[Federal Register Volume 59, Number 244 (Wednesday, December 21, 1994)]
[Unknown Section]
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From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 94-31254]


[[Page Unknown]]

[Federal Register: December 21, 1994]


_______________________________________________________________________

Part V





Environmental Protection Agency





_______________________________________________________________________



40 CFR Part 136



Water Pollution Control; Test Procedures Guidelines; Chlorinated 
Pesticides and PCBs; Proposed Rule
ENVIRONMENTAL PROTECTION AGENCY

40 CFR Part 136

[FRL-5125-3]

 

Guidelines Establishing Test Procedures for the Analysis of 
Pollutants; Chlorinated Pesticides and PCBs by Disk Extraction

AGENCY: Environmental Protection Agency (EPA).

ACTION: Proposed rule and request for comment.

-----------------------------------------------------------------------

SUMMARY: This proposed amendment to 40 CFR part 136 would approve the 
use of an additional procedure for the determination of chlorinated 
pesticides and PCBs in wastewater by adding appropriate citations to 
Tables IC and ID and by amending the incorporation by reference section 
of the regulation accordingly. The proposed method differs from 
currently approved methods in that the proposed method incorporates a 
disk of octadecyl bonded silica enmeshed in a matrix of inert PFTE 
fibrils for extraction of the analytes. The precision and recovery for 
the chlorinated pesticides and PCBs using this technique are not 
substantially different from those obtained using the liquid-liquid 
extraction technique already approved. Use of approved analytical 
techniques 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 January 20, 
1995.

ADDRESSES: Send comments to: James E. Longbottom, Environmental 
Monitoring Systems Laboratory--Cincinnati, U.S. Environmental 
Protection Agency, Cincinnati, OH 45268-0592.
    The comments should be labeled as ``Guidelines Establishing Test 
Procedures for the Analyses of Pollutants Under the Clean Water Act--
Chlorinated Pesticides and PCBs by Disk Extraction''.
    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. An additional copy 
of the record and supporting information is also available to the 
public for inspection and copying at the EPA Public Information 
Reference Unit, Room 2404. 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 procedure and performance data.
     Technical reviews of the proposed analytical techniques.
     Statistical reviews of the performance data.
     Recommendation 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 prohibits 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 available demonstrated control 
technology. 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). 
Dischargers seeking to use such alternate test procedures on a limited 
basis (eg. for their own discharge) must apply to the State or Regional 
EPA permitting office in which the discharge occurs under Sec. 136.4 
(d). As specified below, today's proposed rule would approve an 
optional nationwide alternate procedure for determination of 
chlorinated pesticides and PCBs in wastewater test samples.

III. The Disk Extraction Test Procedure

    The 3 M Corporation, in accordance with the regulations published 
at 40 CFR 136.5, applied for nationwide approval of their 
``Organochlorine Pesticides and PCBs in Wastewater Using EmporeTM 
Disk'' . 3M subsequently presented data to meet the method 
comparability criteria set forth in the EPA ``Protocol for Approval of 
Alternate Test Procedures for Inorganic and Organic Analytes in 
National Pollutant Discharge Elimination System Monitoring'', July 12, 
1993.
    Extraction and concentration are preparation steps that are 
required prior to the determination of many organic analytes that are 
found in wastewater. The disk extraction procedure is proposed as an 
alternate to the presently approved liquid-liquid extraction procedure.

A. Scope of the Procedure

    Method 3M 0222 is designed as an alternate test procedure for 
currently approved EPA Method 608. The EmporeTM disk is used in 
place of liquid-liquid extraction. This method is proposed as an 
alternate procedure for the determination of nineteen organochlorine 
pesticides and seven PCBs listed below:

Aldrin.............................  Heptachlor epoxide                 
alpha-BHC..........................  Methoxychlor                       
beta-BHC...........................  Toxaphene                          
Chlordane..........................  4,4'-DDD                           
delta-BHC..........................  4,4'-DDE                           
Dieldrin...........................  4,4'-DDT                           
Endosulfan I.......................  PCB-1016                           
Endosulfan II......................  PCB-1221                           
Endosulfan sulfate.................  PCB-1232                           
Endrin.............................  PCB-1242                           
Endrin aldehyde....................  PCB-1248                           
gamma-BHC..........................  PCB-1254                           
Heptachlor.........................  PCB-1260                           
                                                                        

    The parameters listed in the table can be determined by this 
method. EPA Method 608 is a gas chromatographic (GC) method applicable 
to the analysis of municipal and industrial discharges as provided 
under 40 CFR 136.1 for determination of the compounds listed. When the 
method is used to analyze unfamiliar samples for any or all of the 
compounds listed, compound identifications should be supported by at 
least one additional qualitative technique. The method describes 
analytical conditions for a second gas chromatographic column that can 
be used to confirm measurements made with the primary column.

B. Summary of the Methods

    A measured volume of sample, approximately 1-L, is extracted using 
a 90 mm EmporeTM disk. The disk is eluted with acetone followed by 
methylene chloride. The eluant is dried by pouring through anhydrous 
sodium sulfate and exchanged to hexane during concentration to a volume 
of 10-mL or less. The eluant is separated by gas chromatography and the 
analytes are then measured with an electron capture detector.
    The method provides a Florisil column cleanup procedure and an 
elemental sulfur removal procedure using activated copper powder to aid 
in the elimination of interferences that may be encountered.

C. Technical Justification for Proposed Procedure

    The recommendation for approval of these procedures is based on the 
data packages submitted by the applicant, 3M Corporation. EPA is 
approving the method based on the method description 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.
    3M Corporation provided test data using both the proposed procedure 
and the appropriate approved procedure to extract pesticides and PCBs 
from 10 wastewaters. The results from the proposed alternate method 
were compared to the approved EPA Method by EPA statisticians and 
chemists, who conducted detailed reviews of the data. The recovery and 
precision of the submitted data for both the approved and proposed 
methods were also compared to the recovery and precision acceptance 
criteria derived for EPA Method 608 from Performance Evaluation Studies 
WP 18 and 23.
    The Agency has judged the currently approved Method 608 method to 
be acceptable in their evaluation of the proposed procedure. EPA's 
Environmental Monitoring Systems Laboratory in Cincinnati, Ohio (EMSL-
Cincinnati) thoroughly reviewed and evaluated the supporting data 
submitted by the 3M Corporation. The reviews indicated that the 
analyses afforded comparable recovery and precision in the recommended 
concentration ranges for the listed organochlorine pesticides and PCBs. 
EPA is proposing approval of the EmporeTM disk procedure and is 
seeking public comment on the suitability of this procedure as an 
alternate procedure for use in the determination of the parameters 
listed. 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. Description of the proposed procedure is also 
available from 3M Corporation, 3M Center Building 220-9E-10, St. Paul, 
MN 55144-1000.
    Based on EMSL-Cincinnati's review, and pursuant to 40 CFR 136.5, 
EPA proposes to approve the 3M Corporation's ``Organochlorine 
Pesticides and PCBs in Wastewater Using EmporeTM Disk'' method as 
an acceptable alternative procedure for nationwide use. Specifically, 
the method exhibits sufficient precision and recovery to establish (1) 
its acceptability under Part 136 and (2) its comparability to the 
approved procedure for analysis of the stated organochlorine pesticides 
and PCBs. As an approved alternate test procedure, this procedure is 
acceptable for use by any person required to test for these parameters 
using Method 608.
    Public comment is requested concerning the suitability of this 
method for the determination of the specified analytes 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 an alternate 
analytical procedure which may be used by laboratories in measuring 
concentrations of organochlorine pesticides and PCBs using EPA Method 
608 and, therefore, would have no adverse economic impacts. This action 
was submitted to OMB for review under the Executive Order.

B. Regulatory Flexibility Act

    This amendment 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 proposed rule would give all 
laboratories the flexibility to use this alternate procedure or not to 
use it.

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.).

List of Subjects in 40 CFR Part 136

    Incorporation by reference, Water pollution control.

    Dated: December 13, 1994.
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:
    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, 
91 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. Section 136.3 is proposed to be amended as follows:
    a. In Table IC of paragraph (a) by revising entries 76. PCB-1016, 
77. PCB-1221, 78. PCB-1232, 79. PCB-1242, 80. PCB-1248, 81. PCB-1254, 
82. PCB-1260; and by adding footnote 8.
    b. In Table ID of paragraph (a) by revising entries 1. Aldrin, 8. 
-BHC, 9. -BHC, 10. -BHC, 11. -BHC 
(Lindane), 15. Chlordane, 18. 4,4'-DDD, 19. 4,4'-DDE, 20. 4,4'-DDT, 28. 
Dieldrin, 32. Endosulfan I, 33. Endosulfan II, 34. Endosulfan sulfate, 
35. Endrin, 36. Endrin aldehyde, 40. Heptachlor, 41. Heptachlor 
epoxide, 46. Methoxychlor, and 69. Toxaphene; and by adding footnote 8.
    c. By adding paragraph (b)(34).


Sec. 136.3   Identification of test procedures.

    (a) * * *

                 Table IC.--List of Approved Test Procedures for Non-Pesticide Organic Compounds                
----------------------------------------------------------------------------------------------------------------
                              EPA method No.\2\,\7\                                                             
       Parameter\1\        ---------------------------   Standard methods      ASTM              Other          
                               GC     GC/MS     HPLC         18th ed.                                           
----------------------------------------------------------------------------------------------------------------
                                                                                                                
                                                  * * * * * **                                                  
76. PCB-1016..............      608      625  .......  6410 B..............  .......  Note 3, p. 43; note 8.    
77. PCB-1221..............      608      625  .......  6410 B..............  .......  Note 3, p. 43; note 8.    
78. PCB-1232..............      608      625  .......  6410 B..............  .......  Note 3, p. 43; note 8.    
79. PCB-1242..............      608      625  .......  6410 B..............  .......  Note 3, p. 43; note 8.    
80. PCB-1248..............      608      625  .......  ....................  .......  Note 3, p. 43; note 8.    
81. PCB-1254..............      608      625  .......  6410 B..............  .......  Note 3, p. 43; note 8.    
82. PCB-1260..............      608      625  .......  6410 B, 6630 B......  .......  Note 3, p. 43; note 8.    
                                                                                                                
                                                  * * * * * * *                                                 
----------------------------------------------------------------------------------------------------------------
\1\All parameters are expressed in micrograms per liter (g/L).                                         
\2\The 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.                                          
* * * * * * *                                                                                                   
\7\Each 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 the part 136) in accordance    
  with procedures each in section 8.2 of each of these Methods. Additionally, each laboratory, on and on-going  
  bases 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.     
\8\``Organochlorine Pesticides and PCBs in Wastewater Using EmporeTM Disk'', 3M Corporation Revised 10/28/94.   


                          Table ID.--List of Approved Test Procedures for Pesticides\1\                         
----------------------------------------------------------------------------------------------------------------
                                                   Method No.                                                   
                            --------------------------------------------------------                            
   Parameter g/L                       Standard methods                                Other           
                              Method   EPA2,7       18th Ed.             ASTM                                   
----------------------------------------------------------------------------------------------------------------
1. Aldrin..................       GC      608  6630 B & C.......  D3086-90.........  Note 3, p. 7; note 4, p.   
                                                                                      30; note 8.               
                               GC/MS      625  6410 B...........  .................  ...........................
                                                                                                                
                                                  * * * * * **                                                  
8. -BHC...........       GC      608  6630 B&C.........  D3086-90.........  Note 3, p. 7; note 8.      
                               GC/MS   \5\625  6410 B...........  .................  ...........................
9. -BHC...........       GC      608  6630 C...........  D3086-90.........  Note 8.                    
                               GC/MS   \5\625  6410 B...........  .................  ...........................
10. -BHC..........       GC      608  6030 C...........  D3086-90.........  Note 8.                    
                               GC/MS   \5\625  6410 B...........  .................  ...........................
11. -BHC (Lindane)       GC      608  6630 B&C.........  D3086-90.........  Note 3, p. 7; note 4, p.   
                                                                                      30; note 8.               
                               GC/MS      625  6410 B...........  .................  ...........................
                                                                                                                
                                                  * * * * * * *                                                 
15. Chlordane..............       GC      608  6630 B&C.........  D3086-90.........  Note 3, p. 7; note 8.      
                               GC/MS      625  6410 B...........  .................  ...........................
                                                                                                                
                                                  * * * * * * *                                                 
18. 4,4'-DDD...............       GC      608  6630 B&C.........  D3086-90.........  Note 3, p. 7; note 4, p.   
                                                                                      30; note 8.               
                               GC/MS      625  6410 B...........  .................  ...........................
19. 4,4'-DDD...............       GC      608  6630 B&C.........  D3086-90.........  Note 3, p. 7; note 4, p.   
                                                                                      30; note 8.               
                               GC/MS      625  6410 B...........  .................  ...........................
20. 4,4'-DDD...............       GC      608  6630 B&C.........  D3086-90.........  Note 3, p. 7; note 4, p.   
                                                                                      30; note 8.               
                               GC/MS      625  6410 B...........  .................  ...........................
                                                                                                                
                                                  * * * * * * *                                                 
28. Dieldrin...............       GC      608  6630 B&C.........  .................  Note 3, p. 7; note 4, p.   
                                                                                      30; note 8.               
                               GC/MS      625  6410 B...........  .................  ...........................
                                                                                                                
                                                  * * * * * * *                                                 
32. Endosulfan I...........       GC     6087  6630 B&C.........  D3086-90.........  Note 3, p. 7; note 8.      
                               GC/MS   \5\625  6410 B...........  .................  ...........................
33. Endosulfan II..........       GC      608  6630 B&C.........  D3086-90.........  Note 3, p. 7; note 8.      
                               GC/MS   \5\625  6410 B...........  .................  ...........................
34. Endosulfan sulfate.....       GC      608  6630 C...........  .................  Note 8.                    
                               GC/MS      625  6410 B...........  .................  ...........................
35. Endrin.................       GC      608  6630 B&C.........  D3086-90.........  Note 3, p. 7; note 4, p.   
                                                                                      30; note 8.               
                               GC/MS   \5\625  6410 B...........  .................  ...........................
36. Endrin aldehyde........       GC      608  .................  .................  Note 8.                    
                               GC/MS      625  .................  .................  ...........................
                                                                                                                
                                                  * * * * * * *                                                 
40. Heptachlor.............       GC      608  6630 B&C.........  D3086-90.........  Note 3, p. 7; note 4, p.   
                                                                                      30; note 8.               
                               GC/MS      625  6410 B...........  .................  ...........................
41. Heptachlor epoxide.....       GC      608  6630 B&C.........  D3086-90.........  Note 3, p. 7; Note 4, p.   
                                                                                      30; note 6, p. S73; note  
                                                                                      8.                        
                               GC/MS      625  6410 B...........  .................  ...........................
                                                                                                                
                                                  * * * * * * *                                                 
46. Methoxychlor...........       GC  .......  6630 B&C.........  D3086-90.........  Note 3, p. 7; note 4, p.   
                                                                                      30; note 8.               
                                                                                                                
                                                  * * * * * * *                                                 
69. Toxaphene..............       GC      608  6630 B&C.........  D3086-90.........  Note 3, p. 7; note 4, p.   
                                                                                      30; note 8.               
                               GC/MS      625  6410 B...........  .................  ...........................
                                                                                                                
                                                  * * * * * * *                                                 
----------------------------------------------------------------------------------------------------------------
\1\Pesticides are listed in this table by common name for the convenience of the reader. Additional pesticides  
  may be found under Table IC, where entries are listed by chemical name.                                       
\2\The 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).                                      
\5\The method may be extended to include -BHC, -BHC, endosulfan I, endosulfan II, and endrin. 
  However, when they are known to exist in the sample, 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).   
\7\Each 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.                       
\8\``Organochlorine Pesticides and PCBs in Wastewater Using EmporeTM Disk'', 3M Corporation, Revised 10/28/94.  

    (b) * * * 
    References, Sources, Costs, and Table citations:
* * * * *
    (34) ``Organochlorine Pesticides and PCBs in Wastewater Using 
EmporeTM Disk'', Test Method 3M 0222, Revised 10/28/94. 3M 
Corporation, 3M Center Building 220-9E-10, St. Paul, MN 55144-1000. 
Methods available from 3M Corporation. Table IC and ID, Note 8.
[FR Doc. 94-31254 Filed 12-20-94; 8:45 am]
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