[Federal Register Volume 60, Number 166 (Monday, August 28, 1995)]
[Rules and Regulations]
[Pages 44670-44672]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 95-21172]




[[Page 44669]]

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Part V





Environmental Protection Agency





_______________________________________________________________________



40 CFR Part 136



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

Federal Register / Vol. 60, No. 166 / Monday, August 28, 1995 / Rules 
and Regulations 

[[Page 44670]]


ENVIRONMENTAL PROTECTION AGENCY

40 CFR Part 136

[FRL-5280-8]


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

AGENCY: Environmental Protection Agency (EPA).

ACTION: Final rule.

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SUMMARY: This amendment approves 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: This rule shall be effective on September 27, 1995.
    In accordance with 40 CFR 23.2 (45 FR 26048), these amendments to 
the regulation shall be considered issued for purposes of judicial 
review at 1 p.m. eastern time, September 11, 1995.
    The incorporation by reference of certain publications listed in 
the regulation is approved by the Office of the Federal Register as of 
September 27, 1995.
    Under section 509(b)(1) of the Clean Water Act, judicial review of 
these amendments can be obtained only by filing a petition for review 
in the United States Court of Appeals within 120 days after they are 
considered issued for purposes of judicial review. Under section 
509(b)(2) of the Clean Water Act, these amendments may not be 
challenged later in civil or criminal proceedings brought by EPA to 
enforce these requirements.
FOR FURTHER INFORMATION CONTACT: Mr. James E. Longbottom, National 
Exposure Research Laboratory, Office of Research and Development, U.S. 
Environmental Protection Agency, Cincinnati, Ohio 45268. Telephone 
number: (513) 569-7308.

SUPPLEMENTARY INFORMATION:

I. Authority

    This 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 rule approves 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 are not available for use to determine TKN 
concentrations greater than 10 mg/L 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. 

[[Page 44671]]


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 approvals of these procedures are based on the data packages 
submitted by the applicant, Perstorp Analytical. EPA is approving 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 Aquatic Research Division of the National Exposure 
Research Laboratory (formerly the Environmental Monitoring Systems 
Laboratory) in Cincinnati, Ohio (NERL-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 proposed approval 
of the TKN procedures and sought public comment on the suitability of 
these three methods as alternate procedures for use in the 
determination of TKN in 60 FR 26600 (May 17, 1995). The administrative 
record is on file at NERL-Cincinnati, 26 W. Martin Luther King Dr., 
Cincinnati, Ohio 45268. The record is available for public inspection. 
The approved procedures are available from Perstorp Analytical Company, 
9445 SW Ridder Rd., Suite 310, P.O. Box 648, Wilsonville, OR 97070.
    Based on EMSL-Cincinnati's review, and pursuant to 40 CFR Section 
136.5, EPA is approving 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.

IV. Public Comments

    The Agency requested written comments on the proposal to approve 
the three methods for TKN, but no comments were received.

V. Regulatory Requirements

A. Executive Order 12866

    Under Executive Order 12866, EPA must judge whether a regulation is 
``significant'' 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 final rule would simply specify 
alternative analytical methods which may be used by laboratories in 
measuring concentrations of TKN and, therefore, will 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 rule 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 the 
Office of Management and Budget (OMB) for review in compliance with the 
Paperwork Reduction Act, (44 U.S.C. 3501 et seq.).

D. Unfunded Mandates

    Under Section 202 of the Unfunded Mandates Reform Act of 1995, 
signed into law on March 22, 1995, EPA must prepare a written statement 
to accompany rules where the estimated costs to State, local, or tribal 
governments, or to the private sector will be $100 million or more in 
any one year. Under Section 205, EPA must select the most cost-
effective and least burdensome alternative that achieves the objective 
of such a rule and that is consistent with statutory requirements. 
Section 203 requires EPA to establish a plan for informing and advising 
any small governments that may be significantly and uniquely affected 
by the rule.
    EPA estimates that the costs to State, local or tribal governments, 
or the private sector, from this rule will be far less than Sec. 100 
million. This rule should have minimal impact, if any, on the existing 
regulatory burden imposed on NPDES permittees required to monitor for 
regulated pollutants because the rule would merely make additional 
options available to the laboratory analyst conducting an existing 
approved test method. EPA has determined that an unfunded mandates 
statement therefore is unnecessary. Similarly, the method 

[[Page 44672]]
approved today does not establish any regulatory requirements that 
might significantly or uniquely affect small governments.

List of Subjects in 40 CFR Part 136

    Environmental protection, Incorporation by reference, Water 
pollution control.

    Dated: August 14, 1995.
Carol M. Browner,
Administrator.

    In consideration of the preceding, EPA amends part 136 of title 40 
of the Code of Federal Regulations 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. (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. In 136.3(a), Table IB is amended by revising entry 31 and by 
adding footnotes 39 through 41 to read as follows:


Sec. 136.3  Identification of test procedures.

    (a) * * *

                                                  Table 1B.--List of Approved Inorganic Test Procedures                                                 
--------------------------------------------------------------------------------------------------------------------------------------------------------
                                                                 Standard methods 18th                                                                  
           Parameter, units and method              EPA\1\\35\            Ed.                      ASTM                   USGS\2\              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.............  D3590-89(A)............  .......................  973.483.     
        Nesslerization...........................        351.3  4500-NH3 C.............  D3590-89(A)............  .......................  .............
        Electrode................................        351.3  4500-NH3 F or G........  .......................  .......................  .............
  Automated phenate colorimetric.................        351.1  .......................  .......................  I-4551-788.............  .............
  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.     
                                                                                                                                                        
                   *                  *                  *                  *                  *                  *                  *                  
--------------------------------------------------------------------------------------------------------------------------------------------------------
\1\ ``Methods for Chemical Analysis of Water and Wastes'', U.S. Environmental Protection Agency, Aquatic Research Division, National Exposure Research  
  Laboratory-Cincinnati, 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.                                   
                                                                                                                                                        
*         *         *         *         *                                                                                                               
\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       
  Corporation.                                                                                                                                          
\40\ Nitrogen, Total Kjeldahl, Method PAI-DK02 (Block Digestion, Steam Distillation, Colorimetric Detection), revised 12/22/94, Perstop Analytical      
  Corporation.                                                                                                                                          
\41\ Nitrogen, Total Kjeldahl, Method PAI-DK03 (Block Digestion, Automated FIA Gas Diffusion), revised 12/22/94, Perstop Analytical Corporation.        
                                                                                                                                                        
*         *         *         *         *                                                                                                               

    3. In 136.3(b) the list entitled ``References, Sources, Costs, and 
Table Citations'' is amended by adding paragraphs (35)-(37) to read as 
follows:


Sec. 136.3  Identification of test procedures.

* * * * *
    (b) * * *

    References, Sources, Costs, and Table citations:
* * * * *
    (35) ``Nitrogen, Total Kjeldahl, Method PAI-DK01 (Block 
Digestion, Steam Distillation, Titrimetric Detection)'', revised 12/
22/94. Available from Perstorp Analytical Corporation, 9445 SW 
Ridder Rd., Suite 310, P.O. Box 648, Wilsonville, OK 97070. Table 
IB, Note 39.
    (36) ``Nitrogen, Total Kjeldahl, Method PAI-DK02 (Block 
Digestion, Steam Distillation, Colorimetric Detection)'', revised 
12/22/94. Available from Perstorp Analytical Corporation, 9445 SW 
Ridder Rd., Suite 310, P.O. Box 648, Wilsonville, OK 97070. Table 
IB, Note 40.
    (37) ``Nitrogen, Total Kjeldahl, Method PAI-DK03 (Block 
Digestion, Automated FIA Gas Diffusion)'', revised 12/22/94. 
Available from Perstorp Analytical Corporation, 9445 SW Ridder Rd., 
Suite 310, P.O. Box 648, Wilsonville, OK 97070. Table IB, Note 41.

[FR Doc. 95-21172 Filed 8-25-95; 8:45 am]
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