# UCMR 3 Laboratory Approval Requirements and
Information Document

Version 2 .0

January 2012

Technical Support Center Standards and Risk Management Division
Office of Ground Water and Drinking Water U.S. Environmental Protection Agency Cincinnati, OH 45268

L aboratory Manager:

________________________________

This signature affirms that the L aboratory M anager and staff anticipated to participate in UCMR 3 have read the
UCMR 3 Laboratory Approval Requirements and Information Document

.Page 2 of 50 Office of Water (4607 M)
EPA 815 -R-11-003 January 2012 http://water.epa.gov/drink/Page 3 of 50 

### Foreword

The Revisions to the Unr egulated Contaminant Monitoring Rule ( UCMR 3 ) for Public Water Systems [40 CFR Part 141, National Primary Drinking Water Regulations] require public water systems ( PWS s) to collect specific data and information during a defined monitoring period . The
rule also establishes requirements and specifications for the reporting of UCMR 3 data to the United States Environmental Protection Agency (EPA). This technical manual serves as a support document for laboratories interested in becoming EPA approved and maintaining their EPA approval to analyz e samples collected at PWS s to meet the UCMR 3 requirements for
chemical contaminants

.

Th e main objective of th is UCMR 3 Laboratory Approval Requirements and Information

Document (referred to as the UCMR 3 Lab Approval Manual) is to provide laboratories with
detailed information on the UCMR 3 laboratory approval process. The document is intended to:

• describe the laboratory approval process for chemical contaminants

,

• describe the procedures that EPA uses to asse ss a laboratory's ability to produce data of

known and acceptable accuracy and precision,

• describe the laboratory data quality control requirements for UCMR 3 chemical analyses,

and

• further describe specific analytical procedures for UCMR 3

.

Laboratories will be required to follow this UCMR 3 Laboratory Approval Manual to process
UCMR 3 samples collected at PWSs and maintain their status as an EPA approved UCMR 3 laboratory

.

This document was prepared by EPA’s Office of Ground Water and Drinking Water ( OGWDW)

, Standards and Risk Management Division (SRMD), Technical Support Center (TSC)

, Cincinnati, Ohio. Additional information on the UCMR 3 program can be found at the UCMR 3 website,



### http://water.epa.gov/lawsregs/rulesregs/sdwa/ucmr/ucmr3/index.cfmPage 4 of 50 

## Disclaimer s

1. Mention of trade names or commercial products does not constitute endorsement or
recommendation for use.

2. This document describes the provisions of the UCMR 3 program, the approved analytical
methods for UCMR 3 chemical contaminant s, and EPA regulations that establish legally binding requirements. However, this document does not substitute for those provisions or regulation s.

3. Laboratory approval to perform UCMR 3 analyses will only apply during UCMR 3 monitoring. If new drinking water regulations are promulgated using similar analyses and/or the same methods, laboratories will then be required to be certified through the process appropriate to their primacy agent (i.e., their State and/or EPA Region).

4. The UCMR 3 approval process is not related to the laboratory certification process for conducting compliance monitoring under other National Primary D rinking W ater Regulations (NPDWRs) . A laboratory’s approval for UCMR 3 analyses has no impact on their certification to perform compliance monitoring under other NPDWRs

.Page 5 of 50 

## Contents

Foreword ........................................................................................................................................ 3

Disclaimers

................................................................................................ ..................................... 4

Acronyms and Abbreviations ...................................................................................................... 7

Se ction 1. Introduction ............................................................................................................... 10

1.1 Background on the Unregulated Contaminant Monitoring Rule ................................ 10

1.2 Ensuring Data Quality for UCMR 3 ........................................................................... 10

Section 2. UCMR 3 Laboratory Approval Process .................................................................. 11

2.1 Registration for the UCMR 3 Laboratory Approval Program .................................... 11

2.2 UCMR 3 LAP Applications ........................................................................................ 11

2.3 UCMR 3 Proficiency Testing ..................................................................................... 12

Section 3. Laboratory Quality Management Plan and UCMR 3 Quality Assurance Project Plan ........................................................................................................................... 14

3.1 Laboratory Quality Management Plan ........................................................................ 14

3.2 UCMR 3 Quality Assurance Project Plan ................................................................... 16

Section 4. Approved Methods for UCMR 3 Monitoring ......................................................... 17

Section 5. Initial Demonstration of a Laboratory's Ability to Perform UCMR 3 Analyses ................................................................................................................. 22

Section 6. Minimum Reporting Levels ...................................................................................... 24

Section 7. Quality Control Requirements ................................................................................. 26

7.1 Initial Calibration of Analytical Instruments .............................................................. 27

7.2 Continuing Calibration Checks ................................................................................... 29

7.3 Surrogate Requirements and Criteria .......................................................................... 31

7.4 Internal Standard Requirements and Criteria .............................................................. 33

7.5 Laboratory Reagent Blank .......................................................................................... 35

7.6 Laboratory Fortified Blank ......................................................................................... 36

7.7 Quality Control Sample (QCS) ................................................................................... 37

7.8 Laboratory Fortified Sample Matrix (Spiked Sample) ............................................... 38

7.9 Analytical Sequence.................................................................................................... 39

Section 8. Sample Handling Requirements .............................................................................. 41

8.1 Field Blanks ................................................................................................................ 41

8.2 Sample T ransport and Storage .................................................................................... 42

8.3 Sample Preservation.................................................................................................... 43Page 6 of 50 8.4 Maximum Holding Times ........................................................................................... 44

8.5 Laboratory Errors or Sampling Deviations ................................................................. 45

Section 9. References .................................................................................................................. 46

Append ix A. Requirements for UCMR 3 Metal Analysis ....................................................... 48

Appendix B. Lowest Concentration Minimum Reporting Level (LCMRL) Data used to Determine UCMR 3 Minimum Reporting Levels (MRLs) .............................................. 49



## Tables

Table 1. UCMR 3 Chemical Analytes and Methods .................................................................... 20

List 1: Assessment Monitoring ......................................................................................... 20

List 2: Screening Survey ................................................................................................... 21

Table 2. IDC Requirements .......................................................................................................... 23

Table 3. Initial Calibration Acceptance Criteria ........................................................................... 29

Table 4. CCC Acceptance Criteria ................................................................................................ 31

Table 5. Surrogate Standards, Concentrations and Criteria .......................................................... 32

Table 6. Internal Standards, Concentrations and Criteria ............................................................. 34

Table 7. Laboratory Reagent Blank Criteria ................................................................................. 36

Table 8. Laboratory Fortified Blank Acceptance Criteria ............................................................ 37

Table 9. QCS Frequency Requirements ........................................................................................ 38

Table 10. Field Blanks .................................................................................................................. 42

Table 11. Requirements for Sample and Extract Storage Temperatures ...................................... 43

Table 12. Sample Preservatives and Dechlorinating Agents (Concentration in Sample) and Acceptance Criteria ................................................................................................................. 44

Table 13. Maximum Holding Times for Samples and Extracts .................................................... 45

Table 14. Determination of Metals for UCMR 3 based on EPA Method 200.8 Rev. 5.4 ............ 48



## Examples

Example 1. Calculation of the PIR Limits .................................................................................... 25

Example 2. Valid Analysis Sequence for Method 537 ................................................................. 40Page 7 of 50 

## Acron yms and Abbreviations

13 C

- PFDA P erfluoro

- n

- [1,2

- 13 C 2 ]decanoic acid

13 C- PFHxA P erfluoro -n-[1,2- 13 C 2 ]hexanoic acid

13 C

- PFOA P erfluoro

- [1,2

- 13 C 2 ]octanoic acid

13 C

- PFOS S odium perfluoro

- 1

- [1,2,3,4

- 13 C 4 ]octanesulfonate

APHA American Public Health Association

ASTM ASTM International

AWWA American Water Works Association

Bi B ismuth

BFB 4

- bromofluorobenzene

C 18 O ctadecyl

- functionalized silica gel

CAS Chemical Abstract Service

CCC C ontinuing calibration check

CFR Code of Federal Regulations

Co C obalt

d 3 - NMeFOSAA N-deuteriomethylperfluoro-1-octanesulfonamidoacetic acid

d 5 - NEtFOSAA N

- deuterioethylperfluoro

- 1

- octanesulfonamidoacetic acid

DCA D ichloroacetate

EPA United States Environmental Protection Agency

Estriol

- d 2 16α

- hydroxyestradiol

- d 2 GC/MS G as chromatograph y /mass spectrometr y
HR PIR H alf range for the prediction interval of results

IC I on chromatograph y
ICP/MS I nductively coupled plasma

- mass spectromet e r
ID I dentification

IDA I nitial demonstration of accuracy
IDC I nitial demonstration of capability

IDP I nitial demonstration of precision

In I ndium

L L iter

LAP Laboratory Approval Program

LCMRL L owest concentration minimum reporting level

LC

- ESI

- MS/MS L iquid chromatography electrospray ionization tandem mass spectrometry

LC/MS/MS L iquid chromatograph y /tandem mass spectrometr y
LFB L aboratory fortified blank

LFSM L aboratory fortified sample matrix

LFSMD L aboratory fortified sample matrix duplicate

LRB L aboratory reagent blank

mL M illiliter

Mo M olybdenumPage 8 of 50 

## Acron yms and Abbreviations

MRL M inimum reporting level

m/z M ass to charge ratio

NA N ot applicable

NERL National Exposure Research Laboratory

OEI Office of Environmental Information

OGWDW Office of Ground W ater and Drinking Water

ORD Office of Research and Development

PFBS P erfluorobutanesulfonic acid PFHpA P erfluoroheptanoic acid

PFHxS P erfluorohexanesulfonic acid

PFNA P erfluorononanoic acid

PFOA P erfluorooctanic acid

PFOS P erfluorooctanesulfon ic acid

PIR P rediction interval of the result

PIR lower L ower PIR limit

PIR upper U pper PIR limit

PT P roficiency testing

PWS P ublic water system
QA Q uality assurance
QAPP Quality Assurance Project Plan
QC Q uality control
QCS Q uality control sample
QMP Quality Management Plan

RSD R elative standard deviation

RPD Relative percent difference

s S tandard deviation

Sc S candium

SDVB P olystyrenedivinylbenzene

SDWA Safe Drinking Water Act

SDWARS Safe Drinking Water Accession and Review System

SIM S elective ion monitoring

SM Standard Methods for the Examination of Water and Wastewater

SOP S tandard o perating p rocedure

SPE S olid phase extraction

Sr S trontium

Tb T erbium

TSC Technical Support Center

THF

- d 8 T etrahydrofuran

- d 8 UCMR Unregulated Contaminant Monitoring RulePage 9 of 50 

## Acron yms and Abbreviations

UCMR 1 F irst Unregulated Contaminant Monitoring Rule

UCMR 2 Second Unregulated Contaminant Monitoring Rule

UCMR 3 T hird Unregulated Contaminant Monitoring Rule
( v:v ) V olume to volume

V V anadium

VOC V olatile organic co ntaminant

WEF Water Environment Federation

x  ̄ M ean μL M icroliterPage 10 of 50 

## Section 1. Introduction

1.1 Background on the U nregulated C ontaminant M onitoring Rule
The Safe Drinking Water Act (SDWA), as amended in 1996, requires EPA to establish criteria for a program to monitor unregulated contaminants and to publish a list of contaminants to be monitored every five years. In fulfillment of this requirement, EPA published the contaminant
lists for the first and second UCMR s (i.e., UCMR 1 and UCMR 2, respectively) in the Federal Register i n S eptember 1999 and January 2007. The UCMR program uses a three -tiered approach for monitoring contaminants based on the availability of analytical methods. UCMR 3 monitoring will occur f rom January 2013 through December 2015.

EPA identified 28 chemical contaminants and two viruses for UCMR 3 . Monitoring for the
chemical contaminants is supported by eleven analytical methods and addressed within this
manual. Virus analyses will be conducted by laboratories under contract with EPA and are not
addressed in this document.



### 1.2 Ensuring Data Quality for UCMR 3
Data reported under UCMR 3 must meet specific precision and accuracy targets to achieve the objectives of the program. During UCMR 3 development, EPA establish ed criteria t o ensure that data generated during the monitoring period are of high quality. Maintaining data comparability

among laboratories is essential, and will allow the data to be used in statistical analyses t o reliably predict the national occurrence of the chemical contaminants in drinking water. EPA ensures the integrity of the data by : 1) defin ing and maintain ing strict requirements for sample
collection , sample handling, processing and analysis , and data reporting, and 2) assist ing the drinking water industry in identifying qualified laboratories that can accurately and reliably perform the analyses required by UCMR 3

.

The laboratory approval process described in this document ensures that analytical data generated for the UCMR are of adequate quality. EPA used a similar laboratory approval approach in UCMR 1 and UCMR 2 and believes this process is effective in yielding high quality
data. An overview of t he L aboratory Approval Program (LAP) and its requir ements for UCMR 3
is presented in this UCMR 3 Lab Approval Manual, includ ing :

• a description of the UCMR 3 laboratory approval process;

• a discussion of the required quality assurance (QA) documentation that must be prepared

and followed at EPA-approved UCMR 3 laboratories;

• a summary of the UCMR 3 chemical contaminant analytical methods, minimum reporting

levels (MRLs), and initial demonstration of capability (IDC) requirements; and

• a summary of the laboratory data quality control (QC) requirements for UCMR 3 analyses

.

Laboratories must follow the procedures outlined in this document to obtain approval for the analysis of UCMR 3 samples.Page 11 of 50 

## Section 2. UCMR 3 Laboratory Approval Process

Laboratories analyzing samples for UCMR 3 chemical contaminants m ust follow the process outlined in this section to obtain approval. Approval is by method and individual laboratory
location. A laboratory may apply for approval for any number of UCMR 3 methods. If a laboratory organization has multiple locations, each la boratory location must complete the process independently.



### 2.1 Registration for the UCMR 3 Laboratory Approval Program

Laboratories interested in UCMR 3 laboratory approval are to contact EPA as soon as possible.
Laboratories must request UCMR 3 registrati on no later than August 1, 2012. Laboratories should send a letter of interest with contact information, including an e-mail address, to the following address:

UCMR Laboratory Approval Coordinator U.S. Environmental Protection Agency Technical Support Cen ter 26 West Martin Luther King Drive (MS 140) Cincinnati, OH 45268

o r to the e- mail address: UCMR_Sampling_Coordinator@epa.gov

Upon receipt of correspondence from a laboratory indicating their interest in participating in the
UCMR 3 LAP, EPA will e- mail UCMR 3 registration information to the laboratory.

The laboratory must complete the UCMR 3 registration sheet, indicating the U CMR 3 chemistry methods for which they are seeking approval, and return it to EPA at the above e- mail address

. Laboratories will be asked to provide their EPA Lab ID code on the registration sheet. If a laboratory does not have an EPA Lab ID code, one will be assigned by EPA. R egistration information must be received by EPA no later than September 1, 2012. Method specific applications must be returned to EPA by September 28, 2012.



### 2.2 UCMR 3 LAP Application s EPA will forward the appropriate application packet to the laboratory based on the information provided on the registration sheet . Th e application packet will include a g eneral a pplication, and
a method- specific application for each method selected on the registration sheet

.

To complete these appli cations, laboratories are required to:

• Document drinking water certification by a state or regional Certification Authority for the

analysis of samples using gas chromatography, liquid chromatography, ion chromatography, and/or inductively coupled plasma mass spectrometry methods, as indicated in the applications;

• Provide personnel and QA information, including a copy of the Table of Contents from the

laboratory’s Quality Management Plan (QMP; see Section 3.1) ;

• Provide information regarding analytical equipment and sample handling procedures;Page 12 of 50 • For each method for which the laboratory is seeking approval, submit data from: 1) an IDC

study (see Section 5) ; 2) analysis of laboratory reagent blank (LRB) sample s (see Section 7.5); and 3) analysis of a set of labo ratory fortified sample matrix ( LFSM ), LFSM duplicate (LFSMD) , and the corresponding unfortified drinking water sample (see Section 7.8). Data
submitted must include labeled chromatographic and/or spectrometric traces , quantitation
reports, surrogate recovery results and internal standard recovery results ; and

• Document that they will post UCMR 3 results to the EPA’s electronic data reporting

system, the Safe Drinking Water Accession and Review System (SDWARS)

. Laboratories must report field sample results and associated QC data, as required by SDWARS

, within
120 days from the sample collection date . Failure to post data to SDWARS may result in EPA revoking the laboratory’s approval status. Once approval is revoked, the laboratory cannot be reapproved du ring the UCMR 3 monitoring period.

Completed applications are to be returned as soon as possible . EPA will acknowledge receipt of application material s in correspondence to the laboratory.

EPA will review the submitted application material s. If all requested information is present and acceptable, EPA will notify the laboratory that they are eligible to participate in a UCMR 3 proficiency testing (PT) study. If deficiencies are identified in the application materials, EPA will identify the a rea(s) of deficiency and necessary corrective actions to be taken in a report to the laboratory. Laboratories who receive a deficiency report will have the opportunity to make
corrective actions and submit new application information. EPA anticipates the U CMR 3 LAP application period will close with the application submission deadline for the last UCMR 3 PT study, September 28, 2012.



### 2.3 UCMR 3 Profi ci ency Testing

EPA conducted at least two PT studies prior to publication of the UCMR 3 f inal r ule and intends
to offer a minimum of three PT studies prior to closing the Laboratory Approval Program. E ach laboratory must pass one PT study for each method for which they are seeking approval. When the laboratory’s application for a specific method is rev iewed and determined to meet the UCMR
3 method criteria, that laboratory can participate in EPA’s UCMR 3 PT stud y for that method. Participation in a PT study is method -specific; i.e., a laboratory is not required to concurrently participate in a PT study for all methods for which they are seeking approval.

EPA will sen d a method- specific PT ampule to laboratories , with instructions and a cover letter specifying a due date for reporting results to EPA. The laboratory will always have a minimum
of two weeks to perform the analysis. Laboratories should not assume that all UCMR 3 analytes for a method will be present in a PT ampule for that method. Laboratories that do not pass the PT study for a given method can participate in the next PT study for that metho d, if one is scheduled. However, laboratories that have passed a PT study for a given method will not receive additional PT samples for that method during subsequent UCMR 3 PT studies.

Upon successful participation in a PT study for a specific method, the laboratory will be notified in writing that it has met the initial approval criteria for each method.

Laboratories that pass ed a PT study prior to publication of the UCMR 3 f inal r ule were granted “Pending Approval” for UCMR 3 , contingent upon: 1) changes applied to the f inal r ule as a result of public comments to the proposed r ule, and 2) resolution of any findings resulting in aPage 13 of 50 laboratory audit. Laboratories are not authorized to analyze UCMR 3 monitoring samples until they r eceive formal “Final A pprov al” in writing from EPA. EPA will not accept analytical
results for UCMR 3 samples collected prior to the monitoring date specified in the final UCMR
3.Page 14 of 50 

## Section 3. Laboratory Quality Management Plan and UCMR 3 Quality Assurance Project Plan

A Quality Management Plan ( QMP ) is a document that describes the general practices of an organization or program. The QMP may be viewed as the "umbrella" document under which individual projects are conducted. A Quality Assurance Project Plan (QAPP) documents details specific to an individual project within the organization or program

.


### 3.1 Laboratory Quality Management Plan
Laboratories analyzing samples for UCMR 3 are required to adhere to defined QA/QC proced ures. This ensures that analytical data generated for UCMR 3 are scientifically valid and are of known and acceptable precision and accuracy

. Each laboratory must have a written description of its QA activities detailed in a QMP, which describes the QA man agement of dayto -day routine operations. A QMP documents how an organization will plan, implement, and assess the effectiveness of its QA and QC operations. Specifically, it describes how an organization structures their quality system, including: quality policies and procedures; areas of application; and roles, responsibilities, and authorities. The QMP must be kept current during the time the laboratory is performing UCMR 3 measurements. Laboratories are required to submit a copy of the Table of Contents from their QMP to EPA as part of the UCMR 3 LAP (see Section 2.2).

Certain sections of the laboratory QMP can reference existing documented procedures, such as the laboratory's standard operating procedures (SOPs), EPA analytical m ethods, or other
litera ture (e.g., Standard Methods for the Examination of Water and Wastewater ). More information regarding laboratory QMPs can be found in EPA Requirements for Quality Management Plans (QA/R -2, see Section 9 References )

.

At a minimum, the laboratory’s QMP will address the following topics:

1. Laboratory organization and responsibility

• The laboratory’s organizational chart showing lines of authority, including QA

Managers ;

• A list of key individuals responsible for produc ing valid measurements and conducting

routine assessments of QC procedures and measurements ;

• Identification of the person(s) responsible for internal audits/reviews of the

implementation of the QMP and its requirements; and

• A description of laboratory training to keep personnel current on regulations, methods,

etc.

2. Field sampling

• Personnel responsible for collecting samples ;

• Procedures for sample collection, preservation, containment, holding times, and

transport to the laboratory;Page 15 of 50 3. Laboratory sample handling p rocedures

• Procedures for sample receipt, including criteria for the rejection of samples that do not

meet shipping, holding time and/or preservation requirements;

• Bench sheets used upon sample receipt, during extraction/digestion of samples, and

during ana lysis of samples, extracts or digestates ;

• Storage requirements for samples, extracts, and digestates , including criteria for

temperature and holding times ; and

• Sample tracking used to maintain the integrity of all samples from receipt by the

laboratory through analysis and reporting to disposal.

4. Chemical, reagent and standard control procedures

• Procedures for preparation, labeling, documentation and storage of reagents, chemicals,

calibration standards, surrogate standard s, internal standards , etc. ; and

• Frequency of initial calibration, continuing calibration checks (CCCs) , and validation

of calibrations

.

5. Analytical procedures

• Reference methods and corresponding SOP numbers/names used for each type of

analysis;

• Location of SOPs ;

• Frequency of SOP review ;

• Analytical instrument identification/labeling ; and

• Identification of which analytical instruments are used for each type of analysis.

6. Data reduction, verification, validation and reporting

• Process for converting raw data to reportable concentrations ;

• Process for ensuring the accuracy of data transcription and calculations;

• Process for validating data ;

• Process and format for reporting results to clients ; and

• P rocedure used for data corrections

.

7. QC Procedures

• Types and frequency of QC sample analysis;

• MRL verification procedures, criteria and frequency ;

• Use and criteria for internal and surrogate standards; and

• Procedures for IDCs , and preparation of control charts

.Page 16 of 50 8. Preventive maintenance

• Equipment manual location and availability ;

• Spare parts inventory ; and

• Schedule and procedures for, and documentation of, preventative maintenance

.

9. Corrective action

• Response to obtaining unacceptable results from the analysis of PT samples or internal

QC checks ;

• Identification of the person(s) responsible for determining that corrective action is necessary, and

ensuring that it is completed; and

• Procedure for d ocumenting action s taken and their effectiveness

.

10. Record Keeping

• Procedure for maintaining records, including duration and location ; and

• Procedure for backing- up databases/electronic files

.

The laboratory QMP is to be concise but responsive to the above- listed items. The Q MP
maintain s and improves data dependability and quality.



### 3.2 UCMR 3 Quality Assurance Project Plan

All laboratories seeking approval to perform chemical analyses for UCMR 3 are required to prepare a QAPP specific to UCMR 3 . The UCMR 3 QAPP supplements the laboratory QMP by documenting the specific changes in sample handling, analytical methods, QC, and data reporting that the laboratory makes to address the UCMR 3 requirements. Laboratories must make this document available to EPA for review, if requested.

Mo re information regarding the preparation of a QAPP can be found in EPA Requirements for Quality Assurance Project Plans (QA/R -5 , see Section 9 References )

.Page 17 of 50 

## Section 4. Approved Methods for UCMR 3 Monitoring

Laboratories must use the methods specified in CFR §141.40(a) (3) Table 1 to perform UCMR analyses during the 3- year monitoring period. UCMR 3 methods are summarized below and
listed in Table 1 of this document. UCMR 3 l aboratories must follow all analytical and QC procedures outlined in the methods and in this document (see Section 7 ). Analyses may be conducted only by laboratories formally approved by EPA for UCMR 3 . Sampling and analysis
for UCMR 3 shall not begin prior to the monitoring period specified in the final rule.

EPA Method 200.8 Rev. 5.4, ASTM Method D5673-10, or SM 3125 Determination of Trace Elements in Waters and Wastes by Inductively Coupled Plasma – Mass Spectrometry

Total recoverable a nalytes in a 100- milliliter ( mL ) water sample are solubilized by gentle heating (i.e., digestion) with nitric acid ( do not use hydrochloric acid ) on a hot plate (or hot block) that is set no higher than 85°C. ( Note: For UCMR 3 , all samples for metals analysis by ICP/MS must be digested, regardless of sample turbidity and method .) Microwave digestion, with a reduced sample volume, is allowed only if all QC require ments are met. When the sample volume has been evaporated to approximately 20 mL (this should take about two hours), it is
refluxed for an additional 30 minutes and then removed from heat and allowed to cool. The cooled sample is quantitatively transferred to a 50- mL Class A glass flask or cylinder

. An al iquot of a solution containing internal standards indium (In), scandium (Sc) , and terbium (Tb) is added
and the solution is diluted to volume. The sample is then introduced by pneumatic nebulization into an argon-based, high- temperature radiofrequency plasma where energy transfer processes cause desolvation, atomization and ionization. The ions are extracted from the plasma through a differentially pumped vacuum i nterface and separated on the basis of their mass

- to

- charge ratio (m/z) by a quadrupole mass spectrometer. The ions are then detected by an electron multiplier or Faraday detector, and the ion information is processed by a computer-based data handling
syst em. See Appendix A of this manual for important details regarding specific UCMR 3 analytical requirements

.

EPA Method 218.7 Determination of Hexavalent Chromium in Drinking Water by Ion Chromatography With Post

column Derivatization and UV- visible Spectroscopic Detection

Ammonium sulfate is added to the sample, along with a buffer, to raise sample pH to a value greater than eight. Free chlorine, which may be present in drinking water, reacts with ammonium ions to form chloramines, effectively inhibiting the chlorine- media ted formation of
Chromium -6 from Chromium -3 during sample storage. Above pH 8, hexavalent chromium exists as the stable and soluble chromate anion, CrO 4 -2 . A measured volume of the sample

, usually 1 mL, is introduced into an ion chromatograph. A guard column removes organic compounds from the sample and CrO 4 -2 is separated from other matrix components on an anionexchange column. Derivatization of the chromate anion with 1,5-diphenylcarbazide in a postcolumn reactor is followed by detection of the resulting colored complex at a wavelength of 530

nm. Chromium -6 is qualitatively identified via retention time, and the concentration of CrO 4 -2 in the sample is calculated using the integrated peak area and the external standard technique.Page 18 of 50 Results are report ed in units of μg/L of Chromium -6 (at omic weight 51.996).

EPA Method 300.1, ASTM Method D6581-08, or SM 4110D Determination of Inorganic Anions in Drinking Water by Ion Chromatography

A 10

- mL aliquot of sample is fortified with the surrogate standard dichloroacetate (DCA) and filtered through a 0.45 micron particulate filter using a syringe filtration apparatus. Fifty microliters (μL) of the filtrate are injected into an ion chromatograph fitted with: an anionexchange guard column, an anion- exchange a nalytical column, a background conductivity suppressor device, a conductivity cell detector and a data acquisition system. The anions in the sample are separated on the basis of their relative affinities for the low

- capacity, strongly basic anion exchange columns. The separated anions are directed through the suppressor device where they are converted to their highly conductive acid forms, while the conductivity of the eluent is greatly decreased. The acid forms of the anions are measured by conductivity an d identified on the basis of retention time as compared to calibration standards analyzed under identical conditions. The concentration of each analyte in the sample is calculated by comparing the area of its peak to a standard curve developed from the analysis of the calibration standards.

EPA Method 522 Determination of 1,4-Dioxane by Solid Phase Extraction (SPE) and Gas Chromatography/Mass Spectrometry (GC/MS) with Selected Ion Monitoring (SIM)

A water sample is spiked with the isotopically labeled surrogate standard 1,4 -dioxane-d 8. The sample is extracted using one of two SPE options. In option 1, a 500- mL sample is passed through a method-specific, pre- packed cartridge composed of a 6 mL polypropylene tube containing 2 g rams of coconut charcoal. These cartridges are commercially available from Restek Corp. or United Chemical Technologies Inc. but equivalent brands with a particle size of
80- 120 mesh (approximately 150 μm) meeting all QC criteria in the method may be used. In option 2, a 100- mL sa mple is extracted on a Waters AC

- 2 Sep -Pak or Supelco ENVI-Carb Plus cartridge or equivalent . In both options, the analytes are eluted from the solid phase with dichloromethane, and the extract is concentrated and fo rtified with the internal standard

tetra hydrofuran-d 8 (THF -d 8 ). The final extract is dried with anhydrous sodium sulfate and injected using splitless injection onto a high- resolution fused silica capillary gas chromatography
column interfaced to a mass spectrometer operated in the SIM mode. Sample extract components are separated by the column and identified by comparing the acquired mass spectra and retention times to reference spectra and retention times for calibration standards acquired under identical
GC/MS conditions. Analyte and surrogate standard concentrations are calculated using the multipoint calibration curve established in the method.

EPA Method 524.3 Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry

A 5 -mL aliquot of sample is transferred to a glass sparging vessel along with internal standard s 1,4-difluorobenzene, chlorobenzene-d 5, and 1,4-dichlorobenzene-d 4 and surrogate standards methyl-t-butyl- ether -d 3 , 4-b romofluorobenzene (BFB), and 1,2-dichlorobenzene-d 4

. VolatilePage 19 of 50 organic co ntaminants (VOCs) are purged from the water using helium, and trapped on sorbent material. After drying, the trap is heated and backflushed with helium to transfer the VOCs directly into the gas chromatograph inlet. Fr om the inlet, operated in split mode, analytes are
transferred onto the capillary GC column where they are separated using a gas chromatograph operated in temperature programming mode. Analytes eluting from the GC column are directed
into a mass spectromet er for detection and quantitation. The method analytes are identified by comparing the acquired mass spectra and retention times to reference spectra and retention times for calibration standards acquired under identical GC/MS conditions. The concentration of each analyte is calculated using the internal standard technique and response curves obtained using procedural calibration.

EPA Method 537 Determination of Selected Perfluorinated Alkyl Acids in Drinking Water by Solid Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS)

A 250- mL water sample is fortified with surrogates p erfluoro -n-[1,2- 13 C 2 ]hexanoic acid ( 13 C- PFHxA) and p erfluoro -n-[1,2- 13 C 2 ] decanoic acid ( 13 C- PFDA . Method analytes and surrogates are extracted by passing the sample through an SPE cartridge containing polystyrenedivinylbenzene (SDVB). The analytes are eluted from the solid phase with a small volume of methanol. The extract is concentrated to dryness with nitrogen in a heated water bath.

I nternal standard s p erfluoro -[1,2- 13 C 2 ]octanoic acid ( 13 C- PFOA) and sodium perfluoro-1- [1,2,3,4- 13 C 4 ]octanesulfonate ( 13 C- PFOS) are added, and the extract is adjusted to a 1mL volume
with 96:4% (v:v) methanol:water. The analytes are chromatographically separated by injecting a 10-μL aliquot onto a C 18 column in a liquid chromatograph system that is interfaced to tandem
mass spectrometers . After elution from the column, method analytes are identified by comparing the acquired mass spectra and retention times to reference spectra and retention times for calibration standards acquired under identical LC/MS/MS conditions. The concentration of each analyte is calculated using the internal standard te chnique.

EPA Method 539 Determination of Hormones in Drinking Water by Solid Phase Extraction (SPE) and Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry (LC- ESI-MS/MS)

A 1

- liter ( L) water sample is fortified with surrogate standards e thynylestradiol-d 4 and bisphenol
A-d 16 . Method analytes and surrogates are extracted by passing the sample through an SPE disk containing C 18 functional groups. The analytes are eluted from the solid phase with a small
volume of methanol. The ex tract is concentrated to dryness with nitrogen in a heated water bath. A solution containing internal standards 16 α -hydroxyestradiol-d 2 (Estriol -d 2 ), 13 C 6 - Estradiol,

13 C 2 -e thynylestradiol, and t estosterone -d 3 is added, and the extract is adjusted to a 1- mL volume with 50:50% (v:v) methanol:water. The analytes are chromatographically separated by injecting an aliquot onto a C 18 column in a liquid chromatography system that is interfaced to tandem
mass spectrometers . After elution from the column, method analytes are identified by comparing the acquired mass spectra and retention times to reference spectra and retention times for calibration standards acquired under identical LC- ESI -MS/MS conditions. The concentration of each analyte is calculated using the internal standard technique.Page 20 of 50 Table 1. UCMR 3 Chemical Analytes and Methods

List 1 : Assessment Monitoring

1- Analytical

Method 2- Contaminant 3- CAS Registry
Number 4

- Suggested Quant Ions Parent/Daughter (m/z) 5- MRL (μg/L)

EPA 200.8,
ASTM D5673

- 10 , or SM 3125
Trace Element Metals by ICP/MS* chromium (Cr) 7440

- 47 -3 52 0.2

c obalt (Co) 7440

- 48 -4 59 1.0

m olybdenum (Mo) 7439

- 98 -7 98 1.0

s trontium (Sr) 7440

- 24 -6 88 0.3

v anadium (V) 7440

- 62 -2 51 0.2

EPA 218.7
Hexavalent chromium by IC chromium -6 ( measured

as CrO 4 -2 ) 13907-45-4 Not applicable 0.0 3

EPA 300.1,
ASTM D6581

- 08, or
SM 4110D Inorganic anions by
IC c hlorate 14866

- 68 -3 Not applicable 20

EPA 522 1,4

- Dioxane by
GC/MS 1,4 -d ioxane 123

- 91 -1 88 0.07

EPA 524.3 VOCs by GC/MS 1,1 -d ichloroethane 75

- 34 -3 63 0.03

1,2,3 -t richloropropane 96

- 18 -4 110 0.03

1,3 -b utadiene 106

- 99 -0 54 0.1

b romochloromethane (h alon 1011) 74

- 97 -5 128 0.06

c hlorodifluoromethane (HCFC- 22) 75

- 45 -6 51 0.08

c hloromethane 74

- 87 -3 50 0.2

b romomethane 74

- 83 -9 94 0.2Page 21 of 50 Table 1. UCMR 3 Chemical Analytes and Methods

List 1 : Assessment Monitoring

1- Analytical

Method 2- Contaminant 3- CAS Registry
Number 4

- Suggested Quant Ions Parent/Daughter (m/z) 5- MRL (μg/L)

EPA 537
Perfluorinated compounds by

LC/MS/MS p erfluorooctanesulfonic acid (PFOS) 1763

- 23 -1 499/80 0.04

p erfluorooctan o ic acid (PFOA) 335

- 67 -1 413/369 0.02

p erfluorohexanesulfonic acid (PFHxS) 355

- 46 -4 399/80 0.03

p erfluoroheptanoic acid (PFHpA) 375

- 85 -9 363/319 0.01

p erfluorononanoic acid (PFNA) 375

- 95 -1 463/419 0.02

p erfluorobutanesulfonic acid (PFBS) 375

- 73 -5 299/80 0.09

List 2 : Screening Survey

EPA 539 Hormones by
LC/MS/MS 17 α -e thynylestradiol 57

- 63 -6 295 .1 /144.7 0.0009

17 β

- e stradiol 50

- 28 -2 271 .2 /144.7 0.0004

e quilin 474

- 86 -2 267 .1 /142.7 0.004

e striol 50

- 27 -1 287/144.7 0.0008

e strone 53

- 16 -7 26 8.9 /144.7 0.002

t estosterone 58

- 22 -0 289 .1 /96.8 0.0001

4-a ndrostene

- 3,17

- dione 63

- 05 -8 287 .1 /96.6 0.0003

* See Appendix A of this manual for specific requirements.

Explanation of Table 1 column headings :

1 Analytical Method: Method number and condensed method name for methods that must be used to analyze samples for the applicable UCMR 3 contaminant(s). Reference informatio n for the methods is
listed in Section 9 References.

2 Contaminant : The name of the contaminant and abbreviation (if applicable) to be analyzed.

3 CAS Registry Number: A unique numerical identifier for the chemical, ass igned by Chemical Abstract Service (CAS), a division of the American Chemical Society.

4 Suggested Quant Ions: Acceptable mass to charge ion ratio to be used for the quantitation of the analyte, for methods using MS . For MS/MS methods, the precursor / produc t ions are listed. For the m etals methods (EPA 200.8, ASTM D5673

- 10 , SM 3125), all isotopes listed in Appendix A must be monitored

.
5 Minimum Reporting Level: The lowest concentration of each analyte that must be reported to EPA.Page 22 of 50 

## Section 5. Initial Demonstration of a Laboratory's Ability to
Perform UCMR 3 Analyses

Each laboratory seeking approval for UCMR 3 methods must complete an initial demonstration
of capability study for each method. EPA recognizes that a laboratory may use multiple instruments and analysts to perform analysis. If more than one analyst perform s UCMR 3 analyses, EPA recommends that each analyst perform an IDC study before they analyze UCMR
3 samples . Similarly, an IDC study is to be performed using each instrument that will be u sed to analyze UCMR 3 samples . This will e nsure that each operator and each instrument maintain s the minimum quality standards. Data from each of these tests are to be maintained at the laboratory
for EPA’s review in the event that the Agency wishes to con duct an audit before or during the
UCMR 3 monitoring and data analysis period.

IDC study data must be submitted as part of the laboratory approval application package. One set of IDC study data, representative of typical performance of the operators and instruments used for the applicable method, is to be included in the application package for each method. The
UCMR 3 method- specific application sheets provide the format for reporting these data.

EPA recommends that the laboratory verify the instrument calibration and sensitivity prior to performing the IDC study. The calibration curve must encompass the MRL concentration. The IDC study involves demonstration of: 1) low system background, 2) precision, 3) accuracy

, and 4) the laboratory’s ability to achieve the MRLs, as follows:

1. Initial Demonstration of Low System Background

– Analyze an LRB to verify that none of the analytes of interest are found above 1⁄3 to 1⁄2 the MRL, depending on the
method used (Table 2 ).

2. Initial Demonstration of Precision (IDP) – Analyze 4 to 7 laboratory fortified blank (LFB) samples, as specified in the method , consisting of reagent water fortified at the "precision demonstration" concentration for each analyte of interest ( i.e., 2xMRL to 5xMRL). EPA recommends that these samples be fortified with a solution of method analytes obtained from a source external to the laboratory and different from the source
of the calibration standards. The relativ e standard deviation (RSD) of the resulting analytical data set must meet the criterion specified in Table 2.

3. Initial Demonstration of Accuracy (IDA)

– Calculate the average recovery for the data set generated for the IDP (see preceding paragraph) using Equation 1. The average recovery must meet the criteria specified in Table 2

.



### %100 1 

### ×÷ 

# ∑

= actual n

i i 

### LFB

n LFB
Equation 1

4. MRL Verification

– Laboratories must verify they can achieve the UCMR 3 MRL for
each analyte according to the procedure outlined in Section 6.Page 23 of 50 Table 2. IDC Requirements

Analytical Method LRB Requirement Acceptable
Precision Acceptable Recovery ( Accuracy ) MRL Requirement

EPA 200.8,
ASTM D5673

- 10

, SM 3125

Metals

No analyte
>1⁄3MRL RSD ≤ 10 % 85

– 115 % of true
value

Achieve laboratory

MRLs at or below
values listed in Table 1
for each of the
UCMR 3 analytes EPA 218.7
Ch romium

- 6 RSD ≤ 15% 85

– 11 5 % of true
value

EPA 300.1, ASTM
D6581

- 08,
SM 4110D

Chlorate RSD ≤ 15 % 75
- 125 % of true
value

EPA 522 1,4

- Dioxane RSD < 20 % 8 0

– 1 2 0% of true
value

EPA 524.3
VOCs No analyte
>1⁄2MRL RSD ≤ 20 % 8 0

– 1 2 0% of true
value

EPA 537 Perfluorinated

Compounds No analyte
>1⁄3MRL RSD < 20 % 70

– 130% of true
value

EPA 539
Hormones RSD ≤ 20 % 70

– 130% of true
valuePage 24 of 50 

## Section 6. Minimum Reporting Levels

The UCMR 3 analyte MRLs are statistically -based and were established by EPA using the lowest concentration minimum reporting levels (LCMRLs) determined by multiple laboratories according to the procedure detailed in Technical Basis for the Lowest Concentration Minimum Reporting Level (LCMRL) Calculator . The MRL s established for the UCMR 3 analytes are presented in Table 1 . All laboratories performing analys is for the UCMR 3 must be able to measure the analyte concentrations at these levels with specified accuracy and precision. (See
Section 7 for the criteria .)

As part of the UCMR 3 LAP application process, laboratories must verify they can achieve the
UCMR 3 MRLs for each analyte according to the procedure in CFR §141.40(a)(5) (iii) and
outlined below.

1. Fortify, process and analyze seven replicate LFBs. These L FBs must: contain all dechlorinating agents and preservatives specified by the method, contain each UCMR 3 analyte of interest at a concentration at or below the UCMR 3 MRL, and be processed through the entire method procedure (i.e., including extraction o r digestion , where applicable). Dechlorinating agents and preservatives are listed in Table 12

.

2. Using the results from the analysis of the seven replicates, calculate the mean ( x ̄ ) and standard deviation (s ) for these replicates. Determine the half range for the prediction interval of results ( HR PIR ) using Equation 2:

s963.3 HR PIR ×= Equation 2

(N ote: the factor 3.963 is specific only to use of seven replicates.)

3. Confirm that the upper and lower limits for the prediction interval of the result (PIR =

x ̄ + HR PIR ) meet the upper and lower recovery limits.

The upper

%150%100 ≤× +

TrueValue HR x PIR PIR limit must be ≤150 percent recovery:

Equation 3

T he lower PIR limit must be ≥50 percent recovery:

%50%100 ≥× − HR x PIR Equation 4 T

rueValue

T he MRL is validated if both the upper and lower PIR limits meet these criteria.

These calculations are illustrated in Example 1.Page 25 of 50 Example 1. Calculation of the PIR Limits (where the true value of the LFB concentratio n is 0.60μg/L)

LFB Results (x) 0.60 0.59 0.55 0.60 0.62 0.58 0.67

Step 1. Calculate the Mean ( x )



### 6014.0 7 21.4 1 

### =→=→ = 

# ∑

= 

### x x

n LFB

x n

i i

Step 2. Calculate the Standard Deviation ( s )



## ( )

0372.0 6 0083.0

1 1 2

=→ =→

− −

= 

## ∑

= s s

n x LFB

s n

i i

Step 3. Calculate the Half Range for the PIR (HR PIR )

147.0 HR 0372.0963.3 HR s963.3 HR PIR PIR PIR =→×=→×=

Step 4. Calculate the Upper PIR Limit (PIR upper )

%7.124 %100 60.0 147.06014.0 %100 = →× +

= →× +

= upper upper PIR

upper PIR PIR TrueValue HR x PIR

→ P asses (≤ 150%)

Step 5. Calculate the Lower PIR Limit (PIR lower )

%7.75 %100 60.0 147.06014.0 %100 = →× −

= →× −

= lower lower PIR
lower PIR PIR TrueValue HR x PIR

→ Passes ( ≥ 50%)Page 26 of 50 

## Section 7 . Quality Control Requirements

Laboratories applying for approval to analyze samples for UCMR 3 must use the analytical methods specified in Section 4 of this manual. Laboratories must follow the QC procedures outlined in the method(s) and in this manual.

Field blank and sampling requirements are discussed in Section 8.1. Appendix A contains UCMR 3 specific requirements for the analysis of metals by ICP/MS , including required isotopes to monitor, and correction equations to be used.

An extraction or digestion batch is defined as all samples prepared/extracted/digested together by the same person during a work day. The same lots of reagents/solvents and internal standard/surrogate stan dard/analyte fortification solutions must be used for all samples included in a batch. For methods that use SPE techniques, it is preferable to use the same lot of pre

- tested SPE medium. A maximum of 20 field samples (i.e., non- QC samples) can be included in an extraction or digestion batch. The extraction/digestion batch must be identified with a unique and
traceable ID code or name.

In preparing samples for analysis, each digestion or extraction batch must include the following QC samples, at a minimum:

• an LRB ;

• an LFB spiked at a concentration less than or equal to the MRL (LFB≤MRL) ;

• and an LFSM/LFSMD pair spiked at a low or mid

- level concentration (rotating concentrations from batch to batch)

.

Results from the analysis of these QC samples are used to evaluate the va lidity of the sample processing procedures and techniques. Further explanation of the UCMR 3 requirements and criteria for these QC samples is presented in Sections 7.5 through 7.8.

An analytical batch is defined as a group of field samples analyzed using the same instrument within a 24-hour period. For UCMR 3 , analytical batches cannot include more than 20 field samples . QC samples are not counted in determining the number of samples in the analytical batch. The 24-hour period begins with the analysis of the first low-level CCC standard and ends with the analysis of the final mid
- or high

- level CCC standard. The analytic al batch may or may not be comprised of field samples that were processed together in the same extraction or digestion batch. Ideally, however, field samples and corresponding QC samples in the same extraction or digestion batch should be analyzed in the s ame analytical batch. Each analytical batch must be identified with a unique and traceable ID code or name that is different than the extraction or digestion batch ID used in processing the samples. Field samples with QC failures may be re- analyzed immediately at the end of the analytical batch, but must be followed by a passing end CCC. I f this is not possible, the re

- analysis will need to be performed in a new analytical batch with a different ID and complete QA/QC analyses as appropriate to the method

an alytical batch

.

All UCMR 3 methods require fortification of field samples, QC samples, and calibration standards with surrogate and/or internal standards, with the exception of 218.7. The method-Page 27 of 50 specific surrogate and internal standard requirements and criteria are summarized in Sections 7.3
and 7 .4, respectively

. The surrogate and internal standards must be monitored during analysis of calibration standards (Section 7.1 and 7 .2) as well as field and QC samples.

Laboratory personnel i nvolved in UCMR 3 must be very familiar with general and methodspecific procedures to:

• prepare, label

, and store standards and reagents;

• prepare samples for analysis;

• calibrate and operate the analytical instrumentation;

• monitor system performance;

• troubleshoot problems;

• maintain thorough documentation of activities; and

• and review and report data.



### 7 .1 Initial Calibration of Analytical Instruments

Each method describes initial calibration procedures used to determine the concentrations of the method analytes. Some methods allow more than one option. The laboratory must select and
follow one of the initial calibration procedures outlined in the approved method in order to meet the requirements of UCMR 3 . For mass spectrometry methods, laboratories mus t meet the
method- specific mass spectrometer tuning criteria prior to performing the initial calibration procedure.

If allowed by the method, d ifferent types of calibration (e.g., linear regression, quadratic fit, response factor calculation) and differen t fit types (e.g., forcing the curve through the origin, ignoring the origin, weighting factors) may be used for different analytes within a given method. However, the same calibration and fit type must be used for a given analyte for all analyses that

are based on a given initial calibration. If modifications to the calibration or fit type are made,
the instrument must be recalibrated.

The calibration curve for each UCMR 3 method must span the expected concentration range of the samples being analyzed, and must include a standard with a concentration less than or equal to the MRL. Some methods specify the minimum number and maximum range of standard concentrations to use for the calibration curve, and some do not. Laboratories must use a minimum of five ca libration standards for all UCMR 3 methods. More than five standards must be used if specified by the method, such as EPA Method s 218.7 and 524.3.

Calibration standards for Methods 218.7, 200.8, 300.1, and 524.3 require the addition of the same preservatives and dechlorinating agents as used in the field samples.

The recovery of UCMR 3 analytes, surrogate standards and internal standard s must be monitored
in the initial calibration standards using the calibration curve created from the initial calibration
data. Recoveries must meet the criteria defined in Table 3 . If any surrogate or internal standard
fails the criterion in a calibration standard, the data from that standard cannot be used in calculating the calibration curve. If all surrogate a nd internal standard s pass the criteria, and a subset (but not all) of the analytes pass the recovery criterion, only the data for the passing analytes may be used in calculating the calibration curve. Standards with failed recoveries must be reanalyzed (and possibly re- prepared) until passing data are generated.Page 28 of 50 Method 537 for perfluorinated compounds has some special considerations for calibration. During Method 537 development, standards containing linear and branched isomers were not available for all the perfluorinated compounds. However, Method 537 requires that all the perfluorinated analytes be purchased as technical grade standards or neat material, if

commer cially available

, to account for the presence of various isomeric forms . Section 12.4 of Method 537 describes how to sum the areas of the isomers, but it only referred to the UCMR 3 compound PFHxS and PFOS which could be purchased at the time as technical grade. I f technical grade PFOA, PFNA, PFHpA and PFBS become commercially available, quantitation should be performed as described in Section 12.4 of the method.

All UCMR 3 methods require verification of t he initial calibration with a Quality Control S ample (QCS) prepared from a source different than that used to prepare the initial calibration standards. If a second source is not available, the QCS is to be prepared from a different lot of the source used to prepare the initial calibration standards. E PA recommends preparing the QCS at a
concentration near the mid -point of the calibration curve. The QCS must contain internal standard(s) from the same source used in the initial calibration standards. The acceptance criteria for the QCS are the same as those for CCC standards with concentrations greater than the MRL (see Section 7.2), with the exception of the metals methods for which the criterion is ±10%. The initial calibration must be verified with a QCS each time a new analyte primary dilution standar d is prepared, and at least quarterly.

Laboratories must adhere to the holding time limitations for standard solutions, as well as other reagents and solutions, as specified in the individual methods. Expiration dates for prepared solutions cannot extend beyond the expiration date for the stock solution(s) from which they were prepared. If multiple stock solutions are used, the shortest expiration date applies. It is critical that laboratories closely monitor the expiration of calibration standards.

La boratories must adhere to the QC criteria limits and are NOT permitted to accept sample data when any QC parameter shows a high bias that exceeds the QC criteria limits. The only exception is limited to two methods (Method 522 and Method 537) and exclusiv ely applies to limited allowance for high CCC recovery, as discussed further in Section 7.2.Page 29 of 50 Table 3. Initial Calibration Acceptance Criteria a

Analytical Method Recovery as % of true value

Internal Standard Response Analytes

>MRL Analytes
≤ MRL Surrogate
Standard

EPA 200.8, ASTM D5673-10,
SM 3125 90 – 110% 50 – 150% NA 60 – 125% of the response in the
calibration blank
Metals

EPA 218.7
Chromium-6 85 – 115% 50 – 150% NA NA

EPA 300.1, ASTM D6581-08,
SM 4110D

Chlorate 85 – 115% b 75 – 125% c 90 – 115% NA

EPA 522 1,4-Dioxane 80 – 120% d 60 – 140% e 70 – 130% of the average IS response in all calibration standards EPA 524.3
VOCs 70 – 130% 50 – 150%

70 – 140% of the average IS
EPA 537 response in all calibration standards Perfluorinated 70 – 130% 50 – 150% e 70 – 130% AND < 20% RPD among IS

Compounds responses in the lowest and highest
calibration standards f

EPA 539
Hormones 70 – 130% 50 – 150% 70 – 130% of the average IS response in all calibration standards

a For methods 218.7, 522, 524.3, 537, and 539 calibration standard responses must be entered into the calibration curve equation and the resultant calculated an alyte concentrations must meet the accuracy criteria
listed in the table

b Applies to all chlorate methods when the true concentration of the analyte is >10xMRL.

c Applies to all chlorate methods when the true concentration of the analyte is ≤ 10xMRL.

d Applies to all Method 522 Initial calibration standards except the lowest concentration.

e Applies only to the lowest Initial calibration concentration for Methods 522 and 537.

f RPD between the high (H) and low (L) areas for each IS is calculated using the following equation: RPD ൌ
ሺୌି୐ሻ
ሺୌା୐ሻ/ଶ ൈ 100%



### 7.2 Continuing Calibration Checks

Once established, the calibration curve for a method must be verified each day that analysis is
conducted. For all UCMR 3 methods, the initial calibration must be verified with a low-level (i.e., concentration ≤ MRL) CCC standard prior to the analysis of field (i.e., non-QC) samples. Even if the calibration curve is establis hed on the day of analysis by analyzing the entire suite of initial calibration standards, laboratories must analyze a low-level CCC standard prior to field samples. The initial calibration must also be verified throughout each day by analyzing a CCC standard after every tenth fiel d sample, and at the end of the analytical batch, alternating between the mid- and high-level concentrations on the calibration curve.Page 30 of 50 CCC standards must meet the criteria defined in Table 4. The low- level CCC standard must meet
the criteria before any samples are analyzed, and all samples must be bracketed by CCC standards that pass the criteria. Analytical results for a group of up to 10 samples are considered valid only if the CCC standa rds analyzed before and after the group meet the criteria.

If criteria are not met for a CCC standard, then the source of the problem must be identified and eliminated. This may require instrument maintenance and the generation of a new instrument calibration curve according to the method initial calibration proce dures. All samples or extracts analyzed between the failing CCC standard and the last acceptable CCC standard must be reanalyzed for the failing analyte(s) after the problem is resolved. If the samples or extracts cannot be reanalyzed, then data for the problem analyte(s) are considered invalid for those samples and the data must not be reported. Laboratories r eporting invalid data will be subject

to revocation of UCMR 3 laboratory approval status. Once approval is revoked, the laboratory cannot be reapprov ed during the UCMR 3 monitoring period.

NOTE – The only exceptions for the CCC criteria apply to the specific allowance for accepting field sample results where no measured target analytes were observed, as applicable and defined
within the following two methods:

1. Method 522 - specific and exclusive to the end CCC results and high recoveries for target analytes and/or surrogate recovery in that end CCC analysis.
2. Method 537 - specific to CCC results and high recoveries exclusive to target analytes.

EPA cautions laboratories that this allowance should rarely be invoked (in less than 5% of analytical batches) . Laboratories using the high bias allowance more frequently are demonstrating a willful disregard for QC criteria by failing to take effective corr ective action to address a serious systematic problem at their laboratory. A quality conscious laboratory will not allow high bias problems to persist and will not find recurring high bias observations in CCC standard analysis. During future EPA audits, if there are findings that document chronic use of this high bias CCC allowance, the laboratory will risk revocation of EPA approval.Page 31 of 50 Table 4 . CCC Acceptance Criteria

Analytical Method Recovery as % of true value

Internal Standard Response Mid and High Level
CCC ( Analytes

>MRL ) Low Level
CCC ( Analytes

≤MRL ) Surrogate
Standard

EPA 200.8,
ASTM D5673

- 10

, SM 3125

Metals 85

– 115% 50

– 150% NA 60

– 125% the response in the
calibration blank

EPA 218.7
Chromium

- 6 85

– 115% 50

– 150% NA NA

EPA 300.1, ASTM
D6581

- 08,
SM 4110D

Chlorate 85

– 115% a 75

– 125% b 90

– 115% NA

EPA 522 1,4

- Dioxane

70

– 130% 50

– 150% 70

– 130% ±30% the response in the most

recent previous CCC and ±50% the

average response in the initial
calibration EPA 524.3
VOCs

EPA 537 Perfluorinated

Compounds 70

- 140% the response in the most

recent previous CCC and ±50% the

average response in the initial
calibration

EPA 539
Hormones ±50% the average response in the
initial calibration

a Applies to all chlorate methods when the true concentration of the analytes is >10xMRL.

b Applies to all chlorate methods when the true concentration of the analyte is ≤10xMRL.



### 7 .3 Surrogate Requirements and Criteria

Surrogate analyte(s) are required for all UCMR 3 methods, with the exception of the metals
methods and Method 218.7 . A surrogate is a pure analyte that is very unlikely to be found in any sample. It is added to the aqueous sample in a known amount before the sample is processed, and
is measured with the same procedures used to measure other sample components. The purpose of

a surrogate analyte is to monitor method performance for each sample, from processing through analysis. Surrogate recovery must be monitored for each field sample, standard and QC sam ple. Therefore, surrogate analyte(s) must be added to all aqueous samples including LRBs, LFBs,
LFSMs and LSFMDs , and to all standards. During IDC studies, such as demonstrations of accuracy and precision and MRL verifications (see Section 5), the surrogat e standard recovery must pass the acceptance criteria.

The method- recommended surrogate analytes are listed in Table 5, along with recommended concentrations and the analytical acceptance criteria. When the method provides flexibility in the selection of the surrogate or its concentration, EPA allows the same flexibility for UCMR 3

.Page 32 of 50 However, the concentration of each surrogate analyte must be the same in field and QC samples

, or their extracts/digestates (whichever is introduced into the analytical instrum ent), as it is in the
calibration standards.

Table 5

. S urrogate Standards , Concentrations and Criteria

Analytical Method Recommended Surrogate Standard Recommended
Concentration in Sample Acceptance
Criteria (% recovery of

true value)

EPA 200.8,
ASTM D5673

- 10

, SM 3125

Metals NA

EPA 218.7
Chromium

- 6 NA

EPA 300.1, ASTM
D6581

- 08,
SM 4110D

Chlorate 0.5 mg/mL DCA a 1 mg/L 90

– 115%

EPA 522 1,4

- Dioxane 200 μg/mL or
2000 μg/mL 1,4

- Dioxane

- d 8 10 μg/L

70

– 130% EPA 524.3
VOCs 1000

– 2500 μg/mL Methyl -t- butyl

- ether -d 3 , BFB, & 1,2

- Dichlorobenzene -d 4 At the mid

- level of
the initial
calibration for analytes b

EPA 537 Perfluorinated

Compounds 1

– 4 ng/μL

13 C- PFHxA, 13 C- PFDA,
& d 5 - NEtFOSAA 40

– 160 ng/L

EPA 539
Hormones 7.0 μg/mL Ethynylestradiol -d 4 70 ng/L

2.5 μg/mL Bisphenol A -d 16 25 ng/L

a A surrogate standard must be used, regardless of which method is selected. A n alternate to DCA may be used

,

provided it is a n analyte not present in drinking water at concentrations greater than 5% of the fortified level.

b For example, 5μg/L if using full scan mode and 0.5μg/L if using SIM mode.

The percent recovery of the surrogate in a sample is calculated by comparing the analytically measured concentration to the fortified concentration, as in Equation 5:

Surrogate % Recovery = Measured [ surrogate ] X 100% Equation 5 Expected [surrogate]

If th e surrogate in a specific sample does not meet the acceptance criteria, then the laboratory should process a new aliquot of the sample. If this is not possible, then the data for that sample are considered suspect for the analysis in question, and is to be flagged as not meeting QC
criteria. D ata for samples with fail ed surrogate standard recovery must not be reported. If possible, the laboratory should process a new aliquot of the sample.Page 33 of 50 If the surrogate recovery in an LRB or LFB fail the acceptance criteria, all data for other samples in the extraction or in the analytical batch for methods that require the direct analysis of samples (i.e., the chlorate methods and EPA 524.3), are invalid and must not be reported. If possible, the laboratory should process new aliquots of the affected samples.

If the surrogate recovery in an LFSM or LFSMD fail the acceptance criteria, but all other batch QC pass, only the fortified matrix sample with the failed surrogate is impacted and cannot be reported. If the LFSM fails, the LFSMD data should be substituted for the LFSM such that accuracy can be assessed. If both LFSM and LFSMD fail, no matrix spike data are reported. Surrogate recovery failure of the LFSM and LFSMD do not invalidate the associated sample
results.



### 7 .4 Internal Standard Requirements and Criteria

I nternal standard s are required for calibration and quantitation purposes in all UCMR 3 methods, with the exception of Method 218.7 and the chl orate methods. An internal standard is a pure analyte that is added to a sample or sample extract/digestate in a known amount. It is used to measure the relative responses of other method analytes and surrogate standards that are components of the same solution. The internal standard must be an analyte that is not a sample component. When used, the internal standard is added to all samples, standards, and QC samples
or their extracts /digestates . During IDC studies, such as demonstrations of accuracy and

pre cision and MRL verifications (see Section 5), the internal standard recovery must pass the acceptance criteria.

For UCMR 3 analysis, EPA is requiring the use of the method specific internal standard s to ensure the comparability of results amongst laboratories. Table 6 lists the internal standards

, along with recommended concentrations and the analytical acceptance criteria. When the method provides flexibility in the concentration of the internal standard, EPA allows the same flexibility
for UCMR 3 . However, the concentration of each internal standard must be the same in field and QC samples

, or their extracts/digestates (whichever is introduced into the analytical instrument)

, as it is in the calibration standards.Page 34 of 50 Table 6 . Internal Standards, Co ncentrations and Criteria

Analytical Method Internal Standard Recommended
Concentration Acceptance Criteria

EPA 200.8,
ASTM D5673

- 10

, SM 3125

Metals In, Sc, & Tb 20
- 200μg/L 60

– 125% the response in
the calibration blank

EPA 218.7
Chromium

- 6 NA

EPA 300.1,
ASTM D6581

- 08,
SM 4110D

Chlorate NA

EPA 522 1,4

- Dioxane THF -d 8 500 ng/mL in final
extract or standard ±30% the most recent previous CCC and ±50%

the average area in the
initial calibration EPA 524.3
VOCs 1,4

- Difluorobenzene,
Chlorobenzene -d 5 , 1,4

- Dichlorobenzene

- d 5 Mid

- level*

EPA 537 Perfluorinated

Compounds 13 C- PFOA, 13 C- PFOS,
d 3 - NMeFOSAA 10
- 40 pg/μL in final
extract or standard 70

- 140% the most recent previous CCC and ±50%

the average area in the
initial calibration

EPA 539
Hormones Estriol

- d 2 , 13 C 6 - Estradiol,

13 C 2 - Ethynylestradiol,

Testosterone

- d 3 5
- 20 ng/mL in the
final extract or
standard ±50% the average area in
the initial calibration

* For example, 5 μg/L if using full scan mode and 0.5 μg/L if using SIM mode.

If the internal standard recovery in a sample fails the acceptance criteria, then the results for that sample are invalid. Data for samples with fail ed internal standard criteria must not be reported

. If possible, the laboratory should process a new aliquot of the sample.

If the internal standard recoveries in an LRB or LFB fail the acceptance criteria, all data for other sample s in the extraction or digestion batch , or in the analytical batch for methods that require the direct analysis of samples, are invalid and must not be reported. If possible, the laboratory should process new aliquots of the affected samples.

If the internal standard recovery in an LFSM or LFSMD fail the acceptance criteria, but all other batch QC pass, only the fortified matrix sample with the failed internal standard is impacted and cannot be reported. If the LFSM fails, the LFSMD data should be substituted for the LFSM such that accuracy can be assessed. If both LFSM and LFSMD fail, no matrix spike data are to be reported. Internal standard recovery failure of the LFSM and LFSMD do not invalidate the associated sample results.Page 35 of 50 

### 7 .5 Laboratory Reagent Blank
Laboratory reagent blanks are required in each batch of field samples for a ll of the methods approved for UCMR 3 monitoring. Methods that require the extraction or digestion of samples to prepare them for analysis must process a minimum of one LRB with every batch of 20 or fewer
field samples and that LRB should be processed with that extraction/digestion batch of field samples . Methods involving the direct analysis of samples (i.e., the chlorate methods and EPA Methods 524.3 and 218.7) require a minimum of one LRB analyzed with every batch of 20 or fewer field samples. For all methods, an LRB is defined as an aliquot of reagent w ater that is treated exactly as a sample, including exposure to all glassware, equipment, solvents, reagents,
internal standards and surrogate standards that are used with the other samples in the batch. This blank determines if method analytes or other in terferences are present in the laboratory environment, reagents or apparatus.

The goal for UCMR 3 is to ensure that background contamination levels are low enough that they do not interfere with accurate measurement of the UCMR 3 analytes . If any of the method analytes are detected in the LRB at a concentration greater than the criterion specified in Table 7, then no further analyses are to be performed until the source of the problem is identified and eliminated. If the source is traced to any material that was used in the preparation of a batch of samples, then a new aliquot of each sample is to be prepared. If the samples cannot be re

proc essed, then all data for the problem analyte(s) are considered invalid for all samples in the
batch , and t he data is to be flagged as not meeting the QC criteria. Data for samples processed
with an LRB that fails the criteria must not be reported

.

Contamination problems that occur during sample processing cannot be detected until the analysis step. If a problem is discovered, then the data for one or more analytes in all the samples in the extraction or digestion batch are lost unless the laboratory has a back -up aliquot of each sample to extract. EPA has limited the extraction/digestion batch to 20 field samples to minimize the number of samples that may be lost due to a contamination problem. More than one batch of samples may be extracted within a day; a n LRB must be extracted with each batch.Page 36 of 50 Table 7 . Laboratory Reagent Blank Criteria

Analytical Method LRB Acceptance Criteria

EPA 200.8,
ASTM D5673

- 10

, SM 3125

Metals

The measured concentration of each target analyte must be < 1⁄3 MRL.
Internal standard and surrogate standard recoveries must meet the criteria specified in Tables 5 and 6 , if applicable

. EPA 218.7
Chromium

- 6

EPA 300.1,
ASTM D6581

- 08,
SM 4110D

Chlorate

EPA 522 1,4

- Dioxane

EPA 524.3
VOCs The measured concentration of each target analyte must be < 1⁄2MRL.
Internal standard and surrogate standard recoveries must meet the criteria specified in Tables 5 and 6.

EPA 537 Perfluorinated Compounds The measured concentration of each target analyte must be < 1⁄3 MRL.
Internal standard and surrogate standard recoveries must meet the criteria specified in Tables 5 and 6. EPA 539
Hormones



### 7.6 Laboratory Fortified Blank

The LFB is an aliquot of reagent water or other blank matrix to which known quantities of the method analytes are added in the laboratory. The LFB is processed exactly like a sample, including the addition of sample dechlorinators/preservatives. The same lot of reagents and
internal standard and/or surrogate standard fortifying solutions must be used for all samples
included in a batch. The same fortification solution used to prepare the LFB should be used to prepare the matrix spike samples. The results from the analysis of LFBs determine whether the methodology is functioning, and whether the laboratory is capable of making accurate and precise measurements. Results from these QC sample s provide information about the entire process, from sample processing to analyte separation and detection.

With the exception of EPA 218.7 and EPA 524.3, all other methods approved for UCMR 3 monitoring require the extraction and analysis of an LFB. Since EPA 218.7 and EPA 524.3 utilize procedural calibration standards, there is no difference between the LFB and the CCC for ONLY these methods. For these two methods, laboratories should prepare the CCCs using the same fortification solution used to prepare the Laboratory Fortified Matrix Sample (LFSM). This will establish a positive control for matrix spike recoveries.

An LFB must be processed with each extraction or digestion batch of 20 or fewer samples, and an LFB must be analyzed for every 20 (or fewer) samples. For UCMR 3 , laboratories are specifically required to analyze an LFB fortified at or below the MRL prior to analyzing field samples

. EPA recommends laboratories also process an additional mid - or high- level LFB, and analyze it later in the analytical batch. The measured concentration for each UCMR 3Page 37 of 50 analyte in the LF Bs must meet the criteria listed in Table 8 . If the recovery for any analyte in the
low- level LFB ( ≤MRL ) is not within the criteria , the analyst may elect to re -run it

. However, if it
fails again , the analyst must correct the problem before analyzing field samples. If the source is traced to any material that was used in the preparation of the batch of samples, then another aliquot of each sample must be prepared for analysis. If this is not possible, then all data for the problem analyte(s) are considered invalid for all samples in the batch , and is to be flagged as not meeting the QC criteria. Data for samples processed with an LFB that fails the criteria must not be reported

.

Table 8

. Laboratory Fortified Blank Acceptance Criteria

Analytical Method Recovery as % of true value

Internal Standard Response Mid and High Level

LFB Analytes

>MRL Low Level
LFB Analytes

≤MRL Surrogate
Standard

EPA 200.8,
ASTM D5673

- 10

, SM 3125

Metals 85

– 115% 50

– 150% NA 60

– 125% the response in the
calibration blank

EPA 300.1,
ASTM D6581

- 08,
SM 4110D

Chlorate 85

– 115% a 75

– 125% b 90

– 115% NA

EPA 522 1,4

- Dioxane

70

– 130% 50

– 150% 70

– 130% ±30% the response in the most

recent previous CCC and ±50%
the mean area measured in the
initial calibration

EPA 537 Perfluorinated

Compounds 70

- 140% the response in the

most recent previous CCC and ±50% the average area measured
in the initial calibration

EPA 539
Hormones ±50% the average response in the
initial calibration

a Applies to all chlorate methods when the true concentration of the analytes is >10xMRL.

b Applies to all chlorate methods when the true concentration of the analyte is ≤10xMRL.



### 7.7 Quality Control Sample (QCS)

All of the UCMR 3 analytical methods require that the laboratory analyze a QCS at least quarterly. A QCS is a solution of method analytes of known concentration used to fortify an aliquot of reagent water or a sample matrix, obtained from a source external to the laboratory, and different from the source of calibration standards. As explained in Section 7.1, EPA recommends the concentration of the QCS be near the midpoint of the calibration curve. If a source separate from the one used to obtain calibration standards is not available, labs should at least purchase standards that are from a different lot than the calibration standards. The QCS is used to check laboratory performance. Laboratories may wish to check their performance using QCSs containing concentrations that are known to them. Laboratories can prepare their ownPage 38 of 50 QCSs or purchase them from a commercial supplier (if available). Splitting samples with another laboratory is another mechanism for evaluating performance. Use of either or both of these procedures is encouraged, especially when a new analyst is developing capabilities to perform a method. Table 9 lists the minimum QCS analysis frequency for each UCMR 3 analytical method. Labs may analyze a QCS more frequently to monitor method/analyte performance, and failure to analyze a QCS at method

- stipulated frequencies is viewed as a deficiency/finding during a laboratory audit.

Table 9. QCS Frequency Requirements
Analytical Method QCS Frequency Requirements

EPA 200.8
ASTM D 5673

- 10
SM 3125 During IDC (beginning method use) At least quarterly

EPA 218.7 During IDC (beginning method use) Each time new calibration standards are prepared At least quarterly

EPA 300.1
ASTM D6581

- 08
SM 4110D During IDC (beginning method use) At least quarterly

EPA 522 During IDC (beginning method use) Each time new calibration standards are prepared At least quarterly

EPA 524.3 During IDC (beginning method use) At least quarterly

EPA 537 During IDC (beginning method use) Each time new analyte primary dilution standards are prepared At least quarterly

EPA 539 During IDC (beginning method use) Each time new analyte primary dilution standards are prepared At least quarterly



### 7. 8 Laboratory Fortified Sample Matrix (Spiked Sample)

An LFSM is an aliquot of an environmental sample to which known quantities of the method analytes are added in the laboratory. This fortified sample is analyzed exactly like a field sample, and its purpose is to determine whether the sample matrix contributes bias to the analytical results. The concentrations of the analytes in the unfortified sample matrix must be determined in a separate aliquot.

A technique to evaluate laboratory precision and accuracy for a method is to determine the precision of replica te analytical results from the separate processing and analysis of duplicate volumes of a sample. However, this technique is only useful when the original sample contains background concentrations of the method analytes. Since the laboratory does not know which samples may contain measurable concentrations of target analytes, LFSMD samples are used to determine the precision of the UCMR 3 monitoring data.

During the UCMR 3 monitoring period, the samples to be fortified must be UCMR 3 field samples, and one set of LFSM/LFSMD/ unfortified field sample must be processed with each
batch. The LFSM/LFSMD fortification concentrations must be alternated between a low and
mid

- level concentration . For example, two analytical batches with a total of 40 field samples wi ll require preparation and analysis of two LFSM/LFSMD sets, one set fortified at the low

- level and
one at the mid

- level concentration

.Page 39 of 50 The low- level LFSM/LFSMD fortification concentration must be within ±50% of the MRL for each contaminant (e.g., for an MRL of 1.0 μ g/L, fortification levels
between 0.50 μ g/L and 1.5 μ g/L are acceptable).

The mid

- level LFSM/LFSMD fortification concentration should be within ± 20%
of the mid

- level calibration standard for each contaminant. Where possible (i.e.,
whe n the labora tory has data from previously analyzed samples), the fortification concentration should approximate the average concentration observed in previous analyses.

If UCMR 3 contaminants are regularly found in field samples at concentrations exceeding the MRL, laboratories may find it difficult to fortify that contaminant at the low

- level concentration. Laboratories may need to apply their experience and adjust their fortification to levels more appropriate and respective of native levels and may also first need to analyze a field sample prior to selecting the appropriate level for fortification.

There are no target analyte recovery acceptance criteria specified for LFSM/LFSMD results.

D ata should not be rejected based on the recovery of fortified target analytes or the precision between the LFSM and LFSMD
, provided that the analysis of the fortified sample yields acceptable internal standard and surrogate standard recoveries and all other batch QC are
valid. LFSM/LFSMD results are to be reported to EPA’s electronic data reporting system.



### 7.9 Analytical Sequence

The sequence with which UCMR 3 field and QC samples are analyzed is important for assessing system performance. As described in Section 7.2, each analysis batch must begin with the analysis of a CCC at or below the MRL for each of the UCMR 3 analytes targeted by the method. This CCC≤MRL is to be analyzed whether or not the initial calibration was generated the same day. Following the CCC≤MRL analysis , the LRB is to be analyzed, then the LFB≤MRL, and then up to 10 field samples. After 10 field samples, the calibration must be verified by the analysis of a mid- or high- level CCC. If this CCC passes the criteria, then u p to 10 additional field samples may be analyzed. T he batch must end with the analysis of a mid - or high- level (whichever was not analyzed after the 10 th sample) CCC. If a second batch is started immediately after one analytical batch is completed , it must begin with the analysis of a CCC≤MRL.Page 40 of 50 Example 2 illustrates a valid analysis sequence for Method 537 that will meet the QC requirements. It provides suggestions for corrective action if the criteria are not met.

Example 2. Valid Analysis Sequence for Method 537

Injection
# Sample Description Accep tance Criteria a Corrective Action

1 CCC≤MRL Recovery for each target analyte is
50

- 150% of the true value

. Instrument maintenance to recover sensitivity, followed by recalibration and verification of sensitivity by a low
level CCC

. 2 LRB All target analytes <1⁄3MRL
concentration Identify and correct source of
contamination

. 3 LFB≤MRL b 50

- 150% of the true value for each target analyte

. Identify and correct source of problem

.

4 through
13 Field Samples

1- 10 Positive ID of an analyte is verified
if the peak passes the retention time
criterion and mass spectral
identification is confirmed. Identify and correct source of problem

.

14 Mid

- level CCC c Recovery for each target analyte is
70

- 130% of the true value

. Instrument maintenance, followed by
recalibration

. 15 LFSM of a Field Sample At low

- level fortification concentrations, 50

- 150% recovery.
At mid

- level fortification concentrations, 70

- 130% recovery d

. If % recovery is out of the designated range, but laboratory performance for all other QC is acceptable, the recovery problem is judged to be matrix related

, but is still reportable.

16 LFSMD of Field Sample RPD between LFSM and LFSMD

≤ 5 0% for low

- level fortification
concentrations and ≤ 30% for mid

level fortification concentrations d

. If % recovery is out of the designated range, but laboratory performance for all other QC is acceptable, the recovery problem is judged to be matrix related

, but is still reportable.

17 through
28 Field Samples
11

- 20 Positive ID of an analyte is verified
if th e peak passes the retention time
criterion and mass spectral
identification is confirmed. Identify and correct source of problem

.

29 Final high

- level
CCC c Recovery for each analyte is 70

- 130% of the true value

. Instrument maintenance, followed by
recalibration

.

a In all field and QC samples
, and standards for Method 537 : The area for the internal standard must be 70

-

14 0% of the area in the most recent CCC and 50

- 150% of the average area measured during the initial calibration. Surrogate recovery m ust be 70

- 130% of the true value

. b Quality conscious labs may choose to include an additional LFB , at rotating concentrations, later in the analysis

batch. The criterion for LFBs fortified at a concentration >MRL is 70

- 130% of the true value for each tar get analyte.

c Subsequent to the initial CCC≤MRL, CCC concentrations are to be r otat ed between the mid and high

concentrations

. d Failing these LFSM/LFSMD target analyte recovery criteria does not invalidate the analysis batch under UCMR

3. See Section 7. 8 for the specifications for low and mid

- level fortification concentrations.Page 41 of 50 

## Section 8. Sample Handling Requirements

Laboratory personnel should be very familiar with the sample collection, preservation, and storage requirements. Laboratories performing UCMR 3 analyses for a large public water system (PWS) should communicate with the PWS and ensure their client has a clear understanding of
the UCMR 3

- specific requirements for sample collection, preservation and transportation. It
should also be noted that UCMR 3 samples must not be composited (i.e., combined, mixed or blended); samples from each sampling point must be collected, preserved and processed separately.

PWSs that must ship the samples for analysis should recognize that samples must be collected early enough in the day to allow adequate time to send these samples for overnight delivery to the laboratory. The PWS should avoid collecting samples on Thursday and should not collect samples on Friday, Saturday, or Sunday unless special arra ngements have been made for the receipt of samples at the laboratory within 48 -hours of collection. Laboratories must examine the samples when they arrive and determine if the proper shipping conditions were used.

Special precautions for hormone ( EPA 539 ) sampling: These sampling precautions are adapted from the US Geological Survey sampling protocols for hormones. to reduce the likelihood of sample contamination (USGS 2004).

• On the day of sampling, persons collecting samples should avoid contact or consumption of hormonal substances (medications, prescription drugs, etc.);

• Samplers should wear powderless nitrile laboratory gloves during sampling and processing;

• Samplers should avoid breathing directly over open samples;

• Samplers should avoid direct contact with the sample; and

• Laboratory analysts should follow the same precautions.

Special note for chlorate (EPA 300.1) sampling : If a water system uses chlorine dioxide as a disinfectant, samples must be sparged at the time of collection. The sample s hould be collected in a clean, wide mouth flask. The sparging gas should be an inert gas such as a lecture bottle of nitrogen or helium fitted with a regulator and connected to a disposable glass Pasteur pipette with PVC tubing. The gas flow should be adjusted to produce a steady flow of bubbles. After 10- 15 minutes of sparging, the chlorine dioxide residual should have be en effectively removed from the sample. The sample can then be poured from the flask into the sample bottle containing the EDA preservati ve.



### 8.1 Field Blanks
Some of the UCMR 3 samples are susceptible to contamination from outside sources. EPA is requiring the collection of field blanks (FBs) for all methods with the exception of chlorate
, hexavalent chromium and 1,4-dioxane. If the target analyte is found in the field sample, a field blank must be analyzed. Field blanks are to be processed, extracted and analyzed in exactly the same manner as the field sample. If the field blank level is at a concentration greater than 1/3 the MRL, then fie ld samples collected with that field blank are invalid and new samples must be
collected.Page 42 of 50 Table 10

. Field Blanks

Analytical Method Collection Requirement

EPA 200.8
ASTM D 5673

- 10
SM 3125 Fill a sample bottle with reagent water and preservatives in the lab, seal and ship with field sample bottles. Open the bottle at the sampling site, then seal and ship with field sample bottles.

EPA 218.7 Not required

EPA 300.1
ASTM D6581

- 08
SM 4110D Not required

EPA 522 Not required

EPA 524.3 Duplicate field blanks are required. Fill two sample bottles with reagent water and preservatives in the lab, seal and ship with field sample bottles. DO NOT OPEN in the field, these field blanks must remain sealed until analysis.

EPA 537 Fill a sample bottle with reagent water and preservatives in the lab, seal and ship with field sample bottles. Also include an empty sealed bottle (no preservatives). At the sampling site, open the bottle containing the reagent water and pour it into the empty bottle.

EPA 539 Fill a sampl e bottle with reagent water and preservatives in the lab, seal and ship with field sample bottles. Also include an empty sealed bottle (no preservatives). At the sampling site, open the bottle containing the reagent water and pour it into the empty bottle.



### 8. 2 Sample Transport and Storage
Samples should arrive at the laboratory packed on ice or with frozen gel packs in a sample bottle constructed of appropriate material as described in the analytical method. Samples that are shipped from the PWS should be sent by priority overnight delivery to the laboratory. UCMR 3 samples that arrive at the laboratory within 48 hours of collection must not exceed 10oC. Samples with water temperatures significantly above 10oC at the time of collection (e.g., summer sampling events with elevated ambient water temperature), may be iced or refrigerated for a period of time prior to shipping to ensure the laboratory receipt temperature criteria are met.
Samples that arrive at the laboratory on the same day of sample collection (exclusively due to the close proximity of a PWS to the laboratory), may not yet have stabilized to 10oC or less when they arrive at the lab. These samples are acceptable ONLY if packe d on ice or with frozen gel packs immediately after sample collection and hence, delivered while samples are in the process of reaching an equilibrium temperature less than 10oC. Samples must not be analyzed if they were not shipped properly. Table 11 provides the temperature and sample bottle material criteria for UCMR 3 samples. Some UCMR 3 methods require protecting the sample from exposure to light. The use of amber sample bottles is effective, but labs and/or PWSs may elect to wrap clear glass bo ttles with foil. Laboratories are responsible for ensuring that their client PWSs utilize the proper sample containers. If improper containers are used (e.g., plastic bottles instead of glass), the laboratory should notify the PWS that a replacement sample must be collected using proper
containers.Page 43 of 50 Table 11

. Requirements for Sample and Extract Storage Temperatures

Analytical Method Sample Bottle Material Temperature Specification for Samples Temperature Specification for Extracts

EPA 200.8
ASTM D 5673

- 10
SM 3125 Plastic OR glass bottles

Shipped on ice or with frozen gel packs, received
at the lab at 10oC or less
within 48 hours of collection. Refrigerated at
6oC or less after arrival at the laboratory or within 48 hours of collection,
whichever is sooner. N/A

EPA 218.7 HDPE OR propylene copolymer bottles N/A

EPA 300.1
ASTM D6581

- 08
SM 4110D Plastic OR glass bottles N/A

EPA 522 Glass bottle with PTFE lined

screw cap ≤

- 5oC, amber vial

EPA 524.3 Amber glass volatile organic analysis (VOA) vials fitted with

PTFE

- faced silicone septa and

polypropylene screw caps N/A

EPA 537 Polypropylene bottles with polypropylene screw caps Room temperature

EPA 539 Amber g lass bottle with PTFE lined screw cap ≤ 0 oC



### 8.3 Sample Preservation

The stability of the UCMR 3 samples is dependent upon proper preservation and/or dechlorination. Both the laboratory and PWS are responsible for e nsuring that the UCMR 3 samples are properly preserved/dechlorinated as stipulated in the analytical methods. Dechlorination and preservation are required at the time of sample collection. There must be clear communication between the laboratory and PWS that assures correct preservatives (including acid, buffer, or microbial inhibitor, as specified in the method and in Table 12) and dechlorinators are used. If the laboratory provides bottles containing the appropriate chemical(s) to the sampler, then the sampler should be notified that the bottles cannot be rinsed or permitted to overflow at the time of sample collection. Further, the lab must adhere to any time limits stipulated in the analytical method that the chemical(s) will be stable in the sample bottle.

Upon sample receipt, laboratories should verify preservation/dechlorination of each sample by conducting the appropriate check listed in Table 12. These checks should be performed at the laboratory, using a small aliquot of sample. Method 524.3 is an exception, since immediately checking for preservation upon receipt would compromise the sample, so for this VOC method the checks must be performed after analysis to avoid loss of analytes. (Note: To avoid possible sample contamination, pH probes or other instruments should never be inserted into the entire volume of sample.) If the criteria are not met, the sa mples must not be analyzed, and a new sample must be collected from the PWS.

To verify pH, either a standard pH meter or test strips are acceptable. The verification of the absence of free chlorine is qualitative, provided the laboratory can measure the presence of free chlorine at and above 0.1 mg/L. Note that a small aliquot of the sample should be used to test pH and/or chlorine content (i.e., probes and/or test strips should not be placed into the bulk sample bottle) to prevent sample contamination.Page 44 of 50 Table 12

. Sample Preservatives and Dechlorinat ing Agents (Concentration in Sample) and Acceptance Criteria
Analytical Method Chemical (concentration) Sample Check/Criteria

EPA 200.8
ASTM D 5673

- 10
SM 3125 2 mL HNO 3 per L of sample a pH < 2

EPA 218.7 Liquid: (NH 4 ) 2 SO 4 (3.3 g in 25mL reagent

H 2 O)/NH 4 OH (6.5 mL concentrate in 100 mL reagent H 2 O); 1 mL of each in 100 mL sample b,d

OR
Solid: Na 2 CO 3 (13.3 mg)/NaHCO 3 (10.5 mg)/ (NH 4 ) 2 SO 4 (33 mg) in 100 mL sample b,d Absence of free chlorine f (< 0.1 mg/L) pH > 8

EPA 300.1
ASTM D6581

- 08
SM 4110D 50 mg/mL ethylene diamine (EDA) c ; sparge sample with inert gas (He, Ar, N 2 ) prior to EDA addition if

plant uses chlorine dioxide (ClO 2 ) for treatment Absence of free chlorine f (< 0.1 mg/L)

EPA 522 50 mg/L sodium sulfite b (solid shipped in sample bottle) 1 g/L sodium bisulfate e (added in field after sodium sulfite has been dissolved) Absence of total chlorine (< 0.1 mg/L) pH < 4

EPA 524.3 0.625 g/L a s corbic acid b 5 g/L maleic acid Absence of free chlorine (< 0.1 mg/L) pH

∼ 2

EPA 537 5.0 g/L trizma b,d Absence of free chlorine (< 0.1 mg/L)

EPA 539 80 mg/L sodium thiosulfate b 65 mg/L 2

- mercaptopyridine

- 1

- oxide, sodium salt e Absence of free chlorine (< 0.1 mg/L)

a Acid may be added in the field or in the lab prior to analysis . If acid is added at the lab, the sample must be held for 16 hours and pH verified again prior to processing.

b dechlorinator

c preservative

d buffer

e microbial inhibitor

f Confirm “Absence of free chlorine” by careful observation. The sample may contain total chlorine present as

chloramine

, due to chemical reaction s of free chlorine as a disinfectant with ammonium (NH 4 + ) in 218.7 or EDA in 300.1. Typical DPD (N,N Diethyl

- 1,4 Phenylenediamine ) tests will work but require immediate
inter pretation since over time a false positive free chlorine result may develop.



### 8. 4 Maximum Holding Times

The laboratory is responsible for ensuring each sample is analyzed within the required holding time. A list of applicable maximum (i.e., not to exceed) holding times is presented in Table 13. These maximum holding times are applicable for samples that are properly preserved and are stored in appropriate sample containers at the appropriate temperatures. The aqueous sample holding time prior to extraction begins on the day the sample is collected. The sample extract holding time begins on the day the sample extraction was initiated.

If a UCMR 3 sample is not extracted or analyzed within the times specified in Table 8. 4, then the data for the sample must not be reported. The laboratory should indicate to the PWS that the sample was invalidated due to a holding time problem, and should request a resample.

The published UCMR 3 analytical methods provide additional information concerning recommended sample collection and holding procedures for samples. These procedures must be observed for UCMR 3 samples.Page 45 of 50 Table 13

. Maximum Holding Times for Samples and Extracts

Analytical Method Holding Time for Sample (days) Holding Time for Extract (days)

EPA 200.8
ASTM D5673 -10
SM 3125 28 28 (recommended)

EPA 218.7 14 N/A

EPA 300.1
ASTM D6581 -08
SM 4110D 28 N/A

EPA 522 28 28

EPA 524.3 14 N/A

EPA 537 14 28

EPA 539 28 28



### 8. 5 Laboratory E rrors or S ampling D eviations

If an error occurs, either in sampling or at the laboratory, which precludes the reporting of valid data, a resample must be collected within 30 days of the PWS being notified of the error. This resampling is not for confirmation sampling, but rather to co rrect the sampling or laboratory error. If resampling cannot be performed, then the PWS should be instructed to notify EPA’s UCMR Sampling Coordinator via e- mail at UCMR_Sampling_Coordinator@epa.gov or the
State.Page 46 of 50 

## Section 9 . References

ASTM Standard D5673-10. Standard Test Method for Elements in Water by Inductively Coupled
Plasma – Mass Spectrometry. American Society for Testing and Materials (ASTM), West Conshohocken, PA. 2005. Available at http://www.astm.org/Standards/D5673.htm

ASTM Standard D6581-08. Standard Test Methods for Bromate, Bromide, Chlorate, and Chlorite in Drinking Water by Suppressed Ion Chromatography. ASTM, West Conshohocken,
PA. 2008. Available at http://ww w.astm.org/Standards/D6581.htm

EPA Method 200.8. Determination of Trace Elements in Waters and Wastes by Inductively Coupled Plasma – Mass Spectrometry , Revision 5.4, EMMC Version. Environmental Monitoring Systems Laboratory, Office of Research and Development (ORD)

, EPA , Cincinnati,
Ohio 45268. Available at https://www.nemi.gov/

EPA Method 300.1. Determination of Inorganic Anions in Drinking Water by Ion Chromatography . National Exposure Research Laboratory (NERL) , O RD, EPA , Cincinnati,
Ohio 45268. Available for download at http://water.epa.gov/scitech/drinkingwater/labcert/analyticalmethods_ogwdw.cfm

EPA Method 522. Deter mination of 1,4 -Dioxane by Solid Phase Extraction (SPE) and Gas Chromatography/Mass Spectrometry (GC/MS) with Selected Ion Monitoring (SIM) , Version 1.0, September, 2008. EPA/600/R-08/101. NERL, ORD, EPA , Cincinnati, Ohio 45268. Available for
download at http:/www.epa.gov/nerlcwww/ordmeth.htm

EPA Method 524.3. Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry , Version 1.0, June 2009. EPA 815-B-09-009. TSC, OGWDW

, EPA , Cincinnati, Ohio 45268. Available for download from http://water.epa.gov/scitech/drinkingwater/labcert/analyticalmethods_ogwdw.cfm

EPA Method 537. Determination of Selected Perfluorinated Alkyl Acids in Drinking Water by
Solid Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS)

, Version 1.1, September 2009. EPA Document #EPA/600/R-08/092. NERL, ORD, EPA

, Cincinnati, Ohio 45268. Available for download at http://www.epa.gov/nerlcwww/ordmeth.htm

EPA Method 539. Determination of Hormones in Drinking Water by Solid Phase Extraction(SPE) and Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry (LCESI -MS/MS) , Version 1.0, November 2010. EPA Document #815-B-10-001. TSC, OGWDW,
EPA , Cincinnati, Ohio 45268. Available at http://water.epa.gov/scitech/drinkingwater/labcert/analyticalmethods_ogwdw.cfm

E PA QA/R -2. EPA Requirements for Quality Management Plans (QA/R-2). EPA Document

# EPA/24 0/B-01/002. Office of Environmental Information (OEI)

, EPA , Washington, DC 20460.

A vailable at http:// www.epa.gov/quality/qmps.html

EPA QA/R -5. EPA Requirements for Quality Assurance Project Plans (QA/R

- 5) EPA Document
#EPA/240/B-01/003. O EI, EPA , Washington, DC 20460. Available for download fromPage 47 of 50 http://www.epa.gov/quality/qs- doc/r5 -final.pdf

Technical Basis for the Lowest Concentration Minimum Reporting Level (LCMRL) Calculator

, Dec ember 20 10. EPA Document #815-R-11- 001

. TSC, OGWDW, EPA , Cincinnati, Ohio
45268. Available for download from http://water.epa.gov/scitech/drinkingwater/labcert/analyticalmethods_ogwdw.cfm

SM Method 3125 , 21 st Ed

. Metals by I nductively Coupled Plasma / Mass Spectrometry (2005). Available for purchase at http://www.standardmethods.org/store/ProductView.cfm?ProductID=211

SM Method 4110D , 21 st Ed

. Ion Chromatographic Determination of Oxyhalides and Bromide (2005)

. Available for purchase at http://www.standardmethods.org/store/ProductView.cfm?ProductID=31

US Geological Survey, Processing of water samples (ver. 2.2): U.S. Geological Sur vey Techniques of Water

- Resources Investigations, Book 9, Chapter A5 Section 5.6.1.F, "Wastewater, pharmaceutical, and antibiotic compounds," April 2004, Available at http://water.usgs.gov/owq/FieldManual/chapter5/5.6.1.F_v-1.1_4-03.pdfPage 48 of 50 

## Appendix A. Requirements for UCMR 3 Metal Analysis

Table 14

. Determination of Metals for UCMR 3 based on EPA Method 200.8 Rev. 5.4

ANALYTES Natural Isotopes ( monitor all of these ) % Relative
Abundance Additional Isotopes
to Monitor Isotope to Report Elemental & Molecular Correction Equations

Vanadium (V) IS: Sc, In, Tb 50 (Ti, Cr)

51 0.250

99.750 52, 53 51 (1.000) ( 51 C)

– (3.127) [( 53 C)

– (0.113) ( 52 C)] Isobaric polyatomic correction for molecular ions produced by a chloride
matrix

. Chromium (Cr) IS: Sc, In, Tb 50 (Ti, V)

52

53 54 (Fe) 4.345

83.789

9.501

2.365 47, 48, 49, 51, 56 52 (1.000) ( 52 C)

Cobalt (Co) IS: Sc, In, Tb 59 100

--- 59 (1.000) ( 59 C)

Strontium (Sr) IS: In, , Sc, Tb 84 (Kr) 86 (Kr) 87 (Rb)

88 0.56

9.86

7.00

82.58 83, 85 88 (1.000) ( 88 C)

Molybdenum (Mo) IS: In, Sc, Tb 92 (Zr) 94 (Zr)

95 96 (Zr, Ru)

97

98 (Ru) 100 (Ru) 14.84

9.25

15.92

16.68

9.55

24.13

9.63 90, 99, 101 98 (1.000) ( 98 C)

– (0.111) ( 101 C)

Elemental correction for Ru on Mo.

INTERNAL STANDARDS
Scandium (Sc) 45 100 45 45 (1.000) ( 45 C) Background molecular ions may interfere.
Indium (In) 113 (Cd)

115 (Sn) 4.3

95.7 106, 108, 111, 114, 118, 120 115 (1.000) ( 115 C)

– (0.016) ( 118 C) If Tin present, use the isobaric elemental correction for Tin.
Terbidium (Tb) 159 100 159 159 (1.000) ( 159 C) For the analytes listed in the first column of the Table above, monitor all of the isotopes listed in the second and fourth columns. Report using the isotopes listed in the fifth column using the Elemental & Molecular Correction Equations listed in the sixth column. The internal standards listed with the analytes are in order of suggested use, but accept any of the inte rnal standards listed in the table. Follow EPA Method 200.8 Revision 5.4 for Total Recoverable Analytes in Aqueous Samples with the following additions/exception s: Method Section 8.0 Sample container: plastic or glass Sample size: 1 00 mL
11.0 Use secti on 11.2.2

– must digest samples regardless of turbidity
11.2.3 Omit the use of Hydrochloric Acid (HCl)
11.2.8 Omit 11.2.8Page 49 of 50 

## Appendix B. Lowest Concentration Minimum Reporting Level (LCMRL) Data used to D etermine
UCMR 3 Minimum Reporting Levels (MRLs)

Hormones Lab A Lab B Lab C MRL (μg/L)

17

- β

- estradiol 0.00020 0.00020 0.00034 0.0004

17

- α

- ethynylestradiol (ethinyl estradiol) 0.00014 0.00018 0.0013 0.0009

estriol 0.00096 0.00035 0.00028 0.0008 equilin 0.00012 0.00078 0.0030 0.004

estrone 0.00018 0.00013 0.0029 0.002

testosterone 0.000068 0.000036 0.000062 0.0001

4

- androstene

- 3,17

- dione 0.000093 0.000079 0.00037 0.0003

Perfluorinated Compounds Lab A Lab B Lab C MRL (μg/L)

perfluorooctane sulfonic acid (PFOS) 0.013 0.0072 0.048 0.04

perfluorooctanoic acid (PFOA) 0.018 0.0054 0.00054 0.02

perfluorononanoic acid (PFNA) 0.012 0.0067 0.00080 0.02

perfluorohexane sulfonic acid (PFHxS) 0.018 0.010 0.033 0.03

perfluoroheptanoic acid (PFHpA) 0.010 0.0052 0.00082 0.01

perfluorobutanesulfonic acid (PFBS) 0.056 0.015 0.077 0.09

Chlorate Lab A Lab B Lab C MRL (μg/L)

c hlorate 14 5.9 1.67 20

Metals Lab A Lab B Lab C MRL (μg/L)

c obalt 1.1 0.036 0.19 1.

m olybdenum 0.62 0.076 0.51 1.

v anadium 0.070 0.048 0.25 0.2

s trontium 0.18 0.11 0.33 0.3

Total Chromium Lab A Lab B Lab C Lab D MRL (μg/L)

total c hromium 0.12 0.073 0.24 0.16 0.2

VOCs Lab A Lab B Lab C Lab D MRL (μg/L)

c hlorodifluoromethane 0.056 0.012 0.024 0.092 0.08

c hloromethane 0.15 0.14 0.070 0.12 0.2 1,3

- Butadiene 0.092 0.044 0.056 0.084 0.1

b romomethane 0.25 0.059 0.058 0.10 0.2 1,1

- Dichloroethane 0.015 0.019 0.014 0.026 0.03

b romochloromethane 0.0064 0.058

--- 0.030 0.06 1,2,3

- Trichloropropane 0.010 0.025 0.017 0.034 0.03Page 50 of 50 1,4 Dioxane Lab A Lab B Lab C MRL (μg/L) 1,4

- Dioxane 0.018 0. 046 0.076 0.07

Chromium

- 6 Lab A Lab B Lab C Lab D Lab E Lab F Lab G Lab H Lab I MRL (μg/L)

chromium

- 6 0.022 0.032 0.0022 0.014 0.010 0.031 0.026 0.0065 0.031 0.03

Note: There were as many as nineteen different laboratories participat ing in the LCMRL studies and generated these data , with a minimum of three labs for each method . Laboratory designations of A, B, C, etc. are arbitrary and do not represent the same laboratory participa nt for
the various methods evaluated.