# UCMR 3 Laboratory Approval Requirements and Information DocumentOffice of Water (MLK 140) EPA 815 -R- 10

- 004 December 2010 http://water.epa.gov/drinkPage 1 of 41 

# UCMR 3 Laboratory Approval Requirements and Info rmation Document

Version 1.0

December 2010

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

Laboratory 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 41 

### Foreword

The proposed Revisions to the Unregulated Contaminant Monitoring Regulation ( UCMR 3) for Public Water Systems [40 CFR Part 141, National Primary Drinking Water Regulations] require public water systems ( PWS s) collect specific data and information during a defined monitoring period. The proposed rule for the third UCMR ( UCMR 3 ) establishes requirements and specifications for the collection and reporting of UCMR 3 data to the United States Environmental Protection Agency (EPA). This technical manual serves as a support document for laboratories inter ested in becoming approved 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 assess a labo ratory's ability to produce data of

known accuracy and precision,

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

and

**•** clarify specific analytical procedures for UCMR 3

.

Within twelve months or less of the publicatio n of the UCMR 3 f inal r ule the UCMR 3 Laboratory Approval Program (LAP) is expected to close and a UCMR 3 Laboratory Manual will be published that supersedes th is Lab Approval Manual. Copies of the UCMR 3 Lab Manual will be sent to all laboratories that a ttain EPA approval to support UCMR 3

. Laboratories will be required to follow the UCMR 3 Laboratory 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/lawsre gs/rulesregs/sdwa/ucmr/ucmr3/index.cfmPage 3 of 41 

## Disclaimers

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

2. This document describes the provisions of the proposed 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 regulations. Contaminants and methods identified in this document are

su bject to change over the course of development and promulgation of the final UCMR 3

. 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 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 4 of 41 

## Contents

Foreword ........................................................................................................................................ 2
Disclaimers

................................................................................................ ..................................... 3 Acronyms and Abbreviations ...................................................................................................... 6
Section 1. Introduction ................................................................................................................. 9 1.1 Background on the Unregulated Contaminant Monitoring Regulation ................................. 9 1.2 Ensuring Data Quality for UCMR 3 ...................................................................................... 9 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 Ch ecks ........................................................................................... 29 7.3 Surrogate Requirements and Criteria .................................................................................. 30 7.4 Internal Standard Requirements and Criteria ...................................................................... 32 7.5 Laboratory Reagent Blank ................................................................................................... 34 7.6 Laboratory Fortified Blank .................................................................................................. 35 7.7 Laboratory Fortified Sample Matrix (Spiked Sample) ........................................................ 36 7.8 Analytical Sequence ............................................................................................................ 37 Appendix A. Requirements for UCMR 3 Metal Analysis ....................................................... 39
Section 8. References .................................................................................................................. 40Page 5 of 41 

## Tables

Table 1. UCMR 3 List 1 Assessment Monitoring Chemical Analytes and Methods ................... 20

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

Table 3. Initial Calibration Acceptance Criteria ........................................................................... 28

Table 4. CCC Acceptance Criteria

................................................................................................ 30

Table 5. Surrogate Standards, Concentrations and Criteria .......................................................... 31

Table 6. Internal Standards, Concentrations and Criteria ............................................................. 33

Table 7. Laboratory Reagent Blank Criteria ................................................................................. 35

Table 8. Laboratory Fortified Blank Acceptance Criteria ............................................................ 36

Table 9. Specifics for the Determination of Metals for UCMR 3 ................................................ 39



## Examples

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

Example 2. Valid Analysis Sequence for Method 537 ................................................................. 38Page 6 of 41 

## Acronyms and Abbreviations

13 C- PFDA

13 C- PFHxA

13 C

- PFOA

13 C

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

- [1,2

- 13 C 2 ]octanoic acid
S odium perfluoro

- 1

- [1,2,3,4

- 13 C 4 ]octanesulfonate
APHA American Public Health Association
ASTM ASTM International
AWWA American Water Wo rks 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- octan esulfonamidoacetic 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 Half range for the prediction interval of results
IC I on chroma tograph y ICP/MS I nductively coupled plasma

- mass spectromet e r ID I dentification
IDA I nitial demonstration of a ccuracy IDC I nitial demonstration of capability
IDP I nitial demonstration of precision
In Indium
L L iter
LAP Laboratory Approval Program
LCMRL L owest concentration minimum reporting level
LC

- ESI

- MS/MS L iquid chromatography electrospray ionization ta ndem mass spectrometry LC/MS/MS L iquid chromatograph y /tandem mass spectrometr y LFB Laboratory fortified blank
LFSM L aboratory fortified sample matrixPage 7 of 41 

## Acronyms and Abbreviations

LFSMD
LRB
mL L aboratory fortified sample matrix duplicate
L aboratory reagent blank
M illiliter
Mo
MRL m/z
NA
NERL OEI Molybdenum
M inimum reporting level
M ass to charge ratio
N ot applicable National Exposure Research Laboratory Office of Environmental Information
OGWDW ORD PFBS Office of Ground W ater and Drinking Water Office of Research and Developmen t P erfluorobutanesulfonic acid PFHpA PFHxS P erfluoroheptanoic acid
P erfluorohexanesulfonic acid
PFNA P erfluorononanoic acid
PFOA P erfluorooctanic acid
PFOS Perfluorooctanesulfon ic acid
PIR Prediction interval of the result
PIR lower L ower PIR l imit
PIR upper PT PWS QA QAPP QC QCS QMP RSD U pper PIR limit
P roficiency testing
P ublic water system Q uality assurance Quality Assurance Project Plan Quality control Q uality control sample Quality Management Plan
R elative standard deviation
RPD

s Re lative percent difference Standard deviation
Sc Scandium
SDVB SDWA SDWARS SIM SM P olystyrenedivinylbenzene Safe Drinking Water Act Safe Drinking Water Accession and Review System
S elective ion monitoring Standard Methods for the Examination of Wa ter and Wastewater SOP Standard o perating p rocedurePage 8 of 41 

## Acronyms and Abbreviations

SPE S olid phase extraction
Sr Strontium Tb Terbium
TSC Technical Support Center
THF -d 8 T etrahydrofuran -d 8 UCMR Unregulated Contaminant Monitoring Regulation UCMR 1 F irst Unregulated Contaminant Monitoring Regulation UCMR 2 Second Unregulated Contaminant Monitoring Regulation UCMR 3 Third Unregulated Contaminant Monitoring Regulation (v:v) Volume to volume
V Vanadium
VOC V olatile organic co ntaminant
WEF Water Environment Federation

x M ean μL M icroliterPage 9 of 41 

## Section 1. Introduction

1.1 Background on the U nregulated C ontaminant M onitoring Regulation

The Safe Drinking Water Act (SDWA), as amended in 1996, requires the 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 proposed contaminant lists for the first and second UCMRs (i.e., UCMR 1 and UCMR 2, respectively) in the Federal Register i n Septem ber 1999 and August 2005. Previous ly UCMR established a three

tiered approach for monitoring contaminants based on the availability of analytical methods. UCMR 3 monitoring will utilize a similar three -tiered approach, and the monitoring period is proposed f rom January 2013 through December 2015.

EPA identified 28 chemical contaminants for the proposed UCMR 3 . Monitoring for these contaminants is supported by ten analytical methods. EPA identified 30 total contaminants for the proposed UCMR 3 , including two viruses. Virus analyses will be conducted by laboratories under contract with EPA and are not addressed in this document.

Laboratories should be aware that this document is based upon the proposed UCMR 3 and will be revised once the final UCMR 3 rule is promulgated. Contaminants and methods identified in this document are subject to change.



### 1.2 Ensuring Data Quality for UCMR 3 Data reported under UCMR 3 must meet specific accuracy and precision 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 high in quality. Maintaining data comparability between laboratories is essential, and will allow the data to be used in sophisticated statistical

a nalyses to reliably predict the national occurrence of the 28 chemical contaminants in drinking
water. EPA e nsure s the integrity of the data by : 1) defining and maintain ing strict requirements for sample collection , sample handling, processing and analysis , data reporting, and 2) assisting the drinking water industry in identifying qualified laboratories which can accurately and reliably perform the analyses required by UCMR 3

. The laboratory approval process described in this document ensures that analyt ical 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 adequate and generates quality data. A description of the consequent L aboratory Approval P rogram (LA P) and its requirements for UCMR 3 are presented in this UCMR 3 Lab Approval Manual, includ ing:Page 10 of 41 **•** a description of the UCMR 3 laboratory approval process;

**•** 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

**•** 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 41 

## 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. A laboratory may apply for approval for any number of UCMR 3 methods. If a laboratory organization has multiple location s , each laboratory must complete the proc ess independently.


### 2.1 Registration for the UCMR 3 Laboratory Approval Program
Laboratories interested in UCMR 3 laboratory approval should contact EPA as soon as possible. Laboratories can request UCMR 3 registration information now, but no later than 90 days after publication of the UCMR 3 f inal rule . EPA anticipates the final UCMR 3 will be published inearly 2012. Laboratories should send a letter of interest with contact information, including an email address, to the following address:

UCMR Laborato ry Approval Coordinator U.S. Environmental Protection Agency Technical Support Center 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, indica ting the UCMR 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. R egistration information must be received by EPA no later than 100 days after publication of the UCMR 3 f inal r ule.



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

. To complete these applications, laboratories are required to:

**•** Doc ument 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.

**•** Provide personn el and QA information , including a copy of the Table of Contents from the

laboratory’s Quality Management Plan (QMP; see Section 3.1).Page 12 of 41 **•** Provide information regarding analytical equipment and sample handling procedures.

**•** 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) a nalysis of a set of laboratory fortified sample matrix ( LFSM ), LFSM duplicate (LFSMD) , and the corre sponding unfortified drinking water sample (see Section 7.7). Data submitted must include labeled chromatographic and/or spectrometric traces , quantitation reports, surrogate recovery results and internal standard recovery results

.

**•** Document that they are willing to 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 the proposed 60 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 during the UCMR 3 monitoring period.

Completed applications should 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 area(s) of deficiency and necessary corrective actions 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 UCMR 3 LAP application period will close in May 2012.



### 2.3 UCMR 3 Profici ency Testing EPA anticipates conducting up to three PT studies prior to, and a minimum of one PT study after, publication of the UCMR 3 f inal rule. Upon successful completion of the application process, each laboratory must pass one PT study for each method for which th ey are seeking approval. When the laboratory’s application for a specific method is reviewed 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 da te 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 p ass the PT study for a given method can participate in the next PT study for that method, 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 UCM R 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.Page 13 of 41 Laboratories that pass a PT study prior to publication of the UC MR 3 f inal rule will be granted “Pending Approval” for UCMR 3 . Final approval may be contingent upon: 1) changes applied to the f inal r ule as a result of public comments to the proposed rule, and 2) resolution of any findings resulting in a laboratory audit . Laboratories are not authorized to analyze UCMR 3 monitoring samples until the y receive 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 41 

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

A 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 individua l 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 procedures. 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 management of day

to -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

co py 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 literature (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 8 References )

.

At a minimum , the laboratory’s QMP should 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

**•** 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 laboratoryPage 15 of 41 3) Laboratory sample handling procedures

**•** 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

analysis of samples, e xtracts or digestates

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

temperature and holding times

**•** 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 standards, internal standards , etc.

**•** 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

**•** 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 trans cription and calculations

**•** Process for validatin JGDWD

. data

**•** Process and format for UHSRUWLQJUHVXOWVWRFOLHQWV

. reporting results to clients

**•** Procedure 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 sur rogate standards

**•** Procedures for IDCs , and preparation of control chartsPage 16 of 41 8) Preventive maintenance

**•** Equipment manual location and availability

**•** Spare parts inventory

**•** 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

**•** Procedure for d ocumenting a ction s taken and their effectiveness

10) Record Keeping

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

**•** Procedure for backing- up databases/electronic files

The laboratory QMP should 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 8 References )

.Page 17 of 41 

## Section 4. Approved Methods for UCMR 3 Monitoring

Laboratories must use the methods specifie d in CFR §141.40(a) (3) Table 1 to perform UCMR analyses during the 3

- year monitoring period. The proposed UCMR 3 methods are summarized below and listed in Table 1. 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 date specified in the final rule.

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

Total recoverable analytes in a 100 milliliter ( mL ) water sample are solubilized by gentle heating (i.e., digestion) w ith 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 must be digested, regardless of sample turbidity and method .) When the sample volume has been evaporated to approxi mately 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 bismuth (Bi), 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, hightemperature radiofrequency plasma where energy transfer processes cause desolvation, atomization and ionization. The ions are extracted from the plasma through a differentially pumped vacuum interface and separated on the basis of their mass- to

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

.

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 is injected into an ion chromatograph fitted with: an anion

exchange guard column, an anion-exchange analytical 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 and identified on the basis of retention time as comp ared to calibration standards analyzed under identicalPage 18 of 41 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 5 22 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 ext racted 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 cartdridges are commercially available from Rest ek 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 100mL sample 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 tetrahydrofuran -d 8 (THF -d 8 ). The final extract is dried with anhydrous sodium sulfat e and injected using splitless injection onto a high

- resolution fused silica capillary gas chromato graphy 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 calibrati on standards acquired under identicalGC/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

m ethyl -t-bu tyl

- ether -d 3 , 4-b romofluorobenzene (BFB), and 1,2-dichlorobenzene-d 4
. Volatile 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. From 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 fro m the GC column are directed into a mass spectrometer 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.Page 19 of 41 EPA Method 537 Determination of Selected Perfluorinated Alkyl Acids in Dri nking 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), p erfluoro -n-[1,2- 13 C 2 ] decanoic acid ( 13 C- PFDA), and N- deuterioethylperfluoro -1- octanesulfonamidoacetic acid (d 5 - NEtFOSAA)

. 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), sodium perfluoro-1-[1,2,3,4- 13 C 4 ]octanesulfonate ( 13 C- PFOS), and N- deuteriomethylperfl uoro-1- octanesulfonamidoacetic acid (d 3 - NMeFOSAA) 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 10μL 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 u nder identical LC/MS/MS conditions. The concentration of each analyte is calculated using the internal standard technique.

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 cartridge contain ing C 18 functional groups. 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. A solution containing internal standards 16 **α** -hydroxyestradiol-d 2 (Estriol -d 2 ), 13 C 6 - Estradiol, 13 C 2 -ethynylestradiol, and testosterone-d 3 is added, and the extract is adjusted to a 1mL 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 chr omatography 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 41 Table 1. UCMR 3 List 1 Assessment Monitoring Chemical Analytes and Methods

1-Analytical

Method 2- Contaminant 3- CAS Registry Number Quant Ions Parent/Daughter (m/z) 5- MRL (μg/L)

EPA 200.8, STM D5673-10, or SM 3125 Trace Element Metals by ICP/MS* c obalt (Co) 7440-48-4 59 1.0

molybdenum (Mo) 7439-98-7 98 1.0

s trontium (Sr) 7440-24-6 88 0.3

vanadium (V) 7440-62-2 51 0.2

EPA 300.1, STM D6581-08, or SM 4110D Inorganic anions by IC c hlorate 14866-68-3 Not applicable (NA) 20

EPA 522 1,4-Dioxane by GC/MS 1,4-dioxane 123-91-1 88 0.07

EPA 524.3 VOCs by GC/MS 1,1-dichloroethane 75-34-3 63 0.03

1,2,3-t ric hloropropane 96-18-4 110 0.03

1,3-butadiene 106-99-0 54 0.1

bromochloromethane (halon 1011) 74-97-5 128 0.06

chlorodifluoromethane (HCFC -22) 75-45-6 51 0.08

chloromethane 74-87-3 50 0.2

bromomethane 74-83-9 94 0.2

n-propylbenzene 103-65-1 91 0.03

sec -butylbenzene 135-98-8 105 0.04 4- Suggested

A

APage 21 of 41 Table 1. UCMR 3 List 1 Assessment Monitoring Chemical Analytes and Methods

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

perfluorooctano ic acid (PFOA) 335-67-1 413/369 0.02

perfluorohexanesulfonic acid (PFHxS) 355-46-4 399/80 0.03

perfluoroheptanoic acid (PFHpA) 375-85-9 363/319 0.01

perfluorononanoic acid (PFNA) 375-95-1 463/419 0.02

p erfluorobutanesulfonic acid (PFBS) 375-73-5 299/80 0.09

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
equilin 474-86-2 267.1/142.7 0.004

e striol 50-27-1 287/144.7 0.0008

estrone 53-16-7 268.9/144.7 0.002

testosterone 58-22-0 289.1/96.8 0.0001
4-androstene-3,17-dione 63-05-8 287.1/96.6 0.0003
* See Appendix A o f 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 informati o n for the methods is listed in Section 8 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, assigned 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/ product ions are listed. For the m etals me thods (EPA 200.8, ASTM D5673

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

. 5 Minimum Reporting Level: The lowest concentration of each analyte that must be reported to EPA.Page 22 of 41 

## 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 an alyst performs UCMR 3 analys es, EPA recommends that each analyst perform an IDC study before they are allowed to analyze UCMR 3 samples . Similarly, an IDC study should be performed using each instrument that will be used to analyze UCMR 3 samples . This wil l e nsure that each operator and each instrument maintain s the minimum quality standards. Data from each of these tests should be maintained at the laboratory for EPA’s review in the event that the Agency wishes to conduct 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 meth od, should 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
pe rforming 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 D emonstration 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, consisting of reagent water fortified at the "precision demonstration" concentration for ea ch 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 relative stan dard 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 Equati on 1. The average recovery must meet the criterion specified in Table 2

.

%100 1 **×÷** 

## ∑

**=** actual n

i i LFB

n LFB Equation 1Page 23 of 41 4. MRL Verification - Laboratories must verify they can achieve the UCMR 3 MRL for each analyte according to the procedure outlined in Section 6.

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 be low values listed in Table 1 for each of the UCMR 3 analytes 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 41 

## Section 6. Minimum Reporting Levels

The UCMR 3 analyte MRLs were statistically established by EPA using the lowest concentration minimum reporting levels (LCMRLs) determined by multiple laboratories according to the procedure detailed in Statistical Protocol for the De termination of The Single-Laboratory Lowest Concentration Minimum Reporting Level (LCMRL) and Validation of the Minimum Reporting Level (MRL) . The MRLs established for the UCMR 3 analytes are presented in Table 1, and are considered technically feasible wi thout placing undue burden on laboratories. All laboratories performing analys i s 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) and outlined below.

1. Fortify, process and analyze seven replicate LFBs. These LFBs must: contain all dec hlorinating 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 or digestion , where applic able).

2. Using the results from the analysis of the 7 replicates, calculate the mean ( **0** ) 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

3. Confirm that the upper and lower limits for the prediction interval of the result (PIR = Mean + HR PIR ) meet the upper and lower recovery limits.

The upper PIR limit must be ≤150 percent recovery:

%150%100 TrueValue HR x PIR **≤×**

**+** Equation 3

The lower PIR limit must be ≥50 percent recovery:

%50%100 TrueValue HR x PIR **≥×**

**−** Equation 4

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

These calculations are illustrated in Example 1.Page 25 of 41 Example 1. Calculation of the PIR Limits (where the true value of the LFB concentration 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 ( )

6014.0x 7 21.4 x n LFB

x n

1i i
**=→=→ =**  

## ∑

**=**

Step 2. Calculate the Standard Deviation ( S )



## ( )

0372.0s 6 0083.0 s 1n x LFB

s n

1i 2 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 )

%7.75 PIR %100 60.0 147.06014.0 PIR %100 TrueValue HR x PIR upper upper PIR
upper **= →×**  **−**

**= →×**  **−**

**=**

**→** Passes Criterion ( ≤ 150%)

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

%7.75 PIR %100 60.0 147.06014.0 PIR %100 TrueValue HR x PIR lower lower PIR lower **= →×**  **−**

**= →×**  **−**

**=**

**→** Passes Criterion ( ≥ 50%)Page 26 of 41 

## 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 UCMR 3 Lab Approval Manual.

EPA ’s LAP is an effort to promote the generation of consistently accurate, precise, comparable and representative data for UCMR 3

. EPA is requiring the implementation of specific QC procedures, some of which may not be required by an individual UCMR 3 method. T he criteria specified in this manual must be followed, even if they are not required by the method. However, this manual is not exhaustive in describing the QC procedures required for UCM R 3 ; method

specific QC requirements that are not described here must also be followed.

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 standard/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 pr eparing 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 a 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 validity 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 end s with the analysis of the final mid - or high- level CCC standard. The analytical 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 same 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 pro cessing the samples. Field samples with QC failures may be re -analyzed at the end of the analytical batch, followed by an ending CCC. However, ifPage 27 of 41 this is not possible, the re- analysis will need to be performed in a new analytical batch with a different ID.

All the UCMR 3 methods require fortification of field samples, QC samples, and calibration standards with surrogate and/or internal standards. The method- 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 involved in UCMR 3 must be very familiar with general an d 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 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 lab oratory 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 spectometry methods, laboratories must meet the method- specific mass spectrometer tuning criteria prior to performing the initial calibration procedure.

If allowed by the method, different types of calibration (e.g., linear regression, quadratic fit, response factor calculation) and different fit types (e.g., forcing the curve through the origin, ign oring 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 t he 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 calibration standards for all UCMR 3 methods. More than five s tandards must be used if specified by the method, such as EPA Method 524.3.

The recovery of UCMR 3 analytes, surrogate standard s and internal standard s must be monitored in the initial calibration standards using the calibration curve created from the ini tial calibration data. Recoveries must meet the criteria defined in Table 3 . If any surrogate or internal standardPage 28 of 41 fails the criterion in a calibration standard, the data from that standard cannot be used in calculating the calibration curve. If all surro gate and 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 reanaly zed (and possibly re- prepared) until passing data are generated.

Table 3. Initial Calibration Acceptance Criteria a

Analytical Method Internal Standard Response Analytes

>MRL Analyt es ≤MRL Surrogate Standard
EPA 200.8, ASTM D5673 -10, SM 3125

Metals 90 – 110% 85 – 115% NA 60 – 125% of the response in the calibration blank

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% 70 – 130% of the response in the most recent previous CCC f EPA 524.3 VOCs

70 – 130% 50 – 150% EPA 537 Perfluorinated

Compounds 70 – 140% of the response in the most recent previous CCC f

EPA 539 Hormones 70 – 130% of the r esponse in the most recent previous CCC f

a For methods 522, 524.3, 537, and 539 calibration standard responses must be entered into the calibration curve equation and the resultant calculated analyte concentrations must meet the accuracy criteria liste d in the table
b Applies to all chlorate methods when the true concentration of the analytes 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 exc ept the lowest concentration.

e Applies only to the lowest Initial calibration concentration for Method 522

. f If there is no previous CCC, the responses for an internal standard in all the i nitial calibration standards must Recovery as % of true value

be within 20% of each other.

All UCMR 3 methods require v erification of t he initial calibration with a Quality Control Sample (QCS) prepared from a source different than that used to prepare the initial calibration standards. If a second source is not available, the QCS should be prepared from a different lot of the source used to prepare the initial calibration standards. EPA 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 us ed in the initial calibration standards. The acceptance criteria for the QCS are the same as those for CCC standards with concentrations greater than the MRLPage 29 of 41 (see Section 7.2), with the exception of the metals methods for which the criterion is ±10%. The i nitial calibration must be verified with a QCS each time a new analyte primary dilution standard 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.



### 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 verif ied 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 established on the day of analysis by analyzing the entire suite of initial calibration standards, laborat ories 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 field sample, and at the end of the analytical batch, alternat ing between th e mid - and high

- level concentrations on the calibration curve. CCC standards must meet the criteria defined in Table 4. The low- level CCC standard must meet method criteria before any samples are analyzed, and all samples must be bracketed by CCC standards that pass method criteria. Analytical results for a group of up to 10 samples are considered valid only if the CCC standards 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 procedures. 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 mus t not be reported. Laboratories reporting invalid data will be subject
to revocation of UCMR 3 laboratory approval status.Page 30 of 41 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% 80 – 120% 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
average response in the initial calibration EPA 524.3 VOCs

EPA 537 Perfluorinated

Compounds 70 - 140% the response in the most

re cent 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. A surrogate is a pure analyte that is v ery 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 sample. Therefore, surrogate analyte (s) must be added to all aqueous samples including LRBs, LFBs, LFSMs and LS FMDs , and to all standards. During IDC studies, such as demonstrations of accuracy and precision and MRL verifications (see Section 5), the surrogate 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 thePage 31 of 41 selection of the surrogate or its concentration, EPA allows the same flexibility for UCMR 3

. However, the concentration o f each surrogate analyte 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.

Table 5. S urrogate Standards , Concentrations and Criteria

An alytical Method Recommended Surrogate Standard Recommended Concentration in Sample Criteria (% recovery of

true value)
EPA 200.8, ASTM D5673 -10, SM 3125

Metals 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

Co mpounds 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. An alternat e 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. Acceptance

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 t he su rrogat e 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 should be flagged as not meeting QC criteria. Data for samples with fail ed surrogate standard recovery must not be reported. IfPage 32 of 41 possible, the laboratory should process a new aliquot of the sample.

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 LF SM 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 should be reported.



### 7 .4 Internal Standard Requirements and Criteria
Internal standards are required for cali bration and quantitation purposes in all UCMR 3 methods, with the exception of the chlorate 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 the ir
extracts /digestates . During IDC studies, such as demonstrations of accuracy and precision 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 standards 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 33 of 41 Table 6 . Internal Standards, Concentrations and Criteria

Analytical Method Internal Standard Recommended Concentration Acceptance Criteria
EPA 200.8, ASTM D5673 -10, SM 3125

Metals Bi, In, Sc, & Tb 20 - 200 μg/L 60 – 125% the response in the calibration blank

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 r equire 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 othe r 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 should be reported

.Page 34 of 41 

### 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 an LRB must be included in every analytical batch . Methods involving the direct analysis of samples (i.e., the chlorate methods and EPA Method 524.3) require a minimum of one LRB analyzed with every batch of 20 or fewer field samples. For all the methods, an LRB is defined as an aliquot of reagent water that is treated exactly as a sample, including exposure to all glassware, equipment, solvents, reagents, internal standards and surrogate standards that are used with the other samples in the batch. This blank determines if method analytes or other interferences 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 should be performed until the source of the problem is identified and eliminated. If the source is traced to any material that was used in the preparation of a batch ofsamples, then a new aliquot of each sample should be prepared. If the samples cannot be reprocessed, then all data for the problem analyte(s) are considered invalid for all samples in the batch , and t he data should be flagged as not meeting the QC criteria. Data for samples processed with an LRB that fail s 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 digestio n batch are lost unless the laboratory has a back -up aliquot of each sample to extract. One reason EPA has limited the extraction/digestion batch to 20 field samples is 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; an LRB must be extracted with each batch.Page 35 of 41 Table 7. Laboratory Reagent Blank Criteria
Analytical Method LRB Acceptance Criteria
EPA 200.8, ASTM D5673 -10, SM 3125

Metals The measured concentrati on 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 300.1, ASTM D6581 -08, SM 4110D

Chlorate

EPA 522 1,4-Dioxane

EPA 524.3 VOCs The measured concentrati on 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 sta ndard and surrogate standard recoveries must meet the criteria specified in Tables 5 and 6. EPA 539 Hormones



### 7.6 Laboratory Fortified Blank With the exception of EPA 524.3, a ll other methods approved for UCMR 3 monitoring require the extraction and an alysis of a n LFB. Since EPA 524.3 utilizes procedural calibration standards, there is no difference between the LFB and the CCC for ONLY this method. The LFB is an aliquot of reagent water or other blank matrix to which known quantities of the method analy tes 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 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.

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 concentrat ion for each UCMR 3 analyte in th e LFB s 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 anotherPage 36 of 41 aliquot of each sample must be prepared for analysis. If this is not possible, then all data for t he problem analyte(s) are considered invalid for all samples in the batch , and should 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% 80 – 120% 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 t he 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 Ap plies 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 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 analyt ical 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 replicate analytical results from the separate processing and analysis of duplicate volumes of a sample. However, this technique is only useful when the original sample containsPage 37 of 41 background concentrations of the method analytes. Since the laboratory does not know which samples may c ontain 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 samples, and one set of LFSM/LFSMD/unfort ified 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, a set of 40 field samples will require preparation and analysis of two LFSM/LFSMD s ets, one set fortified at the low -level and one at the mid- level concentration

.

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 an d 1.5 μ g/L are acceptable).

The mid -level LFSM/LFSMD fortification concentration must be near the mid -level calibration standard for each contaminant. Where possible (i.e., when the laboratory has data from previously analyzed samples), the fortification concentration should approximate the average concentration observed in previous analyses.

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.



### 7 .8 Analytical Sequence The sequence with which UCM R 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 should be analyzed whether or not the initial calibration was generated the same day. Following the CCC≤MRL, the LRB should 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. The 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 within the same 24 -hour period, it must begin with the analysis of a CCC ≤MRL.Page 38 of 41 Example 2 illustrates a valid analysis sequence for Method 537 that will meet the QC requirements. It provides suggestions for corrective action if the crite ria are not met.

Example 2. Valid Analysis Sequence for Method 537

Injection # Sample Description Acceptance Criteria a Corrective Action

1 CCC ≤MRL Recovery for each target analyte is 50-150% of the true value Instrument maintenance to recover sensiti vity, 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 correc t 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 % r ecovery 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 fortifi cation concentrations and ≤ 30% for midlevel 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 reportabl e.
17 through 28 Field Samples 11-20 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

29 Final high

- level CCC c Recovery for each an alyte 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 must 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 forti fied at a concentration >MRL is 70

- 130% of the true value for each target analyte.

c Subsequent to the initia l CCC ≤MRL, CCC concentrations should be r otat ed between the mid and high

concentrations

. d Failing these criteria does not invalidate the analysis batch under UCMR 3

. See Section 7 .7 for the specifications

for low and mid

- level fortification concentrations

.Page 39 of 41 

## Appendix A

. Requirements for UCMR 3 Metal Analysis

Table 9 presents specific requirements for the determination of UCMR 3 metal analytes in samples. The requirements follow EPA Method 200.8 Revision 5.4 for Total Recoverable Analytes in Aqueous Sampl es. In the analysis of UCMR 3 samples, laboratories must adhere to these specifications regardless of which method (EPA 200.8, ASTM D5673-10, or SM 3125) they have certification for. The following exceptions to EPA Method 200.8 apply to UCMR 3 :

1) For Section 11.0, use Section 11.2.2. 2) In Section 11.2.3, omit the use of hydrochloric acid. 3) Omit Section 11.2.8.

Table 9 . Specifics for the Determination of Metals for UCMR 3

Analyte Natural Isotopes a % Relative Abundance Additional Isotopes to

Monitor Isotope to Report Required Elemental & Molecular Equations

Co 59 100

--- 59 (1.000) ( 59 C)

Mo 92 94 95 96 97 98 100 14.84 9.25 15.92 16.68 9.55 24.13 9.63 99 98 (1.000) ( 98 C) – (0.146) ( 99 C) Isobaric elemental correction for Ruthenium.

Sr 84 86 87 88 0.56 9.86 7.00 82.58 85 88 (1.000) ( 88 C)

V 50 51 0.250 99.750 52 53 51 (1.000) ( 51 C) – (3.127) [( 53 C) – (0.113) ( 52 C)] Isobaric polyatomic correction for chloride and sulfate matrix molecular ions.

Bi b 209 100

--- 209 (1.000) ( 209 C)

In b 113 115 4.3 95.7 118 120 115 (1.000) ( 115 C) – (0.016) ( 118 C) If Tin present, use the isobaric elemental correction.

Sc b 45 100

--- 45 (1.000) ( 45 C) Background molecular ions may interfere.

Tb b 159 100

--- 159 (1.000) ( 159 C)

a All must be monitored
b Internal standardPage 40 of 41 

## Section 8 . References

ASTM Standard D5673-10. Standard Test Method for Elements in Water by Inductively Coupled Plasma – Mass Spectrometr y. 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. Availa ble at http://www.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 Res earch 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 Lab oratory (NERL) , O RD, EPA , Cincinnati, Ohio 45268. Available for download at http://water.epa.gov/scitech/drinkingwater/labcert/analyticalmethods_ogwdw. cfm

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) , Version 1.0, September, 2008. EPA/600/R-08/101. NERL, ORD, EPA , Cincinnati, Ohio 45268. Avail able 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)
, Ve rsion 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

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

. EPA Document #EPA/240/B-01/002. Office of Environmental Information (OEI)

, EPA , Washington, DC 20460. A vailable at http:// www.epa.gov/quality/qmps.htmlPage 41 of 41 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 from http://www.epa.gov/quality/qs-doc/r5-final.pdf

Statistical Protocol for the Determination of the Single-Laboratory Lowest Concentration Minimum Reporting Level (LCMRL) and Validation of the Minimum Reporting Level (MRL)
, November 2004. TSC, OGWDW, EPA , Cincinnati, Ohio 45268. Available for download from http://water.epa.gov/scitech/drinkingwater/labcert/analyticalmethods_ogwdw.cfm

SM Method 3125. Metals by I nductively Coupled Plasma/Mass Spectrometry (1997). Available for purchase at http://www.standardmethods.org/store/ProductView.cfm?ProductID=211

SM Method 4110D. Ion Chromatographic Determination of Oxyhalides and Bromide (2000)

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