Federal Register, Volume 60 Issue 95 (Wednesday, May 17, 1995)

[Federal Register Volume 60, Number 95 (Wednesday, May 17, 1995)]
[Proposed Rules]
[Pages 26600-26602]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 95-11901]

[[Page 26599]]

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Part VI

Environmental Protection Agency

_______________________________________________________________________

40 CFR Part 136

Guidelines Establishing Test Procedures for the Analysis of Pollutants;
Total Kjeldahl Nitrogen; Proposed Rule

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

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.

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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 nationally-approved 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 L 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 [[Page 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
block-digested 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-L 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 (EMSL-Cincinnati), 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. [[Page 26602]] (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:

Sec. 136.3 Identification of test procedures.

(a) * * *

Table 1B.--List of Approved Inorganic Test Procedures
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Reference (method number of page)
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Parameter, units and method Std. Methods
EPA^{1,35 18th ed. ASTM USGS^{2 Other
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* * * * * *
*
31. Kjeldahl Nitrogen--Total, (as N), mg/
L;
Digestion and distillation followed 351.3 4500-NH3 B or C. D3590-89(A).....
by:.
Titration....................... 351.3 4500-NH3 E...... 3590-89(A)...... ........... ^{3973.48
Nesslerization.................. 351.3 4500-NH3 C...... 3590-89(A)......
Electrode....................... 351.3 4500-NH3 F or G. ................
Automated phenate colorimetric...... 351.1 ................ ................ ^{8I-4551-78
Semi-automated block digester 351.2 ................ D3590-89(B).....
colorimetric.
Manual or block digester 351.4 ................ D3590-89(A).....
potentiometric.
Block Digester, followed by:
Auto distillation and Titration, ......... ................ ................ ........... Note 39
or.
Nesslerization.............. ......... ................ ................ ........... Note 40
Flow injection gas diffusion.... ......... ................ ................ ........... Note 41

* * * * * *
*
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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.
\2\Fishman, 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).
* * * * *
\8\The approved method is that cited in ``Methods for Determination of Inorganic Substances in Water and Fluvial
Sediments'', USGS TWRI, Book 5, Chapter A1 (1979).
* * * * *
\35\Precision 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]
BILLING CODE 6560-50-P}}}}