[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





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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:
    <bullet> Copy of the proposed procedures and performance data.
    <bullet> Technical reviews of the proposed analytical techniques.
    <bullet> Statistical reviews of the performance data.
    <bullet> 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 <greek-m>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 H<INF>2SO<INF>4 to a 
bromocresol green methyl red indicator endpoint. In the FIA system 
(Method PAI-DK03), a 200-<greek-m>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)                  
                                         -----------------------------------------------------------------------
       Parameter, units and method                     Std. Methods                                             
                                           EPA<SUP>1,35       18th ed.            ASTM           USGS<SUP>2        Other  
----------------------------------------------------------------------------------------------------------------
                                                                                                                
*                  *                  *                  *                  *                  *                
                                                        *                                                       
31. Kjeldahl Nitrogen--Total, (as N), mg/                                                                       
 L;                                                                                                             
    Digestion and distillation followed       351.3  4500-NH<INF>3 B or C.  D3590-89(A).....                         
     by:.                                                                                                       
        Titration.......................      351.3  4500-NH<INF>3 E......  3590-89(A)......  ...........  <SUP>3973.48   
        Nesslerization..................      351.3  4500-NH<INF>3 C......  3590-89(A)......                         
        Electrode.......................      351.3  4500-NH<INF>3 F or G.  .......<INF>.........                         
    Automated phenate colorimetric......      351.1  ................  ................   <SUP>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]
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