United States Office of Water EPA -815-R-01-028
Environmental Protection 4607 December 2001
Agency
&EPA UCMR (1999) List 1 and
List 2 Chemical Analytical
Methods and Quality
Control Manual
Printed on Recycled Paper
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
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 Rule (UCMR) Program. It replaces the previously
issued UCMR Analytical Methods and Quality Control Manual (EPA 815-R-00-006, March
2000) and the Supplement A to the UCMR Analytical Methods and QC Manual (EPA 815-R-OO-
002, March 2000). 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
efforts may add additional contaminants to be monitored and hence, the specific analytical and
technical requirements of the program will need to be identified. For this reason, EPA will
periodically issue additional or replacement pages to this Analytical Methods and Quality Control
Manual. 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 additions to this Manual.
Under the Safe Drinking Water Act (SDWA) as amended in 1996, §1445(a)(2)(A), the
Environmental Protection Agency (EPA) is to promulgate regulations for a monitoring program
for unregulated contaminants by August 1999. In the past, unregulated contaminant monitoring
has been performed according to the program described in CFR 141.40. The 1996 SDWA
Amendments direct a substantially revised UCMR Program.
The revised UCMR Program has a new list of contaminants to monitor, changes the number of
public water systems (PWSs) that must conduct monitoring, and changes the frequency and
schedule for monitoring (§141.40(a)). Additional regulatory actions include cancellation of
unregulated contaminant monitoring for small systems serving 10,000 or fewer people under the
existing unregulated contaminant monitoring program that began in 1989. The data collected in
the revised UCMR will be used to support the development of the Contaminant Candidate List
(CCL), to support the Administrator's determination of whether to regulate a contaminant, and to
support the development of future regulations. The revised monitoring program is one of the
cornerstones of the sound science approach to future drinking water regulation that is an aim of
the 1996 SDWA Amendments.
The SDWA provisions and EPA regulations described in this document contain legally binding
requirements. This document does not substitute for those provisions or regulations, nor is it a
regulation itself. It does not impose legally-binding requirements on EPA, States, or the
regulated community, and may not apply to a particular situation based upon the circumstances.
EPA and State decision makers retain the discretion to adopt approaches on a case-by-case basis
that differ from this guidance where appropriate. Any decisions regarding a particular facility
will be made based on the applicable statutes and regulations. Therefore, interested parties are
free to raise questions and objections about the appropriateness of the application of this manual
to a particular situation, and EPA will consider whether or not the recommendations or
interpretations in the manual are appropriate in that situation based on the law and regulations.
EPA may change this manual in the future without notice or an opportunity for comment.
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
Mention of trade names or commercial products does not constitute endorsement or
recommendation for use.
This guidance document has been prepared based on the revised UCMR regulation and the
specifications found in the identified approved analytical methods. The following Federal
Register (FK) publications, which will all be incorporated into 40 CFR parts 141.35 and 141.40,
are frequently referenced throughout this manual.
• Revisions to the Unregulated Contaminant Monitoring Regulation for Public Water Systems;
September 17, 1999 (64 FR 50556)
• Unregulated Contaminant Monitoring Regulation for Public Water Systems; Analytical
Methods for Perchlorate andAcetochlor; Announcement of Laboratory Approval and
Performance Testing (PT) Program for the Analysis of Perchlorate; March 2, 2000 (65 FR
11372)
• Unregulated Contaminant Monitoring Regulation for Public Water Systems; Analytical
Methods for List 2 Contaminants; Clarifications to the Unregulated Contaminant Monitoring
Regulation; January 11, 2001 (66FR 2273)
• Unregulated Contaminant Monitoring Regulation for Public Water Systems; Amendment to
the List 2 Rule and Partial Delay of Reporting of Monitor ing Re suits; September 4, 2001 (66
FR 46221)
11
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
Table of Contents
Foreword i
Section 1. Introduction 1-1
1.1 Background on the Unregulated Contaminant Monitoring Rule (UCMR) 1-1
1.2 The Unregulated Contaminant Monitoring Rule 1-2
1.3 Contaminants on the UCMR (1999) List 1-3
1.3.1 UCMR (1999) List 1 Contaminants 1-6
1.3.2 UCMR (1999) List 2 1-7
1.3.3 UCMR (1999) List 3 Contaminants 1-9
1.4 Analytical Methods for UCMR (1999) List 1 Contaminants 1-9
1.5 Laboratory Approval and Certification Requirements for UCMR (1999) List 1
Contaminants 1-12
1.5.1 Laboratory Approval for Monitoring Acetochlor 1-13
1.5.2 Laboratory Approval for Monitoring Perchlorate 1-13
1.5.3 Laboratory Approval for Monitoring DCPA, mono- and di-acid degradates ... 1-14
1.6 Analytical Methods for UCMR (1999) List 2 Contaminants 1-14
1.7 Laboratory Certification Requirements for UCMR (1999) List 2 Contaminants . 1-15
Section 2. Sampling Plan 2-1
2.1 Monitoring by Public Water Systems 2-1
2.1.1 Systems Required To Monitor 2-1
2.2 Sampling Frequency 2-1
2.2.1 Sampling Frequency Deviations 2-2
2.3 Sampling Points 2-3
Section 3. Sample Collection and Preservation 3-1
3.1 UCMR (1999) List 1 Assessment Monitoring Chemical Contaminants 3-1
3.1.1 Nitrogen- and Phosphorus-Containing Pesticides 3-1
3.1.2 Chlorinated Hydrocarbon Pesticides 3-2
3.1.3 Acid Herbicides 3-5
3.1.4 Volatile Organic Compounds 3-10
3.1.5 Semi-Volatile Organic Compounds 3-12
3.1.6 Inorganic Compounds 3-13
3.2 UCMR (1999) List 2 Screening Survey for Chemical Contaminants 3-15
3.2.1 Semi-Volatile Organic Compounds 3-16
3.2.2 Phenols 3-17
3.2.3 Phenylureas 3-18
3.3 Monitoring of Routine Water Quality Parameters 3-20
Section 4. Sample Transport 4-1
4.1 UCMR (1999) List 1 contaminants 4-1
4.2 UCMR (1999) List 2 Chemical Contaminants 4-1
Section 5. UCMR Quality Control Requirements 5-1
5.1 Minimum Reporting Level 5-2
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
5.2 Calibration 5-4
5.2.1 Calibration Verification 5-5
5.3 Detection Limit 5-6
5.4 Laboratory Reagent (Method) Blank 5-11
5.4.1 Field Reagent Blank (Shipping or Travel Blank) 5-15
5.5 Quality Control Sample 5-15
5.6 Sample Matrix Spike and Matrix Spike Duplicate 5-15
5.7 Internal Standard 5-20
5.8 Surrogate Standard 5-22
5.9 Confirmation 5-25
5.9.1 Gas Chromatographic Methods 5-25
5.9.2 Gas Chromatography/Mass Spectrometry Confirmation 5-25
5.9.3 Mass Spectrometry Methods 5-27
5.9.4 Ion Chromatography Identification 5-28
5.9.5 High Performance Liquid Chromatography (HPLC) with UV Detection 5-29
5.10 Additional Quality Controls 5-29
5.10.1 Laboratory Fortified Blank 5-29
5.10.2 Matrix Conductivity Threshold Quality Control Requirements 5-30
5.10.2.1 Conductivity Meter Calibration Verification and Conductance Determination
5-30
5.10.2.2 Instrument Performance Check 5-30
5.10.2.3 Additional Quality Control Procedures if Dilution or Pretreatment is Required
5-31
Section 6. Additional Analytical Method Specifications 6-1
6.1 Clarifications Concerning EPA Methods 515.1 and 515.2 and the Approved
Equivalent Methods 6-1
6.2 Recommendations for EPA Method 524.2 and the Approved Equivalent Methods
6-1
6.3 Clarifications Concerning EPA Method 515.3 6-1
6.4 Additional Notes on the Analysis of 2,4- and 2,6-Dinitrotoluene by Method 525.2
6-2
6.5 Additional Notes on the Analysis of Nitrobenzene by Method 524.2 6-3
6.6 Additional Notes on Methods 526 and 528 6-3
Section 7. Reporting 7-1
7.1 Public Water Systems Reporting to EPA 7-1
7.1.1 Reporting of Results Obtained for the DCPA Mono- and Di-Acid Degradates . . 7-2
7.1.2 Reporting of Data Below the Specified Minimum Reporting Level 7-2
7.1.3 Reporting of Water Quality Parameter Data 7-2
7.1.4 Reporting of Matrix Conductance and Pretreated QC Data for Perchlorate .... 7-2
7.1.5 Reporting of Presence/Absence 7-3
7.2 Public Notification of Results (Report of PWS to Consumers) 7-3
IV
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual
December 2001
List of Tables
Table 1.1 UCMR (1999) Contaminants 1-4
Table 1.2 UCMR (1999) List 1 Contaminants 1-6
Table 1.3 UCMR (1999) List 2 Contaminants 1-8
Table 1.4 UCMR (1999) List 3 Contaminants 1-9
Table 1.5 Approved Analytical Methods for UCMR (1999) List 1 Contaminants 1-11
Table 1.6 Approved Analytical Methods for UCMR (1999) List 2 Contaminants 1-14
Table 3.1 Preservation and Holding Times for Approved UCMR (1999) List 1 Analytical
Methods 3-14
Table 3.2 Preservation and Holding Times for Approved UCMR (1999) List 2 Analytical
Methods 3-20
Table 5.1 UCMR (1999) List 1 Methods and Minimum Reporting Levels 5-3
Table 5.1.1 UCMR (1999) List 2 Methods and Minimum Reporting Levels 5-3
Table 5.2 UCMR (1999) List 1 Frequency Requirements for Verifying Calibration 5-7
Table 5.3 UCMR (1999) List 1 Low-Level Calibration Check Standard Concentrations and
Acceptance Criteria 5-8
Table 5.4 UCMR (1999) List 1 Mid-Level Calibration Check Standard Concentrations and
Acceptance Criteria 5-8
Table 5.5 UCMR (1999) List 2 Frequency Requirements for Verifying Calibration 5-9
Table 5.6 UCMR (1999) List 2 Low-Level Calibration Check Standard Concentrations and
Acceptance Criteria 5-9
Table 5.7 UCMR (1999) List 2 Mid-Level Calibration Check Standard Concentrations and
Acceptance Criteria 5-10
Table 5.8 UCMR (1999) List 1 Frequency Requirements for Analyzing Laboratory Reagent
(Method) Blanks 5-12
Table 5.9 UCMR (1999) List 1 Acceptance Criteria for Laboratory Reagent (Method) Blanks
5-13
Table 5.10 UCMR (1999) List 2 Frequency Requirements for Analyzing Laboratory Reagent
(Method) Blanks 5-14
Table 5.11 UCMR (1999) List 2 Acceptance Criteria for Laboratory Reagent (Method) Blanks
5-14
Table 5.12 UCMR (1999) List 1 Frequency Requirements for Performing Spiked Sample
Analyses 5-17
Table 5.13 UCMR (1999) List 2 Requirements for Performing Spiked Sample Analyses . 5-18
Table 5.14 UCMR (1999) List 1 Concentrations for Spiking MS/MSD Samples 5-19
Table 5.15 UCMR (1999) List 2 Concentrations for Spiking MS/MSD Samples 5-20
Table 5.16 UCMR (1999) List 1 Criteria for Internal Standard Response 5-21
Table 5.17 UCMR (1999) List 2 Criteria for Internal Standard Response 5-22
Table 5.18 UCMR (1999) List 1 Requirements for Surrogate Standard Analyses 5-24
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
Table 5.19 UCMR (1999) List 2 Requirements for Surrogate Standard Analyses 5-25
Table 5.20 UCMR (1999) List 1 Recommended Confirmation Ions 5-26
Table 5.21 UCMR (1999) List 2 Recommended Confirmation Ions 5-27
Table 5.22 Estimated Retention Time for Perchlorate Using EPA Method 314.0 5-28
Table 7.1 Unregulated Contaminant Monitoring Reporting Requirements 7-4
VI
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
Appendices
Appendix A. Abbreviations and Acronyms A-l
Appendix B. Definitions B-l
Appendix C. Procedure for Determination of Detection Limits C-l
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
Section 1. Introduction
1.1 Background on the Unregulated Contaminant Monitoring Rule (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 141.40(e), (j), and (n)(ll) 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 required repeat monitoring every 5 years.
Under §1445(a)(2)(A) of the SDWA, as amended in 1996, the Environmental Protection Agency
(EPA) was to promulgate regulations substantially revising the previous unregulated monitoring
program. The revised Unregulated Contaminant Monitoring Rule (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 was 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 also requires
fewer systems to conduct monitoring than was required in the previous 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 and chemical Screening Survey component of the UCMR (§141.40(a)(5) and
§141.40 Appendix A). This manual does not address the method or monitoring requirements for
monitoring the List 2, microbiological contaminant Aeromonas.
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/safewater/ucmr.html.
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
1.2 The Unregulated Contaminant Monitoring Rule
The UCMR is required by the SDWA as amended in 1996. Under the 1996 Amendments, EPA
was 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 based on PWS size, source
water type, and likelihood of finding contaminants; (3) monitoring of only a representative
sample of PWSs serving 10,000 or fewer people; and, (4) 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 drinking 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 contaminants of potential
concern that may occur or are likely to occur in drinking water. 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 Inventory; 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).
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
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 perchl orate and RDX, as well as lead-210 and polonium-210,
were added to the UCMR (1999) List.
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 contaminants listed as occurrence priorities on the CCL (1998) were eventually included on
the final UCMR (1999) 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 Florida. Because radionuclides have potential wide occurrence and consequent health risks
and in response to public comments, EPA added lead-210 and polonium-210 to the UCMR
(1999) List. These 36 contaminants comprise the list of UCMR (1999) contaminants (Table 1.1).
For each of these contaminants, EPA evaluated the availability of analytical methods published
by EPA and voluntary consensus standard organizations such as the American Society for
Testing and Materials (ASTM), the Association of Official Analytical Chemists (AOAC) and the
American Public Health Association (APHA). 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 which analytical methods are currently available.
The UCMR (1999) List 2 contaminants are part of the Screening Survey which is divided into
two parts: a first Screening Survey for chemical contaminants (15 chemical contaminants), and a
second Screening Survey for the microbial contaminant Aeromonas, all of which have uncertain
potential for occurrence. Only 13 of the 15 chemical contaminants on List 2 for which analytical
methods have been developed are included in the chemical Screening Survey. The analytical
method forAeromonas was finalized in November 2001 and, pending subsequent promulgation,
will be the approved method for this monitoring in 2003.
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.
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual
December 2001
Table 1.1 UCMR (1999) Contaminants
Chemical Contaminants
List
1
1
1
1
1
1
1
1
1
1,2
1
1
2
2
2
2
2
2
2
2
2
Contaminant Name
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Acetochlor
DCPA di-acid degradate
DCPA mono-acid
degradate
4,4'-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 and other
acetanilide degradation
products
Diazinon
Disulfoton
Diuron
Potential Environmental Source
Used in the production of isocyanate and explosives
Used as mixture with 2,4-DNT (similar uses)
Herbicide used with cabbage, citrus, coffee, and corn crops
Degradation product of DCPA, an herbicide used on grasses and
weeds with fruit and vegetable crops
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
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual
December 2001
List
2
2
2
2
2
o
J
o
J
Contaminant Name
Fonofos
Linuron
Prometon
RDX
Terbufos
Lead-210
Polonium-210
Potential Environmental Source
Soil insecticide used on worms and centipedes
Herbicide used with corn, soybean, cotton, and wheat crops
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
Part of the uranium decay series; naturally occurring
Microbiological Contaminants
2
3
o
J
3
3
3
3
3
Aeromonas
Adenoviruses
Cyanobacteria (blue-
green algae, other
freshwater algae, and
their toxins)
Caliciviruses
Coxsackieviruses
Echoviruses
Helicobacter pylori
Microsporidia
Present in all freshwater and brackish water
Fecal or hand to mouth transmission
Bloom in surface water bodies; produce toxins
Contaminated food and water; raw shellfish
Fecal or hand to mouth transmission
Fecal or hand to mouth transmission
Fecal or hand to mouth transmission
Occur in rivers, ponds, lakes, and unfiltered water
Note: UCMR (1999) List 1 and List 2 chemical contaminants require monitoring under the Assessment
Monitoring and Chemical Screening Survey component, respectively, of the revised UCMR
(§141.40(a)(3)). The method for Aeromonas is currently being finalized. Following method finalization
and promulgation, quality control and methodology will be clarified in a microbial methods manual. EPA
is conducting analytical methods development for UCMR (1999) 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, Screening Surveys, and Pre-Screen
Testing components of the UCMR, the reader may refer to the proposed UCMR Preamble and Rule (64 FR
23398), the proposed UCMR List 2 Preamble and Rule (65 FR 55362) or the final UCMR Rule (64 FR
50556) and final UCMR List 2 Rule (66 FR 2273).
Because of the evolving nature of the UCMR Program, the specific analytical and technical
requirements for monitoring contaminants may change with supplemental rule-making.
When analytical methods and quality control details for the UCMR (1999) List 2 Screening
Survey for Aeromonas and List 3 contaminant monitoring are developed and approved,
additional or replacement pages for this manual will be issued. 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 additions to this Manual.
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual
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A more complete review of methods availability is summarized in the proposed UCMR
Preamble and Rule (64 FR 23398), the proposed UCMR List 2 Preamble and Rule (65 FR
55362), the final UCMR Rule (64 FR 50556) and the final UCMR List 2 Rule (66 FR 2273), as
well as the Contaminant Selection, Methods, and Sampling: Technical Background Information
for the UCMR (EPA 815-R-99-007). (This background document and other UCMR supporting
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/safewater/ucmr.html.) 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
With the publication of the Direct Final Rule (65 FR 11371), EPA approved analytical methods
for acetochlor and perchlorate, thus completing methods approval for all 12 chemical
contaminants on the UCMR (1999) List 1. Monitoring for these contaminants is to begin in 2001
under the Assessment Monitoring component of the UCMR Program. All UCMR (1999) List 1
contaminants and their corresponding required sampling locations, approved analytical methods,
and other related analytical details are listed in Table 1.2 (§141.40(a)(5)).
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
EPTC
Molinate
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
Approved Analytical Methods
EPA 525. 2
EPA 525. 2
EPA 508, EPA 508.1,
EPA 525.2, D 5812-96, 990.06
EPA 525 .2
EPA 515.1, EPA 515.2, EPA 515.3,
EPA 515.4, D 5317-93, 992.32
EPA 515.1, EPA 515.2, EPA 515.3,
EPA 515.4, D 5317-93, 992.32
EPA 507, EPA 525 .2,
05475-93,991.07
EPA 507, EPA 525 .2,
05475-93,991.07
Minimum
Reporting
Level
2^ig/La
2^ig/La
0.8(ig/La
2^g/Lc
1 Mg/La
1 Mg/La
1 Mg/La
0.9(ig/La
Sampling
Point
EPTDSb
EPTDSb
EPTDSb
EPTDSb
EPTDSb
EPTDSb
EPTDSb
EPTDSb
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Contaminants
MTBE
Nitrobenzene
Perchlorate
Terbacil
CAS#
1634-04-4
98-95-3
1497-73-0
5902-51-2
Approved Analytical Methods
EPA 502.2, EPA 524.2, D 5790-95,
SM 6210D, SM 6200B, SM 6200C
EPA 524.2, D 5790-95, SM 6210D,
SM 6200B
EPA 3 14.0
EPA 507, EPA 525 .2,
05475-93,991.07
Minimum
Reporting
Level
5^g/Ld
10Mg/Ld
4 Mg/Lc
2^g/La
Sampling
Point
EPTDSb
EPTDSb
EPTDSb
EPTDSb
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.
a Minimum Reporting Level (MRL) determined by multiplying by 10 the least sensitive method's minimum
detection limit (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).
b 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 12-month period of
monitoring; sampling must occur at the EPTDS, 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)). If monitoring at
source (raw) water sampling points indicates 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 (§141.40(a)(5)).
0 MRL was established at a concentration, which is at least one-fourth the lowest known adverse health
concentration, at which acceptable precision and accuracy has been demonstrated in spiked matrix samples.
d MRL for VOCs determined by multiplying by 10 either the published MDL or 0.5 ug/L, whichever is
greater. The MDL of 0.5 ug/L (0.0005 mg/L) was selected to conform to the VOC MDL requirements of
40 CFR 141.24(f)(17)(i)(E).
1.3.2
UCMR (1999) List 2
The UCMR (1999) List 2 contaminants and their corresponding required sampling locations,
suitable EPA analytical methods, and other related analytical details are listed in Table 1.3
(§141.40 (a)(3)). There are a total of 16 contaminants; 15 organic chemicals and 1
microorganism (Aeromonas). Nitrobenzene has been added to List 2 from the original UCMR
(1999) List to track its occurrence at a concentration lower than the List 1 nitrobenzene minimum
reporting level (MRL). Polonium-210 has been moved from List 2 to List 3 because further
analytical method research and development is needed. Methods for the analysis of RDX and
Alachlor ESA and other acetanilide degradation products need further refinement before
approval. When methods for these contaminants are approved and ready for use, EPA will issue
an additional supplement. Monitoring for the 13 organic chemicals with approved analytical
methods is scheduled to begin in 2001 for the representative sample of small systems (systems
serving 10,000 persons or less) and 2002 for large systems (serving greater than 10,000 persons).
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Table 1.3 UCMR (1999) List 2 Contaminants
Contaminant
1 ,2-Diphenylhydrazine
2-Methyl-phenol
2,4-Dichlorophenol
2,4-Dinitrophenol
2,4,6-Trichlorophenol
Alachlor ESA and other
acetanilide degradation products
Diazinon
Disulfoton
Diuron
Fonofos
Linuron
Nitrobenzene (low level)
Prometon
RDX
Terbufos
Aeromonas
CAS#
122-66-7
95-48-7
120-83-2
51-28-5
88-06-2
NAd
333-41-5
298-04-4
330-54-1
944-22-9
330-55-2
98-95-3
1610-18-0
121-82-4
13071-79-9
N/Ad
Analytical
Methods
EPA Method 526
EPA Method 528
EPA Method 528
EPA Method 528
EPA Method 528
Reserved °
EPA Method 526
EPA Method 526
EPA Method 532
EPA Method 526
EPA Method 532
EPA Method 526
EPA Method 526
Reserved °
EPA Method 526
Reserved °
Minimum
Reporting
Level
0.5 ng/L a
l.Ojig/L"
1.0jig/LB
5.0Mg/La
l.Ojig/L"
Reserved0
0.5 Mg/L a
0.5 Mg/L a
l.Ojig/L"
0.5 Mg/L a
l.Ojig/L"
0.5 Mg/L a
0.5 Mg/L a
Reserved °
0.5 Mg/L a
Reserved °
Sampling
Point
EPTDSb
EPTDSb
EPTDSb
EPTDSb
EPTDSb
Reserved0
EPTDSb
EPTDSb
EPTDSb
EPTDSb
EPTDSb
EPTDSb
EPTDSb
Reserved °
EPTDSb
Distribution
System
Note: EPA = EPA Methods. See Table 1.6 for the full reference for each analytical method.
a Minimum Reporting Level represents the value of the lowest concentration precision and accuracy
determination made during methods development and documented in the method. If method options are
permitted, the concentration used was for the least sensitive option.
b 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 12-month period of
monitoring; sampling must occur at the EPTDS, source water sampling points are not permitted for List 2
contaminant monitoring (§141.40(a)(5)).
0 To be determined. Neither approved method, MRL, nor monitoring period (except for Aeromonas) has been
defined for these contaminants.
d CAS number is Not Applicable.
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1.3.3 UCMR (1999) List 3 Contaminants
Currently, there are no suitable analytical methods for the UCMR (1999) 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. Table 1.4 contains the current UCMR
(1999) List 3 contaminants, including polonium-210. These contaminants are scheduled to be
monitored during the Pre-Screen Testing component of the UCMR Program, which may be
conducted in 2004, exclusively at selected List 3 systems if methods are available.
Table 1.4 UCMR (1999) List 3 Contaminants
Contaminant
Lead-210
Polonium-210
Adenoviruses
Calici viruses
Coxsackie viruse s
Cyanobacteria (blue
green algae, other
freshwater algae,
and their toxins)
Echoviruses
Helicobacter pylori
Microsporidia
CAS#
14255-04-0
13981-52-7
NAb
NAb
NAb
NAb
NAb
NAb
NAb
Anticipated
Analytical
Method
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Minimum
Reporting Level
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Anticipated
Sampling
Point
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
Reserved a
a To be determined. Neither approved method, MRL, nor monitoring period has been defined for these
contaminants.
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 contaminants listed in this table are grouped according to compound
characteristics. 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 a contaminant when it is present), false-positive test results (either incorrectly
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
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.
The data quality needs of drinking water compliance monitoring differ from 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 (MRL) 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,
the analytical method used, and the capabilities of the laboratory. 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.
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.
The method that has been approved for use in monitoring perchlorate under the UCMR is EPA
Method 314.0. While this method is similar to methods that have been published by the
California Department of Health and Dionex Corporation, neither of these methods incorporates
a quality control element which assesses the impact of high concentrations of total dissolved
solids (TDS), which are frequently present in water samples. The presence of very high TDS
(representing matrix conductance exceeding 3000 uS/cm) in samples can result in inaccurate
quantitation of perchlorate or may even mask its presence. Therefore, EPA incorporated a
quality control element into EPA Method 314.0 that both identifies the presence of high
concentrations of TDS and provides a mechanism to reduce their concentrations, thereby
permitting accurate quantitation of perchlorate. In addition, EPA's Method 314.0 permits the use
of both the California Department of Health and Dionex procedures within its scope; therefore,
laboratories currently using either of these procedures can convert to EPA Method 314.0 simply
by adopting the quality control procedures specified in EPA Method 314.0.
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. Note, however, that whether
an EPA method or alternative method is used, specific quality control measures for UCMR
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December 2001
analyses are required (§141.40 Appendix A). This Manual explains these quality control
requirements and contaminant confirmation procedures that are specified in the revised UCMR
(40 CFR 141.40). The subsequent sections of this Manual provide an overview of methods,
sampling, and quality control procedures to be used throughout the UCMR. EPA method
numbers are used in this Manual as references for the reader. 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
Chemical Contaminant
CAS#
Methodology
EPA Method
Equivalent Methods
Volatile Organic Compounds
MTBE
Nitrobenzene
1634-04-4
98-95-3
EPA 502.2 a'8; EPA 524.2 a
EPA 524.2 a'e
D5790-95b;SM6210Dc;
SM6200BC;SM6200CC'8
D5790-95b;SM6210Dc;
SM 6200B c
Semivolatile Organic Compounds
2,4-Dinitrotoluene
2,6-Dinitrotoluene
121-14-2
606-20-2
EPA 525. 2 a
EPA 525 .2 a
none identified
none identified
Chlorinated Hydrocarbon Pesticides
4,4'-DDE
72-55-9
EPA 525.2 a; EPA 508 a; EPA
508. la
D 5812-96 b;990.06d
Nitrogen- and Phosphorus-Containing Pesticides
Acetochlor
EPTC
Molinate
Terbacil
34256-82-1
759-94-4
2212-67-1
5902-51-2
EPA 525 .2 a
EPA 525 . 2 a; EPA 507 a
EPA 525. 2 a; EPA 507 a
EPA 525 . 2 a; EPA 507 a
none identified
D 5475-93 b;991.07d
D 5475-93 b;991.07d
D5475-93b; 991.07 d
Acid Herbicides
DCPA mono-acid
degradate
DCPA di-acid degradate
887-54-7
2136-79-0
EPA 515. la'e; EPA 515.2 a'e;
EPA 5 15.3 M; EPA 5 15.4 J
EPA 515. la'e; EPA 515.2 a'e;
EPA 5 15.3 M; EPA 5 15.4 J
D 53 17-93 b; 992.32 d
D 53 17-93 b; 992.32 d
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
Chemical Contaminant
CAS#
Methodology
EPA Method
Equivalent Methods
Inorganic Compounds
Perchlorate
14797.73.0
EPA 3 14.0 f
none identified
The version of the EPA methods approved for the UCMR are listed at 40 CFR 141.24 (e).
b Annual Book ofASTM Standards, 1996 and 1998, Vol. 11.02, American Society for Testing and Materials.
MQ\ho&V5%U-96is\ocs\s&in\hQ Annual Book ofASTM Standards, 1998, Vol. 11.02. Methods D5790-
95, D5475-93, and D5317-93 are located in the Annual Book of ASTMStandards, 1996 and 1998, Vol
11.02. Copies may be obtained from the American Society for Testing and Materials, 100 Barr Harbor
Drive, West Conshohocken, PA 19428.
0 SM 6200 B and SM 6200 C are found only in the 20th edition of Standard Methods for the Examination of
Water and Wastewater, 1998. Sample preservation should be conducted as specified in EPA Method
524.2. SM 6210 D is found only 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 from the American Public Health Association, 1015 Fifteenth Street NW,
Washington, DC 20005.
d Official Methods of Analysis ofAOAC (Association of Official Analytical Chemist) International, Sixteenth
Edition, 4th Revision, 1998, Volume I, AOAC International, First Union National Bank Lockbox, PO Box
75198, Baltimore, MD 21275-5198. (800) 379-2622.
e EPA has included specific recommendations regarding the use of EPA Method 524.2 for measuring
nitrobenzene and EPA Methods 515.1 and 515.2 for measuring the DCPA degradates in this document.
f EPA Method 314.0, "Determination of Perchlorate in Drinking Water by Ion Chromatography," EPA
815-B-99-003, November 1999. Also published in "Methods for the Determination of Organic and
Inorganic Compounds in Drinking Water," EPA 815-R-00-014, August 2000. A copy of EPA Method
314.0 is also available by contacting the EPA Safe Drinking Water Hotline at (800) 426-4791 or accessing
the method directly at http://www.epa.gov/safewater/methods/sourcalt.html.
j° Sample preservation and holding times should be conducted as specified in EPA method 524.2.
Since Method 515.3 does not include a solvent wash step following hydrolysis, the parent DCPA is not
removed prior to analysis, therefore, only non-detect data may be reported using Method 515.3. All
samples with results above the MRL must be analyzed by one of the other approved methods (§141.40
= (a)(3)).
EPA Method 515.3, "Determination of Chlorinated Acids in Drinking Water by Liquid-Liquid Extraction,
Derivatization and Gas Chromatography with Electron Capture Detection," EPA 815-R-00-014, "Methods
for the Determination of Organic and Inorganic compounds in Drinking Water, Volume 1," August 2000.
Available from the National Technical Information Service, NTIS PB2000-106981, U.S. Department of
Commerce, 5285 Port Royal Road, Springfield, VA 22161. The toll free number is (800)-553-6847.
Alternatively, the method can be assessed and downloaded directly on-line at
www.epa.gov/safewater/methods/sourcalt.html.
J EPA Method 515.4, "Determination of Chlorinated Acids in Drinking Water by Liquid-Liquid
Microextraction, Derivatization, and Fast Gas Chromatography with Electron Capture Detection," April
2000, EPA 815/B-00/001. Available by requesting a copy from the EPA Safe Drinking Water Hotline
within the United States at (800)-426-4791 (Hours are Monday through Friday, excluding federal holidays,
from 9:00 a.m. to 5:30 p.m. Eastern Time). Alternatively, the method can be assessed and downloaded
directly on-line at www.epa.gov/safewater/methods/sourcalt.html.
1.5 Laboratory Approval and Certification Requirements for UCMR (1999) List 1
Contaminants
Laboratories are automatically approved for the analysis of UCMR contaminants in Table 1.5 if
they are already certified by a State or primacy agency to conduct compliance monitoring for a
contaminant included in the same method being approved for UCMR analysis.
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As noted in the revised UCMR (64 FR 50556), 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
1.5.1 Laboratory Approval for Monitoring Acetochlor
EPA approved the use of EPA Method 525.2 for monitoring acetochlor under the UCMR. No
performance testing sample analyses are required for laboratory approval for the analysis of
acetochlor under the UCMR. All laboratories currently certified by their State to perform
drinking water compliance monitoring using EPA Method 525.2 are automatically approved to
perform acetochlor analyses under the UCMR (§141.40(a)(5)(ii)(G)(l)).
1.5.2 Laboratory Approval for Monitoring Perchlorate
The method that has been approved for monitoring perchlorate under the UCMR is not currently
used nationally for compliance monitoring. Consequently, State certification programs do not
include certification for this method. Because EPA Method 3 14.0 includes matrix specific
quality control criteria, laboratories must have gone through a separate approval process to
analyze samples for perchlorate (§141.40(a)(5)(ii)(G)(2)). The laboratory approval system is
based on previous certification of the laboratory to conduct analyses in support of regulatory
compliance monitoring of drinking water for any inorganic anion using an approved ion
chromatographic method (as listed in §141.28, such as nitrate analysis by EPA Method 300.0).
In addition, a laboratory must have successfully completed the perchlorate Performance Testing
(PT) Program to be approved for UCMR perchlorate analyses (§141.40(a)(5)(ii)(G)(2)).
To obtain a copy of EPA Method 3 14.0, contact the Safe Drinking Water Hotline at: (800) 426-
4791 or access an electronic copy of the method directly on-line at
http://www.epa.gov/safewater/methods/sourcalt.html.
Any laboratory who wished to participate in the perchlorate PT Program and obtain approval
should have submitted a letter of request, received by EPA no later than March 31, 2000
(§141.40(a)(5)(ii)(G)(2)). Any interested laboratory that did not meet this deadline or failed to
successfully pass this initial PT study and still wished to support this monitoring, should have
submitted a request letter by October 6, 2000 in order to have been eligible for a second PT
study. EPA did not consider any laboratory request letters received after October 6, 2000. Any
laboratory that gained approval in the first PT study was not required to participate in the second
PT study. These were the only two PT studies offered, through December 31, 2003, for
laboratories who wished to gain approval to conduct perchlorate analysis in support of UCMR
Assessment Monitoring. Any laboratory which did not request participation by October 6, 2000
and failed to pass either one of these two PT studies was not approved to support this perchlorate
monitoring.
EPA provided each laboratory, upon successful completion of the perchlorate PT Program, with
an approval letter identifying the laboratory by name and the approval date. This letter may be
presented to any PWS as evidence of laboratory approval for perchlorate analysis supporting the
UCMR. Laboratory approval is retained as long as the laboratory maintains certification by a
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State or primacy agency to perform drinking water compliance monitoring using an approved ion
chromatographic method. If a laboratory maintains this certification, the laboratory approval for
perchlorate analysis supporting the UCMR will be limited to the time period beginning on the
date specified in the EPA issued approval letter and extending through January 28, 2004. A list
of perchlorate approved laboratories can be found on-line at:
www.epa.gov/safewater/standard/ucmr/aprvlabs.html.
To allow data on perchlorate occurrence in PWSs obtained prior to January 2001 to be
grandparented, the data must meet the reporting requirements of the UCMR which included the
successful completion of the perchlorate PT Program by a laboratory approved to perform the
original analyses (§141.35(g)).
1.5.3 Laboratory Approval for Monitoring DCPA, mono- and di-acid degradates
As noted in the revised UCMR (66 FR 46221), laboratories certified under §141.28 for
compliance analysis using EPA Method 515.3 are automatically approved to conduct UCMR
analysis for the DCPA mono- and di-acid degradates using EPA Method 515.4
1.6
Analytical Methods for UCMR (1999) List 2 Contaminants
Table 1.6 includes the UCMR (1999) List 2 chemical contaminants that are required for
monitoring under the Screening Survey for chemical contaminants grouped by chemical class (66
FR 2273). EPA has not approved the use of any alternative analytical methods; therefore, only
the EPA approved methods listed in Table 1.6 may be used to obtain data for the UCMR. The
required quality control measures included in the final UCMR (64 FR 50556) and final UCMR
List 2 Rule (66 FR 2273) are explained in this Manual.
Table 1.6 Approved Analytical Methods for UCMR (1999) List 2 Contaminants
Chemical Contaminant
CAS#
Methodology
EPA Method
Equivalent Methods
Semivolatile Organic Compounds
1 ,2-Diphenylhydrazine
Diazinon
Disulfoton
Fonofos
Nitrobenzene (low-level)
Prometon
122-66-7
61790-53-2
298-04-4
944-22-9
98-95-3
1610-18-0
EPA 526 a
EPA 526 a
EPA 526 a
EPA 526 a
EPA 526 a
EPA 526 a
none identified
none identified
none identified
none identified
none identified
none identified
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Chemical Contaminant
Terbufos
CAS#
13071-79-9
Methodology
EPA Method
EPA 526 a
Equivalent Methods
none identified
Phenols
2-Methyl-phenol
2,4-Dichlorophenol
2,4-Dinitrophenol
2,4,6-Trichlorophenol
95-48-7
120-83-2
51-28-5
88-06-2
EPA 528 a
EPA 528 a
EPA 528 a
EPA 528 a
none identified
none identified
none identified
none identified
Phenlyureas
Diuron
Linuron
330-54-1
330-55-2
EPA 532 a
EPA 532 a
none identified
none identified
The version of the EPA methods which must be followed are listed in § 141.40(a)(3).
1.7 Laboratory Certification Requirements for UCMR (1999) List 2 Contaminants
All laboratories currently certified by the appropriate primacy agency to conduct drinking water
compliance monitoring using EPA Method 525.2 will automatically be approved to conduct
UCMR analysis using EPA Method 526 and/or EPA Method 528. Those laboratories currently
certified by the appropriate primacy agency to conduct drinking water analysis using EPA
Methods 549.1 or 549.2 will automatically be approved to conduct UCMR analysis using
Method 532. EPA will select up to eight contract laboratories nationally to analyze UCMR
(1999) List 2 contaminants for small systems. Those laboratories must demonstrate that they
meet certification requirements specified in §141.40 (a)(5)(ii)(G)(3).
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
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, 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 may 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 the Assessment Monitoring portion of this program, all CWSs and NTNCWSs serving
more than 10,000 people (large systems) are required to monitor for unregulated contaminants
(§141.40(a)(l)(ii)). However, PWSs that purchase 100% of their water must only monitor for
UCMR contaminants that must be sampled for in the distribution system (i.e., the sampling point
is listed as "distribution system") (§141.40(a)(l)(iii) and §141.40(a)(l)(v)). For systems serving
10,000 or fewer people (small systems), only a randomly 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)).
The Screening Survey portion of the UCMR requires a smaller, randomly selected sample of 300
systems which represent large and small community and non-transient non-community water
systems. EPA has selected 300 systems (for both the chemical and the microbial screening
surveys), of which 180 are small systems and 120 are large systems, from those required to
conduct Assessment Monitoring. EPA will pay for the reasonable costs of monitoring for the
180 small systems.
2.2 Sampling Frequency
PWSs will conduct their Assessment Monitoring during a 12 consecutive month period of the
Assessment Monitoring period from 2001 to 2003. The year of monitoring and the time of
sample collection may coincide with other scheduled compliance monitoring. For example, a
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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 can be concurrently coordinated with analyses for other
required State primacy compliance monitoring using the same methods approved for compliance
monitoring to help reduce costs.
PWSs using surface water sources, or ground water under the direct influence of surface water,
must sample four times per year for a 12 consecutive month period 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 orEPA(§141.40(a)(5)).
Large PWSs using surface water or ground water under the direct 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 a 12 consecutive month period 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 month in which
samples must be collected (§141.40(a)(4)(iii)(B)).
Monitoring for the Screening Survey for Chemical Contaminants will be conducted for 1 year,
starting in January 2001 for small systems and January 2002 for large systems. EPA is limiting
the time frame for conducting this monitoring (conducted over a one year period not 12 months
over the 3-year period as with List 1 Assessment Monitoring). This proposed timing will allow
monitoring of UCMR (1999) List 2 and List 1 contaminants concurrently at small systems.
Small systems will monitor first because EPA is paying for the small system monitoring and
desires to evaluate methods performance so that any necessary adjustments can be made prior to
large system monitoring, which large systems must pay for themselves. The frequency of
sampling for chemical contaminants on the UCMR (1999) List 2 is the same as for List 1
Assessment Monitoring.
2.2.1 Sampling Frequency Deviations
EPA recognizes that on occasion, circumstances beyond a PWS's or laboratory's control can
invalidate data. Numerous QC failures are possible in the "real" world, from receiving samples
broken or not within temperature parameters, to specific QC problems during sample analysis. If
for any reason the sample data becomes invalid, samples should be recollected as soon as
possible. QC failures that invalidate data could be immediately apparent and related to sample
receipt temperature or storage, or may result from failures within the analysis batch or within a
specific individual sample analysis. These QC problems could be interpreted as "sampling
deviations" as identified in §141.40(a)(5)(ii)(F) of the September 17, 1999 UCMR. Any QC
problems that may occur at the lab will need to be relayed back to the PWS through,
"...notification from the laboratory that you must resample." Resampling should occur
" within 14 days of observing the occurrence of the error" (§141.40(a)(5)(ii)(F)). Specific QC
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criteria can be found in Appendix A to §141.40, in the analytical methods, as well as summarized
in this Manual.
The laboratory should make every effort to inform the utility as soon as they learn of a QC
problem which has invalidated UCMR sample data for a specific method. When a surface water
(SW) system collects sample late in the quarter, and a QC failure is found in the first month of
the next quarter that invalidates the data, the system should immediately recollect the sample,
document the QC problem from the original sampling (verifying the intent to comply with the
regulation), and get valid data from a subsequent sampling. The subsequent sampling event will
be out of the official sampling month, and technically out of the quarter in which the majority of
monitoring has been done, but data slightly out of phase is better than no data at all.
Systems should strive to collect samples within the regulatory defined sampling periods. When
circumstances such as sample QC failures which invalidate data and, in turn, affect the
monitoring frequency, the system should still immediately recollect the sample, document the
QC problem from the original sampling (verifying the intent to comply with the regulation), and
get valid data from a subsequent re-sampling event. The extent of the QC problem and how it
will affect the entire data set should be evaluated. If the entire data set for all UCMR samples
collected are invalid for a system, a determination should be made as to why such universal QC
problems exist in the lab across all methods before proceeding with other analyses. After a
determination has been made, all invalidated samples should be recollected as a second set of
samples. If the impact is on an individual method's data, the system can maintain their original
sampling schedule and just recollect for that method.
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 Tables 1.2 and 1.3 for the UCMR (1999) List 1 and List 2 contaminants,
respectively. Sampling points for the UCMR (1999) List 3 contaminants listed in Table 1.4 are
currently reserved.
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 in 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)). Some
States mandate source water (prior to treatment) sampling for regulated contaminant compliance
monitoring. In these States, source water monitoring of UCMR contaminants allows systems to
concurrently conduct UCMR monitoring with their regulated contaminant compliance
monitoring. 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
regulated contaminant compliance monitoring. However, if monitoring at source water sampling
points indicates detection of any of the contaminants on the UCMR monitoring list, the system
must then shift its unregulated contaminant monitoring (for the detected contaminant(s)) to the
EPTDS (§141.40(a)(5)). This EPTDS monitoring, for a detected contaminant, must then be
conducted for a new complete 12-month cycle at the required frequency respective of surface
water or ground water (§141.40(a)()(ii)(B)). In this case, additional sampling for non-detected
UCMR contaminants at the EPTDS would not be required. An exception to the EPTDS
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resampling requirement applies if the State or EPA determines that no treatment or processing
was in place between the source and EPTDS that would affect the measurement of the
contaminants (§141.40(a)(5)(ii)(C)). The requirement for UCMR samples to be collected at the
EPTDS follows the existing regulatory approach and provides data for exposure assessment.
EPA is seeking a representative result from the 300 systems that are required to monitor for
UCMR (1999) List 2 chemical contaminants. Therefore, EPA requires that all Screening Survey
samples for chemical contaminants be collected from entry points to the distribution system
(EPTDS) to obtain nationally consistent results (§141.40(a)(5)). This condition of specifying
exclusive EPTDS monitoring for List 2 chemicals is based on the fact that the approved methods
for these contaminants are not currently used for any State compliance parameter monitoring and
therefore concurrent compliance monitoring should not be an issue.
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
Section 3. Sample Collection and Preservation
3.1 UCMR (1999) List 1 Assessment Monitoring 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)(ii)(F)).
3.1.1 Nitrogen- and Phosphorus-Containing Pesticides
The three UCMR (1999) List 1 nitrogen- and phosphorus-containing pesticides, EPTC1,
molinate1, and terbacil1, may be analyzed with EPA Method 525.2, EPA Method 507 or the
approved equivalent methods including ASTM Method D 5475-93 or AOAC Method 991.07
(see Table 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, dechlorination, and sample collection, preservation, storage, and holding
times are described below. The sampling and preservation requirements specified for ASTM
Method D 5475-93 and AOAC Method 991.07 closely parallel those identified in EPA Method
507. Consequently, the following specifications also apply when laboratories choose to utilize
those approved equivalent methods.
EPA Method 507 - Determination of Nitrogen- and Phosphorus-Containing Pesticides in Water
by Gas Chromatography with a Nitrogen-Phosphorus Detector
(Also applicable to ASTM Method D 5475-93 and AOAC Method 991.07 for use in the UCMR)
Sample container - Use one-liter or one-quart amber glass bottles fitted with PTFE-lined screw
caps. Amber bottles should be used 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. PTFE-faced cap liners should be extracted with methanol overnight prior to use
to remove any potential contamination.
Sample dechlorination - To dechlorinate the sample, add approximately 80 milligrams of
sodium thiosulfate per liter of sample to the sample containers prior to filling. This is typically
best done by adding the preservative salt to the sample container as part of the sampling kit
preparation process at the laboratory prior to delivery of the kit to the field sampling site. After
samples have been received, laboratories should employ a N,N-diethyl-/?-phenylenediamine
(DPD) test kit to confirm proper sample dechlorination. When effectively dechlorinated, no
immediate red color change should be evident.
1 These pesticides are also semi-volatile organic compounds and therefore are also discussed in Section 3.1.5.
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
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. Sampling equipment 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 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 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 stored at 4°C (± 2°) during shipment and upon receipt at the
laboratory.
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 sample extracts 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'-DDE2, may be analyzed with
EPA Methods 508, 508.1, 525.2 or the approved equivalent methods, including ASTM Method
D 5812-96 and AOAC Method 990.06 (see Table 1.5). For reference, see EPA Method 508 -
Determination of Chlorinated Pesticides in Water by GC with an Electron Capture Detector or
EPA Method 508.1 - Determination of Chlorinated Pesticides, Herbicides, and Organohalides
by Liquid-Solid Extraction and Electron Capture Gas Chromatography. Sampling procedures
based on EPA Method 525.2 are described below in Section 3.1.5. Sampling procedures based
on EPA Methods 508 and 508.1, including sample containers, dechlorination, and sample
collection, preservation, storage, and holding times are described below. The sampling and
The pesticide 4,4'-DDE is a semi-volatile organic compound and is therefore also discussed in Section
3.1.5.
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
preservation requirements specified for ASTM Method D 5812-96 and AOAC Method 990.06
closely parallel those identified in EPA Method 508. Consequently, the specifications below
respective of Method 508 apply when laboratories choose to utilize those approved equivalent
methods.
EPA Method 508 - Determination of Chlorinated Pesticides in Water by GC with an Electron
Capture Detector (see Table 1.5).
(Also applicable to ASTM Method D 5812-96 and AOAC Method 990.06 for use in the UCMR)
Sample container - Use one-liter amber glass bottles fitted with PTFE-lined screw caps. Amber
bottles should be used 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. PTFE-
faced cap liners should be extracted with methanol overnight prior to use to remove any potential
contamination.
Sample dechlorination - To dechlorinate the sample, add approximately 80 milligrams of
sodium thiosulfate per liter of sample to the sample containers prior to filling. This is typically
best done by adding the preservative salt to the sample container as part of the sampling kit
preparation process at the laboratory prior to delivery of the kit to the field sampling site. After
samples have been received, laboratories should employ a N,N-diethyl-/?-phenylenediamine
(DPD) test kit to confirm proper sample dechlorination. When effectively dechlorinated, no
immediate red color change should be evident.
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. Sampling equipment 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 not, therefore,
be used to preserve samples for the UCMR Program.
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 stored at 4°C (± 2°) during shipment and upon receipt at the
laboratory.
Sample holding time - Extract samples within 7 days. Preservation study results indicate that
most of the target contaminants present in the samples are stable for 7 days when stored under
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
these conditions. Contaminant stability may be affected by the matrix. 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 sample extracts are not analyzed within the appropriate
period, discard and replace the samples. (See Table 3.1 for a summary of holding times.)
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 PTFE-lined screw
caps. Amber bottles should be used because some of the method contaminants are sensitive to
light and are oxidized or decomposed upon exposure to light.
Sample dechlorination - To dechlorinate the sample, add approximately 80 milligrams of
sodium sulfite per liter of sample to the sample containers prior to filling. This is typically best
done by adding the preservative salt to the sample container as part of the sampling kit
preparation process at the laboratory prior to delivery of the kit to the field sampling site. After
samples have been received, laboratories should employ a N,N-diethyl-/?-phenylenediamine
(DPD) test kit to confirm proper sample dechlorination. When effectively dechlorinated, no
immediate red color change should be evident.
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. Sampling equipment 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 (PTFE 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.
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, PTFE face
down, invert three or four times, and keep the sample sealed until analysis. After samples have
been received, laboratories should use a pH meter or pH test strip to confirm the sample was
properly acidified to a pH of 2 or less.
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
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 stored at 4°C (± 2°) during shipment and upon receipt at the
laboratory.
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. If samples are not extracted within this period, discard and
replace the samples.
Sample extract holding time - Analyze extracts within 30 days. Extracts can be held for 30
days when stored at 4°C (± 2°). If sample extracts are not analyzed within this period, discard
and replace the samples. (See Table 3.1 for a summary of holding times.)
3.1.3 Acid Herbicides
The two UCMR (1999) List 1 acid herbicide-based contaminants, the mono- and di-acid
degradates of dimethyl tetrachloroterephthalate (DCPA), may be analyzed with EPA Method
515.1, EPAMethod 515.2, EPAMethod 515.3, EPAMethod 515.4, or the approved equivalent
methods including ASTM Method D 5319-93 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, EPA Method 515.2- Determination of
Chlorinated Acids in Water Using Liquid-Solid Extraction and Gas Chromatography with an
Electron Capture Detector, EPAMethod 515.3 -Determination of Chlorinated Acids in
Drinking Water by Liquid-Liquid Extraction, Derivatization and Gas Chromatography with
Electron Capture Detection, or EPA Method 515.4- Determination of Chlorinated Acids in
Drinking Water By Liquid-LiquidMicroextraction, Derivatization, and Fast Gas
Chromatography with Electron Capture Detection (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. If the analytical results using EPA Method 515.3 is equal to or greater
than the MRL, a duplicate sample must be analyzed within the method-specified holding time, or
a replacement sample must be collected and analyzed within the same month as the original
sample using one of the other approved methods, since EPA Method 515.3 does not differentiate
between the DCPA parent compound and the degradates. For specific clarifications concerning
the use of EPA Methods 515.1, 515.2, 515.3, 515.4, or their approved equivalent methods, please
see Section 6.1 of this Manual. Sampling procedures based on EPA Methods 515.1, 515.2,
515.3, and 515.4, including sample containers, and dechlorination, and sample collection,
preservation, storage and holding times are described below. The sampling and preservation
requirements specified for ASTM Method D 5317-93 and AOAC Method 992.32 closely parallel
those identified in EPA Method 515.1. Consequently, the following specifications, respective of
Method 515.1, also apply when laboratories choose to utilize those approved equivalent methods.
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
EPA Method 515.1 - Determination of Chlorinated Acids in Water by Gas Chromatography
with an Electron Capture Detector
(Also applicable to ASTM Method D 5317-93 and AOAC Method 992.32 for use in the UCMR)
Sample container - Use one-liter or one-quart amber glass bottles fitted with PTFE-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. PTFE-faced cap liners should be extracted with methanol overnight prior to use
to remove any potential contamination.
Sample dechlorination - To dechlorinate the sample, add approximately 80 milligrams of
sodium thiosulfate per liter of sample to the sample container prior to filling. This is typically
best done by adding the preservative salt to the sample container as part of the sampling kit
preparation process at the laboratory prior to delivery of the kit to the field sampling site. After
samples have been received, laboratories should employ a N,N-diethyl-/?-phenylenediamine
(DPD) test kit to confirm proper sample dechlorination. When effectively dechlorinated, no
immediate red color change should be evident.
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. Sampling equipment 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 sample bottle, invert
three or four times, and keep the sample bottle sealed until analysis.
Sample preservation - 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 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 stored at 4°C (± 2°) during shipment and upon receipt at the
laboratory.
Sample holding time - Extract samples within 14 days. Preservation study results indicate that
the contaminants (measured as total acid) present in samples are stable 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. Preservation study results indicate that analytes are stable for
28 days. (See Table 3.1 for a summary of holding times.) If sample extracts are not analyzed
within the appropriate period, discard and replace the samples.
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EPA Method 515.2 -Determination of Chlorinated Acids in Water Using Liquid-Solid
Extraction and Gas Chromatography with an Electron Capture Detector
Sample container - Use 250 milliliter amber glass bottles fitted with PTFE-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.
PTFE-faced cap liners should be extracted with methanol overnight prior to use to remove any
potential contamination.
Sample dechlorination - To dechlorinate the sample, add approximately 20 milligrams of
sodium thiosulfate per 250 mL of sample to the sample container prior to filling. This is
typically best done by adding the preservative salt to the sample container as part of the sampling
kit preparation process at the laboratory prior to delivery of the kit to the field sampling site.
After samples have been received, laboratories should employ a N,N-diethyl-/?-phenylenediamine
(DPD) test kit to confirm proper sample dechlorination. When effectively dechlorinated, no
immediate red color change should be evident.
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. Sampling equipment 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 the sample bottle has been filled, close the bottle (PTFE
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 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. After waiting
one minute, adjust the pH to less than 2 by carefully adding 6 N hydrochloric acid (this may
require as much as 1 milliliter of acid). This should retard microbiological degradation of the
contaminants in the water. After samples have been received, laboratories should use a pH meter
or pH test strip to confirm the sample was properly acidified to a pH of 2 or less.
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 stored at 4°C (± 2°) during shipment and upon receipt at the
laboratory.
Sample holding time - Extract samples within 14 days. 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 14 days according to EPA Method 515.2. Preservation study results
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
indicate that most contaminants are stable for 14 days according to EPA Method 515.2. (See
Table 3.1 for a summary of holding times.) If sample extracts are not analyzed within the
appropriate period, discard and replace the samples.
EPA Method 515.3 -Determination of Chlorinated Acids in Drinking Water by Liquid-Liquid
Extraction, Derivatization and Gas Chromatography with Electron Capture Detection.
NOTE: If the analytical results using EPA Method 515.3 is equal to or greater than the MRL, a
duplicate sample must be analyzed within the method-specified holding time, or a replacement
sample must be collected and analyzed within the same month as the original sample using one
of the other approved methods, since EPA Method 515.3 does not differentiate between the
DCPA parent compound and the degradates.
Sample container - Use an amber glass container of at least a 50 milliliter capacity with a PTFE-
lined screw-cap. Meticulously wash and dry container as directed in section 4.1.1 of the EPA
Method to minimize contamination. Amber bottles should be used to protect samples from light.
Sample dechlorination - To dechlorinate the sample, add 4 milligrams of sodium thiosulfate per
50 milliliters of sample to the sample bottle prior to collection. This is typically best done by
adding the preservative salt to the sample container as part of the sampling kit preparation
process at the laboratory prior to delivery of the kit to the field sampling site. After samples have
been received, laboratories should employ a N,N-diethyl-/»-phenylenediamine (DPD) test kit to
confirm proper sample dechlorination. When effectively dechlorinated, no immediate red color
change should be evident.
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 the 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. Sampling equipment 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, cap the bottle, agitate by hand for
15 seconds, and keep the sample bottle sealed until analysis.
Sample preservation - Because of the several pH adjustments made to the samples in the course
of this method, the addition of hydrochloric acid to the samples to retard biological activity has
been omitted. However, the analyst should be aware of the potential for the biological
degradation of the analytes.
Sample storage - Immediately store the samples at 4°C (± 2°) in a refrigerator or packed in ice.
Samples must be protected from light until extraction.
Sample holding time - Extract samples within 14 days. Holding studies performed to date show
that samples, when stored at 4°C (± 2°) or less, protected from light in glass vials with PTFE-
lined caps and preserved with sodium thiosulfate, will remain stable for up to 14 days. If
samples are not extracted within 14 days, discard and replace the samples.
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
Sample extract holding time - Analyze extracts within 14 days. Holding studies performed to
date show that extracts, when stored at 4°C (± 2°) or less, protected from light in glass vials with
PTFE-lined caps, will remain stable for up to 14 days. If extracts are not analyzed within 14
days, discard and replace the samples. (See Table 3.1 for a summary of holding times.)
EPA Method 515.4 - Determination of Chlorinated Acids in Drinking Water by Liquid-Liquid
Microextraction, Derivatization, and Fast Gas Chromatography with Electron Capture
Detection
Sample Container - Use an amber glass container with a PTFE-lined screw cap of at least 125
milliliter capacity. Amber bottles should be used to protect samples from light. Sample bottles
must be washed and dried according to section 4.1 of the Method.
Sample dechlorination - To dechlorinate the sample, add 2 milligrams of sodium sulfite per 40
milliliters of sample volume to the sample bottle prior to collecting the sample. This is typically
best done by adding the preservative salt to the sample container as part of the sampling kit
preparation process at the laboratory prior to delivery of the kit to the field sampling site. After
samples have been received, laboratories should employ a N,N-diethyl-/?-phenylenediamine
(DPD) test kit to confirm proper sample dechlorination. When effectively dechlorinated, no
immediate red color change should be evident.
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 the 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. Sampling equipment 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, cap the bottle, agitate by hand for
15 seconds, and keep the sample bottle sealed until analysis.
Sample preservation - Because of the several pH adjustments made to the samples in the course
of this method, the addition of hydrochloric acid to the samples to retard biological activity has
been omitted. However, the analyst should be aware of the potential for the biological
degradation of the analytes.
Sample storage - All samples should be iced during shipment and must not exceed 10° C during
the first 48 hours. Samples that are stored in the laboratory must be at or below 6° C and
protected from light until extraction, but should not be frozen.
Sample holding time - Extract samples within 14 days. Holding studies performed to date show
that samples, when stored at 6° C or less, protected from light in glass vials with PTFE-lined caps
and preserved with sodium thiosulfate, will remain stable for up to 14 days. If samples are not
analyzed within 14 days, discard and replace the samples.
Sample extract holding time - Analyze extracts within 21 days. Holding studies performed to
date show that extracts, when stored at 6° C or less, protected from light in glass vials with
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
PTFE-lined caps, will remain stable for up to 21 days. If extracts are not analyzed within 21
days, discard and replace the samples. (See Table 3.1 for a summary of holding times.)
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 D 5790-95 or
APHA (Standard Methods) SM 6210D or SM 6200B (see Table 1.5). In addition, MTBE (but
not nitrobenzene) may also be analyzed with EPA Method 502.2, or the approved equivalent
method, APHA (Standard Methods) SM 6200C. For reference, see EPA Method 524.2 -
Measurement ofPurgeable Organic Compounds in Water by Capillary Column Gas
Chromatography/Mass Spectrometry, or EPA Method 502.2 - Volatile Organic Compounds in
Water by Purge and Trap Capillary Column Gas Chromatography with Photoionization and
Electrolytic Conductivity Detectors in Series. 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 and 502.2, including sample containers, dechlorination, sample collection,
sample preservation, and 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 specific to
EPA Method 524.2 must also be followed when using any of the approved equivalent
methods (§141.40(a)(4)(i)(A)) or EPA Method 502.2 (see Table 1, footnote n, §141.40(a)(3)).
EPA Method 524.2 - Measurement ofPurgeable Organic Compounds in Water by Capillary
Column Gas Chromatography/Mass Spectrometry
(Also applicable to ASTM Method D 5790-95, APHA (Standard Methods) SM 6210D and SM
6200B for use in the UCMR)
EPA Method 502.2 - Volatile Organic Compound in Water by Purge and Trap Capillary
Column Gas Chromatography with Photoionization and Electrolytic Conductivity Detectors in
Series
(Also applicable to APHA (Standard Methods) SM 6200C for use in the UCMR)
Sample containers - Use 40-milliliter to 120-milliliter screw cap glass vials, each equipped with
a PTFE-faced silicon septum. To prepare sample bottles: wash vials and septa with detergent
and 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.
Sample dechlorination - To dechlorinate the sample, add approximately 25 milligrams ascorbic
acid (or 3 milligrams sodium thiosulfate3) per 40 milliliters of sample volume to sample
container prior to collecting the sample. This is typically best done by adding the preservative
salt to the sample container as part of the sampling kit preparation process at the laboratory prior
to delivery of the kit to the field sampling site. After samples have been received, laboratories
Because neither MTBE nor nitrobenzene boil below 25°C, sodium thiosulfate may be used to reduce
residual chlorine.
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
should employ a N^-diethyl-^-phenylenediamine (DPD) test kit to confirm proper sample
dechlorination. When effectively dechlorinated, no immediate red color change should be
evident. For these methods, this will likely need to be performed qualitatively on the remaining
volume of sample left in the vial after the autosampler has processed the sample vial. Do not
open the VOC vial prior to processing since the target analytes are volatile and sample integrity
will be compromised.
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.
Sampling equipment 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 (PTFE 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 four 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, PTFE face
down, and invert three or four times. Keep the sample bottle sealed from collection time until
analysis. After samples have been received, laboratories should use a pH meter or pH test strip
to confirm the sample was properly acidified to pH of 2 or less. For these methods, this will
likely need to be performed on the remaining volume of sample left in the vial after the
autosampler has processed the sample vial. Do not open the VOC vial prior to processing since
the target analytes are volatile and sample integrity will be compromised.
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 stored at 4°C (± 2°) during shipment and upon receipt at the
laboratory. The sample storage area must be free of organic solvent vapors, excess heat and
direct light (§141.40 Appendix A).
Sample holding 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.
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
3.1.5 Semi-Volatile Organic Compounds
The seven UCMR (1999) List 1 semi-volatile organic compounds, 2,4-dinitrotoluene, 2,6-
dinitrotoluene, 4,4'- DDE4, acetochlor5, s-ethyl-dipropylthiocarbamate (EPIC)5, molinate5, and
terbacil5, may be analyzed with EPA Method 525.2. In addition, aforementioned equivalent
methods ASTM Method D 5812-96 or AOAC Method 990.06 can be used for 4,4'-DDE, and
ASTM Method D 5475-93 or AOAC Method 991.07 can be used for EPIC, molinate and
terbacil. Note that three of these semi-volatile organic compounds (2,4-dinitrotoluene, 2,6-
dinitrotoluene, and acetochlor) may only be analyzed with EPA Method 525.2; there are no
approved equivalent methods for these three contaminants. See Table 1.5 for a full listing of the
approved 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. General sampling procedures
based on EPA Method 525.2, including sample containers, dechlorination, sample collection,
preservation, storage, and holding times, are described below.
EPA Method 525.2 - Determination of Organic Compounds in Drinking Water by Liquid-Solid
Extraction and Capillary Column Gas Chromatography/Mass Spectrometry
Sample containers - Use one-liter or one-quart amber glass bottles fitted with PTFE-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. This is typically best done by
adding the preservative salt to the sample container as part of the sampling kit preparation
process at the laboratory prior to delivery of the kit to the field sampling site. After samples have
been received, laboratories should employ a N^-diethyl-^-phenylenediamine (DPD) test kit to
confirm proper sample dechlorination. When effectively dechlorinated, no immediate red color
change should be evident.
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 from the tap to a slow but steady stream (about the diameter of a pencil)
and collect the sample from the flowing stream. Sampling equipment must be free of plastic
tubing, gaskets, and other parts that may leach interfering analytes into the water sample
(§141.40 Appendix A).
This semi-volatile organic compound is a pesticide and is specifically identified and listed as a chlorinated
pesticide in Table 1.5.
5 These four 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 (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
Fill sample to almost overflowing, but take care not to flush out any dechlorination chemicals
that are in the sample bottle. After the sample bottle has been filled, close the bottle (PTFE 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 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. 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, PTFE face
down, invert three or four times, and keep the sample sealed until analysis. After samples have
been received, laboratories should use a pH meter or pH test strip to confirm the sample was
properly acidified to pH of 2 or less.
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 stored at 4°C (± 2°) during shipment and upon receipt at the
laboratory. 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. 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 are dechlorinated, preserved, and stored as described
above.
Sample extract holding time - Analyze the extracts within 30 days of extraction. (See Table 3.1
for a summary of holding times.) If samples are not analyzed within this period, discard and
replace the samples.
3.1.6 Inorganic Compounds
Perchlorate is the only inorganic chemical contaminant on List 1 of the UCMR (1999) List.
Under the UCMR, perchlorate must be analyzed with EPA Method 314.0 (see Table 1.5;
§141.40(a)(5)). A copy of Method 314.0 can be obtained at:
http://www.epa.gov/safewater/methods/met314.pdf or in, "Methods for the Determination of
Organic and Inorganic Compounds in Drinking Water" EPA 815-R-00-014, August 2000.
Sampling procedures based on EPA Method 314.0, including sample containers, and sample
collection, storage, and holding times are described below.
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December 2001
EPA Method 314.0 - Determination ofPerchlorate in Drinking Water by Ion Chromatography
Sample containers - Use 30 milliliter, 125 milliliter, or 250 milliliter high density polyethylene
(HDPE) or glass (amber or clear) bottles. The volume collected should be sufficient to ensure a
representative sample, allow for replicate analysis and laboratory fortified matrix (LFM) analysis
(also referred to as the MS/MSD pair), and minimize waste disposal.
Sample dechlorination - This method does not include any dechlorination requirements.
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 from the tap to a slow but steady stream (about the diameter of a pencil)
and collect the sample from the flowing stream. Fill sample to almost overflowing. After the
sample bottle has been filled, close the sample bottle.
Sample preservation - This method does not include any special preservation requirements.
Sample storage - As described in EPA Method 314.0, samples do not need to be shipped iced or
stored cold in a refrigerator, but every effort should be taken to protect the samples from
temperature extremes. As all other UCMR (1999) List 1 samples must be refrigerated
(§141.40(a)(5)), samples for EPA Method 314.0 may be placed with other UCMR samples on ice
or with frozen cold packs in a cooler, or placed in a refrigerator that can maintain the samples at
4°C (± 2°). Samples should not be allowed to freeze, and should be protected from extreme
temperatures from the time of collection until analysis.
Sample holding time - Analyze all samples within 28 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.
Table 3.1 Preservation and Holding Times for Approved UCMR (1999) List 1
Analytical Methods
Method(s)
EPA 3 14.0
EPA 502.2
SM 6200C
EPA 507
D 5475-93
991.07
Preservation
None
Sodium thiosulfate;
l:lHCl-pH<2;
Cool 4 ° C (± 2°);
Dark
Sodium thiosulfate;
Cool 4°C (± 2°); Dark
Sample
Holding
Time
28 days
14 days
14 days
Extract
Holding Time
Not Applicable
Not Applicable
14 days
(<6°C,Dark)
Sample
Size
30 mL,
125 mL, or
250 mL
40 - 120 mL
1L
Container
HDPE or Glass
(Amber or
Clear)
Screw Cap Vial
with PTFE-
lined Septum
Amber Glass
with PTFE-
lined Cap
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual
December 2001
Method(s)
EPA 508
D 5812-96
990.06
EPA 508.1
EPA 515.1
D 53 17-93
992.32
EPA 5 15.2
EPA 5 15.3
EPA 5 15.4
EPA 524.2
D 5790-95
SM6210D
SM 6200B
EPA 525 .2
Preservation
Sodium thiosulfate;
Cool 4°C (± 2°); Dark
Sodium sulfite;
6 N HC1 - pH < 2;
Cool 4°C (± 2°)
Sodium thiosulfate;
Cool 4°C (± 2°); Dark
Sodium thiosulfate;
6 N HC1 - pH < 2;
Cool 4°C (± 2°); Dark
Sodium thiosulfate;
Cool 4° C (± 2°);
Dark
Sodium sulfite;
Maintain < 10° C for
no longer than first 48
hrs (during shipment),
then <6° C; Dark
Ascorbic acid or
Sodium thiosulfate;
l:lHCl-pH<2;
Cool 4° C (± 2°)
Sodium sulfite;
6 N HC1 - pH < 2;
Cool 4° C (± 2°);
Dark
Sample
Holding
Time
7 days
14 days
14 days
14 days
14 days
14 days
14 days
14 days
Extract
Holding Time
14 days
(<6°C, Dark)
30 days
(<6°C,Dark)
28 days
(<6°C, Dark)
14 days
(<6°C,Dark)
14 days
(<6°C, Dark)
21 days
(<6°C,Dark)
Not Applicable
30 days from
extraction
(<6°C,Dark)
Sample
Size
1L
1L
1L
250 mL
50mL
125 mL
40 - 120 mL
1L
Container
Amber Glass
with PTFE-
lined Cap
Amber Glass
with PTFE-
lined Cap
Amber Glass
with PTFE-
lined Cap
Amber Glass
with PTFE-
lined Cap
Amber Glass
with PTFE-
lined Cap
Amber Glass
with PTFE-
lined Cap
Glass with
PTFE-lined
Septum
Amber Glass
with PTFE-
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
UCMR (1999) List 2 Screening Survey for Chemical Contaminants
Table 3.2 provides a summary of the preservation and holding times for approved analytical
methods for UCMR (1999) List 2 chemical contaminants. 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)(ii)(F)).
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3.2.1 Semi-Volatile Organic Compounds
There are seven UCMR (1999) List 2 semi-volatile contaminants, diazinon, 2,4 dichlorophenol,
1,2 diphenolhydrazine, disulfoton, fonofos, prometon, and terbufos, that may be analyzed using
EPA Method 526. For reference, see EPA Method 526 - Determination of Selected Semi-volatile
Organic Compounds in Drinking Water by Solid Phase Extraction and Capillary Column Gas
Chromatography/Mass Spectrometry (GC/MS). A copy of the method can be obtained at:
http://www.epa.gov/safewater/methods/526.pdfor in, "Methods for the Determination of
Organic and Inorganic Compounds in Drinking Water" EPA 815-R-00-014, August 2000.
General sampling procedures, based on EPA Method 526, including sample containers, and
dechlorination, and sample collection, preservation, storage, and holding times, are described
below.
EPA Method 526 - Determination of Selected Semi-volatile Organic Compounds in Drinking
Water by Solid Phase Extraction and Capillary Column Gas Chromatography/Mass
Spectrometry (GC/MS)
Sample containers - Use one-liter or one-quart amber or clear glass bottles fitted with PTFE-
lined screw caps. The bottle should be washed and dried as described in Section 4.1 of the EPA
Method to minimize contamination. 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 - It is important that sodium thiosulfate and sodium sulfite not be used
as they have been found to degrade target analytes. To dechlorinate a sample, add 100
milligrams of ascorbic acid to sample container prior to collection. This is typically best done by
adding the preservative salt to the sample container as part of the sampling kit preparation
process at the laboratory prior to delivery of the kit to the field sampling site. After samples have
been received, laboratories should employ a N,N-diethyl-/»-phenylenediamine (DPD) test kit to
confirm proper sample dechlorination. When effectively dechlorinated, no immediate red color
change should be evident.
Sample preservation - Along with ascorbic acid for dechlorination, three other preservation
reagents must be added to each sample bottle prior to shipment to the field. 350 milligrams per
liter of ethylenediaminetetraacetic acid (EDTA) trisodium salt to inhibit metal-catalyzed
hydrolysis of target analytes, 1000 milligrams per liter of diazolidinyl urea must be added to
inhibit biodegradation of the analytes, and each sample collected must be buffered to a pH of 7
using a mixture of 470 milligrams/L of tris(hydroxymethyl)aminomethane and 7.28 g/L of
tris(hydroxymethyl)aminomethane hydrochloride. Alternately, 7.75 g/L of a commercial buffer
crystal mixture of these constituents blended in the aforementioned proportions can be
substituted.
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. Adjust the flow from the tap to a slow but steady stream (about the diameter of a
pencil). Collect the sample from the flowing stream taking care not to flush out sample
preservation agents. Sampling equipment must be free of plastic tubing, gaskets, and other parts
that may leach interfering analytes into the water sample (§141.40 Appendix A).
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After the sample bottle has been filled to almost overflowing, cap the bottle (PTFE face down),
and invert three or four times until preservatives are dissolved.
Sample storage - All samples should be iced during shipment, or shipped with frozen cold
packs. Laboratories should confirm that samples arrive within 48 hours of collection and are
< 10° C upon receipt. Samples stored in the laboratory must be held at or below 6° C until
extraction but should not be frozen.
Sample holding time - Extract samples within 14 days of sample collection. Results of the
holding time and storage study of all method contaminants show that most are stable for 14 days
in water samples when the samples are dechlorinated, preserved, and stored as described above.
If samples are not extracted within this holding period, discard and replace the samples.
Sample extract holding time - Analyze extracts within 28 days. Sample extracts must be stored
at 0° C or less and analyzed within 28 days after extraction. If samples are not extracted within
this period, discard and replace the samples. (See Table 3.2 for a summary of holding times for
List 2 analytical methods.)
3.2.2 Phenols
There are four UCMR (1999) List 2 phenolic contaminants, 2-methyl-phenol, 2,4
dichlorophenol, 2,4 dinitrophenol, and 2,4,6 trichlorophenol, that may be analyzed using EPA
Method 528. For reference, see EPA Method 528 - Determination of Phenols in Drinking Water
by Solid Phase Extraction and Capillary Column Gas Chromatography/Mass Spectrometry
(GC/MS). A copy of the Method can be obtained at: http://www.epa.gov/nerlcwww/m_528.pdf
or in, "Methods for the Determination of Organic and Inorganic Compounds in Drinking
Water" EPA 815-R-00-014, August 2000. It is important that samples be stored or extracted in
areas free of airborne phenols. General sampling procedures, based on this EPA Method,
including sample containers, and dechlorination, and sample collection, preservation, storage,
and holding times are described below.
EPA Method 528 - Determination of Phenols in Drinking Water by Solid Phase Extraction and
Capillary Column Gas Chromatography/Mass Spectrometry (GC/MS)
Sample container - Use one-liter amber glass bottles with PTFE-lined screw caps. Amber
bottles should be used because method analytes are sensitive to light and may degrade upon
exposure. All glassware must be cleaned and dried according to Section 6.1 of the EPA Method.
Phenolic resin bottle caps should be avoided due to possible contamination.
Sample dechlorination - To dechlorinate the sample, add 40-50 milligrams of sodium sulfite to
the sample bottle prior to transportation to the field or at time of collection. This is typically best
done by adding the preservative salt to the sample container as part of the sampling kit
preparation process at the laboratory prior to delivery of the kit to the field sampling site. After
samples have been received, laboratories should employ a N,N-diethyl-/?-phenylenediamine
(DPD) test kit to confirm proper sample dechlorination. When effectively dechlorinated, no
immediate red color change should be evident.
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
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. 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. Take care not to allow any plastic
tubings, gaskets, and other parts to leach interfering analytes into the sample. Sampling
equipment must be free of plastic tubing, gaskets, and other parts that may leach interfering
analytes into the water sample (§141.40 Appendix A).
The sample should fill the one-liter bottle to almost overflowing, but take care not to flush out
any dechlorination chemicals that are in the sample bottle. After the sample bottle has been
filled, close the bottle (PTFE 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 level of 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, the sample is adjusted to less than pH 2 by using 4 mL of 6 N
hydrochloric acid. This serves to retard microbiological degradation of the contaminants in the
water. Keep sample bottles sealed from collection time until analysis. After sample have been
received, laboratories should use a pH meter or pH test strip to confirm the sample was properly
acidified to pH of 2 or less.
Sample storage - All samples should be iced during shipment, or shipped with frozen cold
packs. Laboratories should confirm that samples arrive within 48 hours of collection and are
< 10° C upon receipt. Samples stored in the laboratory must be held at or below 6° C until
extraction but should not be frozen.
Sample holding time - Extract samples within 14 days of collection. According to results of
holding time studies of all method analytes, samples that are dechlorinated, preserved, and stored
as described above, will remain stable for 14 days. Samples must be extracted within 14 days of
collection. If samples are not analyzed within this period, discard and replace the samples.
Sample extract holding time - Analyze sample extracts within 30 days. Extracted samples must
be analyzed within 30 days after extraction when stored at 0° C or less. If sample extracts are not
analyzed within this period, discard and replace the samples. (See Table 3.2 for a summary of
holding times for List 2 analytical methods.)
3.2.3 Phenylureas
The two UCMR (1999) List 2 phenylurea compounds, diuron and linuron, may be analyzed using
EPA Method 532. For reference, see EPA Method 532 - Determination of Phenylurea
Compounds in Drinking Water by Solid Phase Extraction and High Performance Liquid
Chromatography with UVDetection. A copy of the Method can be obtained at:
http://www.epa.gov/safewater/methods/532.pdfor in, "Methods for the Determination of
Organic and Inorganic Compounds in Drinking Water" EPA 815-R-00-014, August 2000.
General sampling procedures based on this method, including sample containers, dechlorination,
and sample collection, preservation, storage, and holding times, are described below.
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EPA Method 532 - Determination ofPhenylurea Compounds in Drinking Water by Solid Phase
Extraction and High Performance Liquid Chromatography with UV Detection
Sample containers - Use a 500 milliliter clear or amber glass container fitted with a PTFE-lined
screw cap. Sample containers should be cleaned according to the procedures outlined in Section
4.1 of Method 532.
Sample dechlorination - To dechlorinate the sample, add 2.5 grams of Trizma crystals (a
premixed blend of Tris [Tris(hydroxymethyl)aminomethane] and Tris HCL [Tris(hydroxymethyl)
aminomethane hydrochloride] prior to shipment to the field. The Trizma crystals should be
added to the sample bottles in solid form due to the uncertainty of its stability in concentrated
aqueous solution.
Sample preservation - Each 500 milliliter sample bottle must contain 250 milligrams of cupric
sulfate as a means of inhibiting microbiological decay of method analytes. Cupric sulfate must
be added prior to shipment to the field along with the Trizma crystals used for dechlorination.
Additional reagents to change the sample pH are unnecessary due to the buffering capabilities of
the Trizma crystals.
Sample collection - When sampling from a water tap, remove any aeration equipment, open the
tap and allow the system to flush until the temperature has stabilized, usually about two minutes.
Collect the sample directly from the 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 the
samples from the flowing stream. Sampling equipment 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 bottle 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.
Sample storage - All samples should be iced during shipment, or shipped with frozen cold
packs. Laboratories should confirm that samples arrive within 48 hours of collection and are
< 10° C upon receipt. Samples stored in the laboratory must be held at or below 6° C until
extraction but should not be frozen.
Sample holding time - Extract samples within 14 days. Preservation study results indicated that
most method analytes were stable for 14 days when stored under these conditions. Samples that
are not extracted within this period must be discarded and replaced with new samples.
Sample extract holding time - Analyze sample extracts within 21 days of extraction. Sample
extracts may be stored in methanol at 0° C or less for up to 21 days after extraction. Samples that
are exchanged into reagent water/acetonitrile (60/40) for confirmational analysis may be stored
for up to 7 days at 0° C. The combined extract holding time may not exceed 21 days. If sample
extracts are not analyzed within this period, discard and replace the samples. (See Table 3.2 for a
summary of holding times for List 2 analytical methods.)
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Table 3.2 Preservation and Holding Times for Approved UCMR (1999) List 2
Analytical Methods
Method(s)
EPA 526
EPA 528
EPA 532
Preservation
Ascorbic acid; EDTA
trisodium salt;
Diazolindinyl urea;
crystal mixture
(tris(hydroxymethyl)
aminomethane and
tris(hydroxymethyl)
aminomethane
hydrochloride)- pH =
7; Maintain < 10° C for
no longer than first 48
hrs (during shipment),
then <6° C
Sodium Sulfite;
6 N HCL - pH < 2;
Maintain < 10° C for no
longer than first 48 hrs
(during shipment), then
<6°C
Trizma crystals;
Cupric Sulfate
Maintain < 10° C for no
longer than first 48 hrs
(during shipment), then
<6°C
Sample
Holding
Time
14 Days
14 Days
14 Days
Extract
Holding Time
28 days at 0° C
30 days at 0° C
21 days at 0° C
Sample
Size
1 L or Iqt
1L
500 mL
Container
Amber or Clear
Glass with
PTFE-lined Cap
Amber Glass
with PTFE-
lined Cap
Amber or Clear
Glass with
PTFE-lined Cap
Note: EPA = EPA Methods
See Table 1.6 for the full reference for each analytical method.
3.3
Monitoring of Routine Water Quality Parameters
In the final UCMR Preamble and Rule (64 FR 50556), EPA required the monitoring of water
quality parameters (pH) when collecting samples for unregulated chemical contaminants. After
further evaluation of the UCMR Program, EPA believes that analyzing the pH of finished
drinking water will not provide relevant data on chemical contaminant occurrence. While pH is
important when monitoring raw water, finished water goes through many treatments that can
alter pH. For many systems, even if pH were a significant factor in determining the fate of a
particular contaminant reaching the drinking-water supply, such correlations are lost in the
finished water by the purposeful adjustment of the pH. Having pH as a water quality parameter
for chemical contaminants would be of limited use. Therefore, EPA has eliminated the
monitoring of pH for chemical contaminants (§141.40(a)(4)(i)(B)) and has only retained the
requirement for water quality parameters for UCMR microbial contaminant monitoring.
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Section 4. Sample Transport
4.1 UCMR (1999) List 1 contaminants
Immediately after sample collection, place all UCMR (1999) List 1 samples (see below for
perchlorate sample exception), 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 stored at 4°C (± 2°)
during shipment and upon receipt at the laboratory. Do not let any samples freeze (§141.40
Appendix A). If transporting samples to an off-site laboratory, pack samples in insulated
containers or coolers carefully to protect against sample bottle breakage during transport.
Perchlorate samples using EPA Method 314.0 do not need to be shipped in ice or stored cold in a
refrigerator, but every effort should be taken to protect the samples from temperature extremes.
As all other UCMR (1999) List 1 samples must be refrigerated (§141.40 (a)(5)), samples for EPA
Method 314.0 may be placed with other UCMR samples on ice or with frozen cold packs in a
cooler, or placed in a refrigerator that can maintain the samples at 4°C (± 2°). Samples should
not be allowed to freeze, and should be protected from extreme temperatures from the time of
collection until analysis.
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. All samples, except perchlorate, must be processed (meaning either
extracted or analyzed when exclusively applied to methods where no extraction is performed) by
the laboratory within 7 to 14 days of sample collection depending on which respective method is
being used. Therefore, provide adequate time for sample pick-up, transport, delivery, extraction,
and analysis (§141.40 Appendix A). Immediate (i.e., 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 ideal. Overnight
delivery to the laboratory is strongly recommended in order to maintain proper temperature
conditions.
4.2 UCMR (1999) List 2 Chemical Contaminants
All UCMR (1999) List 2 samples collected for chemical contaminants must follow the same
procedures as those previously mentioned for the UCMR (1999) List 1 contaminants (§141.40
Appendix A). However, samples collected for all UCMR (1999) List 2 chemical contaminants
must be received at the lab at 10°C or below for sample transport. In the laboratory, all UCMR
(1999) List 2 samples must be stored at 4°C (± 2°) and must be extracted within 14 days of
sample collection (§141.40 Appendix A).
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Section 5. UCMR Quality Control Requirements
Several methods approved by EPA for UCMR monitoring are currently used for compliance
monitoring. As a result, mechanisms for reviewing laboratory qualifications and establishing
certification for use of these methods are already in place in all states which have primacy over
compliance monitoring to meet National Primary Drinking Water Standards (NPDWSs).
Laboratories are approved to provide data to EPA in support of the UCMR using these methods
if they are currently certified by a State or primacy agency to perform these analytical methods
forNPDWS compliance (§141.40(a)(5)(ii)(G)).
Monitoring for perchlorate, by EPA Method 314.0, has special laboratory approval requirements
(§141.40(a)(5)(ii)(G)). While many of the QC requirements listed in EPA Method 314.0 are the
same as those required for the UCMR, there are a few minor modifications that have been noted
in this manual. In addition, QC requirements unique to EPA Method 314.0 are discussed in
Section 5.10.
UCMR approval for the List 2 chemical screening methods is also built on existing state or
primacy certification. Approval to use EPA Methods 526 and 528 is contingent upon
certification in EPA Method 525.2. UCMR approval to use EPA Method 532, is contingent
upon certification in EPA Method 549.1 or 549.2.(§141.40(a)(5)(ii)(G)).
Approval for EPA Method 515.4 for Assessment Monitoring of the List 1 contaminants DCPA
mono-acid and di-acid DCPA degradates is contingent upon certification in EPA Method 515.3.
UCMR Assessment Monitoring and the Screening Survey for chemical contaminants must be
conducted using only the analytical methods specified in the UCMR (see Tables 1.5 and 1.6;
§141.40(a)(5)). The QC procedures specified in Appendix A of the Rule as well as those
additionally listed in the approved analytical methods are further described in this Manual and
must be followed to ensure accurate and precise data (§141.40 Appendix A). In cases where a
conflict exists between the specifications listed in Appendix A of the Rule and the criteria
identified in the approved analytical method, the Rule defined criteria takes precedent as the
defined QC requirement.
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 are justifiable
circumstances for excluding monitoring data 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
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contaminants detected in the laboratory reagent (method) blank at
concentrations equal to or greater 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.
5.1 Minimum Reporting Level
The minimum reporting level (MRL) concentrations for the UCMR (1999) List 1 Assessment
Monitoring are listed in Table 5.1. They were determined by multiplying by 10 the least
sensitive method's minimum detection limit (MDL),6 or, when available, multiplying by 5 the
least sensitive method's estimated detection limit (EDL)7. 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). The MRLs for perchlorate and
acetochlor were established at a concentration at which acceptable precision and accuracy has
been demonstrated in spiked matrix samples and which is at least l/4th the lowest known adverse
health concentration.
The MRL for the UCMR (1999) List 2 Screening Survey for chemical contaminants are listed in
Table 5.1.2. They represent the value of the lowest concentration at which precision and
accuracy determination were made during methods development and which are documented in
the method. If method options are permitted, the concentration used was for the least sensitive
option.
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).
The MDL equals the standard deviation times the Student's t value for 99% confidence level with n-1
degrees of freedom, where n is the number of replicates samples.
The EDL equals the concentration of compound yielding approximately a five to one signal to noise ratio or
the calculated MDL, whichever is greater.
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Table 5.1 UCMR (1999) List 1 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; D 5812-96;
990.06
EPA 525. 2
EPA 515.1; EPA 515.2; EPA 515.3; EPA
515.4; D 5317-93; 992.32
EPA 507; EPA 525.2; D 5475-93; 991.07
EPA 507; EPA 525.2; D 5475-93; 991.07
EPA 502.2; EPA 524.2; D 5790-95; SM
6210D; SM 6200B; SM 6200C
EPA 524.2; D 5790-95; SM 6210D; SM 6200B
EPA 3 14.0
EPA 507; EPA 525.2; D 5475-93; 991.07
Minimum Reporting
Level
2Mg/L*
2Mg/La
0.8 ng/L a
2 Mg/Lb
l^g/La
l^ig/L3
0.9(ig/La
5^g/Lc
10Mg/Lc
4 Mg/Lb
2^g/La
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.
a Minimum reporting level (MRL) determined by multiplying by 10 the least sensitive method's minimum
detection limit (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).
b MRL was established at a concentration, which is at least l/4th the lowest known adverse health
concentration, at which acceptable precision and accuracy has been demonstrated in spiked matrix samples.
0 MRL for VOCs determined by multiplying by 10 either the published MDL or 0.5 (ig/L, whichever is
greater. The MDL of 0.5 ug/L (0.0005 mg/L) was selected to conform to the VOC MDL requirements of
40 CFR 141.24(f)(17)(i)(E).
Table 5.1.1 UCMR (1999) List 2 Methods and Minimum Reporting Levels
Contaminant
1 ,2-Diphenylhydrazine
2-Methyl-phenol
Approved UCMR Analytical
Methods
EPA 526
EPA 528
Minimum Reporting
Level
0.5 Mg/La
1 Mg/La
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Contaminant
2,4-Dichlorophenol
2,4-Dinitrophenol
2,4,6-Trichlorophenol
Diazinon
Disulfoton
Diuron
Fonofos
Linuron
Nitrobenzene
Prometon
Terbufos
Approved UCMR Analytical
Methods
EPA 528
EPA 528
EPA 528
EPA 526
EPA 526
EPA 532
EPA 526
EPA 532
EPA 526
EPA 526
EPA 526
Minimum Reporting
Level
l^g/La
5 Mg/L a
1 Mg/La
0.5 Mg/La
0.5 Mg/La
1 Mg/La
0.5 Mg/L a
1 Mg/La
0.5 Mg/La
0.5 Mg/La
0.5 ng/La
Note: EPA = EPA Methods
a Minimum Reporting Level represents the value of the lowest concentration precision and accuracy
determination made during methods development and documented in the method. If method options are
permitted, the concentration used was for the least sensitive option.
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 gas
chromatographic/mass spectrometry (GC/MS) methods, which include EPA Methods 524.2,
525.2, 526, and 528 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
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
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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
Laboratories are not required to establish, on a daily basis, completely new calibration curves.
However, the analyst must periodically verify calibration during sample analysis to ensure
accuracy of the analytical results (§141.40 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 (1999) List 1
and List 2 methods and are presented in Table 5.2 and 5.5, respectively (§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 A). Based
on the recommendations from technical experts experienced with these methods, EPA is
specifying calibration verification at low- (MRL level) and mid- levels for each method.
Analysis of the low-level calibration check standard (at or below the UCMR analyte MRL) must
be completed prior to analysis of any samples; each contaminant must meet the acceptance
criteria provided in Table 5.3 for UCMR (1999) List 1 contaminants and in Table 5.6 for the
UCMR (1999) List 2 contaminants (§141.40 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.
For all methods, after analyses of no more than 10 UCMR samples (not including method blanks,
shipping blanks, matrix spikes (MSs), matrix spike duplicates (MSDs), and any independent QC
samples that are analyzed with the UCMR samples), the calibration curve must be verified using
either a low- or mid-level continuing calibration check standard; each contaminant must meet the
respective acceptance criteria listed in Tables 5.3, 5.4, 5.6, or 5.7 (§141.40 Appendix A). If the
criteria are 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 contaminant(s) are considered invalid for those samples and should not be
reported to EPA.
It is important to note that an analysis batch for EPA Method 314.0 is defined as a sequence of
samples which are analyzed within a 30-hour period and include no more than 20 field samples.
The 30-hour period begins with the analysis of the instrument performance check (IPC) standard
(see EPA Method 314.0 and Section 5.10.2.2), and ends with the analysis of the end calibration
check standard. The 30-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 30-hour period still begins with the analysis of the IPC standard.
For EPA Method 314.0, unlike all other methods currently approved for UCMR monitoring, the
method specifically requires the analyst to alternate between mid- and high-level calibration
check standards (rather than low- and mid- level standards) every 10 field samples
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(§141.40(a)(5)). This is the specification listed in the method and contradicts the regulatory
prescribed low- and mid-levels. In addition, the acceptance criteria identified in method 314.0
are tighter than that which is listed in Appendix A of the Rule. To be consistent with the
specifications of the regulation, Appendix A, EPA will accept the more liberal regulatory defined
criteria for acceptance limits on calibration check standards and expects laboratories to alternate
calibration check standards between the low- and mid- levels (data collected with the method
prescribed initial low- followed by alternating mid- and high- calibration standards will not be
rejected).
It is important to note that an acceptable end calibration check standard is highly recommended
at the conclusion of the analysis batch after the analysis of the last field sample. This end
calibration check can be at the low-level or the mid-level and should meet the respective
acceptance criteria listed in Tables 5.3, 5.4, 5.6, or 5.7. This end calibration check standard
might be analyzed soon after the previous calibration check standard as a result of a limited
number (less than ten) of remaining field samples, but it will serve to validate the calibration at
the very end of the analysis batch.
5.3 Detection Limit
The detection limit 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 detection limit concentration are considered qualitative, because
they are not precise enough to meet the needs of the data user. The initial calibration check
standard in a laboratory analysis batch must be conducted at or below this regulatory defined
MRL level and this demonstrates the laboratory's capability to accurately quantify at the MRL
level. In order to ensure that the UCMR data is the highest in quality, do not report data to EPA
below the statutory MRLs (Tables 5.1 and 5.1.1).
Laboratories should refer to the detection limit calculations in each method rather than in CFR
136 Appendix B (§141.40 Appendix A).
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Table 5.2 UCMR (1999) List 1 Frequency Requirements for Verifying Calibration
Methods
EPA 3 14.0
EPA 502.2
SM 6200 C
EPA 507
D 5475-93
991.07
EPA 508
D 5812-96
990.06
EPA 508.1
EPA 515.1
D 53 17-93
992.32
EPA 5 15.2
EPA 5 15.3
EPA 5 15.4
EPA 524.2
D 5790-95
SM 6200 B
SM6210D
EPA 525. 2
Method Specifications
Analyze low-level standard at beginning; alternate between
mid and high level standards after each 10 samples;
analyze standard after last sample. Analysis batch should
not exceed 20 samples or 30 hours
Minimum of 1 CCC in a 12 hour shift; recommend
analyzing CCC at beginning and end of shift and
periodically in between
Analyze CCC every 10 samples or every 12 hours -
whichever is more frequent (6200 A.5.b.2)
Beginning and end of each workday; recommend
periodically during the day
Beginning of each workday; recommend after every 10
samples or at the end of workday
lor 2 CCC daily
Beginning and end of each workday; recommend
periodically during the day
1 or 2 CCC daily
Minimum of 1 CCC in a 12 hour shift; recommend
periodically analyzing during and at end of shift
Beginning and end of each workday; recommend
periodically during the day
Minimum of 1 CCC in a 12 hour shift; recommend
beginning and end of workday
Beginning each batch, after every 10 samples, and after
last sample in batch
Within a 24 hour period: At the beginning, after every 10
samples, and after last sample
Minimum of 1 CCC at the beginning of each 12 hour shift;
recommend periodically analyzing during the shift and at
the end
Minimum of 1 CCC at the beginning of each 12 hour shift
Analyze CCC every 20 samples or every 12 hours -
whichever is more frequent (6200 A.5.b.2)
Calibrate system daily (6210 C.5.c)
Minimum of 1 CCC at the beginning of each 12 hour shift
UCMR
Specifications
Analyze low-level
standard at beginning;
alternate between mid-
and low-level
standards after each 10
samples
Recommend analyzing
a standard after last
sample, if not
specifically required by
method
Note 1: 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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Table 5.3 UCMR (1999) List 1 Low-Level Calibration Check Standard
Concentrations and Acceptance Criteria
Contaminant
2,4-Dinitrotoluene
2,6-Dinitrotoluene
4,4'-DDE
Acetochlor
DCPA mono- and di-acid degradates
EPTC
Molinate
MTBE
Nitrobenzene
Perchlorate
Terbacil
MRL, jig/L
2
2
0.8
2
1
1
0.9
5
10
4
2
Concentration of
Low-Level Standard
< MRL
< MRL
< MRL
< MRL
< MRL
< MRL
< MRL
< MRL
< MRL
< MRL
< MRL
Acceptance
Criteria
± 40 %
± 40 %
± 40 %
± 40 %
± 40 %
± 40 %
± 40 %
± 40 %
± 40 %
± 40 %
± 40 %
Table 5.4 UCMR (1999) List 1 Mid-Level Calibration Check Standard Concentrations
and Acceptance Criteria
Contaminant
2,4-Dinitrotoluene
2,6-Dinitrotoluene
4,4'-DDE
Acetochlor
DCPA mono- and di-acid degradates
EPTC
Molinate
Mid-Level Standard
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
Acceptance
Criteria
± 20 %
± 20 %
± 20 %
± 20 %
± 20 %
± 20 %
± 20 %
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Contaminant
MTBE
Nitrobenzene
Perchlorate
Terbacil
Mid-Level Standard
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
Acceptance
Criteria
± 20 %
± 20 %
± 20 %
± 20 %
Table 5.5 UCMR (1999) List 2 Frequency Requirements for Verifying Calibration
Methods
EPA 526
EPA 528
EPA 532
Method Specifications
Within a 24 hour period: At the
beginning, after every 10 samples,
and after last sample
Within a 24 hour period: At the
beginning, after every 10 samples,
and after last sample
Within a 24 hour period: At the
beginning, after every 10 samples,
and after last sample
UCMR Specifications
Analyze low-level standard at
beginning; alternate between mid-
and low-level standards after each 10
samples
As specified in these methods-
analyze a standard after last sample
Note: EPA = EPA Methods. See Table 1.6 for the full reference for each analytical method
Table 5.6 UCMR (1999) List 2 Low-Level Calibration Check Standard
Concentrations and Acceptance Criteria
Contaminant
1 ,2-Diphenylhydrazine
2-Methyl-phenol
2,4-Dichlorophenol
2,4-Dinitrophenol
2,4,6-Trichlorophenol
Diazinon
MRL, ug/L
0.5
1
1
5
1
0.5
Concentration of
Low-Level
Standard
< MRL
< MRL
< MRL
< MRL
< MRL
< MRL
Acceptance
Criteria
± 40 %
± 40 %
± 40 %
± 40 %
± 40 %
± 40 %
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Contaminant
Disulfoton
Diuron
Fonofos
Linuron
Nitrobenzene
Prometon
Terbufos
MRL, ug/L
0.5
1
0.5
1
0.5
0.5
0.5
Concentration of
Low-Level
Standard
< MRL
< MRL
< MRL
< MRL
< MRL
< MRL
< MRL
Acceptance
Criteria
± 40 %
± 40 %
± 40 %
± 40 %
± 40 %
± 40 %
± 40 %
Table 5.7 UCMR (1999) List 2 Mid-Level Calibration Check Standard
Concentrations and Acceptance Criteria
Contaminant
1 ,2-Diphenylhydrazine
2-Methyl-phenol
2,4-Dichlorophenol
2,4-Dinitrophenol
2,4,6-Trichlorophenol
Diazinon
Disulfoton
Diuron
Fonofos
Linuron
Nitrobenzene
Prometon
Terbufos
Mid-Level Standard
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
middle of calibration range
Acceptance
Criteria
± 20 %
± 20 %
± 20 %
± 20 %
± 20 %
± 20 %
± 20 %
± 20 %
± 20 %
± 20 %
± 20 %
± 20 %
± 20 %
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
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 UCMR Assessment Monitoring and
the Screening Survey for chemical contaminants are listed in Tables 5.8 and 5.10 (§141.40
Appendix A). To meet the objectives of the UCMR, analyze the method blank as the first
sample on the 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)
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. It is strongly recommended, when not
specifically a method requirement, that extraction batches contain a maximum of 20 UCMR
samples, not including method blanks, shipping blanks, any independent QC samples, matrix
spike samples and matrix spike duplicate 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, 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. When samples are invalided, the lab should notify the client PWS regarding
the QC failure and attempt to collect a replacement sample for the analysis within 14 days after
the QC error was found (§141.40(a)(5)(ii)(F)).
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. It is due to this concern that EPA strongly recommends
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limiting the extraction batch to 20 UCMR samples in order to minimize the number of samples
that could be potentially lost as a consequence of a blank contamination problem.
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.
For EPA Method 314.0, the method blank must be analyzed as the first sample on the instrument
(immediately following the IPC standard.) This differs slightly from all other methods approved
for use under the UCMR, as the method blank for EPA Method 314.0 is analyzed immediately
before, rather than immediately after, the ICCS.
For EPA Method 314.0, a second method blank may need to be prepared and analyzed if sample
matrices have been pretreated to reduce the risk of high common anion interference. QC
procedures related to the pretreatment of samples for EPA Method 314.0 are explained further in
Method 314.0 and Section 5.10.2.3 of this Manual. Analysis of a pretreated method blank is
necessary to confirm that no background effects from the pretreatment process are present. If an
analysis batch contains only pretreated samples, then only a pretreated method blank is required
(§141.40(a)(5)).
Table 5.8 UCMR (1999) List 1 Frequency Requirements for Analyzing Laboratory
Reagent (Method) Blanks
Method
EPA 3 14.0
EPA 502.2
SM 6200C
EPA 507
D 5475-93
991.07
EPA 508
D 5812-96
990.06
EPA 508.1
EPA 515.1
D 53 17-93
992.32
EPA 5 15.2
Method Specifications
1 per analysis batch (<20 samples) a
1 per analysis batch
1 per extraction batch or if reagents
changed
1 per extraction batch or if reagents
changed
Frequency not specified
1 per extraction batch processed in a 12
hour shift or with new batch of disks,
cartridges, or new supply of reagents
1 per extraction batch processed in a
work shift or if reagents changed
1 per extraction batch processed in a
work shift or if reagents changed
UCMR Specifications
1 per analysis batch (<20 samples) a
1 per sample analysis batch
1 per sample extraction batch
1 per sample extraction batch
1 per sample extraction batch
1 per sample extraction batch
1 per sample extraction batch
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Method
EPA 5 15.3
EPA 5 15.4
EPA 524.2
D 5790-95
SM6210D
SM 6200 B
EPA 525. 2
Method Specifications
1 per extraction batch or if reagents
changed
Daily or 1 per extraction batch (<20
samples whichever is greater)
1 per batch in a work shift
1 each day
1 each sample batch
1 per extraction batch in a 12 hour shift
UCMR Specifications
1 per sample extraction batch
1 per sample extraction batch
(<20 samples)
1 per sample analysis batch
1 per sample extraction batch
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.
a As required in EPA Method 314.0 and for the UCMR, a pretreated method blank may need to be prepared and
analyzed if a sample matrix has been pretreated to reduce the risk of high common anion interference
(§141.40(a)(5)).
Table 5.9 UCMR (1999) List 1 Acceptance Criteria for Laboratory Reagent
(Method) Blanks
Contaminant
2,4-Dinitrotoluene
2,6-Dinitrotoluene
4,4'-DDE
Acetochlor
DCPA mono- and di-acid
degradates
EPTC
Molinate
MTBE
Nitrobenzene
Perchlorate
Terbacil
Minimum Reporting
Level, jig/L
2
2
0.8
2
1
1
0.9
5
10
4
2
Maximum Allowable Background
Concentration (<. Y2 MRL), ug/L
< 1
< 1
< 0.4
< 1
< 0.5
< 0.5
<0.45
< 2.5
< 5
< 2
< 1
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Table 5.10 UCMR (1999) List 2 Frequency Requirements for Analyzing Laboratory
Reagent (Method) Blanks
Method
EPA 526
EPA 528
EPA 532
Method Specifications
Daily, or 1 per sample batch (<20 samples),
whichever is more frequent
Daily, or 1 per sample batch (<20 samples),
whichever is more frequent
1 per sample batch (<20 samples)
UCMR Specifications
Same as method
Same as method
Same as method
Note: EPA = EPA Methods. See Table 1.6 for the full reference for each analytical method.
Table 5.11 UCMR (1999) List 2 Acceptance Criteria for Laboratory Reagent
(Method) Blanks
Contaminant
1 ,2-Diphenylhydrazine
2-Methyl-phenol
2,4-Dichlorophenol
2,4-Dinitrophenol
2,4,6-Trichlorophenol
Diazinon
Disulfoton
Diuron
Fonofos
Linuron
Nitrobenzene
Prometon
Terbufos
Minimum Reporting
Level, ug/L
0.5
1
1
5
1
0.5
0.5
1
0.5
1
0.5
0.5
0.5
Maximum Allowable Background
Concentration (<. 1A MRL), jig/L
0.25
0.5
0.5
2.5
0.5
0.25
0.25
0.5
0.25
0.5
0.25
0.25
0.25
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
5.4.1 Field Reagent Blank (Shipping or Travel Blank)
In EPA Methods 524.2 and 502.2, and ASTM D 5790-05 (but also recommended for SM 6210 or
SM 6200 B and SM 6200 C) are specifications for the preparation, transport, and possible
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). If no positive is measured for either MTBE or nitrobenzene in the
sample analyzed by the respective method, the field reagent blank does not need to be analyzed.
This blank is an aliquot of reagent water or other blank matrix that is placed in a sample
container in the laboratory and treated as a sample in all respects, including shipment to the
sampling site, storage, preservation, and all analytical procedures. The purpose of this blank is to
determine if method 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 in the field reagent blank, 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.
For EPA Method 314.0, a QC sample must be analyzed after initially establishing or re-
establishing a calibration curve or at least quarterly (§141.40 Appendix A). If the determined
concentrations are not within ± 10% of the stated values, performance of the determinative step
of the method is unacceptable. The source of the problem must be identified and corrected
before either proceeding with the initial demonstration of capability or continuing with on-going
analyses (§141.40(a)(4)).
5.6 Sample Matrix Spike and Matrix Spike Duplicate
Throughout this manual, the terms matrix spike (MS) and matrix spike duplicate (MSD) are
routinely used but several of the approved methods refer to these samples as Laboratory Fortified
Matrix (LFM) and Laboratory Fortified Matrix duplicate (LFM duplicate), respectively. Keep in
mind that these terms are interchangeable and are representative of the exact same type of
sample.
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, either replicate samples
are collected or, where sufficient volume was collected and target analytes are non-volatile, a
sample may be divided into two or more aliquots in the laboratory, and processed and analyzed
as separate samples. This technique is most useful when the original sample contains
background concentrations of the method contaminants.
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To effectively evaluate precision for UCMR contaminants, EPA is requiring preparation and
analysis of an MS and 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 a second identical fortified sample that has
been prepared in exactly the same manner as the MS. 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 if
there are any measurable concentrations of the contaminants in the unspiked sample matrix in a
separate sample analysis of the unfortified field sample.
Laboratories are required to prepare and analyze MS/MSD samples at the frequencies listed in
Table 5.12 for UCMR (1999) List 1 methods and Table 5.13 for UCMR (1999) List 2 methods
(§141.40 Appendix A). Laboratories are required to perform MS/MSD sample analyses on a
minimum of 5% of the UCMR samples (at least one per 20 samples) or with each sample batch,
whichever is more frequent (§141.40 Appendix A). For methods that involve extractions, select
a sample to use to prepare the MS/MSD pair. For methods which require a 1 L sample aliquot
(e.g., EPA 525.2, EPA 526, EPA 528) or the VOC methods (e.g., EPA 524.2), be certain to
collect at least triplicate samples of that respective matrix (quadruplicate are strongly
recommended since the fourth sample will function as a back-up for reanalysis). The triplicate
aliquots will provide sufficient volume for the initial unfortified sample analysis and the
MS/MSD pair. For some of the other methods, where multiple aliquots of sample can be drawn
from a single sample collection bottle and the contaminants are not volatile (e.g., EPA 314.0,
EPA 515.4), the laboratory may separate multiple aliquots from a single sample bottle in order to
prepare the unfortified sample and the MS/MSD pair. For methods that require sample
extraction, spike both the MS and the MSD with a known concentration of the contaminant(s)
prior to extraction. Process the unspiked sample and MS/MSD pair of samples through the entire
extraction and analysis process. For methods that do not involve extractions, spike both the MS
and the MSD with a known concentration of the contaminant(s) and analyze the unspiked sample
and MS/MSD pair of samples in the analysis batch.
Note: As described earlier, an extraction batch is defined as a set of samples prepared/extracted
together at the same time by the same person(s) during a work day. Therefore, 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 a batch with the
same batch of derivatizing agent. It is recommended that laboratories include no more than 20
UCMR samples in an extraction batch. Following extraction, the analysis batch is established as
the set of samples (or extracts) that are processed as a group during a continuous but limited time
period.
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Table 5.12 UCMR (1999) List 1 Frequency Requirements for Performing Spiked
Sample Analyses
Method
EPA 3 14.0
EPA 502.2
SM 6200 C
EPA 507
D 5475-93
991.07
EPA 508
D 5812-96
990.06
EPA 508.1
EPA 515.1
D 53 17-93
992.32
EPA 5 15.2
EPA 5 15.3
EPA 5 15.4
EPA 524.2
D 5790-95
SM6210D
SM 6200 B
EPA 525. 2
Method Specifications
1 per 20 samples or analysis batch,
whichever is more frequent
Not required
1 MS/MSD per batch
1 per 20 samples or each sample set,
whichever is greater
None specified
1 per 10 samples or each sample set,
whichever is greater
10% of samples or 1 per set whichever is
greater
None specified
1 per sample matrix
1 per 10 samples or each sample set,
whichever is greater
1 per 20 samples
1 per 10 samples or each sample set,
whichever is greater
1 per extraction set or 10% of samples
whichever is greater
1 per extraction batch (<20 samples)
Not required unless matrix effects
suspected
Specifies on-going analysis of samples
to known additions - no frequency
specified
1 per analysis batch
1 per extraction batch, 1 per 20 samples
UCMR Specifications
MS/MSD per 20 samples or per
analysis batch, whichever is more
frequent3; alternate low-, mid-level
MS/MSD per 20 samples or per
analysis batch, whichever is more
frequent3; alternate low-, mid-level
MS/MSD per 20 samples or per
extraction batch, whichever is more
frequent3; alternate low-, mid-level
MS/MSD per 20 samples or per
extraction batch, whichever is more
frequent3; alternate low-, mid-level
MS/MSD per 20 samples or per
extraction batch, whichever is more
frequent3; alternate low-, mid-level
MS/MSD per 20 samples or per
extraction batch, whichever is more
frequent3; alternate low-, mid-level
MS/MSD per 20 samples or per
extraction batch, whichever is more
frequent3; alternate low-, mid-level
MS/MSD per 20 samples or per
extraction batch, whichever is more
frequent3; alternate low-, mid-level
MS/MSD per 20 samples or per
extraction batch, whichever is more
frequent3; alternate low-, mid-level
MS/MSD per 20 samples or per
analysis batch, whichever is more
frequent3; alternate low-, mid-level
MS/MSD per 20 samples or per
batch, whichever is more frequent3;
alternate low-, mid-level
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 For example, if a batch contains 20 or fewer samples, then 1 MS/MSD set must be analyzed for that batch.
However, if a batch contains more than 20 samples, then at least two MS/MSD sets must be analyzed
(§141.40 Appendix A). For EPA Method 314.0 and 515.4, a batch may not contain more than 20 samples.
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Table 5.13 UCMR (1999) List 2 Requirements for Performing Spiked Sample
Analyses
Method
EPA 526
EPA 528
EPA 532
Method Specifications
1 per extraction batch of 20 samples or less
1 per extraction batch of 20 samples or less
1 per extraction batch of 20 samples or less
UCMR Specifications
Same as method
Same as method
Same as method
Note: EPA = EPA Methods. See Table 1.6 for the full reference for each analytical method.
The laboratory must choose a spiking concentration from one of the two concentrations listed in
Tables 5.14 and 5.15 for UCMR (1999) List 1 and List 2 contaminants, respectively (§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 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 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 the entire UCMR database as an aggregate. 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 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:
RPD =
x 100%
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RPD = Relative Percent Difference
TJ = 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 will be measured through the use of spiked matrix samples.
For the purposes of the UCMR, analytical accuracy is defined as the percent recovery of the
contaminant in the analyzed MS sample. To calculate the analytical accuracy, laboratories
should use the formula:
Percent Recovery =
x 100%
TJ = matrix spike (MS) analytical result
r3 = sample analytical result
s = spiking concentration of matrix spike
Table 5.14 UCMR (1999) List 1 Concentrations for Spiking MS/MSD Samples
Contaminant
2,4-Dinitrotoluene
2,6-Dinitrotoluene
4,4'-DDE
Acetochlor
DCPA mono- and di-acid
degradates
EPTC
Molinate
MTBE
Nitrobenzene
Perchlorate
Terbacil
Low-Level Spike
Concentration
2 (ig/L ± 20 %
2 (ig/L ± 20 %
0.8(ig/L±20%
2 (ig/L ± 20 %
1 (ig/L ± 20 %
1 (ig/L ± 20 %
0.9 (ig/L ± 20 %
5 (ig/L ± 20 %
10(ig/L±20%
4 (ig/L ± 20 %
2 (ig/L ± 20 %
Mid-Level Spike
Concentration, jig/L
± 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
± 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
± 20% of mid-level standard
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Table 5.15 UCMR (1999) List 2 Concentrations for Spiking MS/MSD Samples
Contaminant
1 ,2-Diphenylhydrazine
2-Methyl-phenol
2,4-Dichlorophenol
2,4-Dinitrophenol
2,4,6-Trichlorophenol
Diazinon
Disulfoton
Diuron
Fonofos
Linuron
Nitrobenzene (low level)
Prometon
Terbufos
Low-Level Spike
Concentration
0.5 ng/L ± 20 %
1 jig/L ± 20 %
1 jig/L ± 20 %
5 ng/L ± 20 %
1 jig/L ± 20 %
0.5 ng/L ± 20 %
0.5 ng/L ± 20 %
1 jig/L ± 20 %
0.5 ng/L ± 20 %
1 jig/L ± 20 %
0.5 ng/L ± 20 %
0.5 ng/L ± 20 %
0.5 ng/L ± 20 %
Mid-Level Spike
Concentration, ug/L
± 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
± 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
± 20 % of mid-level standard
± 20 % of mid-level standard
± 20 % of mid-level standard
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.
The methods 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 extraction (i.e., EPA
525.2), while other methods stipulate the addition to the sample extract prior to instrumental
analysis. Laboratories are required to follow the directions in the method when performing
analyses for the UCMR (§141.40 Appendix A).
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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 Tables 5.16 and 5.17.
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:
IS % Recovery =
Sample IS Detector Response
Calibration Curve Average IS Detector Response
x 100%
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.
Table 5.16 UCMR (1999) List 1 Criteria for Internal Standard Response
Method
EPA 3 14.0
EPA 502.2
SM 6200 C
EPA 507
D 5475-93
991.07
EPA 508
D 5812-96
990.06
EPA 508.1
EPA 515.1
D 53 17-93
992.32
EPA 5 15.2
Method Specifications
Not applicable
IS response should not deviate from the mean IS response
established with the calibration curve by more than 20%
IS response should not deviate from the mean IS response
established with the calibration curve by more than 30%
IS response should not deviate from the daily CCC IS
response by more than 30%
IS response should not deviate from the daily CCC IS
response by more than 30%
IS response should not deviate from the most recent CCC IS
response by more than 30% or from the mean IS response
established with the calibration curve by more than 50%
IS response should not deviate from the daily CCC IS
response by more than 30%
IS response should not deviate from the daily CCC IS
response by more than 30%
UCMR
Specifications
Same as method
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Method
EPA 5 15.3
EPA 5 15.4
EPA 524.2
D 5790-95
SM 6200 B
SM6210D
EPA 525 .2
Method Specifications
IS response should not deviate from the mean IS response
established with the calibration curve by more than 30%
IS response should not deviate from the mean IS response
established with the calibration curve by more than 50%
IS response should not deviate from the most recent CCC IS
response by more than 30% or from the mean IS response
established with the calibration curve by more than 50%
IS response should not deviate from the mean IS response
established with the calibration curve by more than 30%
No criteria listed in method
For CCCs, IS response should not deviate from the most
recent CCC IS response by more than 30% or from the mean
IS response established with the calibration curve by more
than 50%. (If a recovery standard is added to sample
extracts, then IS recovery should be in excess of 70%.)
UCMR
Specifications
Same as method
Same as method -
Labs should at a
minimum apply the
CCC criteria to all
analyses
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 5.17 UCMR (1999) List 2 Criteria for Internal Standard Response
Method
EPA 526
EPA 528
EPA 532
Method Specifications
IS response should not deviate from the mean IS response
established with the calibration curve by more than 50%
IS response should not deviate from the most recent CCC IS
response by more than 30% or from the mean IS response
established with the calibration curve by more than 50%
Not applicable
UCMR
Specifications
Same as method
Note: EPA = EPA Methods. See Table 1.6 for the full reference for each analytical method.
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
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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.
Tables 5.18 (UCMR (1999) List 1) and 5.19 (UCMR (1999) List 2) summarizes 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. The surrogate standards for EPA Methods 526, 528, and 532 are located in Sections
9.9, 9.10, and 9.7 of each method, respectively.
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:
0 , 0/ D Sample Surrogate Detector Response IAAO/
Surrogate % Recovery = *- e Ł x I00°/o
Calibration Curve Average Surrogate Detector Response
Some methods recommend preparing a calibration curve for the surrogate standard similar to the
preparation of a curve for each of the method contaminants. In those cases, the acceptance
criteria are given as percentage recovery which is determined using the following formula:
0 , 0/ D Measured Surrogate Concentration + AAO/
Surrogate % Recovery = e 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.
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Table 5.18 UCMR (1999) List 1 Requirements for Surrogate Standard Analyses
Method
EPA 3 14.0
EPA 502.2
SM 6200C
EPA 507
D 5475-93
991.07
EPA 508
990.06
D 5812-96
EPA 508.1
EPA 515.1
D 53 17-93
992.32
EPA 5 15.2
EPA 5 15.3
EPA 5 15.4
EPA 524.2
D 5790-95
SM 6200 B
SM6210D
EPA 525 .2
Method Specifications
Not Applicable
Surrogate recovery should be 80 - 120% of true value (9.3.3
and 9.7)
Surrogate recovery should be within ± 30% of true value
Surrogate recovery should be 70 - 130% of true value (9.5)
Surrogate recovery should be 70 - 130% of true value (9.5)
No criteria for surrogate recovery
Surrogate recovery should be 70 - 130% of true value
(9.3.5)
Surrogate recovery should be 70 - 130% of true value (10.5)
Surrogate recovery should be 60 - 140% of true value (9.5)
Surrogate recovery should be 70 - 130% of true value (9.8)
Surrogate recovery should be 70 - 130% of true value (9.8)
Surrogate response within 30% of mean response measured
in initial calibration curve (10.3.5)
Surrogate recovery between 70 - 130% of true value (14.3.3
- IDC requirement)
Surrogate recovery should be within ± 30% of true value
No criteria listed in method
Surrogate recovery should be 70 - 130% of true value (9.3.3
- IDC requirement)
UCMR
Specifications
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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Table 5.19 UCMR (1999) List 2 Requirements for Surrogate Standard Analyses
Method
EPA 526
EPA 528
EPA 532
Method Specified Surrogate Recovery
Surrogate recovery between 70 - 130% (9.9)
Surrogate recovery between 70 - 130% except for 2,4,6-
tribromophenol which is between 60 - 130% (9.10)
Surrogate recovery between 70 - 130% (9.7)
UCMR
Specifications
Same as method
Note: EPA = EPA Methods. See Table 1.6 for the full reference for each analytical method.
5.9 Confirmation
5.9.1 Gas Chromatographic Methods
Preliminary identification of contaminant compounds using EPA Methods 507, 508, 508.1,
515.1, 515.2, 515.3 and 515.4, 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 (known as retention time windows), to the retention time
established during calibration of a standard reference compound, then identification is presumed
positive. The UCMR requires analytical confirmation by gas chromatographic/mass
spectrometry (GC/MS) for 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
chromatographically. 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) except for EPA 314.0 and EPA 532. 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 cannot be confirmed by the secondary dissimilar column or if the primary analysis uses
GC/MS as the determinative step.
5.9.2 Gas Chromatography/Mass Spectrometry Confirmation
The UCMR requires that any contaminant detected above the MRL when using a gas
chromatography method must be confirmed using GC/MS (§141.40 Appendix A). Analytes
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detected using ion chromatography do not need to be confirmed (Section 5.9.4) and analytes
detected using HPLC must be confirmed by analysis using a dissimilar second chromatographic
column (Section 5.9.5). 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 Tables 5.20 and 5.21. 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, bracketing
the measured concentration, 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.
Table 5.20 UCMR (1999) List 1 Recommended Confirmation Ions
Contaminant
2,4-Dinitrotoluene
2,6-Dinitrotoluene
4,4'-DDE
Acetochlor
DCPA, mono- and di-acid
EPTC
Molinate
MTBE
Nitrobenzene
Perchlorate
Terbacil
Recommended Confirmation Ions
63, 89, 165
63, 89, 165
246,316,318
59, 132, 146
299, 300, 302
86, 128, 189
83, 126, 187
41,57,73
51,77, 123
Not Applicable
116, 160, 161
Note: 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 choose alternate ions that better characterize the spectra displayed by their mass spectrometer.
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Table 5.21 UCMR (1999) List 2 Recommended Confirmation Ions
Contaminant
1 ,2-Diphenylhydrazine
2-Methyl-phenol
2,4-Dichlorophenol
2,4-Dinitrophenol
2,4,6-Trichlorophenol
Diazinon
Disulfoton
Fonofos
Nitrobenzene
Prometon
Terbufos
Linuron
Diuron
Recommended Confirmation Ions
77,51
108, 79
63, 164
107, 132, 196
137,304
89,97
109, 137
51, 123
168, 183
153, 125
Not Applicable
Not Applicable
5.9.3 Mass Spectrometry Methods
Perform identification and confirmation of a contaminant using EPA Methods 524.2, 525.2, 526
and 528 by comparison of the contaminant's mass spectrum (after background subtraction) to a
reference spectrum in the user-created database. 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
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contaminant spectrum will contain extraneous ions contributed by the co-eluting contaminants.
Because purgeable organic compounds (such as those for some UCMR 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.
5.9.4 Ion Chromatography Identification
EPA Method 314.0 is the only ion chromatography method approved for the UCMR. To confirm
perchlorate detection using this method, compare the retention time of a suspected perchlorate
peak within the retention time window in the sample chromatogram to the actual retention time
of a known analyte peak in a calibration standard. If the retention time of a suspect peak
corresponds, within the acceptable retention time window limits, to the retention time in the daily
calibration check standards, and the retention time is reproducible during the analysis batch, then
identification is presumed positive.
The width of the retention time window used to make identifications should be based on
measurements of actual retention time variations of standards measured over several days. Three
times the standard deviation of retention time may be used as a suggested window size but the
retention time window should not extend beyond ± 5% of the retention time for perchlorate.
Table 5.22 displays an example of the retention time for perchlorate that has been achieved by
this method. However, the experience of the analyst should weigh heavily in the interpretation of
these chromatograms.
Table 5.22 Estimated Retention Time for Perchlorate Using EPA Method 314.0
Analyte
Perchlorate
Retention Time (minutes)
10.1 ±0.2
If a low concentration of perchlorate is suspected in an unknown sample, but the retention time
has drifted to the edge of the retention time window, a low-level perchlorate matrix spike should
be prepared and analyzed to confirm the matrix-induced retention time shift.
Dilution of a sample may also be performed if more complete resolution is needed between a
suspected perchlorate peak and a coeluting (i.e., shoulder) peak. If dilution is performed, the
analyst should realize that the dilution will alter the MRL for that diluted sample analysis by a
proportion equivalent to the dilution. This may result in an unacceptable revised laboratory MRL
which is above the statutory MRL of 4 |ig/L.
Dilution may also be necessary if a perchlorate response exceeds the highest calibration standard
concentration. After conducting the analysis of the diluted sample, back calculate the actual field
sample concentration by applying the correct dilution factor. Report only those values that are
between the MRL and the highest calibration standards.
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5.9.5 High Performance Liquid Chromatography (HPLC) with UV Detection
EPA Method 532 utilizes HPLC to analyze for linuron and diuron. All positive results using
HPLC are to be confirmed by using a second, dissimilar HPLC column (§141.40 Appendix A).
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°), or 10°C or below for UCMR (1999) List 2 samples
should arrive at the laboratory packed in ice or frozen cold packs. Samples should not be
analyzed if they were not shipped properly and/or if they did not arrive in the required
temperature. As the UCMR specifies that resampling is required within 14 days of the
observance of a sampling error (§141.40(a)(5)(ii)(F)), 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 attempt to recollect these samples as soon as possible and
indicate in their official file why recollection was not possible within 14 days and why the
original samples were invalidated.
The laboratory also must invalidate samples that were collected in improper sampling containers
(e.g., plastic bottles instead of glass) or that were improperly filled (e.g., half-filled bottles for
samples that are required to be 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
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 Tables 3.1 and 3.2.
When appropriate, EPA standardized the holding times across analytical methods for the same
contaminant group.
If a UCMR sample is not extracted or analyzed within these holding times, then the data for the
sample should not be reported and the sample should be recollected. As above, the laboratory
should immediately contact the water system and arrange for resampling within the required 14
days(§141.40(a)(5)(ii)(F)).
There are other problems, of course, that may invalidate a sample. Some additional comments
on sampling frequency deviations are identified in 2.2.1.
5.10.1 Laboratory Fortified Blank
A laboratory fortified blank (LFB) analysis must be performed if it is a requirement in the
method (§141.40 Appendix A). Each analysis should be performed to the specifications and
acceptance criteria of each respective method.
Specifically, EPA Method 3 14.0 requires the LFB to be prepared from the same secondary
dilution stock used to fortify the MS/MSD samples. This secondary dilution stock should be
prepared from the same stock used to prepare the calibration standards, and must not be prepared
from an external source stock such as that used to prepare the QC sample (§141.40(a)(5)).
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Laboratories are required to analyze a LFB (filtered, for particulate removal, as if it were a field
sample) with each analysis batch immediately following the ICCS (§141.40(a)(5)). The LFB
must be prepared with the same solution used to prepare the matrix spike and should be prepared
at concentrations no greater than ten times the highest concentration observed in any field sample
and should be varied to reflect the range of concentrations observed in field samples
(§141.40(a)(5)).
If any deviations in the perchlorate secondary dilution stock concentration are present, it will be
reflected in the LFB and not exclusively attributed to a matrix upon analysis of the matrix spike.
Calculate accuracy as percent recovery (see Section 9.4.1.3 of EPA Method 314.0). The recovery
for perchlorate must fall in the range of 85 - 115% prior to analyzing samples (§141.40(a)(5)). If
the LFB recovery for an analysis batch does not meet these recovery criteria, the data are
considered invalid, and the source of the problem should be identified and resolved before
continuing analyses.
5.10.2 Matrix Conductivity Threshold Quality Control Requirements
One of the initial problems in the development of an analytical method for monitoring low-levels
of perchlorate in drinking water was the interference caused by extremely high background
concentrations of total dissolved solids (TDS). To address this problem, EPA Method 314.0
incorporates several steps designed to keep this interference to a minimum. These steps are
centered around a requirement of each laboratory to determine the matrix conductivity threshold
(MCT) of their system during their initial demonstration of capability (see Section 9.2.8 of EPA
Method 314.0; §141.40(a)(5)). If a sample's measured conductivity exceeds this threshold,
certain steps (either dilution or pretreatment of the sample) must be taken to ensure data quality
(§141.40(a)(5)). Once a laboratory determines their MCT, they must also confirm that
perchlorate can be recovered at the MRL (± 30%) from samples that have been prepared with a
conductivity at the MCT (± 10%; see Section 9.2.8.11 of EPA Method 314.0; §141.40(a)(5)).
5.10.2.1 Conductivity Meter Calibration Verification and Conductance Determination
Prior to analyzing a sample for perchlorate, the conductance of that sample matrix must be
measured (§141.40(a)(5)). To ensure the accuracy of these measurements, the conductivity meter
calibration must first be verified or established (as described in Section 10.4 of EPA Method
314.0) for each analysis batch (§141.40(a)(5)).
5.10.2.2 Instrument Performance Check
To verify the MCT as part of each an analysis batch, EPA Method 314.0 requires that an
instrument performance check (IPC) standard be prepared and analyzed prior to the analysis of
any other samples (including the method blank and the ICCS). The IPC should be prepared with
a mixed common anion solution at the MCT (±10%) and spiked with a perchlorate (at a
suggested level of 25 |ig/L). As specified in the method, before any further analyses are
conducted, the analyst must verify that:
1) the IPC solution conductance, measured with the calibrated conductivity
meter, is within ± 10% of original measured value (when the MCT was
initially determined and the solution was originally prepared);
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2) the area to height ratio percent difference (PDA/p; see Section 9.2.8.8 of the
method) for the observed perchlorate response in the IPC is less than 25%;
3) the level of perchlorate measured in the IPC is between 80 -120% of the
spiked level; and
4) the shift in perchlorate retention time is less than 5%.
If the IPC fails to meet any of the above criteria, the source of the problem must be identified
before sample analyses may begin (§141.40(a)(5)). As discussed in the method, if a laboratory
frequently fails to meet these IPC criteria, it may be necessary for that laboratory to revise their
MCT to a more appropriate lower level.
5.10.2.3 Additional Quality Control Procedures if Dilution or Pretreatment is Required
As mentioned in Section 5.10.2.1, before any field sample is analyzed, the conductance of the
sample matrix must be measured (§141.40(a)(5)). If the conductivity of the sample matrix
exceeds the MCT, then dilution or pretreatment of the sample is necessary.
If dilution is necessary, the sample should be diluted with reagent water by a factor large enough
to ensure that the diluted sample conductivity is below the MCT. Dilution will also raise the
required MRL for that sample by the same factor. If perchlorate is measured in the diluted
sample above the elevated MRL, back calculate the actual field sample concentration and report
the results. If the laboratory chooses to dilute, their revised MRL must still be lower than the
statutory MRL of 4 |ig/L for perchlorate.
If dilution does not provide the required results, pretreatment of the sample should be performed.
Pretreatment is described in Section 11.1.4 of the method, and usually requires the addition of
three pretreatment cartridges. If pretreatment is performed, EPA Method 314.0 requires that the
following additional quality control samples must also be prepared:
1. a pretreated laboratory reagent (method) blank;
2. a pretreated laboratory fortified blank (LFB); and
3. a pretreated MS/MSD set.
All of these QC samples should be subject to the same pretreatment techniques employed for the
pretreated field samples. It is important to note that the pretreated method blank and laboratory
fortified blank (LFB) must be prepared and analyzed before any field samples are pretreated
(§141.40(a)(5)). This is required to ensure that no background interference or bias is contributed
by the pretreatment process. If background interference or bias is observed, the appropriate steps
must be taken before field samples are pretreated (§141.40(a)(5)). These steps may include
increasing the volume of rinse for the pretreatment columns. Once the interference has been
eliminated and the pretreated method blank and LFB have met the appropriate acceptance
criteria, the analyst may begin pretreating field samples as appropriate.
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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 methods from voluntary consensus
organizations (D 5317-93 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 the solvent wash listed in Sections 11.1.4 and 11.1.5 of EPA Methods 515.1 and
515.2 (Sections 12.1.4 and 12.1.5 of D 5317-93 and Section F(a) of 992.32) be performed
(§141.40(a)(5)). 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 the 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 D 5790.95, Section 3 of SM 6210D, and Section 2(a)(2) of SM
6200B]. 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 quality control requirements specified in the UCMR and described in this
Manual.
6.3 Clarifications Concerning EPA Method 515.3
EPA Method 515.3 was approved for the analysis of DCPA mono- and di-acid degradates under
the UCMR (see Table 1.6). However, it must be noted that because EPA Method 515.3 does not
require a solvent wash step to remove the DCPA parent, there are conditions which must be met
if Method 515.3 is to be used (§141.40(a)(3)). If DCPA mono- and di-acid degradates are
detected at concentrations greater than or equal to the MRL, then a duplicate sample must be
analyzed within the method specified holding time, or a replacement sample must be collected
and analyzed within the same month as the original sample, using one of the other approved
methods (§141.40(a)(3)). Sampling results greater than the MRL using Method 515.3 should not
be reported to EPA, only the results of the subsequent analysis.
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6.4 Additional Notes on the Analysis of 2,4- and 2,6-Dinitrotoluene by Method 525.2
Since promulgation of the UCMR, some laboratories have reported that they have observed low
recoveries for 2,4- and 2,6-dinitrotoluene. Reasons for low recoveries of these compounds
include: 1) breakthrough from the solid phase sorbent, or 2) loss during evaporation of the excess
solvent. Of these two potential problems, breakthrough may be the most common. This may be
caused by variations between different manufacturers of CIS cartridges or variations in lots that
have been produced.
What can be done to avoid breakthrough?
1. Breakthrough occurs when the analyte is not sufficiently retained on the sorbent. This
can be strongly influenced by the speed at which the sample is pulled through the sorbent.
Slowing down the flow rate will increase the contact time between the analyte and the
sorbent, allowing for better retention.
2. Breakthrough is related to the capacity of the SPE device. Fortifying LFBs with lower
amounts of the analytes can improve recovery. A suggested concentration is 1 |ig/L each
of 2,4- and 2,6-dinitrotoluene. If you are getting poor recoveries, spike less, not more.
3. All SPE products are not created equal. Some brands are more effective than others.
Shopping around can help. Once you find a product you like, stay with that product and
always track lot numbers. Recently, a product has been developed and is expected to be
commercially available by July 2001 which is specifically designed to help minimize this
dinitrotoluene breakthrough (JT Baker, BAKERBOND Speedisk® Extraction Disks CIS:
High Capacity, product # 8055-07, or equivalent).
What if breakthrough is not the problem?
1. The other area where losses may occur is during the solvent evaporation step. 2,4- and
2,6-dinitrotoluene are some of the more volatile analytes in the method. To evaluate this
step, fortify a 50/50 mixture of ethyl acetate and methylene chloride with your analytes.
Use a solvent volume that is representative of your extract volume. Evaporate this
mixture to 1 mL by your typical procedure. If recoveries are low, slow down your
evaporation step. A suggested evaporation rate is 0.2 mL/min at approximately 40°C.
I get poor recoveries of the internal standards in Method 525.2.
There are multiple causes of poor recovery for these compounds. Some are listed here:
1 These internal standards are extremely hydrophobic. They would rather be on the glass
bottle than dissolved in water. Therefore all the glassware that the sample touches must
be rinsed with extraction solvent and added to the extract. The sodium sulfate drying
column must also be well rinsed and the solvent added to the extract.
2. If the sample was not properly dechlorinated, and the sample still contains free chlorine at
the time the internal standards are spiked, the internal standards react with the chlorine
and will not be recovered.
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3. The internal standards can be oxidized during the cartridge or disk drying step (just prior
to elution). Do not dry the sorbent too long. Ten minutes is enough, and longer drying
times can cause oxidation of the internal standards.
4. The internal standards can photodegrade. Be aware of this and limit exposure of samples
and extracts to direct light. Use amber sample bottles and extract vials if possible. Some
examples for controlling light are: 1) if you process samples in the hood, leave the hood
light off and the room lights on, 2) if you process samples in a room with windows,
consider leaving the room lights off, 3) if the lab has separate banks of lights on separate
switches, leave the lights off on one side of the room. How this can be handled depends
on the physical set-up of the laboratory. However, please do not create safety issues by
trying to work in near darkness. That degree of light control is not required to get good
recoveries.
6.5 Additional Notes on the Analysis of Nitrobenzene by Method 524.2
Since beginning preparation for UCMR, some laboratories have reported that they cannot meet
MRL requirements for nitrobenzene. Nitrobenzene does exhibit poor purging efficiency,
however adequate data can be obtained if certain guidelines are followed.
1. The purge and trap unit must contain plumbing that is all glass lined or made of
Silcosteel®. Many older purge and trap units are glass-lined. Newer ones may be made
of Silcosteel® or may just be stainless, or have sections of plumbing that are stainless. If
you are having trouble with nitrobenzene, your first step should be to find out what the
plumbing in your purge and trap unit is made of. Units that are not glass lined or
Silcosteel® may be retrofitted.
2. Purge a 5 mL sample in a 5 mL purge vessel. Purging efficiency can drop dramatically
when you purge a larger sample, i.e. 25 mL. Never purge a 10 mL sample in a 25 mL
purge vessel. This "modification" seems to be gaining popularity in many laboratories.
This is not currently a legal modification and it has a negative effect on purging
efficiency. When the purging efficiency is already low, method modifications that make
it even lower are disastrous. The lower the purging efficiency, the higher the detection or
reporting limit.
3. Contact the manufacturer of your purge and trap unit. Some manufacturers are already
aware of instrument parameters or minor modifications that will help you to get
acceptable data for nitrobenzene.
6.6 Additional Notes on Methods 526 and 528
Some laboratories have raised concerns regarding some of the requirements of Methods 526 and
528. These are both solid phase extraction methods that are similar in many ways to Method
525.2. One way that these methods differ from Method 525.2 is that the internal standards are
added at the end of the sample processing.
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Other questions that have arisen are:
Why can't I use a SPE disk for Method 528?
The solid phase sorbent used for Method 528 is not available in disk format. Phenols are
highly polar and water soluble, and are not well retained on other sorbents.
Do I need to use all three internal standards in Method 526 if no analytes are being
calculated from the third internal standard?
No, you do not need to use the third internal standard, if the second surrogate can be
correctly quantitated off the second internal standard.
Should I use a packed or open liner if I do PTV injection for Method 526?
During the method development an open 0.5 mm i.d. liner was used. In general, packing
materials add to the potential for active sites.
Why does Method 526 have so many additives added to the sample at the time of collection?
One of the common properties among the analytes in Methods 526 is their tendency to be
unstable in water. In order to preserve the analytes from time of collection to time of
analysis, the analytes need to be protected from hydrolysis (both pH and metal catalyzed),
chlorination from free chlorine, and microbial degradation. As a result, the method calls
for a buffer to standardize and hold the pH, EDTA to complex metal ions, ascorbic acid
to eliminate free chlorine, and a microbial inhibitor.
When I extract LFBs for Method 528,1 get little or no recovery of2,4-dinitrophenol, 2-
methyl-4,6-dinitrophenol andpentachlorophenol. The other analytes are well recovered.
What's wrong?
The three compounds listed are strong acids. They can only be extracted if the water
sample is acidified. This includes LFBs.
When I try to elute the cartridges for Method 528,1 have a hard time pulling the methylene
chloride through. My extracts also have a large water layer. Sometimes my recoveries are
poor.
The cartridges must be dry before they are eluted. You can tell that they are fully dried
because the color will change from a dark brown to a light tan. Drying times will vary
because of the strength of the vacuum source and the number of cartridges being
processed at one time. Drying the cartridges too long is not an issue for this method.
During method development samples were dried under vacuum for several hours with no
analyte loss.
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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 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 Accession and Review System (SDWARS/UCMR) for inclusion in the National Drinking
Water Contaminant Occurrence Database (NCOD).
The PWSs are required to report the UCMR monitoring data to EPA for evaluation (§141.35(a)).
The UCMR contaminant 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 (EPA-815-R-
01-029), the Unregulated Contaminant Monitoring Regulation Guidance for Operators of Public
Water Systems Serving 10,000 or Fewer People (EPA 815-R-01-002), and the Reference Guide
for the Unregulated Contaminant Monitoring Regulation (EPA 815-R-01-023), all available
from the EPA Water Docket, telephone (202) 260-3027, Docket Number W-98-02 or from the
internet at http://www.epa.gov/safewater/ucmr.html.
EPA is taking a "one-entry" approach to the electronic reporting process to improve reporting
quality, reduce reporting errors, and reduce the time involved in investigating and correcting
errors at all levels (laboratory, system, State and EPA), thereby making the data more useful
earlier. The SDWARS/UCMR electronic reporting system became fully operational on October
1, 2001. A PWS should instruct the agent or organization that conducts the testing and
laboratory analysis for the unregulated contaminants to enter the data into the UCMR electronic
reporting system. EPA will provide electronic forms via its Internet website or via "batch"
electronic data transfer following a format specified by EPA. The PWS can instruct the
laboratory to enter the UCMR results directly into the electronic template, after which the PWS
can review the results on-line and electronically indicate its approval to submit the data to EPA.
PWSs can also require their laboratories to receive their approval before the UCMR results are
posted on the EPA electronic posting system.
Results of each analysis must be reported to EPA within 30 days following the month the PWS
receives them from the laboratories (§141.35 (c)). For UCMR monitoring data received at the
PWS from the laboratory in 2001, a reporting deadline of April 30, 2002 is being strongly
considered and will likely be promulgated in supplemental UCMR Federal Register notice early
in the 2002 calendar year (for the latest information, closely monitor the UCMR web site at:
www.epa.gov/safewater/ucmr.html). For small systems, EPA will enter and report the results
directly to its electronic reporting system through its contract laboratories. EPA will place all
data received from laboratories and PWSs into the National Drinking Water Contaminant
Occurrence Database (NCOD), which will be updated four times a year, after a 60-day quality
control review.
Monitoring data for all contaminants must be reported according to contaminant type and must
include the 16 specific data elements for each contaminant (§141.35 (d)(3)). Please note that
EPA has reserved data element 17, since it is specifically related to microbiological
contaminants. These data elements, with their revised definitions, are listed in Table 7.1. If a
PWS chooses to report multiple results for a particular contaminant (for example, because more
than one laboratory analyzed the samples collected under §141.40, or because multiple samples
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were collected during the monitoring period at the same sampling point), only the highest
reported value will be used as the official result. PWSs retain final responsibility to ensure that
all monitoring data is reviewed, approved and reported to the EPA.
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. To 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-acid degradates. As a result, data element 5,
Contaminant/Parameter, will not have as acceptable values "DCPA mono-acid degradate" or
"DCPA di-acid 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
Under the final UCMR (1999) List 2 Rule (66 FR 2273), laboratories can no longer report results
obtained below the specified MRL of each contaminant.
7.1.3 Reporting of Water Quality Parameter Data
Because EPA has eliminated pH as a water quality parameter for chemical contaminants, there is
no longer a need to report these data with chemical contaminant results at this time.
7.1.4 Reporting of Matrix Conductance and Pretreated QC Data for Perchlorate
Each laboratory performing perchlorate analyses using EPA Method 314.0 will need to monitor
and record the conductance of every matrix analyzed for perchlorate (§141.40(a)(5)(ii)(G)).
Furthermore, EPA Method 314.0 specifies that when field samples exceed the matrix
conductivity threshold (MCT), and pretreatment is employed to reduce the high ionic character of
the matrix, additional quality control samples must be analyzed (§141.40(a)(5)). These
additional QC requirements are discussed in Section 5 of this Manual and includes a pretreated
method blank, pretreated laboratory fortified blank (LFB), and a pretreated MS/MSD set for each
pretreated matrix.
It is the responsibility of the laboratory to provide the matrix conductance data as well as these
additional pretreated QC data to their client PWS and to retain these data in the laboratory's
official analytical data archive. It should be clarified, however, that the matrix conductance data
are not reported to EPA since they were not promulgated as specific data reporting elements. In
the rare situation in which the field sample selected for the MS/MSD pair required pretreatment,
these QC data would be reported to SDWARS/UCMR for that respective analysis batch.
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7.1.5 Reporting of Presence/Absence
The Presence/Absence data element is being reserved for potential future use, as all of the
contaminants currently being monitored can be accurately and precisely quantified. Therefore,
the presence or absence of a contaminant does not need to be reported. This data element is
being reserved for contaminants and not deleted in order to permit the use of this data element if
warranted in future regulations.
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 regulation
(63 FR 44512), as well as through the revised Public Notification Rule (PNR) (65 FR 25982). 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 SDWARS 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 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.
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. Grandparenting
data is allowed but in order 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)).
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Table 7.1 Unregulated Contaminant Monitoring Reporting Requirements
Data Element
1.
2.
3.
4.
5.
Public Water System
(PWS) Identification
Number
Public Water System
Facility Identification
Number - Sampling
Point Identification
Number and Sampling
Point Type
Identification
Sample Collection Date
Sample Identification
Number
Contaminant/ Parameter
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.
The sampling point identification number and sampling point type
identification must either be static or traceable to previous numbers and
type identifications throughout the period of unregulated contaminant
monitoring. The sampling point identification number is a three-part
alphanumeric designation, made up of:
a. The Public Water System Facility Identification Number is an
identification number established by the State, or at the State's
discretion the PWS, that is unique to the PWS for an intake for each
source of water, a treatment plant, a distribution system, or any other
facility associated with water treatment or delivery and provides for the
relationship of facilities to each other to be maintained;
b. The Sampling Point Identification Number is an identification
number established by the State, or at the State's discretion the PWS,
that is unique to each PWS facility that identifies the specific sampling
point and allows the relationship of the sampling point to other facilities
to be maintained; and
c. Sampling Point Type Identification is one of following:
SR - Untreated water collected at the source of the water system facility.
EP - Entry point to the distribution system.
MD - midpoint in the distribution system where the disinfectant residual
would be expected to be typical for the system such as the location for
sampling coliform indicator bacteria as described in 40 CFR 141.21.
MR - point of maximum retention is the point located the furthest from
the entry point to the distribution system which is approved by the State
for trihalomethane (THM) (disinfectant byproducts (DBP)) and/or total
coliform sampling.
LD - location in the distribution system where the disinfectant residual
is the lowest which is approved by the State for THM (DBP) and/or total
coliform sampling.
The date the sample is collected reported as 4-digit year, 2-digit month,
and 2-digit day.
An alphanumeric value of up to 15 characters assigned by the laboratory
to uniquely identify containers or groups of containers containing water
samples collected at the same time and sampling point.
The unregulated contaminant or water quality parameter for which the
sample is being analyzed.
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Data Element
Definition
6. Analytical Results -
Sign
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."
7. 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.
8. Analytical Result - Unit
of Measure
The unit of measurement for the analytical results reported [e.g.,
micrograms per liter, (|ig/L); colony-forming units per 100 milliliters,
(CFU/lOOmL), etc.].
9. Analytical Method
Number
The identification number of the analytical method used.
10. Sample Analysis Type
The type of sample collected. Permitted values include:
a. RFS - Raw field sample - untreated sample collected and submitted
for analysis under this rule.
b. RDS - Raw duplicate field sample - untreated field sample duplicate
collected at the same time and place as the raw field sample and
submitted for analysis under this rule.
c. TFS - Treated field sample - treated sample collected and submitted
for analysis under this rule.
d. TDS - Treated duplicate field sample - treated field sample duplicate
collected at the same time and place as the treated field sample and
submitted for analysis under this rule.
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Data Element
Definition
11. Sample Batch
Identification Number
The sample batch identification number consists of three parts:
a. Up to a 10-character laboratory identification code assigned by EPA;
b. Up to a 15-character code assigned by the laboratory to uniquely
identify each extraction or analysis batch. Within SDWARS/UCMR,
this variable is known as the "Batch ID."
c. The date that the samples contained in each extraction batch
extracted or in an analysis batch were analyzed, reported as an 8-digit
number in the form 4-digit year, 2-digit month, and 2-digit day.
FOR EXAMPLE:
Sample Batch ID#: KY99999123xyz524220010326
a. KY99999
Fictitious lab in KY that was assigned this number after participating in
a PE study several years ago.
b. 123xyz5242
Just a completely fictitious example of a Method 524.2 analytical batch.
It could be anything alphanumeric, 15 characters or less used by your
lab to refer to a batch of samples. This would likely be the number used
by your LIMS and is the origin of the 15 character or less reference.
c. 20011115
Analysis date of 11/15/2001
12. Minimum Reporting
Level
Minimum Reporting Level (MRL) refers to the lowest concentration of
an analyte that may be reported. Unregulated contaminant monitoring
(UCM) MRLs are established in §141.40 monitoring requirements for
unregulated contaminants.
13. Minimum Reporting
Level Unit of Measure
The unit of measure to express the concentration, count, or other value
of a contaminant level for the Minimum Reporting Level reported [e.g.,
micrograms per liter, (|ig/L); colony-forming units per 100 milliliters,
(CFU/100mL),etc.].
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Data Element
14. Analytical Precision
15. Analytical Accuracy
16. Spiking Concentration
17. Presence/Absence
Definition
Precision is the degree of agreement between two repeated
measurements and is monitored through the use of duplicate spiked
samples. For purposes of the Unregulated Contaminant Monitoring
Rule (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 Relative Percent Difference (RPD) of spiked matrix
duplicates from the mean using:
RPD = absolute value of [(Xj - X2) /((Xj +X2)/2) ] x 100%
where:
Xj is the concentration observed in spiked field sample minus the
concentration observed in unspiked field sample
X2 is the concentration observed in duplicate spiked field sample minus
the concentration observed in unspiked field sample
Accuracy describes how close a result is to the true value measured
through the use of spiked field samples. For the purposes of the UCMR,
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.
Reserved
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Appendix A
Abbreviations and Acronyms
2,4-DNT
4,4'-DDE
AOAC
APHA
ASTM
°C
CAS
CCL
CCR
CFR
CPU
CFU/100 mL
cws
DCPA
DCPA mono-
and di-acid
degradates
DDT
DPD
EDL
EDTA
EPA
EPIC
EPTDS
ESA
FR
GC
GC/MS
HPLC
ICCS
IPC
IS
LFB
LFM
- 2,4-dinitrotoluene
- 4,4'-dichloro dichlorophenyl ethylene, a degradation product of DDT
- Association of Official Analytical Chemists
- American Public Health Association
- American Society for Testing and Materials
- degrees Celsius
- Chemical Abstract Service
- Contaminant Candidate List
- Consumer Confidence Reports
- Code of Federal Regulations
- colony forming unit
- colony forming units per 100 milliliter
- community water system
- dimethyl tetrachloroterephthalate, chemical name of the herbicide
dacthal
- degradation products of DCPA
- dichloro diphenyl trichloroethane, a general insecticide
- jV,jV-diethyl-/?-phenylenediamine, free chlorine colorimetric indicator
- estimated detection limit
- ethlenediaminetetraacetic acid
- Environmental Protection Agency
- s-ethyl-dipropylthiocarbamate, an herbicide
- Entry Point to the Distribution System
- ethanesulfonic acid, a degradation product of alachlor
- Federal Register
- gas chromatography, a laboratory method
- gas chromatography/mass spectrometry, a laboratory method
- high performance liquid chromatography, a laboratory method
- initial calibration check standard
- instrument performance check
- internal standard
- laboratory fortified blank
- laboratory fortified matrix
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MCL
MCT
MDL
mL
MRL
MS
MSD
MTBE
N
NCOD
NPDWS
NTIS
NTNCWS
OGWDW
OMB
PAH
PNR
PT
PTFE
PTV
PWS
QC
RPD
SDWA
SDWARS
SM
SPE
SRF
SW
IDS
UCMR
VOC
maximum contaminant level
matrix conductivity threshold
method detection limit
milliliter
minimum reporting level
sample matrix spike
sample matrix spike duplicate
• methyl tertiary-butyl ether, a gasoline additive
normality
• National Drinking Water Contaminant Occurrence Database
• National Primary Drinking Water Standards
• National Technical Information Service
• non-transient non-community water system
• Office of Ground Water and Drinking Water
Office of Management and Budget
Polycyclic aromatic hydrocarbon
percent difference (perchlorate peak area to height ratio)
Public Notification Rule
performance testing, synonymous with proficiency testing
polytetrafluoroethylene
programmable temperature vaporizing, type of GC sample injection
Public Water System
• quality control
• relative percent difference
Safe Drinking Water Act
• Safe Drinking Water Accession and Review System
Standard Methods
• solid phase extraction, a laboratory method
State Revolving Fund
surface water
total dissolved solids
• Unregulated Contaminant Monitoring Regulation/Rule
• 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.
Listed contaminant means a contaminant identified as an analyte in Table 1, 141.40(a)(3) of the
Unregulated Contaminant Monitoring Rule (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).
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 may 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.
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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 could 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 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 and Screening Survey(s)) and all large
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.
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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 by 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.
Unregulated contaminants means chemical, microbiological, radiological and other substances
that may occur in drinking water or sources of drinking water that are not currently regulated
under the federal 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
of 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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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
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UCMR (1999) List 1 and List 2 Chemical Analytical Methods and Quality Control Manual December 2001
Appendix C
Procedure for Determination of Detection Limits
EPA has removed the reference to the 40 CFR Part 136 Appendix B definition of method
detection limit (MDL) in the Appendix to § 141.40. Under the revised UCMR (66 FR 2273),
laboratories should refer to the detection limit calculations listed in each respective method for
the analyte under consideration.
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