26600 Federal Register / Vol. 60, No. 95 / Wednesday, May 17, 1995 / Proposed Rules

ENVIRONMENTAL PROTECTION

AGENCY

40 CFR Part 136

[FRL–5206–8]

Guidelines Establishing Test

Procedures for the Analysis of

Pollutants; Total Kjeldahl Nitrogen

AGENCY: Environmental Protection

Agency (EPA).

ACTION: Proposed rule and request for

comment.

SUMMARY: This proposed amendment

would approve the use of three

additional test procedures at Part 136

for the determination of Total Kjeldahl

Nitrogen (TKN) in wastewater. Use of

approved test procedures is required

whenever the waste constituent

specified is required to be measured for:

an NPDES permit application; discharge

monitoring reports; state certification;

and other requests from the permitting

authority for quantitative or qualitative

effluent data. Use of approved test

procedures is also required for the

expression of pollutant amounts,

characteristics, or properties in effluent

limitations guidelines and standards of

performance and pretreatment

standards, unless otherwise specifically

noted or defined.

DATES: Comments on this proposal will

be accepted until June 16, 1995.

ADDRESSES: Send comments to: James E.

Longbottom, Environmental Monitoring

Systems Laboratory-Cincinnati, U.S.

Environmental Protection Agency,

Cincinnati, OH 45268–0525. The

comments should be labeled as

‘‘Guidelines Establishing Test

Procedures for the Analyses of

Pollutants Under the Clean Water Act—

Total Kjeldahl Nitrogen.

The record and all supporting

information on this proposal is available

to the public for inspection or copying

during normal business hours at the

Cincinnati Laboratory. The public

should contact James E. Longbottom at

(513–569–7308) for access. A complete

copy of the record and supporting

information is also available to the

public for inspection and copying at the

Water Docket, U.S. Environmental

Protection Agency, 401 M Street, SW.,

Washington, DC 20460. For access to

Water Docket materials, call (202) 260–

3027 between 9 am and 3:30 pm for an

appointment. For information about

materials in the docket see

SUPPLEMENTARY INFORMATION.

FOR FURTHER INFORMATION CONTACT: Mr.

James E. Longbottom, Environmental

Monitoring Systems Laboratory, Office

of Research and Development, U.S.

Environmental Protection Agency,

Cincinnati, Ohio 45268. Telephone

number: (513) 569–7308.

SUPPLEMENTARY INFORMATION:

Docket Materials

Materials in the public docket include

the following:

• Copy of the proposed procedures

and performance data.

• Technical reviews of the proposed

analytical techniques.

• Statistical reviews of the

performance data.

• Recommendations for Nationwide

Approval from the Director,

Environmental Monitoring Systems

Laboratory-Cincinnati.

I. Authority

This proposed regulation is issued

under authority of sections 301, 304(h)

and 501(a) of the Clean Water Act, 33

U.S.C. 1251 et seq. (the Federal Water

Pollution Control Act Amendments of

1972 as amended) (the ‘‘Act’’). Section

301 of the Act forbids the discharge of

any pollutant into navigable waters

unless the discharge complies with a

National Pollutant Discharge

Elimination System (NPDES) permit,

issued under section 402. Section 304(h)

of the Act requires the Administrator of

the EPA to ‘‘promulgate guidelines

establishing test procedures for the

analysis of pollutants that shall include

the factors which must be provided in

any certification pursuant to section 401

of this Act or permit application

pursuant to section 402 of this Act’’.

Section 501(a) of the Act authorizes the

Administrator to ‘‘prescribe such

regulations as are necessary to carry out

his functions under this Act’’.

II. Regulatory Background

The CWA establishes two principal

bases for effluent limitations. First,

existing discharges are required to meet

technology-based effluent limitations.

New source discharges must meet new

source performance standards based on

the best demonstrated technology-based

controls. Second, where necessary,

additional requirements are imposed to

assure attainment and maintenance of

water quality standards established by

the States under Section 303 of the

CWA. In establishing or reviewing

NPDES permit limits, EPA must ensure

that permitted discharges will not cause

or contribute to a violation of water

quality standards, including designated

water uses.

For use in permit applications,

discharge monitoring reports, and state

certification and to ensure compliance

with effluent limitations, standards of

performance, and pretreatment

standards, EPA has promulgated

regulations providing nationallyapproved testing procedures at 40 CFR

Part 136. Test procedures have

previously been approved for 262

different parameters. Those procedures

apply to the analysis of inorganic

(metal, non-metal, mineral) and organic

chemical, radiological, bacteriological,

nutrient, demand, residue, and physical

parameters.

Additionally, some particular

industries may discharge pollutants for

which test procedures have not been

proposed and approved under 40 CFR

Part 136. Under 40 CFR Part 122.41

permit writers may impose monitoring

requirements and establish test methods

for pollutants for which no approved

Part 136 method exists. 40 CFR 122.41(j)

(4). EPA may also approve additional

test procedures when establishing

industry-wide technology-based effluent

limitations guidelines and standards as

described at 40 CFR 401.13.

The procedures for approval of

alternate test procedures (ATPs) are

described at 40 CFR 136.4 and 136.5.

Under these procedures the

Administrator may approve alternate

test procedures for nationwide use

which are developed and proposed by

any person. 40 CFR 136.4 (a). Under

136.4 (d), dischargers seeking to use

such alternate procedures on a limited

basis (e.g. for their own discharge) must

apply to the State or Regional EPA office

in which the discharge occurs. As

specified below, today’s proposed rule

would approve optional nationwide

alternate procedures for the

determination of TKN in wastewater test

samples.

III. The Total Kjeldahl Nitrogen (TKN)

Test Procedures

The Perstorp Analytical Corporation,

in accordance with the regulations

published at 40 CFR 136.5, applied for

nationwide approval of three alternate

procedures for the determination of

TKN in wastewater.

A. Scope of the Procedures

The applicable ranges for the

titrimetric method (PAI–DK01) and

colorimetric method (PAI–DK02) are 0.4

to 10 mg/L, when analyzing a 100 mL

sample. The applicable range for the gas

diffusion method (PAI–DK03) is 0.2 to

10 mg/L when analyzing a 200 μL

sample. The method detection limit has

been determined to be 0.15 mg/L for the

titrimetric and the colorimetric methods

and 0.02 mg/L for the gas diffusion

method. These methods would not be

available for use to determine TKN

concentrations greater than 10 mg/L
Federal Register / Vol. 60, No. 95 / Wednesday, May 17, 1995 / Proposed Rules 26601

unless one of the following two

requirements are met:

a. Dilution of the TKN concentration

of a sample to a level less than, or equal

to 10 mg/L, before the initiation of the

analysis, multiplication of the TKN

concentration observed in the digested,

diluted sample by the appropriate

dilution factor, and demonstration of

acceptable accuracy (percent recovery)

as required in the Quality Control

section of the method.

b. Demonstration of the applicability

of a specific scope extension by

demonstrating calibration range

linearity, laboratory performance, and

analyte percent recovery, particularly in

fortified samples, as outlined in the

Quality Control section.

B. Summary of the Methods

TKN is defined as the sum of free

ammonia and organic nitrogen

compounds which are converted to

ammonium sulfate under the conditions

described. The procedures convert

nitrogen components of biological origin

such as amino acids, proteins and

peptides to ammonia but may not

convert the nitrogenous compounds of

some industrial wastes such as amines,

nitro compounds, hydrazones, oximes,

semicarbazones and some refractory

tertiary amines.

For all three methods, the sample is

heated in a block digester with

concentrated sulfuric acid, potassium

sulfate and copper sulfate and

evaporated until the solution becomes

colorless or pale yellow. The blockdigested sample is cooled and diluted to

volume. For the colorimetric and

titrimetric methods the cooled, diluted

solution is made alkaline with a

hydroxide-thiosulfate solution and

distilled in an automated distillation

system. In the colorimetric method

(Method PAI–DK01) the ammonia in the

alkaline digestate is measured at 400–

425 nm after reaction with Nessler

reagent. In Method PAI–DK02, the

ammonia is distilled into a boric acid

receiving solution and is measured by

automated or manual titration with 0.02

N H2SO4 to a bromocresol green methyl

red indicator endpoint. In the FIA

system (Method PAI–DK03), a 200-μL

aliquot of the digested and diluted

sample is injected into the flow

injection manifold. The subsequent

addition of NaOH releases the ammonia

from the ammonium sulfate originally

present in the digested sample. The

released ammonia passes through a gas

diffusion membrane into an indicator

receiving solution which is monitored at

590 nm. The extent of indicator color

change is proportional to the

concentration of TKN present in the

sample.

C. Technical Justification for Proposed

Procedures

The recommendations for approval of

these procedures are based on the data

packages submitted by the applicant,

Perstorp Analytical. EPA is proposing to

approve the methods based on the

method descriptions in EPA’s

Environmental Monitoring Management

Council format, comparative analyses

using the proposed and approved

procedures, and EPA’s technical and

statistical reviews of each data package.

Perstorp Analytical provided test data

comparing the three proposed

procedures with an appropriate

approved procedure. All three proposed

methods were compared to the

approved EPA Ion Selective Electrode

Method 351.4; EPA statisticians and

chemists conducted independent

reviews of the data. The submitted

recovery data for both the approved and

proposed methods were also compared

to the recovery acceptance criteria

derived from results for block digester

analyses (EPA Method 351.4) in EPA’s

Performance Evaluation Studies WP 18

through 23.

The Agency has judged the block

digester electrode procedure (EPA

Method 351.3), utilized as the reference

approved method by the applicant to be

applicable in the evaluation of the three

proposed procedures. EPA’s

Environmental Monitoring Systems

Laboratory in Cincinnati, Ohio (EMSLCincinnati), thoroughly reviewed and

evaluated the supporting data submitted

by Perstorp. The reviews indicated that

the analyses afforded comparable

recovery and precision in the

recommended concentration ranges for

TKN. EPA is proposing approval of the

TKN procedures and is seeking public

comment on the suitability of these

three methods as alternate procedures

for use in the determination of TKN.

The administrative record is on file at

EMSL-Cincinnati, 26 W. Martin Luther

King Dr., Cincinnati, Ohio 45268. The

record is available for public inspection.

Descriptions of the proposed procedures

are also available from Perstorp

Analytical Company, 1256 Stockton, St.

Helena, CA 94574.

Based on EMSL-Cincinnati’s review,

and pursuant to 40 CFR Section 136.5,

EPA proposes to approve the Perstorp

titrimetric, colorimetric, and FIA gas

diffusion methods for TKN as

acceptable alternative test procedures

for nationwide use. Specifically, the

methods exhibit sufficient precision and

recovery to establish (1) their

acceptability under Part 136 and (2)

their comparability to other approved

procedures for analysis of TKN. As

approved alternate test procedures,

these methods are acceptable for use by

any person required to test for TKN.

Public comment is requested

concerning the suitability of these

methods for the determination of TKN

in wastewater.

IV. Regulatory Requirements

A. Executive Order 12866

Under Executive Order 12866, EPA

must judge whether a regulation is

‘‘major’’ and, therefore, requires a

regulatory impact analysis. EPA has

determined that this regulation is not

major as it will not result in an effect on

the economy of $100 million or more, a

significant increase in cost or prices, or

any of the effects described in the

Executive Order. This proposed rule

would simply specify alternate

analytical methods which may be used

by laboratories in measuring

concentrations of TKN and, therefore,

would have no adverse economic

impacts. The Office of Management and

Budget (OMB) has waived Executive

Order 12866 review of the proposal.

B. Regulatory Flexibility Act

This proposed rulemaking is

consistent with the objectives of the

Regulatory Flexibility Act (5 U.S.C. 602

et seq.) because it will not have a

significant economic impact on a

substantial number of small entities.

The procedure included in this rule

gives all laboratories the flexibility to

use these alternate methods or not to

use them.

C. Paperwork Reduction Act

This rule contains no requests for

information activities and, therefore, no

information collection request (ICR) was

submitted to OMB for review in

compliance with the Paperwork

Reduction Act, (44 U.S.C. 3501 et seq.).

List of Subjects in 40 CFR Part 136

Environmental protection,

Incorporation by reference, Water

pollution control.

Dated: May 8, 1995.

Carol M. Browner,

Administrator.

For the reasons set out in the

preamble, part 136 of title 40 of the

Code of Federal Regulations is proposed

to be amended as follows:

PART 136—[AMENDED]

1. The authority citation for part 136

continues to read as follows:

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

501(a) Public Law 95–217, Stat. 1566, et seq.
26602 Federal Register / Vol. 60, No. 95 / Wednesday, May 17, 1995 / Proposed Rules

(33 U.S.C. 1251 et seq.) (the Federal Water

Pollution Control Act Amendments of 1972

as amended by the Clean Water Act of 1977).

2. Section 136.3 is proposed to be

amended as follows:

a. In Table IB in paragraph (a), by

revising entry 31 and by adding notes 39

through 41.

b. By adding paragraphs (b)(35)

through (b)(37).

The revision and additions read as

follows:

§ 136.3 Identification of test procedures.

(a) * * *

TABLE 1B.—LIST OF APPROVED INORGANIC TEST PROCEDURES

Parameter, units and method

Reference (method number of page)

EPA1, 35 Std. Methods

18th ed. ASTM USGS2 Other

* * * * * * *

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 3590–89(A) . ................... 3 973.48

Nesslerization ................................................................................... 351.3 4500–NH3 C 3590–89(A) .

Electrode .......................................................................................... 351.3 4500–NH3 F

or G.

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

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

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

Manual or block digester potentiometric ................................................. 351.4 ..................... D3590–89(A)

Block Digester, followed by:

Auto distillation and Titration, or ...................................................... ............... ..................... ..................... ................... Note 39

Nesslerization ............................................................................ ............... ..................... ..................... ................... Note 40

Flow injection gas diffusion .............................................................. ............... ..................... ..................... ................... Note 41

* * * * * * *

Table 1B 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).

* * * * *

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).

* * * * *

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’’.

* * * * *

39 Nitrogen, Total Kjeldahl, Method PAI–DK01 (Block Digestion, Steam Distillation, Titrimetric Detection), revised 12/22/94, Perstop Analytical. 40 Nitrogen, Total Kjeldahl, Method PAI–DK02 (Block Digestion, Steam Distillation, Colorimetric Detection), revised 12/22/94, Perstop Analytical. 41 Nitrogen, Total Kjeldahl, Method PAI–DK03 (Block Digestion, Automated FIA Gas Diffusion), revised 12/22/94, Perstop Analytical.

* * * * *

(b) * * *

References, Sources, Costs, and Table Citations:

* * * * *

35 ‘‘Nitrogen, Total Kjeldahl, Method PAI–DK01 (Block Digestion, Steam Distillation, Titrimetric Detection)’’, revised 12/22/94, Perstop Analytical.

Method available from Perstorp Analytical Corporation, 1256 Stockton, St. Helena, CA 94574. Table 1B, Note 39. 36 ‘‘Nitrogen, Total Kjeldahl, Method PAI–DK02 (Block Digestion, Steam Distillation, Colorimetric Detection)’’, revised 12/22/94, Perstop Analytical. Method available from Perstorp Analytical Corporation, 1256 Stockton, St. Helena, CA 94574. Table 1B, Note 40. 37 ‘‘Nitrogen, Total Kjeldahl, Method PAI–DK03 (Block Digestion, Automated FIA Gas Diffusion)’’, revised 12/22/94, Perstop Analytical. Method

available from Perstorp Analytical Corporation, 1256 Stockton, St. Helena, CA 94574. Table 1B, Note 41.

* * * * *

[FR Doc. 95–11901 Filed 5–16–95; 8:45 am]

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