be conducted
over several days.
b. Estimate the detection limit at 2-5 times the
instrument signal to noise level. Analyze a total
of seven replicates of reagent water fortified to
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a concentration in the range of the estimated
detection limit but no more than 25% of the
minimum reporting levels (MRLs) listed in Table
VI. 1.
Calculate the MDL for each analyte according to
the formula listed in CFR §136 Appendix B. Do not
subtract the blank value as suggested in the
procedure.
After determining the MDL according to the
procedure, analyze five replicates of reagent
water fortified to a concentration of % the MRL to
verify that this level can determined within ± 50%
of the expected value.
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Table VI.1. Laboratory Performance Assessment Requirements
Method/Ana lyte(s)
551/THMs
551 /HANS, HKs, CP
551/CH
552.1, 6233B/HAAS
300.0B/C1
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Section VIZ. 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, then concentrations are not reported below the
level at which the necessary precision and accuracy is achieved.
Based on the expertise of chemists from several laboratories
that are experienced with DBF analyses, minimum reporting levels
(MRLs) were determined for the DBP/ICR. A list of MRLs is
presented in Table VII.1. All laboratories performing analyses
for the DBP/ICR must be able to accurately and precisely measure
the analytes at these levels. (A discussion of the accuracy and
precision requirements is included in Section IX.)
EPA recognizes that some laboratories are able to provide
accurate and reliable data at concentrations lower than those
shown in Table VII.1. However, in order to achieve consistency
in the ICR database, laboratories will only be required to report
quantitative results for concentrations above the MRLs. The
laboratory may report lower concentrations to the utility, but
only concentrations equal to or greater than the MRLs will be
entered into the ICR database.
Laboratories must demonstrate that they can achieve reliable
data at the minimum reporting level (MRL) for each analyte.
Therefore, the concentration of the lowest standard in the
calibration curve should be at the MRL.
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Table VII.1. Minimum Reporting Levels (MRLs) for the DBP/ICR
Method
501.1, 501.2, 502.2, 524.2, &
551-THMs
551-nonTHMs
552.1, 6233 B
300. OB
300. OA
Aldehydes
CNC1
TOC
UV254
TOX
MRL
1 /xg/L for each THM
0.5 jtg/L for each analyte
1 pg/L for each HAA
20 jtg/L for C102- & C1O3-
5 jig/L for BrO3'
0.02 mg/L for Br~
5 pg/L
0.5 pg/L
0.5 mg/L
0.009 cm'1
50 jtg Cl'/L
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Section VZZZ. Performance Evaluation (PE) Studies
Laboratories that apply for "approval" to perform analyses
for the DBP/ICR will be required to pass at least one
Performance Evaluation (PE) Study sample for each method for
which the laboratory is seeking approval. Laboratories will not
receive "approval" until this requirement is met. EPA will
conduct a special DBP/ICR PE Study prior to the beginning of the
DBP/ICR monitoring period. Laboratories can participate in the
special study or they can use data from past PE studies.
Historical performance in PE studies will satisfy this
requirement if the laboratory had satisfactory performance on at
least two of three PE samples analyzed by the method in question,
one of the samples was analyzed after June, 1993, and the last PE
sample was satisfactorily analyzed. Satisfactory performance is
defined as meeting the acceptance criteria listed in Table
VIII.1. (These criteria are different from the acceptance
criteria that were applied to the data from past PE studies.)
In addition, to the requirement to pass a PE sample prior to
"approval," laboratories will be required to analyze PE samples
on a quarterly basis for some methods during the DBP/ICR
monitoring period. This requirement applies to laboratories
using the following methods: 501.1, 501.2, 502.2, 524.2, 551,
552.1, 6233 B, 300.0, TOX, TOG, and UVj*. Laboratories must meet
the acceptance criteria listed in Table VIII.1 for each method
they are using for the DBP/ICR. (Acceptance criteria for THMs
may be different from the criteria that laboratories must meet
for certification in some states.) 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. This will allow the laboratories to quickly
demonstrate correction of the analytical problems in order to
restore confidence in the data being generated in their
laboratory. A laboratory that fails two consecutive PE samples
for the same method will not be allowed to continue performing
that analysis for ICR monitoring until successful performance is
demonstrated during later PE studies.
Laboratories that perform the other DBP/ICR analyses (pH,
alkalinity, turbidity, calcium hardness, total hardness, ammonia,
and disinfectant residuals) must analyze and pass a PE sample
annually. PE samples for these analytes can be obtained as part
of the routine EPA Water Supply (WS) or Water Pollution (WP)
Series PE Studies. Acceptance criteria for these analyses are
listed in Table VIII.1.
DBP/ICRmanual-l/28/94draft 21
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Table VIII.1 PE Acceptance Criteria for Initial and Continuing
DBP/ICR Laboratory Approval
ICR Parameter
(# of cpds)
Alkalinity
Ammonia
Bromide
Chloral Hydrate
Chlorine - Combined
Chlorine - Free
Chlorine - Total
Haloacetic Acids (6)
Haloacetonitriles (4)
and Haloketones (2)
Hardness - Calcium
Hardness - Total
oxyhalides (3)
pH
Trihalomethanes (4)
TOC
TOX
Turbidity
UV Absorbance at 254nm
Pass Criteria
(% of True
Value)
±15% (I>
±30% «
±35% m
±40% 0)
NONE
±30% <»
±30% <»
±40% for
each cpd ^
±40% for
each cpd 0)
±10% (1)
±20% (I)
±40% for
each ion 0)
±5% «
±20% for
each cpd (4)
±25% m
±25% m
±20% (1)
±25% (S>
Minimum # of cpds
passing
4 of 5 cpds
(excluding MCAA)
4 of 5 cpds
(excluding TCAN)
3 of 3 ions
3 of 4 cpds
0) These values represent the maximum 2S (as % relative standard
deviation) determined from at least 4 EMSL WS/WP PE studies.
® The listed value was derived from laboratory performance data
given in the method, ASTM laboratory studies and/or EPA PE
studies
DBP/ICRmanual-l/28/94draft
22
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0> These values were established by recommendation of technical
workgroup.
(4) EMSL criterion for TTHMs
(5) Determined from interlaboratory data given in SM 5910. The
value given represent twice the maximum %RSD for absorbances
>0.014 cm'1 at 254nm for KHP concentrations from 0.93 to 100 mg/L
(as DOC).
DBP/ICRmanual-l/28/94draft 23
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Section ZZ. Quality Control Requirements
Laboratories that perform analyses for the DBP/ICR are
required to use the methods that are specified in the ICR. (See
Section V of this manual for a listing of the methods.) These
methods specify quality control (.QC) procedures which must be
followed in order to ensure accurate and precise data.
Descriptions of the QC procedures and the frequencies for
performing the QC measurements vary among methods. In an effort
to standardize the requirements and to obtain consistent
applications of QC protocols by the laboratories performing
analyses for the DBP/ICR, the frequency of performing QC analyses
are specified for the ICR. These frequencies are listed in Table
IX.1.
Many of the methods that are specified in the ICR provide
criteria to be used for evaluating and accepting laboratory
performance based on the QC data. Some of the QC procedures
required by the ICR are not specifically addressed in the
methods, and, in order to meet the ICR objectives, some of the QC
data must meet requirements that are different from those
described in the methods. Therefore, a listing of the criteria
that must be met for the various QC procedures specifically
required by the ICR is also presented in Table IX.1.
Descriptions of the various QC procedures and the rationale
for the the acceptance criteria are described below.
Verify calibration
Each method describes calibration procedures that are used
to determine the concentrations of the method analytes. Some
methods allow several options: 1) a calibration curve based on
either external standards or detector responses to the analyte
relative to an internal standard; 2) an average response factor
for each analyte; or 3) a single point calibration. The mass
spectrometer method has specific tuning criteria that must be met
prior to performing the calibration procedure. 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.
Many of the methods do not require daily calibration of the
instrument. Instead, the analyst must periodically verify the
calibration. The methods vary in the frequency at which
calibration must be checked. In order to meet the objectives of
the ICR, EPA is defining specific frequencies at which the
instrument calibration must be verified. These frequencies are
listed in Table IX.1.
Most of the methods recommend checking the instrument
calibration using a mid-level calibration standard. The method
DBP/lCRnanual-l/28/94draft 24
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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. EPA is requiring laboratories to verify the
instrument calibration at the beginning of each 24 hour period by
analyzing the lowest concentration standard. Additional
calibration checks over the course of each 24 hour period are to
be made by rotating between a mid-level and an upper-level
calibration standard. Concentrations for these three standards
are summarized in Table IX.2. All calibration check standards
must be aqueous standards that are carried through the sample
preparation procedure prior to the instrumental analysis.
The instrument calibration must meet the acceptance criteria
listed in Table IX.1 for the lowest concentration standard prior
to the analysis of any samples. If the criteria cannot be met,
after all sources of problems are eliminated, then a new
instrument calibration must be performed according to one of the
method calibration procedures. (EPA is evaluating whether the
precision and accuracy criteria for the lowest concentration
standard should be the same as for the mid- and upper-level
calibration standards.)
Mid- and upper-level calibration standards must be
intersperced with samples at the frequency listed in Table IX.1.
The instrument calibration must meet the acceptance criteria
listed in Table IX.1 for these standards. 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 after the problem with calibration is
resolved.
Laboratory Reagent Blank (Method Blank)
All of the methods approved for DBP/ICR monitoring require
periodic analysis of a laboratory reagent or 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.
There are several types of blanks specified in the TOX
method and two of them will be required for the DBP/ICR. The
method blank is determined through the analysis of 40 mg of
nitrate-washed carbon. Analysis of reagent water is defined as
the system blank.
The frequency of the laboratory reagent blank analysis
depends upon the type of sample manipulation required prior to
the instrumental analysis. Methods that involve extraction of
DBP/ICRmanual-l/28/94draft 25
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the sample usually stipulate analysis of a laboratory reagent
blank with each set of samples that are extracted together. When
the samples are analyzed using a purge and trap methodology, then
a check for interferences or contamination is made on a daily
basis. In order to meet the' objectives of the ICR, laboratories
will be required to analyze a method blank with each batch of
samples for most of the methods. A sample 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 bottle of extracting solvent,
internal standard spiking solution, and surrogate standard
spiking 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.
Ideally, the level of background interferences or
contamination should be zero. Some methods provide general
guidance by stating that background should be below the method
detection limit for each analyte. Other methods state that the
background should not prevent the determination of an analyte.
The general goal is to be sure that the background levels are low
enough that they do not interfere with an accurate measurement.
The laboratory reagent blank should be analyzed as the first
sample on the instrument (prior to the calibration standard). If
any of the method analytes are detected at a concentration equal
to or greater than half of the lowest calibration standard, 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.
Field Reagent Blank (Shipping Blank or Travel Blank)
Five of the DBF/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 501.1, 501.2, 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
DBP/ICRmanual-l/28/94draft 26
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these methods.) However, laboratories may be required to include
field reagent blanks in their samples 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 preservative
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 and it should
be stored with the samples until processing. This blank should
be processed and analyzed with the samples from that utility. If
any of the analytes are detected at concentrations equal to or
greater than the lowest calibration standard, then all the
samples in the group should be considered suspect and discarded.
Quality Control (QC) sample
Most of the DBP/ICR analytical methods recommend that the
laboratory analyze a quality control (QC) sample at least
quarterly. A QC sample is a sample matrix containing method
analytes or a solution of method analytes in a water miscible
solvent which is used to fortify reagent water or environmental
samples. The QC sample is obtained from a source external to the
laboratory, and it is used to check laboratory performance with
externally prepared test materials.
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.
Based on the above information, EPA has decided to use
Performance Evaluation (PE) studies as EPA's independent check on
laboratory performance. PE samples will be distributed to the
DBP/ICR laboratories on a quarterly basis. The PE samples will
be concentrated solutions of the method analytes in water or
water miscible solvents which the laboratory will use to fortify
aliquots of reagent water. The laboratory will analyze the
diluted PE samples using the same methods as are used for DBP/ICR
samples and the results from those analyses will be reported to
EPA.
DBP/ICRmanual-l/28/94draft 27
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Acceptable performance for DBP/ICR PE studies will be
determined using the criteria described in section VII of this
manual. 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. This will
allow the laboratories to quickly demonstrate correction of
analytical problems in order to restore confidence in the data
being generated in their laboratory. A laboratory that fails two
consecutive PE samples for the same method will not be allowed to
continue performing that analysis for ICR monitoring until
successful performance is demonstrated during later PE studies.
In addition to the DBP/ICR PE studies, many 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 for new
laboratories (or analysts).
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, laboratory replicate analyses will be a valuable tool
for determining the precision of the DBP/ICR monitoring data from
individual laboratories.
The DBP/ICR approved methods vary in their requirements
pertaining to duplicates. Some methods specify the analysis of
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), other methods
require laboratory duplicate analyses (one sample is divided into
two aliquots in the lab and analyzed as two separate samples) for
all samples and field duplicate analyses for a percentage of the
samples. Several methods do not discuss any duplicate analyses.
Laboratories performing analyses for the DBP/ICR will be
required to perform laboratory duplicate analyses at the
frequencies listed in Table IX.1. since duplicate measurements
are only required on one sample in a batch, the precision data
will not reflect the laboratory's performance on samples from a
specific utility unless the laboratory is only analyzing samples
from one utility. The laboratory will randomly select one of the
DBP/ICRmanual-l/28/94draft 28
-------
samples being processed in the batch, unless it has an agreement
with a specific utility to provide duplicate analyses. (Note:
As described earlier in this section under "Laboratory Reagent
Blank", a sample 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 bottle of the extracting solvent, internal standard
spiking solution, and surrogate standard spiking 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
der ivat i z ing agent.)
Laboratories should be able to achieve the precision
criteria listed in Table IX.1. If the relative standard
deviations for two or more analytes in a multianalyte method do
not meet the criteria for duplicate analyses, the laboratory
should carefully evaluate its entire analytical process, minimize
sources of variability, and attempt to bring precision to within
specifications. Data from the batch of samples processed with
the duplicates should be reported, even if the criteria are not
met. The data from duplicate analyses will provide a measure of
the overall precision of the DBP/ICR monitoring data.
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 background concentrations of the analytes in the
sample matrix must be determined in a separate aliquot and the
measured values in the fortified sample corrected for background
concentrations.
Laboratories that are performing analyses for the DBP/ICR
will be required to fortify samples at the frequencies listed in
Table IX.1. The primary analytical standards provided by EPA
must be used as the basis for preparing the fortified samples.
The laboratory should choose a spiking concentration from
one of the three concentrations listed in Table IX.2. In order
to obtain reliable data from laboratory fortified samples, the
spiking concentration must be equal to or greater than the
background concentration of each analyte present in the sample.
If EPA required laboratories to meet this criteria on all
fortified samples, laboratories would have to analyze each sample
prior to spiking it. EPA does not consider this a reasonable
requirement for meeting the ICR objectives. Instead, EPA
recommends that the laboratory select a spiking 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
DBP/ICRmanual-l/28/94draft 29
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should use these "historical" data to select appropriate spiking
concentrations. If there are no data available to predict the
levels of individual analytes, then the laboratory should base
the spike level on the utility's "historical" total
trihalomethane (TTHM) levels. (If the utility's TTHMs are
normally < 20 ng/L, then the lowest level spike should be chosen;
for TTHMs between 20 to 50 M9/L / the mid-level spike should be
chosen; and for TTHMs > 50 nq/l>, the highest level spike should
be used.) EPA realizes that this system will result in analyses
of some fortified samples that are not spiked 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.
Most of the DBP/ICR analytical methods do not provide
criteria for evaluating the results of analyses of laboratory
fortified samples. However, criteria have been established for
the ICR and they are listed in Table IX.1. Matrix effects are
anticipated in some instances, but laboratories should, on
average, be able to meet the criteria. Laboratories must report
all fortified sample recovery data and all data from the batch of
samples processed/analyzed with the fortified sample. Data from
fortified samples spiked at appropriate concentrations (fortified
at concentrations > background concentrations), will be used to
evaluate the quality of the monitoring data. Data from samples
associated with spikes whose data are outside the recovery
acceptance criteria will not be entered into the ICR database.
Internal standard
Several of the DBP/ICR methods require or recommend the use
of an internal standard (IS) for calibration and quantitation
purposes. An internal standard is defined as a pure analyte that
is added to a sample or sample extract in known amount and 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 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 and
other methods stipulate the addition to the sample extract
immediately prior to instrumental analysis. Laboratories will be
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.
DBP/ICRmanual-l/28/94draft 30
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Specific criteria for evaluating the IS are presented in Table
IX.1. If the IS in a specific sample does not meet the
acceptance criteria, then data from the sample will not be
considered valid. If possible, the laboratory should reanalyze
the sample. If this cannot be done, then no data (from the
method in question) should be reported for the sample. The
utility should be notified that the sample was lost due to an
analytical problem with the internal standard. The utility
report to EPA will state that the sample was lost due to an
analytical problem.
Surrogate Standard
Several of the DBP/ICR methods require the use of surrogate
analytes. A surrogate is a pure analyte, which is extremely
unlikely to be found in any sample, and which is added to a
sample aliquot in a known amount before the sample is processed.
It 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.
A list of the methods that require surrogates is included in
Table IX.1 along with the recommended surrogate(s) for each
method. The recovery of the surrogate must be monitored for each
sample, standard and QC sample and the criteria for evaluating
surrogate recoveries are also listed in Table IX.1. Laboratories
should, on average, be able to meet the surrogate recovery
criteria, but matrix effects could interfere in some instances.
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 no data (from
the method in question) should be reported for the sample. The
utility should be notified that the sample was lost due to an
analytical problem with the surrogate analyte. The utility
report to EPA will state that the sample was lost due to an
analytical problem.
DBP/ICRmanual-l/28/94draft 31
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Table IX.1. Requirements for Performing QC Analyses for the DBP/ICR1
Method
Method Specifications
ICR Acceptance Criteria1 | ICR Specifications
Verify Calibration
501.1 &
501.2
502.2
524.2
Daily
Daily
Beginning each 8 hr work
shift
Response for each analyte must
be within ± 20% of predicted
response*
External Standard Calibration;
Response for each analyte must
be within ± 20% of predicted
response
Internal Standard (IS)
Calibration; IS response must
be within ± 30% of last
calibration check and within ±
50% of initial calibration;
Analyte concentration must be
within ± 20% of predicted
concentration*
Responses for internal standard
& surrogate must be within ±
30% of last calibration check
and within ± 50% of initial
calibration; Analyte
concentration must be within ±
20% of predicted concentration*
The lowest-level
standard must be
analyzed at the
beginning of each 24
hour period. The mid-
and highest-level
standards must
alternately analyzed
at the beginning of
each 8-10 hr work
shift and as the last
analysis run on the
instrument for the
remainder of the 24 hr
period
1 Acceptance criteria from the method are used when available and consistent with the DBP/ICR objectives.
Criteria that are different from the method are marked with an "*."
DBP/ICRmanual-l/28/94draft
32
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Method
Method Specifications
ICR Acceptance Criteria1
ICR Specifications
551
552.1
6233 B
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
External Standard Calibration:
Response for each analyte must
be within ± 20% of predicted
response
Internal Standard Calibration;
IS response must be within ±
30% of last calibration check
and within ± 50% of initial
calibration; Analyte
concentration must be within ±^
20% of predicted concentration*
Daily
Response for each analyte must
be within ± 15% of predicted
response
The lowest-level
standard must be
analyzed at the
beginning of each 24
hour period. The mid-
and highest-level
standards must
alternately analyzed
at the beginning of
each 8-10 hr work
shift and as the last
analysis run on the
instrument for the
remainder of the 24 hr
period
With each sample batch
Response for each analyte must
be within ± 15% of predicted
response
300.OA &
300.OB
After every tenth sample plus
at the beginning of each 8
hour period and as the last
analysis run on the
instrument
Response for each analyte must
be within ± 10% of predicted
response
Follow frequency
listed in Method. Use
lowest-level standard
as initial calibration
check, then alternate
between mid- and
upper-level standards
for remainder of
checks.
DBP/ICRmanual-l/28/94draft
33
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Method
Method Specifications
ICR Acceptance Criteria1
ICR Specifications
TOC
Daily
Response within ± 10% of
predicted response
After every tenth
sample plus at the
beginning of each 8-10
hour work shift and as
the last analysis run
on the instrument.
Use lowest-level
standard as initial
calibration check,
then alternate between
mid- and upper-level
standards for
remainder of checks.
UV.
254
Daily
Response within ± 15 % of
predicted response
The lowest-level
standard must be
analyzed at the
beginning of each 24
hour period. The mid-
and highest-level
standards must
alternately analyzed
at the beginning of
each 8-10 hr work
shift and as the last
analysis run on the
instrument for the
remainder of the 24 hr
period
DBP/ICRmanual-l/28/94draft
34
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Method
Method Specifications
ICR Acceptance Criteria1
ICR Specifications
TOX
Perform several
microcoulometer/titration
cell checks with NaCl std
soln at start of each day;
Analyze several nonvolatile
TOX calibration stds daily
NaCl consecutive duplicates
should be within 3% of the true
value;
Measured concentration of
calibration standard should be
within ± 10% of expected value*
Perform 3
microcoulometer/titra-
tion cell checks with
NaCl std soln at start
of each 8-10 hr work
shift; Analyze lowest
level calibration std
at beginning of each
24 hr period & a mid-
or highest level std
as last analysis of
the day
Aldehydes
Daily
Response for each analyte must
be within ± 15% of predicted
response
CNC1
Beginning each 8 hr work
shift
Internal Standard response must
be within ± 30% of last
calibration check and within ±
50% of initial calibration;
Analyte concentration must be
within ± 20% of predicted
concentration*
The lowest-level
standard must be
analyzed at the
beginning of each 24
hour period. The mid-
and upper-level
standards must
alternately analyzed
at the beginning of
each 8-10 hr work
shift and as the last
analysis run on the
instrument for the
remainder of the 24 hr
period
DBP/ICRmanual-l/28/94draft
35
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Method 1 Method Specifications
Method Blank
501.1 &
501.2
502.2
524.2
551-THMs
551-
nonTHMs
552.1
6233 B
300.0A-Br'
300. OB-
ClO,' &
cicv
300. OB-
BrO,'
TOC
UV254
Analyze if interference found
in shipping blank
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
I/ set of samples
I/set of samples
I/set of samples
I/ batch of samples
I/batch of samples
I/ batch of samples
Daily
Initial zero; Check after
each 10 samples
ICR Acceptance Criteria1
<0.5 Mg/L for a single analyte*
<0.25 Mg/L for a single
analyte*
< 0.5 Mg/L for a single
analyte*
< 0.01 mg/L for bromide
< 10 Mg/L for a single analyte*
< 2.5 Mg/L*
< 0.25 mg/L*
< 0.004 cm"1
ICR Specifications
I/batch of samples
processed together
each 8-10 hour work
shift
Follow method
DBP/ICRmanual-l/28/94draft
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Method
TOX
Aldehydes
CNC1
Method Specifications
I/ set of 8 samples - minimum
of 2 /day (nitrate-washed
activated carbon)
I/ set of samples
Daily
ICR Acceptance Criteria1
< 0.8 M9 Cl'/40 mg of activated
carbon*
< 2.5 /ig/L for a single
analyte*
< 0.25 Mg/L*
ICR Specifications
2 nitrate-washed
activated carbon
analyses at beginning
of each day, then
I/ set of 8 samples
(minimum of 3 /day) ;
Analyze 1 system blank
each 24 hour period
I/ extract ion batch** OR
each 24 hours
(whichever is less)
Shipping Blank
501.1 &
501.2
502.2
524.2
Aldehydes
I/ set of samples
I/ set of field samples
I/set of field samples
I/sampling location
Methods do not set acceptance
criteria for these analyses &
no criteria are necessary for
the ICR
< 2.5 /ig/L for a single
analyte*
There will not be an
ICR requirement to
perform these
analyses.
I/utility sample
set/quarter
Quality Control Sample (Performance Evaluation [PE] Sample)
501.1 &
501.2
502.2
524.2
551-THMs
I/quarter
± 20% of true value for each
analyte
I/ quarter
DBP/ICRmanual-l/28/94draft
37
-------
Method
551-
nonTHMs
552.1
6233 B
300. OA &
300. OB
TOC
uv™
TOX
Aldehydes
CNC1
Method Specifications
I/ quarter
I/ quarter
I/quarter
I/quarter
No Requirement
No Requirement
No Requirement
No Requirement
No Requirement
ICR Acceptance Criteria1
± 40% of true value for each
analyte (Must pass 4 of 5
analytes, excluding TCAN)*
± 40% of true value for each
analyte (Must pass 4 of 5
analytes, excluding MCAA)*
± 40% of true value for each
analyte*
± 25% of true value*
± 25% of true value*
± 25% of true value*
ICR Specifications
I/ quarter
EPA intends to perform these analyses. EPA's
laboratory will split samples with one or two other
laboratories that have experience with these methods
'Laboratory Duplicate of a Sample
501.1 &
501.2
502.2
524.2
551
552.1
6233 B
300.0A-Br'
(field dups) 10% of Samples
Plus all samples that deviate
more than 30% from norm
No Requirement
No Requirement
No Requirement
No Requirement
(Field dups) 10% of Samples
No Requirement
< 20% relative standard
deviation*
< 10% relative standard
deviation*
1 laboratory
duplicate/batch of
samples
DBP/ICRmanual-l/28/94dra£t
38
-------
Method
300.0A-
cio • &
cio,-
300. OB-
BrO,*
TOC
UV254
TOX
Aldehydes
CNC1
Method Specifications
No Requirement
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
No Requirement
ICR Acceptance Criteria1
< 10% relative standard
deviation*
< 20% relative standard
deviation*
< 10% relative standard
deviation*
< 20% relative standard
deviation*
< 20% relative standard
deviation*
ICR Specifications
1 laboratory
duplicate /batch of
samples
All Samples Analyzed
in Duplicate
Follow Method
All Samples Analyzed
in Duplicate
I/ batch of samples
Laboratory Fortified Sample Matrix (Spiked Sample or Standard Addition Recovery Sample)
501.1 &
501.2
502.2
524.2
551-THMs
551-
nonTHMs
552.1
No Requirement
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
80 - 120% Recovery*
80 - 120% Recovery*
80 - 120% Recovery*
80 - 120% Recovery*
60 - 140% Recovery*
60 - 140% Recovery*
I/ batch of samples
DBP/ICRmanual-l/28/94draft
39
-------
Method
6233 B
300. OA &
300. OB
TOX
Aldehydes
Method Specifications
10% of samples or I/ set
10% of samples
10% of samples .
10% of samples or I/set
ICR Acceptance Criteria1
60 - 140% Recovery*
75 - 125% Recovery
No Requirement for ICR
60 - 140% Recovery*
ICR Specifications
I/batch of samples
Internal Standard
502.2
524.2
551
552.1
6233 B
Aldehydes
2-Bromo-l-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)
1,2,3-Trichloropropane in
Each Extract
1,2-Dibromopropane OR 1,2,3-
Trichloropropane in Each
Extract
1,2-dibromopropane OR
decaf luorobiphenyl in Each
Extract
Area measurement of IS be
within ±3 standard deviations
of those obtained from
calibration standards
Within 30% of daily calibration
standard IS response*
Within 30% of daily calibration
standard IS response
Within 30% of daily calibration
standard IS response
Within 20% of mean for all
samples processed with same
batch of diazomethane
Within 20% of mean for all
samples processed with same
batch of PFBHA
Use is optional -
depends upon the
calibration procedure
Follow Method & Add to
Each Sample
Follow Method & Add to
Each Sample or Extract
as Directed
DBP/ICRmanual-l/28/94dra£t
40
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Method
CNC1
Method Specifications
Fluorobenzene in Each Sample
ICR Acceptance Criteria1
Within 30% of daily calibration
standard IS response*
ICR Specifications
Follow Method & Add to
Each Sample as
Directed
Surrogate Standard
524.2
552.1
6233 B
Aldehydes
Bromof luorobenzene in Each
Sample
2-bromopropionic acid in Each
Sample
2,3-dibromopropionic acid OR
2,3,5, 6-tetraf luorobenzoic
acid in Each Sample
2 -methyl valeraldehyde OR
2,3,5, 6-tetraf luorobiphenyl
in Each Sample
70 - 130% Recovery*
70 - 130% Recovery
Within 30% of mean for all
samples processed with same
batch of diazome thane
Within 30% of mean for all
samples procesed with same
batch of PFBHA
Add to Each Sample
* Acceptance criteria from the method are used when available and consistent with the DBF/ICR
objectives. Criteria that are different from the method are marked with an "*."
DBP/ICRmanual-l/28/94draft
41
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Table IX.2. Calibration Check Standard Concentrations
Method/ Analyte (s)
501.1, 501.2, 524.2,
551/THMs
551/HANs, HKs, CP
551/CH
552.1, 6233 B/HAAs
300. OA - Br'
300. OB/CIO,', CIO,'
300.0B/Br(V
TOC
uv™
TOX
Aldehydes
CNC1
Lowest-Level
Standard
1 Mg/L
0.5 Mg/L
0.5 Mg/L
1 Mg/L
0.02 mg/L
20 Mg/L
5 Mg/L
0.5 mg/L
0.5 mg/L*
50 Mg Cl'/L
5 Mg/L
0.5 Mg/L
Mid-Level
Standard
20 Mg/L
5 Mg/L
10 Mg/L
20 Mg/L
0.1 mg/L
250 M9/L
10 Mg/L
4 mg/L
6.5 mg/L*
250 Mg Cl'/L
10 M9/L
2 M9/L
Highest
Standard
40 Mg/L
15 Mg/L
25 Mg/L
40 Mg/L
0.3 mg/L
750 M9/L
30 Mg/L
10 mg/L
60 mg/L*
500 Mg Cl'/L
40 M9/L
5 Mg/L
* Potassium Hydrogen Phthalate (KHP) concentration (mg/L) is given as
dissolved organic carbon (DOC)
DBP/ICHmanual-l/28/94draft
42
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Section Z. Quality Control Reporting Requirements
Laboratories that perform analyses for the DBP/ICR are
required to adhere to the quality control requirements described
in Section VIII of this manual. EPA will require the
laboratories to report a- subset of those data in order to verify
that the DBP/ICR monitoring data are of sufficient accuracy and
precision to meet the objectives of the ICR. The QC data that
must be submitted to EPA are summarized in Table X.I. The
DBP/ICR Laboratory Performance Evaluation (PE) Studies are not
included in Table X.I, because they are not directly associated
with the routine monitoring samples. (See Section VII for a
discussion on DBP/ICR PE Studies.)
EPA is considering two options for obtaining the necessary
QC data from the laboratories. In the first option, the
laboratory would report the QC data (listed in Table X.I)
associated with a utility's samples to the utility when the
monitoring data are reported. The utility would combine the
monitoring and QC data with the treatment plant process
information and report everything to EPA. The utility would also
identify the laboratory that performed each analysis, so that the
QC data could be tied to the monitoring data. Using this
approach, some of the QC data would be reported to EPA several
times, because the data are associated with batches of samples
that are processed and analyzed together. Commercial and state
laboratories would have samples from several utilities combined
into batches. The QC data would have to be screened and
associated with the correct sample batches prior to entry into
the ICR database.
The second alternative is to require the laboratories to
report most of their QC data directly to EPA. (Internal standard
responses and surrogate recoveries would be reported through each
utility, because the data are associated with individual samples.
Duplicate data for TOX, UV,54, and TOC analyses would also be
reported through the utility, because each sample is analyzed in
duplicate.) They would also provide a copy of the QC data to the
utility when the monitoring data are reported, but the utility
would not report QC data to EPA. (The utility would identify the
laboratory that performed each analysis.) This approach has
several advantages: 1) It would eliminate some of the reporting
burden on the utilities; 2) It would reduce the potential of
reporting errors in the QC data, because the intermediate
reporting step would be eliminated; and 3) It would reduce the
volume of data that would need to be screened prior to entry into
the ICR database.
The final version of this manual will describe the mechanism
the laboratory will use to report the QC data (and the monitoring
data). Selection of one of the above approaches (or a different,
undefined approach) will be made based on ease of implementation.
Laboratory operations, utility reporting requirements, and
database needs will be considered in the decision.
DBP/ICRmanual-l/28/94draft 43
-------
Table x.l. Quality Control Data to be Included in an ICR Database
QC Data
Comments
Verification of
Calibration
At least two calibration standards will be
associated with each batch of samples.
Laboratory will report expected and measured
concentrations of each analyte in the standards
along with the date the batch of samples was
prepared and the date and time of instrumental
analysis. In commercial, state, and some large
utility laboratories, these data will be
associated with monitoring data from several
water treatment plants.
Laboratory Duplicates
One set of duplicate analyses will be
associated with each batch of samples for most
of the DBF/ICR methods. (TOC, UV254, and TOX
require duplicates of ALL samples.) Laboratory
will report measured concentrations of each
analyte in duplicate samples along with the
date the batch of samples was prepared and the
date and time of instrumental analysis. In
commercial, state, and some large utility
laboratories, these data will be associated
with monitoring data from several water
treatment plants.
Laboratory Fortified
Samples
One fortified sample will be associated with
each batch of samples for most of the DBF/ICR
methods. Laboratory will report the
concentration of each analyte used to fortify
the sample, the concentration of each analyte
measured in the fortified sample, the date and
time the batch of samples was prepared and the
date and time of instrumental analysis. The
background concentration will also be reported
or the data will be tied to monitoring data for
a specific sample. In commercial, state, and
some large utility laboratories, these data
will be associated with monitoring data from
several water treatment plants.
Internal Standard
Response
One data point for each sample (including QCs)
for the appropriate methods.
Surrogate Standard
Recovery
One data point for each sample (including QCs)
for the appropriate methods.
Processing Date
Date that sample was prepared for analysis.
Analysis Date
Date that sample was analyzed by the
instrument.
Lab ID Code
Each laboratory will be assigned a unique code
for ICR reporting purposes.
DBP/ICRmanual-l/28/94draft
44
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Section XI. Laboratory Evaluation During DBP/ICR Monitoring
Period
EPA will use the quality control (QC) data that is described
in Section X and the results from Performance Evaluation Studies
to evaluate the performance of the laboratories generating data
for the ICR. Laboratories must meet the performance criteria for
each analytical method on an ongoing basis in order to remain
"approved" for ICR monitoring. The performance of the method as
it is routinely used in laboratories currently doing the same
analysis was used as a guide for determining feasibility in
meeting the acceptance criteria listed in Table IX.1 in Section
IX of this manual. Laboratories that are certified to perform
THM analyses for THM compliance monitoring and that are reporting
data for -the ICR must meet the ICR QC criteria for THMs in order
for the data to be considered valid for the ICR.
If "approved" laboratories develop problems meeting the QC
criteria during the monitoring period, a number of actions may be
taken. Since the data must meet high QC standards in order to be
useful, EPA will provide technical assistance to laboratories
that are performing ICR analyses, if loss of that laboratory
significantly impacts the overall laboratory capacity for
completing the DBP/ICR monitoring.
Utilities will be notified when a laboratory they are using
is not meeting the QC criteria, and a list of alternate
laboratories will be provided by EPA. EPA will maintain a list
of laboratories that are "approved" for DBP/ICR monitoring.
DBP/ICRmanual-l/28/94draft 45
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Appendix A
Draft Laboratory Registration Form
and Verification Form
DBP/ICRmanual-l/28/94draft 46
-------
Rev. 1/28/94 •
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 check the following groups of ICR parameters that will be analyzed by the lab listed above.
Analyses which will require ICR approval:
_ Ammonia _ Bromide _ 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)
The parameters listed below do not require ICR Approval if state approval or certification can be
demonstrated:
_ Alkalinity __ Calcium Hardness _ pH _ Temperature _ THMs _ Turbidity
(via 501/502/524)
Disinfectant Residuals:
_ free-chlorine _ total-chlorine _ chlorine dioxide _ combined chlorine _ ozone
DBP/ICRmanual-l/28/94draft 47
-------
1/28/94 VERIFICATION OF STATE
CERTIFICATION / APPROVAL
Instructions: Please complete the following form.
Laboratory Type: Utility, Commercial, State Other.
Lab Name:
Address:
Contact Person:
Telephone: - -
Certification
The information requested in this section is necessary to demonstrate certification/approval of the
ICR parameters listed below. Please fill-out completely and supply all requested documentation.
Does your laboratory intend to measure THMs for the ICR? Yes, No
(If "No", proceed to the State Approval section.)
Please check the EPA method used in your lab for determination of THMs.
_ 501.1 _ 501.2 _ 502.2 _ 524.2 _ Other
What is the number of THM samples your lab can analyze per week? /wk
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 full )
(1) (2) (3)
DBP/ICRmanual-l/28/94draft 48
-------
Please attach a copy of your certificate(s)
Has your laboratory ever lost certification for THMs? Yes, No (If yes, attach an explanation of
when and why.)
State Approvals
If your laboratory intends to measure any of the parameters listed in the table below and is approved
by the state to perform the analyses, then complete this section of the form. Please check the appropriate
analyte; list the state(s) in which your lab is approved; indicate the manner of the approval (on-site
inspection, reciprocity, or via a paper evaluation); type of approval (full or provisional, if applicable); and
the number samples your laboratory can analyze per week.
ICR
PARAMETER
(indicate with a /)
( ) Alkalinity
( ) Calcium hardness
( ) PH
( ) Temperature
( ) Turbidity
( ) Free-chlorine
( ) Chlorine dioxide
( ) Total-chlorine
( ) Combined-chlorine
( ) Ozone
STATES IN WHICH
APPROVED
MANNER OF
APPROVAL
(on-site, reciprocity,
paper)
TYPE OF
APPROVAL
(full or provisional)
Please attach a copy of your letter(s) or certificate(s) of approval for conducting the above analyses.
Has your laboratory ever lost approval for analysis of the parameters given in the table above? Yes,
_No
(If yes, attach an explanation of when and why.)
DBP/ICRmanual-l/28/94draft
49
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Appendix B
Draft Application Forms for Laboratory Approval
DBP/ICRmanual-l/28/94draft 50
-------
Rev. 1/14/94
ICR Laboratory Approval Forms
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.
However, should you need additional clarification, please call (to be supplied).
LAB NAME:
ADDRESS:
CONTACT PERSON:
TELEPHONE:
What is your laboratory's EMSL PE Code #.
Please check the following ICR required analyses for which your laboratory is seeking approval.
_ Chloral Hydrate Haloacetic Acids _ Total Organic Carbon _ Total Organic Halide
(EPA 551) (EPA 552.1; SM 6233 B) (SM 5310 C,D) (SM 5320 B)
UV Absorbance Total Hardness Ammonia • Bromide
(SM5910) (SM2340C.D) (SM 4500-NH3 D,F) (EPA 300.0)
Haloacetonitriles, Haloketones and Chloropicrin
(EPA 551)
Oxyhalides - bromate, chlorate and chlorite
(EPA 300.0)
_THMs
(EPA 551)
Lab Manager
Signature:
This signature affirms that the information in the completed package is correct.
DBP/ICRmanual-l/28/94draft
51
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Rev.1/13/94
QUALITY ASSURANCE
Please attach the following quality assurance (QA) information about your laboratory:
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
5) the date of the last revision of your Laboratory QA Plan
CERTIFICATION AND STATE APPROVAL
The information requested in this section is necessary to demonstrate certification/approval of the
ICR parameters listed below. Please fill-out completely and supply all requested documentation.
Certification
Does your laboratory intend to measure THMs for the ICR? _Yes, _No
(If "No", proceed to the State Approval section.)
Please check the EPA method used in your lab for determination of THMs.
_ 501.1,2 _ 502.2 _ 524.2 _ Other
What is the number of THM samples your lab can analyze per week? /wk
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 Is, 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 full )
(1) (2) (3)
Please attach a copy of your certificate(s)
Has your laboratory ever lost certification for THMs? Yes, No
(If yes, attach an explanation of when and why.)
DBP/ICRmanual-l/28/94draft 52
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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 the state to perform the analyses, then complete this section of the form. Please check the appropriate
analyte; list the state(s) in which your lab is approved; indicate the manner of the approval (on-site
inspection, reciprocity, or via a paper evaluation); type of approval (full or provisional, if applicable); and
the number samples your laboratory can analyze per week.
ICR
PARAMETER
(indicate with a /)
( ) Alkalinity
( ) Calcium hardness
( ) PH
( ) Temperature
( ) Turbidity
( ) Free-chlorine
( ) Chlorine dioxide
( ) Total-chlorine
( ) Combined-chlorine
( ) Ozone
STATES IN WHICH
APPROVED
MANNER OF
APPROVAL
(on-site, reciprocity,
paper)
TYPE OF
APPROVAL
(full or provisional)
Please attach a copy of your letter(s) or certificate(s) of approval for conducting the above analyses.
Has your laboratory ever lost approval for analysis of the parameters given in the table above? Yes, _
No
(If yes, attach an explanation of when and why.)
Please list any additional drinking water chemical analyses for which your laboratory is approved.
Parameter Method #
DBP/ICRmanual-l/28/94draft
53
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Rev. 1/13/94
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). 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) [""I „ T- l~~ln r-
\ 1 Full-Time 1 — 1 Part-Time
POSITION CURRENTLY HELD/ ICR ASSOCIATION
EDUCATION r~i r~i
a. High School Graduate or Equivalent I— lies L_IINO
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.)
DBP/ICRmanual-l/28/94draft
54
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PERSONNEL QUALIFICATION
Page 2
Last Name:
LICENSE, CERTIFICATION, OR REGISTRATION
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
POSmON(S)
HELD
EXPERIENCE
e.g.
Micro, Chem,etc.
(also include
experience with
specific analyses
and methods)
REMARKS (Add information pertinent to your education, training, employment, etc., not included
above.)
DBP/ICRmanual-l/28/94draft
55
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Rev. 1/28/94
Method Approval for ICR
Chloral Hydrate, Haloacetonitriles, Haloketones, Chloropicrin,
and Trihalomethanes
Description: This analysis determines the concentration of chloral hydrate (CH), 4
haloaceonitriles (HANs), 2 haloketones (HKs), chloropicrin (CP) and the 4 trihalomethanes
in water. The HANs include bromochloroacetonitrile (BCAN), dibromoacetonitrile (DBAN),
dichloroacetonitrile (DCAN), and trichloroacetonitrile (TCAN). The HKs include 1,1-
dichloropropanone (DCP) and 1,1,1-trichloropropanone (TCP). The trihalomethanes include
chloroform (CHC13), bromodichloromethane (BDCM), dibromochloromethane (DBCM), and
bromoform (CHBrS).
For which analytes are you seeking approval?
_ CH _ HANs, HKs, CP THMs
Which method is used in your laboratory?
_ EPA 551, _ Other
If "Other", please give the name, number or description of the method used by your
laboratory.
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
EQUIPMENT
Please list the equipment used in this analysis.
Manufacturer
Model & Serial #
Gas Chromatograph
Detector(s)
Injector(s)
Analytical Column
Confirmation Column
Sample Storage Unit
Extract Storage Unit
Standard Storage Unit
DBP/ICRmanual-l/28/94draft
56
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SAMPLE HANDLING INFORMATION
ANALYTE
CH
HANs,
HKs, CP
THMs
SAMPLE STORAGE
TEMP (C°)
MAX. HOLDING
TIME
NAME OF
PRESERVATIVE USED
AMT OF PRESERVATIVE
USED (_mg per _mL)
EXTRACT HANDING INFORMATION
ANALYTE
CH
HANs, HKs,
CP
THMs
SOLVENT USED
EXTRACT STORAGE TEMP (C°)
MAXIMUM HOLDING TIME
QC INFORMATION
Primary Column MDL: Using the minimum detection limit procedure described in the DBP/ICR
Analytical Methods Guidance Manual, what is your lab's MDL for this analysis (/xg/L)?
CH:
BCAN:
DBAN:
DCAN:
TCAN:
DCP:
TCP:
CP:
CHC13:
BDCM:
DBCM:
CHBr3:
Have these MDLs been confirmed by analysis of a reagent water spiked near the MDL?
_ Yes _ No
Please attach a copy of the analyte concentrations determined in each of the 7 (or more) replicates
and the concentration of the spike used to calculate the primary column MDLs given above. Also
include an example chromatogram from one of these determinations. Be sure to label each analyte,
giving its retention time, concentration, and detector attenuation.
DBP/ICRmanual-l/28/94draft
57
-------
Confirmation Column MDL: Using the minimum detection limit procedure described in the DBP/ICR
Analytical Methods Guidance Manual, what is your lab's MDL for this analysis Oig/L)?
CH:
BCAN:
DBAN:
DCAN:
TCAN:
DCP:
TCP:
CP:
CHC13:
BDCM:
DBCM:
CHBr3:
Have'these MDLs been confirmed by analysis of a reagent water spiked near the MDL? Yes
No
Please attach a copy of the analyte concentrations determined in each of the 7 (or more) replicates
and the concentration of the spike used to calculate the confirmation column MDLs given above.
Also include an example chromatogram from one of these determinations. 'Be sure to label each
analyte, giving its retention time, concentration, and detector attenuation.
IDC: Please list, in the table below, the Initial Demonstration of Capability (IDC) data that was determined
using the procedure outlined in the DBP/ICR Analytical Methods Manual.
Analyte
CH
BCAN
DBAN
DCAN
TCAN
DCP
TCP
CP
CHC13
BDCM
DBCM
CHBrS
Mean Concentration
-------
Please attach a copy of the analyte concentrations that was determined in each day's analysis used to
calculate the IDC data given above. Also include an example chromatogram from one of these
determinations. Be sure to label each analyte, giving its retention time, concentration, and detector
attenuation.
INTERNAL STANDARD AND SURROGATE
List the name of the chemical, the amount used, and the average recovery for the internal
standard, if one is used.
Name of chemical
Amount added
Average recovery (from IDC)
Internal Standard
(ug/mL)
(%)
METHOD BLANK
What is the ave. concentration in your method blanks?
CH:
TCAN:
CHC13:
BCAN:_
DCP:
BDCM:
DBAN:_
TCP:
DBCM:
DCAN:
CP:
CHBrS:
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 0*g/L)?
CH:
TCAN:.
CHC13:
BCAN:_
DCP:
BDCM-
DBAN:_
TCP:J
DBCM:
DCAN:
CP:
CHBr3:
Briefly describe how the reporting limits are established.
DBP/ICRmanual-l/28/94draft
59
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CALIBRATION CURVE
List the approximate concentrations of the calibration standards used to
establish the standard curve
CH
BCAN
DBAN
DCAN
TCAN
DCPP
TCPP
CP
CHC13
BDCM
DBCM
CHBr3
PERFORMANCE E
Has your lab analyzec
Std#l
Std#2
Std#3
Std#4
Std#5
VALUATION
1 PE samples? Yes No; If yes, please list the three most recent results
Study* _ Date:
Study* _ Date:
Study* ____ Date: _ _
CH
BCAN
DBAN
DCAN
TCAN
DCP
TCP
CP
CHCD
BDCM
DBCM
CHBr3
DBP/ICRmanual-l/28/94draft
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ADDITIONAL INFORMATION
How many samples per week can your laboratory analyze? /wk
List the personnel who will be performing these analyses for the ICR and give their duties (extraction,
GC Analyst, etc.).
Name Duties
DBP/ICRmanual-l/28/94draft 61
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Rev. 1/28/94
Method Approval for ICR
Haloacetic Acids
Description: This analysis determines the concentration of 6 haloacetic acids (HAA) in water,
monochloroacetic acid (MCAA), dichloroacetic acid (DCAA), trichloroacetic acid (TCAA),
monobromoacetic acid (MBAA), dibromoacetic acid (DBAA), and bromochloroacetic acid (BCAA).
Details of the HAA analysis are given in the ICR DBF Analytical Methods Guidance Manual.
Which HAA method is used in your laboratory?
_ EPA 552.1, _ SM 6233 B, _ Other
laboratory.
If "Other", please give the name, number or description of the method used by your
Does your lab have a written SOP for this analysis? Yes No
Is your laboratory currently certified for chlorinated acids (e.g. 2,4D) and/or other similar methods?
Yes No
EQUIPMENT
Please list the equipment to be used in this analysis.
Gas Chromatograph
Detector(s)
Injector(s)
Analytical Column
Confirmation Column
Sample Storage Unit
Extract Storage Unit
Standard Storage Unit
Diazomethane Generator
SPE Apparatus
Temperature Bath
Manufacturer
Model & Serial #
DBP/ICRmanual-l/28/94draft
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SAMPLE HANDLING INFORMATION
Type (& volume) of sample bottles and lids.
Storage Temp: °C Maximum Holding Time: Days
Are samples dechlorinated? _Yes __No ; with ( mg per mL)
Are samples acidified? _Yes _No ; with ( per mL)
EXTRACT HANDING INFORMATION
Storage Temp: °C Maximum Holding Time: Days
QC INFORMATION
Primary Column MDL: Using the minimum detection limit procedure described in the DBP/ICR Analytical
Methods Guidance Manual, what is your lab's MDL for this analysis (ug/L as acid)?
MCAA: DCAA: TCAA: MBAA: DBAA: BCAA:
Have these MDLs been confirmed by analysis of a reagent water spiked near the MDL?
_ Yes _ No
Please attach a copy of the analyte concentrations determined in each of the 7 (or more) replicates
and the concentration of the spike used to calculate the primary column MDLs given above. Also
include an example chromatogram from one of these determinations. Be sure to label each analyte,
giving its retention time, concentration and detector attenuation.
Confirmation Column MDL: Using the minimum detection limit procedure described in the DBP/ICR
Analytical Methods Guidance Manual, what is your lab's MDL for this analysis (ug/L as acid)?
MCAA: DCAA: TCAA: MBAA: DBAA: BCAA:
Have these MDLs been confirmed by analysis of a reagent water spiked near the MDL?
_ Yes _ No
Please attach a copy of the analyte concentrations determined in each of the 7 (or more) replicates
and the concentration of the spike used to calculate the confirmation column MDLs given above.
Also include an example chromatogram from one of these determinations. Be sure to label each
analyte, giving its retention time, concentration and detector attenuation.
DBP/ICRmanual-l/28/94draft 63
-------
IDC: Please list, in the table below, the Initial Demonstration of Capability (IDC) data that was determined
using the procedure outlined in the DBP/ICR Analytical Methods Guidance Manual.
Monochloroacetic
Dichloroacetic
Trichloroacetic
Monobromoacetic
Dibromoacetic
Bromochloroacetic
Mean Concentration
(ug/L as acid)
Mean %
Recovery
(accuracy)
%RSD
(precision)
-
Please attach a copy of the analyte concentrations determined in each day's analysis that was used to
calculate the IDC data given above. Also include an example chromatogram from one of these
determinations. Be sure to label each analyte, giving its retention time, concentration and detector
attenuation.
METHOD BLANK
What is the ave. HAA concentration in your method blanks?
MCAA: DCAA: TCAA: MBAA:
DBAA: BCAA:
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 for HAAs (ug/L as acid)?
MCAA: DCAA: TCAA: MBAA:
DBAA:
BCAA:
Briefly describe how the reporting limits were established.
DBP/ICRmanual-l/28/94draft
64
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CALIBRATION CURVE
List the approximate concentrations of the calibration standards used to
establish the standard curve (ug/L as acid).
MCAA (ug/L)
DCAA (ug/L)
TCAA (ug/L)
MBAA (ug/L)
DBAA (ug/L)
BCAA (ug/L)
Std#l
Std#2
Std#3
Std#4
Std#5
INTERNAL STANDARD AND SURROGATE
List the name of the chemical, the amount used, and the average recovery for the internal
standard and surrogate.
Name of chemical
Amount added
Average recovery (from IDC analyses)
Internal Standard
(ug/mL)
(%)
Surrogate
(ug/L)
(%)
DBP/ICRmanual-l/28/94draft
65
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PERFORMANCE EVALUATION
Has your lab analyzed PE samples for HAAs? Yes No
If yes, please list the three most recent results (ug/L as acid).
Study#_
Study#_
Study#_
DATE OF STUDY
MCAA (ug/L)
DCAA (ug/L)
TCAA (ug/L)
MBAA (ug/L)
DBAA (ug/L)
BCAA (ug/L)
How many HAA samples per week can your laboratory analyze? /wk
List the personnel who will be performing your HAA analyses for the ICR and give their
duties (extraction, GC analyst, etc.).
Name
Duties
DBP/ICRmanual-l/28/94draft
66
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Rev. 1/28/94
Method Approval for ICR
Total Organic Carbon
Description: This analysis determines the total organic carbon (TOG) concentration in water. Details of
this analysis are given in the ICR DBF Analytical Methods Guidance Manual.
Which TOC method is used in your laboratory?
_SM5310C _SM5310D _ Other
If "Other", please give the name, number or description of the method used by your
laboratory.
Does your lab have a written SOP for this analysis? Yes • No
EQUIPMENT
Please list the equipment used in this analysis.
Manufacturer
Model & Serial #
Electronics Detector
Module
Reaction Module
Autosampler
Autoclave
(other).
SAMPLE HANDLING INFORMATION
Type (& volume) of sample bottles and lids:
Storage Temp: °C Maximum Holding Time:
Are samples acidified? _Yes _No ; with
Preserved sample pH?
Days
DBP/ICRmanual-l/28/94draft
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QC INFORMATION
MDL: Using the minimum detection limit procedure described in the DBP/ICR Analytical Methods
Guidance Manual, what is your lab's MDL for this analysis (mg/L)?
Has this MDL been confirmed by analysis of a reagent water spiked near the MDL? Yes No
Please attach a copy of the analyte concentrations determined in each of the 7 (or more) replicates used
to calculate the MDL given above. Also indicate the concentration of the spiked sample.
IDC: Please list, in the table below, the Initial Demonstration of Capability (IDC) data that were
determined using the procedure outlined in the ICR method.
Mean Concentration
(mg/L)
Mean % Recovery
(accuracy)
%RSD
(precision)
TOC
Please attach a copy of the analyte concentrations determined in each day's analysis that was used to
calculate the IDC data given above.
METHOD BLANK
What is the ave. concentration of TOC in your method blanks?
_mg/L
What is your normal (non-ICR) minimum reporting limit for TOC?
Briefly describe how the reporting limits were established.
_mg/L
DBP/ICRmanual-l/28/94draft
68
-------
PERFORMANCE EVALUATION
If your lab has analyzed PE samples, please list the three most recent results.
Study#_
Study#_
Study#_
DATE OF STUDY
TOC (mg/L)
ADDITIONAL INFORMATION
What types of quality control checks are performed for this analysis?.
At what concentration is the quality control check analyzed?.
How many TOC samples per week can your laboratory analyze? /wk
List the personnel who will be performing your analyses for the ICR and list their duties.
Name
Duties
DBP/ICRmanual-l/28/94draft
69
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Rev. 1/28/94
Method Approval for ICR
Total Organic Halide
Description: This analysis determines the total organic halide (TOX) concentration in water. Details of
this analysis are given in the ICR DBF Analytical Methods Guidance Manual.
Which TOX method is used in your laboratory?
_ SM 5320B _ Other
If "Other", please give the name, number or description of the method used by your
laboratory.
Does your lab have a written SOP for this analysis?
EQUIPMENT
Please list the equipment used in this analysis.
Yes No
Manufacturer
Model & Serial #
Instrument
Adsorption Module
Sample Storage
(other).
SAMPLE HANDLING INFORMATION
Type (& volume) of sample bottles and lids:
Storage Temp: °C Maximum Holding Time: Days
Are samples dechlorinated? Yes No ; with
Are samples acidified? Yes No ; with
Preserved sample's pH:
DBP/ICRmanual-l/28/94draft
70
-------
QC INFORMATION
MDL: Using the minimum detection limit procedure described in the DBP/ICR Analytical Methods
Guidance Manual, what is your lab's MDL for this analysis (/xgCl/L)?
Has this MDL been confirmed by analysis of a reagent water spiked near the MDL? Yes No
Please attach a copy of the analyte concentrations determined in each of the 7 (or more) replicates used
to calculate the MDL given above. Also indicate the concentration of the spiked samples.
IDC: Please list, in the table below, the Initial Demonstration of Capability (IDC) data that was
determined using the procedure outlined in the ICR method.
Mean Concentration
(MgCl/L)
Mean % Recovery
(accuracy)
%RSD
(precision)
TOX
Please attach a copy of the analyte concentrations determined in each day's analysis that was used to
calculate the IDC data given above.
METHOD BLANK
What is the ave. concentration of TOX in your method blanks?
igCl/L
What is your normal (non-ICR) minimum reporting limit for TOX?
Briefly describe how the reporting limits were established.
jigCl/L
DBP/ICRmanual-l/28/94draft
71
-------
PERFORMANCE EVALUATION
If your lab has analyzed PE samples, please list the three most recent results.
Study#_
Study#_
Study*.
DATE OF STUDY
TOX (mg/L)
ADDITIONAL INFORMATION
What types of quality control checks are performed for this analysis?__
At what concentration is the quality control check analyzed?.
How many TOX samples per week can your laboratory analyze? /wk
List the personnel who will be performing your analyses for the ICR and list their duties.
Name
Duties
DBP/ICRmanual-l/28/94draft
72
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Rev. 1/28/94
Method Approval for ICR
UV Absorbing Organic Constituents
Description: This analysis determines the UV absorbing organic constituents in water. Details of this
analysis are given in the ICR DBF Analytical Methods Guidance Manual.
Which method is used in your laboratory?
_SM 5910 (draft method) _ Other
If "Other", please give the name, number or description of the method used by your
laboratory.
Does your lab have a written SOP for this analysis? Yes No
EQUIPMENT
Please list any equipment used in this analysis.
Equipment
Spectrophotometer
Filter
Manufacturer
Model & Serial #
SAMPLE HANDLING INFORMATION
Type (& volume) of sample bottles and lids:
Storage Temp: °C Maximum Holding Time: Days
DBP/ICRmanual-l/28/94draft
73
-------
QC INFORMATION
MDL: Using the minimum detection limit procedure described in the DBP/ICR Analytical Methods
Guidance Manual, what is your lab's MDL for this analysis?
Has this MDL been confirmed by analysis of a reagent water spiked near the MDL? _ Yes _ No
Please attach a copy of the analyte concentrations determined in each of the 7 (or more) replicates used to
calculate the MDL given above. Also indicate the concentration of the spiked sample.
IDC: Please list, in the table below, the Initial Demonstration of Capability (IDC) data that was determined
using the procedure outlined in the ICR method.
UV
Concentration of KHP
(mg/L as DOC)
6.5
Mean Absorbance
at 2S4nm (cm'1)
%RSD
(precision)
Please attach a copy of the analyte concentrations determined in each day's analysis that was used to
calculate the IDC data given above.
METHOD BLANK
What is the ave. measurement of UV absorbance in your method blanks?
What is your normal (non-ICR) minimum reporting limit for UV absorbance?
Briefly describe how the reporting limits were established?
cm'1
DBP/ICRmanual-l/28/94draft
74
-------
PERFORMANCE EVALUATION
If your lab has analyzed PE samples, please list the three most recent results (cm'1).
Study#_
Study#.
Study*.
DATE OF STUDY
UV Absorbance
ADDITIONAL INFORMATION
What types of quality control checks are performed for this analysis?.
At what concentration is the quality control check analyzed?.
How many samples per week can your laboratory analyze? .
/wk
List the personnel who will be performing your analyses for the ICR and list their duties.
Name
Duties
DBP/ICRmanual-l/28/94draft
75
-------
Rev. 1/28/94
Method Approval for ICR
Total Hardness
Description: This analysis determines the total hardness concentration in water. Details of this analysis are
given in the ICR DBF Analytical Methods Guidance Manual.
Which method is used in your laboratory?
_ SM 2340B _ SM 2340C _ Other
If "Other", please give the name, number or description of the method used by your
laboratory.
Does your lab have a written SOP for this analysis? Yes No
EQUIPMENT
Please list any equipment used in this analysis.
Equipment
Manufacturer
Model & Serial #
SAMPLE HANDLING INFORMATION
Type (& volume) of sample bottles and lids:
Storage Temp: °C Maximum Holding Time: Days
DBP'/ICRmanual-l/28/94draft
76
-------
QC INFORMATION
MDL: Using the minimum detection limit procedure described in the DBP/ICR Analytical Methods
Guidance Manual, what is your lab's MDL for this analysis (mg/L)?
Has this MDL been confirmed by analysis of a reagent water spiked near the MDL? _ Yes No
Please attach a copy of the analyte concentrations determined in each of the 7 (or more) replicates used
to calculate the MDL given above. Also indicate the concentration of the spiked samples.
IDC: Please list, in the table below, the Initial Demonstration of Capability (IDC) data that was
determined using the procedure outlined in the ICR method.
Mean Concentration
(mg/L)
Mean % Recovery
(accuracy)
%RSD
(precision)
Total Hardness
Please attach a copy of the analyte concentrations determined in each day's analysis that was used to
calculate the IDC given above.
METHOD BLANK
What is the ave. concentration of Total Hardness in your method blanks?
_mg/L
What is your normal (non-ICR) minimum reporting limit for Total Hardness?
Briefly describe how the reporting limits were established?
.mg/L
DBP/ICRmanual-l/28/94draft
77
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PERFORMANCE EVALUATION
If your lab has analyzed PE samples, please list the three most recent results (mg/L).
DATE OF STUDY
Total Hardness
Study#_
Study#_
Study*.
ADDITIONAL INFORMATION
What types of quality control checks are performed for this analysis?.
At what concentration is the quality control check analyzed?
How many samples per week can your laboratory analyze? /wk
List the personnel who will be performing your analyses for the ICR and list their duties.
Name
Dudes
DBP/ICRmanual-l/28/94draft
78
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Rev. 1/28/94
Method Approval for ICR
Ammonia
Description: This analysis determines the concentration of ammonia in water. Details of this analysis are
given in the ICR DBF Analytical Methods Guidance Manual.
Which ammonia method is used in your laboratory?
_ SM 4500-NH3D _ SM 4500-NH3F
Other
If "Other", please give the name, number or description of the method used by your
laboratory.
Does your lab have a written SOP for this analysis? Yes No
EQUIPMENT
Please list the equipment used in this analysis.
Manufacturer
Model & Serial ff
Spectrophotometer
Filter
Photometer
Ammonia Selective
Electrode
Electrometer
(other).
DBP/ICRmanual-l/28/94draft
79
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SAMPLE HANDLING INFORMATION
Type (& volume) of sample bottles and lids:
Storage Temp: °C Maximum Holding Time: Days
Are samples dechlorinated? _Yes _No ; with
Are samples acidified? _Yes _No ; with
Preserved sample's pH:
QC INFORMATION
MDL: Using the minimum detection limit procedure described in the DBP/ICR Analytical Methods
Guidance Manual, what is your lab's MDL for this analysis (mg/L)?' '_
Has this MDL been confirmed by analysis of a reagent water spiked near the MDL? _ Yes _ No
Please attach a copy of the analyte concentrations determined in each of the 7 (or more) replicates used
to calculate the MDL given above. Also indicate the concentration of the spiked samples.
IDC: Please list, in the table below, the Initial Demonstration of Capability (IDC) data that was
determined using the procedure outlined in the ICR method.
Mean Concentration
(mg/L)
Mean % Recovery
(accuracy)
%RSD
(precision)
Please attach a copy of the analyte concentrations determined in each day's analysis that was used to
calculate the IDC data given above.
METHOD BLANK
What is the ave. concentration of ammonia in your method blanks?
_mg/L
What is your normal (non-ICR) minimum reporting limit for ammonia?
Briefly describe how the reporting limits were established?
_mg/L
DBP/ICRmanual-l/28/94draft
80
-------
CALIBRATION CURVE
List the approximate concentrations of the calibration standards used to
establish the standard curve (mg/L).
1
1 Ammonia
Stdll
Std#2
Std#3
Std#4
Std#5
PERFORMANCE EVALUATION
If your lab has analyzed for PE samples, please list the three most recent results.
DATE OF STUDY
Study#_
Study*.
Study#_
Ammonia (mg/L)
ADDITIONAL INFORMATION
What types of quality control checks are performed for this analysis?.
At what concentration is the quality control check analyzed?.
How many ammonia samples per week can your laboratory analyze? /wk
List the personnel who will be performing your analyses for the ICR and list their duties.
Name Duties
DBP/ICRmanual-l/28/94draft
81
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Rev. 1/28/94
Method Approval for ICR
Bromide and the Oxyhalides
Description: This analysis determines the concentration of bromide(Br) and the three oxyhalides,
bromate(BrO3'), chlorate(ClOj'), and chlorite(ClCV). Details of the bromide and oxyhalide analyses are
given in the ICR DBF Analytical Methods Guidance Manual.
Which method is used in your laboratory for the analysis of bromide and the oxyhalides?
_ EPA 300, _ Other
If "Other", please give the name, number or description of the method used by your
laboratory.
Does your lab have a written SOP for this analysis? Yes No
EQUIPMENT
Please list the equipment to be used in this analysis.
Manufacturer
Model & Serial #
Ion Chromatograph
Separator Column
Detector(s)
Suppressor
LLUENT AND SUPrKLaaUK lUArlUNEJ&AlN 1
Concentration (mM)
Flow rate (mL/min)
Frequency prepared
Eluent
Suppressor Regenerant
(N)
DBP/ICRmanual-l/28/94draft
82
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SAMPLE HANDLING INFORMATION
Type (& volume) of sample bottles and lids
Storage Temp: °C . Maximum Holding Time:
Are samples preserved? _Yes _No ; with
.Days
(_mg per_mL)
QC INFORMATION
MDL: Using the minimum detection limit procedure described in the DBP/ICR Analytical Methods
Guidance Manual, what is your lab's MDL for this analysis (/ig/L)?
Br:
BrO,-:_
CKV:_
C102-:.
Have these MDLs been confirmed by analysis of a reagent water spiked near the MDL?
_Yes _No -
Please attach a copy of the analyte concentrations determined in each of the 7 (or more) replicates and
the concentration of the spike used to calculate the MDLs given above. Also include an example
chromatogram from one of these determinations. Be sure to label each analyte, giving its retention
time, concentration, and detector attenuation.
IDC: Please list, in the table below, the Initial Demonstration of Capability (IDC) data that was
determined using the procedure outlined in the DBP/ICR Analytical Methods Manual.
Mean Concentration
(jig/L)
Mean % Recovery
(accuracy)
%RSD
(precision)
Br
BKV
cio3-
C1O2-
Please attach a copy of the analyte concentrations determined in each day's analysis that was used to
calculate the IDC data given above. Also include an example chromatogram from one of these
determinations. Be sure to label each analyte, giving its retention time, concentration, and detector
attenuation.
DBP/ICRmanual-l/28/94draft
83
-------
METHOD BLANK
What is the ave. concentration in your method blanks?
Br: _ BrO3: _ C1O3: _ CIO/:
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? (pg/L)
Br: BrO3': C1O3': CIO/:
Briefly describe how the reporting limits were established.
CALIBRATION CURVE
List the approximate concentrations of the calibration standards used to establish the standard
curve (/ig/L).
Br
BrO3-
cio3-
ClCv
Std#l
Std#2
Std#3
Std#4
Std#5
INTERNAL STANDARD
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
DBP/ICRmanual-l/28/94draft
84
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PERFORMANCE EVALUATION
If your lab has analyzed PE samples, please list the three most recent results (ug/L).
DATE OF STUDY
cio3-
cio2-
Study#_
Study#_
Study#_
ADDITIONAL INFORMATION
What types of quality control checks are performed for this analysis?.:
How many samples per week can your laboratory analyze? /wk
List the personnel who will be performing your bromide and oxyhalide analyses for the ICR and give
their duties.
Name
Duties
DBP/ICRmanual-l/28/94draft
85
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Appendix C
DRAFT Method 5910: UV Absorbing Organic Constituents
Proposed for Inclusion in the 19th Edition of
Standard Methods for the Analysis of Water and Wastewater
DBP/ICRmanual-l/28/94draft 86
-------
DBP/ICR Specifications for UV Measurements
In order to have comparable interlaboratory data from the DBP/ICR monitoring, some
additional specifications must be placed on draft Method 5910. These center on two areas of
the method: 1) the wavelength used for determining UV absorbance; and 2) whether the
sample pH should be adjusted prior to filtration.
Section l.a. of the method states that UV absorbance is measured at 2S3.7 nm (often
rounded off to 254 nm), but that alternate wavelengths may be selected. For purposes of the
ICR, all UV absorbance measurements should be made at 254 nm. The analyst may not
select an alternate wavelength, because data between laboratories would not be comparable.
The draft method states that adjustment of the sample pH prior to filtration is
optional. Although pH adjustment is useful in some situations, it should not be used for the
DBP/ICR. Adjusting the pH to a specific level such as 7 will probably not significantly
change the UV absorbance based on research by Edzwald et.al.1' The procedure also
introduces the possibility of forming precipitates or of accidentally contaminating the sample.
Therefore, for purposes of the ICR, the pH of the samples should not be adjusted for UV^
measurements..
Many UV absorbing compounds are potentially subject to biological degradation.
Therefore, samples should be analyzed as soon as possible after collection. For ICR
purposes, samples must be placed on ice at the time of collection and they must be analyzed
with 24 hours (sooner if possible).
1. Edzwald, J.K., W.C. Becker & K.L. Wattier. 1985. Surrogate
parameters for monitoring organic matter and THM precursors.
J. Amer. Water Works Assoc. 77:122.
DBP/ICRmanual-l/28/94draft 87
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DRAfT
1993 Version
5910 UV ABSORBING ORGANIC CONSTITUENTS'
5910 A. Introduction
Some organic compounds commonly found in water and wastewater, such as lignin,
tannin, humic substances, and various aromatic compounds, strongly absorb ultraviolet (UV)
radiation. UV absorbance is a useful surrogate measure of selected organic constituents in
fresh waters1*3, salt waters44, and wastewater74. Strong correlations may exist between UV
absorbance and nonvolatile total organic carbon (NVTOQ, color, and precursors of
trihalomethanes (THMs) and other organohalides9-10. UV absorbance also has been used to
monitor industrial wastewater effluents11 and to evaluate organic removal by coagulation10,
carbon adsorption12"13, and other water treatment processes10. Specific absorbance, the ratio
of UV absorbance to organic carbon concentration, has been used as an indicator of humic
substances10*14.
Although UV absorbance can be used to detect certain individual organic
contaminants after separation (e.g., by HPLC), as described in Part 6000, the method
described here is not suitable for detection of trace concentrations of individual chemicals. It
is intended to be used to provide an indication of the aggregate concentration of UV-
absorbing organic constituents.
The choice of wavelength is arbitrary. Historically, 253.7 nm has been used as the
standard wavelength; however, experienced analysts may choose a wavelength that minimizes
interferences from compounds other than those of interest while maximizing
"Approved by Standard Methods Committee, 199_.
Section 5910 1
-------
absorbance by the compound(s) of interest. If a wavelength other than 253.7 nm is used,
state that wavelength when reporting results
5910 B. Ultraviolet Absorbance Method
1. General Discussion
a. Principle: UV-absorbing organic constituents in the sample absorb UV light in
proportion to their concentration in the sample. Samples are filtered to control variations in
UV absorbance caused by particles. Adjustment of pH prior to filtration is optional. UV
absorbance is measured at 253.7 nm (often rounded off to 254 nm); however, alternate
wavelengths may be selected.
b. Interferences: The primary interferences in UV-absorbance measurements are
from colloidal particles, UV-absorbing organics other than those of interest, and UV-
absorbing inorganics, notably ferrous iron, nitrate, nitrite, and bromide. Certain oxidants
and reducing agents, such as ozone, chlorate, chlorite, chloramines, and thiosulfate also will
absorb ultraviolet light at 253.7 nm. Many natural waters and waters processed in drinking
water treatment plants have been shown to be free of these interferences.
Evaluate and correct for UV absorbance contributed by the specific interfering
substances. If cumulative corrections exceed 10% of the total absorbance, select an alternate
wavelength and/or use another method. Because UV absorbance by organic matter may vary
at pH values below 4 or above 10 theses values should be avoided.10
A UV absorption scan from 200 to 400 nm can be used to determine the presence of
interferences. Typical absorption scans of natural organic matter are featureless curves of
Section 5910 2
DRAfT
-------
increasing absorbance with decreasing wavelength. Sharp peaks or irregularities in the
absorption scan may be indicative of inorganic interferences or unexpected organic
contaminants. Because many organic compounds in water and wastewater (e.g., carboxylic
acids and carbohydrates) do not absorb significantly in the UV wavelengths, it is desirable to
correlate UV absorbance to dissolved organic carbon (DOC) or soluble chemical oxygen
demand (COO). However, use such correlations with care because they may vary from
water to water, seasonally on the same water, and between raw and treated waters. In
addition, chemical oxidation (e.g., ozonation, chlorination) of the organic material may
reduce UV absorbance without removing the organics and thus may change correlations.
Since UV absorbance and correlations with UV absorbance are site specific they may not be
comparable from one water source to another.
c. Minimum detectable concentration: The minimum detectable concentration cannot
be determined rigorously because this is a nonspecific measurement. For precise
measurement, select cell path length to provide an absorbance of approximately 0.005 to
0.900 cm'1. Alternatively, dilute high-strength samples. The minimum detectable
concentration of a particular constituent depends on the relationship between UV absorbance,
the desired characteristic (e.g., trihalomethane formation potential (THMFP), DOC) and any
interfering substances. For example, a solution containing aquatic fulvic acid had an
absorbance of 0.110 cm'1, when 1-cm cells were used, which was found to be approximately
equal to 2.5 mg/L DOC.
Section 5910 3
DRAfT
-------
2. Apparatus
a. Spectrophotometer, for use between 200 and 400 nm with matched quartz cells
providing a light path of 1 cm. For low-absorbance samples use a path length of 5 or 10
cm. A scanning spectrophotometer is useful.
b. Filter: Use a glass-filter' without organic binder. Other filters that neither sorb
UV-absorbing organics of interest nor leach interfering substances (e.g., nitrate or organics)
into the water may be used, especially if colloidal matter must be removed. Alternatively
use filters of teflon, polycarbonate, or silver. Prerinse filter with sample or organic-free
water to remove soluble impurities. If alternate separation techniques or filters are used,
demonstrate that equivalent results are produced.
c. Filter assembly, glass, TFE, or stainless steel, capable of holding the selected
filters.
3. Reagents
a. Organic-free water: Type I reagent water (see Section 1080) or equivalent water
containing less than O.OS mg/L DOC.
b. Hydrochloric acid (optional), HC1, 0.1N.
c. Sodium hydroxide (optional), NaOH, 0.1N.
d. Phosphate buffer (optional): Dissolve 4.08 g dried anhydrous KH2PO4 and 2.84 g
dried anhydrous Na2HPO4 in 800 mi, organic-free water. Verify that pH'is 7.0, and dilute to
Whatman grade 934H; Gelman type A/E; Millipore type AP40; ED Scientific
Specialties grade 161; or other products that give demonstrably equivalent results.
Practical filter diameters are 2.2 to 4.2 cm.
Section 5910 4
DRAfT
-------
1 L with organic-free water. Store in brown glass bottle at 4°C. Prepare fresh weekly or
more frequently if bacterial growth is observed.
4. Procedure
a. Sample volume: Select sample volume on basis of the cell path length or dilution
required to produce a UV absorbance between 0.005 and 0.90 cm'1. For most applications a
50-mL sample is adeqimte. Use 100 mL sample if a 10-cm cell path length is required.
b. Sample preparation: Wash filter and filter assembly by passing at least SO mL
organic-free water through the filter. For specific applications and correlations, the analyst
may choose to adjust sample pH. pH adjustment using HC1 or NaOH is recommended. In
poorly buffered samples an appropriate non-UV absorbing buffer system such as a phosphate
buffer may be used. Care must be taken to avoid precipitate formation" during pH
adjustment Work by Edzwald et al.10 suggests that UV absorbance of fulvic acid solutions
remains constant between pH 4 and 10. The sample pH value used should be reported along
with the recorded absorbance. Once sample pH has been adjusted and/or measured, then
filter the sample. Prepare an organic-free water blank in exactly the same way the sample is
prepared.
c. Spectrophotometric measurement: Let spectrophotometer equilibrate according to
manufacturer's instructions. Set wavelength to 253.7 nm and adjust spectrophotometer to
read zero absorbance with the organic-free water blank. Measure UV absorbance at 253.7
nm of at least two filtered portions of sample at room temperature.
Section 5910 5
DRAFT
-------
5. Calculation
Report mean UV absorbance in units of cm'1 using the following notation. Analysts
may also choose to report units in m*1: by simply multiplying the equation by one hundred.
AXPH (cm -1) =
A
D
where:
AfH = mean UV absorbance, cm'1; subscript should denote wavelength used
(nm); superscript should denote pH used if other than 7.0.
b = cell path length, cm,
A = mean absorbance recorded, and
D — dilution factor resulting from pH adjustment and/or dilution with
organic-free water.
_ final sample volume
initial sample volume
Correct results for absorbance contributed by known interfering substances. If UV
absorbance contributed by interfering substances exceeds 10% of the total UV absorbance do
not use UV absorbance at 253.7 nm as an indicator of organics.
6. Quality Control
a. Replicate measurements: Use at least two portions of filtered sample.
b. Duplicate analyses: Analyze every tenth sample in duplicate (i.e., duplicating the
entire procedure) to assess method precision.
Section 5910 6
DRAfT
-------
c. Baseline absorbance: Check system baseline UV absoibance at least after every
10 samples by measuring the absorbance of organic-free water blank. A non-zero
absorbance reading for the blank may indicate need for cell cleaning, problems with the
reference cell if a dual-beam instrument is being used, or variation in the spectrophotometer
response caused by heating or power fluctuations over time.
d. Spectrophotometer check: Difficulties in comparing UV data from different
spectrophotometers have been reported. Therefore potassium hydrogen phthalate (KHP) also
known as potassium biphthalate standards were prepared in Type I water without acidification
(refer to section S310.B.3.C for details on preparation) and analyzed using five laboratories.
The results are shown in Table 5910:1 and these data suggest acceptable precision. These
data are also useful in correlating UV^ with KHP standards commonly used for DOC and/or
COD analysis. The resulting correlation equation is:
-2 _ n007
UV^cm'1) = 0.0144 (KHP-mg/L as DOC) + 0.0018 rQ ; JJp'
This equation can assist analysts in verifying spectrophotometer performance. For example,
if a set of UV^ analyses are performed and the results are in the 0.010 range the analyst can
prepare a KHP standard of 0.5 mg/L as DOC. The projected UV^ of this KHP standard
would be 0.009 cm'1. If the analyst measures the UV^ to be outside 13% relative standard
deviation (USD) of 0.009 cm'1 the spectrophotometer may be suspect and require
maintenance.
Section 5910 7
DRAFT
-------
7. Precision and Bias
Table 5910:1 shows inteiiaboratory precision data for forty samples. The percent
relative standard deviations (% RSD) ranged from 9.38 to 12.8.
Single-operator precision data are presented in Table 5910:11 for dissolved organic
carbon (DOC) concentrations typically found in natural waters13. The % RSD ranged from
0.9 to 6%. Because UV absorbance is an aggregate measure of organic carbon, true
standards are not available and bias cannot be determined.
8. References
1. DOBBS, R.A., R.H. WISE & R.B. DEAN. 1972. The use of ultra-violet
absorbance for monitoring the total organic carbon of water and wastewater. Water
Res. 6:1173.
2. WILSON, A.L. 1959. Determination of fulvic acids in water. J. Appl. Chan.
9:501.
3. COOPER, W.J. & J.C. YOUNG. 1984. Chemical Non-specific Organic Analysis.
In R.A. Minear & L. Keith, Eds. Water Analysis, Vol. 3. Academic Press, New
York, NY.
4. OGURA, N. & T. HANYA, 1968. Ultra-violet absorbance of the seawater, in
relation to organic and inorganic matters. Int. J. Oceanol. Limnol. 1:91.
5. OGURA, N. & T. HANYA, 1968. Ultra-violet absorbance as an index of pollution
of seawater. J. Water Pottut. Control Fjed. 40:464.
Section 5910 8 DRAFT
-------
6. FOSTER, P. & A.W. MORRIS. 1971. The use of ultra-violet absorption
measurements for the estimation of organic pollution in inshore sea waters. Water
Res. 5:19.
7. BUNCH, R.L., E.F. EARTH & M.B. ETTINGER. 1961. Organic materials in
secondary effluents. /. Water Pollut. Control Fed. 33:122.
8. MRKVA, M. 1971. Use of ultra-violet spectrophotometry in the determination of
organic impurities in sewage. Wasserwirtsch-Wassertech. 21:280.
9. SINGER, P.C., JJ. BARRY, HI, G.M. PALEN & A.E. SCRIVNER. 1981.
Trihalomethane formation in North Carolina drinking waters. /. Amer. Water Works
Assoc. 73:392.
10. EDZWALD, J.K., W.C. BECKER & K.L. WATTIER. 1985. Surrogate parameters
for monitoring organic matter and THM precursors. J. Amer. Water Works Assoc.
77:122.
11. BRAMER, H.C., M.J. WALSH & S.C. CARUSO. 1966. Instrument for
monitoring trace organic compounds in water. Water Sewage Works 113:275.
12. BISHOP, D.F., L.S. MARSHALL, T.P. O'FARRELL, R.B. DEAN, B.
O'CONNOR, R.A. DOBBS, S.H. GRIGGS & R.V. VILLIERS. 1967. Studies on
activated carbon treatment. J. Water Pollut. Control Fed. 39:188.
13. SONTHEIMER, H.N., E. HEILKER, M.R. JEKEL, H. NOLTE, & F.H.
VOLIMER. 1978. The Mulheim process. /. Amer. Water Works Assoc. 70:393.
14. THURMAN, E.M. 1985. Organic Geochemistry of Natural Waters. Martinus
Nijhoff/Dr. W. Junk Publishers, Dordrecht, Netherlands.
Section 5910 9
-------
15. MALLEY, J.P., JR. 1988. A Fundamental Study of Dissolved Air Flotation for
Treatment of Low Turbidity Waters Containing Natural Organic Matter. Ph.D. thesis
(unpublished), Univ. Massachusetts, Amherst
Section 5910 10
-------
TABLE 5910:1 PRECISION OF UV ANALYSES AND CORRELATION TO DOC
MEASUREMENTS OF KHP SAMPLES
Parameter
0.54
0.93
KHP Samples (mg/L as DOC)
1.79 4.87 9.61 25.0
50.0
100.0
UV2J4 Results (cm'1)
Laboratory
Laboratory
Laboratory
Laboratory
Laboratory
Mean
1
2
3
4
5
Std Deviation
%RSD
0.008
0.009
0.010
0.007
0.009
0.0086
0.0011
12.8
0.015
0.016
0.017
0.020
0.018
0.0142
0.0019
11.1
0.034
0.026
0.027
0.033
0.030
0.0300
0.0035
11.7
0.079
0.070
0.081
0.070
0.087
0.0774
0.0074
9.56
0.158
0.134
0.161
0.132
0.140
0.1450
0.0136
9.38
0.323
0.401
0.353
0.319
0.394
0.3580
0.0384
10.7
0,638
0.803
0.695
0.750
0.643
0.7058
0.4)708
10.0
1.282
1.612
1.343
1.590
1.447
•
1.4548
0.1461
10.0
TABLE 5910:H SINGLE-OPERATOR PRECISION FOR UV ABSORBANCE
MEASUREMENTS OF FULVIC ACID SOLUTIONS
Replicate
No.
1
2
3
4
5
6
7
8
9
10
Mean
Std. Deviation
%RSD*
DOC - 2.5 mg/L
0.110
0.120
0.110
0.100
0.110
0.100
0.110
0.110
0.120
0.110
0.110
0.00667
6.06
DOC = 4.9 mg/L
UV2J4 Results (cm'1)
0.240
0.230
0.240
0.230
0.240
0.240
0.240
0.230
0.240
0.240
0.237
0.00483
2.05
DOC = 10.0 mg/L
0.480
0.480
0.470
0.480
0.480
0.470
0.480
0.480
0.480
0.480
0.478
0.00422
0.882
"The percent relative standard deviation (% RSD) is given by:
_cr. [standard deviation (S)
KaU - — .
mean (X)
x 100
Section 5910 11
-------
Appendix D
DRAFT Method 6252: Ozonation Byproducts: Aldehydes
Proposed for Inclusion in the 19th Edition of
Standard Methods for the Analysis of Water and Wastewater
DBP/ICRmanual-l/28/94draft 99
-------
6252 OZONATION BYPRODUCT'S: ALDEHYDES
6252 A. Introduction
1. Sources and Significance
Ozone reactions during water treatment are complex and often form a wide range of
unstable oxidation byproducts usually oxygenated and polar in nature. Among the intermediate
products formed, when ozone attacks the organic matter present in raw waters, are low molecular
weight byproducts such as aldehydes. If oxidized further, these aldehydes can produce aldo-acids
and carboxylic acids. Formaldehyde, a ubiquitous component of the environment may be
introduced into the drinking water supply by ozone treatment, natural metabolism, and
commercial processes.
There are two postulated mechanisms for aldehyde formation during ozone treatment. The
first involves a two-step Criegee attack at unsaturated C-C bonds by molecular ozone with
ozonides or epoxides formed as intermediates1. The second involves an indirect reaction of OH
radicals2. Although the levels of aldehyde formation are usually a function of ozone dose, their
concentrations are often controlled in water treatment by increasing the pH and thus the alkalinity
of the water.
Aldehydes are unlikely to pose a serious health hazard to the consumer at the parts per
billion (ppb) levels usually encountered in drinking water treatment However, they are known
to react with nucleophiles even at these low levels and could therefore be a potential threat3.
Thus, for example, formaldehyde, acetaldehyde, and crotonaldehyde are known animal
carcinogens and formaldehyde is a known human carcinogen4. Aldehydes may also serve as
important components of assimilable organic carbon in promoting undesirable bioactivity in water
treatment
2. Selection of Method
The most effective methodology for the determination of aldehydes in aqueous solutions
involves the use of O-(2,3,4,5,6- pentafluorobenzyl)-hydroxylamine (PFBHA)* as a derivatizing
agent. PFBHA reacts with low molecular weight carbonyl compounds, including aldehydes, in
aqueous solutions to form the corresponding oxiraes. Unless the carbonyl compound is a
symmetrical ketone or formaldehyde, two geometric isomers of the oxime derivatives are formed,
namely the entgegen (E) and zusaramen (Z) isoraers. These derivatives are extractable with
organic solvents and are highly sensitive to analysis by gas chroraatography with electron capture
detection (GC/ECD) and gas chromatography with selective ion mass spectrometric detection
(GC/SIM-MS).
* This reagent appears in the literature under various synonyms. The more commonly found
are O-(2,3,4,5,6-pentafluorophenyl)methylhydroxylamine hydrochloride with CAS RN 57981-02-
9, pentafluorobenzyloxylamine hydrochloride (PFBOA). It also has appeared with the acronym
PFBHOX.
-------
An alternate method employing aqueous derivatization of the aldehydes using 2,4-
dinitrophenylhydrazone has not been widely demonstrated for sample analyses in water treatment
plants. This methodology utilizes high performance liquid chromatography (HPLC) for the
analysis of the derivatives and does not achieve the necessary ppb sensitivity to accurately
measure aldehyde occurrence in drinking water when compared to the PFBHA method.
3. References
1. Glaze, W. H., M. Koga, and D. Concilia. 1989. Ozonation By-products. 2.
Improvement of an Aqueous-Phase Derivatization Method for the Detection of
Formaldehyde and Other Carbonyl Compounds Formed by the Ozonation of Drinking
Water. Environ. Sci. Technol., 23(7):838-847
2. Bailey, P.S. 1978. Ozonation in Organic Chemistry, Vol. I, Olefinic Compounds. New
York: Academic Press. Ch. 4.
3. National Academy of Sciences, 1987. Drinking water and health. Washington, D.C., pp.
152-153.
4. American Conference of Governmental Industrial Hygienists. Documentation of the
Threshold Limit Values and Biological Exposure Indices, 6th edition. ACGIH, Cincinnati,
Ohio, 1993.
6252B. PFBHA Liquid-Liquid Extraction Gas Chroraatographic Method
This method has been demonstrated for the aqueous-phase derivatization of straight-chain, low
molecular weight aldehydes in raw and treated drinking water supplies and can simultaneously
analyze for C,-C,0 mono-carbonyl saturated aliphatic aldehydes, benzaldehyde, the dialdehyde
glyoxal, and the keto-aldehyde dimethyl glyoxal1. The effectiveness of the derivatizing agent
(PFBHA) in its reactions with these carbonyl compounds has also been reviewed2.
1. General Discussion
a. Principle: Samples at room temperature are buffered to pH 6, PFBHA is added and
then the samples are placed in a constant temperature water bath. The carbonyl compounds are
converted to their corresponding oximes during reaction with PFBHA. Sulfuric acid is used to
quench excess PFBHA and the oxime derivatives are extracted with hexane. Following a sulfuric
acid cleanup step, the organic extract is analyzed by gas chromatography where the volatile
derivatives are easily separated. A temperature programmable gas chromatograph using a fused
silica capillary column and either an electron capture detector or selective ion mass spectroscopy
is used for analysis. Simultaneous analysis and confirmation using a single injection can be
effected by setting up both the analytical column and the confirmation column to share a
common injection port Alternatively, use separate analytical and confirmation columns. Aqueous
calibration standards are derivatized, extracted and analyzed in the same manner. A surrogate
recovery standard is added to the samples prior to derivatization to indicate any variation in
derivatization and extraction efficiency.
-------
With the exception of symmetrical ketones and formaldehyde, most carbonyl compounds
form two geometrical isomers of oxime derivative. Methyl glyoxal, however, produces only one
prominent isomer which may be attributable to some steric hindrance.
b. Interferences: Dissolved ozone, residual chlorine, and other oxidizing substances
interfere with the PFBHA reaction. The quantitative addition of sodium thiosulfate as a reducing
agent is recommended .prior to derivatization. The presence of ketones and quinones or large
quantities of aldehydes due to either ozonolysis or water pollution, may deplete the PFBHA
reagent excess necessary to ensure complete reaction. Waters with high sulfide content are known
to inhibit the derivatization of carbonyl compounds. The occurrence of artifacts by aldehyde
formation from thermal decomposition of water components is a potential positive interference.
Since formaldehyde is used as a preservative for membranes, purified water production from
reverse osmosis is also a potential positive interference. In addition, formaldehyde and
acetaldehyde are air pollutants and some formaldehyde in the air can be traced to the presence
of certain insulation materials.
c. Detection limits: The method detection limits (MDL) "and precision data for .those
aldehydes most commonly found in ozonated waters are given in Table 6252:1. These limits were
evaluated for the extracted oximes in hexane from aldehyde-free water. The minimum reporting
levels (MRL) for these aldehydes are usually set at 5 times the MDL. In effect, the MRL for all
aldehydes analyzed by this method is 0.5 ug/L except for acetaldehyde and glyoxal where the
value is 1 ug/L. The precision data as presented in the table may be matrix sensitive and
recovery, by the method of known standard additions to the matrix, should be evaluated if oxime
standards are not available.
This method has been shown to be useful for detecting carbonyl compounds such as short-
chain aldehydes (Q - C10), benzaldehyde, glyoxal and methyl glyoxal in the range of 1 to 100
ug/L. A clean laboratory reagent water blank, free of these contaminants, is very important
Table 6252:1 METHOD DETECTION LIMITS (MDL) AND PRECISION DATA IN
ORGANIC-PURE WATER
Formaldehyde
Acetaldehyde
Heptanal
Benzaldehyde
Glyoxal
Methyl glyoxal
Added
Cone.
ug/L)
0.550
0.435
0.255
0.245
0.445
0.420
Found
Cone.
(ug/L)
0.518
0.318
0.191
0.227
0.315
0.355
Standard
Devn.
(ug/L)
0.026
0.061
0.025
0.022
0.073
0.033
Relative
Standard
Devn. (%)
5.04
19.3
13.1
9.9
23
9.4
MDL
(ug/L)
0.082
0.193
0.079
0.079
0.228
0.105
Based on the analysis of seven portions of organic-pure water with known additions
-------
d. Safety: The toxicity or carcinogenicity of each reagent used in this method has not been
defined precisely. Acetaldehyde, crotonaldehyde, and formaldehyde are carcinogens and should
be handled in laminar-flow hoods. Handlers should wear quantitatively-fitted negative pressure
respirators with charcoal air-purifying filter canisters, and wear gloves (such as Butyl but not
natural rubber. Latex or Nitrile2) and protective garments resistant to the degrading effects and
permeation of these chemicals. Glyoxal and methyl glyoxal are mutagenic in vitro tests and the
former has subchronic oral toxicity. Care should be taken when handling high concentrations of
aldehydes, during preparation of primary standards. When handling the hexane solutions of the
oxime derivatives, Nitrile gloves (not Butyl or Latex) should be worn.
2. Sampling & Storage
See section 6010B.1 and note the following additional requirements.
The vials in which the aqueous samples are collected and stored must be sealed with teflon-
lined polypropylene screw caps*. Bakelite black caps which are made from a formulation
containing phenol and formaldehyde should not be used. If free chlorine is present in the
samples, ammonium chloride or sulfate (0.1 mL of a 20% by weight solution per 40mL sample)
should be present in the vials prior to sample collection. Monochloramine would be formed but
will not change the aldehyde concentration of samples subsequently stored at 4°C. If residual
ozone is present in collected samples, the levels of aldehydes may change as the ozone-natural
organic matter reaction continues. In this case, the quantitative addition of sodium thiosulfate to
the empty vials is recommended as a reducing agent of ozone. An alternative means of quenching
residual ozone is to add 0.1 mL of a 3g/L solution of potassium iodide to each 40mL vial.
The field reagent blanks need to be prepared from the same special high purity aldehyde-free
reagent water that is used throughout this method (see section 4e).
Samples for aldehyde analysis should be derivatized and extracted within 48 hours of
collection.
3. Apparatus
a. Sample containers and extraction vials: 40mL screw-top, glass sample vials must be used
with aldehyde-free caps (see section 2 above). These, together with the 14raL amber vials for
storing stock solutions, should be prepared in the following way,
(i) initial wash with detergent
(ii) rinse with tap-water
(iii) soak in 10% nitric acid for at least 30 minutes
(iv) rinse with tap water
(v) final rinse with laboratory organic-pure water (see section 4e below)
(vi) oven dry at 180°C for at least 1 hour.
Caps and septa are cleaned by rinsing with methanol then hexane and are dried in an oven at
80°C for no more than one hour in a clean, forced-air convection oven.
b. Microsyringes or Eppendorf micro-pipettes with glass tips, to measure the following
volumes, 5, 10, 25, 50, 100, 250, 500, and 1000 uL.
* I-Chem Research, Hayward, Ca.
-------
c. Volumetric flasks: 5raL, lOmL, and 25mL pyrex glass flasks are prepared initially by the
method of section 3(a) (i) to (v). After rinsing with organic-pure water, the flasks are rinsed with
raethanol and then inverted to drain. These flasks should be air-dried only. DO NOT DRY IN
OVENS. Any attempt to do so will invalidate the calibration of the flask.
d. Syringe: 20mL glass hypodermic, metal luer lock tip with 8.9-cm- (3.5-in.-) long x 17
gauge stainless steel pipetting needle (alternatively use a 20-mL volumetric pipette). Clean
according to the procedure of section 3a above.
e. Automatic pipette dispensers: In order to simplify batch processing, reagent addition is best
achieved by the use of these dispensettes. Adjustable 1-mL ( 2 required) and 4-raL sizes with
PTFE transfer lines that can be mounted on the suppliers' reagent bottles are preferred. If these
are not available use ImL and 4mL volumetric pipettes.
/. Constant temperature water bath or incubator, capable of holding multiple 40mL sample
vials and maintaining 45°C ± 0.5°C.
g. Pasteur pipettes: A selection of short-tipped (14.6cm or 5.75 in) and long-tipped (23cm
or 9 in) should be available.
h. Mechanical shaker*, to automate hexane extraction (see method 6233B, section 3e).
Alternatively use a vortex mixer or manual shaking for one minute.
i. Storage vials: ImL glass, screw-cap vials with PTFE lined silicone septa cleaned in the
manner described in part a above.
j. Gas chromatograph, which can accommodate capillary columns, is required for sample
analysis. The instrument should be temperature programmable and be supplied with a temperature
controlled injector and electron-capture detector.
1) Gas handling equipment: Use carrier (helium) and make-up (nitrogen or 95% argon/5%
methane) gases of high purity (99.999%) grade that pass through indicating calcium sulfate,
molecular sieve 5A, activated charcoal, and an oxygen purifying cartridge. Use two-stage metal
diaphragm high-purity regulators at the compressed gas sources. Use flow controllers to regulate
carrier gas flow. Ensure that all gas lines use 0.3-cra (1/8 in.) copper (or stainless steel) tubing:
rinse with high-purity acetone and bake before use.
2) Injector, split/splitless (using straight open bore insert).
3) Analytical column,** 30 m long x 0.25 ram ID, fused silica capillary column with a 0.25-
um film thickness or equivalent
4) Confirmation column*** 30 m long x 0.25 mm ID, fused silica capillary column with
a 0.25-nm film thickness or equivalent
5) Detectors, a constant current pulse modulated MNi BCD with standard size cell (use two
ECDs for simultaneous confirmation analysis).
* Erebach or equivalent
** Durabond-5, J&W Scientific, or equivalent
*** Durabond-1701, J&W Scientific, or equivalent
-------
4. Reagents
a. Extraction solvent, GC/MS and capillary grade hexane*.
b. Solvent for standard preparation, GC/MS grade methanol1.
c. Preservation agents, ammonium chloride or sulfate, sodium thiosulfate, all of ACS reagent
grade or equivalent.
d. Sulfiiric acid, HjSO4, concentrated and 0.2N.
e. Organic-pure reagent water: In view of the inability of most commercially available water
filter systems to consistently remove all traces of aldehydes, it is necessary to further treat such
water in order to remove these high background levels. Two methods have been demonstrated
to this effect:
(i) Subject the reagent water produced by a laboratory purification system* to UV irradiation of
1 hour,
(ii) distill the reagent water from acidified potassium permanganate (SOOmL water with 64mg
potassium permanganate and IraL concentrated sulfuric acid).
Alternative purification techniques, such as the addition of an additional granular activated carbon
filtration step, might be employed if they can be shown to effectively eliminate background levels
of aldehydes. DO NOT USE A REAGENT WATER WITH FORMALDEHYDE
CONTAMINATION TO QUANTIFY FORMALDEHYDE IN AQUEOUS SAMPLES.
/ Buffer pH 6 reagent: The buffer reagent is prepared in a 200mL volumetric flask by
mixing lOOmL of a 0.5M potassium hydrogen phthalate solution in aldehyde-free water with 43.6
mL of a 1M sodium hydroxide and bringing to the total volume with water. ImL of this solution
is added to each 20mL aliquot of aqueous sample prior to derivatization.
An alternative buffer solution can be prepared by dissolving 0.2g Hydrion buffer salt*
g. Derivations agent, PFBHA': O-(2,3,4^,6-pentafluorobenzyl)-hydroxylamine hydrochloride
is weighed gravimetrically into organic-pure water to give a solution concentration of 15mg/mL.
This solution is to be prepared fresh daily. Prepare a sufficient quantity to allow for the addition
of ImL of this reagent to each 20mL of aqueous sample.
h. Standard materials, see Table 6252.H for source and physical characteristics of the
standards. The purity assay of each purchased standard should be obtained from the supplier prior
to use.
1) Individual aldehyde standard stock solutions: These are prepared by gravimetric
measurement of the aldehyde standards in methanol. Weigh between 20 and 70rag of each
standard into a lOraL volumetric flask. Solid standards should be weighed directly into the empty
flask which is then filled to the mark with methanol. Liquid standards should be added to the
flask which has previously been filled to the neck with methanol, placed on a weighing balance
and the weight stabilized. The liquid standard should be injected with a raicrosyringe directly into
the bulk of the methanol and the exact weight determined after addition.
* Burdick & Jackson, Muskegon, Mich., or equivalent
1 Sigma Chemical Co., St. Louis, MO, or equivalent
* Milli-Q, Millipore Corp.. Bedford, Mass., or equivalent
Micro Essential Lab., Inc., Brooklyn, NY
T Aldrich Chemical Co. or equivalent
-------
TABLE 6252.H ANALYTICAL STANDARDS OF CARBONYL COMPOUNDS USED IN
THE PFBHA METHOD
Compound
Formaldehyde
Acetaldehyde
Propanal (propionaldehyde)
Butanal (n-butyraldehyde)
Pentanal(n-valeraldehyde)
Hexanal (caproaldehyde)
Heptanal (heptaldehyde)
Octanal (caprylic aldehyde)
Nonanal (nonyl aldehyde)
Decanal (decyl aldehyde)
Benzaldehyde
Glyoxal (ethanedial)
Source
Aldrich*
CheraSvc1
Aldrich
ChemSvc
Aldrich
Aldrich
Aldrich
Aldrich
ChemSvc
CheraSvc
ChemSvc
ChemSvc
Purity
t
97
99
98
95
99
t
Molecular
Weight
(mg/mmol)
33.03
44.05
58.08
72.11
86.13
100.16
114.19
128.22
142.24
156.27
106.12
58.04
Boiling
Point
96
21
46-50
75
103
131
153
171
93
207-209
178-179
50
Density
(g/raL)
1.083
0.788
0.805
0.800
0.810
0.834
0.818
0.821
0.827
0.830
1.044
1.14
Methyl glyoxal
(pyruvic aldehyde or
2-oxopropionaldehyde)
Aldrich
72.06
72
1.045
Note: Compound purity is assumed to be 99.9 percent unless otherwise stated.
*Aldrich Chemical Company, Inc., Milwaukee, Wis.
'Formaldehyde is available in 37-percent solution (by weight) in water
tChemService, Inc., West Chester, Pa.
*Glyoxal and methyl glyoxal are available in 40-percent solutions (by weight) in water
Since some of the aldehyde standards are supplied as aqueous solutions, the weight of actual
standard component must be evaluated and an approximate determination of the required volume
to be added to methanol can be calculated from either the density (for pure liquids) or the
percentage by weight (for solutions). Due to the high volatility of acetaldehyde, this standard
should be kept in the refrigerator at all times and the syringe used to measure the standard for
the stock solution placed in the freezer for ten minutes prior to preparing the stock solution. After
diluting to lOmL with methanol, cap the flask and invert 3 times to mix. Transfer the stock
solutions to separate 14mL amber vials with screw-caps and PTFE liners and store at 4°C bound
with Parafilm®. The stock solutions, which are usable for up to 3 months (except in the case
of formaldehyde), are allowed to come to room temperature before aliquoting. The occurrence
-------
of turbidity or a precipitate can be overcome by ultrasonication in warm water. If a precipitate
persists, the stock solution must be remade. Formaldehyde stock solutions should be prepared
freshly each month.
The aldehyde concentrations of the aqueous solutions can be verified after filtration through
0.45um FIFE filters by the sodium bisulfite-iodine titration method3.
2) Multicomponent aldehyde additive standards: Prepare the additive standards solution
using the individual stock solutions of those aldehydes which you are interested in quantifying.
As this solution should be freshly made each week, it may not be necessary to include all
aldehyde components each time. The resulting concentration of each component in this additive
standard solution should be about 10 mg/L when used for spiking 20mL aqueous samples. When
used for preparing a calibration curve in lOOmL of organic-pure water, it may be appropriate to
prepare two or more multicomponent additive standards from which a volume in die range 10-
lOOuL can be injected directly into the water to give the required calibration range. For example,
if the stock solution concentration is SOmg in lOraL or Sg/L, you would require 20uL of this
stock solution in lOraL methanol to produce a lOrag/L additive standard. This is best achieved
by first filling the lOmL volumetric flask to just above the neck with methanol. Inject the
required volume of each of the stock solutions, using a clean microsyringe for each component,
into the bulk of the methanol. After adding all stock solutions, fill to the mark of the flask with
methanol. Cap and invert 3 times to mix.
i. Standards derivatives: In order to determine the reaction efficiency and extraction
efficiency of each aldehyde in different matrices it is necessary to compare the chromatographic
response of the derivatized standard in the matrix to that of authentic standards of the oximes.
The surrogate standard employed in this method has been used to establish optimum conditions
for derivatization and laboratory synthesized oximes for six of the aldehydes have been used to
verify the recovery of derivatized aldehydes from organic pure water. These results are shown
in Table 6252:111. Nevertheless, unforseen matrix effects can still occur, and because PFBHA
derivatized aldehyde standards (oxiraes) are not available commercially, some representative
syntheses of these derivatives are available4.
TABLE 6252:in RECOVERY OF OXIME DERIVATIVES FROM ORGANIC-PURE
WATER
Compound
Formaldehyde
Acetaldehyde
Heptaldehyde
Benzaldehyde
Glyoxal
Methyl glyoxal
Recovery (%)
90.4
100
84.3
107
82.0
92.5
8
-------
j. Internal standard, 1,2-dibromopropane and decafluorobiphenyl both 98% purity, Aldrich
Chemical Company, Inc., Milwaukee, Wis.
1) Internal standard stock solution, Weigh SO mg into a 10-mL volumetric flask containing
methanol up to the neck. Fill flask to the mark with methanol. This will yield a 5 g/L stock
solution which can be used for up to six months when stored as described under section hi.
2) Internal standard working solvent, 100 ug/L in hexane: Deliver 20uL internal standard
stock solution directly .into 1-L of hexane in the solvent bottle to be used in the extraction
procedure. Cap the bottle and invert 3 times to ensure thorough mixing. This dilution can be used
for 4 weeks. In order to ensure suitability for extraction, always run a sample of this working
solvent on the GC prior to extraction of aqueous samples. Before processing samples, ensure that
there is sufficient working solvent to extract all the calibration and aqueous samples to be
analyzed. NEVER MAKE UP FRESH WORKING SOLVENT FOR USE DURING SAMPLE
PROCESSING.
k. Surrogate, (SUR) 2,3,5,6-tetrafluorobenzaldehyde, 98% pure, Aldrich Chemical Company,
Inc., Milwaukee, Wis.
1) Surrogate stock solution, 20g/L: Weigh 0.2g SUR into a 10-mL volumetric flask
containing methanol up to its neck. After determining the weight difference, fill to the mark with
methanol. Stock solutions can be used for up to 6 months if stored under the conditions described
in section hi.
2) Surrogate additive solution, 20mg/L. Deliver 10 (iL SUR stock solution into a 10-mL
volumetric flask and dilute to the volume with methanol. This solution can be used for up to 3
months when stored at 4°C.
At the beginning of sample processing, add lOuL of this surrogate additive solution to each 20-
mL aqueous sample portion yielding a surrogate concentration in the aqueous sample at 10 ug/L.
/. Calibration standards: Prepare aqueous calibration standards in lOOraL organic-pure water
by injecting a measured amount of the multicoraponent aldehyde additive standard solution
directly into water using the solvent flush technique. Prepare five different concentration levels
within the expected range of expected results. These would normally be in the range 0.5 - 30
ug/L.
5. Procedure
a. Sample preparation: Samples and standard solutions are removed from storage and
allowed to reach room temperature.
b. Derivatization: A 20-raL aliquot of sample water is withdrawn from the sample vial using
a 20-mL glass syringe or glass pipette. The remaining sample is thrown away, the vial shaken
dry by hand and the syringe contents returned to the vial.
A lOuL volume of the surrogate additive solution is added, with either a microsyringe or
automatic pipettor, to all sample aliquots including calibration samples.
Add 1 mL of the pH 6 KHP/NaOH buffer to each aliquot with an automatic pipettor and swirl
to mix the contents.
Add 1 raL of freshly prepared 15mg/mL PFBHA solution to each vial by automatic pipette,
secure cap and swirl vial to gently mix. Place all samples in a constant temperature water bath
set at 45 ± 0.5°C for 1 hour and 45 minutes. After this time, remove the vials and allow to cool
to room temperature for 15 minutes.
3 —
J
-------
c. Microextraction: To each vial add; 0.05 mL (approximately 2 drops) of concentrated
sulfuric acid (H2SO4) to quench the derivatization reaction followed by 4 mL of the hexane
working solvent containing the internal standard.
When using automated extraction, place the vials in a mechanical wooden shaker box. Shake the
vials on fast setting for 3-1/2 minutes. Remove the vials and place upright. Allow to stand for
approximately 5 minutes to permit the phases to separate.
d. Extraction cleanup: The top hexane layer is drawn off using a clean 14.6 cm (5.75 in.)
disposable pasteur pipette for each sample into a smaller 7-mL clear vial containing 3 raL of
0.2N sulfuric acid. These vials are then shaken for 30 seconds by hand and allowed to stand for
approximately 5 minutes to allow the 'two phases to separate. The top hexane layer is again
drawn off using another clean 14.6 cm (5.75 in.) disposable pasteur pipette for each sample and
placed into two 1.8-mL autosampler vials per sample. Store the extra autosampler vials in a 4°C
refrigerator as a backup extract
e. Gas chromatography: Operating conditions for the gas chromatograph are as follows:
Injector temperature 180°C; split valve open at 0.5 minutes; split flow at 50 mL/min.
Temperature program: 50°C for 1 minute, rising at 4°C per minute to 220°C and then at 20°C
per minute to 250°C.
Detector temperature: 300°C
Carrier gas flow: 1.5mL/min at 100°C
Make-up gas flow: 27 mL/min
At the beginning of each analysis, inject one hexane solvent blank to condition the GC and to
verify that there are no interferences present A 1-uL volume is injected onto the splitless
injector. See Figures 6252:1 and 6252:2 for examples of chromatograras obtained with the above
GC conditions for both the analytical and confirmation columns. If dual-column analysis is
unavailable, the use of a DB-5 (or equivalent) is acceptable. However, be aware of possible
interferences. Table 6252:IV lists retention times for both columns.
/ Calibration: The use of five levels of calibration define the quantitation range. The lowest
standard is based on the lowest level of quantitation for each component Standard levels are
prepared by adding the aldehydes to reagent grade water which are then derivatized with the
same PFBHA solution as the samples. This corrects for any recovery characteristics inherent with
the method. Analyze the calibration standards under the same GC conditions as the samples.
6. Calculation
a. Standards procedure: Use this procedure when evaluating external, internal, surrogate and
calibration standards. Calculate individual response factors (RFs) for each standard as follows:
RF = Response (peak area)
Amount of compound (ug)
For each compound, determine the average RF and standard deviation of the RF values for all
the standards. If the percent relative standard deviation (%RSD) is greater than 10%, take
corrective action to improve method precision. When %RSD is less than 10%, then the mean RF
is acceptable for use in calculating the Relative Response ratio of the surrogate/calibration
standard RF to the internal standard RF.
b. Determination of analyte concentration: A calibration curve for each target analyte is
constructed from the total relative response factor of all isomers (compared to one of the internal
standards). Calculate the individual relative response factor (RRF) for each component as follows:
.- « j.-j 10
-------
TABLE 6252.IV. RETENTION TIMES (RTs) FOR DERIVATIZED ALDEHYDES,
SURROGATE AND INTERNAL STANDARDS ON ELECTRON-CAPTURE DETECTOR
Compounds
1 ,2-Dibromopropane1
Surr - TFB"
Formaldehyde (HCHO-PFBO)
E-Acetaldehyde (E-CH3CHO-PFBO)§
Z-Acetaldehyde (Z-CH3CHO-PFBO)§
E-Heptanal (E-C6H13CHO-PFBO)§
Z-Heptanal (Z-C6H13CHO-PFBO)§
Surr - TFB-PFBO*
Benzaldehyde (C6HSCHO-PFBO)§
E-Glyoxal (E-OHCCHO-PFBO)§
Z-Glyoxal (Z-OHCCHO-PFBO)§
Methyl glyoxal (OCH3CCHO-PFBO)
RTsb
(min)
5.21
7.27
9.61
12.88
13.15
27.82
27.93
32.37
31.41
39.09
39.48
41.09
RTsc
(min)
6.25
10.88
11.21
14.42
14.70
28.95
29.09
32.77
33.78
43.87
44.09
45.72
"Internal standard
"Retention times on a DB-5 column
Detention times on a DB-1701 column
§These aldehydes form E- and Z-PFBO isomers whose order of elution is assumed but has not
been confirmed (-PFBO = pentafluorobenzyloxime)
"This is the retention time for the underivatized surrogate aldehyde TFB (2,3,5,6-
tetrafluorobenzaldehyde)
*This is the retention time for the derivatized surrogate aldehyde
11
-------
Hrog Slope *» or Linear;: mj rori
Flourate/Gas: 1.5 He Split Ratio: SPI
Oet 1-Type i Tenp: ECD8300C Oet Z-Type & Tenp: ECD8300C
Notes: UYSIUYG
Start tlwe-
Plot Range - 29
Stop tine** 44.00 minutes
Offset - -3 nV
-------
-------
RRF =
where R, = total area of the calibration standard E- and Z-isomers
R. = area of the internal standard
Calculate the average RRF for each compound, standard deviation of the RRF values and %RSD
from triplicate sample analyses. If %RSD is less than 10%, then use the average RRF in linear
regression (plotting the RRF against standard concentrations) and a linear regression equation:
RRF, = m(CJ + b
where RRF, = relative response factor of analyte
Cx = calibration standard concentration in samples, ug/L
m = slope of line
b = intercept of the y-axis
Use this internal standard calibration curve to determine unknown concentrations in aqueous
samples from the RRF values for each target analyte.
7. Quality Control
a. General considerations: PFBHA is a highly reactive (^substituted hydroxylamine. Like
hydroxylamine, PFBHA reacts readily with a variety of carbonyl functional groups to produce
corresponding oxiraes. The ease with which PFBHA reacts with carbonyl containing compounds
makes the potential contamination of samples a serious concern. Lower molecular weight
aldehydes are commonly found in laboratory and outside air and can ultimately contaminate
water samples, leading to incorrect calculation of aldehyde concentrations in water. As a further
concern, there is some evidence that PFBHA, especially in moist laboratory environments, can
react to form oxiraes when directly exposed to aldehydes in air. For these reasons, care must be
exercised to reduce the sources and exposure of samples, standard solutions, and PFBHA reagents
to aldehyde contaminants. Considerations include storing PFBHA in a desiccator under an inert
atmosphere, drying laboratory solvents with molecular sieves, using purified water and making
fresh derivatizing stocks on a regular basis. If, after analysis of appropriate sample blanks,
contamination remains a problem, the source of the problem may be in the PFBHA reagent and
solutions. Recrystallization of PFBHA may have to be undertaken as a method of removing
oxiraes formed as a result of reagent contamination.
The effects of chromatographic and analytical conditions on E/Z ratios of the oximes have not
been fully explored. The possibility of changing E/Z ratios under differing analytical conditions,
such as injection temperature, requires that analytical conditions be carefully controlled. As a
further concern, there is evidence that E/Z ratios may change as a function of time. Samples
should therefore be analyzed as soon as possible after preparation and within groups and both
calibration and quantification should use the the sum of the isoraer peak areas for each analyte.
With dicarbonyl species such as glyoxal, E/Z isoraerism occurs from oxirae formation with both
carbonyl groups, increasing the number of possible isomers. Formation of the mono-denvatives
from these di-carbonyl species may pose a problem if analytical conditions do not favor the
tpefy. v*a» '« aarn 14
" *
-------
complete derivaiizaiion of both carbonyl groups. Mono-deiivadves have been shown to have
similar retention and mass spectral characteristics as single carbonyl containing oxime derivatives,
potentially leading to incorrect identification and underestimation of the amounts of di-carbonyl
species present in water samples.
This method has been validated for the recovery of oxime derivatives of aldehydes from organic-
pure water and the recovery of the surrogate standard from this matrix appears to reflect method
performance. Consequently, the RRF of surrogate standard extracted from aqueous samples
should be compared to the value obtained when building the calibration curve. If these values are
outside the range for accepted mean recovery values of 30% (see method 6233B, section 7c),
authentic oxime standards may have to be utilized in order to validate the method for the new
matrix. In this case, if pure standards are unavailable, the quantification of aldehyde levels should
be recognized as being semi-quantitative in nature and should be reported as such.
b. Monitoring for interferences:
1) Method blank - See method 6233B, section 7b.
2) Travel or shipping blanks for each sampling location are prepared in the laboratory by
filling 40-mL vials, as described in section 2, with organic-pure water and should contain the
same reagents that are present (if any) in the sample vials. These are shipped to the sampling site
and back to the laboratory with the sample bottles.
3) Internal standard working solvent - Each reagent bottle of hexane containing internal
standard is analyzed before it is used. If there are any spurious peaks present in the
chroraatogram then the solvent purity has been compromised and the working solvent should be
remade. Injections of the hexane extracts are acceptable if the area counts of the internal standard
peak do not vary more than ± 20% from the mean of all the samples analyzed with the same
batch of PFBHA. Samples which do not meet with this precision and which, after reinjection, do
not fulfill this criteria should be reanalyzed if the sample holding time has not been exceeded and
the same working solvent used for constructing the calibration curve is still available.
4) Surrogate standard recovery - The surrogate (2,3,5,6-tetrafluorobenzaldehyde) is added
directly into the 20m L aqueous sample aliquots prior to reagent addition in order to monitor
analyte recovery from the sample matrix. If the surrogate area is low or absent, there is likely
to be a problem with derivatization or extraction which needs to be resolved before analyte
quantification can be undertaken (see method 6233B, section 7e). A sample extract is acceptable
if the area counts of the surrogate peak (or the RRF values compared to an acceptable internal
standard area) do not vary more than ± 30% from other samples analyzed with the same batch
of PFBHA.
c. Sample quantification: see method 6233B, sections 7f-7h.
15
-------
References
1. Scliraenti, M.J., S.W. Krasner, W.H. Glaze, and H.S. Weinberg. 1990. Ozone Disinfection
By-products: Optimization of the PFBHA Derivatization Method for the Analysis of
Aldehydes. In Proceedings of the American Water Works Association Water Quality
Technology Conference, San Diego, Calif.
2. Forsberg, K. 1989. Chemical protective clothing performance index book. Wiley, New York,
pp. 104-109.
3. 1989 Annual Book of ASTM Standards: Water and Environmental Technology, 1989. Vol.
11.01. American Society for Testing and Materials, Philadelphia, PA, pp. 45-47.
4. Cancilla, D.A., C.-C. Chou, R. Barthel, and S.S. Que Hee. 1992. Characterization of the 0
(2,3,4,5.6-pentafluorobenzyl)-hydroxylamine hydrochloride (PFBOA) derivatives of some
aliphatic mono- and dialdehydes and quantitative water analysis of these aldehydes. J. AOAC
Int., 75(5):842-854.
16
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Appendix E
Definition and Procedure for the Determination
of the Method Detection Limit
Revision 1.11 (CFR Pt. 136, App. B)
DBP/ICBmanual-l/28/94draft 115
-------
ft. m,
APPKHOIZ B TO PART 136—DtnmnoH
AMD PROCEDURE FOR TBI DETERKX-
RATION or THE METHOD DETECTION
LOOT—REVISION. 1.11
Definition
The method detection limit (MDL) la de-
fined as the minimum concentration of a
substance that can be measured and report-
ed with 99% confidence that the analyte
concentration Is greater than zero and Is de-
termined from analysis of a sample In a
given matrix containing the analyte.
Scope and Application
This procedure Is designed for applicabil-
ity to a wide variety of sample types ranging
from reagent (blank) water containing ana-
lyte to wastewater containing analyte. The
MDL for an analytical procedure may vary
as a function of sample type. The procedure
requires a complete, specific, and well de-
fined analytical method. It Is essential that
all sample processing steps of the analytical
method be Included In the determination of
the method detection limit.
The MDL obtained by this procedure la
used to Judge the •ign'***"'T of a single
measurement of a future sample.
The MDL procedure was designed for ap-
plicability to a broad variety of physical and
chenical methods. To •^yympitaii thia, the
procedure was made device- or Instrument-
1. Make an estimate of the detection limit
using one of the following:
(a) The concentration value that corre-
sponds to an instrument signal/noise In the
range of 2.S to S.
(b) The concentration equivalent of three
times the standard deviation of replicate In-
strumental measurements of the analyte In
reagent water.
(e) That region of the standard curve
where there Is a •*g*i*^1i^g*?ly i
desirable to evaluate the estimated method
detection limit before proceeding with 4a.
This will: (1) Prevent repeating this entire
procedure when the costs of «Miyp«« 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 de-
tection limit Is a good estimate. It Is neces-
sary to determine that a lower concentra-
tion of analyte will not result In a slgnlfl-
565
DBP/ICRmanual-l/28/94draft
116
-------
Pt. 136, App. •
cantly lower method detection limit. Take
two allquota of the sample to be used to cal-
culate the method detection limit and proc-
ess each through the entire method. Includ-
ing blank measurements aa described above
In 4a. Evaluate these data:
(1) If these measurements indicate the
sample la In desirable range for determina-
tion of the MDL. take five additional all-
quota and proceed. Use all seven measure-
ment for calculation of the MDL.
(2) If these measurements Indicate the
sample la not in correct range, reestlmate
the MDL, obtain new sample as in 3 and
repeat either 4a or 4b.
5. Calculate the variance (81) and stand-
ard deviation (8) of the replicate measure-
ments, aa follows:
„-,[**•-(* *)'/•]
n-l[ii V'-' / / J
8*
where:
Zi: 1=1 to n. are the analytical results in the
final method reporting units obtained
from the n sample aliquots and X refers
to the sum of the X values from i»l to
n.
6. (a) Compute the MDL as follows:
MDL = t«..,.i, . o.tn (8)
where:
MDL - the method detection limit
tte-i.i-. . M> m the students' t value appro-
priate for a 99% confidence level and a
standard deviation estimate with n-1 de-
grees of freedom. See Table.
8 = standard deviation of the replicate
analyses.
(b) The 95% confidence Interval estimates
for the MDL derived In 6a are computed ac-
cording to the following equations derived
from pereentlles of the chi square over de-
grees of freedom distribution (,Vdf).
LCL - 0.64 MDL
UCL = 2.20 MDL
where: LCL and UCL are the lower and
upper 95% confidence limits respectively
based on seven aliquots.
7. Optional Iterative procedure to verify
the reasonableness of the estimate of the
MDL and subsequent MDL determinations.
(a) If this la the Initial attempt to com-
pute MDL based on the estimate of MDL
formulated In Step 1. take the MDL as cal-
culated in Step 6. spike the matrix at this
calculated MDL and proceed through the
procedure starting with Step 4.
(b) If this Is the second or later Iteration
of ttjQ MDL cttlnilattftTii UK 8* from the cur-
' rent MDL calculation and 8' from the previ-
ous MDL ualfliilatlftn to compute the P-
40 CM Ch. I (7.1-92
ratio. The F-ratio la calculated by substltut.
Ing the larger 8* Into the numerator 8'. «JM
the other Into the denominator 8V Th,
computed F-ratlo la then compared with th!
F-ratlo found In the table which la 3 OS i!
follows: U SVS\<3.05. then compute
pooled standard deviation by the
equation:
if 8 VSt>3.05. rcsplke at the most recent
calculated MDL and process the samplei
through the procedure starting «tu!
Step 4. If the most recent calculated
MDL does not permit qualitative identi
flcatlon when samples are spiked at that
level, report the MDL aa a concentration
between the current and previous MDL
which permits qualitative Identification
(c) Use the SM* as calculated In Tb to
compute the final MDL according to the fol
lowing equation:
MDL-2.681'«,,,.'
where 2.681 la equal to W i-. =.„).
(d) The 96% confidence limits for MDL
derived In 7c are computed according to the
following equations derived from pracenuia
of the ehi squared over degrees of freedom
distribution.
LCL-0.72 MDL
UCL° 1.65 MDL
where LCL and UCL are the lower sad
upper 95% confidence limits respectively
bated on 14 allquota.
TABLES OF STUDENTS' t VALUES AT THE 99
PERCENT CONFIDENCE LEVEL
10.....
11.
16..
21.....
as.
31....
61..
00..
-------
Environmental Protection Agoncy pt. 134, App. C
affect the method detection limit. theM
conditions must be specified with the MDL
value. The sample matrix used to determine
the MDL must also be Identified with MDL
value. Report the mean analyte level with
the MDL and indicate if the MDL procedure
was iterated. If a laboratory standard or a
sample that contained a known amount ana-
lyte 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 PR 43430. Oct. 26. 1984: SO PR 494. 696.
Jan. 4. 196S. as amended at 61 PR 23703.
June 30.1986)
567
OBP/ICRmanual-l/28/94draft 118
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