14976 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

ENVIRONMENTAL PROTECTION

AGENCY

40 CFR Parts 136 and 141

[FRL–5800–2]

RIN 2040–AC93

Guidelines Establishing Test

Procedures for the Analysis of

Pollutants and National Primary

Drinking Water Regulations; Flexibility

in Existing Test Procedures and

Streamlined Proposal of New Test

Procedures

AGENCY: Environmental Protection

Agency.

ACTION: Proposed rule.

SUMMARY: The Environmental Protection

Agency (EPA) proposes to streamline

the process for EPA approval of

analytical methods (and modifications

thereof) under the Clean Water Act

(CWA) and the Safe Drinking Water Act

(SDWA). The current methods approval

process applies to and is used by public

and private laboratories, manufacturers

of analytical equipment and analysts

who modify analytical methods or who

develop new methods for use in

compliance monitoring under the CWA

and SDWA. The proposed rule only

affects states if they choose to adopt the

proposed streamlined process as part of

their laboratory auditing programs.

Under the streamlined methods

approval system, EPA would increase

the analyst’s flexibility to modify

existing test procedures, expedite

approval of new and modified test

procedures, establish and require the

use of standardized quality control (QC)

and QC acceptance criteria in existing

and new test procedures, and

recommend use of standard data

elements for reporting test results.

Today’s action responds to the

Administration’s Environmental

Technology and Reinventing

Government Initiatives and the National

Technology Transfer and Advancement

Act by promoting use of emerging

technologies and encouraging

participation of consensus standards

organizations and other organizations in

developing test procedures (analytical

methods). The action proposed in

today’s rule would increase the options

available to the regulated community in

complying with EPA regulations under

the CWA and SDWA. These actions are

only an initial and interim step in the

Agency’s pursuit of a performancebased approach to environmental

measurements, and are not meant to

define or limit the Agency’s ultimate

implementation of a ‘‘pure’’

performance-based measurement

system. The increased flexibility

provided by this proposed action should

significantly reduce the need for Agency

review of alternate test procedures and

make it easier for the analyst to select

analytical methods that are most suited

to specific regulatory measurement

needs.

DATES: Comments on this proposed rule

will be accepted until June 26, 1997.

ADDRESSES: Send written comments to

the Streamlining Methods Docket Clerk,

Water Docket (MC–4101), USEPA, 401

M Street, SW., Washington, DC 20460.

Please submit an original and three

copies of your comments and enclosures

(including references). To ensure that

EPA can read, understand and therefore

properly respond to comments, the

Agency would prefer that commenters

cite, where possible, the paragraph(s) or

sections in the proposed regulation or in

the supporting documents to which

each comment refers. Commenters

should use a separate paragraph for each

issue discussed. Commenters who want

EPA to acknowledge receipt of their

comments should enclose a selfaddressed, stamped envelope. No

facsimiles (faxes) or electronic mail

(email) will be accepted because EPA

cannot ensure that they will be

submitted to the Water Docket. A copy

of the supporting documents cited in

this proposal are available for review at

EPA’s Water Docket, 401 M Street, SW.,

Washington, DC 20460. For access to

docket materials, call 202/260–3027

between 9:00 a.m. and 3:30 p.m. for an

appointment.

FOR FURTHER INFORMATION CONTACT: Dr.

Richard Reding, USEPA, Office of

Ground Water and Drinking Water (MS–

140), 26 W. Martin Luther King Drive,

Cincinnati, OH 45268, 513/569–7961.

SUPPLEMENTARY INFORMATION: The

supporting documents that are a part of

the administrative record for this

proposal may be obtained from the

National Center for Environmental

Publications and Information (NCEPI)

(513/489–8190), from the National

Technical Information Service (NTIS)

(703/487–4650), from the Educational

Resources Information Center (ERIC)

(800/276–0462), and via the Internet on

the EPA Office of Water home page at

http://www.epa.gov/watrhome. These

documents are titled, Guide to Method

Flexibility and Approval of EPA Water

Methods, December 1996 Draft, EPA–

821–D–96–004, NTIS PB97–117766,

ERIC D–A43 or D–A46 (diskette)

(Streamlining Guide, EPA 1996a),

Methods for Organic Chemical Analysis

of Municipal and Industrial Wastewater,

December 1996, EPA–821–B–96–005,

NTIS PB97–125298, ERIC D–A44 or D–

A47 (diskette) (Organic Methods, EPA

1996b), and Guidelines and Format for

Methods to Be Proposed at 40 CFR Part

136 or Part 141, July 1996, EPA–821–B–

96–003, NTIS PB96–210448, ERIC D–

A42 or D–A45 (diskette) (Method

Guidelines and Format, EPA 1996c).

Regulated Entities

Entities potentially regulated by this

action are those who seek EPA approval

of analytical technologies for monitoring

under the provisions of the CWA and

SDWA. Entities potentially regulated by

this action are listed in the table below.

These entities potentially include

consensus methods organizations that

publish compendiums of analytical

methods for water, and equipment

manufacturers, instrument

manufacturers and laboratories that

modify compliance methods or seek

approval of new methods for

compliance monitoring.

Category Examples of regulated entities

Public ....... Government laboratories that develop analytical methods for

compliance with the CWA and

the SDWA.

Private ..... Commercial laboratories, consensus methods organizations, instrument manufacturers, vendors, and other entities that develop or publish analytical methods for compliance with the CWA and the

SDWA.

This table is not intended to be

exhaustive, but rather provides a guide

for readers regarding entities likely to be

regulated by this action. This table lists

the types of entities that EPA is now

aware could potentially be regulated by

this action. Other types of entities not

listed in the table could also be

regulated. To determine whether your

organization is likely to be regulated by

this action, you should carefully read

the applicability language of today’s

rule at §§ 136.4, 136.5 and 141.27. If you

have questions regarding the

applicability of this action to a

particular entity, consult the individual

listed in the preceding FOR FURTHER

INFORMATION CONTACT section.

Table of Contents

I. Authority

A. Clean Water Act

B. Safe Drinking Water Act

II. Background and History

A. Introduction

B. Current Office of Water Methods

Approval Programs

C. Streamlining Initiative

D. Streamlining Objectives
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 14977

E. Public Meetings and Stakeholder

Participation in Streamlining

Development

F. Preamble Structure

III. Summary of Proposed Rule

A. Method Flexibility

1. Reference Method

2. Method Modifications

B. Quality Control

1. Standardized Quality Control Elements

2. Development of QC Acceptance Criteria

C. Method Validation for Modified or New

Methods

1. Validation Study Plan

2. Testing

Table I. Summary of Validation

Requirements for New Methods and

Method Modifications

3. Validation Study Report

4. Further Validation of a New Method

5. Approval of a Screening Method as a

New Method

D. Method Review and Approval

Table II. EPA Review and Action for New

and Modified Methods

1. Review and Approval of New Methods

2. Review and Approval of Modified

Methods

3. Submission Package

4. Regulatory Assistance Provided by

Submitter

5. EPA Review of Submission Package

6. Proposal of Methods

E. Other Issues

1. Legal Impacts

2. Method-defined Analytes

3. Biological Methods

4. Proprietary Reagents, Instruments, and

Methods

5. Restrictions by Consensus Standards

Organizations

6. Standard Data Format

7. Withdrawal of Outdated Methods

8. Administrative Record: Organic

Methods, Streamlining Guide, and

Method Guidelines and Format

9. Coordination with Other Federal

Register Proposals

IV. Regulatory Analysis

A. Executive Order 12866

B. Unfunded Mandates

C. Regulatory Flexibility Act

D. Paperwork Reduction Act

V. Request for Comments

A. General

B. Specific

VI. References

I. Authority

A. Clean Water Act

The Clean Water Act (CWA) requires

the U.S. Environmental Protection

Agency (EPA) Administrator to

promulgate effluent limitations

guidelines for specified categories and

classes of point sources. Section 301 of

CWA prohibits the discharge of any

pollutant into navigable waters unless

the discharge complies with a National

Pollutant Discharge Elimination System

(NPDES) permit issued under CWA

section 402. Section 307 requires the

EPA Administrator to publish

regulations establishing pretreatment

standards for introduction of pollutants

into publicly owned treatment works

(POTWs). Section 401 requires State and

Tribal certification of a federal license

that may result in any discharge into the

navigable waters.

Section 304(h) of CWA requires the

EPA Administrator to promulgate

guidelines establishing test procedures

for data gathering and for monitoring

compliance with published guidelines.

EPA’s promulgation of analytical

methods is authorized under this

section of CWA, as well as the general

rulemaking authority in CWA section

501(a). The section 304(h) test

procedures (analytical methods) are

published or incorporated by reference

at 40 CFR part 136. They include

Methods for Chemical Analysis of Water

and Wastes (MCAWW); the EPA 200-,

600-, and 1600-series methods; methods

published by consensus standards

organizations such as ASTM, AOACInternational, and Standard Methods for

the Examination of Water and

Wastewater (Standard Methods)

published jointly by the American

Public Health Association (APHA), the

American Water Works Association

(AWWA), and the Water Environment

Federation (WEF); methods used by the

U.S. Geological Survey; methods

developed by third parties; and other

methods referenced in CWA regulations.

These methods support development of

effluent limitations guidelines and

standards promulgated at 40 CFR parts

405–503, establish compliance with

NPDES permits issued under CWA

section 402, allow implementation of

the pretreatment standards issued under

CWA section 307, and apply to the

certification of compliance with State

water quality standards under CWA

section 401.

B. Safe Drinking Water Act

The Safe Drinking Water Act (SDWA)

requires the EPA Administrator to

promulgate national primary drinking

water regulations (NPDWRs) that

specify maximum contaminant levels

(MCLs) or treatment techniques for

listed drinking water contaminants

(section 1412). Section 1445(a)

authorizes the Administrator to

establish regulations for monitoring to

assist in determining whether persons

comply with the requirements of

SDWA. EPA’s promulgation of

analytical methods is authorized under

these sections of SDWA, as well as the

general rulemaking authority in SDWA

section 1450(a).

SDWA section 1401(1)(D) specifies

that NPDWRs contain criteria and

procedures to ensure a supply of

drinking water that dependably

complies with MCLs, including quality

control (QC) and testing procedures to

ensure compliance with such levels and

to ensure proper operation and

maintenance of drinking water supply

and distribution systems. These test

procedures are promulgated at 40 CFR

part 141 and include three MCAWW

methods, the 200-, 300-, and 500-series

EPA methods, methods published by

consensus standards organizations, and

other methods referenced in SDWA

regulations. EPA uses these test

procedures to establish MCLs under

SDWA section 1412 and to establish

monitoring requirements under SDWA

section 1445(a).

II. Background and History

A. Introduction

Within EPA, the Office of Water (OW)

publishes analytical methods for use in

data gathering and environmental

monitoring under the Clean Water Act

(CWA) and the Safe Drinking Water Act

(SDWA). These methods have been

developed by EPA, by consensus

standards organizations, and by others.

Many of these methods, especially those

published before 1988, are prescriptive,

with limited flexibility to change

technologies to respond to specific

situations or to incorporate advances in

measurement technology. There has

been a growing awareness, both within

EPA and in the analytical community,

that the requirement to use prescriptive

measurement methods to comply with

Agency regulations has imposed an

unintended regulatory burden and

potentially created a barrier to

innovation in environmental

monitoring.

To reduce this regulatory burden and

to lower the barriers to innovation, the

Agency in a future rulemaking may

propose to adopt a completely

performance-based approach to

environmental measurements. As

envisioned under such an approach, the

Agency would specify the question(s) to

be answered by the measurement, the

decision(s) to be supported by the data,

and the level of uncertainty that is

acceptable. EPA would specify

performance criteria for the

measurement and data producers would

be required to demonstrate that their

proposed measurement system (i.e.,

methods, sample handling procedures)

meets these specific performance

criteria. Data producers would be

required to document performance and

certify that they have used appropriate

quality assurance and QC procedures.

The system would apply to physical,

chemical, and biological measurements
14978 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

conducted either in laboratories or in

the field (EPA 1996d).

In a series of steps designed to adopt

the performance-based approach, each

program office in the Agency has

developed (or will develop) an

implementation plan that describes how

the performance-based approach would

be put into practice. The Agency’s goal

is to have these implementation plans as

consistent as possible (i.e.,

‘‘harmonized’’) from program to

program (EPA 1996e). The streamlining

initiative proposed in today’s notice

describes how EPA’s Office of Water is

taking immediate steps to remove some

of the regulatory barriers to the use of

new technologies for environmental

measurements of chemical analytes

under the CWA and SDWA. This

initiative would use reference chemical

methods that contain performance

criteria and methods that are already

approved at 40 CFR parts 136 and 141.

Other implementation approaches to a

performance-based measurement

system, such as listing in the CFR only

the required performance criteria for the

measurement, are also possible; these

approaches, which are not the subject of

today’s proposal, may be the subject of

future rulemakings.

Today’s rule proposes a process that

would use standardized QC, QC

acceptance criteria, and method

validation procedures for stakeholders

to gain approval of new and modified

methods for compliance monitoring

under the SDWA and CWA. Today’s

rule also proposes to designate certain

approved drinking water and

wastewater methods as reference

methods. The approved reference

methods either presently contain QC

acceptance criteria, are supplemented

with these criteria in today’s proposal,

or would be supplemented with these

criteria in a future rulemaking. In

subsequent rulemakings, EPA intends to

extend the streamlined method approval

process to physical and biological

(including microbiological)

measurements in the water programs.

Through public meetings,

announcements, and technical

presentations, EPA’s Office of Water has

coordinated this streamlining initiative

with various EPA Headquarters offices,

EPA Regions, the States, other

governmental agencies, industry,

consensus standards organizations,

environmental laboratories, and other

interested parties. With today’s

proposal, EPA attempts to define a

comprehensive program to increase

analytical choices in selection of

compliance monitoring methods and to

streamline the procedures for approval

of water methods. In this initiative, EPA

seeks to promote rapid introduction of

innovative technologies, to encourage

non-EPA organizations to participate in

the method development and approval

process, and to implement procedures

to expedite the review and approval of

new and modified methods. Most

importantly, EPA believes that this

initiative also offers the opportunity to

improve the quality of environmental

monitoring.

The proposed streamlined procedures

for approval of water methods would

allow analysts to use professional

judgement to modify and develop

alternatives to established Agency

methods and to take advantage of

emerging technologies that reduce costs,

overcome analytical difficulties, and

enhance data quality. The proposal to

increase the flexibility to modify

reference methods would be governed

by QC acceptance criteria designed to

ensure that the quality of the

environmental data would not be

compromised. These criteria would be

used to demonstrate that a modified

method produces results equal or

superior to results produced by the

reference method. EPA also proposes to

require that all new methods contain

such QC acceptance criteria so that

modifications could be made to new

methods.

EPA believes that allowing reference

method modifications and providing

rapid approval of new methods would

yield several benefits. On behalf of

regulated entities, analysts could select

the analytical method that yields the

best performance in a specific situation.

The QC acceptance criteria in the

reference method would enable the

analyst to document equivalent or

superior performance to the satisfaction

of reviewing authorities. New

technologies could be utilized to

overcome matrix interference problems,

lower detection limits, improve

laboratory productivity, or reduce the

amount of hazardous materials used and

hazardous wastes produced in the

laboratory.

A more flexible method approval

program is consistent with the

Administration’s Environmental

Technology and Reinventing

Government initiatives and the National

Technology Transfer and Advancement

Act of 1995 (NTTAA). The proposed

program would empower stakeholders

while decreasing demands on Agency

resources and is intended to accelerate

environmental technological innovation

while enhancing and maintaining

environmental protection. EPA believes

that the incentives provided by a more

flexible water test methods approval

program would spur the development of

new technologies and, with them, new

jobs. EPA also anticipates that the use

of new technologies may lower the cost

of environmental measurements,

thereby reducing costs of environmental

compliance for American industries and

municipalities.

B. Current Office of Water Methods

Approval Programs

Requirements for approval of alternate

analytical techniques (methods) are

specified at 40 CFR 136.4 and 136.5 for

wastewater and at 40 CFR 141.27 for

drinking water methods. These

requirements are the basis for the

Agency’s alternative test procedures

(ATP) program for water methods.

Under the ATP program, persons may

request approval to modify steps in a

reference method or approval to use a

new method. The person that submits

the ATP application is responsible for

validating the new or modified method.

Agency staff review the ATP validation

package and, if required, successful

applications undergo formal

rulemaking. Rulemaking is required

when a new or revised method is to be

added to the list of approved methods

in the CFR. The ATP and rulemaking

processes make heavy demands on

stakeholder, contractor, EPA, and Office

of Federal Register resources. The

process can require one to two years to

gain approval of a method. Because

advances in analytical technology

continue to outpace the capacity of

OW’s methods approval program, the

program is slow to respond to emerging

technologies and has been underutilized. Under the streamlining

initiative described below, EPA

proposes to increase method flexibility

by amending the procedures at 40 CFR

136.4, 136.5 and 141.27 to specify a

more rapid and less resource intensive

process for approval of new

technologies.

C. Streamlining Initiative

The proposed streamlining initiative

is designed to improve overall resource

use while making the method

development process more efficient and

accessible to non-EPA organizations.

The goals of the initiative are to

decrease the need for developers of

modified methods to use the ATP

program and to speed up the approval

(or disapproval) of methods subject to

ATP review. EPA believes the

streamlining initiative would (1)

encourage the use of emerging

technologies by increasing the flexibility

to modify approved methods without

formal EPA approval, (2) provide a

mechanism for non-EPA organizations

to develop and submit new methods for
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 14979

approval, and (3) expedite the approval

of new and modified methods by

improving the current ATP program.

This initiative applies to approval of

wastewater and drinking water

methods. Because of current emphases

on decreasing redundant activities,

forming partnerships with stakeholders,

and more quickly adopting advances in

technology, EPA believes this is an

appropriate time to look to

organizations outside of EPA for

assistance in developing new methods

that take advantage of emerging

technologies that reduce costs,

overcome analytical difficulties, and

enhance data quality. Once the

streamlining initiative is in place, EPA

expects to increase its reliance on

outside organizations as the developers

of many new methods. EPA would focus

its method development activities on

specialized or esoteric methods needed

to support regulation development or

compliance monitoring.

OW has coordinated the development

of the streamlining initiative with

various governmental entities, industry,

consensus standards organizations,

environmental laboratories, and other

interested parties. These organizations

include the National Environmental

Laboratory Accreditation Committee

(NELAC), and the Interagency Steering

Committee for Quality Assurance for

Environmental Measurements, which

includes representatives from the

Department of Energy, Department of

Defense, EPA, Air Force, U.S. Army

Corps of Engineers, U.S. Geological

Survey (USGS), Bureau of Reclamation,

and other organizations.

D. Streamlining Objectives

The purpose of the streamlining

initiative is to implement a more

performance-based approach to

environmental measurements under the

SDWA and CWA. The proposed

streamlined methods approval

procedures would revolutionize the

water methods approval program to

expand the flexibility to modify existing

methods, provide a mechanism for nonEPA organizations to gain approval of

new methods, and expedite the

approval of new and modified methods.

EPA has defined several specific

streamlining objectives:

• Increase the current flexibility to modify

approved chemical test procedures (methods)

without formal EPA approval; this would

allow laboratories to overcome matrix

interferences and would facilitate early

introduction of innovative technologies.

• Designate a reference method for each

unique combination of analyte and

determinative technique and establish

standardized QC tests for approved methods

to ensure data quality.

• Develop and publish QC acceptance

criteria for any reference method that does

not have these criteria so that laboratories

can demonstrate equivalent or superior

performance of a modified method.

• Provide a standard method format and

mechanism for validation and approval of

new methods to expedite method approval

and to increase confidence in the validity of

the methods and resulting data.

• Encourage stakeholder participation in

method development to keep pace with

emerging technologies.

• Harmonize the wastewater and drinking

water test procedures to eliminate

unnecessary inconsistencies.

• Increase standardized data reporting by

recommending use of standard data elements

for reporting analytical results for

environmental and QC samples.

• Identify and propose withdrawal of

outdated or obsolete methods from 40 CFR

parts 136 and 141 to modernize approved test

methods and to eliminate methods that are

no longer published by the issuing

government agency, consensus methods

organization, or vendor.

• Work with the Office of Federal Register

to incorporate more methods by reference to

reduce the volume of material published in

the CFR while ensuring and improving

access to those methods by all interested

parties.

E. Public Meetings and Stakeholder

Participation in Streamlining

Development

EPA conducted four public meetings

to develop a streamlined water test

methods approval program. EPA held

the meetings in Seattle, Washington, on

September 28, 1995; in Boston,

Massachusetts, on January 25, 1996; in

Chicago, Illinois, on February 14, 1996;

and in Denver, Colorado, on July 24,

1996. The purpose of the meetings was

to present and discuss EPA’s draft of the

streamlining initiative and obtain

stakeholder advice for refining the

streamlining approach prior to proposal.

All meetings were announced in the

Federal Register in advance. The first

meeting, held in Seattle, was announced

on September 12, 1995, in a Federal

Register notice titled, ‘‘A Public

Meeting and Availability of Documents

on Streamlining Approval of Analytical

Methods at 40 CFR part 136 and

Flexibility in Existing Test Methods’’

(60 FR 47325). This Federal Register

notice provided supplementary

information regarding the streamlining

effort and made available several

supporting documents. Subsequent

public meetings in Boston and Chicago

were announced on December 18, 1995

(60 FR 65207), and the fourth public

meeting in Denver was announced on

July 10, 1996 (61 FR 36328). The

supporting documents and summaries

of the four public meetings are in the

rule docket.

In addition to the public meetings,

EPA solicited support and expertise

from each of the consensus standards

organizations and government agencies

that developed the methods already

approved for use under the wastewater

and drinking water programs. These

groups include the American Public

Health Association (APHA), American

Water Works Association (AWWA), and

Water Environment Federation (WEF) as

publishers of Standard Methods for the

Examination of Water and Wastewater

(Standard Methods); ASTM (formerly,

American Society for Testing and

Materials); AOAC-International

(formerly, the Association of Official

Analytical Chemists); and the USGS.

EPA also provided the opportunity for

individuals, the regulated industry, the

States, local permitting authorities,

vendors, laboratories, and laboratory

organizations such as the International

Association of Environmental Testing

Laboratories (IAETL), to voice opinions

at the meetings. The groups offered

valuable insight concerning problems

with the current program and

recommended areas of improvement.

Through the public meeting process

and through individual meetings with

key stakeholder organizations, EPA

received input from more than 400

stakeholders, including all major

stakeholder organizations.

Following the first three public

meetings, EPA compiled and reviewed

preliminary stakeholder advice to assess

the initial response to streamlining and

revise the approach accordingly. In

response to stakeholder suggestions,

EPA made the following changes to the

streamlining initiative:

• Included drinking water methods (40

CFR part 141);

• Expanded flexibility to allow changes to

the determinative technique;

• Qualified flexibility to clarify that

flexibility in front-end techniques does not

apply to sample collection and preservation;

• Expanded Tier 1 validation to allow

single-laboratory application of a method

modification to multiple matrix types;

• Added an option to have EPA review

Tier 2 and Tier 3 method modifications upon

request;

• Added an option to have EPA formally

approve, upon request, Tier 2 and Tier 3

method modifications through rulemaking;

and

• Added an option to submit screening

methods to EPA for approval.

The Streamlining Guide (EPA 1996a)

and Method Guidelines and Format

(EPA 1996c) served as the revised draft

of the streamlining initiative that was

discussed at the final public meeting on

streamlining held in Denver. This
14980 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

proposed rule incorporates suggestions

received at the Denver public meeting,

at previous public meetings, by mail, by

electronic mail, and in informal

discussions with and among EPA

personnel, EPA contractors, and

stakeholders.

Based upon the extensive

involvement of internal and external

parties, and the generally favorable

response, EPA anticipates that the

proposed regulations will be well

received by regulatory authorities, the

regulated community, the technology

development community, and the

laboratory service community.

F. Preamble Structure

Section III of this preamble outlines

the key elements of streamlining.

Section III.A describes EPA’s proposal

for increased flexibility within the

method approval program and increased

flexibility for modifications to existing

methods. Section III.B describes the

standardized QC requirements and QC

acceptance criteria associated with

implementation of flexibility. Section

III.C describes the requirements for

validating new methods and method

modifications, using a system based on

the intended application of the method

or modification. Section III.D describes

the expedited method approval process

and includes procedures for submitting

validated methods to EPA for approval.

Section III.E describes other issues

associated with the streamlining

initiative. The descriptions in Section III

delineate the framework of EPA’s

method flexibility and methods

approval streamlining initiative. The

Streamlining Guide (EPA 1996a) and

other supporting documents cited in

this notice contain specifics about the

start-up and operation of the proposed

streamlining initiative.

III. Summary of Proposed Rule

A. Method Flexibility

In developing plans to improve the

method approval program for drinking

water and wastewater methods, EPA

concluded that the program’s success

would depend largely on its ability to

reflect the latest advances in technology.

This required, in turn, that the program

be efficient and flexible enough to

encourage the development and use of

new measurement techniques. To meet

these objectives, EPA determined that

the improved program would have two

types of flexibility:

(1) Flexibility to modify reference

methods without seeking formal

approval through the regulatory process,

and

(2) Flexibility to develop and submit

for approval entirely new methods.

The first type of flexibility is

primarily an expansion of the flexibility

already provided in some approved

water methods. Under the streamlining

program, it would no longer be

necessary to apply for ATP approval of

a method modification, because an

analyst would only need to demonstrate

and document that the modified method

produces results equal or superior to

results produced by an EPA-designated

reference method. A designated

reference method that contains QC

acceptance criteria against which

performance of a method modification

could be measured would be the

primary control to ensure data quality.

Other controls would include specific

multi-laboratory and multi-matrix

requirements for validating modified

methods and checklists for documenting

equivalency.

The second type of flexibility would

expand the ATP concept by providing a

mechanism whereby entirely new

techniques would be submitted to the

Agency for approval, even when these

techniques would not serve as alternates

to currently approved methods.

In designing a framework through

which this flexibility could be

implemented, EPA sought to balance the

advantages of increased flexibility

against the concern that results

produced by modifications would be

inferior to results produced by approved

methods. To ensure that these

competing objectives could be met, EPA

has devised a framework that is based

on:

(1) Use of a standardized QC program

with elements that could be applied to

all new and existing methods, and that

is stringent enough to meet compliance

monitoring objectives, extensive enough

to be applied to a wide variety of

analytical procedures, and yet simple

enough to avoid unwieldy or

unnecessary restrictions;

(2) Development and application of

QC acceptance criteria for each QC

element against which method

modifications could be assessed and

documented; and

(3) Designation of a single reference

method for each unique combination of

analyte and determinative technique.

This reference method would contain

the QC acceptance criteria used to

assess each QC element for method

equivalency.

In today’s proposed revisions to 40

CFR parts 136 and 141, EPA would

define the QC elements and associated

acceptance criteria (e.g., calibration,

sensitivity, accuracy, precision)

necessary to demonstrate the

equivalency of a modified method to a

reference method. These proposed QC

requirements are based on the three

components outlined above. Once

equivalency was demonstrated, a

modified method could be used

immediately without review by EPA

because EPA would have

‘‘preapproved’’ the modified method.

EPA believes that incorporating

method flexibility into approved

analytical methods would improve

laboratory operations by allowing

analysts to rely on professional

judgement to ascertain the procedures

and protocols necessary to obtain the

best results. Analysts could employ new

technologies to overcome matrix

interferences, lower detection limits,

improve the reliability of results, reduce

the generation of hazardous wastes,

improve laboratory productivity, and

reduce analytical costs.

1. Reference Method

The foundation of the flexibility

concept is the use of a reference

method. For each unique combination

of analyte and determinative technique,

EPA has identified or would designate

one approved method as the reference

method. If the performance of the

modified method is equal or superior to

the performance of the reference

method, the method modification would

be allowed. EPA believes that the use of

a reference method with defined QC

acceptance criteria as the performance

measure provides a means for

implementing the streamlining

initiative. This approach would clarify

and reduce the effort required to

demonstrate the equivalency of method

modifications.

To implement the streamlining

initiative, all reference methods would

need to specify standardized QC and QC

acceptance criteria. The QC and QC

acceptance criteria would be necessary

to demonstrate method equivalency.

Some methods, such as those approved

at 40 CFR part 136, Appendix A, already

contain the necessary standardized QC

and QC acceptance criteria. Some other

methods do not specifically identify

acceptance criteria for all of the

standardized QC elements, but EPA has

the data from which such criteria could

be developed. For this proposed rule,

selection of reference methods was

based either on the existence of QC

acceptance criteria in the method or the

availability of data from which QC

acceptance criteria could be developed.

EPA is proposing QC acceptance criteria

for some inorganic analytes and

reference methods. These criteria are

specified at 40 CFR 136.3 Table IF and

at 141.27(d) in the proposed rule text.
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The remaining criteria for other analytes

and reference methods would be

developed and proposed in subsequent

rulemaking(s).

For some determinative techniques,

no currently approved method

contained either all of the QC

acceptance criteria proposed in today’s

rule (e.g., Table ID in 40 CFR part 136)

or sufficient data from which to develop

such criteria. In these cases, no

reference method has been proposed;

therefore, all of those methods would be

classified as other approved methods.

Without a reference method, users

would not be able to implement the

method flexibility proposed in this

streamlining initiative.

EPA plans to include standardized QC

with QC acceptance criteria in all water

methods under development and for all

future water methods. However, for

drinking water methods, some of the QC

acceptance criteria (e.g., laboratory

certification criteria) are currently (and

may continue to be) specified in

drinking water regulations because

these criteria are an integral part of

EPA’s compliance monitoring

requirements.

In the future, the selection of a new

reference method would depend upon

requirements imposed by the submitting

organization, the availability of

standardized QC and QC acceptance

criteria in the method, and the timing of

the selection. EPA intends to rely on

outside organizations to develop the

majority of the new methods. Therefore,

it is anticipated that new reference

methods for a particular determinative

technique would be designated by being

the first method approved for the given

combination of analyte and

determinative technique. To become a

reference method, the new method

would need to contain standardized QC

and QC acceptance criteria, and be

approved through an Agency

rulemaking.

The purpose of specifying a single

reference method for a specific

combination of analyte and

determinative technique is to avoid the

possible confusion that could be created

if two or more reference methods

contained differing QC acceptance

criteria. The QC acceptance criteria

associated with the single reference

method would be the sole criteria

against which a method modification

would be tested.

In today’s action, EPA proposes to

retain all methods approved for use at

40 CFR parts 136 or 141, but would recategorize each of these methods as

either a ‘‘reference method’’ or an ‘‘other

approved method.’’ Both types of

methods would carry equal regulatory

status. The difference between the

methods would be that the reference

method would contain (or would be

supplemented with) detailed QC

acceptance criteria that would need to

be used to assess the equivalency of a

method modification.

2. Method Modifications

Currently, explicit flexibility to

modify a method is provided in some of

the approved 200-, 300-, 500-, 600-, and

1600-series methods published by EPA.

The allowed flexibility is typically

specified through use of the term

‘‘should’’ or the words ‘‘or equivalent.’’

Substitution of a 500-mL beaker for a

250-mL beaker or use of an ‘‘equivalent’’

chromatographic column are examples

of such explicit flexibility. The EPA

600- and 1600-series wastewater

methods approved at 40 CFR part 136,

Appendix A, also provide limited

flexibility to improve separations and

reduce the cost of measurements as long

as method performance is not sacrificed.

As specified in those methods, analysts

who choose to exercise explicit

flexibility are required to meet the QC

acceptance criteria of the approved

method and to maintain a record of the

performance of the modified method for

review at the request of an auditor. In

the development of more recent

methods (e.g., Method 1664 and Method

1613), EPA expanded its definition of

‘‘allowed flexibility’’ to further

encourage use of new techniques that

provide equal or better performance at

lower costs. However, no approved

methods provide unlimited flexibility

and few provide the extensive flexibility

that EPA proposes in this initiative.

The categories of method

modifications considered in this

proposal are: (1) Sample collection and

holding procedures, (2) front-end

techniques, (3) determinative

techniques, and (4) analyte addition.

These categories are defined below and

described in terms of present and

proposed flexibility to modify the

procedures or techniques included in

each category.

The first category, sample collection

and holding procedures, includes

procedures and reagents used in the

field, in transit, and at the laboratory.

This category includes sample

containers, sample holding times,

preservation reagents and procedures,

and shipping and storage procedures

and conditions. Currently, the Regional

Administrator may approve

modifications to these procedures for

wastewater methods if the submitter so

requests as specified at 40 CFR 136.3(c).

In the drinking water program, except as

explicitly allowed in the compliance

method, modifications of sample

collection and holding procedures

would be approved through the ATP

specification at 40 CFR 141.27.

The flexibility proposed in today’s

rule would not extend to sample

collection or holding procedures. Upon

implementation of streamlining,

modifications to sample collection and

preservation conditions would continue

to require EPA approval as specified at

40 CFR 136.3(c) and 141.27(b). The

latter section, 141.27(b), is a proposed

amendment of 40 CFR 141.27 that was

written to conform more closely with

the modification provisions at 40 CFR

136.3.

Front-end techniques, the second

category of method modifications, are

steps in the analytical process used at

the laboratory that precede the

determinative technique and include all

procedures, equipment, solvents, etc.,

that are used to prepare a sample for

analysis. The third category is the

determinative technique, which is

defined as the physical and/or chemical

process by which an analyte is

identified and its concentration

measured. For most methods, the

determinative technique consists of an

instrumental measurement (e.g., a

detector). The fourth category covers

increasing the analytical scope of a

reference method to include additional

analytes.

Historically, the wastewater program

has allowed some changes to front-end

techniques, but only a few methods

allow changes to the determinative step.

The drinking water program has

allowed similar changes provided the

chemistry of the method is not changed.

This means that some modifications,

such as changing the extraction solvent,

are not allowed in drinking water

methods unless they receive formal EPA

approval.

This proposed rule expands and more

clearly defines proposed modifications

to approved methods. EPA proposes to

allow the laboratory analyst the

flexibility to modify any and all frontend techniques, provided the

modification is not explicitly prohibited

in the reference method and provided

the analyst demonstrates and

documents that the modification

produces results equal or superior to

results produced by the reference

method. The laboratory analyst would

keep on file the documents that

demonstrate equivalency. Readers are

referred to the Streamlining Guide (EPA

1996a) for more guidance on this

subject.

EPA considered restricting the

flexibility to change front-end

procedures, such as extraction solvents,
14982 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

solvent-to-sample volumes, extraction

media, and pH, because such changes

require a deeper understanding of the

measurement science than some users

may have. However, EPA is not

proposing to restrict front-end flexibility

because EPA believes it is appropriate to

allow the method development and

auditing communities an opportunity to

comment on a far-reaching change to the

current system. The developer of a

modified method always would have

the option to ask EPA or another

regulatory authority for a technical

opinion on the acceptability of the

validation data that supports the

method. In the list of questions at the

end of this preamble, EPA invites public

comment on what, if any, additional QC

would be needed to document the

acceptability of front-end modifications

to a reference method.

EPA proposes to allow use of an

alternate determinative technique that is

not explicitly prohibited in the

reference method, provided that the

analyst could demonstrate and

document equivalency as outlined

above, and provided that four

conditions could be met: (1) The

alternate determinative technique

measures a property similar to the

prescribed technique, (2) the alternate

technique is demonstrated to be more

specific (i.e., provides better separation

of the analyte from interferences) and/

or more sensitive (i.e., produces a lower

detection limit) for the analyte of

concern than the determinative

technique in the reference method, (3)

there is not another approved method

that uses the alternate determinative

technique for the determination of that

analyte, and (4) use of the alternate

determinative technique would not

result in a nonsensical combination of

analyte, front-end technique, and

determinative technique.

Examples of allowed changes to a

determinative technique would be

substitution of a photoionization

detector for a flame ionization detector

for determination of polynuclear

aromatic hydrocarbons, substitution of a

nitrogen-phosphorous detector for an

electron capture detector (ECD) for

determination of analytes containing

nitrogen or phosphorous, and

substitution of a fluorescence detector

for an ultraviolet or visible wavelength

detector. Substitution of a mass

spectrometer (MS) for an ECD would not

be allowed if there is an approved MS

method that measures the analyte of

concern. Readers are referred to the

Streamlining Guide (EPA 1996a) for

more guidance on this subject.

EPA proposes to limit changes to a

determinative technique by the four

conditions described above to preclude

nonsensical combinations of analyte

and determinative technique, to

encourage a net benefit (increased

sensitivity and/or specificity), and to

preclude multiple reference methods

with the same determinative technique

but with different QC acceptance

criteria for the same analyte(s) of

concern. For example, if a mass

spectrometer were substituted for the

conventional detectors in EPA methods

601–612, all of these methods would

become GC/MS methods, but all would

contain different QC acceptance criteria.

Further, they would all conflict with

approved GC/MS Methods 625 and

1625. The proposed criteria for detector

substitution also would be consistent

with EPA’s decision in the December 5,

1994, drinking water methods final rule

(59 FR 62456) not to allow substitution

of MS in methods that specify

conventional GC detectors.

Another reason for proposing to limit

changes to the determinative technique

is that there are techniques, such as

immunoassay, for which EPA has no

reference method and therefore no

history to ensure that the standardized

QC proposed in today’s rule would be

germane to, or adequate for, assurance

of the quality of data produced by the

novel determinative technique. EPA

would prefer that a new method be

written and submitted for approval

when a novel determinative technique

is developed. EPA invites public

comment on the suitability of the

conditions EPA proposes to place on the

flexibility to modify determinative

techniques in EPA reference methods.

In today’s proposed rule, EPA also has

specified how the analyst would modify

the analytical scope of a reference

method to add additional analytes. This

option is proposed in response to public

comment on previous rules (59 FR

62456, December 5, 1994; 58 FR 65622,

December 15, 1993) to extend the scope

of a reference method to the

determination of other analytes. Method

developers seek this approval when

they want to adapt an existing method

rather than develop a new one to obtain

occurrence data for a new analyte. EPA

believes these requests would have

merit when there is a potential for new

regulatory requirements and historical

monitoring data would be useful in

making process, treatment, or regulatory

decisions. Examples of monitoring for a

new analyte would include industrial or

POTW monitoring for ethers in a

discharge, public water system (PWS)

monitoring for unregulated pesticides or

pesticide metabolites, and PWS

monitoring for analytes on the drinking

water priority list. EPA also believes

these requests would have merit when

technological advances would make the

measurement of additional analytes

feasible (e.g., adding lead to the scope

of EPA Method 200.7). Under the

proposed flexibility procedures for

modified and new methods, developers

would obtain approval for the addition

of analytes to a reference method as an

allowed method modification if the

conditions below would be met.

An analyst may add a new target

analyte to a reference method provided

(1) it could be demonstrated that the

analyte would not interfere with

determination of the analytes of concern

in that method, (2) QC acceptance

criteria were developed and employed

for determination of the target analyte,

(3) there would not be another approved

method that uses the same

determinative technique for that

analyte, and (4) that the reason for

adding the analyte would not be to

avoid the sample preservation or sample

(or extract) holding time conditions that

are already required for that analyte in

another approved method. The third

and fourth criteria would preclude

method shopping whereby an analyst

might add analytes to a reference

method with less rigid QC acceptance,

sample collection or holding time

criteria. Under the criteria proposed

above, if a reference method for an

analyte of concern required acidification

of the sample, an analyst would not

have the flexibility to modify a method

that does not require sample

acidification to include analysis of the

analyte of concern. Modifications of this

type would require EPA approval as a

new method.

If QC acceptance criteria do not exist

to allow addition of a new analyte, the

guidelines specified at 40 CFR part 136

Appendix E, at 40 CFR 136.4, 136.5 and

141.27 would be followed to develop

and obtain approval for these criteria.

Alternatively, QC acceptance criteria for

the new analyte could be transferred

from the criteria for an analyte with

similar chemical characteristics in the

same method or from the criteria for the

analyte in another approved method.

EPA provides additional guidance on

developing QC acceptance criteria in

Chapter 3 of the Streamlining Guide

(EPA 1996a).

B. Quality Control

In order to establish that method

modifications do not degrade method

performance, a standard would be

required against which changes could

be compared. This standard would

consist of standardized QC elements

and QC acceptance criteria that would

be listed in the reference method and/
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 14983

or in the regulations at 40 CFR parts 136

and 141. These criteria would serve as

definitive test criteria for evaluating the

performance of a method modification.

As proposed, new methods would be

required to include QC acceptance

criteria that were developed from a

method validation study according to

procedures specified at 40 CFR 136.5,

141.27(c) and (e).

1. Standardized Quality Control

Elements

The standardized QC elements,

described below, when paired with the

relevant QC acceptance criteria for each

element, would allow analysts to

establish and document method

performance. These elements would be

specified at 40 CFR part 136 Appendix

E and at 40 CFR 136.4, 136.5 and

141.27. Additional guidance on

procedures and requirements for these

QC elements are provided in the

Streamlining Guide (EPA 1996a).

• Calibration—the process of establishing

the relationship between the concentration or

amount of material introduced into an

instrument or measurement process and the

output signal.

• Calibration Verification—the means of

establishing that instrument performance

remains within pre-established limits.

• Initial Precision and Recovery (IPR)—the

mechanism to demonstrate that a laboratory

would produce reliable results with the

method prior to analysis of environmental

samples. IPRs also would demonstrate that a

method modification produces results equal

or superior to those produced by a reference

method.

• Ongoing Precision and Recovery—a

process that demonstrates that a laboratory is

able to produce reliable results continuously.

• Matrix Spike (MS)—a means to assess

method performance (especially analyte

recovery) on a sample by adding a known

amount of the tested analyte.

• Matrix Spike Duplicate—a process to test

the precision of an analysis by repeating the

MS test.

• Method Blank—a test that checks for

laboratory contamination.

• Method Detection Limit (MDL)—the

MDL test, as specified at Appendix B of 40

CFR part 136, is used to confirm that a

laboratory is capable of detecting an analyte

of concern at the level specified in the

method or at an acceptable level for

regulatory compliance monitoring.

• Reference Sample—a test that serves as

an external check on method accuracy.

• Retention Time and Relative Retention

Time Precision—a means to assess the

performance of a chromatographic separation

system; used to aid in the identification of

each target analyte in a complex mixture.

• Surrogate—a means to assess the

performance of the method within the given

sample matrix by adding a known amount of

a different but chemically similar analyte.

The results of these tests would be used to

assess method and laboratory performance.

For each reference method, each QC

test would have acceptance criteria that

define data acceptability.

2. Development of QC Acceptance

Criteria

QC acceptance criteria would be used

to ensure that a modified method

produces results that are reliable,

defensible and suitable for regulatory

decisions. QC acceptance criteria would

be specified as numeric limits. For

example, the QC acceptance criteria for

a MS/MSD test may be 75–125 percent

recovery with a relative percent

difference (RPD) of 20 or less. If these

criteria were met for the MS/MSD test,

and all other QC acceptance criteria

were met, results produced using the

modified method could be used for

regulatory compliance purposes; if not,

corrective action would need to be taken

and the sample reanalyzed.

Some methods currently approved at

40 CFR parts 136 and 141 explicitly

specify QC acceptance criteria for all of

the standardized QC elements outlined

in today’s proposal, but many do not. In

selecting reference methods for today’s

proposal, EPA chose those methods that

contained QC acceptance criteria or data

from which QC acceptance criteria

could be developed. For those methods

that did not contain QC acceptance

criteria, QC acceptance criteria were

developed from results of singlelaboratory or interlaboratory study data

contained in the method or from criteria

contained in Appendix D of 40 CFR part

136. These criteria are provided at 40

CFR 141.27(d) and 136.3 Table IF for

drinking water and wastewater

reference methods, respectively. EPA

would develop QC acceptance criteria

for certain approved methods that do

not presently contain these criteria. EPA

would propose to designate these

approved methods as reference methods

in a future rulemaking.

C. Method Validation for Modified or

New Methods

Method validation is the process by

which an analyst or vendor would

establish the performance of a new

method or would substantiate the

performance of a method modification

to a reference method. Validation would

be necessary to demonstrate and

document that the new or modified

method could yield reliable data for

compliance monitoring and other

purposes. The party who developed the

method or method modification would

be responsible for validating the method

or method modification.

The requirements for validation

would depend on the level of intended

use for the method modification or new

method, and the characteristics of the

sample to which the method

modification or new method would be

applied. Based on interactions with

stakeholders, EPA proposes to establish

three levels of validation:

• Tier 1 methods would be used in a single

laboratory in a single matrix type from one

industrial category or subcategory, or in

additional matrix types from any industrial

category or subcategory.

• Tier 2 methods would be used by all

laboratories in one or more matrix types

within one industrial category or

subcategory.

• Tier 3 methods would be used by all

laboratories in matrix types from all

industrial categories or subcategories.

Proposed definitions of the terms

laboratory, matrix type, medium, and

tier are in the definitions sections at 40

CFR 136.2 and 141.2. In the

streamlining initiative, the term matrix

type would be defined and used to

identify a sample medium with

common characteristics across a given

industrial category or subcategory. The

terms facility or system would identify

places where an industrial discharge

activity occurs or where a water source

is treated and distributed as drinking

(potable) water. For example, all POTWs

that comprise the municipal wastewater

treatment industry would be considered

to be in one industrial category. A

typical municipal POTW has three

matrix types: untreated wastewater,

treated wastewater, and sludge. All

PWSs that comprise the drinking water

industry would be considered to be in

one industrial category and to be one

matrix type—potable water. Similar

definitions would apply to matrix types

in other industrial categories and

subcategories. EPA invites public

comment on these definitions and seeks

suggestions on additional terms or

concepts for which the public believes

a regulatory definition would be useful

in implementing and administering

EPA’s methods approval system.

Method validation would comprise

three steps: (1) development of a

validation study plan, (2) testing, and

(3) preparation of a validation study

report.

1. Validation Study Plan

A validation study plan would be

required for development of a new

method at any tier or for modification of

a reference method at Tiers 2 and 3. The

organization responsible for conducting

the study would prepare the validation

study plan. Requirements for method

validation would be specified at 40 CFR

136.4, 136.5 and 141.27 and at 40 CFR

part 136 Appendix E. Additional

guidance on suggested validation study
14984 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

plans is available in the Streamlining

Guide (EPA 1996a).

A validation study plan would not be

required for Tier 1 method

modifications, because EPA would

expect that single-laboratory use

modifications would be simple and

straightforward, and that requiring a

validation study plan for singlelaboratory modifications would impose

an unnecessary regulatory burden on

small laboratories.

2. Testing

The number of testing laboratories,

matrices, and replicate QC tests for the

method validation would depend on the

tier at which the new or modified

method would be validated, as

indicated in Table I below. The specific

requirements and procedures for

performing QC validation testing are

specified at 40 CFR 136.4, 136.5 and at

141.27; additional guidance is available

in the Streamlining Guide (EPA 1996a).

Table I, which is taken from 40 CFR

136.5(d), summarizes validation

requirements at each tier.

TABLE I.—SUMMARY OF VALIDATION REQUIREMENTS FOR NEW METHODS AND METHOD MODIFICATIONS 1

Method application

Number of Number of analyses required

Labs Matrix types Facilities/

PWSs

IPR-reagent

water 2

IPR-sample

matrix 3 MS/MSD MDL 4

Tier 1-Single-lab WW/DW—First matrix

type or first PWS ................................... 1 1 1 4 4 5 2 7

WW—Each addt’l matrix type (8 max.)

from any industrial category .................. 1 1 1 6 0 6 0 5 2 6 0

DW—Each addt’l PWS (2 max.) ............... 1 1 1 6 0 6 0 5 2 6 0

Tier 2-Multi-lab, single matrix type WW/

DW—Each matrix type in a single industrial category .................................... 3 1 3 12 0 7 6 21

Tier 3-Multi-lab, multiple matrix types WW

only—All matrix types, all industrial categories ................................................... 8 9 9 9 36 0 7 18 63

1 Numbers of analyses in this table do not include background analyses or additional QC tests such as calibration, blanks, etc. Validation requirements are based on the intended application of the method. Method application would be designated by tier for wastewater (WW) and drinking water (DW) programs. Three would be the maximum number of public water systems (PWSs) that would be required to validate a new or

modified drinking water method at Tier 1 or 2. Nine would be the maximum number of matrix types (or facilities) that would be required to validate a new or modified wastewater method at Tier 1 or 3; at Tier 2 the number would be three matrix types. 2 IPR reagent water analyses would be used to validate a method modification and to establish QC acceptance criteria for initial precision and

recovery (IPR) and ongoing precision and recovery (OPR) for a new method. The required number of IPR analyses, except as noted under footnote 7, would be four times the number of laboratories required to validate a method modification or new method because each laboratory would

perform a 4-replicate IPR test. 3 IPR sample matrix analyses would be used to establish QC acceptance criteria for matrix spike/matrix spike duplicate (MS/MSD) recovery

and precision for a Tier 1 new method only. Would not be required for validation of Tier 2 or 3 new methods because this variability data would

be obtained from MS/MSD tests. Would not be required for validation of a method modification because MS/MSD data from the reference method would be used. 4A method detection limit (MDL) test would be performed in each laboratory using the new or modified method. 40 CFR part 136 Appendix B

requires a minimum of seven analyses per laboratory to determine an MDL. Each lab involved in validation of a wastewater modification would

demonstrate that the modified method would achieve the detection limits specified in the regulations at 40 CFR parts 136 and 141 and/or in

chapter 6 of the Streamlining Guide (EPA 1996a). 5 MS/MSD analyses would be required only for a method modification because, for new methods, the MS/MSD QC acceptance criteria would

be established by the 4-replicate sample matrix IPR test. For modified methods, the MS/MSD test would demonstrate that the reference method

MS/MSD QC acceptance criteria have been met. 6The MDL, reagent water IPR, and sample matrix IPR tests would not have to be repeated after the first matrix type, facility, or PWS was validated. 7For validation of a new method, the MS/MSD analyses would establish QC acceptance criteria for MS/MSD recovery and precision. For validation of a method modification, the MS/MSD analyses would demonstrate that reference method MS/MSD recovery and precision have been

met. The required number of MS/MSD analyses would be two times the number of facilities, PWSs or matrix types tested. 8The number of laboratories and samples would vary if a conventional interlaboratory study is used.

The tiered approach to validating new

and modified methods would

accommodate variability in the

analytical performance of a method that

can be attributed to the type of sample

analyzed. This variability is termed a

matrix effect and can be observed in

samples taken at different locations in

matrices of the same type (intramatrix)

or in samples from different locations

and in different matrix types

(intermatrix). Under the streamlining

initiative, each successive tier addresses

matrix effects to a greater degree

through increasing levels of sample

matrix effect validation, broadly defined

as a test of the extent to which

differences, if any, in method

performance could be attributed to

variability between samples obtained

from different industrial matrices,

facilities, or PWSs. Matrix effects would

need to be tested by the IPR sample

matrix and MS/MSD analyses listed in

Table I. Intramatrix effects would need

to be tested in water samples taken from

different PWSs or from different waste

streams. Intermatrix effects would need

to be validated on a group of samples

taken from discharge samples collected

from several different industrial

categories. In all cases, the laboratory

would try to determine if the

measurement result for the target

analyte using a new or modified method

differed from the result obtained in a

reagent water matrix or in a previously

validated matrix type or PWS sample.

As indicated in Table I, a Tier 1 new

or modified method would be validated

in a single laboratory on one or more

matrix types obtained from one or more

facilities, or on samples obtained from

one or more PWSs. Validation of

additional facilities or PWSs would

require analysis of MS/MSD samples for

each additional facility or PWS.

However, in response to stakeholder

requests that there should be some

maximum number of single-laboratory

validations after which further

validation would be unnecessary

because sample matrix effects would

have been sufficiently addressed, EPA
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 14985

added a provision for a maximum

number of matrix type, facility or PWS

analyses for Tier 1 methods. For a

wastewater method, the maximum

number of matrix types or facilities

tested under Tier 1 would be nine, each

from a different industrial category or

subcategory. For a drinking water

method, the maximum number of PWS

samples tested under Tier 1 would be

three samples, each from a PWS with

different water quality characteristics.

EPA proposes to require validation in

three rather than nine PWSs, because

three is consistent with the validation

data in many EPA drinking water

methods and because the variability in

drinking water samples (and therefore

the probability of matrix effects) is

usually less in drinking water samples

than in wastewater samples.

Tier 2 validation would be applicable

to one or more matrix types within a

single industrial category or

subcategory. Because Tier 2 new and

modified methods would apply to each

matrix across all laboratories, EPA

developed Tier 2 validation

requirements to incorporate intramatrix

variability. Tier 2 would require

validation of the method in drinking

water samples obtained from three

PWSs, or wastewater samples of one or

more matrix types obtained from three

or more facilities within a single

industrial category or subcategory.

Tier 3 validation would be applicable

to all matrix types in all industrial

categories. Consequently, Tier 3

validation requirements would include

provisions to account for both

intramatrix and intermatrix variability.

However, Tier 3 validation would not

apply to the drinking water program

because the program regulates only one

matrix type, drinking (potable) water.

The wastewater program regulates

several industrial categories, each of

which may contain more than one

matrix type. Tier 3 would require

validation of the method in wastewater

samples of up to nine matrix types

obtained from nine different facilities.

For all multi-matrix tiers, it would be

extremely important to select suitable

samples and matrix types for validation.

The matrix types, facilities, or PWSs

selected for matrix effect validation

would need to have sufficiently

different water quality characteristics so

that the matrix effects, if any, could be

observed. Proposed criteria for selecting

matrix types, facilities, or PWSs from

which to obtain these samples is

specified at 40 CFR 136.4(a)(2)(i) and

141.27(b)(iii). Additional guidance on

testing sample matrix effects is available

in the Streamlining Guide (EPA 1996a).

EPA invites public comment on the

number of tests, laboratories, matrix

types, facilities, and PWSs that EPA is

proposing for validation of Tier 1, 2, or

3 methods. EPA is specifically

interested in suggestions for adding,

deleting, or modifying the tests listed in

Table I. Commenters should provide

EPA with reasons for (and preferably

data to support) any suggested changes.

3. Validation Study Report

A validation study report would be

required for a new method or method

modification at all tiers to document

successful validation. The primary

documents to be included in the report

would be the Checklist for Initial

Demonstration of Method Performance,

the Checklist for Continuing

Demonstration of Method Performance

(collectively, the ‘‘Checklists’’), and a

Certification Statement. The Checklists

would document that all requirements

for establishing equivalency were met;

the certification statement would

commit the persons involved in the

method development or modification

effort to the statements made in the

Checklists and the supporting

information provided. The proposed

Checklists would be specified at 40 CFR

part 136 Appendix E. The checklists

also would be published in the

Streamlining Guide (EPA 1996a) with

additional guidance on how to complete

a checklist for a typical water method.

This guidance would be provided to aid

the method modifier or developer in

understanding the information and test

data to be provided. The Checklists and

certification statement would be

required as part of the validation study

report. For Tier 1 method modifications,

the Checklists and certification

statement would comprise the data

validation report. For all tiers, each

laboratory involved in validation of a

method modification would need to

complete the Checklists and

Certification Statement. More extensive

documentation would be required for a

modification at Tiers 2 and 3 and for all

new methods.

The validation study report for Tiers

2 and 3 would need to specify the

following information, as appropriate,

for validation of a new or modified

method:

• Narrative—includes (a) a description of

the method being validated and the matrices,

matrix types, and media to which the method

is applicable; (b) an indication of whether the

method is a modification of an approved

reference method or a new method; (c) reason

for and description of the modification, if

applicable; and (d) information on the

organization responsible for developing the

new method or method modification.

• Analyte(s)—name and Chemical

Abstracts Service (CAS) Registry Number or

an EPA Environmental Monitoring Methods

Index (EMMI) Number. If a CAS Registry

Number has not been assigned, the submitter

should attempt to obtain a number from the

CAS Registry. If the CAS Registry will not

assign a number, the submitter should

contact the AMS Director for assignment of

an EMMI Number. A report for a modified

method should indicate whether the

modification includes all forms of the

analyte(s) in the scope of the reference

method. The definition of AMS Director is at

40 CFR parts 136.2 and 141.2.

• Method or modified test procedure—

prepared in a standard format; modified test

procedures would be prepared in the format

of the reference method.

• Methodology and procedures—indicates

the tier level at which the new or modified

method was tested, describes the approach

used to implement the study, describes the

procedures used to report and validate the

data, and identifies the problems

encountered during implementation of the

study.

• Results—for modified methods, includes

a summary of QC results required by the

reference method and corresponding QC

results obtained with the modified method.

• Conclusions—describes the conclusions

and limitations of the study.

• Discussion—critically examines the

study results.

The following items would need to be

included in appendixes to the

validation study report:

• Calculations;

• Raw data to allow an independent

reviewer to verify each determination and

calculation performed by the laboratory;

• For instruments involving data systems,

raw data on magnetic tape or disk (upon

request only);

• Names, titles, addresses, and phone

numbers of analysts who performed analyses

and QA Officer who verified analyses; and

• Completed Checklists and Certification

Statement.

The validation study report for a new

or modified method would need to be

retained on file by the organization

responsible for developing or applying

the modification, and by regulated

entities whose samples are tested with

the method modification. The party

responsible for developing and

submitting the new method also would

need to maintain on file the complete

records of all validation study tests

including the study plan, all laboratory

results, the validation study report,

completed Checklists and Certification

Statement, and other information that

supports the new method or method

modification. All records would need to

be made available for review upon

request to an auditor, permitting

authority, or other regulatory authority.

These records would need to be

submitted to EPA if the method
14986 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

developer elected to request formal

approval of a method modification at

Tier 2 or 3.

4. Further Validation of a New Method

After completing a Tier 1, 2, or 3

validation study of a new method, the

organization responsible for developing

the method would need to document

the study results in accordance with

requirements proposed at 40 CFR part

136 Appendixes E, F, and G and would

need to submit the results and the

method to EPA for review and approval.

If, based on its review of the method,

EPA concluded that the method was not

sufficiently rugged or reliable for its

intended use, EPA would require

further method development and

testing. The tests and studies that would

be performed would need to be

determined on a case-by-case basis as

these situations arise and would depend

on the analyte(s) and the analytical

system.

5. Approval of a Screening Method as a

New Method

Methods currently approved for

compliance monitoring at 40 CFR parts

136 and 141 are considered to be

confirmatory methods if the method is

sufficiently selective and quantitative so

that most positive results do not have to

be verified by analysis with another

method. The term ‘‘confirmatory’’ is

used to distinguish these methods from

screening methods. When using a

screening method, all positive results

should be verified by re-analysis with a

confirmatory method because screening

methods can be less selective and/or

quantitative and, therefore, more subject

to false positives or imprecise results

than confirmatory methods.

Characteristics of screening methods are

described in more detail in Chapter 2 of

the Streamlining Guide (EPA 1996a).

EPA has been asked by many

stakeholders to allow use of screening

methods for wastewater and drinking

water analyses. Although screening

methods may be less selective and

quantitative than confirmatory methods,

they also could be designed to serve

meaningful uses under those statutes.

Screening methods could be especially

useful when measuring trends in the

contamination of a water source or

when knowledge of the performance of

a waste treatment process would be

more important than an exact

knowledge of the absolute amount and

identity of the contaminant or pollutant.

Historically, EPA has not considered

screening methods for approval at 40

CFR part 136 or part 141. Under the

streamlining initiative, EPA proposes to

consider the approval of screening

methods for compliance monitoring

under the Safe Drinking Water Act

provided that: (1) the method would

meet all the requirements specified in

the regulations at 40 CFR 141.27, (2) all

positive sample results obtained with

the method would be confirmed and

reported using an approved

confirmatory method, and (3) the

probability of the method producing a

false negative result at concentrations of

regulatory interest would be no more

than one percent (1%). EPA has not yet

specified how it intends to implement

the use of screening methods under the

SDWA; the term was only recently

added in the 1996 SDWA amendments.

Under the Clean Water Act, EPA is

considering the appropriateness of

screening methods for use in NPDES

permit applications and ambient water

quality monitoring by States. EPA

proposes to publish a separate table at

40 CFR parts 136 and 141 to list

approved screening methods. The

Agency invites comment on the

approval criteria for screening methods

for the uses described in the SDWA, as

well as for NPDES permit applications

and ambient water quality monitoring.

D. Method Review and Approval

Under this proposed rule, EPA

expects to significantly reduce the

number of methods that would pass

through the ATP review and rulemaking

processes. EPA has this expectation

because, once implemented, the

streamlining initiative would make it

easier for method modifications to be

judged as being ‘‘within the flexibility

allowed by the streamlining initiative.’’

Method modifications demonstrated

and documented to be within the

flexibility allowed by the streamlining

initiative would be preapproved by EPA

for use at the tier for which the

modification was validated. Stakeholder

remarks suggest that most laboratories

and method development organizations

would welcome and use this allowed

flexibility.

Stakeholders also have asked EPA to

approve more quickly revised versions

of approved methods that are

periodically published by EPA,

consensus standards organizations, and

other government agencies. In the past,

EPA approved these revisions through a

formal proposal and public comment

process. Using the flexibility provisions

of today’s rule, users would be able to

use a revised version of a reference

method as soon as it is published,

provided that the results produced were

demonstrated to meet the QC

acceptance criteria of the reference

method. This benefit alone would

relieve much stakeholder frustration,

decrease the Agency’s rulemaking

burden, and improve EPA’s partnership

with other government agencies and

consensus standards organizations.

Table II summarizes EPA’s review and

rulemaking responsibilities for new and

modified methods by tier.

TABLE II.—EPA REVIEW AND ACTION FOR NEW AND MODIFIED METHODS

New Method Modified Method

Tier 1, Single-lab ............................ EPA review required; EPA issues a letter of approval.No EPA review.

Tier 2, Multi-lab, single matrix type EPA review required; approved through rulemaking If requested, EPA reviews and

—issues letter of approval, or

—conducts rulemaking.

Tier 3, Multi-lab, multiple matrix

types.

EPA review required; approved through rulemaking If requested, EPA reviews and

—issues letter of approval, or

—conducts rulemaking.

1. Review and Approval of New

Methods

Currently, all new methods must be

approved by EPA through ‘‘formal’’ EPA

approval including rulemaking and

publication at 40 CFR part 136 or 141

before use. In today’s rule, EPA

proposes to grant letter approvals of

new methods that would be submitted

under Tier 1 (i.e., single-laboratory,

limited-use methods). New methods

developed for use under Tiers 2 or 3

would still require rulemaking. The

purpose for not requiring formal

rulemaking at Tier 1 would be to
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 14987

provide the means by which (1) a new

technology could be introduced, (2)

confidentiality of a new technology

could be maintained if desired by the

user of the new method, and (3) specific

matrix interference problems could be

overcome. Allowing use of Tier 1 new

methods would enable multiple single

laboratories to use a new technology

until a sufficient number of devices

were available for interlaboratory

validation as a Tier 2 or 3 new method.

EPA recognizes that allowing singlelaboratory use of a new technology for

regulatory compliance carries with it the

risk that results produced with the new

technology may not agree with results

produced by a reference method.

However, EPA believes that sufficient

controls would be included in the

streamlining program to ensure data

quality. EPA also believes that there

would be a net benefit to the regulated

community by allowing new

technologies that overcome matrix

interference problems. EPA solicits

comment on this aspect of streamlining,

and is particularly interested in

alternative ways EPA might allow

introduction of new technologies

without rulemaking.

2. Review and Approval of Modified

Methods

Under the streamlining initiative

proposed in today’s rule, method

modifications would not require formal

EPA approval; they would be

preapproved provided the analyst

demonstrates and documents

equivalency with or superiority to the

reference method QC criteria. Although

formal approval of a modification would

not be required under the streamlining

initiative, several stakeholders have

commented that, in practice, use of a

method modification would require the

consent of the regulated entity and

responsible regulatory authority. These

stakeholders also expressed concern

that without formal EPA approval,

obtaining consent from the regulated

entity and/or regulatory authority would

be difficult. In response to these

comments, EPA proposes to allow, but

not require, laboratories, industry

associations, consensus standards

organizations, instrument

manufacturers, and others to submit

Tier 2 or Tier 3 method modifications

for EPA review with the anticipation of

a letter from EPA documenting

approval. Also, for those seeking public

recognition that their Tier 2 or 3 method

modifications have been demonstrated

to be acceptable for use, EPA proposes

to work with the organization to

approve the method at 40 CFR part 136

or 141. EPA would not review, provide

letters of approval, or conduct formal

rulemaking for Tier 1 method

modifications.

EPA recognizes that preapproving

method modifications poses additional

burdens for regulatory authorities, who

may need to assess the reasonableness

and effectiveness of each modification.

EPA believes, however, that the

Checklists, certification statement, and

accompanying instructions, which are

proposed at 40 CFR part 136 Appendix

E, and the validation report for the

method modification, which is

proposed at 40 CFR part 136

Appendixes F and G, would provide a

regulatory authority the information

necessary to make equivalency

assessments, and that this information

would be presented in a standardized

and readily understandable format. To

further assist regulatory authorities in

implementing this initiative, EPA has

included detailed guidance on assessing

method modifications for equivalency.

This guidance is provided in Chapter 6

and in the appendixes of the

Streamlining Guide (EPA 1996a).

3. Submission Package

The items to be submitted to EPA for

proposal of a new method at Tier 2 or

3 would include the method validation

study report, which would include the

method prepared in a standard format.

If the submitter requested formal

rulemaking to propose the method for

publication in the CFR, information in

a format suitable for inclusion in a draft

preamble would also be required.

Additionally, the submission packet

would need to include all relevant

supporting documents.

To preclude a proliferation of

potentially confusing formats, a method

should be submitted in a standard

format. EPA recommends and specifies

the format that would be specified at 40

CFR part 136 Appendix F. This format

is also detailed in Method Guidelines

and Format (EPA 1996c). Appendix F

describes all elements of the format

prescribed by EPA’s Environmental

Monitoring Management Council

(EMMC). An objective of the EMMC

format is to standardize all Agency

analytical methods. A standardized

format used by a government agency

such as the U.S. Geological Survey or

from a consensus standards organization

such as Standard Methods, ASTM, or

AOAC-International could be used, but

EPA recommends that these formats be

reserved for those organizations to avoid

the possible confusion over authorship.

EPA would not accept methods in nonstandard formats because of the

confusion that could be created by a

proliferation of method formats.

A new method would need to include

the standardized QC elements and QC

acceptance criteria. The QC acceptance

criteria would need to be developed

from data gathered in the method

validation study. Chapter 3 of the

Streamlining Guide (EPA 1996a)

provides guidance on the detailed

technical requirements for developing

criteria that meet the requirements that

would be specified at 40 CFR 136.4,

136.5 and 141.27 and at 40 CFR part 136

Appendix E.

4. Regulatory Assistance Provided by

Submitter

Using procedures that would be

specified at 40 CFR part 136 Appendix

G, EPA would ask method submitters to

assist EPA by providing, as part of the

submission package for methods to be

proposed in the Federal Register,

information that would facilitate EPA’s

drafting of a proposed rule. EPA would

also ask submitters to provide technical

assistance, when necessary, in

responding to public comments on the

submitter’s method. Other assistance

could be requested by EPA. The

information should be submitted in a

format corresponding to the preamble

drafting conventions specified by the

Office of the Federal Register. Citations

of examples for preambles are given in

40 CFR part 136 Appendix G and in the

Streamlining Guide (EPA 1996a).

Instructions for drafting documents for

the Office of the Federal Register are

given in the Document Drafting

Handbook, for sale by the

Superintendent of Documents, Mail

Stop: SSOP, Washington, DC 20402–

9328 (Document 1993 O—351–677

QL3).

5. EPA Review of Submission Package

Upon receipt of a request for

approval, EPA would first check the

submission packet for completeness. If

all of the documentation was in order,

EPA would use an internal workgroup

to assess the scientific merit of the

method or modification and to evaluate

the validation study for consistency and

appropriateness. Should any problems

be identified, the workgroup would

contact the submitter to resolve the

outstanding issues. If these issues could

not be resolved, EPA would take no

further action on the submission. If all

validation requirements were met and

the submission passed internal review,

EPA would either issue a letter of

approval or begin the rulemaking

process. All method modifications are

preapproved, but a submitter would

have the option to request an EPA letter

of approval or to request a formal

rulemaking for Tier 2 and 3 method
14988 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

modifications. All new methods would

be subject to EPA review. For Tier 1

new methods, EPA would issue letter

approvals; Tier 2 and 3 new methods

would require formal Agency

rulemaking.

6. Proposal of Methods

For rulemaking, EPA would prepare

the proposed rule based on the draft

preamble provided by the submitter.

EPA would add the appropriate updates

to CFR tables or language and submit

the proposed rule to the Office of the

Federal Register for publication. The

proposed rule would request public

comment and allow a specified

comment period (typically 60 days after

publication in the Federal Register). At

the end of the comment period, EPA

would forward significant public

comments, if any, to the method

submitter. The submitter would need to

provide technical assistance to EPA in

drafting responses to the comments. If

the comments could not be adequately

addressed, EPA would not take final

action to approve the method. If all

comments are addressed, EPA (with

assistance from the submitter) would

need to complete a response-tocomments document and prepare a final

rule to approve the proposed method.

The final rule would state the date that

the rule becomes effective, typically 30

days after rule publication. As of this

effective date, the method would be

approved (promulgated) and the

appropriate tables in the CFR would be

updated.

To expedite approval of

noncontroversial updates to methods,

such as revisions to the methods

published by EPA, other government

organizations, and consensus standards

organizations, EPA intends to use

‘‘direct final’’ rulemaking. Direct final

rules would be warranted when the

action would not be expected to elicit

public comment to which the Agency

would normally respond (i.e., no

adverse comment). In this process, the

final rule and the companion proposal

would be published simultaneously as a

‘‘direct final rule’’ in the Federal

Register. In a direct final rule, the

proposed rule has a specific comment

period and the final rule has a later

effective date. If no adverse public

comments are received during the

comment period for the proposed rule,

the actions become effective on the

effective date of the final rule. If adverse

comment is received, the companion

final rule is withdrawn and a second

final rule that responds to the public

comments is prepared and published

with a new effective date.

E. Other Issues

1. Legal Impacts

Stakeholders expressed concern

regarding potential conflicts between

regulators and regulated entities when

using modified methods. For example,

there was widespread concern over a

situation in which a discharger used a

modified method and demonstrated

compliance with a regulatory

concentration limit while a regulatory

authority used the unmodified reference

method and obtained results suggesting

that the discharger was out of

compliance.

Based on internal EPA discussions, it

became apparent that the streamlining

initiative would work only if the

modified method, once demonstrated to

be equivalent to the reference method,

carried the same legal force and effect as

the reference method. Therefore, the

difference in results produced by the

modified and unmodified methods

would be attributable not to the

modification, but to differences in

results produced by two laboratories.

This situation is no different than the

existing situation where two

laboratories can produce different

results, one set of which is above and

the other below, a regulatory

compliance limit. The legal resolution

would therefore remain the same as

today—a decision would be made based

on examination of all the relevant data.

2. Method-Defined Analytes

The method flexibility introduced in

today’s proposal does not extend to

methods in which some part of the

method ‘‘defines’’ the analyte of

concern. This type of analyte is termed

a method-defined analyte. Because

method-defined analytes do not have a

specific, known composition, the result

of the analytical measurement depends

totally on how the measurement is

made. Examples of method-defined

analytes include adsorbable organic

halides, biochemical oxygen demand,

total organic carbon, and whole effluent

toxicity. Changes to the front-end steps

or the determinative techniques in these

methods have the potential of changing

the result produced. EPA believes,

however, that certain parts of

procedures for method-defined analytes

could be modified without adversely

affecting method performance.

3. Biological Methods

EPA intends to expand method

flexibility to include biological

methods, but not in today’s proposal.

Biological methods include both the

testing of an environmental sample for

the presence of microbiological material

(e.g., bacteria, protozoa and viruses) and

the use of biological organisms to

measure whole effluent toxicity (WET)

of an environmental sample. EPA

believes that flexibility in testing for

biological material would be similar to

the flexibility allowed in the

modification to chemical analytical

methods. Both the front-end and

determinative techniques should be able

to be modified when the modifications

produce equivalent or superior results.

EPA has protocols for some

microbiological methods that are

currently used in the ATP program (EPA

1995a, b). In a future rulemaking, EPA

may revise the microbiology protocols

to conform with streamlining and

method flexibility procedures. In

keeping with Agency goals for a more

performance-based approach to all

environmental measurements, EPA also

may develop and propose method

flexibility and new method approval

procedures for biological methods and

for microbiological parameters not

covered under current EPA protocols.

For WET methods, both new and

modified methods are possible. New

methods may involve the use of a

different taxonomic category other than

those currently listed at 40 CFR part

136. Method modifications may be

defined as the variation of one of the

established summary test conditions of

the method, such as temperature or

salinity. Method modifications to the

summary test conditions would not

change the acceptance criteria (e.g.,

control survival) which serve to identify

the standards of comparison of the

‘‘reference method.’’ EPA has not

sufficiently explored this issue to

propose the specific requirements to

allow flexibility in all approved

biological methods. Until EPA can

clarify the extent of acceptable

flexibility, requests for changes in

biological methods would be reviewed

and approved on an individual basis.

4. Proprietary Reagents, Instruments,

and Methods

Stakeholders expressed concern over

the role of proprietary components in

the streamlined water method approval

process. EPA separates proprietary

components into three categories:

proprietary reagents, proprietary

instruments, and proprietary methods.

EPA intends to attempt to accommodate

the inclusion of proprietary reagents

and instruments in the approval of

analytic methods for compliance

purposes to the extent that such

inclusion still provides an adequate

opportunity for public review and

comment under the Administrative

Procedure Act. EPA does not anticipate,
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 14989

however, that it could approve the use

of proprietary methods for determining

compliance with regulatory

requirements where the entire method is

claimed as ‘‘confidential business

information’’ because the opportunity

for public review and comment might

be restricted too severely. If a

proprietary method is patented, the

method would be considered for

approval as a compliance method

because the public would be able to

comment on the patented method. EPA

believes the restriction on approval of

proprietary methods is not serious

because reagents or instruments, not

complete methods, will continue to be

the most common proprietary

components used in compliance

methods.

Proprietary reagents and instruments

are currently included for use in

approved methods and would continue

to be allowed in approved methods. The

details of the proprietary elements

would need to be disclosed to EPA, but

would be withheld from the public if

the person requesting protection for the

confidential business information (CBI)

demonstrates that the information is

entitled to confidential treatment under

40 CFR part 2. Examples of proprietary

components may include immunoassay

reagents and antibodies and liquid

phases in GC columns; e.g., DB–1 ,

SPB-octyl, Dexsil ’’, etc. A new or

modified method submitted for EPA

approval would need to include

language stating that the proprietary

reagent or instrument could be replaced

by an equivalent. Changes made to the

method after EPA approval would

require the manufacturer to

demonstrate, through supporting

documentation, that the new proprietary

equipment, substance, or reagent would

produce results equal or superior to

results produced with the material

originally tested and on which the

method approval is based. Additionally,

EPA would not propose a method

containing a proprietary reagent without

accurate, specific instructions for

handling the reagent and for safe

disposal of each spent proprietary

reagent and/or reaction product. When

a material safety data sheet (MSDS)

would need to accompany the

proprietary material, the MSDS would

be the appropriate vehicle to provide

these instructions. Submission of a

complete MSDS with a new method

would satisfy EPA’s need for

instructions for safe handling and

disposal of the reagent.

5. Restrictions by Consensus Standards

Organizations

As envisioned, this initiative allows

modification to a reference method,

provided that the QC acceptance criteria

are met. Many of the methods approved

at 40 CFR parts 136 and 141 were

developed by consensus standard

organizations such as Standard

Methods, ASTM, and AOACInternational. EPA expects to rely on

these and other consensus standards

organizations for future methods, as

required by the National Technology

Transfer and Advancement Act of 1995

(NTTAA) and because of limited

Agency resources for method

development.

Consensus standards organizations

have expressed concern that a

modification to their methods would

constitute a violation of the method

being considered a ‘‘standard.’’

Standard Methods, ASTM, and AOACInternational have declined to allow

unlimited modification of their

approved methods and, therefore, their

methods could not serve as reference

methods nor be modified under the

procedures outlined in this initiative, as

can be seen in the proposed CFR tables.

This restriction would not greatly affect

the streamlining initiative because an

EPA method exists that would be used

as a reference method for nearly all

analytes, and because most methods

from consensus standards organizations

have sufficient internal flexibility to

meet the objectives of streamlining or

are updated frequently to reflect recent

advances in technologies.

6. Standard Data Format

For this proposed rule, EPA would

not establish a standard format for the

submission of analytical data because of

the large variety of formats currently in

use. However, EPA strongly

recommends the Department of Energy’s

Environmental Management Electronic

Data Deliverable Master Specification

(DEEMS) because it is comprehensive

and it would expedite processing of a

submitter’s request. DEEMS is a list of

data elements that laboratories should

submit to document the method

modification process. A DEEMS data

element dictionary is provided in the

Streamlining Guide (EPA 1996a).

7. Withdrawal of Outdated Methods

EPA also is considering withdrawal of

methods that the Agency believes are

obsolete or are no longer used. For

example, 40 CFR part 136, Table ID,

footnote 3, references methods

published in 1978 that include thinlayer chromatography (TLC) methods.

Because gas chromatography and high

performance liquid chromatography

methods provide better monitoring data

and are more cost effective, most, if not

all, laboratories no longer use TLC

methods. The TLC methods were

proposed for withdrawal in a previous

notice (60 FR 53988, October 18, 1995),

and EPA believes there may be similar

outdated methods. EPA is conducting a

careful examination of Tables IA

through IE of 40 CFR part 136 and of the

tables at 40 CFR part 141, for obsolete

or outdated methods, and intends to

propose withdrawal of those methods

for which newer methods are available.

8. Administrative Record: Organic

Methods, Streamlining Guide, and

Method Guidelines and Format

EPA specifies several 600- and 1600-

series analytical methods at 40 CFR part

136 Appendix A for analysis of organic

chemicals. If the Office of the Federal

Register approves incorporation by

reference of the Appendix A methods,

EPA will withdraw Appendix A and

publish all of these methods in the

document Methods for Organic

Chemical Analysis of Municipal and

Industrial Wastewater, December 1996,

EPA–821–B–96–005, NTIS PB97–

125298, ERIC D–A44/D–A47 (Organic

Methods, EPA 1996b). This document is

part of the administrative record for this

proposed rule; copies can be inspected

or obtained from NTIS or other sources

as described in the ADDRESSES section

above.

EPA also has drafted two guidance

documents that are an integral part of

the administrative record for this

proposed rule. The first document,

Guide to Method Flexibility and

Approval of EPA Water Methods,

December 1996 Draft, EPA–821–D–96–

004, PB97–117766 (Streamlining Guide,

EPA 1996a), provides detailed guidance

on the overall streamlining initiative.

The second document, Guidelines and

Format for Methods to Be Proposed at

40 CFR Part 136 or Part 141, EPA–821–

B–96–003, PB96–210448, July 1996

(Method Guidelines and Format, EPA

1996c), specifies the content and format

required for new methods developed by

outside organizations. These documents

are readily and widely available to the

public through NTIS, online, and other

sources listed in the ADDRESSES section

above.

The Streamlining Guide (EPA 1996a)

in particular was drafted to help method

developers use the procedures proposed

in today’s rule to validate and obtain

approval of new or modified methods.

The guidance was written for use by

laboratory auditors, permittees, water

utilities, regulatory authorities,
14990 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

purveyors of new technology, and

analytical laboratory personnel. The

document is organized into seven

chapters, some of which are procedural

and others are descriptive, as

appropriate to the topic. Chapter 1

summarizes the proposed streamlining

initiative. Chapter 2 describes the

proposed expanded method flexibility.

Chapter 3 describes the proposed

standard quality control tests and useful

statistical procedures for developing QC

acceptance criteria for new methods.

Chapter 4 describes the proposed tiered

system for validating a new method or

a method modification. Chapter 5

describes the proposed method approval

process, a standard method format, and

procedures for submitting validated

methods to EPA for approval. Chapter 6

provides guidance for assessing the

method equivalency. Chapter 7

describes possible future plans to

extend method flexibility to

microbiological and macrobiological

methods.

The Streamlining Guide (EPA 1996a)

also includes eight appendixes.

Appendix A provides a list of acronyms

and abbreviations. Appendix B provides

a glossary of terms used in the

streamlining initiative. Appendix C

provides examples of currently allowed

method modifications. Appendix D

contains a DEEMS data element

dictionary, which is a Department of

Defense reporting format that EPA

suggests would speed review of method

validation data. Appendix E provides

the EMMC method equivalency

checklists and certification statement.

Appendix F provides an example of a

completed Appendix E checklist.

Appendix G contains bibliographic

references. Appendix H describes EPA

derived the proposed QC acceptance

criteria for inorganic chemicals, which

are proposed at 40 CFR 136.3 Table IF

and 141.27(d)., were calculated.

EPA proposes to make some of the

information in the Streamlining Guide

(EPA 1996a) and Method Guidelines

and Format (EPA 1996c) a regulatory

requirement. Specifically, EPA proposes

to include much of the information in

Chapter 2 (Method Flexibility), Chapter

6 (Assessing Method Equivalency),

Chapter 5 (Method Approval Process)

and Appendix E (Equivalency

Checklists) as a requirement for

approval of drinking and wastewater

methods. EPA proposes to accomplish

this by designating the excerpts from

Chapters 2, 5 and 6 as 40 CFR part 136

Appendix G and the equivalency

checklists in Appendix E as 40 CFR part

136 Appendix E. Other provisions of the

Streamlining Guide (EPA 1996a),

including, but not limited to, Table 4–

2, definitions of standardized QC

elements, QC acceptance criteria for

inorganic chemicals, would also be

included at 40 CFR 136.2, 136.3 Table

IF, 136.4, 136.5, 141.2, and 141.27. EPA

would also adopt most of the provisions

in Method Guidelines and Format (EPA

1996c) as Appendix F at 40 CFR part

136. EPA invites public comment on

these two guidance documents and

solicits comments on whether

additional guidance in these documents

should be a regulatory requirement.

9. Coordination with Other Federal

Register Proposals

On October 18, 1995 (60 FR 53988),

EPA proposed to amend the list of

approved methods at 40 CFR part 136

by adding new or revised methods for

certain metal and inorganic analytes and

by adding method citations to Table IB

and amending the incorporation by

reference section accordingly. EPA also

proposed to withdraw approval of

certain outdated or rarely used

analytical methods, as well as certain

methods that require use of hazardous

or toxic reagents. As of today, EPA has

not promulgated a final rule

implementing the proposed actions.

The methods proposed for withdrawal

that relate to this streamlining initiative

are primarily the EPA 200-series flame

atomic absorption spectrophotometry

(FLAA) methods. Although approval of

the EPA FLAA methods is proposed to

be withdrawn, FLAA methods

published by ASTM, Standard Methods,

AOAC-International, and USGS would

remain approved and would remain

listed in 40 CFR 136.3, Table IB.

Withdrawal of approval of EPA FLAA

methods would remove these methods

as reference methods and would remove

the QC acceptance criteria associated

with these methods. The net impact

would be that there would be no FLAA

method against which modifications

would be made. EPA does not consider

this a serious limitation because four

FLAA methods (ASTM, Standard

Methods, AOAC-International, and

USGS) would remain approved for

nearly all metals and the flexibility

afforded by these methods should

adequately cover method modifications.

In 1997, EPA intends to amend the

regulations at parts 136 and 141, as

appropriate, to update outdated versions

of methods to versions published in the

19th edition of Standard Methods

(APHA 1995), the 1996 Annual Book of

ASTM Standards, Vols. 11.01 and 11.02

(ASTM 1996), and in EPA’s August

1995 manual titled, Methods for the

Determination of Organic Compounds

in Drinking Water—Supplement III

(EPA 1995c). If and when the provisions

of today’s rule are promulgated, EPA

expects to be able to list these 1995 and

1996 versions of the compliance

methods as approved methods in the

tables listed at 40 CFR parts 136 and

141. If inclusion of these more recent

versions would provide a basis to

change any of the QC acceptance criteria

for the reference methods, the public

would be notified and provided with

the opportunity to comment on the new

criteria.

10. Laboratory Certification and

Laboratory Auditing

Broad requirements for States to have

an approved laboratory certification

program for analysis of drinking water

samples are specified at 40 CFR

142.10(b)(3). EPA provides more

specific help to State certification

officers through written and verbal

guidance. To improve the uniformity of

these certification programs, some

laboratory certification officers, method

developers, and vendors have asked

EPA to provide more specific regulatory

requirements. Today’s rule responds to

these requests by proposing

standardized QC elements for all water

compliance methods at 40 CFR 136.2

and 141.2, and at Appendix G of 40 CFR

part 136. To standardize and facilitate

laboratory audits, EPA also would

recommend use of several detailed

checklists for auditing both modified

and unmodified methods. These

standardized checklists would be

specified at Appendix E of 40 CFR part

136. EPA understands that increasing

the analyst’s current flexibility to

modify steps in a compliance method

could make the conduct of laboratory

audits more difficult. However, EPA

believes that the proposal to specify

standardized QC elements for all

methods and to require that laboratories

use standardized checklists to document

and check method performance will

ameliorate these potential problems.

EPA invites public comment and is

especially interested in what additional

action, if any, the Agency should take to

facilitate the auditing of water

laboratories.

IV. Regulatory Analysis

A. Executive Order 12866

Under Executive Order 12866 [58 FR

51,735 (October 4, 1993)], the Agency

must determine whether the regulatory

action is ‘‘significant’’ and therefore

subject to OMB review and the

requirements of the Executive Order.

The Order defines ‘‘significant

regulatory action’’ as one that is likely

to result in a rule that may: (1) Have an

annual effect on the economy of $100
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 14991

million or more or adversely affect in a

material way the economy, a sector of

the economy, productivity, competition,

jobs, the environment, public health or

safety, or State, local, or tribal

governments or communities; (2) create

a serious inconsistency or otherwise

interfere with an action taken or

planned by another agency; (3)

materially alter the budgetary impact of

entitlements, grants, user fees, or loan

programs or the rights and obligations of

recipients thereof; or (4) raise novel

legal or policy issues arising out of legal

mandates, the President’s priorities, or

the principles set forth in the Executive

Order.

This regulation is not major because

it is intended to reduce costs through

flexibility and innovation. Therefore,

this regulation would not result in a cost

to the economy of $100 million or more;

would not result in a major increase in

costs or prices for consumers or

individual industries; and would not

have significant adverse effects on

competition, investment, innovation, or

international trade.

It has been determined that this rule

is not a ‘‘significant regulatory action’’

under the terms of Executive Order

12866 and is therefore not subject to

OMB review.

B. Unfunded Mandates

Title II of the Unfunded Mandates

Reform Act of 1995 (UMRA), Pub. L.

104–4, establishes requirements for

Federal agencies to assess the effects of

their regulatory actions on State, local,

and tribal governments and the private

sector. Under section 202 of the UMRA,

EPA generally must prepare a written

statement, including a cost-benefit

analysis, for proposed and final rules

with ‘‘Federal mandates’’ that may

result in expenditures to State, local,

and tribal governments, in the aggregate,

or to the private sector, of $100 million

or more in any one year. Before

promulgating an EPA rule for which a

written statement is needed, section 205

of the UMRA generally requires EPA to

identify and consider a reasonable

number of regulatory alternatives and

adopt the least costly, most costeffective or least burdensome alternative

that achieves the objectives of the rule.

The provisions of section 205 do not

apply when they are inconsistent with

applicable law. Moreover, section 205

allows EPA to adopt an alternative other

than the least costly, most cost-effective

or least burdensome alternative if the

Administrator publishes with the final

rule an explanation of why that

alternative was not adopted. Before EPA

establishes any regulatory requirements

that may significantly or uniquely affect

small governments, including tribal

governments, it must have developed

under section 203 of the UMRA a small

government agency plan. The plan must

provide for notifying potentially

affected small governments, enabling

officials of affected small governments

to have meaningful and timely input in

the development of EPA regulatory

proposals with significant Federal

intergovernmental mandates, and

informing, educating, and advising

small governments on compliance with

the regulatory requirements.

EPA has determined that this rule

does not contain a Federal mandate that

may result in expenditures of $100

million or more for State, local, and

tribal governments, in the aggregate, or

the private sector in any one year. EPA

has further determined that this rule

contains no regulatory requirements that

might significantly or uniquely affect

small governments. This rulemaking

should have minimal financial impact,

if any, on the current regulatory burden

imposed on regulated entities and

regulators because the rulemaking does

not establish any additional regulatory

requirements. The proposed rule simply

provides the option to modify approved

methods or propose new methods, if

desired. EPA believes that method

modifications and new methods would

not be used if not cost effective. Thus,

today’s rule is not subject to the

requirements of sections 202, 203, and

205 of the UMRA.

C. Regulatory Flexibility Act

The Regulatory Flexibility Act, 5

U.S.C. 601 et seq., requires EPA and

other agencies to prepare a final

regulatory flexibility analysis for

regulations that have a significant

impact on a substantial number of small

entities. This regulatory action does not

have any adverse impact on either small

or large entities. Therefore, a regulatory

flexibility analysis is not required.

Pursuant to section 605(b) of the

Regulatory Flexibility Act, 5 U.S.C.

605(b), the Administrator certifies that

this rule will not have a significant

economic impact on a substantial

number of small entities.

D. Paperwork Reduction Act

The information collection

requirements in this proposed rule will

be submitted for approval to the Office

of Management and Budget (OMB)

under the Paperwork Reduction Act, 44

U.S.C. 3501 et seq. shortly. EPA is

preparing an information collection

request (ICR) document for this

proposed rule and will solicit public

comment on it prior to promulgating a

final regulation. Comments on the

proposed rule, preamble, and ICR will

all be considered before a final rule is

promulgated. The information

collection requirements in this proposal

are described in Parts III.A (Method

Flexibility), III.B (Quality Control), III.C

(Method Validation), III.D (Method

Review), and III.E.6 (Standard Data

Format). The information collection

requirements in this proposal are

specified in Appendix E (Equivalency

Checklists), Appendix F (Guidelines

and Format for Methods) and Appendix

G (Method Flexibility, Equivalency, and

Approval) of 40 CFR part 136 and at 40

CFR 136.3(d); 136.4 (b) and (c); 136.5

(a), (b), (c), and (d); and at 40 CFR

141.27 (a), (b), and (c).

The information requirements are not

effective until OMB approves them. An

Agency may not conduct or sponsor,

and a person is not required to respond

to a collection of information unless it

displays a currently valid OMB control

number. The OMB control numbers for

EPA’s regulations are listed in 40 CFR

part 9 and 48 CFR chapter 15.

V. Request for Comments

A. General

EPA is interested in eliciting

constructive comments that would

allow the Agency to incorporate

flexibility into existing methods and to

streamline the proposal and

promulgation of new methods at 40 CFR

parts 136 and 141. On the other hand,

EPA is interested in compelling reasons

why such a program may not work, even

with extensive built-in controls to

ensure that the results produced by

modified or new analytical methods are

reliable. EPA looks forward to working

with all interested and concerned

parties to produce an improved system

for methods approval under the water

methods program.

B. Specific

EPA is soliciting public comment on

the following specific questions and

options that relate to technical and

policy decisions that EPA may need to

make to implement the streamlining

initiative.

1. As described in this preamble and

the Streamlining Guide (EPA 1996a), the

streamlining initiative would use a

performance-based approach in which a

reference method that contains or is

supplemented with QC acceptance

criteria is the standard against which a

method modification would be tested to

demonstrate equivalency. In contrast to

the proposed performance-based

reference-method approach, another

performance-based approach would be

to specify only the QC acceptance
14992 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

criteria without the need for a reference

method. Should EPA retain the

proposed reference method approach

with QC acceptance criteria? Or should

EPA change to a QC acceptance criteria

approach only?

2. Regarding question number one

above, for what analytes, methods or

monitoring situations, if any, do you

believe EPA should allow use of either

the performance-based reference

method approach or the QC acceptance

criteria only approach?

3. It may not be appropriate to

develop QC acceptance criteria to allow

modification of methods for ‘‘methoddefined parameters,’’ such as

biochemical oxygen demand or total

suspended solids. What chemical,

microbiological, or biological analytes

or analytical procedures do you believe

might not be amenable to streamlining

or method flexibility procedures?

4. Should EPA implement

streamlining and method flexibility

procedures only for new regulatory

actions? Should EPA apply these

procedures to existing regulatory

requirements but only when these

requirements are updated for some other

purpose? Or should EPA apply these

proposed procedures to existing

regulations now?

5. EPA has undertaken several pilot

studies of new methods to test the

streamlined method approval process,

and expects the pilots to be completed

prior to promulgation of a final rule.

Should EPA conduct more extensive

pilot studies, e.g., several pilots at each

tier, or should the changeover take place

as soon as possible? If a pilot or phasein approach is adopted, should EPA

phase-in by analyte group (e.g., VOCs,

metals, pesticides)? Or by the

technologies employed by the reference

method (electron capture, mass

spectrometry)?

6. Is the proposed flexibility to modify

the front-end and determinative steps in

a reference method broad enough to be

of value to the methods development

community? For what steps in a

reference method, if any, would you

increase or decrease the flexibility to

modify a method? If method flexibility

were broadened, what additional

standardized QC elements or checklist

items should be added to ensure and

document acceptable performance of the

modification?

7. If you believe that the proposed

flexibility is too broad for some

methods, would you prefer that EPA

limit flexibility by revising approved

methods to indicate the steps that could

or could not be changed? If yes, for

which steps in a method (e.g.,

extraction/digestion, concentration,

determinative) or for which types of

method (e.g., those with method-defined

analytes) should changes be allowed or

prohibited? If possible, please cite

methods listed in 40 CFR part 136 or

141 as examples.

8. If method flexibility were

implemented as proposed, are the

standardized QC elements (accuracy,

precision, detection limit, calibration,

reference sample, matrix spikes, etc.)

described in part III.C of this proposal

and in the Streamlining Guide (EPA

1996a) adequate to validate the

acceptability of a modification to a

reference method? If not, which QC

elements should be added? On the other

hand, are the QC elements too

extensive? If yes, which QC elements

should be deleted? And why?

9. There has been some concern about

the effect that changes to the chemistry

of a method may have on a laboratory

or method developer’s ability to validate

the performance of a modified method

using the Checklists and other

requirements in the Streamlining Guide

(EPA 1996a). For example, what effect,

if any, might changing the extraction

solvent have on extract holding times

that would not be picked up by the

Checklists’ criteria? What effect, if any,

might use of a different extraction

technique or a different solvent-tosample ratio have that would not be

picked up by the standardized QC?

What, if any, QC elements should be

changed or added to mitigate these

concerns?

10. Once EPA adopts streamlining

and method flexibility procedures,

should EPA continue to develop and

publish new methods or should EPA

rely on the private sector and consensus

standards organizations? In addressing

this question, please consider the effect

on small laboratories, PWSs, and

POTWs, if EPA discontinued providing

EPA methods.

11. EPA has determined that, for

wastewater programs, a modified

method, once validated and

documented in accordance with the

details in this proposal, would carry the

same force and legal effect as a reference

method. Do stakeholders believe that a

modified method should have equal

status with a reference method? Or

should EPA require different levels of

documentation for data gathered with

the modified method? If a modified

method had a different level of

documentation, would stakeholders

accept that it has legal status equal to

that of an unmodified method?

12. Should EPA change the QC

acceptance criteria in a reference

method when a significant technological

advance or some other factor

demonstrates that the criteria could be

made more rigorous? In your response,

you may assume that changing the

criteria would not adversely decrease

the number of qualified laboratories

needed to conduct compliance

monitoring with the more rigorous

method.

13. EPA plans to implement

streamlining and method flexibility for

water methods through informal

gathering of public comment and

through rulemaking (Federal Register

proposal, public comment, and final

rule), of which this proposal is a part.

Are there additional measures needed to

ensure that all stakeholders would be

aware of the initiative and, if so, what

additional steps should EPA take?

14. Given that a laboratory would be

able to modify a method without prior

EPA approval, how would current EPA

and state laboratory auditing and

certification programs continue to

ensure that the regulated community is

properly conducting monitoring

activities and documenting monitoring

system performance? Should

documentation be retained at the testing

laboratory? At the facility? Or should

EPA require that the data be submitted

to EPA or other regulatory authority

with each data package that results from

use of the modification?

15. Adoption of streamlining and

method flexibility procedures would

require a deeper understanding of the

science behind measurement methods.

Consequently, ‘‘first-line’’ compliance

and enforcement efforts may require

additional resources and training of

auditors. What training would EPA, the

Regions, the States, laboratories, and the

regulated community need to employ to

successfully implement streamlining or

method flexibility procedures? What

courses could be developed, and who

should be responsible for their

development?

16. Under the streamlining initiative,

requests for approval of new methods

(i.e., new technologies or determinative

techniques) would be submitted to EPA

under a streamlined ATP-type program.

Should EPA process these requests in

the order received or should EPA have

the discretion to accelerate review of

methods that provide the most benefit to

the Agency’s regulatory program and/or

to the needs of the regulated

community?

17. What additional steps, if any,

should the Agency take to ensure that

the use of method flexibility does not

compromise enforceability of applicable

statutes and regulatory requirements?

Will additional training be sufficient or

will inspectors need additional

qualifications to be able to assess the
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 14993

quality of CWA and SDWA compliance

data produced by a modified or new

reference method? What resources

would be required to mitigate concerns

about the need for appropriate training

of inspectors?

18. EPA proposes to define several

administrative (e.g., Assistant

Administrator, AMS Director) and

technical (e.g. screening method,

standardized quality control) terms in

the definitions at 40 CFR 136.2 and

141.2 and invites public comment on

these definitions. Should EPA omit any

of the proposed definitions to avoid

unnecessary confusion or restrictions?

Are there additional terms or concepts

for which a regulatory definition would

be useful in implementing and

administering EPA’s proposed methods

approval system?

19. EPA invites public comment on

the guidance contained in the

Streamlining Guide (EPA 1996a) and in

Method Guidelines and Format (EPA

1996c). These documents, which are

part of the administrative record for this

proposal, provide guidance on method

flexibility and method validation

procedures under the proposed

streamlining initiative. The documents

also provide examples of certification

statements and checklists that would

satisfy EPA’s proposed requirements for

documenting the performance and

equivalency of a modified or new

method. Portions of these documents

are proposed to be regulatory

requirements (for example, see the

proposed Appendixes E, F, and G and

other amendments to 40 CFR parts 136

and 141). Which, if any, of the proposed

requirements should EPA remove from

the regulations and only keep as

guidance?

20. In future rulemakings, EPA may

propose to make more of the

information in the two documents

described above regulatory

requirements. EPA would accomplish

this by amending the wastewater and

drinking water regulations or, with the

approval of the Office of the Federal

Register, incorporate by reference all or

parts of the Streamlining Guide (EPA

1996a) and Method Guidelines and

Format (EPA 1996c) into the CFR. What,

if any, additional guidance from these

documents should EPA propose as a

regulatory requirement?

VI. References

• APHA. 1995. Nineteenth edition of

Standard Methods for the Examination of

Water and Wastewater, 1992, American

Public Health Association, 1015 Fifteenth

Street NW, Washington, D.C. 20005.

• ASTM. 1996. Annual Book of ASTM

Methods, 1996, Vol. 11.01 and 11.02,

American Society for Testing and Materials,

101 Barr Harbor Drive, West Conshohocken,

PA 19428.

• EPA. 1995a. Protocol for Alternate Test

Procedures for Coliform Bacteria in

Compliance with Drinking Water

Regulations: Presence/Absence Liquid

Culture Methods for Finished Waters, Ver.

1.2, December 1995, U.S. Environmental

Protection Agency.

• EPA. 1995b. Protocol for Alternate Test

Procedures for Coliform Bacteria in

Compliance with Drinking Water

Regulations: Presence/Absence Membrane

Filter Methods for Finished Waters, Ver. 1.2,

December 1995, U.S. Environmental

Protection Agency.

• EPA. 1995c. Methods for the

Determination of Organic Compounds in

Drinking Water—Supplement III, EPA–600/

R–95–131, August 1995, NTIS PB95–261616.

• EPA. 1996a. Guide to Method Flexibility

and Approval of EPA Water Methods,

December 1996 Draft, EPA–821–D–96–004,

NTIS PB97–117766, ERIC D–A43/D–A46

(Streamlining Guide, EPA 1996a).

• EPA. 1996b. Methods for Organic

Chemical Analysis of Municipal and

Industrial Wastewater, December 1996, EPA–

821–B–96–005, NTIS PB97–125298, ERIC D–

A44/D–A47 (Organic Methods, EPA 1996b).

• EPA. 1996c. Guidelines and Format for

Methods to Be Proposed at 40 CFR Part 136

or Part 141, EPA–821–B–96–003, NTIS

PB96–210448, ERIC D–A42/D–A45, July 1996

(Method Guidelines and Format, EPA 1996c).

• EPA. 1996d. Draft Memorandum from

Assistant Administrators, ‘‘Implementation

Plan for the Agency Performance-Based

Measurement System,’’ October 25, 1996,

U.S. Environmental Protection Agency.

• EPA. 1996e. Memorandum from Robert

Perciasepe, ‘‘Agency-wide Adoption of the

Performance-Based Measurement System

Approach,’’ November 1, 1996, U.S.

Environmental Protection Agency.

List of Subjects

40 CFR Part 136

Environmental protection,

Laboratories, Water pollution control,

Reporting and recordkeeping

requirements.

40 CFR Part 141

Environmental protection,

Laboratories, Water supply, Reporting

and recordkeeping requirements.

Dated: March 17, 1997.

Carol M. Browner,

Administrator.

For the reasons set out in the

preamble, title 40 of the Code of Federal

Regulations is proposed to be amended

as set forth below:

PART 136—GUIDELINES

ESTABLISHING TEST PROCEDURES

FOR THE ANALYSIS OF POLLUTANTS

1. The authority for part 136 is

proposed to be revised to read as

follows:

Authority: Secs. 301, 304(h), 307, and

501(a), Pub. L. 95–217, 91 Stat. 1566, et seq.

(33 U.S.C. 1251, et seq.).

* * * * *

2. Section 136.2 is proposed to be

revised to read as follows:

§ 136.2 Definitions.

As used in this part, the term:

Accuracy means the degree of

agreement between an observed value

and an accepted reference value.

Accuracy includes random error

(precision) and systematic error (bias)

that are caused by sampling and

analysis.

Act means the Clean Water Act.

Administrator means the

Administrator of the U.S.

Environmental Protection Agency

(EPA).

Analyte or Analyte of concern means

a substance or property that is to be

measured by an analysis.

Approved method means a testing

procedure or analytical method

promulgated at this part or at 40 CFR

parts 405 through 500.

Assistant Administrator (AA) means

the EPA Assistant Administrator for

Water.

Calibration (CAL) means the process

of establishing the relationship between

the concentration or amount of material

introduced into an instrument or

measurement process and the output

signal.

Calibration linearity means the degree

to which calibration points lie along a

straight line.

Calibration verification means the

means of establishing that instrument

performance remains within preestablished limits.

Determinative technique means the

process (physical or chemical or both) to

measure the identity and concentration

of an analyte. In test methods, the

determinative technique follows the

front-end techniques.

Director means the Director of the

State Agency authorized to carry out an

approved National Pollutant Discharge

Elimination System Program under

section 402 of the Act.

Front-end technique means any

technique in the analytical process that

precedes the determinative technique,

including all procedures, equipment,

solvents, etc. that are used in the

laboratory in the preparation and

cleanup of a sample but this excludes

conditions and/or procedures for the

collection, preservation, shipment and

storage of the sample.

Initial precision and recovery test

(IPR) means analysis of a minimum of

four spiked replicate reference matrix

samples under the same conditions as
14994 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

will be used for analysis of

environmental samples. The IPR is used

to demonstrate that a laboratory is able

to produce reliable results with the

method prior to analysis of

environmental samples.

Interference means a positive or

negative effect on a measurement

caused by a substance other than the

analyte being determined.

Matrix means the component or

substrate that contains the target

analyte.

Matrix spike (MS) means a sample

prepared by adding a known quantity of

target analyte to a specified amount of

a sample matrix for which an

independent estimate of target analyte

concentration is available.

Matrix spike duplicate (MSD) means a

duplicate of the matrix spike. The MS/

MSD are used in combination to test the

precision of an analysis.

Matrix type means a sample medium

with common characteristics across a

given industrial category or industrial

subcategory. Examples include: C-stage

effluents from chlorine bleach mills in

the Pulp, Paper, and Paperboard

industrial category; effluent from the

continuous casting subcategory of the

Iron and Steel industrial category;

publicly owned treatment work (POTW)

sludge; and in-process streams in the

Atlantic and Gulf Coast Hand-shucked

Oyster Processing subcategory.

Medium means the physical phase of

a sample matrix. Air, water, soil,

sediment, rock, and sludge are sample

media.

Method means an orderly and

systematic arrangement of procedures

and techniques for performing an

analysis.

Method blank (or blank) means a

sample absent the analytes of interest

and interferences, which is processed

through all steps of a method

simultaneously with and under the

same conditions as samples that may

contain an analyte of interest.

Method detection limit (MDL) means

the minimum concentration of a

substance that can be measured and

reported with 99% confidence that the

analyte concentration is greater than

zero as determined by the procedure set

forth in appendix B of this part.

Method Guidelines and Format means

the procedures set forth in appendix F

of this part.

Method modification means a change

to a reference method. The change may

be to a front-end technique or to the

determinative technique.

Method validation means a process by

which a laboratory or vendor establishes

the performance of a new method or

substantiates the performance of a

method modification.

Minimum level (ML) means the lowest

level at which an entire analytical

system gives a recognizable signal and

acceptable calibration point for an

analyte. It is equivalent to the

concentration of the lowest calibration

standard, assuming that all methodspecified sample weights, volumes, and

clean-up procedures have been

employed.

National Pollutant Discharge

Elimination System (NPDES) means the

national system for the issuance of

permits under section 402 of the Clean

Water Act and includes any State or

interstate program which has been

approved by the Administrator, in

whole or in part, pursuant to section

402 of the Clean Water Act.

New method means a combination of

analyte of concern and determinative

technique that is different from those in

the approved methods.

Ongoing precision and recovery

sample (OPR) means a spiked reference

matrix sample that is processed through

all steps of a method simultaneously

with and under the same conditions as

samples that may contain an analyte of

interest. Also called a laboratory control

sample (LCS), the OPR/LCS is used to

demonstrate that a laboratory is able to

produce reliable results continuously.

Organic Methods means the

document titled: Methods for the

Determination of Organic Compounds

in Drinking Water—Supplement III

(available from the National Technical

Information Service (NTIS), U.S.

Department of Commerce, Springfield,

Virginia, 22161, 703/487–4600, at NTIS

publication PB97–125298).

Other approved method means a

promulgated method that is not

designated as a reference method.

Percent recovery means the recovery

multiplied by one hundred.

Person means an individual;

corporation; company; association;

partnership; municipality; or State,

Federal, or tribal agency.

Precision means the degree to which

a set of observations or measurements of

the same property, usually obtained

under similar conditions, conform.

Precision is usually expressed as

standard deviation, variance, or range,

in either absolute or relative terms.

Preparation means processing

performed on a sample prior to analysis,

including extraction, concentration, and

cleanup.

Procedure means a set of systematic

instructions for performing an activity.

Promulgated method means a method

that has been published or incorporated

by reference into 40 CFR parts 136 or

405 through 500.

Quality assurance (QA) means an

integrated system of activities involving

planning, quality control, quality

assessment, reporting, and quality

improvement to ensure that a product or

service meets defined standards of

quality with a stated level of confidence.

Quality control (QC) means the

overall system of technical activities

conducted to measure and control the

quality of a product or service so that it

meets the needs of a user. The purpose

of QC is to provide quality that is

satisfactory, adequate, dependable, and

economical.

Quality control acceptance criteria

(QC acceptance criteria) means

performance specifications developed

from validation data and used to control

the limits within which an analytical

method is operated.

Recovery means the total amount of

analyte found divided by the amount of

analyte added as a spike.

Reference method means an approved

method that is designated as a standard

to which a modified method can be

compared. A reference method includes

standardized QC and QC acceptance

criteria as well as sample preparation,

cleanup, and other procedures.

Regional Administrator means an EPA

Regional Administrator.

Screening method means a method

that employs a qualitative determinative

technique for an analyte of interest that

is different from the determinative

techniques used in the approved

methods for that analyte. The screening

method should produce a false negative

probability less than 1%.

Selectivity means the capability of a

method or instrument to respond to an

analyte in the presence of interferences.

Sensitivity means the capability of a

method or instrument to differentiate

between different amounts or

concentrations of an analyte.

Spike means the process of adding a

known amount of an analyte to a sample

to determine the recovery.

Spike amount means a known

quantity of analyte added to a sample

and used to determine the recovery of

a method.

Standard deviation means the

measure of the dispersion of observed

values expressed as the positive square

root of the sum of the squares of the

difference between the individual

values of a set and the arithmetic mean

of the set, divided by one less than the

number of values in the set.

Standardized quality control

(standardized QC) means a uniform set

of performance testing procedures that

ensure reliable results. Depending on
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 14995

the method, standardized QC

procedures include, but are not limited

to, the following: calibration, calibration

linearity, calibration verification,

absolute retention time, absolute and

relative retention time precision, initial

precision and recovery, ongoing

precision and recovery (laboratory

control sample), surrogate or labeled

compound recovery, analysis of blanks,

matrix spike and matrix spike duplicate

recovery and precision, demonstration

of method detection limit(s), and

analysis of a reference sample.

Surrogate means a substance with

properties that mimic the behavior of an

analyte, that is unlikely to be found in

an environmental sample, and that is

added to the sample for quality control

purposes.

Tier 1 means the application of a new

or modified method in a single

laboratory to one or more matrix types.

Tier 2 means the application of a new

or modified method by all laboratories

to one or more matrix types within a

single industrial category or

subcategory.

Tier 3 means the application of a new

or modified method by all laboratories

to all matrix types in all industrial

categories and subcategories

(nationwide use).

3. Section 136.3 is proposed to be

amended by revising the last two

sentences and Tables IB, IC, and ID in

paragraph (a); by adding Table IF in

paragraph (a); by revising paragraphs (c)

and (d); and by removing paragraph (e)

(Table II following paragraph (e) is

unchanged) to read as follows:

§ 136.3 Identification of test procedures.

* * * * *

(a) * * *

The discharge parameter values for

which reports are required must be

determined by one of the standard

analytical test procedures incorporated

by reference and described in Tables IA,

IB, IC, ID, and IE, or by any alternate test

procedure which has been approved by

the Administrator or Assistant

Administrator under the provisions of

paragraph (d) of this section and

§§ 136.4 and 136.5. Under paragraphs

(b), (c) of this section and 40 CFR 401.13

alternate test procedures may be used

when such other test procedures have

been previously approved by the

Administrator, Assistant Administrator,

or Regional Administrator of the Region

in which the discharge will occur, and

providing the Director of the State in

which such discharge will occur does

not object to the use of such alternate

test procedure. Standardized QC and QC

acceptance criteria for modifications of

the inorganic contaminant reference

methods in Table IB are specified in

Table IF.

* * * * *

TABLE IB.—LIST OF APPROVED INORGANIC TEST PROCEDURES

Parameter/methodology Reference

method 1, 35

Other approved methods

Standard methods

18th Ed.39 ASTM 39 USGS2, 39 AOAC—Intl.39 Other

1. Acidity, as CaCO3, mg/L:

Electrometric endpoint or phenolphthalein endpoint.305.1 2310 B(4a) D1067–92

2. Alkalinity, as CaCO3, mg/L:

Electrometric or Colorimetric titration to

pH 4.5, manual or automated.

310.1

310.2

2320 B D1067–92 I–1030–85

I–2030–85

973.43 3

3. Aluminum—Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration 36 ............................ 202.1 3111 D I–3051–85

AA furnace ............................................. 202.2 3113 B

Inductively Coupled Plasma/Atomic

Emission Spectrometry (ICP/AES).36.

5 200.7 3120 B

Direct Current Plasma (DCP) 36 ............. .................... D4190–82(88) AES0029 34

Colorimetric (Eriochrome cyanine R) .... .................... 3500–AI D

4. Ammonia (as N), mg/L:

Manual, distillation (at pH 9.5) 6 followed by:.350.2 4500–NH3 B 973.49 3

Nesslerization ........................................ 350.2 4500–NH3 C D1426–93(A) I–3520–85 973.49 3

Titration .................................................. 350.2 4500–NH3 E

Electrode ................................................ 350.3 4500–NH3 F or G D1426–93(B)

Automated phenate ............................... 350.1 4500–NH3 H I–4523–85

Automated electrode .............................. .................... 379–75WE7

5. Antimony—Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration 36 ............................ 204.1 3111 B

AA furnace ............................................. 204.2 3113 B

ICP/AES36 ............................................. 5 200.7 3120 B

6. Arsenic—Total,4 mg/L:

Digestion 4 followed by ........................... 206.5

AA gaseous hydride .............................. 206.3 3114 B 4.d D2972–93(B) I–3062–85

AA furnace ............................................. 206.2 3113 B D2972–93(C)

ICP/AES36 ............................................. 5 200.7 3120 B

Colorimetric (SDDC) .............................. 206.4 3500–As C D2972–93(A) I–3060–85

7. Barium—Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration 36 ............................ 208.1 3111 D I–3084–85

AA furnace ............................................. 208.2 3113 B D4382–91

ICP/AES36 ............................................. 5 200.7 3120 B

DCP36 .................................................... .................... AES0029 34

8. Beryllium—Total,4 mg/L; Digestion 4 followed by:
14996 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

TABLE IB.—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued

Parameter/methodology Reference

method 1, 35

Other approved methods

Standard methods

18th Ed.39 ASTM 39 USGS2, 39 AOAC—Intl.39 Other

AA direct aspiration ............................... 210.1 3111 D D3645–

93(88)(A)

I–3095–85

AA furnace ............................................. 210.2 3113 B D3645–

93(88)(B)

ICP/AES ................................................. 5 200.7 3120 B

DCP ....................................................... .................... D4190–82(88) AES0029 34

Colorimetric (aluminon) .......................... .................... 3500–Be D

9. Biochemical oxygen demand (BOD5), mg/

L:

Dissolved Oxygen Depletion ................. 405.1 5210 B I–1578–78 8 973.44 3 p. 17 9

10. Boron 37—Total, mg/L:

Colorimetric (curcumin) .......................... 212.3 4500–B B I–3112–85

ICP/AES ................................................. 5 200.7 3120 B

DCP ....................................................... .................... D4190–82(88) AES0029 34

11. Bromide, mg/L:

Titrimetric ............................................... 320.1 D1246–

82(88)(C)

I–1125–85 p. S44 10

12. Cadmium—Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration 36 ............................ 213.1 3111 B or C D3557–90

(A or B)

I–3135–85

or

I–3136–85

974.27 3 p. 37 9

AA furnace ............................................. 213.2 3113 B D3557–90(C)

ICP/AES36 ............................................. 5200.7 3120 B I–1472–85

DCP36 .................................................... .................... D4190–82(88) AES0029 34

Voltametry 11 .......................................... .................... D3557–90(C)

Colorimetric (Dithizone) ......................... .................... 3500–Cd D

13. Calcium-Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration ............................... 215.1 3111B 511–93(B) I–3152–85

ICP/AES ................................................. 5 200,7 3120 B

DCP ....................................................... .................... AES0029 34

Titrimetric (EDTA) .................................. 215.2 3500–Ca D 511–93(A)

14. Carbonaceous biochemical oxygen demand (CBOD5), mg/L12:

Dissolved Oxygen Depletion with nitrification inhibitor..................... 5210B

15. Chemical oxygen demand (COD), mg/L;

Titrimetric

410.1 5220 C D1252–88(A) I–3560–85 973.46 3 p. 17 9

410.2 I–3562–85

410.3

Spectrophotometric, manual or automated.410.4 5220 D D1252–88(B) I–3561–85 Notes 13 or

14

16. Chloride, mg/L:

Titrimetric (silver nitrate) ........................ .................... 4500–Cl¥B D512–89(B) I–1183–85

(Mercuric nitrate) .................................... 325.3 4500–Cl¥C D512–89(A) I–1184–85 973.51 3

Colorimetric, manual .............................. .................... I–1187–85

Automated (Ferricyanide) ...................... 325.1 or

325.2

4500–Cl¥E I–2187–85

17. Chlorine-Total residual, mg/L; Titrimetric:

Amperometric direct ............................... 330.1 4500–Cl D D1253–86(92)

Iodometric direct .................................... 330.3 4500–Cl B

Back titration ether end-point 15 ............. 330.2 4500–Cl C

DPD-FAS ............................................... 330.4 4500–Cl F

Spectrophotometric, DPD ...................... 330.5 4500–Cl G

or Electrode ........................................... .................... Note 16

18. Chromium VI dissolved, mg/L; 0.45 micron filtration followed by:

AA chelation-extraction .......................... 218.4 3111 C I–1232–85

Colorimetric (Diphenylcarbazide) ........... .................... 3500–Cr D D1687–92(A) I–1230–85

19. Chromium-Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration 36 ............................ 218.1 3111 B D1687–92(B) I–3236–85 974.27 3

AA chelation-extraction .......................... 218.3 3111 C

AA furnace ............................................. 218.2 3113 B D1687–92(C)

ICP/AES36 ............................................. 5 200.7 3120 B

DCP36 .................................................... .................... D4190–82(88) AES0029 34

Colorimetric (Diphenylcarbazide) ........... .................... 3500–Cr D
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 14997

TABLE IB.—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued

Parameter/methodology Reference

method 1, 35

Other approved methods

Standard methods

18th Ed.39 ASTM 39 USGS2, 39 AOAC—Intl.39 Other

20. Cobalt-Total,4 mg/L; Digestion 4 followed

by:

AA direct aspiration ............................... 219.1 3111 B or C D3558–90(A or

B)

I–3239–85 p. 37 9

AA furnace ............................................. 219.2 3113 B D3558–90(C)

ICP/AES ................................................. 5 200.7 3120B

DCP ....................................................... .................... D4190–82(88) AES0029 34

21. Color platinum cobalt units or dominant

wavelength, hue, luminance purity:

Colorimetric (ADMI) ............................... 110.1 2120 E Note 18

(Platinum cobalt) .................................... 110.2 2120 B I–1250–85

Spectrophotometric ................................ 110.3 2120 C

22. Copper—Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration 36 ............................ 5 220.1 3111 B or C D1688–90(A or

B

I–3270–85

or I–

3271–85

974.27 3 p. 37 9

AA furnace ............................................. 220.2 3113 B D1688–90(C)

ICP/AES36 ............................................. 5 200.7 3120 B

DCP36 .................................................... .................... D4190–82(88) AES0029 34

Colorimetric (Neocuproine) .................... .................... 3500–Cu D

(Bicinchoninate) ..................................... .................... Or E 8506 19

23. Cyanide—Total, mg/L:

Manual distillation with MgCl2 followed

by.

.................... 4500–CN C D2036–91(A)

Titrimetric ............................................... .................... 4500–CN D p. 22 9

Spectrophotometric, manual .................. 31335.2 4500–CN E D2036–91(A) I–3300–85

Automated 20 .......................................... 31335.3

24. Cyanide amenable to chlorination, mg/L:

Manual distillation with MgCl2 followed

by titrimetric or Spectrophotometric.

335.1 4500–CN G D2036–91(B)

25. Fluoride—Total, mg/L:

Manual distillation 6 followed by ............. .................... 4500–F B

Electrode, manual .................................. 340.2 4500–F C D1179–93(B)

Automated .............................................. .................... I–4327–85

Colorimetric (SPADNS) ......................... 340.1 4500–F D D1179–93(A)

Automated complexone ......................... 340.3 4500–F E

26. Gold—Total,4 mg/L; Digestion 4 followed

by:

AA direct aspiration ............................... 231.1 3111 B

AA furnace ............................................. 231.2

DCP ....................................................... .................... AES0029 34

27. Hardness—Total, as CaCO3, mg/L:

Automated colorimetric .......................... 130.1

Titrimetric (EDTA), or Ca plus Mg as

their carbonates, by inductively coupled plasma or AA direct aspiration.

(See Parameters 13 and 33)..

130.2 2340 B or C D1126–86(92) I–1338–85 973.52B3

28. Hydrogen ion (pH), pH units:

Electrometric measurement ................... 150.1 4500–H∂ B D1293–84(90)

(A or B)

I–1586–85 973.41 3

Automated electrode .............................. .................... 378–

75WA21

29. Iridium—Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration ............................... 235.1 3111 B

AA furnace ............................................. 235.2

30. Iron—Total,4 mg/L; Digestion 4 followed

by:

AA direct aspiration 36 ............................ 236.1 3111 B or C D1068–90

(A or B)

I–3381–85 974.27 3

AA furnace ............................................. 236.2 3113 B D1068–90(C)

ICP/AES36 ............................................. 5 200.7 3120 B

DCP36 .................................................... .................... D4190–82(88) AES0029 34

Colorimetric (Phenanthroline) ................ .................... 3500–Fe D D1068–90(C) 8008 22

31. Kjeldahl Nitrogen—Total, (as N), mg/L:

Digestion and distillation followed by .... 351.3 4500–NH3 B or C D3590–89(A)

Titration .................................................. 351.3 4500–NH3 E D3590–89(A) 973.48 3

Nesslerization ........................................ 351.3 4500–NH3 C D3590–89(A)
14998 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

TABLE IB.—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued

Parameter/methodology Reference

method 1, 35

Other approved methods

Standard methods

18th Ed.39 ASTM 39 USGS2, 39 AOAC—Intl.39 Other

Electrode ................................................ 351.3 4500–NH3 F or G

Automated phenate colorimetric ............ 351.1 I–4551–78 8

Semi-automated block digestor colorimetric.351.2 D3590–89(B)

Manual or block digestor Potentiometric 351.4 D3590–89(A)

32. Lead—Total,4 mg/L; Digestion 4 followed

by:

AA direct aspiration 36 ............................ 239.1 3111 B or C D3559–90

(A or B)

I–3399–85 974.27 3

AA furnace ............................................. 239.2 3113 B D3559–90(C)

ICP/AES36 ............................................. 5 200.7 3120 B

DCP36 .................................................... .................... D4190–82(88) AES0029 34

Voltametry 11 .......................................... .................... D3559–90(C)

Colorimetric (Dithizone) ......................... .................... 3500–Pb D

33. Magnesium—Total,4 mg/L;

Digestion 4 followed by:

AA direct aspiration ............................... 242.1 3111 B D511–93(B) I–3447–85 974.27 3

ICP/AES ................................................. 5 200.7 3120 B

DCP ....................................................... .................... AES0029 34

Gravimetric ............................................. .................... 3500–Mg D

34. Manganese—Total 4, mg/L; Digestion 4

followed by:

AA direct aspiration 36 ............................ 243.1 3111 B D858–90

(A or B)

I–3454–85 974.27 3

AA furnace ............................................. 243.2 3113 B D858–90(C)

ICP/AES36 ............................................. 200.7 3120 B

DCP36 .................................................... 5 200.7 3120 B AES0029 34

Colorimetric (Persulfate) ........................ .................... 3500–Mn D 920.203 3

(Periodate) ............................................. .................... 8034 23

35. Mercury—Total4, mg/L:

Cold vapor, manual ............................... 245.1 3112 B D3223–91 I–3462–85 977.22 3

Automated .............................................. 245.2

36. Molybdenum—Total 4, mg/L; Digestion 4

followed by:

AA direct aspiration ............................... 246.1 3111 D I–3490–85

AA furnace ............................................. 246.2 3113 B

ICP/AES ................................................. 5 200.7 3120 B

DCP ....................................................... .................... AES0029 34

37. Nickel—Total 4, mg/L; Digestion 4 followed by:

AA direct aspiration 36 ............................ 249.1 3111 B or C D1886–90

(A or B)

I–3499–85

AA furnace ............................................. 249.2 3113 B D1886–90(C)

ICP/AES36 ............................................. 5 200.7 3120 B

DCP36 .................................................... .................... D4190–82(88) AES0029 34

Colorimetric (heptoxime) ........................ .................... 3500–Ni D

38. Nitrate (as N), mg/L:

Colorimetric (Brucine sulfate), or Nitrate-nitrite N minus Nitrite N (See

parameters 39 and 40).

352.1 973.50 3 419 D 17, p.

28 9

39. Nitrate-nitrite (as N), mg/L:

Cadmium reduction, manual .................. 353.3 4500–NO3

¥ E D3867–90(B)

Automated .............................................. 353.2 4500–NO3

¥F D3867–90(A) I–4545–85

Automated hydrazine ............................. 353.1 4500–NO3

¥H

40. Nitrite (as N), mg/L; Spectrophotometric:

Manual ................................................... 354.1 4500–NO2

¥ B 8507 25

Automated (Diazotization) ..................... .................... I–4540–85

41. Oil and grease—Total recoverable, mg/

L:

Gravimetric (extraction) ......................... 413.1 5520 B38

42. Organic carbon—Total (TOC), mg/L:

Combustion or oxidation ........................ 415.1 5310 B, C, or D D2579–93

(A or B)

973.47 3 p. 14 24

43. Organic nitrogen (as N), mg/L:

Total Kjeldahl N (Parameter 31) minus

ammonia N (Parameter 4)..

....................

44. Orthophosphate (as P), mg/L Ascorbic

acid method:

Automated .............................................. 365.1 4500–P F I–4601–85 973.56 3
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 14999

TABLE IB.—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued

Parameter/methodology Reference

method 1, 35

Other approved methods

Standard methods

18th Ed.39 ASTM 39 USGS2, 39 AOAC—Intl.39 Other

Manual single reagent ........................... 365.2 4500–P E D515–88(A) 973.55 3

Manual two reagent ............................... 365.3

45. Osmium—Total 4, mg/L; Digestion4 followed by:

AA direct aspiration ............................... 252.1 3111 D

AA furnace ............................................. 252.2

46. Oxygen, dissolved, mg/L:

Winkler (Azide modification) .................. 360.2 4500–O C D888–92(A) I–1575–78 8 973.45B3

Electrode ................................................ 360.1 4500–O G D888–92(B) I–1576–78 8

47. Palladium—Total 4, mg/L; Digestion 4 followed by:

AA direct aspiration ............................... 253.1 3111 B p. S27 10

AA furnace ............................................. 253.2 p. S28 10

DCP ....................................................... .................... AES0029 34

48. Phenols, mg/L:

Manual distillation 26 ............................... 420.1 Note 27

Followed by:

Colorimetric (4AAP) manual ........... 420.1 Note 27

Automated 19 ................................... 420.2

49. Phosphorus (elemental), mg/L:

Gas-liquid chromatography .................... .................... Note 28

50. Phosphorus—Total, mg/L:

Persulfate digestion followed by ............ 365.2 4500–P B,5 973.55 3

Manual ................................................... 365.2 or

365.3

4500–P E D515–88(A)

Automated ascorbic acid reduction ....... 365.1 4500–P F I–4600–85 973.56 3

Semi-automated block digestor ............. 365.4 D515–88(B)

51. Platinum—Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration ............................... 255.1 3111 B

AA furnace ............................................. 255.2

DCP ....................................................... .................... AES0029 34

52. Potassium—Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration ............................... 258.1 3111 B I–3630–85 973.53 3

ICP/AES ................................................. 5 200.7 3120 B

Flame photometric ................................. .................... 3500–K D

Colorimetric ............................................ .................... 317 B17

53. Residue—Total, mg/L:

Gravimetric, 103°–105° .......................... 160.3 2540 B I–3750–85

54. Residue—filterable, mg/L: 160.1

Gravimetric, 180° ................................... .................... 2540 C I–1750–85

55. Residue—nonfilterable (TSS), mg/L:

Gravimetric, 103°–105° post washing of

residue.

160.2 2540 D I–3765–85

56. Residue—settleable, mg/L:

Volumetric, (Imhoff cone), or

gravimetric.

160.5 2540 F

57. Residue—Volatile, mg/L:

Gravimetric, 550° ................................... 160.4 I–3753–85

58. Rhodium—Total 4 mg/L; Digestion 4 followed by:

AA direct aspiration ............................... 265.1 3111 B

AA furnace ............................................. 265.2

59. Ruthenium—Total 4 mg/L; Digestion 4 followed by:

AA direct aspiration ............................... 267.1 3111 B

AA furnace ............................................. 267.2

60. Selenium—Total 4 mg/L; Digestion 4 followed by:

AA furnace ............................................. 270.2 3113 B D3859–93(B)

ICP/AES36 ............................................. 5 200.7 3120 B

AA gaseous hydride .............................. .................... 3114 B D3859–93(A) I–3667–85

61. Silica 37—Dissolved, mg/L; 0.45 micron

filtration followed by:

Colorimetric, manual .............................. 370.1 4500–Si D D859–88 I–1700–85

Automated (Molybdosilicate) ................. .................... I–2700–85

ICP ......................................................... 5 200.7 3120 B

62. Silver—Total 4, mg/L; Digestion 4, 29 followed by:
15000 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

TABLE IB.—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued

Parameter/methodology Reference

method 1, 35

Other approved methods

Standard methods

18th Ed.39 ASTM 39 USGS2, 39 AOAC—Intl.39 Other

AA direct aspiration ............................... 272.1 3111 B or C I–3720–85 974.27 3 p. 37 9

AA furnace ............................................. 272.2 3113 B

ICP/AES ................................................. 5 200.7 3120 B

DCP ....................................................... .................... AES0029 34

63. Sodium-Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration ............................... 273.1 3111 B I–3735–85 973.54 3

ICP/AES ................................................. 5 200.7 3120 B

DCP ....................................................... .................... AES0029 34

Flame photometric ................................. .................... 3500 Na D

64. Specific conductance, micromhos/cm at

25 °C:

Wheatstone bridge ................................. 120.1 2510 B D1125–91(A) I–1780–85 973.40 3

65. Sulfate (as SO4), mg/L:

Automated colorimetric (barium

chloranilate).

375.1

Gravimetric ............................................. 375.3 4500–SO4

¥2C or

D

925.54 3

Turbidimetric .......................................... 375.4 D516–90 426C 30

66. Sulfide (as S), mg/L:

Titrimetric (iodine) .................................. 376.1 4500–S¥2E I–3840–85

Colorimetric (methylene blue) ................ 376.2 4500–S¥2D

67. Sulfite (as SO3), mg/L:

Titrimetric (iodine-iodate) ....................... .................... 377.1 4500–SO3¥2B

68. Surfactants, mg/L:

Colorimetric (methylene blue) ................ 425.1 5540 C D2330–88

69. Temperature, °C:

Thermometric ......................................... 170.1 2550 B Note 32

70. Thallium—Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration ............................... 279.1 3111 B

AA furnace ............................................. 279.2

ICP/AES ................................................. 5 200.7 3120 B

71. Tin—Total,4 mg/L; Digestion 4 followed

by:

AA direct aspiration ............................... 282.1 3111 B I–3850–78 8

AA furnace ............................................. 282.2 3113 B

ICP/AES ................................................. 5 200.7

72. Titanium—Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration ............................... 283.1 3111 D

AA furnace ............................................. 283.2

DCP ....................................................... .................... AES0029 34

73. Turbidity, NTU:

Nephelometric ........................................ 180.1 2130 B D1889–88(A) I–3860–85

74. Vanadium—Total,4 mg/L; Digestion 4 followed by:

AA direct aspiration ............................... 286.1 3111 D

AA furnace ............................................. 286.2 D3373–93

ICP/AES ................................................. 5 200.7 3120 B

DCP ....................................................... .................... D4190–82(88) AES0029 34

Colorimetric (Gallic acid) ....................... .................... 3500–V D

75. Zinc—Total,4 mg/L; Digestion 4 followed

by:

AA direct aspiration 36 ............................ 289.1 3111 B or C D1691–90(A or

B)

I–3900–85 974.27 3 p. 37 9

AA furnace ............................................. 289.2

ICP/AES36 ............................................. 5 200.7 3120 B

DCP36 .................................................... .................... D4190–82(88) AES00290 34

Colorimetric (Dithizone) ......................... .................... 3500-Zn E

(Zincon) .................................................. .................... 3500–Zn F 8009 33

Table IB notes:

1 ‘‘Methods for Chemical Analysis of Water and Wastes’’, Environmental Protection Agency, Environmental Monitoring Systems Laboratory-Cincinnati (EMSL–CI), EPA–600/4–79–020, Revised March 1983 and 1979 where applicable. 2Fishman, M.J., et al. ‘‘Methods for Analysis of Inorganic Substances in Water and Fluvial Sediments’’, U.S. Department of the Interior, Techniques of Water—Resource Investigations of the U.S. Geological Survey, Denver, CO, Revised 1989, unless otherwise stated. 3 ‘‘Official Methods of Analysis of the Association of Official Analytical Chemists’’, methods manual, 15th ed. (1990).
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15001

4For the determination of total metals the sample is not filtered before processing. A digestion procedure is required to solubilize suspended

material and to destroy possible organic-metal complexes. Two digestion procedures are given in ‘‘Methods for Chemical Analysis of Water and

Wastes, 1979 and 1983’’. One (Section 4.1.3), is a vigorous digestion using nitric acid. A less vigorous digestion using nitric and hydrochloric

acids (Section 4.1.4) is preferred; however, the analyst should be cautioned that this mild digestion may not suffice for all sample types. Particularly, if a colorimetric procedure is to be employed, it is necessary to ensure that all organo-metallic bonds be broken so that the metal is in a reactive state. In those situations, the vigorous digestion is to be preferred making certain that at no time does the sample go to dryness. Samples

containing large amounts of organic materials may also benefit by this vigorous digestion, however, vigorous digestion with concentrated nitric

acid will convert antimony and tin to insoluble oxides and render them unavailable for analysis. Use of ICP/AES as well as determinations for

certain elements such as antimony, arsenic, the noble metals, mercury, selenium, silver, tin, and titanium require a modified sample digestion

procedure and in all cases the method write-up should be consulted for specific instructions and/or cautions.

NOTE: If the digestion procedure for direct aspiration AA included in one of the other approved references is different than the above, the EPA

procedure must be used.

Dissolved metals are defined as those constituents which will pass through a 0.45 micron membrane filter. Following filtration of the sample,

the referenced procedure for total metals must be followed. Sample digestion of the filtrate for dissolved metals (or digestion of the original sample solution for total metals) may be omitted for AA (direct aspiration or graphite furnace) and ICP analyses, provided the sample solution to be

analyzed meets the following criteria:

a. has a low COD (<20),

b. is visibly transparent with a turbidity measurement of 1 NTU or less,

c. is colorless with no perceptible odor, and

d. is of one liquid phase and free of particulate or suspended matter following acidification.

5The full text of Method 200.7, ‘‘Inductively Coupled Plasma Atomic Emission Spectrometric Method for Trace Element Analysis of Water and

Wastes’’, is given at Appendix C of this Part 136. 6 Manual distillation is not required if comparability data on representative effluent samples are on company file to show that this preliminary

distillation step is not necessary: however, manual distillation will be required to resolve any controversies. 7Ammonia, Automated Electrode Method, Industrial Method Number 379–75 WE, dated February 19, 1976, Bran & Luebbe (Technicon) Auto

Analyzer II, Bran & Luebbe Analyzing Technologies, Inc., Elmsford, N.Y. 10523. 8The approved method is that cited in ‘‘Methods for Determination of Inorganic Substances in Water and Fluvial Sediments’’, USGS TWRI,

Book 5, Chapter A1 (1979). 9American National Standard on Photographic Processing Effluents, Apr. 2, 1975. Available from ANSI, 1430 Broadway, New York, NY 10018.

10 ‘‘Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency’’, Supplement to the Fifteenth Edition of Standard Methods for the Examination of Water and Wastewater (1981). 11The use of normal and differential pulse voltage ramps to increase sensitivity and resolution is acceptable. 12 Carbonaceous biochemical oxygen demand (CBOD5) must not be confused with the traditional BOD5 test which measures ‘‘total BOD’’. The

addition of the nitrification inhibitor is not a procedural option, but must be included to report the CBOD5 parameter. A discharger whose permit

requires reporting the traditional BOD5 may not use a nitrification inhibitor in the procedure for reporting the results. Only when a discharger’s

permit specifically states CBOD5 is required can the permittee report data using the nitrification inhibitor. 13OIC Chemical Oxygen Demand Method, Oceanography International Corporation, 1978, 512 West Loop, P.O. Box 2980, College Station, TX

77840. 14 Chemical Oxygen Demand, Method 8000, Hach Handbook of Water Analysis, 1979, Hach Chemical Company, P.O. Box 389, Loveland, CO

80537. 15The back titration method will be used to resolve controversy. 16Orion Research Instruction Manual, Residual Chlorine Electrode Model 97–70, 1977, Orion Research Incorporated, 840 Memorial Drive,

Cambridge, MA 02138. The calibration graph for the Orion residual chlorine method must be derived using a reagent blank and three standard

solutions, containing 0.2, 1.0, and 5.0 mL 0.00281 N potassium iodate/100 mL solution, respectively. 17The approved method is that cited in Standard Methods for the Examination of Water and Wastewater, 14th Edition, 1976. 18 National Council of the Paper Industry for Air and Stream Improvement, (Inc.) Technical Bulletin 253, December 1971. 19 Copper, Biocinchoinate Method, Method 8506, Hach Handbook of Water Analysis, 1979, Hach Chemical Company, P.O. Box 389, Loveland,

CO 80537. 20After the manual distillation is completed, the autoanalyzer manifolds in EPA Methods 335.3 (cyanide) or 420.2 (phenols) are simplified by

connecting the re-sample line directly to the sampler. When using the manifold setup shown in Method 335.3, the buffer 6.2 should be replaced

with the buffer 7.6 found in Method 335.2. 21 Hydrogen ion (pH) Automated Electrode Method, Industrial Method Number 378–75WA, October 1976, Bran & Luebbe (Technicon)

Autoanalyzer II. Bran & Luebbe Analyzing Technologies, Inc., Elmsford, NY 10523. 22 Iron, 1,10-Phenanthroline Method, Method 8008, 1980, Hach Chemical Company, P.O. Box 389, Loveland, CO 80537. 23 Manganese, Periodate Oxidation Method, Method 8034, Hach Handbook of Wastewater Analysis, 1979, pages 2–113 and 2–117, Hach

Chemical Company, Loveland, CO 80537. 24Wershaw, R.L., et al, ‘‘Methods for Analysis of Organic Substances in Water’’, Techniques of Water-Resources Investigation of the U.S. Geological Survey, Book 5, Chapter A3, (1972 Revised 1987) p. 14. 25 Nitrogen, Nitrite, Method 8507, Hach Chemical Company, P.O. Box 389, Loveland, CO 80537. 26 Just prior to distillation, adjust the sulfuric-acid-preserved sample to pH 4 with 1+9 NaOH. 27The approved method is cited in Standard Methods for the Examination of Water and Wastewater, 14th Edition. The colorimetric reaction is

conducted at a pH of 10.0±0.2. The approved methods are given on pp. 576–81 of the 14th Edition: Method 510A for distillation, Method 510B

for the manual colorimetric procedure, or Method 510C for the manual spectrophotometric procedure. 28 R.F. Addison and R.G. Ackman, ‘‘Direct Determination of Elemental Phosphorus by Gas-Liquid Chromatography’’, Journal of Chromatography, Vol. 47, No. 3, pp. 421–426, 1970. 29Approved methods for the analysis of silver in industrial wastewaters at concentrations of 1 mg/L and above are inadequate where silver exists as an inorganic halide. Silver halides such as the bromide and chloride are relatively insoluble in reagents such as nitric acid but are readily

soluble in an aqueous buffer of sodium thiosulfate and sodium hydroxide to pH of 12. Therefore, for levels of silver above 1 mg/L, 20 mL of sample should be diluted to 100 mL by adding 40 mL each of 2 M Na2S2O3 and NaOH. Standards should be prepared in the same manner. For levels of silver below 1 mg/L the approved method is satisfactory. 30The approved method is that cited in Standard Methods for the Examination of Water and Wastewater, 15th Edition. 31EPA Methods 335.2 and 335.3 require the NaOH absorber solution final concentration to be adjusted to 0.25 N before colorimetric determination of total cyanide. 32Stevens, H.H., Ficke, J.F., and Smoot, G.F., ‘‘Water Temperature—Influential Factors, Field Measurement and Data Presentation’’, Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 1, Chapter D1, 1975. 33Zinc, Zincon Method, Method 8009, Hach Handbook of Water Analysis, 1979, pages 2–231 and 2–333, Hach Chemical Company, Loveland,

CO 80537. 34 ‘‘Direct Current Plasma (DCP) Optical Emission Spectrometric Method for Trace Elemental Analysis of Water and Wastes, Method

AES0029’’, 1986—Revised 1991, Fison Instruments, Inc., 32 Commerce Center, Cherry Hill Drive, Danvers, MA 01923. 35Precision and recovery statements for the atomic absorption direct aspiration and graphite furnace methods, and for the spectrophotometric

SDDC method for arsenic are provided in Appendix D of this part titled, ‘‘Precision and Recovery Statements for Methods for Measuring Metals’’. 36 ‘‘Closed Vessel Microwave Digestion of Wastewater Samples for Determination of Metals’’, CEM Corporation, P.O. Box 200, Matthews, NC

28106–0200, April 16, 1992. Available from the CEM Corporation. 37When determining boron and silica, only plastic, PTFE, or quartz sampling and laboratory ware may be used from time of collection until

completion of analysis.
15002 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

38Only the trichlorofluoromethane extraction solvent is approved. 39 Methods published by this organization and approved for use under this part may not be modified beyond the modifications expressly allowed and defined in each method.

TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS

Parameter 1/methodology Reference

method 27

Other approved methods

Standard

methods 18th

Ed.8

ASTM 8 Other

1. Acenaphthene:

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B D4657–92

2. Acenaphthylene:

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B D4657–92

3. Acrolein:

GC/FID .......................................................................................................... 603

GC/MS ........................................................................................................... 4 604

GC/MS/Isotope .............................................................................................. 1624

4. Acrylonitrile:

GC/FID .......................................................................................................... 603

GC/MS ........................................................................................................... 4 624

GC/MS/Isotope .............................................................................................. 1624

HPLC/UV ....................................................................................................... 610

5. Anthracene:

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B D4657–92

6. Benzene:

GC/PID .......................................................................................................... 602 7220 B

GC/MS ........................................................................................................... 624

GC/MS/Isotope .............................................................................................. 1624

HPLC/UV ....................................................................................................... ....................

7. Benzidine: Note 3, p. 1.

GC/MS ........................................................................................................... 5 625

GC/MS/Isotope .............................................................................................. 1625

HPLC/ELCD .................................................................................................. 605

8. Benzo(a)anthracene:

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6440 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B D4657–92

9. Benzo(a)pyrene:

GC/FID .......................................................................................................... 610 6410 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B D4657–92

10. Benzo(b)fluoranthene:

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B D4657–92

11. Benzo(g, h, i)perylene:

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B D4657–92

12. Benzo(k)fluoranthene:

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B D4657–92

13. Benzyl chloride ............................................................................................... .................... Note 3, p. 130:

Note 6, p.

S102.

14. Benzyl butyl phthalate:

GC/ECD ......................................................................................................... 606

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15003

TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued

Parameter 1/methodology Reference

method 27

Other approved methods

Standard

methods 18th

Ed.8

ASTM 8 Other

15. Bis(2-chloroethoxy) methane:

GC/ELCD ....................................................................................................... 611

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

16. Bis(2-chloroethyl) ether:

GC/ELCD ....................................................................................................... 611

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

17. Bis (2-ethylhexyl) phthalate:

GC/ECD ......................................................................................................... 606 6230 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

18. Bromodichloromethane:

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

19. Bromoform:

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

20. Bromomethane:

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6410 B

GC/MS/Isotope .............................................................................................. 1624

21. 4-Bromophenylphenyl ether:

GC/ELCD ....................................................................................................... 611

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

22. Carbon tetrachloride: Note 3, p. 130.

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6410 B

GC/MS/Isotope .............................................................................................. 1624

23. 4-Chloro-3-methylphenol:

GC/FID .......................................................................................................... 604 6420 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

24. Chlorobenzene: Note 3, p. 130.

GC/ELCD ....................................................................................................... 601 6230 B

GC/PID .......................................................................................................... 602 6220 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

25. Chloroethane:

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

26. 2-Chloroethylvinyl ether:

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

27. Chloroform: Note, p. 130.

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

28. Chloromethane:

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

29. 2-Chloronaphthalene:

GC/ECD ......................................................................................................... 612

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

30. 2-Chlorophenol:

GC/FID .......................................................................................................... 604 6420 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

31. 4-Chlorophenylphenyl ether:

GC/ELCD ....................................................................................................... 611

GC/MS ........................................................................................................... 625 6410 B
15004 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued

Parameter 1/methodology Reference

method 27

Other approved methods

Standard

methods 18th

Ed.8

ASTM 8 Other

GC/MS/Isotope .............................................................................................. 1625

32. Chrysene:

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B D4657–92

33. Dibenzo(a,h)anthracene:

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B D4657–92

34. Dibromochloromethane:

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

35. 1,2-Dichlorobenzene:

GC/ELCD ....................................................................................................... 601 6230 B

GC/PID .......................................................................................................... 602 6220 B

GC/ECD ......................................................................................................... 612

GC/MS ........................................................................................................... 624, 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

36. 1,3-Dichlorobenzene:

GC/ELCD ....................................................................................................... 601 6230 B

GC/PID .......................................................................................................... 602 6220 B

GC/ECD ......................................................................................................... 612

GC/MS ........................................................................................................... 624, 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

37. 1,4-Dichlorobenzene:

GC/ELCD ....................................................................................................... 601 6230 B

GC/PID .......................................................................................................... 602 6220 B

GC/ECD ......................................................................................................... 612

GC/MS ........................................................................................................... 624, 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

38. 3,3-Dichlorobenzidine:

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/ELCD .................................................................................................. 605

39. Dichlorodifluoromethane:

GC/ELCD ....................................................................................................... 601 6230 B

40. 1,1-Dichloroethane:

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

41. 1,2-Dichloroethane:

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

42. 1,1-Dichloroethene:

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

43. trans-1,2-Dichloroethene:

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

44. 2,4-Dichlorophenol:

GC/FID .......................................................................................................... 604 6420 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

45. 1,2-Dichloropropane:

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

46. cis-1,3-Dichloropropene:

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

47. trans-1,3-Dichloropropene:
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15005

TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued

Parameter 1/methodology Reference

method 27

Other approved methods

Standard

methods 18th

Ed.8

ASTM 8 Other

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

48. Diethyl phthalate:

GC/ECD ......................................................................................................... 606

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

49. 2,4-Dimethylphenol:

GC/FID .......................................................................................................... 604 6420 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

50. Dimethyl phthalate:

GC/ECD ......................................................................................................... 606

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

51. Di-n-butyl phthalate:

GC/ECD ......................................................................................................... 606

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

52. Di-n-octyl phthalate:

GC/ECD ......................................................................................................... 606

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

53. 2,3-Dinitrophenol:

GC/FID .......................................................................................................... 604 6420 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

54. 2,4-Dinitrotoluene:

GC/ECD ......................................................................................................... 609

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

55. 2,6-Dinitrotoluene

GC/ECD ......................................................................................................... 609

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

56. Epichlorohydrin ............................................................................................... .................... Note 3, p. 130;

Note 6, p.

S102.

57. Ethylbenzene:

GC/PID .......................................................................................................... 602 6220 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

58. Fluoranthene:

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B D4657–92

59. Fluorene:

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440B D4657–92

60. Hexachlorobenzene:

GC/ECD ......................................................................................................... 612

GC/MS ........................................................................................................... 625 6410B

GC/MS/Isotope .............................................................................................. 1625

61. Hexachlorobutadiene:

GC/ECD ......................................................................................................... 612

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

62. Hexachlorocyclopentadiene:

GC/ECD ......................................................................................................... 612

GC/MS ........................................................................................................... 5 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

63. Hexachloroethane: .................... 616

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

64. Ideno(1,2,3-cd) pyrene:
15006 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued

Parameter 1/methodology Reference

method 27

Other approved methods

Standard

methods 18th

Ed.8

ASTM 8 Other

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B D4657–92

65. Isophorone:

GC/ECD ......................................................................................................... 609

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

66. Methylene chloride: .................... Note 3, p. 130

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624

GC/MS/Isotope .............................................................................................. 1624

67. 2-Methyl-4,6-dinitrophenol:

GC/ECD ......................................................................................................... .................... 6420 B

GC/FID .......................................................................................................... 604 6420 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

68. Naphthalene:

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B

69. Nitrobenzene:

GC/ECD ......................................................................................................... 609

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

70. 2-Nitrophenol:

GC/ECD ......................................................................................................... .................... 6420 B

GC/FID .......................................................................................................... 604 6420 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

71. 4-Nitrophenol:

GC/ECD ......................................................................................................... .................... 6420B

GC/FID .......................................................................................................... 604 6420B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

72. N-Nitrosodimethylamine:

GC/NPD ......................................................................................................... 607

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

73. N-Nitrosodi-n-propylamine:

GC/NPD ......................................................................................................... 607

GC/MS ........................................................................................................... 5 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

74. N-Nitrosodiphenylamine:

GC/NPD ......................................................................................................... 607

GC/MS ........................................................................................................... 5 625 6410B

GC/MS/Isotope .............................................................................................. 1625

75. 2,2-Oxybis(1-chloropropane):

GC/ELCD ....................................................................................................... 611

GC/MS ........................................................................................................... 614 6410 B

GC/MS/Isotope .............................................................................................. 1625

76. PCB–1016: .................... Note 3, p. 43.

GC/ECD ......................................................................................................... 608

GC/MS ........................................................................................................... 625 6410 B

77. PCB–1221: .................... Note 3, p. 43.

GC/ECD ......................................................................................................... 608

GC/MS ........................................................................................................... 625 6410 B

78. PCB–1232: .................... Note 3, p. 43.

GC/ECD ......................................................................................................... 608

GC/MS ........................................................................................................... 625 6410 B

79. PCB–1242: .................... Note 3, p. 43.

GC/ECD ......................................................................................................... 608

GC/MS ........................................................................................................... 625 6410 B

80. PCB–1248:

GC/ECD ......................................................................................................... 608

GC/MS ........................................................................................................... 625

81. PCB–1254: .................... Note 3, p. 43.
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TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued

Parameter 1/methodology Reference

method 27

Other approved methods

Standard

methods 18th

Ed.8

ASTM 8 Other

GC/ECD ......................................................................................................... 608

GC/MS ........................................................................................................... 625 6410 B

82. PCB–1260: .................... Note 3, p. 43.

GC/ECD ......................................................................................................... 608 6630 B

GC/MS ........................................................................................................... 625 6410 B

83. Pentachlorophenol: .................... Note 3, p. 140.

GC/ECD ......................................................................................................... .................... 6630 B

GC/FID .......................................................................................................... 604

GC/MS ........................................................................................................... 625

GC/MS/Isotope .............................................................................................. 1625 6410 B

84. Phenanthrene: ....................

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440 B D4657–92

85. Phenol: ....................

GC/FID .......................................................................................................... 604 6420 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

86. Pyrene: ....................

GC/FID .......................................................................................................... 610 6440 B

GC/MS ........................................................................................................... 625

GC/MS/Isotope .............................................................................................. 1625

HPLC/UV ....................................................................................................... 610 6440B D4675–92

87. 2,3,7,8-Tetrachlorodibenzo-p-dioxin: .................... Note 3, p. 130.

GC/MS ........................................................................................................... 5a 613

88. 1,1,2,2-Tetrachloroethane: .................... Note 3, p. 130.

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

89. Tetrachloroethene: .................... Note 3, p. 130.

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

90. Toluene: ....................

GC/PID .......................................................................................................... 602 6220 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

91. 1,2,4-Trichlorobenzene: .................... Note 3, p. 130.

GC/ECD ......................................................................................................... 612

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

92. 1,1,1-Trichloroethane: ....................

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

93. 1,1,2-Trichloroethane: .................... Note 3, p. 130.

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

94. Trichloroethene: ....................

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

95. Trichlorofluoromethane: ....................

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

96. 2,4,6-Trichlorophenol:

GC/FID .......................................................................................................... 604 6240 B

GC/MS ........................................................................................................... 625 6410 B

GC/MS/Isotope .............................................................................................. 1625

97. Vinyl chloride: ....................

GC/ELCD ....................................................................................................... 601 6230 B

GC/MS ........................................................................................................... 624 6210 B

GC/MS/Isotope .............................................................................................. 1624

Table IC notes:

1All parameters are expressed in micrograms per liter (μg/L).
15008 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

2The full text of Methods 601–613, 624, 625, 1624, and 1625, are given at Appendix A, ‘‘Test Procedures for Analysis of Organic Pollutants’’,

of this Part 136. The standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at

Appendix B, ‘‘Definition and Procedure for the Determination of the Method Detection Limit’’ of this Part 136. 3 ‘‘Methods for Benzidine: Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater’’, U.S. Environmental

Protection Agency, September 1978. 4 Method 624 may be extended to screen samples for Acrolein and Acrylonitrile. However, when they are known to be present, the preferred

method for these two compounds is Method 603 or Method 1624. 5 Method 625 may be extended to include benzidine, hexachlorocyclopentadiene, N-nitrosodimethylamine, and N-nitrosodiphenylamine. However, when they are known to be present, Methods 605, 607, and 612, or Method 1625, are preferred methods for these compounds. 5a 625, Screening only. 6 ‘‘Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency’’, Supplement to the Fifteenth Edition of Standard Methods for the Examination of Water and Wastewater (1981). 7Each Analyst must make an initial, one-time demonstration of their ability to generate acceptable precision and accuracy with Methods 601–

603, 624, 625, 1624, and 1625 (See Appendix A of this Part 136) in accordance with procedures each in Section 8.2 of each of these Methods.

Additionally, each laboratory, on an on-going basis must spike and analyze 10% (5% for Methods 624 and 625 and 100% for methods 1624 and

1625) of all samples to monitor and evaluate laboratory data quality in accordance with Sections 8.3 and 8.4 of these methods. When the recovery of any parameter falls outside the warning limits, the analytical results for that parameter in the unspiked sample are suspect and cannot be

reported to demonstrate regulatory compliance.

NOTE: These warning limits are promulgated as an ‘‘interim final action with a request for comments’’. 8 Methods published by this organization and approved for use under this part may not be modified beyond the modifications expressly allowed

and defined in each method.

NOTE: The following acronyms are used in this table:

ECD Electron Capture Detector

ELCD Electrolytic Conductivity Detector/Electrochemical Detector

FID Flame Ionization Detector

GC Gas Chromatography

GC/MS Gas Chromatography/Mass Spectrometry

HPLC High Performance Liquid Chromatography

NPD Nitrogen Phosphorous Detector

PID Photoionization Detector

UV Ultraviolet Detector

TABLE ID.—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1

Parameter/methodology Method Reference

method 2 7

Other approved methods

Standard

methods

18th ed.8

ASTM 8 Other

1. Aldrin .............................. GC/ECD 608 6630 B & C D3086–90 Note 3, p. 7; Note 4, p. 30.

GC/ELCD .................... 3086–90

GC/MS 625 6410 B

2. Ametryn ......................... GC .................... Note 3, p. 83; Note 6, p. S68.

3. Aminocarb ...................... TLC .................... Note 3, p. 94; Note 6, p. S16.

4. Atraton ........................... GC .................... Note 3, p. 83; Note 6, p. S68.

5. Atrazine .......................... GC .................... Note 3, p. 83; Note 6, p. S68.

6. Azinphos methyl ............ GC .................... Note 3, p. 25; Note 6, p. S51.

7. Barban ........................... TLC .................... Note 3, p. 104; Note 6, p. S64.

8. α–BHC ........................... GC/ECD 608 6630 B &C 3086–90 Note 3, p. 7.

GC/ELCD .................... D3086–90

GC/MS 5 625 6410 B

9. β–BHC ........................... GC/ECD 608 6630 3086–90

GC/ELCD .................... D3086–90

GC/MS 5 625 6410 B

10. δ–BHC ......................... GC/ECD 608 6630 B & C D3086–90

C/ELCD .................... D3086–90

GC/MS 5 625 6410 B

11. γ–BHC (Lindane) ......... GC/ECD 608 6630 B & C 3086–90 Note 3, p. 7; Note 4, p. 30.

GC/ELCD .................... D3086–90

GCMS 625 6410 B

12. Captan ......................... GC/ECD .................... 6630 B D3086–90 Note 3, p. 7.

GC/ELCD .................... D3086–90

13. Carbaryl ....................... TLC .................... Note 3, p. 94; Note 6, p. S60.

14. Carbophenothion ......... GC .................... Note 4, p. 30; Note 6, p. S73.

15. Chlordane .................... GC/ECD 608 6630 B & C 3086–90 Note 3, p. 7.

GC/ELCD .................... D3086–90

GC/MS 625 6410 B

16. Chloropropham ............ TLC .................... Note 3, p. 104; Note 6, p. S64.

17. 2,4–D ........................... GC/ECD .................... 6640 B Note 3, p. 115; Note 4, p. 35.

18. 4,4′–D–DDD ................ GC/ECD 608 6630 B & C D3086–90 Note 3, p. 7; Note 4, p. 30.

GC/ELCD .................... D3086–90

GC/MS 625 6410 B

19. 4,4′–DDE ..................... GC/ECD 608 6630 B &C 3086–90 Note 3, p. 7; Note 4, p. 30.

GC/ELCD .................... D3086–90

GC/MS 625 6410 B
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TABLE ID.—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1—Continued

Parameter/methodology Method Reference

method 2 7

Other approved methods

Standard

methods

18th ed.8

ASTM 8 Other

20. 4,4′–DDT ..................... GC/ECD 608 6630 B & C D3086–90 Note 3, p. 7; Note 4, p. 30.

GC/ELCD .................... D3086–90

GC/MS 625 6410 B

21. Demeton–O ................. GC .................... Note 3, p. 25; Note 6, p. S51.

22. Dementon–S ................ GC .................... Note 3, p. 25; Note 6, p. S51.

23. Diazinon ....................... GC .................... Note 3, p. 25; Note 4, p. 30; Note 6, p. S51.

24. Dicamba ....................... GC .................... Note 3, p. 115.

25. Dichlofenthion .............. GC .................... Note 4, p. 30; Note 6, p. S73.

26. Dichloran ...................... GC/ECD .................... 6630 B & C Note 3, p. 7.

27. Dicofol .......................... GC/ECD .................... D3086–90

GC/ELCD .................... D3086–90

28. Dieldrin ......................... GC/ECD 608 6630 B & C Note 3, p. 7; Note 4, p. 30.

GC/MS 625 6410 B

29. Dioxathion .................... GC .................... Note 4, p. 30; Note 6, p. S73.

30. Disulfoton ..................... GC .................... Note 3, p. 25; Note 6, p. S51.

31. Diuron .......................... TLC .................... Note 3, p. 104; Note 6, p. S64.

32. Endosulfan I ................. GC/ECD 608 6630 B & C D3086–90 Note 3, p. 7.

GC/ELCD .................... D3086–90

GC/MS 5 625 6410 B

33. Endosulfan II ................ GC/ECD 608 6630 B & C D3086–90 Note 3, p. 7.

GC/ELCD .................... D3086–90

GC/MS 5 625 6410 B

34. Endosulfan Sulfate ...... GC 608 6630 C

GC/MS 625 6410 B

35. Endrin .......................... GC/ECD 608 6630 B & C D3086–90 Note 3, p. 7; Note 4, p. 30.

GC/ELCD .................... D3086–90

GC/MS 5 625 6410 B

36. Endrin aldehyde ........... GC/ECD 608

37. Ethion ........................... GC .................... Note 4, p. 30; Note 6, p. S73.

38. Fenuron ....................... TLC .................... Note 3, p. 104; Note 6, p. S64.

39. Fenuron-TCA ............... TLC .................... Note 3, p. 104; Note 6, p. S64.

40. Heptachlor ................... GC/ECD 608 6630 B & C D3086–90 Note 3, p. 7; Note 4, p. 30.

GC/ELCD .................... D3086–90

GC/MS 625 6410 B

41. Heptachlor epoxide ...... GC/ECD 608 6630 B D3086–90 Note 3, p. 7; Note 4, p. 30.

GC/ELCD .................... D3086–90

GC/MS 625 6410 B Note 6, p. S73.

42. Isodrin .......................... GC .................... Note 4, p. 30; Note 6, p. S73.

43. Linuron ......................... GC .................... Note 3, p. 104; Note 6, p. S64.

44. Malathion ..................... GC/ECD .................... 6630 C Note 3, p. 25; Note 4, p. 30; Note 6, p. S51.

45. Methiocarb ................... TLC .................... Note 3, p. 94; Note 6, p. S60.

46. Methoxychlor ............... GC/ECD .................... 6630 B & C D3086–90 Note 3, p. 7; Note 4, p. 30.

GC/ELCD .................... D3086–90

47. Mexacarbate ................ TLC .................... Note 3, p. 94; Note 6, p. S60.

48. Mirex ............................ GC/ECD .................... 6630 B & C Note 3, p. 7.

49. Monuron ....................... TLC .................... Note 3, p. 104; Note 6, p. S64.

50. Monuron ....................... TLC .................... Note 3, p. 104; Note 6, p. S64.

51. Nuburon ....................... TLC .................... Note 3, p. 104; Note 6, p. S64.

52. Parathion methyl .......... GC/ECD .................... 6630 C Note 3, p. 25; Note 4, p. 30.

53. Parathion ethyl ............. GC/ECD .................... 6630 C Note 3, p. 25.

54. PCNB ........................... GC/ECD .................... 6630 B & C Note 3, p. 7.

55. Perthane ...................... GC/ECD .................... D3086–90

GC/ELCD .................... D3086–90

56. Prometron .................... GC .................... Note 3, p. 83; Note 6, p. S68.

57. Prometryn .................... GC .................... Note 3, p. 83; Note 6, p. S68.

58. Propazine ..................... GC .................... Note 3, p. 83; Note 6, p. S68.

59. Propham ...................... TLC .................... Note 3, p.104; Note 6, p. S64

60. Propoxur ...................... TLC .................... Note 3, p. 94; Note 6, p. S60.

61. Secbumeton ................. TLC .................... Note 3, p. 83; Note 6, p. S68.

62. Siduron ........................ TLC .................... Note 3, p. 104; Note 6, p. S64.

63. Simazine ...................... GC .................... Note 3, p. 83; Note 6, p. S68.

64. Strobane ...................... GC/ECD .................... 6630 B & C Note 3, p. 7.

65. Swep ............................ TLC .................... Note 3, p. 104; Note 6, p. S64.

66. 2,4,5-T ......................... GC/ECD .................... 6640 B Note 3, p. 115; Note 4, p. 35.

67. 2,4,5-TP (Silvex) .......... GC/ECD .................... 6640 B Note 3, p. 115.

68. Terbuthylazine ............. GC .................... Note 3, p. 83; Note 6, p. S68.

69. Toxaphene ................... GC/ECD 608 6630 B & C Note 3, p. 7; Note 4, p. 30.

GC/ELCD .................... 3086–90
15010 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

TABLE ID.—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1—Continued

Parameter/methodology Method Reference

method 2 7

Other approved methods

Standard

methods

18th ed.8

ASTM 8 Other

GC/MS 625 6410 B D3086–90

70. Trifluralin ...................... GC .................... 6630 B Note 3, p. 7.

Table ID notes:

1Pesticides are listed in this table by common name for the convenience of the reader. Additional pesticides may be found under Table 1C,

where entries are listed by chemical name. 2The full text of Methods 608 and 625 are given at Appendix A. ‘‘Test Procedures for Analysis of Organic Pollutants’’ of this Part 136. The

standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at Appendix B. ‘‘Definition and Procedure for the Determination of the Method Detection Limit’’, of this Part 136. 3 Methods for Benzidine, Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater’’ U.S. Environmental

Protection Agency, September 1978. This EPA publication includes thin-layer chromatography (TLC) methods. 4 ‘‘Methods for Analysis of Organic Substances in Water and Fluvial Sediments’’, Techniques of Water-Resources Investigations of the U.S.

Geological Survey, Book 5, Chapter A3 (1987). 5The method may be extended to include α-BHC, γ-BHC, endosulfan I, endosulfan II, and endrin. However, when they are known to exist,

Method 608 is the preferred method. 6 ‘‘Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency’’. Supplement to the Fifteenth Edition of Standard Methods for the Examination of Water and Wastewater (1981). 7Each analyst must make an initial, one-time, demonstration of their ability to generate acceptable precision and accuracy with Methods 608

and 625 (See Appendix A of this Part 136) in accordance with procedures given in Section 8.2 of each of these methods. Additionally, each laboratory, on an on-going basis, must spike and analyze 10% of all samples analyzed with Method 608 or 5% of all samples analyzed with Method

625 to monitor and evaluate laboratory data quality in accordance with Sections 8.3 and 8.4 of these methods. When the recovery of any parameter falls outside the warning limits, the analytical results for that parameter in the unspiked sample are suspect and cannot be reported to demonstrate regulatory compliance. These quality control requirements also apply to the Standard Methods, ASTM Methods, and other Methods

cited.

Note: These warning limits are promulgated as an ‘‘Interim final action with a request for comments.’’ 8 Methods published by this organization and approved for use under this part may not be modified beyond the modifications expressly allowed

and defined in each method.

Note: The following acronyms are used in this table:

ECD: Electron Capture Detector.

ELCD: Electrolytic Conductivity Detector/Electrochemical Detector.

FID: Flame Ionization Detector.

GC: Gas Chromatography.

GC/MS: Gas Chromatography/Mass Spectrometry.

* * * * *

BILLING CODE 6560–50–P
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BILLING CODE 6560–50–C
15018 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

(c) Under certain circumstances, the

Regional Administrator or the Director

in the Region or State where the

discharge will occur may determine that

an additional parameter or pollutant of

concern must be reported. Under such

circumstances, an additional test

procedure for the analysis of the

pollutant may be specified by the

Regional Administrator, or the Director,

upon the recommendation of the

Director of the Analytical Methods Staff.

(d) Sample preservation procedures,

container materials, and maximum

allowable holding times for parameters

and pollutants cited in Tables IA, IB, IC,

ID, and IE are prescribed in Table II.

Any person may apply for a variance

from the prescribed preservation

techniques, container materials, and

maximum holding times applicable to

samples collected from a specific

discharge. An application for a variance

may be made by letter to the Regional

Administrator in the Region in which

the discharge will occur. Sufficient data

should be provided to ensure such

variance does not adversely affect the

integrity of the sample. Such data will

be forwarded by the Regional

Administrator to the Director of the

Analytical Methods Staff for technical

review and recommendations for action

on the variance application. Upon

receipt of a recommendation from the

Director of the Analytical Methods Staff,

the Regional Administrator may grant a

variance applicable to samples collected

from the specific discharge for which

the application for variance was made.

A decision to approve or deny a

variance will be made within 90 days of

receipt of a complete application by the

Regional Administrator.

* * * * *

4. Section 136.4 is proposed to be

revised to read as follows:

§ 136.4 Modifications to reference

methods.

A reference method listed in tables IB,

IC, or ID of this part 136 may be

modified to improve separations, lower

the costs of measurements, reduce or

eliminate interferences, or for other

purposes, provided that the

modification is not explicitly prohibited

in the reference method and provided

that the laboratory modifying the

reference method meets the

requirements in this section, performs

the standardized QC tests, and

demonstrates that the QC acceptance

criteria and the requirements specified

at Appendixes E, F, and G of this part

are met. A laboratory that wishes to use

a new or modified wastewater method

must demonstrate that the method

detection limit (MDL) specified in the

reference method can be achieved.

Alternatively, if the effluent limitation

to be measured is above the MDL,

laboratories must demonstrate that the

minimum level (ML) determined with

the new or modified wastewater method

is at or below 1⁄3 the effluent limitation.

Demonstration of a valid detection limit

requires use of an MDL study in

accordance with the procedure at 40

CFR part 136 Appendix B. If the MDL

determined with the new or modified

method is not acceptable, the method

may not be used. Specified detection

limits are usually analyte-specific. For

any given analyte, the specified

detection limit may vary between a

wastewater and drinking water

reference method.

(a) Tier 1: modification of a reference

method for application in a single

laboratory to one or more matrix types.

(1) Application to a single matrix

type.

(i) A laboratory may modify a

reference method listed in tables IB, IC,

and ID for determination of an analyte

of concern in a specific matrix type,

provided that the laboratory:

(A) Performs the standardized QC

tests, including a test of initial precision

and recovery (IPR) on a reagent water

matrix;

(B) Performs the matrix spike (MS)

and matrix spike duplicate (MSD) tests

on the matrix type to which the

modification is to be applied;

(C) Meets the QC acceptance criteria

in the reference method or that apply to

the reference method in the table of QC

acceptance criteria for wastewater

methods at § 136.3 Table IF;

(D) Documents the results of the QC

tests using the checklists in Appendix E

of this part;

(E) Maintains the results of the QC

tests and other tests on file for

inspection by EPA and/or the approved

State NPDES authority.

(ii) After the laboratory has

demonstrated application of a method

modification to a given matrix type by

meeting the MS/MSD QC acceptance

criteria, only that laboratory may

subsequently apply that method

modification to that given matrix type.

(iii) A laboratory may apply a given

method modification to additional

matrix types if the laboratory validates

the modification on each matrix type by

performing a matrix spike (MS) and

matrix spike duplicate (MSD) test and

meeting the MS/MSD QC acceptance

criteria for precision and recovery for

each matrix type.

(2) Application to multiple matrix

types. After a laboratory has validated a

given method modification on a

minimum of nine (9) matrix types in

accordance with the procedures given in

paragraph (a)(1) of this section, the

laboratory may subsequently apply that

method modification to other matrix

types without validating the method

modification on those subsequent

matrix types, provided that:

(i) The following are included in the

matrix types validated:

(A) Effluent from a publicly-owned

treatment works (POTW);

(B) ASTM D 5905, Standard

Specification for Substitute Wastewater;

(C) Sewage sludge, if sludge will be in

the permit; and

(D) ASTM D 1141, Standard

Specification for Substitute Ocean

Water, if ocean water will be in the

permit.

(ii) At least one of the matrix types in

paragraph (a)(2)(i) of this section has at

least one of the following

characteristics: total suspended solids

(TSS) greater than 40 mg/L, total

dissolved solids (TDS) greater than 100

mg/L, oil and grease greater than 20 mg/

L, sodium chloride (NaCl) greater than

120 mg/L, and calcium carbonate

(CaCO3) greater than 140 mg/L.

(iii) The matrix spike (MS) and matrix

spike duplicate (MSD) recovery and the

relative percent difference are within

the QC acceptance criteria given for the

analyte in the reference method or as

supplemented by the QC acceptance

criteria specified for wastewater

methods at § 136.3 Table IF. If the

method modification is to be applied to

multiple media, validation must include

a minimum of one matrix type from

each additional medium in addition to

the matrix types listed in this paragraph.

If all QC acceptance criteria are not met

for a given matrix type, the modification

may not be applied to that matrix type.

(b) Tier 2: modification of a reference

method for application by all

laboratories to one or more matrix types

within a single industrial category or

subcategory.

(1) A person may modify a reference

method for application by all

laboratories to determination of an

analyte of concern in a single matrix

type in a single industrial category or

subcategory, provided that the

modification is not explicitly prohibited

in the reference method and provided

that the modification is validated in a

minimum of three (3) laboratories, each

of which test the same three (3) matrix

types and each matrix type is from a

different facility in the industrial

category or subcategory (a minimum of

nine (9) tests). Each laboratory must

meet the requirements in paragraph

(a)(1)(i) of this section. After the tests in

all three laboratories have met all QC

acceptance criteria for the reference
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15019

method, the modified reference method

may be applied by laboratories

nationwide to that matrix type in that

industrial category or subcategory only.

(2) A person who modifies and

validates a method modification under

Tier 2 may submit that modification to

EPA for a letter of approval using the

procedures specified in Appendix F and

G of this part. The information that must

be submitted includes the results of the

performance tests required by paragraph

(b)(1) of this section. This information

and other detailed information that

must be submitted and the format for

submission are given in Appendixes E,

F, and G of this part.

(3) A person who modifies and

validates a method modification under

Tier 2 may submit that modification to

EPA and for approval and inclusion in

a table in this part 136. The information

that must be submitted includes the

results of the performance tests required

by paragraph (b)(1) of this section, and

the detailed information specified in

Appendixes E, F, and G of this part.

(4) A person may modify a reference

method for application by all

laboratories to determination of an

analyte of concern in additional matrix

types within a single industrial category

or subcategory, provided that the

modification is validated in each

additional matrix type according to the

requirements in paragraph (b)(1) of this

section.

(c) Tier 3: modification of a reference

method for application by all

laboratories to all matrix types in all

industrial categories and subcategories

(nationwide modification).

(1) A person may modify a reference

method for application by all

laboratories to determination of an

analyte of concern in all matrix types,

provided that the modification is

validated in an interlaboratory method

validation study or in a study with a

minimum of nine (9) different

laboratories each of which test a

minimum of one sample from a set

representing a minimum of nine (9)

different matrix types for a total of a

minimum of nine unique samples. Each

of the nine (9) matrix types must be

from a different industrial category or

subcategory. Each laboratory must meet

the requirements in paragraph (a)(1)(i)

of this section and, the nine matrix

types must collectively meet all of the

criteria in paragraphs (a)(2)(i), (ii), and

(iii) of this section. After the

modification has been validated, it may

be applied by laboratories nationwide to

all matrix types.

(2) A person who modifies and

validates a method modification under

Tier 3 may submit that modification to

EPA for a letter of approval. The

information that must be submitted

includes the results of the performance

tests required by paragraph (b)(1) of this

section. This information and other

detailed information that must be

submitted and the format for submission

are given in Appendixes E, F, and G of

this part.

(3) A person who modifies and

validates a method modification under

Tier 3 may submit that modification to

EPA and for approval and inclusion in

a table in this part 136. The information

that must be submitted includes the

results of the performance tests required

by paragraph (c)(1) of this section. This

information and other detailed

information that must be submitted and

the format for submission are given in

Appendixes E, F, and G of this part.

(d) A decision to recommend proposal

of a Tier 2 or Tier 3 method

modification will be made by the

Director of the Analytical Methods Staff

within 90 days of receipt of a complete

application.

5. Section 136.5 is proposed to be

revised to read as follows:

§ 136.5 New methods.

A person may apply to EPA for use of

a new method for determination of an

analyte of concern, provided that the

new method meets the requirements for

validation and format as set forth in this

section and in appendixes E, F, and G

of this part. A new method must meet

the MDL criteria specified at § 136.4. A

new method must: be documented in

accordance with requirements in

appendixes E, F, and G of this part;

contain standardized QC as defined at

§ 136.2; contain QC acceptance criteria

that have been developed in accordance

with the requirements detailed in

appendixes E, F, and G of this part;

employ a determinative technique for an

analyte of concern with selectivity or

sensitivity equal or superior to the

selectivity or sensitivity of the

determinative technique in any

approved method, and that differs from

the determinative techniques employed

for that analyte in all approved

methods; and be accompanied by the

information specified at appendix G of

this part. A decision to recommend

proposal of a new method will be made

by the Director of the Analytical

Methods Staff within 90 days of receipt

of a complete application.

(a) Tier 1: application of a new

method in a single laboratory to one or

more matrix types.

(1) A person may develop a new

method for determination of an analyte

of concern in one or more matrix types

by validating the method and

developing QC acceptance criteria from

an interlaboratory method validation

study or from a single-laboratory

validation study on each specific matrix

type. Details of the single-laboratory

method validation study and

development of QC acceptance criteria

from a single-laboratory or

interlaboratory method validation study

are specified at § 136.4(a) (1) and (2) and

in appendixes E, F, and G of this part.

(2) A person who develops a new

method under Tier 1 must submit the

method to EPA for a letter of approval.

The information that must be submitted

and the format for submission is

specified at in appendixes E, F, and G

of this part.

(b) Tier 2: application of a new

method in all laboratories to one or

more matrix types within a single

industrial category or subcategory.

(1) A person may develop a new

method for determination of an analyte

of concern in one or more matrix types

within a single industrial category or

subcategory by validating the method

and developing QC acceptance criteria

on each matrix type from an

interlaboratory method validation study

or from multiple, single-laboratory

validation studies. Details of the

multiple, single-laboratory method

validation studies and development of

QC acceptance criteria from these

studies or from an interlaboratory

method validation study are specified at

§ 136.4(b) (1) and (4) and in appendixes

E, F, and G of this part.

(2) A person who develops a new

method under Tier 2 must submit the

method to EPA for approval and

inclusion in a table in this part 136. The

information that must be submitted

includes the results of the performance

tests required by paragraph (b)(1) of this

section. This information and other

detailed information that must be

submitted and the format for submission

are given in appendixes E, F, and G of

this part.

(c) Tier 3: application of a new

method by all laboratories to all matrix

types in all industrial categories and

subcategories (nationwide use).

(1) A person may develop for

nationwide use a new method for

determination of an analyte of concern

in all matrix types by validating the

method and developing QC acceptance

criteria on the matrix type from an

interlaboratory method validation study

or from multiple, single-laboratory

validation studies. Details of the

multiple, single-laboratory method

validation studies and development of

QC acceptance criteria from these

studies or from an interlaboratory

method validation study are specified at
15020 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

§ 136.4(c)(1) and in appendixes E, F,

and G of this part.

(2) A person who develops a new

method under Tier 3 must submit the

method to EPA for approval and

inclusion in a table in this part 136. The

information that must be submitted

includes the results of the performance

tests required by paragraph (c)(1) of this

section. This information and other

detailed information that must be

submitted and the format for submission

are given in appendixes E, F, and G of

this part.

(d) The number and type of required

tests, testing laboratories, matrices, and

replicate QC tests for the method

validation specified at §§ 136.4, 136.5

(a), (b), and (c) and 141.27 depend on

the tier at which the new or modified

wastewater or drinking water method is

validated. These requirements are

summarized in the following table:

SUMMARY OF VALIDATION REQUIREMENTS FOR NEW METHODS AND METHOD MODIFICATIONS 1

Method application

Number of Number of analyses required

Labs Matrix types Facilities

PWSs

IPR-reagent

water 2

IPR-sample

matrix 3 MS/MSD MDL 4

Tier 1-Single-lab:

WW/DW—First matrix type or first

PWS ............................................... 1 1 1 4 4 5 2 7

WW—Each addt’l matrix type (8

max.) from any industrial category 1 1 1 6 0 6 0 5 2 6 0

DW—Each addt’l PWS (2 max.) ........ 1 1 1 6 0 6 0 5 2 6 0

Tier 2-Multi-lab, single matrix type ............ 3 1 3 12 0 7 6 21

WW/DW—Each matrix type in a single industrial category

Tier 3-Multi-lab, multiple matrix types ....... 8 9 9 9 36 0 7 18 63

WW only—All matrix types, all industrial categories

1 Numbers of analyses in this table do not include background analyses or additional QC tests such as calibration, blanks, etc. Validation requirements are based on the intended application of the method. Method application would be designated by tier for wastewater (WW) and drinking water (DW) programs. Three would be the maximum number of public water systems (PWSs) that would be required to validate a new or

modified drinking water method at Tier 1 or 2. Nine would be the maximum number of matrix types (or facilities) that would be required to validate a new or modified wastewater method at Tier 1 or 3; at Tier 2 the number would be three matrix types. 2 IPR reagent water analyses would be used to validate a method modification and to establish QC acceptance criteria for initial precision and

recovery (IPR) and ongoing precision and recovery (OPR) for a new method. The required number of IPR analyses, except as noted under footnote 7, would be four times the number of laboratories required to validate a method modification or new method because each laboratory would

perform a 4-replicate IPR test. 3 IPR sample matrix analyses would be used to establish QC acceptance criteria for matrix spike/matrix spike duplicate (MS/MSD) recovery

and precision for a Tier 1 new method only. Would not be required for validation of Tier 2 or 3 new methods because this variability data would

be obtained from MS/MSD tests. Would not be required for validation of a method modification because MS/MSD data from the reference method would be used. 4A method detection limit (MDL) test would be performed in each laboratory using the new or modified method. 40 CFR part 136 Appendix B

requires a minimum of seven analyses per laboratory to determine an MDL. Each lab involved in validation of a wastewater modification would

demonstrate that the modified method would achieve the detection limits specified in the regulations at 40 CFR parts 136 and 141 and/or in

chapter 6 of the Streamlining Guide (EPA 1996a). 5 MS/MSD analyses would be required only for a method modification because, for new methods, the MS/MSD QC acceptance criteria would

be established by the 4-replicate sample matrix IPR test. For modified methods, the MS/MSD test would demonstrate that the reference method

MS/MSD QC acceptance criteria have been met. 6The MDL, reagent water IPR, and sample matrix IPR tests would not have to be repeated after the first matrix type, facility, or PWS was validated. 7For validation of a new method, the MS/MSD analyses would establish QC acceptance criteria for MS/MSD recovery and precision. For validation of a method modification, the MS/MSD analyses would demonstrate that reference method MS/MSD recovery and precision have been

met. The required number of MS/MSD analyses would be two times the number of facilities, PWSs or matrix types tested. 8The number of laboratories and samples would vary if a conventional interlaboratory study is used.

6. Appendix A to 40 CFR part 136 is

removed and reserved. Appendix E,

Appendix F, and Appendix G are added

to 40 CFR part 136 to read as follows:.

Appendix A to Part 136 [Removed and

Reserved]

* * * * *

Appendix E to Part 136—Equivalency

Checklists

The Checklist for Initial Demonstration of

Method Performance, Checklist for

Continuing Demonstration of Method

Performance, and Certification Statement

(collectively called ‘‘Checklists’’) and

instructions for their completion are

provided in this appendix. Because these

checklists were developed by EPA’s

Environmental Monitoring Management

Council (EMMC) for general application

across all EPA programs, the lists contain

categories that are not relevant to approval of

drinking water or wastewater methods.

Therefore, these categories are indicated in

this appendix by ‘‘NA’’ (not applicable). The

EMMC instructions have been annotated,

where appropriate, to clarify each checklist

item’s applicability to the approval of

drinking water and wastewater methods.

Checklist for Initial Demonstration of

Method Performance

For the demonstration of equivalency,

provide a checklist for each matrix in each

medium.

Date:

Page llll of llll

Laboratory Name & Address:

Facility Name:

Discharge Point ID:

EPA Program and Applicable Regulation:

Medium:

(e.g., wastewater, drinking water, soil, air,

waste solid, leachate, sludge, other)

Analyte or Class of Analytes:

(e.g., barium, trace metals, benzene, volatile

organics, etc.)
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15021

INITIAL DEMONSTRATION OF METHOD PERFORMANCE 1

Category

Performance criteria 2

based on

Results obtainedPerf. spec.

Measure- achieved (√)

ment quality

objective

Reference

method

1. Written method (addressing all elements in the EMMC format) attached

2. Title, number and date/rev. of ‘‘reference method’’, if applicable 3

3. Copy of the reference method, if applicable, maintained at facility

4. Differences between PBM and reference method (if applicable) attached

5. Concentrations of calibration standards

6. %RSD or correlation coefficient of calibration regression

7. Performance range tested (with units)

8. Sample(s) used in initial demonstration have recommended preservative, where applicable.

9. Sample(s) used in initial demonstration met recommended holding times, where applicable

10. Interferences

11. Qualitative identification criteria used

12. Performance Evaluation studies performed for analytes of interest, where available:

Latest study sponsor and title:

Latest study number:

13. Analysis of external reference material

14. Source of reference material

15. Surrogates used, if applicable

16. Concentrations of surrogates, if applicable

17. Recoveries of surrogates appropriate to the proposed use, if applicable

18. Sample preparation

19. Clean-up procedures

20. Method Blank Result

21. Matrix (reagent water, drinking water, sand, waste solid, ambient air, etc.)

22. Spiking system, appropriate to method and application

23. Spike concentrations (w/ units corresponding to final sample concentration)

24. Source of spiking material

25. Number of replicate spikes

26. Precision (analyte by analyte)

27. Bias (analyte by analyte)

28. Detection Limit (w/ units; analyte by analyte)

29. Confirmation of Detection Limit, if applicable

30. Quantitation Limit (w/ units: analyte by analyte)

31. Qualitative Confirmation

32. Frequency of performance of the Initial Demonstration

33. Other criterion (specify)

34. Other criterion (specify)

1Provide a detailed narrative description of the initial demonstration.

2For multi-analyte methods, enter ‘‘see attachment’’ and attach a list or table containing the analyte-specific performance criteria from the reference method or those needed to satisfy measurement quality objectives. 3 If a reference method is the source of the performance criteria, the reference method should be appropriate to the required application, and

the listed criteria should be fully consistent with that reference method.

Name and signature of each analyst

involved in the initial demonstration of

method performance (includes all steps

in the proposed method/modification):

lllllllllllllllllllll

Name

lllllllllllllllllllll

Signature

lllllllllllllllllllll

Date

lllllllllllllllllllll

Name

lllllllllllllllllllll

Signature

lllllllllllllllllllll

Date

lllllllllllllllllllll

Name

lllllllllllllllllllll

Signature

lllllllllllllllllllll

Date

The certification above must

accompany this form each time it is

submitted.

Checklist for Continuing Demonstration of

Method Performance

For the demonstration of equivalency,

provide a checklist for each matrix in each

medium.

Pagell of ll

Date:

Laboratory Name & Address:

Facility Name:

Discharge Point ID:

EPA Program and Applicable Regulation:

Medium:

(e.g., wastewater, drinking water, soil, air,

waste solid, leachate, sludge, other)

Analyte or Class of Analytes:

(e.g., barium, trace metals, benzene, volatile

organics, etc.)
15022 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

1True: Consistent with supporting data.

CONTINUING DEMONSTRATION OF METHOD PERFORMANCE

Category Required

frequency

Specific

performance criteria

Results

obtained

Performance

specific

achieved

(✔)

1. Method blank result (taken through all steps in the procedure)

2. Concentrations of calibration standards used to verify working range (with units),

where applicable

3. Calibration verification

4. Laboratory control sample

5. External QC sample (where available)

6. Performance evaluation (PE) studies, if applicable

Latest study sponsor and title:

Latest study number:

7. List analytes for which results were ‘‘not acceptable’’ in PE study .................... .................... .................... ....................

8. Surrogates used, if applicable

9. Concentration of surrogates, if applicable

10. Recovery of surrogates (acceptance range for multi-analyte methods), if applicable

11. Matrix

12. Matrix spike compounds

13. Concentration of matrix spike compounds

14. Recoveries of matrix spike compounds

14a. Recoveries of matrix spike duplicate compounds

15. Qualitative identification criteria used

16. Precision (analyte by analyte)

17. Other category (specify)

18. Other category (specify)

Name and signature of each analyst

involved in continuing demonstration of

method performance (includes all steps

in the proposed method/modification):

lllllllllllllllllllll

Name

lllllllllllllllllllll

Signature

lllllllllllllllllllll

Date

lllllllllllllllllllll

Name

lllllllllllllllllllll

Signature

lllllllllllllllllllll

Date

lllllllllllllllllllll

Name

lllllllllllllllllllll

Signature

lllllllllllllllllllll

Date

The certification above must

accompany this form each time it is

submitted.

Certification Statement

Pagell of ll

Date:

Laboratory Name & Address:

Facility Name:

Discharge Point ID:

EPA Program and Applicable Regulation:

Medium:

(e.g., water, soil, air)

Analyte or Class of Analytes:

(e.g., barium, trace metals, benzene, volatile

organics, etc.; Attach separate list, as

needed.)

We, the undersigned, CERTIFY that:

1. The method(s) in use at this facility for

the analysis/analyses of samples for the

programs of the U.S. Environmental

Protection Agency have met the Initial and

any required Continuing Demonstration of

Method Performance Criteria specified by

EPA.

2. A copy of the method used to perform

these analyses, written in EMMC format, and

copies of the reference method and

laboratory-specific SOPs are available for all

personnel on-site.

3. The data and checklists associated with

the initial and continuing demonstration of

method performance are true, accurate,

complete and self-explanatory.1

4. All raw data (including a copy of this

certification form) necessary to reconstruct

and validate these performance related

analyses have been retained at the facility,

and that the associated information is well

organized and available for review by

authorized inspectors.

lllllllllllllllllllll

Facility Manager’s Name and Title

lllllllllllllllllllll

Signature

lllllllllllllllllllll

Date

lllllllllllllllllllll

Quality Assurance Officer’s Name

lllllllllllllllllllll

Signature

lllllllllllllllllllll

Date

This certification form must be completed

when the method is originally certified, each

time a continuing demonstration of method

performance is documented, and whenever a

change of personnel involves the Facility

Manager or the Quality Assurance Officer.

Accurate: Based on good laboratory

practices consistent with sound scientific

principles/practices.

Complete: Includes the results of all

supporting performance testing.

Self-Explanatory: Data properly labeled

and stored so that the results are clear and

require no additional explanation.

EMMC Checklists Instructions

Checklists Overview

The Checklists were arrived at through

consensus among EPA’s programs by

developing performance ‘‘categories’’ that

allow use of the same Checklists across the

Agency’s various programs/projects. The

Checklists may be applied to screening and

field techniques as well as laboratory

procedures.

Implementation of the Checklists is

program-specific and a category that does not

apply within a given EPA program will be

indicated by NA (not applicable). Criteria for

a specific EPA program are to be filled in

under the ‘‘Performance Criteria’’ column;

e.g., an Office of Water Reference Method

may specify 20% RSD or a correlation

coefficient of 0.995 for the category that

specifies calibration linearity, whereas an

Office of Solid Waste Project may specify a

Measurement Quality Objective of 12% RSD

or a correlation coefficient of 0.998 for this

category.

For each EPA program, the Checklists are

to be completed for each matrix within each

medium for all matrices and media to which

an alternate method or method modification

applies. The EMMC definition of media is

equivalent to the definition at 136.2 of matrix

type. Each completed Checklist must be

retained on file at the laboratory that uses the
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15023

performance-based method (PBM) or method

modification and at the regulated facility

from which samples are collected, and must

be submitted to the appropriate Regulatory

Authority upon request to support analysis of

those samples to which the PBM or modified

method was applied. (For wastewater and

drinking water methods, the term ‘‘PBM

method’’ in the preceding sentence is

replaced with the term ‘‘new method’.)

Header:

Each page of the checklist contains seven

lines of header information, consisting of:

(1) Date (enter the date that the checklist

was completed—Program/Project

implementation plans should indicate

whether the checklist must be submitted to

the Regulatory Authority, as well as, retained

on file at the laboratory and regulated

facility).

(2) Laboratory Name & Address (If a

commercial contract laboratory uses the

method on behalf of one or more applicable

clients, enter the name and address of the

laboratory.)

(3) Facility Name (enter the name of the

water treatment facility, system, or regulated

facility or other program or project specified

entity where the facility maintains an on-site

analytical laboratory. If the method is being

employed by a commercial contract

laboratory on behalf of one or more

applicable clients, enter the name of the

laboratory followed by a listing of the

appropriate clients).

(4) Discharge Point Identification Number

(enter the discharge point identification

number, if applicable).

(5) EPA Program & Applicable Regulation

(enter the name of the Agency Program or

Project to whom the results will be reported,

or under the auspices of which the data are

collected, e.g., ‘‘CAA’’ for Clean Air Act

monitoring and ‘‘SDWA’’ for analyses

associated with the Safe Drinking Water Act).

(6) Medium (enter the type of

environmental sample, e.g., drinking water—

Note: A separate checklist shall be prepared

for each medium, e.g., for checklists

associated with performance-based methods

for SDWA, enter ‘‘Drinking Water’’ as the

matrix type. As the evaluations of a

performance-based method involve matrixspecific performance measures, a separate

checklist shall be prepared for each matrix.

The ‘‘medium’’ is the environmental sample

type to which the performance-based method

applies, whereas the performance category

‘‘matrix’’, appearing in the body of the

checklists refers to the specific sample type

within the ‘‘Medium’’ that was spiked, e.g.,

for ‘‘medium’’ hazardous waste, the checklist

category ‘‘matrix’’ may be solvent waste. For

wastewater and drinking water methods, the

term ‘‘medium’’ is replaced with the term

‘‘matrix’.

(7) Analyte or Class of Analytes, where

available. (As many methods apply to a large

number of analytes, it is not practical to list

every analyte in this field, as indicated on the

form, the class of analytes may be specified

here, i.e., volatile organics. However, if such

a classification is used, a separate list of

analytes and their respective Chemical

Abstract Service Registry Numbers (CAS #)

must be attached to the checklist).

Initial Demonstration of Method

Performance Checklist

The Initial Demonstration of Method

Performance involves multiple spikes into a

defined sample matrix (e.g., wastewater

medium, paper plant effluent matrix), to

demonstrate that the Performance-based

Method meets the Program or Project

Performance Criteria based on the

performance of established ‘‘Reference

Method’’ or based on ‘‘Measurement Quality

Objectives’’ (formerly called Data Quality

Objectives). This exercise is patterned after

the ‘‘Initial Demonstration of Capability’’

delineated in a number of the Agency’s

published methods (Reference Methods).

Footnote #1 indicates that a detailed

narrative description of the initial

demonstration procedure is to be provided.

Footnote #2 indicates that for multi-analyte

methods, the range of performance criteria

for the analytes may be entered, but an

analyte-specific performance criteria is to be

attached. In general, when using the

checklists, if the criteria or performance are

lengthy, attach as a separate sheet, and enter

‘‘see attached’’ for this item.

Footnote #3 indicates that if a reference

method is the source of the performance

criteria, the reference method should be

appropriate to the required application and

the listed criteria should be fully consistent

with that reference method. The reference

method name and EPA number (where

applicable) should be delineated in the

program/project implementation plan, e.g.,

by the Program Office or the Project Officer/

Manager.

There are 34 numbered entries in the body

of the checklist—NOTE: Under normal

circumstances, it would never be acceptable

to answer ‘‘No’’ to any of these performance

categories, or fail to attach the requested

materials (categories not applicable to

drinking or wastewater methods are marked

with ‘‘NA’’):

#1. Written Method (addressing all

elements in the EMMC format)

The details of the method used for analysis

must be described in a version of the method

written in EMMC format, which is specified

for drinking water and wastewater methods

at 40 CFR part 136 Appendix F. The EMMC

method format includes the following: 1.0

Scope & Application; 2.0 Summary of

Method; 3.0 Definitions; 4.0 Interferences; 5.0

Safety; 6.0 Equipment & Supplies; 7.0

Reagents & Standards; 8.0 Sample Collection,

Preservation & Storage; 9.0 Quality Control;

10.0 Calibration & Standardization; 11.0

Procedures; 12.0 Data Analysis &

Calculations; 13.0 Method Performance; 14.0

Pollution Prevention; 15.0 Waste

Management; 16.0 References; 17.0 Tables,

Diagrams, Flowcharts & Validation Data.

While this format may differ from that used

in standard operation procedures (SOPs) in a

given laboratory, the use of a consistent

format is essential for the efficient and

effective evaluation by inspectors, program

and project managers/officers.

#2. Title, Number and date/revision of

‘‘Reference Method’’ if applicable.

For Example Polychlorinated Dioxins and

Furans, EPA Method 1613, Revision B,

October, 1994.

#3. Copy of the reference method, if

applicable, maintained at the facility.

A copy of the reference method must be

kept available for all laboratory personnel,

however, it need not be attached to the

checklist itself.

#4. Differences between PBM and reference

method attached.

The laboratory must summarize the

differences between the reference method

and the performance-based method and

attach this summary to the checklist. This

summary should focus on significant

difference in techniques (e.g., changes

beyond the flexibility allowed in the

reference method), not minor deviations such

as the glassware used.

#5. Concentrations of calibration standards.

The range of the concentrations of

materials used to establish the relationship

between the response of the measurement

system and analyte concentration. This range

must bracket any action, decision or

regulatory limit. In addition, this range must

include the concentration range for which

sample results are measured and reported

(when samples are measured after sample

dilution/concentration).

#6. % RSD or Slope/Correlation Coefficient

of Calibration Regression.

This performance category refers to

quantitative measures describing the

relationship between the amount of material

introduced into the measurement system and

the response of the system, e.g., analytical

instrument. A linear response is generally

expected and is typically measured as either

a linear regression or inorganic analytes, or

as the relative standard deviation (or

coefficient of variation) of the response

factors or calibration factors for organic

analytes. Traditional performance

specifications considered any regression line

with a correlation coefficient (r) of 0.995 or

greater as linear. Also, for organic analytes,

a relative standard deviation (RSD) of 25% or

less is considered linear. The calibration

relationship is not necessarily limited to a

linear relationship. However, it should be

remembered if the Program/Project Office or

Officer/Managers specifies other calibration

relationships, e.g., quadratic fit, more

calibration standards are generally necessary

to accurately establish the calibration. If

applicable, a calibration curve, graphical

representation of the instrument response

versus the concentration of the calibration

standards, should be attached.

#7. Performance Range Tested (with units).

This range must reflect the actual range of

sample concentrations that were tested and

must include the concentration units. Since

the procedures may include routine sample

dilution or concentration, the performance

range may be broader than the range of the

concentrations of the calibration standards.

#8. Sample(s) used in initial demonstration

have recommended preservative, where

applicable.

Unless preservation have been specifically

evaluated, this entry should be taken directly

from the reference method/standard. If

preservation has been evaluated, include the

study description and conclusions of that

evaluation, with a reference to the specific

study description. The data must be attached.
15024 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

#9. Sample(s) used in the initial

demonstration must be within the

recommended holding times, where

applicable.

Unless holding time (time from when a

sample is collected until analysis) has been

specifically evaluated, this entry should be

taken directly from the reference method/

standard. If holding time has been evaluated,

include the study description and

conclusions of that evaluation here, with a

reference to the specific study description.

The data must be attached.

#10. Interferences.

Enter information on any known or

suspected interferences with the

performance-based method. Such

interferences are difficult to predict in many

cases, but may be indicated by unacceptable

spike recoveries in environmental matrices,

especially when such recovery problems

were not noted in testing a clean matrix such

as reagent water. The inferences associated

with the reference method are to be

indicated, as well as, the affect of these

interferences on the performance-base

method.

#11. Qualitative identification criteria

used.

Enter all relevant criteria used for

identification, including such items as

retention time, spectral wavelengths, ion

abundance ratios. If the instrumental

techniques for the performance-based

method are similar to the reference method,

use the reference method as a guide when

specifying identification criteria. If the list of

criteria is lengthy, attach it on a separate

sheet, and enter ‘‘see attached’’ for this item.

#12. Performance Evaluation Studies

performed for analytes of interest, where

available (last study sponsor and title:; last

study number:).

Several EPA Programs conduct periodic

performance evaluation (PE) studies.

Organizations outside of the Agency also may

conduct such studies. Enter the sponsor, title,

and date of the most recent study in which

the performance-based method was applied

to the matrix of interest. For the performancebased method to be acceptable, the

performance on such studies must be ‘‘fully

successful’’, i.e., within the study QC

acceptance criteria.

#13. Analysis of external reference

material.

Enter the results of analyses on reference

material from a source different from that

used to prepare calibration standards (where

applicable). This performance category is

especially important if Performance

Evaluation Studies are not available for the

analytes of interest. Analysis of a reference

sample is one of standardized QC elements

specified for wastewater and drinking water

methods at 40 CFR 136.4, 136.5 and 141.27.

A common (and recommended) reference

sample is a Reference Material from the

National Institute of Standards and

Technology.

#14. Source of reference material.

Enter criteria, if applicable, for traceability

of materials used to verify the accuracy of the

results, e.g., obtained from the National

Institute of Science and Technology (NIST).

#15. Surrogates used if applicable.

Surrogates may be added to samples prior

to preparation, as a test of the entire

analytical procedure. These compounds are

typically brominated, fluorinated or

isotopically labeled compounds, with

structural similarities to the analytes of

interest. Also, they are not expected to be

present in environmental samples. Surrogates

are often used in the analysis for organic

analytes. Enter the names of the surrogate

compounds in this category.

#16. Concentrations of surrogates (if

applicable).

Enter the concentration of surrogates once

spiked into the sample (i.e., final

concentration).

#17. Recoveries of Surrogates appropriate

to the proposed use (if applicable).

Enter the summary of the surrogate

recovery limits and attach a detailed listing

if more space is needed.

#18. Sample Preparation.

Enter necessary preliminary treatments

necessary, e.g., digestion, distillation and/or

extraction. A detailed listing may be attached

if more space is needed.

#19. Clean-up Procedures.

Enter necessary intermediatory steps

necessary prior to the determinative step

(instrumental analysis), e.g., GPC, copper

sulfate, alumina/Florisil treatment, etc.

#20. Method Blank Result.

A clean matrix (i.e., does not contain the

analytes of interest) that is carried through

the entire analytical procedure, including all

sample handling, preparation, extraction,

digestion, cleanup and instrumental

procedures. The volume or weight of the

blank should be the same as that used for

sample analyses. The method blank is used

to evaluate the levels of analytes that may be

introduced into the samples as a result of

background contamination in the laboratory.

Enter the analyte(s) and concentration

measured in the blank.

#21. Matrix (reagent water, drinking water,

soil, waste solid, air, etc.).

Refers to the specific sample type within

the broader ‘‘Medium’’ that was spiked, e.g.,

for the Medium ‘‘Hazardous Waste,’’ an

example matrix spiked as part of the initial

demonstration of method performance might

be ‘‘solvent waste’’. For wastewater and

drinking water methods, the term ‘‘medium’’

is replaced with ‘‘matrix’.

#22. Spiking System, appropriate to the

method and application.

Enter the procedure by which a known

amount of analyte(s) (‘‘spike’’) was added to

the sample matrix. This may include the

solvent that is employed and the technique

to be employed (e.g., permeation tube, or

volumetric pipet delivery techniques spiked

onto a soil sample and allowed to equilibrate

one day, etc.). Solid matrices are often

difficult to spike and considerable detailed

narrative may be necessary to delineate the

procedure. For spikes onto aqueous samples,

generally a water miscible solvent is

specified.

#23. Spike levels (w/units corresponding to

final sample concentration).

Enter the amount of the analyte(s)

(‘‘spike’’) that was added to the sample

matrix in terms of the final concentration in

the sample matrix. For wastewater and

drinking water methods, initial spikes, also

known as initial precision and recovery (IPR)

standards, will be performed in reagent

water. Using reagent water will allow the

comparison of IPR spike recoveries

determined with the modified method

against IPR criteria specified in the reference

method because reference method IPR

specifications are developed from reagent

water spikes.

#24. Source of spiking material.

Enter the organization or vendor from

which the ‘‘spiking’’ material was obtained.

This should include specific identification

information, e.g., lot#, catalogue number, etc.

#25. Number of Replicate Spikes.

The initial demonstration of method

performance involves the analyses of

replicate spikes into a defined sample matrix

category #21. Enter the number of such

replicates. In general, at least four replicates

should be prepared and analyzed

independently.

#26. Precision (analyte by analyte).

Precision is a measure of agreement among

individual determinations. Statistical

measures of precision include standard

deviation, relative standard deviation or

percent difference.

#27. Bias (analyte by analyte).

Bias refers to the systematic or persistent

distortion of a measurement process which

causes errors in one direction. Bias is often

measured at the ratio of the measured value

to the ‘‘true’’ value or nominal value. Bias is

often (erroneously) used interchangeably

with ‘‘accuracy’’, despite the fact that the two

terms are complementary, that is, high

‘‘accuracy’’ implies low ‘‘bias’’, and vice

versa. Enter the name of the Bias measure (%

recovery, difference from true, etc.), the

numeric value with associated units for each

analyte obtained for each analyte spiked in

the initial demonstration procedure.

#28. Detection Limit (w/units; analyte by

analyte).

A general term for the lowest concentration

at which an analyte can be detected and

identified. There are various measures of

detection which include Limit of Detection

and Method Detection Limit. Enter the

detection measure (e.g., ‘‘MDL’’) and the

analytical result with units for each analyte

in the matrix (#21). For wastewater and

drinking water methods MDL requirements

are specified at 40 CFR 136.4 and 141.27.

#29. Confirmation of Detection Limit.

In addition to spikes into the matrix of

interest (#21) it may be beneficial to perform

the detection measurements in a clean

matrix, e.g., laboratory pure water. Results of

the spikes in the clean matrix are frequently

available in the Agency’s published methods.

Determining MDLs in a clean matrix using

the performance-based method will allow a

comparison to the MDLs published in the

Agency methods.

Also, the detection limit technique may

specify specific procedures to verify that the

obtained limit is correct, e.g., the ‘‘iterative

process’’ detailed in the 40 CFR part 136,

Appendix B, MDL procedures.

#30. Quantitation Limit (w/units; analyte

by analyte).

The lowest concentration that the analyte

can be reported with sufficient certainty that
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15025

an unqualified numeric value is reportable.

Measures of Quantitation limits include the

Minimum Level (ML), Interim Minimum

Level (IML), Practical Quantitation Level

(PQL), and Limit of Quantitation (LOQ).

Enter the measure of quantitation limit, and

the units for each analyte.

#31. Qualitative confirmation.

Enter all relevant criteria used for

identification, including such items as:

retention time; use of a second

chromatographic column; use of second

(different) analytical technique; spectral

wavelengths; and ion abundance ratios. If the

instrumental techniques for the modified

method are similar to those of the reference

method, use the reference method as a guide

when specifying confirmation criteria. If the

list of criteria is lengthy, attach it on a

separate sheet, and enter ‘‘see attached’’ for

this item.

#32. Frequency (initial Demonstration to be

performed).

Enter the frequency that the initial

demonstration has to be repeated, e.g., with

each new instrument or once a year, which

ever is more frequent.

#33–#34. Other Criteria.

Enter other necessary program/project

specific method performance categories. For

wastewater and drinking water methods,

Categories 33 and 34 are used as follows:

#33. Matrix Spike/Matrix Spike Duplicate.

Enter the percent recoveries of analytes

spiked into the sample matrix. For method

modifications, only one set of matrix spike/

matrix spike duplicate (MS/MSD) samples

are required. For new methods, two sets of

MS/MSD samples must be analyzed to

provide sufficient data for QC acceptance

criteria development.

#34. Matrix Spike/Matrix Spike Duplicate

Relative Percent Deviation.

Enter the calculated relative percent

deviation between the MS and MSD analyte

recoveries.

Signatures:

The name, signature and date of each

analyst involved in the initial demonstration

of method performance is to be provided at

the bottom of the check sheet.

Continuing Demonstration of Capability

Checklist

The process by which a laboratory

documents that their previously established

performance of an analytical procedure

continues to meet performance specifications

as delineated in this checklist.

#1. Method Blank.

A clean matrix (i.e., one that does not

contain the analytes of interest) that is

carried through the entire analytical

procedure, including all sample handling,

preparation, extraction, digestion, cleanup

and instrumental procedures. The volume or

weight of the blank should be the same as

that used for sample analyses. The method

blank is used to evaluate the levels of

analytes that may be introduced into the

samples as a result of background

contamination in the laboratory. Enter the

analyte(s) and concentration measured in the

blank.

#2. Concentrations of calibration standards

used to verify working range, where

applicable (include units).

The range of the concentrations of

materials used to confirm the established

relationship between the response of the

measurement system and analyte

concentration. This range must bracket any

action, decision or regulatory limit. In

addition, this range must include the

concentration range for which sample results

are measured and reported (when samples

are measured after sample dilution/

concentration). Enter the concentrations of

the calibration standards.

#3. Calibration Verification.

A means of confirming that the previously

determined calibration relationship still

holds. This process typically involves the

analyses of two standards with

concentrations which bracket the

concentrations measured in the sample(s).

Enter the procedure to be used to verify the

calibration and the results obtained for each

analyte.

#4. Calibration check standard.

A single analytical standard introduced

into the instrument as a means of

establishing that the previously determined

calibration relationship still holds. Enter the

concentrations and result for each analyte.

#5. External QC sample (where applicable).

Enter the results of analyses for reference

material (e.g., Quality Control samples/

ampules) from a source different from that

used to prepare calibration standards (where

applicable). Enter the concentration, as well

as, the source of this material. This

performance category is of particular

importance if Performance Evaluation studies

are not available for the analytes of interest.

#6. Performance Evaluation studies

performed for analytes of interest, where

available (Last study sponsor and title: Last

study number:).

Several EPA Programs conduct periodic

performance evaluation (PE) studies. Other

organizations, outside of the Agency, also

conduct such studies. Enter the sponsor, title,

and date of the most recent study in which

the performance-based method was applied

to the matrix of interest. For the Performancebased method to be acceptable the

performance on such studies must be ‘‘fully

successful’’, i.e., within the study QC

acceptance criteria.

#7. List of analytes for which results were

‘‘not acceptable’’ in PE study.

#8. Surrogate Compounds used (if

applicable).

Surrogates may be added to samples prior

to preparation, as a test of the entire

analytical procedure. These compounds are

typically brominated, fluorinated or

isotopically labeled compounds, with

structural similarities to the analytes of

interest. They are compounds not expected to

be present in environmental samples.

Surrogates are often used in analyses for

organic analytes. Enter the names of the

surrogate compounds in this performance

category.

#9. Concentration of surrogates (if

applicable).

Enter the concentration of surrogates once

spiked into the sample (i.e., final

concentration), with units.

#10. Recoveries of Surrogates appropriate

to the proposed use (if applicable).

Enter the summary of the surrogate

recovery limits and attached a detailed listing

(each surrogate compound), if more space is

needed.

#11. Matrix (reagent water, drinking water,

soil, waste solid, air, etc.).

Refers to the specific sample type within

the broader ‘‘Medium’’ that was spiked, e.g.,

for the Medium ‘‘Hazardous Waste,’’ an

example matrix spiked as part of the initial

demonstration of method performance might

be ‘‘solvent waste’’.

#12. Matrix Spike Compounds.

In preparing a matrix spike a known

amount of analyte is added to an aliquot of

a real-world sample matrix. This aliquot is

analyzed to help evaluate the effects of the

sample matrix on the analytical procedure.

Matrix spike results are typically used to

calculate recovery of analytes as a measure of

bias for that matrix. Enter the analytes

spiked.

#13. Matrix Spike Concentrations (w/units

corresponding to final sample concentration).

Enter the amount of the analyte(s)

(‘‘spike’’) that was added to the sample

matrix in terms of the final concentration in

the sample matrix.

#14. Recovery of Matrix Spike (w/units).

The ratio of the standard deviation of a

series of at least three measurements to the

mean of the measurements. This value is

often expressed as a percentage of the mean.

Note: Some programs/projects have

utilized matrix spike duplicates (a separate

duplicate of the matrix spike) to help verify

the matrix spike result and to provide

precision data for analytes which are not

frequently found in real-world samples, i.e.,

duplication of non-detects provides little

information concerning the precision of the

method.

#15. Qualitative identification criteria

used.

Enter all relevant criteria used for

identification, including such items as

retention times, spectral wavelengths, ion

abundance ratios. If the instrumental

techniques for the Performance-based

method are similar to the reference method,

use the reference method as a guide when

specifying identification criteria. If the list of

criteria is lengthy, attach it on a separate

sheet, and enter ‘‘see attached’’ for this item.

#16. Sample Preparation.

Enter necessary preliminary treatments

necessary, e.g., digestion, distillation and/or

extraction. A detailed listing may be attached

if more space is needed.

#17. Clean-up Procedures.

Enter intermediatory steps necessary to

prior to the determinative step (instrumental

analysis), e.g., GPC, copper sulfate, alumina/

florisil treatment, etc.

#18. Confirmation.

Qualitative identification criteria used.

Enter all relevant criteria used for

identification, including such items as:

retention time; use of second

chromatographic column; use of second

(different) analytical technique; spectral

wavelengths, ion abundance rations. If the

instrumental techniques for the Performancebased method are similar to the reference

method, use the reference method as a guide

when specifying confirmation criteria. If the
15026 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

list of criteria is lengthy, attach it on a

separate sheet, and enter ‘‘see attached’’ for

this item.

#19–20. Other.

Enter other necessary program/project

specific method performance categories.

Signatures:

The name, signature and date of each

analyst involved in the continuing

demonstration of method performance is to

be provided at the bottom of the checklist.

Appendix F to Part 136—Guidelines and

Format for Methods to be Proposed at 40

CFR Part 136 or Part 141

This appendix has been prepared to

promote consistency among analytical

methods and to streamline the method

promulgation process. The elements in this

appendix are mandatory for all methods

proposed for approval at 40 CFR part 136 or

141. The appendix has four sections. The

first section specifies standard elements that

must be included in the method, the second

section specifies the required method format,

the third section specifies conventions to be

used when preparing the method, and the

fourth section specifies the required method

content.

1.0 Elements

1.1 Cover Page

For methods submitted to EPA from other

organizations or individuals, no cover page is

required. Prior to method publication, EPA

will prepare the cover page in the standard

EPA format. The cover page will use black

ink on white or colored paper stock and may

include a cover graphic that illustrates the

method.

EPA will assign a three- or four-digit

method number that correlates with the EPA

method series to which the method belongs.

The method number is included as the first

part of the method title on the cover page.

1.2 Title Page

There are two types of title page: a title

page prepared by an organization or

individual that is submitting a method to

EPA, and the final title page that appears in

the EPA-published method.

1.2.1 Individuals or organizations

submitting methods to EPA should include

the following information on the title page of

the method: Method title, Date, and

Sponsoring organization with address and

telephone number.

1.2.1.1 When titling the method, use a

concise title that cites (in sequence) the

particular analyte(s) or property being

determined, the type of sample or sample

matrix(ces) to which the method is

applicable, as appropriate, and the

determinative technique or instrumentation.

Apply the following guidelines in titling

methods:

1.2.1.1.1 If the method applies to

numerous matrices (such as water, soil,

sediment, sludge, tissue, and others), it may

not be practical to include matrices in the

title. However, if the method applies to a

single matrix or a limited number of

matrices, the matrix(ces) should be specified

in the title.

1.2.1.1.2 If the method is used to

determine a number of analytes or properties,

analytes or properties can be named as a

group (e.g., trace elements), and the names of

specific analytes or properties omitted.

1.2.1.1.3 Avoid the use of the terms

‘‘analysis of...’’ or ‘‘determination of...’’ in

method titles, since these terms are

understood within the context of the term

‘‘method.’’

1.2.1.1.4 Method titles should use

abbreviations or acronyms for familiar parts

of the method title, e.g., HRGC/HRMS. The

acronym or abbreviation should be defined at

first use in the method. Examples of suitable

method titles are: ‘‘Mercury in Water by

Oxidation, Purge and Trap, and Cold Vapor

Atomic Fluorescence Spectrometry’’ and

‘‘Tetra-through Octa-Chlorinated Dioxins and

Furans by Isotope Dilution HRGC/HRMS’’.

1.2.1.2 For a methods manual, use a title

that identifies the category of methods

included in the manual. Examples of suitable

methods manual titles are: ‘‘Analytical

Methods for Pulp and Paper Industry

Wastewater’’ and ‘‘Analytical Methods for

the Determination of Pollutants in

Pharmaceutical Manufacturing Industry

Wastewater’.

1.2.2 Before publishing the method, EPA

will generate a title page that mimics the

cover page (excluding any cover graphics).

11.3 Acknowledgments

Acknowledgments should identify the

author and editor, and provide credit to

researchers, peer reviewers, and

organizations or individuals that contributed

directly and substantively in the

development and writing of the method.

These acknowledgments are independent of

references listed at the end of the method.

1.4 Disclaimer

The disclaimer may appear on the same

page with the acknowledgments or may be on

the page following the acknowledgments. It

may contain one or more disclaimer

statements. All disclaimers should include

the following statement: ‘‘The mention of

trade names or commercial products does not

constitute endorsement or recommendation

for use.’’

The disclaimer may not state explicitly or

imply that EPA has granted any approval of

the method. Once the method has been

validated and submitted to EPA for proposal,

however, the following statement may be

included: ‘‘This method has been submitted

to the U.S. Environmental Protection Agency

for use in EPA’s water programs but has not

been approved for use by EPA.’’

For draft methods, include the following

statement: ‘‘This method is in draft form. It

has not been released by the U.S.

Environmental Protection Agency and should

not be construed as an Agency-endorsed

method. It is being circulated for comments

on its technical merit.’’

When preparing the method for proposal at

40 CFR part 136 or 141, EPA will edit the

disclaimer to cite the Agency review process

that the method has undergone.

1.5 Table of Contents

A table of contents is required for methods

manuals and is recommended for single

methods that exceed 25 pages in length. The

table of contents should cite the titles and

page numbers of all first-and second-order

headings (see section 2.9 of this appendix)

and all tables and figures.

1.6 Introduction

In the introduction, provide background on

the method, describe the purpose of the

method, and include a summary-level

description of the method. Identify the name,

organization, address, and telephone number

to contact for questions regarding the

method.

When preparing the validated method for

submission to EPA for proposal at 40 CFR

part 136 or 141, include the following

instructions at the end of the introduction:

Questions concerning this method or its

application should be addressed to: W. A.

Telliard, USEPA Office of Water, Analytical

Methods Staff, Mail Code 4303, 401 M Street,

S.W., Washington, DC 20460, 202/260–7120.

Requests for additional copies of this

publication should be directed to: Water

Resource Center, Mail Code RC–4100, 401 M

Street, SW., Washington, DC 20460, 202/260–

7786.

1.7 Notice of Performance-based Method

All methods prepared should be

performance-based and should contain the

following notice on a separate page directly

preceding the body of the method: ‘‘Note:

This method is performance-based. The

laboratory is permitted to modify or omit any

step or procedure, provided that all

performance requirements set forth in this

method and in the applicable regulations at

40 CFR parts 136 and 141 are met. The

laboratory may not omit any quality control

analyses. The terms ‘‘shall,’’ ‘‘must,’’ and

‘‘may not’’ indicate steps and procedures

required for producing reliable results. The

terms ‘‘should’’ and ‘‘may’’ indicate optional

steps that may be modified or omitted if the

laboratory can demonstrate that the modified

method produces results equivalent or

superior to results produced by this method.’’

1.8 Body of Method

The body of the method must be presented

in the EMMC format. See Section 4.0 of this

appendix for a detailed description of this

format.

2.0 Format

2.1 Page Numbering

Page numbers should appear in the bottom

center of the page. For methods prepared

double-sided, page numbers may appear on

the outside bottom corner of the page (i.e., on

the bottom right for right-hand pages and on

the bottom left for left-hand pages). 2.1.1

Numbering front matter—Number the front

matter (i.e., everything preceding the body of

the method) consecutively using lower-case

Roman numerals. The numerals should

appear on the bottom of each page of the

front matter, except for the cover and title

pages. The cover page is unnumbered. The

title page holds the place of page i, but the

numeral is not displayed.

2.1.2 Numbering body of method—

Number the body of the method

consecutively with Arabic numerals on the

bottom of each page, starting with the

number 1.
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15027

2.2 Method Identification

2.2.1 The method introduction page(s)

should contain a header that identifies the

method number and revision number or

letter. The first page of the body of the

method (preceding 1.0 Scope and

Application) should start with the method

number and title in the top center of the page

with no header. Each pursuant page of the

method should contain a header that

identifies the method number and revision

number or letter. The header also must be

separated from the main body of the method

by a horizontal line running the width of the

page.

2.2.2 If the method was assigned a nonEPA method number during its development

and validation, when preparing the method

for submission to EPA for proposal at 40 CFR

part 136 or 141, edit the header to reflect the

method number assigned by EPA (i.e.,

Method 1664).

2.3 Method Date

The date of the method (month and year)

should appear on the bottom of each page of

the method.

2.4 Font

For text, use an 11-point Times Roman font

(typeface). For first-order headings, use a

bold, 14-point Univers font. For section

numbering, use a bold, 12-point Univers font.

For headers and footers, use an italics, 9-

point Univers font. Univers or Times Roman

fonts may be used in tables as appropriate.

If Univers is unavailable, Helvetica may be

substituted.

2.5 Margins

Left and right margins should be one inch.

The header should be 0.5 inch from the top

of the page, with the text starting one inch

from the top of the page. The page number

should appear 0.5 inch from the bottom of

the page, with the text starting one inch from

the bottom of the page.

2.6 Justification

Use left justification for text. This results

in a ragged-right margin.

2.7 Line Spacing

The method should be single-spaced. (If

preferred, 1.1 line spacing can be used to

enhance readability.) One blank line should

appear between each paragraph and section.

2.8 Method Sections

Each method must contain the sections

given in the EMMC method format. See

Section 4.0 for a detailed description of this

format. If a section does not apply to a

particular method, include the section with

a statement that it is not applicable to that

method.

2.9 Section Headings and Numbering

Use the Modified Decimal Numbering

(MDN) system to organize material presented

in methods and methods manuals. In this

system, each method section and subsection

is assigned a unique number that shows the

relationship of a specific section/subsection

to all previous sections/subsections and

allows for easy reference. This numbering

system is used in this document.

The first-order headings are the 17 sections

identified in Section 4, starting with ‘‘1.0

Scope and Application’’. First-order headings

must appear on a separate line, with a blank

line appearing between the heading and the

section text. Subsections are numbered and

may or may not have a heading preceding the

text. Second-order headings or sections are

numbered 1.1, 1.2, 1.3, 1.4, etc. Third-order

headings or sections are numbered 1.1.1,

1.1.2, 1.1.3, etc. Fourth-order headings or

sections are numbered 1.1.1.1, 1.1.1.2,

1.1.1.3, etc.

Do not number beyond the fourth-order

heading or section. If additional subdivisions

are necessary, use (a), (b), (c), etc. to identify

further divisions. Use of subdivisions below

the fourth-order heading or section should be

avoided where possible by organizing the

material differently.

2.10 Indentation

First-order headings should appear flush

left. Each subsequent order heading should

be block-indented to align with the text of the

previous order heading. This indentation

method is illustrated in this document.

2.11 Electronic Submission

Methods and methods manuals must be

prepared and submitted to EPA in both

hardcopy and electronic formats.

2.11.1 Hardcopy methods should be

produced in black type on white or off-white

recycled paper and printed or copied doublesided.

2.11.2 Electronic methods must be

submitted in machine-readable format, either

ASCII or Agency standard (Novell

WordPerfect 6.1 or later).

2.11.3 To enable anyone accessing a

method electronically to be certain they have

retrieved the entire section or method

accessed, include a ‘‘section end’’ notice at

the end of each first-order section. This is

illustrated as follows:

2.12 References

Use the following format for order, content,

and punctuation when listing references.

2.12.1 Books—author’s name or names

(initials last), title of book (underline, period,

no quotation marks), name of publisher,

address of publisher (city and state), year of

publication, and page number, if applicable

2.12.2 Magazines and Journals—author’s

name or names (initials last), ‘‘title of paper’’

(quotation marks, comma), volume number,

issue number (this may be omitted if the

journal page numbers are continuous

throughout the volume), date of publications,

and page numbers. Example: Jones, J.J., and

Smith, R.R., ‘‘Correlation of Brinell Hardness

and Tensile Strength, Materials in Design

Engineering. Vol. 10, No. 2, February 1958,

pp. 52–67.

2.12.3 Proceedings, Transactions,

Reports, Bulletins, etc.—author’s name or

names (initials last), ‘‘title of paper’’ (in

quotation marks), name of publication

(underline, no quotation marks, comma),

name of publisher, volume number, if any

date of publication, and page numbers.

2.12.4 Symposium Volumes or Other

Books Comprising Collections of Papers—

Follow style for books, above and add title

of paper, in quotes, after author’s name.

2.12.5 Patents—patent number and data.

2.12.6 EPA methods—Method number

and name, EPA report number, U.S.

Environmental Protection Agency, laboratory

and/or office, location, date.

3.0 Conventions

3.1 Capitalization, Italics, Underlining, and

Boldface

3.1.1 Capitalization

3.1.1.1 For first-order headings

(numbered 1.0, 2.0, 3.0, etc.), use initial

capitalization of major words.

3.1.1.2 For second-, third-, or fourth-order

headings, capitalize the first word of the

heading only.

3.1.2 Italics—Italicize words or blocks of

text for emphasis. Equations and notes

interspersed in the text also should be

italicized.

3.1.3 Underlining—Underline words that

are defined in the Definitions section (or

glossary). Use underlining in tables as

appropriate for clear presentation of material.

Do not use underlining for emphasis; use

italics instead but avoid overuse of emphasis.

3.1.4 Boldface—Boldface the following

items:

3.1.4.1 The method number and title on

the cover page, title page, and page 1 of the

method.

3.1.4.2 Acknowledgments, Disclaimer,

and Introduction headings.

3.1.4.3 First-order headings.

3.1.4.4 Section numbering.

3.1.4.5 Equation numbers.

3.1.4.6 The word ‘‘Note:’’ preceding text

notes.

3.2 Punctuation

3.2.1 Always use a comma after the

second to last entry in a series.

3.2.2 A dash may be used between a

subheading and text that directly follows the

subheading. There should be no blank space

before or after the dash, e.g., ‘‘Matrix

Spikes—The laboratory must spike...’’

3.2.3 As a general rule, use a hyphen in

compound modifiers to avoid ambiguity, e.g.,

1–L flask. (In some cases, the hyphen can be

left out without ambiguity, e.g., toxic

chemical waste.) Do not use a hyphen after

an adverb ending in ‘‘ly,’’ e.g., commonly

accepted practice.

3.2.4 Bullets are not to be used in the

body of the method. If used in introductory

material, the text following the bullet should

start with a capital letter. Short bullets do not

require periods at the end; long (multipleline) bullets do. Semicolons or commas

should not be used after bulleted text.

3.3 Footnotes

Use footnotes only in tables. Footnotes

should be designated with numbers or lower

case letters in superscript, and should appear

below the body of the table.

3.4 Text Notes

Notes may be used within the text to

highlight important information regarding

use of the method. Use a margin-to-margin

line across the page both preceding and

following the note to set it off from the text.

3.5 Equations

Equations should be numbered Equation 1,

Equation 2, etc., consecutively as they appear

in the text. Use a margin-to-margin line

across the page both preceding and following
15028 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

the equation to set it off from the text.

Equations should be presented in italics. The

equation is followed by ‘‘where:’’ and a list

of terms used in the equation (e.g., where: n

= number of samples, x = concentration in

each sample).

3.6 Tables and Figures

Tables and figures appear in Section 17.0.

3.6.1 Number tables and figures

consecutively with Arabic numerals, and

give each a title that is complete and

descriptive.

3.6.2 In table column headings, specify

the quantity being tabulated, followed by the

units of measurement shown in parentheses.

For example, ‘‘Amount spiked (μg/L)’’.

3.6.3 Place table and figure titles above

the information presented.

3.6.4 Figures may be enclosed in a box if

desired.

3.7 Trademarks

3.7.1 Avoid the use of trademarks or

brand names whenever possible. For

examples, use the term ‘‘borosilicate glass’’

rather than the trademarks Pyrex or Kimax;

use ‘‘fluoropolymer’’ rather than Teflon. (See

Section 4.6.4.)

3.7.2 When a trademark or brand name is

used, capitalize it.

3.8 Text References

Text references are references to other

locations within the method, not references

to any outside source. References to other

sources appear in Section 16.0. Do not

incorporate essential information into the

method by referring to another method.

In the method text, refer to other sections

of the method capitalizing the word

‘‘Section.’’ Section references should appear

in parentheses at the end of the phrase or

sentence to which the reference applies, for

example, (Section 9.6).

3.9 Units, Symbols, Abbreviations, and

Acronyms

3.9.1 Units and symbols from the

international metric system (SI, from the

French name, Le Syste`me International des

Unites) are to be used. SI is based on seven

basic units that are dimensionally

independent. The SI unit of time is the

second (symbol = s) which should be used

if practical. The SI unit of volume is the

cubic meter (symbol = m3) but the spectral

name liter (symbol = L) can be used for

liquids and gases. Although the SI unit for

mass is kilogram (symbol = kg), the use of

gram (g) with or without prefixes is

appropriate.

3.9.2 Symbols, not abbreviations, should

be used for units. Symbols are not followed

by a period except when used at the end of

a sentence. Unit symbols are written in lower

case except for the symbol for liter (L) or

where the unit name was derived from a

proper name, such as Pa, from Pascal. When

a quantity is expressed as a numerical value

and a unit symbol, a space should be left

between them, except between the number

and symbol for degree Celsius (e.g., 20°C) and

for degree, minute, and second of plane

angle.

3.9.3 Use commonly accepted acronyms

and abbreviations in text and tables. An

acronym is a word formed from the first or

first few letters of other words; everything

else is an abbreviation. In many cases, an

acronym or abbreviation is more readily

identifiable than its narrative counterpart.

Always spell out the term the first time it is

used and follow it with the acronym or

abbreviation shown in parentheses, e.g.,

material safety data sheet (MSDS), relative

percent difference (RPD), or United States

Environmental Protection Agency (EPA).

Acronyms and nearly all abbreviations have

no periods or spaces between letters. As

depicted in these examples, although the

acronym or abbreviation is capitalized, the

narrative version of it is not capitalized

unless it is a proper name such as a

government agency, society, or association.

Once an acronym or abbreviation is

introduced in this manner, use only the

acronym or abbreviation subsequently.

3.9.4 When a long word or phrase for

which there is no standard acronym or

abbreviation is used frequently, it may be

replaced by an acronym or abbreviation that

is explained when it first occurs. For

example, relative centrifugal force (RCF).

3.10 Numerals

3.10.1 Spell out single-digit numbers (one

through nine), with the following exceptions:

3.10.1.1 Use numerals when the quantity

is partly fractional, e.g., 1.15, 11⁄2.

3.10.1.2 Use numerals when the number

is followed by a unit symbol, e.g., 1 m, 9%,

3 ppm. In the method text, units should be

spelled out, so the numbers one through nine

associated with the units would be spelled

out also (e.g., one meter, nine percent, three

parts per million).

3.10.1.3 Use numerals to identify

equations and tables (e.g., Equation 2, Table

5).

3.10.1.4 In sentences containing multiple

numbers, if some numbers must be numerals,

use numerals for all (e.g., 2 tests and 16

weighings).

3.10.2 Use numerals for multiple-digit

numbers (10 and above), with the following

exceptions:

3.10.2.1 Do not begin a sentence with a

numeral. When the numeral is spelled out,

also spell out the unit following (e.g., One

gram is usually sufficient.)

3.10.2.2 Spell out round numbers that are

used in an indefinite sense (e.g., a hundred

feet or so).

3.10.3 When a number is used as an

adjective, insert a hyphen between the

number and the unit symbol (e.g., 100-mL

volumetric flask, 1-L sample).

3.10.4 When writing decimal numbers of

value less than one, place a zero before the

decimal point (e.g., 0.45 g).

3.10.5 Do not point-off numbers of four

figures (1234) except in tables when they

occur in a column containing numbers of

more than four figures. Point-off numbers of

more than four figures, using commas with

no spaces (e.g., 1,325,000).

3.10.6 In expressing ranges and ratios in

text, use 1 to 10 or 1:10, not 1–10. A hyphen

may be used for ranges in tables.

3.11 Significant Digits

Handle numbers with careful regard for

correspondence between the data accuracy

and the given number of digits. The number

of significant digits should neither sacrifice

nor exaggerate accuracy.

3.11.1 Any digit that is necessary to

define the specific value or quantity is

significant and should be used. For example,

when measured to the nearest 1 m, a distance

may be 157 m, which has three significant

figures; when measured to the nearest 0.1 m,

the distance may be 157.4 m, which has four

significant figures.

3.11.2 When adding or subtracting

numbers with different degrees of precision,

the answer should contain no digits farther

to the right than the least precise number.

Numbers should first be rounded to one digit

farther to the right than that of the least

precise number. The answer is then rounded

to the same number of significant figures as

the least precise number.

3.11.3 For multiplication and division,

the product or quotient should contain no

more significant figures than are contained in

the number with the fewest significant

figures.

3.11.4 Examples to distinguish the

addition/subtraction and multiplication/

division rules are:

Addition: 113.2+1.43=114.63, rounded to

114.6

Subtraction: 113.1¥1.43=111.77, rounded to

111.8

Multiplication: 113.2×1.43=161.876, rounded

to 162

Division: 113.1÷1.43=79.16, rounded to 79.2

Note: The product and quotient above

should contain only three significant figures

because the number 1.43 contains only three

significant figures. The above sum and

difference, however, contain four significant

figures, because digits that occur to the right

of the last significant in the least precise

number are rounded.

3.12 Order of Magnitude

Zeros may be used to indicate a specific

value or to indicate the order of magnitude

of a number. For example, in the number

203,185,000, representing population

rounded to thousands, the first six digits are

significant. The last three digits are zeros that

indicate the order of magnitude.

3.13 Rounding

3.13.1 When the first digit discarded is

less than five, the last digit retained is not

changed.

3.13.2 When the first digit discarded is

five or greater, or when five is followed by

a digit other than zero, the last digit retained

is increased by one.

3.13.3 When the first digit discarded is

exactly five followed only by zeros, the last

digit retained is rounded upward if it is an

odd number and is not adjusted if it is an

even number.

4.0 Content

In accordance with EMMC format, each

analytical method must contain 17 specific

topical sections in a designated order. The

required order and content of these sections

are listed and described below. All of these

sections are mandatory for all methods.

1.0 Scope and Application

2.0 Summary of Method

3.0 Definitions

4.0 Interferences
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15029

5.0 Safety

6.0 Equipment and Supplies

7.0 Reagents and Standards

8.0 Sample Collection Preservation and

Storage

9.0 Quality Control

10.0 Calibration and Standardization

11.0 Procedure

12.0 Data Analysis and Calculations

13.0 Method Performance

14.0 Pollution Prevention

15.0 Waste Management

16.0 References

17.0 Tables, Diagrams, Flowcharts, and

Validation Data

Starting with section 11.0 Procedure,

additional numbered sections may be

inserted as required by the particular

method; however, the sections listed above

must appear in each method in the order

listed.

Note: Subsections within each of the 17

required sections do not need to correlate

directly to the subsections included here. In

other words, the information mentioned in

4.1.1 below might be covered in two or more

subsections in a method.

4.1 Scope and Application

This section outlines the purpose, range,

limitations, and intended use of the method,

and identifies target analytes.

4.1.1 Define the purpose and intended

use of the method. State what the method is

based upon, noting any relationship of the

method to other existing analytical methods.

Indicate whether the method is associated

with a sampling method. Include the

following statement: ‘‘This method is for use

in the Environmental Protection Agency’s

(EPA’s) data gathering and monitoring

programs under the Clean Water Act, the

Resource Conservation and Recovery Act, the

Comprehensive Environmental Response,

Compensation, and Liability Act, and the

Safe Drinking Water Act.’’

4.1.2 List analytes that can be measured

by the method, including each analyte’s

Chemical Abstracts Service Registry Number

(CASRN). If regulations cite other than the

most commonly used analyte name, refer to

the regulation. For pesticides, use

‘‘acceptable common names.’’ The use of

registered trade names is permitted.

4.1.3 Identify the matrix(ces) for which

the method has been found satisfactory.

4.1.4 Indicate the statistically determined

method detection limit (MDL) and the

analyte concentration range over which the

method is applicable. State the matrix(ces) in

which MDL was determined. If the MDL is

not available, report an instrumental

detection limit and define how it was

derived. Indicate the minimum level (ML)

and water quality criteria if appropriate to

the analyte and method.

4.1.5 Describe method limitations, such

as ‘‘This method is not applicable to saline

water,’’ or ‘‘This method is not intended for

determination of metals at concentrations

normally found in treated and untreated

discharges from industrial facilities.’’

Indicate any means of recognizing cases

where the method may not be applicable to

the sample under test.

4.1.6 List any restrictions that may apply,

such as ‘‘This method is restricted to use by

or under the supervision of analysts

experienced in * * *’’

4.1.7 Include the following statement

regarding performance-based methods: ‘‘This

method is performance-based. The laboratory

is permitted to omit any step or modify any

procedure (e.g., to overcome interferences, to

lower the cost of measurements), provided

that all performance requirements in this

method are met. Requirements for

establishing method equivalency are given in

Section 9.1.2.’’

4.1.8 Include the following statement:

‘‘Each laboratory that uses this method must

demonstrate the ability to generate acceptable

results using the procedure in section 9.1.2.’’

4.2 Summary of Method

This section provides an overview of the

method procedure and quality assurance.

4.2.1 Outline, specifying amounts of

sample and reagent, the procedure that is

followed to determine the presence or

absence of the listed analytes. Include any

sample pretreatment, such as filtration or

digestion. In this description, identify the

basic steps involved in performing the

method, but omit the details that are a

necessary part of the complete statement of

procedure.

4.2.1.1 For chemical methods, state the

type of procedure (colorimetric,

electrometric, volumetric, etc.) and describe

the source of color, major chemical reaction,

including pertinent chemical equations, etc.

For instrumental methods, state the

technique.

4.2.1.2 In the ‘‘Summary of Method’’

section, use the passive voice, e.g.,

‘‘Instrumental drift is corrected by using

internal standardization,’’ rather than

‘‘Correct instrumental drift by using internal

standardization.’’

4.2.2 Identify the determinative step in

the method.

4.2.3 State in a summary fashion how

quality is assured in the method.

4.2.4 List options to the method, if

applicable.

4.3 Definitions

This section includes definitions of terms,

acronyms, and abbreviations used in the

method. If preferred, definitions may be

provided in a glossary at the end of the

method or manual. In this case, the

definitions section must still appear in the

method, with a notation that definitions are

provided in a glossary at the end of the

method. Refer to the specific section number

of the glossary.

4.3.1 Include an introductory statement

as follows: ‘‘The definitions and purposes

below are specific to this method, but have

been conformed to common usage as much

as possible.’’

4.3.2 List units of weight and measure

and their abbreviations or acronyms used in

the method.

4.3.3 Alphabetically list and define terms,

acronyms, and abbreviations used in the

method. Where appropriate, include the

purpose (e.g., the purpose of the field blank

is to determine if the field or sample

transporting procedures and environments

have contaminated the sample).

4.3.4 Include definitions of the terms

may, may not, must, and should, as follows:

4.3.4.1 May: This action, activity, or

procedural step is neither required nor

prohibited.

4.3.4.2 May not: This action, activity, or

procedural step is prohibited.

4.3.4.3 Must: This action, activity, or

procedural step is required.

4.3.4.4 Shall: This action, activity, or

procedural step is required.

4.3.4.5 Should: This action, activity, or

procedural step is suggested but not required.

4.4 Interferences

This section identifies known or potential

interferences that may occur during use of

the method, and describes ways to reduce or

eliminate interferences.

4.4.1 Describe any known or potential

problem(s) (e.g., sample or equipment

contamination, instrument noise) that may be

encountered during the performance of the

method and the source of the problem(s).

Recommend techniques to avoid or minimize

the problem(s) (e.g., ways to reduce sample

or equipment contamination, or instrument

noise).

4.4.2 Identify any substances, ions, or

properties that are known to or likely to

cause interference and the amounts that are

known to or likely to interfere. Sometimes

this information can be obtained only by

observation during the analysis. In such

cases, include appropriate notes under

‘‘Procedure’’ or ‘‘Data Analysis and

Calculations.’’

4.5 Safety

This section describes special precautions

needed to ensure personnel safety during the

performance of the method. Procedures

described here should be limited to those

which are above and beyond good laboratory

practices. The section must contain

information regarding specific toxicity of

analytes or reagents.

4.5.1 Identify and warn analysts of

potential hazards associated with using the

method (e.g., toxicity or carcinogenicity of

analytes or reagents, explosions, fire,

radiation). Recommend techniques to

minimize hazards where possible (e.g.,

performing operations in a hood or glove

box).

4.5.2 Where the toxicity or

carcinogenicity of each compound or reagent

has not been precisely determined, include

the following statement: ‘‘The toxicity or

carcinogenicity of each analyte or reagent has

not been precisely determined; however,

each chemical should be treated as a

potential health hazard. Exposure to these

chemicals should be reduced to the lowest

possible level. It is suggested that the

laboratory perform personal hygiene

monitoring of each analyst using this method

and that the results of this monitoring be

made available to the analyst.’’

4.5.3 Indicate the steps in the procedure

at which hazards that could damage

equipment may occur by use of the word

CAUTION in boldface type, followed by the

details of the precautionary measures that

must be taken. If any step in the procedure

could result in personal injury or death,

include the word WARNING in boldface

type, followed by the details of the protective

measures that must be taken.
15030 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

4.5.4 Include the following statements:

‘‘This method does not address all safety

issues associated with its use. The laboratory

is responsible for maintaining a safe work

environment and a current awareness file of

OSHA regulations regarding the safe

handling of the chemicals specified in this

method. A reference file of material safety

data sheets (MSDSs) should be available to

all personnel involved in these analyses.

Additional information on laboratory safety

can be found in References lll.’’

4.6 Equipment and Supplies

This section lists and describes all

nonconsumable supplies and equipment

needed to perform the method.

4.6.1 Include the following statement as a

note preceding the list of equipment and

supplies:

‘‘Note: Brand names, suppliers, and part

numbers are cited for illustrative purposes

only. No endorsement is implied. Equivalent

performance may be achieved using

equipment and materials other than those

specified here, but demonstration of

equivalent performance that meets the

requirements of this method is the

responsibility of the laboratory.’’

4.6.2 Categorize and list required

equipment and supplies by the logical order

of use; e.g., sampling equipment, equipment

for glassware cleaning, equipment for

calibration, equipment for sample extraction,

etc. Do not list common laboratory

equipment, but do include special or

modified forms of unusual sizes or numbers

of common equipment that are required or

that may require special preparation.

4.6.3 Describe the essential features of

each required item. Include schematic

drawings as needed to clarify or supplement

apparatus descriptions.

4.6.4 Avoid the use of trademarks, brand

names, trade names, or suppliers unless a

specific manufacturer’s product is required

for a well-defined reason or the availability

of the product is limited (i.e., the apparatus

is unique or unusual). For example, when

special types of glassware are required, such

as heat-resistant, chemical-resistant, etc.,

state the significant characteristic desired

rather than a trademark (’’borosilicate glass’’

rather than Pyrex or Kimax). If only a single

source is known, that supplier may be

identified.

4.6.5 Whenever a brand name is used,

include ‘‘or equivalent’’ following the brand

name or part number to demonstrate that use

of another product is acceptable.

4.6.6 Include any special glassware

cleaning instructions.

4.6.7 List special facilities required, such

as a special room for handling hazardous

materials.

4.7 Reagents and Standards

This section lists and describes all reagents

and standards required to perform the

method, and provides preparation

instructions and/or suggested suppliers as

appropriate.

4.7.1 List the name of the reagent and the

necessary purity, followed by any descriptive

terms. List reagents in a logical order (e.g., by

order of occurrence or use, by group). The

method should require that reagents be ACS

Reagent Grade unless otherwise specified.

4.7.2 Spell out the full name of inorganic

reagents when first used, and include within

parentheses the exact chemical formula,

showing its water of crystallization, etc.

Subsequently, refer to inorganic compounds

by formula if they can be specified clearly in

this way. As exceptions, always spell out the

word ‘‘water’’ and the names of substances in

their elemental state (e.g., ‘‘lead’’ not ‘‘Pb,’’

‘‘oxygen’’ not ‘‘02’’).

4.7.3 Spell out organic, organometallic, or

complex inorganic compounds; chemical

formulae are not necessary. Cite the CASRN

to avoid ambiguity.

4.7.4 Avoid the use of trademarks and

names of patented products. Use chemical

names and common names, unless a specific

product is required for a well-defined reason.

The use of registered trade names is

permitted.

4.7.5 Unique and unusual reagents can be

named by brand. Whenever a brand name is

used, include ‘‘or equivalent’’ following the

brand name to demonstrate that another

product can be used.

4.7.6 Specify the concentration of

inorganic reagents in applicable terms, as

follows:

Concentrated acids and bases: density

Dilute acids and bases: volume ratio, x+y (x

volume of reagent added to y volume by

water)

Nonstandardized solutions: normality,

expressed decimally; or the equivalent of 1

mL of solution in terms of grams of a given

element expressed as 1 mL = x.xx g of

* * *

4.7.7 Specify filter paper by describing

the significant characteristic such as porosity,

rate of filtering ash content, etc., or by

reference to ASTM Specification D1100 for

Filter Paper for Use in Chemical Analysis.

4.8 Sample Collection, Preservation, and

Storage

This section provides requirements and

instructions for collecting, preserving, and

storing samples.

4.8.1 Give detailed directions for

collecting, filtering (if applicable),

preserving, shipping, and storing samples.

4.8.2 Use preservation procedures and

holding times consistent with those specified

in current EPA publications or regulations

and with other methods for the same

analytes.

4.9 Quality Control

This section cites the procedures and

analyses required to fully document the

quality of data generated by the method. The

required components of the laboratory’s

quality assurance (QA) program and specific

quality control (QC) analyses are described in

this section. For each QC analysis, the

complete analytical procedure, the frequency

of required analyses, and interpretation of

results are specified.

Note: To ensure data quality, water

methods must specify a comprehensive

laboratory QA program. The minimum QC

requirements that must be included in

methods proposed at 40 CFR part 136 or part

141 are specified at 40 CFR 136.3 table IF,

136.4, 136.5 and 141.27. The method should

specify QC acceptance criteria.

4.9.1 Include the following statements in

the first subsection (Section 9.1): ‘‘Each

laboratory that uses this method is required

to operate a formal quality assurance program

(Reference lll). The minimum

requirements of this program consist of an

initial demonstration of laboratory capability,

ongoing analyses of standards and blanks as

a test of continued performance, and

[complete as appropriate to the method].

Laboratory performance is compared to

established performance criteria to determine

if the results of analyses meet the

performance characteristics of the method.’’

‘‘The analyst shall make an initial

demonstration of the ability to generate

acceptable accuracy and precision with this

method. This ability is established as

described in Section 9.2.’’

4.9.2 In Section 9.1, cite any options that

the analyst is permitted, e.g., alternate

extraction, concentration, or cleanup

procedures; changes in columns or detectors.

Specify that the analyst is required to repeat

the required initial demonstration of

laboratory capability each time a

modification is made to the method. Include

the following statements: ‘‘Each time a

modification is made to the method, the

analyst is required to repeat the procedure in

section 9.2. If the change will affect the

detection limit of the method, the laboratory

is required to demonstrate that the MDL (40

CFR part 136, Appendix B) is lower than the

MDL for that analyte in this method, or onethird the regulatory compliance level,

whichever is higher. If the change will affect

calibration, the analyst must recalibrate the

instrument according to section 10.’’;

‘‘Changes that degrade method

performance are not allowed. If an analytical

technique other than the techniques specified

in this method is used, that technique must

have a specificity equal to or better than the

specificity of the techniques in this method

for the analytes of interest.’’; and

‘‘The laboratory is required to maintain

records of modifications made to this

method. These records include the following,

at a minimum:

—The names, titles, addresses, and telephone

numbers of the analyst(s) who performed

the analyses and modification, and of the

quality control officer who witnessed and

will verify the analyses and modification.

—A listing of analytes measured, by name

and CASRN.

—A narrative stating reason(s) for the

modification(s).

—Results from all QC tests comparing the

modified method to this method,

including:

(a) Calibration (section 10)

(b) Calibration verification (section 9.5)

(c) Initial precision and recovery (section

9.2.2)

(d) Analysis of blanks (section 9.4)

(e) Accuracy assessment (section 9.3)

(f) Ongoing precision and recovery (section

9.6)

—Data that will allow an independent

reviewer to validate each determination by

tracing the instrument output (weight or
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15031

other signal) to the final result. These data

are to include:

(a) Sample numbers and other identifiers

(b) Extraction dates

(c) Analysis dates and times

(d) Analysis sequence/run chronology

(e) Sample weight or volume

(f) Extract volume

(g) Make and model of analytical balance and

weights traceable to NIST

(h) Copies of logbooks, printer tapes, and

other recordings of raw data

(i) Data system outputs, and other data to link

the raw data to the results reported

4.9.3 In the remainder of section 9.1,

outline the QC requirements that will be

described in the section, and the purpose for

each type of QC (e.g., blanks, matrix spikes/

matrix spike duplicates, calibration

verification).

4.9.4 In section 9.2, describe in detail the

initial demonstration of laboratory capability.

4.9.5 Describe the procedure for matrix

spikes, calculating percent recoveries, and

calculating relative percent difference for

duplicates.

4.9.6 Provide instructions for analysis of

blanks, e.g., laboratory reagent blanks,

method blanks.

4.9.7 Specify requirements for calibration

verification.

4.9.8 Provide instructions for analysis of

ongoing precision and recovery standards.

4.9.9 Include requirements for analysis of

quality control samples (QCS).

4.9.10 Include the following statement at

the end of section 9.0: ‘‘Depending upon

specific program requirements, field

replicates and field spikes of the analytes of

interest into samples may be required to

assess the precision and accuracy of the

sampling and sample transporting

techniques.’’

4.10 Calibration and Standardization

This section describes the method/

instrument calibration and standardization

process, and required calibration verification.

Corrective actions are described for cases

when performance specifications are not met.

4.10.1 Specify operating conditions or

refer to manufacturer’s recommended

operating conditions. If appropriate, specify

a precalibration routine as needed to

document instrument stability.

4.10.2 Give detailed instructions for the

use of standards to prepare calibration lines

or tables. Include the number of calibration

standards, the need for blanks, the frequency

of calibration checks, the critical range, etc.

4.10.3 Give detailed instructions for

internal standardization, including number

and concentration of internal standards.

4.10.4 Include instructions for calibration

data storage.

4.11 Procedure

This section describes the sample

processing and instrumental analysis steps of

the method, and provides detailed

instructions to analysts.

4.11.1 For methods used for

determination of a method-defined analyte,

include the following statement in the

introductory portion of Section 11.0

Procedure: ‘‘This method is entirely

empirical. Acceptable results can be obtained

only by strict adherence to all details.’’ Do

not include this statement in methods for

which the analyte is a chemical or physical

parameter, the characteristics of which are

known (e.g., oil and grease, COD, BOD).

4.11.2 Include in proper sequence

detailed directions for performing the

analysis.

4.11.2.1 Include steps that are essential to

the process and avoid unnecessarily

restrictive instructions.

4.11.2.2 Organize the procedure by

logical order of activity, e.g., sample

preparation, extraction, analysis.

4.11.2.3 Describe the procedure in the

imperative mood, present tense, e.g., ‘‘Heat

the sample aliquot,’’ rather than ‘‘The sample

aliquot should be heated.’’ Comments and

descriptive information that are not in the

imperative mood may be included, as

appropriate.

4.11.2.4 Write the text so that it is concise

and easily understandable.

4.11.2.5 When alternative procedures are

given, state which is preferred.

4.11.3 In chemical methods, specify the

size of sample aliquot and indicate the

required measurement accuracy. (There is no

need to weigh a sample to five significant

figures in a spectrophotometric method

where the final absorbance measurement

yields data with only three significant

figures).

4.11.4 Include ‘‘Notes’’ throughout the

procedure to highlight critical points. Include

notes of ‘‘WARNING’’ or ‘‘CAUTION’’ as

appropriate to identify known or potential

hazards to the analyst or the equipment,

respectively.

4.11.5 Indicate steps in which timing is

critical, e.g., if a determination may not be

interrupted overnight. For a color reaction,

indicate how long the color is stable.

4.12 Data Analysis and Calculations

This section provides instructions for

analyzing data, and equations and definitions

of constants used to calculate final sample

analysis results.

4.12.1 Calculations—Provide directions

for calculating the results of the analysis,

including any equations.

4.12.1.1 Use the imperative mood, e.g.,

‘‘Report results to three significant figures,’’

rather than ‘‘Results should be reported to

three significant figures.’’

4.12.1.2 Where there may be ambiguity of

meaning, spell out names in the text (e.g.,

total Kjeldahl nitrogen) but use the

abbreviations (e.g., TKN) in text where the

meaning is clear, and in equations.

4.12.1.3 Define the symbols used in the

equation immediately under the equation.

4.12.1.4 Use numerical values for any

constants. Identify dilution factors, titration

factors, etc.

4.12.2 Reporting Results

4.12.2.1 Indicate the units in which the

results are to be reported (e.g., ®g/L, mg/kg).

4.12.2.2 If the sample is a solid material

such as a sediment or sludge, indicate

whether results are to be reported as wet

weight or dry weight.

4.12.2.3 Specify the number of significant

figures to be reported.

4.12.2.4 Require that all values obtained

by various QC procedures are reported along

with the calculated results of the analysis.

4.12.3 Interpretation of results—Use this

heading in place of Calculations when the

results of the analysis must be expressed in

descriptive form, relative terms, or abstract

values. List and define the descriptive terms

or classifications used.

4.13 Method Performance

This section provides method performance

criteria for the method, including precision/

bias statements regarding detection limits

and source/limitations of data produced

using the method.

Note: Requirements for validating new

methods are specified in [cite the volume and

page number of the Federal Register in

which the streamlining initiative is

promulgated].

4.13.1 Explain how the method was

validated. Provide a detailed description of

method performance, including data on

precision, bias, detection limits (including

the method by which they were determined

and matrices to which they apply), and

statistical procedures used to develop

performance specifications.

Note: This information can be provided

through reference to the method validation

study.

4.13.2 At a minimum, state singleoperator precision and accuracy on reagent

water. If other sample types have been

investigated, also provide this information

for them.

4.13.3 If a collaborative study has been

completed, describe the study and report the

number of participating operators and

laboratories, spike concentrations, level of

replication, types of background waters, and

any other significant aspects. If the study has

been documented, cite the study report and

include it in the References section. When

citing reference documentation, the details of

the study do not have to be included in this

section.

4.14 Pollution Prevention

This section describes aspects of the

method that minimize or prevent pollution

known to be or potentially attributable to the

method.

4.14.1 Cite potential sources of pollution

attributable to the method.

4.14.2 Recommend ways to minimize

pollution.

4.15 Waste Management

This section describes minimization and

proper disposal of waste and samples.

4.15.1 Include the following statement as

the first subsection: ‘‘It is the laboratory’s

responsibility to comply with all federal,

state, and local regulations governing waste

management, particularly the hazardous

waste identification rules and land disposal

restrictions, and to protect the air, water, and

land by minimizing and controlling all

releases from fume hoods and bench

operations. Compliance with all sewage

discharge permits and regulations is also

required.’’

4.15.2 Provide instructions for sample

and waste handling and disposal.
15032 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

4.15.3 Include the following statement as

the last subsection: ‘‘For further information

on waste management, consult The Waste

Management Manual for Laboratory

Personnel and Less is Better: Laboratory

Chemical Management for Waste Reduction,

both available from the American Chemical

Society’s Department of Government

Relations and Science Policy, 1155 16th

Street NW., Washington DC, 20036.’’

4.16 References

This section lists references for source

documents and publications that contain

ancillary information.

Note: Each method should be a freestanding document, providing all

information necessary for the method user to

perform the method may be found.

References within a method should be

restricted to associated or source material.

Procedural steps or instructions should not

be referenced as being found elsewhere, but

should be included in total within the

method.

4.16.1 Include references for other,

related EPA methods; and published studies/

articles relating to method performance,

techniques, or analytes, and health and

safety.

4.16.2 List references in the order cited in

the method, and assign each reference an

identification number using Arabic numerals.

4.16.3 As a rule, do not list documents

that are not readily accessible to the reader

(e.g., unpublished theses, personal

communications, private correspondence). If

it is important to list these types of

documents, identify where the reader may

obtain a copy of the document.

4.17 Tables, Diagrams, Flowcharts, and

Validation Data

This section contains all method tables and

figures (diagrams and flowcharts), and may

contain validation data referenced in the

body of the method.

4.17.1 In addition to tables and figures,

include additional useful information.

Examples of such information include:

4.17.1.1 Notes on significance and

interpretation of the method, used to amplify

the statement in the text.

4.17.1.2 Development of equations used

in the calculations.

4.17.1.3 Charts or supplementary

information for computations.

4.18 Glossary

This optional section contains a glossary of

terms, acronyms, abbreviations, and symbols

used in the method.

Note: This information may appear in the

Definitions section of the method (Section

3.0) or may be included in a glossary at the

end of the method.

4.18.1 In the first subsection of the

glossary, identify units of weight and

measure used in the method and their

abbreviations.

4.18.2 In the second subsection, define

key terms and all acronyms used in the

method.

4.18.2.1 List terms, acronyms, and

abbreviations alphabetically.

4.18.2.2 Definitions should appear only

once. Where an acronym or abbreviation

represents a term that is defined under its

full name, reference the full name as the

definition for acronym or abbreviation.

Appendix G to Part 136—Method

Flexibility, Equivalency and Approval

Section 1 of this appendix defines the

analyst’s flexibility to modify certain steps in

a reference method. Section 2 specifies

requirements for assessing the equivalency of

a method modification. Section 3 specifies

requirements for submitting method

modifications or new methods for approval.

1.0 Method Flexibility

This section specifies requirements for

exercising method flexibility (i.e.,

‘‘allowable’’ method modifications). Under

requirements specified at 40 CFR 136.4 and

141.27(b), an analyst is allowed to modify a

reference method without seeking formal

approval through the regulatory process

provided the modification is not explicitly

forbidden in the reference method and

provided the analyst demonstrates and

documents that the modified method

produces results that are equal or superior to

results produced by the reference method.

An EPA-designated reference method that

contains (or is supplemented with) QC

acceptance criteria against which to measure

performance of a method modification is the

primary control used to ensure data quality.

Other controls include specific multilaboratory and multi-matrix requirements for

validating modified methods (as specified at

40 CFR 136.4, 136.5(d), 141.27 (b) and (e))

checklists for documenting equivalency (as

specified at Appendix E of this part).

The QC elements and associated QC

acceptance criteria (e.g., calibration,

sensitivity, accuracy, precision) necessary to

demonstrate the equivalency of a modified

method to a reference method are defined at

40 CFR 136.2 and 141.2 and specified at 40

CFR 136.3 Table IF, 136.4, 141.27 (b) and (d).

1.1 Types of Method Modifications

There are two types of method

modifications:

1.1.1 Explicit modifications to approved

methods may be made as explicitly specified

within those methods. Explicit flexibility

exists for all approved methods including

EPA, Standard Methods, ASTM, AOACInternational, and other methods approved at

40 CFR parts 136 and 141.

1.1.2 Allowable modifications beyond

those explicitly allowed in an approved

method that has been designated as a

reference method are allowed provided that

the modification meets the requirements

specified in this appendix, at 40 CFR 136.4,

136.5(d) or 141.27(b) and (e), and at

Appendixes E, F, and G of this part.

Allowable modifications do not apply to

Standard Methods, ASTM, and AOACInternational methods, none of which have

been designated as reference methods.

1.2 Controls on Allowable Modifications

(Method Flexibility)

The controls on method flexibility are:

1.2.1 A requirement to demonstrate and

document equivalency when method

modifications are used.

1.2.2 Designation of a reference method

that contains (or is supplemented with) QC

acceptance criteria for use in demonstrating

equivalency.

1.2.3 Standard procedures for validating

new methods and demonstrating equivalency

of method modifications, based on the

intended use of the method.

1.2.4 Detailed requirements for preparing

the method validation package and

supporting data when new or modified

methods are validated.

1.2.5 Requirements for assessing

equivalency of method modifications.

1.3 Reference Method

All methods approved for use at 40 CFR

parts 136 and 141 have been categorized as

either a ‘‘reference method’’ or an ‘‘other

approved method’’; both types of methods

carry equal regulatory status. The difference

between the methods is that the reference

method contains (or is supplemented with)

detailed QC acceptance criteria that are

required to assess the equivalency of an

allowable method modification.

A reference method is specified at 40 CFR

136.3, 141.23(k), 141.24(e) and 141.40(n). For

some determinative techniques, no currently

approved method contains either all of the

QC acceptance criteria proposed in today’s

rule (e.g., Table ID in 40 CFR part 136) or

sufficient data from which to develop such

criteria. In these cases, no reference method

has been designated; therefore, all of these

methods are classified as other approved

methods. Without a reference method,

analysts are not allowed to modify approved

methods that use that determinative

technique.

Only one reference method is designated

for each unique combination of analyte and

determinative technique to avoid the possible

confusion if two or more reference methods

contained different QC acceptance criteria.

The QC acceptance criteria associated with

the reference method are the sole criteria

against which a method modification is

tested.

1.4 Categories of Allowable Method

Modifications

The four categories of allowable method

modifications are (1) sample collection and

holding procedures, (2) front-end techniques,

(3) determinative techniques, and (4) analyte

addition. These categories are defined below

and described in terms of allowed flexibility

to modify the procedures or techniques

included in each category.

The first category, sample collection and

holding procedures, includes procedures and

reagents used in the field, in transit, and at

the laboratory. This category includes sample

containers, sample holding times,

preservation reagents and procedures, and

shipping and storage procedures and

conditions. Requirements for modifying

sample collection and preservation

conditions are specified at 40 CFR 136.3(c)

and 141.27(b).

Front-end techniques, the second category

of method modifications, include any step in

the analytical process used at the laboratory

that precedes the determinative technique

and includes all procedures, equipment,

solvents, etc., that are used to prepare a

sample for analysis. The third category is the

determinative technique, which is defined as
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15033

the physical and/or chemical process by

which an analyte is identified and its

concentration measured. For most methods,

the determinative technique consists of an

instrumental measurement (e.g., a detector).

The fourth category covers increasing the

analytical scope of a reference method to

include additional analytes.

A person may modify any and all front-end

techniques in the reference method, provided

the modification is not explicitly prohibited

in the reference method and provided the

analyst demonstrates and documents that the

modification produces results equal or

superior to results produced by the reference

method. The person must keep on file the

documents that demonstrate equivalency.

Method developers are cautioned that

modifications to the front-end chemistry of

the method (e.g., extraction solvents, solventto-sample volumes, extraction media, and

pH) require a thorough understanding of the

measurement science that was used to

develop and validate the reference method.

The developer of a modified method may ask

EPA or another regulatory authority for a

technical opinion on the acceptability of the

validation data that supports the method

modification(s).

A reference method may be modified to

allow use of an alternate determinative

technique that is not explicitly prohibited in

the reference method, provided that

equivalency with the reference method

performance is demonstrated and

documented, and provided that four

conditions are met: (1) the alternate

determinative technique must measure a

property similar to the prescribed technique,

(2) the alternate technique must be

demonstrated to be more specific (i.e.,

provides better separation of the analyte from

interferences) and/or more sensitive (i.e.,

produces a lower detection limit) for the

analyte of concern than the determinative

technique in the reference method, (3) there

is not another approved method that uses the

alternate determinative technique for the

determination of that analyte, and (4) use of

the alternate determinative technique would

not result in a nonsensical combination of

analyte, front-end technique, and

determinative technique.

Examples of allowed changes to a

determinative technique are substitution of a

photoionization detector for a flame

ionization detector for determination of

polynuclear aromatic hydrocarbons,

substitution of a nitrogen-phosphorous

detector for an electron capture detector

(ECD) for determination of analytes

containing nitrogen or phosphorous, and

substitution of a fluorescence detector for an

ultraviolet or visible wavelength detector.

Substitution of a mass spectrometer (MS) for

an ECD would not be allowed if there is an

approved MS method that measures the

analyte of concern.

Modifications to the determinative

technique are limited by the four conditions

described above to preclude nonsensical

combinations of analyte and determinative

technique, to encourage a net benefit

(increased sensitivity and/or specificity), and

to preclude multiple reference methods with

the same determinative technique but with

different QC acceptance criteria for the same

analyte(s) of concern. For example, if a mass

spectrometer were substituted for the

conventional detectors in EPA Methods

601—612, all of these methods would

become GC/MS methods, but all would

contain different QC acceptance criteria.

Further, they would all conflict with

approved EPA GC/MS Methods 625 and

1625. Another reason for limiting changes to

the determinative technique is that there are

techniques, such as immunoassay, for which

EPA has no reference method and therefore

no history to ensure that the standardized QC

proposed in today’s rule would be germane

to, or adequate for, assurance of the quality

of data produced by the novel determinative

technique. A new method must be written

and submitted to EPA for approval when a

novel determinative technique is developed.

An analyst may add a new target analyte

to a reference method provided (1) it is

demonstrated that the analyte does not

interfere with determination of the analytes

of concern in that method, (2) QC acceptance

criteria are developed and employed for

determination of the target analyte, (3) there

is not another approved method that uses the

same determinative technique for that

analyte, and (4) that the reason for adding the

analyte is not to avoid the sample

preservation or sample (or extract) holding

time conditions that are already required for

that analyte in another approved method.

The third and fourth conditions preclude

‘‘method shopping’’, whereby an analyst

might add analytes to a reference method

with less rigid QC acceptance, sample

collection, or holding time criteria. Thus, if

a reference method for an analyte of concern

required acidification of the sample, an

analyst does not have the flexibility to

modify a method that does not require

sample acidification to include analysis of

the analyte of concern. Modifications of this

type require EPA approval as a new method.

If QC acceptance criteria do not exist to

allow addition of a new analyte, the

requirements specified at 40 CFR part 136

Appendix E, and at 40 CFR 136.4, 136.5, and

141.27 must be used to develop and obtain

approval for these criteria. Alternatively, QC

acceptance criteria for the new analyte could

be transferred from the criteria for an analyte

with similar chemical characteristics in the

same method or from the criteria for the

analyte in another approved method.

1.5 Method-Defined Analytes

Some techniques may not produce results

equivalent to results produced by techniques

employed for ‘‘method-defined analytes’’. A

method-defined analyte is an analyte that

does not have a specific, known composition

so that the analytical result depends totally

on how the measurement is made. Therefore,

a change to either the front-end steps or the

determinative technique for a methoddefined analyte has the potential of changing

the numerical value of the result for a given

sample. Examples of method-defined

analytes include adsorbable organic halides

(AOX), biochemical oxygen demand (BOD),

total radioactivity, and whole effluent

toxicity (WET).

Until the nature and extent of allowable

flexibility for method-defined analytes is

defined by EPA, these methods may not be

modified using the requirements specified in

this section unless the modified method is

reviewed and approved by EPA. A person

may attempt to demonstrate that the new

technique produces results that are

equivalent to the reference method on a

matrix-by-matrix basis. When these data are

submitted to EPA, EPA will work with the

method developer to determine whether the

submitted combination of analyte and

determinative technique is new and whether

a new method for a method-defined analyte

is desirable.

1.6 New Methods, Screening Methods, and

Modified Methods This section clarifies the

differences between new and modified

methods and the requirements that pertain to

each. This section also describes how

screening methods might be approved in the

future for compliance monitoring under the

CWA and the SDWA.

A new method is a set of procedures that:

(1) Is documented in accordance with the

requirements detailed as specified at

Appendix F of this part,

(2) Contains the standardized QC elements

defined at 40 CFR 136.2 and 141.2,

(3) Contains QC acceptance criteria that

have been developed in accordance with the

requirements at 40 CFR 136.5 and 141.27(c),

(4) Employs a determinative technique for

an analyte of concern that differs from

determinative techniques employed for that

analyte in methods previously approved at

40 CFR part 136 or 141, and

(5) Employs a determinative technique that

is more sensitive and/or selective (specific)

than the determinative techniques in all

methods previously approved for the analyte.

Methods that meet all five of these

characteristics are considered to be definitive

methods, if the method also is sufficiently

selective and quantitative that most positive

results do not have to be verified by analysis

with another method. The term ‘‘definitive’’

is used to distinguish these methods from

screening methods. All methods currently

approved at 40 CFR parts 136 and 141 are

definitive methods.

In this appendix, a screening method is

defined as a method that meets the first four

of the five conditions described above for

new methods and that has been

demonstrated to produce a false negative

probability of no more than one percent (1%)

at the limit(s) of regulatory concern. Methods

can fail the fifth condition for a new method,

if they are non-selective or not quantitative

for the target analyte. A non-selective method

is a method in which the determinative (or

other step) technique in the method may

produce a result for any one of several

analytes that share common physical or

chemical characteristics with the target

analyte. For example, an atrazine

immunoassay might respond to any triazine

(atrazine, simazine, cyanazine) pesticide in

the sample.

In the future, screening methods may be

considered for approval as compliance

monitoring methods provided: (1) the

method meets all the requirements described

in the regulations at 40 CFR 136.5 and

141.27(c), (2) all positive sample results

obtained with the method are confirmed and
15034 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

reported using an approved definitive

method, and (3) the probability of the method

producing a false negative result at

concentrations of regulatory interest is no

more than one percent (1%). For part 141

approval, these criteria may be amended

when the Agency implements the

requirements for screening methods that are

in the August 2, 1996 amendments to the

SDWA.

2.0 Assessing Method Equivalency

This section provides requirements for

assessing the equivalency of a method that

has been modified according to the

requirements specified at 40 CFR 136.4,

136.5(d), 141.27 (b) and (e). Analysts and

regulatory authorities may use these

equivalency requirements to verify and

document that equivalent or better method

performance relative to the reference method

has been achieved and documented by the

laboratory using the method modification.

This section also specifies requirements for

documenting the performance of new

methods and method modifications.

Good communication among analytical

laboratories, regulated entities, and

regulatory authorities is essential for the

method modification assessment process.

Although many compliance monitoring

analyses are performed by contract

laboratories on behalf of the regulated entity,

the responsibility for maintaining validation

documentation for new and modified

methods rests with the regulated entity.

Regulated entities, therefore, must inform

their contract laboratories about the

requirements for detailed documentation of

method modifications.

2.1 Requirements for Documenting

Validation of New and Modified Methods

Although validation requirements vary

depending on the intended use of the new or

modified method, the documentation

requirements are the same. A validation

study report must be prepared for every

study conducted to validate new or modified

methods. The primary basis for documenting

method validations studies are the Checklist

for Initial Demonstration of Method

Performance, the Checklist for Continuing

Demonstration of Method Performance, and

the Certification Statement (collectively

called the ‘‘Checklists’’). The Checklists must

be used by auditors, drinking water

laboratory certification officers, and other

reviewers to evaluate new methods and

method modifications against reference

methods promulgated at 40 CFR parts 136

and 141.

The Checklists and instructions for their

completion are provided at Appendix E in

this part. Regulated entities must make the

Checklists available to the contract

laboratories to document method

modifications. In turn, contract laboratories

are responsible for returning validation study

reports including completed Checklists to the

regulated entities.

The data reviewer should verify that all

validation and documentation requirements

appropriate to the intended tier of the new

or modified have been met as specified at 40

CFR 136.4, 136.5(d), 141.27 (b) and (e). For

Tier 1 method modifications, the completed

Checklists are adequate to document method

equivalency. For all other validation tiers, the

data reviewer must ensure that the validation

study report is complete and includes all

supporting raw data. The following sections

must be included in the report:

2.1.1 A background section that describes

the method and the responsible organization.

2.1.2 A section that describes the study

design and objectives.

2.1.3 A section that describes the study

methodology and implementation

2.1.4 A section that describes the

procedures that were used to report and

validate data.

2.1.5 A results section. (Note: Since

different instruments provide different data,

the specific form of the supporting analytical

data will differ according to the method. For

example, gas chromatography/mass

spectrometry procedures produce

chromatograms, while colorimetric

determinations do not.)

2.1.6 A section for a discussion of the

study results.

2.1.7 A section that describes conclusions

from the study.

2.1.8 An appendix that contains the

Checklists.

2.2 Data Review Guidance for EPA Water

Methods

This section provides guidance for

reviewing data submitted to EPA and state

authorities under CWA and SDWA. The

guidance provides a tool for authorities who

want to perform detailed inspection of data

analyzed by methods under 40 CFR parts 136

and 141. The material presented in this

section is technically detailed and is

intended for data reviewers familiar with

analytical methods.

2.2.1 Standardized Quality Assurance/

Quality Control

Standardized QA/QC is specified for each

reference method and contains the following

elements:

2.2.1.1 Calibration linearity.

2.2.1.2 Calibration verification.

2.2.1.3 Absolute and relative retention

time precision (for chromatographic

analyses).

2.2.1.4 Initial precision and recovery or

‘‘start-up’’ tests.

2.2.1.5 Ongoing precision and recovery.

2.2.1.6 Analysis of blanks.

2.2.1.7 Surrogate or labeled compound

recovery.

2.2.1.8 Matrix spike and matrix spike

duplicate precision and recovery (for nonisotope dilution analyses).

2.2.1.9 Demonstration of method

detection limits.

2.2.1.10 Analysis of reference

sample.When reviewing method validation

data, the permit writer, PWS, or other

individual or organization has the authority

and responsibility to ensure that the test data

submitted contain the elements listed above;

otherwise, the data can be considered

noncompliant.

2.2.2 Details of Data Review

The details of the data review process

depend to a great extent upon the specific

analytical method. Even for data from the

same method, there may be many approaches

to data review. However, given the

standardized QC requirements of the

streamlined methods approval program, a

number of basic concepts apply. The

following sections provide the details for

reviewing data submitted and a rationale for

the QC tests. Results from all QC tests must

be within the QC acceptance criteria

specified in, or associated with, the reference

method to validate that results produced by

a method modification are equivalent or

superior to results produced by the reference

method.

2.2.2.1 Calibration linearity

The relationship between the response of

an analytical instrument to the concentration

or amount of an analyte introduced into the

instrument typically is represented by an

averaged response or calibration factor, a

calibration line, or a calibration curve. An

analytical instrument can be said to be

calibrated in any instance in which an

instrumental response can be related to a

single concentration of an analyte. The

response factor or calibration factor is the

ratio of the response of the instrument to the

concentration (or amount) of analyte

introduced into the instrument.

Nearly all analytical methods focus on the

range over which the response is a linear

function of the concentration of the analyte.

This range usually extends from the

minimum level of quantitation (ML) on the

low end to the point at which the calibration

becomes non-linear on the high end. For

regulatory compliance, it is important that

the concentration of regulatory interest (e.g.,

permit limit; MCL) fall within this range.

Calibration can also be modeled by quadratic

or higher order mathematical functions. The

advantage of a calibration line that passes

through the origin is that an averaged

response factor or calibration factor can be

used to represent the slope of this line. Use

of a single factor simplifies calculations and

the interpretation of the data. Also, it is

easier to discern when an inaccurate

calibration standard has been prepared if the

calibration function is a straight line.

Many analytical methods, particularly

recent methods, specify some criterion for

determining the linearity of the calibration.

When this criterion is met, the calibration

function is sufficiently close to a straight line

that passes through the origin to permit the

laboratory to use an averaged response factor

or calibration factor. Linearity is determined

by calculating the relative standard deviation

(RSD) of the response factor or calibration

factor for each analyte and comparing this

RSD to the limit specified in the method. If

the RSD does not exceed the specification,

linearity through the origin is assumed. If the

specification is not met, a calibration curve

must be used.

For whatever calibration range is used, a

reference method should contain a

specification for the RSD of the response or

calibration factor to establish the breakpoint

between linear calibration through the origin

and a line not through the origin or a

calibration curve. For new methods, the

method developer must provide the RSD

results by which one can judge linearity,

even in instances where the laboratory is

using a calibration curve. In instances where
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15035

the laboratory employs a curve rather than an

average response or calibration factor, the

data reviewer should review each calibration

point to ensure that the response increases as

the concentration increases. If it does not, the

instrument is not operating properly, or the

calibration curve is out of the range of that

instrument, and data are not considered

valid.

2.2.2.2 Calibration Verification

Calibration verification involves the

analysis of a single standard at the beginning

of each analytical shift or after the analysis

of a fixed number of samples (e.g., 10). The

concentration of each analyte in this standard

is normally at the same level as in one of the

calibration standards, typically at 1—5 times

the ML. The concentration of each analyte in

this standard is calculated using the

calibration data. The calculated

concentration is compared to the

concentration of the standard. Calibration is

verified when the concentration is within the

calibration verification limits specified in the

method. If the results are within the

specifications, the laboratory is allowed to

proceed with analysis without recalibrating

and allowed to use the calibration data to

quantify the sample concentration or amount

of each analyte in samples, blanks, and QC

tests.

If calibration cannot be verified, the

laboratory may either recalibrate the

instrument or prepare a fresh calibration

standard and make a second attempt to verify

calibration. If calibration cannot be verified

with a fresh calibration standard, the

instrument must be recalibrated. If

calibration is not verified, subsequent data

are considered to be invalid until the

instrument is recalibrated.

2.2.2.3 Absolute and Relative Retention

Time Precision

Retention time specification aid in the

identification of analytes in chromatographic

analyses. In some methods, a minimum

retention time is specified to ensure adequate

separation of analytes in complex mixtures.

If retention time QC criteria cannot be

verified, chromatographic identification of

analytes is suspect and reanalysis is

necessary.

2.2.2.4 Initial Precision and Recovery

The laboratory must demonstrate that it

can meet the IPR QC acceptance criteria in

the method. This test is required prior to the

use of the method by a laboratory. It is

sometimes termed the ‘‘start-up test.’’

Difficulty in passing the start-up test

frequently leads to marginal performance by

the laboratory in the routine operation of the

method. Performing the start-up test ‘‘after

the fact’’ or after samples have been analyzed

is not acceptable.

The start-up test consists of spiking the

analytes of interest into a set of four or more

aliquots of a reference matrix and analyzing

these four aliquots. The reference matrix

simulates the medium being tested. A

separate IPR test must be performed for each

medium. The mean concentration and the

standard deviation of the concentration are

calculated for each analyte and compared to

QC acceptance criteria in the method. If the

mean and standard deviation are within the

limits specified, the analysis system is in

control and the laboratory can use the system

for analysis of blanks, field samples, and

other QC tests samples. For some methods

(e.g., EPA Methods 625 and 1625), a repeat

test is allowed because of the large number

of analytes being tested simultaneously.

If there are no start-up test data, or if these

data fail to meet the QC acceptance criteria

in the method, all data produced by that

laboratory using that method are not

considered valid. It is important to remember

that if a change is made to a method, the

start-up test must be repeated with the

change as an integral part of the method.

Such changes may involve alternative

extraction, concentration, or cleanup

processes; alternative GC columns, GC

conditions, or detectors; or other procedures

designed to address a particular matrix

problem. If the start-up test is not repeated

when a procedure is changed, added, or

deleted, data produced by the modified

method are considered invalid.

2.2.2.5 Ongoing Precision and Recovery

An ongoing precision and recovery (OPR)

standard (also termed a ‘‘laboratory control

sample’’ (LCS) or a ‘‘laboratory fortified

blank’’ (LFB)) must be analyzed with each

sample batch prior to the analysis of a blank,

sample, or matrix spike or duplicate. The

number of samples in the batch is usually 10

or 20, depending on the method, or the OPR

is required at the beginning of an analysis

shift, regardless of the number of samples

analyzed during that shift. The data reviewer

must determine if the OPR standard has been

run with each sample batch or at the

beginning of the shift and if all criteria have

been met. If the standard was not run with

a given set of samples, or if the criteria are

not met, the results for that set of samples are

considered invalid.

2.2.2.6 Analysis of blanks

Blanks must be analyzed either on a

periodic basis or with each sample batch,

depending on the method. Blanks may

contain contamination at levels no higher

than specified in the method. Samples

associated with a contaminated blank must

be reanalyzed.

2.2.2.7 Surrogate or Labeled Compound

Recovery

Surrogate or labeled compounds are used

to assess the performance of the method on

each sample. Recoveries of these compounds

from each sample must be within QC

acceptance criteria to demonstrate acceptable

method performance on the sample. If the

recovery is not within the criteria, the sample

is normally diluted and the dilute sample

analyzed to demonstrate that a matrix effect

precluded reliable analysis of the undiluted

sample.

2.2.2.8 Matrix Spike and Matrix Spike

Duplicate

Non-isotope dilution methods require a

spike of the analytes of interest into a

separate aliquot of the sample for analysis

with the sample. The purpose of the matrix

spike (sometimes termed a ‘‘laboratory

fortified sample matrix’’ (LFM)) is to

determine if the method is applicable to the

sample in question. While many of the

approved methods were tested using

effluents from a wide variety of industries,

samples from some sources may not yield

acceptable results. It is, therefore, important

to evaluate method performance in the

sample matrix of interest. If the recovery for

the MS/MSD is not within the QC acceptance

criteria, a matrix interference may be the

cause. The sample is usually diluted and the

diluted sample spiked and analyzed. If the

QC acceptance criteria are met with the

diluted MS/MSD, a matrix problem exists.

Cleanup and other processing of the sample

are then required to overcome the matrix

interference if analysis of the undiluted

sample is required to establish compliance.

2.2.2.9 Demonstration of Method Detection

Limits

A laboratory that wishes to use a new or

modified wastewater method must

demonstrate that the method detection limit

(MDL) specified in the reference method can

be achieved. Alternatively, if the regulatory

wastewater compliance limit is above the

MDL, laboratories must demonstrate that the

minimum level (ML) determined with the

new or modified method is at or below 1⁄3 the

compliance limit. A laboratory that wishes to

use a new or modified drinking water

method must demonstrate that the MDL

determined with that method meets the

detection limits specified at 40 CFR parts

141.23, 141.24 and 141.89 and/or as specified

at 40 CFR 141.27(d). For both drinking water

and wastewater determinations,

demonstration of a valid detection limit

requires use of an MDL study in accordance

with the procedure at 40 CFR part 136

Appendix B. If the MDL determined with the

new or modified method is not acceptable,

the method may not be used because the

laboratory has not demonstrated an ability to

detect the analyte at the level required.

Note: Required detection limits specified

in regulations and/or in the reference

method(s) are usually analyte-specific; for the

same analyte, the requirement may differ

between the wastewater and the drinking

water reference method.

2.2.2.10 Reference Sample Analysis

Provided such acceptance limits are

specified by EPA or other regulatory

authorities, a laboratory must be able to

demonstrate the ability to quantitate the

analyte in a reference material to within the

acceptance range specified for the reference

material. Currently, EPA specifies at 40 CFR

141.23, 141.24 and 141.89 acceptance limits

for analysis of performance evaluation (PE)

samples that are provided by EPA under the

drinking water studies (WS) PE-sample

program.

3.0 Method Approval Process

Use of the procedures specified in this

section will expedite the approval of

drinking and wastewater methods by

ensuring that methods submitted to EPA for

approval contain the appropriate elements,

have been validated, and contain all

supporting documentation. This section

details procedures for preparing and

submitting method documentation, and

describes the rulemaking process required to
15036 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

approve a new method or method

modification. All new wastewater and

drinking water methods are subject to EPA

review. New methods recommended for

approval will be subject to one of two

actions: an approval letter or an Agency

rulemaking. Tier 1 new methods will receive

a letter of approval from EPA/EAD. Tier 2

and 3 new methods will be approved in a

formal rulemaking. Rulemaking involves

publishing in the Federal Register a

proposed rule containing the method(s) for

public comment, responding to public

comment, and approving the method(s) in a

final rule. The approved method(s) will be

cited in the applicable parts of the CFR. The

text of the approved method(s) will be

incorporated by reference rather than

published in the CFR. The method submitter

will be responsible for developing, writing,

and validating the method; providing

information in a format suitable for a

proposed rule; providing the necessary

supporting documentation; and assisting EPA

in responding to public comments to support

approval. EPA will review the method and

supporting documents, draft the regulatory

language, and submit the proposed rule to

the Office of the Federal Register (OFR) for

publication in the Federal Register. New

methods must undergo the processes detailed

above; no other types of action will be

substituted.

Method modifications can be used directly

after the method validation study confirms

method equivalency. EPA, only upon

request, will review Tier 2 and Tier 3 method

modifications. The option to request EPA

review of a modified method is provided to

allow interested parties to substantiate EPA

approval of a method modification. Any

party associated with method modification

and/or development can request review,

including: permittees, publicly owned

treatment works (POTWs), public water

systems (PWSs), commercial laboratories,

vendors, or States. Upon determination that

a method modification is appropriate, EPA

either will issue a letter of approval or

conduct a rulemaking, whichever action is

requested by the method submitter. The text

of the approved method(s) will be

incorporated by reference rather than

published in the CFR. The method submitter

will be responsible for developing, writing,

and validating the method; providing

information in a format suitable for a

proposed rule; providing the necessary

supporting documentation; and assisting EPA

in responding to public comments to support

approval. EPA’s role will be to review the

method and documentation; to write the rule

language; and to submit the rule to the OFR,

if appropriate.

3.1 Pre-Submission Procedures

EPA must review all new methods, and

will review Tier 2 and Tier 3 method

modifications upon request. Prior to EPA

review, a party developing a new or modified

method will proceed through up to four

steps: (1) method development, (2) method

validation, (3) information in a format

suitable for proposal in the Federal Register

(if appropriate), and (4) submission to EPA.

3.1.1 Method Development

Any person can develop a new method or

method modification if they identify a new

or improved procedure or technique for

analyzing an analyte of interest. A new

method must be a unique combination of

analyte and determinative technique, as

discussed in Section 1. Otherwise, it would

qualify as a modification of an existing

method. The method development process

will typically include drafting, checking, and

modifying testing procedures. Once the

person has confidence in the new or

modified testing procedures, the procedures

should be finalized into a standardized

format. The method description should

identify the anticipated application of the

new procedures: single laboratory; multilaboratory, single matrix type; or multilaboratory, multiple matrix types.

The requirement to provide the method in

standard format is needed to preclude

confusion. Specific details on the standard

format for the new or modified method can

be found at Appendix F of this part.

Appendix F specifies the analytical methods

format developed by EPA’s Environmental

Monitoring Management Council (EMMC).

The EMMC format is directed at

standardizing all Agency analytical methods.

For new methods submitted for approval at

40 CFR part 136 or part 141, a format from

another organization may be used provided

that it is standardized and contains the same

elements specified in the Method Guidelines

and Format. For example, the method format

documents from Standard Methods, ASTM,

AOAC-International, or USGS are acceptable

because these formats are documented and

routinely followed by these organizations.

However, method submitters other than these

organizations must use the EPA format

specified at Appendix F of this part.

Reserving method formats for those specific

organizations avoids misleading the

analytical community concerning the

authorship of the method. EPA will review

and approve standardized formats from

governmental authorities and industrial

associations upon request, but will not

approve miscellaneous formats written by

instrument manufacturers, individual

laboratories, and others because of the

potential proliferation of different method

formats. The format provided in Appendix F

of this part meets the needs of a format for

new methods.

3.1.2 Method Validation

Each new method or method modification

must be tested to assess its performance. The

process of establishing or substantiating

method performance is called validation. To

approve a new method or method

modification, EPA must be provided with a

report describing and including results of the

validation study. When undertaking method

validation, the method submitter is

responsible for performing the validation

study at the appropriate tier as specified at

§§ 136.4, 136.5 and 141.27. The study will be

detailed in a method validation report

submitted to EPA that includes the required

Checklists and Certification Statement as

specified at Appendix E of this part.

For new methods, QC acceptance criteria

must be included in the method and the

details of development of these criteria must

be included in the validation report. QC

acceptance criteria are used to ensure that a

method produces results that are reliable,

defensible, and suitable for regulatory

decisions. QC acceptance criteria must be

developed from data gathered in a method

validation study. When an analyte is being

added to an approved method, however, QC

acceptance criteria may be (1) developed

from validation data, (2) transferred from

another analyte already included in the

approved method, (3) transferred from

another analyte in another approved method,

or (4) transferred from another approved

method for the same analyte. For a transfer

from another analyte to be appropriate, the

chemical characteristics of the analyte from

which the criteria are transferred should

simulate, as closely as possible, the chemical

characteristics of the newly regulated

analyte. For example, if 2,4-dimethyl-3-

chlorophenol is added to Method 625, and

data from a method validation study are not

available from which QC acceptance criteria

can be derived, QC acceptance criteria can be

transferred from 2,4-dimethylphenol or 4-

chloro-3-methylphenol in Method 625. For

newly regulated analytes added to an existing

method, it is highly likely that EPA would

require that the QC acceptance criteria be

developed from validation data rather than

transferring criteria from another analyte to

ensure proper validation.

3.1.3 Draft Federal Register Preamble

When Tier 2 and Tier 3 methods are to

undergo the rulemaking process (e.g., for all

new methods and modified methods

requests), the submitter must provide

information in a format suitable for proposal

of the method at 40 CFR parts 136 or 141.

This information should describe the basis

and purpose for the proposed rule and

should be written to communicate the import

of the rule to the general public. The OFR

requires a specific format for the preamble.

Examples of appropriate and pertinent

preambles include 49 FR 43234, October 26,

1984; 56 FR 5090, February 7, 1991; 60 FR

53988, October 18, 1995; and 61 FR 1730,

January 23, 1996.

3.1.4 Submission to EPA

When all the pre-submission steps are

completed, the method submitter should

generate a single packet for submission to

EPA. This packet will include the method in

a standard format, the method validation

report, the draft preamble (if rulemaking will

occur), and any necessary supporting

documents. If this streamlining proposal is

promulgated, the submission packet will be

submitted to the Director of the Analytical

Methods Staff in EPA’s Office of Water.

3.2 EPA Review

EPA must review all new methods, and

will review Tier 2 and Tier 3 method

modifications if requested. When a method

package is submitted for review, EPA will

first check the documentation for

completeness. The documentation must

include the final method in standard format,

the validation report, and information that

would facilitate EPA’s drafting of a proposed

rule (if rulemaking will occur). If all of the
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15037

documentation is in order, EPA will begin an

internal review of the method for scientific

merit, consistency, and appropriateness. The

internal review may involve multiple

programs and workgroups. Should any

problems or questions arise, EPA will

communicate with the submitter to resolve

the outstanding issues. Depending on the

circumstances, EPA may return the

submission to the submitter for revision.

If internal review recommends acceptance,

EPA will issue a letter of acceptance for a

Tier 1 new method. For Tier 2 and Tier 3

new methods, EPA will begin the rulemaking

process. For Tier 2 and Tier 3 method

modifications, the method submitter has the

option of receiving a letter of approval or

proceeding with the rulemaking process.

TABLE 1–1.—EPA REVIEW AND APPROVAL OF METHODS

New method Modified method

Tier 1: Single-lab ............................................... • EPA review required .....................................

• EPA issues a letter of approval

No EPA review.

Tier 2: Multi-lab, single matrix type .................. • EPA review required .....................................

• Approved through rulemaking

• If requested, EPA reviews and issues letter

of approval, or conducts rulemaking.

Tier 3: Multi-lab, multiple matrix type ............... • EPA review required .....................................

• Approved through rulemaking

• If requested, EPA reviews and issues letter

of approval, or conducts rulemaking.

3.3 Limited Use Methods

Currently, EPA reviews single-laboratory,

limited-use methods only for special

applications. Examples of special

circumstances could include procedures to

remove sulfate interferences in drinking

water matrices and, as described below,

technologies that can eliminate total cyanide

false positives in some wastewater

measurements.

Use of limited-use methods as Tier 1

methods for both wastewater and drinking

water methods is allowed. The purpose of

this allowance is to provide the means by

which (1) a new technology can be

introduced and (2) specific matrix

interference problems can be overcome.

Furthermore, additional single laboratories

can use the technology until a sufficient

number of devices are available for

interlaboratory validation.

Tier 1 new methods must be submitted to

EPA for review. Upon recommendation for

approval, a letter of approval will be issued.

Tier 1 modified methods can be used directly

upon validation. EPA will not review Tier 1

method modifications.

3.4 Rulemaking Process

The customary rulemaking process consists

of four phases: proposal of the rule, public

comment, response to comments, and

publication of the final rule. The proposed

rule requests public comment and allows a

specified comment period, for example, 30 to

90 days depending on the magnitude of the

proposed change. At the end of the comment

period, EPA will forward any significant

comments to the method submitter. The

submitter would then provide technical

assistance to EPA in drafting responses to

comments. All comments that have scientific

or legal merit, or raise substantive issues with

the proposed rule, must be answered to

complete the rule-making process.

EPA will review the comment responses

and complete a response-to-comments

document that must be included in the final

rule. EPA will prepare and submit the final

rule to the OFR for publication. The final rule

will state the date that the rule becomes

effective; as of this date, the method is

approved.

3.5 Proprietary Components

Proprietary components can be classified

into three categories: proprietary reagents,

proprietary instruments, and proprietary

methods. Proprietary reagents and

instruments are allowed in the approval of

analytical methods for compliance purposes

to the extent that such inclusion still

provides an adequate opportunity for public

review and comment under the

Administrative Procedure Act. Use of

proprietary methods for determining

compliance with regulatory requirements

where the entire method is claimed as

‘‘confidential business information’’ (CBI) is

not allowed. However, if the proprietary

method is patented it could be considered for

approval because the public would have the

opportunity to comment on the patented

method.

Proprietary reagents and instruments are

allowed in approved methods. The details of

the proprietary elements must be disclosed to

EPA, but will be withheld from the public if

the person requesting protection for the CBI

demonstrates that the information is entitled

to confidential treatment under the

applicable regulations. Examples of these

proprietary components are immunoassay

reagents and antibodies, and liquid phases in

GC columns, e.g., DB–1, SPB-octyl,

Dexsil, etc. A new or modified method

submitted for EPA approval must include

language stating that the proprietary reagent

or instrument can be replaced by an

equivalent. Changes made to the method after

EPA approval would require the

manufacturer to demonstrate through

supporting documentation that the new

proprietary equipment, substance, or reagent

would produce results equal or superior to

results produced with the material originally

tested and on which the method approval is

based. For proprietary reagents, a method

must contain accurate, specific instructions

for the safe handling of each proprietary

reagent listed in the method, and for safe

disposal of each spent proprietary reagent

and/or reagent product. When a material

safety data sheet (MSDS) accompanies the

proprietary material, the MSDS will serve as

these instructions, and the submission of an

MSDS with the method shall be evidence

that the requirements for instructions for safe

handling and disposal of the reagent have

been met.

PART 141—NATIONAL PRIMARY

DRINKING WATER REGULATIONS

1. The authority citation for part 141

continues to read as follows:

Authority: 42 U.S.C. 300f, 300g–1, 300g–2,

300g–3, 300g–4, 300g–5, 300g–6, 300j–4, and

300j–9.

2. Section 141.2 is proposed to be

amended by adding the following

definitions in alphabetical order to read

as follows:

§ 141.2 Definitions.

As used in this part, the term:

Accuracy means the degree of

agreement between an observed value

and an accepted reference value.

Accuracy includes random error

(precision) and systematic error (bias)

that are caused by sampling and

analysis.

* * * * *

Administrator means the

Administrator of the U.S.

Environmental Protection Agency

(EPA).

Analyte or Analyte of concern means

a substance or property that is to be

measured by an analysis.

Approved method means a testing

procedure (analytical method) promulgated

at this part or at 40 CFR part 142 or 143.

Assistant Administrator (AA) means

the EPA Assistant Administrator for

Water.

* * * * *

Calibration (CAL) means the process

of establishing the relationship between

the concentration or amount of material

introduced into an instrument or

measurement process and the output

signal.

Calibration linearity means the degree

to which calibration points lie along a

straight line.

Calibration verification means the

means of establishing that instrument
15038 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

performance remains within preestablished limits.

* * * * *

Determinative technique means the

process (physical or chemical or both) to

measure the identity and concentration

of an analyte. In test methods, the

determinative technique follows the

front-end techniques.

* * * * *

Front-end technique means any

technique in the analytical process that

precedes the determinative technique,

including all procedures, equipment,

solvents, etc. that are used in the

laboratory in the preparation and

cleanup of a sample but this excludes

conditions and/or procedures for the

collection, preservation, shipment and

storage of the sample.

* * * * *

Initial precision and recovery test

(IPR) means analysis of a minimum of

four spiked reagent water samples under

the same conditions as will be used for

analysis of environmental samples. The

IPR is used to demonstrate that a

laboratory is able to produce reliable

results with the method prior to analysis

of environmental samples.

Interference means a positive or

negative effect on a measurement

caused by a substance other than the

analyte being investigated.

* * * * *

Matrix means the component or

substrate that contains the target

analyte.

Matrix spike (MS) means a sample

prepared by adding a known mass of

target analyte to a specified amount of

a sample matrix for which an

independent estimate of target analyte

concentration is available.

Matrix spike duplicate (MSD) means a

duplicate of the matrix spike. The MS/

MSD are used in combination to test the

precision of an analysis.

Matrix type is any potable water

sample provided by a PWS.

* * * * *

Medium means the physical phase of

a sample matrix. Air, water, soil,

sediment, rock, and sludge are sample

media.

* * * * *

Method means an orderly and

systematic arrangement of procedures

and techniques for performing an

analysis.

Method blank (or blank) means a

sample absent the analytes of interest

and interferences that is processed

through all steps of a method

simultaneously with and under the

same conditions as samples that may

contain an analyte of interest.

Method detection limit (MDL) means

the minimum concentration of a

substance that can be measured and

reported with 99% confidence that the

analyte concentration is greater than

zero as determined by the procedure set

forth in appendix B of this part.

Method Guidelines and Format means

the procedures set forth in appendix F

of part 136.

Method modification means a change

to a reference method. The change may

be to a front-end technique or to the

determinative technique.

Method validation means a process by

which a laboratory or vendor establishes

the performance of a new method or

substantiates the performance of a

reference method modification.

Minimum level (ML) means the lowest

level at which an entire analytical

system gives a recognizable signal and

acceptable calibration point for an

analyte. It is equivalent to the

concentration of the lowest calibration

standard, assuming that all methodspecified sample weights, volumes, and

clean-up procedures have been

employed.

* * * * *

New method means a combination of

analyte of concern and determinative

technique that is different from those in

the approved methods.

* * * * *

Ongoing precision and recovery

sample (OPR) means a spiked reference

matrix sample that is processed through

all steps of a method simultaneously

with and under the same conditions as

samples that may contain an analyte of

interest. Also called a laboratory control

sample (LCS), the OPR/LCS is used to

demonstrate that a laboratory is able to

produce reliable results continuously.

* * * * *

Organic Methods means the

document titled: Methods for the

Determination of Organic Compounds

in Drinking Water—Supplement III

(available from the National Technical

Information Service (NTIS), U.S.

Department of Commerce, Springfield,

Virginia, 22161, 703/487–4600, at NTIS

publication PB97–125298).

Other approved method means a

promulgated method that is not

designated as a reference method.

Percent recovery means the recovery

multiplied by one hundred.

* * * * *

Precision means the degree to which

a set of observations or measurements of

the same property, usually obtained

under similar conditions, conform to

themselves. Precision is usually

expressed as standard deviation,

variance, or range, in either absolute or

relative terms.

Preparation means processing

performed on a sample prior to analysis,

including extraction, concentration, and

cleanup.

Procedure means a set of systematic

instructions for performing an activity.

Promulgated method means a method

that has been published or incorporated

by reference into 40 CFR parts 141, 142,

or 143.

* * * * *

Quality assurance (QA) means an

integrated system of activities involving

planning, quality control, quality

assessment, reporting, and quality

improvement to ensure that a product or

service meets defined standards of

quality with a stated level of confidence.

Quality control (QC) means the

overall system of technical activities

whose purpose is to measure and

control the quality of a product or

service so that it meets the needs of a

user. The aim is to provide quality that

is satisfactory, adequate, dependable,

and economical.

QC acceptance criteria means

performance specifications developed

from validation data and used to control

the limits within which an analytical

method is operated.

Range means the amounts or

concentrations over which an

instrument or analytical system is

calibrated.

Recovery means the total amount of

analyte found divided by the amount of

analyte added as a spike.

Reference method means an approved

method that is designated as a standard

to which a modified method can be

compared. A reference method will

include standardized QC and QC

acceptance criteria as well as sample

preparation, cleanup, and other

procedures.

Regional Administrator means an EPA

Regional Administrator.

* * * * *

Sample means a portion of a larger

whole or a single item of a group; a

finite part or subset of a statistical

population; the medium subjected to

analysis. A sample serves to provide

data or information concerning the

properties of the whole or population.

Sample matrix effect validation

means to verify that the performance of

a modified or new analytical method on

samples obtained from different PWSs

does not differ from the results

validated in reagent water samples.

* * * * *

Screening method means a method

that employs a qualitative determinative

technique for an analyte of interest that
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15039

is different from the determinative

techniques used in all approved

methods for that analyte. The screening

method must produce a false negative

probability less than 1%.

* * * * *

Selectivity means the capability of a

method or instrument to respond to an

analyte in the presence of interferences.

Sensitivity means the capability of a

method or instrument to differentiate

between different amounts or

concentrations of an analyte.

* * * * *

Spike means the process of adding a

known amount of an analyte to a sample

to determine the recovery.

Spike amount means a known mass of

analyte added to a sample and used to

determine the recovery of a method.

Standard deviation means the

measure of the dispersion of observed

values expressed as the positive square

root of the sum of the squares of the

difference between the individual

values of a set and the arithmetic mean

of the set, divided by one less than the

number of values in the set.

* * * * *

Standardized quality control

(standardized QC) means a uniform set

of performance testing procedures that

ensure reliable results. Depending on

the method, standardized QC

procedures include, but are not limited

to, the following: calibration, calibration

linearity, calibration verification,

absolute retention time, absolute and

relative retention time precision, initial

precision and recovery, ongoing

precision and recovery (laboratory

control sample), surrogate or labeled

compound recovery, analysis of blanks,

matrix spike and matrix spike duplicate

recovery and precision, demonstration

of method detection limit(s), and

analysis of a reference sample.

* * * * *

Surrogate means a substance with

properties that mimic the behavior of an

analyte, that is unlikely to be found in

an environmental sample, and that is

added to the sample for quality control

purposes.

* * * * *

Tier 1 means the application of a new

or modified method in a single

laboratory to one or more PWSs .

Tier 2 means the application of a new

or modified method by all laboratories

to all PWSs (nationwide use).

* * * * *

3. Section 141.23, paragraph (k)(1), is

proposed to be amended by revising the

table to read as follows:

§ 141.23 Inorganic chemical sampling and

analytical requirements.

* * * * *

(k) * * *

(l) * * *

TABLE 141.23(k)(1)—LIST OF APPROVED INORGANIC TEST PROCEDURES

Contaminant Methodology

Reference

method

Other approved methods

EPA ASTM 3,13 SM4,13 Other

Antimony ICP-Mass Spectrometry 2 200.8

Hydride-Atomic Absorption D–3697–92

Atomic Absorption; Platform 2 200.9

Atomic Absorption; Furnace 3113B

Arsenic Inductively Coupled Plasma 2 200.7 3120B

ICP-Mass Spectrometry 2 200.8

Atomic Absorption; Platform 2 200.9

Atomic Absorption; Furnace D–2972–93C 3113B

Hydride-Atomic Absorption D–2972–93B 3114B

Asbestos Transmission Electron Microscopy 10 100.2 9 100.1

Barium Inductively Coupled Plasma 2 200.7 3120B

ICP-Mass Spectrometry 2 200.8

Atomic Absorption; Direct 3111D

Atomic Absorption; Furnace 3113B

Beryllium Inductively Coupled Plasma 2 200.7 3120B

ICP-Mass Spectrometry 2 200.8

Atomic Absorption; Platform 2 200.9

Atomic Absorption; Furnace D–3645–93B 3113B

Cadmium Inductively Coupled Plasma 2 200.7

ICP-Mass Spectrometry 2 200.8

Atomic Absorption; Platform 2 200.9

Atomic Absorption; Furnace 3113B

Chromium Inductively Coupled Plasma 2 200.7 3120B

ICP-Mass Spectrometry 2 200.8

Atomic Absorption; Platform 2 200.9

Atomic Absorption; Furnace 3113B

Cyanide Manual Distillation followed by 4500–CN–C

Spectrophotometric, Amenable D–2036–91B 4500–CN–G

Spectrophotometric, Manual D2036–91A 4500–CN–E 5 I–3300–85

Semi-automated 6 335.4

Selective Electrode 4500–CN–F

Fluoride Ion Chromatography 6 300.0 D4327–91 4110B

Manual Distill.; Color. SPADNS 4500–F–B,D

Manual Electrode D1179–93B 4500–F–C

Automated Electrode 4500–F–E 11 380–75WE

Automated Alizarin 11 129–71W

Mercury Manual, Cold Vapor 2 245.1 D3223–91 3112B

Automated, Cold Vapor 1 245.2

ICP-Mass Spectrometry 2 200.8

Nickel Inductively Coupled Plasma 2 200.7 3120B

ICP-Mass Spectrometry 2 200.8

Atomic Absorption; Platform 2 200.9

Atomic Absorption; Direct 3111B
15040 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

TABLE 141.23(k)(1)—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued

Contaminant Methodology

Reference

method

Other approved methods

EPA ASTM 3,13 SM4,13 Other

Atomic Absorption; Furnace 3113B

Nitrate Ion Chromatography 6 300.0 D4327–91 4110B 8B–1011

Automated Cadmium Reduction 6 353.2 D3867–90A 4500–NO3–F

Ion Selective Electrode 4500–NO3–D 7 601

Manual Cadmium Reduction D3867–90B 4500–NO3–E

Nitrite Ion Chromatography 6 300.0 D4327–91 4110B 8B–1011

Automated Cadmium Reduction 6 353.2 D3867–90A 4500–NO3–F

Manual Cadmium Reduction D3867–90B 4500–NO3–E

Spectrophotometric 4500–NO2–B

Selenium Hydride-Atomic Absorption D3859–93A 3114B

ICP-Mass Spectrometry 2 200.8

Atomic Absorption; Platform 2 200.9

Atomic Absorption; Furnace 3859–93B 3113B

Thallium ICP-Mass Spectrometry 2 200.8

Atomic Absorption; Platform 2 200.9

Lead Atomic Absorption; Furnace D3559–90D 3113B

ICP-Mass Spectrometry 2 200.8

Atomic Absorption; Platform 2 200.9

Copper Atomic Absorption; Furnace D1688–90C 3113B

Atomic Absorption; Direct Aspiration D1688–90A 3111B

ICP 2 200.7 3120B

ICP-Mass Spectrometry 2 200.8

Atomic Absorption; Platform 2 200.9

pH Electrometric 1 150.2 1 150.1 D1293–84 4500–H∂–B

Conductivity Conductance D1125–91A 2510B

Calcium EDTA Titrimetric D511–93A 3500–Ca–D

Atomic Absorption; Direct Aspiration D511–93B 3111B

Inductively Coupled Plasma 2 200.7 3120B

Alkalinity Titrimetric D1067–92B 2320B

Electrometric Titration 5 I–1030–85

Orthophosphate 12 Colorimetric, Automated, Ascorbic Acid 6 365.1 4500–P–F

Colorimetric, Ascorbic Acid, Single ReagentD515–88A 4500–P–E

Colorimetric, Phosphomolybdate; 5 I–1601–85

Automated-segmented flow; 5 I–2601–90

Automated discrete 5 I–2598–85

Ion Chromatography 6 300.0 D4327–91 4110

Silica Colorimetric, Molybdate Blue; 5 I–1700–85

Automated-segmented flow 5 I–2700–85

Colorimetric D859–88

Molybdosilicate 4500–Si–D

Heteropoly Blue 4500–Si–E

Automated Method for Molybdate-Reactive Silica4500–Si–F

Inductively Coupled Plasma 2 200.7 3120B

Temperature Thermometric 2550

Sodium Inductively Coupled Plasma 2 200.7

Atomic Absorption; Direct Aspiration 3111B

1 Methods 150.1, 150.2 and 245.2 are available from U.S. EPA, NERL, Cincinnati, OH 45268. The identical methods were formerly in ‘‘Methods for Chemical Analysis of Water and Wastes’’, EPA–600/4–79–020, March 1983, which is available at NTIS, PB84–128677. 2 ‘‘Methods for the Determination of Metals in Environmental Samples—Supplement 1’’, EPA–600/R–94–111, May 1994. Available at NTIS, PB

94–184942. 3The procedures shall be done in accordance with the Annual Book of ASTM Standards, 1994, Vols. 11.01 and 11.02, American Society for

Testing and Materials. This incorporation by reference was approved by the Director of the Federal Register in accordance with 5 U.S.C. 552(a)

and 1 CFR Part 51. Copies may be obtained from the American Society for Testing and Materials, 1916 Race Street, Philadelphia, PA 19103.

Copies may be inspected at EPA’s Drinking Water Docket, 401 M Street, S.W., Washington, DC 20460; or at the Office of the Federal Register,

800 North Capitol Street, N.W., Suite 700, Washington, DC. 4The procedures shall be done in accordance with the 18th edition of Standard Methods for the Examination of Water and Wastewater, 1992,

American Public Health Association. This incorporation by reference was approved by the Director of the Federal Register in accordance with 5

U.S.C. 552(a) and 1 CFR Part 51. Copies may be obtained from the American Public Health Association, 1015 Fifteenth Street, N.W., Washington, DC 20005. Copies may be inspected at EPA’s Drinking Water Docket, 401 M Street, S.W., Washington, DC 20460; or at the Office of the

Federal Register, 800 North Capitol Street, N.W., Suite 700, Washington, DC. 5Available from Books and Open-File Reports Section, U.S. Geological Survey, Federal Center, Box 25425, Denver, CO 80225–0425.

6 ‘‘Methods for the Determination of Inorganic Substances in Environmental Samples’’, EPA–600/R–93–100, August 1993. Available at NTIS,

PB94–121811. 7The procedure shall be done in accordance with the Technical Bulletin 601 ‘‘Standard Method of Test for Nitrate in Drinking Water’’, July

1994, PN 221890–001, Analytical Technology, Inc. This incorporation by reference was approved by the Director of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR Part 51. Copies may be obtained from ATI Orion, 529 Main Street, Boston, MA 02129. Copies may be

inspected at EPA’s Drinking Water Docket, 401 M Street, S.W., Washington, DC 20460; or at the Office of the Federal Register, 800 North Capitol Street, N.W., Suite 700, Washington, DC. 8 Method B–1011, ‘‘Waters Test Method for Determination of Nitrite/Nitrate in Water Using Single Column Ion Chromatography’’, Millipore Corporation, Water Chromatography Division, 34 Maple Street, Milford, MA 01757.
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15041

9 Method 100.1, ‘‘Analytical Method for Determination of Asbestos Fibers in Water’’, EPA–600/4–83–043, EPA, September 1983. Available at

NTIS, PB83–260471. 10 Method 100.2, ‘‘Determination of Asbestos Structure Over 10 μm in Length in Drinking Water’’, EPA–600/R–94–134, June 1994. Available at

NTIS, PB94–201902. 11The procedures shall be done in accordance with the Industrial Method No. 129–71W, ‘‘Fluoride in Water and Wastewater’’, December

1972, and Method No. 380–75WE, ‘‘Fluoride in Water and Wastewater’’, February 1976, Technicon Industrial Systems. This incorporation by reference was approved by the Director of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR Part 51. Copies may be obtained

from the Technicon Industrial Systems, Tarrytown, NY 10591. Copies may be inspected at EPA’s Drinking Water Docket, 401 M Street, S.W.,

Washington, DC 20460; or at the Office of the Federal Register, 800 North Capitol Street, N.W., Suite 700, Washington, DC. 12 Unfiltered, no digestion or hydrolysis. 13 Methods published by this organization and approved for use under this part may not be modified beyond the modifications expressly allowed and defined.

* * * * *

4. Section 141.24, paragraph (e), is

proposed to be amended by revising the

table to read as follows:

§ 141.24 Organic chemicals other than

total trihalomethanes, sampling and

analytical requirements.

* * * * *

(e) * * *

TABLE 141.24(e).—LIST OF APPROVED ORGANIC TEST PROCEDURES

Parameter/methodology Reference

method

Other approved methods

EPA

Standard

method

18th Ed.1

Other

1. Benzene

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

2. Carbon Tetrachloride

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

GC/ECD ................................................................................................................. 551

3. Chlorobenzene

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

4. 1,2-Dichlorobenzene

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

5. 1,4-Dichlorobenzene

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

6. 1,2-Dichloroethane

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

7. cis-Dichloroethylene

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

8. Trans-Dichloroethylene

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

9. Dichloromethane

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

10. 1,2-Dichloropropane

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

11. Ethylbenzene

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

12. Styrene

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

13. Tetrachloroethylene

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

GC/ECD ................................................................................................................. 551

14. 1,1,1-Trichloroethane

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

GC/ECD ................................................................................................................. 551

15. Trichloroethylene

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

GC/ECD ................................................................................................................. 551

16. Toluene

GC/ELCD ............................................................................................................... 502.2
15042 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

TABLE 141.24(e).—LIST OF APPROVED ORGANIC TEST PROCEDURES—Continued

Parameter/methodology Reference

method

Other approved methods

EPA

Standard

method

18th Ed.1

Other

GC/MS ................................................................................................................... 524.2

17. 1,2,4-Trichlorobenzene

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

18. 1,1-Dichloroethylene

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

19. Vinyl chloride

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

20. Xylenes (total) ...................... 515.1

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

21. 2,3,7,8-TCDD (dioxin) ...................... 515.1

GC/MS ................................................................................................................... 1613

22. 2,4-D

GC/ECD ................................................................................................................. 515.2

HPLC/UV ............................................................................................................... 555

23. 2,4,5-TP (Silvex)

GC/ECD ................................................................................................................. 515.2

HPLC/UV ............................................................................................................... 555

24. Alachlor

GC/NPD ................................................................................................................. 507

GC/ECD ................................................................................................................. 508.1 505

GC/MS ................................................................................................................... 525.2

25. Atrazine

GC/NPD ................................................................................................................. 507

GC/ECD ................................................................................................................. 508.1 505

GC/MS ................................................................................................................... 525.2

26. Benzo(a)pyrene

GC/MS ................................................................................................................... 525.2

HPLC/Fl-UV ........................................................................................................... 550.1 550 6610

27. Carbofuran

HPLC/Fl ................................................................................................................. 531.1

28. Chlordane

GC/NPD ................................................................................................................. 507

GC/ECD ................................................................................................................. 508.1 505

GC/MS ................................................................................................................... 525.2

29. Dalapon

GC/ECD ................................................................................................................. 515.1 552.1

30. Di-(2-ethylhexyl) adipate

GC/PID .................................................................................................................. 506

GC/MS ................................................................................................................... 525.2

31. Di-(2-ethylhexyl) phthalate

GC/PID .................................................................................................................. 506

GC/MS ................................................................................................................... 525.2

32. Dibromochloropropane (DBCP)

GC/ECD ................................................................................................................. 504.1 551

33. Dinoseb

GC/ECD ................................................................................................................. 515.2 515.1

HPLC/UV ............................................................................................................... 555

34. Diquat

HPLC/UV ............................................................................................................... 549.1

35. Endothall

GC/MS ................................................................................................................... 548.1

36. Endrin

GC/NPD ................................................................................................................. 507

GC/ECD ................................................................................................................. 508.1 505

GC/MS ................................................................................................................... 525.2

37. Ethylene Dibromide (EDB)

GC/ECD ................................................................................................................. 504.1 551

38. Glyphosate

HPLC/Fl ................................................................................................................. 547 6651

39. Heptachlor

GC/ECD ................................................................................................................. 508.1 505, 508

GC/MS ................................................................................................................... 525.2

40. Heptachlor Epoxide

GC/ECD ................................................................................................................. 508.1 505, 508
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15043

TABLE 141.24(e).—LIST OF APPROVED ORGANIC TEST PROCEDURES—Continued

Parameter/methodology Reference

method

Other approved methods

EPA

Standard

method

18th Ed.1

Other

GC/MS ................................................................................................................... 525.2

41. Hexachlorobenzene

GC/ECD ................................................................................................................. 508.1 505, 508

GC/MS ................................................................................................................... 525.2

42. Hexachlorocyclopentadiene

GC/ECD ................................................................................................................. 508.1 505, 508

GC/MS ................................................................................................................... 525.2

43. Lindane

GC/ECD ................................................................................................................. 508.1 505, 508

GC/MS ................................................................................................................... 525.2

44. Methoxychlor

GC/ECD ................................................................................................................. 508.1 505, 508

GC/MS ................................................................................................................... 525.2

45. Oxamyl

HPLC/Fl ................................................................................................................. 531.1 6610

46. PCBs

GC/ECD, As decachlorobiphenyl .......................................................................... 508A

GC/ECD, As Aroclors ............................................................................................ 508 505

47. Pentachlorophenol 515.1

GC/ECD ................................................................................................................. 515.2

HPLC/UV ............................................................................................................... 555

GC/MS ................................................................................................................... 525.2

48. Picloram ...................... 515.1

GC/ECD ................................................................................................................. 515.2

HPLC/UV ............................................................................................................... 555

49. Simazine ...................... 505

GC/NPD ................................................................................................................. 507

GC/ECD ................................................................................................................. 508.1

GC/MS ................................................................................................................... 525.2

50. Toxaphene ...................... 505

GC/ECD ................................................................................................................. 508

GC/MS ................................................................................................................... 525.2

51. Total Trihalomethanes

GC/ELCD ............................................................................................................... 502.2

GC/MS ................................................................................................................... 524.2

GC/ECD ................................................................................................................. 551

1 Methods published by this organization and approved for use under this part may not be modified beyond the modifications expressly allowed

and defined in each method.

Note: The following acronyms are used in this table:

ECD—Electron Capture Detector.

ELCD—Electrolytic Conductivity Detector.

Fl—Fluorescence.

GC—Gas Chromatography.

GC/MS—Gas Chromatography/Mass Spectrometry.

HPLC—High Performance Liquid Chromatography.

NPD—Nitrogen Phosphorous Detector.

PID—Photoionization Detector.

UV—Ultraviolet Detector.

* * * * *

5. Section 141.27 is proposed to be

revised to read as follows:

§ 141.27 New and alternate analytical

methods.

(a) Sample preservation procedures,

container materials, and maximum

allowable holding times for

contaminants cited in tables in

§§ 141.23(k)(1), 141.24(e) and

141.40(n)(11) are prescribed in these

methods except as specified in the table

in § 141.23(k)(2). Any person may apply

for a variance from the prescribed

preservation techniques, container

materials, and maximum holding times

applicable to samples collected from a

public water system (PWS) supply or

tap water. An application for a variance

may be made by letter to the Regional

Administrator in the Region in which

the water supply system is located.

Sufficient data should be provided to

ensure such variance does not adversely

affect the integrity of the sample. Such

data will be forwarded by the Regional

Administrator to the Director of the

Analytical Methods Staff for technical

review and recommendations for action

on the variance application. Upon

receipt of a recommendation from the

Director of the Analytical Methods Staff,

the Administrator may grant a variance

applicable to samples collected from the

specific PWS for which the application

for variance was made. A decision to

recommend approval or denial of a

variance will be made within 90 days of

receipt of a complete application.

(b) A reference method listed in the

tables in §§ 141.23(k)(1), 141.24(e), and

141.40(n)(11) of this section may be

modified to improve separations, lower

the costs of measurements, reduce or

eliminate interferences, or for other

purposes, provided that the

modification is not explicitly prohibited

in the reference method and provided
15044 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

that the laboratory modifying the

reference method meets the

requirements in this section, performs

the standardized QC tests, and

demonstrates that the QC acceptance

criteria and the requirements specified

at Appendixes E, F, and G of 40 CFR

part 136 are met. A laboratory that

wishes to use a new or modified

drinking water method must

demonstrate that the MDL determined

with that method meets the detection

limits specified at §§ 141.23, 141.24 and

141.89 and/or at § 141.27(d).

Demonstration of a valid detection limit

requires use of an MDL study in

accordance with the procedure at 40

CFR part 136, Appendix B. If the MDL

determined with the new or modified

method is not acceptable, the method

may not be used. Specified detection

limits are usually analyte-specific. For

any given analyte, the specified

detection limit may vary between a

wastewater and a drinking water

reference method.

(1) Tier 1: modification of a reference

method for application in a single

laboratory to one or more PWSs.

(i) Application to a single PWS.

(A) A laboratory may modify a

reference method listed in the tables in

§§ 141.23(k)(1), 141.24(e) and

141.40(n)(11) of this section for

determination of an analyte of concern

in a specific PWS, provided that the

laboratory:

(1) Performs the standardized QC

tests, including a test of initial precision

and recovery (IPR) on a reagent water

matrix;

(2) Performs the matrix spike (MS)

and matrix spike duplicate (MSD) tests

on a sample from the PWS to which the

modification is to be applied;

(3) Meets the QC acceptance criteria

in the reference method as

supplemented in the table of QC

acceptance criteria for drinking water

methods at § 141.27(d);

(4) Documents the results of the QC

tests using the Checklist for Initial

Demonstration of Method Performance

and the Checklist for Continuing

Demonstration of Method Performance

which are specified in 40 CFR part 136,

Appendix E; and

(5) Maintains the results of the QC

tests and other tests on file for

inspection by EPA and/or the State.

(B) After the laboratory has

demonstrated application of a method

modification to a given PWS by meeting

the MS/MSD QC acceptance criteria,

only that laboratory may subsequently

apply that method modification to

samples from that PWS.

(C) A laboratory may apply a given

method modification to additional

PWSs if the laboratory validates the

modification on a sample from each

PWS by performing a matrix spike (MS)

and matrix spike duplicate (MSD) test

and meeting the MS/MSD QC

acceptance criteria for precision and

recovery for each PWS.

(ii) Application to multiple public

water systems (PWSs). After a laboratory

has validated a given modification on

samples from a minimum of three (3)

PWSs in accordance with the

procedures given in paragraph

(b)(1)(i)(A) of this section, the laboratory

may subsequently apply that method

modification to other PWSs, provided

that the matrix spike (MS) and matrix

spike duplicate (MSD) recovery and the

relative percent difference are within

the QC acceptance criteria given for the

analyte in the reference method as

supplemented by the applicable QC

acceptance criteria for drinking water

methods at § 141.27(d). If all QC

acceptance criteria are not met for a

sample from a given PWS, the

modification may not be applied to

samples from that PWS.

(iii) To test the modified method for

potential matrix effects, the three (3)

PWS samples must be collected from

PWSs with water quality characteristics

that are sufficiently different that

sample matrix effects, if any, can be

observed. In all cases, the laboratory

must try to determine if the

measurement result for the target

analyte using a new or modified method

differs from the result obtained in a

reagent water matrix or in a previously

validated matrix type or PWS sample.

Selection of suitable PWSs requires a

knowledge of the chemistry of the

method. Analysts may review an

applicable approved or published

method for indications of matrix effects

that are unique to the analyte separation

and measurement technologies used in

the new or modified method. Water

quality characteristics that can affect

analysis of drinking water samples

include, but are not limited to pH, total

organic carbon content, turbidity, total

organic halogen content, ionic strength,

sulfate contamination, metal

contamination, and trihalomethane

contamination of the drinking water

sample.

(2) Tier 2: modification of a reference

method for application by all

laboratories to all PWSs in the water

supply and distribution industry

(nationwide modification).

(i) A person may modify a reference

method for application by all

laboratories to determination of an

analyte of concern in sample matrices

from any PWS provided that the

modification is validated in a minimum

of three (3) laboratories each of which

test a sample from each of three (3)

different PWS for a minimum of nine (9)

tests. To test the modified method for

potential matrix effects, the three (3)

PWS samples must be collected from

PWSs with sufficiently different water

quality characteristics according to

criteria specified at paragraph (b)(1)(iii)

of this section. Each laboratory must

meet the requirements in paragraph

(b)(1)(i)(A) of this section. After the tests

in all three laboratories have met all QC

acceptance criteria for the reference

method, the modified method may be

applied by laboratories nationwide to

PWSs in the water supply and

distribution industry.

(ii) A person who modifies a reference

method and validates the method

modification under Tier 2 may submit

that modification to EPA for a letter of

approval. The information that must be

submitted includes the results of the

performance tests required by paragraph

(b)(1)(i)(A) of this section. This

information and other information that

must be submitted and the format for

submission are specified at 40 CFR part

136, Appendixes E, F, and G.

(iii) A person who modifies a

reference method and validates the

method modification under Tier 2 may

submit that modification to EPA for

approval and inclusion in a table in this

part 141. The information that must be

submitted includes the results of the

performance tests required by paragraph

(b)(1)(i)(A) of this section. This

information and other detailed

information that must be submitted and

the format for submission are specified

at 40 CFR part 136, Appendixes E, F,

and G.

(iv) A decision to recommend

proposal of a Tier 2 method

modification will be made by the

Director of the Analytical Methods Staff

within 90 days of receipt of a complete

application.

(c) A person may apply to EPA for use

of a new method for determination of an

analyte of concern, provided that the

new method meets the requirements for

validation and format as specified in

this section and in 40 CFR part 136,

Appendixes E, F, and G.

(1) The new method must

demonstrate an acceptable MDL for each

analyte as specified in § 141.27(b).

(i) A new method must:

(A) Be documented in accordance

with requirements in 40 CFR part 136,

Appendixes E, F, and G.

(B) Contain standardized QC as

defined at § 141.2.

(C) Contain QC acceptance criteria

that have been developed in accordance
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with the requirements detailed in 40

CFR part 136, Appendixes E, F, and G.

(D) Employ a determinative technique

for an analyte of concern with

selectivity or sensitivity equal or

superior to the selectivity or sensitivity

of the determinative technique in any

approved method, and that differs from

the determinative techniques employed

for that analyte in all approved

methods.

(E) Be accompanied by the

information specified at 40 CFR part

136, Appendix G.

(ii) A decision to recommend

proposal of a new method will be made

by the Director of the Analytical

Methods Staff within 90 days of receipt

of a complete application.

(2) Tier 1: application of a new

method by a single laboratory to one or

more PWSs.

(i) A person may develop a new

method for determination of an analyte

of concern by a single laboratory by

validating the method and developing

QC acceptance criteria from an

interlaboratory method validation study

or from a single-laboratory validation

study on a drinking water sample.

Details of the single-laboratory method

validation study and development of QC

acceptance criteria from a singlelaboratory or interlaboratory method

validation study are specified at

paragraph (b)(1) of this section and at 40

CFR part 136, Appendix E.

(ii) A person who develops a new

method under Tier 1 must submit the

method to EPA for a letter of approval.

The information that must be submitted

and the format for submission are

specified at 40 CFR part 136,

Appendixes E, F, and G.

(3) Tier 2: application of a new

method by all laboratories to all PWSs

in the water supply and distribution

industry (nationwide use).

(i) A person may develop a new

method for determination of an analyte

of concern in all PWSs in the water

supply and distribution industry by

developing QC acceptance criteria from

an interlaboratory method validation

study or from multiple, singlelaboratory validation studies as

specified in the Streamlining Guide, and

by validating the new method in a

minimum three (3) laboratories each of

which test samples from a minimum of

three (3) different PWS for a minimum

of nine (9) tests. In the method

validation study, each laboratory will

test all of the samples from the same set

of PWS samples and this set will

contain samples from a minimum of

three (3) different PWSs. To test the

modified method for potential matrix

effects, the three (3) PWS samples must

be collected from PWSs with

sufficiently different water quality

characteristics according to criteria

specified at paragraph (b)(2) and

(b)(1)(iii) of this section.

(ii) A person who develops a new

method under Tier 2 must submit the

method to EPA for approval and

inclusion in a table in this part 141. The

information that must be submitted

includes the results of the performance

tests required by paragraph (b)(2)(i) of

this section. This information and other

detailed information that must be

submitted and the format for submission

are specified at 40 CFR part 136,

Appendixes E, F, and G.

(d) Standardized QC and QC

acceptance criteria for modifications of

inorganic contaminant reference

methods at § 141.23(k)(1) of this section

are as follows:

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15046 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules
Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules 15047
15048 Federal Register / Vol. 62, No. 60 / Friday, March 28, 1997 / Proposed Rules

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(e) The number and type of required

tests, testing laboratories, matrices, and

replicate QC tests for method validation

depend on the tier at which the new or

modified wastewater or drinking water

method is validated. These

requirements are specified at paragraphs

(a), (b), (c) of this section and in the

table at § 136.5(d).

6. Section 141.40, paragraph (n)(11),

is proposed to be amended by revising

the table to read as follows:

§ 141.40 Special monitoring for inorganic

and organic contaminants.

* * * * *

(n) * * *

(11) * * *

TABLE 141.40(n)(11)

Parameter/methodology Reference

method

Other approved methods

EPA

Standard

methods

18th ed.1

Other

1. aldicarb

HPLC/Fl 531.1 6610

2. aldicarb sulfone

HPLC/Fl 531.1 6610

3. aldicarb sulfoxide

HPLC/Fl 531.1 6610

4. aldrin

GC/ECD 508.1 505, 508

GC/MS 525.2

5. butachlor

GC/MS 525.2

GC/NPD 507

6. carbaryl

HPLC/Fl 531.1 6610

7. dicamba

GC/ECD 515.2 515.1

HPLC

12. metribuzin

GC/ECD 508.1

GC/MS 525.2

GC/NPD 507

13. propachlor

GC/ECD 508.1 508

GC/MS 525.2

Note: The following acronyms are used in this table:

ECD—Electron Capture Detector.

Fl—Fluorescence.

GC—Gas Chromatography.

GC/MS—Gas Chromatography/Mass Spectrometry.

HPLC—High Performance Liquid Chromatography.

NPD—Nitrogen Phosphorous Detector.

UV—Ultraviolet Detector.

* * * * *

[FR Doc. 97–7221 Filed 3–27–97; 8:45 am]

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