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

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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