Unregulated Contaminant Monitoring Regulation Analytical Methods and Quality Control Manual


         Wed States       Office of Water      EPA # 815-R-00-006
         Sbnmfntal Protection   4607        March 2000
         Agency
&EPA
         Co.ntap.tn.ant Monitoring
         Regulation Analytical
         Methods and Quality
         Control Manual
                              Printed on Recycled Paper

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UCMR Analytical Methods and Quality Control Manual Marcn 2000

Foreword

This document provides guidance regarding sampling, analytical methods, and related quality control
issues for the States, EPA offices, water systems, and analytical laboratories participating in the
Unregulated Contaminant Monitoring Regulation (UCMR) Program. This document is written for
the personnel at a water system, laboratory, or agency who will-be responsible for UCMR Program
planning, implementation, and oversight.
Please Note: Because of the evolving nature of the UCMR Program, supplemental rule-making
feffoTttsWyTadd additional contaminants to be monitored and hence, the specific analytical and^
teclpicai requirements^of the"program will need to be identified. .For this reasQh^EPA will
"pepoaicaliylssue supplements to this, Analytical Methods and Quality Control Manual. ,For
example, at the time of publication of tiie UCMR, a supplement addressing analytical methods s
for perchlorate arid acet6chlpr, two of fcUCMR(1999) List 1 contaminants, was already in
teyeioprnefk~EPAaiiti&^^
:TOeraoVar£approyelfor rndnitoring* the UCMR fl§99) List2 and 3 cpntammants'in subsequent
lulesfrHowever,'these^addltional supplements may also,include,minor modifications^ fee,
requ&emenfs-note
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UCMR Analytical Methods and Quality Control Manual
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UCMR Analytical Methods and Quality Control Manual
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Disclaimers

This euidance document is designed to implement national policy concerning the UCMR Program.
?S document does not, howeVer, substitute for the SDWA or EPA's regulations nor is tins
dolmenTregulation itself. Thus, it cannot impose legally-binding requirements on Estate*.
or Z regulated community, and may not apply to a particular situation based upon the
drcumstSces EPA decision makers retain the discretion to adopt approaches on a case-by-case
bSSers from this guidance where appropriate. EPA may change this guidance in the future.

Mention of trade names or commercial products does not constitute endorsement or recommendation

for use.
111
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UCMR Analytical Methods and Quality Control Manual March 2000
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UCMR Analytical Methods and Quality Control Manual
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Acknowledgments
i uv^iviis.) iui E.r.rv a v^Aiiv^ uj. vjiv/miv* , .«._~i.—u 0 — - . -T, I/-H-J?
leader for development of the UCMR and James Taft as Targeting and Analysis Branch Chief.
Rachel Sakata and Yvette Selby served.as Work Assignment Managers. The UCMR Work Group
provided technical guidance throughout, in particular David Munch, James Sinclair, and Jeanne
Campbell provided scientific and editorial guidance. External expert reviewers and many
stakeholders provided valuable advice to improve the UCMR Program and this document. The
Cadmus Group, Inc., served as the prime contractor providing support for this work. The major
contributions of Chris Higgins, Jonathan Koplos, and Maureen Devitt are gratefully acknowledged
as are the contributions of UHL subcontractors Michael Wichman, George Breuer, Nelson Moyer,
and others. George Hallberg served as Cadmus' Project Manager.
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VI
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UCMR Analytical Methods and Quality Control Manual March 2000

Table of Contents
Foreword [[[ .....

Disclaimers ..... [[[ m

Acknowledgments . ............... ............................................ v

Section 1. Introduction .......................... ;• v • v • ' ' " V-" "rr\™/ro\ ..... \
1.1 Background on the Unregulated Contaminant Monitoring Regulation (UCMR) ---- 1
12 The Unregulated Contaminant Monitoring Regulation ..... ..... . .............. 1
1.3 Contaminants on the UCMR (1999) List ............... .... ................ 3
1.3.1 UCMR (1999) List 1 Contaminants .............. ....................... °
1 3 2 UCMR (1999) List 2 and List 3 Contaminants .................. . .......... /
1.4 Analytical Methods for UCMR (1999) List 1 Contaminants ................... 9
Section 2. Sampling Plan .......... ..
2.1 Monitoring By Public Water Systems
2.1.1 Systems Required To Monitor
2.2 Sampling Frequency
2.3 Sampling Points
Section 3. Sample Collection and Preservation ................................... 15
3.1 Chemical Contaminants ............................................... 15
3.1.1 Nitrogen- and Phosphorus-Containing Pesticides ............. ............. 15
3.1.2 Chlorinated Hydrocarbon Pesticides ............................... ..... j°
3.1.3 Acid Herbicides ..... . ....... ............ ---- ...................... ^
3.1.4 Volatile Organic Compounds ......................................... fU
3.1.5 Semi-volatile Organic Compounds ..... . ............................. '• • 22
3.2 Monitoring of Routine Water Quality Parameters ........................... 24

Section 4. Sample Transport .......... . ....... .................... ............ - • 27

Section 5. UCMR Quality Control Requirements . ---- ............................ 29
5.1 Minimum Reporting Level ............................................ 3y
5.2 Calibration ........................... .............................. ^
5.2.1 Calibration Verification ............. ................................. ^
5.3 Method Detection Limit ................................. • ............. 35
5.4 Laboratory Reagent (Method) Blank ..... ... ...... ....................... 35
5.4.1 Field Reagent Blank (Shipping or Travel Blank) ..... . .................... 38
5.5 Quality Control Sample .......... . .................... • ................ 38
5.6 Sample Matrix Spike and Matrix Spike Duplicate ......... ' ................. 38
5.7 Internal Standard ...... .......... . ................. .................. 41
5.8 Surrogate Standard ....... ............................................ 43
5.9 Confirmation .................... • .................... .............. 45
5.9.1 Gas Chromatographic Methods ...................................... -45
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UCMR Analytical Methods and Quality Control Manual
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5.9.3 Mass Spectrometry Methods
5.10 Additional Quality Controls
46
Section 6. Additional Analytical Method Specifications , . ..... •••••••• ...... : ...... 49
61 ClarificationsConcernmgEPAMethods515.1and515.2andthe Approved
Equivalent Methods ....... . ............. • • • • ...... • • • • : • • • • ' .........
6.2 Recommendations for EPA Method 524.2 and the Approved Equivalent
•» *• . * ^j_
Metnoas
Section 7. Reporting
7.1 Public Water Systems Reportin
7.1.1 Reporting of Results Obtained^
7 1.2 Reporting of Data Below the
7.1.3 Reporting of Water Quality ~
7.2 Public Notification of Results
to EPA 51
for the DCPA Mono- and Di-Acid Degradates ... 51
„ pecified Minimum Reporting Level 51
P irameter Data • 52
(Report of PWS to Consumers) = 52
51
Vlll
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UCMR Analytical Methods and Quality Control Manual
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List of Tables
Table 1.1 UCMR (1999) Contaminants 3
Table 1.2 UCMR (1999) List 1 Contaminants 6
Table 1.3 UCMR (1999) List 2 Contaminants 8
Table 1.4 UCMR List 3 (1999) Contaminants 9
Table 1.5 Approved Analytical Methods for UCMR (1999) List 1 Contaminants 10

Table 3.1 Preservation and Holding Times for Approved Analytical Methods 24
'Table 3.2 Water Quality Parameters to be Monitored with UCMR (1999) List 1
Contaminants 25

Table 5.1 UCMR Methods and Minimum Reporting Level - 30
Table 5.2 Frequency Requirements for Verifying Calibration 33
Table 5.3 UCMR Low-Level Calibration Check Standard Concentrations and
Acceptance Criteria • • • • 33
Table 5.4 Mid-Level Calibration Check Standard Concentrations and Acceptance
Criteria 34
Table 5.5 Frequency Requirements for Analyzing Laboratory Reagent (Method) Blanks . 36
Table 5.6 UCMR Acceptance Criteria for Laboratory Reagent (Method) Blanks 37
Table 5.7 Requirements for Performing Spiked Sample Analyses 39
Table 5.8 Concentrations for Spiking MS/MSD Samples 41
Table 5.9 Requirements for Internal Standard Analyses 42
Table 5.10 Requirements for Surrogate Standard Analyses 44
Table 5.11 Recommended Confirmation Ions 46
Table 5.12 Maximum Holding Times for Samples and Extracts 48

Table 7.1 UCMR Reporting Requirements 53

Appendices

Appendix A. Abbreviations and Acronyms A-1
Appendix B. Definitions • B"1
Appendix C. Procedure for Determination of Method Detection Limits C-l
IX
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UCMR Analytical Methods and Quality Control Manual March 2000

Section 1. Introduction

1.1 Background on the Unregulated Contaminant Monitoring Regulation (UCMR)

The requirement to monitor unregulated contaminants was established by the 1986 Amendments to
the Safe Drinking Water Act (SDWA). Public water systems (PWSs) were required to report the
monitoring results for up to 48 unregulated contaminants to the States or primacy agency under
several regulations (40 CFR i41.40(e),(j),and(n)(il)and(12)). Systems with less than 150 service
connections were exempt, provided those systems made their facilities available for the States to
monitor. The rules require repeat monitoring every 5 years.

Under §1445(a)(2)(A) of the SDWA, as amended in 1996, the Environmental Protection Agency
(EPA) is to promulgate regulations that will substantially revise the existing unregulated monitoring
program The revised Unregulated Contaminant Monitoring Regulation (UCMR) Program has a
new list of contaminants, changes the PWSs that must conduct monitoring, and changes the
frequency and schedule for monitoring (§ 141.40(a)).

The UCMR has been developed in coordination with the Contaminant Candidate List (CCL) and the
National Drinking Water Contaminant Occurrence Database (NCOD). The UCMR and the CCL will
operate on an evolving 5-year cycle to assess the impact of new drinking water contaminants. The
data collected through the UCMR Program will be used to support the development of the
subsequent CCL, to support the Administrator's determination of whether or not to regulate a
contaminant, and to develop regulations. The revised monitoring program is part of a sound science
approach to future drinking water regulation, which is an aim of the 1996 SDWA Amendments.

The revised UCMR includes new and emerging contaminants. The revised UCMR will also require
fewer systems to conduct monitoring than is required in the existing unregulated contaminant
monitoring program (§141.40(a)(l)). Therefore, the quality of data collected is a very important
issue for the success of the revised program. This document provides a brief overview of the revised
UCMR and outlines the required analytical methods and quality control procedures that PWSs and
participating laboratories must adhere to while implementing the Assessment Monitoring component
of the UCMR (§141.40(a)(5) and §141.40 Appendix A).

Further detailed information about the revised UCMR Program can be found in the Preamble to the
proposed regulation (64 FR 23398) and the final Rule (64 FR 50556), as well as other supporting
documents. These documents are available from the EPA Water Docket, (202) 260-3027, Docket
Number W-98-02. General information can also be obtained from the EPA Safe Drinking Water
Hotline, (800) 426-4791, or through the EPA Office of Ground Water and Drinking Water Internet
Homepage at www.epa.gov/ogwdw.

1.2 The Unregulated Contaminant Monitoring Regulation

The UCMR is required by SDWA as amended in 1996. Under the 1996 Amendments, EPA is
required to promulgate a new regulation for monitoring unregulated contaminants. The regulation
must include: (1) a new list of contaminants, of which not more than 30 may be required for
monitoring, (2) a frequency and schedule for monitoring as based on PWS size, source water type,
and likelihood of finding contaminants; (4) monitoring of only a representative sample of PWSs

1
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UCMR Analytical Methods and Quality Control Manual March 2000

servin^ 10 000 or fewer people; and, (5) requirements for placement of the monitoring data in the
NCOD (in accordance with §1445 (g) of SDWA). PWSs must monitor to provide the location,
concentration and related information regarding the occurrence of these contaminants in public.
drinking water (§ 141.35(d)). EPA will analyze the monitoring data to identify which contaminants
occur nationally and at concentrations that may Warrant regulation. EPA will determine which
contaminants pose the greatest risks to human health and, if necessary, will set priorities for
regulation of the contaminants. Conversely, EPA may remove contaminants from consideration for
regulation if UCMR monitoring indicates that these contaminants are not detected at significant
levels in drinkin^ water. EPA was required to develop a list of contaminants, the, UCMR (1999)
List, and regulations for monitoring the contaminants by August 1999. This list will be revised every
5 years. •

EPA used the CCL (1998) contaminants listed as occurrence priorities as the primary basis for
selecting contaminants for the UCMR (1999) List. The CCL identifies cont^nants of potential
concern that may occur or are likely to occur in drinking water. In order to establish the CCL (1998)
EPA convened a Work Group to develop the CCL based on the results of previous unregulated
contaminant monitoring and information from other data sources. The CCL team worked from a
compendium of 10 lists containing approximately 391 chemical contaminants. The lists used in this
process were- 1991 Drinking Water Priority List; Health Advisories; Integrated Risk Information
System- Non-Target Analytes in Public Water Supply Samples; Comprehensive Environmental
Response Compensation, and Liability Act Priority List; stakeholder responses; Toxic Release
Inventory1 pesticides identified by the EPA Office of Pesticide Programs; a list of contaminants
identified by the Safe Drinking Water Hotline; and a list of contaminants suspected of causing
endocrine disruption.

The National Drinking Water Advisory Council's Working Group on Contaminant Occurrence and
Selection formed under the Federal Advisory Committee Act, developed the criteria for the CCL
to address a contaminant's potential risk to public health and frequency of contaminant occurrence
Criteria for selecting contaminants for the CCL focused on occurrence in water at levels of health
concern or indications of occurrence (production and release, coupled with contaminant properties).
Health effects concentrations were used to determine the significance of occurrence. The CCL
(1998) contains 50 chemical contaminants and 10 microbiological contaminants.

In establishing the CCL (1998), EPA divided the contaminants into three priority categories: those
contaminants requiring additional research; those which need additional occurrence data; and those
which are priorities for consideration for rule-making. EPA published a draft of the 1998 Drinking
Water Contaminant Candidate List in the October 6, 1997 Federal Register (62 FR 52193)
Comments submitted in response to the draft CCL were reviewed and considered in creating the final
CCL, which was published in the March 2, 1998 Federal Register (63 FR 10273).

For purposes of the UCMR, EPA initially used the CCL occurrence priorities list to identify
contaminants that were of national concern. The UCMR (1999) List, as initially proposed, included
32 of the 34 contaminants listed as occurrence priorities on the CCL (1998). At the time of the
publication of the proposed UCMR, perchlorate and RDX were excluded from the UCMR (1999)
List because it was thought that their occurrence was only a localized issue. As more data became
available and after many public comments were received supporting the inclusion of these
compounds, both perchlorate and RDX, as well as lead-210 and polonium-210, were added to the
UCMR (1999) List.
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UCMR Analytical Methods and Quality Control Manual
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1.3 Contaminants on the UCMR (1999) List

Although only 32 contaminants (24 chemical and 8 microbiological contaminants) listed on the CCL
as occurrence priorities were initially proposed for inclusion on the UCMR (1999) List all 34
ronterinants listed as occurrence priorities on the CCL (1998) were eventually included on the final
UCMR 0999) List Two additional contaminants, lead-210 and polonium-210, were not included
on the CCL (1998) but have been found in drinking water and in shallow aquifers in Honda.
Because radionuclides have potential wide occurrence and consequent health risks and in response
SS^oSnSjEPA added lead-210 and polonium-210 to the UCMR (1999) List. These 36
contarninants comprise the revised list of UCMR (1999) contaminants (Table L.I) For each of these
conSSs, Devaluated the availability of analytical methods PubllshfAJyEP^.d_v^f^
consensus standard organizations such as American Society for Testing and Materials (ASTM) the
AsscSation of Official Analytical Chemists (AOAC) and the American Public Health Association
fAPHA) In addition, EPA prioritized analytical methods development activities for those chemical
and microbiological contaminants that did not have suitable analytical methods currently available.

The revised UCMR Program consists of three distinct monitoring components based upon the
availability of suitable analytical methods. The Assessment Monitoring component of the UCMR
Program will monitor for UCMR (1999) List 1 contaminants; these are the.UCMR contaminants for
Sh&lytical methods are currently available.1 These are the only UCMR contaminants for
which monitoring is currently required under the revised UCMR Program (§141.40(a)(3)).

The other UCMR (1999) contaminants, those on List 2 and List 3, will require monitoring when
suitableanalytical methods are developed. The Screening Survey component of the UCMR Program
will monitor for UCMR (1999) List 2 contaminants for which analytical methods are nearly
developed, and which have uncertain potential for occurrence. The Pre-Screen Testing component
of the UCMR Program will monitor for UCMR (1999) List 3 contaminants for which analytical
methods are in the early stages of development, and which may have newly emerged as concerns.
Table 1.1 UCMR (1999) Contaminants
List
Chemical Contaminants
Contaminant Name
••P^WB^™^^^™*^^"^^

2,4-dinitrotoluene
Potential Environmental Source
Used in the production of isocyanate and explosives
2,6-dinitrotoluene
Used as mixture with 2,4-DNT (similar uses)
Acetochlor
Herbicide used with cabbage, citrus, coffee, and corn crops
DCPA di-acid degradate
Degradation product of DCPA, an herbicide used on grasses and
weeds with fruit and vegetable crops
The two exceptions to this are perchlorate and acetochlor, for which analytical methods are currently being
finalized. It is anticipated that these methods will be available before monitoring is to begin in 2001.
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UCMR Analytical Methods and Quality Control Manual
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List
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
Contaminant Name
DCPA mono-acid
degradate
DDE
EPTC (s-ethyl-
dipropylthio-carbamate)
Molinate
MTBE (methyl tertiary-
butyl ether)
Nitrobenzene '
Perchlorate
Terbacil
1 ,2-diphenylhydrazine
2-methyl-phenol
2,4-dichlorophenol
2,4-dinitrophenol
2,4,6-trichlorophenol
Alachlor ESA
Diazinon
Disulfoton
Diuron
Fonofos
Linuron
Polonium-210
Prometon
RDX
Terbufos
Lead-210
Potential Environmental Source
Degradation product of DCPA, an herbicide used on grasses and
weeds with fruit and vegetable crops
Degradation product of DDT, a general insecticide
Herbicide used on annual grasses, weeds, with potatoes and corn
Selective herbicide used with rice, controls watergrass
Octane enhancer in unleaded gasoline
Used in the production of aniline, which is used to make dyes,
herbicides, and drugs
Oxygen additive in solid fuel propellant for rockets, missiles, and
fireworks
Herbicide used with sugarcane, alfalfa, and some fruit, etc.
Used in the production of benzidine and anti-inflammatory drugs
Released in automobile and diesel exhaust, coal tar and petroleum
refining, and wood pulping
Chemical intermediate in herbicide production
Released from mines, metal, and petroleum plants
By-product of fossil fuel burning, used as bactericide and wood/glue
preservative •
Degradation product of alachlor, an herbicide used with corn, bean,
peanut, and soybean crops to control grasses and weeds
Insecticide used with rice, fruit, vineyards, and corn crops
Insecticide used with cereal, cotton, tobacco, and potato crops
Herbicide used on grasses in orchards and with wheat crops
Soil insecticide used on worms and centipedes
Herbicide used with corn, soybean, cotton, and wheat crops
Part of the uranium decay series; naturally occurring
Herbicide used on annual and perennial weeds and grasses
Used in explosives; ammunition plants
Insecticide used with corn, sugar beet, and grain sorghum crops
Part of the uranium decay series; naturally occurring
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UCMR Analytical Methods and Quality Control Manual
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List
Contaminant Name
Potential Environmental Source
Microbiological Contaminants
Aeromonas hydrophila
Present in all freshwater and brackish water
Adenoviruses
Fecal or hand to mouth transmission
Cyanobacteria (blue-
green algae, other
freshwater algae, and
their toxins)
Bloom in surface water bodies; produce toxins
Caliciviruses
Contaminated food and water; raw shellfish
Coxsackieviruses
Fecal or hand to mouth transmission
Echoviruses
Fecal or hand to mouth transmission
Helicobacter pylori
Fecal or hand to mouth transmission
lote UCMR (1999) List 1 contaminants require monitoring under the Assessment Monitoring compo^nt of the
revised UCMR (§141 40(a)(3)). EPA is conducting analytical methods development for UCMR (1999) List 2
and List 3 contaminants. When methods for these contaminants are ready for use, EPA will issue supplements
to this Analytical Methods and Quality Control Manual. For more information on the Assessment Monitoring
Screenin- Surveys and Pre-Screen Testing components of the UCMR, the reader may refer to the proposed
UCMR Preamble and Rule (64 FR 23398) or the final Rule (64 FR 50556).

This Analytical Methods and Quality Control Manual provides guidance for sampling and analytical
and quality control procedures only for the UCMR (1999) List 1 contaminants. However, this
Manual does not include quality control (QC) requirements pertaining to analyses of acetochlor and
perchlorate as the analytical methods for these compounds have not yet been approved for UCMR
monitoring EPA is currently refining analytical methods for acetochlor and perchlorate, and will
be proposing a new regulation specifying both the approved analytical methods for the analyses of
these compounds and the related implementation of a laboratory approval system. When these
regulations are finalized, EPA will issue a supplement to this Manual detailing any additional QC
procedures that must be followed while monitoring for these compounds under the revised UCMR.
In addition, because of the evolving nature of the UCMR Program, the specific analytical and
technical requirements for monitoring contaminants may change with supplemental rule-
making. To ensure compliance with the UCMR, you should contact the Safe Drinking Water
Hotline at (800) 426-4791 to be directed to the most recent supplements to this manual.

Analytical methods and quality control procedures for the UCMR (1999) List 2 and List 3
contaminants are not discussed in this Manual. When suitable analytical methods are developed and
approved for these other contaminants, a supplement (or supplements) to this Manual will be issued
The supplement(s) will provide the analytical methods and quality control details for UCMR (1999)
List 2 and List 3 contaminant monitoring. A more complete review of methods availability is
summarized in the proposed UCMR Preamble and Rule (64 FR 23398) and the final Rule (64 FR
50556) as well as the Contaminant Selection, Methods, and Sampling: Technical Background
Information for the UCMR. (This background document and other UCMR supporting documents
are available from the EPA Water Docket, (202) 260-3027, Docket Number W-98-02. General
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UCMR Analytical Methods and Quality Control Manual
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information can also be obtained from the EPA Safe Drinking Water Hotline, (800) 426-4791, or
through the EPA Office of Ground Water and Drinking Water Internet Homepage at
www°epa.gov/ogwdw.) For identification of terms used throughout this Manual, see Appendix A
(for a list of abbreviations and acronyms) and Appendix B (for a list of definitions).
1.3.1 UCMR (1999) List 1 Contaminants

The UCMR (1999) List 1 contaminants and their corresponding required sampling locations, suitable
EPA analytical methods, and other related analytical details are listed in Table 1.2 (§ 141.40(a)(5)).
There are a total of 12 chemical contaminants on the UCMR (1999) List 1. With the exceptions of
perchlorate and acetochlor, EPA has approved suitable laboratory analytical methods for these
contaminants, and monitoring is to begin in 2001 under the Assessment Monitoring component of
the UCMR Program. As mentioned above, EPA plans to approve analytical methods for perchlorate
and acetochlor and possibly an additional analytical method for nitrobenzene shortly. These methods
should be approved and ready for use before monitoring is to begin in 2001. When methods for
these contaminants are ready for use, EPA will issue a supplement to this Analytical Methods and
Quality Control Manual.
Table 1.2 UCMR (1999) List 1 Contaminants
Contaminants
2,4-Dinitrotoluene
2,6-Dinitrotoluene
4,4'-DDE
Acetochlor
DCPA mono-acid
degradate
DCPA di-acid
degradate
EPIC
Molinate
MTBE
CAS #
121-14-2
606-20-2
72-55-9
34256-82-1
887-54-7
2136-79-0
759-94.4
2212-67-1
1634-04-4
Approved Analytical
Methods
EPA 525.2
EPA 525.2
EPA 508, EPA 508.1,
EPA 525.2, D58 12.96, 990.06
Reserved0
EPA 515.1, EPA 515.2, .
D53 17-93, 992.32
EPA 515.1, EPA 515.2,
D53 17-93, 992.32
EPA 507, EPA 525.2,
D5475-93, 991.07
EPA 507, EPA 525.2,
D5475-93, 991.07
EPA 524.2, D5790.95,
SM6210D, SM6200B
Minimum
Reporting
Level
2,ug/La
2;Ug/La
0.8Mg/La
Reserved0
lMg/La
Mg/La
lMg/La
0.9^g/La
5,ug/Ld
Sampling Point
EPTDS b
EPTDS b
EPTDS b
EPTDS "•
EPTDS b
EPTDS b
EPTDS b
EPTDS b
EPTDS b
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UCMR Analytical Methods and Quality Control Manual
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Contaminants
Nitrobenzene
Perchlorate
Terbacil
CAS #
98-95-3
1497-73-0
5902-51-2
Approved Analytical
Methods
EPA 524.2, D5790.95,
SM6210D, SM6200B
Reserved0
EPA 507, EPA 525.2,
D5475-93, 991.07
Minimum
Reporting
Level
lQMg/Ld
Reserved0
2^g/La

Sampling Point
EPTDS b
EPTDSb
EPTDS b
Note- EPA = EPA Methods, D = ASTM Methods, SM = APHA Standard Methods, 900 series - AOAC Methods. See
Table 1.5 for the full reference for each analytical method.
Minimum Reporting Level (MRL) determined by multiplying by 10 the least sensitive method s minimumdetection
imit (MDL=standard deviation times the Student's T value for 99% confidence level with n-1 degrees of freedom)
or when available, multiplying by 5 the least sensitive method's estimated detection limit (EDL=concentration of
compound yielding approximately a five to one signal to noise ratio or the calculated MDL, whichever is greater)
Entrv Point to the Distribution System. This sample collection location is located at the entry point, after treatment,
that represents each non-emergency water source in routine use over the 12-month period of monitoring; sampling
must occur at the EPTDS, unless the State has specified other sampling points that are used for compliance
monitorin- under 40 CFR 141.24(f)(l), (2) and (3) (§ 141.40(a)(5)). If monitoring at source (raw) water sampling
points mdfcates detection of any of the contaminants on the UCMR (1999) monitoring list then the system must
change the location of its unregulated contaminant monitoring to the EPTDS (§141.4U(a)Ci)).

MRL fSvOCsdetermined by multiplying by 10 either the published MDL or 0.5 /^g/L, whichever is greater. The
MDL of 0.5 Mg/L (0.0005 mg/L) was selected to conform to the VOC MDL requirements of 40 CFR
1.3.2 UCMR (1999) List 2 and List 3 Contaminants

Currently there are no suitable analytical methods for the UCMR (1999) List 2 and List 3
contaminants. Therefore, monitoring is not currently required for these contaminants but will be
required in the future as analytical methods are developed and finalized. Listed in Table 1.3 are the
UCMR (1999) List 2 contaminants, and related sampling and analytical information. Note that the
analytical methods referenced here are only anticipated and have not been finalized. Analytical
method development should be completed in time for Screening Survey monitoring to be conducted
in 2001 and 2003. When methods for these contaminants are ready for use, EPA will issue
supplements to this Analytical Methods and Quality Control Manual.
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I
Table 1.3 UCMR (19S
==========
Contaminant
1 ,2-diphenylhydrazine
2-methyl-phenol
2,4-dichlorophenol
2,4-dinitrophenol
2,4,6-trichlorophenol
Alachlor ESA
Diazinon
Disulfoton
Diuron
Fonofos
Linuron
Polonium-210
Prometon
RDX
Terbufos
Aeromonas hydrophila
>9) List 2 Conta
=====
CAS #
122-66-7
95-48-7
120-83-2
51-28-5
88-06-2
NAe
333-41-5
298-04-4
330-54-1
944-22-9
330-55-2
13981-52-7
1610-18-0
121-82-4
13071-79-9
NAe
=====
=======================
minants
T^SS
Anticipated
Analytical
Methods
EPA 525.2 a
SPE/GC/MSd
SPE/GC/MSd
SPE/GC/MS d
SPE/GC/MSd
Reserved b
EPA 525 .2 f
EPA 525 .2 f
SPE/HPLC/UV s
EPA 525 .2 a
SPE/HPLC/UV s
Reserved11
EPA 525.2 f
Reserved11
EPA 525 .2 f
Reserved b
======================
=====================
Minimum
Reporting
Level
Reserved b
Reserved b
Reserved b
Reserved b
Reserved b
Reserved1"
Reserved b
Reserved b
Reserved15
Reserved b
Reserved11
Reserved15
Reserved"
Reserved b
Reserved15
Reserved15
=================

Sampling Point
EPTDSC
EPTDSC
EPTDS c
EPTDS c
EPTDS °
EPTDS c
EPTDS0
EPTDS0
EPTDS0
EPTDS °
EPTDS °
Reserved15
EPTDS0
EPTDS0
EPTDS0
Reserved15
=====================1
m/*nt in an nttp.mnf fT>
Contaminant currently not iisiea as anaiyic m uua uicmuu. ivituujua unvi<-i vunvui ^.^,^^^^~^- ~- — r —
add this contaminant to the scope of this method. See Table 1.5 for full method reference.

Entry Point to the Distribution System. This sample collection location is located at the entry point, after treatment,
that represents each non-emergency water source in routine use over the twelve-month period of monitoring;
samolinff must occur at the EPTDS, unless the State has specified other sampling points that are used tor
SpUalce monitoring under 40 CFR 141 24(f)(l) (2) and (3) (§141.40(a)(5^If™fing at.puree (raw)
water sampling points indicates detection of any of the contaminants on the UCMR (1999) mon tonnglist, then
the system must change the location of its unregulated contaminant monitonng to the EPTDS (§141.40(a)(5)).
Methods development currently in progress to develop a solid phase extraction/gas chromatography/mass
spectrometry (SPE/GC/MS) method for the determination of this compound.

Contaminant listed to be analyzed with this method. However, adequate sample preservation for this contaminant
is not provided by the procedures for this method. Preservation studies are currently being developed for suitable
sample preservation for this contaminant.
Methods development currently in progress to develop a solid phase extraction/high performance liquid
chromatography/ultraviolet (SPE/HPLC/UV) method for the determination of this compound.
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UCMR Analytical Methods and Quality Control Manual
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Listed in Table 1.4 are the UCMR (1999) List 3 contaminants and related sampling and analytical
information. Completion of method(s) development is not expected prior to the Assessment
Monitoring or Screening Survey components of the UCMR Program. Instead, UCMR (1999) List
3 contaminants will be monitored during the Pre-Screen Testing component of the UCMR Program,
most likely to be conducted in 2004.
Table 1.4 UCMR List 3 (1999) Contaminants
Contaminant
Lead-210
Adenoviruses
Caliciviruses
Coxsackie viruses
Cyanobacteria (blue green
algae, other freshwater
algae, and their toxins)
Echoviruses
Helicobacter pylori
Microsporidia
CAS#
14255-04-0
NAb
NAb
NAb
NAb
NAb
NAb
NAb
Anticipated
Analytical
Method
Reserved a
Reserved2
Reserved3
Reserved a
Reserved3
Reserved0
Reserved3
Reserved3
Minimum
Reporting
Level
Reserved 3
Reserved3
Reserved3
Reserved3
Reserved3
Reserved3 ,
Reserved3
Reserved3
Anticipated
Sampling
Point
Reserved3
Reserved 3
Reserved a
Reserved3
Reserved3
Reserved3
Reserved3
Reserved3
a To be determined.
b CAS number is Not Applicable.
1.4 Analytical Methods for UCMR (1999) List 1 Contaminants

Table 1.5 includes the UCMR (1999) List 1 contaminants and related analytical methods that are
required for monitoring under the Assessment Monitoring component of the revised UCMR
(§141.40(a)(3)). The purpose of the revised UCMR is to obtain contaminant occurrence data in
support of future regulatory decisions. The data required for regulatory decision-making must be
of high quality. Most analytical methods are subject to some degree of false-negative test results (not
detecting an contaminant when it is present), false-positive test results (either incorrectly identifying
or detecting a contaminant, or introducing a contaminant into a sample when it is not present), and
errors in the accuracy and precision of quantitative results.

For the UCMR (1999) List 1 contaminants laboratory analyses, EPA has approved the use of
alternative (i.e., non-EPA) analytical methods of the voluntary consensus standard organizations
(including the ASTM, AOAC, and APHA). These methods are identified and listed with the
equivalent EPA method in Table 1.5. Note, however, that whether EPA or one of the alternative
methods are used, additional quality control measures for UCMR analyses are required (§141.40
Appendix A). The additional quality control measures are included in the revised UCMR (40 CFR
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UCMR Analytical Methods and Quality Control Manual
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141.40) and are explained in this Manual. In the following sections of this Manual, EPA method
numbers are used as references for the reader.

The data Quality needs of drinking water compliance monitoring data are different compared to the
evaluation and use of occurrence data. The purpose of compliance monitoring is to determine
whether or not a contaminant is present in the drinking water above the established Maximum
Contaminant Level (MCL). Unless the concentration of the contaminant closely approaches the
MCL even imprecise data can be used to assure the data user that the contaminant is not present at
a concentration above the MCL. In contrast, the usefulness of occurrence data is much more
dependent on the precision of the measurement. The ability to perform valid and meaningful
statistical analyses is directly dependent on the precision of the data when determining, for example
the percentage of U S. waters which have contaminant X above the minimum reporting level (MKL)
or if contaminant X occurs more frequently or at higher concentrations in one type of water or
geographical region than in another.

The ability to correctly identify a chemical contaminant is directly related to the type of chemical and
the analytical method used. For example, contaminants such as the disinfection by-products are far
less likely to be misidentified than pesticides or herbicides, because disinfection by-products are
typically present at relatively high concentrations in disinfected waters, while pesticides and
herbicides are much less likely to be present, or are present at much lower concentrations. The
analytical method selected will also determine the accuracy of the qualitative identification. In
general the most reliable qualitative identifications come from methods which use mass spectral
data for contaminant identification. However, these methods are typically less sensitive than
methods that rely on less selective detectors.

To ensure that the data collected under this regulation are of. sufficient quality to meet the
requirements of these regulatory decisions, EPA is specifying that only the analytical methods and
procedures listed in Table 1.5 be used in obtaining these data. This Manual explains additional
quality control requirements and contaminant confirmation procedures that are specified in the
regulation The subsequent sections of this Manual provide an overview of methods, sampling and
quality control procedures to be used in the UCMR Assessment Monitoring program. As methods
are approved for perchlorate and acetochlor, EPA will issue a supplement to this Analytical Methods
and Quality Control Manual. Furthermore, EPA will issue additional supplements to this Manual
as new methods become available for the additional contaminants listed in Tables 1.3 and 1.4.
Table 1.5 Approved Analytical Methods for UCMR (1999) List 1 Contaminants

Methodology
Chemical Contaminant
CAS#
EPA Method
Equivalent Methods
Volatile Organic Compounds
MTBE
1634-04-4
EPA 524.2a
D5790-95b; SM6210DC;
SM6200BC
Nitrobenzene
98-95-3
EPA 524.2 a-e
D5790-95b;SM6210Dc;
SM6200BC
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============
Chemical Contaminant
======
CAS#
—
Methodology
EPA Method
Equivalent Methods
Semivolatile Organic Compounds
2,4-Dinitrotoluene
2,6-Dinitrotoluene
121-14-2
606-20-2
EPA 525.2 a
EPA 525.2 a
Chlorinated Hydrocarbon Pesticides
DDE
72-55-9
EPA 525. 2 a; EPA 508 a;
EPA 508. T
Nitrogen- and Phosphorus-Containing Pesticides
EPTC
Molinate
Terbacil
759-94-4
2212-67-1
5902-51-2
EPA 525. 2 a; EPA 507 a
EPA 525. 2 a; EPA 507 a
EPA 525.2 a; EPA 507 a
Acid Herbicides
DCPA mono-acid degradate

887-54-7
2136-79-0
EPA 5 15. l«-f; EPA 515.2lf
EPA 515.1 "•'; EPA 515.2 ••'
none identified
none identified

D5812-96b;990.06d

D5475-93b;991.07d
D5475-93b;991.07d
D5475-93b;991.07d

D53 17-93 b; 992.32 d
D53 17-93 b; 992.32 d
Annual BookofASTM Standards, 1996 and 1998, Vol. 11.02, American Society for Testing and Materials.Method
D5812-96 is located in the Annual Book ofASTM Standards, 1998, Vol. 11.02. Methods D5790-95, D5475-93,
and D5317 93^re located in the Annual Book ofASTM Standards, 1996 and 1998, Vol 11.02. Copies may be
obtained from the American Society for Testing and Materials, 100 Barr Harbor Dnve, West Conshohocken, PA

SM26200 B is only found in the 20th edition of Standard Methods for the Summation of^tera^Wastewater
1998 Sample preservation must be conducted as specified in EPA Method 524.2 (§ 141.40(a)(4)(i)(A)). SM 6210
D is onlv found in the 18th and 19th editions of Standard Methods for the Examination of Water and Wastewater,
1992 and 1995 American Public Health Association; either edition may be used. Copies may be obtained trom
the American Public Health Association, 1015 Fifteenth Street NW, Washington, DC 20005.
Official Methods of Analysis of AOAC (Association of Official Analytical Chemist) Internationa^ Sixteen*
Edition 4th Revision, 1998, Volume I, AOAC International, First Union National Bank Lockbox, PO Box 75198,
Baltimore MD 21275-5198. (800) 379-2622. . .
Specific recommendations regarding the use of EPA Method 524.2 for measuring nitrobenzene are included in
Section 6 of this Manual. Note that EPA is currently conducting methods development research to determine it
nitrobenzene is compatible with the preservation requirements of EPA Method 525.2. If research indicates that
EPA Method 525 2 is suitable for monitoring nitrobenzene, EPA will issue a public notice and provide for a public
comment period prior permitting the use of EPA Method 525.2 for measuring nitrobenzene.
Additional recommendations for these methods are listed in Section 6 of this Manual.
11
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UCMR Analytical Methods and Quality Control Manual
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UCMR Analytical Methods and Quality Control Manual
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Section 2. Sampling Plan

2.1 Monitoring By Public Water Systems

The focus of the monitoring in the revised UCMR is on occurrence or likely occurrence of
contaminants in the drinking water of community and non-transient, non-community water systems.
For regulatory purposes, public water systems (PWSs) are categorized as "community water
systems " or "non-community water systems". Community water systems (CWSs) are specifically
defined as "public water systems which serve at least 15 service connections used by year-round
residents or regularly serve at least 25 year-round residents," while a non-transient non-community
water system (NTNCWS) means "a public water system that is not a community water system (40
CFR § 141 2) These non-community systems are available to serve the public, but do not do so on
a year-round basis in most cases, or do so but are used by people on a temporary basis (e.g., used by
people traveling).

PWSs will monitor at the sampling sites and at the sampling frequencies specified in the revised
UCMR (40 CFR 141 40) EPA or the State will provide further specifications and guidance on the
monitoring schedule and other requirements to the PWSs. The subsequent general discussion of
sampling is for informational purposes only and does not alter the requirements specified in the
regulation or in directions from the State or EPA to PWSs.

2.1.1 Systems Required To Monitor

Under this program, all CWSs and NTNCWSs serving more than 10,000 people (large systems) are
requkedtomonitorforunregulatedcontaminants(§141.40(a)(l)(ii)). However, PWSs that purchase
their water must only monitor for UCMR contaminants that must be sampled for in the distribution
system (ie the sampling point is listed as "distribution line") (§141.40(a)(l)(m) and
5141 40(a¥l¥v)) For systems serving 10,000 or fewer people (small systems), only a statistically
selected nationally representative sample of 800 CWSs and NTNCWSs must monitor
(§141 40(a)(l)(iv)) EPA will pay for the reasonable costs of monitoring for this representative
sample of small systems. The State or EPA will notify those systems selected for inclusion in the
national representative sample. Transient non-community water systems will not be included in this
monitoring (§141.40(a)(l)(i)).

From the representative sample of 800 systems, EPA will select 20 to 30 systems to serve as "Index"
systems. Information collected from these systems will provide a broader understanding of small
systems Index Systems must monitor each year during the 5-year UCMR cycle (§141.40(a)(5)(iii)).
Data coilected from Index Systems will provide information on the effects of seasonal and annual
variability pumping cycles, and other environmental and program factors that may affect UCMR
monitoring results. EPA will provide additional guidance and instructions to the Index Systems.
EPA will provide contractor support to collect and ship samples as well as gather additional Index
System data.

2.2 Sampling Frequency

PWSs will conduct their Assessment Monitoring during 1 year of the Assessment Monitoring period
2001 to 2003 (except for the Index Systems, which will monitor every year from 2001-2005, as
13
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UCMR Analytical Methods and Quality Control Manual
March 2000
discussed above) The year of monitoring and the time of sample collection should coincide, to the
extent practical, with other scheduled compliance monitoring. For example, a low-vulnerability
system that may only monitor for compliance purposes during 1 year in a 3-year period could collect
its required UCMR samples during that same year. Further, to the extent practical, analyses for the
UCMR should be coordinated with analyses for other required monitoring using the same methods
to help reduce costs.

PWSs usin<* surface water sources, or ground water under the influence of surface water, must
sample fourtimes per year for I year during the Assessment Monitoring period (§141.40(a)(5)). One
of the sampling times must occur between May 1 and July 31, or another period of greatest
vulnerability specified by the State or EPA (§141.40(a)(5)). Large PWSs using surface water or
ground water under the influence of surface water must select either the first, second, or third month
of a quarter and sample in that same month of each of four consecutive quarters (§ 141.40(a)(5)) In
other words systems must monitor under one of the following quarterly sampling schedules:
January April July, October; or February, May, August, November; or March, June, September,
December PWSs using ground water sources will sample two times per year for 1 year during the
Assessment Monitoring period, with one of these sampling times occurring between May 1 and July
31 or another period of greatest vulnerability as specified by the State or EPA. The second set of
samples for ground water systems must be collected 5 to .7 months before or after the vulnerable
period sampling event (§141.40(a)(5)). For all small PWSs participating in the national
representative sample of small systems, the State or EPA will specify the day, plus or minus 2 weeks,
on which samples must be collected (§ 141.40(a)(4)(iii)(B)).

'2.3 Sampling Points

Sampling must be performed at the locations specified in the UCMR Program (§141.40(a)(5)).
These UCMR sampling locations, referred to as sampling points, are contaminant- specific and are
summarized in Table 1.2 for the UCMR (1999) List 1 contaminants. Possible sampling points for
the UCMR (1999) List 2 and List 3 contaminants are listed in Tables 1.3 and 1.4, respectively.

For contaminants on the UCMR (1999) List 1, samples must be collected at entry points to the
distribution system (EPTDSs) representing each non-emergency water source m routine use over the
12-month period of monitoring, unless the State has specified other sampling points that are used
for compliance monitoring under 40 CFR 141.24(f)(l), (2), and (3) (§141.40(a)(5)). Thus UCMR
samples may be collected from either the EPTDS or from the source (raw) water if the State has
specified that source water sampling points are to be used for standard compliance monitoring.
However if monitoring at source water sampling points indicates detection of any of the
contaminants on the monitoring list, then the system must shift its unregulated contaminant
monitoring to the EPTDS for all future monitoring under the UCMR, unless the State or EPA
determines that no treatment or processing was in place that would affect the measurement of the
contaminants (§141.40(a)(5)). In that case, the additional sampling at the EPTDS would not be
required. The requirement for UCMR samples to be collected at the EPTDS follows the existing
regulatory approach and provides data for exposure assessment.
14
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UCMR Analytical Methods and Quality Control Manual March 2000

Section 3. Sample Collection and Preservation

3.1 Chemical Contaminants

Sample preservation and holding times for the contaminant-specific analytical determinative
methods specified in the UCMR Program are summarized in Table 3.1. The sample collection and
preservation procedures as summarized below must be followed for all samples collected for the
UCMR (§141 40 Appendix A). If these procedures are not followed, the Rule specifies that
resampling is required within 14 days of the observance of the error (§ 141.40(a)(5)).

3.1.1 Nitrogen-and Phosphorus-Containing Pesticides

The three UCMR (1999) List 1 nitrogen- and phosphorus-containing pesticides, EPTC2, molinate2,
and terbacil2 may be analyzed with EPA Method 525.2, EPA Method 507 or the approved
SuivJen'mkS including ASTM Method D5475-93 or AOAC Method 991.07 (seeTable 1.5).
For reference see EPA Method 507 - Determination of Nitrogen- and Phosphorus-Containing
Pesticides in Water by Gas Chromatography with a Nitrogen-Phosphorus Detector (Table 1.5).
(Sampling procedures based on EPA Method 525.2 are described below in Section 3.1.5) Sample
procedures based on EPA Method 507, including sample containers, chlorine testing and
dechlorination, and sample collection, preservation, storage, and holding times are described below:

Sample container - Use one-liter or one-quart amber glass bottles fitted with Teflon-lined screw
caps Amber bottles should be used for the UCMR to protect samples from light. The bottle should
be washed and dried as described in Section 4.1.1 of the EPA Method before use to minimize
contamination. Cap liners are cut to fit from sheets (Pierce Catalog No. 012736 or equivalent) and
extracted with methanol overnight prior to use.

Residual chlorine determination - If water to be sampled is known or suspected to contain residual
chlorine determination of the level of residual chlorine is necessary. Diemyl-p-phenylenediamine
(DPD) test-kits are commercially available and can be used to determine the level of residual
chlorine in the field. Determine and record the level of residual chlorine in the water to be sampled.
If the water to be sampled contains residual levels of chlorine, each sample will need to be
dechlorinated.

Sample dechlorination - To dechlorinate the sample, add approximately 80 milligrams of sodium
thiosulfate per liter of sample to the sample containers prior to filling. If needed, add as much
additional sodium thiosulfate as necessary to eliminate all residual chlorine.

Sample collection - When sampling from a water tap, remove any aeration equipment, open the tap
and allow the system to flush until the water temperature has stabilized, usually about two minutes.
Collect the sample directly from a tap and not through any plastic or rubber hoses or tubing. Adjust
the flow to a slow but steady stream (about the diameter of a pencil) and collect samples from the
flowing stream. When using automatic samplers, use refrigerated glass sample containers if
possible. Sampling equipment, including automatic samplers, must be free of plastic tubing, gaskets,
and other parts that may leach interfering analytes into the water sample (141.40 Appendix A).
These pesticides are also semi-volatile organic compounds and therefore are also discussed in Section 3.1.5

15
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UCMR Analytical Methods and Quality Control Manual March 2000

Fill the sample bottles until almost full, but take care not to flush out any dechlorination chemicals
from the sample bottle. After the sample bottle has been filled, close the bottle, invert three or four
times, and keep the sample bottle sealed until analysis.

The method specifies the addition of the biocide mercuric chloride to the sample to retard
microbiological degradation. Mercuric chloride, however, is being withdrawn because it is highly
toxic and poses handling and disposal problems. Mercuric chloride should not, therefore, be used
to preserve samples for the UCMR Program.

Sample holding time - Extract samples within 14 days. Preservation study results indicated that
most method contaminants present in samples were stable for 14 days when stored under these
conditions. The contaminants EPTC and terbacil exhibited recoveries of less than 60% after 14 days;
consequently, the maximum sample holding time for these contaminants is 14 days. If samples are
not extracted within this period, discard and replace the samples.

Sample extract storage and holding time - Analyze extracts within 14 days. Store extracts at 4°C
(±2°) away from light. Preservation study results indicate that most contaminants are stable for 28
days; however, a 14-day maximum extract storage time is recommended. (See Table 3.1 for a
summary of holding times.) If samples are not analyzed within the appropriate period, discard and
replace the samples.

3.1.2 Chlorinated Hydrocarbon Pesticides

The UCMR (1999) List 1 chlorinated hydrocarbon pesticide, 4,4'-DDE3, may be analyzed with EPA
Method 508,508.1,525.2 or the approved equivalent methods, including ASTM Method D5812-96
and AOAC Method 990.06 (see Table 1.5). Sampling procedures based on EPA Method 525.2,
including sample containers, chlorine testing and dechlorination, and sample collection,
preservation, storage, and holding times are described below in Section 3.1.5. Sampling procedures
based on EPA Methods 508 and 508.1 are described below:

EPA Method 508 - Determination of Chlorinated Pesticides in Water by GC with an Electron
Capture Detector (see Table 1.5).

Sample container - Use one-liter Amber glass bottles fitted with Teflon-lined screw caps. Amber
bottles should be used for the UCMR to protect samples from light. The container should be washed
and dried before use as described in Section 4.1.1 of the EPA Method to minimize contamination.
Cap liners are cut to fit from sheets (Pierce Catalog No. 012736) and extracted with methanol
overnight prior to use.

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UCMR Analytical Methods and Quality Control Manual March 2000

(DPD) test-kits are commercially available and can be used to determine the level of residual
chlorine in the field. Determine and record the level of residual chlorine in the water to be sampled.
If the water to be sampled contains residual levels of chlorine, each sample will need to be
dechlorinated. •

Sample collection - When sampling from a water tap, remove any aeration equipment, open the tap
and allow the system to flush until the water temperature has stabilized, usually about two minutes.
Collect the sample directly from a tap and not through any plastic or rubber hoses or tubing. Adjust
the flow to a slow but steady stream (about the diameter of a pencil) and collect samples from the
flowing stream. When using automatic samplers, use refrigerated glass sample containers, if
possible. Sampling equipment, including automatic samplers, must be free of plastic tubing, gaskets,
and other similar parts or materials that may leach chemicals into the sample (141.40 Appendix A).

Fill the sample bottles until almost full, but take care not to flush out any dechlorination chemicals
from the sample bottle. After the sample has been collected, close the bottle, invert three or four
times, and keep the sample sealed from collection time until analysis.

The method specifies the addition of the biocide mercuric chloride to the sample to retard
microbiological degradation. Mercuric chloride, however, is being withdrawn because it is highly
toxic and poses handling and disposal problems. Mercuric chloride should hot, therefore, be used
to preserve samples for the UCMR Program.

Sample holding time - Preservation study results indicate that most of the target contaminants
present in the samples are stable for 7 days when stored under these conditions. Contaminant
• stability may be affected by the matrix; therefore, the analyst should verify that the preservation
technique is applicable to the samples under study. (See Table 3.1 for a summary of holding times.)
If samples are not extracted within the appropriate period, discard and replace the samples.

Sample extract storage and holding time - Store sample extracts at 4°C (±2°), away from light.
A 14-day maximum extract storage time is recommended. However, contaminant stability may be
affected by the matrix; therefore, the analyst should verify appropriate extract holding times
applicable to the samples under study. If samples are not analyzed within the appropriate period,
discard and replace the samples.

EPA Method 508.1 - Determination of Chlorinated Pesticides, Herbicides, and Organohalides by
Liquid-Solid Extraction and Electron Capture Gas Chromatography (see Table 1.5).

Sample container - Use one-liter or one-quart amber glass bottles fitted with Teflon-lined screw
caps. Amber bottles should be used for the UCMR because some of the method contaminants are
sensitive to light and are oxidized or decomposed upon exposure to light.

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UCMR Analytical Methods and Quality Control Manual . March 2000

Residual chlorine determination - If water to be sampled is known or suspected to contain residual
chlorine determination of the level of residual chlorine is necessary. Diethyl-p-phenylenediamme
(DPD) test-kits are commercially available and can be used to determine the level of residual
chlorine in the field. Determine and record the level of residual chlorine in the water to be sampled.
If the water to be sampled contains residual levels of chlorine, each sample will need to be
dechlorinated.

Sample dechlorination - To dechlorinate the sample, add approximately 80 milligrams of sodium
sulfite per liter of sample to the sample containers prior to filling. If needed, add as much additional
sodium sulfite as necessary to eliminate all residual chlorine.

Sample collection - When sampling from a water tap, remove any aeration equipment, open the tap
and allow the system to flush until the water temperature has stabilized, usually about two minutes.
Collect the sample directly from a tap and not through any plastic or rubber hoses or tubing. Adjust
the flow to a slow but steady stream (about the diameter of a pencil) and collect samples from the
flowino- stream. When using automatic samplers, use refrigerated glass sample containers if
possible Sampling equipment, including automatic samplers, must be free of plastic tubing, gaskets,
and other parts that may leach interfering analytes into the water sample (141.40 Appendix A).

Fill the sample bottles until almost full, but take care not to flush out any dechlorination chemicals
from the sample bottle. After collecting the sample, close the bottle (Teflon face down), invert three
or four times, and wait one minute until preserving the sample with acid.

Sample preservation - The one-minute waiting period after sample collection is crucial; it is
important to reduce the level of residual chlorine before preserving the sample with acid. If the acid
is added immediately following collection, the dechlorination reaction may be incomplete. This
allows residual free chlorine to oxidize and/or chlorinate PAHs in the sample, including the surrogate
standard specified by the method. Also, do not directly mix hydrochloric acid and sodium sulfite
prior to sampling.

After waiting one minute, adjust the pH to less than 2 by carefully adding 6 N hydrochloric acid (this
may require as much as 4 milliliters of acid). This should retard the microbiological degradation of
the contaminants in water. Also, this is the same pH used in the extraction, and is necessary to
support the recovery of acidic compounds. Close the sample bottle, Teflon face down, invert three
or four times, and keep the sample sealed until analysis.

Sample storage - Samples should be iced or refrigerated at 4°C (±2°) from the time of collection
until extraction. Immediately store the samples at 4°C (±2°). To do so, place the samples on ice or
with frozen cold packs in a cooler, or place in a refrigerator that can maintain the samples at 4 C
(±2°). Keep the samples at 4°C (±2°) from the time of collection until analysis.

Sample holding time - Extract samples within 14 days. Preservation study results show that the
UCMR contaminants are stable for 14 days in samples that are preserved as described in Sections
8.2 and 8.3 of the EPA Method. (See Table 3.1 for a summary of holding times.) If samples are not
extracted within this period, discard and replace the samples.

Sample extract holding time - Analyze sample extracts within 30 days (refrigerated sample extracts
may be stored up to 30 days prior to analysis). If sample extracts are not analyzed within this period,
discard and replace the samples.

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UCMR Analytical Methods and Quality Control Manual March 2000

3.1.3 Acid Herbicides

The two UCMR (1999) List 1 acid herbicide-based contaminants, the mono- and di-acid degradates
of dimethyl tetrachloro terephthalate (DCPA), may be analyzed with EPA Method 515.1, EPA
Method 515.2 or the approved equivalent methods including ASTM Method D5319-93 and AOAC
Method 992.32 (see Table 1.5). For reference, see EPA Method 515.1 - Determination of
Chlorinated Acids in Water by Gas Chromatography with an Electron Capture Detector or EPA
Method 515.2 - Determination of Chlorinated Acids in Water Using Liquid-Solid Extraction and
Gas Chromatography with an Electron Capture Detector (Table 1.5). It is important to note that
because the approved methods do not allow for the identification and quantification of the individual
acids, the single analytical result obtained should be reported as total DCPA mono- and di-acid
degradates. For specific clarifications concerning the use of EPA Methods 515.1 and 515.2 or their
approved equivalent methods, please see Section 6.1 of this Manual. Sampling procedures based
on EPA Methods 515.1 and 515.2, including sample containers, chlorine testing and dechlorination,
and sample collection, preservation, storage and holding times are described below:

Sample container - If samples are being collected for EPA Method 515.1 or an approved equivalent
method, use one-liter or one-quart amber glass bottles fitted with Teflon-lined screw caps. If
samples are being collected for EPA Method 515.2 or an approved equivalent method, use 250
milliliter amber glass bottles fitted with Teflon-lined screw caps. Amber bottles should be used to
protect samples from light. The container should be washed and dried as described in Section 4.1.1
of the EPA Methods before use to minimize contamination. Cap liners are cut to fit from sheets
(Pierce Catalog No. 012736) and extracted with methanol overnight prior to use.

Residual chlorine determination - If water to be sampled is known or suspected to contain residual
chlorine, determination of the level of residual chlorine is necessary. Diethyl-p-phenylenediarnine
(DPD) test-kits are commercially available and can be used to determine the level of residual
chlorine in the field. Determine and record the level of residual chlorine in the water to be sampled.
If the water to be sampled contains residual levels of chlorine, each sample will need to be
dechlorinated.

Sample dechlorination - To dechlorinate the sample, add approximately 80 milligrams of sodium
thiosulfate per liter of sample to the sample container prior to filling. If needed, add as much
additional sodium thiosulfate as necessary to eliminate all residual chlorine.

Fill the sample bottles until almost full, but take care not to flush out any dechlorination chemicals
from the sample bottle. After collecting the sample, close the sample bottle, invert three or four
times, and keep the sample bottle sealed until analysis.

The method specifies the addition of the biocide mercuric chloride to the sample to retard
microbiological degradation. Mercuric chloride, however, is being withdrawn because it is highly

19
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UCMR Analytical Methods and Quality Control Manual March 2000

toxic and poses handling and disposal problems. Mercuric chloride should not, therefore, be used
to preserve samples for the UCMR Program.

Sample preservation procedures in EPA Method 515.2 are similar to those listed in EPA Method
515 1 with the exception that samples collected for EPA Method 515.2 must be acidified via the
addition of 6N HC1 (§ 141.40 Appendix A). If samples are being collected for EPA Method 515.2,
be sure to wait one minute after dechlorinating the sample before preserving it with acid to ensure
that the dechlorination reaction is complete.

Sample holding time - Extract samples within 14 days. However, contaminant stability will very
likely be affected by the matrix; therefore, the analyst should verify that the preservation technique
is applicable to the samples under study. Preservation study results from EPA Method 515.1 indicate
that the contaminants (measured as total acid) present in samples are stable for 14 days when stored
under these conditions. Preservation study results for EPA Method 515.2 indicate that the sample
contaminants (measured as total acid) are stable in water for 14 days when stored under these
conditions. If samples are not extracted within the appropriate period, discard and replace the
samples.

Sample extract storage and holding time - Store extracts at 4°C (±2°) away from light. Analyze
extracts within 28 days, according to EPA Method 515.1 and 14 days according to EPA Method
5152 However, the analyst should verify that appropriate extract holding times are applicable to
the samples under study. Preservation study results indicate that most contaminants are stable for
28 days according to EPA Method 515.1 and 14 days according to EPA Method 515.2. (See Table
3.1 for a summary of holding times.) If samples are not extracted within the appropriate period,
discard and replace the samples.

3.1.4 Volatile Organic Compounds

The two UCMR (1999) List 1 volatile organic compounds (VOCs) monitored under the revised
UCMR Program, methyl tertiary-butyl ether (MTBE) and nitrobenzene, may be analyzed with EPA
Method 524.2 or an approved equivalent method, such as ASTM Method D5790-95 or APHA
(Standard Methods) SM6210D or SM6200B (see Table 1.5). For reference, see EPA Method 524.2 -
Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas
Chromatography/Mass Spectrometry, or an approved equivalent method. It is important to keep the
sample bottles in an area known to be free of VOCs prior to sample collection. General sampling
procedures based on EPA Method 524.2, including sample containers, chlorine testing,
dechlorination, sample collection, sample preservation, storage and holding times, are described
below For specific analytical method recommendations pertaining to the use of EPA Method 524.2
for measuring nitrobenzene, please see Section 6.2 of this Manual. The sampling requirements
detailed in EPA Method 524.2 must also be followed when using any of the approved equivalent
methods (§141.40(a)(4)(i)(A)).

Sample containers - Use 40-milliliter to 120-milliliter screw cap glass vials, each equipped with
a Teflon-faced silicon septum. To prepare sample bottles: wash vials and septa with detergent and

20
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UCMR Analytical Methods and Quality Control Manual March 2000

rinse with distilled water; air dry the vials and septa at room temperature; place in a 105°C oven for
one hour; then remove and allow to cool in an area known to be free of organics.

Residual chlorine determination - If water to be sampled is known or suspected to contain residual
chlorine, determination of the level of residual chlorine is necessary. Diethyl-p-phenylenediamine
(DPD) test-kits are commercially available and can be used to determine the level of residual
chlorine in the field. Determine and record the level of residual chlorine in the water to be sampled.
If the water to be sampled contains residual levels of chlorine, each sample will need to be
dechlorinated.

Sample dechlorination - To dechlorinate the sample, add approximately 25 milligrams ascorbic
acid (or 3 milligrams sodium thiosulfate4) per 40 milliliter of sample volume to sample container
prior to collecting the sample. If necessary to eliminate all residual chlorine, add an additional 25
milligrams ascorbic acid (or 3 milligrams sodium thiosulfate) per each 5 milligrams per liter residual
chlorine in the sample.

Sample collection - Collect all samples in duplicate or triplicate. When sampling from a water tap,
remove any aeration equipment, open the tap and allow the system to flush until the water
temperature has stabilized, usually about two minutes. Collect the sample directly from a tap and
not through any plastic or rubber hoses or tubing. Adjust the flow from the tap to a slow but steady
stream (about the diameter of a pencil) and collect the sample from the flowing stream. When using
automatic samplers, use refrigerated glass sample containers, if possible. Sampling equipment,
including automatic samplers, must be free of plastic tubing, gaskets, and other parts that may leach
interfering analytes into the water sample (141.40 Appendix A).

Fill sample to almost overflowing, but take care not to flush out any dechlorination chemicals that
are in the sample bottle. Do not let air bubbles pass through the sample as the sample bottle is filled,
and, when sealed, the sample bottle should not contain air bubbles. After the sample bottle has been
filled, close the bottle (Teflon face down), invert three or four times, and then wait one minute before
preserving the sample with acid.

Sample preservation - The one-minute waiting period after sample collection is crucial; it is
important to reduce the residual chlorine before preserving the sample with acid. If the acid is added
immediately following sample collection, the dechlorination reaction may be incomplete.

After one minute, adjust the pH to less than 2 by carefully adding two drops of 1:1 hydrochloric acid
for every 40 milliliters of sample. (The hydrochloric acid preservation reduces sample pH in order
to retard microbiological degradation of the contaminants being analyzed.) Ensure that no air
bubbles are trapped in the completely full sample bottle. Close the sample bottle, Teflon face down,
and invert three or four times. Keep the sample bottle sealed from collection time until analysis.

Sample storage - Immediately store the samples at 4°C (± 2°). To do so, place the samples on ice
or with frozen cold packs in a cooler, or place in a refrigerator that can maintain the samples at 4°C
(± 2°). Keep the samples at 4°C (± 2°) from the time of collection until analysis. The sample
storage area must be free of organic solvent vapors, excess heat and direct light (§141.40 Appendix
A).
Because neither MTBE nor nitrobenzene boil below 25°C, sodium thiosulfate may be used to reduce
residual chlorine.

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UCMR Analytical Methods and Quality Control Manual March 2000

Sample holdin<* time - Analyze all samples within 14 days of collection (see Table 3.1 for a
summary of holding times). If samples are not analyzed within this period, discard and replace the
samples.

3.1.5 Semi-volatile Organic Compounds

The six5 UCMR (1999) List 1 semi-volatile organic compounds, 2,4-dinitrotoluene, 2,6-
dinitrotoluene, 4,4'- DDE6, s-ethyl-dipropylthiocarbamate (EPTC)7, molinate7 and terbacil may be
analyzed with EPA Method 525.2 or the approved equivalent methods including ASTM Methods
D5812-96 and D5475-93, or AOAC Methods 990.06 or 991.07. Note that two of these semi-volatile
organic compounds (2,4-dinitrotoluene and 2,6-dinitrotoluene) can be analyzed with only the EPA
approved analytical method; there are no approved equivalent methods for these two contaminants.
See Table 1 5 for a listing of the approved equivalent analytical methods for each contaminant. For
reference see EPA Method 525.2 - Determination of Organic Compounds in Drinking Water by
Liquid-Solid Extraction and Capillary Column Gas Chromatography/Mass Spectrometry, or an
approved equivalent method. General sampling procedures based on EPA Method 525.2, including
sample containers, chlorine testing and dechlorination, and sample collection, preservation, storage,
and holding times, are described below:

Sample containers - Use one-liter or one-quart amber glass bottles fitted with Teflon-lined screw
caps Amber bottles should be used for the UCMR because some of the method contaminants are
very sensitive to light and are oxidized or decomposed upon exposure to light. It is important to
keep the sample bottles in an area known to be free of volatile and semi-volatile organic compounds
prior to sample collection.

Sample dechlorination - To dechlorinate the sample, add approximately 40-50 milligrams of
sodium sulfite to sample container prior to collecting the sample. If needed, add as much sodium
sulfite as necessary to eliminate all residual chlorine.
5 It is anticipated that acetochlor and possibly nitrobenzene will be added to the scope of this method once
further methods development research has been completed. If EPA Method 525.2 and the equivalent
voluntary consensus standards are approved for measuring acetochlor and nitrobenzene, a supplement to
this Manual will be issued.

6 This semi-volatile organic compound is a pesticide and is specifically identified and listed as a chlorinated
pesticide in Table 1.5.

7 These three semi-volatile organic compounds are pesticides and are specifically identified and listed as
nitrogen/phosphorus pesticides in Table 1.5.

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UCMR Analytical Methods and Quality Control Manual
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Sample collection - When sampling from a water tap, remove any aeration equipment, open the tap
^dX low the system to flush until the water temperature has stabilized usually about two minutes
Collect the sample directly from a tap and not through any plastic or rubber hoses or tubing Adjust
me flow from the tap to a slow but steady stream (about the diameter of a pencil) and collect the
sample from the flowing stream. When using automatic samplers, use refrigerated glass sample
containers, if possible. Sampling equipment, including automatic samplers, must be free of plasUc
tubing, gaskets, and other parts that may leach interfering analytes into the water sample (141.40
Appendix A).

Fill sample to almost overflowing, but take care not to flush out any dechlorination chemicals that
•areinSample bottle. After the sample bottle has been filled, close the bottle (Teflon face down),
invert three or four times, and then wait one minute before preserving the sample with acid.

Sample preservation - The one-minute waiting period after sample collection is crucial to reduce
me level of residual chlorine before preserving the sample with acid. If the acid is added
immediately following collection, the dechlorination reaction may be incomplete This allows
residual free chlorine to oxidize and/or chlorinate poly-aromatic hydrocarbons (PAHs) in the sample
(as noted in Section 13.2.1 of the Method) including the internal and surrogate standards specified
bv the method Because of the degradation/oxidation of the internal standards, calculated results
bLed on internal standard recovery can be erroneously elevated. Also, do not directly mix
'hydrochloric acid and sodium sulfite prior to sampling.

After waiting one minute, adjust the pH to less than 2 by carefully adding 6 N hydrochloric acid (this
may rebuke as much as 4 milliters of acid). This should retard the microbiological degradation of
Se contaminants in water. Also, this is the same pH used in the extraction, and is necessary to
support the recovery of acidic compounds. Close the sample bottle, Teflon face down, invert three
or four times, and keep the sample sealed until analysis.

Sample storage - Immediately store the samples at 4°C (±2°). To do so, place the samples on ice
or with frozen cold packs in a cooler, or place in a refrigerator that can maintain the samp es at 4 C
(12°) Keep the samples at 4°C (± 2°) from the time of collection until analysis. Sample storage
area must be free of organic contaminants, excess heat, and direct light (§141.40 Appendix A).

Sample holding time - Extract the samples within 14 days of sample collection and analyze the-
extracts within 30 days of sample collection. Results of the holding time and storage study of all
method contaminants showed that most are stable for 14 days in water samples when the samples
Se dechlorinated, preserved, and stored as described above. (See Table,3.1 for a summary of
holding times.) If samples are not analyzed within this period, discard and replace the samples.
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UCMR Analytical Methods and Quality Control Manual
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Table 3.1 Preservation and Holding Times for Approved Analytical Methods
Method(s)
EPA 507
D5475-93
991.07
EPA 508
D58 12-96
990.06
EPA 508.1
D58 12-96
990.06
EPA 5 15.1
D53 17-93
992.32
EPA 5 15.2
D53 17-93
992.32
EPA 524.2
D5790-95
SM6210D
SM6200B
EPA 525.2
Preservation
Sodium
thiosulfate;
Cool 4°C; Dark
Sodium
thiosulfate;
Cool 4°C; Dark
Sodium sulfite;
6 N HC1 - pH < 2;
Cool 4°C
Sodium
thiosulfate;
Cool 4°C; Dark
Sodium
thiosulfate;
6 N HC1 - pH < 2;
Cool 4°C; Dark
Ascorbic acid or
Sodium
thiosulfate;
l:lHCl-pH<2;
Cool 4°C
Sodium sulfite;
6 N HC1 - pH < 2;
Cool 4°C; Dark
Sample
Holding
Time
14 days
7 days
14 days
14 days
14 days
14 days
14 days
Extract
Holding
Time
14 days
(4°C, Dark)
14 days
(4°C, Dark)
30 days
28 days
(4°C, Dark)
14 days
(4°C, Dark)
N/A
30 days
from
collection
Sample Size
1L
1L
1L
1L
250 mL
40 - 120 mL
1L
Container
Amber Glass
with Teflon-
lined Cap
Amber Glass
with Teflon-
lined Cap
Amber Glass
with Teflon-
lined Cap
Amber Glass
with Teflon-
lined Cap
Amber Glass
with Teflon-
lined Cap
Glass with
Teflon-lined
Septum
Amber glass
with Teflon-
lined Cap
Note: EPA = EPA Methods, D = ASTM Methods, SM = APHA Standard Methods, 900 series = AOAC Methods. See
Table 1.5 for the full reference for each analytical method.
3.2 Monitoring of Routine Water Quality Parameters

In addition to the requirement that systems monitor for UCMR contaminants, the revised UCMR
also specifies that certain chemical and physical parameters must be measured in the field at each
sampling point from which UCMR samples are collected (§141.40(a)(4)(i)(B)). These parameters
are being required because they are important indicators of water quality and may contribute to the
likelihood of the contaminants being found in drinking water. EPA believes that these parameters
will allow for a more thorough scientific understanding of the occurrence of unregulated
contaminants. As all UCMR (1999) List 1 contaminants are chemicals, EPA is only requiring that
the pH of the water being sampled is measured and reported (§141.40(a)(4)(i)(B)). For UCMR
(1999) List 2 and List 3 contaminants, some of which are microbiological in nature, monitoring of
24
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UCMR Analytical Methods and Quality Control Manual
March 2000
additional water quality parameters such as temperature, total disinfectant residual, etc., may be
required. The analytical methods approved for measuring pH are included in Table 3.2 below.
Table 3.2 Water Quality Parameters to be Monitored with UCMR (1999) List 1
Contaminants
Parameter
Contaminant
Type
Methodology
EPA
Method
Standard
Methods
Other
pH
Chemical
150. la
150.2£
4500-H+Bb
ASTMD1293-84°
ASTMD1293-95c
Methods 150.1 and 150.2 are available .from US EPA, NERL, 26 W Martin Luther King Dr., Cincinnati Ohio
45268 The identical methods are also in "Methods for Chemical Ana ysis of Water and Wastes EPA-600/4-79-
020 March 1983 available from the National Technical Information Service (NJIS) U.S. Department of
Cornrnerce?5285 Port Royal Rd., Springfield, Virginia 22161, PB84-128677. The NTIS toll-free number is (800)

The~18*7and 19ltl Editions of Standard Methods for the Examination of Water and Wastewater, 1992 and 1995
Method 4500-HT B can also be found in the 20* Edition Standard Methods for the Examination of Water and
SwoLr 1998 American Public Health Association, 1015 Fifteenth St. NW, Washington, DC, 20005.
SS Book of ASTM Standards, Editions 1994 and 1996,Volumes 11.01, American Society for Testing and
Serials, ?OOBarr Harbor Drive, West Conshohocken, PA 19428 Version D1293-84 is located in toe Annual
BookbfASTM Standards,l994r, Volumes 11.01. Version D1293-95 is located in the Annual Book ofASTM
Standards, 1996, Volumes 11.01.
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UCMR Analytical Methods and Quality Control Manual March 2000
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UCMR Analytical Methods and Quality Control Manual March 2000

Section 4. Sample Transport

Immediately after sample collection place all UCMR samples on ice or with frozen cold packs in an
insulated container, cooler, or place in a refrigerator to cool the samples to 4 C (±2 ). Keep the
samples at 4°C (±2°) from the time of collection until analysis, including during any necessary
transport Do not let any samples freeze. If transporting samples to an off-site laboratory, pack
samples in insulated containers or coolers carefully to protect against sample bottle breakage during
transport Samples are commonly transported to off-site laboratories via laboratory pick-up service,
delivery by the water system's own personnel, or delivery with a commercial courier service.

Transport the appropriately cooled [i.e., 4°C (±2°)] and packed samples to the analytical laboratory
as soon as possible after sample-collection. Note that samples must be packed with sufficient ice or
frozen cold packs to ensure that samples are maintained at 4°C (± 2°) during the entire transport
period but do not let any samples freeze (§141.40 Appendix A). All samples must be processed by
the laboratory within 7 to 14 days of sample collection; therefore, provide adequate time for sample
pick-up transport, delivery, extraction, and analysis (§141.40 Appendix A). Immediate (sample
collection day) transport of samples to the laboratory will ensure adequate sample analysis time and
will greatly reduce the chance that systems will need to re-collect samples due to late samples
•exceeding holding times. Transporting the samples within 2 days of sample collection is strongly
recommended; transporting the samples immediately—the same day of sample collection—is
advised.
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UCMR Analytical Methods and Quality Control Manual March 2000
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UCMR Analytical Methods and Quality Control Manual March 2000

Section 5. UCMR Quality Control Requirements

Several quality control (QC) methods required for UCMR monitoring by EPA are methods currently
required and in use under other SDWA regulations. As a result, mechanisms for reviewing
laboratory qualifications are already in place for determination of other chemical contaminants
determined by these methods. Laboratories that provide data to EPA in support of the UCMR must
document that they are currently approved by a State and that they have State certification and/or
approval to perform those analyses using UCMR-specified methods (§141.40(a)(5)(ii)(G)).

UCMR Assessment Monitoring must be conducted only using the analytical methods specified in
the UCMR (see Table 1.5; §141.40(a)(5)). The QC procedures specified in these approved analytical
methods and in Appendix A of the Rule are further described in this Manual and must be followed
to ensure accurate and precise data (§141.40 Appendix A).

QC procedures and the frequency of QC testing vary among the methods. Many of the methods
specified in the UCMR provide criteria to be used in evaluating and accepting laboratory
performance based on related QC data. This section describes the various QC procedures EPA
requires as part of the UCMR and the rationale for acceptance criteria. Because EPA cannot accept
monitoring data if the applicable QC requirements are not met, laboratories must strictly adhere to
the QC described in this section (§141.40 Appendix A). The following will cause monitoring data
to be excluded from the database:

• failure to use the correct calibration check standard concentration

• failure to verify the calibration curve at the specified frequency

• failure to meet the acceptance criteria for verifying calibration

• contaminants detected in the laboratory reagent (method) blank at concentrations equal
to or more than one-half the minimum reporting level (MRL)

• when applicable, failure to meet the acceptance criteria for the internal standard

• when applicable, failure to meet the acceptance criteria for the surrogate standard

• failure to analyze samples and/or extracts within the specified holding times

Certain QC data must also be reported as part of the analytical services performed for the UCMR
(§141.35(d)). These data are being collected to evaluate the quality of the monitoring data. These
reporting requirements are noted in the reporting elements in Section 7 of this Manual.
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UCMR Analytical Methods and Quality Control Manual
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5.1 Minimum Reporting Level

The minimum reporting level (MRL) concentrations listed in Table 5.1 were determined by
multiplying by 10 the least sensitive method's minimum detection limit (MDL),8 or, when available,
multiplying by 5 the least sensitive method's estimated detection limit (EDL). The MRL for VOCs
was determined by multiplying by 10 either the published MDL or 0.5 micrograms per liter,
whichever is greater. The MDL of 0.5 micrograms per liter (0.0005 milligrams per liter) was
selected to conform to the VOC MDL requirements of 40 CFR 141.24(f)(17)(i)(E).
Table 5.1 UCMR Methods and Minimum Reporting Levels
Contaminant
2,4-Dinitrotoluene
2,6-Dinitrotoluene
4,4'-DDE
Acetochlor
DCPA mono- and di-
acid degradates
EPTC
Molinate
MTBE
Nitrobenzene
Perchlorate
Terbacil
Approved UCMR Analytical Methods
EPA 525.2
EPA 525. 2
EPA 508; EPA 508.1; EPA 525.2; D5812.96;
990.06
Reserved b
EPA 515.1; EPA 515.2; D5317-93; 992.32
EPA 507; EPA 525.2; D5475-93; 991.07
EPA 507; EPA 525.2; D5475-93; 991.07
EPA 524.2; D5790.95; SM6210D; SM6200B
EPA 524.2; D5790.95; SM6210D; SM6200B
Reserved15
EPA 507; EPA 525.2; D5475-93; 991.07
Minimum Reporting
Level
2^g/La
2Mg/La
0.8 Mg/L a
Reserved b
l^g/La
l/^g/La
0.9Mg/La
5//g/Lc
10^g/Lc
Reserved b
2A
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UCMR Analytical Methods and Quality Control Manual
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* MRL for VOCs determined by multiplying by 10 either the published MDL or 0.5 Mg/L, whichever is greater The
MDL of 0.5 Mg/L (0.0005 mg/L) was selected to conform to the VOC MDL requirements of 40 CFR
Laboratories must demonstrate that they can achieve reliable data at the MRL for each contaminant.
Therefore the calibration curve must encompass the MRL concentration (§141.40 Appendix A).
The laboratory must verify the accuracy of the curve at the MRL by analyzing a calibration check
standard at the MRL concentration (see Section 5.2 of this Manual; § 141.40 Appendix A).

EPA recognizes that some laboratories are able to provide reliable data at concentrations lower than
those shown in Table 5.1. To achieve consistency in the National Drinking Water Contaminant
Occurrence Database (NCOD), laboratories are only required to report quantitative results for
concentrations equal to or greater than the MRLs (§ 141 .35(d)). However, EPA also recognizes the
usefulness of receiving more complete results to allow evaluation of the analytical method
implementation. Systems and laboratory that are able to reliably report results below the MRL are
encouraged to do so. To report reliable results obtained below the MRL, laboratories and/or water
systems should do three things:

1) For data element 6, Analytical Results - Sign, report a "<," indicating that the result
obtained is less than the MRL listed in Table 5.1.

2) For data element 7, Analytical Result - Value, report the actual concentration value
obtained for the contaminant.

3) For data element 17, Presence/Absence, report the contaminant as "Present."

The combination of these three steps will allow for the reporting of data below the MRL, and will
enable EPA to more fully evaluate the MRL for the respective contaminant and assist m determining
what the final MRL might be if EPA requires future monitoring of the contaminant.

5.2 Calibration

Each method describes calibration procedures that are used to determine the concentrations of the
method contaminants. Some methods allow several options:

• a calibration curve based on either external standards or detector responses to the
contaminant relative to an internal standard

• an average response factor for each contaminant

The laboratory must select and follow one of the calibration procedures outlined in the approved
method to meet the requirements of the UCMR (§141.40 Appendix A). In addition, the mass
spectral (MS) methods, EPA Methods 524.2 and 525.2, have specific tuning criteria that must be met
prior to performing the calibration procedure (§141.40 Appendix A).

All methods specified in the UCMR require that calibration span the expected concentration range
of the samples being analyzed. The number of calibration standards necessary to meet this

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UCMR Analytical Methods and Quality Control Manual Marcft 2000

requirement varies from three to six, depending on the method. The UCMR does not require
laboratories to change method calibration procedures with the exception that the low level standard
must be at or below the MRL specified for each contaminant, and the mid-level standard must
simply be near the midpoint of the calibration range (§ 141.40 Appendix A).

5.2.1 Calibration Verification

Complete calibration curves are not required on a daily basis. However, the analyst must
periodically verify calibration during sample analysis to ensure accuracy of the analytical results
(5141 40 Appendix A). The frequency for verifying calibration varies according to the analytical
method used Frequency requirements for verifying calibration have been established by EPA to
meet the accuracy requirements for the UCMR and are presented in Table 5.2 (§ 141.40 Appendix
A).

Most of the methods recommend checking the instrument calibration using a mid-level calibration
check standard The method acceptance criteria for verifying calibration are based on this standard
However to meet the objectives of the UCMR, calibration must be verified across the range of
contaminant concentrations that are being measured (§141.40 Appendix AX Based on the
recommendations from technical experts experienced with these methods, EPA is specifying
calibration verification at low- and mid- levels for each method.

The frequency of verifying calibration for UCMR samples is based on the number of samples
analyzed together in an analysis batch. For Assessment Monitoring, an analysis batch is defined as
samples analyzed using the same instrument within a 24-hour period. However, the maximum
number of UCMR samples that can be included in one analysis batch is 30. The 24-hour period
begins with the analysis of the low-level calibration check standard and it ends with the analysis ot
the final calibration check standard. The 24-hour period does not necessarily include the analysis
time used to generate the calibration curve. However, if a new curve is prepared each time samples
are analyzed; the 24-hour period still begins with the analysis of the low-level calibration check
standard.

When determining the 30 sample maximum, do not count method blanks, shipping blanks mitial
and continuing calibration check standards, matrix spikes (MSs), matrix spike duplicates (MSDs),
and any independent QC samples that are analyzed with the UCMR samples.

Analysis of the low-level calibration check standard should be completed prior to analysis of any
samples; each contaminant must meet the acceptance criteria provided m Table 5.3 (§141 4U
Appendix A) If the criteria cannot be met, identify and eliminate the source of the problem, then
perform a new instrument calibration according to the method calibration procedures.

It is important to note that an acceptable end calibration check standard should be analyzed before
analyses of other samples (i.e., non-UCMR samples) may begin. Thus, if the last five samples
analyzed were part of the UCMR, the analyst should perform an acceptable end calibration check
standard before starting non-UCMR analyses.

For all methods, after analyses of no more than 10 UCMR samples, the calibration curve must be
verified using either a low- or mid-level continuing calibration check standard; each contaminant
must meet the acceptance criteria listed in Table 5.3 or 5.4 (§ 141.40 Appendix A). If the criteria are
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UCMR Analytical Methods and Quality Control Manual
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not met reanalyze all samples or extracts that were analyzed between this standard and the last
standard meeting acceptance criteria for the problem contaminant(s) after the calibration problem
is resolved If the samples or extracts cannot be re-analyzed, then the data for the problem
contaminants) are considered invalid for those samples and should not be reported to EPA.
Table 5 2 Frequency Requirements for Verifying Calibration
Methods
EPA 507
D5475-93
991.07
EPA 508
D58 12-96
990.06
EPA 508.1
D58 12-96
992.32
EPA 515.1
D53 17-93
992.32
EPA 5 15.2
D53 17-93
992.32
EPA 524.2
D5790-95
SM6210D
SM6200B
EPA 525.2
Method
Specifications
each working day
each working day
each 12 hour shift
each working day
each working shift
every 12 hours
every 12 hours
UCMR Specifications
Initial
each batch of 30
samples or daily
(whichever is more
frequent)
Continuing
alternate between low- and
mid-level standard after
every 10 samples
Note: EPA = EPA Methods, D = ASTM Methods, SM = APHA Standard Methods, 900 series = AOAC Methods. See
Table 1.5 for the full reference for each analytical method.
Table 5.3 UCMR Low-Level Calibration Check Standard Concentrations and
Acceptance Criteria
Contaminant
2,4-dinitrotoluene
2,6-dinitrotoluene
4,4'-DDE
MRLO-ig/L)
2//g/L
2Aig/L
0.8yUg/L
Concentration of
Low-Level Standard
<;MRL
sMRL
*MRL
Acceptance
Criteria
±40%
±40%
±40%
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UCMR Analytical Methods and Quality Control Manual
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Contaminant
Acetochlor
DCPA mono- and di-acid degradates
EPTC
Molinate
MTBE
Nitrobenzene
Perchlorate

MRL GugflL)
Reserved a
lMg/L
lA
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UCMR Analytical Methods and Quality Control Manual
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5.3 Method Detection Limit

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 contaminant 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. If accurate and precise data are required, do
not report below the level at which the necessary precision and accuracy are achieved.

Laboratories must calculate their MDLs for each analysis (using the primary column) according to
the procedure in CFR § 136 Appendix B (included in this Manual as Appendix C), with the following
additional requirements (§ 141.40 Appendix A):

• Include all sample processing steps in the determination. Conduct extractions and
analyses over at least 3 days.

• Select a spiking concentration which is less than or equal to the established MRL for
each contaminant monitored by the UCMR. Analyze a total of seven duplicates of
reagent water spiked at a concentration less than or equal to the established MRL as
listed in Table 5.1. From the data collected from these analyses, calculate measurement
accuracy. Each data point must be within ±50% of the value of the spiked solution
concentration.

• Calculate the MDL for each contaminant according to the formula listed in CFR § 136
Appendix B (included in this Manual as Appendix C). Do not subtract the blank value
as suggested in the procedure.

• To ensure the accuracy of data reported for the UCMR, laboratory calculated MDL levels
for each contaminant must be less than or equal to one-half of the MRL listed m Table
5.1.

5.4 Laboratory Reagent (Method) Blank

All of the methods approved for the UCMR require periodic analysis of a laboratory reagent
(method) blank For all methods, a method blank 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 contaminants or other interferences are present in the laboratory environment, the reagents,
or the apparatus.

The frequency of the method blank analysis depends on the type of sample manipulation required
prior to the instrumental analysis. Methods that involve extraction of the sample usually stipulate
analysis of a method blank with each set of samples that are extracted together. When the samples
are analyzed directly, a blank is analyzed on a daily basis.

The required frequencies for analyzing method blanks for the UCMR are listed in Table 5.5 (§141.40
Appendix A). To meet the objectives of the UCMR, analyze the method blank as the first sample
on me instrument (immediately following the initial calibration check standard). For methods that
involve extractions, carry the method blank through the extraction process. Each extraction batch
of samples must include a method blank (§141.40 Appendix A).

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An extraction batch is defined as all samples prepared/extracted together by the same person(s)
during a work day (normally an 8-10 hour period for routine working schedules). Use the same lot
of extracting solvent, internal standard spiking solution, and surrogate standard spiking solution for
all samples included in a batch. When applicable, derivatize all samples in an extraction batch with
the same batch of derivatizing agent. Include a maximum of 20 UCMR samples in an extraction
batch. When determining the 20 sample maximum, do not count method blanks, shipping blanks,
calibration check standards, any independent QC samples, duplicate samples, and spiked samples
that are extracted with UCMR samples, .^ ^^

While some methods state that background interferences should be below the MDL, the general goal
for all methods approved for the UCMR is to ensure that the background levels are low enough to
not interfere with an accurate measurement. If any of the method analytes are detected at a
concentration equal to or greater than one-half the MRLs (see Table 5.6), then perform no further
analyses 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 discard all these
prepared samples (or extracts) and repeat the preparation procedure using another aliquot of each
sample. If the samples cannot be re-extracted, then consider all data for the problem contaminant(s)
invalid for all samples in the extraction or analysis batch, as appropriate, and flag the monitoring data
as not meeting QC criteria. Data not meeting UCMR QC criteria should not be reported to EPA.

Contamination problems in the extraction process cannot be detected until the analysis step. If a
problem is discovered, then the data for the contaminants affected by the contamination problem in
all the samples in the extraction batch are lost unless the laboratory has a back-up aliquot of each
sample which can be extracted. EPA limited the extraction batch to 20 UCMR samples to minimize
the number of samples that could be potentially lost because of a contamination problem. More than
one batch of samples may be extracted within a day.

Laboratories should be aware of the potential for carry-over between samples when highly
contaminated samples are analyzed. To avoid this, laboratories may find that additional blanks are
needed to "rinse" the system after high concentration samples are analyzed. If blanks are analyzed
for this purpose, the laboratory is not required to report data from these analyses.
Table 5.5 Frequency Requirements for Analyzing Laboratory Reagent (Method)
Blanks
Method
EPA 507
D5475-93
991.07
EPA 508
D58 12-96
990.06
EPA 508.1
D58 12-96
992.32 •
Method Specifications
1 per sample set or if reagents changed
1 per sample set or if reagents changed
1 per sample set per 12 hour shift ^
UCMR Specifications
1 per sample batch (<20 samples)
1 per sample batch (<20 samples)
1 per sample batch (<20 samples)
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Method
EPA 5 15.1
D53 17-93
992 32
EPA 5 15.2
D53 17-93
99232
EPA 524.2
D5790-95
SM6210D
SM6200B
EPA 525.2
-— ;^-=—^=a:
Note: EPA = EPAMethc
Table 1.5 for the i
================== =====
Method Specifications
1 per sample set
1 per sample set
each batch or 1 per 20 samples
every 12 hour extractipn batch
===============================
UCMR Specifications
1 per sample batch (<20 samples)
1 per sample batch (<20 samples)
1 per sample batch (<20 samples)
1 per sample batch (<;20 samples)
)ds,D = ASTM Methods, SM = APHA Standard Methods, 900 series = AOAC Methods. See
ull'reference for each analytical method.
Table 5.6 UCMR Acceptance Criteria for Laboratory Reagent (Method) Blanks
Contaminant
,4-Dinitrotoluene
Minimum Reporting Level
Maximum Allowable Background

Concentration (z l/2 MRL)
1
2,6-Dinitrotoluene
4,4'-DDE
0.8 //g/L
< 0.
Acetochlor
Reserved
Reserved
DCPA mono- and di-acid

deradates
0.5 /^g/L
EPTC
l^g/L
0.5
Molinate
^0.45
MTBE
< 2.5 yUg/L
Nitrobenzene
< 6/^g/L
Perchlorate
Reserved
Reserved
Terbacil
====
1 To be determined.
2fj,g/L
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UCMR Analytical Methods and Quality Control Manual March 2000

5.4.1 Field Reagent Blank (Shipping or Travel Blank)

EPA Method 524.2 and the approved equivalent methods are the only methods specified in the
UCMR that require the preparation and analysis of a field reagent blank (sometimes referred to as
a shipping or travel blank) with each group of samples collected from the same general sample site
at approximately the same time (§ 141.40 Appendix A). 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 m
all respects including shipment to the sampling site, storage, preservation, and all analytical
procedures 'The purpose of this blank is to determine if method contaminants or other interferences
are present in the field or shipping environment. If any of the contaminants are detected at
concentrations equal to or greater than one half the MRL, consider all data for the problem
contaminant(s) for all samples in the shipping batch invalid and flag the monitoring data as not
meeting QC criteria. Data not meeting UCMR QC criteria should not be reported to EPA.

5.5 Quality Control Sample

Most of the UCMR methods recommend that the laboratory analyze a quality control (QC) sample
at least quarterly A QC sample is a solution of method contaminants of known concentration which
is either used to spike an aliquot of reagent water or sample matrix or analyzed similar to a
calibration standard. Obtain the QC sample from a source external to the laboratory and different
from the source of calibration standards. Use the analysis of the QC sample to check the integrity
of the calibration standard.

5.6 Sample Matrix Spike and Matrix Spike Duplicate

One technique that is useful in evaluating a laboratory's precision and accuracy for a method is to
determine the precision and accuracy of duplicate analyses. To do this, a sample is divided into two
or more aliquots in the laboratory, and is processed and analyzed as two separate samples. This
technique is only useful when the original sample contains background concentrations of the method
contaminants.

To effectively evaluate precision for UCMR contaminants, the EPA is requiring preparation and
analysis of a sample matrix spike (MS) and matrix spike duplicate (MSD) (§ 141.40 Appendix A).
A laboratory-spiked MS sample is an aliquot of an environmental sample to which known quantities
of the method contaminants are added in the laboratory. A laboratory MSD sample is an additional
aliquot of that same environmental sample to which the same known quantities of the method
contaminants are added in the laboratory. For the purposes of the UCMR, EPA is not requiring that
the standards used to spike the MS/MSD samples be obtained from a second source. Analyze these
MS/MSD samples exactly like a typical monitoring sample; the purpose is to determine whether the
sample matrix contributes bias to the analytical results. Determine the concentrations of the
contaminants in the unspiked sample matrix in a separate aliquot.

Laboratories are required to prepare and analyze MS/MSD samples at the frequencies listed in Table
5 7 (§141 40 Appendix A). Laboratories are required to perform MS/MSD sample analyses on a
minimum of 5% of the UCMR samples that are processed together (§141.40 Appendix A). For
methods that involve extractions, divide one sample from each extraction batch into two aliquots
(one MS one MSD), and spike each with a known concentration of the contaminants prior to
extraction Carry the entire set of unspiked sample and MS/MSD samples through the entire
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UCMR Analytical Methods and Quality Control Manual
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extraction and analysis process. For methods that do not involve extractions and for analysis batches
of 20 orS ^ike and analyze two aliquots of one of the UCMR samples in the batch. If the
analyses batch contains more than 20 UCMR samples, then divide, spike, and analyze two samples.

Note- As described earlier, an extraction batch is defined as all samples prepared/extracted together
by he same persons) during a work day. Therefore, use the same lot of extracting solvent, internal
standard spildng solution, and surrogate standard spiking solution for all samples included in a batch.
wSpSle, derivatize all samples in abatch with the same batch of denvatizmg agent, fcdude
amSiSmof 20 UCMR samples in an extraction batch. Additionally, an analysis batch is defined
as samples analyzed within a 24-hour period with 30 as the maximum number of samples that can
be included in one analysis batch.
Table 5.7 Requirements for Performing Spiked Sample Analyses
UCMR Specifications
Method Specifications
EPA 507
D5475-93
991.07
EPA 508
D5812-96
990.06

EPA 508.1
D5812-96
992 32
1 per 20 samples or each sample set
whichever is greater
1 per 10 samples or each sample set
whichever is greater
1 per sample matrix
MS/MSD per 20 samples or a batch,
whichever is smaller; alternate low-
mid-level
MS/MSD per 20 samples or a batch,
whichever is smaller; alternate low-
mid-level
MS/MSD per 20 samples or a batch,
whichever is smaller; alternate low-
mid-level
EPA 515.1
D5317-93
992.32
1 per 10 samples or each sample set
whichever is greater
MS/MSD per 20 samples or a batch,
whichever is smaller; alternate low-
mid-level
EPA 515.2
D5317-93
992.32
1 per 10 samples or each sample set
whichever is greater
MS/MSD per 20 samples or a batch,
whichever is smaller; alternate low-
mid-level
EPA 524.2
D5790-95
SM6210D
SM6200B
Not required unless matrix effects
suspected
MS/MSD per 20 samples or a batch,
whichever is smaller; alternate low-
mid-level
EPA 525.2
1 per extraction batch 1 per 20 samples
MS/MSD per 20 samples or a batch,
whichever is smaller; alternate low-
mid-level
tote- EPA=EPA Methods, D = ASlMMethods, SM = APHA Standard Methods, 900 series = AOAC Methods. See
Table 1.5 for the full reference for each analytical method.

The laboratory must choose a spiking concentration from one of the two concentrations listed in
Table 5 8 (§ 141 40 Appendix A). The spiking concentration should be within ± 20% of one of the
levels provided in the table. To determine precision data from laboratory MS/MSD samples at the
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MRL level and at a higher concentration, spike the samples at the concentrations listed in
approximately a 50% ratio. For example, if a set of 40 samples are received, spike two aliquots of
a sample from the first 20 samples with the low-level (± 20 % MRL) spike, and spike the MS/MSD
for the second set of 20 samples with the mid-level spike.

Laboratories must report all MS/MSD sample recovery data and all data from the batch of samples
processed/analyzed with the MS/MSD sample (§141.35(d)). In addition, laboratories must also
report the spiking concentration for all MS/MSD samples (§141.35(d)). To facilitate this, data
element 16 Spiking Concentration, has been included in the UCMR data elements. Values for this
data element should only be reported for MS/MSD samples, and the unit of measure for the value
reported should match the unit of measure used to report the sample analytical result reported in data
element 7 Analytical Result - Value (this unit of measure is reported in data element 8, Analytical
Result - Unit of Measure). Data from MS/MSD samples will be used by EPA to evaluate the quality
of the monitoring data. Water systems and laboratories may also use these data to determine the
appropriateness of the methodology used to analyze the UCMR samples.

EPA plans to use the data from MS/MSD analyses to provide an estimate of the precision and
accuracy of measurements made by individual laboratories. Subsets of the UCMR data may be
selected for specific modeling or correlational analyses, based on laboratory precision for the
contaminants of interest. Laboratories will not be required to meet specific percent recovery or
precision requirements for the MS/MSD analyses. Monitoring data will not be rejected based on
MS/MSD sample recovery data.

The precision of measurements will be evaluated on the basis of values reported for data element 14,
Analytical Precision. For the UCMR, analytical precision is defined as the relative percent
difference (RPD) between MS and MSD results. For each analytical result obtained, the laboratories
and/or systems must report the RPD for the MS/MSD set analyzed in the same batch of samples as
the analytical result being reported (§141.35(d)). Analytical precision is calculated using the
formula:
x 100%
RPD = Relative Percent Difference
rt = matrix spike (MS) analytical result
r2 = matrix spike duplicate (MSD) analytical result

EPA will also be evaluating the analytical accuracy of measurements reported by examining the
values reported for data element 15, Analytical Accuracy. Analytical accuracy describes how close
a result is to the true value, and is measured through the use of spikes, standards, surrogates or
performance evaluation samples. For the purposes of the UCMR, analytical accuracy is defined as
the percent recovery of the contaminant in the MS sample analyzed in the same analytical batch as
the sample result being reported. To calculate the analytical accuracy, laboratories should use the
formula:
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UCMR Analytical Methods and Quality Control Manual
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r-, =
Percent Recovery =

matrix spike (MS) analytical result
sample analytical result
spiking concentration of matrix spike
r —
r\
x 100%
Table 5.8 Concentrations ft
===============================:======:
Contaminant
2,4-Dinitrotoluene
2,6-Dinitrotoluene
4,4'-DDE
Acetochlor
DCPA mono- and di-acid
degradates
EPTC
Molinate
MTBE
Nitrobenzene
Perchlorate
Terbacil
-•••. '" ' "
a To be determined.
>r Spiking MS/MSD Samples
Low-Level Spike
Concentration
2 Mg/L ± 20 %
2 Mg/L ± 20 %
0.8 Aig/L ± 20 %
Reserved a
1 //g/L ± 20 %
1 fj.g/L ± 20 %
0.9 Mg/L ± 20 %
5 ,ug/L ± 20 %
10 Mg/L ± 20 %
Reserved11
2 Aig/L ± 20 %

==================================
Mid-Level Spike
Concentration
± 20% of mid-level standard
± 20% of mid-level standard
± 20% of mid-level standard
Reserved a
± 20% of mid-level, standard
± 20% of mid-level standard
± 20% of mid-level standard
± 20% of mid-level standard
± 20% of mid-level standard
Reserved11
± 20% of mid-level standard
1
5.7 Internal Standard

Several of the UCMR methods require or recommend the use of an internal standard (IS) for
calibration and quantification purposes. An IS is a pure contaminant that is added to a sample or
sample extract in a known amount. It is used to measure the relative responses of other method
contaminants and surrogates that are components of the same solution. The IS must be a
contaminant that is not a sample component (§ 141.40 Appendix A). When used, the IS is added to
all samples, standards, and QC samples or their extracts.
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The methods usually recommend specific compounds and concentrations for use as ISs. When the
method provides flexibility in the selection of the IS or IS concentration, EPA allows the same
flexibility for analyses of UCMR samples.

The methods vary in their specifications of when the IS is added during the sample processing steps.
Some methods require the addition of the IS to the sample prior to any processing, while other
methods stipulate the addition to the sample extract immediately prior to"instrumental analysis.
Laboratories are required to follow the directions in the method when performing analyses for the
UCMR (§ 141.40 Appendix A).
Table 5.9 Requirements for Internal Standard Analyses
Method
Method Specifications
UCMR
Specifications
UCMR
Acceptance
Criteria
GC Criteria for Sample Extract IS Response
EPA 507
D5475-93
991.07
EPA 508
D58 12-96
990.06
EPA 508.1
D58 12-96
992.32
EPA 5 15.1
D53 17-93
992.32
EPA 5 15.2
D53 17-93
992.32
< 30% deviation from daily calibration
check standard's IS response
^ 30% deviation from daily calibration
check standard's IS response
± 30% of continuing calibration check
standard or ± 50% of initial calibration
< 30% deviation from daily calibration
check standard's IS response
<; 30% deviation from daily calibration
check standard's IS response
Same as
method
Same as
method
GC/MS Criteria for IS Response in Continuing Calibration
EPA 524.2
D5790-95
SM6210D
SM6200B
EPA 525.2
IS response should not have decreased by
more than 30% of last continuing
calibration or increased by more than 50%
of initial calibration
IS response should not have decreased by
more than 30% of last continuing
calibration or increased by more than 50%
of initial calibration
Same as
method
Same as
method
Note: EPA = EPA Methods, D = ASTM Methods, SM = APHA Standard Methods, 900 series = AOAC Methods. See
Table 1.5 for the full reference for each analytical method.
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The methods also vary in the criteria used to evaluate the IS recovery, when IS techniques are
utilized In general, monitor the detector response to the IS in each sample; it should be relatively
constant during the period in which a batch of samples is analyzed. Specific criteria for evaluating
the IS responses are listed in the methods and summarized in Table 5.9. Compare each sample s IS
detector response to the average IS detector response obtained for the calibration curve The
acceptance criteria are given as percentage recovery which is determined using the following
formula:

Sample IS Detector Response mn%
TV % Recovery = — ~ x 1UU/0
" ' KecuvKry Calibration Curve Average IS Detector Response

If the IS in a specific sample does not meet the acceptance criteria specified in the method, then
consider data from that sample analysis invalid. If possible, re-analyze the sample If this cannot
be done, then the data for that sample are considered invalid for the analysis and should not be
reported to EPA.
5.8 Surrogate Standard

Several of the UCMR methods require the use of surrogate analytes. A surrogate is a pure analyte
which is extremely unlikely to be found in any sample. It is added to a sample aliquot in a known
amount before the sample is processed, and is measured with the same procedures used to measure
other sample target contaminants. The purpose of a surrogate analyte is to monitor method
performance with each sample. When used, the surrogate is added to all samples, standards, and QC
samples.

The methods usually recommend specific compounds and concentrations for.use as surrogate
standards When the method provides flexibility in the selection of the surrogate standard or its
concentration, EPA allows the same flexibility for analyses of UCMR samples.

Table 5 10 lists the UCMR methods that require surrogates as well as percent recovery acceptance
criteria where specified by the appropriate methods (§ 141.40 Appendix A).

For EPA Methods 524.2 and 525.2, the surrogate criteria are listed in Section 10.2.6.1 of each
method.

There are two techniques for monitoring the surrogate standard. If the method specifies that the
same concentration of surrogate standard must be added to all samples, standards and QC samples,
then compare the surrogate detector response in each analysis to the average surrogate detector
response obtained for the calibration curve. The acceptance criteria are given as percentage recovery
which is determined using the following formula:

Sample Surrogate Detector Response x 100%
Surrogate % Recovery - Ca//z?ra^-on Curve Average Surrogate Detector Response
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Some methods recommend preparing a calibration curve for the surrogate standard similar to the
preparation of a curve for each of the method contaminants,, In those cases, the acceptance criteria
are <>iven as percentage recovery which is determined using the following formula:
Surrogate % Recovery
Measured Surrogate Concentration
x 100%
Expected Surrogate Concentration
If the surrogate in a specific sample does not meet the acceptance criteria, re-analyze the sample if
possible. If this cannot be done, then the data for that sample are considered suspect for the analysis
in question, and should not be reported to EPA.

EPA recognizes that failure to meet the surrogate standard recovery criteria could be the result of
matrix interferences in a small number of instances. Even if this is the reason for failure, the data
are suspect for all the contaminants in the analysis.
======s==s=: — —
Table 5.10 Requi

Method
EPA 507
D5475-93
991.07
EPA 508
D58 12-96
990.06
EPA 508.1
D5812-96
992.32
EPA 515.1
D53 17-93
992.32
EPA 5 15.2
D53 17-93
992.32
EPA 524.2
D5790-95
SM6210D
SM6200B

irements for Surrogate Standard Analyses
Method Specified
Surrogate Recovery
±30%
• ± 30%
±30%
±30%
±40%
±30%
+ 30%
UCMR
Specifications
Same as method
UCMR
Acceptance Criteria
Same as method
"WV}tf»* 4 ^ ^.^.^^
Table L5 for the fuil'reference for each analytical method.
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5.9 Confirmation

5.9.1 Gas Chromatographic Methods

Preliminary identification of contaminant compounds using EPA Methods 507, 508, 508.1, 515.1,
and 5152 as well as in the approved alternative methods (see Table 1.5), is performed by
comparison of the target contaminant retention time to the retention time of a standard reference
chromatogram. If the retention time of an unknown contaminant corresponds, within standard
acceptable limits, to the retention time of a standard reference compound, then identification is
presumed positive. The UCMR requires analytical confirmation by gas chromatographic/mass
spectrometry (GC/MS) of positive identification (§141.40 Appendix A).

The length of the retention time window used to make identifications should be based on
measurements of actual retention time variations of standards over the course of a day. A suggested
window size for a particular contaminant can be calculated using three times the standard deviation
of a retention time for that particular contaminant. However, the experience of the analyst should
weigh heavily in the interpretation of chromatograms.

Identification requires expert judgement when sample components are not resolved
chrornatographically. When peaks obviously represent more than one sample contaminant (i.e., a
broadened peak with shoulder[s] or a valley between two or more maxima), or any time when doubt
exists over the identification of a peak on a chromatogram, use appropriate alternative techniques
to help confirm peak identification. Positive identification of contaminants is required for results
by GC/MS (§141.40 Appendix A). False positives can be minimized by the use of a second
dissimilar chromatography column. Primary columns and suggested alternative dissimilar
confirmation columns are described in each of the methods. GC/MS analysis for confirmation is not
necessary if positive results from the primary column are not confirmed by the secondary dissimilar
column.

5.9.2 Gas Chromatography/Mass Spectrometry Confirmation

The UCMR requires confirmation of any contaminant detected above the MRL by Gas
Chromatography/Mass Spectrometry (GC/MS) methods (§141.40 Appendix A). Laboratories have
the option of confirming the presence of an analyte using a second chromatography column prior to
submitting the sample for GC/MS analyses, or may go directly from the primary column analyses
to GC/MS confirmation. If the contaminant detection is confirmed by the secondary column, then
reconfirm the contaminant by GC/MS using three specified ion peaks for contaminant identification.
Recommended ion peaks for identification purposes are listed in Table 5.11. The UCMR allows
single point calibration of the GC/MS system for confirmation purposes only as long as the
calibration standard is at a concentration within ± 50% of the concentration determined by the initial
analysis. As an option, laboratories may prefer to perform a three-point calibration with single point
daily calibration verification of the GC/MS system regardless of whether that verification standard
concentration is within ± 50% of sample response. If GC/MS analysis confirms the initial
contaminant detection, report the results determined from the initial analysis.
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Table 5.11 Recommended Confirmation Ions
Contaminant
Recommended Confirmation Ions
2,4-dinitrotoluene
63, 89, 165
2,6-dinitrotoluene
63, 89, 165
4,4'-DDE
246,316,318
Acetochlor
Reserved£
DCPA dimethyl ester
299, 300, 302
EPTC
86, 128, 189
Molinate
83, 126,187
MTBE
41. 57, 73
Nitrobenzene
51,77, 123
Perchlorate
Reserveda
Terbacil
116, 160, 161
•Tote- These ions are recommended for use in confirming all positive results. However, since mass spectrometers using
' different mass selection techniques may display spectra with different mass intensities, the analyst may need to
choose alternate ions that better characterize the spectra displayed by their mass spectrometer.

To be determined.
5.9.3 Mass Spectrometry Methods

Perform identification and confirmation of a contaminant using EPA Methods 524.2 and 525.2 by
comparison of the contaminant's mass spectrum (after background subtraction) to a reference
spectrum in the user-created database. For the DCPA degradates, confirm the identification by
injecting the extract obtained during the primary analyses into a mass spectrometer. The GC
retention time of the contaminant should be within three standard deviations of the mean retention
time of the reference contaminant in the calibration mixture.

In general, all ions that are present above 10% relative abundance in the mass spectrum of the
standard should be present in the mass spectrum of the sample and should agree within ±20%. For
example, if an ion has a relative abundance of 30% in the standard spectrum, its abundance in the
sample (contaminant) spectrum should be in the range of 10-50%. Some ions, particularly the
molecular ions, are of special importance and should be evaluated even if they are below 10%
relative abundance.

Identification requires expert judgment when sample contaminants are not resolved
chromatographically and produce mass spectra containing ions that are contributed by more than one
contaminant. When GC peaks obviously represent more than one sample contaminant (i.e., a
broadened peak with shoulder[s] or a valley between two or more maxima), select appropriate
contaminant spectra and background spectra by examining plots of characteristic ions for tentatively
identified contaminants. When target contaminants co-elute (i.e., when only one GC peak is
apparent for two or more contaminants), the identification criteria can be met, but each contaminant
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UCMR Analytical Methods and Quality Control Manual March 2000

spectrum will contain extraneous ions contributed by the co-eluting contaminants. Because
pur<*eable organic compounds (such as those for some UGMR contaminants) are relatively small
molecules and produce comparatively simple mass spectra, this is not a significant problem for most
contaminants determined according to EPA Method 524.2.

Structural isomers that produce very similar mass spectra can be explicitly identified only if they
have sufficiently different GC or retention times. Acceptable resolution is achieved if the height of
the valley between two peaks is less than 25% of the average height of the two peaks. Otherwise,
structural isomers are identified as isomeric pairs.

5.10 Additional Quality Controls

The laboratory should examine the samples when they arrive in the laboratory to determine if the
proper shipping procedures were used and the required shipping conditions were maintained.
Samples requiring storage at 4°C (± 2°) should arrive at the laboratory packed in ice or frozen cold
packs If there is no visible ice or the cold packs are completely thawed, the laboratory should report
the conditions to the water system. Samples should not be analyzed if they were not shipped
properly and/or if they did not arrive in the required condition. As the UCMR specifies that
resampling is required within 14 days of the observance of a sampling error (§141.40(a)(5)), the
laboratory should immediately contact the water system and arrange for resampling. If resampling
cannot be performed within this time period, then the water system should indicate in the report to
EPA that the samples were invalidated because of a shipment problem and no data should be
reported.

The laboratory also must invalidate samples that were collected in improper sampling containers
(e K plastic bottles instead of glass) or that were improperly filled (e.g., half-filled bottles for
samples that are required to be completely full) (§141.40(a)(5)). As above, the laboratory should
immediately contact the water system and arrange for resampling within the required 14 days
(§ 141 40(a)(5)). If resampling cannot be performed within this time period, then the water system
should indicate in the report to EPA that the samples were invalidated because of a sampling error
and no data should be reported.

Finally, the laboratory must ensure each sample is analyzed within the required holding time
(§141.40 Appendix A). A list of applicable holding times is presented in Table 5.12. When
appropriate, EPA standardized the holding times across analytical methods for the same contaminant
group.
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Table 5. 12 Maximum Holding Times for Samples and Extracts
Approved Analytical Methods
EPA 507
D5475-93
991.07
EPA 508
D58 12-96
990.06
EPA 508.1
D58 12-96
992.32
EPA 5 15.1
D53 17-93
992.32
EPA 515.2
D53 17-93
992.32
EPA 524.2
D5790-95
SM6210D
SM6200B
EPA 525.2
Sample
14 days
7 days-
14 days
14 days
14 days
14 days
14 days
Extract
14 days
14 days
'30 days
28 days
14 days
Not Applicable
30 days from collection
>fote: EPA = EPA Methods, D = ASTM Methods, SM = APHA Standard Methods, 900 series = AOAC Methods. See
Table 1.5 for the full reference for each analytical method.

If a UCMR sample is not extracted or analyzed within the times specified in Table 5.12, then the data
for the sample should not be reported. The laboratory should indicate to the water system that the
sample was invalidated because of a holding time problem. This information would then be reported
to EPA when the system submits its report for that sampling period.
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Section 6. Additional Analytical Method Specifications

6.1 Clarifications Concerning EPA Methods 515.1 and 515.2 and the Approved Equivalent
Methods

EPA Methods 515.1 and 515.2, as well as their equivalent voluntary consensus standards (D5317-93
and 992 32) have been approved for use in measuring the DCPA mono- and di-acid degradates
under the UCMR (see Table 1.5). However, EPA is specifically requiring that the5 solvent wash
listed in Sections 11.1.4 and 11.1.5 of the EPA Methods (Sections 12.1.4 and 12.1.5 of D5317-93
and Section F(a) of 992.32) be performed (§141.40(a)(4)(i)(A)). The use of this wash is being
emphasized in the QC requirements because it washes away the parent compound, DCPA.

If this wash is not performed, the data generated will reflect not just the total of the mono- and di-
acid degradates of DCPA, but will include the concentration of the parent compound in addition to
the concentration of the two degradates. As noted previously, because the approved methods do not
allow for the identification and quantification of the individual acids, the single analytical result
obtained from these methods should be reported as total DCPA mono- and di-acid degradates.

Please note that the hydrolysis step listed immediately prior to the solvent wash step (i.e., Section
11 1 3 of die EPA Methods) is not strong enough to hydrolyze the parent compound (DCPA) to
either the mono- or di-acid degradate if it is performed as described in the EPA Methods.

6.2 Recommendations for EPA Method 524.2 and the Approved Equivalent Methods

Although EPA is not altering the method specifications for EPA Method 524.2 for use with the
UCMR EPA emphasizes that laboratories should use the three stage trap listed in Section 6.2.2 of
the Method [Section 7.2.2.1 of D5790.95, Sections of SM6210D, and Section 2(a)(2) of SM6200B].
Alternate traps may not be capable of retaining adequate concentrations of nitrobenzene, therefore,
nitrobenzene can not be detected at reasonable concentrations in either standards or samples. Thus,
the data generated for nitrobenzene with this method will not be capable of meeting the strict quality
control requirements specified in the UCMR and described in this Manual.
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Section 7. Reporting

7.1 Public Water Systems Reporting to EPA

The appropriate and consistent reporting of UCMR monitoring data from the participating Public
Water Systems (PWSs) is critical to EPA's efforts to evaluate the data for future regulatory
development. The UCMR monitoring data are reported according to specific data elements
through the Safe Drinking Water Information System/Federal Information System (SDWIS/FED)
for inclusion in the NCOD.

The PWSs are required to report the UCMR monitoring data to EPA for evaluation (§141.35(a)).
The UCMR contakinant occurrence data will be included in the NCOD and will be made available
to the public For a detailed description of reporting responsibilities and requirements refer to the
Unregulated Contaminant Monitoring Regulation Reporting Guidance, the Unregulated
ContamLnt Monitoring Regulation Guidance for Operators of Public ^r .%^J*™%,
JO 000 or Fewer People and the Unregulated Contaminant Monitoring Regulation Integrated
GuTnce Documental available from the EPA Water Docket, telephone (202) 260-3027, Docket
Number W-98-02.

Monitoring data for all contaminants must be reported according to contaminant type and must
Sde 7 specific data elements for each contaminant (§ 141.35(d)). These dataelements are listed
n Table 7 1 Many of the data elements will be furnished by the laboratory to the PWS and the PWS
will provide the remainder of the data elements. A brief definition of.each dat a element is also
included PWSs can arrange to have laboratories report analytical data directly to EPA. However.
the PWSs retain final responsibility to ensure that all monitoring data is reported. In this regard, tne
final reporting responsibility of the PWS is the same as for SDWA compliance monitoring.

The required data elements will help to optimize the utility and quality of UCMR analytical data.
The reporting of the data elements listed in Table 7.1 is important to provide details needed to
evaluate possible regulatory development related to UCMR contaminants and methods.

7.1.1 Reporting of Results Obtained for the DCPA Mono- and Di-Acid Degradates

The analytical methods approved under the UCMR for measuring the DCPA mono- and di-acid
degradates do not, as approved, allow for the identification and quantification of the individual acids.
T?provide for the consistent reporting of results to the NCOD and to avoid confusion EPA is
specifying that the single analytical result obtained from these methods should be reported as total
DCPA mono- and di-add degradates. As a result, data element 5, Contaminant/Parameterwill not
havet^cceptable values "DCPA mono-acid degradate" or "DCPA di-add degradate." Instead, the
appropriate acceptable value for this data element will be "Total DCPA mono- and di-acid
degradates."

7.1.2 Reporting of Data Below the Specified Minimum Reporting Level

As previously mentioned in Section 5.1 of this Manual, EPA recognizes that some laboratories are
able to provide reliable data at concentrations lower than the MRLs specified in the UCMK. lo
achieve consistency in the NCOD, laboratories are only required to report quantitative results tor
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concentrations equal to or greater than the MRLs (§141,35(d)). However, EPA also recognizes the
usefulness of receiving more complete results to allow evaluation of the analytical method
implementation. Systems and laboratory that are able to reliably report results below the MRL are
encouraged to do so. To report reliable results obtained below the MRL, laboratories and/or water
systems should do three things:

1) For data element 6, Analytical Results - Sign, report a "<," indicating that the result
obtained is less than the MRL listed in Table 5.1.

2) For data element 7, Analytical Result - Value, report the actual concentration value
obtained for the contaminant.

3) For data element 17, Presence/Absence, report the contaminant as "Present."

The combination of these three steps will allow for the reporting of data below the MRL, and will
enable EPA to more fully evaluate the MRL for the respective contaminant and assist in determining
what the final MRL might be if EPA requires future monitoring of the contaminant.

7.1.3 Reporting of Water Quality Parameter Data

As mentioned in Section 3.2 of this Manual, the revised UCMR specifies that certain chemical and
physical parameters must be measured in the field at each sampling point from which UCMR
samples are collected (§ 141.40(a)(4)(i)(B)). These parameters are being required because they are
important indicators of water quality and may contribute to the likelihood of the contaminants being
found in drinking water. EPA believes that these parameters will allow for a more thorough
scientific understanding of the occurrence of unregulated contaminants. As all UCMR (1999) List
1 contaminants are chemicals,, EPA is only requiring that the pH of the water being sampled is
measured and reported. The pH of the water being sampled must be reported along with other
UCMR (1999) List 1 data (§141.40(a)(4)(i)(B)). To facilitate this reporting, data element 5,
Contaminant/Parameter, will have "pH" as an acceptable value.

7.2 Public Notification of Results (Report of PWS to Consumers)

The results of UCMR monitoring will be reportable through the Consumer Confidence Reports
(CCR), as required by SDWA §1441(c)(4)(B) and the Consumer Confidence Reports (CCR)
regulation (63 FR 44512), as well as through the revised Public Notification Rule (PNR) proposed
on May 13,1999 (64 FR 25964) and expected to be finalized in early 2000. It is anticipated that
reporting through the PNR and CCR rules would satisfy the notification provision for unregulated
contaminants. Failure to monitor for unregulated,contaminants required through the UCMR would
be reportable under the PNR.

The results reported through the PNR and CCR rules should be based on the same monitoring data
EPA and the States will receive. UCMR data will be submitted to SDWIS/FED for inclusion in the
NCOD. Information in the NCOD will be available to the public.

Reporting of unregulated contaminants not on the UCMR (1999) List is not required by EPA under
the CCR or PNR, except as directed by the State. Therefore, any "emerging" contaminants of local
or State concern alternatively could be reported voluntarily to the NCOD. This reporting would

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assist in the determination of whether an emerging contaminant is a problem of national extent and
should be considered for health-based standards or advisories. EPA will issue guidance explaining
how data on the occurrence of contaminants not on the UCMR (1999) List may be voluntarily
reported to the NCOD.

Large PWSs may also wish to report previously collected data on the occurrence of UCMR (1999)
List 1 contaminants in lieu of participating in Assessment Monitoring. To ensure the quality of data
included in the NCOD, EPA is requiring that any data previously collected and submitted in lieu of
UCMR monitoring must meet all analytical method and quality control requirements specified in
the UCMR (§141.35(g)).
Table 7.1 UCMR Reporting Requirements Sample Data Elements
Data Element
1 . Public Water System
(PWS) Identification
Number
2. Public Water System
Facility Identification
Number - Source,
Treatment Plant, and
Sampling Point
3. Sample Collection Date
4. Sample Identification
Number
5. Contaminant/Parameter
6. Analytical Results - Sign
7. Analytical Result - Value
8. Analytical Result - Unit of
Measure
9. Analytical Method
• Number
Definition
The code used to identify each PWS. The code begins with the standard two-
character postal State abbreviation; the remaining seven characters are unique to
each PWS.
An identification number established by the State, or, at the State's discretion,
the PWS, that is unique to the system for an intake for each source of water, a
treatment plant, and a sampling point. Within each PWS, each intake, treatment
plant, and sampling point must receive a unique identification number,
including, for intake; surface water intake, ground water well, or wellfield
centroid; and including, for sampling point; entry points to the distribution
system, wellhead, intake, locations within the distribution system, or other
representative sampling point specified by the State (§141.35(d)). The same
identification number must be used consistently through the history of
unregulated contaminant monitoring to represent the facility (§141.35(d)).
The date the sample is collected reported as 4-digit year, 2-digit month, and 2-
digit .day.
A unique identifier assigned by the PWS for each sample.
The unregulated contaminant or water quality parameter for which the sample is
being analyzed.
An alphanumeric value indicating whether the sample analysis result was:
(a) (<) "less than" means the contaminant was not detected or was detected at a
level "less than" the MRL.
(b) (=) "equal to" means the contaminant was detected at a level "equal to" the
value reported in "Analytical Result - Value."
The actual numeric value of the analysis for chemical and microbiological
results, or the Minimum Reporting Level (MRL) if the analytical result is less
than the specified contaminant's MRL.
The unit of measurement for the analytical results reported [e.g., micrograms
per liter, (Mg/L); colony-forming units per milliliter, (CFU/mL), etc.].
The identification number of the analytical method used.
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.
10. Sample Analysis Type
11. Sample Batch
Identification Number
12. Detection Level
13. Detection Level Unit of
Measure
14. Analytical Precision
15. Analytical Accuracy
16. Spiking Concentration
17. Presence/Absence
Definition
The type of sample collected. Permitted values include:
(a) Field Sample - sample collected and submitted for analysis under this
(b) Batch Spike/Spike Duplicate - Samples associated with a batch used for
calculating analytical precision and accuracy. A batch is defined as the set
of field samples plus one spiked sample and one spiked duplicate sample
to analyzed for contaminant concentrations.
A number assigned by the laboratory to the batch of samples analyzed with the
spiked sample (at the spiking concentration reported), to be reported as 9-digit
laboratory number (assigned by the State or EPA), 4-digit year, 2-digit month,
2-digit day, and 2-digit batch number.
"Detection level" is referring to the detection limit applied to both the method
and equipment. Detection limits are the lowest concentration of a target
contaminant that a given method or piece of equipment can reliably ascertain
and report as greater than zero ( e.g., Instrument Detection Limit, Method
Detection Limit, or Estimated Detection Limit).
The unit of measure to express the concentration, count, or other value of a
contaminant level for the detection level reported [e.g., micrograms per liter,
Og/L); colony-forming units per milliliter, (CFU/mL), etc.].
Precision is the degree of agreement among a set of repeated measurements and
is monitored through the use of replicate samples or measurements. For the
purposes of the UCMR, Analytical Precision is defined as the relative percent
difference (RPD) between spiked matrix duplicates. The RPD for the spiked
matrix duplicates analyzed in the same batch of samples as the analytical result
being reported is to be entered in this field. Precision is calculated as the RPD
between spiked matrix duplicates using;
RPD = [(X, - X2) / {(X, + X2)/2}] x 100
Accuracy describes how close a result is to the true value measured through the
use of spikes, standards, surrogates or performance evaluation samples. For the
purposes of the UCMR, Analytical Accuracy is defined as the percent recovery
of the contaminant in the spiked matrix sample analyzed in the same analytical
batch as the sample result being reported and calculated using;
% recovery = [(amount found in Spiked sample - amount found in sample) /
amount spiked] x 100
The concentration of method analytes added to a sample to be analyzed for
calculating analytical precision and accuracy where the value reported uses the
same unit of measure reported for Analytical Results.
Chemicals: Presence- a response was produced by the analysis (i.e., greater than
or equal to the MDL but less than the MRL)/Absence- no response was
produced by the analysis (i.e., less than the MDL).
Microbiolosicals: Presence- indicates a response was produced by the analysis
/Absence- indicates no response was produced by the analysis.
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^ Appendix A

Abbreviations and Acronyms
2,4-DNT - 2,4-dinitrotoluene
2,6-DNT - 2,6-dinitrotoluene
4,4'-DDE - 4,4'-dichloro dichlorophenyl ethylene, a degradation product of DDT

Alachlor ES A - alachlor ethanesulfonic acid, a degradation product of alachlor
AOAC - Association of Official Analytical Chemists
APHA - American Public Health Association
ASDWA - Association of State Drinking Water Administrators
ASTM - American Society for Testing and Materials

BGM - Buffalo Green Monkey cells, a specific cell line used to grow viruses

CAS - Chemical Abstract Service
CASRN - Chemical Abstract Service Registry Number
CCL - Contaminant Candidate List
CCR - Consumer Confidence Reports
CERCLA - Comprehensive Environmental Response, Compensation & Liability Act
CFR - Code of Federal Regulations
CPU - colony forming unit
CFU/mL - colony forming units per milliliter
CWS - community water system

DCPA - dimethyl tetrachloroterephthalate, chemical name of the herbicide dacthal
DCPA mono-
and di-acid
degradates - degradation products of DCPA
DDE - dichloro dichlorophenyl ethylene, a degradation product of DDT
DDT - dichloro diphenyl trichloroethane, a general insecticide
DNA - deoxyribonucleic acid

EDL - estimated detection limit
EPA - Environmental Protection Agency
EPTC - s-ethyl-dipropylthiocarbamate, an herbicide
EPTDS - Entry Point to the Distribution System
ES A - ethanesulfonic acid, a degradation product of alachlor

FACA - Federal Advisory Committee Act
FTE ' - full-time equivalent

GC - gas chromatography, a laboratory method
GLI method - Great Lakes Instruments method
GW - ground water
GUDI - ground water under the direct influence (of surface water)

HPLC - high performance liquid chromatography, a laboratory method

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ICR - Information Collection Request / Rule
IRFA - initial regulatory flexibility analysis
IMS - irrrmunomagnetic separation
IRIS - Integrated Risk Information System
IS - internal standard

LLE - liquid/liquid extraction, a laboratory method

MAC - Mycobacterium avium complex
MOA - Memorandum of Agreement
MCL - maximum contaminant level
MDL - method detection limit
MRL - minimum reporting level
MS - mass spectrometry, a laboratory method
MS - sample matrix spike
MSD - sample matrix spike duplicate
MTBE - methyl tertiary-butyl ether, a gasoline additive

NAWQA • - National Water Quality Assessment Program
NCOD - National Drinking Water Contaminant Occurrence Database
NDWAC - National Drinking Water Advisory Council
NERL - National Environmental Research Laboratory
NFS - National Pesticide Survey
NTIS - National Technical Information Service
NTNCWS - non-transient non-community water system
NTTAA - National Technology Transfer and Advancement Act

OGWDW - Office of Ground Water and Drinking Water
OMB - Office of Management and Budget

PAH - Polycyclic aromatic hydrocarbon
PB - particle beam
PBMS - Performance-Based Measurement System
pCi/L - picocuries per liter
PCR - polymerase chain reaction
210Pb - Lead-210 (also Pb-210), a lead isotope and radionuclide; part of the uranium decay
series
210Po - Polonium-210 (also Po-210), a polonium isotope and radionuclide; part of the
- uranium decay series
PWS - Public Water System
PWSF - Public Water System Facility

QA - quality assurance
QC - quality control

RDX - royal demolition explosive, hexahydro-1,3,5-trinitro-1,3,5-triazine
RFA - Regulatory Flexibility Act
RPD - relative percent difference
RSD - relative standard deviation
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SBREFA
SD
SDWA
SDWIS
SDWIS FED
SM
SMF
SOC
SPE
SRF
STORET
SW

TBD
TNCWS

UCMR
UCM
UMRA
USEPA
UV

VOC
Small Business Regulatory Enforcement Fairness Act
standard deviation
Safe Drinking Water Act ,
Safe Drinking Water Information System
the Federal Safe Drinking Water Information System
Standard Methods
Standard Compliance Monitoring Framework
synthetic organic compound
solid phase extraction, a laboratory method
State Revolving Fund
Storage and Retrieval System
surface water

to be determined
transient non-community water system

Unregulated Contaminant Monitoring Regulation/Rule
Unregulated Contaminant Monitoring
Unfunded Mandates Reform Act of 1995
United States Environmental Protection Agency
ultraviolet

volatile organic compound

micrograms per liter
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Appendix B

Definitions

Assessment Monitoring means sampling, testing, and reporting of listed contaminants that have
available analytical methods and for which preliminary data indicate their possible occurrence in
drinking water. Assessment Monitoring will be conducted for the UCMR (1999) List 1
contaminants.

Index Systems means a limited number of small CWSs and NTNCWSs, selected from the
Assessment Monitoring systems in State Plans, that will be required to provide more detailed and
frequent monitoring for the UCMR (1999) List 1 contaminants (§ 141.40(a)(6)). The Index Systems
will be selected to geographically coincide with watersheds and areas studied under the United States
Geological Survey's National Water Quality Assessment program. In' addition to the reporting
information required for Assessment Monitoring, the Index Systems must also report information
on system operating conditions (such as water source, pumping rates, and environmental setting)
(§141 40(a)(6)). These systems must monitor each year of the 5-year UCMR cycle, with EPA paying
for all reasonable monitoring costs (§141.40(a)(4)(i)(A)). This more detailed and frequent
monitoring will provide important information with which EPA can more fully evaluate the
conditions under which small systems operate.

Listed contaminant means a contaminant identified as an analyte in Table 1, 141.40(a)(3) of the
Unregulated Contaminant Monitoring Regulation (UCMR). To distinguish the current 1999 UCMR
listed contaminants from potential future UCMR listed contaminants, all references to UCMR
contaminant lists will identify the appropriate year in parenthesis immediately following the acronym
UCMR and before the referenced list. For example, the contaminants included in the UCMR (1999)
List include the component lists identified as UCMR (1999) List 1, UCMR (1999) List 2 and UCMR
(1999) List 3 contaminants.

Listing cycle means the 5-year period for which each revised UCMR list is effective and during
which no more than 30 unregulated contaminants from the list may be required to be monitored.
EPA is mandated to develop and promulgate a new UCMR List every 5 years.

Monitored systems means all community water systems serving more than 10,000 people, and the
national representative sample of community and non-transient non-community water systems
serving 10,000 or fewer people that are selected to be part of a State Plan for the UCMR. (Note that
for this round of Assessment Monitoring, systems that purchase their primary source of water are
not included in the monitoring.)

Monitoring (as distinct from Assessment Monitoring) means all aspects of determining the quality
of drinking water relative to the listed contaminants. These aspects include drinking water sampling
and testing, and the reviewing, reporting, and submission to EPA of analytical results.

Most vulnerable systems for Systems most vulnerable) means a subset of 5 to not more than 25
systems of all monitored systems in a State that are determined by that State in consultation with the
EPA Regional Office to be most likely to have the listed contaminants occur in their drinking waters,
considering the characteristics of the listed contaminants, precipitation, system operation, and
environmental conditions (soils, geology and land use).

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Pre-Screen Testing means sampling, testing, and reporting of the listed contaminants that may have
newly emerged as drinking water concerns and, in most cases, for which methods are in an early
stage of development. Pre-Screen Testing will be conducted by a limited number of systems (up to
200) States will nominate up to 25 of the most vulnerable systems per State for Pre-Screen Testing.
The actual Pre-Screen Testing systems will be selected from the list of nominated systems through
the use of a random number generator. Pre-Screen Testing will be performed to determine whether
a listed contaminant occurs in sufficient frequency in the most vulnerable systems or sampling
locations to warrant its being included in future Assessment Monitoring or Screening Surveys. Pre-
Screen Testing will be conducted for the UCMR (1999) List 3 contaminants.

Random Sampling is a statistical sampling method by which each member of the population has an
equal probability (an equal random chance) of being selected as part of a sample (the sample being
a small subset of the population which represents the population as a whole).

Representative Sample (or National Representative Sample) means a small subset of all community
and non-transient non-community water systems serving 10,000 or fewer people which EPA selects
using a random number generator. The systems in the representative sample are selected using a
stratified random sampling process that ensures that this small subset of systems will proportionally
reflect (is "representative" of) the actual number of size- and water type-categories of all small
systems nationally. In finalizing State Plans, a State may substitute a system from the replacement
list for a system selected as part of the original representative sample, if a system on the
representative sample list in the State Plan is closed, merged or purchases water from another
system.

Sampling means the act of collecting water from the appropriate location in a public water system
(from the applicable point from an intake or well to the end of a distribution line, or in some limited
cases, a residential tap) following proper methods for the particular contaminant or group of
contaminants.

Sampling Point means a unique location where samples are to be collected.

Screening Survey means sampling, testing, and reporting of the listed contaminants for which
analytical methods are recently developed, and have uncertain potential for occurrence in drinking
water by a subset of approximately 300 systems from all monitored systems selected through use of
a random number generator for public water system identification numbers. These systems must
conduct the Screening Survey for the contaminants on UCMR (1999) List 2 as will be further
described in the List 2 Rule (§141.40(a)(7)). Two Screening Surveys may be conducted for the
UCMR (1999) List 2 contaminants.

State means, for the purposes of this section, each of the fifty States, the District of Columbia, U.S.
Territories, and Tribal lands. For the national representative sample, Guam, the Commonwealth of
Puerto Rico, the Northern Mariana Islands, the Virgin Islands, American Samoa, and the Trust
Territories of the Pacific Islands are each treated as an individual State. All Tribal water systems in
the U.S. which have status as a State under Section 1451 of the Safe Drinking Water Act for this
program will be considered collectively-as one State for the purposes of selecting a representative
sample of small systems.

State Monitoring Plan (or State Plan) means a State's portion of the national representative sample
of CWSs and NTNCWSs serving 10,000 or fewer people which must monitor for unregulated
contaminants (Assessment Monitoring, Screening Survey(s) and Index Systems) and all large

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systems (systems serving greater than 10,000 people) which are required to monitor for Screening
Survey contaminants. A State Plan may be developed by a State's acceptance of EPA s
representative sample for that State, or by a State's selection of systems from a replacement list for
systems specified in the first list that are closed, are merged, or purchase water from another system
A State Plan also includes the process by which the State will inform each public water system of
its selection for the plan and of its responsibilities to monitor. A State Plan will also include the
systems required to conduct Pre-Screen Testing, selected from the State's designation of vulnerable
systems. The State Plan may be part of the Partnership Agreement (PA) between the State and EPA.

Stratified Random Sampling is a procedure to draw a random sample from a population that has been
divided into subpopulations or strata, with each stratum comprised of a population subset sharing
common characteristics. Random samples are selected from each stratum proportional to that
stratum's proportion of the entire population. The aggregate random sample (compiled from all the
strata samples) provides a random sample of the entire population that reflects the proportional
distribution of characteristics of the population. In the context of the UCMR, the population served
bv public water systems was stratified by size (with size categories of 500 or fewer people served,
501 to 3 300 people served, and 3,301 to 10,000 people served) and by water source type supplying
the water system (ground water or surface water). This stratification was done to ensure that systems
randomly selected as nationally representative sample systems would proportionally reflect the actual
number of size and water type categories nationally.

Testing means for the purposes of the UCMR and distinct from Pre-Screen Testing, the submission
and/or shipment of samples following appropriate preservation practices to protect the integrity of
the sample- the chemical, radiological, physical and/or microbiological analysis of samples; and the
reporting of the sample's analytical results for evaluation. Testing is a subset of activities defined
as monitoring.
drinking water program. EPA has not issued standards for these substances in drinking water (i.e.,
maximum contaminant levels or treatment technology requirements). EPA is required by Congress
to establish a program to monitor for selected unregulated contaminants in public water systems to
determine whether they should be considered for future regulation to protect public health. The
selected contaminants are listed in 141.40(a)(3), Table 1, the UCMR List.

Vulnerable time (or vulnerable period) means the time (or, in some cases, the 3-month quarter) of
the year determined as the most likely to have the listed group of contaminants present at their
highest concentrations or densities in drinking water. The vulnerable determination, in the case ol
the UCMR is made by the EPA or by the State (under arrangement with the EPA) for a system,
subset of systems or all systems in a State. The vulnerable determination is based on characteristics
of the contaminants, precipitation, system operations, and environmental conditions such as soil
types geology and land use. This determination does not indicate or imply that the listed
contaminants will be identified in the drinking water with certainty, but only that sampling
conducted during the vulnerable period presumably has the highest likelihood of identifying those
contaminants in higher concentrations relative to other sampling times, of the year, if and when the
contaminants occur.
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Appendix C

Procedure for Determination of Method Detection Limits

Definition

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
and is determined from analysis of a sample in a given matrix containing the analyte.

Scope and Application

This procedure is designed for applicability to a wide variety of sample types ranging from reagent
(blank) water containing analyte to wastewater containing analyte. The MDL for an analytical
procedure may vary as a function of sample type. The procedure requires a complete, specific, and
well defined 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 is used to judge the significance of a single measurement of
a future sample. The MDL procedure was designed for applicability to a broad variety of physical
and chemical methods. To accomplish this, the procedure was made device- or
instrument-independent.

Procedure

1. Make an estimate of the detection limit using one of the following:

1. The concentration value that corresponds to an instrument signal/noise in the range of 2.5 to
5.

2. The concentration equivalent of three times the standard deviation of replicate instrumental
measurements of the analyte in reagent water.

3. That region of the standard curve where there is a significant change in sensitivity, i.e., a break
in the slope of the standard curve.

4 Instrumental limitations. It is recognized that the experience of the analyst is important to this
pjrocess. However, the analyst must include the above considerations in the initial estimate of
the detection limit.

2 Prepare reagent (blank) water that is as free of analyte as possible. Reagent or interference free
water is defined as a water sample in which analyte and interfering concentrations are not
detected at the method detection limit of each analyte of interest. Interferences are defined as
systematic errors in the measured analytical signal of an established procedure caused by the
presence of interfering species (interfering). The interfering concentration is presupposed to be
normally distributed in representative samples of a given matrix.
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3.
(a) If the MDL is to be determined in reagent (blank) water, prepare a laboratory standard (analyte
in reagent water) at a concentration which is at least equal to or in the same concentration
range °as the estimated method detection limit. (Recommend between 1 and 5 times the
estimated method detection limit.) Proceed to Step 4.

(b) If the MDL is to be determined in another sample matrix, analyze the sample. If the measured
level of the analyte is in the recommended range of one to five times the estimated detection
limit proceed to Step 4. If the measured level of analyte is less than the estimated detection
limit' add a known amount of analyte to bring the level of analyte between one and five times
the estimated detection limit. If the measured level of analyte is greater than five times the
estimated detection limit, there are two options.

(1) Obtain another sample with a lower level of analyte in the same matrix if possible.

(2) The sample may be used as is for determining the method detection limit if the analyte
level does not exceed 10 times the MDL of the analyte in reagent water. The variance of
the analytical method changes as the analyte concentration increases from the MDL, hence
the MDL determined under these circumstances may not truly reflect method variance at
lower analyte concentrations.
4.
(a) Take a minimum of seven aliquots of the sample to be used to calculate the method detection
limit and process each through the entire analytical method. Make all computations according
to the defined method with final results in the method reporting units. If a blank measurement
is required to calculate the measured level of analyte, obtain a separate blank measurement for
each sample aliquot analyzed. The average blank measurement is subtracted from the
respective sample measurements.

(b) It may be economically and technically desirable to evaluate the estimated method detection
limit before proceeding with 4a. This will:

(1) prevent repeating this entire procedure when the costs of analyses are high, and

(2) ensure that the procedure is being conducted at the correct concentration. It is quite
possible that an inflated MDL will be calculated from data obtained at many times the real
MDL even though the level of analyte is less than five times the calculated method
detection limit. To insure that the estimate of the method detection limit is a good estimate,
it is necessary to determine that a lower concentration of analyte will not result in a
significantly lower method detection limit. Take two aliquots of the sample to be used to
calculate the method detection limit and process each through the entire method, including
blank measurements as described above in 4a. Evaluate these data:

I (1) If these measurements indicate the sample is in desirable range for determination of
;;., the MDL, take five additional aliquots and proceed. Use all seven measurements for
; calculation of the MDL.

S (2) If these measurements indicate the sample is not in correct range, reestimate the MDL,
obtain new sample as in 3 and repeat either 4a or 4b.
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5. Calculate the variance (S²) and standard deviation (S) of the replicate
measurements, as follows:
where:
X-; i = 1 to n, are the analytical results in the final method reporting units obtained from the
n sample aliquots and £ refers to the sum of the X values from i=l to n.
6.
(a) Compute the MDL as follows:
where:
MDL = the method detection limit t(n.: ^ 99) = the students' t value appropriate for a 99%
confidence level and a standard deviation estimate with n- 1 degrees of freedom. (See Table.)
S = standard deviation of the replicate analyses.

(b) The 95% confidence interval estimates for the MDL derived in 6a are computed according to
the following equations derived from percentiles of the chi square over degrees of freedom
distribution (x2/df).

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 is the initial attempt to compute MDL based on the estimate of MDL formulated in Step
1, take the MDL as calculated 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 the MDL calculation, use S2 from the current MDL
calculation and S2 from the previous MDL calculation to compute the F-ratio. The F-ratio is
calculated by substituting the larger S2 into the numerator S2A and the other into die
denominator S2B. The computed F-ratio is then compared with the F-ratio found in the table
which is 3.05 as follows:
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if S2A/S2B<3.05, then compute the pooled standard deviation by the following equation:
pooled
if S2A/S2B<3-05' re-spike at the most recent calculated MDL and process the samples through
the procedure starting with Step 4. If the most recent calculated MDL does not permit
qualitative identification when samples are spiked at that level, report the MDL as a
concentration between the current and previous MDL which permits qualitative identification.

MDL=2.681 (Spoo!ed)

where 2.681 is equal to t(12i i_«=o.99) •

(d) The 95% confidence limits for MDL derived in 7c are computed according to the following
equations derived from percentiles of the chi squared over degrees of freedom distribution.

LCL=0.72 MDL
UCL=1.65 MDL

where LCL and UCL are the lower and upper 95% confidence limits, respectively, based on
14 aliquots.
Table of Students' t Values at the 99 Percent Confidence Level
Number of replicates
7
8
9
10
11
16
21
26
31
61
00
Degrees of Freedom (n-1)
6
7
8
9
10
15
20
25
30
60
00
tfoi-1..99)
3.143
2.998
2.896
2.821
2.764
2.602 .
2.528
2.485
2.457
2.390
2.326
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Reporting

The analytical method used must be specifically identified by number or title and the MDL for each
analyte expressed in the appropriate method reporting Units. If the analytical method permits options
whichaffect the method detection limit, these conditions must be specified withthe MDL value. The
sample matrix used to determine the MDL must also be identified with MDL value. Report the mean
analvte level with the MDL and indicate if the MDL procedure was iterated. If a laboratory standard
or a sample that contained a known amount analyte was used for this determination, also report the
mean recovery.

(This procedure is from Title 40 - Protection of Environment, Chapter I - Environmental Protection
Asency Part 136 - Guidelines Establishing Test Procedures for the Analysis of Pollutants.
Annendix B to Part 136 - Definition and Procedure for the Determination of the Method Detection
UmU-Revision 1.11.) [49 FR 43430, Oct. 26, 1984; 50 FR 694, 696, Jan. 4, 1985, as amended
at 51 FR 23703, June 30, 1986]
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