# UCMR 4 Laboratory Approval Requirements
and Information

Document

Version 1.0

November 2015

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: ________________________________ Date:___________ This signature affirms that the Laboratory Manager
and the staff who are anticipated to participate in UCMR 4 have read the UCMR 4 Laboratory Approval Requirements and Information Document

.i Office of Water (4607 M)
EPA 815

- B

- 15

- 004
November 2015ii 

## Foreword

The proposed Revisions to the Unregulated Contaminant Monitoring Rule (UCMR 4) for Public Water Systems require public water systems (PWSs) to collect specific data and information during a defined monitoring period. The UCMR rule also establishes requirements and specifications for the reporting of UCMR 4 data to the United States Environmental Protection Agency (EPA). This document, the UCMR 4 Laboratory Approval Requirements and Information Document

, serves as a support document for
laboratories interested in bec oming EPA approved and maintaining their EPA approval to analyze samples collected at PWSs to meet the future UCMR 4 requirements for contaminants. The main objective of th is document, the UCMR 4 Laboratory Approval Requirements and Information Document

, i s to provide laboratories with detailed information on the UCMR 4 laboratory approval process. The
document is intended to describe the proposed :

• laboratory approval process,

• procedures that EPA uses to assess a laboratory's ability to produce data of know n and acceptable

accuracy and precision,

• sample collection and handling requirements,

• laboratory data quality control requirements for UCMR 4 chemical analyses, and

• specific analytical procedures for UCMR 4.
Laboratories will be required to follow this UC MR 4 Laboratory Approval Requirements and Information
Document to process UCMR 4 samples collected at PWSs and maintain their status as an EPA approved UCMR 4 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 45268 . Additional information on the UCMR program can be found at the UCMR Homepage

. This manual was prepared as supporting documentation to launch the UCMR 4 Laboratory Approval Program based upon the proposed UCMR 4. This document will be updated as Version 2.0, once the UCMR 4 final rule is published. Any references within this document to “approved” methods or program “requirements” are conditional and subject to change with the promulgation o f the UCMR 4 final rule.



## Disclaimers

1. Mention of trade names or commercial products does not constitute endorse ment or recommendation for use.
2. This document describes the provisions of the proposed UCMR 4 program, the analytical
methods for UCMR 4 contaminants , and EPA regulations that once final

, establish legally binding requirements. However, this document does not substitute for t hose future provisions or regulations.
3. Laboratory approval to perform UCMR 4 analyses will only apply during UCMR 4 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 , that is, their State or EPA Region.

4. The UCMR 4 laboratory approval process is not related to the laboratory certification process for conducting compliance monitoring under other N ational Primary Drinking Water Regulations (NPDWRs). A laboratory’s approval for UCMR 4 analyses has no impact on their certification to perform compliance monitoring under other NPDWRs.iii 

## Abbreviations

ADDA (all

- S ,all

- E )

- 3

- Amino

- 9

- methoxy

- 2,6,8

- trimethyl

- 10

- phenyldeca

- 4,6

- dienoic acid
APHA American Public Health Association
ASTM ASTM International
AWWA American Water Works Association
C 8 Octyl

- functionalized silica gel
C 18 Octadecyl

- functionalized silica gel
CAS Chemical Abstract Service
CCC Continuing calibration check
CFR Code of Federal Regulations
ELISA Enzyme

- linked immunosorbent assay
EPA United States Environmental Protection Agency
GC

- MS Gas chromatography/mass spectrometry
HR PIR Half range for the prediction interval of results
IC Ion chromatography
ICP

- MS Inductively coupled plasma mass spectrometer
ID Identification
IDA Initial demonstration of accuracy
IDC Initial demonstration of capability
IDP Initial demonstration of precision
IG EPA Inspector General
LAP Laboratory Approval Program
LCMRL Lowest concentration minimum reporting level
LC

- ESI

- MS

- MS Liquid chromatography electrospray ionization tandem mass spectrometry
LC

- MS

- MS Liquid chromatography tandem mass spectrometry
LFB Labor atory fortified blank
LFSM Laboratory fortified sample matrix
LFSMD Laboratory fortified sample matrix duplicate
LRB Laboratory reagent blank
MRL Minimum reporting level m/z Mass

- to

- charge ratio
NA Not applicable
NERL National Exposure Research Laboratory
NPDWR National Primary Drinking Water Regulation
OGWDW Office of Ground Water and Drinking Water
ORD Office of Research and Development
PIR Prediction interval of results
PIR L ower Lower PIR limit
PIR U pper Upper PIR limit
PT Proficiency testing
PWS Public water system QA Quality assurance QAPP Quality Assurance Project Plan QC Quality controliv 

## Abbreviations

QCS Quality control sample QMP Quality Management Plan
RPD Relative percent difference
RSD Relative standard deviation

s Standard deviation
SDVB Styrene divinylbenzene
SDWA Safe Drinking Water Act
SDWARS Safe Drinking Water Accession and Review System
SIM Selective ion monitoring
SM Standard Methods for the Examination of Water and Wastewater
SOP Standard operating procedure
SPE Solid phase extraction
SRMD Standards and Risk Management Division
Tris t ris(hydroxymethyl)aminomethane
TSC Technical Support Center
UCMR Unregulated Contaminant Monitoring Rule
UCMR 1 First Unregulated Contaminant Monitoring Rule
UCMR 2 Second Unregulated Contaminant Monitoring Rule
UCMR 3 Third Unregulated Contaminant Monitoring Rule
UCMR 4 Fourth Unregulated Contaminant Monitoring Rule
UPLC U ltra performance liquid chromatography

v:v Volume

- to

- volume
WEF Water Environment Federationv 

## Table of Contents

Foreword

................................ ................................ ................................ ................................ ....................... ii

Disclaimers

................................ ................................ ................................ ................................ .................... ii

Abbreviations

................................ ................................ ................................ ................................ ............... iii

1 Introduction

................................ ................................ ................................ ................................ .......... 1

1.1 Background on the Unregulated Contaminant Monitoring Rule

................................ .................. 1

1.2 Ensuring Data Quality for UCMR 4

................................ ................................ ................................ 1

2 UCMR 4 Laboratory Approval Process

................................ ................................ ................................ .. 1

2.1 Registration for the UCMR 4 Laboratory Approval Program

................................ ........................ 2

2.2 UCMR 4 LAP Applications

................................ ................................ ................................ .............. 2

2.3 EPA Review of Submitted Application Material

................................ ................................ ............ 3

2.4 UCMR 4 Proficiency Testing

................................ ................................ ................................ .......... 3

2.5 Procedure for Revocation of UCMR Approval Status

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

3 Laboratory Quality Management Plan and UCMR 4 Quality Assurance Project Plan

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

3.1 Quality Management Plan for UCMR 4

................................ ................................ ......................... 5

3.2 Quality Assurance Project Plan for UCMR 4

................................ ................................ ................. 6

4 Methods for UCMR 4 Monitoring

................................ ................................ ................................ ......... 7

4.1 EPA Method 200.8 Rev. 5.4, ASTM Method D5673

- 10, SM 3125B (Referred to as EPA 200.8)

... 7

4.2 EPA ELISA Method

................................ ................................ ................................ ......................... 8

4.3 EPA Method 525.3

................................ ................................ ................................ ........................ 8

4.4 EPA Method 530

................................ ................................ ................................ ........................... 8

4.5 EPA Me thod 541

................................ ................................ ................................ ........................... 9

4.6 EPA Method 544

................................ ................................ ................................ ........................... 9

4.7 EPA Method 545

................................ ................................ ................................ ........................... 9

4.8 EPA Method 557

................................ ................................ ................................ ......................... 10

4.9 Table 1: UCMR 4 Chemical Analytes and Methods: Assessment Monitoring.

........................... 10

5 Initial Demonstration of Capability for UCMR 4 Analyses

................................ ................................ .. 11

5.1 Submission of IDC Data

................................ ................................ ................................ ............... 11

5.2 IDC Study Elements

................................ ................................ ................................ ..................... 12

5.3 Ta ble 2: IDC Quality Control Requirements for MRL Verification and for Precision and Accuracy
12

6 Minimum Reporting Level Verifica tion

................................ ................................ ............................... 13

6.1 Fortify, Process, and Analyze Seven Replicate LFBs at or Below Proposed MRL

........................ 13vi 6.2 Calculate the mean and standard deviation

................................ ................................ ............... 13

6.3 Half range for the prediction interval of results

................................ ................................ ......... 13

6.4 Confirm PIR limits are within QC criteria

................................ ................................ .................... 13

6.5 Example Calculation of the PIR limits

................................ ................................ ......................... 14

7 Quality Control Requirements

................................ ................................ ................................ ............ 14

7.1 Extraction Batch and Digestion Batch

................................ ................................ ......................... 14

7.2 Analysis Batch

................................ ................................ ................................ ............................. 15

7.3 Initial Calibration of Analytical Instruments

................................ ................................ ............... 15

7.4 Continuing Calibration Checks (CCCs)

................................ ................................ ......................... 17

7.5 Surrogate Requirements and Criteria

................................ ................................ ......................... 18

7.6 Internal Standard Requirements and Criteria

................................ ................................ ............. 20

7.7 Laboratory Reagent Blank

................................ ................................ ................................ ........... 21

7.8 Laboratory Fortified Blank (LFB)

................................ ................................ ................................ . 23

7.9 Quality Control Sample (QCS)

................................ ................................ ................................ ..... 24

7.10 Laboratory Fortified Sample Matrix & Laboratory Fortified Sample Matrix Duplicate

.............. 25

7.11 Sequence of Injection for Analysis Batch

................................ ................................ .................... 26

7.12 Exceeding the Calibration Range

................................ ................................ ................................ 27

7.13 Legal Defensibility of Data

................................ ................................ ................................ .......... 28

8 Sample Handling Requirements

................................ ................................ ................................ .......... 28

8.1 Sample Collection Time and Date

................................ ................................ ............................... 28

8.2 Sample Transport and Storage

................................ ................................ ................................ .... 29

8.3 Sample Preservation

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

8.4 Extract Holding Times and Temperatures

................................ ................................ ................... 32

8.5 Invalid Sample

................................ ................................ ................................ ............................. 32

8.6 Method Information Concerning Collection and Holding

................................ .......................... 32

8.7 Sample Volume

................................ ................................ ................................ ........................... 33

8.8 Laboratory Errors or Sampling Deviations

................................ ................................ .................. 33

9 Uploading Data to EPA database

................................ ................................ ................................ ........ 33

9.1 Table 14. Unregulated Contaminant Monitoring Reporting Requirements

............................... 33

9.2 HAAs Reported as Groups

................................ ................................ ................................ ........... 33

10 References

................................ ................................ ................................ ................................ ...... 38

11 Appendix A: Requirements for Water Quality Parameters and Indicators

................................ .... 39

11.1 Total Organic Carbon (TOC) and Bromide

................................ ................................ .................. 39vii 11.2 Temperature and pH Data for ELISA method

................................ ................................ ............. 39

12 Appendix B: Requirements for UCMR 4 Method 200.8 Analysis

................................ .................... 40

12.1 Isotopes and Internal Standards

................................ ................................ ................................ . 40

12.2 Additions and Exceptions to Method 200.8 for UCMR 4

................................ ............................ 40

12.3 Table 16. Determination of Metals for UCMR 4 by EPA Method 200.8 Rev. 5.4

....................... 41

13 Appendix C: LCMRL s and MRLs for UCMR 4 Target Analytes

................................ ......................... 41

13.1 Table 17: LCMRLs and MRLs for UCMR 4 analytes by EPA Method 200.8 (SIM).

....................... 41

13.2 Table 18: LCMRLs and MRLs for UCMR 4 analytes by EPA Method 525.3 (SIM)

. ....................... 41

13.3 Table 19: LCMRLs and MRLs for UCMR 4 analytes by EPA Method 530.

................................ ... 41

13.4 Table 20: LCMRLs and MRLs for UCMR 4 analytes by EPA Method 541.

................................ ... 42

13.5 Table 21: LCMRLs and MRLs for UCMR 4 analytes by EPA Method 544.

................................ ... 42

13.6 Table 22: LCMRLs and MRLs for UCMR 4 analytes by EPA Method 545.

................................ ... 42

13.7 Table 23: LCMRLs and MRLs for UCMR 4 analytes by EPA Method 552.3.

................................ 421 

## 1 Introduction

1.1 Background on the Unregulated Contaminant Monitoring 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

, second, and third UCMRs , that is, UCMR 1
, UCMR 2, UCMR 3, respectively

, in the Feder al Register in September 1999

, January 2007 , and May 2012 . The UCMR program uses a three

- tiered approach for monitoring contaminants that takes into account the availability of analytical methods , the source water supply and the contaminants likely to be f ound . UCMR 4 monitoring period is scheduled to occur from January 2018 through December 2020

. EPA identified thirty chemical contaminants for UCMR 4. Monitoring for the se contaminants is supported by eleven a nalytical methods.



### 1.2 Ensuring Data Quality for UCMR 4 Data reported under UCMR 4 must meet specific precision and accuracy targets to achieve the objectives of the program. During UCMR 4 development, EPA established criteria to 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 to reliably predict the
national occurrence of the contaminants in drinking water. EPA ensures the integrity of the data by: 1)
def ining and maintaining strict requirements for sample collection, sample handling, processing and analysis, and data reporting, and 2) assisting the drinking water industry in identifying qualified laboratories that can accurately and reliably perform the a nalyses required by UCMR 4.



### 1.2.1 Laboratory Approval Approach 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 previous UCM R s and believes this process is effective in yielding high quality data. An overview of the Laboratory Approval Program (LAP) and its requirements for UCMR 4 is presented in this UCMR 4 Laboratory Approval Requirements and Information Document

, including:

• a description of the UCMR 4 laboratory approval process;

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

followed at EPA

- approved UCMR 4 laboratories;

• a summary of the UCMR 4 contaminant analytical methods, minim um reporting levels (MRLs), and

initial demonstration of capability (IDC) requirements; and

• a summary of the laboratory data quality control (QC) requirements for UCMR 4 analyses.
Laboratories must follow the procedures outlined in this document to obtain approval for the analysis of UCMR 4 samples.



## 2 UCMR 4 Laboratory Approval Process
Laboratories analyzing samples for UCMR 4 contaminants in Table 1 must follow the process outlined in this section to obtain approval. Approval is by method and by individual l aboratory location. A laboratory may apply for approval for any number of UCMR 4 methods. If a laboratory organization has multiple locations, each laboratory location must complete the process independently. Water systems2 analyzing samples for bromide or total organic carbon must follow the process outlined in in Section
11. 1 , Appendix A

. 

### 2.1 Registration for the UCMR 4 Laboratory Approval Program Laboratories interested in UCMR 4 laboratory approval are to contact EPA as soon as possible. Laboratories must request UCMR 4 registration within 120 days of publication of the Final UCMR 4. Laboratories should send a letter of interest with contact information, including an e

- mail address, to the following address:

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

or use the e

- mail address: UCMR_Sampling_Coor dinator@epa.gov

.

Upon receipt of correspondence from a laboratory indicating their interest in participating in the UCMR 4 LAP, EPA will e

- mail UCMR 4 registration information to the laboratory.



### 2.1.1 Completing the UCMR 4 Registration Sheet The laboratory must complete the UCMR 4 registration sheet, indicating the UCMR 4 chemistry methods for which they are seeking approval, and promptly return it to EPA at the above e

- mail address. EPA will
issue a UCMR

- specific laboratory ID to each participating laboratory. Registration information should be received by EPA no later than 30 days after receiving the registration materials from EPA

. 

### 2.2 UCMR 4 LAP Applications EPA will forward the appropriate application packet to the laboratory based on the information provided on the registration sheet. The application packet will include a general application, and a
method

- specific application for each method sele cted on the registration sheet. Completed applications
are to be returned to EPA as soon as possible for review

. Firm application deadlines are established with each proficiency testing study ( Section 2.4 )

. EPA will acknowledge receipt of application materials in correspondence to the laboratory. To complete these applications, labor atories must take the following
six steps shown in Sections 2.2.1 to 2.2.6

. 

### 2.2.1 Drinking Water Certification Document drinking water certification by a state or regional Certification Authority for the analysis of samples using gas chromatography, liquid chromatography, ion chromatography, or inductively coupled plasma mass spectrometry methods, as indicated in the applications

. Certification is not required in the specific technique used in the method for which the laboratory is seeking approval. However, certification in a minimum of one drinking water method is required.



### 2.2.2 Personnel Information
Provide information about the personnel who will be involved in UCMR 4 work.



### 2.2.3 Provide QA Information
Provide QA information, including a copy of the table of content s from the laboratory’s Quality Management Plan (QMP ), ( Section 3.1 )

.3 

### 2.2.4 Analytical Equipment a nd Sample Handling Procedures Provide information regarding analytical equipment and sample handling procedures

. 

### 2.2.5 Data Submission For each method for which the laboratory is seeking approval, submit data from: 1) an IDC study ( Section 5 ); 2) analysis of laboratory reagent blank (LRB) samples ( Section 7. 7 ); and 3) analysis of a set of laboratory fortified sample matrix (LFSM), LFSM duplicate (LFSMD), and the corresponding unfortified drinking water sample ( Section 7. 10 ). Data submitte d mu st include labeled chromatograms or spectrometric traces, include quantitation reports with surrogate recovery results and internal standard

response results

. 

### 2.2.6 EPA Electronic Reporting System
Document that the laborator y will post UCMR 4 results to the EPA’s electronic data reporting system, accessible at the UCMR Homepage ( Section 9 ) . Laboratories must report field sample results and associated QC data, as required by the EPA electronic data reporting system , within 120 days from the sample collection date. Failure to post data to the EPA electronic data reporting system will result in EPA revoking the laboratory’s approval status. Once approval is revoked, the laboratory c annot be reapproved during the UCMR 4 monitoring period.



### 2.3 EPA Review of Submitted Application Material EPA will review the submitted application materials. If deficiencies are identified in the application
materi als, EPA will identify the area s of deficienc y 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. If all requested information is present and acceptable, EPA will notify the laboratory that they are eligible to participate in a UCMR 4 proficiency testing (PT) study. EPA anticipates the UCMR 4 LAP application period for UCMR 4 will close in mid

- 2017 with the application submission deadline fo r the final PT study

. 

### 2.4 UCMR 4 Proficiency Testing EPA will conduct at least two PT studies prior to publication of the UCMR 4 final rule and intends to offer a minimum of three PT studies prior to closing the Laboratory Approval Program. Each laboratory must pass one PT study for each method for which the y are seeking approval. When the laboratory’s application for a specific method is reviewed and determined to meet the UCMR 4 method criteria, that laboratory can participate in EPA’s UCMR 4 PT study for that method. Participation i n a PT study is
method

- s pecific. A laboratory is not required to concurrently participate in a PT study for all methods for which they are seeking approval.



### 2.4.1 Method Specific PT
EPA will send a method

- specific PT ampule to participating laboratories, with instructions and a cover
l etter 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 4 analytes for a method will be present in a PT ampule for that method. L aboratories that do not pass 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 met hod during subsequent UCMR 4 PT studies.



### 2.4.2 Successful Completion of Method Specific PT Study 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 passed a PT study4 prior to publication of the UCMR 4 final rule w ill be granted a “Pending Approval” for UCMR 4, contingent upon: 1) changes applied to the final rule as a result of public comments to the proposed rule, and 2) res olution of any findings resulting in a laboratory audit. Laboratories are not authorized to analyze UCMR 4 monitoring samples until they receive formal “Final Approval” in writing from EPA. EPA will not accept analytical results for UCMR 4 samples collecte d prior to the monitoring date specified in
the final UCMR 4.



### 2.5 Procedure for Revocation of UCMR Approval Status EPA may consider revoking UCMR approval status for several reasons. Once approval is revoked , the laboratory cannot be reapproved during the UCMR 4 monitoring period. When revocation is deemed

necessary, a pproval will be revoke d in writing, via a letter from EPA, stating the reasons for EPA’s
decision . Laboratories receiving such notice are to stop analyzing samples as of the effective date specified in the letter.



### 2.5.1 Reasons for Revocation of Approval Laboratories reporting invalid data are subject to revocation of UCMR 4 laboratory approval , depending on the frequency or severity of the data validity issue. Laboratories that do not report data in a complete, timely manner are likewise subject to revocation of approval , depending on the frequency or severity of the reporting delay

. Laboratories must report field sample results and associated QC data, following the instructions for the EPA electr onic data reporting system , within 120 days from the sample
collection date , as required by the rule

. 

### 2.5.2 Fraudulently R eporting D ata
Laboratories suspected of reporting fraudulent d ata will not only risk revocation of their UCMR 4 laboratory approval status but may also be subject to investigation by the EPA Inspector General (IG). An
IG determination of lab fraud m ay preclude the laboratory from participating in future UCMR monitoring p rograms.


### 2.5.3 Deviating from M ethod Procedures An EPA approved UCMR 4 laboratory must follow the UCMR 4 analytical methods and the specifications found throughout this manual to maintain their s tatus as an EPA

- approved UCMR laboratory. When a
method i ncludes fl exibility options , the laboratory may consider these options but any procedural modifications within the scope of the method

- defined flexibility must be clearly identified i n the appropriate sections of the laboratory’s UCMR 4 method application. Laborator ies must p erform the
method as identified in their UCMR 4 method application , or must request and receive EPA
authorization to substantively modify those application details during active implementation of UCMR 4. To avoid jeopardizing their approval, l abo ratories are encouraged to seek early clarification from EPA regarding any matter involving method modifications

.



## 3 Laboratory Quality Management Plan and UCMR 4 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. More information regarding laboratory QMPs can be found in EPA Requirements for Quality Management Plans (QA/R

- 2)

. A Quality Assurance Project Plan (QAPP) documents details specific to an individual project within the organization or program

.5 

### 3.1 Quality Management Plan for UCMR 4 Laboratories analyzing samples for UCMR 4 are required to adhere to defined QA and QC procedures. This ensures that analytical data generated for UCMR 4 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 effectivenes s of its QA and QC operations. The QMP is a tool to help the laboratory maintain and improve data dependability and quality. Specifically, it describes how an organization structures their quality system, including: quality policies and procedures; areas o f application; and roles, responsibilities, and authorities. The QMP must be kept current during the time the laboratory is performing UCMR 4 measurements. Laboratories are required to submit a copy of the Table of Contents from their QMP to EPA as part of the UCMR 4 LAP ( Section 2.2 ). The laboratory QMP should be concise and, a t a minimum, address the following topics in Sections 3.1.1 through 3.1.5.



### 3.1.1 QMP References Certain sections of the laboratory QMP can reference existing documented procedures, such as the laboratory's standard operating procedures (SOPs), EPA analytical methods, or other literature, such as Standard Methods for the Examination of Water and Waste water

. 

### 3.1.2 Laboratory organization and responsibility

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

• A list of key individuals responsible for producing valid measurements and conducting routine

assessments of QC proce dures and measurements;

• Identification of the person responsible for internal audits and r eviews of the implementation of

the QMP and its requirements;

• A description of laboratory training to keep personnel curr ent on regulations and methods ; and

• Documentation of ethics training

. 

### 3.1.3 Field sampling

• Personnel responsible for collecting samples; and

• Procedures for sample collection, preservation, containment, holding times, and transport to the

laboratory

. 

### 3.1.4 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 processing, extraction , and digestion of samples,

and during analysis 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.


### 3.1.5 Chemical, reagent and standard control procedures

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

calibration standards, surrogat e standards, internal standards ; and6 • Freque ncy of initial calibration, continuing calibration checks (CCCs), and validation of calibrations.


### 3.1.6 Analytical procedures

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

• Location of SOPs;

• Frequency of SOP review;

• Analyti cal instrument identification/labeling; and

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


### 3.1.7 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.



### 3.1.8 QC Procedures

• Types and frequency of QC sample analysis;

• MRL verificati on procedures, criteria and frequency;

• Use and criteria for internal and surrogate standards; and

• Procedures for IDCs, and preparation of control charts.


### 3.1.9 Preventive maintenance

• Equipment manual location and availability;

• Spare parts inventory; and

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


### 3.1.10 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 correc tive action is necessary, and

ensuring that it is completed; and

• Procedure for d ocumenting actions taken and their effectiveness.


### 3.1.11 Record Keeping

• Procedure for maintaining records, i ncluding duration and location;

• Procedure for backing

- up databases and elec tronic files; and

• Procedures in place to document the secondary review of log records including those for

instrument maintenance, standard and reagent preparation, balances, refrigerators and water purification system s

. 

### 3.2 Quality Assurance Project Plan for UCMR 4 All laboratories seeking approval to perform chemical analyses for UCMR 4 are required to prepare a QAPP specific to UCMR 4. The QAPP supplements the laboratory QMP by documenting the specific changes in sample handling, analytical methods, QC, and data reporting that the laboratory makes to7 address the UCMR 4 requirements. Laboratories must make this document available to EPA for review, if requested. More information regarding the preparation of a QAPP can be found in EPA Requirements for Quality Assurance Project Plans (QA/R

- 5 )

. 

### 3.2.1 General Procedures Laboratory personnel must be familiar with procedures such as :

• prepar ation , label ing , and storage of standards and reagents;

• prepar ation of samples for analysis;

• calibrat ion and operat ion of analytical instrumentation;

• monitor ing system performance;

• troubleshoot ing ;

• maintenance of thorough documentation of activities;

• maintenance of QC review of log records; and

• review ing and report ing data.



### 3.2.2 Standard and Reagent Identifiers Unique identifiers must be assigned to all chemicals, reagents, solvents, and standards, including purchased stock and neat materials, laboratory

- prepared stock standards, calibrations standard, QCSs,
fortification s olutions, surrogate solutions, and internal standard solutions.



### 3.2.3 Standard Preparation Log Records Standard preparation log records must document the detail necessary to determine concentrations by calculation, including the solvent used, lot number and man ufacturer, and preparation and expiration dates. The standards that are used in a particular batch must be readily traceable to the standard prep log. For instance, the ID of a standard, rather than generic descriptors such as “Ical standard 1,” should
be r eferred to in the analytical sequence and on the quantitation reports.



### 3.2.4 Significant Figures of Reported Results Calculations must use all available digits of precision, but final reported concentrations should be rounded to an appropriate number of significant figures, typically two, and not more than three significant figures. Some data in Appendix B are reported with more than two significant figures. This is done to better illustrate the method performance data.



## 4 Methods for UCMR 4 Monitoring

Labor atories must use the methods specified in 40 CFR 141.40 (a)(3)

, Table 1, to perform UCMR analyses during the 3

- year UCMR 4 monitoring period. UCMR 4 methods are summari zed below and listed in Table 1, Section 4.10

, of this document. UCMR 4 laboratories 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 E PA for UCMR 4. Sampling and analysis for UCMR 4 shall not begin prior to the monitoring period specified in the final rule.



### 4.1 EPA Method 200.8 Rev. 5.4, ASTM Method D5673

- 10, SM 3125 B (Referred to as EPA 200.8) Determination of Trace Elements in Waters and W astes by Inductively Cou pled Plasma

– Mass Spectrometry Total recoverable analytes in a 100 mL water sample are solubilized by heating in nitric acid at 85 °C . For UCMR 4, all samples for metals analysis by ICP

- MS must be digested, regardless of sample turbidity and8 method. Microwave digestion, with a reduced sample volume, is allowed only if all QC requirements are met. When the sample volume has been evaporated to approximately 20 mL, it is refluxed for an
addi tional 30 min 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 aliquot of a solution containing internal
standard 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 differentia lly pumped vacuum interface 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 . See Section 12, Appendix B

, for details regarding specific UCMR 4 analytical requirements.


### 4.2 EPA ELISA Method

Based on Ohio EPA Total (Extracellular and Intracellular) Microcystins

- ADDA by ELISA Analytical Methodology, Version 2.0, January 2015 EPA anticipates having an EPA e nzyme

- linked immunosorbent assay (ELISA ) method available by the publication of the final rule and anticipates that this method will be similar to the Ohio EPA methodology. The EPA method for ELISA is an immunoassay for the detection of microcystins in water samples. This procedure is an indirect competitive ELISA which allow s microcystins and nodularin to be
detected in a congener

- independent manne r through recognition by specific antibodies. Microcystins
and nodularin in a sample compete with an immobilized microcystin

- protein analogue for the binding
sites of antibodies in solution

. After a washing step and the addition of the substrate solution, a color signal is generated. The intensity of the color is inversely proportional to the concentration of the microcystin present in the sample. The color reaction is stopped after a specific time and the color is evaluated using a microplate reader at 450 nm. See Section 11.2, Appendix A concerning the measurement of temperature and pH at the time of collection.



### 4.3 EPA Method 525.3 Determination of Semivolatile Organic Chemicals in Drinking Water by Solid Phase Extractio n and Capillary Column Gas Chromatography

- Mass Spectrometry (GC

- MS)

A 1 L water sample is fortified with surrogate analytes and passed through a solid phase extraction (SPE) device to extract the target analytes and surrogates. The compounds are eluted from the solid phase with a small amount of organic solvents. The solvent extract is dried by passing it through a column of anhydrous sodium sulfate and is concentrated by eva poration with nitrogen gas . The volume is then adjusted to 1 m L with ethyl acetate after adding the internal standards. A splitless injection is made into a GC equipped with a high

- resolution fused silica capillary column that is interfaced to an MS. The analytes are separated and identified by comparing the acquired mass spectra and r etention times for calibration standards acquired under identical GC

- MS conditions. The GC

- MS is operated in selected ion

monitoring ( SIM ) mode. The GC

- MS may be calibrated using standards prepared in solvent or using
matrix

- matched standards. The concentr ation of each analyte is calculated by using its integrated peak

area with t he internal standard technique.



### 4.4 EPA Method 530 Determination of Select Semivolatile Organic Chemicals in Drinking Water by Solid Phase Extraction and Gas Chromatography Mass Spectr ometry (GC

- MS)9 A 1 L water sample is fortified with surrogate analytes and passed through a solid phase extraction device to extract the target analytes and surrogates. The compounds are eluted from the solid phase with a small amount of organic solvents. The solvent extract is dried by passing it through a column of anhydrous sodium sulfate and is concentrated by evaporation with nitrogen gas . The volume is then adjusted to 1 mL with dichloromethane after adding the internal standards. A splitless injectio n is made into a GC equipped with a high

- resolution fused silica capillary column that is interfaced to an MS. The analytes are separated and identified by comparing the acquired mass spectra and retention times for calibration standards acquired under id entical GC

- MS conditions. The GC

- MS is operated in SIM mode of
detection . The GC

- MS may be calibrated using standards prepared in solvent or using matrix

- matched standards. The concentration of each analyte is calculated by using its integrated peak area with t he internal standard technique.



### 4.5 EPA Method 541 Determination of 1

- Butanol, 2

- Methoxyethanol, and 2

- Propen

- 1

- ol in Drinking Water by Solid Phase Extraction and Gas Chromatography

- Mass Spectrometry Fifty milliliter s amples are preserv ed with sodium sul fite and sodium bisulfate . M ethod and surrogate analytes are isolated from water using SPE. The SPE cartridges are dried to remove adsorbed water and
eluted with 2 mL of 5% methanol in dichloromethane. Extracts are analyzed, without further

conce ntration, by GC

- MS in the SIM mode of detection. The method analytes are identified by comparing the retention times and mass spectra to reference retention times and spectra obtained from calibration standards acquired under identical GC

- MS conditions. The concentr ations of method

ana l ytes are calculated using the integrated peak area and internal standard technique.


### 4.6 EPA Method 544 Determination of Microcystins and Nodularin in Drinking Water by Solid Phase Extra ction and Liquid Chromatography

- Tandem Mass Spectroscopy (LC

- MS

- MS)

A 500 mL water sample , fortified with a surrogate, is filtered and b oth the filtrate and the filter are collected. The filter is placed in a solution of 20% reagent water in methanol and held for at least one
hour at

– 20 °C to relea se the intracellular toxins from the cyanobacteria cells that were captured on the filter. The liquid is drawn off the filter and added to the 500 mL aqueous filtrate. The combined sample is passed through a solid phase extraction cartridge to extract the method analytes and surrogate. Analytes are eluted from the solid phase with a solution of 10% reagent water in methanol

. The extract is concentrated to dryness by evaporation with nitrogen in a heated water bath, and then adjusted to a

1 mL volume with a solution of 10% reagent water in methanol . A 10 μL injection is made into an LC equipped with a C 8 column that is interfaced to an MS

- MS. Analytes are separated and identified by comparing the acquired mass spectra and retention time to reference spectra a nd retention times for calibration standards acquired under identical LC

- MS

- MS conditions. The concentration of each analyte is determined by external standard calibration. The use of ultra

- performance liquid chromatography (UPLC) is allowed as part of method flexibility.



### 4.7 EPA Method 545 Determination of Cylindrospermopsin and Anatoxin

- a in Drinking Water by Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry (LC

- ESI

- MS

- MS) In the field, a water sample is added to a bottle or vial that contain s ascorbic acid (dechlorination agent)
and sodium bi sulfate (microbial inhibitor). In the laboratory, 1 mL of sample is taken for analysis, and internal standards are added. An aliquot of the sample is injected into an LC equipped with an analytica l10 column that is interfaced to an MS

- MS. The analytes are separated and identified by comparing retention times and reference signals produced by unique mass transitions to retention times and reference signals for procedural calibration standards acquired under identical LC

- MS

- MS conditions. The concentration of each analyte is determined using the integrated peak area and the internal standard technique. EPA Method 552.3 Determination of Haloacetic Acids and Dalapon in Drinking Water by Liquid

- Liquid Microextraction, Derivatization, and Gas Chromatography with Electron Capture Detection

F orty milliliters of sample , fortified with a surrogate standard

, are adjusted to pH 0.5 or less . Sodium
sulfate is added to the sample , which is then e xtracted with 4 mL of organic solvent , either methyl tert

butyl ether or tert

- amyl methyl ether

, which co ntains the internal standard. The solvent phase, containing t he haloacetic acids

, is pipetted off and placed into a tube . A solution of 10% sulfuric acid in
methanol is added to the solvent extract , and the solution is heated for 2 h . The carboxylic acid groups
on the haloacetic acids are converted to methyl esters . C oncentrated aqueous sodium sulfate is added
to separate t he solvent phase containing the methylated haloacetic acid s. T he aqueous phase is
discarded. The extract is neutralized with a solution of sodium bicarbonate and the solvent layer is removed for analysis. The target analytes are identified and quantified by capillary column gas chromatography using an electron capture detector. Analytes are quantified using procedural stan dard
calibration.



### 4.8 EPA Method 557 Determination of Haloacetic Acids, Bromate, and Dalapon in Drinking Water by Ion Chromatography Electrospray Ionization Tandem Mass Spectrometry (IC

- ESI

- MS

- MS) An aliquot of the sample is injected without cleanup or concent ration onto an ion exchange column specifically designed to separate method analytes from chloride, carbonate, sulfate, and nitrate , which

are monitored via conductivity detection and then diverted to waste . T he analytes of interest are
directed into the E SI

- MS

- MS system. Acetonitrile is added post

- column to enhance desolvation of the method analytes in the ESI interface. Each method analyte is quantitatively identified via a unique mass transition, and the concentration is calculated using integrated peak area and the internal standard technique

. 

### 4.9 Table 1: UCMR 4 Chemical Analytes and Methods: Assessment Monitoring

.

Analytical Method Contaminants Chemical Abstract Service Registry Number Min imum Reporting Level ( μg /L) EPA 200.8, ASTM D5673

- 10, or G ermanium 7440

- 56

- 4 0.3
SM 3125 B M anganese 7439

- 96

- 5 0.4
EPA ELISA method Total microcystins NA 0.3 EPA Method 525.3 alpha

- H exachlorocyclohexane 319

- 84

- 6 0.01
C hlorpyrifos 2921

- 88

- 2 0.03
D imethipin 55290

- 64

- 7 0.2 Ethoprop 13194

- 48

- 4 0.03 Oxyfluorfen 42874

- 03

- 3 0.05 Profenofos 41198

- 08

- 7 0.3 Tebuconazole 107534

- 96

- 3 0.2 Total permethrin (cis & trans) 52645

- 53

- 1 0.0411 Analytical Method Contaminants Chemical Abstract Service Registry Number Min imum Reporting Level ( μg /L)
Tribufos 78

- 48

- 8 0.07 EPA Method 530 Butylated hydrox y anisole 25013

- 16

- 5 0.03

o

- T o l uidine 95

- 53

- 4 0.007 Quinoline 91

- 22

- 5 0.02 EPA Method 541 1

- B utanol 71

- 36

- 3 2 .0
2

- M ethoxyethanol 109

- 86

- 4 0.4
2

- P ropen

- 1

- ol 107

- 18

- 6 0.5 EPA Method 544 Microcystin

- LA 96180

- 79

- 9 0.008 Microcystin

- LF 154037

- 70

- 4 0.006 Microcystin

- LR 101043

- 37

- 2 0.02 Microcystin

- LY 123304

- 10

- 9 0.009 Microcystin

- RR 111755

- 37

- 4 0.006 Microcystin

- YR 101064

- 48

- 6 0.02 Nodularin 118399

- 22

- 7 0.005 EPA Method 545 Anatoxin

- a 64285

- 06

- 9 0.03 Cylindrospermopsin 143545

- 90

- 8 0.09 EPA Method 552.3 or Bromochloroacetic acid (BCAA) 5589

- 96

- 8 0.3 EPA Method 557 Bromodichloroacetic acid (BDCAA) 71133

- 14

- 7 0.5 Chlorodibromoacetic acid (CDBAA) 5278

- 95

- 5 0.3 Tribromoacetic acid (TBAA) 75

- 96

- 7 2.0 Monobromoacetic acid (MBAA) 79

- 08

- 3 0.3 Dibromoacetic acid (DBAA) 631

- 64

- 1 0.3 Dichloroacetic acid (DCAA) 79

- 43

- 6 0.2 Monochloroacetic acid (MCAA) 79

- 11

- 8 2.0 Trichloroacetic acid (TCAA) 76

- 03

- 9 0.5



## 5 Initial Demonstration of Capability for UCMR 4 Analyses
Each laboratory seeking approval for UCMR 4 methods must complete an I nitial D emonstration of Capability (IDC) study for each method. EPA recognizes that a laboratory may use multiple instruments and analysts to perform analys e s . If more than one analyst performs UCMR 4 analyses, each analyst

must perform an IDC study before they analyze UCMR 4 samples. Similarly, an IDC study must be performed using each instrument that will be used to analyze UCMR 4 samples. This will ensure that each operator and each instrument maintains the minimum quality standards. Data from each of th ese tests are to 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 4 monitoring period.



### 5.1 Submission of IDC Data IDC study data must be submitted as part of the laboratory appro val 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 4 method

specific application sheets provide the f ormat for reporting these data.12 

### 5.2 IDC Study Elements EPA recommends that the laboratory verify the instrument calibration and sensitivity prior to performing the IDC study. The lowest calibration curve standard must contain the analytes a t a
concentration at or below the MRL

. The IDC study

, as described in Sections 5.2.1 through 5.2.4 below,
involves demonstration of : 1) low system background, 2) precision, 3) accuracy, and 4) the ability of the laboratory to achieve the MRLs

. 

### 5.2.1 Initial Demonstration of Low System Background Analyze an LRB to verify that all analyte s of interest are found to be less than or equal to one

- third the

MRL. See Section 7.7 .4
, Table 8 , for acceptable LRB criteria.



### 5.2.2 Initial Demonstration of Precision (IDP) Analyze four to seven laboratory fortified blank (LFB) samples 

### (Section 7.8) that are fortified at a mid

level concentration. The relative standard deviation (RSD) of the resulting analytical data set must meet the criterion specified in Table 2 , Section 5. 3

. 

### 5.2.3 Initial Demonstration of Accuracy (IDA) Calculate the average recovery fo r the data set generated for the IDP ( 

### Section 5.2 .2 )

. AAAAAAAAAAAAAA RR RRRR RR = MMMMMMMM oooo LLLLLLLL
FFFFFF FFFF FFFF CC

. × 100% Equation 1

A verage recovery must meet the criteria specifie d in Table 2, Section 5. 3

. 

### 5.2.4 MRL Verification Laboratories must verify they can achieve the UCMR 4 MRL for each analyte according to the procedure
outlined in 

### Section 6

. 

### 5.3 Table 2: IDC Quality Control Requirements for MRL Verification and for Precision and Accuracy Analytical Method MRL Verification Requirement Acceptable
Precision Acceptable Accuracy

EPA 200.8, ASTM
D5673

- 10, or SM 3125 B Metals Lower PIR ≥ 50% recovery and Upper PIR ≤ 150% recovery. RSD less than or equal to 10% 85 to 115%

EPA ELISA method Total Microcystins Lower PIR ≥ 50% recovery and Upper PIR ≤ 150% recovery. TBD TBD

EPA 525.3 Pesticides Lower PIR ≥ 50% recovery and Upper PIR ≤ 150% recovery. RSD less than or equal to 20% 7 0 to 130%, except for Dimethipin at 60 to 130%
EPA 530 Semivolatiles Lower PIR ≥ 50% recovery and Upper PIR ≤ 150% recovery. RSD less than or equal to 20% 70 to 130% , except for

o

- toluidine at 50 to
130%
EPA 541 Alcohols Lower PIR ≥ 50% recovery and Upper PIR ≤ 150% recovery. RSD less than or equal to 20% 70 to 130 %

EPA 544 Microcy s tins & Nodularin Lower PIR ≥ 50% recovery and Upper PIR ≤ 150% recovery. RSD less than or equal to 3 0% 70 to 130 %

EPA 545 Cylindrospermopsin &
A natoxin

- a Lower PIR ≥ 50% recovery and Upper PIR ≤ 150% recovery. RSD less than or equal to 20% 70 to 130%13 Analytical Method MRL Verification Requirement Acceptable
Precision Acceptable Accuracy

EPA 552.3 Haloacetic Acids Lower PIR ≥ 50% recovery and Upper PIR ≤ 150% recovery. RSD less than or equal to 20% 8 0 to 1 2 0%

EPA 557 Haloacetic Acids Lower PIR ≥ 50% recovery and Upper PIR ≤ 150% recovery. RSD less than or equal to 20% 7 0 to 1 3 0%



## 6 Minimum Reporting Level Verification

The MRLs for the UCMR 4 analyte s were established by EPA according to the procedure detailed in Technical Basis for the Lowest Concentration Minimum Reporting Level Calculator

. Data from L CMRLs
det ermined by multiple laboratories were used. The MRLs established for the UCMR 4 analytes are presented in Table 1, Section 4.10 . All laboratories performing analysis for the UCMR 4 must be able to measure the analyte conce ntrations at these levels with sp ecified accuracy and precision as given in
Table 3 , Section 7.3.8

. As part of the UCMR 4 LAP application process, laboratories must verify they can achieve the UCMR 4 MRLs for each analyte according to the procedure in 40 CFR 141.40(a)(5)(iii) and
outlined in Sections 6.1 through 6. 5 that follow

. 

### 6.1 Fortify, P rocess , and A na lyze S even R eplicate LFBs at or Below Proposed MRL

Seven LFBs , which contain method analytes at or below the proposed MRL for UCMRL 4, are processed through the entire method procedure. The se LFBs must contain all method specified dechlorinati on agents and preser vatives, which are listed in Table 1 2, Section 8.3. 4

. The lowest calibration standard used in the initial calibration must contain the method analytes at or below the fortification level of
these LFBs.


### 6.2 C alculate the mean and standard deviation

Us e the results from the analysis of the seven LFB replicates to calculate the mean and standard deviation ( s ) for these replicates.



### 6.3 H alf range for the prediction interval of results Determine the half range for the prediction interval of results ( HR PIR ) using Equation 1 : 

### HH PPPPPP 

### = 3

. 963 × ss Equation 2

Note that the factor 3.963 is specific only to use of seven replicates.


### 6.4 Confirm PIR limits are within QC criteria Confirm that the upper and lower limits for the predic tion interval of the result (PIR ) satisfy the upper and lower recovery limits.

The lower PIR limit must be greater than or equal to 50 percent recovery:

PPPP LL LL = mm

− HH PPPPPP
TT TT TT TTTT × 100% 

### Equation 3

The upper PIR limit must be less than or equal to 150 percent recovery:

PPPP UUUUUU = mm + HH PPPPPP
TT TT TT TTTT × 100% 

### Equation 4 The MRL is validated if both the upper and lower PIR limits meet these criteria.
These calculations are illustr ated in the Example Calculation of Section 6.5

.14 

### 6.5 Example Calculation of the PIR limits

Th e true value of the LFB concentration is 0.60 0 μg/L and LFB analytical results are 0.60 2 , 0.5 86 , 0.5 49
, 0 .60 6 , 0.62 2 , 0.5 7 8, and 0.6 6 7 μg /L. The given data ha ve a t least three significant figures so that

, during calculations, the variance is not censored.



### 6.5.1 Step 1 : Calculate the m ean

mm mm = SS oooo LLLLLL

nn oooo = 0

. 6014



### 6.5.2 Step 2: Calculate the standard deviation (s)

ss = � ∑ ( LLLLLL

− mm ) 2

nn ii = 1 (

− 1 ) = � 0

. 00829

6 = 0

. 0372



### 6.5.3 Step 3. Calculate the Half Range for the PIR (HR PIR 

### )

HH = 3

. 963 × ss = 3

. 963 × 0

. 0372 = 0

. 147



### 6.5.4 Step 4. Calculate the Lower PIR Limit (PIR lower 

### )

PPPP LL LL = mm

− HH PPPPPP
TT TT TT TTTT × 100% = 0

. 6014

− 0

. 147

0

. 60 × 100% = 75

. 7% which passes criteria of greater than or equal to 50%.



### 6.5.5 Step 5 . Calculate the Upper PIR Limit (PIR upper 

### )

PPPP UUUUUU = mm + HH PPPPPP
TT TT TT TTTT × 100% = 0

. 6014 + 0

. 147

0

. 60 × 100% = 124

. 7%

which passes criteria of less than or equal to 150%. The MRL is validated if both the Upper and Lower
PIR Limits mee t the criteria described in this section

.



## 7 Quality Control Requirements
Laboratories must follow the QC procedures outlined in the methods and in Section 4 of this manual. Before field samples are analyzed, an IDC ( Section 5 ) must be performed. During the analysis of field samples, o ngoing QC require m ents must be met for Calibration and for Analysis, Extraction, and Digestion Batch

. These include continuing calibration checks (CCCs), surrogate standards , internal standards, laboratory reagent blank (LRB), laboratory fortified blank ( LFB), quality control sample (QCS), and Laboratory Fortified Sample Matrix es (LFSM and LFSMD). These QC requir e m ents are con s ide r ed
the m ini m u m acceptable. L ab o r a tor i es a r e e n couraged to add Q C pract i ces that m eet the i r speci f ic

n ee ds , however, additional practices must also meet method criteria to consider analytical results valid

. 

### 7.1 E xtraction Batch and D igestion B atch

An E xtraction Batch is defined as all samples prepared and extracted together by the same person during a work day. A Di gestion B atch includ es all samples digested together by the same person during a15 work day

. The same lots of reagents , solvents, internal standard

, surrogate standard , and analyte fortification solutions must be used for all samples included in a n Extraction or Digestion B atch . For methods that use solid phase extraction ( SPE ) techniques, it is preferable to use the same lot of pre

tested SPE media . A maximum of twenty field samples , not including QC samples

, can be in an E xtraction
Batch or D igestion B atch. The E xtraction Batch or D igestion B atch must be identified with a unique and
traceable ID code or name. E ach Extraction Batch or Di gestion B atch must include at a minimum a n LRB ( Section 7.7 )

, an LFB ( Section 7.8 ) spiked at a concentration less than or equal to the MRL

, and an LFSM

LFSMD pair ( Section 7.10 )

. Results from the analysis of these QC samples are used to evaluate the
valid ity of the sample processing procedures

. 

### 7.2 A naly sis B atch

An Analysis B atch is defined as a group of field samples analyzed using the same instrument within a 24
h our period that begins and ends with the analysi s of the appropriate CCC standards

. A n A naly sis Batch
cannot include more than twenty field samples. QC samples

, such as the LRB, LFBs, FD, LFSM , LFSMD
and CCCs

, are not counted as part of the twenty field sample limit

. Conditions for the Analysis Batch
must be the same a s those used during calibration

. 

### 7.2.1 Analysis Batch Field Samples

An A naly sis B atch may be comprised of field samples from t he same E xtraction Batch or D igestion B atch
or from several batches . Ideally, field samples and corresponding QC samples from the same E xtraction

or D igestion B atch ar e analyzed in the same A naly sis B atch. Field samples with QC failures may be re

analyzed immediately within the same Analysis B atch , or i f this is not possible in a new A nal ysis B atch with the appropriate QC samples ( see Section 7.1 1 )

. 

### 7.2.2 Analysis Batch Identifier
Each A naly sis B atch must be identified with a unique and traceable ID code or name that is different
than the E xtraction or D igestion B atch ID used in processing the sa mples.


### 7.3 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 4. For mass spectrometry methods, laboratories must meet the method

- specific mass spectrometer tuning criteria prior to performing the initial calibra tion procedure.



### 7.3.1 Calibration Fit If allowed by the method, different types of calibration

, such as linear regression, quadratic regression

, and response factor

, and different fit types , such as forcing the curve through the origin, ignoring the origin, and 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. See Section 10.2.8

, Appendix B for special instructions on EPA Method 200.8

. 

### 7.3.2 Calibration Range The calibration curve for each UCMR 4 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. Laboratories must use a minimum of five calibration stand ards for all UCMR 4 methods. More than five standards must be used if specified by the method, such as EPA Methods 530, 525.3, 541 and ELISA. See Appendix B
, Sections 10.2.7 and 10.2.9 for special instructions on EPA Method 200.8

.16 

### 7.3.3 Preservatives in Calibration Standards for Some Methods Calibration standards for Methods 200.8, 545, 552.3 and 557 require the addition of the preservatives
and dechlorination agents that are used in the field samples. Method 525.3 and 530 require the addition of the preservatives and dechlorination agents when matrix matched calibration solutions are prepared.



### 7.3.4 Surrogate Recovery and Internal Standard Re sponse in Initial Calibration Standards
The recovery of UCMR 4 analytes, surrogate standards

, and internal standards 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 , Section 7.3.8 . If any surrogate fails the criterion in a calibration standard, the data from that standard cannot be used in calculating the calibration curve. If

an internal standard fails criteria in a calibration standard, then the calibration standard cannot be used
in the calibration. If all surrogate and internal standards pass the criteria, but only some of the ana lytes pass the recovery criteria, only the data for the passing an alytes may be used in ca lculating the
calibration curve

. 

### 7.3.5 Holding Time for Standard Solutions Laboratories must adhere to the holding time limitations for standard solutions

, reagents
, and solutions, as specified in the individual methods. If multiple stock solutions are used, the shortest expiration date applies. It is critical that laboratories closely monitor the expir ation of calibration standards.



### 7.3.6 Initial Calibration Acceptance Criteria Laboratories must adhere to QC criteria limits and are not permitt ed to accept sample data when any QC parameter fails QC criteria limits . All QC criteria must be implemented. For methods 525.3, 530, 541, 544, 545, 552.3 and 557

, calibration standard responses must be entered into the calibration curve equation and the r e calculated concentrations must meet the accuracy criteria listed in Table 3, Section

7. 3. 7

. All criteria in Table 3, Section 7. 3. 7 must pass or the result must not be used in the ge neration of the calibration curve. For instance, if a surrogate fails criteria in a calibration standard, then the results for that standard, for all analytes, must not be used. If an internal standard f ail s criteria, then the
associated analyte results ca nnot be used for calibration

. The calibration curve for each analyte is valid only if it includes data for five, or more if specified by the method, concentration levels, including one at
or below the MRL concentration.



### 7.3.7 Table 3. Initial Calibration Acceptance Criteria

Analytical Methods Analyte
Percent Recovery Greater than
MRL Analyte Percent Recovery Near
MRL Surrogate
Percent Recovery Internal Standard Response

EPA 200.8,
ASTM D5673

- 10,
SM 3125 B Metals 90 to 110% 50 to 150% NA 60 to 125%

ELISA m ethod Total Microcystins TBD TBD NA TBD

EPA 525.3 Pesticides 70 to 130% 50 to 150% 70 to 130% 50 to 150% of mean in initial calibration

.17 Analytical Methods Analyte
Percent Recovery Greater than
MRL Analyte Percent Recovery Near
MRL Surrogate
Percent Recovery Internal Standard Response

EPA 530 Semivolatiles 70 to 130% 50 to 150% 70 to 130% for Quinoline

- d 7 and 50 to 130% for o

T oluidine

- d 9 50 to 150% of mean in initial calibration

EPA 541 Alcohols 70 to 130% 50 to 150% 70 to 130% 50 to 150% of mean in initial calibration
EPA 544 Microcystins & Nodularin 70 to 130% 50 to 150% 70 to 130% NA

EPA 545
C

y lindro spermopsin & Anatoxin

- a 70 to 130% 50 to 150% NA 50 to 150% of mean in initial calibration

EPA 552.3 Haloacetic acids 70 to 130% 50 to 150% 70 to 130% 50 to 150% of mean in initial calibration
EPA 557 Haloacetic acids 70 to 130% 50 to 150% NA 50 to 150% of mean in initial calibration


### 7.4 Continuing Calibration Checks (CCCs)

7.4.1 Initial Low

- Level CCC

P rior to the analysis of field samples

, the initial calibration must be verified with a low

- level CCC
standard at a concentration at or below the MRL

. Even if initial calibration standards are analyzed on the day of analysis, laboratories must analyze a low

- level CCC standard prior to field samples. The initial low

level CCC standard must meet QC criteria fo r the results of the Analysis Batch to be acceptable.



### 7.4.2 Mid

- and High

- Level CCC

A CCC stan dard, alternating between the mid

- and high

- level concentrations

, must be run after every

ten , or less, field sample s and at the end of the Analysis Batch

. CCC standards must meet the criteria
defined in Table 4. A ll samples must be preceded and followed b y CCC standards that pass the criteria. Analy tical results for a group of up to ten samples are considered valid only if the CCC standards analyzed before and after the group meet the criteria. Note that the high

- level CCC can be less than the highest conc entration on the calibration curve.



### 7.4.3 CCC Criteria “High” Exception
The limited exception for the CCC criteria is when no measured result for a target analyte is found in field sample s and a CCC result for that analyte fails because of high bias. This exception does not apply to surrogate or internal standard recoveries in any samples

, field or QC. This exception is expected to be rare and not routinely applied by the laboratory. Corrective action must be taken by the lab to investigate the root cause a nd minimize the frequency of target analyte high bias CCC results.



### 7.4.4 Trouble

- Shooting CCC Failure
If criteria are not met for a n analyte in a CCC standard, then the source of the problem affecting the problem analyte must be identified and eliminated. This may require instrument maintenance and the18 generation of a new instrument calibration curve. A fter the problem is resolved , a ll samples or extracts analyzed between the failing CCC standard and the previously acceptable CCC standard must be reanalyzed for the analyte that failed QC criteria . If the samples or extracts cannot be reanalyzed, then data for the problem analyte are considered invalid for those samples and the data must not be reported

. 

### 7.4.5 Table 4. CCC Acceptance Criteria

Analytical Methods Analyte Percent Recovery Mid and High Level Analyte Percent Recovery Low Level Surrogate
Percent Recovery Internal Standard Response

EPA 200.8,
ASTM D5673

- 10,
SM 3125 B Metals 85 to 115% 50 to 150% NA 60 to 125% of response in calibration blank

EPA ELISA m ethod Total Microcysti ns TBD TBD NA NA

EPA 525.3 Pesticides 70 to 130% 50 to 150% 70 to 130% 50 to 150% of mean in initial calibration and 70

to 130% of previous CCC.
EPA 530 Semivolatiles 70 to 130% 50 to 150% 70 to 130% 50 to 150% of mean in initial calibration and 70

to 130% of previous CCC
EPA 541 Alcohols 70 to 130% 50 to 150% 70 to 130% 50 to 150% mean in initial calibration
EPA 544 Microcystins & Nodularin 70 to 130% 50 to 150% 70 to 130% NA

EPA 545
C

ylindrospermopsin
& Anatoxin

- a 70 to 130% 50 to 150% NA 50 to 150% of mean in initial calibration

EPA 552.3 Haloacetic acids 70 to 130% 50 to 150% 70 to 130% 50 to 150% of mean in initial calibration
EPA 557 Haloacetic acids 70 to 130% 50 to 150% NA 50 to 150% mean in initial calibration and 70 to 130 % of previous CCC.


### 7.5 Surrogate Requirements and Criteria A surrogate is a pure analyte that is used to monitor method performance from processing through analysis for methods involving sample extraction

. A surrogate stand ard is added to the aqueous sample in a known amount before the sample is processed . A surrogate is measured with the same procedures used to measure other sample components. A surrogate analyte must be added to all aqueous samples

, including LRBs, LFBs, LFSMs and LSFMDs, and to all standards. A s urrogate analyte is required for

M ethods 525.3, 530, 541, 544, and 552.3

. The surrogate analytes are listed in Table 5, Section 7.5.1

, along with reco very criteria. When the method provides flexibility in the selection of the surrogate or its concentration, EPA allows the same flexibility for UCMR 4. However, the concentration of each surrogate analyte must be the same in calibration standards as it is in field and QC samples, or their extracts or digestates

, whichever is introduced into the analytical instrument

.19 

### 7.5.1 Surrogate Recovery The percent recovery of the surrogate in a sample is calculated by comparing the analytically measured
concentration to the fortified concentration, as shown in Equation 5

. SSSS SS % RR RRRR RR = MMMMMM MMMM SS SS
EEEE SS SS × 100% Equation 5



### 7.5.2 Trouble

- Shooting Surrogate Failure in the Sample

A s am ple that fails QC criteria for surrogate recovery should be rerun in case a mis

- injection occur red . If the sample continues to fail surrogate QC criteria, the laboratory should process a new aliquot of the sample. Typically, d ata for samples with failed su rrogate recovery must not be reported . If surrogate recovery fails criteria, but is close to QC limits, contact EPA to discuss. E xcessive surrogate recovery failure , though, could lead to an EPA audit.



### 7.5.3 Surrogate Failure in LRB or LFB If the surrogate recovery fail s the acceptance criteria in an LRB or in a required LFB
, the LRB or LFB may be reanalyzed later in the Analysis . If surrogate recovery fails again, all field sample results for the Extraction or Digestion Batch for that LRB or LFB are invalid and must not be reported. I f the surrogate

recovery fails in an LRB that is needed to pass an Analysis Batch

, all data for that Analysis Batch are invalid and must not be reported

. If possible, the laboratory should process new al iquots of the affected

sa mples; if this is not possible, the affected field samples must be recollected. One LFB must pass surrogate recovery within a 24

- h period of analysis. If not, the samples in the Analysis Batches that correspond to that required LFB, cannot be reported.



### 7.5.4 Sur rogate Failure in LFSM or LFSMD If the surrogate recovery in an LFSM or LFSMD fail s the acceptance criteria, but all other batch QC pass, only the fortified matrix sample with the failed surrogate is impacted and must not be reported. If the surrogate recovery in the LFSM fails and the LFSMD passes , the n the LFSMD data should be reported as
the LFSM so 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 es not invalidate the associated
unfortified sample results.



### 7.5.5 Table 5. Surrogate Standards, Concentrations

, and Recovery Criteria

Analytical Method Surrogate Standard Concentration in Sample Acceptance Criteria as Percent Recovery EPA 200.8, ASTM
D5673

- 10, SM 3125 B Metals NA NA NA



### ELISA m ethod Total Microcystin s NA NA NA



### EPA 525.3 Pesticides 1,3

- dimethyl

- 2

- nitrobenzene Triphenyl phosphate Benzo[a]pyrene

- d 12 5 μg /L
5 μg /L
5 μg /L 70 to 130%



### EPA 530 Semivolatiles o

- toluidine

- d 9 quinolone

- d 7 5 μg /L
5 μg /L 70 to 130%



### EPA 541 Alcohols 1

- Butanol

- d 10 2

- Propen

- 1

- ol

- d 6 10 μg /L
10 μg /L 70 to 130%20 Analytical Method Surrogate Standard Concentration in Sample Acceptance Criteria as Percent Recovery


### EPA 544 Microcystins & Nodularin Ethylated microcystin

- LR, d 5 0.260 μg /L 60 to 130%

EPA 545 Cylindrospermopsin &
Anatoxin

- a NA NA NA

EPA 552.3 Haloacetic acids 2

- Bromobutanoic acid 10 μg /L 70 to 130%

EPA 557 Haloacetic acids NA NA NA



### 7.6 Internal Standard Requirements and Criteria An internal standard is a pure compound that is added to standards, extracts, digestates, and direct

inject samples in a known amount and that is used to estimate the relative response of a method analyte and surrogate analyte that are contained in the same solution. T h e internal standard must respond to instrument conditions and sample matrix in a similar manner as the m ethod analy t es

. The
internal standard must have no poten t ial to be pre s e n t in the collected water sa m ples and must n o t be a

m ethod a nalyte. Internal standards are required for calibration and quantitation purposes in all UCMR 4 methods, with the exception of Method 544 and the ELISA method.



### 7.6.1 Calculation of Internal Standard Recovery
Internal Standard (IS) recovery is calculated using E quation 6

. II SSSS SS SS RR RRRR RR = AA SS

AAAA AA oooo CC × 100% Equation 6



### 7.6.2 Internal Standard Recovery Criteria
Table 6 of Section 7.6.6 lists the internal standards and the analytical acceptance criteria. When the method provides flexibility in the c oncentration of the internal standard, EPA allows the same flexibility for UCMR 4. However, the internal standard concentration in the calibration standards must be the

same as is in the field samples, QC samples, and extracts or digestates

, whichever is i ntroduced into the analytical instrument.



### 7.6.3 Internal Standard Failure in Sample If the internal standard recovery in a sample fails the acceptance criteria, then the results for the analytes that are associated with the internal standard in that sample are i nvalid. Data that fail internal standard criteria must not be reported. If possi ble, the laboratory should process a new aliquot of the sample ; if this is not possible, the field sample must be recollected

. 

### 7.6.4 Internal Standard Failure in LRB or LFB

For an E xtraction Batch or D igestion B atch , if the internal standard recoveries in an LRB or LFB fail the acceptance criteria, all data for the analytes that are associated with that internal standard in that

E xtraction Batch or D igestion B atch are invalid and mus t not be reported

. If the internal standard recoveries in an LRB fail the acceptance criteria in an Analysis Batch , all data for the analytes that are associated with that internal standard in the Analysis Batch are invalid and must not be reported. If

pos sible, the laboratory should process new al iquots of the affected samples.21 

### 7.6.5 Internal Standard Failure in LFSM or LFSMD 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 data for the analytes that are associated with that internal standard 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 es not invalidate the associated sample results in the Extraction, Digestion, or Analysis Batch

. 

### 7.6.6 Table 6. Internal Standards Crite ria

Analytical Method Internal Standard Recommended
Concentration in Method Acceptance Criteria

EPA 200.8, ASTM
D5673

- 10, SM 3125 B Metals Scandium Indium Terbium 20 to 200 μg/L
20 to 200 μg/L
20 to 200 μg/L 60 to 125% of mean in initial calibration



### ELISA m ethod Total Microcystin s NA NA NA



### EPA 525.3 Pesticides Acenaphthene

- d 10 Phenanthrene

- d 10 Chrysene

- d 12 1 μg /mL (SIM)
1 μg /mL (SIM)
1 μg /mL (SIM) 70 to 130% of previous
CCC and 5 0 to 150 % of

mean in initial calibration

. 

### EPA 530 Semivolatiles Acenaphethen

- d 10 Phenanthrene

- d 10 500 μg /L (SIM)
500 μg /L (SIM) 70 to 130% of previous
CCC and 5 0 to 150% of

mean in initial calibration

. 

### EPA 541 Alcohols 1,4

- dioxane

- d 8 Chlorobenzene

- d 5 0.25 μg /mL
0.25 μg /mL 70 to 130% of previous
CCC and 50 to 150% of
mean in initial calibration


### EPA 544 Microcystins & Nodularin No internal standard NA NA

EPA 545
C

ylindrospermopsin
& Anatoxin

- a L

- Phenylamine

- d 5 Uracil

- d 4 5.00 μg /L
20.0 μg /L 50 to 150% of mean in initial calibration

.

EPA 552.3 Haloacetic acids 1,2,3

- trichloropropane 1 .00 μg /mL 50 to 150% of mean in initial calibration

. EPA 557 Haloacetic acids Monochloroacetic acid

- 2

- 13 C Monobromoacetic acid

- I

13 C Dichloroacetic acid

- 2

- 13 C Trichloroacetic acid

- 2

- 13 C 4 ng/mL 4 ng/mL 4 ng/mL 4 ng/mL 50 to 150% of mean in initial calibration

.



### 7.7 Laboratory Reagent Blank A laboratory reagent blank ( LRB ) is an aliquot of reagent water that is treated exactly as a sample . The
LRB is expose d to all glassware, equipment, solvents, reagents, internal standards

, and surrogate
standards that are used with th e other samples in the Extraction Ba tch. The LRB is used to show that method analytes or interferences are not present in the laboratory environment, reagents

, or22 apparatus. F or all methods approved for UCMR 4 monitoring , an LRB is required in each Extraction or Digestion Batch . Methods that require the ext raction or digestion of samples must process a minimum of one LRB with every batch of twenty or fewer field samples

. Methods , such as Method 545, which
involv e the direct analysis of samples

, require a minimum of one LRB analyzed for every twenty or fewer field samples. When m ore than one Extraction or Digestion B atch of samples are processed within a 24

- her period

, an LRB must be processed with each Ext raction or Digestion B atch.



### 7.7.1 Laboratory Reagent Blank Acceptance Criteria
Internal s tandard recovery for the LRB must pass acceptance criteria given in Table 5 of Section 7. 5

. 5
and s urrogate s tandard recovery must pass acceptance criteria in Table 6 of Section 7 .6

. 6

. Also,
b ackground contamination must not interfere with accurate measurement of the UCMR 4 analytes. If a method analyte is detected in the LRB at a concentration greater than the criteri a specified in Table 7 of
Section 7.7. 2 , then all data for the problem analyte are considered invalid for all samples of an associated Extraction or Dig estion Batch

, or for an Analysis Batch when samples are directly injected. If the samples cannot be re

- processed, t he failed data must be flagged as not meeting the QC criteria and must not be reported and t hose samples must be recollected

. T he source of t he problem should be
identified and eliminated before more samples are processed

. 

### 7.7.2 Table 7: LRB Analytes Must Be Less Than or Equal to One

- Third the MRL

Analytical Method Contaminants Analytes Must Be Less than or Equal to One

- Third the MRL ( μg /L) EPA 200.8, ASTM D5673

- 10, or G ermanium 0. 10
SM 3125 B M anganese 0. 13 EPA ELISA method Total microcystins 0. 10 EPA Method 525.3 alpha

- H exachlorocyclohexane 0.0 033
C hlorpyrifos 0.0 10
D imethipin 0. 067 Ethoprop 0.0 10 Oxyfluorfen 0.0 17 Profenofos 0. 10 Tebuconazole 0. 067 Total permethrin (cis & trans) 0.0 13 Tribufos 0.0 23 EPA Method 530 Butylated hydrox y anisole 0.0 10

o

- T o l uidine 0.00 23 Quinoline 0.0 067 EPA Method 541 1

- B utanol 0.67
2

- M ethoxyethanol 0. 13
2

- P ropen

- 1

- ol 0. 17 EPA Method 544 Microcystin

- LA 0.00 27 Microcystin

- LF 0.00 20 Microcystin

- LR 0.0 067 Microcystin

- LY 0.00 30 Microcystin

- RR 0.00 20 Microcystin

- YR 0.0 067 Nodularin 0.00 1723 Analytical Method Contaminants Analytes Must Be Less than or Equal to One

- Third the MRL ( μg /L)
EPA Method 545 Anatoxin

- a 0.010 Cylindrospermopsin 0.030 EPA Method 552.3 or Bromochloroacetic acid (BCAA) 0. 10 EPA Method 557 Bromodichloroacetic acid (BDCAA) 0. 17 Chlorodibromoacetic acid (CDBAA) 0. 10 Tribromoacetic acid (TBAA) 0

. 67 Monobromoacetic acid (MBAA) 0. 10 Dibromoacetic acid (DBAA) 0.10 Dichloroacetic acid (DCAA) 0.067 Monochloroacetic acid (MCAA) 0.67 Trichloroacetic acid (TCAA) 0.17


### 7.8 Laboratory Fortified Blank (LFB)

The Laboratory Fortified Blank ( LFB ) is an aliquot of reagent water 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 reagents for sample dechlorinat ion and p reservati on . The same lot of rea gent s, internal standard, and surrogate standard solutions must be used for all samples included in a n Extraction Batch or Digestion B atch. Results from the LFB samples provide information about the entire method , from sample processing to an alyte separation a nd detection. An LFB must be processed with each E xtraction
Batch or D igestion B at ch of twenty or fewer samples

. The LFB is fortified at or below the MRL. An LFB is required to be analyzed as a daily performance check . As described in ( 40 CFR 141.40(a)(5)( iii) (B)(2 )

, once the laboratory has performed an IDC ( Section 5.2 ), a daily performance check is performed for each analyte and method. A fortified laboratory blank, at or below the MRL for each analyte, must be processed through the entire method procedure during each 24

- h period of analysis

. I f the recovery is
50% to 150%

, inclusive, the daily performance of the laboratory has been validated. The results for any analyte for which 50% to 150% recovery cannot be de monstrated during the daily check are not valid. Laboratories may elect to re

- run the daily performance check sample if the performance for any analyte or analytes cannot be validated. If performance is validated for these analytes, the laboratory performa nce is considered validated. Alternatively, the laboratory may re

- calibrate and repeat the performance validation process for all analytes.



### 7.8.1 Method Requirement s for LFB

EPA M ethods 200.8, 525.3, 530, and 544 require the extraction and analysis of an LFB. Si nce Methods 545, 552.3 and 557 use procedural calibration standards

, a CCC is the same as an LFB, so a separate LFB is not required. LFB acceptance criteria for analyte, surrogate, and internal standard are listed in Table 8,
Section 7.8.3

. 

### 7.8.2 Laboratory Fortified Blank Criteria Failure
If the LFB recovery fails criteria listed in Table 8, Section 7.8.3

, then all data for the problem analyte are considered invalid for all samples in the Extraction or Digestion B atch . D ata of the analyte that fails recovery criteria for the LFB must not be reported for that Extraction or Digestion Batch

. If the LFB
surrogate or internal standard fails QC criteria, all data for the Extraction or Dige stion Batch must not be reported and EPA should be contacted

.24 

### 7.8.3 Table 8. Laboratory Fortified Blank Acceptance Criteria

Analytical Method Analyte Recovery Low Level Surrogate Recovery Internal Standard Response

EPA 200.8, ASTM
D5673

- 10, SM 3125 Metals 50 t o 150% No Surrogate 60 to 125% of mean in initial calibration

ELISA m ethod Total Microcystins No LFB No LFB No LFB

EPA 525.3 Pesticides 50 to 150% 70 to 130% 50 to 150% of mean in initial calibration and 7 0 to 130% of previous CCC.
EPA 530 Semivolatiles 50 to 150% 70 to 130% 50 to 150% of mean in initial calibration and 7 0 to 130% of previous CCC.
EPA 541 Alcohols 50 to 150% 70 to 130% 50 to 150% of mean in initial calibration and 7 0 to 130% of previous CCC.
EPA 544 Microcystins & Nodularin 50 to 150% 70 to 130% No Internal Standard

EPA 545 Cylindrospermopsin
& Anatoxin a No LFB N o LFB No LFB

EPA 552.3 Haloacetic acids No LFB No LFB No LFB

EPA 557 Haloacetic acids No LFB No LFB No LFB



### 7.9 Quality Control Sample (QCS)

A quality control sample ( QCS ) is a solution containing method analytes of known concentration that is
obtained from a second source that is different from the source used to prepare the calibration
standards. The purpose of the QCS is to verify the accuracy of the primary calibration standards. The
QCS must contain internal standard s from the same source used in the initial calibration standards. The frequency requirements and the analyte recovery criteria for the QCS are given in Section 7.9.2, Table 9.
EPA recomme nds the concentration of the QCS be near the midpoint of the calibration curve. When a second source is not available, lab oratories may use a different lot than was used for the calibration
standards. The QCS must b e run within an Analysis Batch.



### 7.9.1 Analysis Frequency of QCS
Table 9 of Section 7.9.2 lists the minimum QCS analysis frequency for each UCMR 4 analytical method.
Lab oratories may analyze a QCS more frequently to monitor method and analyte performance . F ailure

to analyze a QCS at method

- required frequencies is viewed as a deficiency and a “ finding ” during a laboratory audit. If a QCS fails QC criteria, do not report QCS results to the EPA electronic data reporting
system

. 

### 7.9.2 Table 9. QCS Frequency Requirements and Analyte Recovery Criteria

Analytical Method Analyte Recovery
Criterion QCS Frequency Requirement

EPA 200.8, ASTM D5673

- 10,
SM 3125 Metals 90 to 110% During IDC and a t least quarterly

.25 Analytical Method Analyte Recovery
Criterion QCS Frequency Requirement



### ELISA method Total Microcystin s 75 to 125% During IDC and e very batch of samples



### EPA 525.3 Pesticides 70 to 130% During IDC and after every initial calibration



### EPA 530 Semivolatiles 70 to 130% During IDC and after every initial calibration



### EPA 541 Alcohols 80 to 120% During IDC and a t least quarterly



### EPA 544 Microcystins & Nodularin 70 to 130% During IDC

EPA 545 Cylindrospermopsin &
Anatoxin

- a 70 to 130% During IDC and at least quarterly

EPA 552.3 Haloacetic acids 70 to 130% During IDC and at least quarterly

EPA 557 Haloacetic acids 70 to 130% During IDC, each time new analyte primary standard is prepared and at least quarterly.


### 7.10 Laboratory Fortified Sample Matrix & Laboratory Fortified Sample Matrix Duplicate

7.10.1 

### Labo ratory Fortified Sample Matrix

A laboratory fortified sample matrix ( LFSM ) is a field sample containing pre servatives to which known quantities of the method analytes are added in the laboratory. The LFSM is processed and analyzed as a field sample, and its purpose is to determine whether the sample matrix contributes bias to the analytical results. The concent rations of the analytes in the unfortified sample matrix must be determined in a separate aliquot.

7.10.2 

### Laboratory Fortified Sample Matrix Duplicate Field duplicate samples are collected at the same time, shipped, and stored under identical conditions

. Field duplicate results are often used to estimate method precision. However, when method analytes are rarely found at concentrations greater than the MRL

, a laboratory fortified sample matrix duplicate ( LFSMD ) is used t o assess method precision. LFSMD samples are used to determine the precision of UCMR 4 monitoring data, b ecause it may not be possible to know which samples may contain
measurable concentrations of method analytes

. 

### 7.10.3 Frequency and Concentration Level of LFSM and LFSMD

O ne LFSM and one LFSMD must be processed with the associated unfortified field sample in each
Extraction B atch or Digestion Batch

. In subsequent Extraction Batch or Digestion Batch , t he fortification
concentration of the LFSM and the LFSMD must be alternated between a low

- and mid

- leve l concentration. For example, two Extraction B atches will require prepa ration and analysis of two LFSM

LFSMD sets, one set fortified at the low

- level and one at the mid

- level concentration. Laboratories must ensure they receive sufficient sample volume to meet the UCMR 4 required frequency of 1 LFSM

- LFSMD set per Extraction Batch or Digestion Batch, which consists of 20 or fewer field samples.26 

### 7.10.4 Fortification Levels of LFSM

- LFSMD

T he fortification concentration of the LFSM and the LFSMD must be alternated between a
low

- and mid

- level concentration from batch to batch . For example, two e xtraction b atches will require the preparation and analysis of two LFSM/LFSMD sets, 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 to 150 % of the MRL for each contaminant . For example, for
an MRL of 1.0 μg/L, fortification levels between 0.50 μg/L and 1.5 μg/L are acceptable. The
mid

- level LFSM

- LFSMD fortification concentration should be 80 to 120% of the mid

- level
calibration standard for each contaminant. Wh en the laboratory has data from previously analyzed samples, the fortification concentration should approximate the average
concentration o bserved in previous analyses. If UCMR 4 contaminants are regularly found in field samples at concentrations exceeding the MRL, laboratories may find it difficult to derive meaningful results from samples fortif ied with that contaminant at the low

- level

con centration. In such cases, l aboratories should apply their experience to adjust fortification to levels more appropriate for native levels

. 

### 7.10.5 Recovery Criteria Not Specified for LFSM and LFSMD
For UCMR 4, t here are no method analyte recovery acceptance crit eria specified for LFSM and LFSMD results. D ata should not be rejected based on the recovery of fortified target analytes or on the precision between the LFSM and LFSMD, provided internal standard and surrogate standard recoveries and all other QC results are valid. LFSM and LFSMD results are to be reported to EPA’s electronic data reporting system. If surrogate or internal standard recovery fail criteria in the LFSM and LFSMD , do not report results. If one of the fortified samples fails QC, then the resul ts of the fortified sample that

passe s , should be reported as the LFSM. The entire Analysis Batch does not need to be reanalyzed because of a failure of a surrogate or internal standard in the LFSM or LFSMD. Recollection of the field sample is not required as a result of a surrogate or internal standard failure in the LFSM/LFSMD.



### 7.11 Sequence of Injection for Analy sis Batch The sequence of analysis for field and QC samples is important for assessing system performance. As
described in Section 7.2 , each A nalysis B atch must begin with an initial low

- level CCC
, at or below the
MRL
, for each of the UCMR 4 method analytes. This initial low

- level CCC must be analyzed whether or
not the initial calibration was generated the same day. The analysis of up to ten field samples can then
follow . After the se ten field samples, the calibration must be verified by the analysis of a mid

- or high

level CCC. If this CCC passes QC criteria, then up to ten additional field sa mples may be analyzed. The Analysis Batch must end with the analysis of a mid

- or high

- level CCC, whichever level was not analyzed
after the first ten sample s

. Each Analysis Batch must contain an LRB. An LFB does not have to be in each Analysis Batch but o ne LFB must be run during each 24

- h period of analysis. For example, if two Analysis
Batches are run within 24

- h, only one has to contain an LFB. The LRB, LFB, LFSM, and LFSMD can be run in any order, though it is recommended that the LRB and LFB be run at the beginning of that Analysis Batch because if the LRB and LFB fail QC criteria, all samples in the Analysis Batch cannot be reported.



### 7.11.1 Example of Analytical Sequence for an Analysis Batch
Table 10 of Section 7.11.2 illustrates a valid analy tical sequence for an Analysis Batch for Method 525.3
that meet s QC requirements. Note that Method 525 .3 has an LFB, but when procedural standards are
used or when samples are directly injected without processing, an LFB would be the same as a CCC

, and

so an LFB would not processed

. The acquisition start time of the final CCC must be within twenty

- four27 hours of the acquis ition start time of the initial CCC , which marked the beginning of the A nalysis B atch.
More than one A nalysis B a tch is permitted within 24 h

. A hard copy or electronic copy of the analytical
sequence must be retained with the data package.



### 7.11.2 Table 10: Example 2. Valid Analysis Batch for Method 525 .3

.

Injection # Sample Description Acceptance Criteria for Method Analyte Corrective Action

1 CCC less than or equal to MRL 50 to 150% Instrument maintenance to recover sensitivity, followed by recalibration and verification of sensitivity by a low level CCC
2 LRB All target analytes less than or equal to 1/3 MRL Identify and correct source of
contamination
3 LFB Fortified near MRL, 50 to
150% Identify and correct source of problem
4 through
1 3 Field Samples 1 to
10 Positive ID of analyte is verified if peak retention
time criteri a is satisfied and mass spectral identification is confirmed. Identify and correct source of problem

1 4 Mid

- level CCC 70 to 130 % Instrument maintenance followed by recalibration
15 Field sample 11 associated with LFSM and LFSMD Positive ID of analyte is verified if peak retention time criterion is satisfied and mass spectral identification is confirmed. Identify and correct source of problem

1 6 LFSM of Field Sample At low

- level fortification

, 50 to 150% recovery and a t mid

- level, 70 to 130% LFSM method analyte recovery failure does not invalidate A nalysis
B atch , Extraction or Digestion Batch

. 1 7 LFSMD of Field Sample At low

- level fortification

, 50 to 150% recovery and a t mid

- level, 70 to 130% LFSMD method analyte recovery failure does not invalidate A nalysis
B atch , Extraction or Digestion Batch

. 1 8 through
2 8 Field Samples 1 2 to 20 Positive ID of analyte is verified if peak retention time criterion is satisfied and mass spectral identification is confirmed. Identify and correct source of problem

2 9 C lose

- out high

level CCC 70 to 130% Instrument maintenance followed by recalibration.


### 7.12 Exceeding the Calibration Range The analyst must not extrapolate beyond the established calibration range , except as described for EPA Method 200.8 in Appendix B
, Section 10.2.9

. If an analyte result exceeds the range of the calibration

curve, a sample dilution may be made. Dilute with the same solvent to match the original solvent composition, and if an internal standard is us ed, add an amount to match the original concentration in28 the vial

. T he dilution must be factor ed into the calculation of final concentration

. The resulting data must be annotated as a dilution. Dilutions must be run within an Analysis Batch and count as a field sample. The surrogate recovery of the original injection is reported. For the analyzed dilution, report

o nly method analytes that required the dilution. The associated internal standard in the dilution is reported.


### 7.13 Legal Defensibility of Data The sample analyte result that is reported to the EPA electronic data reporting system must be legally defensible because results are ultimately used for regulatory determinations. EPA must be able to track through record keeping all information that has t o do with the sample for a reported result from sample collection to analysis. For example, EPA must have the ability to check that reagents are not expired, check that the correct SPE cartridges were used, and check that the associated QC samples passed

c riteria.



## 8 Sample Handling Requirements
Laboratory personnel must be familiar with the sample collection, preservation, and storage requirements. Laboratories performing UCMR 4 analyses for a large public water system (PWS) are responsible for communicat ing with the PWS and ensure their client has a clear understanding of the
UCMR 4

- specific requirements for sample collection, preservation and transportation. Note that UCMR 4 samples must not be composited , that is, combined, mixed or blended . S amples from ea ch sampling point must be collected, preserved and processed separately. Calculate final analyte recoveries based on the measured or weighed volume of sample (Section 8.7)

. 

### 8.1 Sample Collection Time and Date 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 arrangements have been made for the receipt of samples at the laboratory within 48 h of collection.



### 8.1.1 Sample Bottle Criteria and Sample Hold Time The laboratory is responsible for m aking certain each field sample is analyzed within the required holding time. A list of maximum holding times

, and sample bottle material, is listed in Table 11 of
Section 8. 2.5 . These maximum holding times appl y when field samples are properly preserved and stored in appropriate sample containers at appropriate temperatures. The field sample holding time begins on the day the sample is collected. Table 11 of Section 8. 2.5 provides the temperature and sample bottle material criteria for UCMR 4 samples. Some UCMR 4 methods require protecting the sample from exposure to light. In such cases, the PWS or laboratory may use either amber sample
bottl es or clear glass bottles wrap ped with foil. Laboratories are responsible for ensuring that their client
PWSs u se proper sample containers. If improper containers are used , for example, plastic bottles instead of glass, the laboratory should notify the PWS that a replacement sample mus t be collected using proper containers. Samples must not be analyzed if they were not shipped properly.29 

### 8.1.2 Table 11. Requirements for Sample Bottle Material and Sample Hold Time

.

Analytical Method Sample Bottle Materials Holding Time for Sample (days)
EPA 200.8,ASTM D5673

- 10,
SM 3125 Metals Plastic or glass bottles 28



### ELISA method Total Microcystin s TBD TBD



### EPA 525.3 Pesticides Amber glass bottles fitted with polytetrafluoroethylene (PTFE)

- line d screw caps preferred

. 14



### EPA 530 Semivolatiles Amber glass bottles with PTFE

- lined screw caps preferred. Clear glass bottles may be substituted if sample bottles are wrapped with foil, stored in boxes, or otherwise protected from light during sample shipping and storage

. 14



### EPA 541 Alcohols Amber g lass bottles or vials with PTFE

- lined screw

cap 28



### EPA 544 Microcystins & Nodularin Amber glass bottle with PTFE

- lined screw cap 28

EPA 545
C

ylindrospermopsin &
Anatoxin

- a Amber glass bottles, at least fifty

- mL, fitted with
PTFE

- lined screw caps 28

EPA 552.3 Haloacetic acids Amber glass bottles, at lea st 50

- mL, fitted with
PTFE

- lined screw caps 14

EPA 557 Haloacetic acids Amber glass bottles fitted with PTFE

- lined screw

caps 14



### 8.2 Sample Transport and Storage Laboratories must examine the samples when they arrive and determine if the proper shipping
conditions were used. Samples should arrive at the laboratory packed on ice or with frozen gel packs in a sample bottle made of appropriate material as described in the analytical method. Samples that are shipped from the PWS should be sent by priority overni ght delivery to the laboratory. Except for Method
20 0 .8, s amples must be received at the lab oratory within 48 h of collection and must be at 10 °C or less. After arrival, or within 48 h of collection, whichever is sooner , the samples must be r efrigerated at 6 °C
or less

. Samples received more than 48 hours after collection are valid only if they are received at ≤6°C
and if the receiving laboratory can verify and document that they were refrigerated betw een collection and shipment.



### 8.2.1 Warm Weather Transport During the summer , the ambient water temperature can be significant ly above 10 °C at the time of
collection . In such a case, samples may be iced or refrigerated for a period of time prior to shipping to

e nsure that the laboratory receipt temperature is within QC criteria. EPA suggests collecting such samples in the morning and refrigerating them for several hours before packing them in the cooler with the ice or frozen gel packs for transport.30 

### 8.2.2 Same Day Del ivery It is possible that w ater s amples may arrive at the laboratory on the same business day as sample
collection due to close proximity of a PWS to the laboratory . In such a case the sample temperature may not yet have stabilized to 10 °C or less when th ey arrive at the lab. Such samples are acceptable only if the samples are packed with ice or frozen gel packs immediately after collection

. 

### 8.2.3 Temperature Documentation

• Sample temperature must be checked by the receiving laboratory even if they send the sampl e on to a subcontractor laboratory; the subcontractor must also check sample temperature.

• A minimum of one bottle for every analytical method must be checked for temperature. If the bottle that is checked meets the temperature criterion, then the laborator y can assume that the other bottles for the same method also meet the temperature criterion. If the bottle that is checked does not meet the temperature criterion, then the sample in that bottle is invalid. The temperature of the other samples collected fo r that method should be checked to determine if a valid sample was received.

• All sample temperatures as well as other sample receipt parameters, such as chlorine and pH, must be recorded, rather than only recording non

- conformances.

• A s ample that contain s ice inside the bottle is invalid and must be recollected.

• It is not acceptable to sample the temperature of the ice slush in the kit as a determination of sample temperature.

• The use of temperature blanks is not allowed unless there is a temperature blank for every bottle type in the kit.

• If samples are received more than 48 h after collection and meet the temperature criteria, the laboratory must check with the party that held the sample, for example, a subcontractor or PWS that sampled

, to make sure that the sample was held at 10 °C

, or less

, for the first 48 h and 6 °C

,
o r less

, thereafter while in their possession.



### 8.3 Sample Preservation The stability of the UCMR 4 samples is dependent upon proper preservation and dechlorination. Both

t he laboratory and PWS are responsible for ensuring that the UCMR 4 samples are properly preserved and dechlorinated as stipulated in the analytical methods . Dechlorination and preservation are required at the time of sample collection. There must be clear communication betw een the laboratory and PWS that assures correct use of dechlorination agents and preservatives as specified in the method and in
Table 12 of Section 8. 3.4 . If the laboratory provides bottles containing the appropriate c hemical 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 oratory must adhere to any time limits stipulated in the analytical method that the chemicals will be stable in the sample bottle.



### 8.3.1 Preservation and Dechlorination Agents For the UCMR 4 methods, the reagents in Table 12 of Sect ion 8. 3.4 serve a number of functions in the field sample. Acid preservation agents, such as nitric acid (pH 2), sodium bisulfate (pH 3), and p otassium dihydrogen citrate (pH 3.8), inhibit microbial growth. Diazolidinyl urea and 2

- chloroacetamide are
micro bial inhibitors that are still effective at pH 7. Ascorbic acid and sodium sulfite are dechlorination agents. Ammonium chloride forms a chloramine residual in chlorinated finished water that reduces oxidative power of the chlorination to an extent that ana lytes in Methods 552.3 and 557 are not affected, but the chlor am ine residual still has an anti

- microbial effect. Ethylenediaminetetraacetic acid31 trisodium salt isolates metals that might otherwise promote reactions that degrade analytes. Trizma at pH 7.0 i s a commercial buffer mixture of t ris(hydroxymethyl)aminomethane (Tris) and Tris hydrochloride. For EPA Methods 530 and 544, a n alternative to Trizma, pH 7.0, is to weigh out the individual compounds, which are Tris, 0.47g/L, and Tris hydrochloride, 7.28 g /L.



### 8.3.2 Checking Samples for Proper Preservation On same day of sample receipt , or within 48

- h of collection , laboratories should verify preservation and dechlorination of each sample by conducting the appropriate check listed in Table 12 of Section 8 .3.4

. These checks must be performed at the laboratory where the sample will be processed . If the criteria are not met, the samples must not be analyzed, and a new sample must be collected from the PWS.



### 8.3.3 Verification of pH and Ab sence of Free Chlorine Verify pH with either a standard pH meter or a test strip. 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 al iquot of the sample should be used to test pH and chlorine content. In order to prevent sample contamination, probes and test strips should not be placed into the bulk sample bottle. When a positive free chlorine result occurs, recheck with a test strip of a second method, such as the
free chlorine DPD method. Be sure to collect enough sample volume to account for the free chlorine tests and any other measurement, such as for pH.



### 8.3.4 Table 12. Sample Preservation and Dechlorination Agents; Acceptance Criteria Minimum weights and volumes are shown. Ten percent over the given weight or volume is acceptable.

Analytical Method Chemical and Concentration Sample Check or Criteria EPA 200.8,
ASTM D5673

- 10,
SM 3125 Metals Two mL of concentrated nitric acid per liter of sample

. Acid may be added in field or in lab prior to analysis. If acid is added at lab, sample must be held for sixteen hours and pH verified again prior to processing pH 2 or less



### EPA ELISA method Total Microcystins TBD TBD



### EPA 525.3 Pesticides Asc orbic acid, 0.10 g/L Ethylenediaminetetraacetic acid, 0.35 g/L Potassium dihydrogen citrate, 0.4 g/L Absence of free chlorine

, less than 0.1 mg/L



### EPA 530 Semivolatiles Trizma, 7.75 g/L Ascorbic acid, 0.10 g/L Ethylenediaminetetraacetic acid, 0.35 g/L Diazolidinyl urea, 1.0 g/L Absence of free chlorine

, less than 0.1 mg/L and pH about 7



### EPA 541 Alcohols Sodium sulfite, 50 mg/mL Sodium bisulfate, 1.0 g/L Absence of free chlorine

, less than 0.1 mg/L and pH less than 3


### EPA 544 Microcystins & Nodularin pH 7.0 Trizma, 7.75 g/L
2

- Chloroacetamide, 2 g/L
A scorbic Acid , 0.10 g/L Ethylenediaminetetraacetic acid trisodium salt

, 0.35 g/L Absence of free chlorine

, less than 0.1 mg/L

EPA 545
C

ylindrospermopsin & Anatoxin

- a Ascorbic acid, 0.10 g/L Sodium bisulfate, 1.0 g/L Absence of free chlorine

, less than 0.1 mg/L32 Analytical Method Chemical and Concentration Sample Check or Criteria
EPA 552.3 Haloacetic acids Ammonium chloride, 0.10 g/L Absence of free chlorine

, less than 0.1 mg/L
EPA 557 Haloacetic acids Ammonium chloride, 0.10 g/L Absence of free chlorine

, less than 0 .1 mg/L


### 8.4 Extract Holding Times and Temperatures The laboratory is responsible for ensuring each sample extract is analyzed within the required holding time. A list of maximum holding times and temperature specifications for extracts are listed in Table 13
of Section 8. 4.3

. The sample extract holding time begins on the day the sample extraction was begun

. 

### 8.4.1 Table 13. Maximum Holding Time and Holding Time Temperature for Extracts.

Analytical Method Extract Holding Time (days) Temperature Specification for Extracts

EPA 200.8, ASTM D5673

- 10,
SM 3125 Metals 28 recommended for digested samples No temperature specification



### EPA ELISA method Total Microcystin s NA NA



### EPA 525.3 Pesticides 28

– 5 °C or lower.



### EPA 530 Semivolatiles 14

– 5 °C or lower.



### EPA 541 Alcohols 28

– 10 °C or lower



### EPA 544 Microcystins & Nodularin 28

– 4 °C or lower.

EPA 545 Cylindrospermopsin &
Anatoxin

- a NA NA

EPA 552.3 Haloacetic acids 28

– 10 °C or lower.

EPA 557 Haloacetic acids NA NA



### 8.5 Invalid Sample If a UCMR 4 sample is not extracted or analyzed within the times specified in sample hold times of Table
11 of Section 8. 2.5 and the extract hold times and temperatures of Table 13 of Section 8.4.3 , 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 proble m, and the PWS should resample. Metals s amples that are not digested within the 28 day holding time should not be discarded or invalidated. Metals samples can be digested up to 6 months after collection. The laboratory should inform EPA of metals samples that are digested more than 28 days after collection.


### 8.6 Method Information Concerning Collection and Holding The published UCMR 4 analytical methods provide additional information concerning recommended sample collection and holding procedures for samples. These procedures must be observed for UCMR 4 samples.33 

### 8.7 Sample Volume The volume of sample processed must be quantitatively measured, and the measured volume must be
documented on the preparation/digestion/extraction batch bench sheet . If volume is determined by weighing the sample bottle before and after removing the volume for processing, then the before and after weights must be recorded. If there is not enough volume in a method

- specific sample bottle, and multiple bottles of sample were collected from the same location and for the same method an d meet the sample receipt acceptance criteria, then the laboratory may combine the volumes to obtain enough volume for processing. If the volume of sample that is processed varies from the method

- specified volume by more than 5%, then sample results must b e adjusted accordingly. Ass u m e a sa m ple densi t y of
1.00 g/ m L. The sample volume will be used in the calc u la t ion of analyte sample c oncent ra tion

. 

### 8.8 Laboratory Errors or Sampling Deviations If a sampling or laboratory error occurs which preclu des 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 correct the sampling or laboratory error. Only method analytes that failed in the original a nalysis need to be reported in the resample. 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

. 

### 8.8.1 Matrix Interference in Field Sample If matrix interference is suspected in a field sample, reanalyze the sample. If the result is similar, collect enough volume to run an LFSM, an LFSMD, and an unfortified sample and process to confirm matrix
interfe rence. Provide argument for matrix interference to EPA and ask for a determination on how to proceed.



## 9 Uploading Data to EPA database
Any deviations from the standard procedures for processing, analyzing, and generating results for field samples must be app roved by EPA prior to uploading the data to the EPA electronic data reporting
system

. EPA anticipates laboratories will be required to submit quality control information associated with sample results to the EPA electronic data reporting system. EPA will i ssue instructions for submitting data to the EPA electronic data reporting system in a separate document.



### 9.1 Table 14

. Unregulated Contaminant Monitoring Reporting Requirements

Data element Definition 1. Public Water System Identification (PWSID) Code The code used to identify each PWS. The code begins with the standard 2

- character postal State abbreviation or Region code; the remaining 7 numbers are unique to each PWS in the State. The same identification code must be used to represent the PWS identificati on for all current and future UCMR monitoring. 2. Public Water System Name Unique name, assigned once by the PWS.

3. Public Water System Facility Identification Code An identification code established by the State or, at the State’s discretion, by the PW S, following the format of a 5

- digit number unique within each PWS for each applicable facility ( i.e. , for each source of water, treatment plant, distribution system, or any other facility associated with water treatment or34 Data element Definition delivery). The same identificati on code must be used to represent the facility for all current and future UCMR monitoring. 4. Public Water System Facility Name Unique name, assigned once by the PWS, for every facility ID (e.g., Treatment Plant).
5. Public Water System Facility Type That code that identifies that type of facility as either:
CC = consecutive connection
DS = distribution system IN = source water intake
SS = sampling station
TP = treatment plant
OT = other 6. Water Source Type The type of source water that supplies a w ater system facility. Systems must report one of the following codes for each sampling location:
SW = surface water (to be reported for water facilities that are served all or in part by a surface water source at any time during the twelve

- month period).
GW = ground water (to be reported for water facilities that are served
enti rely by a ground water source).
GU = ground water under the direct influence of surface water (to be reported for water facilities that are served all or in part by ground water under the direct influence of surface water at any time during the twelve

month sampling period), and are not se rved at all by surface water during this period

. 7. Sampling Point Identification Code An identification code established by the State, or at the State’s discretion, by the PWS, that uniquely identifies each sampling point. Each sampling code must be unique within each applicable facility, for each applicable sampling location ( i.e. , entry point to the distribution system, source water intake or distribution system sample at maximum residence time). The same identification code must be used to represen t the sampling location for all current and future UCMR monitoring. 8. Sampling Point
Name Unique sample point name, assigned once by the PWS, for every sample point ID (e.g., Entry Point). 9. Sampling Point Type Code A code that identifies the location of the sampling point as either:
SR = source water taken from plant intake; untreated water entering the water treatment plant (i.e., a location prior to any treatment).
EP = entry point to the distribution system.
MR = distribution system sample at maxi mum residence time. 10. Disinfectant Type All of the primary disinfectants/oxidants that have been added in the treatment plant to the water being sampled. To be reported by systems for each sampling point.
PEMB = Permanganate (applied before SR sample location)
PEMA = Permanganate (applied after SR sample location)
HPXB = Hydrogen peroxide (applied before SR sample location)
HPXA = Hydrogen peroxide (applied after SR sample location)
CLGA = Gaseous chlorine
CLO F = Offsite Generated Hypochlorite (stored as a liquid form)35 Data element Definition
CLON = Onsite Generated Hypochlorite
CAGC = Chloramine (formed from gaseous chlorine)
CAOF = Chloramine (formed from offsite hypochlorite)
CAON = Chloramine (formed from onsite hypochlorite)
CLDB = Chlorine dioxide (applied before SR sample location)
CLDA = Chlorine dioxide (applied after SR sample location)
OZON = Ozone
ULVL = Ultraviolet light
OTHD = All other types of disinfectant/oxidant
NODU = No disinfectant/oxidant used
11. Treatment Information Treatment information associated with the water being sampled.
CON = Conventional (non

- softening)
SCO = Softening conventional
RBF = River bank filtration
PSD = Pre

- sedimentation
INF = In

- line filtration
DFL = Direct filtration
PCF = Precoat fi ltration
SSF = Slow sand filtration
BIO = Biological filtration
REC = Reactor clarification (e.g. solids contact clarification, slurry recirculation clarification, Aciflo®)
SBC = Sludge blanket clarification (e.g. Pulsator®, Super Pulsator®, contact adsor ption clarifiers, floc

- blanket clarifiers)
ADC = Adsorption clarification (contact adsorption clarification)
UTR = Unfiltered treatment
PAC = Application of powder activated carbon
GAC = Granular activated carbon (not part of filters in CON, SCO, INF, DFL, or SSF)
AIR = Air stripping (packed towers, diffused gas contactors)
POB = Pre

- oxidation/disinfection with chlorine (applied before SR sample location)
POA = Pre

- oxidation/disinfection with chlorine (applied after SR sample location)
MFL = Membrane filtra tion
IEX = Ionic exchange
UVT = Ultraviolet light
AOX = Advanced oxidation (ultraviolet light with hydrogen peroxide and/or ozone)
DAF = Dissolved air floatation
CWL = Clear well/finished water storage without aeration
CWA = Clear well/finished water storage with aeration
ADS = Aeration in distribution system (localized treatment)
OTH = All other types of treatment
NTU = No treatment used 12. Disinfectant Residual Type Secondary disinfectant type added in the distribution system for each finished water sample.36 Data element Definition
CL2 = Chlorine (i.e., originating from addition of free chlorine only)
CLM = Chloramines (originating from with addition of chlorine and ammonia or pre

- formed chloramines)
CAC = Chlorine and chloramines (if being mix ed from chlorinated and chloraminated water)
NOD = No disinfectant residual 13. Sample Collection
Date The date the sample is collected, reported as 4

- digit year, 2

- digit month, and
2

- digit day (YYYY/MM/DD). 14. Sample Identification Code An alphanumeric value up to 30 characters assigned by the laboratory to uniquely identify containers, or groups of containers, containing water samples collected at the same sampling location for the same sampling date.
15. Contaminant The unregulated contaminant for wh ich the sample is being analyzed. 16. Analytical Method Code The identification code of the analytical method used.

17. Extraction Batch Identification Code Laboratory assigned extraction batch ID. Must be unique for each extraction batch within the lab oratory for each method. For CCC samples report the Analysis Batch Identification Code as the value for this field. For methods without an extraction batch, leave this field null.
18. Extraction Date Date for the start of the extraction batch (YYYY/MM/DD) . For methods without an extraction batch, leave this field null. 19. Analysis Batch Identification Code Laboratory assigned analysis batch ID. Must be unique for each analysis batch within the laboratory for each method. 20. Analysis Date Date for the s tart of the analysis batch (YYYY/MM/DD). 21. Sample Analysis Type The type of sample collected and/or prepared, as well as the fortification level. Permitted values include:
CF = concentration fortified; the concentration of a known contaminant added to a field sample reported with sample analysis types LFSM, LFSMD, LFB, CCC and QCS.
CCC = continuing calibration check; a calibration standard containing the contaminant, the internal standard, and surrogate analyzed to verify the existing calibration for those contaminants.
FS = field sample; sample collected and submitted for analysis under this rule.
IS = internal stan dard; a standard that measures the relative response of
contaminants.
LFB = lab fortified blank; an aliquot of reagent water fortified with known quantities of the contaminants and all preservation compounds

. LRB = lab reagent blank; an aliquot of reagent water treated exactly as a field sample, including the addition of preservatives, internal standards, and surrogates to determine if interferences are present in the laboratory, reagents, or other equipment.
LFSM = laboratory fortified sample matrix; a UC MR field sample with a known amount of the contaminant of interest and all preservation compounds added.
LFSMD = laboratory fortified sample matrix duplicate; duplicate of the laboratory fortified sample matrix.37 Data element Definition QCS = quality control sample; a sample pre pared with a source external to the one used for initial calibration and CCC. The QCS is used to check calibration standard integrity. QH = quality HAA; HAA sample collected and submitted for quality control

purposes. SUR = surrogate standard; a standard that assesses method performance for each extraction. 22. Analytical Results

— Sign A value indicating whether the sample analysis result was: (<) “less than” means the contaminant was not detected, or was detected at a level below the Minimum Reporting Le vel. (=) “equal to” means the contaminant was detected at the level reported in “Analytical Result

— Measured Value.” 23. Analytical Result

— Measured Value The actual numeric value of the analytical results for: field samples; laboratory fortified matrix s amples; laboratory fortified sample matrix duplicates; and concentration fortified. 24. Additional Value Represents the true value or the fortified concentration for spiked samples for QC Sample Analysis Types (CCC, EQC, LFB, LFSM and LFSMD). For Sample
A nalysis Type FS and LRB and for IS and surrogate QC Contaminants, leave this field null. 25. Laboratory Identification Code The code, assigned by EPA, used to identify each laboratory. The code begins with the standard two

- character State postal abbreviation; the remaining five numbers are unique to each laboratory in the State. 26. Sample Event Code A code assigned by the PWS for each sample event. This will associate samples with the PWS monitoring plan to allow EPA to track compliance and completeness. Systems must assign the following codes: SEC1, SEC2, SEC3, SEC4, SEC5, SEC6, SEC7 and SEC8

- repr esent samples collected to meet UCMR Assessment Monitoring requirements for cyanotoxins; where “SEC1” represents the first sampling period, “SEC2” the second period and so forth, for all eight sampling events. SEA1, SEA2, SEA3 and SEA4

- represent samples collected to meet UCMR Assessment Monitoring requirements for the additional chemicals; where “SEA1” and “SEA2” represent the first and second sampling period for all water types; and “SEA3” and “SEA4” represent the third and fourth sampling period for SW and GU sources only.


### 9.2 HAAs Reported as Groups The proposed contaminant list for UCMR 4 presents the Haloacetic Acids (HAAs) as groups. Since no method currently exists to analyze samples for the HAAs in groups, laboratories are required to report
HAA resu lts to the EPA electronic data reporting system as individual analytical results for each HAA, along with the associated batch QC. HAAs will be grouped accord ing to Table 15 (Section 9.2.1)

.38 

### 9.2.1 Table 15. Haloacetic Acid Groups

1

- Contaminant 2

- CAS Registry
Nu mber 3

- Analytical Methods a 4

- Minimum Reporting Level b 5

- HAA6Br Group 6

- HAA9 Group 7

- HAA5 Group

Bromochloroacetic acid (BCAA) 5589

- 96

- 8 EPA 552.3 or
EPA 557 0.3 μ g/L HAA6Br HAA9

---

Bromodichloroacetic acid (BDCAA) 71133

- 14

- 7 EPA 552.3 or
EPA 557 0.5 μ g/L HAA6Br HAA9

---

Chlorodibromoacetic acid (CDBAA) 5278

- 95

- 5 EPA 552.3 or
EPA 557 0.3 μ g/L HAA6Br HAA9

---

Tribromoacetic acid (TBAA) 75

- 96

- 7 EPA 552.3 or
EPA 557 2.0 μ g/L HAA6Br HAA9

---

Monobromoacetic acid (MBAA) 79

- 08

- 3 EPA 552.3 or
EPA 557 0.3 μ g/L HAA6Br HAA9 HAA5

Dibromoacetic acid (DBAA) 631

- 64

- 1 EPA 552.3 or
EPA 557 0.3 μ g/L HAA6Br HAA9 HAA5

Dichloroacetic acid (DCAA) 79

- 43

- 6 EPA 552.3 or
EPA 557 0.2 μ g/L

--- HAA9 HAA5

Monochloroacetic acid (MCAA) 79

- 11

- 8 EPA 552.3 or
EPA 557 2.0 μ g/L

--- HAA9 HAA5

Trichloroacetic acid (TCAA) 76

- 03

- 9 EPA 552.3 or
EPA 557 0.5 μ g/L

--- HAA9 HAA5



## 10 References
Revisions to the Unregulated Contaminant Monitoring Rule (UCMR 4) for Public Water Systems

. Ohio EPA Total (Extracellular and Intracellular) Microcystins

- ADDA by ELISA Analytical Methodology, Version 2.0, January 2015 

### 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.


### 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

, U.S. EPA, Cincinnati, Ohio 45268

. 

### EPA Method 525.3

. Determination of Semivolatile Organic Chemicals in Drinking Water by Solid Phase
Extraction and Ca pillary Column Gas Chromatography

- Mass Spectrometry (GC

- MS)) , Version 1.0, February 2012. EPA/600/R

- 12/101. National Exposure Research Laboratory

, Office of Research and Development

, U.S. EPA, Cincinnati, Ohio 45268. 

### EPA Method 530

. Determination of Select Semivolatile Organic Chemicals in Drinking Water by Solid Phase Extraction and Gas Chromatography

- Mass Spectrometry (GC

- MS) , Version 1.0, J anuary 2015. EPA
Document # 600 /R

- 14/442. National Exposure Research Laboratory, Office of Research and Development

, U.S. EPA, Cincinnati, Ohio 45268.


### EPA Method 541

. Determination of 1

- Butanol, 1,4

- Dioxane, 2

- Methoxymethanol and 2

- Propen

- 1

- ol, in Drinking Water By Solid Phase Extraction and Gas Chromatography

- Mass Spectrometry
, Version 1.0
, November 2015, EPA Document # 815

- R

- 15

- 011

. Technical Support Center

, Standards and Risk Management Division

, Office of Ground Water and Drinking Water , U.S. EPA, Cincinnati, Ohio 45268.39 

### EPA Method 544

. Determination of Microcystins and Nodularin in Drinking Water by Solid Phase Extraction and Liquid Chromatography/Mass Spectrometry (LC/MS/MS) , Version 1.0, February 2015. EPA
Document # 600/R

- 14/474. Nationa l Exposure Research Laboratory

, Off i ce of Research and Development

, U.S. EPA, Cincinnati, Ohio 45268. 

### EPA Method 545

. Determination of Cylindrospermopsin and Anatoxin

- a in Drinking Water by Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry (LC

- ESI

- MS

- MS) , Version 1.0,
EPA Document #815

- R

- 15

- 009. Technical Support Center

, Standards and Risk Management Division

, Office of Ground Water and Drinking Water , U.S. EPA, Cincinnati, Ohio 45268. 

### EPA Method 552.3

. Determination of Haloacetic acid Dalapon in Drinking Water by Liquid

- Liquid Microextraction , Deri vatization, and Gas Chromatography with Electron Capture Detection , Version 1.0

. EPA Document #815

- B

- 03

- 002. Technical Support Center

, Standards and Risk Management Division

, Office of Ground Water and Drinking Water , U.S. EPA, Cincinnati, Ohio 45268. 

### EPA Method 557

. Determination of Haloacetic Acids, Bromate, and Dalapon in Drinking Water by Ion Chromatography Electrospray Ion ization Tandem Mass Spectrometry (IC

- ESI

- MS/MS)

, Version 1.0
, September 2009 . EPA Document #815

- B

- 09

- 012

. Technical Support Center, Standar ds and Risk Management Division , Office of Ground Water and Drinking Water

, U.S.EPA, Cincinnati, Ohio 45268. EPA Requirements for Quality Assurance Project Plans

. EPA QA/R

- 5, March 2001, U.S. EPA Document #EPA/240/B

- 01/003. O ffice of Environmental Information

, U.S. EPA, Washington, DC 204 60. 

### Technical Basis for the Lowest Concentration Minimum Reporting Level Calculator

. December
2010. EPA Document #815

- R

- 11

- 001. Technical Support Center, Standar ds and Ris k Management Division, Office of Ground Water and Drinking Water

, U.S.EPA, Cincinnati, Ohio 45268. 

### SM Method 3125

. Met a ls by Inductively C oupled Plasma/Mass Spectrometry in Standard Methods for the Examination of Water and Wastewater, 21 st Ed. 2005, Prepared and Published Jointly by APHA, AWWA, and WEF, Eaton, A.D., Clesceri, L.S., Rice, E.W., Greenberg, A.E., Eds.; American Public Health Association, 800 I Street, NW, Washington, DC 20001

- 3710. 

### U.S. Geological Survey, P rocessing of water samples (ver. 2.2)

. U.S. Geological Survey Techniques of

Water

- Resources Investigations, Book 9, Ch apter A5 Section 5.6.1.F, "Wastewater, pharmaceutical, and antibiotic compounds"

, April 2 004.



## 11 Appendix A: Requirements for Water Quality Parameters and
Indicators

11.1 Total Organic Carbon (TOC) and Bromide Water systems analyzing samples for bromide or total o rganic carbon as required in association with
HAA results should follow the procedure described in Section 2.1 and Section 2.2.1. This entails contacting the UCMR Laboratory Approval Coordinator to register and submit ting paperwork that certifies your prim acy state permits you to submit data for any of the water quality parameters, as SDWA compliance data, under Stage 2 DBP Rule

.



### 11.2 Temperature and pH Data for ELISA method EPA anticipates having an EPA ELISA method available by the publication of the final ru le and anticipates that this method will be similar to the Ohio EPA methodology. At this time EPA expects to have water systems report data for temperature and pH into the EPA electronic data reporting system for samples40 associated with the ELISA method. M onitoring includes measuring for water temperature using on e of the following metho d s: SM 2550 or SM 2550

- 00

. Monitoring also includes measuring for pH using one of the following methods: EPA Method 150.1 and 150.2, ASTM D1293

- 12, SM 4500

- H+ B, and SM 4500

- H+
B

- 00

.



## 12 Appendix B : Requirements for UCMR 4 Method 200.8 Analysis

12.1 Isotopes and Internal Standards For the analytes of Table 14, Section 10. 3 , monitor all of the isotopes listed in the second and fourth
colu mns. Report using the isotopes listed in the fifth column using the Elemental & Molecular Correction Equations listed in the sixth column. These Elemental and Molecular Correction Equations in Table 14,
Section 1 0. 3 must be used. The internal standards listed are in order of suggested use, but any of the
internal standards listed in the table are acceptable.



### 12.2 A dditions and Ex ceptions to Method 200.8 for UCMR 4

Follow EPA Method 200.8 Revision 5.4 for Total Recovera ble Analytes in Aqueous Samples with the
additions and exceptions given in this s ection

. 

### 12.2.1 Sample Container

In Method 200.8, Section 8.0

, sample container can be plastic or glass and sample size is one

- hundred

mL.



### 12.2.2 Turbidity

In Method 200.8, Section 11.2.2 , s amples must be digested regardless of turbidity.



### 12.2.3 Do Not Use Hydrochloric Acid

In Method 200,8 Section 11.2.3 , o mit the use of Hydrochloric Acid.



### 12.2.4 Do Not Adjust Chloride Concentration

Omit Method 200.8, Section 11.2.8 that concerns adjustment of chloride concentration

. 

### 12.2.5 Cell Type A collision cell or dynamic reaction cell or a dynamic reaction cell technology may NOT be used.



### 12.2.6 Nitric Acid Standards as well as the IS stock solution and calibration blanks must be prepared i n one percent nitric acid. Two percent nitric acid is not acceptable.



### 12.2.7 Calibration Points If five calibration points are required, the calibration blank does not count towards those five points. A
calibration curve for Method 200. 8 must contain a minimum of five standards that contain the analyte
in addition to the calibration blank.



### 12.2.8 Calibration fit and regression Linear calibration, not forced through zero, and with no weighting, must be used.



### 12.2.9 Linear Dynamic Range Check Check the linear dynamic range (LDR) daily, when the method is used. The LDR check can be performed at any point in the Analysis Batch. An LDR check does not have to be performed on the standard with the highest concentration.41 

### 12.3 Table 1 6 . Determination of Metals for UCMR 4 by 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

Germanium 72
74 27.4
36.5 --- 74 TBD

Manganese 55 100

--- 55 (1.000) ( 55 C)
Internal standard: Scandium (SC), 45 100

--- 45 (1.000) ( 55 C)

, background molecular ions may interfere
Internal standard: 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 is present, use the isobaric elemental correction for Tin. Internal standard: Terbium (Tb) 159 100

--- 159 (1.000) ( 159 C)



## 13 Appendix C : LCMRLs and MRLs for UCMR 4 Target Analytes

There were sixteen different laboratories that participat ed in the LCMRL studie s and that generated the
data in the following tables.


### 13.1 Table 1 7 : LCMRLs and MRLs for UCMR 4 analytes by EPA Method 200.8 (SIM)

.

Contaminants CASRN LCMRL ( μg /L) LCMRL ( μg /L) LCMRL ( μg /L) MRL ( μg /L)
Germanium 7440

- 56

- 4 0.02 7 0.14 0.083 0.27 Manganese 7439

- 96

- 5 0.06 9 0.24 0 .3 1 0.34


### 13.2 Table 1 8 : LCMRLs and MRLs for UCMR 4 analytes by EPA Method 525.3 (SIM)

.

Contaminants CASRN LCMRL ( μg /L) LCMRL ( μg /L) LCMRL ( μg /L) MRL ( μg /L) Chlorpyrifos 2921

- 88

- 2 0.017 0.023 0.026 0.029 Dimethipin 55290

- 64

- 7 0.072 0.12 0.082 0.12 Ethoprop 13194

- 48

- 4 0.026 0.012 0.011 0.027 alpha

- Hexachlorocyclohexane 319

- 84

- 6 0.0069 0.0023 0.0064 0.010
Hexazinone 51235

- 04

- 2 0.074 0.0053 0.013 0.046 Oxyfluorfen 42874

- 03

- 3 0.015 0.011 0.13 0.046
cis

- and trans

- Permethrin 52645

- 53

- 1 0.015 NA 0.031 0.036 Profenofos 41198

- 08

- 7 0.16 0.012 0.098 0.21 Tebuconazole 107534

- 96

- 3 0.061 0.0078 0.16 0.17 Tribufos 78

- 48

- 8 0.020 0.072 0.037 0.061 Vinclozolin 50471

- 44

- 8 0.022 0.0036 0.010 0.020


### 13.3 Table 1 9 : LCMRLs and MRLs for UCMR 4 analytes by EPA Method 530

.

Contaminants CASRN LCMRL ( μg /L) LCMRL ( μg /L) LCMRL ( μg /L) LCMRL ( μg /L) MRL ( μg /L) Butylated hydroxyanisole (BHA) 25013

- 16

- 5 0.013 0.0036 0.031 0.0057 0.02842 Contaminants CASRN LCMRL ( μg /L) LCMRL ( μg /L) LCMRL ( μg /L) LCMRL ( μg /L) MRL ( μg /L) Dimethipin 55290

- 64

- 7 0.0028 0.077 0.010 0.0097 0.021 Quinoline 91

- 22

- 5 0.0046 0.0032 0.026 0.0014 0.013

o

- Toluidine 95

- 53

- 4 0.0028 0.0060 0.0018 0.0018 0.0061


### 13.4 Table 20 : LCMRLs and MRLs for UCMR 4 analytes by EPA Method 541

.

Contaminants CASRN LCMRL ( μg /L) LCMRL ( μg /L) LCMRL ( μg /L) LCMRL ( μg /L) MRL ( μg /L)
1

- Butanol 71

- 36

- 3 0.44 0.61 2.0 0.94 1.5
2

- Methoxyethanol 109

- 86

- 4 0.37 0.30 0.24

--- 0.38
2

- Propen

- 1

- ol 107

- 18

- 6 0.30 0.17 0.23 0.43 0.46


### 13.5 Table 21 : LCMRLs and MRLs for UCMR 4 analytes by EPA Method 544.

Contaminants CASRN LCMRL ( μg /L) LCMRL ( μg /L) LCMRL ( μg /L) MRL ( μg /L) Microcystin

- LA 96180

- 79

- 9 0.0029 0.0090 0.0023 0.0076 Microcystin

- LF 154037

- 70

- 4 0.0035 0.0025 0.0049 0.0060 Microcystin

- LR 101043

- 37

- 2 0.0066 0.013 0.015 0.016 Microcystin

- LY 123304

- 10

- 9 0.0046 0.0029 0.014 0.0088 Microcystin

- RR 111755

- 37

- 4 0.0056 0.00093 0.0026 0.0054 Microcystin

- YR 101064

- 48

- 6 0.022 0.0043 0.0037 0.020 Nodularin

- R 118399

- 22

- 7 0.0073 0.0020 0.0026 0.0047


### 13.6 Table 2 2 : LCMRLs and MRLs for UCMR 4 analytes by EPA Method 545.

Contaminants CASRN LCMRL ( μg /L) LCMRL ( μg /L) LCMRL ( μg /L) LCMRL ( μg /L) MRL ( μg /L)
Anatoxin

- a 64285

- 06

- 9 0.018 0.0027 0.0064 0.018 0.021 Cylindrospermopsin 143545

- 90

- 8 0.063 0.0042 0.046 0.038 0.083


### 13.7 Table 2 3 : LCMRLs and MRLs for UCMR 4 analytes by EPA Method 552.3.

Analytes LCMRL ( μg /L) LCMRL ( μg /L) LCMRL ( μg /L) MRL ( μg /L)
Monochloroacetic acid 3.0 0.42 0.43 1.6 Dichloroacetic acid 0.075 0.12 0.098 0.17 Trichloroacetic acid 0.29 0.42 0.28 0.43 Monobromoacetic acid 0.13 0.19 0.14 0.24 Dibromoacetic acid 0.10 0.44 0.58 0.30 Bromochloroacetic acid 0.075 0.26 0.58 0.24 Bromodichloroacetic acid 0.18 0.37 0.17 0.41 Chlorodibromoacetic acid 0.10 0.23 0.091 0.24 Tribromoacetic acid 0.57 0.68 1.9 1.7